TWI510518B - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Description

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

The present invention relates to a liquid crystal alignment agent used for producing a liquid crystal alignment film, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film, and a novel diamine suitable for the same.

A liquid crystal display element used for a liquid crystal display such as a liquid crystal display, a liquid crystal display, or a liquid crystal display is used in the liquid crystal display device. The polyimine-based liquid crystal alignment film is used at most for reasons of excellent productivity and excellent chemical and thermal durability. The polyimine-based liquid crystal alignment film is obtained by applying a solution of a polyimide or a solution of a polyamidene precursor to a substrate, and is usually fired at a temperature of about 200 to 250 ° C. Production.

The firing process in the production of a polyimine-based liquid crystal alignment film is particularly necessary in the process of producing a liquid crystal display device, and is preferably a high-temperature process, and has hitherto been used for the purpose of using a plastic substrate or for a color filter. A polyfluorene-based liquid crystal alignment film material which can be fired at a low temperature of 200 ° C or lower is proposed for the reason of the heat resistance and the reduction of the energy cost (see, for example, Patent Document 1).

After the polyimine-based liquid crystal alignment film is fired, it is rubbed by a cloth such as cotton, nylon, or enamel, and is subjected to an alignment treatment by a so-called rubbing method. In recent years, in place of this friction, an alignment treatment method of irradiating polarized ultraviolet rays or the like, or a liquid crystal display element of a vertical alignment mode which is not required to be aligned has been developed, and some of them have been put into practical use. However, the alignment treatment by friction at this stage is also an important position in the process of manufacturing a liquid crystal alignment film.

In recent years, when the polyimine-based liquid crystal alignment film is fired at a low temperature, the mechanical strength of the film subjected to the rubbing treatment is insufficient. That is, when the rubbing treatment is performed, a flaw is generated on the surface of the liquid crystal alignment film, or a part of the film is peeled off by the substrate or the like. In the case of low-temperature firing, the film strength is insufficient when compared with the normal firing temperature, so that the improper situation caused by the rubbing treatment becomes a serious problem. For a liquid crystal alignment film which improves the friction resistance at the time of low-temperature baking, a method of using a specific tetracarboxylic dianhydride for a raw material of polyamic acid (for example, refer to Patent Document 2) and a method of using an additive have been proposed (for example, refer to the patent document) 3) A method of using a diamine in which an acrylic residue is introduced at the side of a side chain (for example, refer to Patent Document 4).

[Advanced technical literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 5-158047

[Patent Document 2] Japanese Patent Laid-Open No. 2000-298279

[Patent Document 3] Japanese Special Opening 2002-357831

[Patent Document 4] Japanese Special Open 2008-203332

An object of the present invention is to provide a material for a liquid crystal alignment film which does not cause film peeling or scratching during rubbing at 200 ° C or lower, and which can provide good liquid crystal alignment, and can be fired at 200 ° C or lower. A liquid crystal alignment film which does not cause film peeling or scratching during rubbing, and which has good liquid crystal alignment properties, and energy cost at the time of production is reduced, and liquid crystal is applied even if a substrate having low heat resistance such as a plastic substrate is used. Display elements, as well as novel diamines suitable for use herein.

The inventors of the present invention have made a detailed review of the above problems, and by using the diamine component having a specific structure of a diamine having a novel diamine compound before the application of the present invention, it can be obtained even if it is fired at 200 ° C or lower. The present invention has been completed by liquid crystal alignment film which does not cause film peeling or scratching during rubbing. That is, the present invention is intended to be as follows.

1. A liquid crystal alignment agent containing a polyfluorene obtained by polymerizing a diamine component represented by the following formula [1] and a tetracarboxylic dianhydride component represented by the following formula [2]. A liquid crystal alignment agent of at least one polymer of a group consisting of an amine acid and a polyimine obtained by subjecting the polyamic acid to dehydration ring closure, wherein the diamine component contains a diamine represented by the following formula [3]

[Chemical 1]

H ₂ NR ₁ -NH ₂ [1]

(R ₁ is a divalent organic group)

[Chemical 2]

(R ₂ is a tetravalent organic group)

[Chemical 3]

Wherein R ³ represents a group selected from the group consisting of -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, and -NH-; R ⁴ represents a single bond or An alkylene group having 1 to 10 carbon atoms, 1 or a plurality of -CH ₂ - of the alkylene group may be substituted by -CF ₂ -, and any of the groups exemplified below may be adjacent to each other, Substituted into these groups; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-; R ⁵ represents a single bond, -CH ₂ -, -O- or NH-; R ⁶ represents a divalent organic group having 5 or 18 carbon atoms at the terminal and having at least one aromatic ring at the terminal, wherein the ring may be a carbocyclic ring or a heterocyclic ring, and 1 or a plurality of hydrogens of the ring may be a fluorine atom. Substituted; R ⁷ is hydrogen, methyl or trifluoromethyl).

2. The liquid crystal alignment agent according to the above 1, wherein R ³ in the formula [3] is -O- or -COO-.

3. The liquid crystal alignment agent according to the above 1 or 2, wherein R ⁴ in the formula [3] is an alkylene group having 1 to 4 carbon atoms.

4. The liquid crystal alignment agent according to any one of the above 1 to 3, wherein R ⁵ in the formula [3] is -O-.

5. The liquid crystal alignment agent according to any one of the above 1 to 4, wherein R ⁶ in the formula [3] is a 1,4-phenylene group.

6. The liquid crystal alignment agent according to any one of the above 1 to 5, wherein R ⁷ in the formula [3] is a methyl group.

7. The liquid crystal alignment agent according to any one of the above-mentioned items 1 to 6, wherein the diamine component represented by the formula [1] contains 30 mol% or more of the diamine represented by the above formula [3].

R 8. The liquid crystal 1 to 7 according to any one of the above-described alignment agent, wherein in the formula [2] shown tetracarboxylic acid dianhydride component, comprising the formula [2] ₂ having the ring structure of the alicyclic tetracarboxylic acid Diacid anhydride.

A liquid crystal alignment film obtained by the liquid crystal alignment agent according to any one of the above 1 to 8.

10. A liquid crystal alignment film which is obtained by applying the liquid crystal alignment agent according to any one of the above 1 to 8 to a substrate, baking it at a temperature of 200 ° C or lower, and then rubbing it.

A liquid crystal display device comprising the liquid crystal alignment film according to the above 9 or 10.

A diamine characterized by the following formula [3];

[Chemical 4]

Wherein R ³ represents a group selected from the group consisting of -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, and -NH-; R ⁴ represents a single bond or The alkylene group having 1 to 10 carbon atoms, 1 or a plurality of -CH ₂ - of the alkylene group may be substituted by -CF ₂ -, and any of the groups exemplified below may be adjacent to each other. Substituted into these groups; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-; R ⁵ represents a single bond, -CH ₂ -, -O- or NH-; R ⁶ represents a divalent organic group having 5 or 18 carbon atoms and having at least one aromatic ring at the terminal, wherein the ring may be a carbocyclic ring or a heterocyclic ring, and 1 or a plurality of hydrogens of the ring may be a fluorine atom. Substituted; R ⁷ is hydrogen, methyl or trifluoromethyl).

The liquid crystal alignment agent of the present invention does not cause film peeling or scratching by rubbing treatment even at a baking temperature of 200 ° C or lower, and a liquid crystal alignment film having a good liquid crystal alignment can be obtained. Further, the liquid crystal alignment agent of the present invention can obtain high reliability even when a liquid crystal display element which is subjected to an alignment treatment method such as irradiation of polarized ultraviolet rays or an alignment treatment method in which ultraviolet rays or the like is applied while applying a voltage.

Type of implementation of the invention

The diamine used in the production of the liquid crystal alignment agent of the present invention contains a diamine represented by the following formula [3].

[Chemical 5]

Wherein R ³ represents a group selected from the group consisting of -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, and -NH-; R ⁴ represents a single bond or An alkylene group having 1 to 10 carbon atoms, 1 or a plurality of -CH ₂ - of the alkylene group may be substituted by -CF ₂ -, and any of the groups exemplified below may be adjacent to each other, Substituted into these groups; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-; R ⁵ represents a single bond, -CH ₂ -, -O- or -NH-; R ⁶ And a divalent organic group having 5 or 18 carbon atoms and having at least one aromatic ring at the terminal, wherein the ring may be a carbocyclic ring or a heterocyclic ring, and 1 or a plurality of hydrogens of the ring may be Substituted by a fluorine atom; R ⁷ represents hydrogen, methyl or trifluoromethyl) wherein R ³ -R ⁴ -R ⁵ -R ⁶ in the formula [3] is a spacer moiety in the side chain, and R ³ represents the interval a bonding group of a diamine benzene skeleton in the object site. The bonding group is selected from the group consisting of -CH ₂ - (ie, methyl group), -O- (ie, ether), -CONH- (ie, decylamine), -NHCO- (ie, ruthenium), -COO- (ie, The esters, -OCO- (ie, reverse esters), and -NH- (ie, amine groups) are grouped. These bond groups can be formed by general organic synthesis methods, and from the viewpoint of ease of synthesis, preferably -CH ₂ -, -O-, -COO-, -NHCO- or -NH-, -O- or -COO - is better.

R ⁴ in the formula [3] is a portion which is a center of the spacer portion, and has a single bond or an alkylene group having 1 to 10 carbon atoms. However, any -CH ₂ - of the alkylene group may be substituted by -CF ₂ -. Further, the substituted -CH ₂ - may have no one or plural. And 1 or a plurality of -CH ₂ - of the alkylene group may be substituted for the bonding group in the case where any of the bonding groups mentioned next are not adjacent to each other; -O-, -NHCO-, -CONH -, -COO-, -OCO-, -NH-, -NHCONH-, -NH. This means that R ⁴ may contain a structure of a so-called alkylene group - the bonding group - an alkylene group. Further, when R ³ is -CH ₂ -, it means that the terminal on the R ³ side in R ⁴ may be the bonding group. Similarly, when R ⁵ is -CH ₂ -, it means that the terminal on the R ⁵ side in R ⁴ may be the bonding group. Wherein R ³ is -CH ₂ -, and R ⁵ is -CH ₂ -, meaning that R ⁴ is a so-called bond group - alkylene group - the bond group, or R ⁴ may be the bond Any of the bases. Further, -CH ₂ - may be substituted by the bonding group, and may be a complex position if the bonding groups are not adjacent to each other. R ⁴ is preferably an alkylene group having 1 to 6 carbon atoms, and an alkylene group having 4 carbon atoms is particularly preferred.

R ⁵ in the formula [3] represents a bond group with R ^{6 in} the spacer moiety. The bonding group is selected from the group consisting of a single bond, -CH ₂ -, -O-, and -NH-, but preferably -O-.

R ⁶ in the formula [3] represents a divalent organic group having 5 or 18 carbon atoms which is composed of 1 or a plurality of rings and has at least one aromatic ring at the terminal. The ring may be a carbocyclic ring or a heterocyclic ring. Specific examples of the structure of such an organic group include the following structures, but are not limited thereto. Further, one or a plurality of hydrogens of the ring may be substituted by a fluorine atom.

[Chemical 6]

[Chemistry 7]

Further, it is desired to increase the reactivity of the propylene group and the methacryl group (i.e., the substituent represented by -OC(=O)-CH=CH ₂ or -OC(=O)-C(=CH ₂ )-CH ₃ ). It is preferred that the acryl or methacryl group is bonded to the aromatic ring. From such a viewpoint, as R ⁶ , for example, a 1,4-phenylene group or the like is preferred.

R ⁷ in the formula [3] is hydrogen, methyl or trifluoromethyl, but a methyl group is preferred.

With respect to the above formula [3], the bonding position of the two amine groups on the benzene ring is not particularly limited. The two amine groups may have a 2,3-position, a 2,4-position, a 2,5-position, a 2,6-position, and a 3,4-position for the substituent having an acrylate structure at the terminal. The position, the position of 3,5-, preferably the position of 2,4- or the position of 3,5-.

<Synthesis method of diamine compound>

The method for synthesizing the diamine compound represented by the above formula [3] is not particularly limited. For example, a nitro group of the dinitro compound represented by the following formula [4] can be reduced and converted into an amine group.

[化8]

(R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ in the formula [4] are synonymous with the definition of the formula [3].)

When the above dinitro compound is reduced, the terminal double bond is not hydrogenated and reduced using a catalyst. The reduction reaction is preferably carried out using a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane or an alcohol, such as zinc, tin, tin chloride or iron, ammonium chloride or hydrogen chloride.

The dinitro compound represented by the above formula [4] can be obtained by a method of bonding a dinitro compound containing -R ⁶ -R ⁵ -R ⁴ -R ^{3 to} a methacrylic compound or an acryl compound. . As an example, a dinitro compound containing -R ⁶ -R ⁵ -R ⁴ -R ³ in which R ⁶ is substituted by a hydroxyl group (-OH), an acrylic compound or an acrylic compound, such as DCC (N, N), may be mentioned. a method of reacting a condensing agent of '-dicyclohexylcarbodiimide) or EDC (1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride), or R ⁶ is a method in which a dinitro compound of -R ⁶ -R ⁵ -R ⁴ -R ³ substituted by a hydroxyl group (-OH) is reacted with an acrylic acid chloride compound or an acrylic acid chloride compound in the presence of a base.

The dinitro compound containing -R ⁶ -R ⁵ -R ⁴ -R ³ may be a method of binding an alcohol compound containing -R ⁶ to R ⁵ with respect to a dinitrobenzene compound containing -R ⁴ -R ³ . Income. For example, when R ⁵ is a carbon bond (-CH ₂ -), a dinitrobenzene compound using -R ⁴ -R ³ containing R ⁴ and a R ⁵ side having R ⁶ -R ⁵ may be mentioned. A method in which an alcohol compound having an oxidized unsaturated bond is subjected to a heck reaction or a Sonogashira coupling reaction to synthesize it.

When R ⁵ is an ether bond in the (-O-), may include containing R ^{4 4} -R ³ bis nitrobenzene compound binding to two R ⁶ hydroxyl groups present in the diol compound via a base halogenated -R The method of making it react.

When the bond to R ⁵ is an amine (-NH-), may include containing R ^{4 4} -R ³ bis nitrobenzene with an alcohol compound to a compound having a group R ⁶ in the presence of a base after halogenation of -R The method of its reaction.

The dinitrobenzene compound containing -R ⁴ -R ³ is available from a method in which R ^{3 is} bonded to -R ⁴ with respect to dinitrobenzene.

For example, when R ³ is a guanamine bond (-CONH-), a method of reacting a dinitrobenzoic acid chloride with an amine compound containing R ⁴ in the presence of a base can be mentioned. Further, when R ³ is a ruthenium bond (-HNCO-), a method of reacting an amine group-containing dinitrobenzene with an acid chloride containing R ⁴ in the presence of a base can be mentioned.

When R ³ is an ester bond (-COO-), a method of reacting a dinitrobenzoic acid chloride with an alcohol compound containing R ⁴ in the presence of a base can be mentioned. Further, when R ³ is a reverse ester bond (-OCO-), a method of reacting a dinitrobenzene containing a hydroxyl group with an acid chloride containing R ⁴ in the presence of a base can be mentioned.

When R ³ is an ether bond (-O-), a method of reacting a halogen group-containing dinitrobenzene with an R ⁴ -containing alcohol compound in the presence of a base can be mentioned.

When R ³ is an amine bond (-NH-), a method of reacting a halogen group-containing dinitrobenzene with an R ⁴ -containing amine compound in the presence of a base can be mentioned.

When R ³ is a carbon bond (-CH ₂ -), a compound in which a halogen group-containing dinitrobenzene and an unsaturated bond having an R ³ -terminal end having R ⁴ -R ³ are oxidized may be used in a Heck reaction. Or the method of Sonogashira coupling reaction.

Examples of the dinitrobenzoic acid chloride include 3,5-dinitrobenzoic acid chloride, 3,5-dinitrobenzoic acid, 2,4-dinitrobenzoic acid chloride, and 3,5. - Dinitrobenzyl chloride, 2,4-dinitrobenzyl chloride, and the like. Further, examples of the nitrobenzene containing an amine group include 2,4-dinitroaniline, 3,5-dinitroaniline, and 2,6-dinitroaniline. Examples of the nitrobenzene containing a hydroxyl group include 2,4-dinitrophenol, 3,5-dinitrophenol, and 2,6-dinitrophenol. Examples of the dinitrobenzene containing a halogen group include 2,4-dinitrofluorobenzene, 3,5-dinitrofluorobenzene, 2,6-dinitrofluorobenzene, and 2,4-dinitro group. Iodobenzene, 3,5-dinitroiodobenzene, 2,6-dinitroiodobenzene, and the like.

The liquid crystal alignment agent of the present invention contains a polyamic acid obtained by polymerizing a diamine component represented by the above formula [1] and a tetracarboxylic dianhydride component represented by the above formula [2], And a liquid crystal alignment agent of at least one polymer of the polyimine obtained by dehydration ring-closure, and the diamine component contains the diamine represented by the above formula [3].

The diamine component may have one type of diamine represented by the formula [3], and may be mixed in two or more types.

The content ratio of the diamine represented by the formula [3] to the diamine component of the formula [1] used for the polymerization reaction of poly-proline is not particularly limited, but it is possible to suppress film peeling or frictional damage at the time of rubbing. From the viewpoint, it is preferably 10 mol% or more, preferably 30 mol% or more. 100 mol% of the diamine component may be a diamine represented by the formula [3].

When the diamine content ratio of the formula [3] is less than 100 mol%, the structure and composition of the remaining diamine component are not particularly limited. Specific examples of the diamine component other than the diamine represented by the formula [3] include diamines of the formula [1] in which R ₁ is a divalent organic group represented by the following table, and these may be one type. Or use 2 or more types together.

When R ₁ is a diamine of B-83 to B-104 in a part of the diamine component, the tilt angle of the liquid crystal can be increased when it is used as a liquid crystal alignment film.

The structure and composition of the tetracarboxylic dianhydride component represented by the formula [2] used for the polymerization reaction of poly-proline are not particularly limited, and may be one type of compound, or two or more types of compounds may be used in combination. Specific examples of the compound include R ₄ of the formula [2], which is a tetravalent organic dianhydride of the tetravalent organic group shown in the following table.

When a tetracarboxylic dianhydride having an organic group in which R ₂ of the formula [2] is an alicyclic structure is used as the tetracarboxylic dianhydride component, the friction resistance is further improved. In this case, the content ratio of the tetracarboxylic dianhydride having an organic group of R ₂ having an alicyclic structure of the formula [2] is preferably 10 mol% or more, preferably 20 mol% or more, based on the entire tetracarboxylic dianhydride component. More preferably, it is 50 mol% or more, and may be 100 mol%. Examples of R ₂ having an alicyclic structure include A-1 to A-24 in the above table. As R ₂ having an alicyclic structure, A-1 in the above table is preferred.

In order to obtain a polymerization reaction of poly-proline, the diamine component and the tetracarboxylic dianhydride component may be mixed in an organic solvent. The organic solvent in this case is not particularly limited as long as it can dissolve the produced polyamic acid, and examples thereof include N,N-dimethylformamide and N,N-dimethylacetamide. , N-methyl-2-pyrrolidone, N-methyl caprolactam, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethylarylene, γ-butyrolactone and the like. These can be used singly or in combination. Moreover, even if it is a solvent which does not melt|dissolve poly-prolinic acid, it can mix with the solvent, and can be used after it is not the precipitation of the poly- The water in the organic solvent hinders the polymerization reaction of the poly-proline and becomes the cause of the poly-proline produced by the hydrolysis. Therefore, it is preferred that the organic solvent be dried as described above.

A method of mixing a tetracarboxylic dianhydride component and a diamine component in an organic solvent includes a solution in which a diamine component is dispersed or dissolved in an organic solvent, and a tetracarboxylic dianhydride component is directly added or dispersed or dissolved. A method of adding an organic solvent, a method of adding a diamine component to a solution in which a tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent, a method of mutually adding a tetracarboxylic dianhydride component and a diamine component, and the like. Further, when the tetracarboxylic dianhydride component or the diamine component is formed of a plurality of types of compounds, the polymerization reaction may be carried out in a state in which the plurality of components are mixed in advance, or the polymerization reaction may be carried out in an individual order.

The temperature at which the polyaminic acid is polymerized is usually -20 to 150 ° C, preferably 0 to 100 ° C, more preferably 10 to 80 ° C. The higher the temperature, the earlier the polymerization reaction ends, but if it is too high, there is a case where a high molecular weight polylysine cannot be obtained. Further, the polymerization reaction can be carried out at any concentration. However, when the concentration is too low, it becomes difficult to obtain a high molecular weight polymer. When the concentration is too high, the viscosity of the reaction liquid becomes too high and it is difficult to uniformly stir. 1 to 50% by mass, preferably 5 to 30% by mass. The initial stage of the polymerization reaction is carried out at a high concentration, and thereafter an organic solvent may be added.

The molecular weight of the obtained poly-proline can be controlled by the molar ratio of the tetracarboxylic dianhydride component to the diamine component used in the polymerization reaction, and the closer the molar ratio is to 1:1, the larger the molecular weight becomes. The molecular weight of the polyaminic acid used in the present invention or the polyimine obtained by subjecting the polyamic acid to dehydration ring closure is based on the ease of handling and the stability of properties when used as a liquid crystal alignment film, and the weight average molecular weight is More preferably, it is 2,000 to 200,000, and preferably 5,000 to 100,000.

The dehydration ring-closure reaction (oxime imidization reaction) in which the polyimine is to be obtained from the poly-proline is carried out by stirring the polyamine in the presence of a basic catalyst and an acid anhydride in an organic solvent. Examples of the basic catalyst at this time include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferred because it has moderate alkalinity for carrying out the reaction. Further, examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic dianhydride. Among them, the purification of the obtained polyimine is easy to be obtained after the end of the imidization of acetic anhydride. Can be used as an organic solvent The solvent used in the polymerization of the aforementioned polyaminic acid.

The imidization ratio of the polyimine can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time. The amount of the basic catalyst is preferably 0.5 to 30 moles per mole of the amidate group, preferably 2 to 20 moles. Further, the amount of the acid anhydride is preferably from 1 to 50 moles per mole of the amidate group, preferably from 3 to 30 moles. The reaction temperature is preferably -20 to 250 ° C, preferably 0 to 180 ° C. The polyimide imidization ratio of the polyimine used in the liquid crystal alignment agent of the present invention is not necessarily 100%, and may be a part of the ruthenium imidization.

The polylysine or polyimine thus obtained can be precipitated by filtration and filtered by a weak solvent in stirring, and recovered. The weak solvent to be used at this time is not particularly limited, and examples thereof include methanol, acetone, hexane, ethylene glycol dibutyl ether, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene. Wait.

The liquid crystal alignment agent of the present invention can be obtained by dissolving at least one polymer of polylysine obtained as described above or polyimine which is subjected to dehydration ring closure of the polyamic acid in an organic solvent. Further, the reaction solution of polylysine or polyimine may be used as it is, or it may be diluted with an organic solvent and used.

The organic solvent used for the dissolution of the polymer or the dilution of the reaction solution is not particularly limited as long as it can dissolve the polymer component contained therein. To cite such a specific example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-methylcaprolactam are mentioned. , 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl hydrazine, tetramethylurea, pyridine, dimethyl hydrazine, hexamethylarylene, γ-butyrolactone, etc., may also be used These types are used or mixed with a plurality of types.

Further, even in the case where the solvent of the polymer component cannot be dissolved alone, the liquid crystal alignment agent of the present invention can be mixed in the range in which the polymer component is not precipitated. It is particularly known that the uniformity of the coating film can be improved when the substrate is coated by moderately mixing a solvent having a low surface tension, and is also applicable to the liquid crystal alignment agent of the present invention. Specific examples of such a solvent include ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, and 1- Methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol II Acetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propane Alcohol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, and the like.

The solid content concentration of the liquid crystal alignment agent of the present invention can be appropriately changed depending on the thickness of the film formed to form a uniform and defect-free film, preferably from 1 to 10% by mass, and from 3 to 8% by mass. % is preferred.

The liquid crystal alignment agent of the present invention may contain other polylysine or polyimine which is additionally polymerized within a range not impairing the effects of the present invention. Similarly, it may contain a resin other than polyamine or polyimine. In order to further improve the coating film adhesion to the substrate, a known additive such as a decane coupling reaction agent may be added.

In the present invention, the liquid crystal alignment agent of the present invention can form a film after coating, drying, and baking on a substrate, and a liquid crystal alignment film can be obtained by performing an alignment treatment of the film surface by rubbing.

The substrate to which the liquid crystal alignment agent is applied is not particularly limited as long as it has high transparency, and a glass substrate or the like can be used. Further, in the reflective liquid crystal display device, an opaque substance such as a germanium wafer may be used as the single-sided substrate, and a material that reflects light such as aluminum may be used as the electrode.

Examples of the coating method of the liquid crystal alignment agent include a spin coating method, a printing method, a spray method, and the like. From the viewpoint of productivity, industrially, a transfer printing method such as stencil printing is widely used, and the present invention is also applicable to the present invention. Liquid crystal alignment agent. Further, it is preferred that the liquid crystal alignment agent is filtered using a membrane filter having a pore diameter of 0.1 μm to 1 μm.

Although the drying step after the application of the liquid crystal alignment agent is not essential, the drying step is preferably carried out when the time from the application to the baking is not constant for each substrate, or when the baking is not performed immediately after the application. This drying is not intended to cause the shape of the coating film to be deformed by evaporation of the solvent when the substrate is conveyed or the like, and the drying means is not particularly limited. To cite a specific example, a method of drying at 50 to 150 ° C, preferably 80 to 120 ° C, for 0.5 to 30 minutes, preferably 1 to 5 minutes is used.

The firing after application of the liquid crystal alignment agent is preferably carried out at any temperature of from 100 to 350 °C. Further, even if the liquid crystal alignment agent of the present invention is fired at 200 ° C or lower, a good liquid crystal alignment film can be obtained. For example, at 100 ° C to 200 ° C, a good liquid crystal alignment film can be obtained even at a firing temperature of 100 to 160 °C. This baking can be performed in a hot plate, a hot air circulation furnace, an infrared furnace, or the like.

When the thickness of the film after firing is too thick, it is disadvantageous in terms of the power consumption level of the liquid crystal display element. When the film thickness is too thin, the reliability of the liquid crystal display element may be lowered, so it is preferably 5 to 300 nm, more preferably 10 to ～. 100nm.

Examples of the material of the rubbing cloth used for the rubbing treatment include cotton, nylon, and enamel.

In the liquid crystal display device of the present invention, a substrate having a liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention can be obtained by the above-described method, and a cell is produced by a known method as a liquid crystal display element.

An example of the production of the unit cell is a pair of substrates on which a liquid crystal alignment film is to be formed, and a spacer is spread on the liquid crystal alignment film of the single-sided substrate, and the other single surface is bonded to the inside of the liquid crystal alignment film surface. A method in which a liquid crystal is injected under reduced pressure and then sealed, or a method in which a liquid crystal is dropped onto a liquid crystal alignment film surface on which a spacer is dispersed, and a substrate is bonded and sealed. The thickness of the spacer at this time is preferably from 1 to 30 μm, more preferably from 2 to 10 μm.

[Examples]

The invention is further illustrated by the following examples, but the invention is not limited thereto. Further, the abbreviation of tetracarboxylic dianhydride and diamine which are used in the synthesis examples and the structure are as follows.

[Chemistry 9]

[化10]

The abbreviations of the organic solvents used in the examples and the like are as follows.

NMP: N-methyl-2-pyrrolidone

BCS: ethylene glycol dibutyl ether

THF: tetrahydrofuran

DMF: N,N-dimethylformamide

PhMe: toluene

<Measurement of molecular weight of polymer>

The molecular weight of the polyimine or polylysine in the synthesis example is a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Co., Ltd., and a pipe column (KD-803, KD-805) manufactured by Shodex. As determined below.

Column temperature: 50 ° C

Dissolution: N,N-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr‧H2O) is 30 mmol/L, phosphoric acid ‧ anhydrous crystal (o-phosphoric acid) is 30 mmol/L, tetrahydrofuran (THF) is 10ml/L)

Flow rate: 1.0 mL / min

Standard sample for the production of calibration lines: TSK standard polyethylene oxide (molecular weight of about 900,000, 150,000, 100,000, 30,000) manufactured by Tosho Co., Ltd., and polyethylene glycol (molecular weight of approximately 12,000, 4,000, 1,000) manufactured by Polymer Laboratories Ltd. .

<Measurement of ¹ H NMR>

Device: Fourier transform type superconducting nuclear magnetic resonance apparatus (FT-NMR) INOVA-400 (manufactured by Varian) 400 MHz

Solvent: deuterated dimethyl hydrazine (DMSO-d ₆ ), hydrazine-chloroform (CDCl ₃ )

Reference material: tetramethyl decane (TMS)

(Example 1) Synthesis of DA-1

[11]

(Synthesis Example 1) Synthesis of DA-1 precursor D-1-1

[化12]

56.8 g of 2,4-dinitrofluorobenzene, 300 mL of toluene, 137.0 g of 1,4-butanediol, and 37.0 g of triethylamine were placed in a 500 mL three-necked flask, and the system was heated to 100 ° C and stirred. After the completion of the reaction, 1N hydrochloric acid was added to bring the pH to 6 to 7. The organic layer was extracted with ethyl acetate, and anhydrous sodium sulfate was added to the organic layer and dried over anhydrous, and filtered, and the solvent was distilled off using a rotary distillation apparatus to obtain 69.9 g of the object (yellow-yield) (yield 89%) . The results of ¹ H-NMR measurement of the target product are shown below. From the results, it was confirmed that the obtained solid was the intended DA-1-1. And ¹ H-NMR represents a nuclear magnetic resonance spectrum of intramolecular hydrogen.

¹ H NMR (400 MHz, [D ₆ ]-DMSO): δ 8.75-8.76 (d, 1H), 8.48-8.51 (d, 2H), 7.57 (s, 1H), 4.33-4.36 (t, 2H) , 3.44 - 3.47 (t, 2H), 1.76-1.84 (m, 2H), 1.43-1.60 (m, 2H)

(Synthesis Example 2) Synthesis of DA-1 precursor DA-1-2

[Chemistry 13]

38.43 g of DA-1-1, 350 mL of dichloromethane, 20.6 g of methanesulfonyl chloride and 37.9 g of triethylamine were placed in a 500 mL three-necked flask, and stirred at room temperature. After the completion of the reaction, the organic layer was extracted with ethyl acetate. anhydrous sodium sulfate was added to the organic layer and dried over anhydrous. After filtration, the solvent was distilled off using a rotary distiller to obtain 48.8 g of an object (orange viscous). The rate is 97%). The results of measurement by ¹ H-NMR of the objective product are shown below. From the results, it was confirmed that the obtained solid was the intended DA-1-2.

¹ H NMR (400 MHz, [D ₆ ]-DMSO): δ 8.75-8.77 (d, 1H), 8.48-8.52 (d, 1H), 7.57-7.60 (d, 1H), 4.25-4.40 (m, 4H), 3.18-3.19(t, 3H), 1.84-1.89 (m, 4H)

(Synthesis Example 3) Synthesis of DA-1 precursor DA-1-3

[Chemistry 14]

20.0 g of DA-1-2, 200 mL of dimethylformamide, 20.0 g of hydroquinone, and 12.4 g of potassium carbonate were placed in a 500 mL three-necked flask, and the inside of the amine system was heated to 80 ° C and stirred. After the completion of the reaction, 1N hydrochloric acid was added to bring the pH to 6 to 7. The organic layer was extracted with ethyl acetate. anhydrous sodium sulfate was added to the organic layer and dried over anhydrous, and filtered, and then evaporated. The residue was washed with hot water and filtered, and the filtrate was dissolved in methanol, and the insoluble matter was filtered and removed. The solvent was distilled off again using a rotary distiller, and the residue was separated by silica gel column chromatography (ethyl acetate:hexane = 1:3 by volume) to obtain 16.2 g of the object (yellow solid) (yield 77%) ). The results of measurement by ¹ H-NMR of the objective product are shown below. From the results, it was confirmed that the obtained solid was the intended DA-1-3.

¹ H NMR (400 MHz, [D ₆ ]-DMSO): δ 8.88 (s, 1H), 8.76 (s, 1H), 8.49-8.52 (d, 1H), 7.58-7.60 (d, 1H), 6.72 6.75(d,2H),6.64-6.67(d,2H),4.38-4.41(t,2H),3.90-3.93(t,2H),1.79-1.93(m,4H)

(Synthesis Example 4) Synthesis of DA-1 precursor DA-1-4

[化15]

10.0 g of DA-1-3, 3.8 g of triethylamine and 200 mL of THF were placed in a 500 mL three-necked flask. To the 0 ° C in the cooling system, 3.9 g of methacrylic acid chloride was added, and the mixture was stirred at room temperature. After the completion of the reaction, 50 mL of pure water was added and stirred, and ethyl acetate was added thereto, and the organic layer was extracted. Anhydrous magnesium sulfate was added to the organic layer and dried under reduced pressure. After filtration, the solvent was distilled off using a rotary distillation apparatus. The residue was recrystallized from ethyl acetate / hexane = 2 / 8 to give 10.0 g of the object (yellow solid) (yield 84%). The results of measurement by ¹ H-NMR of the objective product are shown below. From the results, it was confirmed that the obtained solid was the intended DA-1-4.

¹ H NMR (400 MHz, [D ₆ ]-DMSO): δ 8.77 (s, 1H), 8.49-8.52 (d, 1H), 7.59-7.61 (d, 1H), 7.05-7.07 (d, 2H), 6.94-6.97(d,2H), 6.25(s,1H), 5.87(s,1H), 4.40-4.43(t,2H),4.03-4.05(t,2H),1.89-1.99(m,7H)

(Synthesis Example 5) Synthesis of DA-1

[Chemistry 16]

4.2 g of DA-1-4, 40 mL of tetrahydrofuran and 40 ml of pure water were placed in a 200 mL three-necked flask, stirred in the system, and 13.2 g of tin chloride was added thereto, and the system was heated to 70 ° C and stirred. After the completion of the reaction, 200 ml of a 5% aqueous sodium hydrogencarbonate solution was added to adjust the pH to 7 to 8. 80 ml of ethyl acetate was added, and the white precipitate was filtered and removed, and the organic layer was extracted with ethyl acetate. anhydrous sodium sulfate was added to the organic layer and dried over anhydrous, filtered, and the solvent was distilled off using a rotary distillation apparatus. The residue was recrystallized from ethyl acetate / hexane = 3 / 7 to give 1.0 g of object (yellow solid) (yield 30%). The results of measurement by ¹ H-NMR of the objective product are shown below. From the results, it was confirmed that the obtained solid was the intended DA-1.

¹ H NMR (400 MHz, [D ₆ ]-DMSO): δ 7.56-7.08 (d, 2H), 6.95-6.97 (d, 2H), 6.47-6.50 (d, 1H), 6.25 (s, 1H), 5.95 (s, 1H), 5.87 (s, 1H), 5.73-5.76 (d, 1H), 4.42 (s, 2H), 4.34 (s, 2H), 4.00-4.03 (t, 2H), 3.81-3.84 ( t, 2H), 1.99 (s, 3H), 1.81-1.86 (m, 4H)

(Example 2) Synthesis of DA-2

[化17]

(Synthesis Example 6) Synthesis of DA-2 precursor DA-2-1

[化18]

To a 300 mL three-necked flask, 16.2 g of 3,5-dinitrobenzhydryl chloride, 150 mL of tetrahydrofuran, and 13.9 g of 4-bromo-1-butanol were placed, and the mixture was stirred at room temperature. After the completion of the reaction, the organic layer was extracted with ethyl acetate. anhydrous sodium sulfate was added to the organic layer and dried over anhydrous. After filtration, the solvent was distilled off using a rotary distiller to obtain 23.0 g of the object (yellow-yield). Rate 95%). The results of measurement by ¹ H-NMR of the objective product are shown below. From the results, it was confirmed that the obtained solid was the intended DA-2-1.

¹ H NMR (400 MHz, [D ₆ ]-DMSO): δ 9.04 (s, 1H), 8.92 (s, 2H), 4.43-4.46 (t, 2H), 3.62-3.65 (t, 2H), 1.90 -1.99 (m, 4H)

(Synthesis Example 7) Synthesis of DA-2 precursor DA-2-2

[Chemistry 19]

To a 300 mL three-necked flask, 10.0 g of DA-2-1, 100 mL of dimethylformamide, 6.6 g of hydroquinone, 7.2 g of potassium iodide, and 4.4 g of potassium carbonate were placed, and the amine system was heated to 80 ° C and stirred. After the completion of the reaction, 1N hydrochloric acid was added to bring the pH to 6 to 7. The organic layer was extracted with ethyl acetate. anhydrous sodium sulfate was added to the organic layer and dried over anhydrous, and filtered, and then evaporated. The residue was washed with hot water and filtered, and the filtrate was dissolved in methanol, and the insoluble matter was filtered and removed. The solvent was distilled off again using a rotary distiller, and the residue was separated by silica gel column chromatography (ethyl acetate:hexane = 1:3 volume ratio) to give 5.7 g of object (yellow solid) (yield 53%) ). The results of measurement by ¹ H-NMR of the objective product are shown below. From the results, it was confirmed that the obtained solid was the target DA-2-2.

¹ H NMR (400 MHz, [D ₆ ]-DMSO): δ 9.03 (s, 1H), 8.89 (s, 2H), 8.86 (s, 1H), 6.69-6.67 (d, 2H), 6.59-6.63 ( d, 2H), 4.45-4.49 (t, 2H), 3.99-3.95 (t, 2H), 1.82-1.97 (m, 4H)

(Synthesis Example 8) Synthesis of DA-2 precursor DA-2-3

[Chemistry 20]

5.7 g of DA-2-2, 2.0 g of triethylamine and 100 mL of tetrahydrofuran were placed in a 300 mL three-necked flask. To the 0 ° C in the cooling system, 2.0 g of methacrylium ruthenium chloride was added, and the mixture was stirred at room temperature. After the completion of the reaction, 50 mL of pure water was added and stirred, and ethyl acetate was added thereto, and the organic layer was extracted. Anhydrous magnesium sulfate was added to the organic layer and dried under reduced pressure. After filtration, the solvent was distilled off using a rotary distillation apparatus. The residue was purified by silica gel column chromatography (ethyl acetate:hexane = 1:1 ratio) to afford 3.6 g (yellow solid) (yield 54%). The results of measurement by ¹ H-NMR of the objective product are shown below. From the results, it was confirmed that the obtained solid was the intended DA-2-3.

¹ H NMR (400 MHz, [D ₆ ]-DMSO): δ 9.03 (s, 1H), 8.89 (s, 2H), 7.02-7.04 (d, 2H), 6.93-6.96 (d, 2H), 6.24 ( s, 1H), 5.87 (s, 1H), 4.47-4.50 (t, 2H), 4.04-4.07 (t, 2H), 1.89-2.00 (m, 7H)

(Synthesis Example 9) Synthesis of DA-2

[Chem. 21]

3.6 g of DA-2-3, 30 mL of tetrahydrofuran, and 30 ml of pure water were placed in a 200 mL three-necked flask, stirred in the system, and 10.6 g of tin chloride was added thereto, and the system was heated to 70 ° C and stirred. After the completion of the reaction, 200 ml of a 5% aqueous sodium hydrogencarbonate solution was added to adjust the pH to 7 to 8. 80 ml of ethyl acetate was added, and the white precipitate was filtered and removed, and the organic layer was extracted with ethyl acetate. anhydrous sodium sulfate was added to the organic layer and dried over anhydrous, filtered, and the solvent was distilled off using a rotary distillation apparatus. The residue was recrystallized from ethyl acetate / hexane = 3 / 7 to afford 2.8 g (yield of white solid) (yield: 93%). The results of measurement by ¹ H-NMR of the objective product are shown below. From the results, it was confirmed that the obtained solid was the target DA-2.

¹ H NMR (400 MHz, [D ₆ ]-DMSO): δ 7.05-7.08 (d, 2H), 6.95-6.98 (d, 2H), 6.44 (s, 2H), 6.25 (s, 1H), 6.02 (s, 1H), 5.87 (s, 1H), 4.98-5.00 (t, 2H), 4.23 (s, 2H), 4.01 (s, 2H), 2.00-2.08 (t, 2H), 1.99 (s, 3H) ), 1.83-1.84 (m, 4H)

(Example 3) Synthesis of DA-5

[化22]

(Synthesis Example 10) Synthesis of DA-5 precursor DA-5-1

[化23]

To a 300 mL three-necked flask, 10.4 g of DA-2-1, acetone 160 mL, 4,4'-bisphenol 14.2 g, potassium iodide 6.0 g, and potassium carbonate 5.5 g were placed, and the system was heated to 50 ° C and stirred. After the reaction was completed, 1N hydrochloric acid was added to bring the pH to 6-7. The organic layer was extracted with ethyl acetate. anhydrous sodium sulfate was added to the organic layer and dried over anhydrous, and filtered, and then evaporated. The residue was dissolved in isopropyl alcohol, and the insoluble matter was filtered and removed. The solvent was distilled off again using a rotary distiller, and the residue was recrystallized using isopropyl alcohol / hexane = 1/2 to obtain 6.2 g of the object (yellow brown solid) (yield 46%). The results of measurement by ¹ H-NMR of the objective product are shown below. The resulting solid was confirmed to be DA-5-1 for the purpose.

¹ H NMR (400 MHz, [D ₆ ]-DMSO): δ 9.43 (s, 1H), 8.99 (s, 1H), 8.88 (s, 2H), 7.41-7.43 (d, 2H), 7.35-7.38 ( d, 2H), 6.92-6.94 (d, 2H), 6.78-6.80 (d, 2H), 4.47-4.50 (t, 2H), 4.06-4.09 (t, 2H), 1.90- 1.95 (m, 4H)

(Synthesis Example 11) Synthesis of DA-5 precursor DA-5-2

[Chem. 24]

6.0 g of DA-5-1, triethylamine 1.3 g and tetrahydrofuran (120 mL) were placed in a 300 mL three-necked flask. To the 0 ° C in the cooling system, 2.7 g of methacrylium ruthenium chloride was added, and the mixture was stirred at room temperature. After the reaction was completed, 50 mL of pure water was added and stirred, and then ethyl acetate was added and the organic layer was extracted. Anhydrous magnesium sulfate was added to the organic layer and dried under reduced pressure. After filtration, the solvent was distilled off using a rotary distiller, and the residue was used. Recrystallization from ester/hexane = 1/9 gave 5.5 g of title compound (yellow solid) (yield: 79%). The results of measurement by ¹ H-NMR of the objective product are shown below. From the results, it was confirmed that the obtained solid was the intended DA-5-2.

¹ H NMR (400 MHz, [D ₆ ]-DMSO): δ 9.07 (s, 1H), 8.90 (s, 2H), 7.62-7.64 (d, 2H), 7.55-7.58 (d, 2H), 7.21. 7.23 (d, 2H), 7.00-7.02 (d, 2H), 6.30 (s, 1H), 5.92 (s, 1H), 4.49-4.52 (t, 2H), 4.01-4.13 (t, 2H), 2.02 ( s, 3H), 1.93-1.99 (m, 4H)

(Synthesis Example 12) Synthesis of DA-5

[化25]

5.2 g of DA-5-2, 50 mL of tetrahydrofuran and 50 ml of pure water were placed in a 200 mL three-necked flask, stirred in the system, 13.3 g of tin chloride was added, and the system was heated to 70 ° C and stirred. After the completion of the reaction, a 5% aqueous sodium hydrogencarbonate solution was added to bring the pH to 7-8. 80 ml of ethyl acetate was added, and the white precipitate was filtered and removed, and the organic layer was extracted with ethyl acetate. anhydrous sodium sulfate was added to the organic layer and dried over anhydrous, filtered, and the solvent was distilled off using a rotary distillation apparatus. The residue was recrystallized from ethyl acetate / hexane = 3 / 7 to afford 2.8 g (yellow white solid) (yield 87%). The results of measurement by ¹ H-NMR of the objective product are shown below. From the results, it was confirmed that the obtained solid was the intended DA-5.

¹ H NMR (400 MHz, [D ₆ ]-DMSO): δ 7.65-7.67 (d, 2H), 7.59-7.65 (d, 2H), 7.21 - 7.24 (d, 2H), 7.02-7.04 (d, 2H) ), 6.45 (s, 2H), 6.30 (s, 1H), 6.03 (s, 1H), 5.91 (s, 1H), 5.00 (s, 4H), 4.24 - 4.26 (t, 2H), 4.01-4.13 ( t, 2H), 2.02 (s, 3H), 1.84-1.86 (m, 4H)

(Example 4) Synthesis of DA-6

[Chem. 26]

(Synthesis Example 13) Synthesis of DA-6 precursor DA-6-1

[化27]

11.2 g of DA-2-1, acetone 180 mL, 4,4'-dihydroxybenzophenone 7.7 g, potassium iodide 6.5 g, and potassium carbonate 4.6 g were placed in a 300 mL three-necked flask, and the system was heated to 50 ° C and stirred. After the reaction was completed, 1N hydrochloric acid was added to bring the pH to 6-7. The organic layer was extracted with ethyl acetate. anhydrous sodium sulfate was added to the organic layer and dried over anhydrous, and filtered, and then evaporated. The residue was dissolved in isopropyl alcohol, and the insoluble matter was filtered and removed. The solvent was distilled off again using a rotary distiller, and the residue was recrystallized using isopropyl alcohol / hexane = 1 / 1 to obtain 6.2 g of the object (yellow solid) (yield 50%). The results of measurement by ¹ H-NMR of the objective product are shown below. From the results, it was confirmed that the obtained solid was the intended DA-6-1.

¹ H NMR (400 MHz, [D ₆ ]-DMSO): δ 10.34 (s, 1H), 9.03 (s, 1H), 8.90 (s, 2H), 7.59-7.65 (m, 4H), 7.04-7.06 ( d, 2H), 6.87-6.89 (d, 2H), 4.48-4.51 (t, 2H), 4.16-4.19 (t, 2H), 1.94-1.97 (m, 4H)

(Synthesis Example 14) Synthesis of DA-6 precursor DA-6-2

[化28]

5.8 g of DA-6-1, 1.6 g of triethylamine and 60 mL of tetrahydrofuran were placed in a 300 mL three-necked flask. To the 0 ° C in the cooling system, 2.5 g of methacrylic acid chloride was added, and the mixture was stirred at room temperature. After the reaction was completed, 50 mL of pure water was added and stirred, and then ethyl acetate was added and the organic layer was extracted. Anhydrous magnesium sulfate was added to the organic layer and dried under reduced pressure. After filtration, the solvent was distilled off using a rotary distiller, and the residue was passed through a rubber hose. Purification by column chromatography (ethyl acetate:hexane = ield: 4: 4) gave 5.6 g of object (yellow white solid) (yield 85%). The results of measurement by ¹ H-NMR of the objective product are shown below. From the results, it was confirmed that the obtained solid was the intended DA-6-2.

¹ H NMR (400 MHz, [D ₆ ]-DMSO): δ 9.03 (s, 1H), 8.90 (s, 2H), 7.70-7.77 (m, 4H), 7.36-7.38 (d, 2H), 7.07- 7.09(d,2H), 6.33(s,1H), 5.95(s,1H), 4.48-4.51(t,2H), 4.17-4.20(t,2H),2.03(s,3H),1.96-1.99( m, 4H)

(Synthesis Example 15) Synthesis of DA-6

[化29]

5.5 g of DA-6-2, tetrahydrofuran 50 mL, and pure water 50 ml were placed in a 200 mL three-necked flask, stirred in the system, 13.3 g of tin chloride was added, and the system was heated to 70 ° C and stirred. After the end of the reaction, a 5% aqueous sodium hydrogencarbonate solution was added to bring the pH to 7-8. 80 ml of ethyl acetate was added, and the white precipitate was filtered and removed, and the organic layer was extracted with ethyl acetate. anhydrous sodium sulfate was added to the organic layer and dried over anhydrous, filtered, and the solvent was distilled off using a rotary distillation apparatus. The residue was recrystallized using ethyl acetate / hexane = 1 / 9 to afford 2.8 g of the desired material (yellow viscous solid) (yield 84%). The results of measurement by ¹ H-NMR of the objective product are shown below. From the results, it was confirmed that the obtained solid was the intended DA-6.

¹ H NMR (400 MHz, [D ₆ ]-DMSO): δ 7.74-7.79 (m, 4H), 7.36-7.38 (d, 2H), 7.10-7.12 (d, 2H), 6.44 (s, 2H), 6.33(s,1H), 6.02(s,1H), 5.95(s,1H),4.99(s,4H),4.23-4.26(t,2H),4.14-4.17(t,2H),2.02(s, 3H), 1.84-1.87 (m, 4H)

(Example 5) Synthesis of DA-7

[化30]

(Synthesis Example 16) Synthesis of DA-7 precursor DA-7-1

[化31]

To a 300 mL three-necked flask, 7.7 g of p-(trans-4-hydroxycyclohexyl)phenol, 4.4 g of triethylamine, and 100 mL of tetrahydrofuran were placed. To the 0 ° C in the cooling system, 4.4 g of methacrylium ruthenium chloride was added, and the mixture was stirred at room temperature. After the reaction was completed, 50 mL of pure water was added and stirred, and then ethyl acetate was added and the organic layer was extracted. Anhydrous magnesium sulfate was added to the organic layer and dried under reduced pressure. After filtration, the solvent was distilled off using a rotary distiller, and the residue was used. The ester/hexane = 1/9 was recrystallized to give 7.5 g of the object (yield of white solid) (yield: 72%). The results of measurement by ¹ H-NMR of the objective product are shown below. From the results, it was confirmed that the obtained solid was the intended DA-7-1.

¹ H NMR (400 MHz, [D ₆ ]-DMSO): δ 7.25-7.27 (d, 2H), 7.04-7.06 (d, 2H), 6.25 (s, 1H), 5.88 (s, 1H), 4.58 ( s, 1H), 3.41-3.50 (m, 1H), 2.44 - 2.50 (m, 1H), 1.99 (s, 3H), 1.87-1.93 (m, 2H), 1.75-1.78 (m, 2H), 1.41 1.51 (m, 2H), 1.23-1.33 (m, 2H)

(Synthesis Example 17) Synthesis of DA-7 precursor DA-7-2

[化32]

5.2 g of DA-7-1, 2.0 g of triethylamine and 50 mL of tetrahydrofuran were placed in a 300 mL three-necked flask. To the 0 ° C in the cooling system, 4.6 g of 3,5-dinitrobenzhydryl chloride was added, and the mixture was stirred at room temperature. After the completion of the reaction, 50 mL of pure water was added and stirred, and ethyl acetate was added thereto, and the organic layer was extracted. Anhydrous magnesium sulfate was added to the organic layer and dried under reduced pressure. After filtration, the solvent was distilled off using a rotary distillation apparatus. The residue was purified by silica gel column chromatography (ethyl acetate:hexane = 1:1) to afford 6.8 g of object (yield of white solid) (yield 75%). The results of measurement by ¹ H-NMR of the objective product are shown below. From the results, it was confirmed that the obtained solid was the intended DA-7-2.

¹ H NMR (400 MHz, [D ₆ ]-DMSO): δ 9.05 (s, 1H), 8.93 (s, 2H), 7.32-7.37 (d, 2H), 7.08-7.11 (d, 2H), 6.26 ( s, 1H), 5.89 (s, 1H), 5.09-5.10 (m, 1H), 2.66-2.67 (m, 1H), 2.18-2.21 (m, 2H), 1.99 (s, 3H), 1.91-1.94 ( m, 2H), 1.68-1.76 (m, 5H)

(Synthesis Example 18) Synthesis of DA-7

[化33]

6.8 g of DA-7-2, 60 mL of tetrahydrofuran, and 60 ml of pure water were placed in a 200 mL three-necked flask, stirred in the system, and 19.9 g of tin chloride was added thereto, and the system was heated to 70 ° C and stirred. After the completion of the reaction, a 5% aqueous sodium hydrogencarbonate solution was added to bring the pH to 7-8. 80 ml of ethyl acetate was added, and the white precipitate was filtered and removed, and the organic layer was extracted with ethyl acetate. anhydrous sodium sulfate was added to the organic layer and dried over anhydrous, filtered, and the solvent was distilled off using a rotary distillation apparatus. The residue was recrystallized from ethyl acetate / hexane = 1 / 9 to give 5.8 g (yield of white solid) (yield 98%). The results of measurement by ¹ H-NMR of the objective product are shown below. From the results, it was confirmed that the obtained solid was DA-7.

¹ H NMR (400 MHz, [D ₆ ]-DMSO): δ 7.33-7.35 (d, 2H), 7.07-7.10 (d, 2H), 6.43 (s, 2H), 6.26 (s, 1H), 6.02 ( s, 1H), 5.89 (s, 1H), 5.02 (s, 4H), 4.85-4.90 (m, 1H), 2.59-2.65 (m, 1H), 2.07-2.10 (m, 2H), 2.00 (s, 3H), 1.86-1.89 (m, 2H), 1.69-1.89 (m, 4H)

(Example 6) Synthesis of liquid crystal alignment agent

1.94 g (0.0099 mol) of CBDA and 3.84 g (0.01 mol) of DA-2 were reacted in NMP 23.14 g at room temperature for 16 hours to prepare a polyaminic acid solution (PAA-1). The polyamic acid has a number average molecular weight of about 5,000 and a weight average molecular weight of about 8,000. NMP and BCS were added to 10 g of the polyaminic acid solution and stirred to prepare a polyamine acid (PAA-1) of 6 mass%, NMP of 74 mass%, and BCS of 20 mass%, and then a pore diameter of 1 μm. The membrane filter was subjected to pressure filtration to obtain a liquid crystal alignment agent.

(Example 7) Synthesis of liquid crystal alignment agent

1.17 g (0.009 mol) of CBDA and 4.60 g (0.01 mol) of DA-5 were reacted in NMP 36.10 g at room temperature for 16 hours to prepare a polyaminic acid solution (PAA-4). The polyamic acid has a number average molecular weight of about 10,000 and a weight average molecular weight of about 80,000. NMP and BCS were added to 10 g of the polyamidic acid solution, and the mixture was stirred to prepare a polyamine acid (PAA-4) of 6 mass%, NMP of 74 mass%, and BCS of 20 mass%, and a pore diameter of 1 μm. The membrane filter was subjected to pressure filtration to obtain a liquid crystal alignment agent.

(Example 8) Synthesis of liquid crystal alignment agent

CBDA 1.94 g (0.099 mol) and 4.60 g (0.01 mol) of DA-6 were reacted in NMP 27.31 g at room temperature for 16 hours to prepare a polyaminic acid solution (PAA-5). The polyamine has a number average molecular weight of about 20,000 and a weight average molecular weight of about 200,000. NMP and BCS were added to 10 g of the polyamic acid solution and stirred to prepare a polyamine acid (PAA-5) of 6 mass%, NMP of 74 mass%, and BCS of 20 mass%, and then a pore diameter of 1 μm. The membrane filter was subjected to pressure filtration to obtain a liquid crystal alignment agent.

(Example 9) Synthesis of liquid crystal alignment agent

CBDA 1.94 g (0.099 mol) and 3.94 g (0.01 mol) of DA-7 were reacted in NMP 33.35 g at room temperature for 16 hours to prepare a polyaminic acid solution (PAA-6). The polyamic acid has a number average molecular weight of about 7,000 and a weight average molecular weight of about 30,000. NMP and BCS were added to 10 g of the polyamic acid solution and stirred to prepare a polyamine acid (PAA-6) of 6 mass%, NMP of 74 mass%, and BCS of 20 mass%, and then a pore diameter of 1 μm. The membrane filter was subjected to pressure filtration to obtain a liquid crystal alignment agent.

(Comparative Example 1) Synthesis of liquid crystal alignment agent

A polyaminic acid solution (PAA-2) was prepared by reacting CBDA 1.94 g (0.0099 mol) with 2.64 g (0.01 mol) of DA-3 in NMP 18.34 g at room temperature for 16 hours. The polyamine has a number average molecular weight of about 22,000 and a weight average molecular weight of about 62,000. 10 g of the polyaminic acid solution was added to NMP and BCS and stirred to prepare a film having a pore diameter of 1 μm after the polyaminic acid (PAA-2) was 6 mass%, the NMP was 74 mass%, and the BCS was 20 mass%. The filter was subjected to pressure filtration to obtain a liquid crystal alignment agent.

(Comparative Example 2) Synthesis of crystal alignment agent

CBDA 1.86 g (0.095 mol) and 1.08 g (0.01 mol) of DA-4 were reacted in NMP 16.68 g at room temperature for 16 hours to prepare a polyaminic acid solution (PAA-3). The polyamine has a number average molecular weight of about 8,000 and a weight average molecular weight of about 18,000. NMP and BCS were added to 10 g of the polyamic acid solution and stirred to prepare a polyamine acid (PAA-3) of 6 mass%, NMP of 74 mass%, and BCS of 20 mass%, and a pore diameter of 1 μm. The membrane filter was subjected to pressure filtration to obtain a liquid crystal alignment agent.

With respect to the liquid crystal alignment agents prepared in the above Examples 6 to 9 and Comparative Examples 1 and 2, a substrate having a liquid crystal alignment film was produced as follows.

<Evaluation of friction resistance>

The liquid crystal alignment agent was spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at 70 ° C for 70 seconds, and then fired on a hot plate at 120 ° C for 10 minutes to form a coating having a film thickness of 100 nm. membrane. The coating film surface was rubbed with a rubbing apparatus having a roll diameter of 120 mm at a roll rotation speed of 1000 rpm, a roll speed of 50 mm/sec, and a pushing amount of 0.5 mm to obtain a substrate with a liquid crystal alignment film. The surface of the obtained liquid crystal alignment film was observed by a confocal laser microscope, and the following evaluation was performed. The evaluation results of the friction resistance are shown below.

○: No shaving or frictional damage was observed.

△: A shaving or a rubbing injury was observed.

×: Film peeling was observed or a scratch was visually observed.

Industrial availability

Since the liquid crystal alignment agent of the present invention can obtain a liquid crystal alignment film having a uniform liquid crystal alignment and no misalignment, the cost of firing the alignment film can be reduced, and of course, it can be applied to a glass substrate or a plastic substrate. Liquid crystal display elements, etc.

The contents of the specification, the scope of the patent application, and the abstract of the Japanese Patent Application No. 2010-148647, filed on June 30, 2010, are hereby incorporated by reference.

Claims (13)

A liquid crystal alignment agent comprising: a polyamine derivative obtained by polymerizing a diamine component represented by the following formula [1] and a tetracarboxylic dianhydride component represented by the following formula [2]; a polymer comprising at least one polymer of the polyamidene obtained by subjecting the polyamic acid to dehydration ring closure, wherein the diamine component comprises a diamine represented by the following formula [3]; H ₂ NR ₁ -NH ₂ [1] (R ₁ is a divalent organic group) (R ₂ is a tetravalent organic group) Wherein R ³ represents a group selected from the group consisting of -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, and -NH-; R ⁴ represents a single bond or The alkylene group having 1 to 10 carbon atoms, 1 or a plurality of -CH ₂ - of the alkylene group may be substituted by -CF ₂ -, and any of the groups exemplified below are not adjacent to each other, Can be substituted for these groups; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-; R ⁵ represents a single bond, -CH ₂ -, -O- or NH-; R ⁶ A divalent organic group having 5 or 18 carbon atoms and having at least one aromatic ring at the terminal, wherein the ring may be a carbocyclic ring or a heterocyclic ring, and 1 or a plurality of hydrogens of the ring may be Substituted by a fluorine atom; R ⁷ represents hydrogen, methyl or trifluoromethyl). The liquid crystal alignment agent of claim 1, wherein R ³ in the formula [3] is -O- or -COO-. A liquid crystal alignment agent according to claim 1 or 2, wherein R ⁴ in the formula [3] is an alkylene group having 1 to 4 carbon atoms. The liquid crystal alignment agent of claim 1 or 2, wherein R ⁵ in the formula [3] is -O-. The liquid crystal alignment agent of claim 1 or 2, wherein R ⁶ in the formula [3] is a 1,4-phenylene group. The liquid crystal alignment agent of claim 1 or 2, wherein R ⁷ in the formula [3] is a methyl group. The liquid crystal alignment agent of the first aspect or the second aspect of the invention, wherein the diamine component represented by the formula [1] contains 30 mol% or more of the diamine represented by the above formula [3]. The patentable scope of application liquid crystal alignment agent of paragraph 1 or 2, the formula [2] in which the tetracarboxylic dianhydride component shown in formula [2] contained in R ₂ has the structure of four aliphatic cyclic acid dianhydride. A liquid crystal alignment film characterized by being obtained from a liquid crystal alignment agent according to any one of claims 1 to 8. A liquid crystal alignment film which is obtained by applying a liquid crystal alignment agent according to any one of claims 1 to 8 to a substrate, baking at a temperature of 200 ° C or lower, and then rubbing it. A liquid crystal display element characterized by having a liquid crystal alignment film according to item 9 or item 10 of the patent application. a diamine characterized by the following formula [3]; Wherein R ³ represents a group selected from the group consisting of -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, and -NH-; R ⁴ represents a single bond or The alkylene group having 1 to 10 carbon atoms, 1 or a plurality of -CH ₂ - of the alkylene group may be substituted by -CF ₂ -, and any of the groups exemplified below are not adjacent to each other, Can be substituted for these groups; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-; R ⁵ represents a single bond, -CH ₂ -, -O- or NH-; R ⁶ A divalent organic group having 5 or 18 carbon atoms and having at least one aromatic ring at the terminal, wherein the ring may be a carbocyclic ring or a heterocyclic ring, and 1 or a plurality of hydrogens of the ring may be Substituted by a fluorine atom; R ⁷ represents hydrogen, methyl or trifluoromethyl). a diamine characterized by the following formula DA1, formula DA2, formula DA5, formula DA6 or a diamine represented by formula DA7;