KR20140009447A - Composition, liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

(식 [1] 중, X 는 치환기이고, n 은 0 ∼ 4 의 정수이다.)Provided are a composition, in particular a liquid crystal alignment treatment agent, capable of forming a high quality polyimide film, particularly a liquid crystal alignment film, of uniform properties by a low heat treatment temperature.
The polyimide precursor obtained by making the diamine component containing 1 or more types chosen from the group which consists of unsubstituted metaphenylenediamine and substituted metaphenylenediamine, and tetracarboxylic dianhydride component react, and / or its polyimide precursor The imidized polyimide and the cyclic ketone solvent which melt | dissolves the polyimide precursor and / or polyimide are contained, The composition characterized by the above-mentioned.

(In formula [1], X is a substituent and n is an integer of 0-4.)

Description

A composition, a liquid-crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element {COMPOSITION, LIQUID CRYSTAL ALIGNING AGENT, LIQUID CRYSTAL ALIGNMENT FILM, AND LIQUID CRYSTAL DISPLAY ELEMENT}

This invention relates to the composition used for film formation, especially the liquid-crystal aligning agent used for liquid crystal aligning film formation, the liquid crystal aligning film obtained, and the liquid crystal display element using this liquid crystal aligning film.

Films made of organic materials such as polymer materials have attracted attention for ease of formation, insulation performance, and the like, and are widely used as interlayer insulating films, protective films, and the like in electronic devices. In the liquid crystal display element well known as a display device, the organic film which consists of organic materials is used as a liquid crystal aligning film.

The liquid crystal aligning film is formed in the surface of the board | substrate which clamps a liquid crystal in a liquid crystal display element, and plays a role which orientates a liquid crystal in a fixed direction. Further, the liquid crystal alignment film has a role of controlling the pretilt angle of the liquid crystal in addition to the role of orienting the liquid crystal in a certain direction.

Moreover, in recent years, while a liquid crystal display element has become high functional and its use range expands gradually, the liquid crystal aligning film also requires the performance and reliability for suppressing the display defect of a liquid crystal display element and realizing high display quality.

The main liquid crystal aligning film currently used industrially is excellent in durability, and the polyimide organic film suitable for control of the pretilt angle of a liquid crystal is used widely. The liquid crystal aligning film which consists of this polyimide organic film is formed of the liquid-crystal aligning agent which is a composition containing the polyamic acid (also called polyamic acid) which is a polyimide precursor, and / or the polyimide solution which imidated the polyamic acid. That is, a polyimide-type liquid crystal aligning film is formed by apply | coating the liquid-crystal aligning agent which consists of a polyamic-acid solution which is a polyimide solution or a polyimide precursor to a board | substrate, and baking at high temperature of about 200 degreeC-300 degreeC normally ( For example, refer patent document 1).

Japanese Patent Application Laid-Open No. 09-278724

The baking process for forming a polyimide-type liquid crystal aligning film requires especially high temperature in the process of manufacturing a liquid crystal display element. Therefore, when the board | substrate of a liquid crystal display element uses a thin, lightweight but low heat resistance plastic substrate instead of a normal glass substrate, it is calculated | required to enable lower temperature baking. Similarly, low temperature plasticization of a liquid crystal aligning film is calculated | required in order to suppress deterioration, such as the fall of the color characteristic in a color filter, and to reduce the energy cost in manufacture of a liquid crystal display element. Moreover, also in suppressing the fall of the reliability of a liquid crystal display element (deterioration of characteristic in long-term use etc.), the low temperature of a baking process is calculated | required.

Moreover, also in formation of films, such as an interlayer insulation film and a protective film, in another electronic device etc., the low temperature of the heat processing process is calculated | required. Low temperature plasticization prevents the deterioration of the characteristics of the electronic device and is effective for reducing the energy cost.

Therefore, this invention is the composition which can form the polyimide organic film formed by the heating at low temperature, The liquid-crystal aligning agent which can form a liquid crystal aligning film by heating at low temperature especially, The liquid crystal aligning film obtained from this liquid-crystal aligning agent. And it aims at providing the liquid crystal display element using this liquid crystal aligning film.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to achieve the said objective, this inventor acquired the new knowledge through the following process.

That is, generally, formation of a polyimide film, for example, a liquid crystal aligning film, uses the polyimide solution obtained by melt | dissolving a polyimide or a polyimide precursor in the solvent, or the polyimide precursor solution as mentioned above, It apply | coats these solutions to a board | substrate, and is normally performed by heat-processing at high temperature, about 200 degreeC-300 degreeC.

By this heat treatment, when a polyimide precursor solution is used for film formation, for example, dehydration waste ring reaction (thermal imidization) of polyamic acid is performed, and solvent removal is performed simultaneously to form a film.

When the polyimide solution is used for film formation, the main purpose is to remove the solvent in the heat treatment. Therefore, although the heat processing temperature in the case of using a polyimide solution is influenced by the boiling point of the solvent used, it can usually be made low compared with the case of using polyamic acid. For example, as disclosed in JP-A-9-194725, the film can be formed by a heat treatment temperature of about 200 ° C. Therefore, at low temperature of heat processing temperature, it is more preferable to use a polyimide solution.

On the other hand, when preparing a polyimide solution, since it will melt | dissolve the polyimide which is hard to melt normally, selection of a solvent becomes important. As the solvent for this purpose, a high polar solvent such as N-methyl-2-pyrrolidone (hereinafter also referred to as NMP) has been used. The boiling point of a high polar solvent is as high as the boiling point of NMP is 200 degreeC or more, for example. When forming a film by the polyimide solution which used NMP for the solvent, the high heat processing temperature of about 200 degreeC near the boiling point of NMP is needed. At lower temperatures, the solvent (NMP) remains in the resulting film. As a result, in the case of a liquid crystal aligning film, etc., a fall of a characteristic occurs and the characteristic of a liquid crystal display element falls.

Moreover, in the case of NMP which is a high polar solvent, since it has comparatively high surface tension characteristic, when the film is formed using the polyimide solution which uses NMP as a solvent, the wet-diffusion characteristic on a board | substrate is not favorable. If the surface tension of the solvent to be used can be made lower, the applicability | paintability to a board | substrate will become more favorable. As a result, a high quality polyimide film having more uniform characteristics can be formed without defects in printing coating such as cratering and pinholes.

As mentioned above, the low temperature of heat processing at the time of film formation and the improvement of applicability become important in formation of the polyimide film for the purpose of the insulating film and protective film of an electronic device, especially a liquid crystal aligning film.

MEANS TO SOLVE THE PROBLEM This inventor researched in order to improve the low temperature of heat processing temperature and coating property in formation of a polyimide type film, especially a polyimide type liquid crystal aligning film, The diamine component and tetracarboxylic dianhydride component of a specific structure. The polyimide precursor obtained by using as a raw material and / or the polyimide which imidated the polyimide precursor is melt | dissolved in the solvent containing cyclic ketone which has a low boiling point and low surface tension characteristic, and, as a result, this objective We found out that we could achieve enough.

This invention is based on said knowledge and has the following summary.

(1) A polyimide precursor obtained by reacting a diamine component containing at least one member selected from the group consisting of unsubstituted metaphenylenediamine and substituted metaphenylenediamine with a tetracarboxylic dianhydride component and / or poly The polyimide which imidated the mid precursor, and the cyclic ketone solvent which melt | dissolves this polyimide precursor and / or polyimide are contained, The composition characterized by the above-mentioned.

(2) The composition as described in said (1) whose said substituted metaphenylenediamine is diamine represented by following formula [1].

[Formula 1]

(In formula [1], X is a substituent and n is an integer of 0-4.)

3, the X in the above formula _{[1] - (CH 2)} a -COOH group (a is an integer of 0-4), - (CH _{2) b} -OH groups (b is an integer of 0 to 4.) The composition as described in said (2) which is group represented by the di-substituted amino group substituted by the C8-C22 hydrocarbon group, the C1-C6 hydrocarbon group, or following formula [2].

(2)

A (a is an integer of 1 ~ 15), -O-, -CH 2 O-, -COO- or -OCO-, - (formula [2], Y ¹ is a single bond, - (CH _{2) a} Y ² is a single bond or-(CH ₂ ) _b- (b is an integer of 1 to 15), Y ³ is a single bond,-(CH ₂ ) _c- (c is an integer of 1 to 15),- O-, -CH ₂ O-, -COO- or -OCO-.

Y ⁴ is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring (any hydrogen atom on these cyclic groups may be an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, or 1 to 3 carbon atoms). May be substituted with a fluorine-containing alkyl group of 3, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms or a fluorine atom), or a divalent organic group selected from an organic group having 12 to 25 carbon atoms having a steroid skeleton, and Y ⁵ is benzene. A cyclic group selected from the group consisting of a ring, a cyclohexane ring and a heterocyclic ring (any hydrogen atom on these cyclic groups may be an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, or a fluorine having 1 to 3 carbon atoms). May be substituted with an alkyl group, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms or a fluorine atom), and Y ⁶ is an alkyl group having 1 to 18 carbon atoms and a fluorine containing 1 to 18 carbon atoms. It is an alkyl group, a C1-C18 alkoxyl group, or a C1-C18 fluorine-containing alkoxyl group, n is an integer of 0-4.)

4, the X in the above formula _{[1] - (CH 2)} a -COOH group (a is an integer from 0 to 4) The composition as set forth in the above (3).

5 is X in the above formula _{[1] - (CH 2)} a -COOH group (a is an integer from 0 to 4) or the formula [2] to the above (2) or the composition according to (3).

(6) The composition as described in any one of said (2)-(5) whose content of the diamine represented by the said Formula [1] is 15-100 mol% in a diamine component.

(7) The composition as described in any one of said (1)-(6) whose said tetracarboxylic dianhydride is a compound represented by following formula [3].

(3)

(In the formula [3], Z ₁ is a quadrivalent organic group having 4 to 13 carbon atoms and further contains a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms.)

(8) The composition as described in said (7) whose Z < ₁ > of the said Formula [3] is a structure shown by following formula [3a]-[3j].

[Chemical Formula 4]

(In formula [3a], Z <_2> -Z <_5> is a hydrogen atom, a methyl group, a chlorine atom, or a benzene ring, respectively, may be same or different, and in formula [3g], Z <_6> and Z <_7> are a hydrogen atom or a methyl group. , May be the same or different from each other.)

(9) The composition as described in any one of said (1)-(8) in which the said cyclic ketone solvent contains at least one cyclic ketone among a 5-membered ring and a 6-membered cyclic ketone.

(10) The liquid-crystal aligning agent which consists of a composition in any one of said (1)-(9).

(11) The liquid crystal aligning film obtained from the liquid-crystal aligning agent as described in said (10).

(12) A liquid crystal layer is disposed between a pair of substrates provided with electrodes, and a liquid crystal composition comprising a polymerizable compound polymerized by at least one of active energy rays and heat is disposed between the pair of substrates. The liquid crystal aligning film as described in said (11) used for the liquid crystal display element manufactured through the process of superposing | polymerizing the said polymeric compound, applying a voltage between the said electrodes.

The liquid crystal display element which has a liquid crystal aligning film as described in said (11).

(14) A liquid crystal comprising a polymerizable compound having a liquid crystal layer between an electrode and a pair of substrates provided with the liquid crystal alignment film and polymerizing by at least one of active energy rays and heat between the pair of substrates. The liquid crystal display element as described in said (13) manufactured through the process of superposing | polymerizing the said polymeric compound, disposing a composition and applying a voltage between the said electrodes.

ADVANTAGE OF THE INVENTION According to this invention, the composition which is excellent in applicability | paintability and which can form the high quality polyimide type film of more uniform characteristic by the low heat processing temperature without the defect at the time of printing application, such as a cratering and a pinhole, is provided.

Especially, according to this invention, since it is excellent in applicability | paintability and can be baked at low temperature, the liquid-crystal aligning agent which can form the liquid crystal aligning film excellent in the electrical characteristic without a defect is provided. From the liquid crystal aligning film obtained using the liquid-crystal aligning agent of this invention, since the electrical characteristic is excellent, the liquid crystal display element which has high reliability is obtained.

Diamine component and tetracarboxylic acid 2 which are used in order to obtain the polyimide used for this invention, and / or the polyimide which imidated the polyimide precursor (henceforth generically called the polyimide of this invention). Anhydride component is demonstrated.

<Metaphenylenediamine>

The metaphenylenediamine of the present invention includes unsubstituted metaphenylenediamine and substituted metaphenylenediamine.

Metaphenylenediamine used by this invention is a diamine represented by following formula [1].

[Chemical Formula 5]

In [1], X is a substituent, n is an integer of 0-4. When n is 0, Formula [1] is metaphenylenediamine.

Specifically, in the formula (1), the substituent represented by X is, - (CH _{2) a} -COOH group (a is an integer of 0 ~ 4), - (CH 2) b -OH groups (b is 0 It is an integer of -4), a C8-C22 hydrocarbon group, the di-substituted amino group substituted by the C1-C6 hydrocarbon group, or group represented by following formula [2].

[Chemical Formula 6]

In formula [2], Y ¹ is a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Among these, a single _{bond, - (CH 2) a -} (a is an integer of 1 ~ 15), -O-, -CH 2 O- or -COO- is preferable in view of facilitating the synthesis of the side chain structure Do. In addition, a single _{bond, - (CH 2) a -} (a is an integer of 1 ~ 10), -O-, -CH 2 O- or -COO- is more preferable.

In formula [2], Y ² is a single bond or - (CH ₂ ) _b - (b is an integer of 1 to 15). Among these, a single bond or - (CH _{2) b} - is preferably a (b is an integer of 1-10).

In formula [2], Y ³ is a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Among them, a single bond,-(CH ₂ ) _c- (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO- facilitates the synthesis of the side chain structure. It is preferable from a viewpoint. In addition, a single _{bond, - (CH 2) c -} (c is an integer of 1 ~ 10), -O-, more preferably a -CH ₂ O-, -COO- or -OCO-.

Y <^4> is cyclic group chosen from the group which consists of a benzene ring, a cyclohexane ring, and a heterocyclic ring in formula [2] (The arbitrary hydrogen atoms on these cyclic groups are a C1-C3 alkyl group, C1-C3. May be substituted by an alkoxyl group, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms or a fluorine atom), or a divalent compound selected from an organic group having 12 to 25 carbon atoms having a steroid skeleton. It is an organic group. Especially, the C12-C25 divalent organic group which has any of a benzene ring, a cyclohexane ring, and a steroid skeleton is preferable.

In formula [2], Y <^5> is a cyclic group chosen from the group which consists of a benzene ring, a cyclohexane ring, and a heterocyclic ring, and the arbitrary hydrogen atoms on these cyclic groups are a C1-C3 alkyl group and C1-C3 May be substituted with any of an alkoxyl group, a C1-C3 fluorine-containing alkyl group, a C1-C3 fluorine-containing alkoxyl group, and a fluorine atom.

In the formula [2], n is an integer of 0 to 4. Preferably, it is an integer of 0-2.

Y <^6> is either a C1-C18 alkyl group, a C1-C18 fluorine-containing alkyl group, a C1-C18 alkoxyl group, and a C1-C18 fluorine-containing alkoxyl group in formula [2]. Especially, it is preferable that it is any of a C1-C18 alkyl group, a C1-C10 fluorine-containing alkyl group, a C1-C18 alkoxyl group, and a C1-C10 fluorine-containing alkoxyl group. More preferably, it is either of a C1-C12 alkyl group and a C1-C12 alkoxyl group. More preferably, it is either of a C1-C9 alkyl group and a C1-C9 alkoxyl group.

Preferred combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in formula [2] for constituting substituent X in formula [1] are shown in Tables 1 to 42 below. In addition, it is as showing as 2-1-2-629.

In this invention, use of substituted metaphenylenediamine is preferable compared with unsubstituted metaphenylenediamine (Hereinafter, it may describe as metaphenylenediamine.).

In formula [1], substituted metaphenylenediamine whose X is a disubstituted amino group substituted by the C1-C6 hydrocarbon group is shown by following formula [1A].

[Formula 7]

(In formula [1A], R <_1> , R <_2> is a C1-C6 hydrocarbon group each independently.)

As a preferable example of substituted metaphenylenediamine shown by Formula [1A], the compound which has N-allyly aniline structure, for example, the compound shown by following formula [1B] is mentioned.

[Formula 8]

(In formula [1B], R <_1> represents a C1-C6 hydrocarbon group.)

It is preferable that the hydrocarbon group of R <_1> contains a carbon-carbon double bond, and it is more preferable that this double bond exists between 2nd carbon and 3rd carbon from a nitrogen atom. Moreover, 4 or less are preferable from the point of the printability of a composition or the liquid-crystal aligning agent using the same, and carbon number of R <_1> , More preferably, it is 3 or less.

In formula [1B], R <_3> , R <_4> and R <_5> are respectively independently a hydrogen atom or a methyl group. In Formula [1B], the preferable position of two amino groups is 2, 4 position, 2, 5 position, or 3,5 position on a benzene ring with respect to N-allyl group.

As a preferable example of the diamine represented by a formula [1B], the compound represented by a following formula [1C] is mentioned.

[Chemical Formula 9]

Preferable specific examples of the compound represented by formula [1C] are shown by the following formulas [1C-1] to [1C-6]. Especially, the diamine of formula [1C-1] is especially preferable. About the diamine of the structure shown by a formula [1C], it is not limited to these examples.

[Formula 10]

Moreover, the diamine of a following formula [1D] structure is mentioned as another example of the diamine represented by Formula [1A].

[Formula 11]

More specifically, it is a compound shown by following formula [1D-1]-[1D-6]. Especially, the diamine of a formula [1D-1] is especially preferable. The diamine represented by a formula [1D] is not limited to these examples.

[Chemical Formula 12]

Substituted metaphenylenediamine represented by the formula [1A] is characterized by solubility in a solvent when the polyimide is used, or properties such as the orientation of the liquid crystal, the voltage retention, and the stored charge when the liquid crystal alignment film is used, for example. Therefore, you may mix and use one type or two types or more.

In addition, although the specific example of substituted metaphenylenediamine shown by Formula [1] is given below, it is not limited to these examples.

M-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diamino In addition to benzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 3,5-diaminobenzoic acid, 2,4-diaminobenzoic acid, and the like, the following formula [1-1] to formula [ 1-35] metaphenylenediamine.

[Chemical Formula 13]

(A <_1> is a C1-C22 alkyl group or a fluorine-containing alkyl group in formula [1-1]-formula [1-4].)

[Formula 14]

[Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

(Formula [1-23] - formula [1-25] of, R ₁ is _{-O-, -OCH 2 -, -CH 2} O-, -COOCH 2 - or a -CH ₂ OCO-, R ₂ has a carbon number 1-22 alkyl group, alkoxy group, fluorine-containing alkyl group, or fluorine-containing alkoxy group.)

[Chemical Formula 20]

(Formula [1-26] - formula [1-28] of, R ₃ is _{-COO-, -OCO-, -COOCH 2 -,} -CH 2 OCO-, -CH 2 O-, -OCH 2 - or CH ₂ -and R ₄ is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.)

[Chemical Formula 21]

(Formula [1-29] and formula [1-30] of, R ₅ is _{-COO-, -OCO-, -COOCH 2 -,} -CH 2 OCO-, -CH 2 O-, -OCH 2 -, - CH ₂ -or O-, and R ₆ is a fluorine group, cyano group, trifluoromethane group, nitro group, azo group, formyl group, acetyl group, acetoxy group or hydroxyl group.)

[Chemical Formula 22]

(In formula [1-31] and formula [1-32], R <_7> is a C3-C12 alkyl group and the cis-trans isomer of 1, 4- cyclohexylene is a trans isomer, respectively.)

(23)

(In formula [1-33] and formula [1-34], R <_8> is a C3-C12 alkyl group and the cis-trans isomer of 1, 4- cyclohexylene is a trans isomer, respectively.)

&Lt; EMI ID =

(Wherein [1-35], B ₄ is an alkyl group having 3 to 20 carbon atoms that may be substituted by fluorine atoms, B ₃ is 1,4-cyclohexyl, and xylene group or 1,4-phenylene group, B ₂ is oxygen Atom or COO- * (wherein the number of bonds attached with "*" is bonded to B ₃ ), B ₁ is an oxygen atom or COO- * (wherein the number of bonds attached with "*" is (CH ₂ ) a ₂ ) and Joins). A ₁ is an integer of 0 or 1, a ₂ is an integer of 2 to 10, and a ₃ is an integer of 0 or 1).

The said metaphenylenediamine mixes 1 type, or 2 or more types according to the property, such as the solubility with respect to the solvent at the time of using polyimide, the orientation of the liquid crystal, the voltage retention, and the accumulated charge, etc. when it is set as a liquid crystal aligning film, Can also be used.

<Synthesis method of methaphenylenediamine>

Although the method of manufacturing the metaphenylenediamine shown by Formula [1] is not specifically limited, What is shown below is mentioned as a preferable method.

As an example, the metaphenylenediamine of this invention is obtained by synthesize | combining the dinitro body shown by following formula [1E], reducing a nitro group, and converting into an amino group.

(25)

There is no restriction | limiting in particular in the method of reducing two nitro groups, Usually, palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium-alumina, platinum sulfide carbon etc. are used as a catalyst, ethyl acetate, toluene, tetrahydrofuran , Solvents such as dioxane, alcohol solvents, etc., may be carried out by hydrogen gas, hydrazine, hydrogen chloride, or the like. In addition, X and n in Formula [1E] are the same meaning as the definition in Formula [1] in said metaphenylenediamine.

<Other diamines>

In the present invention, as described later, when obtaining a polyimide precursor, other diamines other than metaphenylenediamine and / or substituted metaphenylenediamine (also referred to as other diamines), unless the effect of the present invention is inhibited. It is good also as a polyimide precursor in combination. Specific examples of other diamines applicable in the present invention are given below.

As other diamine, for example, p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 2,5-diamino Toluene, 2,5-diaminophenol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'- Diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro -4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2 , 2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenyl Methane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 3,3'-diaminodiphenylether, 3,4 ' -Diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldiyl Lean, 3,3'-sulfonyldianiline, bis (4-aminophenyl) silane, bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane , 4,4'-thiodaniline, 3,3'-thiodaniline, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenyl Amine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, N-methyl (3,3'-dia Minodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (2,2'-diaminodiphenyl) amine, N-methyl (2,3'-diaminodi Phenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'-diaminobenzo Phenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diamino Naphthalene, 2,6-diaminonaphthalene, 2,7-dia Minonaphthalene, 2,8-diaminonaphthalene, 1,2-bis (4-aminophenyl) ethane, 1,2-bis (3-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4-bis (3-aminophenyl) butane, bis (3,5-diethyl-4- Aminophenyl) methane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3- Bis (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4 '-[1,4-phenylenebis ( Methylene)] dianiline, 4,4 '-[1,3-phenylenebis (methylene)] dianiline, 3,4'-[1,4-phenylenebis (methylene)] dianiline, 3,4 ' -[1,3-phenylenebis (methylene)] dianiline, 3,3 '-[1,4-phenylenebis (methylene)] dianiline, 3,3'-[1,3-phenylenebis ( Methylene)] dianiline, 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis [(3-aminophenyl) methanone], 1,3-phenylenebis [ (4-aminofe ) Methanone], 1,3-phenylenebis [(3-aminophenyl) methanone], 1,4-phenylenebis (4-aminobenzoate), 1,4-phenylenebis (3-aminobenzo 8), 1,3-phenylenebis (4-aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), bis (4-aminophenyl) terephthalate, bis (3-aminophenyl) Terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N, N '-(1,4-phenylene) bis (4-aminobenzamide), N, N'- (1,3-phenylene) bis (4-aminobenzamide), N, N '-(1,4-phenylene) bis (3-aminobenzamide), N, N'-(1,3-phenyl Len) bis (3-aminobenzamide), N, N'-bis (4-aminophenyl) terephthalamide, N, N'-bis (3-aminophenyl) terephthalamide, N, N'-bis (4- Aminophenyl) isophthalamide, N, N'-bis (3-aminophenyl) isophthalamide, 9,10-bis (4-aminophenyl) anthracene, 4,4'-bis (4-aminophenoxy) di Phenylsulfone, 2,2'-bis [4- (4 -Aminophenoxy) phenyl] propane, 2,2'-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2'-bis (4-aminophenyl) hexafluoropropane, 2 , 2'-bis (3-aminophenyl) hexafluoropropane, 2,2'-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2'-bis (4-aminophenyl) propane, 2,2'-bis (3-aminophenyl) propane, 2,2'-bis (3-amino-4-methylphenyl) propane, 2,5-diaminobenzoic acid, 1,3-bis (4-aminophenoxy ) Propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,4-bis (3-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,5-bis (3-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) hexane, 1,6-bis (3-aminophenoxy) hexane , 1,7-bis (4-aminophenoxy) heptane, 1,7- (3-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,8-bis (3- Aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,9-bis (3-aminophen Nonoxy) nonane, 1,10- (4-aminophenoxy) decane, 1,10- (3-aminophenoxy) decane, 1,11- (4-aminophenoxy) undecane, 1,11- (3 Aromatic diamines such as -aminophenoxy) undecane, 1,12- (4-aminophenoxy) dodecane, 1,12- (3-aminophenoxy) dodecane; bis (4-aminocyclohexyl) methane; Alicyclic diamines such as bis (4-amino-3-methylcyclohexyl) methane; 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane , 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diamino degree Aliphatic diamines, such as decane; These etc. are mentioned.

Moreover, as another diamine, what has an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, or a heterocyclic ring in the diamine side chain, or the thing which has the large cyclic substituent which consists of these, etc. can be mentioned. Specifically, the diamine shown by the following formula [DA1]-[DA8] can be illustrated.

(26)

(A <_1> is a C1-C22 alkyl group or a fluorine-containing alkyl group in a formula [DA1].)

(27)

(Wherein [DA2] ~ [DA7] of, A ₂ is -COO-, -OCO-, -CONH-, -NHCO-, -CH 2 -, -O-, and -CO-, or -NH-, A ₃ Is a C1-C22 alkyl group or a fluorine-containing alkyl group.)

(28)

(P is an integer of 1-10 in a formula [DA8].)

Moreover, unless the effect of this invention is impaired, the diamine shown by following formula [DA9]-[DA16] can also be used.

[Chemical Formula 29]

(M is an integer of 0-3 in a formula [DA13], and n is an integer of 1-5 in a formula [DA16].)

Moreover, unless the effect of this invention is impaired, you may use the diamine which has a carboxyl group in the molecule | numerator shown by following formula [DA17]-DA21.

(30)

(Wherein [DA17] of, m ₁ is an integer from 1 to 4, wherein [DA18], A ₄ represents a single _{bond, -CH 2 -, -C 2 H} 4 -, -C (CH 3) 2 -, -CF _2- , -C (CF ₃ )-, -O-, -CO-, -NH-, -N (CH ₃ )- _, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON (CH ₃ )-or -N (CH ₃ ) CO-, m ₂ and m ₃ are each an integer of 0 to 4, and m ₂ + m ₃ is 1 It is an integer of -4.

M <_4> and m <_5> are the integers of 1-5 in a formula [DA19], respectively.

In formula [DA20], A <_5> is a C1-C5 linear or branched alkyl group, m <_6> is an integer of 1-5.

In formula [DA21], A ₆ is a single bond, -CH _2- , -C ₂ H _4- , -C (CH ₃ ) _2- , -CF _2- , -C (CF ₃ )- _, -O-, -CO-, -NH-, -N (CH ₃ )- _, -CONH-, -NHCO-, -CH ₂ O-, -OCH _2- , -COO-, -OCO-, -CON (CH ₃ )- Or -N (CH ₃ ) CO-, m ₇ is an integer from 1 to 4.

Moreover, unless the effect of this invention is impaired, the diamine shown by following formula [DA22] and formula [DA23] can also be used.

(31)

Said other diamine can also be used 1 type or in mixture of 2 or more types according to the characteristics, such as the solubility with respect to the solvent of a polymer, and a liquid crystal aligning film, the orientation of a liquid crystal, voltage retention, and an accumulated charge.

<Tetracarboxylic dianhydride>

In order to obtain the polyimide precursor and / or polyimide used by this invention, tetracarboxylic dianhydride (also called specific tetracarboxylic dianhydride) which has alicyclic structure is used as a tetracarboxylic dianhydride component. . As such specific tetracarboxylic dianhydride, tetracarboxylic dianhydride which has an alicyclic structure shown by following formula [3] is preferable.

(32)

In formula [3], Z <_1> is a C4-C13 tetravalent organic group and contains a C4-C10 non-aromatic cyclic hydrocarbon group.

Specifically, Z ₁ is a structure represented by the following formulas [3a] to [3j].

(33)

Z <_2> -Z <_5> is group chosen from the group which consists of a hydrogen atom, a methyl group, a chlorine atom, and a benzene ring in formula [3a], and may be same or different, respectively.

In formula [3g], Z <_6> and Z <_7> is a hydrogen atom or a methyl group, and may be same or different, respectively.

In formula [3], the particularly preferred structure of Z ₁ is, in terms of polymerization reactivity or ease of synthesis, formula [3a], formula [3c], formula [3d], formula [3e], formula [3f] or formula [3g]. ]. Especially, the structure shown by Formula [3e], Formula [3f], or Formula [3g] is preferable.

When using the tetracarboxylic dianhydride of the structure of formula [3e], a formula [3f], or a formula [3g], the usage-amount is made 20 mass% or more in all the tetracarboxylic dianhydride components, and a desired effect is obtained. It is obtained, and it is more preferable to set it as 25 mass% or more.

In this invention, as long as the effect of this invention is not impaired, other tetracarboxylic dianhydride other than specific tetracarboxylic dianhydride can be used.

Specific examples thereof include pyromellitic acid, 2,3,6,7-naphthalene tetracarboxylic acid, 1,2,5,6-naphthalene tetracarboxylic acid, 1,4,5,8- Naphthalenetetracarboxylic acid, 2,3,6,7-anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid , 2,3,3 ', 4-biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3', 4,4'-benzophenonetetracarboxylic acid, bis (3, 4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro Rho-2,2-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4 , 5-pyridinetetracarboxylic acid, 2,6-bis (3,4-dicarboxyphenyl) pyridine, 3,3 ', 4,4'-diphenylsulfontetracarboxylic acid, 3,4,9,10 Perylenetetracarboxylic acid, 1,3-diphenyl-1,2,3,4-cyclobutane Tra and the like acids.

In the composition of this invention, in said other tetracarboxylic dianhydride, for example, in the case of a liquid crystal aligning film, in consideration of characteristics, such as liquid crystal alignability, voltage holding | maintenance characteristic, and an accumulated charge, one type or two or more types are selected. Can be selected and used.

<Polyimide Precursor and Polyimide>

The polyimide precursor and polyimide used in the composition of the present invention are preferably obtained as follows. Here, a polyimide precursor represents polyimide acid (it is also called polyamic acid). That is, the polyimide precursor used by this invention is obtained by making the diamine component containing said metaphenylenediamine, and the tetracarboxylic dianhydride component which has the said alicyclic structure react. And since the polyimide obtained by dehydrating the waste ring by polyimide precursor is manufactured from the diamine component containing metaphenylenediamine, solubility to a solvent improves and it can become low temperature baking as mentioned later.

When obtaining a polyimide precursor, it is preferable that the usage-amount of the said metaphenylenediamine in the diamine component used as a raw material shall be 40 mol% or more, and it is more preferable to set it as 45 mol% or more. In particular, when using the substituted metaphenylenediamine which has group represented by Formula [2], it is preferable to use it as 15 mol% or more in a diamine component, and it is more preferable to set it as 30 mol% or more. Moreover, the said metaphenylenediamine may be sufficient as 100 mol% in a diamine component.

As a method of obtaining a polyimide precursor by reaction of a diamine component and tetracarboxylic dianhydride, a well-known synthetic method can be used. For example, the use of the method of making a diamine component and tetracarboxylic dianhydride react in an organic solvent is possible. This method is preferable in that the reaction proceeds relatively efficiently in an organic solvent and the generation of by-products is small.

As an organic solvent used for reaction of a diamine component and tetracarboxylic dianhydride, if the produced polyamic acid melt | dissolves, it will not specifically limit. Specific examples thereof include, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, methylethylketone, cyclohexanone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone. These may be used alone or in combination.

Moreover, even if it is a solvent which does not melt | dissolve a polyimide precursor, if it is the range in which the produced polyamic acid does not precipitate, you may mix and use it with the said solvent. In addition, since moisture in an organic solvent inhibits a polymerization reaction and causes hydrolysis of the produced polyimide precursor, it is preferable to use what dried the organic solvent.

When reacting a diamine component and tetracarboxylic dianhydride in an organic solvent, the solution which disperse | distributed or dissolved the diamine component in the organic solvent is stirred, and tetracarboxylic dianhydride is disperse | distributed or dissolved in an organic solvent as it is It is possible to use the method of adding. Moreover, the method of adding a diamine component to the solution which disperse | distributed or dissolved tetracarboxylic dianhydride in the organic solvent, the method of adding the tetracarboxylic dianhydride and a diamine component alternately, etc. are also mentioned. In the present invention, any of these methods may be used. Moreover, when a diamine component or tetracarboxylic dianhydride consists of several types of compounds, it may be made to react in the state mixed previously, may be made to react individually one by one, and the low molecular weight reacted individually may be mixed-reacted, and a high molecular weight body may be made. You may make it.

Although the temperature at which a diamine component and tetracarboxylic dianhydride are made to react can be arbitrarily selected within the range of -20-150 degreeC, it is preferable to set it as -5-100 degreeC in consideration of reaction efficiency. The reaction can be carried out at any concentration. However, when concentration is too low, it will become difficult to obtain a high molecular weight polyimide precursor. On the other hand, when the concentration is too high, the viscosity of the reaction solution becomes too high, making uniform stirring difficult. Therefore, Preferably it is 1-50 mass%, More preferably, it is 5-30 mass%. In addition, the reaction initial stage can be performed in high concentration | density, and can also add an organic solvent after that.

In the polymerization reaction for obtaining a polyimide precursor, it is preferable that ratio of the total mole number of a diamine component and the total mole number of tetracarboxylic dianhydride is 0.8-1.2. As in the conventional polycondensation reaction, the closer the molar ratio is to 1.0, the higher the molecular weight of the polymer produced. Therefore, it is possible to determine the total molar ratio by appropriately selecting in some cases.

The polyimide used in the present invention is obtained by dehydrating the above-mentioned polyimide precursor. This polyimide can be used as a polymer for obtaining a liquid crystal aligning film.

In the polyimide used in the present invention, the dehydration ring closure rate (imidization rate) of the polyimide precursor does not necessarily need to be 100%, depending on the use and purpose, for example, in the range of 35 to 95%, Preferably, it can adjust in 50 to 80% of range.

As a method of imidating a polyimide precursor, thermal imidation which heats a polyimide precursor solution as it is, catalyst imidation which adds a catalyst to a polyimide precursor solution, etc. are mentioned.

The temperature at the time of thermally imidating a polyimide precursor in a solution is 100-400 degreeC, Preferably it is 120-250 degreeC. In imidation of a polyimide precursor, it is preferable to carry out, removing the water produced | generated by the imidation reaction outside the reaction system.

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

Pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. are mentioned as a basic catalyst, Especially, pyridine is preferable at the point which has moderate basicity for advancing reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like, and among them, acetic anhydride is preferable in view of ease of purification after completion of the reaction. The imidation ratio by catalyst imidation can be controlled by adjusting catalyst amount, reaction temperature, and reaction time.

When recovering the produced polyimide from the reaction solution of the polyimide, the reaction solution may be poured into an empty solvent and precipitated. Examples of poor solvents to be used in the precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene and water. The polymer precipitated by being poured into the poor solvent can be recovered by filtration and then dried by normal temperature or heating under normal pressure or reduced pressure. Moreover, the impurity in a polymer can be reduced by redissolving the polymer which precipitated and collect | recovered in a solvent, and repeating the operation of reprecipitation recovery 2 to 10 times. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons, and the like, and three or more types of poor solvents selected from these are preferable since the purification efficiency increases.

The molecular weight of the polymer (polyimide precursor or polyimide) contained in the composition of the present invention is GPC (Gel Permeation Chromatography) in consideration of the strength of the coating film obtained by using the same, the workability at the time of coating film formation and the uniformity of the coating film. It is preferable to set it as 5,000-1,000,000 by the weight average molecular weight measured by the method, More preferably, it is 10,000-150,000.

<Composition for film formation>

The composition for film formation of this invention, for example, a liquid-crystal aligning agent is a composition containing the imide polymer of this invention obtained as mentioned above, and the solvent which melt | dissolved this polyimide polymer, and is a coating liquid for forming a liquid crystal aligning film. to be. As for content of the polyimide polymer of this invention contained in a composition, 1-20 mass% is preferable, More preferably, it is 3-15 mass%, Especially preferably, it is 3-10 mass%.

In this invention, the polyimide of this invention may be sufficient as all the polymer components contained in a composition. Moreover, in addition to the polyimide of this invention, the polyimide of the other structure manufactured without using metaphenylenediamine may be mixed. In that case, content of the polyimide of the other structure in a polymer component can be 0.5-15 mass%, Preferably it is 1-10 mass%.

In the composition of this invention, the polymer component containing the polyimide of this invention is contained in the dissolved state. As a solvent, the cyclic ketone which melt | dissolves the polyimide of this invention, is low solvent compared with NMP, and has a low surface tension characteristic is used.

Examples of the cyclic ketones include cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclononanone, and cyclodecanone. In particular, any of cyclohexanone and cyclopentanone, or a mixture thereof is preferable.

By using a cyclic ketone as a solvent, the liquid-crystal aligning agent which is excellent in applicability | paintability and can form a liquid crystal aligning film at lower temperature can be prepared from the said composition.

It is preferable that content of an organic solvent is 70-99 mass% from a viewpoint of forming a uniform film | membrane by application | coating of the composition of this invention, for example, a liquid-crystal aligning agent. This content can be suitably changed with the film thickness of the liquid crystal aligning film made into the objective.

In addition, although it is possible to use only a cyclic ketone solvent as a solvent in that case, it is also possible to mix and contain another organic solvent suitably within the range which does not prevent low temperature plasticization and applicability improvement.

Specific examples of other organic solvents include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, (gamma) -butyrolactone, 1, 3- dimethyl- imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, or 4-hydroxy-4-methyl-2-pentanone. These may be used alone or in combination.

Even when these other organic solvents are contained, the content of the cyclic ketone solvent is preferably 50 mass% or more in the total solvent, more preferably 60 mass% or more, and particularly preferably 70 mass% or more.

The composition of this invention, for example, a liquid-crystal aligning agent, is another organic solvent for improving applicability | paintability for the purpose of further improving the uniformity and surface smoothness of the film thickness of the film formed, unless the effect of this invention is impaired. (Hereinafter also referred to as poor solvent) can be contained.

As a specific example, the following is mentioned. Examples of the solvent include isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl But are not limited to, carbitol acetate, carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, Monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl Ether, dipropylene glycol monopro Fill ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, di Isobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, lactic acid Ethyl, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3- Ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, butyl 3-methoxypropionate, 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, dipropylene glycol, 2- (2- Solvents having low surface tension, such as ethoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, and lactic acid isoamyl ester. These poor solvents may be used by one type, and may be used in mixture of multiple types.

In the case of containing the poor solvent, the content of the cyclic ketone solvent is preferably 50 mass% or more, more preferably 60 mass% or more, and particularly preferably 70 mass% or more.

Moreover, the composition of this invention is a compound which improves the thickness uniformity and surface smoothness of the film at the time of apply | coating a composition or a liquid-crystal aligning agent, and the adhesiveness of the film | membrane formed to a board | substrate, and a board | substrate, unless the effect of this invention is impaired. It may include a compound to improve.

As a compound which improves the uniformity and surface smoothness of the film thickness of the film | membrane formed, a fluorochemical surfactant, silicone type surfactant, nonionic surfactant, etc. are mentioned. For example, F-top EF301, EF303, EF352 (made by Tochem Products), Megapuck F171, F173, R-30 (made by Dainippon Ink Corporation), Florade FC430, FC431 (made by Sumitomo 3M Corporation), Asahi Guard AG710, Supron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.) etc. are mentioned. The use ratio of these surfactant becomes like this. Preferably it is 0.01-2 mass parts with respect to 100 mass parts of the resin component contained in a composition, More preferably, it is 0.01-1 mass part.

As a specific example of the compound which improves the adhesiveness of the film | membrane formed and a board | substrate, a functional silane containing compound and an epoxy group containing compound shown next are mentioned. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy (3-aminopropyl) Aminopropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N- -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3- Aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 Tetraglycidyl-2,4-hexanediol, N, N, N ', N', tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylamino Methyl) cyclohexane, N, N, N ', N'- tetraglycidyl-4,4'- diamino diphenylmethane, etc. are mentioned.

When using the compound which improves the adhesiveness of the film | membrane formed and a board | substrate, it is preferable that the addition amount of this compound is 0.1-30 mass parts with respect to 100 mass parts of the polymer component contained in a composition, More preferably, it is 1-20. It is a mass part. If it is less than 0.1 mass part, the effect of adhesive improvement cannot be expected, and when more than 30 mass parts, the orientation of a liquid crystal may worsen.

The composition of the present invention, for example, a liquid-crystal aligning agent, a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group, and the like, as long as the effects of the present invention are not impaired. It may also contain a crosslinkable compound having at least one substituent selected from the group consisting of lower alkoxyalkyl groups or a crosslinkable compound having a polymerizable unsaturated bond.

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolak epoxy resin, triglycidyl isocyanurate, tetraglycidyl amino diphenylene Tetraglycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetate Diglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis 2- (4- (2,3-epoxypropoxy) phenyl) -2- (4-methylpentanoyloxyphenyl) octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl methadienyldiamine, 2- (4- (1, 4- (2,3-epoxypropoxy) phenyl) ethyl) phenyl) propane, 1,3- Oxy) phenyl) -1- (4- (1- (4- ( 2,3-epoxypropoxyphenyl) -1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol, etc. are mentioned.

The crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [4].

(34)

Specifically, it is a crosslinkable compound shown by following formula [4-1]-[4-11].

(35)

(36)

[Formula 37]

As a crosslinkable compound which has a cyclocarbonate group, it is a crosslinkable compound which has at least two cyclocarbonate groups represented by following formula [5].

(38)

Specifically, it is a crosslinking | crosslinked compound shown by following formula [5-1]-[5-37].

[Chemical Formula 39]

[Formula 40]

(41)

(42)

(43)

(44)

[Chemical Formula 45]

(46)

 (N is an integer of 1-5 in a formula [5-24], n is an integer of 1-5 in a formula [5-25], n is an integer of 1-100 in a formula [5-36]) And n is an integer of 1-10 in a formula [5-37].)

Moreover, the polysiloxane which has at least 1 sort (s) of structure shown by following formula [5-38]-[5-40] is also mentioned.

[Formula 47]

(In formula [5-38]-[5-40], R <_1> , R <_2> , R <_3> , R <_4> and R <_5> are respectively independently the structure represented by Formula [5], a hydrogen atom, a hydroxyl group, C1-C10. Is an alkyl group, an alkoxyl group, an aliphatic ring or an aromatic ring, and at least one is a structure represented by formula [5].)

More specifically, the compound of following formula [5-41] and formula [5-42] is mentioned.

(48)

(In formula [5-41], R <_6> is respectively independently a structure represented by Formula [5], a hydrogen atom, a hydroxyl group, a C1-C10 alkyl group, an alkoxyl group, an aliphatic ring, or an aromatic ring, At least 1 is a formula. It is a structure shown by [5], and n is an integer of 1-10 in a formula [5-42].)

As a crosslinkable compound which has at least 1 sort (s) of substituent chosen from the group which consists of a hydroxyl group and an alkoxyl group, For example, Amino resin which has a hydroxyl group or an alkoxyl group, For example, Melamine resin, Urea resin, Guanamine resin, glycoluril-formaldehyde resin, succinylamide-formaldehyde resin, ethylene urea-formaldehyde resin, etc. are mentioned. Specifically, a melamine derivative, a benzoguanamine derivative, or glycoluril in which the hydrogen atom of the amino group is substituted with a methylol group and / or an alkoxymethyl group can be used. This melamine derivative or benzoguanamine derivative can also exist as a dimer or a trimer. They preferably have 3 or more and 6 or fewer methylol groups or alkoxymethyl groups per one triazine ring.

Examples of melamine derivatives or benzoguanamine derivatives include MX-750, which has an average of 3.7 methoxymethyl groups substituted per triazine ring, and MW-30, which has an average of 5.8 methoxymethyl groups substituted per triazine ring. (Above, Sanwa Chemical Co., Ltd.) and methoxymethyl melamine such as Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, Cymel 235, 236, 238, 212, 253, 254 Methoxymethylated butoxymethylated melamine such as methoxymethylated butoxymethylated melamine, cymel 506, 508, carboxyl group-containing methoxymethylated isobutoxymethylated melamine such as cymel 1141, and methoxymethylated ethoxymethylated benzogua such as cymel 1123 Methoxymethylated butoxymethylated benzoguanamine such as namin, cymel 1123-10, butoxymethylated benzoguanamine such as cymel 1128, carboxyl group-containing methoxymethylated ethoxymethylated benzoguanamine such as cymel 1125-80 ( this In addition, Mitsui Cyanamid Co., Ltd.) etc. are mentioned.

Examples of glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylolated glycoluril such as Cymel 1172, and methoxymethylolated glycoluril such as Powder Link 1174.

As a benzene or phenolic compound which has a hydroxyl group or an alkoxyl group, it is 1,3, 5- tris (methoxymethyl) benzene, 1,2, 4- tris (isopropoxymethyl) benzene, 1, for example. , 4-bis (sec-butoxymethyl) benzene, 2,6-dihydroxymethyl-p-tert-butylphenol and the like.

Specifically, it is a crosslinking | crosslinked compound shown by following formula [6-1]-[6-48].

(49)

(50)

(51)

(52)

(53)

As a crosslinkable compound which has a polymerizable unsaturated bond, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tri (meth) ) Crosslinking | crosslinked compound which has three polymerizable unsaturated groups in a molecule | numerator, such as acryloyloxyethoxy trimethylol propane and a glycerin polyglycidyl ether poly (meth) acrylate; Ethylene glycol di (meth) acrylate, Diethylene glycol Di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di ( Meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide bis Phenol type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth Polymerizable unsaturated such as acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl ester di (meth) acrylate, and hydroxy pivalate neopentyl glycol di (meth) acrylate Crosslinkable compounds having two groups in a molecule; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2- Hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2 -(Meth) acryloyloxye Polymerizable unsaturated group such as a phosphoric acid ester, N- methyl-roll (meth) acrylamide crosslinking compound having in one molecule; and the like.

Furthermore, the compound shown by following formula [7] can also be used.

[Formula 54]

In formula [7], E <_1> is group chosen from the group which consists of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring, and a phenanthrene ring. And E ₂ are groups selected from the following formulas [7a] and [7b], and n is an integer of 1 to 4;

(55)

The said compound is an example of a crosslinkable compound, It is not limited to these. Moreover, one type may be sufficient as the crosslinking | crosslinked compound contained in the composition of this invention, and may be combined two or more types.

It is preferable that content of the crosslinkable compound in the composition of this invention is 0.1-150 mass parts with respect to 100 mass parts of polymer components. In order for a crosslinking reaction to advance and to express an objective effect, and not to reduce the orientation of a liquid crystal, 0.1-100 mass parts is more preferable with respect to 100 mass parts of polymer components, and 1-50 mass parts is the most preferable especially.

In addition to the above, in the composition of this invention, especially a liquid-crystal aligning agent, as long as the effect of this invention is not impaired, you may add the dielectric and electrically conductive material for the purpose of changing electrical characteristics, such as a dielectric constant and electroconductivity of a liquid crystal aligning film.

Moreover, when the composition of this invention is a liquid-crystal aligning agent, it is a compound which promotes the charge transfer in the liquid crystal aligning film formed, and promotes the charge leakage of the liquid crystal cell using this liquid crystal aligning film, with following formula [M1]-[M156]. The nitrogen containing heterocyclic amine compound shown can also be added. Although this amine compound may be added directly to the solution of a polymer, it is preferable to add, after making it the solution of density | concentration 0.1-10 mass%, Preferably 1-7 mass% with a suitable solvent. It will not specifically limit, if it is an organic solvent in which a polyimide is dissolved other than the cyclic ketone solvent mentioned above as this solvent.

(56)

(57)

(58)

[Chemical Formula 59]

(60)

(61)

<Liquid Crystal Alignment Film / Liquid Crystal Display Device>

The case where a liquid crystal aligning film is formed from a liquid-crystal aligning agent is demonstrated using the liquid-crystal aligning agent which is one of the compositions of this invention as an example. After apply | coating a liquid-crystal aligning agent on a board | substrate and baking by heat processing, it carries out an orientation process by a rubbing process, light irradiation, etc., and forms a liquid crystal aligning film. Moreover, in the case of a vertical alignment use etc., a liquid crystal aligning film can be formed even without an orientation processing.

The substrate is not particularly limited as long as it is a substrate having high transparency, and besides the glass substrate, plastic substrates such as an acrylic substrate and a polycarbonate substrate can be used. From the viewpoint of process simplification, it is preferable to use a substrate on which an ITO electrode or the like for liquid crystal driving is formed. In the reflective liquid crystal display element, an opaque substrate such as a silicon wafer can also be used as long as the substrate on one side, and in this case, a material that reflects light such as aluminum can also be used.

Although the coating method of a liquid-crystal aligning agent is not specifically limited, Industrially, the method of performing by screen printing, offset printing, flexographic printing, the inkjet method, etc. is common. Examples of other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method, and a spraying method, and they may be used depending on the purpose. Applicability | paintability is favorable even if the liquid-crystal aligning agent of this invention uses the above coating method.

After apply | coating a liquid-crystal aligning agent on a board | substrate, a solvent is heated at 50 degreeC-180 degreeC, Preferably it is 80 degreeC-150 degreeC by heating means, such as a hotplate, a thermocyclic oven, and an IR (infrared) oven. It can be made into a coating film by evaporation. When the thickness of the coating film after baking is too thick, it is unpreferable from the viewpoint of the power consumption of a liquid crystal display element, and when too thin, the reliability of a liquid crystal display element may fall. Therefore, the thickness of the coating film after baking becomes like this. Preferably it is 5-300 nm, More preferably, it is 10-100 nm. When the liquid crystal is horizontally oriented or tilted, the coated film after firing is subjected to rubbing, polarized ultraviolet irradiation, or the like.

The liquid crystal display element obtains the board | substrate with a liquid crystal aligning film from the liquid-crystal aligning agent of this embodiment by said method, and manufactures a liquid crystal cell by a well-known method, and makes it a liquid crystal display element.

As a liquid crystal cell manufacturing method, a pair of board | substrate with which the liquid crystal aligning film was formed is prepared, a spacer is sprayed on the liquid crystal aligning film of one board | substrate, and the other board | substrate is bonded together so that a liquid crystal aligning film surface may become inner side. And a method of injecting and sealing the liquid crystal under reduced pressure, or a method of bonding the substrate and sealing after dropping the liquid crystal onto the surface of the liquid crystal alignment film spreading the spacer.

A liquid crystal aligning film consists of a liquid crystal layer between a pair of board | substrates provided with an electrode, arrange | positions the liquid crystal composition containing the polymeric compound superposed | polymerized by at least one of an active energy ray and a heat between a pair of board | substrates, It is preferably used also for the liquid crystal display element manufactured through the process of superposing | polymerizing a polymeric compound by at least one of irradiation and heating of an active energy ray, applying a voltage between electrodes. Here, as the active energy ray, ultraviolet ray is preferable.

The liquid crystal display device controls the pretilt of the liquid crystal molecules by a polymer sustained alignment (PSA) method. In the PSA system, a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer is mixed in a liquid crystal material, and after assembling a liquid crystal cell, ultraviolet rays or the like are irradiated to the photopolymerizable compound in a state in which a predetermined voltage is applied to the liquid crystal layer. Then, the pretilt of the liquid crystal molecules is controlled by the produced polymer. Since the alignment state of the liquid crystal molecules when the polymer is produced is stored even after the voltage is removed, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field or the like formed on the liquid crystal layer. Moreover, since a rubbing process is not required with the PSA system, it is suitable for formation of the vertically-aligned liquid crystal layer which is difficult to control the pretilt by the rubbing process.

That is, after a liquid crystal display element obtains the board | substrate with a liquid crystal aligning film from the liquid-crystal aligning agent of this invention by said method, it manufactures a liquid crystal cell and polymerizes a polymeric compound by at least one of irradiation and heating of an ultraviolet-ray. By doing so, the orientation of the liquid crystal molecules can be controlled.

If an example of PSA system liquid crystal cell manufacture is given, a pair of board | substrate with which the liquid crystal aligning film was formed is prepared, a spacer is spread | dispersed on the liquid crystal aligning film of one board | substrate, and the other board | substrate is made so that the liquid crystal aligning film surface may become inner side. The method of bonding together, inject | pouring a liquid crystal under reduced pressure, and sealing it, the method of bonding a board | substrate together and sealing after dropping a liquid crystal on the liquid crystal aligning film surface which spread | dispersed the spacer, etc. are mentioned.

The liquid crystal is mixed with a polymerizable compound which is polymerized by irradiation with heat or ultraviolet rays. Examples of the polymerizable compound include a compound having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in the molecule. In that case, it is preferable that a polymeric compound is 0.01-10 mass parts with respect to 100 mass parts of liquid crystal components, More preferably, it is 0.1-5 mass parts. If the amount of the polymerizable compound is less than 0.01 part by mass, the polymerizable compound will not polymerize and the alignment of the liquid crystal can not be controlled. If more than 10 parts by mass, the unreacted polymerizable compound increases, .

After manufacturing a liquid crystal cell, heat or an ultraviolet-ray is irradiated and a polymeric compound is polymerized, applying an alternating current or direct current voltage to a liquid crystal cell. Thereby, the orientation of liquid crystal molecules can be controlled.

Moreover, the liquid-crystal aligning agent of this invention consists of having a liquid crystal layer between a pair of board | substrates provided with an electrode, and contains the polymeric group which superposes | polymerizes by at least one of an active energy ray and a heat between said pair of board | substrates. It is also used suitably also for the liquid crystal display element manufactured through the process of arrange | positioning a liquid crystal aligning film and applying a voltage between electrodes. Here, as the active energy ray, ultraviolet ray is preferable. As an ultraviolet-ray, wavelength is 300-400 nm, Preferably it is 310-360 nm. In the case of superposition | polymerization by heating, heating temperature is 40-120 degreeC, Preferably it is 60-80 degreeC.

In order to obtain the liquid crystal aligning film containing the polymeric group superposed | polymerized by at least one of an active energy ray and a heat | fever, the method of adding the compound containing this polymeric group in a liquid-crystal aligning agent, or using the polymer component containing a polymeric group is used. A method is mentioned. Since the liquid-crystal aligning agent of this invention contains the specific compound which has a double bond site | part which reacts by heat or irradiation of an ultraviolet-ray, the orientation of a liquid crystal molecule can be controlled by at least one of irradiation and heating of an ultraviolet-ray.

If an example of liquid crystal cell manufacture is given, a pair of board | substrate with which the liquid crystal aligning film was formed is prepared, the spacer is spread | dispersed on the liquid crystal aligning film of one board | substrate, the other board | substrate is bonded together so that a liquid crystal aligning film surface may become inward, The method of injecting and sealing a liquid crystal under reduced pressure, the method of bonding a board | substrate together and sealing after dropping a liquid crystal on the liquid crystal aligning film surface which spread | dispersed the spacer, etc. are mentioned.

A liquid crystal display element is obtained by passing through the above process. Since these liquid crystal display elements use the liquid crystal aligning film of this invention as a liquid crystal aligning film, a manufacturing process becomes lower temperature, is excellent in reliability, and can be used suitably for a large screen high definition liquid crystal television etc.

Example

Although an Example is given to the following and demonstrated, this invention is limited to these and is not interpreted. The abbreviation used by the Example and a comparative example is as follows.

<Metaphenylenediamine>

D1: m-phenylenediamine

D2: 3,5-diaminobenzoic acid

D3: N, N-diallyl-2,4-diaminoaniline

D4: 1,3-diamino-4- (octadecyloxy) benzene

D5: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene

D6: 1,3-diamino-4- {4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy} benzene

(62)

<Other diamines>

D7 ： p-phenylenediamine

(63)

<Tetracarboxylic dianhydride>

M1: 1,2,3,4-cyclobutanetetracarboxylic dianhydride

M2: Bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride

M3: 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid dianhydride

M4: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride

M5 ： Pyromellitic Acid 2 Anhydride

&Lt; EMI ID =

<Cyclic ketone organic solvent>

CHN: Cyclohexanone

CPN ： cyclopentanone

<Other organic solvent>

NMP: N-methyl-2-pyrrolidone

BCS: Ethylene Glycol Monobutyl Ether

PGME: Propylene glycol monomethyl ether

In Examples, physical properties such as molecular weight and imidation ratio related to the polyimide were evaluated as follows.

(Measurement of Molecular Weight of Polyimide)

The molecular weight of the polyimide in a synthesis example uses the room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (made by Showa Denko), and a column (KD-803, KD-805) (made by Shodex) Was measured as follows.

Column temperature: 50 ° C.

Eluent: N, N'-dimethylformamide (as additive, lithium bromide-hydrate (LiBr.H ₂ O) is 30 mmol / L (liter), phosphoric acid and anhydrous crystals (o-phosphate) is 30 mmol / L, tetra Hydrofuran (THF) 10 ml / l)

Flow rate: 1.0 ml / min

Standard sample for calibration curve preparation: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000, and 30,000) (made by Tosoh Corporation) and polyethylene glycol (molecular weight; about 12,000, 4,000, and 1,000) (made by Polymer Laboratories) .

(Measurement of imidization rate)

The imidation ratio of the polyimide in a synthesis example was measured as follows.

Polyimide powder (20 mg) was placed in an NMR sample tube (NMR sampling tube standard φ 5 (manufactured by Kusano Scientific Co., Ltd.)), and deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane) mixed product) (0.53 Ml) was added, and ultrasonic waves were added to dissolve completely. 500 MHz of proton NMR was measured for this solution by the NMR (nuclear magnetic resonance) measuring instrument (JNW-ECA500) (made by Nippon Electron Datum). The imidation ratio is determined based on the proton derived from the structure which does not change before and after imidization as a reference proton, and the peak integration value derived from the peak integration value of this proton and the NH group of the amic acid appearing around 9.5-10.0 ppm. It was calculated | required by the following formula using the following.

Imidation ratio (%) = (1-αx / y) × 100

In the above formula, x is the proton peak integrated value derived from the NH group of the amic acid, y is the peak integrated value of the reference proton, and α is the NH of the amic acid when the polyamic acid (imidization ratio is 0%). The ratio of the number of reference protons to one proton.

<Synthesis of polyimide>

&Lt; Synthesis Example 1 &

M2 (2.75 g, 11.0 mmol), D3 (2.68 g, 13.2 mmol), and D5 (3.35 g, 8.8 mmol) were mixed in NMP (26.4 g) and reacted at 80 ° C. for 5 hours, followed by M1 (2.14 g , 10.9 mmol) and NMP (17.3 g) were added, and it reacted at 40 degreeC for 6 hours, and obtained the polyamic-acid solution.

After adding NMP to this polyamic-acid solution (20.0g) and diluting to 6 mass%, acetic anhydride (4.11g) and pyridine (1.59g) were added as imidation catalyst, and it was made to react at 100 degreeC for 3 hours. . The reaction solution was poured into methanol (253 mL), and the obtained precipitate was separated by filtration. Methanol wash | cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder (A) was obtained. The imidation ratio of this polyimide was 80%, the number average molecular weight was 21,500 and the weight average molecular weight was 68,700.

&Lt; Synthesis Example 2 &

M2 (2.50 g, 10.0 mmol), D3 (2.44 g, 12.0 mmol), and D5 (3.04 g, 8.0 mmol) were mixed in NMP (24.0 g) and reacted at 80 ° C. for 5 hours, followed by M5 (2.15 g , 9.9 mmol) and NMP (16.6 g) were added, and it reacted at 40 degreeC for 6 hours, and obtained the polyamic-acid solution.

After adding NMP to this polyamic acid solution (20.0g) and diluting to 6 mass%, acetic anhydride (4.02g) and pyridine (1.56g) were added as imidation catalyst, and it was made to react at 100 degreeC for 3 hours. . The reaction solution was poured into methanol (253 mL), and the obtained precipitate was separated by filtration. Methanol wash | cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder (B) was obtained. The imidation ratio of this polyimide was 79%, the number average molecular weight was 18,700 and the weight average molecular weight was 57,800.

&Lt; Synthesis Example 3 &

M2 (8.07 g, 32.3 mmol), D2 (4.58 g, 30.1 mmol), and D6 (5.61 g, 12.9 mmol) were mixed in NMP (54.8 g) and reacted at 80 ° C. for 5 hours, followed by M1 (2.05 g , 10.5 mmol) and NMP (26.5 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution.

After adding NMP to this polyamic-acid solution (80.0g) and diluting to 6 mass%, acetic anhydride (17.3g) and pyridine (5.35g) were added as an imidation catalyst, and it was made to react at 100 degreeC for 3 hours. . This reaction solution was poured into methanol (1010 mL), and the obtained precipitate was separated by filtration. Methanol wash | cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder (C) was obtained. The imidation ratio of this polyimide was 80%, the number average molecular weight was 20,500 and the weight average molecular weight was 53,100.

&Lt; Synthesis Example 4 &

M2 (3.94 g, 15.7 mmol), D7 (1.14 g, 10.5 mmol), and D5 (4.00 g, 10.5 mmol) were mixed in NMP (27.2 g) and reacted at 40 ° C. for 5 hours, followed by M1 (0.99 g , 5.0 mmol) and NMP (13.0 g) were added, and it reacted at 40 degreeC for 6 hours, and obtained the polyamic-acid solution.

NMP was added to this polyamic acid solution (20.0g), and it diluted to 6 mass%, acetic anhydride (2.12g) and pyridine (1.65g) were added as imidation catalyst, and it was made to react at 80 degreeC for 3 hours. . This reaction solution was poured into methanol (247 mL), and the obtained precipitate was separated by filtration. Methanol wash | cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder (D) was obtained. The imidation ratio of this polyimide was 55%, the number average molecular weight was 15,100 and the weight average molecular weight was 51,200.

&Lt; Synthesis Example 5 &

M2 (3.94 g, 15.7 mmol), D2 (1.60 g, 10.5 mmol), and D6 (4.56 g, 10.5 mmol) were mixed in NMP (30.3 g) and reacted at 80 ° C. for 5 hours, followed by M1 (1.01 g , 5.2 mmol) and NMP (14.1 g) were added, and it reacted at 40 degreeC for 6 hours, and obtained the polyamic-acid solution.

NMP was added to this polyamic acid solution (20.0 g), and it diluted to 6 mass%, acetic anhydride (3.85 g) and pyridine (1.49 g) were added as imidation catalyst, and it was made to react at 100 degreeC for 3 hours. . This reaction solution was poured into methanol (252 mL), and the obtained precipitate was separated by filtration. Methanol wash | cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder (E) was obtained. The imidation ratio of this polyimide was 80%, the number average molecular weight was 21,500 and the weight average molecular weight was 63,200.

&Lt; Synthesis Example 6 &

M2 (4.32 g, 17.3 mmol), D2 (2.80 g, 18.4 mmol), and D6 (2.00 g, 4.6 mmol) were mixed in NMP (27.3 g) and reacted at 80 ° C. for 5 hours, followed by M1 (1.07 g , 5.5 mmol) and NMP (13.4 g) were added, and it reacted at 40 degreeC for 6 hours, and obtained the polyamic-acid solution.

NMP was added to this polyamic acid solution (20.0 g), and it diluted to 6 mass%, acetic anhydride (4.59 g) and pyridine (1.78 g) were added as imidation catalyst, and it was made to react at 100 degreeC for 3 hours. . This reaction solution was poured into methanol (256 mL), and the obtained precipitate was separated by filtration. Methanol wash | cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder (F) was obtained. The imidation ratio of this polyimide was 78%, the number average molecular weight was 18,300 and the weight average molecular weight was 56,400.

&Lt; Synthesis Example 7 &

M2 (9.01 g, 36.0 mmol), D2 (6.57 g, 43.2 mmol), and D6 (2.09 g, 4.8 mmol) were mixed in NMP (53.0 g) and reacted at 80 ° C. for 5 hours, followed by M1 (2.21 g , 11.3 mmol) and NMP (26.5 g) were added, and it reacted at 40 degreeC for 6 hours, and obtained the polyamic-acid solution.

After adding NMP to this polyamic-acid solution (20.0g) and diluting to 6 mass%, acetic anhydride (4.90g) and pyridine (1.90g) were added as imidation catalyst, and it was made to react at 100 degreeC for 3.5 hours. . This reaction solution was poured into methanol (257 mL), and the obtained precipitate was separated by filtration. Methanol wash | cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder (G) was obtained. The imidation ratio of this polyimide was 77%, the number average molecular weight was 17,500 and the weight average molecular weight was 48,900.

&Lt; Synthesis Example 8 &

M2 (11.9 g, 47.7 mmol), D2 (6.57 g, 43.2 mmol), and D6 (2.09 g, 4.8 mmol) were mixed in NMP (81.7 g) and reacted at 80 ° C. for 16 hours to give a polyamic acid solution. Got it.

After adding NMP to this polyamic acid solution (20.0g) and diluting to 6 mass%, acetic anhydride (4.74g) and pyridine (1.84g) were added as an imidation catalyst, and it was made to react at 100 degreeC for 3.5 hours. . This reaction solution was poured into methanol (256 mL), and the obtained precipitate was separated by filtration. Methanol wash | cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder (H) was obtained. The imidation ratio of this polyimide was 76%, the number average molecular weight was 17,200 and the weight average molecular weight was 51,100.

<Synthesis example 9>

M2 (9.01 g, 36.0 mmol), D2 (6.57 g, 43.2 mmol), and D6 (2.09 g, 4.8 mmol) were mixed in NMP (53.0 g) and reacted at 80 ° C. for 5 hours, followed by M1 (2.21 g , 11.3 mmol) and NMP (26.5 g) were added, and it reacted at 40 degreeC for 6 hours, and obtained the polyamic-acid solution.

After adding NMP to this polyamic-acid solution (20.0g) and diluting to 6 mass%, acetic anhydride (2.44g) and pyridine (1.90g) were added as an imidation catalyst, and it was made to react at 90 degreeC for 2.5 hours. . This reaction solution was poured into methanol (249 mL), and the obtained precipitate was separated by filtration. Methanol wash | cleaned this deposit, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (I). The imidation ratio of this polyimide was 52%, the number average molecular weight was 15,700 and the weight average molecular weight was 50,100.

&Lt; Synthesis Example 10 &

M2 (11.3 g, 45.0 mmol), and D1 (6.49 g, 60.0 mmol) were mixed in NMP (53.2 g) and reacted at 80 ° C. for 5 hours, followed by M1 (2.73 g, 13.9 mmol) and NMP (28.7 g ) Was added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution.

NMP was added to this polyamic acid solution (30.0g), and it diluted to 6 mass%, acetic anhydride (4.44g) and pyridine (3.44g) were added as imidation catalyst, and it was made to react at 90 degreeC for 2.5 hours. . This reaction solution was poured into methanol (378 mL), and the obtained precipitate was separated by filtration. Methanol wash | cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder (J) was obtained. The imidation ratio of this polyimide was 50%, the number average molecular weight was 17,600 and the weight average molecular weight was 52,000.

&Lt; Synthesis Example 11 &

M2 (5.07 g, 20.3 mmol), and D2 (4.11 g, 27.0 mmol) were mixed in NMP (27.5 g) and reacted at 80 ° C. for 5 hours, followed by M1 (1.22 g, 6.2 mmol) and NMP (14.1 g ) Was added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution.

After adding NMP to this polyamic-acid solution (20.0g) and diluting to 6 mass%, acetic anhydride (2.63g) and pyridine (2.04g) were added as an imidation catalyst, and it was made to react at 90 degreeC for 2.5 hours. . This reaction solution was poured into methanol (250 mL), and the obtained precipitate was separated by filtration. Methanol wash | cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder (K) was obtained. The imidation ratio of this polyimide was 49%, the number average molecular weight was 15,700 and the weight average molecular weight was 47,000.

&Lt; Synthesis Example 12 &

M2 (6.13 g, 24.5 mmol) and D2 (3.80 g, 25.0 mmol) were mixed in NMP (39.7 g) and reacted at 80 ° C. for 16 hours to obtain a polyamic acid solution.

After adding NMP to this polyamic-acid solution (20.0g) and diluting to 6 mass%, acetic anhydride (5.08g) and pyridine (1.97g) were added as an imidation catalyst, and it was made to react at 100 degreeC for 3.5 hours. . This reaction solution was poured into methanol (258 mL), and the obtained precipitate was separated by filtration. Methanol wash | cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder (L) was obtained. The imidation ratio of this polyimide was 75%, the number average molecular weight was 14,500 and the weight average molecular weight was 41,200.

&Lt; Synthesis Example 13 &

M1 (4.29 g, 21.9 mmol), D3 (3.13 g, 15.4 mmol), and D5 (2.51 g, 6.6 mmol) were mixed in NMP (39.7 g) and reacted at 25 ° C for 24 hours to give a polyamic acid solution. Got it.

NMP was added to this polyamic acid solution (10.0g), and it diluted to 6 mass%, acetic anhydride (1.35g) and pyridine (0.56g) were added as imidation catalyst, and it was made to react at 40 degreeC for 2 hours. . This reaction solution was poured into methanol (123 mL), and the obtained precipitate was separated by filtration. Methanol wash | cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder (M) was obtained. The imidation ratio of this polyimide was 53%, the number average molecular weight was 19,800 and the weight average molecular weight was 55,900.

&Lt; Synthesis Example 14 &

M3 (6.01 g, 20.0 mmol), D1 (1.51 g, 14.0 mmol), and D5 (2.28 g, 6.0 mmol) were mixed in NMP (39.2 g) and reacted at 40 ° C. for 40 hours to obtain a polyamic acid solution. Got it.

After adding NMP to this polyamic-acid solution (10.0g) and diluting to 6 mass%, acetic anhydride (4.17g) and pyridine (1.94g) were added as imidation catalyst, and it was made to react at 40 degreeC for 1 hour. . This reaction solution was poured into methanol (138 mL), and the obtained precipitate was separated by filtration. Methanol wash | cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder (N) was obtained. The imidation ratio of this polyimide was 80%, the number average molecular weight was 11,900 and the weight average molecular weight was 28,100.

&Lt; Synthesis Example 15 &

M4 (5.13 g, 22.9 mmol), D1 (1.74 g, 16.1 mmol), and D5 (2.63 g, 6.9 mmol) were mixed in NMP (38.0 g) and reacted at 40 ° C. for 24 hours to give a polyamic acid solution. Got it.

After adding NMP to this polyamic-acid solution (10.0g) and diluting to 6 mass%, acetic anhydride (1.23g) and pyridine (0.96g) were added as an imidation catalyst, and it was made to react at 90 degreeC for 3.5 hours. . This reaction solution was poured into methanol (124 mL), and the obtained precipitate was separated by filtration. Methanol wash | cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder (O) was obtained. The imidation ratio of this polyimide was 60%, the number average molecular weight was 14,800 and the weight average molecular weight was 30,500.

&Lt; Synthesis Example 16 &

M4 (5.13 g, 22.9 mmol), D1 (1.74 g, 16.1 mmol), and D5 (2.63 g, 6.9 mmol) were mixed in NMP (38.0 g) and reacted at 40 ° C. for 24 hours to give a polyamic acid solution. Got it.

NMP was added to this polyamic acid solution (10.0 g), and it diluted to 6 mass%, acetic anhydride (2.47 g) and pyridine (0.96 g) were added as imidation catalyst, and it was made to react at 100 degreeC for 3 hours. . This reaction solution was poured into methanol (124 mL), and the obtained precipitate was separated by filtration. Methanol wash | cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder (P) was obtained. The imidation ratio of this polyimide was 77%, the number average molecular weight was 14,200 and the weight average molecular weight was 30,000.

<Synthesis example 17>

M2 (17.7 g, 70.5 mmol), D2 (8.21 g, 54.0 mmol), and D6 (12.6 g, 29.1 mmol) were mixed in NMP (115 g) and reacted at 80 ° C. for 5 hours, followed by M1 (2.28 g , 11.6 mmol) and NMP (47.6 g) were added, and it reacted at 40 degreeC for 6 hours, and obtained the polyamic-acid solution.

After adding NMP to this polyamic-acid solution (80.0g) and diluting to 6 mass%, acetic anhydride (9.94g) and pyridine (5.14g) are added as an imidation catalyst, and it is 100 hours at 2 degreeC. Reacted. This reaction solution was poured into methanol (986 mL), and the obtained precipitate was separated by filtration. Methanol wash | cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder (Q) was obtained. The imidation ratio of this polyimide was 70%, the number average molecular weight was 18,900 and the weight average molecular weight was 51,400.

<Synthesis example 18>

M2 (4.50 g, 18.0 mmol), D1 (1.82 g, 16.8 mmol), and D4 (2.71 g, 7.2 mmol) were mixed in NMP (27.1 g) and reacted at 80 ° C. for 5 hours, followed by M1 (1.12 g , 5.7 mmol) and NMP (13.5 g) were added, and it reacted at 40 degreeC for 6 hours, and obtained the polyamic-acid solution.

NMP was added to this polyamic acid solution (20.0g), and it diluted to 6 mass%, acetic anhydride (2.40g) and pyridine (1.86g) were added as imidation catalyst, and it was made to react at 80 degreeC for 3 hours. . This reaction solution was poured into methanol (248 mL), and the obtained precipitate was separated by filtration. Methanol wash | cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder (R) was obtained. The imidation ratio of this polyimide was 53%, the number average molecular weight was 17,700 and the weight average molecular weight was 50,300.

<Synthesis example 19>

M2 (2.87 g, 11.5 mmol), D7 (1.24 g, 11.5 mmol), and D2 (0.70 g, 4.6 mmol), D6 (3.00 g, 6.9 mmol) were mixed in NMP (23.5 g) and 5 at 80 ° C. After reacting for a time, M1 (2.21 g, 11.3 mmol) and NMP (16.7 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution.

NMP was added to this polyamic acid solution (20.0g), and it diluted to 6 mass%, acetic anhydride (4.66g) and pyridine (1.81g) were added as imidation catalyst, and it was made to react at 50 degreeC for 3 hours. . This reaction solution was poured into methanol (256 mL), and the obtained precipitate was separated by filtration. Methanol wash | cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder (S) was obtained. The imidation ratio of this polyimide was 49%, the number average molecular weight was 20,700 and the weight average molecular weight was 61,100.

<Synthesis example 20>

M3 (6.61 g, 22.0 mmol), D7 (2.02 g, 18.7 mmol), and D5 (1.26 g, 3.3 mmol) were mixed in NMP (39.5 g) and reacted at 40 ° C. for 40 hours to obtain a polyamic acid solution. Got it.

NMP was added to this polyamic acid solution (10.0g), and it diluted to 6 mass%, acetic anhydride (4.54g) and pyridine (2.11g) were added as imidation catalyst, and it was made to react at 40 degreeC for 30 minutes. . This reaction solution was poured into methanol (140 mL), and the obtained precipitate was separated by filtration. Methanol wash | cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder (T) was obtained. The imidation ratio of this polyimide was 82%, the number average molecular weight was 11,000 and the weight average molecular weight was 22,100.

<Synthesis example 21>

M2 (4.13 g, 16.5 mmol), D7 (1.67 g, 15.4 mmol), and D6 (2.87 g, 6.6 mmol) were mixed in NMP (26.0 g) and reacted at 40 ° C. for 5 hours, followed by M1 (1.03 g , 5.3 mmol) and NMP (13.2 g) were added, and it reacted at 40 degreeC for 6 hours, and obtained the polyamic-acid solution.

After adding NMP to this polyamic-acid solution (20.0g) and diluting to 6 mass%, acetic anhydride (2.31g) and pyridine (1.79g) were added as imidation catalyst, and it was made to react at 80 degreeC for 3 hours. . This reaction solution was poured into methanol (248 mL), and the obtained precipitate was separated by filtration. Methanol wash | cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder (U) was obtained. The imidation ratio of this polyimide was 51%, the number average molecular weight was 15,100 and the weight average molecular weight was 45,200.

<Synthesis example 22>

M2 (1.65 g, 6.6 mmol), D2 (2.18 g, 14.3 mmol), and D6 (3.35 g, 7.7 mmol) were mixed in NMP (21.5 g) and reacted at 80 ° C. for 5 hours, followed by M1 (2.93 g , 14.9 mmol) and NMP (18.9 g) were added, and it reacted at 40 degreeC for 6 hours, and obtained the polyamic-acid solution.

NMP was added to this polyamic acid solution (25.0 g), and it diluted to 6 mass%, acetic anhydride (2.75 g) and pyridine (2.13 g) were added as imidation catalyst, and it was made to react at 50 degreeC for 3 hours. . This reaction solution was poured into methanol (310 mL), and the obtained precipitate was separated by filtration. Methanol wash | cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder (V) was obtained. The imidation ratio of this polyimide (V) was 67%, the number average molecular weight was 15,700 and the weight average molecular weight was 41,400.

<Synthesis example 23>

M2 (5.63 g, 22.5 mmol), and D7 (3.24 g, 30.0 mmol) were mixed in NMP (26.6 g) and reacted at 40 ° C. for 5 hours, followed by M1 (1.24 g, 6.3 mmol) and NMP (13.8 g ) Was added and reacted at 25 ° C. for 6 hours to obtain a polyamic acid solution.

NMP was added to this polyamic acid solution (20.0g), and it diluted to 5 mass%, acetic anhydride (2.96g) and pyridine (2.29g) were added as imidation catalyst, and it was made to react at 90 degreeC for 2.5 hours. . This reaction solution was poured into methanol (298 mL), and the obtained precipitate was separated by filtration. Methanol wash | cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder (W) was obtained. The imidation ratio of this polyimide was 51%, the number average molecular weight was 15,300 and the weight average molecular weight was 68,800. In addition, this polyimide did not use metaphenylenediamine as a diamine component.

The composition and imidation ratio of the polyimide obtained by the synthesis examples 1-5 are put together in Table 43, and are shown.

<Solubility Test of Polyimide>

<Examples 1-22 and Comparative Example 1>

The solubility test with respect to cyclohexanone (CHN) and cyclopentanone (CPN) which are cyclic ketone solvents was performed using the polyimide powder obtained by the synthesis examples 1-23.

CHN (15.7g) was added to each polyimide powder (1.0g) of polyimide powder (A)-(W), it stirred at 25 degreeC for 24 hours, and the presence or absence of turbidity and precipitation was visually confirmed.

Next, CPN (15.7g) is added to each polyimide powder (1.0g) of polyimide powder (A)-(W), it stirred at 25 degreeC for 24 hours, and the presence or absence of turbidity, precipitation, etc. visually Confirmed.

The results of the solubility test are shown in Table 44.

From the above results, it was confirmed that the polyimide powders of Examples 1 to 22 were uniformly dissolved in the cyclic ketone solvent. On the other hand, the polyimide powder (W) of the comparative example 1 was insoluble in the cyclic ketone solvent.

<Preparation of the composition containing a polyimide and a solvent, and a liquid-crystal aligning agent>

<Examples 23-44>

CHN (27.6g) was added to each of the polyimide powder (A)-(V) (each 1.0g) of the synthesis examples 1-22, it stirred at 50 degreeC for 24 hours, and dissolved each polyimide. Abnormalities, such as haze and precipitation, were not seen with any polyimide solution, and it was confirmed that it was a uniform solution.

Next, about each obtained polyimide solution, it filtered under pressure with the membrane filter of 1 micrometer of pore diameters, and obtained the liquid-crystal aligning agent (1)-(22) whose polyimide component content is 3.5 mass%.

<Examples 45-66>

CPN (27.6g) was added to each of the polyimide powder (A)-(V) (each 1.0g) of the synthesis examples 1-22, it stirred at 50 degreeC for 24 hours, and dissolved each polyimide. Abnormalities, such as haze and precipitation, were not seen with any polyimide solution, and it was confirmed that it was a uniform solution.

Then, about each obtained polyimide solution, it filtered under pressure with the membrane filter of 1 micrometer of pore diameters, and obtained the liquid-crystal aligning agent (23)-(44) whose polyimide component content is 3.5 mass%.

<Examples 67-70>

CHN (13.3 g) is added to each of the polyimide powder (E) of the synthesis example 5, and the polyimide powders (O)-(Q) (each 1.0 g) of the synthesis examples 15-17, and it stirred at 50 degreeC for 24 hours. And each polyimide was dissolved. Then, NMP (14.3g) was further added and stirred to each obtained solution, and each polyimide solution containing CHN and NMP was obtained. Abnormalities, such as haze and precipitation, were not seen with any polyimide solution, and it was confirmed that it was a uniform solution.

Then, it filtered under pressure with the membrane filter of 1 micrometer of pore diameters about each solution containing CHN and NMP, and obtained the liquid-crystal aligning agent (45)-(48) whose polyimide component content is 3.5 mass%.

<Examples 71-74>

CHN (13.3 g) is added to each of the polyimide powder (E) of the synthesis example 5, and the polyimide powders (O)-(Q) (each 1.0 g) of the synthesis examples 15-17, and it stirred at 50 degreeC for 24 hours. And each polyimide was dissolved. Then, NMP (5.71g) and BCS (8.57g) were further added and stirred to each obtained solution, and each polyimide solution containing CHN, NMP, and BCS was obtained. Abnormalities, such as haze and precipitation, were not seen with any polyimide solution, and it was confirmed that it was a uniform solution.

Subsequently, it pressure-filtered by the membrane filter of 1 micrometer of pore diameters about each polyimide solution containing CHN, NMP, and BCS, and obtained the liquid-crystal aligning agent (49)-(52) whose polyimide component content is 3.5 mass%. .

<Examples 75 to 78>

CPN (13.3g) is added to each of the polyimide powder (E) of the synthesis example 5, and the polyimide powder (O)-(Q) (each 1.0g) of the synthesis examples 15-17, and it stirred at 50 degreeC for 24 hours. And each polyimide was dissolved. Then, NMP (14.3g) was further added and stirred to each obtained solution, and each polyimide solution containing CPN and NMP was obtained. Abnormalities, such as haze and precipitation, were not seen with any polyimide solution, and it was confirmed that it was a uniform solution.

Subsequently, it filtered under pressure with the membrane filter of 1 micrometer of pore diameters about each polyimide solution containing CPN and NMP, and obtained the liquid-crystal aligning agent (53)-(56) whose polyimide component content is 3.5 mass%.

<Examples 79-82>

CPN (13.3g) is added to each of the polyimide powder (E) of the synthesis example 5, and the polyimide powder (O)-(Q) (each 1.0g) of the synthesis examples 15-17, and it stirred at 50 degreeC for 24 hours. And each polyimide was dissolved. Then, NMP (5.71g) and BCS (8.57g) were further added and stirred to each obtained solution, and each polyimide solution containing CPN, NMP, and BCS was obtained. Abnormalities, such as haze and precipitation, were not seen with any polyimide solution, and it was confirmed that it was a uniform solution.

Next, about each polyimide solution containing CPN, NMP, and BCS, it filtered under pressure with the membrane filter of 1 micrometer of pore diameters, and obtained the liquid-crystal aligning agent (57)-(60) whose polyimide component content is 3.5 mass%. .

<Examples 83 to 86>

CHN (19.0g) is added to each of the polyimide powder (E) of the synthesis example 5, and the polyimide powder (O)-(Q) (each 1.0g) of the synthesis examples 15-17, and it stirred at 50 degreeC for 24 hours. And each polyimide was dissolved. Then, PGME (8.57g) was further added and stirred to each obtained solution, and each polyimide solution containing CHN and PGME was obtained. Abnormalities, such as haze and precipitation, were not seen with any polyimide solution, and it was confirmed that it was a uniform solution.

Subsequently, it filtered under pressure with the membrane filter of 1 micrometer of pore diameters about each polyimide solution containing CHN and PGME, and obtained the liquid-crystal aligning agent (61)-(64) whose polyimide component content is 3.5 mass%.

<Examples 87-90>

CPN (19.0g) is added to each of the polyimide powder (E) of the synthesis example 5, and the polyimide powders (O)-(Q) (1.0 g) of the synthesis examples 15-17, and it stirred at 50 degreeC for 24 hours. And each polyimide was dissolved. Then, PGME (8.57g) was further added and stirred to each obtained solution, and each polyimide solution containing CPN and PGME was obtained. Abnormalities, such as haze and precipitation, were not seen with any polyimide solution, and it was confirmed that it was a uniform solution.

Next, about each polyimide solution containing CPN and PGME, it filtered under pressure with the membrane filter of 1 micrometer of pore diameters, and obtained the liquid-crystal aligning agent (65)-(68) whose polyimide component content is 3.5 mass%.

<Comparative Example 2-Comparative Example 6>

NMP (31.3 g) to each of the polyimide powder (D) of the synthesis example 4, the polyimide powder (E) of the synthesis example 5, and the polyimide powders (O)-(Q) (each 2.0 g) of the synthesis examples 15-17. ) Was added and stirred at 50 ° C. for 24 hours to dissolve each polyimide. Abnormalities, such as haze and precipitation, were not seen with any polyimide solution, and it was confirmed that it was a uniform solution.

Next, about each obtained polyimide solution, it filtered under pressure with the membrane filter of 1 micrometer of pore diameters, and obtained the liquid-crystal aligning agent (69)-(73) whose polyimide component content is 6 mass%.

The kind and solubility of the polyimide and a solvent of the liquid-crystal aligning agent obtained in Examples 23-90 and Comparative Examples 2-6 are shown to Tables 45-48.

<Manufacture of a liquid crystal aligning film and a liquid crystal display element>

The liquid crystal aligning film was produced using the liquid-crystal aligning agent obtained in Examples 23-66, and the liquid crystal display element using the liquid crystal aligning film was manufactured. As a liquid crystal display element, the liquid crystal cell of the parallel orientation, or the liquid crystal cell of the vertical alignment was produced corresponding to the characteristic of the liquid crystal aligning film.

As a manufacturing method of a liquid crystal cell, a liquid-crystal aligning agent is spin-coated to the glass substrate (40 mm x 30 mm, thickness 0.7 mm) with an ITO electrode, and thermocycle type clean for 5 minutes on an 80 degreeC hotplate. After heat-processing for 30 minutes at 220 degreeC in oven, the liquid crystal aligning film was formed as a coating film with a film thickness of 100 nm, and the board | substrate with a liquid crystal aligning film was obtained. It turned out that the liquid crystal aligning film formed on the board | substrate all was excellent in the uniformity of film thickness, and the liquid-crystal aligning agent showed the outstanding applicability | paintability.

In the liquid crystal aligning film for parallel orientation, the well-known rubbing process was performed with respect to the obtained board | substrate with a liquid crystal aligning film.

Moreover, the rubbing process was not performed in the board | substrate with a liquid crystal aligning film for vertical alignment.

After preparing two board | substrates with this liquid crystal aligning film, and spread | dispersing a 6 micrometers spacer on one liquid crystal aligning film surface, the sealing compound (XN-1500T, Mitsui Chemicals Corporation) was printed from on this. Subsequently, after bonding together the other board | substrate and the liquid crystal aligning film surface, the sealing agent was hardened by heat-processing at 150 degreeC for 90 minute (s) in a thermocycling clean oven, and manufactured the empty cell. The nematic liquid crystal was inject | poured into this empty cell by the pressure reduction injection method, the injection hole was sealed and the liquid crystal cell of the parallel orientation or the liquid crystal cell of the vertical orientation was obtained. In that case, the liquid crystal cell for parallel orientation (MLC-2003, Merck Corporation make) was used for the liquid crystal cell of parallel alignment, and the liquid crystal for vertical alignment (MLC-6608, Merck Corporation make) was used for the vertical alignment liquid crystal cell.

About the obtained liquid crystal cell, when the orientation state of the liquid crystal was observed with the polarization microscope (ECLIPSE E600WPOL, Nikon Corporation make), it was confirmed that the parallel orientation or the vertical orientation of the uniform liquid crystal without a defect is formed.

Table 49 and Table 50 show the results of the alignment state of the liquid crystal of the liquid crystal display element.

Next, Example 26, Example 27, Examples 37-39, Example 48, Example 49, Examples 59-61, Example 83, Example 86, Example 87, Example 90, and Comparative Example The liquid crystal display element was manufactured using the liquid crystal cell manufactured using the 2-6 liquid-crystal aligning agent. The liquid crystal display element was manufactured by the method mentioned above. A voltage of 1 V was applied to these liquid crystal display elements at a temperature of 80 ° C., a voltage of 50 μm was measured, and the voltage retention was measured as voltage retention as compared with just after application. In addition, the measurement was performed using the VHR-1 voltage retention measuring apparatus (made by Toyo Techni Co., Ltd.) with the settings of Voltage: ± 1 V, Pulse Width: 60 Hz, and Flame Period: 50 Hz.

Table 51 shows the results of the voltage retention of the liquid crystal display element.

The above result shows that the liquid-crystal aligning agent of this invention can be obtained from the polyimide obtained using the diamine component containing metaphenylenediamine, and this liquid-crystal aligning agent is excellent in applicability | paintability. Moreover, it turns out that manufacture of the liquid crystal aligning film using the liquid-crystal aligning agent of this invention is possible by low temperature baking.

Industrial availability

The composition of the present invention can be widely used for forming films such as interlayer insulating films and protective films in electronic devices and the like, and in particular, as a liquid-crystal aligning agent, the coating properties are excellent and the properties can be baked at low temperatures. It is used for liquid crystal aligning film formation used for a high liquid crystal display element.

In addition, the JP Patent application 2011-049431, the claim, and all the content of the abstract for which it applied on March 7, 2011 are referred here, and it takes in as an indication of the specification of this invention.

Claims (14)

The polyimide precursor obtained by making the diamine component containing 1 or more types chosen from the group which consists of unsubstituted metaphenylenediamine and substituted metaphenylenediamine, and tetracarboxylic dianhydride component react, and / or its polyimide precursor The imidized polyimide and the cyclic ketone solvent which melt | dissolves the polyimide precursor and / or polyimide are contained, The composition characterized by the above-mentioned. The method of claim 1,
The composition in which the said substituted metaphenylenediamine is diamine represented by following formula [1].
[Chemical Formula 1]

(In formula [1], X is a substituent and n is an integer of 0-4.) 3. The method of claim 2,
The X in the above formula _{[1] - (CH 2)} a -COOH group (a is an integer of 0-4), - (CH _{2) b} -OH groups (b is an integer of 0-4), a carbon number of 8 The composition represented by the group represented by following formula [2] or the di-substituted amino group substituted by the hydrocarbon group of -22, the C1-C6 hydrocarbon group.
(2)

A (a is an integer of 1 ~ 15), -O-, -CH 2 O-, -COO- or -OCO-, - (formula [2], Y ¹ is a single bond, - (CH _{2) a} Y ² is a single bond or-(CH ₂ ) _b- (b is an integer of 1 to 15), Y ³ is a single bond,-(CH ₂ ) _c- (c is an integer of 1 to 15),- O-, -CH ₂ O-, -COO- or -OCO-.
Y ⁴ is a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring (any hydrogen atom on these cyclic groups may be an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, or 1 to 3 carbon atoms). May be substituted with a fluorine-containing alkyl group of 3, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms or a fluorine atom), or a divalent organic group selected from an organic group having 12 to 25 carbon atoms having a steroid skeleton, and Y ⁵ is benzene. A cyclic group selected from the group consisting of a ring, a cyclohexane ring and a heterocyclic ring (any hydrogen atom on these cyclic groups may be an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, or a fluorine having 1 to 3 carbon atoms). An alkyl group, a C1-C3 fluorine-containing alkoxyl group, or a fluorine atom), and Y ⁶ Is a C1-C18 alkyl group, a C1-C18 fluorine-containing alkyl group, a C1-C18 alkoxyl group, or a C1-C18 fluorine-containing alkoxyl group, n is an integer of 0-4.) The method of claim 3, wherein
The above formula [1] X in the - (CH _{2) a} -COOH group (a is an integer of 0-4) in the composition. The method according to claim 2 or 3,
The X in the above formula _{[1] - (CH 2)} a -COOH group (a is an integer from 0 to 4) or the formula [2] the composition. 6. The method according to any one of claims 2 to 5,
The composition whose content of the diamine represented by said Formula [1] is 15-100 mol% in a diamine component. 7. The method according to any one of claims 1 to 6,
The said tetracarboxylic dianhydride is a compound represented by following formula [3].
(3)

(In the formula [3], Z ₁ is a quadrivalent organic group having 4 to 13 carbon atoms and further contains a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms.) The method of claim 7, wherein
The composition whose Z < ₁ > is a structure shown by following formula [3a]-[3j].
[Chemical Formula 4]

(In formula [3a], Z <_2> -Z <_5> is a hydrogen atom, a methyl group, a chlorine atom, or a benzene ring, respectively, may be same or different, and in formula [3g], Z <_6> and Z <_7> are a hydrogen atom or a methyl group. , May be the same or different from each other.) The method according to any one of claims 1 to 8,
The cyclic ketone solvent comprises a cyclic ketone of at least one of a 5-membered ring and a 6-membered ring cyclic ketone. The liquid-crystal aligning agent which consists of a composition of any one of Claims 1-9. The liquid crystal aligning film obtained from the liquid-crystal aligning agent of Claim 10. The method of claim 11,
A liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes and containing a polymerizable compound capable of polymerizing by at least one of active energy rays and heat is disposed between the pair of substrates, Wherein the polymerizable compound is polymerized while applying a voltage between the polymerizable compound and the polymerizable compound. The liquid crystal display element which has a liquid crystal aligning film of Claim 11. The method of claim 13,
A liquid crystal composition is formed between a pair of substrates provided with an electrode and the liquid crystal alignment film, and a liquid crystal composition comprising a polymerizable compound polymerized by at least one of active energy rays and heat between the pair of substrates. And a step of polymerizing the polymerizable compound while applying a voltage between the electrodes.