TW201536863A - Novel liquid crystal orientation agent, diamine, and polyimide precursor - Google Patents

Abstract

Provided is a liquid crystal orientation agent from which it is possible to obtain a liquid crystal orientation film which has a high voltage retention rate and high rubbing resistance, and is capable of quickly reducing a stored charge, and specifically, is capable of suppressing a shift in the rubbing direction and in the liquid-crystal orientation direction in an in-plane switching device. Provided are: a polyimide precursor obtained by reacting a tetracarboxylic acid derivative component with a diamine component containing a diamine represented by formula (1); and a liquid crystal orientation agent containing one or more types of polymer selected from a group consisting of polyimides obtained by ring-closing the polyimide precursor. (R1 represents hydrogen or a monovalent organic group. Q1 represents a C1-5 alkylene group, Cy is a divalent group comprising azetidine, pyrrolidine, piperidine, or hexamethyleneimine, and a substituent group may be bonded to the ring segment of these groups. R2 and R3 are monovalent organic groups, and q and r each independently represent an integer of 0-4. In addition, when the sum of q and r is 2 or more, the plurality of R2 and R3 are as defined above).

Description

Novel liquid crystal alignment agents, diamines, and polyimine precursors

The present invention relates to a novel liquid crystal alignment agent, a novel diamine suitable as a raw material for a polymer used as the liquid crystal alignment agent, a polyamidene precursor obtained by using the same, and a polyimine.

The liquid crystal display element is used in the past and widely used as a display unit of a computer, a mobile phone, a television receiver, etc., and a driving method is known as a vertical electric field method such as a TN (Twisted Nematic) method or a VA (Vertical Alignment) method, or A transverse electric field method such as IPS (In-Plane-Switching) or FFS (Fringe Field Switching).

In general, an electrode is formed only on one side of a substrate, and a transverse electric field method in which an electric field is applied in parallel with the substrate is compared with a conventional method of applying a voltage to an electrode formed on the upper and lower substrates to drive a liquid crystal. It is known as a liquid crystal display element having a wide viewing angle characteristic and having high quality display. A method of aligning liquid crystals in a certain direction, for example, forming a polymer film such as polyimide on a substrate, wiping the surface with a cloth, that is, a method of performing a so-called rubbing treatment, and widely used in industrial applications. on.

A conventional problem can be, for example, a voltage holding ratio or an accumulation of electric charges caused by a DC voltage component applied by an active matrix structure. When the electric charge is accumulated in the liquid crystal display element, the alignment of the liquid crystal is often caused, or the display content is affected by the afterimage, and the display quality of the liquid crystal display element is remarkably lowered. Or, in the case of driving in the state of accumulating charge, immediately after the driving, the control of the liquid crystal molecules cannot be performed normally, and flickering (light flickering) may occur.

In the polyimine-based liquid crystal alignment film, various proposals have been made in response to the above requirements. For example, a liquid crystal alignment agent containing a tertiary amine having a specific structure in addition to a poly-proline or a ruthenium-containing polyphthalic acid is used as a film which can shorten the application of a DC voltage to disappear. A liquid crystal alignment film of the time (Patent Document 1), or a liquid crystal alignment agent containing a soluble polyimine which is used as a raw material, such as a pyridine skeleton, is proposed (Patent Document 2).

A liquid crystal alignment agent having a liquid crystal alignment film having excellent voltage holding ratio, such as light resistance, high temperature and high humidity resistance, re-workability, and printability, is disclosed in Patent Document 3, and A liquid crystal alignment agent of an amine polyimine.

Further, a method of forming a liquid crystal alignment film which is excellent in liquid crystal alignment, abrasion resistance, and light transmittance and which can effectively reduce image sticking over a wide temperature range is disclosed. In Patent Document 4, it is disclosed that a specific diamine is contained. An aromatic tetracarboxylic acid derivative is a liquid crystal alignment agent characterized by a liquid crystal.

Moreover, a liquid crystal having a high liquid crystal alignment and a low tilt alignment angle is obtained. In the method of the alignment film, Patent Document 5 discloses a liquid crystal alignment treatment agent containing a polydiimine precursor containing a specific diamine.

Recently, with the increase in definition, higher display quality has been sought, and the problem of voltage retention or charge accumulation has become more prominent. In particular, in the liquid crystal display device of the transverse electric field type, when the electrode portion formed in the substrate is small and the voltage holding ratio of the liquid crystal alignment film is weak, not only the sufficient voltage cannot be supplied to the liquid crystal, but also the display contrast is lowered. When the longitudinal electric field method is compared, since the distance between the pixel electrode and the common electrode is closer, the alignment film or the liquid crystal layer is subjected to a strong electric field, so that the poor state will be more likely to cause significant problems. Further, in the IPS method or the FFS driving method, the liquid crystal alignment of the liquid crystal molecules in which the substrates are parallel-aligned is also important in the stability of the liquid crystal alignment. In the absence of alignment stability, when the liquid crystal is driven for a long time, the liquid crystal will not return to the initial state, which is also the cause of the contrast reduction, or residual image or burn. In addition, in the substrate with a large step difference, there is also a demand for higher friction resistance.

[Previous Technical Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 9-316200

[Patent Document 2] Japanese Patent Laid-Open No. Hei 10-104633

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2013-152421

[Patent Document 4] International Publication No. WO2013/062115

[Patent Document 5] Japanese Patent Laid-Open No. Hei 10-123532

In the method of aligning the liquid crystal, the rubbing treatment has been widely used in the industry. However, depending on the liquid crystal alignment film to be used, the rubbing direction does not coincide with the alignment direction of the liquid crystal, and a so-called twist angle phenomenon occurs. That is, in the case of the lateral electric field element, the state in which no voltage is applied is indicated by a black display. In this phenomenon, even if the voltage is not applied, the brightness is improved, and as a result, the display contrast is lowered.

The present invention provides a liquid crystal which can be obtained with a high voltage holding ratio and abrasion resistance, can quickly alleviate the accumulated electric charge, and in particular can suppress the deviation of the rubbing direction and the liquid crystal alignment direction which cause problems in the transverse electric field driving mode. For the purpose of the liquid crystal alignment agent of the alignment film.

The inventors of the present invention have conducted intensive studies and found that a polyimide precursor having a diamine component containing a diamine having the following formula (1) and a tetracarboxylic acid derivative component is used, and The above object can be attained when the liquid crystal alignment agent of the selected polymer of the polyimine imine obtained by ring-closing the polyimine precursor is closed, and thus the present invention has been completed.

The gist of the present invention is as follows.

A liquid crystal aligning agent comprising a polyimine precursor obtained by reacting a diamine component of a diamine of the following formula (1) with a tetracarboxylic acid derivative component, and the polybenzazole The imine precursor is obtained by ring closure At least one polymer selected from the group consisting of amines.

(R ₁ represents hydrogen, or a monovalent organic group. Q ₁ represents an alkylene group having 1 to 5 carbon atoms. Cy represents an aliphatic group formed of trimethyleneimine, pyrrazine, piperidine or hexamethyleneimine. a divalent group of a heterocyclic ring, wherein the ring moiety may bond a substituent. R ₂ and R ₃ are each independently a monovalent organic group. q and r are each independently an integer of 0 to 4. However, q In the case where the total of r is 2 or more, the plural R ₂ and R ₃ have the above definitions).

2. The liquid crystal alignment agent according to the above 1, wherein the polyimine precursor is a polymer having a structural unit represented by the following formula (9).

(X ₁ is a tetravalent organic group derived from a tetracarboxylic acid derivative, Y ₁ is a divalent organic group derived from a diamine of the formula (1), and R ₄ is a hydrogen atom or a carbon number of 1 to 5 Alkyl).

3. The liquid crystal alignment agent according to the above 2, wherein X1 is the following formula (X-1) to (X-14).

(R ₅ to R ₈ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or a phenyl group).

4. The liquid crystal alignment agent according to any one of the above 1 to 3, wherein the ratio of the diamine represented by the formula (1) is from 30 to 100 mol% based on 1 mol of the total diamine component.

5. The liquid crystal alignment agent according to the above 1, wherein the diamine of the formula (1) is represented by the following formula (2).

(R ₁ is a hydrogen atom, a methyl group, or a tert-butoxycarbonyl group. R ₂ is a hydrogen atom or a methyl group. Q ₁ is a linear alkyl group having 1 to 5 carbon atoms).

A liquid crystal alignment film obtained by coating and sintering the liquid crystal alignment agent described in any one of the above 1 to 5.

7. The liquid crystal alignment film according to the above 6, wherein the film thickness after sintering is 5 to 300 nm.

A liquid crystal display device comprising the liquid crystal alignment film according to the above 6 or 7.

A diamine represented by the formula (1).

(In the formula (1), R ₁ , Q ₁ , Cy, R ₂ , R ₃ , q, r are as defined in the above 1).

10. The diamine according to the above 9, wherein R ₁ is an alkyl group having 1 to 3 carbon atoms, a hydrogen atom, or a thermally dissociable group substituted with a hydrogen atom via heat, and R ₂ and R ₃ are each independently It is a methyl group, a trifluoromethyl group, a cyano group, or a methoxy group.

11. The diamine according to 10 above, wherein R ₁ is a linear alkyl group having 1 to 3 carbon atoms, a hydrogen atom or a tert-butoxycarbonyl group, and Cy is a pyrrolizine or a piperidine ring.

A diamine represented by the following formula (2).

(R ₁ , R ₂ , and Q ₁ are as defined in the above 5).

A polymer comprising a polyimine precursor obtained by reacting a diamine component of the diamine described in any one of the above 9 to 12 with a tetracarboxylic acid derivative component, and At least one selected from the group consisting of polyimine imines obtained by ring closure of the polyimine precursor.

The liquid crystal alignment agent of the invention can produce a high voltage holding ratio and abrasion resistance, can quickly alleviate the accumulated electric charge, and in particular can suppress the deviation of the rubbing direction and the liquid crystal alignment direction caused by the problem in the transverse electric field driving mode. Liquid crystal alignment film.

The liquid crystal alignment agent of the present invention is a group comprising a polyimine precursor obtained by using the novel diamine of the present invention as a raw material, and a polyimine obtained by ring-closing the polyimine precursor. At least one polymer selected.

[Formation of the Invention] <Polyimine precursors, and polyimines>

The liquid crystal alignment agent of the present invention contains a diamine containing the following formula (1) At least one selected from the group consisting of a polydiimide component obtained by reacting a diamine component with a tetracarboxylic acid derivative component and a polyimine obtained by ring-closing the polyimine precursor Polymer.

The polyimine precursor of the present invention is preferably a polymer containing a structural unit represented by the following formula (9).

In the above formula (9), X ₁ is a tetravalent organic group derived from a tetracarboxylic acid derivative, Y ₁ is a divalent organic group derived from a diamine of the formula (1), and R ₄ is a hydrogen atom. Or an alkyl group having 1 to 5 carbon atoms.

Diamine

R ₁ represents hydrogen or a monovalent organic group, preferably a hydrogen atom, or a linear alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom, or a methyl group.

Further, R ₁ may be a protecting group which is substituted with a hydrogen atom by a dissociation reaction via heat. The protective group does not dissociate at room temperature from the viewpoint of storage stability of the liquid crystal alignment agent, and is preferably dissociated at 80 ° C or higher, more preferably 100 ° C or higher, and particularly preferably 150 to 200 ° C to form hydrogen. The atom is better. For example, 1,1-dimethyl-2-chloroethoxycarbonyl, 1,1-dimethyl-2-cyanoethoxycarbonyl, tert-butoxycarbonyl, etc., preferably tert-butoxy Alkylcarbonyl.

Q ₁ represents an alkylene group having 1 to 5 carbon atoms, and is preferably a linear alkyl group having 1 to 5 carbon atoms in terms of ease of synthesis. Cy represents a divalent group of an aliphatic heterocyclic ring formed of trimethyleneimine, pyrroleazine, piperidine, or hexamethyleneimine, and in terms of ease of synthesis, trimethyleneimine, pyrroleazine, Or piperidine is preferred. Also, the ring moieties may bond substituents.

R ₂ and R ₃ are each independently a monovalent organic group, and q and r are each independently an integer of 0 to 4. However, the total of q and r is 2 or more, and the plural R ₂ and R ₃ have the above definitions. In terms of ease of synthesis, it is preferred that R ₂ and R ₃ are a methyl group.

Further, the bonding position of the amine group in the benzene ring constituting the above diamine is not particularly limited, and the amine group is 3 or 4 positions with respect to the nitrogen atom respectively with respect to Cy, with respect to Q ₁ and R The nitrogen atom of the ₁ bond is preferably 3 or 4, and is 4 positions with respect to the nitrogen atom on Cy and 4 positions with respect to the nitrogen atom bonded to Q ₁ and R ₁ . It is better.

The diamine represented by the above formula (1) of the present invention is preferably the following formula (2).

In the formula (2), R ₁ is a hydrogen atom, a methyl group, or a tert-butoxycarbonyl group. R ₂ is a hydrogen atom or a methyl group. Q ₁ is a linear alkyl group having 1 to 5 carbon atoms.

Specific examples of the diamine represented by the above formula (2) include, for example, a diamine represented by the following formulas (2-1) to (2-10). In the following formula, Boc represents a tert-butoxycarbonyl group.

The method for producing the diamine represented by the formula (1) is not particularly limited, and preferred methods include, for example, the following production methods [1] or [2].

System of law [1]

The dinitro compound (3-3) is produced by reacting 2 equivalents or more of the nitro compound (3-1) and the aliphatic amine compound (3-2). Further, if necessary, a monovalent organic group formed of R ₁ may be introduced, and then, the diamine of the target product may be obtained by reducing the nitro group. Further, the nitro compound (3-1) and the aliphatic amine compound (3-2) are easily obtained as commercially available products.

In the nitro compound (3-1), X represents a halogen atom and is intended to be an F, Cl, Br or I atom. R ₂ is a monovalent organic group, q is an integer of 0 to 4, q is 2 or more, and the plural R ₂ has the above definition.

X is a F or Cl atom, and when the NO ₂ group is at the 2-position with respect to X or at the 4-position, the halogenated aryl group can be reacted with the aliphatic amine compound in the presence of a suitable base to obtain two Nitro (3-3).

As the base to be used, for example, an inorganic base such as sodium hydrogencarbonate, potassium hydrogencarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate or cesium carbonate; trimethylamine, triethylamine or tripropylamine can be used. An amine such as triisopropylamine, tributylamine, diisopropylethylamine, pyridine, quinoline or colin base; a base such as sodium hydride or potassium hydride.

As the solvent, any solvent can be used as long as it does not react with the raw material. For example, an aprotic polar organic solvent (N,N-dimethylformamide (DMF), dimethyl hydrazine (DMSO), N,N-dimethylacetamide (DMAc), N- can be used. Methyl-2-pyrrolidone (NMP), etc., ethers (diethyl ether (Et ₂ O), diisopropyl ether (i-Pr ₂ O), tert-butyl methyl ether (TBME), cyclopentyl methyl ether ( CPME), tetrahydrofuran (THF), dioxane, etc.), aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, trimethylbenzene, chlorobenzene) , dichlorobenzene, nitrobenzene, tetrahydronaphthalene, etc.), halogen hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate) , butyl acetate, methyl propionate, etc.), nitriles (acetonitrile, propionitrile, butyronitrile, etc.). These solvents can be appropriately selected and used in view of the possibility of causing a reaction or the like. In this case, the above solvents may be used alone or in combination of two or more. Depending on the circumstances, a suitable dehydrating agent or desiccant may be used as the dehydrating and drying solvent.

The reaction temperature may be in the range of from -100 ° C to the boiling point of the solvent to be used, and any temperature is selected, preferably in the range of -50 to 150 ° C. The reaction time can be arbitrarily selected in the range of 0.1 to 1000 hours, preferably 0.1 to 100 hours.

The product can be purified by recrystallization, distillation, hydrazine gel column chromatography or the like.

When X is Br or I atom, the NO ₂ group may be 2, 3 or 4 with respect to X. It contains a suitable metal catalyst and a ligand, and uses CN interlaced reaction in the presence of a base. In this way, a dinitrogen can be obtained.

For the metal catalyst, for example, palladium acetate, palladium chloride, palladium chloride-acetonitrile complex, palladium-activated carbon, bis(dibenzylideneacetone)palladium, bis(dibenzylideneacetone)dipalladium, bis( Acetonitrile) dichloropalladium, bis(benzonitrile) dichloropalladium, CuCl, CuBr, CuI, CuCN, etc., but is not limited to these contents.

Examples of the ligand include, for example, triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,2-bis(diphenylphosphino)B. Alkane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,1'-bis(diphenylphosphino)ferrocene, trimethyl The phosphite, triethyl phosphite, triphenyl phosphite, tri-tert-butyl phosphine, etc., are not limited to these contents.

As the base, for example, the aforementioned base can be used.

The reaction solvent and the reaction temperature are based on the above description.

The product can be purified by recrystallization, distillation, hydrazine gel column chromatography or the like.

In the above reaction formula (4), in the dinitro compound (3-3), a monovalent organic group formed by R ₁ may be introduced as necessary.

The compound to be introduced into R1 may be a compound which can react with an amine, and examples thereof include acid halides, acid anhydrides, isocyanates, epoxy resins, propylene oxides, halogenated aryl groups, and halogenated alkyl groups. Further, an alcohol which is substituted with a leaving group such as Oms (methanesulfonate group), OTf (trifluoromethanesulfonate group) or OTs (sulfonyl group) may be used.

The method of introducing the monovalent organic group formed by R ₁ into the NH group includes, for example, the following methods, but is not particularly limited.

For example, a method of reacting an acid halide in the presence of a suitable base or the like.

Examples of the acid halides include, for example, acetic acid chloride, propionic acid chloride, methyl chloroformate, ethyl chloroformate, n-propyl chloroformate, i-propyl chloroformate, n-butyl chloroformate, and chlorine. I-butyl formate, t-butyl chloroformate, benzyl chloroformate, or 9-nonyl chloroformate.

As an example of the base, for example, the aforementioned base can be used.

The reaction solvent and the reaction temperature are based on the above description.

It is also possible to introduce an NH group and an acid anhydride to introduce R ₁ .

Examples of the acid anhydride include acetic anhydride, propionic anhydride, dimethyl dicarbonate, diethyl dicarbonate, di-tert-butyl dicarbonate, and dibenzyl dicarbonate.

To promote the reaction, a catalyst may be added. For example, pyridine, Colin base, N,N-dimethyl-4-aminopyridine or the like may be used. Catalyst amount, relative to dinitro The amount of the body (3-3) used (1 mol) is 0.0001 to 1 mol, preferably 0.0005 to 0.2 mol.

The reaction solvent and the reaction temperature are based on the above description.

It is also possible to react the NH group with an isocyanate, and it is also possible to introduce R ₁ .

Examples of the isocyanate include methyl isocyanate, ethyl isocyanate, n-propyl isocyanate, and phenyl isocyanate.

The reaction solvent and the reaction temperature are based on the above description.

The NH group may be reacted with an epoxy compound or a propylene oxide compound, and R ₁ may be introduced.

Examples of the epoxy resin or the propylene oxide include ethylene oxide, propene oxide, 1,2-butylene oxide, and trimethylene oxide.

The reaction solvent and the reaction temperature are based on the above description.

Further, R ₁ may be introduced into the NH group by reacting a metal catalyst with a ligand in the presence of a base and a halogenated aryl compound.

Examples of the halogenated aryl group include, for example, iodobenzene, bromobenzene, chlorobenzene and the like.

Examples of the metal catalyst include, for example, palladium acetate, palladium chloride, palladium chloride-acetonitrile complex, palladium-activated carbon, bis(dibenzylideneacetone)palladium, and bis(dibenzylideneacetone). Palladium, bis(acetonitrile) dichloropalladium, bis(benzonitrile)dichloropalladium, CuCl, CuBr, CuI, CuCN, etc., but are not limited thereto.

Examples of the ligand include, for example, triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,2-bis(diphenylphosphine). Ethylene, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,1'-bis(diphenylphosphino)ferrocene , trimethyl phosphite, triethyl phosphite, triphenyl phosphite, tri-tert-butyl phosphine, etc., but is not limited to these contents.

As the base, for example, the aforementioned base can be used.

The reaction solvent and the reaction temperature are based on the above description.

In the presence of a suitable base, the alcohol obtained by substituting a hydroxyl group of the alcohol with a dissociative group such as OMs, OTf or OTs may be reacted, and R ₁ may be introduced into the NH group.

Examples of the alcohols include methanol, ethanol, and 1-propanol, and the alcohols are passed through methanesulfonium chloride, trifluoromethanesulfonate chloride, p-toluenesulfonic acid, and the like. The reaction is replaced by an alcohol obtained by dissociation of OMs, OTf, OTs or the like.

As the base, for example, the aforementioned base can be used.

The reaction solvent and the reaction temperature are based on the above description.

It is also possible to carry out a reaction with a halogenated alkyl group in the presence of a suitable base, and it is also possible to introduce R ₁ into the NH group.

Examples of the halogenated alkyl group include methyl iodide, ethyl iodide, n-propyl iodide, methyl bromide, ethyl bromide, and n-propyl bromide.

In the case of the base, in addition to the above-mentioned base, a metal alkoxide such as potassium-tert-butoxide or sodium-tert-butoxide may be used.

The reaction solvent and the reaction temperature are based on the above description.

Next, in the above reaction formula (5), the nitro group in the obtained dinitro group (4-1) is reduced, and the diamine of the target substance can be obtained. (5-1). For the reduction of the nitro group, a palladium carbide powder or a platinum carbide powder or the like can be used. The reduction reaction can be carried out under a hydrogen atmosphere under normal pressure or under pressure.

Further, a metal such as Fe, Sn or Zn, or a metal salt thereof may be used together with a proton source to reduce the nitro group. Further, the metal and the metal salt may be used singly or in combination.

As the proton source, an acid such as hydrochloric acid, an ammonium salt such as ammonium chloride, a protic solvent such as methanol or ethanol, or the like can be used.

The solvent can be used as long as it can withstand the environment under a reducing atmosphere. For example, an aprotic polar organic solvent (DMF, DMSO, DMAC, NMP, etc.), an ether (Et ₂ O, i-Pr ₂ O, TBME) can be used. , CPME, THF, dioxane, etc.), aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, trimethylbenzene, chlorobenzene, dichloro Benzene, nitrobenzene, tetrahydronaphthalene, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), nitriles (acetonitrile, propionitrile, butyronitrile, etc.), alcohol Classes (methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, etc.) and the like.

The solvent may be appropriately selected in consideration of the degree of the reaction, and may be used singly or in combination of two or more. Depending on the circumstances, the solvent may be dehydrated and dried using a suitable dehydrating or drying agent.

The reaction temperature may be any temperature in the range from -100 ° C to the boiling point of the solvent to be used, preferably in the range of -50 to 150 ° C.

The reaction time can be arbitrarily selected in the range of 0.1 to 1000 hours, preferably It is 0.1~100 hours.

The product may be purified by recrystallization, distillation, gel column chromatography, activated carbon or the like.

System of law [2]

The nitro compound ((3-1), or (6-1)) is reacted with the aliphatic amine compound (6-2) protected by a protecting group to obtain a nitro compound ((6-3) , or (6-4)). Subsequently, after deprotection, the reaction with a nitro compound ((3-1), or (6-1)) is carried out to obtain the following dinitrogen ((8-1), or (8-2)) . Further, when necessary, the monovalent organic group represented by R ₁ is introduced into the NH group in the same manner as in the production method [1], and then the nitro group is reduced to obtain a diamine of the target compound.

Nitro compound (6-1). The aliphatic amine compound (6-2) protected by the protected group is easily obtained as a commercially available product.

In the following reaction formula (6), X, R ₂ and q are as described above, R ₃ is a monovalent organic group, r is an integer of 0 to 4, and r is 2 or more, and plural R ₃ Each has its own definition.

Pro represents a protecting group which represents an ethyl fluorenyl group, a trifluoroethenyl group, a trimethylethenyl group, a tert-butoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, a 2,2,2-three group. Chloroethoxycarbonyl, benzyloxycarbonyl, trimethylsulfanyl, triethyl decyl, dimethyl benzoalkyl, tert-butyl dimethyl decyl, tert]-butyl dimethyl cyano, 9-fluorene Methyl oxycarbonyl, o-phthalic acid, allyloxycarbonyl, p-toluenesulfonyl, o-nitrophenylsulfonate Base.

The synthesis method of the nitro compound ((6-3), or (6-4)) can be used according to the method when the nitro compound ((3-1), or (6-1)) is used in an amount of 1 equivalent or more. The reaction formula (3) of the equation is carried out in the same manner. The protecting group is preferably one which does not deprotect under alkaline conditions, and a tert-butoxycarbonyl group is preferred from the viewpoint of easy deprotection and availability after the reaction.

In the following reaction formula (7), an intermediate ((7-1), or (7-) can be obtained by deprotecting a nitro compound ((6-3), or (6-4)). 2)).

The method for deprotecting the protecting group is not particularly limited, and the object can be obtained by neutralizing it in the presence of an acid or a base after hydrolysis.

Examples of the acid to be used include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and hydrobromic acid, and organic acids such as formic acid, acetic acid, oxalic acid, and trifluoroacetic acid.

Examples of the base to be used, for example, sodium hydroxide or hydrogencarbonate can be used. An inorganic base such as sodium, potassium hydrogencarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate or cesium carbonate, trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine An organic amine such as diisopropylethylamine, pyridine, quinoline or colin base.

Further, it is also preferable to use a Lewis acid compound such as aluminum chloride or a trifluoroboron-diethyl ether complex to carry out deprotection. However, in the debenzylation reaction under a hydrogen atmosphere, it is not preferable because it reduces the aromatic nitro group to an amine group.

The solvent can be used as long as it does not interfere with the hydrolysis of the solvent. For example, an aprotic polar organic solvent (DMF, DMSO, DMAc, NMP, etc.), an ether (Et ₂ O, i-Pr ₂ O, TBME, CPME, THF, dioxane, etc.), an aliphatic hydrocarbon can be used. (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, nitrobenzene, tetrahydronaphthalene, etc.), halogenated hydrocarbons Classes (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), nitriles (acetonitrile, C) Nitrile, butyronitrile, etc.), alcohols (methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, etc.), or water. These solvents may be appropriately selected in consideration of easiness of the reaction, and may be used singly or in combination of two or more.

When considering the use of Lewis acid or the like, the solvent may be dehydrated and dried using a suitable dehydrating agent or a desiccant.

The reaction temperature may be any temperature ranging from -100 ° C to the boiling point of the solvent to be used, preferably in the range of -50 to 150 ° C.

The reaction time can be arbitrarily selected in the range of 0.1 to 1000 hours. Good for 0.1~100 hours.

The product can be purified by recrystallization, distillation, hydrazine gel column chromatography or the like.

For the intermediate ((7-1), or (7-2)), use 1 equivalent or more of the nitro compound ((3-1), or (6-1)), and according to the reaction formula of the method [1] ( 3) The same method can be used to prepare a dinitro body ((8-1), or (8-2)) (reaction formula (8)).

In the obtained dinitrogen ((8-1), or (8-2)), if necessary, a method of introducing R ₁ may be carried out according to the reaction conditions of the reaction formula (4) of the production method [1]. get on. Subsequently, the diamine of the target substance can be obtained by reducing the nitro group.

The method for reducing the dinitro group may be carried out under the same reaction conditions as the reaction formula (5) of the method [1].

2. Polyimine precursors and polyimine

The polyimine precursor of the present invention is a polyimide precursor obtained by reacting a diamine component containing a diamine represented by the formula (1) with a tetracarboxylic acid derivative component. Among them, the polyimide precursor is poly-proline or polyphthalate.

Examples of the tetracarboxylic acid derivative include an acid dianhydride, a dicarboxylic acid diester, a chlorinated diester dicarboxylic acid, and the like.

Polylysine can be obtained by reacting a diamine component with an acid dianhydride, and the polyphthalate can be reacted with a dicarboxylic acid diester or a chlorinated diester dicarboxylic acid. be made of.

The polyimine of the present invention. The polyimine obtained by subjecting the polyimine precursors to ring closure is also useful for the polymer for producing a liquid crystal alignment film.

The content of the diamine represented by the formula (1) is not limited in the production of the diamine component of the above polyimide precursor, but the effect of the present invention is easily achieved when the amount is large. The ratio of the diamine represented by the formula (1) is preferably from 10 to 100 mol%, preferably 20, based on 1 mol of the total diamine component. ~100% by mole, more preferably 30~100% by mole.

The polyimine precursor of the present invention is preferably a polymer containing a structural unit represented by the following formula (9).

In the above formula (9), X ₁ is a tetravalent organic group derived from a tetracarboxylic acid derivative, Y ₁ is a divalent organic group derived from a diamine of the formula (1), and R ₄ is a hydrogen atom. Or an alkyl group having 1 to 5 carbon atoms. From the viewpoint of being easily imidized by heating, R _{4 is} preferably a hydrogen atom, a methyl group or an ethyl group.

When X ₁ is a tetravalent organic group, it is not particularly limited. In the polyimine precursor, X ₁ may be a mixture of two or more types.

For example, a specific example of X ₁ may be, for example, a structure of the following formulas (X-1) to (X-43). From the viewpoint of easy availability, (X-1) to (X-14) are preferred.

R ₅ to R ₈ in the above formula (X-1) each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an alkynyl group having 2 to 6 carbon atoms. , or phenyl. When R ₅ to R ₈ are in a high-volume structure, there is a possibility of lowering the liquid crystal alignment property, so that a hydrogen atom, a methyl group or an ethyl group is more preferable, and a hydrogen atom or a methyl group is particularly preferable.

Further, the polyimine precursor of the present invention may contain a structural unit represented by the following formula (10), in addition to the above formula (9), without departing from the effects of the present invention.

In the formula (10), R ₄ is the same as defined in the above formula (9). X ₂ is a tetravalent organic group, and includes a preferred example, which is the same as the definition of X ₁ in the above formula (9). Z ₁ and Z ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, an alkenyl group having 2 to 10 carbon atoms or an alkynyl group having 2 to 10 carbon atoms.

Specific examples of the alkyl group having 1 to 10 carbon atoms include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group, a decyl group, a cyclopentyl group, a cyclohexyl group, and a dicyclohexyl group. Wait.

Examples of the alkenyl group having 2 to 10 carbon atoms include those in which one or more CH ₂ -CH ₂ groups present in the above alkyl group are substituted by CH=CH. More specifically, for example, vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-hexene A group, a cyclopropenyl group, a cyclopentenyl group, a cyclohexenyl group, and the like.

Examples of the alkynyl group having 2 to 10 carbon atoms include those in which one or more of CH ₂ -CH _{2 of the} above alkyl group is replaced by C≡C. More specifically, an ethynyl group, a 1-propynyl group, a 2-propynyl group, etc. are mentioned, for example.

The alkyl group having 1 to 10 carbon atoms, the alkenyl group having 2 to 10 carbon atoms, and the alkynyl group having 2 to 10 carbon atoms, and the substituent may have a substituent in a total of not more than 10 carbon atoms, and may have a substituent. A ring structure may also be formed via a substituent. Further, when a ring structure is formed via a substituent, it means that the substituents are bonded to each other or a part of the substituent is bonded to a part of the parent skeleton to form a ring structure.

Examples of the substituent include a halogen group, a hydroxyl group, a thiol group, a nitro group, an aryl group, an organic oxy group, an organic thio group, an organic decyl group, a decyl group, an ester group, a thioester group, a phosphate group, and the like. Amidino, alkyl, alkenyl, alkynyl and the like.

In the polyimide precursor precursor, when a high volume structure is generally introduced, the reactivity of the amine group or the liquid crystal alignment property is lowered, so Z ₁ and Z ₂ may have a hydrogen atom or a carbon number of 1 to 5 which may have a substituent. The alkyl group is more preferably a hydrogen atom, a methyl group or an ethyl group.

In the above formula (10), Y ₂ is a divalent organic group derived from a diamine component other than the formula (1), and the structure thereof is not particularly limited. Specific examples of Y ₂ include the following formulas (Y-1) to (Y-114). Further, the diamine component may be two or more kinds.

Among them, from the viewpoint of obtaining good liquid crystal alignment, it is preferred to use a diamine which forms a polyimine having high linearity. Therefore, from the viewpoint of liquid crystal alignment, Y ₂ is Y-7, Y-10, Y-11, Y-12, Y-13, Y-21, Y-22, Y-23, Y-25, Y- 26, Y-27, Y-41, Y-42, Y-43, Y-44, Y-45, Y-46, Y-48, Y-61, Y-63, Y-64, Y-71, Y-72, Y-73, Y-74, Y-75 or Y-98 are preferred.

The ratio of the above diamine is preferably from 40 to 100 mol%, more preferably from 60 to 100 mol%, based on 1 mol of the total diamine component.

Further, in order to increase the pretilt angle, it is preferred to use a diamine having a long-chain alkyl group, an aromatic ring, an aliphatic ring, a cholesterol skeleton, or a combination thereof in a side chain. From the viewpoint of pretilt angle, Y ₂ is Y-76, Y-77, Y-78, Y-79, Y-80, Y-81, Y-82, Y-83, Y-84, Y-85, Y -86, Y-87, Y-88, Y-89, Y-90, Y-91, Y-92, Y-93, Y-94, Y-95, Y-96 or Y-97 are preferred. When the diamine is added in an amount of from 1 to 50 mol%, more preferably from 5 to 20 mol%, based on the total diamine component, an arbitrary pretilt angle can be produced.

3. Method for producing polylysine

The polyphthalic acid which is the polyimine precursor of the present invention can be obtained by reacting a diamine component containing the diamine of the present invention with a tetracarboxylic acid derivative component.

Specifically, for example, a tetracarboxylic dianhydride and a diamine are synthesized and reacted in the presence of an organic solvent.

The organic solvent is not particularly limited as long as it can dissolve the produced polyamic acid. Specific examples include, for example, N,N-dimethylformamidine Amine, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methyl caprolactam, dimethyl hydrazine, γ-butyrolactone, and the like. Further, in order to increase the solubility of the polyimide precursor, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following formula may be used ( D-1)~ an organic solvent represented by the formula (D-3).

In the formula (D-1), D ¹ represents an alkyl group having 1 to 3 carbon atoms, and in the formula (D-2), D ² represents an alkyl group having 1 to 3 carbon atoms, and in the formula (D-3), D ³ It represents an alkyl group having 1 to 4 carbon atoms.

These may be used singly or in combination. Further, even if it is a solvent which does not dissolve the polyamic acid alone, it may be used in combination with the above solvent as long as the range of the produced polyamic acid is not precipitated. Further, the moisture in the organic solvent causes only the polymerization reaction to be inhibited, and even the hydrolysis of the produced polyaminic acid is caused. Therefore, it is preferred that the organic solvent be dehydrated and dried as much as possible.

In the organic solvent, the method of mixing the diamine component and the tetracarboxylic dianhydride may, for example, be a solution obtained by dispersing or dissolving an organic solvent of a diamine, and stirring the tetracarboxylic dianhydride under no treatment. Or dispersing or dissolving in an organic solvent for addition, in a solution obtained by dispersing or dissolving an organic solvent of tetracarboxylic dianhydride, adding a diamine to make tetracarboxylic acid A method in which the acid dianhydride and the diamine are alternately or simultaneously added to an organic solvent, and any of the methods may be used.

The temperature at which the polyamic acid is synthesized may be selected from any temperature of from -20 to 150 ° C, preferably from -5 to 100 ° C, more preferably from 0 to 80 ° C.

Further, the reaction time can be arbitrarily selected as long as the polymerization time of the poly-proline is more stable, and it is preferably 30 minutes to 24 hours, more preferably 1 to 12 hours.

The reaction can be carried out at any concentration. When the concentration of the diamine component and the tetracarboxylic dianhydride of the raw material is too low, a polymer having a high molecular weight is not easily obtained. When the concentration is too high, the viscosity of the reaction solution is too high. It is not easy to carry out uniform stirring, so it is preferably from 1 to 50% by mass, more preferably from 5 to 20% by mass. The initial stage of the reaction can be carried out at a high concentration, and then an organic solvent can be added.

In the synthesis reaction of polyamine, the molar ratio of the tetracarboxylic dianhydride molar number is preferably 0.8 to 1.2 with respect to the molar number of the diamine component. As with the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the produced polyamine.

The polyamic acid obtained in the above manner can be recovered by precipitating the polymer when the reaction solution is sufficiently stirred and injected into a poor solvent. Further, the precipitated powder is washed several times, washed with a poor solvent, and then heated or dried by heating to obtain a purified powder of poly-proline.

The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, 2-propanol, hexane, cellosolve, acetone, toluene, etc., and water, methanol, ethanol, and 2- Propanol and the like are preferred.

4. Polyurethane production

The polyglycolate which is the precursor of the polyimine of the present invention can be produced by the method of the following [1], [2] or [3].

[1] Cases made of polylysine

Polyurethane can be produced by esterifying the polylysine produced in the above manner.

Specifically, for example, polylysine and an esterifying agent are preferably used in the presence of an organic solvent at -20 to 150 ° C, preferably 0 to 50 ° C, for 30 minutes to 24 hours, preferably. It can be manufactured in a manner of 1 to 4 hours of reaction.

The esterifying agent is preferably one which can be easily removed by refining, and examples thereof include N,N-dimethylformamide dimethyl acetal and N,N-dimethylformamide diethyl acetal. , N,N-dimethylformamide dipropyl acetal, N,N-dimethylformamide dinepentyl butyl acetal, N,N-dimethylformamide di-t- Butyl acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p-tolyltriazene, 4-(4,6-dimethoxy-1,3,5-three -2-yl)-4-methylmorpholinium chloride and the like. The amount of the esterifying agent to be added is preferably 2 to 6 mol equivalents per 1 mol of the repeating unit of the polyamic acid.

Organic solvent, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N,N-dimethylformamide, N,N-dimethyl Ethyl acetamide, dimethyl hydrazine or 1,3-dimethyl-tetrahydroimidazolidone. Further, in the case where the polyimine precursor has high solubility in a solvent, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or The solvent represented by the above formula (D-1) to formula (D-3).

The solvent may be used singly or in combination. Further, even if the solvent of the polyimine precursor is not dissolved, the solvent can be used in combination with the solvent as long as the range of the produced polyimide intermediate is not precipitated. Further, the moisture in the solvent hinders the polymerization reaction and may cause the hydrolysis of the produced polyimide precursor, so that the solvent is preferably dried by dehydration.

The solvent used in the above reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone or γ-butyrolactone in terms of solubility of the polymer. These may be used alone or in combination of two or more. The concentration at the time of production is less likely to cause precipitation of the polymer, and it is preferable to obtain a high molecular weight body, preferably from 1 to 30% by mass, and preferably from 5 to 20% by mass.

[2] A case where a tetracarboxylic acid diester dichloride is reacted with a diamine to produce

The polyglycolate can be obtained from a tetracarboxylic acid diester dichloride and a diamine component containing the diamine of the present invention.

Specifically, for example, the tetracarboxylic acid diester dichloride and the diamine are allowed to stand in the presence of a base and an organic solvent at -20 to 150 ° C, preferably 0 to 50 ° C for 30 minutes. It can be obtained by reacting for 24 hours, preferably 1 to 4 hours.

As the base, pyridine, triethylamine or 4-dimethylaminopyridine can be used, and pyridine is preferred from the viewpoint of allowing the reaction to proceed stably. The amount of the base added is easily removed, and the viewpoint of easily obtaining a high molecular weight body is preferably 2 to 4 times the molar amount of the tetracarboxylic acid diester dichloride, and 2 to 3 times the molar amount. Preferably.

The solvent used in the above reaction is preferably N-methyl-2-pyrrolidone or γ-butyrolactone from the viewpoint of solubility of the monomer and the polymer, and one or two of them may be used. More than one kind of mixture is used.

The polymer concentration at the time of production is less likely to cause precipitation of the polymer, and it is preferable to obtain a high molecular weight body, preferably from 1 to 30% by mass, and preferably from 5 to 20% by mass.

Further, in order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, it is preferred that the solvent used in the production of the polyglycolate is dehydrated as much as possible, and it is preferable to prevent the incorporation of other gases in a nitrogen atmosphere.

[3] Case where tetracarboxylic acid diester and diamine are produced

The polyglycolate can be obtained by polycondensation of a tetracarboxylic acid diester and a diamine component containing the diamine of the present invention.

Specifically, for example, the tetracarboxylic acid diester and the diamine are allowed to stand in the presence of a condensing agent, a base, and an organic solvent at 0 to 150 ° C, preferably 0 to 100 ° C for 30 minutes. It can be obtained by reacting for 24 hours, preferably 3 to 15 hours.

As the condensing agent, triphenylphosphite, dicyclohexylcarbonyldiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbonyldiimide hydrochloride, N, N'-carbonyldiimidazole, dimethoxy-1,3,5-three Methylmorpholinium, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate, O-(benzotriazole-1- -N,N,N',N'-tetramethyluronium hexafluorophosphate, diphenyl (2,3-dihydro-2-thioketo-3-benzoxazolyl)phosphonate Wait. The amount of the condensing agent added is preferably 2 to 3 times moles, more preferably 2 to 2.5 times moles, based on the tetracarboxylic acid diester.

As the base, a tertiary amine such as pyridine or triethylamine can be used. The amount of the base to be added is easily removed, and the viewpoint of easily obtaining a high molecular weight body is preferably 2 to 4 times the molar amount of the diamine component, and preferably 2.5 to 3.5 times the molar amount.

Further, in the above reaction, when Lewis acid is added as an additive, the reaction can be efficiently carried out. Lewis acid is preferably lithium halide such as lithium chloride or lithium bromide. The amount of Lewis acid added is preferably 0 to 1.0 times the molar amount of the diamine component, and preferably 0 to 0.7 times the molar amount.

In the method for producing the above three polyglycolates, from the viewpoint of obtaining a high molecular weight polyglycolate, the method of the above [1] or the above [2] is particularly preferred.

The solution of the polyamidoate obtained by the above method can be poured into a poor solvent with sufficient agitation to precipitate a polymer. After several times of precipitation, washing with a poor solvent, it can be dried at room temperature or by heating to obtain a purified polyphthalate powder. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, cellosolve, acetone, toluene, and the like.

5. Polyimine production method

The polyimine used in the present invention can be obtained by subjecting the aforementioned polyimine precursor to a ruthenium imidization method.

In the polyimine of the present invention, the prolyl group or the guanylate group is blocked The ring rate (醯 imidization rate) is not necessarily 100% and can be adjusted arbitrarily for use or purpose.

The method of ring-closing the polyimine precursor may, for example, be a method in which the polyimide is heated without a catalyst, and the polyimide is imidized by heating, and the catalyst is imidized by a catalyst.

In the case where the polyimide precursor is thermally imidized, the solution of the polyimide precursor is heated at 100 to 400 ° C, preferably 120 to 250 ° C, and the hydrazine imidization reaction is continuously generated. It is preferred that the water or alcohol be excluded from the reaction system.

The catalyst of the polyimine precursor is imidized, and the alkaline catalyst and the acid anhydride may be added to the solution of the polyamic acid, and the mixture is stirred at -20 to 250 ° C, preferably 0 to 180 ° C. get on. The amount of the alkaline catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the prolyl group, and the amount of the anhydride is 1 to 50 moles of the amidate group, preferably 3 to 30 moles.

Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc., wherein pyridine is maintained in an appropriate basic state during the reaction, and Preferably.

Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, when acetic anhydride is used, it is preferred to carry out purification after completion of the reaction. The imidization rate of the imidization of the catalyst can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

In the case where the polymer component is recovered from the reaction solution of the polyimine, the reaction solution may be poured into a poor solvent to precipitate. The poor solvent used for precipitation, for example, methanol, acetone, hexane, butyl Cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, and the like. The polymer which is precipitated by the lean solvent can be filtered and recovered, and then dried under normal pressure or reduced pressure, and then heated or dried to make it dry.

6. Liquid crystal alignment agent

The liquid crystal alignment agent is a coating liquid used for producing a liquid crystal alignment film, and its main component is a composition containing a resin component forming a resin film and an organic solvent in which the resin component is dissolved. In the liquid crystal alignment agent of the present invention, the resin component is at least one selected from the group consisting of the polyimine precursor described above and the polyimine obtained by ring-closing the polyimide precursor. Things.

The concentration of the polymer in the liquid crystal alignment agent can be appropriately changed depending on the setting of the thickness of the coating film to be formed. From the viewpoint of forming a coating film which is uniform and free from defects, it is preferably 1% by mass or more, and more preferably 10% by mass or less from the viewpoint of storage stability of the solution. The concentration of the particularly preferred polymer is 2 to 8% by mass.

The resin component in the liquid crystal alignment agent may be all the polymer of the present invention, and may be mixed with other polymers other than the polymer of the present invention. In the other polymer, the diamine component may, for example, be a polyimine precursor obtained by using a diamine other than the formula (1) or a polyimine.

The organic solvent contained in the liquid crystal alignment agent is not particularly limited as long as the polymer component can be uniformly dissolved. List their In the case of, for example, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N -ethyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl hydrazine, dimethyl hydrazine, γ-butyl Lactone, 1,3-dimethyl-tetrahydroimidazolidone, 3-methoxy-N,N-dimethylpropane decylamine, and the like. These may be used alone or in combination of two or more. Further, even if it is a solvent which does not uniformly dissolve the polymer component alone, it may be used in combination with the above-mentioned organic solvent as long as it does not precipitate a polymer.

In addition to the organic solvent for the purpose of dissolving the polymer component, the liquid crystal alignment agent may further contain a solvent for improving the uniformity of the coating film when the liquid crystal alignment agent is applied to the substrate. The solvent is generally a solvent which has a lower surface tension than the above organic solvent. Specific examples thereof include ethyl cellosolve, cellosolve, 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 Diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, butyl cellosolve acetate, dipropylene glycol, 2-(2- Ethoxypropoxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, and the like. These solvents may be used in combination of two or more kinds.

The above solvent is a poor solvent which is low in solubility to the resin. The solvent is preferably contained in an amount of 5 to 60% by mass, preferably 10 to 50% by mass, based on the organic solvent contained in the liquid crystal alignment agent.

In the liquid crystal alignment agent, in addition to the above, when the effect of the present invention is not impaired, a polymer other than the polymer of the present invention may be added, and a dielectric for changing the dielectric constant or conductivity of the liquid crystal alignment film may be added. a cross-linking compound for the purpose of improving the hardness or density of the film when used as a liquid crystal alignment film, or a fluorinated compound for the purpose of improving the adhesion between the liquid crystal alignment film and the substrate, and When the film is sintered, a ruthenium imidization accelerator for the purpose of efficiently ruthenium imidization of the polyimide precursor is used.

In the case of a crosslinkable compound containing a compound containing a functional decane or a compound containing an epoxy group, the content thereof is preferably 0.1 to 30 parts by mass, preferably 1 part, per 100 parts by mass of the resin component. ~20 parts by mass, particularly preferably 1 to 10 parts by mass.

7. Method for manufacturing liquid crystal alignment film

The liquid crystal alignment film is a film obtained by applying the above liquid crystal alignment agent to a substrate, drying and sintering.

The substrate to which the liquid crystal alignment agent is applied is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as a glass substrate, a tantalum nitride substrate, an acrylic substrate, or a polycarbonate substrate can be used. In particular, when a substrate on which an ITO electrode or the like for liquid crystal driving is formed is used, it is preferable from the viewpoint of simplification of the process.

Further, in the case of a reflective liquid crystal display device, an opaque material such as a germanium wafer may be used only for a single-sided substrate, and in this case, a material that reflects light such as aluminum may be used.

The coating method of the liquid crystal alignment agent may, for example, be a spin coating method, a printing method, an inkjet method, or the like. Other methods of using the coating liquid include, for example, a dipping method, a roll coating method, a slit coating method, a spin coating method, and the like, and these methods can be used for the purpose.

The drying and sintering steps after coating the liquid crystal alignment agent may be selected to any temperature and time. Usually, the purpose of sufficiently removing the organic solvent is generally carried out at 50 to 120 ° C, preferably 50 to 80 ° C, for 1 to 10 minutes, preferably for 3 to 5 minutes, and then at 150 to 300 ° C. Preferably, it is 200 to 240 ° C, and is sintered for 5 to 120 minutes, preferably 10 to 40 minutes.

The thickness of the coating film after sintering is not particularly limited. When it is too thin, the reliability of the liquid crystal display element may be lowered, and it is usually 5 to 300 nm, preferably 10 to 200 nm.

The method of performing the alignment treatment on the obtained liquid crystal alignment film may, for example, be a rubbing method or a photoalignment treatment method. In the rubbing treatment, a rayon cloth, a nylon cloth, a cotton cloth or the like can be used. Since the liquid crystal alignment film for vertical alignment is not easily subjected to a rubbing treatment to obtain a uniform alignment state, it can be used as a liquid crystal alignment agent for vertical alignment without using friction.

Specific examples of the photo-alignment treatment method include, for example, irradiating the surface of the coating film with radiation that is deflected in a certain direction, and depending on the case, heat treatment may be performed at a temperature of 150 to 250 ° C to impart liquid crystal alignment ability. Method and so on. For the radiation, ultraviolet rays and visible rays having a wavelength of 100 to 800 nm can be used. Among them, it has a temperature of 100~400nm. Ultraviolet light of a wavelength is preferred, and it is particularly preferable to have a wavelength of 200 to 400 nm.

Further, in order to improve the alignment of the liquid crystal, the coated substrate can be continuously heated at 50 to 250 ° C, and the radiation can be irradiated.

The radiation exposure to 1 ~ 10,000mJ / cm ² preferably, to 100 ~ 5,000mJ / cm ² is particularly preferred. According to the liquid crystal alignment film produced in the above manner, the liquid crystal molecules can be stably aligned in a certain direction.

In the above, the film irradiated with the polarized radiation may be further subjected to a contact treatment with at least one type of solvent selected from water and an organic solvent.

The solvent to be used in the contact treatment is not particularly limited as long as it is a solvent capable of dissolving the decomposition product generated by light irradiation. Specific examples thereof include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, and 1-methoxy-2-propanol acetate. Cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, cyclohexyl acetate Ester and the like. These solvents may be used in combination of two or more kinds.

From the viewpoint of versatility or safety, at least one selected from the group consisting of water, 2-propanol, 1-methoxy-2-propanol and ethyl lactate is preferred. It is particularly preferred to use 1-methoxy-2-propanol or ethyl lactate.

In the present invention, the film which irradiates the polarized radiation and the solution containing the organic solvent are subjected to a contact treatment to perform an immersion treatment, a spray treatment, or the like, so that the film and the liquid are sufficiently contacted. It is better. Further, it is preferred to subject the film to a solution containing an organic solvent, preferably for 10 seconds to 1 hour, more preferably 1 to 30 minutes. The contact treatment may be carried out at normal temperature or under heating, preferably at 10 to 80 ° C, more preferably between 20 and 50 ° C. Moreover, if necessary, it can also be implemented by means of improving contact such as ultrasonic waves.

After the above contact treatment, the purpose of removing the organic solvent in the solution used may be carried out by washing (washing) or drying with a low boiling point solvent such as water, methanol, ethanol, 2-propanol, acetone or methyl ethyl ketone. Either one or both can be implemented at the same time.

Further, the film which is subjected to the contact treatment with the solvent can be heated at 150 ° C or higher for the purpose of drying the solvent and realigning the molecular chains in the film.

The heating temperature is preferably 150 to 300 ° C. When the temperature is higher, the molecular chain re-alignment is promoted, but when the temperature is too high, the molecular chain may be accompanied by decomposition. Therefore, the heating temperature is preferably 180 to 250 ° C, and particularly preferably 200 to 230 ° C.

When the heating time is too short, there is a possibility that the effect of the present invention cannot be obtained. When the temperature is too long, there is a possibility that the molecular chain is decomposed, so it is preferably 10 seconds to 30 minutes, preferably 1 to 10 minutes. .

8. Liquid crystal display element

The liquid crystal display element is obtained by preparing a liquid crystal alignment cell using a liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention, and using the liquid crystal cell as a liquid crystal display element.

An example of a method of fabricating a liquid crystal cell, for example, a liquid crystal display device having a passive matrix structure will be described as an example. Further, a liquid crystal display element having an active matrix structure of a response element such as a TFT (Thin Film Transistor) may be provided for each pixel portion constituting the image display.

First, a transparent glass substrate is prepared, and a common electrode is provided on one substrate, and a segment electrode is provided on the other substrate. The electrodes may be, for example, ITO electrodes, and patterned in such a manner as to form a desired image display. Next, an insulating film covering the common electrode and the segment electrode is provided on each of the substrates. As the insulating film, for example, a film formed of SiO ₂ -TiO ₂ formed by a sol-gel method can be used.

Next, a liquid crystal alignment film of the present invention is formed on each substrate. Next, the substrate on one side and the substrate on the other side are superimposed so that the alignment film faces are opposed to each other, and the periphery is followed by a sealing material. In the sealing material, in order to control the gap between the substrates, a spacer is usually mixed. Further, it is preferable that the inner portion of the surface of the sealing material is not provided, and the spacer for controlling the gap of the substrate is also dispersed. One part of the sealing material is an opening portion through which the liquid crystal can be externally filled.

Next, the liquid crystal material is injected into the space surrounded by the two substrates and the sealing material by being provided in the opening of the sealing material. Subsequently, this opening is sealed with an adhesive. The injection method may be a vacuum injection method or a capillary phenomenon in the atmosphere. Further, the sealing material can be drawn on the substrate, and the liquid crystal can be dropped, and the liquid crystal can be filled by laminating under reduced pressure.

Liquid crystal material, which can be used in positive liquid crystal materials and negative liquid crystal materials Either. In particular, in the case of using a negative-type liquid crystal material having a lower voltage holding ratio than a positive-type liquid crystal material, when the liquid crystal alignment film of the present invention is used, it is possible to form a film having excellent image sticking properties.

Next, the setting of the polarizing plate is performed. Specifically, for example, a pair of polarizing plates are attached to the surface of the two substrates which are opposite to the liquid crystal layer. Through the above steps, the liquid crystal display element of the present invention can be obtained. The liquid crystal display element is a liquid crystal alignment film obtained by using the method for producing a liquid crystal alignment film of the present invention as a liquid crystal alignment film, so that it has excellent afterimage characteristics, and is suitable for a high-definition multi-function mobile phone (smart type) Mobile phone), or lithographic computer, LCD TV, etc.

[Examples]

Hereinafter, the embodiments of the present invention and the like will be specifically described, but the present invention is not limited by the embodiments. Further, the abbreviations of the compound and the solvent are as follows.

Boc:tert-butoxycarbonyl

BCS: butyl cellosolve (cellosolve)

(Example 1) Synthesis of (DA-1)

Under a nitrogen atmosphere, a 4-neck flask was charged with dimethylformamide (390 g), 4-fluoronitrobenzene (65.0 g, 0.461 mol), 4-aminomethylpiperidine (25.0 g, 0.219 mol). And potassium carbonate (90.9 g, 0.658 mol), and the reaction was carried out at 60 °C. After heating and stirring for 22 hours, it was confirmed by HPLC that the intermediate disappeared. Subsequently, potassium carbonate was removed by filtration, and then potassium carbonate was washed twice with 250 g of dimethylformamide. The obtained solution was distilled off under reduced pressure until the content was 295 g, and then, 1.50 kg of water was added, and the compound (11) was precipitated. Subsequently, the precipitate is recovered by filtration, and after drying, the crude product of the compound (11) is obtained. The obtained crude product was purified by recrystallization from tetrahydrofuran to give Compound (11) (58.8 g, 0.165 mol, yield: 75.3%).

HPLC measurement; Prominence Series, NMR measurement by Shimadzu Corporation; Apparatus: Varian NMR System 400NB (400MHz)

Reference material: tetramethyl decane (TMS) (δ = 0.0 ppm)

The structure of the compound (11) was confirmed by ¹ H-NMR analysis, and the following spectrum data was confirmed.

The compound obtained by the following synthesis was confirmed by ¹ H-NMR analysis in the same manner as the compound (11).

¹ H-NMR (DMSO): δ = 8.05-7.98 (m, 4H), 7.41 (t, 1H J = 6.8), 7.02 (d, 2H, J = 9.6), 6.68 (d, 2H, J = 9.2) , 4.09 (d, 2H, J = 13.6), 3.10 (t, 2H, J = 6.0), 2.98 (t, 2H, J = 12.0), 1.91-1.89 (m, 1H), 1.89-1.83 (m, 2H) ), 1.29-1.19 (m, 2H).

Tetrahydrofuran (400 g), compound (11) (20.0 g, 0.0561 mol), and N,N-dimethyl-4-aminopyridine (77.4 mg, 0.634 mmol) were added to a 4-neck flask under a nitrogen atmosphere. Heat to 50 °C. A mixture of di-tert-butyl dicarbonate (15.3 g, 0.0699 mol) and 15.0 g of tetrahydrofuran was dropped into the solution, and the reaction was carried out for 24 hours. Subsequently, the disappearance of the raw materials was confirmed using HPLC. Next, the content was distilled off under reduced pressure, and then recrystallized from toluene. The precipitated crystals were collected by filtration and dried to give the compound (12) as a yellow solid, yield: 87.3% (22.3 g, 0.0489 mol).

¹ H-NMR (DMSO): δ = 8.21 (d, 2H, J = 8.8), 8.01 (d, 2H J = 9.2), 7.61 (d, 2H, J = 9.2), 6.98 (d, 2H, J = 9.6), 4.02 (d, 2H, J = 13.6), 3.69 (d, 2H, J = 7.2), 2.91 (t, 2H, J = 11.6), 1.86-1.70 (m, 1H), 1.66 (d, 2H) , J = 11.2), 1.42 (s, 9H), 1.22 - 1.10 (m, 2H).

After adding tetrahydrofuran (447 g), compound (12) (22.3 g, 0.0489 mol), and palladium carbide powder (1.16 g) to a 4-neck flask under nitrogen atmosphere, the flask was replaced with a hydrogen atmosphere and stirred at room temperature. 23 hours. Subsequently, it was confirmed by HPLC that the starting material disappeared. Subsequently, palladium carbide was filtered, and the resulting solution was evaporated under reduced pressure to give a crude product. Chloroform (206 g) was added to the obtained crude product, and the mixture was warmed to 60 °C. Subsequently, the liquid separation operation was repeated twice with water (100 g) at 60 °C. To the obtained organic layer, activated carbon (0.754 g) was added and stirred, and then activated carbon was removed by filtration. The contents were concentrated and recrystallized from toluene. Subsequently, as a result of drying, the title compound (DA-1) of a creamy solid was obtained, yield 71.3% (13.8 g, 0.0349 mol).

¹ H-NMR (DMSO): δ = 6.83 (d, 2H, J = 8.0), 6.65 (d, 2H J = 8.4), 6.50 (d, 2H, J = 8.4), 6.45 (d, 2H, J = 8.4), 5.05 (br, 2H), 4.54 (br, 2H), 3.41 (d, 2H, J = 6.8), 3.29 (d, 2H, J = 12.4), 2.36 (t, 2H, J = 10.8), 1.64 (d, 2H, J = 11.6), 1.42-1.19 (br, 12H).

(Example 2) Synthesis of (DA-2)

To a four-necked flask, tetrahydrofuran (534 g), (11) (21.4 g, 0.0601 mol), and potassium-tert-butoxide (8.10 g, 0.0722 mol) were added to a 4-neck flask. Methyl iodide (9.35 g, 0.0660 mol) was added dropwise to the solution stirred at room temperature, and the temperature was raised to 40 °C. After 24 hours of reaction, methyl iodide (10.2 g, 0.0717 mol) and potassium-tert-butoxide (2.98 g, 0.0266 mol) were further added, and the disappearance of the starting material was confirmed by HPLC. Subsequently, 100 g of water was added to stop the reaction. The reaction liquid was distilled off under reduced pressure, and 500 g of water was added to the obtained crude product, and the mixture was stirred for 24 hours in a slurry state, and the solid was filtered and dried. Subsequently, it was recrystallized from tetrahydrofuran to obtain Compound (13) as a yellow solid, yield: 78.2% (17.4 g, 0.0470 mol).

¹ H-NMR (DMSO): δ = 8.03 (d, 4H, J = 9.2), 7.01 (d, 2H J = 9.6), 6.82 (d, 2H, J = 9.2), 4.10 (d, 2H, J = 13.6), 3.42 (d, 2H, J = 7.2), 3.09 (s, 3H), 2.95 (t, 2H, J = 12.0), 2.15-2.10 (m, 1H), 1.68 (d, 2H, J = 11.2) ), 1.33-1.23 (m, 2H).

After adding tetrahydrofuran (697 g), compound (13) (17.4 g, 0.0470 mol), and palladium carbide powder (0.930 g) in a 4-neck flask under nitrogen atmosphere, the flask was replaced with a hydrogen atmosphere and stirred at 60 ° C. 40 hours. Subsequently, it was confirmed by HPLC that the starting material disappeared. Subsequently, the solution obtained by filtering the palladium carbide was distilled off under reduced pressure to obtain a crude product. 450 g of ethyl acetate was added to the obtained crude product, and the liquid separation operation was repeated twice with 450 g of water. To the obtained organic layer, activated carbon (0.739 g) was added and stirred, and then activated carbon was removed by filtration. The obtained filtrate was concentrated, and the obtained crude product was recrystallized from toluene. Next, the crystals were dried to give the objective compound (DA-2) as a thin purple solid, yield 71.6% (10.5 g, 0.0337 mol).

¹ H-NMR (DMSO): δ = 6.67 (d, 2H, J = 9.2), 6.54-6.45 (m, 6H), 4.54 (br, 2H), 4.36 (br, 2H), 3.32 (m, 2H) , 2.98 (d, 2H, J = 6.8), 2.75 (s, 3H), 2.40 (t, 2H, J = 10.0), 1.70-1.60 (br, 3H), 1.31-1.23 (m, 2H).

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

Under a nitrogen atmosphere, a 4-neck flask was charged with dimethylformamide (144 g), potassium carbonate (65.6 g, 0.475 mol), 4-fluoronitrobenzene (33.5 g, 0.237 mol), and 4-hydroxypiperone. Pyridine (24.0 g, 0.237 mol) was stirred at 80 ° C for 16 hours. Subsequently, the inorganic salt was removed by filtration under reduced pressure, and the filtrate was diluted with ethyl acetate (288 g). Next, the organic phase was washed three times with pure water (288 g) and dehydrated with sodium sulfate. Subsequently, concentration and drying were carried out to obtain 45.5 g (0.205 mol, yield 86.3%, yellow solid) of Compound (14).

¹ H-NMR (DMSO): δ = 8.02 (d, 2H J = 9.6), 7.00 (d, 2H J = 9.6), 4.79 (d, 1H, J = 4.0), 3.90-3.72 (m, 3H), 3.26-3.19 (m, 2H), 1.86-1.76 (m, 2H), 1.47-1.35 (m, 2H).

Sodium hydride (60% by mass, mobile paraffin dispersion) (3.24 g, 0.0810 mol) was added to a 4-neck flask under nitrogen atmosphere, and then tetrahydrofuran was added. Mult (30.0g). Subsequently, a solution obtained by dissolving the compound [6] (15.0 g, 0.0675 mol) in tetrahydrofuran (120 g) was added dropwise over 10 minutes under ice-cooling. Next, a solution obtained by dissolving 4-fluoronitrobenzene (10.0 g, 0.0709 mol) in tetrahydrofuran (30.0 g) was added dropwise, followed by stirring at room temperature for 5 hours. Subsequently, ethyl acetate (300 g) and pure water (300 g) were added, and the precipitated crystals were washed at room temperature, and the crystals were filtered under reduced pressure. Subsequently, the obtained crystals were taken out, and then ethyl acetate (300 g) and pure water (300 g) were added, and the slurry was washed at room temperature. Subsequently, the crystals were filtered and dried to give Compound (15) 20.0 g (0.0583 mol, yield 86.4%, yellow solid).

¹ H-NMR (DMSO): δ = 8.19 (d, 2H, J = 9.6), 8.05 (d, 2H J = 9.6), 7.22 (d, 2H, J = 9.6), 7.06 (d, 2H, J = 9.6), 4.96-4.86 (m, 1H), 3.89-3.80 (m, 2H), 3.48-3.40 (m, 2H), 2.12-2.05 (m, 2H), 1.77-1.67 (m, 2H).

Tetrahydrofuran (300 g), compound (15) (20.01 g, 0.0583 mol), and palladium carbide powder (4.00 g) were placed in an autoclave under a nitrogen atmosphere. Subsequently, the inside of the vessel was replaced with hydrogen 0.8 MPa at 50 ° C. Stir for 4 hours. Next, the palladium carbide was filtered, and the filtrate was concentrated and dried. Subsequently, the precipitated crystals were suspended in methanol (120 g). The suspension was stirred at 60 ° C for 1 hour, dissolved, and then stirred for 30 minutes in an ice bath. The precipitated crystal was filtered, washed with methanol (10.0 g), and dried to give the object (DA-4) 8.80 g (0.0311 mol, yield 53.3%, purple crystal).

¹ H-NMR (DMSO): δ=6.72-6.64 (m, 4H), 6.52-6.44 (m, 4H), 4.63 (br, 2H), 4.56 (br, 2H), 4.19-4.10 (m, 1H) , 3.24 - 3.15 (m, 2H), 2.77 - 2.68 (m, 2H), 2.00-1.91 (m, 2H), 1.71-1.60 (m, 2H).

[Viscosity measurement]

The viscosity of the polyaminic acid solution is, in the example or the comparative example, the E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) is used, and the sample amount is 1.1 mL, and the cone-shaped rotary viscometer is TE-1 (1). °34', R24), measured at a temperature of 25 ° C.

(Example 3)

In a 50 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 1.98 g (5.00 mmol) of DA-1 was weighed, and 20.8 g of NMP was added thereto, and the mixture was stirred and dissolved. The diamine solution was stirred, and 1.03 g (4.75 mmol) of acid dianhydride (A) was added, and 5.20 g of NMP was added thereto. The mixture was stirred at 23 ° C for 3 hours under a nitrogen atmosphere to obtain a polyamic acid solution (PAA-1). The polyamic acid solution had a viscosity of 134 mPa ‧ at a temperature of 25 ° C.

In a 100 mL Erlenmeyer flask in which a stirrer was placed, 7.92 g of the polyamidonic acid solution (PAA-1) obtained in Synthesis Example 2 was added, and 2.56 g of NMP was added, and 3-glycidoxypropyltriethoxydecane was contained. 0.67 g of a 1% by mass NMP solution and 3.72 g of BCS were stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal alignment agent (A-1).

(Example 4)

In a 50 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 2.17 g (7.00 mmol) of DA-2 was weighed, and 24.7 g of NMP was added thereto, and the mixture was stirred and dissolved. The diamine solution was stirred, and 1.26 g (5.77 mmol) of acid dianhydride (A) was added, and 6.19 g of NMP was further added thereto, and the mixture was stirred at 23 ° C for 3 hours under a nitrogen atmosphere to obtain a polyaminic acid solution (PAA-2). ). The viscosity of this polyaminic acid solution at a temperature of 25 ° C was 150 mPa ‧ s.

In a 100 mL Erlenmeyer flask in which a stirrer was placed, 8.84 g of the polyamidonic acid solution (PAA-2) obtained in Synthesis Example 1 was added, and NMP 4.09 g was added to contain 3-glycidoxypropyltriethoxydecane. 0.81 g of a 1% by mass NMP solution and 4.59 g of BCS were stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal alignment agent (A-2).

(Comparative Example 2)

In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 5.13 g (20.0 mmol) of DA-3 was weighed, and 52.2 g of NMP was added thereto, and it was fed. The mixture was stirred and dissolved in nitrogen. The diamine solution was stirred, and 4.17 g (19.1 mmol) of acid dianhydride (A) was added thereto, and 31.8 g of NMP was further added thereto, and the mixture was stirred at 23 ° C for 3 hours under a nitrogen atmosphere to obtain a polyaminic acid solution (PAA-3). ). The viscosity of this polyaminic acid solution at a temperature of 25 ° C was 140 mPa ‧ s.

In a 100 mL Erlenmeyer flask in which a stirrer was placed, 15.2 g of the polyaminic acid solution (PAA-3) obtained in Comparative Synthesis Example 2 was added, and 7.18 g of NMP was added, and 3-glycidoxypropyltriethoxy group was contained. 1.43 g of a 1 mass% NMP solution of decane and 7.94 g of BCS were stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal alignment agent (B-1).

(Comparative Example 3)

In a 100 mL four-necked flask equipped with a stirring device and a nitrogen introduction tube, 1.42 g (5.00 mmol) of DA-4 was weighed, and 16.7 g of NMP was added thereto, and the mixture was stirred and dissolved in nitrogen gas. The diamine solution was stirred, and 0.948 g (4.30 mmol) of acid dianhydride (A) was added thereto, and 4.18 g of NMP was further added thereto, and the mixture was stirred at 23 ° C for 3 hours under a nitrogen atmosphere to obtain a polyaminic acid solution (PAA-4). ). The viscosity of the polyaminic acid solution at a temperature of 25 ° C was 110 mPa ‧ s.

In a 100 mL Erlenmeyer flask in which a stirrer was placed, 10.4 g of the polyamidonic acid solution (PAA-4) obtained in Comparative Synthesis Example 3 was added, and 3.36 g of NMP was added thereto, and 3-glycidoxypropyltriethoxy group was contained. 0.878 g of a 1% by weight decane NMP solution and 4.88 g of BCS were stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal alignment agent (B-2).

The following is a description of the liquid crystal cell I used to evaluate the relaxation characteristics of the accumulated charge, and the liquid crystal used for evaluating the voltage holding ratio and the twist angle. Method of making unit cell II.

[Production of Liquid Crystal Cell I]

A liquid crystal cell having a structure of an FFS liquid crystal display element was produced. First, a substrate to which an electrode is attached is prepared. The substrate was a glass substrate having a size of 30 mm × 35 mm and a thickness of 0.7 mm. The first layer on the substrate is a counter electrode, and an IZO electrode is formed over the entire surface. On the counter electrode of the first layer, a SiN (tantalum nitride) film formed by a CVD method of the second layer is formed. The SiN film of the second layer has a film thickness of 500 nm and has the function of an interlayer insulating film. On the SiN film of the second layer, a pixel-shaped pixel electrode formed by patterning of the IZO film as the third layer is disposed, and the first pixel and the second pixel are respectively formed. 2 pixels. The size of each pixel is 10 mm in length and 5 mm in width. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are subjected to the action of the SiN film of the second layer, and are electrically insulated.

The pixel electrode of the third layer is a serrated shape composed of electrode elements having a "ㄑ" shape in which the central portion of the plurality of columns is in a buckling shape. The width of each electrode element in the short-side direction was 3 μm, and the interval between the electrode elements was 6 μm. Since the pixel electrodes constituting each pixel have the constituent contents of the electrode elements of the "ㄑ" shape in which the central portion of the plurality of pixels is arranged in a complex shape, the shape of each pixel is not rectangular, but has the same shape as the electrode elements. In general, the central part is the shape of the word "ㄑ" which approximates the bold type of buckling. Each of the pixels is divided into upper and lower sides by the central buckling portion as a boundary, and has a first region on the upper side of the flexion portion and a second region on the lower side.

When the first region of each pixel is compared with the second region, the direction in which the electrode elements constituting the pixel electrodes are formed is different. In other words, in the first region of the pixel, the electrode element of the pixel electrode is formed at an angle of +10° (clockwise) in the first region of the pixel, and the second region of the pixel is in the first region of the pixel. The electrode element of the pixel electrode is formed at an angle of -10° (clockwise). In other words, in the first region and the second region of each pixel, a voltage is applied to the direction of the liquid crystal in the plane of the substrate (transverse electric field effect; IN PLANE SWITCHING) caused by the pixel electrode and the counter electrode. , in order to have the opposite direction of each other.

Next, the liquid crystal alignment agent was filtered using a 1.0 μm filter, and then applied onto the prepared electrode-attached substrate by spin coating. After drying on a hot plate at 50 ° C for 5 minutes, it was sintered in a hot air circulating oven at 230 ° C for 20 minutes to obtain a polyimide film having a film thickness of 60 nm. The polyimide film was rubbed with a rayon cloth (roller diameter: 120 mm, number of drum revolutions: 500 rpm, moving speed: 30 mm/sec, plunging length: 0.3 mm, rubbing direction: relative to a 3-layer IZO dentate electrode After tilting 10°, the ultrasonic waves were irradiated for 1 minute in pure water to remove water droplets using an air flow. Subsequently, it was dried at 80 ° C for 15 minutes to obtain a substrate with a liquid crystal alignment film. Further, in the opposite substrate, a glass substrate having an ITO electrode and a columnar spacer having a height of 4 μm was used, and a polyimide film was formed in the same manner as above, and was subjected to the same procedure as described above. A substrate coated with a liquid crystal alignment film. The two substrates with the liquid crystal alignment film are used as one set, and the sealant is printed on the substrate so as to retain the liquid crystal injection port, and the other substrate is provided with liquid crystal. The film faces are facing each other, and the rubbing direction is antiparallel. Subsequently, the sealant was hardened to prepare an empty unit cell having a cell pitch of 4 μm. Liquid crystal ZLI-4792 (manufactured by Moker Corporation) was injected into the empty cell by a vacuum injection method, and then the injection port was sealed to obtain an FFS liquid crystal cell. Subsequently, the obtained liquid crystal cell was heated at 110 ° C for 1 hour and left at 23 ° C for one night for evaluation.

[Production of Liquid Crystal Cell II]

First, a substrate to which an electrode is attached is prepared. The substrate was a glass substrate having a size of 30 mm × 40 mm and a thickness of 1.1 mm. On the substrate, an ITO electrode having a film thickness of 35 nm was formed, and the electrode was a linear pattern of 40 mm in length and 10 mm in width.

Next, the liquid crystal alignment agent was filtered using a 1.0 μm filter, and then applied to the prepared electrode-attached substrate by spin coating. Next, it was dried on a hot plate at 50 ° C for 5 minutes. Subsequently, it was sintered in an IR oven at 230 ° C for 20 minutes to form a coating film having a film thickness of 100 nm, and a substrate having a liquid crystal alignment film was obtained. The liquid crystal alignment film was rubbed with a rayon cloth (roller diameter: 120 mm, number of drum rotations: 1000 rpm, moving speed: 20 mm/sec, and plunging length: 0.4 mm), and then ultrasonic waves were irradiated for 1 minute in pure water. Wash and remove water droplets with air flow. Subsequently, it was dried at 80 ° C for 15 minutes to obtain a substrate with a liquid crystal alignment film subjected to rubbing treatment. Two sheets of the substrate having the liquid crystal alignment film were prepared, and a spacer having a diameter of 4 μm (manufactured by Nikko Kasei Co., Ltd.) was spread on one of the liquid crystal alignment film surfaces. Subsequently, the sealant is printed thereon, and the other substrate is rubbed. The rubbing direction is the reverse direction, and the film faces are attached in a relatively opposite manner. Subsequently, the sealant is hardened to obtain an empty unit cell. Liquid crystal ZLI-4792 (manufactured by Moker Corporation) was injected into the empty cell by a vacuum injection method, and the injection port was sealed to obtain a liquid crystal cell. Subsequently, the obtained liquid crystal cell was heated at 110 ° C for 1 hour and left at 23 ° C for one night for evaluation.

[Alleviation characteristics of accumulated charge]

The liquid crystal cell I is disposed between two polarizing plates arranged in a vertically staggered manner on the polarization axis, and the pixel electrode and the counter electrode are short-circuited to the same potential state, and the LEDs are illuminated by the lower portions of the two polarizing plates. The backlight adjusts the angle of the liquid crystal cell to minimize the brightness of the transmitted light from the LED backlight measured above the two polarizing plates.

Next, a rectangular wave having a 30 Hz cycle number was continuously applied to the liquid crystal cell, and the V-T characteristic (voltage-transmittance characteristic) at a temperature of 23 ° C was measured, and an AC voltage at a relative transmittance of 23% was calculated. Since the AC voltage is equivalent to a region where the luminance of the voltage changes greatly, the accumulated charge can be evaluated by the luminance.

Next, an AC voltage having a relative transmittance of 23% was used, and a rectangular wave having a 30-Hz number of cycles was applied for 5 minutes, and then a DC voltage of +1.0 V was superimposed and driven for 30 minutes. Subsequently, the DC voltage was cut off, and only a rectangular wave having a relative transmittance of 23% was applied, and a rectangular wave having a cycle number of 30 Hz was applied for 30 minutes.

When the accumulated electric charge is moderated, the charge accumulation of the liquid crystal cell is also faster when the DC voltage is superimposed, so that the accumulation of the charge can be moderated. The relative transmittance immediately after the DC voltage was superimposed was reduced from 23% or more to 23%, and the time required was evaluated. The shorter the time, the better the relaxation characteristics of the accumulated charges.

[voltage retention rate]

The liquid crystal cell II was subjected to a voltage of 1 V at 60 ° C at a temperature of 85 ° C, and the voltage after 50 msec was measured, and the voltage holding ratio was evaluated in such a manner as to maintain the voltage.

[twist angle]

The torsion angle in the liquid crystal cell II was evaluated using an AxoScan Mueller matrix polarometer manufactured by OPTOMETRICS. Originally, if the rubbing direction is the same as the liquid crystal alignment direction, no twist angle is generated in the liquid crystal cell II. The meaning of the twist angle is that the rubbing direction is inconsistent with the liquid crystal alignment direction.

[friction resistance]

The liquid crystal alignment agent was spin-coated on the ITO surface of the glass substrate on which the ITO electrode was entirely attached, and dried on a hot plate at 50 ° C for 5 minutes. Subsequently, sintering was carried out in an IR oven at 230 ° C for 20 minutes to obtain a substrate having a liquid crystal alignment film formed by forming a coating film having a film thickness of 100 nm. This liquid crystal alignment film was rubbed with a rayon cloth (roller diameter: 120 mm, number of drum rotations: 1000 rpm, moving speed: 20 mm/sec, and plunging length: 0.4 mm). The substrate was observed with a microscope, and no friction was found on the film surface. The way the textured person is marked as "good" and the marker is marked as "bad" is evaluated.

(Example 5)

The liquid crystal alignment agent (A-1) obtained in Example 3 was filtered through a 1.0 μm filter, and then subjected to the above-described treatment to prepare a liquid crystal cell I. As a result of evaluating the relaxation characteristics of the accumulated charge of the liquid crystal cell I, it was found that the time required for the relative transmittance to decrease to 23% was 2 minutes, and the result was good.

Next, the liquid crystal alignment agent (A-1) obtained in Example 3 was filtered through a 1.0 μm filter, and then subjected to the above-described treatment to prepare a liquid crystal cell II. As a result of evaluation of the liquid crystal cell II, the voltage holding ratio was 91% and the twist angle was 0.1 degree.

Then, the liquid crystal alignment agent (A-1) obtained in Example 3 was filtered through a 1.0 μm filter, and the results of the evaluation of the abrasion resistance were confirmed. No frictional texture was observed, and the result was good.

(Example 6)

A liquid crystal cell I was produced in the same manner as in Example 5 except that the liquid crystal alignment agent (A-2) obtained in Example 4 was used. As a result of evaluating the relaxation characteristics of the accumulated charges on the liquid crystal cell I, it was found that the time required for the relative transmittance to fall to 23% was 4 minutes, and the result was good.

Next, a liquid crystal cell II was produced in the same manner as in Example 5 except that the liquid crystal alignment agent (A-2) obtained in Example 4 was used. The liquid crystal The evaluation result of the unit cell II was that the voltage holding ratio was 92% and the twist angle was 0.1 degree.

In the same manner as in Example 5 except that the liquid crystal alignment agent (A-2) obtained in Example 4 was used, the results of the evaluation of the abrasion resistance were confirmed, and it was confirmed that no rubbing texture was observed.

(Comparative Example 4)

A liquid crystal cell I was produced in the same manner as in Example 5 except that the liquid crystal alignment agent (B-1) obtained in Comparative Example 2 was used. As a result of evaluating the relaxation characteristics of the accumulated electric charge of the liquid crystal cell I, it was found that the relative transmittance did not decrease to 23% even after 30 minutes passed, and as a result, the result was poor.

Next, a liquid crystal cell II was produced in the same manner as in Example 5 except that the liquid crystal alignment agent (B-1) obtained in Comparative Example 2 was used. As a result of evaluation of the liquid crystal cell II, the voltage holding ratio was 40% and the twist angle was 1.1 degrees.

(Comparative Example 5)

The evaluation of the rubbing resistance was carried out in the same manner as in Example 5 except that the liquid crystal alignment agent (B-2) obtained in Comparative Example 3 was used, and it was confirmed that a large number of rubbing lines were generated, and as a result, it was defective.

Also, in Table 1, "-" indicates that the evaluation was not performed.

[industrial use]

The liquid crystal alignment agent of the present invention is suitable as a liquid crystal display element for an IPS driving method or an FFS driving method, a liquid crystal alignment film used for a multi-function mobile phone (smart phone), a lithographic computer, a liquid crystal television, or the like.

In addition, the specification, the scope of the patent application, and the abstract of the Japanese Patent Application No. 2014-025438, filed on Jan.

Claims (13)

A liquid crystal alignment agent comprising a polyimine precursor obtained by reacting a diamine component containing a diamine of the following formula (1) with a tetracarboxylic acid derivative component, and the polyazonia At least one polymer selected from the group consisting of polyamidimides obtained by ring closure of an amine precursor, (In the formula (1), R ₁ represents hydrogen or a monovalent organic group; Q ₁ represents an alkylene group having 1 to 5 carbon atoms; and Cy represents a trimethylene imine, pyrrazine, piperidine or hexamethylene a divalent group of an aliphatic heterocyclic ring formed by an amine, wherein the ring moiety may bond a substituent; R ₂ and R ₃ are each independently a monovalent organic group; q and r are each independently 0~ An integer of 4; however, the total of q and r is 2 or more, and the plural R ₂ and R ₃ have the above definitions). The liquid crystal alignment agent of claim 1, wherein the polyimine precursor is a polymer having a structural unit represented by the following formula (9), (In the formula (9), X ₁ is a tetravalent organic group derived from a tetracarboxylic acid derivative, Y ₁ is a divalent organic group derived from a diamine of the formula (1), and R ₄ is a hydrogen atom. Or an alkyl group having 1 to 5 carbon atoms). The liquid crystal alignment agent according to claim 2, wherein X ₁ is the following formula (X-1) to (X-14), (In the formula (X-1), R ₅ to R ₈ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkynyl group having 2 to 6 carbon atoms. , or phenyl). The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the ratio of the diamine represented by the formula (1) is from 30 to 100 mol% based on 1 mol of the total diamine component. The liquid crystal alignment agent of claim 1, wherein the diamine of the formula (1) is represented by the following formula (2); (In the formula (2), R ₁ is a hydrogen atom, a methyl group, or a tert-butoxycarbonyl group; R 2 is a hydrogen atom or a methyl group; and Q ₁ is a linear alkyl group having 1 to 5 carbon atoms). A liquid crystal alignment film obtained by coating and sintering a liquid crystal alignment agent according to any one of claims 1 to 5. The liquid crystal alignment film of claim 6, wherein the film thickness after sintering is 5 to 300 nm. A liquid crystal display element characterized by having the liquid crystal alignment film of claim 6 or 7. a diamine represented by the formula (1); (In the formula (1), R ₁ represents hydrogen or a monovalent organic group; Q ₁ represents an alkylene group having 1 to 5 carbon atoms; and Cy represents a trimethylene imine, pyrrazine, piperidine or hexamethylene a divalent group of an aliphatic heterocyclic ring formed by an amine, wherein the ring moiety may bond a substituent; R ₂ and R ₃ are each independently a monovalent organic group; q and r are each independently 0 to 4 An integer; however, the sum of q and r is 2 or more, and the plural R ₂ and R ₃ have the above definitions). The diamine of claim 9, wherein R ₁ is an alkyl group having 1 to 3 carbon atoms, a hydrogen atom, or a thermally dissociable group substituted with a hydrogen atom via heat, and R ₂ and R ₃ are each independently Methyl, trifluoromethyl, cyano, or methoxy. The diamine of claim 10, wherein R ₁ is a linear alkyl group having 1 to 3 carbon atoms, a hydrogen atom, or a tert-butoxycarbonyl group, and Cy is a pyrrolidine or piperidine ring. a diamine represented by the following formula (2); (In the formula (2), R ₁ is a hydrogen atom, a methyl group, or a tert-butoxycarbonyl group; R ₂ is a hydrogen atom or a methyl group; and Q ₁ is a linear alkyl group having 1 to 5 carbon atoms). A polymer characterized by reacting a diamine component containing a diamine of any one of claims 9 to 12 with a tetracarboxylic acid derivative component, and polymerizing the polyfluorene precursor At least one selected from the group consisting of polyimine groups obtained by ring closure of the imine precursor.