TW201421129A - Liquid crystal alignment agent, liquid crystal alignment film and method for forming the same, phase difference film and liquid crystal element of liquid crystal display device - Google Patents

Abstract

A liquid crystal alignment agent, a liquid crystal alignment film and a method for forming the same, a phase difference film and a liquid crystal element of a liquid crystal display device are provided. The liquid crystal alignment agent stably shows a relatively low pre-tilt angle through a light alignment method, and has an excellent coating property (printability) even when an universal solvent is used. The liquid crystal alignment agent is characterized by having at least one polymer selected from a group consisting of poly organic siloxane, polyamide, poly(thio)ester and (meth)acrylic acid copolymer, wherein the polymer has a divalent group represented by the following formula (1).

Description

Liquid crystal alignment agent, liquid crystal alignment film and forming method thereof, retardation film of liquid crystal display element, and liquid crystal cell

This invention relates to a liquid crystal alignment agent.

More specifically, the present invention relates to a liquid crystal alignment agent which can impart good liquid crystal alignment property through a photo-alignment method and has a high degree of freedom in selection using a substrate.

In a liquid crystal display element, a retardation film having a liquid crystal layer, or the like, The liquid crystal molecules are aligned in a predetermined direction with respect to the substrate, and a liquid crystal alignment film is provided on the surface of the substrate. This liquid crystal alignment film is usually formed by a method (rubbing method) of rubbing the surface of the organic film formed on the surface of the substrate in one direction by a cloth material such as rayon. However, when the liquid crystal alignment film is formed by the rubbing treatment, dust or static electricity is likely to be generated in the rubbing step. Therefore, dust adheres to the surface of the alignment film to cause display failure, and in addition, it has a thin film transistor ( Thin Film In the case of a substrate of a Transistor (TFT) device, there is also a problem that the circuit of the TFT element is broken by the generated static electricity, resulting in a decrease in product yield. Therefore, as another method of aligning liquid crystals in a liquid crystal display element, a photo-alignment method is disclosed in which a radiation-sensitive organic thin film formed on a surface of a substrate is irradiated with polarized or non-polarized radiation, thereby imparting liquid crystal alignment. Capability (refer to Patent Document 1 to Patent Document 4). This photo-alignment method is expected to be applied to a retardation film having a liquid crystal layer, in addition to being expected to be applied to a liquid crystal display element.

Regarding liquid crystal display elements, in addition to twisted nematic (Twisted Nematic, In-Plane Switching (IPS), other than liquid crystal display elements of liquid crystal cells having a vertical electric field type such as a TN) type, a Super Twisted Nematic (STN) type, or a Vertical Alignment (VA) type. A liquid crystal display device of a transverse electric field type such as a Fringe Field Switching (FFS) type, which forms electrodes on only one side of a pair of substrates arranged in opposite directions, is also known. An electric field is generated in a direction parallel to the substrate (Patent Documents 5 to 7). This lateral electric field type liquid crystal display element has wider viewing angle characteristics than a vertical electric field type liquid crystal display element, and can perform high quality display. In the liquid crystal display device of the transverse electric field type, since the liquid crystal molecules respond to the electric field only in a direction parallel to the substrate, the refractive index change in the long-axis direction of the liquid crystal molecules is not a problem, even when the viewing angle is changed, the observer sees Since the contrast and the display color have little change in shade, high-quality display can be performed regardless of the angle of view. In order to obtain such an advantageous effect, it is advantageous that the incidence angle of the incident polarized light is less, so the liquid crystal in the transverse electric field mode In the display element, it is desirable that the pretilt angle of the initial alignment characteristic when no electric field is applied is low.

In the liquid crystal display element of the transverse electric field mode, in the liquid crystal alignment film In order to avoid the disadvantages of the rubbing method, it is preferable to use a photo-alignment method. However, the liquid crystal alignment agent which can be used for the photo-alignment method contains an aromatic structure in a large ratio in order to impart photosensitivity to the polymer contained therein. However, when a liquid crystal alignment film containing an aromatic structure in a large proportion is used, the pretilt angle is inevitably increased, and the advantageous effects as described above in the liquid crystal display device of the transverse electric field type are canceled.

As a liquid which stably exhibits a relatively low pretilt angle by a photo-alignment method As a crystal alignment film material, a technique of introducing a cyclobutane ring into a main chain of a polyimine has been disclosed (Patent Document 8). This technique is based on the idea of decomposing a cyclobutane ring existing in a rigid polyimine by light irradiation, forming an uneven shape in a polymer film, and expressing the liquid crystal alignment ability by the uneven shape. This technology was an old technology that was filed in 1997 but has not yet reached practicality. The reason can be considered as the following two points.

(1) The polyimine is a solution of the following, that is, as a poly The coating film formed by the solution of the polyamine acid of the precursor of the amine is formed by thermal imidization, but the thermal imidization is not completely performed. Therefore, a soft guanamine structure remains in a part of the polymer, so decomposition of the cyclobutane ring due to light irradiation becomes insufficient, so that it is difficult to obtain a desired liquid crystal alignment ability; and (2) polyproline Or polyimine has a lack of solubility in a general organic solvent, so in order to ensure coatability, the solvent can only use a specific non-solubility which is extremely high in solubility. Protic polar solvent. Since such a solvent erodes most of the general-purpose plastics, the liquid crystal alignment agent containing the solvent cannot be applied to the resin substrate, and is not suitable for the weight reduction of the liquid crystal display element, and in addition, the use of triacetyl cellulose ( The use of Triacetyl Cellulose (TAC) as a retardation film for a substrate is greatly limited.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-307736

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2004-163646

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2002-250924

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2004-83810

[Patent Document 5] US Patent No. 5,958,333

[Patent Document 6] Japanese Patent Laid-Open Publication No. SHO 56-91277

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2008-46184

[Patent Document 8] Japanese Patent Laid-Open No. Hei 9-297313

[Non-patent literature]

[Non-Patent Document 1] "Ultraviolet (UV) curing liquid crystal and

Its Application, Liquid Crystal, Vol. 3 No. 1 (1999), pp 34~pp 42

The present invention is intended to break through the current situation as described above.

It is an object of the present invention to provide a liquid crystal alignment agent which can stably exhibit a relatively low pretilt angle through a photo-alignment method, and even When a general-purpose solvent is used, coatability (printability) is also excellent.

According to the present invention, the object and advantages of the present invention are attained by a liquid crystal alignment agent characterized by containing a polyorganosiloxane selected from the group consisting of polyorganosiloxane, polyamine, and poly At least one polymer of the group consisting of a poly(thio)ester and a (meth)acrylic copolymer, wherein the polymer has a divalent group represented by the following formula (1) ;

(In the formula (1), R ^I to R ^IV are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms; and Y ¹ and Y ² are each independently two. The valence organic group, "*" denotes a bonding bond bonded to a polymer chain, respectively).

Since the liquid crystal alignment agent of the present invention can stably exhibit a relatively low pretilt angle by the optical alignment method, it can be suitably applied to the formation of a liquid crystal alignment film used in a liquid crystal display device of a transverse electric field type.

Further, since the polymer contained in the liquid crystal alignment agent of the present invention is excellent in solubility, even when a general-purpose organic solvent is used, the coating property is excellent. In order to form a liquid crystal alignment film having high uniformity.

The liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention can be suitably applied to a liquid crystal display element (particularly, a liquid crystal display element of a transverse electric field type), a retardation film having a liquid crystal layer, or the like.

A‧‧‧glass substrate

b‧‧‧Liquid alignment film

c‧‧‧Top electrode

D‧‧‧ nitride film

e‧‧‧Bottom electrode

f‧‧‧Direction of polarized surface of polarized ultraviolet light

Fig. 1 is a schematic cross-sectional view for explaining a structure of an electrode pair of a liquid crystal display element produced in an embodiment.

2(a) and 2(b) are plan schematic views for explaining the comb-tooth structure of the top electrode included in the liquid crystal display element manufactured in the embodiment.

Hereinafter, the present invention will be described in detail.

The liquid crystal alignment agent of the present invention contains a polymer having a divalent group represented by the above formula (1) (hereinafter referred to as "specific polymer").

<specific polymer>

The specific polymer of the present invention is at least one polymer selected from the group consisting of polyorganosiloxanes, polyamines, poly(thio)esters, and (meth)acrylic copolymers, and has the formula (1) The divalent group represented.

The bond having a "*" in the divalent group represented by the formula (1) is bonded to the polymer chain, meaning that the divalent group is present in the main chain of the polymer, or The polymer chains are present in the form of a portion of a cross-linking bond that is two-dimensionally or three-dimensionally bonded to each other. That is, the divalent group is not present in the form of a side chain of the polymer or a part thereof, or a side chain of a crosslinked structure or a part thereof. Wherein, the specific polymer is not limited to the case where the divalent group represented by the formula (1) is present in the main chain or the crosslinked structure of the polymer: the side chain of the polymer or a part thereof or the cross The side chain of the joined structure or a part thereof has the same structure.

The content ratio of the divalent group represented by the formula (1) in the specific polymer is preferably 1.0 × 10 ^-4 mol / g or more, more preferably 3.0 × 10 ^-4 mol / g to 2.0 × 10 ^-3 Mol/g.

The specific polymer may be, for example, a polyamine which is a polycarboxylic acid having a diamine and a compound represented by the following formula (C) (hereinafter referred to as "compound (C)").

A poly(thio)ester obtained by reacting at least one compound selected from the group consisting of a diol compound, a dithiol compound, and a diepoxy compound, and comprising the following formula (C) Polycarboxylic acid

Obtained as a reaction; a poly(thio)ester which is at least one compound selected from the group consisting of a diol compound, a dithiol compound, and a diepoxide compound (wherein at least a part of the compound is as follows) a compound represented by the formula (E) (hereinafter referred to as "compound (E)"))), and a polycarboxylic acid

A (meth)acrylic acid copolymer obtained by reacting a polymerizable unsaturated compound containing (meth)acrylic acid and a compound represented by the following formula (A) (hereinafter referred to as "compound (A)")) a mixture obtained by addition polymerization; and a polyorganosiloxane which is obtained by hydrolyzing and condensing a decane compound containing a compound represented by the following formula (S) (hereinafter referred to as "compound (S)"); .

(Formula ^{(C),, R I ~ R IV, Y} 1 Y ² respectively and R ^I (1) of the formula ~ R ^IV, Y ¹ meaning and Y ² are the same)

(In the formula ^{(E), R I ~ R} IV, Y 1 and Y ^2, respectively, in the formula (1) R ^I ~ R ^IV, Y ¹ and Y ² are the same meanings; the Z ¹ and Z ² are each independently The ground is a hydroxyl group, a thiol group or an epoxy group)

(In the formula ^{(S), R I ~ R} IV, Y 1 and Y ^2, respectively, in the formula (1) R ^I ~ R ^IV, Y ¹ and Y ² are the same meanings; R & lt ¹ and R ² are each independently The ground is an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms; X ¹ and X ² are each independently an alkoxy group having 1 to 12 carbon atoms or a halogen atom; n1 and n2 are each independently 1 An integer of ~3)

(In the formula ^{(A), R I ~ R} IV, Y 1 and Y ^2, respectively, in the formula (1) R ^I ~ R ^IV, Y ¹ and Y ² are the same meanings; R ³ and R ⁴ are each independently The ground is a hydrogen atom or a methyl group)

The chemical formula indicates that the divalent group represented by the formula (1) is derived from the compound (C), the compound (E), the compound (A) or the compound (S). These compounds can be obtained by a reaction of a tetracarboxylic dianhydride represented by the following formula (T) with a primary amine compound.

(In the formula (T), R ^I to R ^IV have the same meanings as R ^I to R ^IV in the formula (1), respectively)

Examples of the tetracarboxylic dianhydride represented by the formula (T) include 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2,3,4-tetramethyl-1. As the 2,3,4-cyclobutanetetracarboxylic dianhydride or the like, one or more selected from the group consisting of these tetracarboxylic dianhydrides can be used.

The primary amine compound which should be reacted with the tetracarboxylic dianhydride as described above will be described in the description about the compound (C), the compound (E), the compound (A) or the compound (S).

[Synthesis of Compound (C)]

The compound (C) can be obtained, for example, by a reaction of a tetracarboxylic dianhydride represented by the formula (T) with an amino acid. The amino acid is a compound having a primary amine group and a carboxyl group in the molecule. In this case, in the formula (C) ¹ the Y group (therefore in the formula (1) the group Y ¹⁾ is removed from the resultant amine and the carboxyl group of the amino acid divalent base.

Examples of the amino acid include glycine, alanine, leucine, isoleucine, phenylalanine, valine, 4-aminobutyric acid, and the like, and those selected from these amino acids can be used. More than one of them.

The reaction of the tetracarboxylic dianhydride represented by the formula (T) with an amino acid can be carried out by heating a mixture of these compounds in a suitable solvent.

The ratio of the two compounds in the reaction is preferably from 1.0 mol to 4.0 mol, more preferably from 1.5, based on the ratio of the amino acid to the tetracarboxylic dianhydride of 1 mol. Moules are ~3.0 moles, and further preferably set to 1.8 moles to 2.5 moles.

The solvent used in the reaction is preferably an organic solvent, and for example, an aprotic polar solvent, a phenol and a derivative thereof, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, a hydrocarbon, or the like can be used.

Specific examples of the organic solvent include, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide. , dimethyl hydrazine, γ-butyrolactone, tetramethyl urea, hexamethylphosphonium triamine, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, etc.; Examples of the derivative include m-cresol, xylenol, and halogenated phenol; and examples of the alcohol include methanol, ethanol, isopropanol, and cyclohexanol. Ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, etc.; examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, Cyclohexanone or the like; examples of the ester include ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, and oxalic acid. Diethyl ester, diethyl malonate, etc.; examples of the ether include diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, and ethylene glycol. Dibutyl 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, diethyl Glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, etc.; the halogenated hydrocarbons include, for example, dichloromethane, 1,2-dichloroethane, 1,4-dichloro Butane, trichloroethane, chlorobenzene, o-dichlorobenzene, etc.; examples of the hydrocarbon include hexane, heptane, octane, benzene, toluene, xylene, isoamyl propionate, isobutyric acid Isoamyl ester And the like, is preferable to use one or more selected from these solvents.

The ratio of use of the solvent is preferably from 50 parts by weight to 5,000 parts by weight, more preferably from 100 parts by weight to 3,000 parts by weight, based on 100 parts by weight of the total of the tetracarboxylic dianhydride and the amino acid. It is further preferred to set it to 100 parts by weight to 2,000 parts by weight.

The reaction of the tetracarboxylic dianhydride with the amino acid is carried out at a temperature of preferably from 50 ° C to 300 ° C, more preferably from 80 ° C to 200 ° C, preferably from 0.1 to 20 hours. The time is preferably 0.1 hour to 10 hours. The reaction may be carried out while gradually increasing the reaction temperature stepwise or continuously within the range of the temperature and the reaction time as needed.

[Synthesis of Compound (E)]

The compound in which Z ¹ and Z ² in the compound (E) are a hydroxyl group or a thiol group can pass, for example, the tetracarboxylic dianhydride represented by the above formula (T), and an amino alcohol according to the kinds of Z ¹ and Z ² . Or obtained by the reaction of an amino mercaptan. In this case, in the formula (E) the group Y ¹ (therefore (1) is a group of the formula Y ¹⁾ be removed from the amino group of an alcohol or thiol group and A divalent group derived from a hydroxy group or a thiol group.

Examples of the amino alcohol include 2-aminoethanol, 3-aminopropanol, and 4- Aminophenol, 4-aminobenzyl alcohol, 2-(4-aminophenyl)ethanol, etc.; the amine mercaptan may, for example, be 3-thiol aniline, 4-thiol aniline, 1- Mercaptan-3-aminopropane and the like.

The reaction of tetracarboxylic dianhydride with an amino alcohol or an amine thiol can be passed through To proceed: it is preferred to heat a mixture of these compounds in a suitable solvent.

Regarding the ratio of use of the two compounds in the reaction, with an amino alcohol or an amine The ratio of the base thiol to the tetracarboxylic dianhydride 1 mole is preferably set to 1.0 mole to 4.0 moles, more preferably 1.5 moles to 3.0 moles, and particularly preferably Set to 1.8 moles to 2.5 moles.

The solvent used in the reaction can be used as a compound as described above The solvent which can be used for the synthesis of (C) is the solvent of the solvent exemplified. About dissolution The ratio of use of the agent is preferably 50 parts by weight to 5,000 parts by weight, more preferably 100 parts by weight, based on 100 parts by weight of the total amount of the tetracarboxylic dianhydride and the amino alcohol or the amine thiol. It is preferably 3,000 parts by weight, and more preferably 100 parts by weight to 2,000 parts by weight.

The reaction is carried out at a temperature of preferably from 50 ° C to 300 ° C, more preferably from 80 ° C to 200 ° C, preferably from 0.1 to 10 hours, more preferably from 0.1 to 20 hours. The reaction may be carried out while gradually increasing the reaction temperature stepwise or continuously within the range of the temperature and the reaction time as needed.

Thus, a diol compound in which the group Z ¹ and the group Z ² in the formula (E) are each a hydroxyl group, or a dithiol compound in which the group Z ¹ and the group Z ² are each a thiol group can be obtained.

The compound in which each of Z ¹ and Z ² in the compound (E) is an epoxy group can be obtained, for example, by a reaction of a diol compound or a dithiol compound obtained as described above with a compound having an epoxy group and a halogen atom. In this case, in the formula (E) the group Y ¹ (therefore (1) is a group of the formula Y ¹⁾ becomes the following divalent group, i.e., the diol compound obtained as described above Or a divalent group in which a divalent group Y ¹ in a dithiol compound and a divalent group obtained by removing an epoxy group and a halogen atom from a compound having an epoxy group and a halogen atom are bonded via an ether bond.

Here, the epoxy group may be any of oxyheteropropyl group and oxetanyl group. Examples of the compound having an oxiranyl group and a halogen atom include epichlorohydrin, 2-(chloromethyl)-1,2-epoxypropane, and 2-(chloromethyl)-1,2-epoxy. Butane, 2-(bromomethyl)-1,2-epoxypropane, 2-(bromomethyl)-1,2-epoxybutane, etc.; Examples of the compound having an oxetanyl group and a halogen atom include 3-(chloromethyl)oxetane, 3-(chloromethyl)-3-methyloxetane, and 3-( Bromomethyl)oxetane, 3-(bromomethyl)-3-methyloxetane, etc.; a compound having a (meth)acrylonyl group and a halogen atom is exemplified by (meth) Acrylic ruthenium chloride or the like; one or more selected from these compounds can be used.

The reaction can be carried out by: preferably, in the presence of a suitable catalyst, preferably in a suitable solvent, the diol compound or the dithiol compound obtained as described above, and having A mixture of an epoxy group and a compound of a halogen atom is heated.

With respect to the use ratio of the diol compound or the dithiol compound to the compound having an epoxy group and a halogen atom, it is preferred to use 0.5 mol to 10 mol of the latter with respect to 1 mol of the former, and more preferably Use 1.0 mer ~ 3.0 m, especially good use 1.8 m ~ 2.5 m.

The catalyst which can be used for the reaction is, for example, a quaternary ammonium salt or the like, and specific examples thereof include tetrabutylammonium chloride and tetrabutylammonium bromide. The use ratio of the catalyst is preferably set to 20 parts by weight or less, more preferably 0.001 part by weight to 10 parts by weight, based on 100 parts by weight of the diol compound or the dithiol compound.

The solvent used herein is preferably an organic solvent, and the same solvent as the solvent exemplified above as the solvent which can be used in the synthesis of the compound (C) can be used.

The ratio of use of the solvent is 100 parts by weight based on the total amount of the diol compound or the dithiol compound and the compound having an epoxy group and a halogen atom. It is preferably set to 10 parts by weight to 3,000 parts by weight, more preferably 50 parts by weight to 2,000 parts by weight, still more preferably 50 parts by weight to 1,000 parts by weight.

The reaction is carried out at a temperature of preferably -100 ° C to 60 ° C, more preferably -80 ° C to 40 ° C, preferably 0.5 hours to 30 hours, more preferably 2 hours to 15 hours. The reaction may be carried out while gradually increasing the reaction temperature stepwise or continuously within the range of the temperature and the reaction time as needed.

[Synthesis of Compound (A)]

The compound (A) can be obtained, for example, by a reaction of a diol compound in which the group Z ¹ and the group Z ² are each a hydroxyl group in the formula (E) with (meth)acrylic acid. In this case, the formula (A) is a group Y ¹ (Y ¹ is therefore (1) is a group of the formula) with a compound used as starting material (E) is the same as group Y ^1. Here, (meth)acrylic acid is preferably subjected to hydrazine chlorination by a known method for the reaction.

With respect to the use ratio of the compound (E) as the diol compound and preferably the fluorinated (meth)acrylic acid, it is preferred to use (meth)acrylic acid relative to the compound (E) 1 mol. The ratio is set to 0.5 m to 10 m, more preferably 1.0 m to 3.0 m, and particularly preferably 1.8 m to 2.5 m.

The reaction can be carried out by dissolving the compound (E) as a diol compound in a suitable solvent in advance, preferably by subjecting the ruthenium chlorinated (meth)acrylic acid to be dissolved in a suitable solvent as needed. The method of dropping is performed.

As the solvent which can be used here, the same solvent as that exemplified above as the solvent which can be used in the synthesis of the compound (C) can be used. Regarding the ratio of use of the solvent, preferred are the compound (E) and (meth) propylene as the diol compound. The ratio of the total weight of the acid in the reaction solution is from 0.5% by weight to 50% by weight, more preferably from 1% by weight to 30% by weight.

The reaction is preferably at a temperature of -100 ° C to 100 ° C, more preferably -20 ° C to 40 ° C. Under the degree. Here, in the case of directly reacting (meth)acrylic acid, it is preferred to set the reaction temperature to a temperature of room temperature (25 ° C) or more; and to carry out the reaction after chlorination of (meth)acrylic acid Next, it is preferred to set the reaction temperature to a temperature lower than room temperature. The reaction time is preferably from 0.1 to 40 hours, more preferably from 0.5 to 20 hours. In the case where the reaction is carried out by dropwise addition (preferably fluorinated chlorinated) (meth)acrylic acid, the reaction time is measured from the end of the dropwise addition.

[Synthesis of Compound (S)]

The compound (S) can be obtained, for example, by dehydrating a diol compound in which the group Z ¹ and the group Z ² in the formula (E) are a hydroxyl group, and forming a double bond at the terminal, and then hydrogen hydride (hydrosilation). The reaction adds an alkoxydecane compound to the double bond. In this case, in the formula (S) the group Y ¹ (Y ¹ is therefore (1) is a group of the formula) with a compound used as starting material (E) is the same as group Y ^1.

The dehydration reaction of the diol compound is carried out by: preferably The diol compound is contacted with sulfuric acid in a suitable organic solvent.

Examples of the organic solvent that can be used herein include acetic acid, acetic anhydride, and Tetrahydrofuran, acetonitrile, chloroform, dichloromethane, diethyl ether, benzene, toluene, xylene, acetone, methyl ethyl ketone, dimethylformamide, dimethyl hydrazine, hexane, 1,4-dioxin Alkane, etc. The organic solvent is preferably used in an amount of from 50 parts by weight to 2,000 parts by weight, more preferably 100% by weight based on 100 parts by weight of the compound (E) as the diol compound. Parts to 1,000 parts by weight.

The use ratio of sulfuric acid is preferably from 0.0001 part by weight to 100 parts by weight, more preferably from 0.001 part by weight to 10 parts by weight, per 100 parts by weight of the compound (E) as the diol compound. Sulfuric acid is preferably added slowly to the reaction system.

The dehydration reaction of the diol compound is carried out at a temperature of preferably from 0 ° C to 300 ° C, more preferably from 25 ° C to 150 ° C, preferably from 0.1 to 40 hours, more preferably from 0.5 to 20 hours. In the case where the reaction is carried out by dropwise addition of sulfuric acid, the reaction time is measured from the end of the dropwise addition.

The reaction of adding an alkoxydecane compound to the dehydrated product obtained as described above can be carried out in accordance with a well-known hydrazine hydrogenation reaction.

The alkoxydecane compound used herein is a compound having at least one H-Si bond and at least one alkoxy-Si bond, and specific examples thereof include dimethyl methoxy decane and dimethyl ethoxylate. As the organic hydrogenated decane such as decane, methyl dimethoxy decane, diethyl methoxy decane or diphenyl methoxy decane, one or more selected from these compounds can be used.

With respect to the use ratio of the alkoxydecane compound, it is preferably set to 0.5 mol to 5.0 mol, more preferably 1.0 mu, based on the ratio of the alkoxydecane compound to the dehydration product 1 mole. ~3.0 Moule, the best is set to 1.8 Mo ~ 2.5 Mo.

The rhodium hydrogenation reaction is preferably carried out in the presence of a suitable catalyst, preferably in a suitable organic solvent.

Examples of the catalyst which can be used here include chloroplatinic acid, Wilkinson complex (RhCl(P(C ₆ H ₅ ) ₃ ) ₃ ), and Karsted Catalyst (chlorine). One or more selected from these catalysts can be used, such as a vinyl siloxane complex of a platinum acid, a Speier Catalyst (an alcohol solution of chloroplatinic acid), or the like. The catalyst is preferably used in a ratio of 0.01 micromolar (μmol) to 200 micromolar, more preferably 0.05 micromolar to 50 micromolar, relative to the dehydrated product 1 mole.

The organic solvent which can be used here may, for example, be a hydrocarbon, a halogenated hydrocarbon, an ether, an ester or the like. Among these organic solvents, hydrocarbons are preferably used, and it is particularly preferred to use at least one selected from the group consisting of toluene, heptane, hexane, benzene, toluene, xylene, and the like. The use ratio of the organic solvent is preferably set to 10 parts by weight to 2,000 parts by weight, more preferably 50 parts by weight to 1,000 parts by weight, based on 100 parts by weight of the dehydrated product.

The rhodium hydrogenation reaction is carried out at a temperature of preferably from 30 ° C to 200 ° C, more preferably from 50 ° C to 120 ° C, preferably from 0.1 to 60 hours, more preferably from 0.5 to 40 hours.

[Manufacture of specific polymers]

Next, a method of producing the specific polymer of the present invention will be described.

(1) Production of polyamine

The polyamine which is an example of the specific polymer of the present invention can be obtained by reacting a diamine with a polyvalent carboxylic acid containing the compound (C) obtained as described above. Here, the polycarboxylic acid is preferably subjected to hydrazine chlorination for the reaction by a well-known method.

Examples of the diamine include p-phenylenediamine and 4,4'-diaminodiphenyl. Alkane, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2- Bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4- Aminophenyl)hexafluoropropane, ethyl 2-(2,4-diaminophenoxy)methacrylate, dodecyloxy-2,4-diaminobenzene, octadecyloxy- 2,4-Diaminobenzene, dodecyloxy-2,5-diaminobenzene, octadecyloxy-2,5-diaminobenzene, cholestyloxy-3,5-di Aminobenzene, cholesteneoxy-3,5-diaminobenzene, cholestyloxy-2,4-diaminobenzene, cholesteneoxy-2,4-diaminobenzene, 3 , 5-diaminobenzoic acid cholesteryl, 3,5-diaminobenzoic acid cholesteryl, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4 - heptylcyclohexane, 1,1-bis(4-((aminophenoxy)methyl)phenyl)-4-heptylcyclohexane, or the like, one or more selected from these diamines .

The polycarboxylic acid may be used only for the compound (C), or may be used in combination. (C) with other polycarboxylic acids. The other polycarboxylic acid used herein is preferably a dicarboxylic acid, and examples thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, phthalic acid, and isophthalic acid. For terephthalic acid, 5-nonoxyisophthalic acid or the like, one or more selected from these dicarboxylic acids can be used.

In the case of using compound (C) in combination with other polycarboxylic acids, The ratio of the compound (C) to the other polybasic carboxylic acid is preferably 5 mol% or more, and more preferably 10 mol% or more.

When another polyvalent carboxylic acid is used together with the compound (C) in the production of polyamine, a part of the other polycarboxylic acid may be replaced with a tetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride which can be used herein include pyromellitic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo- 3-furyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro- 2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 3-oxabicyclo[3.2.1]octane-2,4-di Keto-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexane Alkene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ]undecane-3,5,8,10-tetraketone, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride, and the like.

Regarding the ratio of use of the polycarboxylic acid to the diamine, it is preferred to compare the diamine The total use ratio of the carboxyl group (and the acid anhydride group in the case where the acid anhydride group is present) of the polyvalent carboxylic acid is set to 0.7 mol to 1.2 mol, and more preferably set to 0.9 mol to 1.1. Moor.

The reaction can be carried out by dissolving the diamine in a suitable solvent in advance. In the above, the polycarboxylic acid is preferably subjected to hydrazine chlorination, and if necessary, it is added dropwise in a state of being dissolved in a suitable solvent (for example, tetrahydrofuran).

The solvent that can be used here can be used as the compound (C) above. The solvent which can be used in the synthesis is the same solvent as the solvent exemplified. The ratio of use of the solvent is preferably such that the ratio of the total weight of the polycarboxylic acid and the diamine to the reaction solution is 3% by weight to 50% by weight.

The reaction is preferably from -100 ° C to 200 ° C, more preferably from -20 ° C to 150 ° C. Perform at temperature. Here, when the polycarboxylic acid is directly reacted, it is preferred to set the reaction temperature to a temperature of room temperature (25 ° C) or higher; in the case where the polycarboxylic acid is chlorinated and then reacted, It is preferred to set the reaction temperature to a temperature lower than room temperature. The reaction time is preferably 0.1 hour ~40 hours, more preferably 0.5 hours to 20 hours. In the case where the reaction is carried out by dropwise addition (preferably, ruthenium chlorinated) polycarboxylic acid, the reaction time is measured from the end of the dropwise addition.

The Mw of the polyamine which is a specific polymer of the present invention (the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography, the same applies hereinafter) is preferably 1,000 to 500,000, more preferably The best is 5,000~300,000.

(2) Production of poly(thio)ester

The poly(thio)ester which is an example of the specific polymer of the present invention can be obtained by at least one selected from the group consisting of a diol compound, a dithiol compound, and a diepoxide compound. a method of reacting a polycarboxylic acid of the compound (C); or at least one compound selected from the group consisting of a diol compound, a dithiol compound, and a diepoxide compound (wherein at least a part of the compound is as follows) A method of reacting a compound represented by the formula (E) with a polyvalent carboxylic acid.

Examples of the diol compound include 3,6-dihydroxycholestane, 3,5-dihydroxybenzoic acid-3-cholestyl group, 3,5-dihydroxybenzoic acid, ethylene glycol, and 1 , 3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,4-cyclohexanediol, phenyl-1,2-ethanediol, dimethyl-2,3-butene Glycol, α,α'-p-xylene glycol, α,α'-m-xylene glycol, hydroquinone, methyl hydroquinone, tert-butyl hydroquinone, chloro-p-benzene Phenol, 2-methoxy hydroquinone, phenyl hydroquinone, 2,3-dimethyl hydroquinone, 2,3,5,6-tetramethyl hydroquinone, 2,3 ,5,6-tetrachlorohydroquinone, resorcinol, 2-methylisophthalic acid Diphenol, 4-hexyl resorcinol, 5-phenyl resorcinol, 1,4-dihydroxynaphthalene, etc.; the dithiol compound may, for example, be benzene-1,4-dithiol, 2-methylpropane-1,1-dithiol, butane-1,1-dithiol, 2-methylbutane-1,1-dithiol, 3-methylbutane-1,1 -dithiol,pentane-1,1-dithiol, 2-methylpentane-1,1-dithiol, 3-methylpentane-1,1-dithiol, hexane-1 , 1-dithiol, 2-methylhexane-1,1-dithiol, 3-methylhexane-1,1-dithiol, etc.; the diepoxide compound may, for example, be: B 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-hexyl As the diol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, or the like, one or more selected from the group consisting of the above compounds can be used.

Pass through selected from a diol compound, a dithiol compound, and a bicyclic oxidation In the case where a poly(thio)ester is synthesized by reacting at least one of the group consisting of the compound and the polycarboxylic acid containing the compound (C), the polyvalent carboxylic acid may be the compound (C) alone or the compound ( C) with other polycarboxylic acids. As the other polycarboxylic acid used herein, a polyvalent carboxylic acid which is the same as the polyvalent carboxylic acid exemplified above as the polyvalent carboxylic acid which can be used together with the compound (C) as a synthetic polyamine can be used. Further, a part or all of the polycarboxylic acid may be replaced with a tetracarboxylic dianhydride. The tetracarboxylic dianhydride which can be used here is the same as the tetracarboxylic dianhydride exemplified above as the tetracarboxylic dianhydride which can be used when producing a polydecylamine.

In the case of using compound (C) in combination with other polycarboxylic acids, The total amount of the compound (C) and other polycarboxylic acids, the ratio of the use of the compound (C) It is preferably set to 5 mol% or more, and more preferably set to 10 mol% or more.

The ratio of use of at least one selected from the group consisting of a diol compound, a dithiol compound, and a diepoxide compound to a polycarboxylic acid containing the compound (C), relative to the amount of a carboxyl group possessed by the polycarboxylic acid And a total amount of two times the amount of the acid anhydride group in the case of the acid anhydride group is 1 mole, and at least one selected from the group consisting of a diol compound, a dithiol compound, and a diepoxy compound is preferably used. It is set to 0.7 m to 1.2 m, and more preferably set to 0.9 m to 1.1 m.

A synthesis reaction of a poly(thio)ester by reacting at least one selected from the group consisting of a diol compound, a dithiol compound, and a diepoxide with a polycarboxylic acid containing the compound (C) In addition to the use of at least one selected from the group consisting of a diol compound, a dithiol compound, and a diepoxide, in place of the diamine, it can be carried out in substantially the same manner as the synthesis of the polyamine.

At least one compound selected from the group consisting of a diol compound, a dithiol compound, and a diepoxide compound (wherein at least a part of the compound is a compound represented by the following formula (E)) and a plurality of In the case of a method of reacting a carboxylic acid to synthesize a poly(thio)ester, the compound (E) to be used is preferably a diepoxy group in which both Z ¹ and Z ² in the formula (E) are epoxy groups. Compound. The compound (E) as the diepoxy compound may be used singly or in combination with the compound (E) and other diepoxide compounds. As the other diepoxy compound used herein, a diepoxy compound which is the same as the diepoxide compound exemplified above as the diepoxy compound which can be used in the former method for synthesizing the poly(thio)ester can be used. When the compound (E) and other diepoxides are used in combination, the use ratio of the compound (E) is preferably set to 5 mol% or more, based on the total amount of the compound (E) and other diepoxide compounds. It is preferable to set it to 10 mol% or more.

The compound (E) as the diepoxy compound and the other diepoxy compound are preferably dioxetane compounds, respectively.

As the polyvalent carboxylic acid in the reaction, a polyvalent carboxylic acid exemplified above as a polyvalent carboxylic acid which can be used together with the compound (C) as a synthetic polyamine can be used. Further, a part or all of the polycarboxylic acid may be replaced with tetracarboxylic dianhydride and used. The tetracarboxylic dianhydride which can be used here is the same as the tetracarboxylic dianhydride exemplified above as the tetracarboxylic dianhydride which can be used when producing a polydecylamine.

The use ratio of the compound (E) to the polyvalent carboxylic acid is 1 mol of the total amount of the carboxyl group which the polyvalent carboxylic acid has and the amount of the acid anhydride group, and the compound (E) is used. The ratio is preferably set to 0.7 m to 1.2 m, and more preferably set to 0.9 m to 1.1 m.

For the synthesis reaction of a poly(thio)ester which is carried out by reacting the compound (E) with a polycarboxylic acid, in place of the use of the compound (E) (or a mixture of the compound (E) and another diepoxide) Other than the amine, it can be carried out in substantially the same manner as the synthesis of the polyamine.

The poly(thio)ester which is a specific polymer of the present invention preferably has a Mw of 1,000 to 500,000, more preferably 5,000 to 300,000.

(3) Manufacture of (meth)acrylic acid copolymer

(meth)acrylic copolymer as an example of a specific polymer of the present invention It can be obtained by subjecting a mixture of a polymerizable unsaturated compound containing (meth)acrylic acid and the compound (A) to addition polymerization.

In this case, as the unsaturated compound, only (meth)acrylic acid and the compound (A) may be used, and other polymerizable unsaturated compounds may be used in combination with the (meth)acrylic acid and the compound (A). Examples of the other polymerizable unsaturated compound which can be used herein include a conjugated diene, an aromatic vinyl compound, a (meth) acrylate, an α, β-unsaturated nitrile compound, and a maleimide compound. Specific examples of the compound include, for example, 1,3-butadiene, 2-methyl-1,3-butadiene, and 2,3-dimethyl-1,3. - butadiene, 2-chloro-1,3-butadiene, etc., and examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, and vinyltoluene. Chlorostyrene, divinylbenzene, etc.; the (meth) acrylate may, for example, be methyl (meth) acrylate, ethyl (meth) acrylate or 2-ethylhexyl (meth) acrylate. Ester, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 4-(4-n-propylcyclohexyl) phenyl (meth) acrylate, etc.; the α, β-unsaturated nitrile compound For example, acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethyl acrylonitrile, vinylidene cyanide, etc.: a maleidene compound can be mentioned, for example, an N-ring Hexamolin, N-phenylmaleimine, etc.; one or more selected from the group consisting of the above compounds may be used.

In the (meth)acrylic copolymer,

The content of the repeating unit derived from (meth)acrylic acid is preferably 0.1 weight. The amount of % to 80% by weight, more preferably 5% by weight to 60% by weight; the content of the repeating unit derived from the compound (A) is preferably from 0.1% by weight to 15% by weight, more preferably from 0.5% by weight to 10% by weight. %.

(Meth)acrylic acid copolymer can use polymerizable unsaturated as described above The compound is synthesized by, for example, well-known solution polymerization. The solution polymerization can be carried out in an organic solvent in the presence of a suitable polymerization initiator, preferably in the presence of a suitable chain transfer agent.

The organic solvent can be used, for example, alcohol, ether, glycol ether, ethylene glycol. Alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether propionate, aromatic hydrocarbon, ketone, ester, and the like. The organic solvent is preferably used in an amount of from 120 parts by weight to 600 parts by weight, more preferably from 150 parts by weight to 400 parts by weight, based on 100 parts by weight of the total of the polymerizable unsaturated compound.

The polymerization initiator may, for example, be cumene hydroperoxide (cumene) Hydroperoxide), benzammonium peroxide, t-butyl hydroperoxide, ethidium peroxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl Hydrogen peroxide (1,1,3,3-tetramethyl butyl hydroperoxide), azobisisobutyronitrile, 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobis (2,4 One or more selected from these polymerization initiators can be used, for example, dimethyl valeronitrile. The use ratio of the polymerization initiator is preferably from 2 parts by weight to 10 parts by weight, more preferably from 3 parts by weight to 8 parts by weight, per 100 parts by weight of the total amount of the polymerizable unsaturated compound.

Examples of the chain transfer agent include xanthogen compound, thiuram compound, phenol derivative, allyl compound, halogenated hydrocarbon compound, vinyl ether compound, triphenylethane, and five. Phenylethane, acrolein, methacrolein, thioglycolic acid, thiomalic acid, 2-ethylhexyl thioglycolate, α-methylstyrene dimerization For the substance or the like, one or more selected from the group consisting of these chain transfer agents can be used. The use ratio of the chain transfer agent is preferably 3 parts by weight or less, more preferably 0.1 parts by weight to 1.5 parts by weight, based on 100 parts by weight of the total amount of the polymerizable unsaturated compound.

The solution polymerization for synthesizing the (meth)acrylic copolymer is preferably at a temperature of from 50 ° C to 100 ° C, more preferably from 60 ° C to 90 ° C, preferably from 30 minutes to 500 minutes, more preferably 60. The reaction time is from minute to 300 minutes.

The Mw of the (meth)acrylic copolymer as the specific polymer of the present invention is preferably from 1,000 to 500,000, more preferably from 5,000 to 300,000.

(4) Manufacture of polyorganosiloxane

The polyorganosiloxane which is an example of the specific polymer of the present invention can be obtained by subjecting the decane compound containing the compound (S) to hydrolysis and condensation in the presence of a suitable organic solvent and a catalyst.

As the decane compound, the compound (S) may be used alone, or the compound (S) may be used in combination with other decane compounds. Other decane compounds which can be used herein include, for example, tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, and 3-(methyl) propylene oxy propylene. Trimethoxy decane, 3-(meth) propylene methoxy propyl triethoxy decane, vinyl trimethoxy decane, vinyl three Ethoxy decane, allyl trimethoxy decane, allyl triethoxy decane, octadecyl trimethoxy decane, octadecyl triethoxy decane, phenyl trimethoxy decane, phenyl Triethoxy decane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, decylmethyltrimethoxydecane, decylmethyltriethoxydecane, dimethyldimethoxy Baseline, dimethyldiethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldi Methoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyldimethylmethoxydecane, 3-glycidoxypropyldimethylethoxylate Pyridinium, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, etc., which may be selected from these decane compounds More than one of them.

When the compound (S) and other decane compounds are used in combination, the ratio of the compound (S) to the total amount of the compound (S) and the other decane compound is preferably set to 5 mol% or more, more preferably set. It is 10 mol% or more.

The organic solvent which can be used for the synthesis of the polyorganosiloxane is, for example, a hydrocarbon, a ketone, an ester, an ether or an alcohol, and one or more selected from these organic solvents can be used. Specific examples of the organic solvent may be the same as those exemplified as the hydrocarbon, ketone, ester, ether or alcohol in the solvent which can be used in the synthesis of the compound (C). The organic solvent is preferably a water-insoluble organic solvent. The organic solvent is preferably used in an amount of from 10 parts by weight to 10,000 parts by weight, more preferably from 50 parts by weight to 1,000 parts by weight, based on 100 parts by weight of all of the decane compound.

The catalyst can be used, for example, an acid, a base, an organic base, a titanium compound, Zirconium compounds and the like. Among these compounds, a base is preferably used.

The base may, for example, be an organic base, a basic alkali metal compound or the like. Specific examples of the base include, for example, ethylamine, diethylamine, pyridazine, acridine, pyrrolidine, pyrrole, and the like, a primary organic amine to a secondary organic amine; triethylamine and tri-negative; a tertiary organic amine such as propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine or diazabicycloundecene; a fourth-order organic amine such as tetramethylammonium hydroxide. Among these organic bases, triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine or tetramethylammonium hydroxide is preferably used. Examples of the basic alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide.

a total of 1 mole relative to the decane compound used as a raw material, catalyst The use ratio is preferably set to 0.01 mol to 3 mol, more preferably 0.05 mol to 1 mol.

a synthetic total of 1 mole relative to the total amount of decane compound used as a raw material The proportion of water used in the case of the oxime is preferably from 0.5 mol to 100 mol, more preferably from 1 mol to 30 mol.

The synthesis reaction of the polyorganosiloxane is preferably from 0 ° C to 200 ° C, more preferably The reaction time is preferably from 0.1 to 40 hours, more preferably from 0.5 to 20 hours, at a temperature of from 10 ° C to 150 ° C.

The Mw of the polyorganosiloxane which is a specific polymer of the present invention is preferably 1,000 to 500,000, more preferably 5,000 to 300,000.

The specific polymer of the present invention from the viewpoint of easiness of monomer synthesis and the like It is preferred to use one or more selected from the group consisting of polyamines, polyesters, and polyorganosiloxanes in the compound.

<Other ingredients>

The liquid crystal alignment agent of the present invention contains a specific polymer as described above as an essential component. The liquid crystal alignment agent of the present invention may contain other components arbitrarily used in addition to the specific polymer.

Examples of other components which can be used herein include a polymer other than a specific polymer, a compound having at least one epoxy group in the molecule (hereinafter also referred to as "epoxy compound"), a functional decane compound, and the like.

[Polymers other than specific polymers]

Polymers other than the specific polymer can be used to improve solution properties and electrical properties. The other polymer is a polymer which does not have the divalent group represented by the formula (1), and may be, for example, a polymer selected from the group consisting of polyamidic acid and polyaminic acid. Polymers, polyphthalates, polyesters, polyamines, polyoxyalkylenes, cellulose derivatives, polyacetals, polystyrenes and their derivatives, poly(styrene-phenylmaleimide) And one or more of the derivatives and the poly(meth) acrylate group, and does not have the divalent group represented by the formula (1).

The ratio of use of the polymer other than the specific polymer is preferably 50% by weight based on the total amount of the polymer (refer to the total amount of the polymer other than the specific polymer and the specific polymer. The same applies hereinafter). More preferably, it is set to 20% by weight or less, and more preferably 10% by weight or less. Particularly preferred are polymers other than the specific polymer.

[epoxy compound]

Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl Alcohol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, N ,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl-benzylamine, N,N-diglycidyl-aminomethylcyclohexane, N, N-diglycidyl-cyclohexylamine or the like may be one or more selected from the group consisting of these epoxy compounds.

The ratio of use of these epoxy compounds is preferably 40 parts by weight or less, more preferably 0.1 parts by weight to 30 parts by weight, based on 100 parts by weight of the total amount of the polymer.

[functional decane compound]

Examples of the functional decane compound include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, and 2-aminopropylpropane. Triethoxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyl dimethyl Oxydecane, 3-ureidopropyltrimethoxydecane, 3-mercaptopropylpropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-B Oxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylenetriamine, N-trimethoxydecylpropyltriethylenetriamine, 10-trimethoxy矽alkyl-1,4,7-triazadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diaza Heteroalkyl acetate, 9- Trimethoxydecyl-3,6-diazadecyl acetate, 9-triethoxydecyl-3,6-diazadecyl acetate, 9-trimethoxydecyl-3 , methyl 6-diazepine, methyl 9-triethoxydecyl-3,6-diazepine, N-benzyl-3-aminopropyltrimethoxydecane, N- Benzyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, glycidol Oxymethyltrimethoxydecane, glycidoxymethyltriethoxydecane, 2-glycidoxyethyltrimethoxydecane, 2-glycidoxyethyltriethoxydecane, 3- As the glycidyloxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, or the like, one or more selected from the group consisting of these functional decane compounds can be used.

These functional decaneizations relative to 100 parts by weight of the total amount of the polymer The use ratio of the compound is preferably 2 parts by weight or less, more preferably 0.02 part by weight to 0.2 part by weight.

<Preparation of liquid crystal alignment agent>

The liquid crystal alignment agent of the present invention is formed in the form of a solution-like composition. The solution-like composition is preferably obtained by dissolving a specific polymer and other components arbitrarily used as needed in an organic solvent.

The organic solvent used in the liquid crystal alignment agent of the present invention can be exemplified, for example: Benzyl alcohol, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, diethylene glycol Monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol methyl ether, propylene glycol Ether, propylene glycol propyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate Ester, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, propylene glycol methyl ether propionate, propylene glycol diethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, toluene, xylene, methyl Ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl isoamyl ketone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2-hydroxypropionic acid Ethyl ester, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl glycolate, methyl lactate, lactate B Ester, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy-3-methyl Methyl butyrate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, ethoxylate Propyl propyl acetate, butyl ethoxy acetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxy propyl acetate, butyl propyl acetate, methyl butoxyacetate, butoxy Ethyl acetate Propyl butyloxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-methoxypropene Butyl acrylate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, 2-butoxypropane Methyl ester, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, 3-methoxypropane Ethyl acetate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxypropane Propyl acrylate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, 3-propoxypropane Butyl acrylate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N,N-dimethylformamide, N,N-dimethylacetamide, 4-hydroxy-4- Methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ether, Ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol Alcohol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate , isoamyl isobutyrate, diisoamyl ether, ethyl carbonate, propyl carbonate, etc.; may be selected from the group consisting of the specific polymer used and the substrate of the liquid crystal alignment agent of the present invention. One or more of organic solvents.

Since the specific polymer of the present invention has high solubility in a general organic solvent, excellent coating properties are exhibited even when a solvent which does not attack a lightweight resin substrate is selected and used. Therefore, the liquid crystal alignment agent of the present invention has an advantage that the degree of freedom in substrate selection is high. Since the liquid crystal alignment agent of the present invention has a high degree of freedom in substrate selection, it is particularly advantageous from the viewpoint of using a general-purpose TAC film as a substrate when applied to a retardation film.

The solid content concentration in the liquid crystal alignment agent of the present invention (the ratio of the total weight of the components other than the solvent in the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) is appropriately selected in consideration of viscosity, volatility, etc., and is preferably selected. It is in the range of 1% by weight to 10% by weight. By setting the solid content concentration in this range, a liquid crystal alignment film having a suitable film thickness can be formed with good coatability, which is preferable.

The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably from 10 ° C to 50 ° C. More preferably 20 ° C ~ 30 ° C.

<Use of Liquid Crystal Aligning Agent of the Present Invention>

The liquid crystal alignment film can be formed using the liquid crystal alignment agent of the present invention as described above. The liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is suitable as a liquid crystal display element having a liquid crystal cell such as a TN type, an STN type, an IPS type or an FFS type, and a liquid crystal alignment film suitable for use as a retardation film.

When the liquid crystal alignment film is formed by using the liquid crystal alignment agent of the present invention, for example, a method of forming a coating film by coating the liquid crystal alignment agent of the present invention on a substrate (coating film forming step); and The coating film imparts a liquid crystal alignment property (liquid crystal alignment imparting step). Here, the step of imparting liquid crystal alignment property may be a rubbing treatment or a light irradiation treatment.

Hereinafter, the case where the liquid crystal alignment agent of the present invention is applied to a liquid crystal display element and the case where it is applied to a retardation film will be sequentially described.

<Application in liquid crystal display element>

(1) Coating film forming step

The liquid crystal alignment agent of the present invention is applied to a TN type, an STN type, or the like In the case of a liquid crystal display element of a liquid crystal cell of a vertical electric field type, two substrates provided with a patterned transparent conductive film are used as a pair of substrates, and the liquid crystal of the present invention is applied to each of the surfaces of the transparent conductive film. An alignment agent forms a coating film. When the liquid crystal alignment agent of the present invention is applied to a liquid crystal display element having a liquid crystal cell of a transverse electric field type such as an IPS type or an FFS type, the transparent conductive film or the metal film is patterned in a comb shape on one surface. a pair of electrodes of a pair of electrodes and an electrode not provided The counter substrate serves as a pair of substrates, and the liquid crystal alignment agent of the present invention is applied to each of the surface on which the comb-shaped electrodes are formed and the one surface of the opposite substrate to form a coating film.

In any of the above cases, the substrate may be, for example, glass such as float glass or soda glass; and includes polyethylene terephthalate, polybutylene terephthalate, polyether oxime, and polycarbonate. Ester and other plastics

Transparent substrate, etc. The transparent conductive film may be used: Indium tin oxide containing In ₂ O ₃ -SnO ₂ oxide (Indium Tin Oxide, ITO) film, comprising a SnO NESA ₂ (Naise registered trademark) film. As the metal film, for example, a film containing a metal such as chromium can be used. When the transparent conductive film and the metal film are patterned, for example, a method of forming a pattern by a photolithography method, a sputtering method, or the like after forming a transparent conductive film having no pattern can be used, and a method of forming a transparent conductive film can be used. A method of masking a desired pattern, and the like.

When the liquid crystal alignment agent is applied to the substrate, in order to improve the adhesion between the substrate and the electrode and the coating film, a functional decane compound, titanate or the like may be applied to the substrate and the electrode in advance and then heated. Pre-processing.

The application of the liquid crystal alignment agent to the substrate is preferably carried out by an appropriate coating method such as an offset printing method, a spin coating method, a roll coating method, or an inkjet printing method. After coating, the coated surface can be formed by preheating (prebaking) the coated surface and then calcining (post-baking). The prebaking conditions are, for example, a heating temperature of 40 ° C to 120 ° C and a heating time of 0.1 minutes to 5 minutes, and the post-baking conditions are, for example, a heating temperature of 120 ° C to 300 ° C, preferably 150 ° C to 250 ° C. And for example 5 minutes to 200 minutes The clock is preferably a heating time of 10 minutes to 100 minutes. The film thickness of the coating film after post-baking is preferably set to 0.001 μm to 1 μm, and more preferably set to 0.005 μm to 0.5 μm.

(2) Liquid crystal alignment imparting step

[friction treatment step]

The coating film formed by the (1) coating film forming step can be subjected to a rubbing treatment to impart a liquid crystal alignment ability to the coating film to form a liquid crystal alignment film.

In the rubbing treatment, the coating film formed by the (1) coating film forming step is subjected to the following rubbing treatment, that is, rubbing in a certain direction by a roll wound with a cloth containing, for example, long fibers such as nylon, rayon, or cotton. . Thereby, the alignment ability of the liquid crystal molecules can be imparted to the coating film to form a liquid crystal alignment film.

[Light irradiation processing step]

The coating film formed by the (1) coating film forming step can impart a liquid crystal alignment ability to the coating film by irradiating the polarized light thereto to form a liquid crystal alignment film.

As the light to be irradiated here, for example, ultraviolet rays, visible rays, or the like containing light having a wavelength of 150 nm to 800 nm can be used. Ultraviolet rays containing light having a wavelength of 200 nm to 400 nm are preferred. As the light source to be used, for example, a low pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an Hg-Xe lamp, an excimer laser or the like can be used. The ultraviolet light preferably in the wavelength range can be obtained by a method of using the light source in combination with, for example, a filter, a diffraction grating, or the like.

When the light used for light irradiation is polarized (linearly polarized or partially polarized), the coated surface may be irradiated from the vertical direction or from the inclined side. Irradiation is performed to impart a pretilt angle. On the other hand, in the case of irradiating non-polarized light, it is preferred that the irradiation is performed on the coating film surface from the oblique direction.

Light irradiation amount is preferably ^{1,000J / m 2 ~ 10,000J / m} 2, more preferably ^{1,500 J / m 2 ~ 7,000J /} m 2. A well-known liquid crystal alignment film material which imparts liquid crystal alignment property by photolysis of a cyclobutane ring requires a large irradiation amount of more than 10,000 J/m ² . In the liquid crystal alignment agent of the present invention, even when the amount of light irradiation is set to, for example, 5,000 J/m ² or less, good liquid crystal alignment property can be imparted, and in particular, even when it is set to 3,000 J/m ² or less, good liquid crystal alignment property can be obtained.

(3) Manufacturing of liquid crystal display elements

A pair of bases in which a liquid crystal alignment film is formed as described above can be used. The board was manufactured as follows in the liquid crystal display element.

First, a liquid crystal cell constituting the following structure, that is, a liquid crystal will be formed A structure in which a liquid crystal is sandwiched between gaps (cell gaps) in which a pair of substrates of the alignment film face each other.

In the case of constituting the liquid crystal cell, the two substrates on which the liquid crystal alignment film is formed may be bonded together by a sealant disposed on the peripheral portion thereof so that the liquid crystal alignment film faces face each other, and the liquid crystal alignment film surface and a method of injecting a liquid crystal into a cell gap divided by a sealant to seal the injection hole; and arranging, for example, an ultraviolet curable sealing material on a predetermined portion of one of the two substrates on which the liquid crystal alignment film is formed, and further, in the liquid crystal After arranging the liquid crystal at a predetermined portion on the alignment film surface, the liquid crystal alignment film is laminated to face each other. The other substrate is pressure-bonded, thereby ejecting the liquid crystal on the front surface of the liquid crystal alignment film, and then irradiating the entire surface of the substrate with ultraviolet rays to harden the sealant.

In any of the above cases, it is preferable to arrange in such a manner that when the rubbing treatment is performed when the liquid crystal alignment film is formed, the rubbing direction of the liquid crystal alignment film of the two substrates becomes orthogonal or anti-parallel. In the case where the polarized light is irradiated when the liquid crystal alignment film is formed, the direction in which the polarizing surface of the irradiation light is projected on the two substrate surfaces is orthogonal or antiparallel.

Then, the polarizing plate is attached to the outer surface of the liquid crystal cell in a predetermined direction, whereby the liquid crystal display element can be manufactured.

As the sealant, for example, an epoxy resin containing a hardener and an alumina ball as a spacer can be used.

The liquid crystal may use a nematic liquid crystal or a smectic liquid crystal. Among these liquid crystals, nematic liquid crystals are preferred. Specific examples thereof include a Schiff base liquid crystal, an oxidized azo liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, and a biphenyl ring. An alkane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cubane liquid crystal, or the like. It is also possible to use the following substances in these liquid crystals: cholesteric liquid crystals such as cholesteryl chloride, cholesteryl citrate, and cholesteryl carbonate; as the product names "C-15" and "CB-15" (Merck) A chiral agent that is sold as a product; a ferroelectric liquid crystal such as p-oxybenzylidene-p-amino-2-methylbutyl cinnamate.

The polarizing plate attached to the outer surface of the liquid crystal cell can be exemplified by A polarizing plate obtained by sandwiching a polarizing film called "H film" in which polyvinyl alcohol is stretched and iodine is formed by a cellulose acetate protective film, or a polarizing plate including the H film itself.

<Application in retardation film>

(1) Coating film forming step

When the liquid crystal alignment agent of the present invention is applied to a retardation film, it is used. The substrate can be suitably exemplified: comprising triacetyl cellulose (TAC), polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polyamine, polyimine, polymethyl A transparent substrate of a synthetic resin such as methyl acrylate or polycarbonate. Among these substrates, TAC is generally used as a protective layer of a polarizing film in a liquid crystal display element.

In many cases, the retardation film is used in combination with a polarizing film. At this time, it must The retardation film is bonded to the specific direction by precisely controlling the angle of the polarizing axis of the polarizing film so as to exhibit the desired optical characteristics. Therefore, if a liquid crystal alignment film having a liquid crystal alignment ability in a direction of a predetermined angle is formed on the TAC film, the step of laminating the retardation film on the polarizing film while controlling the angle thereof can be omitted, which can contribute to The productivity of the liquid crystal display element is improved. The formation of the liquid crystal alignment film having the liquid crystal alignment ability in the direction of the predetermined angle can be carried out by the liquid alignment method using the liquid crystal alignment agent of the present invention.

Therefore, by using a TAC film as a substrate, in addition to the advantages In addition, it contributes to downsizing and weight reduction of the liquid crystal display element, and is also preferable in that it can also be applied to a flexible display.

The application of the liquid crystal alignment agent to the substrate can be carried out in the same manner as in the case of application to a liquid crystal display element.

Further, the film thickness of the coating film formed here is preferably from 1 nm to 1,000 nm, more preferably from 5 nm to 500 nm.

(2) Liquid crystal alignment imparting step

The coating film formed by the (1) coating film forming step is subjected to a rubbing treatment step or a light irradiation treatment step in the same manner as in the case of being applied to a liquid crystal display device, thereby imparting liquid crystal alignment property to the coating film. Liquid crystal alignment film.

(3) Fabrication of retardation film

Next, the liquid crystal alignment film formed on the substrate is formed as described above. The coating film of the polymerizable liquid crystal is subjected to one or more kinds of treatments selected from the group consisting of heating and light irradiation to form a liquid crystal layer to form a retardation film.

The polymerizable liquid crystal coated on the liquid crystal alignment film is transmitted through heat and light A liquid crystal compound or a liquid crystal composition which is polymerized by at least one of the treatments. Such a polymerizable liquid crystal is, for example, a nematic type disclosed in Non-Patent Document 1 ("UV-curable liquid crystal and its application", "Liquid crystal", Vol. 3, No. 1 (1999), pp 34 to pp 42). In addition to the liquid crystal compound, a cholesteric liquid crystal, a discotic liquid crystal, a twisted nematic liquid crystal to which a chiral agent is added, or the like may be used. The polymerizable liquid crystal may also be a mixture of a plurality of liquid crystal compounds. The polymerizable liquid crystal may be a composition further containing a well-known polymerization initiator, a suitable solvent, and the like.

When the polymerizable liquid crystal as described above is applied onto the liquid crystal alignment film, for example, a suitable coating such as a bar coating method, a roll coating method, a spin method, a printing method, or an inkjet method can be employed. method.

The coating film of the polymerizable liquid crystal formed as described above is selected from the group consisting of One or more processes of heat and light irradiation thereby harden the coating film to form a liquid crystal layer. In the case where these treatments are carried out in an overlapping manner, a good alignment can be obtained, which is preferable.

The heating temperature of the coating film should be adapted to the type of polymerizable liquid crystal used. When choosing. For example, in the case of using RMS03-013C manufactured by Merck, it is preferred to carry out heating at a temperature ranging from 40 °C to 80 °C. The heating time is preferably from 0.5 minutes to 5 minutes.

As the irradiation light, non-polarized ultraviolet rays having a wavelength in the range of 200 nm to 500 nm can be preferably used. The amount of light to be irradiated is preferably set to 50 mJ/cm ² to 10,000 mJ/cm ² , and more preferably set to 100 mJ/cm ² to 5,000 mJ/cm ² .

The thickness of the formed liquid crystal layer is appropriately set according to desired optical characteristics set. For example, in the case of producing a 1/2 wavelength plate of visible light having a wavelength of 540 nm, the phase difference of the formed retardation film is selected to be a thickness of 240 nm to 300 nm, and when it is a quarter wave plate, the phase difference is selected to be 120 nm. 150nm thickness. The thickness of the liquid crystal layer in which the target phase difference can be obtained varies depending on the optical characteristics of the polymerizable liquid crystal to be used. For example, in the case of using RMS03-013C manufactured by Merck, the thickness for producing a quarter-wave plate is in the range of 0.6 μm to 1.5 μm.

As described above, a retardation film can be produced.

The retardation film produced by using the liquid crystal alignment agent of the present invention may suitably A retardation film as a liquid crystal display element is applied.

[Examples]

In the following synthesis examples, the synthesis is repeated as needed according to the scale described below, thereby ensuring the necessary amounts of the compounds used in the following synthesis examples and examples.

<Synthesis of a monomer having a divalent group represented by the formula (1)>

[Synthesis of Compound (E)]

Synthesis Example E-1

Compound (E-1) was synthesized according to the following Scheme E-1.

Mix 1,2,3,4-cyclobutane tetracarboxylate in a 2L three-necked flask equipped with a reflux tube After 196.11 g of acid dianhydride, 152 g of 3-aminopropanol and 1,000 mL of dimethylformamide, the mixture was stirred at 40 ° C for 2 hours, and then refluxed for 4 hours to carry out a reaction. After the reaction, distilled water was added to the reaction mixture to carry out crystallization, and then the solid was collected by filtration. The solid recovered was washed with ethanol, and then dried under reduced pressure to 60 ° C to obtain 301 g of Compound (E-1).

Synthesis Example E-2

Compound (E-2) was synthesized according to the following Scheme E-2.

After mixing 1,196.11 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 220 g of 4-aminophenol and 1,000 mL of pyridine in a 2 L three-necked flask equipped with a reflux tube, at 40 ° C The mixture was stirred for 2 hours and then refluxed for 4 hours to carry out a reaction. After the reaction, distilled water was added to the reaction mixture to carry out crystallization, and then the solid was collected by filtration. After the recovered solid was washed with ethanol, it was dried by heating to 60 ° C under reduced pressure to obtain 359 g of Compound (E-2).

Synthesis Example C-1

Compound (C-1) was synthesized according to the following Scheme C-1.

Mix 1,2,3,4-cyclobutane tetracarboxylate in a 2L three-necked flask equipped with a reflux tube After 196.11 g of acid dianhydride, 180 g of β-alanine, and 1,000 mL of dimethylformamide, the mixture was stirred at 40 ° C for 2 hours, and then refluxed for 4 hours to carry out a reaction. After the reaction, in the opposite After crystallization was added to the mixture by adding distilled water, the solid was collected by filtration. After the recovered solid was washed with ethanol, it was dried by heating to 60 ° C under reduced pressure, whereby 311 g of the compound (C-1) was obtained.

Synthesis Example S-1

The compound (S-1) was synthesized according to the following Scheme S-1.

[化10]

Into a 2 L three-necked flask equipped with a dropping funnel, 310.3 g of a compound (E-1) and 800 mL of acetic acid synthesized in the same manner as in the above-mentioned Synthesis Example E-1 were added. Thereto, 200 mL of sulfuric acid was slowly added dropwise from the dropping funnel. During the dropping process, use an ice bath to cool The flask was kept at an internal temperature of not more than 10 °C. After the completion of the dropwise addition, the reaction was carried out for 6 hours at room temperature. After the reaction was completed, 2,000 mL of ethyl acetate was added to the reaction mixture. The following liquid separation cleaning operation was performed, in which 500 mL of distilled water was added thereto, liquid separation washing was performed, and the water layer was discarded. This liquid separation cleaning operation was repeated, and a total of four liquid separation cleaning operations were performed. Then, the solvent was removed by distillation under reduced pressure to obtain a crude product as a liquid. This crude product was dissolved in ethyl acetate and purified using a ruthenium dioxide column, and then the solvent was removed under reduced pressure to obtain 155 g of Compound (S-1a).

27.4 g of the compound (S-1a) obtained above, 50 mL of toluene, and a concentration of 0.2 mol/L of chloroplatinic acid hexahydrate were added to a 1,000 mL three-necked flask equipped with a reflux tube and a nitrogen introduction tube. 5 μL of a propanol solution was bubbling with a nitrogen stream for about 10 minutes to carry out nitrogen substitution in the system, and then 18.1 g of dimethyl monomethoxydecane was added, and the reaction was carried out under nitrogen under reflux for 10 hours. . After completion of the reaction, the reaction mixture was passed through a short column of a cerium oxide gel, and further purified by a cerium oxide column, and then the solvent was removed by pressure reduction to obtain 8.2 g of the compound (S-1).

<Synthesis of specific polymers>

[Synthesis of Polyamine]

Synthesis Example PA-1

In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, 100 mol% of 1,4-diaminobenzene was added, and tetrahydrofuran was added and dissolved so that the total concentration of the compound became 20% by weight. Further adding three in an amount equivalent to 300 mol% with respect to the molar number of the 1,4-diaminobenzene Ethylamine was mixed at room temperature. In the above, the following solution was slowly added dropwise from the dropping funnel, that is, 100 mol% of the compound (C-1) obtained in the synthesis example C-1 was chlorinated with thionyl chloride. The obtained product was dissolved in tetrahydrofuran at a concentration of 20% by weight, and polymerization was carried out for 4 hours at room temperature. After the end of the reaction, the reaction mixture was poured into a large excess of methanol to precipitate a reaction product. The recovered precipitate was washed with methanol, and dried under reduced pressure at 40 ° C for 15 hours to obtain polyamine (PA-1).

[Synthesis of Polyester]

Synthesis Example PE-1~ Synthesis Example PE-4

In the synthesis example PA-1, the species and the molar ratio described in Table 1 were used. A dihydroxy compound or a diepoxy compound is used in place of 1,4-diaminobenzene, and a compound of the type and molar ratio described in Table 1 is used as the polyvalent carboxylic acid, and the synthesis example PA-1 is used. The synthesis was carried out in the same manner, and polyester (PE-1) to polyester (PE-4) were obtained, respectively.

Synthesis Example PE-5

In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 31 g of the compound (E-1) obtained in Synthesis Example E-1 was dissolved in 211.2 g of N-methylpyrrolidone. 21.8 g of pyromellitic dianhydride was added thereto, and the reaction was carried out at 40 ° C for 12 hours to obtain a solution containing 20% by weight of a polyester (PE-5).

The abbreviations of the compound names in Table 1 have the following meanings, respectively.

DA-1: 1,4-diaminobenzene

EP-1: 1,4-diglycidyloxybenzene

CA-1: terephthalic acid

CA-2: 2,2-bis(4-(4-carboxyphenoxy)phenyl)propane

PYA: pyromellitic dianhydride

[Synthesis of polyorganosiloxanes]

Synthesis example PS-1

Into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, 45.47 g of the compound (S-1) obtained in Synthesis Example S-1 was added, and 181.88 g of methyl isobutyl ketone was added and dissolved. . 1.01 g of triethylamine was added thereto and mixed at room temperature. Then, 36 g of deionized water was added dropwise from the dropping funnel, and then the reaction was carried out at 80 ° C for 6 hours.

After the completion of the reaction, the organic layer was taken out and washed with a 0.2% by weight aqueous solution of ammonium nitrate until the wastewater after washing became neutral, and the solvent and the solvent were reduced under reduced pressure. The water was distilled off, whereby 40 g of polyoxyalkylene (PS-1) was obtained.

[Synthesis of polyglycine]

Comparative synthesis example p-1

In a reaction vessel equipped with a stirrer and a thermometer, 41.0 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane and 1,2,3,4-cyclobutanetetracarboxylic acid 19.2 g of an anhydride was dissolved in 343.5 g of N-methylpyrrolidone, and the reaction was carried out for 10 hours at room temperature to obtain a solution containing polylysine (p-1).

<Preparation and evaluation of liquid crystal alignment agent>

[Application in liquid crystal display elements]

Example 1

(1) Preparation of liquid crystal alignment agent

100 parts by weight of the polymer (polyamine (PA-1)) obtained in the synthesis example PA-1 as a polymer was dissolved in N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC). A mixed solvent (NMP: BC = 50:50 (mass ratio)) was used to prepare a solution having a solid concentration of 6.5% by weight. After the solution was thoroughly stirred, it was filtered through a filter having a pore size of 0.2 μm to prepare a liquid crystal alignment agent.

(2) Evaluation of printability

The liquid crystal alignment agent prepared above was applied on a transparent electrode surface of a glass substrate with a transparent electrode including an ITO film using a liquid crystal alignment film printer (manufactured by Japan Photoprinting Co., Ltd.), and a hot plate at 80 ° C was used. After heating (prebaking) for 1 minute to remove the solvent, it was heated (post-baked) on a hot plate at 200 ° C for 10 minutes to form a coating film having an average film thickness of 600 Å. The film was made using a microscope with a magnification of 20 times. Observations were made to investigate the unevenness of printing and the presence or absence of pinholes. As a result, uneven printing and pinholes were not observed, and the printability was "good".

(3) Manufacturing of liquid crystal display elements

2 pairs of electrode pairs on one side (will have no pattern bottom) A glass substrate in which a pole, a tantalum nitride film, and a patterned top electrode are sequentially laminated, and a facing glass substrate not provided with an electrode are used as a pair of substrates, and the electrode has one surface and a facing surface of the glass substrate. On one side of the glass substrate, the liquid crystal alignment agent prepared above was coated with a spinner, and prebaked on a hot plate at 80 ° C for 1 minute, and then heated at 200 ° C in a nitrogen-substituted oven in the chamber. (post-baking) For 1 hour, a coating film having an average film thickness of 1,000 Å was formed.

Hereinafter, each system of the electrode pairs of the two systems is referred to as an "electrode" A" and "electrode B." A schematic cross-sectional view of these electrode pairs and a plan view of the top electrode are shown in Fig. 1 and Fig. 2 (a) and Fig. 2 (b), respectively. Fig. 2 (b) is Fig. 2 (a) An enlarged view of a portion surrounded by a broken line.

For each surface of the coating film formed above, a high-pressure mercury lamp and a glan-taylor prism were respectively used, and a polarized ultraviolet ray having a bright line of 254 nm of 2,500 J/m ^{2 was} irradiated from the normal direction of the substrate to obtain A pair of substrates of a liquid crystal alignment film.

On the outer circumference of a face of the one of the substrates having the liquid crystal alignment film, After the epoxy resin adhesive having a diameter of 5.5 μm is applied by screen printing, the liquid crystal alignment film faces of the pair of substrates are opposed to each other to project the polarizing surface of the polarized ultraviolet light on the substrate. Become parallel and overlap and crimp, at 150 The adhesive was thermally cured at ° C for 1 hour. Then, the liquid crystal "MLC-6221" manufactured by Merck was filled in the substrate gap from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy resin adhesive. Then, in order to remove the flow alignment at the time of liquid crystal injection, it was heated to 150 ° C and then slowly cooled to room temperature.

Next, a polarizing plate was bonded to both outer surfaces of the substrate to manufacture a liquid crystal display element. At this time, one of the polarizing plates is attached in such a manner that the polarizing direction thereof is parallel to the direction in which the polarizing surface of the polarized ultraviolet ray of the liquid crystal alignment film is parallel to the projection direction of the substrate surface, and the other sheet is polarized with the polarization direction of the polarizing plate. Attached in a vertical direction.

(4) Evaluation of liquid crystal alignment

In the liquid crystal display device manufactured above, the presence or absence of an abnormal region of light and dark change when a voltage of 5 V was applied/released (ON/OFF) was observed with a microscope having a magnification of 50 times. The case where the abnormal region was not observed was evaluated as "good" in the liquid crystal alignment property, and the case where the abnormal region was observed was evaluated as the liquid crystal alignment "bad", and as a result, the liquid crystal alignment property of the liquid crystal display element was "good".

Embodiment 2 to Embodiment 5 and Embodiment 7

In the above-mentioned Example 1, a liquid crystal alignment agent was prepared and evaluated in the same manner as in Example 1 except that the types of the polymers used in the preparation of the liquid crystal alignment agent were set as described in Table 2, respectively.

The evaluation results are shown in Table 2.

Example 6

In the first embodiment, a liquid crystal alignment agent was prepared as follows. Various evaluations were carried out in the same manner as in Example 1 except that the liquid crystal alignment agent was used.

(1) Preparation of liquid crystal alignment agent

In a solution containing the polyester (PE-5) prepared in the synthesis example PE-5, N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) were added to prepare a solvent composition ratio of NMP. : BC = 50:50 (mass ratio), a solution having a solid concentration of 6.5% by weight. After the solution was thoroughly stirred, it was filtered through a filter having a pore size of 0.2 μm to prepare a liquid crystal alignment agent.

The evaluation results are shown in Table 2.

Comparative example 1

In the above-mentioned Example 6, a solution containing the polyamic acid (p-1) obtained in the comparative synthesis example p-1 was used instead of the solution containing the polyester (PE-5), and Example 6 A liquid crystal alignment agent was prepared in the same manner and evaluated.

The evaluation results are shown in Table 2.

In Comparative Example 1, although slight darkness was observed in the evaluation of the liquid crystal alignment property, a plurality of abnormal regions were observed, and it was considered that the liquid crystal was not uniformly aligned, and thus the liquid crystal alignment property was regarded as "poor".

[Application in retardation film]

Example 8

The liquid crystal alignment agent prepared in Example 1 was applied to one surface of a TAC film as a substrate using a bar coater, and baked in an oven at 120 ° C for 2 minutes to form a coating film having a film thickness of 100 nm. Then, a high-pressure mercury lamp and a Glan-Taylor prism were used for the surface of the coating film, and a polarized ultraviolet ray having an open line of 254 nm was directly irradiated from the normal direction of the substrate at 2,500 J/m ² to form a liquid crystal alignment film.

Then, the polymerizable liquid crystal (RMS03-013C, manufactured by Merck) was filtered using a filter having a pore size of 0.2 μm, and then coated on the liquid crystal alignment film using a bar coater, and the temperature inside the chamber was set. The film was baked in an oven at 50 ° C for 1 minute to form a film of a polymerizable liquid crystal. The film of the polymerizable liquid crystal was irradiated with a non-polarized ultraviolet ray of 1,000 mJ/cm ² containing an open line of 365 nm, and the polymerizable liquid crystal was polymerized and cured to produce a retardation film.

(2) Evaluation of retardation film

i) Liquid crystal alignment

The alignment of the retardation film produced above was observed by visual observation under a crossed nicols and observation by a polarizing microscope (magnification: 50 times). In the case where no abnormal region was observed by both the visual observation and the polarizing microscope observation, the liquid crystal alignment property was evaluated as excellent "A"; the liquid crystal alignment property was good at the time of visual observation, but an abnormal region was observed when observed by a polarizing microscope. Evaluation of liquid crystal alignment is good "B"; in the case where abnormality of liquid crystal alignment is confirmed by visual observation, evaluation The liquid crystal alignment is poor "C".

As a result, the liquid crystal alignment of the retardation film was evaluated as excellent "A".

Ii) Adhesion

With respect to the retardation film manufactured above, slits were formed at intervals of 1 mm using a spacer with equally spaced spacers to form a 10 × 10 lattice pattern. Then, after the cellophane tape is adhered to the lattice pattern, the glass tape is peeled off from the lattice pattern.

Here, the notched portion of the lattice pattern from which the glass tape was peeled off was observed, and when the peeled portion was not observed along the intersection of the slit line or the lattice pattern, the adhesion was evaluated as excellent "A"; When the number of grids of the lattice of the part is 14 or less, the adhesion is evaluated as good "B", and when the number of grids of the lattice of the peeled portion is 15 or more, the adhesion is evaluated as poor. "C".

As a result, the adhesion of the retardation film was evaluated as excellent "A".

Claims (11)

A liquid crystal alignment agent comprising at least one polymer selected from the group consisting of polyorganosiloxanes, polyamines, poly(thio)esters, and (meth)acrylic copolymers, wherein The polymer has a divalent group represented by the following formula (1); In the formula (1), R ^I to R ^IV are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms; and Y ¹ and Y ² are each independently divalent. The organic group, "*" represents a bonding bond bonded to a polymer chain, respectively. The liquid crystal alignment agent according to claim 1, wherein the polymer is a polyorganosiloxane obtained by hydrolyzing and condensing a decane compound containing a compound represented by the following formula (S); In the formula ^{(S), R I ~ R} IV, Y 1 and Y ^2, respectively, in the formula (1) R ^I ~ R ^IV, Y ¹ and Y ² are the same meanings; R & lt ¹ and R ² are each independently The alkyl group having 1 to 12 carbon atoms or the aryl group having 6 to 12 carbon atoms; X ¹ and X ² are each independently an alkoxy group having 1 to 12 carbon atoms or a halogen atom; n1 and n2 are each independently 1~ An integer of 3. The liquid crystal alignment agent according to claim 1, wherein the polymer is a polyamine obtained by reacting a diamine with a polycarboxylic acid containing a compound represented by the following formula (C); In formula ^{(C), R I ~ R} IV, Y 1 and Y ^2, respectively, in the formula (1) R ^I ~ R ^IV, Y ¹ and Y ² are the same meanings. The liquid crystal alignment agent according to claim 1, wherein the polymer is at least one compound selected from the group consisting of a diol compound, a dithiol compound, and a diepoxide compound, and includes a poly(thio)ester obtained by reacting a polycarboxylic acid of a compound represented by the following formula (C); In formula ^{(C), R I ~ R} IV, Y 1 and Y ^2, respectively, in the formula (1) R ^I ~ R ^IV, Y ¹ and Y ² are the same meanings. The liquid crystal alignment agent according to claim 1, wherein the polymer is at least one compound selected from the group consisting of a diol compound, a dithiol compound, and a diepoxide compound, and a plurality of a poly(thio)ester obtained by a carboxylic acid reaction, wherein at least a part of the compound is a compound represented by the following formula (E); In the formula ^{(E), R I ~ R} IV, Y 1 and Y ^2, respectively, in the formula (1) R ^I ~ R ^IV, Y ¹ and Y ² are the same meanings; the Z ¹ and Z ² are each independently It is a hydroxyl group, a thiol group or an epoxy group. Liquid crystal alignment as described in any one of claims 1 to 5 An agent for forming a liquid crystal alignment film in a retardation film of a liquid crystal display element. The liquid crystal alignment agent according to any one of the items 1 to 5, which is used for forming a liquid crystal alignment film of a liquid crystal cell of a liquid crystal display element. A liquid crystal alignment film which is formed by the liquid crystal alignment agent according to any one of claims 1 to 7. A retardation film of a liquid crystal display device comprising: a liquid crystal alignment film formed by the liquid crystal alignment agent according to claim 6 of the patent application. A liquid crystal cell of a liquid crystal display device comprising: a liquid crystal alignment film formed by the liquid crystal alignment agent according to claim 7 of the patent application. A method for forming a liquid crystal alignment film, comprising: coating a liquid crystal alignment agent according to any one of claims 1 to 7 on a substrate to form a coating film, and then forming the coating film The coating film is irradiated with light.