KR102344228B1 - Novel liquid crystal orientation agent, diamine, and polyimide precursor - Google Patents

Abstract

(R₁ 은 수소, 또는 1 가의 유기기를 나타낸다. Q₁ 은 탄소수 1 내지 5 의 알킬렌을 나타내고, Cy 는 아제티딘, 피롤리딘, 피페리딘 또는 헥사메틸렌이민으로 이루어지는 2 가의 기이며, 이들의 고리 부분에 치환기가 결합되어 있어도 된다. R₂, R₃ 은, 1 가의 유기기이고, q, r 은, 각각 독립적으로 0 ∼ 4 의 정수이다. 단, q 와 r 의 합계가 2 이상인 경우, 복수의 R₂, R₃ 은, 상기 정의를 갖는다.)The liquid crystal aligning agent from which voltage retention and rubbing tolerance are high, can relieve|moderate accumulated charge quickly, and can suppress the shift|offset|difference of the rubbing direction and the orientation direction of a liquid crystal in especially a transverse electric field drive system is provided.
At least one polymer selected from the group consisting of a polyimide precursor obtained by reacting a diamine component containing a diamine represented by the formula (1) with a tetracarboxylic acid derivative component, and a polyimide obtained by ring closure of the polyimide precursor The liquid crystal aligning agent to contain.

(R ₁ represents hydrogen or a monovalent organic group. Q ₁ represents alkylene having 1 to 5 carbon atoms, Cy is a divalent group consisting of azetidine, pyrrolidine, piperidine or hexamethyleneimine, and these A substituent may be bonded to the ring portion of R ₂ , R ₃ is a monovalent organic group, and q and r are each independently an integer of 0 to 4. However, when the sum of q and r is 2 or more , a plurality of R ₂ , R ₃ has the above definition.)

Description

New liquid crystal aligning agent, diamine, and polyimide precursor {NOVEL LIQUID CRYSTAL ORIENTATION AGENT, DIAMINE, AND POLYIMIDE PRECURSOR}

This invention relates to a novel liquid crystal aligning agent, the novel diamine useful as a raw material of the polymer used for this liquid crystal aligning agent, the polyimide precursor obtained using this diamine, and a polyimide.

BACKGROUND ART Liquid crystal display elements have conventionally been widely used as display units for personal computers, mobile phones, television sets, and the like, and as a driving method, a conventional electric field system such as a TN (Twisted Nematic) system and a VA (Vertical Alignment) system, or IPS Transverse electric field methods such as an (In-Plane-Switching) method and a Fringe Field Switching (FFS) method are known.

In general, in a transverse electric field method in which electrodes are formed on only one side of a substrate and an electric field is applied in a direction parallel to the substrate, a wide viewing angle characteristic compared to a conventional vertical electric field method in which a voltage is applied to electrodes formed on upper and lower substrates to drive liquid crystal It is known as a liquid crystal display element capable of high-quality display. As a method for aligning the liquid crystal in a certain direction, there is a method of forming a polymer film such as polyimide on a substrate and rubbing the surface with a cloth, so-called rubbing treatment, which has been widely used industrially.

As a conventional problem, a voltage retention and accumulation of charges by a DC voltage component applied from an active matrix structure are exemplified. When an electric charge accumulates in a liquid crystal display element, a display will be influenced as a disorder of a liquid-crystal orientation, or an afterimage, and the display quality of a liquid crystal display element will be reduced remarkably. Alternatively, when driving in a state in which electric charges are accumulated, control of liquid crystal molecules is not performed normally immediately after driving, causing flicker (flickering) or the like.

In a polyimide-type liquid crystal aligning film, in order to respond to the above requests, various proposals have been made. For example, as a liquid crystal aligning film with a short time until afterimages generated by direct voltage disappear, a liquid crystal aligning agent containing a tertiary amine of a specific structure in addition to polyamic acid or imide group-containing polyamic acid is used. What was used (refer patent document 1), the thing using the liquid crystal aligning agent containing the soluble polyimide which used the specific diamine which has pyridine skeleton etc. for a raw material (refer patent document 2) etc. are proposed.

As a liquid crystal aligning agent for obtaining the liquid crystal aligning film excellent in the light resistance of voltage retention, high temperature and high humidity resistance, rework property, and printability, the liquid crystal aligning agent containing the polyimide containing specific diamine in patent document 3 is disclosed.

In addition, as a means for forming a liquid crystal aligning film that is excellent in liquid crystal alignment, rubbing resistance, and light transmittance, and is effective for reducing afterimages in a wide temperature range, Patent Document 4 contains a specific diamine and an aromatic tetracarboxylic acid derivative, characterized in that A liquid crystal aligning agent is disclosed.

Moreover, the liquid-crystal aligning agent containing the polyimide precursor containing specific diamine is disclosed by patent document 5 as a means for obtaining the liquid crystal aligning film with high liquid-crystal orientation high and a low diagonal orientation angle.

In recent years, higher display quality than before is requested|required with high definition, and the problem of voltage retention and electric charge accumulation has come to appear more conspicuously. In particular, since the liquid crystal display element of the transverse electric field system has few electrode portions formed in the substrate, if the voltage retention of the liquid crystal aligning film is weak, sufficient voltage is not applied to the liquid crystal, and display contrast decreases. In comparison, since the distance between the pixel electrode and the common electrode is close, a strong electric field acts on the alignment film or the liquid crystal layer, and there is a problem that these problems are likely to become significant. In addition, in the method of driving the liquid crystal molecules aligned parallel to the substrate by a transverse electric field, such as the IPS method or the FFS drive method, the stability of the liquid crystal alignment also becomes important. When the stability of orientation is insufficient, when a liquid crystal is driven for a long time, a liquid crystal will not return to an initial state, and it will become a cause of the fall of contrast, an afterimage, or burn-in. Moreover, in a board|substrate with a large level|step difference, higher rubbing resistance is calculated|required.

Japanese Patent Laid-Open No. 9-316200 Japanese Laid-Open Patent Publication No. 10-104633 Japanese Patent Laid-Open No. 2013-152421 International Publication No. WO2013/062115 pamphlet Japanese Laid-Open Patent Publication No. 10-123532

As a method of aligning the liquid crystal, rubbing treatment is widely used industrially, but depending on the liquid crystal aligning film to be used, the rubbing direction and the alignment direction of the liquid crystal do not match, a phenomenon that a so-called twist angle is expressed may occur. That is, in the transverse electric field element, black display is displayed in the state where no voltage is applied, but by this phenomenon, the luminance increases even in the state where no voltage is applied, and as a result, the display contrast decreases. There was a problem with throwing it away.

The present invention provides a liquid crystal aligning film that has high voltage retention and rubbing resistance, can quickly relieve accumulated charges, and can suppress the deviation between the rubbing direction and the alignment direction of the liquid crystal, which is a problem especially in the transverse electric field driving method. It aims at providing a liquid crystal aligning agent.

As a result of earnest examination, the present inventors consist of a polyimide precursor obtained by reacting a diamine component containing a diamine of the following formula (1) with a tetracarboxylic acid derivative component, and a polyimide obtained by ring-closing the polyimide precursor. With the liquid crystal aligning agent containing the polymer chosen from the group, what could achieve the said subject was discovered, and it led to this invention.

The gist of the present invention is as follows.

1. At least one selected from the group consisting of a polyimide precursor obtained by reacting a diamine component containing a diamine of the following formula (1) with a tetracarboxylic acid derivative component, and a polyimide obtained by ring closure of the polyimide precursor A polymer is contained, The liquid crystal aligning agent characterized by the above-mentioned.

[Formula 1]

(R ₁ represents hydrogen or a monovalent organic group. Q ₁ represents alkylene having 1 to 5 carbon atoms. Cy represents an aliphatic heterocyclic ring comprising azetidine, pyrrolidine, piperidine or hexamethyleneimine 2 It is a valent group, and the substituent may be bonded to these ring moieties.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 and When the sum of r is 2 or more, a plurality of R ₂ and R ₃ have the above definition.)

2. The said polyimide precursor is a polymer which has a structural unit represented by following formula (9), The liquid crystal aligning agent of 1 said.

[Formula 2]

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

3. Liquid crystal aligning agent of said 2 whose X1 is the following formulas (X-1) - (X-14).

[Formula 3]

(R ₅ to R ₈ are each independently 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. Liquid crystal aligning agent in any one of said 1-3 whose ratio of diamine represented by Formula (1) is 30-100 mol% with respect to 1 mol of all the diamine components.

5. Liquid crystal aligning agent of said 1 in which diamine of Formula (1) is represented by following formula (2).

[Formula 4]

(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 alkylene having 1 to 5 carbon atoms.)

6. The liquid crystal aligning film obtained by apply|coating and baking the liquid crystal aligning agent in any one of said 1-5.

7. The liquid crystal aligning film of said 6 whose film thickness after baking is 5-300 nm.

8. It has liquid crystal aligning film of said 6 or 7, The liquid crystal display element characterized by the above-mentioned.

9. Diamine represented by Formula (1).

[Formula 5]

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

10. R ₁ is an alkyl group having 1 to 3 carbon atoms, a hydrogen atom, or a thermally leaving group substituted with a hydrogen atom by heat, R ₂ and R ₃ are each independently a methyl group, a trifluoromethyl group, a cyano group, or a methoxy group Phosphorus, the diamine as described in said 9.

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 pyrrolidine or piperidine ring.

12. Diamine represented by the following formula (2).

[Formula 6]

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

13. At least selected from the group consisting of a polyimide precursor obtained by reacting the diamine component according to any one of 9 to 12 with a tetracarboxylic acid derivative component, and a polyimide obtained by ring closure of the polyimide precursor. 1 type of polymer.

According to the liquid crystal aligning agent of the present invention, the voltage retention and rubbing resistance are high, the accumulated charge can be quickly relieved, and the deviation of the rubbing direction and the alignment direction of the liquid crystal, which is a problem especially in the transverse electric field driving method, can be suppressed. A liquid crystal aligning film that can be

The liquid crystal aligning agent of this invention contains the at least 1 sort(s) of polymer chosen from the group which consists of a polyimide precursor which uses the novel diamine of this invention as a raw material, and the polyimide obtained by ring-closing this polyimide precursor.

<Polyimide precursor and polyimide>

The liquid crystal aligning agent of this invention is the polyimide obtained by making the diamine component containing the diamine of following formula (1) react, and the polyimide precursor obtained by making a tetracarboxylic-acid derivative component react, and this polyimide precursor From the group which consists of It contains at least 1 sort(s) of polymer selected.

It is preferable that the polyimide precursor of this invention is a polymer containing the structural unit represented by following formula (9).

[Formula 7]

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 the diamine of the formula (1), and R ₄ is a hydrogen atom or carbon number It is an alkyl group of 1-5.

1. Diamine

[Formula 8]

R<_1> represents hydrogen or a monovalent organic group, Preferably it is a hydrogen atom or a C1-C3 linear alkyl group, More preferably, it is a hydrogen atom or a methyl group.

Moreover, R<_1> may raise|generate a detachment reaction by heat|fever, and the protective group substituted with a hydrogen atom may be sufficient as it. From the viewpoint of storage stability of the liquid crystal aligning agent, this protecting group does not detach at room temperature, preferably 80°C or higher, more preferably 100°C or higher, particularly preferably 150-200°C, to form a hydrogen atom it is preferable For example, 1,1-dimethyl-2-chloroethoxycarbonyl group, 1,1-dimethyl-2-cyanoethoxycarbonyl group, tert-butoxycarbonyl group, etc. are mentioned, Preferably, tert-butoxycarbonyl group is mentioned. to be.

Q<_1> represents a C1-C5 alkylene group, Preferably it is a C1-C5 linear alkylene from synthetic|combination simplicity. Cy is a divalent group representing an aliphatic heterocyclic ring consisting of azetidine, pyrrolidine, piperidine, or hexamethyleneimine, and azetidine, pyrrolidine, or piperidine is preferable from the viewpoint of simplicity of synthesis. Moreover, the substituent may couple|bond with these ring moieties.

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, when the sum total of q and r is 2 or more, some R<_2> and R<_3> has the said definition. From the viewpoint of synthesis simplicity, R ₂ and R ₃ are preferably a methyl group.

In addition, the bonding position of the amino group in the benzene ring constituting the diamine is not limited, but the amino group is 3 to the nitrogen atom on Cy, or 4 to the nitrogen atom to which Q ₁ and R ₁ are bonded. It is preferably at the position or the 4-position, more preferably the 4-position with respect to the nitrogen atom on Cy, and the 4-position with respect to the nitrogen atom to which Q ₁ and R ₁ are bonded.

It is preferable that the diamine represented by the said Formula (1) of this invention is a following formula (2).

[Formula 9]

In 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 alkylene having 1 to 5 carbon atoms.

As a specific example of the diamine represented by said (2) formula, the diamine represented, for example by following formula (2-1) - (2-10) is mentioned. In the following formula, Boc represents a tert-butoxycarbonyl group.

[Formula 10]

Although the method of manufacturing the diamine represented by Formula (1) is not specifically limited, The following manufacturing method [1] or [2] is mentioned as a preferable method.

recipe [1]

The dinitro body (3-3) is manufactured by making 2 or more equivalents of a nitro compound (3-1) and an aliphatic amine compound (3-2) react. Moreover, the target diamine can be obtained by introduce|transducing the monovalent organic group which consists of R<_{1> as needed, and reducing a nitro group after that.} In addition, the nitro compound (3-1) and the aliphatic amine compound (3-2) can be obtained easily as a commercial item.

[Formula 11]

[Formula 12]

[Formula 13]

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

When X is an F or Cl atom, and the NO ₂ group is at the 2 or 4 position with respect to X, the dinitro body (3-3) is obtained by reacting an aryl halide with an aliphatic amine compound in the presence of an appropriate base. can

Examples of the base to be used include inorganic bases such as sodium hydrogencarbonate, potassium hydrogencarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate; amines such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, quinoline, and collidine; bases such as sodium hydride and potassium hydride; can be used

As for the solvent, any solvent can be used as long as it does not react with the raw material. For example, aprotic polar organic solvents (N,N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone ( NMP), etc.), ethers (diethyl ether (Et ₂ O), isopropyl ether (i-Pr ₂ O), tert-butylmethyl ether (TBME), cyclopentylmethyl ether (CPME), tetrahydrofuran (THF) ), dioxane, etc.), aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.) , Halogenated hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), nitriles (acetonitrile, propionitrile, butyrate) ronitrile, etc.) can be used. These solvents can be suitably selected in consideration of the easiness of reaction and the like. In this case, the said solvent can be used individually by 1 type or in mixture of 2 or more types. In some cases, the solvent may be dehydrated and dried using an appropriate dehydrating agent or desiccant before use.

Although the reaction temperature can select arbitrary temperatures from the range from -100 degreeC to the boiling point of the solvent used, Preferably it is the range of -50-150 degreeC. Although the reaction time can be arbitrarily selected from the range of 0.1-1000 hours, Preferably it is 0.1-100 hours.

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

When X is a Br or I atom, the NO ₂ group may be in the 2-position, 3-position, or 4-position with respect to X, containing a suitable metal catalyst and a ligand, and using a CN cross-coupling reaction in the presence of a base to dinitrate roche can be obtained.

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

Examples of ligands include triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenyl). Phosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,1'-bis(diphenylphosphino)ferrocene, trimethylphosphite, triethylphosphite, triphenylphosphite, tri-tert- Butylphosphine etc. are mentioned, However, It is not limited to these.

As an example of a base, the above-mentioned base can be used.

The reaction solvent and reaction temperature are in accordance with the above description.

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

In the reaction formula (4), the monovalent organic group composed of _{R 1 may be introduced into the dinitro body (3-3) as needed.}

When R1 is introduced, any compound capable of reacting with amines is sufficient, and examples thereof include acid halides, acid anhydrides, isocyanates, epoxies, oxetanes, aryl halides, and alkyl halides. Moreover, alcohol etc. which substituted the hydroxyl group of alcohol with leaving groups, such as Oms (mesyl group), OTf (triflate group), and OTs (tosyl group), can be used.

Although the method shown below is mentioned as a method of introduce|transducing the monovalent organic group which consists of R<_{1> into the NH group, There is no restriction|limiting in particular.}

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

Examples of acid halides include acetyl chloride, propionic acid chloride, methyl chloroformate, ethyl chloroformate, n-propyl chloroformate, i-propyl chloroformate, n-butyl chloroformate, i-butyl chloroformate, t-butyl chloroformate, and benzyl chloroformate, or chloroformate-9-fluorenyl.

As an example of a base, the above-mentioned base can be used.

The reaction solvent and reaction temperature are in accordance with the above description.

_{R 1} may be introduced by reacting the NH group with an acid anhydride.

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

In order to accelerate the reaction, a catalyst may be added, for example, pyridine, collidine, N,N-dimethyl-4-aminopyridine or the like may be used. A catalyst amount is 0.0001-1 mol, Preferably it is 0.0005-0.2 mol with respect to the usage-amount (1 mol) of dinitro body (3-3).

The reaction solvent and reaction temperature are in accordance with the above description.

You may introduce _R<1> by making isocyanates react with NH group.

Methyl isocyanate, ethyl isocyanate, n-propyl isocyanate, phenyl isocyanate etc. are mentioned as an example of isocyanate.

The reaction solvent and reaction temperature are in accordance with the above description.

_{R 1} may be introduced by reacting the NH group with epoxy compounds or oxetane compounds.

Ethylene oxide, propylene oxide, 1,2-butylene oxide, trimethylene oxide etc. are mentioned as an example of epoxies and oxetanes.

The reaction solvent and reaction temperature are in accordance with the above description.

Moreover, you may introduce|transduce _R<1> into an NH group by making an aryl halide compound react in presence of a metal catalyst, a ligand, and a base.

Examples of the aryl halide include iodobenzene, bromobenzene, and chlorobenzene.

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

Examples of ligands include triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenyl). Phosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,1'-bis(diphenylphosphino)ferrocene, trimethylphosphite, triethylphosphite, triphenylphosphite, tri-tert- Butylphosphine etc. are mentioned, However, It is not limited to these.

As an example of a base, the above-mentioned base can be used.

The reaction solvent and reaction temperature are in accordance with the above description.

In the presence of an appropriate base, alcohols in which the hydroxyl group of the alcohol is substituted with a leaving group such as OMs, OTf, or OTs may be _{reacted to introduce R 1 into the NH group.}

Examples of alcohols include methanol, ethanol, 1-propanol, and the like. By reacting these alcohols with methanesulfonyl chloride, trifluoromethanesulfonyl chloride, paratoluenesulfonic acid chloride, etc., OMs, OTf, An alcohol substituted with a leaving group such as OTs can be obtained.

As an example of a base, the above-mentioned base can be used.

The reaction solvent and reaction temperature are in accordance with the above description.

_{R 1} may be introduced into the NH group by reacting the alkyl halide in the presence of an appropriate base.

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

As examples of the base, in addition to the above-mentioned base, metal alkoxides such as potassium-tert-butoxide and sodium-tert-butoxide can be used.

The reaction solvent and reaction temperature are in accordance with the above description.

Next, in the said reaction formula (5), the nitro group in the obtained dinitro body (4-1) can be reduced, and the objective diamine (5-1) can be obtained. A palladium carbon powder, a platinum carbon powder, etc. can be used for the reduction|restoration of a nitro group. The reduction reaction is carried out in a hydrogen atmosphere, under normal pressure or under pressure.

Moreover, you may reduce|reduce a nitro group using metals, such as Fe, Sn, Zn, or these metal salts together with a proton source. In addition, the said metal and a metal salt may be used individually or in mixture of two or more.

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

As long as the solvent can withstand the environment under a reducing atmosphere, aprotic polar organic solvents (DMF, DMSO, DMAC, NMP, etc.), ethers (Et ₂ O, i-Pr ₂ O, TBME, CPME, THF) , dioxane), aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.), Lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), nitriles (acetonitrile, propionitrile, butyronitrile, etc.), alcohols (methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, etc.) can be used.

These solvents can be suitably selected in consideration of the easiness of reaction, etc., and can be used individually by 1 type or in mixture of 2 or more types. In some cases, the solvent may be dehydrated and dried using an appropriate dehydrating agent or desiccant before use.

Although the reaction temperature can select arbitrary temperatures from the range from -100 degreeC to the boiling point of the solvent used, Preferably it is the range of -50-150 degreeC.

Although the reaction time can be arbitrarily selected from the range of 0.1-1000 hours, Preferably it is 0.1-100 hours.

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

recipe [2]

By reacting a nitro compound ((3-1) or (6-1)) with an aliphatic amine compound (6-2) protected with a protecting group, a nitro compound ((6-3), or (6-4)) to get Then, after performing deprotection, the following dinitro body ((8-1) or (8-2)) is obtained by making a nitro compound ((3-1) or (6-1)) react. Moreover, the target diamine can be obtained by introduce|transducing the monovalent organic group represented _{by R<1>} into NH group by the method similar to manufacturing method [1], and reducing a nitro group after that if needed.

The nitro compound (6-1) and the aliphatic amine compound (6-2) protected by a protecting group can be easily obtained as a commercial item.

In the following Reaction Scheme (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 when r is 2 or more, a plurality of R ₃ are each independently has the above definition.

Pro represents a protecting group, acetyl group, trifluoroacetyl group, pivaloyl group, tert-butoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonyl group, 2,2,2-trichloroethoxycarbonyl group, benzyloxycarbonyl group, Trimethylsilyl group, triethylsilyl group, dimethylphenylsilyl group, tert-butyldimethylsilyl group, tert-butyldiethylsilyl group, 9-fluorenylmethyloxycarbonyl group, phthaloyl group, allyloxycarbonyl group, p-toluenesulfo group nyl group, o-nitrobenzenesulfonyl group, etc. are shown.

The synthesis method of the nitro compound ((6-3) or (6-4)) uses 1 equivalent or more of the nitro compound ((3-1), or (6-1)), the reaction scheme (3) of the manufacturing method [1] ) can be carried out in the same way as It is preferable that the protecting group is not deprotected depending on the basic conditions, and a tert-butoxycarbonyl group is preferable from the viewpoint of ease of deprotection after reaction and availability.

[Formula 14]

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

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

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 include inorganic bases such as sodium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate and cesium carbonate, trimethylamine, triethylamine, tripropylamine, triisopropyl You may use organic amines, such as an amine, tributylamine, diisopropylethylamine, a pyridine, a quinoline, and collidine.

Moreover, you may perform deprotection using Lewis acid compounds, such as aluminum chloride and a trifluoroborane- diethyl ether complex. However, the debenzylation reaction in a hydrogen atmosphere is not preferable because reduction of the aromatic nitro group to the amino group occurs.

As for the solvent, any solvent that does not interfere with hydrolysis can be used. For example, aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.), ethers (Et ₂ O, i-Pr ₂ O, TBME, CPME, THF, dioxane, etc.), aliphatic hydrocarbons (pentane) , hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.), halogen-based hydrocarbons (chloroform, dichloromethane, 4 Carbon chloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), nitriles (acetonitrile, propionitrile, butyronitrile, etc.), alcohols (methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, etc.), or water. These solvents can be suitably selected in consideration of the easiness of reaction, etc., and can be used individually by 1 type or in mixture of 2 or more types.

In consideration of the use of a Lewis acid or the like, depending on the solvent, an appropriate dehydrating agent or drying agent may be used to dehydrate and dry the use.

Although the reaction temperature can select arbitrary temperatures from the range from -100 degreeC to the boiling point of the solvent used, Preferably it is the range of -50-150 degreeC.

Although the reaction time can be arbitrarily selected from the range of 0.1-1000 hours, Preferably it is 0.1-100 hours.

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

[Formula 15]

With respect to the intermediate ((7-1) or (7-2)), 1 equivalent or more of the nitro compound ((3-1) or (6-1)) is used, and the reaction scheme (3) of the manufacturing method [1] and In the same manner, the dinitro body ((8-1) or (8-2)) can be obtained (Scheme (8)).

[Formula 16]

_{The method of introduce|transducing R<1>} into the obtained dinitro body ((8-1) or (8-2)) as needed should just be reaction conditions similar to the reaction formula (4) of manufacturing method [1]. Then, the target diamine can be obtained by reducing a nitro group.

What is necessary is just to implement the reduction method of a dinitro body on reaction conditions similar to reaction formula (5) of manufacturing method [1].

2. Polyimide precursors and polyimides

The polyimide precursor of this invention is a polyimide precursor obtained by reaction of the diamine component containing the diamine represented by Formula (1), and a tetracarboxylic-acid derivative component. Here, a polyimide precursor is a polyamic acid or polyamic acid ester.

Examples of the tetracarboxylic acid derivative include acid dianhydride, dicarboxylic acid diester, and diester dicarboxylic acid chloride.

A polyamic acid is obtained by making a diamine component and acid dianhydride react, and polyamic acid ester is obtained by reaction of a diamine component, dicarboxylic acid diester, or diester dicarboxylic acid chloride.

The polyimide of this invention is a polyimide obtained by ring-closing these polyimide precursors, All are useful as a polymer for obtaining a liquid crystal aligning film.

The diamine component for obtaining the said polyimide precursor WHEREIN: Although there is no restriction|limiting in the content rate of the diamine represented by Formula (1), The effect of this invention is easy to be acquired by many. As for the ratio of the diamine represented by Formula (1), 10-100 mol% is preferable with respect to 1 mol of all the diamine components, More preferably, it is 20-100 mol%, More preferably, it is 30-100 mol%.

It is preferable that the polyimide precursor of this invention is a polymer containing the structural unit represented by following formula (9).

[Formula 17]

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 the diamine of Formula (1), and R ₄ is a hydrogen atom or carbon number. It is an alkyl group of 1-5. From the viewpoint of easiness of imidation by heating, R ₄ is preferably a hydrogen atom, a methyl group, or an ethyl group.

X ₁ is not particularly limited as long as it is a tetravalent organic group. Two or more types of X<_{1> may be mixed in a polyimide precursor.}

If the specific example of X<_1> is shown, the structure of following formula (X-1) - (X-43) will be mentioned. From the viewpoint of availability, (X-1) to (X-14) are more preferable.

[Formula 18]

[Formula 19]

[Formula 20]

_{R 5} to R ₈ in the formula (X-1) are each independently 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 It is a phenyl group. Since R ₅ ~ R ₈ is it likely to lower the liquid crystal orientation when the volume of the large structure, is a hydrogen atom, a methyl group, or ethyl group, and more preferably, it is a hydrogen atom, or methyl group, especially preferable.

Moreover, the polyimide precursor of this invention is the range which does not impair the effect of this invention other than said Formula (9). WHEREIN: The structural unit represented by following formula (10) may be included.

[Formula 21]

In the formula (10), R ₄ is the same as defined in the formula (9). X ₂ is a tetravalent organic group, and it is the same as that _{of X 1} and the definition in said Formula (9) including a preferable example. Z ₁ and Z ₂ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, 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 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, a bicyclohexyl group, etc. can be heard

Examples of the alkenyl group having 2 to 10 carbon atoms include those in which one or more CH ₂ -CH ₂ present in the alkyl group is substituted with CH=CH. More specifically, vinyl group, allyl group, 1-propenyl group, isopropenyl group, 2-butenyl group, 1,3-butadienyl group, 2-pentenyl group, 2-hexenyl group, cyclopropenyl group, cyclopentene group A nyl group, a cyclohexenyl group, etc. are mentioned.

Examples of the alkynyl group having 2 to 10 carbon atoms include those in which one or more CH ₂ -CH ₂ present in the alkyl group is substituted with C≡C. More specifically, an ethynyl group, 1-propynyl group, 2-propynyl group, etc. are mentioned.

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 may have a substituent within the range in which the total number of carbon atoms, including the substituent, does not exceed 10, and further You may form ring structure with a substituent. In addition, the formation of a ring structure by a substituent means that substituents or a substituent and a part of the parent skeleton couple|bond 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 organooxy group, an organothio group, an organosilyl group, an acyl group, an ester group, a thioester group, a phosphoric acid ester group, an amide group, an alkyl group. , an alkenyl group, an alkynyl group, and the like.

Polyimide precursor WHEREIN: When introduce|transducing a bulky structure generally, since the reactivity of an amino group and liquid-crystal orientation may be reduced, as Z<_1> and Z<_2> , C1-C5 which may have a hydrogen atom or a substituent An alkyl group of is more preferable, and a hydrogen atom, a methyl group or an ethyl group is particularly preferable.

In said Formula (10), Y<_2> is a divalent organic group derived from diamine components other than Formula (1), The structure is not specifically limited. If the specific example of Y<_2> is given, following formula (Y-1) - (Y-114) will be mentioned. Moreover, 2 or more types may be sufficient as a diamine component.

[Formula 22]

[Formula 23]

[Formula 24]

[Formula 25]

[Formula 26]

[Formula 27]

[Formula 28]

Especially, in order to acquire favorable liquid-crystal orientation, it is preferable to use the diamine which forms a polyimide with high linearity. Therefore, in the liquid crystal alignment points, Y is _2, 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, It is preferably Y-72, Y-73, Y-74, Y-75 or Y-98.

Preferably the ratio of the said diamine is 40-100 mol% with respect to 1 mol of all the diamine components, More preferably, it is 60-100 mol%.

Moreover, when making a pretilt angle high, it is preferable to use for a side chain the diamine which has a long-chain alkyl group, an aromatic ring, an aliphatic ring, steroid skeleton, or the structure which combined these. In terms of the 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 desirable. An arbitrary pretilt angle can be expressed by adding 1-50 mol% of these diamines, More preferably, 5-20 mol% of all the diamine components.

3. Manufacturing method of polyamic acid

The polyamic acid which is a polyimide precursor of this invention can be obtained by making the diamine component containing the diamine of this invention, and a tetracarboxylic-acid derivative component react.

Specifically, it is compoundable by making tetracarboxylic dianhydride and diamine react in presence of an organic solvent.

As an organic solvent, if the produced|generated polyamic acid melt|dissolves, it will not specifically limit. Specific examples include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, and γ-butyrolactone. Moreover, when the solubility of a polyimide precursor is high, methyl ethyl ketone, cyclohexanone, a cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or a following formula (D-1) - a formula (D- The organic solvent represented by 3) can be used.

[Formula 29]

In formula (D-1), D ¹ represents an alkyl group having 1 to 3 carbon atoms, in formula (D-2), D ² represents an alkyl group having 1 to 3 carbon atoms, and in formula (D-3), D ³ represents a C1-C4 alkyl group.

These may be used independently and may be mixed and used. Furthermore, even if it is a solvent in which a polyamic acid is not dissolved independently, you may use it in the range in which the produced|generated polyamic acid does not precipitate, mixing with the said solvent. Moreover, since the water|moisture content in an organic solvent inhibits a polymerization reaction and becomes a cause of hydrolyzing the produced|generated polyamic acid by extension, it is preferable to use the thing which dehydrated and dried as much as possible as an organic solvent.

As a method of mixing a diamine component and tetracarboxylic dianhydride in an organic solvent, a solution in which diamine is dispersed or dissolved in an organic solvent is stirred, and tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent as it is or The method of adding, the method of adding diamine to the solution which disperse|distributed or dissolved tetracarboxylic dianhydride in the organic solvent, the method of adding tetracarboxylic dianhydride and diamine to the organic solvent alternately or simultaneously, etc. are mentioned. and any of these methods may be used.

Although the temperature at the time of the synthesis|combination of a polyamic acid can select the arbitrary temperature of -20-150 degreeC, Preferably it is the range of -5-100 degreeC, More preferably, it is 0-80 degreeC.

Moreover, although reaction time can be arbitrarily selected from the range longer than the time for which superposition|polymerization of a polyamic acid stabilizes, Preferably it is 30 minutes - 24 hours, More preferably, they are 1 to 12 hours.

Although the reaction can be carried out at any concentration, when the concentration of the diamine component and tetracarboxylic dianhydride as raw materials is too low, it becomes difficult to obtain a high molecular weight polymer, and when the concentration is too high, the viscosity of the reaction solution is too high. Since it becomes high and uniform stirring becomes difficult, Preferably it is 1-50 mass %, More preferably, it is 5-20 mass %. The reaction initial stage may be performed at high concentration, and you may add an organic solvent after that.

Synthesis reaction of a polyamic acid WHEREIN: It is preferable that ratio of the number of moles of tetracarboxylic dianhydride with respect to the number of moles of a diamine component is 0.8-1.2. As in a typical polycondensation reaction, the closer this molar ratio to 1.0, the greater the molecular weight of the produced polyamic acid.

The polyamic acid obtained as mentioned above can precipitate and collect|recover a polymer by inject|pouring into a poor solvent, stirring a reaction solution well. Moreover, after performing precipitation for several times and washing|cleaning with a poor solvent, the powder of the refined polyamic acid can be obtained by making it normal temperature or heat-drying.

Although the poor solvent is not specifically limited, Water, methanol, ethanol, 2-propanol, hexane, a butyl cellosolve, acetone, toluene, etc. are mentioned, Water, methanol, ethanol, 2-propanol, etc. are preferable.

4. Preparation of polyamic acid ester

The polyamic acid ester which is a polyimide precursor of this invention can be manufactured by the manufacturing method of [1], [2], or [3] shown below.

[1] In case of manufacturing from polyamic acid

Polyamic acid ester can be manufactured by esterifying the polyamic acid manufactured as mentioned above.

Specifically, the polyamic acid and the esterification agent are reacted in the presence of an organic solvent at -20 to 150°C, preferably at 0 to 50°C, for 30 minutes to 24 hours, preferably for 1 to 4 hours. can

The esterifying agent is preferably one that can be easily removed by purification, and includes N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dimethylformamide dipropyl acetal, N,N-dimethylformamide dineopentylbutyl acetal, N,N-dimethylformamide di-t-butyl acetal, 1-methyl-3-p-tolyltriazine, 1-ethyl-3-p-tolyltriazine , 1-propyl-3-p-tolyltriazine, 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride, and the like. As for the addition amount of an esterification agent, 2-6 molar equivalent is preferable with respect to 1 mol of repeating units of a polyamic acid.

Examples of the organic solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide or 1,3-dimethyl-imidazolidinone. Moreover, when the solubility to the solvent of a polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or said Formula (D-1) - The solvent represented by Formula (D-3) can be used.

A solvent may be used independently and may be mixed and used for it. Moreover, even if it is a solvent in which a polyimide precursor is not dissolved, you may use it in the range in which the produced|generated polyimide precursor does not precipitate, mixing with the said solvent. Moreover, since the water|moisture content in a solvent inhibits a polymerization reaction and becomes a cause to hydrolyze the produced|generated polyimide precursor by extension, it is preferable to use what was dehydrated and dried as a solvent.

The solvent used for the reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone from the viewpoint of polymer solubility, and these are one type or a mixture of two or more types. You may use it. As for the density|concentration at the time of manufacture, from the point which polymer precipitation does not occur easily and a high molecular weight body is easy to obtain, 1-30 mass % is preferable, and its 5-20 mass % is more preferable.

[2] When prepared by reaction of tetracarboxylic acid diester dichloride with diamine

Polyamic acid ester can be manufactured from the diamine component containing tetracarboxylic-acid diester dichloride and the diamine of this invention.

Specifically, tetracarboxylic-acid diester dichloride and diamine are -20-150 degreeC in presence of a base and an organic solvent, Preferably it is 0-50 degreeC for 30 minutes - 24 hours, Preferably 1 - It can manufacture by making it react for 4 hours.

As the base, although pyridine, triethylamine, 4-dimethylaminopyridine, etc. can be used, pyridine is preferable because the reaction proceeds mildly. The addition amount of the base is a quantity that can be easily removed, and is preferably 2 to 4 moles, and more preferably 2 to 3 moles, relative to the tetracarboxylic acid diester dichloride from the viewpoint of being easy to obtain a high molecular weight product.

As for the solvent used for the said reaction, N-methyl- 2-pyrrolidone or (gamma)-butyrolactone is preferable from a monomer and polymer solubility point, and these may be used 1 type or in mixture of 2 or more types. .

The polymer concentration at the time of production is preferably from 1 to 30 mass%, more preferably from 5 to 20 mass%, from the viewpoint that polymer precipitation does not occur easily and a high molecular weight body is easily obtained.

Moreover, in order to prevent hydrolysis of tetracarboxylic-acid diester dichloride, it is preferable that the solvent used for manufacture of polyamic acid ester is dehydrated as much as possible, and it is preferable to prevent mixing of external air in nitrogen atmosphere.

[3] When prepared from tetracarboxylic acid diester and diamine

Polyamic acid ester can be manufactured by polycondensing the diamine component containing tetracarboxylic-acid diester and the diamine of this invention.

Specifically, tetracarboxylic-acid diester and diamine are 0-150 degreeC in presence of a condensing agent, a base, and an organic solvent, Preferably 0-100 degreeC WHEREIN: 30 minutes - 24 hours, Preferably 3 It can manufacture by making it react for -15 hours.

Examples of the condensing agent include triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, N,N'-carbonyldiimidazole, dimethoxy-1, 3,5-triazinylmethylmorpholinium, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate, O-(benzotriazole-1 -yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzooxazolyl)phosphonic acid diphenyl, etc. can be used. have. 2-3 times mole is preferable with respect to tetracarboxylic-acid diester, and, as for the addition amount of a condensing agent, 2-2.5 times mole is more preferable.

As the base, tertiary amines such as pyridine and triethylamine can be used. 2-4 times mole is preferable with respect to a diamine component, and, as for the addition amount of a base, it is a quantity with easy removal, and from the point which a high molecular weight body is easy to obtain, 2.5-3.5 times mole is more preferable.

Moreover, in the said reaction, reaction advances efficiently by adding a Lewis acid as an additive. As a Lewis acid, lithium halides, such as lithium chloride and lithium bromide, are preferable. 0-1.0 times mole is preferable with respect to a diamine component, and, as for the addition amount of a Lewis acid, 0-0.7 times mole is more preferable.

Among the manufacturing methods of said three polyamic acid esters, since high molecular weight polyamic acid ester is obtained, the manufacturing method of said [1] or said [2] is especially preferable.

A polymer can be deposited by inject|pouring into a poor solvent, stirring well the solution of polyamic acid ester obtained by doing as mentioned above. After performing precipitation several times and washing|cleaning with a poor solvent, it can dry by normal temperature or heat and can obtain the refined powder of polyamic acid ester. Although the poor solvent is not specifically limited, Water, methanol, ethanol, hexane, a butyl cellosolve, acetone, toluene, etc. are mentioned.

5. Method for producing polyimide

The polyimide used for this invention can be manufactured by imidating the said polyimide precursor.

The polyimide of this invention WHEREIN: The ring closure rate (imidization rate) of an amic acid group or an amic acid ester group does not necessarily need to be 100 %, What is necessary is just to adjust arbitrarily according to a use and the objective.

As a method of ring-closing a polyimide precursor, the thermal imidation which heats a polyimide precursor without using a catalyst, and catalyst imidation using a catalyst are mentioned.

When the polyimide precursor is thermally imidized, the solution of the polyimide precursor is heated to 100 to 400 ° C, preferably 120 to 250 ° C, and water or alcohol generated by the imidization reaction is removed outside the system. it is preferable to

Catalyst imidation of a polyimide precursor is -20-250 degreeC, adding a basic catalyst and an acid anhydride to the solution of a polyamic acid, Preferably it can perform by stirring at 0-180 degreeC. The quantity of a basic catalyst is 0.5-30 mole times of an amic acid group, Preferably it is 2-20 mole times, and the quantity of an acid anhydride is 1-50 mole times of an amic acid group, Preferably it is 3-30 mole times.

Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine, and among them, pyridine is preferable because it has suitable basicity to advance the reaction.

Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride, and among these, acetic anhydride is preferably used because purification after completion of the reaction becomes easy. The imidation rate by catalytic imidation can be controlled by adjusting the catalyst amount, reaction temperature, and reaction time.

When recovering the polymer component from the polyimide reaction solution, the reaction solution may be poured into a poor solvent for precipitation. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. It is preferable that the polymer injected|thrown-in to the poor solvent and precipitated is filtered and collect|recovered, Then, it is normal temperature or under normal pressure or reduced pressure, to heat, and to make it dry.

6. Liquid crystal aligning agent

A liquid crystal aligning agent is a coating liquid for producing a liquid crystal aligning film, The main component is a composition containing the resin component for forming a resin film, and the organic solvent in which this resin component is dissolved. The at least 1 sort(s) of polymer chosen from the group which consists of polyimide obtained by ring-closing an above-described polyimide precursor and this polyimide precursor as a resin component is used for the liquid crystal aligning agent of this invention.

The density|concentration of the polymer in a liquid crystal aligning agent can be suitably changed with thickness setting of the coating film which you want to form. It is preferable that it is 1 mass % or more from the point of forming a uniform and defect-free coating film, and it is preferable to set it as 10 mass % or less from the point of storage stability of a solution. A particularly preferable concentration of the polymer is 2 to 8% by mass.

As for the resin component in a liquid crystal aligning agent, all may be the polymer of this invention, and other polymers other than the polymer of this invention may be mixed. As such another polymer, the polyimide precursor or polyimide obtained using diamines other than what is represented by Formula (1) as a diamine component is mentioned.

The organic solvent contained in a liquid crystal aligning agent will not be specifically limited if a polymer component melt|dissolves uniformly. Specific examples thereof include N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone Don, N-methylcaprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl sulfoxide, dimethyl sulfone, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, 3- and methoxy-N,N-dimethylpropanamide. You may use these 1 type or in mixture of 2 or more types. Moreover, even if it is a solvent which cannot melt|dissolve a polymer component uniformly independently, if it is a range in which a polymer does not precipitate, you may mix with the said organic solvent.

A liquid crystal aligning agent may contain the solvent for improving the coating-film uniformity at the time of apply|coating a liquid crystal aligning agent to a board|substrate other than the organic solvent for melt|dissolving a polymer component. As such a solvent, a solvent having a lower surface tension than the organic solvent is generally used. Specific examples thereof include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 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, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl Ester etc. are mentioned. These solvents may use 2 or more types together.

The said solvent turns into a poor solvent with low solubility of resin. It is preferable that these solvents are 5-60 mass % of the organic solvent contained in a liquid-crystal aligning agent, More preferably, it is 10-50 mass %.

In the liquid crystal aligning agent, as long as the effect of the present invention is not impaired other than the above, a dielectric or conductive material for the purpose of changing electrical properties such as a polymer other than the polymer of the present invention, a dielectric constant or conductivity of the liquid crystal aligning film, a liquid crystal aligning film and a substrate A silane coupling agent for the purpose of improving the adhesion of a crosslinking compound for the purpose of increasing the hardness and density of the film when it is used as a liquid crystal aligning film, and furthermore, for the purpose of efficiently advancing imidization of a polyimide precursor when baking a coating film You may add an imidation accelerator etc.

When a crosslinkable compound such as a functional silane-containing compound or an epoxy group-containing compound is contained, the amount thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, particularly with respect to 100 parts by mass of the resin component. Preferably it is 1-10 mass parts.

7. Manufacturing method of liquid crystal aligning film

A liquid crystal aligning film is a film|membrane obtained by apply|coating the said liquid crystal aligning agent to a board|substrate, drying and baking.

It will not specifically limit if it is a board|substrate with high transparency as a board|substrate which apply|coats a liquid crystal aligning agent, Plastic substrates, such as a glass substrate, a silicon nitride board|substrate, an acryl board|substrate, a polycarbonate board|substrate, etc. can be used. In particular, it is preferable from a viewpoint of process simplification to use the board|substrate with which the ITO electrode etc. for liquid crystal drive were formed.

Moreover, in a reflection type liquid crystal display element, if it is only one side board|substrate, even opaque things, such as a silicon wafer, can be used, and a material which reflects light, such as aluminum, can also be used for the electrode in this case.

As a coating method of a liquid crystal aligning agent, the spin coating method, the printing method, the inkjet method, etc. are mentioned. In addition, as a method of using a coating liquid, there exist a dip, a roll coater, a slit coater, a spinner, etc., You may use these according to the objective.

Drying after apply|coating a liquid crystal aligning agent, and a baking process can select arbitrary temperature and time. Usually, in order to fully remove the organic solvent contained, it is 50-120 degreeC, Preferably it is 50-80 degreeC, 1 to 10 minutes, Preferably it is 3 to 5 minutes, It dries, and 150-300 degreeC after that, Preferably Preferably, it is 200-240 degreeC, 5-120 minutes, Preferably it bakes for 10-40 minutes.

Although the thickness of the coating film after baking is not specifically limited, Since reliability of a liquid crystal display element may fall when it is too thin, it is 5-300 nm, Preferably it is 10-200 nm.

As a method of orientating the obtained liquid crystal aligning film, the rubbing method, the photo-alignment processing method, etc. are mentioned. A rayon cloth, a nylon cloth, a cotton cloth, etc. can be used for a rubbing process. Since it is difficult for the liquid crystal aligning film for vertical alignment to obtain a uniform orientation state by a rubbing process, when using it as a liquid crystal aligning agent for vertical alignment, it can also be used, without rubbing.

As a specific example of the photo-alignment treatment method, the coating film surface is irradiated with radiation deflected in a certain direction, and in some cases, heat treatment is further performed at a temperature of 150 to 250 ° C., and a method of imparting liquid crystal alignment ability. can As the radiation, ultraviolet rays and visible rays having a wavelength of 100 to 800 nm can be used. Among these, the ultraviolet-ray which has a wavelength of 100-400 nm is preferable, and what has a wavelength of 200-400 nm is especially preferable.

Moreover, in order to improve liquid-crystal orientation, you may irradiate a radiation, heating a coating-film board|substrate at 50-250 degreeC.

The radiation dose is preferably from 1 to 10,000 mJ/cm 2 , and particularly preferably from 100 to 5,000 mJ/cm 2 . The liquid crystal aligning film produced as mentioned above can orientate a liquid crystal molecule stably in a fixed direction.

In the above, you may contact-process the film|membrane which irradiated the polarized radiation with the solvent containing at least 1 type selected from water and an organic solvent then.

The solvent used for the contact treatment is not particularly limited as long as it is a solvent that dissolves the decomposition product produced by light irradiation. Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate. , diacetone alcohol, 3-methoxy methyl propionate, 3-ethoxy ethyl propionate, propyl acetate, butyl acetate, cyclohexyl acetate, etc. are mentioned. These solvents may use 2 or more types together.

From the viewpoint of versatility and safety, at least one selected from the group consisting of water, 2-propanol, 1-methoxy-2-propanol and ethyl lactate is more preferable. Particular preference is given to 1-methoxy-2-propanol or ethyl lactate.

In the present invention, the contact treatment of the film irradiated with polarized radiation and the solution containing the organic solvent is preferably performed by a treatment in which the film and the liquid are sufficiently contacted, such as immersion treatment and spraying (spray) treatment. Especially, the method of immersing a film|membrane in the solution containing an organic solvent, Preferably it is 10 second - 1 hour, More preferably, it is 1 to 30 minutes is preferable. Although normal temperature or heating may be sufficient as a contact process, Preferably it is 10-80 degreeC, More preferably, it is 20-50 degreeC. Moreover, if necessary, a means for increasing the contact such as an ultrasonic wave can be provided.

After the contact treatment, for the purpose of removing the organic solvent in the used solution, either rinsing (rinsing) or drying with a low-boiling solvent such as water, methanol, ethanol, 2-propanol, acetone, or methyl ethyl ketone, or both, or both. should be carried out.

In addition, you may heat the film|membrane which performed the contact process with a solvent at 150 degreeC or more for the purpose of drying the solvent and reorientation of the molecular chains in a film|membrane.

As temperature of heating, 150-300 degreeC is preferable. Although the reorientation of molecular chains is accelerated|stimulated so that a temperature is high, when the temperature is too high, there exists a possibility of accompanying decomposition of a molecular chain. Therefore, as heating temperature, 180-250 degreeC is more preferable, and 200-230 degreeC is especially preferable.

When the heating time is too short, the effect of the present invention may not be obtained, and if too long, the molecular chain may be decomposed. Therefore, 10 seconds to 30 minutes are preferable, and 1 to 10 minutes are more preferable.

8. Liquid crystal display element

After obtaining the board|substrate with the liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention, a liquid crystal display element produces a liquid crystal cell by a known method, and sets it as a liquid crystal display element using the liquid crystal cell.

As an example of the manufacturing method of a liquid crystal cell, the liquid crystal display element of a passive matrix structure is taken as an example and demonstrated. Moreover, the liquid crystal display element of the active matrix structure in which switching elements, such as TFT (Thin Film Transistor) was provided in each pixel part which comprises an image display may be sufficient.

First, a transparent glass substrate is prepared, a common electrode is formed on one substrate, and a segment electrode is formed on the other substrate. These electrodes can be made into an ITO electrode, for example, and are patterned so that a desired image display may be possible. Next, an insulating film is formed on each substrate so as to cover the common electrode and the segment electrode. The insulating film can be, for example, a film made of _{SiO 2} -TiO _{2 formed by a sol-gel method.}

Next, on each board|substrate, the liquid crystal aligning film of this invention is formed. Next, the other board|substrate is superimposed on one board|substrate so that the mutual orientation film|membrane surfaces may oppose, and the periphery is adhere|attached with a sealing material. In order to control a board|substrate clearance gap, a spacer is usually mixed in a sealing material. Moreover, it is preferable to spread|disperse the spacer for board|substrate gap|interval control also to the in-plane part which does not form a sealing material. An opening in which liquid crystal can be filled from the outside is formed in a part of the sealing material.

Next, a liquid crystal material is inject|poured into the space surrounded by the board|substrate of 2 sheets and the sealing material through the opening part formed in the sealing material. After that, this opening is sealed with an adhesive. A vacuum injection method may be used for injection|pouring, and the method which utilized the capillary phenomenon in air|atmosphere may be used. Moreover, after drawing a sealing material on a board|substrate, a liquid crystal can also be filled by dripping a liquid crystal and bonding together under reduced pressure.

As the liquid crystal material, either a positive liquid crystal material or a negative liquid crystal material may be used. Even when voltage retention uses the negative liquid crystal material lower than the positive liquid crystal material in particular, when the liquid crystal aligning film of this invention is used, it will be excellent in an afterimage characteristic.

Next, a polarizing plate is installed. Specifically, a pair of polarizing plates are affixed to the surface on the opposite side to the liquid crystal layer of two board|substrates. The liquid crystal display element of this invention is obtained by passing through the above process. Since this liquid crystal display element uses the liquid crystal aligning film obtained by the manufacturing method of the liquid crystal aligning film of this invention as a liquid crystal aligning film, it becomes the thing excellent in an afterimage characteristic, and a high-definition multifunctional mobile phone (smartphone) and tablet personal computer , a liquid crystal television, and the like.

Example

Hereinafter, although an Example etc. are given and demonstrated concretely about this invention, this invention is not limited to these Examples. In addition, the abbreviation of a compound and a solvent is as follows.

[Formula 30]

Boc: tert-butoxycarbonyl group

BCS : Butyl Cellosolve

(Example 1)

Synthesis of (DA-1)

[Formula 31]

Dimethylformamide (390 g), 4-fluoronitrobenzene (65.0 g, 0.461 mol), 4-aminomethylpiperidine (25.0 g, 0.219 mol), and potassium carbonate (90.9 mol) in a 4-neck flask under nitrogen atmosphere g, 0.658 mol) was added, and it was made to react at 60 degreeC. After 22 hours of heating and stirring, disappearance of the intermediate was confirmed by HPLC. Then, potassium carbonate was removed by filtration, and also potassium carbonate was wash|cleaned twice with 250 g of dimethylformamides. The obtained solution was distilled off under reduced pressure until the contents were 295 g, and then 1.50 kg of water was added to precipitate compound (11). Then, the precipitate was collect|recovered by filtration, and it dried and obtained the crude substance of compound (11). The obtained crude was recrystallized from tetrahydrofuran and purified to obtain compound (11) as a yellow solid (58.8 g, 0.165 mol, yield 75.3%).

HPLC measurement; Shimadzu Corporation Prominence Series,

NMR measurement;

Device: Varian NMR System 400 NB (400 MHz)

Reference material: tetramethylsilane (TMS) (δ = 0.0 ppm)

The structure of compound (11) was confirmed by obtaining the following spectral data by ^{1 H-NMR analysis.}

Also about the compound obtained by the subsequent synthesis|combination, the structure was confirmed by <^{1>H-NMR analysis similarly to compound (11).}

[Formula 32]

In a nitrogen atmosphere, 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 four-necked flask, , and heated to 50 °C. A liquid mixture of di-tert-butyl dicarbonate (15.3 g, 0.0699 mol) and 15.0 g of tetrahydrofuran was added dropwise to the solution and reacted for 24 hours. Thereafter, it was confirmed that the raw material had disappeared by HPLC. Subsequently, the contents were distilled off under reduced pressure, and then recrystallized from toluene. The precipitated crystals were collected by filtration and dried to obtain compound (12) as a yellow solid in a yield of 87.3% (22.3 g, 0.0489 mol).

[Formula 33]

In a nitrogen atmosphere, after adding tetrahydrofuran (447 g), compound (12) (22.3 g, 0.0489 mol), and palladium carbon powder (1.16 g) to a four-neck flask, the inside of the flask was replaced with a hydrogen atmosphere, The mixture was stirred at room temperature for 23 hours. Thereafter, it was confirmed that the raw material had disappeared by HPLC. Then, palladium carbon was filtered, and the obtained solution was distilled off under reduced pressure, and the crude substance was obtained. Chloroform (206 g) was added to the obtained crude, and the mixture was heated to 60°C. Then, liquid separation operation was repeated twice with 60 degreeC water (100g). After adding and stirring activated carbon (0.754 g) to the obtained organic layer, the activated carbon was removed by filtration. The contents were concentrated and recrystallized from toluene. Then, it dried and obtained the target substance (DA-1) of a pale cream solid with a yield of 71.3% (13.8 g, 0.0349 mol).

(Example 2)

Synthesis of (DA-2)

[Formula 34]

In a nitrogen atmosphere, tetrahydrofuran (534 g), compound (11) obtained in (Example 1) (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 heated up at 40°C. After reacting for 24 hours, methyl iodide (10.2 g, 0.0717 mol) and potassium-tert-butoxide (2.98 g, 0.0266 mol) were further added, and it was confirmed by HPLC that the raw material had disappeared. Thereafter, 100 g of water was added to stop the reaction. 500 g of water was added to the crude substance obtained by distilling off the reaction liquid under reduced pressure, stirring was performed in a slurry state for 24 hours, solid was filtered and dried. Then, it recrystallized from tetrahydrofuran, and obtained the compound (13) of a yellow solid in yield 78.2% (17.4 g, 0.0470 mol).

[Formula 35]

In a nitrogen atmosphere, after adding tetrahydrofuran (697 g), compound (13) (17.4 g, 0.0470 mol), and palladium carbon powder (0.930 g) to a four-neck flask, the inside of the flask was replaced with a hydrogen atmosphere, It stirred at 60 degreeC for 40 hours. Thereafter, it was confirmed that the raw material had disappeared by HPLC. Then, the solution obtained by filtering palladium carbon was distilled off under reduced pressure, and the crude substance was obtained. 450 g of ethyl acetate was added to the obtained crude substance, and liquid separation operation was repeated twice with 450 g of water. After adding and stirring activated carbon (0.739 g) to the obtained organic layer, the activated carbon was removed by filtration. The resulting filtrate was concentrated, and the crude product was recrystallized from toluene. Subsequently, the crystals were dried to obtain the target product (DA-2) as a pale purple solid in a yield of 71.6% (10.5 g, 0.0337 mol).

(Comparative Example 1)

Synthesis of (DA-4)

[Formula 36]

Dimethylformamide (144 g), potassium carbonate (65.6 g, 0.475 mol), 4-fluoronitrobenzene (33.5 g, 0.237 mol), and 4-hydroxypiperidine (24.0) in a 4-neck flask under nitrogen atmosphere g, 0.237 mol) and stirred at 80°C for 16 hours. Thereafter, the inorganic salt was removed by filtration under reduced pressure, and the filtrate was diluted with ethyl acetate (288 g). Then, the organic phase was washed 3 times with pure water (288 g) and dehydrated with sodium sulfate. Then, it concentrated to dryness and obtained 45.5 g (0.205 mol, yield 86.3%, yellow solid) of compound (14).

[Formula 37]

Sodium hydride (60 mass %, liquid paraffin dispersion) (3.24 g, 0.0810 mol) was inject|poured into the 4-necked flask under nitrogen atmosphere, and tetrahydrofuran (30.0 g) was added. Then, the solution which melt|dissolved compound [6] (15.0 g, 0.0675 mol) in tetrahydrofuran (120 g) was dripped over 10 minutes, stirring with ice. Then, 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. Thereafter, ethyl acetate (300 g) and pure water (300 g) were added, and the precipitated crystals were slurry washed at room temperature, and the crystals were filtered under reduced pressure. Then, the obtained crystal|crystallization was taken out, ethyl acetate (300g) and pure water (300g) were further added, and slurry washing|cleaning was carried out at room temperature. Thereafter, this crystal was filtered and dried to obtain 20.0 g (0.0583 mol, yield 86.4%, yellow solid) of compound (15).

[Formula 38]

In an autoclave under a nitrogen atmosphere, tetrahydrofuran (300 g), compound (15) (20.01 g, 0.0583 mol), and palladium carbon powder (4.00 g) were injected. Then, the inside of the container was replaced with hydrogen 0.8 Mpa, and it stirred at 50 degreeC for 4 hours. Then, the palladium carbon was filtered, and the filtrate was concentrated and dried. Thereafter, the precipitated crystals were suspended in methanol (120 g). The suspension was stirred at 60°C for 1 hour to dissolve, and further stirred for 30 minutes under an ice bath. The precipitated crystals were filtered, washed with 10.0 g of methanol and dried to obtain 8.80 g (0.0311 mol, yield 53.3%, purple crystals) of the target product (DA-4).

[Viscosity Measurement]

In Examples or Comparative Examples, the viscosity of the polyamic acid solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Industries, Ltd.), the sample amount was 1.1 ml, and the cone rotor was TE-1 (1°34', R24). , was measured at a temperature of 25 °C.

(Example 3)

1.98 g (5.00 mmol) of DA-1 was weighed and taken to a 50 mL four-necked flask equipped with a stirring apparatus and a nitrogen introduction tube, 20.8 g of NMPs were added, and it stirred and dissolved, sending nitrogen. 1.03 g (4.75 mmol) of acid dianhydride (A) is added, stirring this diamine solution, 5.20 g of NMPs are further added, and it stirs at 23 degreeC in nitrogen atmosphere for 3 hours, and a polyamic-acid solution (PAA) -1) was obtained. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 134 mPa*s.

7.92 g of the polyamic acid solution (PAA-1) obtained by the synthesis example 2 was fractionated in the 100 ml Erlenmeyer flask with a stirrer, and 2.56 g and 3-glycidoxypropyl triethoxysilane for NMP were 1 mass 0.67 g and BCS 3.72g were added to the NMP solution containing %, it stirred with a magnetic stirrer for 2 hours, and the liquid crystal aligning agent (A-1) was obtained.

(Example 4)

2.17 g (7.00 mmol) of DA-2 was weighed and taken to a 50 ml four-neck flask equipped with a stirring device and a nitrogen introduction tube, 24.7 g of NMP was added, and it stirred and dissolved, sending nitrogen. 1.26 g (5.77 mmol) of acid dianhydride (A) is added, stirring this diamine solution, 6.19g of NMP is further added, and it stirs at 23 degreeC in nitrogen atmosphere for 3 hours, and a polyamic-acid solution (PAA) -2) was obtained. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 150 mPa*s.

In a 100 ml Erlenmeyer flask with a stirrer, 8.84 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 1 is fractionated, NMP containing 4.09 g and 3-glycidoxypropyltriethoxysilane in an amount of 1 mass% 0.82g and 4.59g of BCS were added to the solution, and it stirred with a magnetic stirrer for 2 hours, and the liquid crystal aligning agent (A-2) was obtained.

(Comparative Example 2)

5.16 g (20.0 mmol) of DA-3 was weighed and taken to a 100 ml four-necked flask equipped with a stirring device and a nitrogen introduction tube, 52.2 g of NMP was added, and it stirred and dissolved, sending nitrogen. Stirring this diamine solution, 4.17 g (19.1 mmol) of acid dianhydride (A) is added, 31.8 g of NMP is further added, and it stirs at 23 degreeC in nitrogen atmosphere for 3 hours, and polyamic-acid solution (PAA) -3) was obtained. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 140 mPa*s.

15.2 g of the polyamic acid solution (PAA-3) obtained in Comparative Synthesis Example 2 was fractionated in a 100 ml Erlenmeyer flask with a stirrer, and 7.18 g of NMP and 1-glycidoxypropyltriethoxysilane were contained in an amount of 1% by mass 1.43 g of NMP solution and 7.94g of BCS were added, it stirred with a magnetic stirrer for 2 hours, and the liquid crystal aligning agent (B-1) was obtained.

(Comparative Example 3)

1.42 g (5.00 mmol) of DA-4 was weighed and taken to a 100 ml four-necked flask with a stirring device and a nitrogen introduction tube, 16.7 g of NMP was added, and it stirred and melt|dissolved, sending nitrogen. 0.948 g (4.30 mmol) of acid dianhydride (A) is added, stirring this diamine solution, 4.18 g of NMP is further added, and it stirs at 23 degreeC in nitrogen atmosphere for 3 hours, and polyamic-acid solution (PAA) -4) was obtained. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 110 mPa*s.

10.4 g of polyamic acid solution (PAA-4) obtained in Comparative Synthesis Example 3 was aliquoted into a 100 ml Erlenmeyer flask with a stirrer, and NMP was contained in 3.36 g and 3-glycidoxypropyltriethoxysilane in an amount of 1 wt% 0.878 g of NMP solution and 4.88g of BCS were added, it stirred with a magnetic stirrer for 2 hours, and the liquid crystal aligning agent (B-2) was obtained.

Below, the manufacturing method of liquid crystal cell I for evaluating the relaxation characteristic of an accumulation|storage electric charge, and liquid crystal cell II for evaluating voltage retention and twist angle are shown.

[Production of liquid crystal cell I]

The liquid crystal cell provided with the structure of the liquid crystal display element of an FFS system is produced. First, a substrate on which electrodes were formed was prepared. The substrate is a glass substrate having a size of 30 mm × 35 mm and a thickness of 0.7 mm. On the board|substrate, the IZO electrode which comprises a counter electrode as a 1st layer is formed in the whole surface. On the counter electrode of the 1st layer, the SiN (silicon nitride) film|membrane formed into a film by the CVD method as a 2nd layer is formed. The film thickness of the SiN film of the second layer is 500 nm, and functions as an interlayer insulating film. On the SiN film of the 2nd layer, the comb-tooth-shaped pixel electrode formed by patterning the IZO film as 3rd layer is arrange|positioned, and two pixels of a 1st pixel and a 2nd pixel are formed. The size of each pixel is 10 mm long and about 5 mm wide. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the action of the SiN film of the second layer.

The pixel electrode of the 3rd layer has the comb-tooth-shaped shape comprised by arranging a plurality of "<"-shaped electrode elements in which the center part was bent. The width in the transverse direction of each electrode element is 3 µm, and the distance between the electrode elements is 6 µm. Since the pixel electrode forming each pixel is constituted by arranging a plurality of "<"-shaped electrode elements in which the central part is bent, the shape of each pixel is not a rectangle, but a bold letter bent in the central part like the electrode element. It has a shape similar to the letter や. And each pixel is divided|segmented up and down with the curved part in the center as a boundary, and has a 1st area|region which is an upper side of a curved part, and a 2nd area|region below.

Comparing the 1st area|region and 2nd area|region of each pixel, the formation direction of the electrode element of the pixel electrode which comprises them differs. That is, when the rubbing direction of the liquid crystal aligning film described later is taken as a reference, in the first region of the pixel, the electrode element of the pixel electrode is formed to form an angle of +10° (clockwise), and in the second region of the pixel, the pixel electrode The electrode elements of are formed to form an angle (clockwise) of -10°. That is, in the first region and the second region of each pixel, the directions of the rotational operation (in-plane switching) of the liquid crystal caused by the voltage application between the pixel electrode and the counter electrode in the substrate plane are opposite to each other. has been

Next, after filtering a liquid crystal aligning agent with a 1.0-micrometer filter, it apply|coated to the board|substrate with the prepared said electrode by spin coat application|coating. After drying for 5 minutes on a 50 degreeC hotplate, 230 degreeC hot-air circulation type oven performed baking for 20 minutes, and the polyimide film with a film thickness of 60 nm was obtained. Rubbing this polyimide film with rayon cloth (roller diameter: 120 mm, number of roller rotations: 500 rpm, moving speed: 30 mm/sec, indentation length: 0.3 mm, rubbing direction: a direction inclined by 10° with respect to the 3rd layer IZO comb electrode ), washing was performed by ultrasonic irradiation for 1 minute in pure water, and water droplets were removed by air blowing. Then, it dried at 80 degreeC for 15 minutes, and obtained the board|substrate with a liquid crystal aligning film. Moreover, also in the glass substrate which has a columnar spacer with a height of 4 micrometers by which the ITO electrode is formed in the back surface as a counter board|substrate, the polyimide film was formed similarly to the above, and the liquid crystal aligning film to which the orientation process was given in the same procedure as above. This formed substrate was obtained. A set of these two substrates on which the liquid crystal aligning film was formed, a sealing compound was printed in the form that left the liquid crystal injection port on the substrate, and the other substrate was attached so that the liquid crystal aligning film faces were facing each other and the rubbing direction was antiparallel. did Then, the sealing compound was hardened and the cell gap produced the 4 micrometers empty cell. Liquid crystal ZLI-4792 (made by Merck Corporation) was inject|poured into this empty cell by the reduced pressure injection method, the injection port was sealed, and the liquid crystal cell of the FFS system was obtained. Then, after heating the obtained liquid crystal cell at 110 degreeC for 1 hour and leaving it to stand at 23 degreeC overnight, it was used for each evaluation.

[Production of liquid crystal cell II]

First, a substrate on which electrodes were formed was prepared. The substrate is 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 is formed, and the electrode is a stripe pattern having a length of 40 mm and a width of 10 mm.

Next, after filtering a liquid crystal aligning agent with a 1.0-micrometer filter, it apply|coated to the board|substrate with the prepared said electrode by spin coat application|coating. Then, it dried for 5 minutes on a 50 degreeC hotplate. Then, it baked in 230 degreeC IR type oven for 20 minutes, the coating film with a film thickness of 100 nm was formed, and the board|substrate with a liquid crystal aligning film was obtained. After rubbing this liquid crystal aligning film with a rayon cloth (roller diameter: 120 mm, number of roller rotations: 1000 rpm, moving speed: 20 mm/sec, press-fit length: 0.4 mm), ultrasonic irradiation is performed for 1 minute in pure water to wash. and water droplets were removed by air blowing. Then, it dried at 80 degreeC for 15 minutes, and obtained the board|substrate with the liquid crystal aligning film to which the rubbing process was performed. Two board|substrates with this liquid crystal aligning film were prepared, and on the liquid crystal aligning film surface of 1 sheet, the spacer (made by Nikki Catalyst Chemical Company) with a diameter of 4 micrometers was spread|dispersed. Then, the sealing compound was printed from the top, and a rubbing direction was a reverse direction, and a film surface was affixed to the board|substrate of another 1 sheet facing. Then, the sealing compound was hardened and the empty cell was produced. Liquid crystal ZLI-4792 (made by Merck Corporation) was inject|poured into this empty cell by the reduced pressure injection method, the injection port was sealed, and the liquid crystal cell was obtained. Then, after heating the obtained liquid crystal cell at 110 degreeC for 1 hour and leaving it to stand at 23 degreeC overnight, it was used for each evaluation.

[Relief properties of accumulated charge]

Liquid crystal cell I is installed between two polarizing plates arranged so that the polarization axes are orthogonal to each other, and in a state where the pixel electrode and the counter electrode are short-circuited to the same potential, LED backlight is irradiated from below the two polarizing plates, and on the two polarizing plates The angle of the liquid crystal cell was adjusted so that the brightness|luminance of the LED backlight transmitted light to be measured might be minimized.

Next, the V-T characteristic (voltage-transmittance characteristic) under 23 degreeC temperature was measured, applying the square wave of frequency 30Hz to this liquid crystal cell, and the relative transmittance|permeability computed the alternating voltage used as 23 %. Since this AC voltage corresponds to a region where the change in luminance with respect to voltage is large, it is suitable for evaluating the accumulated charge through the luminance.

Next, the relative transmittance was an alternating voltage of 23%, and further applied a square wave with a frequency of 30 Hz for 5 minutes, followed by superimposing a DC voltage of +1.0V and driving for 30 minutes. Then, the DC voltage was cut|disconnected, and only the square wave with a frequency of 30 Hz was applied with the alternating voltage from which a relative transmittance will be 23 % again for 30 minutes.

The faster the relaxation of the accumulated charge, the faster the charge accumulation in the liquid crystal cell when the DC voltage is superimposed. The time required until it fell to 23 % evaluated. The shorter this time, the better the relaxation characteristic of the accumulated charge.

[Voltage retention rate]

To liquid crystal cell II, under 85 degreeC temperature, 60 microseconds of voltage of 1V was applied, the voltage 50 msec after was measured, and how much voltage is maintained was evaluated as voltage retention.

[twist angle]

The twist angle in liquid crystal cell II was evaluated using the AxoScan Muller matrix polarometer by Optometrics. Originally, if a rubbing direction and the orientation direction of a liquid crystal correspond, a twist angle will not generate|occur|produce in liquid crystal cell II. That there is a twist angle means that a rubbing direction and the orientation direction of a liquid crystal do not correspond.

[rubbing resistance]

The liquid crystal aligning agent was spin-coated on the ITO surface of the glass substrate in which the ITO electrode was formed in the whole surface, and it was dried for 5 minutes on a 50 degreeC hotplate. Then, it baked in 230 degreeC IR type oven for 20 minutes, the coating film with a film thickness of 100 nm was formed, and the board|substrate with a liquid crystal aligning film was obtained. This liquid crystal aligning film was rubbed with rayon cloth (Roller diameter: 120 mm, roller rotation speed: 1000 rpm, moving speed: 20 mm/sec, press-fit length: 0.4 mm). This board|substrate was observed with the microscope, and the thing in which the stripe by rubbing was not seen on the film surface was evaluated as "good|favorableness", and that in which the stripe was seen was evaluated as "poor".

(Example 5)

After filtering the liquid crystal aligning agent (A-1) obtained in Example 3 with a 1.0-micrometer filter, it processed as above and produced the liquid crystal cell I. About this liquid crystal cell I, when the relaxation characteristic of an accumulation|storage charge was evaluated, time required until the relative transmittance|permeability fell to 23 % was 2 minutes, and it was favorable.

Next, after filtering the liquid crystal aligning agent (A-1) obtained in Example 3 with a 1.0 micrometer filter, it processed as above and produced liquid crystal cell II. As for the evaluation result of this liquid crystal cell II, voltage retention was 91 %, and the twist angle was 0.1 degree|times.

Next, after filtering the liquid crystal aligning agent (A-1) obtained in Example 3 with a 1.0-micrometer filter, when rubbing tolerance was evaluated, a stripe was not seen but it was favorable.

(Example 6)

Liquid crystal cell I was produced by the method similar to Example 5 except having used the liquid crystal aligning agent (A-2) obtained in Example 4. About this liquid crystal cell I, when the relaxation characteristic of an accumulation|storage charge was evaluated, the time required before the relative transmittance|permeability fell to 23 % was 4 minutes, and it was favorable.

Next, liquid crystal cell II by the method similar to Example 5 was produced except having used the liquid crystal aligning agent (A-2) obtained in Example 4. As for the evaluation result of this liquid crystal cell II, voltage retention was 92 %, and the twist angle was 0.1 degree|times.

Next, except having used the liquid crystal aligning agent (A-2) obtained in Example 4, when rubbing tolerance was evaluated similarly to Example 5, a stripe was not seen but it was favorable.

(Comparative Example 4)

Liquid crystal cell I was produced by the method similar to Example 5 except having used the liquid crystal aligning agent (B-1) obtained by the comparative example 2. About this liquid crystal cell I, when the relaxation characteristic of an accumulation|storage electric charge was evaluated, even if 30 minutes passed, the relative transmittance did not fall to 23 %, but was unsatisfactory.

Next, liquid crystal cell II was produced by the method similar to Example 5 except having used the liquid crystal aligning agent (B-1) obtained by the comparative example 2. As for the evaluation result of this liquid crystal cell II, voltage retention was 40 %, and twist angle was 1.1 degree|times.

(Comparative Example 5)

When the rubbing tolerance was evaluated similarly to Example 5 except having used the liquid crystal aligning agent (B-2) obtained by the comparative example 3, many stripes were seen and it was unsatisfactory.

In addition, in Table 1, "-" represents that which was not evaluated.

Industrial Applicability

The liquid crystal aligning agent of this invention is useful as a liquid crystal aligning film used for the liquid crystal display element of an IPS drive system or an FFS drive system, a multifunctional mobile phone (smartphone), a tablet-type personal computer, a liquid crystal television, etc.

In addition, the specification of the JP Patent application 2014-025438 for which it applied on February 13, 2014, a claim, and the abstract are referred here, and it takes in as an indication of this specification.

Claims (13)

At least one polymer selected from the group consisting of a polyimide precursor obtained by reacting a diamine component containing a diamine of the following formula (2) with a tetracarboxylic acid derivative component, and a polyimide obtained by ring closure of the polyimide precursor It contains, The liquid crystal aligning agent characterized by the above-mentioned.

(In 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 alkylene having 1 to 5 carbon atoms.) The method of claim 1,
The liquid crystal aligning agent whose said polyimide precursor is a polymer which has a structural unit represented by following formula (9).

(In formula (9), X ₁ is a tetravalent organic group derived from a tetracarboxylic acid derivative, Y ₁ is a divalent organic group derived from diamine of Formula (2), and R ₄ is a hydrogen atom or a carbon number of 1 to 5 is an alkyl group) 3. The method of claim 2,
The liquid crystal aligning agent whose X1 is the following formulas (X-1) - (X-14).

(In formula (X-1), R ₅ to R ₈ are each independently 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 to be) The method of claim 1,
The liquid crystal aligning agent whose ratio of the diamine represented by Formula (2) is 30-100 mol% with respect to 1 mol of all the diamine components. delete The liquid crystal aligning film obtained by apply|coating and baking the liquid crystal aligning agent in any one of Claims 1-4. 7. The method of claim 6,
The liquid crystal aligning film whose film thickness after baking is 5-300 nm. It has the liquid crystal aligning film of Claim 6, The liquid crystal display element characterized by the above-mentioned. Diamine represented by Formula (2).

(In 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 alkylene having 1 to 5 carbon atoms.) delete delete delete At least one polymer selected from the group consisting of a polyimide precursor obtained by reacting a diamine component containing the diamine according to claim 9 and a tetracarboxylic acid derivative component, and a polyimide obtained by ring closure of the polyimide precursor.