KR20140045556A - Composition liquid crystal alignment treatment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

The composition used for formation of a film, especially the liquid-crystal aligning agent used for formation of a liquid crystal aligning film, the liquid crystal aligning film obtained, and a liquid crystal display element are provided.
A composition containing the polyimide which imidated the polyimide precursor obtained by making the diamine component containing the diamine compound which has a carboxyl group, and the tetracarboxylic acid component and / or this polyimide precursor, and the compound represented by following formula [1] .
(Formula 1)

(In formula [1], R <_1> is a C1-C4 alkyl group.)

Description

COMPOSITION LIQUID CRYSTAL ALIGNMENT TREATMENT AGENT, LIQUID CRYSTAL ALIGNMENT FILM, AND LIQUID CRYSTAL DISPLAY ELEMENT

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

The film | membrane which consists of organic materials, such as a polymeric material, pays attention to ease of formation, insulation performance, etc., and is widely used as an interlayer insulation film, a protective film, etc. in an electronic device. 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.

A liquid crystal aligning film is a structural member of the liquid crystal display element widely used as a display device, is formed in the surface of the board | substrate which sandwiches a liquid crystal, and plays a role which orientates a liquid crystal in a fixed direction. Moreover, the liquid crystal aligning film has a role which controls the pretilt angle of a liquid crystal other than the role which orientates a liquid crystal.

Moreover, in recent years, as a liquid crystal display element becomes high functional and its use range expands, the liquid crystal aligning film has calculated | required 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 the 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 with the liquid-crystal aligning agent which is a composition containing the solution of the polyimide which imidated the polyamic acid (polyamic acid) and / or polyamic acid which is a polyimide precursor. That is, the liquid crystal aligning film of a polyimide system is formed by apply | coating the liquid-crystal aligning agent which consists of a solution of polyimide or the solution of the polyamic acid which is a polyimide precursor, to a board | substrate, and baking at the temperature of about 250 degreeC normally ( For example, refer patent document 1).

Japanese Patent Application Laid-Open No. 09-278724

The polyimide-based liquid crystal aligning film is formed by applying a liquid crystal aligning agent composed of a solution of polyimide or a solution of polyamic acid that is a polyimide precursor to a substrate, and then baking the coating film. In particular, there is a need for an improvement in wet diffusion to substrates. By the improvement of wet-diffusion, defects, such as a crater and a pinhole at the time of print application, can be suppressed in the application | coating process in the process of liquid crystal aligning film formation.

The organic film of a polyimide system is widely used also in an interlayer insulating film, a protective film, etc. in an electronic device, and can be formed from the composition containing the solution of polyamic acid or polyimide which is a polyimide precursor, and the case of a liquid crystal aligning film Similarly, improvement of applicability is demanded. The improvement of applicability becomes effective for suppressing the defect at the time of print application.

Therefore, the present invention is a liquid crystal capable of forming a composition capable of forming a polyimide-based organic film having a high wet diffusion property on a substrate with improved coating properties, in particular, a liquid crystal alignment film in which defects such as cratering and pinholes are suppressed. It aims at providing the liquid crystal aligning film obtained from an orientation processing agent, this liquid-crystal aligning agent, and this liquid crystal aligning film.

This invention has the following summary.

(1) It contains the polyimide which imidated the polyimide precursor and / or polyimide precursor obtained by making the diamine component containing the diamine compound which has a carboxyl group, and the tetracarboxylic-acid component, and the compound represented by following formula [1] A composition, characterized in that.

[Chemical Formula 1]

(In formula [1], R <_1> is a C1-C4 alkyl group.)

(2) The composition as described in said (1) whose compound represented by said Formula [1] is a compound represented by following formula [2] or following formula [3].

(2)

(3)

(3) a diamine compound having the carboxyl group, - (CH _{2) a} -COOH group (a is an integer from 0 to 4) the composition according to the diamine compound (1) or (2) with.

(4) The composition as described in any one of said (1)-(3) whose diamine compound which has the said carboxyl group is a diamine compound of the structure shown by following formula [4].

[Chemical Formula 4]

(A shows the integer of 0-4 in formula [4], and n shows the integer of 1-4.)

(5) The composition as described in any one of said (1)-(4) whose content of the said diamine compound is 20-100 mol% in the said diamine component.

(6) The composition according to any one of (1) to (5), in which the diamine component contains a second diamine compound having a structure represented by the following Formula [5].

[Chemical Formula 5]

(Equation [5], X is, - (CH _{2) b} -OH groups (b is an integer from 0 to 4), substituted hydrocarbon groups having 1 to 22 hydrocarbon group, having 1 to 6 carbon atoms of the di-substituted amino group Or a group represented by following formula [6], n shows the integer of 1-4.)

[Chemical Formula 6]

(Formula [6] of the, Y ¹ represents a single _{bond, - (CH 2) a -} . (A 1 to an integer of 15), is -O-, -CH ₂ O-, -COO- or OCO- 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 divalent cyclic group selected from a benzene ring, a cyclohexyl ring, and a hetero 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 having 1 to 3 carbon atoms). It may be substituted by a fluorine-containing alkyl group, a C1-C3 fluorine-containing alkoxyl group, or a fluorine atom), or a C12-C25 divalent organic group which has a steroid skeleton. Y ⁵ Is a divalent cyclic group selected from a benzene ring, a cyclohexyl ring and a heterocyclic ring (any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine atom having 1 to 3 carbon atoms Containing alkyl group, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom). Y ⁶ Is a hydrogen atom, 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. and n represents an integer of 0 to 4.)

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

[Formula 7]

(In formula [7], Z <_1> is a C4-C13 tetravalent organic group and contains a C4-C10 non-aromatic cyclic hydrocarbon group.)

(8) Z ₁ The composition as described in said (7) which is a structure shown by following formula [7a]-[7j].

[Chemical Formula 8]

(Wherein _{[7a], Z 2 ~ Z} 5 Is a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different, respectively, and is represented by Z <_6> and Z < ₇ > in a formula [7g] Is a hydrogen atom or a methyl group, and may be the same or different, respectively.)

(9) The liquid-crystal aligning agent containing the composition in any one of said (1)-(8).

(10) The liquid crystal aligning film obtained from the liquid-crystal aligning agent as described in said (9).

(11) The liquid crystal aligning film obtained by the inkjet method using the liquid-crystal aligning agent as described in said (9).

(12) having a liquid crystal layer between a pair of substrates provided with electrodes, and disposing a liquid crystal composition containing a polymerizable compound polymerized by at least one of active energy rays and heat between the pair of substrates; The liquid crystal aligning film as described in said (10) or (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 (10) or (11).

(14) A liquid crystal comprising a liquid crystal layer between an electrode and a pair of substrates provided with the liquid crystal alignment film, and containing a polymerizable compound polymerized 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) characterized by arrange | positioning a composition and manufacturing through the process of superposing | polymerizing the said polymeric compound, applying a voltage between the said electrodes.

According to this invention, the composition which can form the polyimide film excellent in applicability | paintability is provided. In particular, the liquid-crystal aligning agent which is excellent in applicability | paintability and which can form the liquid crystal aligning film in which defects, such as a cratering and a pinhole, was suppressed is provided.

The liquid crystal aligning film obtained using the liquid-crystal aligning agent of this invention can form a film without a defect, and the liquid crystal display element which has such a liquid crystal aligning film has high characteristics and reliability.

Formation of a polyimide-based film, in particular a polyimide-based liquid crystal alignment film, is carried out using a solution of polyimide obtained by dissolving a polyimide or polyimide precursor in a solvent, or a solution of a polyimide precursor, as described above. It consists of forming and apply | coating to a board | substrate and baking at the temperature of about 200-300 degreeC normally.

When polyamic acid which is a polyimide precursor is used for formation of a polyimide-type liquid crystal aligning film, dehydration ring-closure reaction (thermal imidation) of polyamic acid is performed by heating.

On the other hand, when forming a polyimide-type liquid crystal aligning film using the solution of a polyimide, the main objective of a baking process is to remove a solvent from a coating film.

Therefore, although the heating temperature in the case of using a polyimide solution is influenced by the boiling point of the solvent to be used, it can usually be made low compared with the case of using a polyamic acid.

When preparing the solution of polyimide in order to form a polyimide-type liquid crystal aligning film, since it is necessary to melt | dissolve the polyimide which is hard to melt normally, use of an appropriate solvent is needed. About conventional polyimide, high polar solvents, such as N-methyl- 2-pyrrolidone (henceforth NMP), are selected and used. The high polar solvent has high surface tension as a characteristic, and has high surface tension characteristic also in NMP. Therefore, when the coating to the substrate is made using a polyimide solution containing NMP as a solvent, the wet diffusion property on the substrate is not good. As a result, the coating film WHEREIN: The defect at the time of print application | coating, such as a cratering and a pinhole, generate | occur | produced, and formation of the high quality liquid crystal aligning film of a uniform characteristic may become difficult.

When preparation of the solution of the polyimide becomes possible using a solvent having a lower surface tension, the applicability of the polyimide solution to the substrate can be improved, and the occurrence of defects during printing application such as cratering or pinhole can be suppressed. .

That is, if the solvent of a lower surface tension characteristic is selected and a polyimide can be melt | dissolved and the solution of a polyimide can be prepared, it becomes possible to implement | achieve favorable coating characteristic. Such improvement of applicability is also required in the formation of polyimide-based films such as insulating films and protective films of electronic devices. Improvement in applicability enables formation of a more uniform polyimide film with fewer defects in printing application such as cratering and pinholes.

In order to form a polyimide film, especially the liquid crystal aligning film of a polyimide, it turned out that the selection of a solvent is necessary, while improving the solubility to the solvent of a polyimide. It is preferable that the solvent selected has a lower surface tension characteristic in consideration of applicability. In that case, the selection of the polyimide structure corresponding to the solubility of a solvent is also required simultaneously.

MEANS TO SOLVE THE PROBLEM This inventor discovered that the polyimide precursor which has a specific structure is obtained by using the diamine compound of a specific structure, and the polyimide which the solubility improved was obtained by imidating this polyimide precursor. Furthermore, the compound (also called a solvent) of the low surface tension which melt | dissolves this polyimide was found.

That is, in this invention, the composition which melt | dissolved the polyimide of a specific structure in the specific solvent can be obtained, and a liquid-crystal aligning agent can be comprised. Moreover, the liquid-crystal aligning agent obtained from the obtained composition is excellent in applicability | paintability, and it is preferable in order to form a liquid crystal aligning film. The obtained liquid crystal aligning film is suitable for provision of the high reliability liquid crystal display element.

The composition of this invention contains the polyimide obtained by dehydrating and ring-closing a polyimide precursor. This composition can comprise a liquid-crystal aligning agent especially.

The composition of this invention is a polyimide which imidated the polyimide precursor obtained by carrying out (polycondensation) reaction of the diamine component and the tetracarboxylic-acid component containing the diamine compound which has a carboxyl group, and / or this polyimide precursor, and the following formula It is characterized by containing the compound shown by [1].

[Chemical Formula 9]

R <_1> is a C1-C4 alkyl group in formula [1].

It is preferable that the compound represented by said formula [1] is a compound shown by following formula [2] or following formula [3]. The compound represented by Formula [1], Preferably, it contains as a solvent in a composition.

[Chemical formula 10]

(11)

It is preferable that the diamine component which forms a polyimide precursor contains the diamine compound which has a carboxyl group of following formula [4]. Moreover, it is possible to contain a 2nd diamine compound in addition. As a 2nd diamine compound, the diamine compound of the structure shown by following formula [5] is preferable.

[Chemical Formula 12]

A is an integer of 0-4 in formula [4], and n shows the integer of 1-4.

[Chemical Formula 13]

The formula [5], X is, - (CH _{2) b} -OH groups (b is an integer from 0-4), C 1 -C 22 hydrocarbon groups, substituted hydrocarbon groups having 1 to 6 carbon atoms di-substituted amino group or It is group shown by following formula [6], n shows the integer of 0-4.

[Chemical Formula 14]

Equation [6] of the, Y ¹ represents a single _{bond, - (CH 2) a -} (a is an integer of 1 to 15), is -O-, -CH ₂ O-, -COO- or OCO-. 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 divalent cyclic group selected from a benzene ring, a cyclohexyl ring, and a hetero 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 having 1 to 3 carbon atoms). It may be substituted by a fluorine-containing alkyl group, a C1-C3 fluorine-containing alkoxyl group, or a fluorine atom), or a C12-C25 divalent organic group which has a steroid skeleton. Y ⁵ Is a divalent cyclic group selected from a benzene ring, a cyclohexyl ring and a heterocyclic ring (any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine atom having 1 to 3 carbon atoms Containing alkyl group, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom). Y ⁶ Is a hydrogen atom, 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. and n represents an integer of 0 to 4.

<Diamine compound which has a carboxyl group>

A diamine compound having a carboxyl group to obtain the polyimide precursor of the present invention, in the molecule, it is preferred that (CH _{2) a} -COOH group of a diamine compound having a (a is an integer from 0 to 4).

For example, the diamine compound of the structure shown by following formula [4] is mentioned.

[Chemical Formula 15]

A is an integer of 0-4 in formula [4], and n shows the integer of 1-4.

Moreover, the diamine compound which has a carboxyl group in the molecule | numerator shown by following formula [4-1]-[4-4] is mentioned.

[Chemical Formula 16]

In formula [4-1], A ₄ 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 ₂ and m ₃ are each an integer of 0 to 4, and m ₂ + m ₃ is an integer of 1 to 4;

M <_4> and m <_5> are the integers of 1-5 in a formula [4-2], respectively.

A <_5> is a C1-C5 linear or branched alkyl group in formula [4-3], and m <_6> is an integer of 1-5.

In formula [4-4], 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 of 1 to 4;

It is preferable that the usage-amount of the diamine compound which has a carboxyl group is 10-100 mol% in all the diamine components, More preferably, it is 20-100 mol%.

The diamine compound which has said carboxyl group is one type or two types according to the characteristics, such as the solubility and coating property with respect to the solvent at the time of setting it as a composition, the liquid crystal alignability, voltage retention, and an accumulated charge in the case of using a liquid crystal aligning film. The above can also be mixed and used.

&Lt; Synthesis method of diamine compound &gt;

Although the method of manufacturing the diamine compound shown by Formula [4] is not specifically limited, What is shown below is mentioned as a preferable method.

For example, the diamine compound shown by Formula [4] is obtained by synthesize | combining the dinitro body shown by following formula [4A], reducing a nitro group, and converting into an amino group.

[Chemical Formula 17]

(A shows the integer of 0-4 in a formula [4A], and n shows the integer of 1-4.)

There is no restriction | limiting in particular in the method of reducing a dinitro group, Usually, palladium-carbon, platinum oxide, raninickel, 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.

<2nd diamine compound>

The diamine component contained in the composition of this invention can contain the diamine compound shown by following formula [5] as a 2nd diamine compound.

[Chemical Formula 18]

In formula [5], X is a substituent. and n represents an integer of 0 to 4.

Specifically, the expression according to [5], X is - (CH _{2) b} -OH groups (b is an integer from 0 to 4), substituted with a hydrocarbon group having 1 to 22 hydrocarbon group, having 1 to 6 carbon atoms in the It is a substituted di-substituted amino group or group represented by following formula [6].

[Chemical Formula 19]

Equation [6] of the, Y ¹ represents a single _{bond, - (CH 2) a -} (a is an integer of 1 to 15), is -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 from the viewpoint of facilitating the synthesis of the side chain structure , a single bond, and _{- (CH 2) a - (} a is an integer of 1 ~ 10), -O-, -CH 2 O- , or more preferably COO-.

In formula [6], 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 preferred (b is an integer of 1-10).

In formula [6], 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 from 1 to 15), -O-, -CH ₂ O-, -COO- or OCO- facilitates the synthesis of the side chain structure. It preferred in view of and a single _{bond, - (CH 2) c -} (c is an integer of 1 ~ 10), -O-, more preferably a -CH ₂ O-, -COO- or OCO-.

In formula [6], Y ⁴ Is a divalent 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 a carbon atom having 1 to 3 carbon atoms). 3 may be substituted with a fluorine-containing alkyl group, a C1-C3 fluorine-containing alkoxyl group or a fluorine atom), or a C12-C25 divalent organic group having a steroid skeleton. Especially, the C12-C25 divalent organic group which has a bivalent cyclic group or steroid skeleton chosen from the group which consists of a benzene ring and a cyclohexane ring is preferable.

In formula [6], Y ⁵ Is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a hetero ring, and 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 C carbon atoms. It may be substituted by the fluorine-containing alkyl group of 3, the fluorine-containing alkoxyl group of 1 to 3 carbon atoms, or fluorine atom.

N is an integer of 0-4 in formula [6]. Preferably, it is an integer of 0-2.

In formula [6], Y ⁶ Is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluoro-containing alkoxyl group having 1 to 18 carbon atoms. Especially, it is preferable that they are a C1-C18 alkyl group, a C1-C10 fluorine-containing alkyl group, a C1-C18 alkoxyl group, or a C1-C10 fluorine-containing alkoxyl group. More preferably an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. More preferably an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.

Constituting the substituent X in the formula [5], formula as ^{[6] Y 1, Y 2} , Y 3, Y 4, Y 5, Y 6 , and preferred combination of n in the International Publication No. WO2011 / 132751 (2011 The same combination as (2-1)-(2-629) published in Tables 6-47 of page 13-34 of the 10.27 publication) is mentioned. In addition, in each table of International Publication, Y ¹ ~ Y in the present invention ⁶ It is, but is represented as Y1 ~ Y6, Y1 ~ Y6 is, Y to be read replaced by ¹ ~ Y ^6.

Although the specific example of the 2nd diamine compound of the structure shown by Formula [5] is given below, these are not limited to an example.

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- diamino benzyl alcohol, and 4, 6- diamino resorcinol, the diamine compound of the structure shown by following formula [5-1]-[5-41] is mentioned.

[Chemical Formula 20]

(A <_1> is a C1-C22 alkyl group or a fluorine-containing alkyl group in formula [5-1]-[5-4].)

[Chemical Formula 21]

[Chemical Formula 22]

(23)

&Lt; EMI ID =

(25)

(26)

(27)

(Formula [5-29] - [5-31] of, R ₁ is _{-O-, -OCH 2 -, -CH 2} O-, -COOCH 2 - , or a CH ₂ OCO-, R ₂ Is a C1-C22 alkyl group, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group.)

(28)

(R < ₃ > in formula [5-32]-[5-34]. Is -COO-, -OCO-, -COOCH _2- , -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -or CH _2- , R ₄ Is a C1-C22 alkyl group, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group.)

[Chemical Formula 29]

(In formula [5-35] and formula [5-36], R ₅ Is -COO-, -OCO-, -COOCH _2- , -CH ₂ OCO-, -CH ₂ O-, -OCH _2- , -CH ₂ -or O-, R ₆ Is a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group or a hydroxyl group.

(30)

(R < ₇ > in formula [5-37] and formula [5-38].) Is a C3-C12 alkyl group, and the cis-trans isomer of 1, 4- cyclohexylene is a trans isomer, respectively.)

(31)

(R < ₈ > in formula [5-39] and formula [5-40].) Is a C3-C12 alkyl group, and the cis-trans isomerization of 1, 4- cyclohexylene is a trans isomer, respectively.)

(32)

(Wherein [5-41], 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- *, provided that "*" is bonded to B _3. B ₁ represents an oxygen atom or COO- *, provided that "*" is a bond (CH ₂ ) a. ₂ )). A ₁ is an integer of 0 or 1, and a ₂ Is an integer of 2 to 10, and a ₃ Is an integer of 0 or 1)

The said 2nd diamine compound is 1 type, or 2 or more types according to the characteristics, such as the solubility and coating property with respect to the solvent at the time of setting it as a composition, the orientation of the liquid crystal in the case of using a liquid crystal aligning film, voltage retention, and an accumulated charge. It can also mix and use.

<The synthesis method of a 2nd diamine compound>

Although the method of manufacturing the diamine compound shown by Formula [5] is not specifically limited, What is shown below is mentioned as a preferable method.

For example, the diamine compound represented by Formula [5] is obtained by synthesize | combining the dinitro body represented by following formula [5A], reducing a nitro group, and converting into an amino group.

(33)

There is no restriction | limiting in particular in the method of reducing a dinitro group, Usually, palladium-carbon, platinum oxide, raninickel, 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 [5A] are synonymous with the definition in Formula [5] in said 2nd diamine compound.

&Lt; Other diamine compounds &gt;

Unless the effect of this invention is impaired, the diamine compound (also called other diamine compound) of another structure other than the diamine compound which has a carboxyl group in a molecule | numerator, and the 2nd diamine compound of the structure shown by Formula [5] is mentioned. Can be used. After using together and obtaining a polyimide precursor, it is set as a polyimide, the composition containing the obtained polyimide is prepared, and it is good also as a liquid-crystal aligning agent.

The specific example of another diamine compound is illustrated below.

As another diamine compound, p-phenylenediamine, 4,4'- diamino biphenyl, 3,3'- dimethyl-4,4'- diamino biphenyl, 3,3'- dimethoxy, for example. -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 '-Diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 3,3'-diaminodiphenyl Ether, 3,4'-diaminodiphenylether, 2,2'-diaminodiphenylether, 2,3'-diaminodiphenylether, 4,4'-sulfonyldianiline, 3,3'-sulfo Nyldianiline, bis (4-aminophenyl) silane, bis (3-aminophenyl) silane, dimethyl-bis (4- Minophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4,4'-thiodaniline, 3,3'-thiodaniline, 4,4'-diaminodiphenylamine, 3,3'- Diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-diamino Diphenyl) amine, N-methyl (3,3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (2,2'-diaminodiphenyl ) Amine, N-methyl (2,3'-diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1 , 4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene , 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis (4-aminophenyl ) Ethane, 1,2-bis (3-aminophenyl) , 1,3-bis (4-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, 1,4-bis (4aminophenyl) 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-phenyl Lenbis (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-aminophenyl) methanone], 1,3-phenylenebis [(3-aminophenyl) methanone], 1,4-phenylene (4-aminobenzoate), 1,4-phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate), 1,3-phenylenebis (3-amino Benzoate), 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-phenylene) 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) diphenylsulfone, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, 2,2'-bis 4- (4-aminophenoxy) Yl] 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, 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-aminophenoxy) nonane , 1,10- (4-aminophenoxy) decane, 1,10- (3-aminophenoxy) decane, 1,11- (4-ami Aromatics such as phenoxy) undecane, 1,11- (3-aminophenoxy) undecane, 1,12- (4-aminophenoxy) dodecane, 1,12- (3-aminophenoxy) dodecane Diamine; alicyclic diamines such as bis (4-aminocyclohexyl) methane and 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- Aliphatic diamines such as diaminoundecane and 1,12-diaminododecane; and the like.

Moreover, as another diamine compound, what has an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, or a heterocyclic ring in a diamine side chain, what has a macrocyclic substituent which consists of these, etc. are mentioned. Specifically, the diamine compound shown by following formula [DA1]-[DA13] can be illustrated.

(34)

(Wherein [DA1] ~ [DA6] of, A ₂ is -COO-, -OCO-, -CONH-, -NHCO-, -CH 2 - is, -O-, -CO- or NH-, A ₃ is A linear or branched alkyl group having 1 to 22 carbon atoms, or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms.)

(35)

(P is an integer of 1-10 in a formula [DA7].)

Unless the effect of this invention is impaired, the diamine compound shown by following formula [DA8]-[DA13] can also be used.

(36)

(M is an integer of 0-3 in a formula [DA10], n is an integer of 1-5 in a formula [DA13].)

Moreover, the diamine compound shown by following formula [DA14] and formula [DA15] can also be used.

[Formula 37]

According to the characteristic which becomes important in liquid crystal aligning films, such as the solubility and coating property with respect to the solvent at the time of setting it as a composition, the liquid crystal aligning film in the case of using this other diamine compound as a composition, voltage retention, a stored charge, You can also use 1 type or in mixture of 2 or more types.

<Tetracarboxylic acid component>

In order to obtain the polyimide precursor of this invention, using tetracarboxylic dianhydride (also called specific tetracarboxylic dianhydride) which has alicyclic structure shown by following formula [7] as a part of tetracarboxylic-acid component desirable.

(38)

In formula [7], Z <_1> is a C4-C13 tetravalent organic group and contains a C4-C10 non-aromatic cyclic hydrocarbon group. Specifically, the group shown by following formula [7a]-[7j] is preferable.

[Chemical Formula 39]

In the formula _{[7a], Z 2 ~ Z} 5 Is a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different, respectively.

In formula [7g], Z ₆ and Z ₇ Is a hydrogen atom or a methyl group, and may be the same or different, respectively.

In formula [7], a preferable group of Z < ₁ > is a formula [7a], a formula [7c], a formula [7d], a formula [7e], a formula [7f], or a formula [7g] from a polymerization reactivity and the ease of synthesis. It is a group to represent. Especially, group represented by a formula [7a], a formula [7e], a formula [7f], or a formula [7g] is preferable, and a formula [7e] or a formula [7f] is the most preferable.

When using tetracarboxylic dianhydride of the structure of formula [7f], a desired effect is acquired by making it the 20 mass% or more in the whole component of tetracarboxylic dianhydride. More preferably, it is 30 mass% or more. It is also possible to make all the tetracarboxylic-acid components used for polyimide synthesis into tetracarboxylic dianhydride of the structure of formula [7f].

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

As other tetracarboxylic-acid component, the esterified product which tetraalkylated, tetracarboxylic-acid dihalide, tetracarboxylic dianhydride, the carboxylic acid group of tetracarboxylic-acid dialkyl-esterified, and tetracarboxylic-acid dihalide And esterified products obtained by dialkyl esterifying a carboxylic acid group.

Specific examples thereof include pyromellitic acid, 2,3,6,7-naphthalene tetracarboxylic acid, 1,2,5,6-naphthalene tetracarboxylic acid, 1,4,5,8-naphthalene tetra Carboxylic acid, 2,3,6,7-anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic 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- 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-pe Relenetetracarboxylic acid, 1,3-diphenyl-1,2,3,4-cyclo part And the like can be mentioned tetracarboxylic acid.

Said other tetracarboxylic-acid component can select and use one type or two types or more in consideration of characteristics, such as liquid crystal alignability, voltage holding | maintenance characteristic, and accumulated charge of the liquid crystal aligning film formed.

<Specific polymer and solvent>

The specific polymer of this invention is a polyimide obtained by dehydrating and ring-closing the polyimide precursor (polyamic acid) obtained by making the diamine component containing the diamine compound which has a carboxyl group, and the tetracarboxylic acid component and / or its polyimide precursor It is a polymer which consists of.

The polyimide precursor of this invention is a structure shown by following formula [A].

(40)

(In the formula [A], R ₁ is a tetravalent organic group and R ₂ Is a divalent organic group, A <_1> and A <_2> are a hydrogen atom or a C1-C8 alkyl group, respectively, may be same or different, and n represents a positive integer).

The specific polymer of this invention is obtained by the following formula [D] because it is obtained relatively easily by making the diamine component shown by following formula [B] and the tetracarboxylic dianhydride shown by following formula [C] as a raw material. The polyimide which imidated the polyamic acid which consists of a structural formula of the repeating unit shown is preferable.

(41)

(R <_1> and R < ₂ > in formula [B] and formula [C]. Is synonymous with what was defined by Formula [A]).

(42)

(R <_1> and R < ₂ > in formula [B] and formula [C]. Is synonymous with what was defined by Formula [A]).

Although the method of synthesize | combining a specific polymer is not specifically limited, Usually, as mentioned above, it is obtained by making a diamine component and the tetracarboxylic-acid component react. Therefore, the polyimide obtained from a polyimide precursor is prepared with the polyimide precursor obtained by making a diamine component and the tetracarboxylic acid component react.

Generally, the polyamic acid is obtained by making at least 1 sort (s) of tetracarboxylic-acid component selected from the group which consists of tetracarboxylic acid and its derivative (s), and the diamine component which consists of 1 type or multiple types of diamine compound react. Specifically, there are a method of polycondensation of a tetracarboxylic acid dianhydride and a diamine component to obtain a polyamic acid, a method of obtaining a polyamic acid by dehydration polycondensation reaction of a tetracarboxylic acid and a diamine component or a method in which a tetracarboxylic acid dihalide and a diamine To obtain a polyamic acid.

To obtain the polyamide acid alkyl ester, a method of polycondensation of a tetracarboxylic acid having a carboxylic acid group with a dialkyl ester and a diamine component, a method of polycondensation of a diamine component with a tetracarboxylic dihalide obtained by dialkyl esterifying a carboxylic acid group Or a method of converting a carboxyl group of a polyamic acid into an ester is used.

To obtain the polyimide, a method of converting the above polyamic acid or polyamide acid alkyl ester into a polyimide by ring closure is used.

The specific polymer of this invention is obtained by making the diamine component containing the diamine compound which has a carboxyl group in a molecule | numerator, and the tetracarboxylic-acid component which has said alicyclic structure, and is obtained by imidating the obtained polyimide precursor. .

The solubility to a solvent improves the specific polymer obtained from the said diamine component and the tetracarboxylic-acid component. Moreover, the applicability | paintability of the composition containing a specific solvent improves.

In order to obtain the specific polymer of this invention, it is preferable to use the diamine compound of the structure shown by said formula [4], and the usage-amount is 10-100 mol% of the whole diamine component used for reaction which obtains a polyimide. Preferably, it is 20-100 mol% more preferably.

When the diamine compound of the structure shown by said formula [5] is contained in the diamine component used in order to obtain the specific polymer of this invention, it is preferable that the usage-amount is 90 mol% or less of the whole diamine component used for reaction which obtains a specific polymer. More preferably, it is 80 mol% or less. In that case, it is preferable to set it as 20 mol% or more in relationship with the preferable usage-amount of the diamine compound which has a carboxyl group in a molecule | numerator.

In order to obtain the specific polymer of this invention, polyamic acid can be obtained by reaction of a diamine component and a tetracarboxylic-acid component using a well-known synthetic method, and a polyimide can be obtained after that. As a method of obtaining a polyamic acid, the method of making a diamine component and a tetracarboxylic-acid component react in an organic solvent, for example 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.

After synthesize | combining a polyimide precursor in a suitable organic solvent mentioned later, carrying out a dehydration ring-closure reaction, and obtaining a polyimide, polyimide is isolate | separated and contains at least 1 sort (s) of compound chosen from the group which consists of a compound represented by said Formula [1] The composition of the present invention can be obtained by dissolving in a solvent.

The organic solvent used for the reaction of the diamine component and the tetracarboxylic acid component is not particularly limited as long as the produced polyimide precursor is dissolved.

Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone And methyl ethyl ketone, cyclohexanone, cyclopentanone, and 4-hydroxy-4-methyl-2-pentanone.

These may be used independently, or may mix and use them. Moreover, even if it is a solvent which does not melt a polyimide precursor, if it is a range in which the produced polyimide precursor does not precipitate, you may mix and use for the said organic solvent. In addition, since water in an organic solvent inhibits a polymerization reaction and causes hydrolysis of the produced | generated polyimide precursor, it is preferable to use what dehydrated the organic solvent.

When reacting a diamine component and a tetracarboxylic-acid component in an organic solvent, the solution which disperse | distributed or melt | dissolved the diamine component in the organic solvent is stirred, and the tetracarboxylic-acid component is disperse | distributed or dissolved in the organic solvent, and added It is possible to use a method. Moreover, the method of adding a diamine component to the solution which disperse | distributed or dissolved the tetracarboxylic-acid component in the organic solvent, the method of adding the tetracarboxylic-acid component and the diamine component alternately, etc. are also mentioned. In the present invention, any of these methods may be used. Moreover, when a diamine component or a tetracarboxylic-acid component consists of multiple 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 separately may be mixed and made into a high molecular weight body. You may also

The temperature at which the diamine component and the tetracarboxylic acid component are reacted can be arbitrarily selected within the range of -20 to 150 ° C, but in consideration of the reaction efficiency, the temperature is preferably in the range of -5 to 100 ° C. 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 and uniform stirring becomes 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 a tetracarboxylic-acid component 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 select suitably the sum total molar ratio as needed.

As described above, the polyimide of the present invention is obtained by dehydrating and closing the polyimide precursor. This polyimide is useful as a polymer for obtaining a liquid crystal aligning film.

In the polyimide of 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 or purpose, for example, in the range of 35 to 95%, more preferably. Preferably, it can adjust in 45 to 80% of range.

As a method of imidating a polyimide precursor, the heat | fever imidation which heats the solution of a polyimide precursor as it is, the catalyst imidation which adds a catalyst to the solution of a polyimide precursor, 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 the solution of a polyimide precursor, and stirring at -20-250 degreeC, Preferably it is 0-180 degreeC. The quantity of a basic catalyst is 0.5-30 mol times of amic acid groups, Preferably it is 2-20 mol times, and the quantity of an acid anhydride is 1-50 mol times of amic acid groups, Preferably it is 3-30 mol times.

Pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. are mentioned as a basic catalyst. Especially, pyridine is preferable at the point which has moderate basicity in advancing reaction.

Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Especially, acetic anhydride is preferable at the point which the purification after completion | finish of reaction becomes easy. 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 polyimide, the reaction solution may be thrown into the precipitation solvent to precipitate. Examples of the precipitation solvent used for the precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water and the like. The polymer precipitated by being poured into the precipitation solvent can be dried by normal temperature or heating under normal pressure or reduced pressure after filtration and recovery. Moreover, if the operation which re-dissolves the polymer which precipitated and collect | recovered in a solvent and collects and collects again 2 to 10 times is repeated, an impurity in a polymer can be reduced. The precipitation solvent mentioned above is mentioned as a precipitation solvent at this time, When using three or more types of solvents selected from these, since the efficiency of further refine | purification rises, it is preferable.

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

&Lt; Liquid crystal alignment treatment agent &

The liquid-crystal aligning agent of this invention consists of the composition mentioned above, is a coating liquid for forming a liquid crystal aligning film, and is a solution composition obtained by melt | dissolving the polymer component for forming a polymer film in a solvent. The polymer component contains at least one polymer selected from the above-described specific polymers of the present invention. 0.1-20 mass% is preferable, as for content of the polymer component in a liquid-crystal aligning agent, More preferably, it is 1-15 mass%, Especially preferably, it is 2-10 mass%.

In this invention, the specific polymer of this invention may be sufficient as all the polymer components contained in a liquid-crystal aligning agent. Moreover, the polymer other than the specific polymer of this invention may be mixed. In that case, content of the other polymer in a polymer component is 0.5-15 mass%, Preferably it is 1-10 mass%.

As another polymer, the imide of the polyimide precursor and / or the polyimide precursor other than the specific polymer obtained by making the diamine component containing the diamine compound which has a carboxyl group in the said molecule, and the tetracarboxylic-acid component which have alicyclic structure react Polyimide is mentioned.

Furthermore, polymers other than polyimide, specifically, an acrylic polymer, a methacryl polymer, polystyrene, polyamide, etc. are mentioned.

In the liquid-crystal aligning agent of this invention, the said specific polymer is contained in the state melt | dissolved in the solvent. As a solvent used, the solvent which melt | dissolves the polyimide which is a specific polymer of this invention, and contains the compound which has a low surface tension characteristic compared with NMP, for example is preferable.

Specifically, the solvent is preferably used as a solvent containing a compound represented by the following formula [1].

(43)

R <_1> is a C1-C4 alkyl group in formula [1].

Especially, it is preferable that the compound represented by said Formula [1] is a compound shown by following formula [2] or following formula [3].

(44)

[Chemical Formula 45]

1 type may be sufficient as the compound represented by said Formula [1], and 2 or more types of mixtures may be sufficient as it. By using the compound shown by said formula [1] as a solvent, the liquid-crystal aligning agent excellent in applicability | paintability can be provided.

In the liquid-crystal aligning agent of this invention, it is preferable that content of a solvent is 70-99 mass% from a viewpoint of forming a uniform film | membrane by application | coating. Content can be suitably changed with the film thickness of the liquid crystal aligning film made into the objective. As a solvent, the mixture of the some compound represented by any of the compound shown by said Formula [1], or the compound shown by Formula [1] is used.

Moreover, as a solvent in a liquid-crystal aligning agent, other organic solvents other than the compound shown by said Formula [1] can be mixed and contained in the range which does not inhibit the applicability improvement.

Specific examples of the other organic solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, and 1,3-dimethyl. -Imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, etc. are mentioned. These may be used alone or in combination.

When it contains such another organic solvent, the content is 50 mass% or less in all the solvent, Preferably it is 40 mass% or less. More preferably, it is 30 mass% or less.

As long as the liquid-crystal aligning agent of this invention does not impair the effect of this invention, it is a bin for improving applicability | paintability for the purpose of further improving the film thickness uniformity and surface smoothness of the film | membrane when apply | coating a liquid-crystal aligning agent ( Iii) It may contain a solvent.

The following are mentioned as a specific example of the said poor solvent. Butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, Butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl- Butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,3-propanediol, Butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, Ethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl Acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2- (Methoxymethoxy) ethanol, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, Propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, 1- (butoxyethoxy) propanol , Propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono Butyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene Glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-meth Methyl cipropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl, 3-methoxypropionic acid butyl, lactic acid methyl ester, lactic acid Ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester and the like. These poor solvents may be used by one type, and may be used in mixture of multiple types.

When it contains such a poor solvent, content of the compound shown by said Formula [1] is 90 mass% or less in all the solvent, Preferably it is 70 mass% or less. More preferably, it is 40 mass% or less.

In addition, the liquid-crystal aligning agent of this invention is a compound which improves the film thickness uniformity and surface smoothness of the film at the time of apply | coating a liquid-crystal aligning agent, and the adhesiveness of a liquid-crystal aligning film and a board | substrate, unless the effect of this invention is impaired. The compound to improve can be used.

As a compound which improves the uniformity and surface smoothness of the film thickness of a film | membrane, a fluorochemical surfactant, silicone type surfactant, nonionic surfactant, etc. are mentioned. More specifically, it is possible to use, for example, EFTOP EF301, EF303, EF352 (manufactured by TOKEM PRODUCTS CO., LTD.), Megafac F171, F173, R-30 (manufactured by Dainippon Ink and Chemicals Inc.), FLORAD FC430 and FC431 (manufactured by Sumitomo 3M Ltd.) ), Asahi Guard AG710, Surfron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.). 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 liquid-crystal aligning agent, More preferably, it is 0.01-1 mass part.

As a specific example of the compound which improves the adhesiveness of a liquid crystal aligning film and a board | substrate, what is a functional silane containing compound and an epoxy group containing compound shown next is 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 adhesiveness with a board | substrate, it is preferable that the addition amount is 0.1-30 mass parts with respect to the resin component contained in a liquid-crystal aligning agent, ie, 100 mass parts of said specific polymer, More preferably, Is 1-20 mass parts. If the amount is less than 0.1 part by mass, the effect of improving the adhesion can not be expected, and if it is more than 30 parts by mass, the alignment property of the liquid crystal may be deteriorated.

The liquid-crystal aligning agent of this invention is a group which consists of a crosslinkable compound which has an epoxy group, an isocyanate group, an oxetane group, or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group, unless the effect of this invention is impaired. It may contain a crosslinkable compound having at least one substituent selected from 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 novolak epoxy resin, cresol novolak epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, (Aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetate di Glycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4- 2- (4- (2,3-epoxypropoxy) phenyl) -2- (4-methylphenyl) Phenyl) propane, 1,3-bis (4- (1- (4- (2,3-epoxypropoxy) ) Phenyl) -1- (4- (1- ( 4- (2,3-epoxypropoxyphenyl) -1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol etc. are mentioned.

As a crosslinkable compound which has an oxetane group, it is a crosslinkable compound which has at least two oxetane groups shown by following formula [8].

(46)

Specifically, it is a crosslinkable compound shown by following formula [8-1]-[8-11].

(47)

(48)

(49)

As a crosslinkable compound which has a cyclocarbonate group, it is a crosslinkable compound which has at least two cyclocarbonate groups shown by following formula [9].

(50)

Specifically, it is a crosslinkable compound shown by following formula [9-1]-[9-37].

(51)

(52)

(53)

[Formula 54]

(55)

(56)

(57)

(58)

(N is an integer of 1-5 in formula [9-24], n is an integer of 1-5 in formula [9-25], n is an integer of 1-100 in formula [9-36]. And n is an integer of 1-10 in a formula [9-37].)

Moreover, the polysiloxane which has at least 1 sort (s) of structure shown by following formula [9-38]-[9-40] is also mentioned.

[Chemical Formula 59]

(R <_1> , R <_2> , R <_3> , R <_4> and R < ₅ > in formula [9-38]-[9-40]. Each independently represents a structure represented by formula [9], a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group, an aliphatic ring or an aromatic ring, and at least one is a structure represented by formula [9]).

More specifically, the compound of following formula [9-41] and formula [9-42] is mentioned.

(60)

(In formula [9-41], R ₆ Are each independently the structure represented by Formula [9], a hydrogen atom, a hydroxyl group, a C1-C10 alkyl group, an alkoxyl group, an aliphatic ring, or an aromatic ring, and at least 1 is a structure shown by Formula [9]. N is an integer of 1-10 in a formula [9-42].)

Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include an amino resin having a hydroxyl group or an alkoxyl group such as a melamine resin, Nylon resin, glycolluryl-formaldehyde resin, succinylamide-formaldehyde resin, ethylene urea-formaldehyde resin, and the like. Specifically, a melamine derivative in which the hydrogen atom of the amino group is substituted with a methylol group and / or an alkoxymethyl group, a benzoguanamine derivative, or glycoluril can be used. The melamine derivative and the benzoguanamine derivative may be present as a dimer or trimer. These groups preferably have 3 to 6 on average of methylol groups or alkoxymethyl groups per one triazine ring.

Examples of such melamine derivatives or benzoguanamine derivatives include MX-750 having an average of 3.7 methoxymethyl groups substituted per triazine ring in a commercial product, and MW- having an average of 5.8 methoxymethyl groups substituted per triazine ring. Methoxymethylated melamine, cymel 235, 236, 238, 212, 253, such as 30 (above, manufactured by Sanwa Chemical Co., Ltd.) and Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc. Methoxymethylated butoxymethylated melamine such as 254, methoxymethylated butoxymethylated melamine such as Cymel 506, 508, carboxyl group-containing methoxymethylated isobutoxymethylated melamine such as Cymel 1141, and methoxymethylated ethoxymethylated benzo such as Cymel 1123 Methoxymethylated butoxymethylated benzoguanamine such as guanamine, cymel 1123-10, butoxymethylated benzoguanamine such as cymel 1128, carboxyl group-containing methoxymethylated ethoxymethylated benzoine such as cymel 1125-80 Guanamine (above, Mitsui cyanamid company) etc. are mentioned. Examples of the glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylol glycoluril such as Cymel 1172, methoxymethylolglycoluril such as Powderlink 1174, and the like.

Examples of the benzene or phenolic compound having a hydroxyl group or an alkoxyl group include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 4-bis (sec-butoxymethyl) benzene, 2,6-dihydroxymethyl-p-tert-butylphenol and the like.

Specific examples thereof include crosslinkable compounds represented by the formulas [6-1] to [6-48], which are listed on pages 62 to 66 of International Publication No. WO2011 / 132751 (published on October 27, 2011).

As a crosslinkable compound which has a polymerizable unsaturated bond, for example, trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tri (meth) Crosslinkable compounds having three polymerizable unsaturated groups in a molecule such as acryloyloxyethoxytrimethylolpropane or 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 oxa Dibisphenol type di (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, glycerindi (meth) acrylate, pentaerythritoldi (meth) acrylate, ethylene glycol diglycidyl ether di ( Polymerizable properties such as meth) 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 unsaturated 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) acrylo The crosslinkable compound which has one polymerizable unsaturated group, such as a monooxyethyl phosphate ester and N-methylol (meth) acrylamide, in a molecule | numerator; etc. are mentioned.

Moreover, the compound shown by following formula [11] can also be used.

(61)

E <_1> is group selected 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 in formula [11]. , E ₂ Is group chosen from following formula [11a] and formula [11b], n is an integer of 1-4.

(62)

The above compound is an example of a crosslinkable compound, but is not limited thereto.

Moreover, one type may be sufficient as the crosslinking | crosslinked compound contained in the liquid-crystal aligning agent of this invention, and may be combined two or more types.

It is preferable that content of the crosslinking | crosslinked compound in the liquid-crystal aligning agent 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 the target 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.

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

As a compound which promotes the charge transfer in the liquid crystal aligning film formed using a liquid-crystal aligning agent, and promotes the charge leakage of the liquid crystal cell using this liquid crystal aligning film, page 69 of WO2011 / 132751 (October 27, 2011 publication) The nitrogen-containing heterocyclic amine compound shown by the formula [M1]-[M156] shown to -73 pages can also be added. Although these amine compounds may be added directly to the solution of a composition, it is preferable to add them 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 polyamic acid and a polyimide are dissolved other than the compound of the said Formula [1] as a solvent.

<Liquid Crystal Alignment Film and Liquid Crystal Display Device>

The liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film after being applied and baked on a substrate and subjected to an orientation treatment by rubbing treatment, light irradiation, or the like. Moreover, in the case of a vertical alignment use, a liquid crystal aligning film can be formed even without an orientation processing.

As a board | substrate, if it is a board | substrate with high transparency, it will not specifically limit, In addition to a glass substrate, plastic substrates, such as an acryl substrate and a polycarbonate board | substrate, etc. can also be used. From the viewpoint of simplification of the process, 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 be used as long as it is a substrate on one side, and a material for reflecting light such as aluminum can be used as the electrode in this case.

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. Other coating methods include a dip method, a roll coater method, a slit coater method, a spinner method, a spray method, and the like, and may be used depending on the purpose. Applicability | paintability is favorable even if the orientation treatment agent of this invention uses the above coating method.

After apply | coating a liquid-crystal aligning agent on a board | substrate, when polyimide is mainly contained as a specific polymer, it is 50-300 degreeC by heating means, such as a hotplate, a thermocyclic oven, and an IR (infrared) type oven, Preferably The solvent can be evaporated at 80 to 250 ° C to form a coating film.

When the thickness of the coating film after baking is too thick, it becomes disadvantageous in terms of the power consumption of a liquid crystal display element, and when too thin, the reliability of a liquid crystal display element may fall, 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.

After the liquid crystal display element of this invention 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 by a well-known method, and makes it a liquid crystal display element.

As a manufacturing method of a liquid crystal cell, 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 inward. And a method of sealing a liquid crystal by injecting the liquid crystal under reduced pressure, dropping the liquid crystal onto the liquid crystal alignment film surface on which the spacer is applied, and then bonding the substrate to perform sealing.

The liquid crystal aligning film of this invention consists of a liquid crystal layer between a pair of board | substrates provided with an electrode, and contains the liquid crystal composition containing the polymeric compound superposed | polymerized by at least one of an active energy ray and heat between a pair of board | substrates. It is used also suitably 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, arrange | positioning and applying a voltage between electrodes. The active energy ray is preferably ultraviolet ray.

The liquid crystal display element described above controls the pretilt of liquid crystal molecules by a PSA (Polymer Sustained Alignment) method. In the PSA system, a small amount of a photopolymerizable compound such as a photopolymerizable monomer is mixed into a liquid crystal material, and a liquid crystal cell is assembled. Then, a predetermined voltage is applied to the liquid crystal layer, And controls the pretilt of the liquid crystal molecules 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, in PSA system, it is suitable for formation of the vertically-aligned liquid crystal layer which does not require a rubbing process and is difficult to control pretilt by a rubbing process.

That is, the liquid crystal display element of this invention produces a liquid crystal cell after obtaining the board | substrate with which the liquid crystal aligning film was formed from the liquid-crystal aligning agent by the above-mentioned method, and superpose | polymerizes a polymeric compound by at least one of irradiation and heating of an ultraviolet-ray. By doing so, the alignment of the liquid crystal molecules can be controlled.

As an example of liquid crystal cell manufacture of a PSA system, 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, and the other board | substrate is bonded together so that a liquid crystal aligning film surface may become inner side. And the method of sealing by inject | pouring and sealing a liquid crystal under reduced pressure, the liquid crystal is dripped at the liquid crystal aligning film surface which spread | dispersed the spacer, and the board | substrate is bonded together and sealed.

The liquid crystal is mixed with a polymerizable compound which is polymerized by irradiation with heat or ultraviolet rays. As a polymeric compound, the compound which has 1 or more of polymerizable unsaturated groups, such as an acrylate group and a methacrylate group, in a molecule | numerator is mentioned. At that time, the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the liquid crystal component. When the polymerizable compound is less than 0.01 part by mass, the polymerizable compound is not polymerized and the orientation of the liquid crystal cannot be controlled. When the polymerizable compound is more than 10 parts by mass, the unreacted polymerizable compound is increased and the exposure characteristics of the liquid crystal display element are increased. Degrades.

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 the liquid crystal molecules can be controlled.

Further, the liquid crystal alignment treatment agent of the present invention is a liquid crystal alignment treatment agent comprising a liquid crystal layer between a pair of substrates provided with electrodes, and containing a polymerizable group polymerized by at least one of active energy rays and heat between the pair of substrates And a liquid crystal display device manufactured by a process of applying a voltage between electrodes. The active energy ray is preferably ultraviolet ray.

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, and the method of using the polymer component containing a polymeric group Etc. can be mentioned. Since the liquid crystal alignment treatment agent of the present invention contains a specific compound having a double bonding site that reacts by irradiation with heat or ultraviolet rays, the orientation of the liquid crystal molecules can be controlled by at least one of irradiation of ultraviolet rays and heating have.

As an example of liquid crystal cell manufacture, a pair of board | substrates 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 inside, and a liquid crystal is carried out. The method of injecting and sealing under reduced pressure, the method of bonding a board | substrate and sealing after dropping a liquid crystal on the liquid crystal aligning film surface which spread | dispersed the spacer, etc. are mentioned.

By passing through the above-mentioned process, the liquid crystal display element of this invention is obtained. Since these liquid crystal display elements have the liquid crystal aligning film of this invention, a manufacturing process becomes lower temperature, it is excellent in reliability, and can be used suitably for a liquid crystal television etc. which is highly precise with a big screen.

The composition of this invention can be used in order to form a polyimide film in uses other than the liquid-crystal aligning agent used for formation of a liquid crystal aligning film. For example, in another electronic device, it can use for formation of an interlayer insulation film and a protective film. In that case, it is possible to add various components to the composition of this invention according to the use.

Example

Although an Example is given to the following, this invention is limited to these and should not be interpreted.

The abbreviation used by a present Example and a comparative example is as follows.

<Diamine compound which has a carboxyl group in a molecule>

D1 ： 3,5-diaminobenzoic acid

D2 ： 1,4-diaminobenzoic acid

(63)

<2nd diamine compound of the structure shown by formula [5]>

D3 ： m-phenylenediamine

D4 ： diamine 5 ： 1,3-diamino-4- (octadecyloxy) benzene

D5 ： diamine 6 ： 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

&Lt; EMI ID =

&Lt; Other diamine compounds &gt;

D7 ： p-phenylenediamine

(65)

&Lt; Tetracarboxylic acid dianhydride &gt;

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 2 anhydride

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

(66)

<Compound (organic solvent) of the structure shown by Formula [1]>

DEME ： Diethylene Glycol Monomethyl Ether

DEEE ： diethylene glycol monoethyl ether

<Other compound (solvent)>

NMP: N-methyl-2-pyrrolidone

BCS: ethylene glycol monobutyl ether

Physical properties, such as molecular weight and imidation ratio, regarding the polyamic acid and the polyimide were evaluated as follows.

(Measurement of molecular weight of polyamic acid and polyimide)

The molecular weight of the polyamic acid and the polyimide was measured using a room temperature gel permeation chromatography (GPC) device (GPC-101) (manufactured by Showa Denko), and a column (KD-803, KD-805) (manufactured by Shodex). It 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, tetrahydro Furan (THF) 10 ml / l)

Flow rate: 1.0 ml / min

Standard samples for preparing calibration curves: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight: about 12,000, 4,000 and 1,000 manufactured by Polymer Laboratories).

(Measurement of imidization rate)

The imidization rate of the polyimide in the synthesis example was measured in the following manner. 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) mixture) (0.53 Ml) was added, and ultrasonic waves were added to dissolve completely. Proton NMR of 500 MHz was measured for this solution by the NMR measuring instrument (JNW-ECA500) (made by Nippon-E-Datom). 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 proton peak integration 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 calculated | required by the following formula using the value.

Imidization ratio (%) = (1 -? X / y) x 100

In the above formula, x is the proton peak integrated value derived from the NH group of the amide acid, y is the peak integrated value of the reference proton, and? Is the NH of the amide acid in the case of the polyamic acid (the imidization rate is 0% The ratio of the number of reference protons to one protopertone.

<Synthesis of polyimide>

&Lt; Synthesis Example 1 &

M2 (3.94 g, 15.7 mmol), D1 (1.60 g, 10.5 mmol), and D6 (4.56 g, 10.5 mmol) were mixed in NMP (30.31 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 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 (1.93g) and pyridine (1.49g) were added as imidation catalyst, and it was made to react at 80 degreeC for 3 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 (A) was obtained. The imidation ratio of this polyimide (A) was 55%, the number average molecular weight was 21,300 and the weight average molecular weight was 63,800.

&Lt; Synthesis Example 2 &

M2 (4.32 g, 17.3 mmol), D1 (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 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 (2.29g) and pyridine (1.78g) were added as imidation catalyst, and it was made to react at 80 degreeC for 3 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 (B) was obtained. The imidation ratio of this polyimide (B) was 51%, the number average molecular weight was 18,400 and the weight average molecular weight was 57,100.

&Lt; Synthesis Example 3 &

M2 (9.01 g, 36.0 mmol), D1 (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 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 (2.44g) and pyridine (1.90g) 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 (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 (C) was obtained. The imidation ratio of this polyimide (C) was 52%, the number average molecular weight was 15,700 and the weight average molecular weight was 50,100.

&Lt; Synthesis Example 4 &

M2 (5.07 g, 20.3 mmol), and D1 (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.

NMP was added to this polyamic acid solution (20.0g), and it diluted to 6 mass%, acetic anhydride (2.63g) and pyridine (2.04g) 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 (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 (D) was obtained. The imidation ratio of this polyimide (D) was 49%, the number average molecular weight was 15,700 and the weight average molecular weight was 47,000.

&Lt; Synthesis Example 5 &

M2 (6.13 g, 24.5 mmol) and D1 (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 (2.54g) and pyridine (1.97g) were added as imidation catalyst, and it reacted at 90 degreeC for 3.5 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 (E) was obtained. The imidation ratio of this polyimide (E) was 49%, the number average molecular weight was 14,800 and the weight average molecular weight was 42,200.

&Lt; Synthesis Example 6 &

M2 (17.7 g, 70.7 mmol), D1 (8.20 g, 53.9 mmol), and D6 (12.6 g, 29.0 mmol) were mixed in NMP (115.5 g) and reacted at 80 ° C. for 5 hours, followed by M1 (2.35 g , 12.0 mmol) and NMP (47.6 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 (20.0g) and diluting to 6 mass%, acetic anhydride (2.48g) and pyridine (1.28g) were added as imidation catalyst, and it was made to react at 90 degreeC for 2 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 (F) was obtained. The imidation ratio of this polyimide (F) was 53%, the number average molecular weight was 18,900 and the weight average molecular weight was 51,400.

&Lt; Synthesis Example 7 &

M2 (5.25 g, 21.0 mmol), D1 (4.15 g, 27.3 mmol), and D6 (6.40 g, 14.7 mmol) were mixed in NMP (47.4 g) and reacted at 80 ° C. for 5 hours, followed by M1 (4.10 g , 20.9 mmol) and NMP (31.9 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 (20.0g) and diluting to 6 mass%, acetic anhydride (2.15g) and pyridine (1.67g) were added as imidation catalyst, and it reacted at 80 degreeC for 3.5 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 (G) was obtained. The imidation ratio of this polyimide (G) was 63%, the number average molecular weight was 19,400 and the weight average molecular weight was 60,400.

&Lt; Synthesis Example 8 &

M2 (1.67 g, 6.7 mmol), D1 (2.14 g, 14.1 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 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 (2.20g) and pyridine (1.71g) were added as imidation catalyst, and it was made to react at 50 degreeC for 1.5 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 (H) was obtained. The imidation ratio of this polyimide (H) was 55%, the number average molecular weight was 21,600 and the weight average molecular weight was 61,400.

&Lt; Synthesis Example 9 &

M2 (4.13 g, 16.5 mmol), D1 (2.34 g, 15.4 mmol), and D4 (2.49 g, 6.6 mmol) were mixed in NMP (26.9 g) and reacted at 80 ° C. for 5 hours, followed by M1 (1.03 g , 5.3 mmol) and NMP (13.1 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 (20.0g) and diluting to 6 mass%, acetic anhydride (2.24g) and pyridine (1.73g) were added as imidation catalyst, and it was made to react at 80 degreeC for 3 hours. This reaction solution was poured into methanol (250 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 (I) was 55%, the number average molecular weight was 18,900 and the weight average molecular weight was 59,000.

&Lt; Synthesis Example 10 &

M2 (4.13 g, 16.5 mmol), D1 (2.34 g, 15.4 mmol), and D5 (2.51 g, 6.6 mmol) were mixed in NMP (27.0 g) and reacted at 80 ° C. for 5 hours, followed by M1 (1.04 g , 5.3 mmol) and NMP (13.1 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 (2.23g) and pyridine (1.73g) were added as imidation catalyst, and it was made to react at 80 degreeC for 3 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 (J) was obtained. The imidation ratio of this polyimide (J) was 50%, the number average molecular weight was 19,700 and the weight average molecular weight was 60,000.

&Lt; Synthesis Example 11 &

M2 (4.13 g, 16.5 mmol), D2 (2.34 g, 15.4 mmol), and D5 (2.51 g, 6.6 mmol) were mixed in NMP (27.0 g) and reacted at 80 ° C. for 5 hours, followed by M1 (1.06 g , 5.4 mmol) and NMP (13.2 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 (2.23g) and pyridine (1.73g) were added as imidation catalyst, and it was made to react at 80 degreeC for 3 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 (K) was 52%, the number average molecular weight was 17,900 and the weight average molecular weight was 57,600.

&Lt; Synthesis Example 12 &

M2 (8.07 g, 32.3 mmol), D1 (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.

NMP was added to this polyamic acid solution (80.0g), and it diluted to 6 mass%, acetic anhydride (17.25g) and pyridine (5.35g) were added as 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 (L) was obtained. The imidation ratio of this polyimide (L) was 80%, the number average molecular weight was 20,500 and the weight average molecular weight was 53,100.

&Lt; Synthesis Example 13 &

M2 (17.7 g, 70.7 mmol), D1 (8.18 g, 53.8 mmol), and D6 (12.5 g, 28.8 mmol) were mixed in NMP (115.5 g) and reacted at 80 ° C. for 5 hours, followed by M1 (2.28 g , 11.7 mmol) and NMP (47.6 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 (2.48g) and pyridine (1.28g) were added as imidation catalyst, and it was made to react at 100 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 (M) was obtained. The imidation ratio of this polyimide (M) was 70%, the number average molecular weight was 19,300 and the weight average molecular weight was 54,000.

&Lt; Synthesis Example 14 &

M3 (6.91 g, 23.0 mmol), D1 (2.45 g, 16.1 mmol), and D5 (2.63 g, 6.9 mmol) were mixed in NMP (47.9 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 (20.0g), and it diluted to 6 mass%, acetic anhydride (3.92g) and pyridine (3.04g) were added as imidation catalyst, and it was made to react at 40 degreeC for 1.5 hours. This reaction solution was poured into methanol (260 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 (N) was 69%, the number average molecular weight was 10,900 and the weight average molecular weight was 24,400.

&Lt; Synthesis Example 15 &

M4 (5.13 g, 22.9 mmol), D1 (2.45 g, 16.1 mmol), and D5 (2.63 g, 6.9 mmol) were mixed in NMP (40.8 g) and reacted at 60 ° C. for 24 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 (2.30g) and pyridine (1.78g) were added as imidation catalyst, and it reacted at 90 degreeC for 2 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 (O) was obtained. The imidation ratio of this polyimide (O) was 49%, the number average molecular weight was 15,800 and the weight average molecular weight was 36,500.

&Lt; Synthesis Example 16 &

M4 (5.13 g, 22.9 mmol), D1 (2.45 g, 16.1 mmol), and D5 (2.63 g, 6.9 mmol) were mixed in NMP (40.8 g) and reacted at 60 ° C. for 24 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 (4.59g) and pyridine (1.78g) were added as imidation catalyst, and it was made to react at 100 degreeC for 3 hours. This reaction solution was poured into methanol (260 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 (P) was 77%, the number average molecular weight was 14,600 and the weight average molecular weight was 32,200.

<Synthesis example 17>

M2 (5.07 g, 20.3 mmol), and D1 (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 (5.26g) and pyridine (2.04g) were added as imidation catalyst, and it was made to react at 100 degreeC for 4 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 (Q) was obtained. The imidation ratio of this polyimide (Q) was 79%, the number average molecular weight was 15,000 and the weight average molecular weight was 45,700.

<Synthesis example 18>

M2 (2.87 g, 11.5 mmol), D3 (1.24 g, 11.5 mmol), D1 (0.70 g, 4.6 mmol), and 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 (R) was obtained. The imidation ratio of this polyimide (R) was 49%, the number average molecular weight was 20,700 and the weight average molecular weight was 61,100.

<Synthesis example 19>

M2 (2.87 g, 11.5 mmol), D7 (1.24 g, 11.5 mmol), D1 (0.70 g, 4.6 mmol), and 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 (2.24 g, 11.4 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 (S) was 51%, the number average molecular weight was 16,200 and the weight average molecular weight was 49,900.

<Synthesis example 20>

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.

After adding NMP to this polyamic-acid solution (20.0g) and diluting 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 (300 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 (T) was 51%, the number average molecular weight was 15,300 and the weight average molecular weight was 68,800. This polyimide did not use the diamine compound which has a carboxyl group in a molecule | numerator as a diamine component.

<Synthesis example 21>

M2 (11.2 g, 44.8 mmol), and D3 (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, 14.0 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 (380 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 (U) was 50%, the number average molecular weight was 17,600 and the weight average molecular weight was 52,000. This polyimide did not use the diamine compound which has a carboxyl group in a molecule | numerator as a diamine component.

It shows in Table 1 collectively about the composition and imidation ratio of the polyimide obtained by the synthesis examples 1-21.

<Solubility Test of Polyimide>

<Examples 1-19, Comparative Example 1, and Comparative Example 2>

As Examples 1-19, each solvent of DEME (diethylene glycol monomethyl ether) and DEEE (diethylene glycol monoethyl ether) was used using the polyimide powder (A)-(S) obtained by the synthesis examples 1-19. Solubility comparison was performed.

Similarly, as the comparative examples 1 and 2, the solubility comparison with respect to each solvent of DEME and DEEE was performed using the polyimide powder (T) and (U) obtained by the synthesis examples 20 and 21.

The test method is as follows. That is, DEME (15.7g) is added to each polyimide powder (A)-(S) (1.0g), and it stirred at 25 degreeC for 24 hours, visually confirms the presence or absence of turbidity and precipitation, and confirms solubility. did.

Moreover, using DEEE, the test was done by the same method as the above, and the presence or absence of turbidity, precipitation, etc. was visually confirmed and the solubility was confirmed.

At that time, turbidity and precipitation did not occur, and what obtained a uniform solution was made into the melting furnace, and what made haze and precipitation insoluble.

The result of the solubility test of Examples 1-19, the comparative example 1, and the comparative example 2 is put together in Table 2, and is shown.

From the result obtained in Examples 1-19, it confirmed that the polyimide powder (A)-(S) of an Example melt | dissolves in DEME and DEEE uniformly. On the other hand, it turned out that the polyimide powder (T) and (U) of a comparative example are insoluble in these solvents.

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

<Examples 20-27>

Polyimide powder obtained by the synthesis example 1, the synthesis example 8, the synthesis example 9, the synthesis example 10, the synthesis example 12, the synthesis example 14, the synthesis example 15, and the synthesis example 16 (A), (H), (I), (J ), (L), (N), (O), and (P) DEME (28.0g) was added to each (2.0g), and 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.

Subsequently, each obtained polyimide solution was filtered under pressure with the membrane filter of 1 micrometer of pore diameters, and content of the polyimide component obtained the liquid-crystal aligning agent (1)-(8) which is 5 mass%.

<Examples 28-35>

Polyimide powder obtained by the synthesis example 1, the synthesis example 8, the synthesis example 9, the synthesis example 10, the synthesis example 12, the synthesis example 14, the synthesis example 15, and the synthesis example 16 (A), (H), (I), (J ), (L), (N), (O), and (P) DEEE (28.0g) was added to each (2.0g), and 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, each obtained polyimide solution was filtered under pressure with the membrane filter of 1 micrometer of pore diameters, and the liquid-crystal aligning agent (9)-(16) whose content of a polyimide component is 5 mass% was obtained.

<Examples 36-39>

DEME (26.0 g) was added to each of the polyimide powders (A), (J), (L) and (P) (2.0 g each) obtained in Synthesis Example 1, Synthesis Example 10, Synthesis Example 12 and Synthesis Example 16. It added and stirred at 50 degreeC for 24 hours, and melt | dissolved each polyimide. Furthermore, NMP (12.0g) was added and stirred to each obtained each solution, and each polyimide solution 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, each obtained polyimide solution was filtered under pressure with the membrane filter of 1 micrometer of micropore diameters, and content of the polyimide component obtained the liquid-crystal aligning agent (17)-(20) which is 5 mass%.

<Examples 40-43>

DEME (18.0 g) was added to each of the polyimide powders (A), (J), (L) and (P) (2.0 g each) obtained in Synthesis Example 1, Synthesis Example 10, Synthesis Example 12 and Synthesis Example 16. It added and stirred at 50 degreeC for 24 hours, and melt | dissolved each polyimide. Furthermore, NMP (12.0g) and BCS (8.0g) were added and stirred to each obtained solution, respectively, and each polyimide solution 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, each obtained polyimide solution was filtered under pressure with the membrane filter of 1 micrometer of pore diameters, and the liquid-crystal aligning agent (21)-(24) whose content of a polyimide component is 5 mass% was obtained.

<Examples 44-47>

To each of the polyimide powders (A), (J), (L) and (P) (2.0 g each) obtained in Synthesis Example 1, Synthesis Example 10, Synthesis Example 12 and Synthesis Example 16, DEEE (18.0 g) was added. It added and stirred at 50 degreeC for 24 hours, and melt | dissolved each polyimide. Furthermore, NMP (12.0g) was added and stirred to each obtained solution, and each polyimide solution 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, each obtained polyimide solution was filtered under pressure with the membrane filter of 1 micrometer of micropore diameters, and content of the polyimide component obtained the liquid-crystal aligning agent (25)-(28) which is 5 mass%.

&Lt; Comparative Example 3 &

NMP (31.3g) was added to the polyimide powder (A) of Example 1, and (2.0 g) was stirred at 50 degreeC for 24 hours, and the polyimide was dissolved. Abnormalities such as haze and precipitation were not seen in this polyimide solution, and it was confirmed that it was a uniform solution.

Next, each obtained polyimide solution was filtered under pressure with the membrane filter of 1 micrometer of micropore diameters, and the liquid-crystal aligning agent (29) whose content of a polyimide component is 6 mass% was obtained.

It shows in Table 3 and Table 4 about the solvent in the liquid-crystal aligning agent obtained in Examples 20-47, and the comparative example 3, and its solubility.

<Production of Liquid Crystal Alignment Film and Production of Liquid Crystal Display Element>

The liquid crystal aligning film was produced using the liquid-crystal aligning agent (1)-(28) obtained in Examples 20-47, and the liquid crystal display element which has this liquid crystal aligning film was manufactured. As a liquid crystal display element, the liquid crystal cell of the vertical alignment was produced corresponding to the characteristic of a liquid crystal aligning film.

As a manufacturing method of a liquid crystal cell, a liquid-crystal aligning agent (1)-(28) is spin-coated to the glass substrate (0.7 mm in thickness, 30 mm in width, 40 mm in length) in which the ITO electrode was formed, and it is 5 minutes on an 80 degreeC hotplate. After drying, it baked at 220 degreeC, 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 was all excellent in the uniformity of film thickness, and liquid-crystal aligning agent (1)-(28) showed the outstanding applicability | paintability.

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 company) was printed from on this. Subsequently, after bonding so that the other board | substrate and liquid crystal aligning film surface may face, it hardened | cured by heat-processing the sealing compound at 150 degreeC for 90 minute (s) in a thermocycling clean oven. The nematic liquid crystal (MLC-6608, Merck Corporation make) was injected into this empty cell by the pressure reduction injection method, the injection hole was sealed, and the liquid crystal cell of the vertical orientation was obtained.

About the obtained liquid crystal cell, the orientation state of the liquid crystal was observed with the polarization microscope, and it was confirmed that the vertical orientation of the uniform liquid crystal without a defect is formed.

The result of the orientation state of the liquid crystal of a liquid crystal display element is put together in Table 5, and is shown.

<Printability test>

Printing was performed using the liquid-crystal aligning agent obtained in Example 20, Example 28, Example 36, Example 40, Example 44, and the comparative example 3. The printing is temporarily dried from a printing area of 8 cm × 8 cm, a printing pressure of 0.2 mm, five discard substrates, and printing on a cleaned chromium vapor deposition substrate using a simple printing machine (S15 type, manufactured by Nippon Photographic Co., Ltd.) as a printer. It carried out by time 90 seconds, the temporary drying temperature of 70 degreeC, and 5 minutes of temporary drying time.

The pinhole was visually observed under the sodium lamp. Specifically, the entire coating film surface was visually observed under the sodium lamp, and the number of pinholes present on the coating film surface was counted.

Confirmation of the film thickness nonuniformity was performed using the optical microscope. Specifically, the coating film surface was observed with an optical microscope to show that there was no film thickness nonuniformity on the coating film surface, that the film thickness nonuniformity was partially seen on the coating film surface, and that the film thickness nonuniformity was observed on the entire coating film surface. It was set as C judgment.

The results are summarized in Table 6.

From the above result, the liquid crystal of this invention from the composition containing the polyimide and the compound (solvent) which imidated the polyimide precursor and / or polyimide precursor obtained using the diamine component containing the diamine compound of the specific structure which has a carboxyl group. It was found that an alignment treatment agent was obtained, and the liquid crystal alignment treatment agent was excellent in coatability. Moreover, it turned out that the liquid crystal aligning film obtained using the liquid-crystal aligning agent of this invention is small in defect, and can provide a highly reliable liquid crystal display element.

Industrial availability

The composition of this invention can be widely used for formation of films, such as an interlayer insulation film and a protective film, etc. in an electronic device, Especially, as a liquid-crystal aligning agent, it is excellent in applicability | paintability, and reliability by which defects, such as a cratering and a pinhole, was suppressed It is used for formation of this high liquid crystal aligning film.

In addition, the JP Patent application 2011-153523, the claim, and all the content of the abstract for which it applied on July 12, 2011 are referred here, and it takes in as an indication of the specification of this invention.

Claims (14)

What contains the polyimide which imidated the polyimide precursor obtained by making the diamine component containing the diamine compound which has a carboxyl group, and the tetracarboxylic-acid component and / or this polyimide precursor, and the compound represented by following formula [1] Characterized by a composition.
[Chemical Formula 1]

(In formula [1], R <_1> is a C1-C4 alkyl group.) The method according to claim 1,
The compound represented by said formula [1] is a compound shown by following formula [2] or following formula [3].
(2)

(3)

3. The method according to claim 1 or 2,
A diamine compound having the carboxyl group, - (CH _{2) a} -COOH group composition has a (a is an integer from 0 to 4). 4. The method according to any one of claims 1 to 3,
The diamine compound which has the said carboxyl group is a composition of the diamine compound of the structure shown by following formula [4].
[Chemical Formula 4]

(In formula [4], a is an integer of 0-4 and n shows the integer of 1-4.) 5. The method according to any one of claims 1 to 4,
Content of the said diamine compound is 20-100 mol% in the said diamine component. 6. The method according to any one of claims 1 to 5,
The said diamine component is a composition containing the 2nd diamine compound of the structure shown by following formula [5].
[Chemical Formula 5]

(Wherein [5], X is - (CH _{2) b} -OH groups (b is an integer from 0-4), C 1 -C 22 hydrocarbon groups, substituted hydrocarbon groups having 1 to 6 carbon atoms di-substituted amino group or It is group represented by following formula [6], n shows the integer of 1-4.)
[Chemical Formula 6]

(Formula [6] of the, Y ¹ represents a single _{bond, - (CH 2) a -} . (A 1 to an integer of 15), is -O-, -CH ₂ O-, -COO- or OCO- 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 divalent cyclic group selected from a benzene ring, a cyclohexyl ring, and a hetero 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 having 1 to 3 carbon atoms). It may be substituted by a fluorine-containing alkyl group, a C1-C3 fluorine-containing alkoxyl group, or a fluorine atom), or a C12-C25 divalent organic group which has a steroid skeleton. Y ⁵ Is a divalent cyclic group selected from a benzene ring, a cyclohexyl ring and a heterocyclic ring (any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine atom having 1 to 3 carbon atoms Containing alkyl group, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom). Y ⁶ Is a hydrogen atom, 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. and n represents an integer of 0 to 4.) 7. The method according to any one of claims 1 to 6,
The said tetracarboxylic dianhydride is a compound represented by following formula [7].
(7)

(In formula [7], Z <_1> is a C4-C13 tetravalent organic group and contains a C4-C10 non-aromatic cyclic hydrocarbon group.) The method of claim 7, wherein
Z ₁ The composition which is a structure shown by this formula [7a]-[7j].
[Chemical Formula 8]

(Wherein _{[7a], Z 2 ~ Z} 5 Is a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different, respectively, and is represented by Z <_6> and Z < ₇ > in a formula [7g] Is a hydrogen atom or a methyl group, and may be the same or different, respectively.) The liquid-crystal aligning agent containing the composition of any one of Claims 1-8. The liquid crystal aligning film obtained from the liquid-crystal aligning agent of Claim 9. The liquid crystal aligning film obtained by the inkjet method using the liquid-crystal aligning agent of Claim 9. The method according to claim 10 or 11,
A liquid crystal layer is formed between a pair of substrates provided with electrodes, and a liquid crystal composition containing 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 used for the liquid crystal display element manufactured through the process of superposing | polymerizing the said polymeric compound, applying a voltage to it. The liquid crystal display element which has a liquid crystal aligning film of Claim 10 or 11. 14. The method of claim 13,
A liquid crystal layer is disposed between a pair of substrates provided with an electrode and the liquid crystal alignment layer, and a liquid crystal composition containing a polymerizable compound polymerized by at least one of active energy rays and heat is disposed between the pair of substrates. And a step of polymerizing the polymerizable compound while applying a voltage between the electrodes.