KR20100103554A - Liquid crystal aligning agent and liquid crystal display device using the same - Google Patents

Abstract

(식［1］중, R₁ 은 4 가의 유기기이고, R₂ 는 하기의 식［2］를 함유하는 2 가의 유기기이다)
[화학식 2]

(식［2］중, X₁ 은 페닐렌이고, X₂ 는 시클로헥실렌 또는 페닐렌이고, X₃ 은 시클로헥실렌이다. X₄ 는 탄소수 3 ∼ 12 의 알킬기, 탄소수 3 ∼ 12 의 알콕시기, 탄소수 3 ∼ 12 의 플루오로알킬기 또는 탄소수 3 ∼ 12 의 플루오로알콕시기이다)Providing the liquid-crystal aligning agent which has the characteristic which enlarges the pretilt angle of a liquid crystal, which can orientate a liquid crystal perpendicularly even with a small use ratio, and the liquid crystal display element using the same.
The following (A) component and following (B) component are contained, The liquid-crystal aligning agent characterized by the above-mentioned.
(A) component: The polymer which imidated the polyamic acid which has a structural formula of the repeating unit shown by following formula [1], and has a carboxyl group in the molecule | numerator in this polymer.
(B) Component: The amine compound which has one primary amino group and nitrogen containing aromatic heterocyclic ring in a molecule | numerator, and the said primary amino group couple | bonded with the aliphatic hydrocarbon group or the non-aromatic cyclic hydrocarbon group.
[Formula 1]

(In formula [1], R <_1> is a tetravalent organic group and R <_2> is a divalent organic group containing following formula [2].)
(2)

(In formula [2], X <_1> is phenylene, X <_2> is cyclohexylene or phenylene, X <_3> is cyclohexylene. X <_4> is a C3-C12 alkyl group and a C3-C12 alkoxy group. , A fluoroalkyl group having 3 to 12 carbon atoms or a fluoroalkoxy group having 3 to 12 carbon atoms)

Description

Liquid crystal aligning agent, and liquid crystal display element using the same {LIQUID CRYSTAL ALIGNING AGENT AND LIQUID CRYSTAL DISPLAY DEVICE USING THE SAME}

This invention relates to the liquid-crystal aligning agent used when manufacturing a liquid crystal aligning film, and the liquid crystal display element using the same.

As a liquid crystal aligning film of a liquid crystal display element, what is called a polyimide-type liquid crystal which apply | coated and baked the liquid-crystal aligning agent (also called liquid crystal aligning agent) which mainly uses the solution of polyimide precursors, such as a polyamic acid, and a soluble polyimide, and bakes this. An alignment film is mainly used.

As one of the characteristics required for the liquid crystal aligning film, there is a so-called pretilt angle control of the liquid crystal which maintains the alignment inclination angle of the liquid crystal molecules with respect to the substrate surface at an arbitrary value. It is known that the magnitude | size of this pretilt angle can be changed by selecting the structure of the polyimide which comprises the liquid crystal aligning film.

Among the techniques for controlling the pretilt angle by the structure of the polyimide, the method of using a diamine having a side chain as a part of the polyimide raw material increases the pretilt angle depending on the ratio of use of this diamine. It is relatively easy to control the tilt angle and is useful as a means for increasing the pretilt angle. As a side chain structure of the diamine which enlarges the pretilt angle of a liquid crystal, what contains ring structures, such as a steroid skeleton (for example, patent document 1), a phenyl group and a cyclohexyl group, is proposed (for example, a patent document) 2). Furthermore, the diamine which has 3 to 4 of such ring structures in a side chain is also proposed (for example, refer patent document 3).

On the other hand, in the process of liquid crystal aligning film manufacture, when apply | coating the solution of polyamic acid and the solution of solvent-soluble polyimide to a board | substrate, it is common to industrially perform flexographic printing etc., and the solvent of a coating liquid In addition to N-methyl-2-pyrrolidone, γ-butyrolactone, etc., which are excellent in solubility of the polymer, butyl cellosolve and the like are mixed for the purpose of forming a uniform and defect-free thin film. However, solvents such as butyl cellosolve are inferior in ability to dissolve polyamic acid and polyimide, and thus have a problem that precipitation occurs when mixed in large amounts (see Patent Document 4, for example). This problem is particularly pronounced in solutions of solvent soluble polyimides. Moreover, since the polyimide obtained using the diamine which has a side chain as mentioned above tends to fall the coating uniformity of a solution, it is necessary to increase the mixing amount of coating property improvement solvents, such as butyl cellosolve. The mixing tolerance of such a solvent is also an important characteristic of the polyimide.

In addition, with high definition of the liquid crystal display element, from the viewpoint of suppression of contrast reduction of the liquid crystal display element and reduction of afterimage phenomenon, the liquid crystal alignment film used therein has a high voltage retention and a direct current voltage. It has become increasingly important that the accumulated charges when applied are small and the relaxation of the residual charges accumulated by the direct current voltage is fast.

In the liquid crystal aligning film of a polyimide system, the time until the afterimage which generate | occur | produced by a direct current voltage disappears is short, The liquid crystal aligning agent containing the tertiary amine of a specific structure in addition to a polyamic acid or an imide group containing polyamic acid. The thing using the liquid crystal aligning agent containing the (using patent document 5) and the soluble polyimide which used the specific diamine which has a pyridine skeleton etc. as a raw material (for example, patent document 6), etc. are known. . In addition, the voltage retention is high and the time until the afterimage generated by the direct current voltage disappears is short, and in addition to the polyamic acid or the imidized polymer, the compound containing one carboxylic acid group in the molecule, 1 in the molecule, Liquid crystal aligning agent (for example, refer patent document 7) using the liquid crystal aligning agent containing the minimum amount of the compound chosen from the compound containing two carboxylic acid anhydride groups, and the compound containing one tertiary amino group in a molecule | numerator is known.

However, in recent years, large-screen and high-definition liquid crystal televisions have been widely used, and in the liquid crystal display device in such a use, the demand for afterimages is higher than that in conventional display applications mainly displaying characters and still images. There is a demand for properties that are more stringent and capable of withstanding long-term use in harsh use environments. Therefore, the liquid crystal aligning film used there is required to be more reliable than the conventional one, and also the electrical properties of the liquid crystal aligning film are not only excellent in initial characteristics, but are also exposed to ultraviolet rays of the backlight for a long time, for example, for a long time. It is desired to maintain good properties even after exposure.

Japanese Unexamined Patent Publication No. 4-281427 Japanese Patent Laid-Open No. 9-278724 Japanese Unexamined Patent Publication No. 2004-67589 Japanese Patent Laid-Open No. 2-37324 Japanese Patent Laid-Open No. 9-316200 Japanese Unexamined Patent Publication No. 10-104633 Japanese Patent Laid-Open No. 8-76128

The objective of this invention has the characteristic which enlarges the pretilt angle of a liquid crystal when it is set as a liquid crystal aligning film, can align a liquid crystal perpendicularly even with a small use ratio, and is a poor solvent in the coating liquid of a liquid-crystal aligning agent. It is providing the liquid-crystal aligning agent which precipitation hardly arises even when mixing. In addition to these characteristics, liquid crystals having a high voltage retention and a rapid relaxation of residual charges accumulated by DC voltage even after long-term exposure at high temperatures, and can suppress a drop in voltage retention even after long-term exposure to ultraviolet rays of the backlight. It is providing the liquid-crystal aligning agent from which an oriented film is obtained. Furthermore, it is providing the highly reliable liquid crystal display element which can endure long-term use in severe use environment.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to achieve the said objective, this inventor discovered the novel liquid-crystal aligning agent which achieves this. This invention is based on this knowledge and has the following summary.

(1) The following (A) component and following (B) component are contained, The liquid-crystal aligning agent characterized by the above-mentioned.

(A) Component: The polymer which imidated the polyamic acid which has a structural formula of the repeating unit represented by following formula [1], and has a carboxyl group in the molecule | numerator in this polymer.

(B) Component: The amine compound which has one primary amino group and nitrogen containing aromatic heterocyclic ring in a molecule | numerator, and the said primary amino group couple | bonded with the aliphatic hydrocarbon group or the non-aromatic cyclic hydrocarbon group.

[Formula 1]

(In formula [1], R <_1> is tetravalent organic group and R <_2> is bivalent organic group containing following formula [2].)

[Formula 2]

(In formula [2], X <_1> is phenylene, X <_2> is cyclohexylene or phenylene, X <_3> is cyclohexylene. X <_4> is a C3-C12 alkyl group and a C3-C12 alkoxy group. , A fluoroalkyl group having 3 to 12 carbon atoms or a fluoroalkoxy group having 3 to 12 carbon atoms)

(2) formula X ₂ [2] is cyclohexyl, and xylene, or phenylene group, X ₄ is an alkoxy group, a fluoroalkyl group or having 3 to 6 carbon atoms in a carbon number of 3-6 in alkyl group having 3 to 6 carbon atoms, having 3 to 6 carbon atoms The liquid-crystal aligning agent as described in said (1) which is a fluoroalkoxy group of.

(3) The liquid-crystal aligning agent as described in said (1) whose R < ₂ > in Formula [1] is a divalent organic group containing following formula [3].

(3)

(In formula [3], n is an integer of 2-11. The cis-trans isomerization of 1, 4- cyclohexylene is a trans isomer.)

(4) The liquid-crystal aligning agent as described in said (1) whose R < ₂ > in Formula [1] is a divalent organic group containing following formula [4].

[Formula 4]

(In formula [4], n is an integer of 2-11. The cis-trans isomerization of 1, 4- cyclohexylene is a trans isomer.)

(5) (A) Component is a polymer which imidated the polyamic acid which has a structural formula of a repeating unit represented by Formula [1], and the quantity of the carboxyl group which the polymer has is 0.1-3 as an average value with respect to the repeating unit of this polymer. Individual The liquid-crystal aligning agent in any one of said (1)-(4).

(6) In the structural formula of the repeating unit in which (A) component is represented by said Formula [1], a part or all of the repeating units imidized the polyamic acid which has a structural formula which has a unit represented by following formula [5] It is a polymer and the liquid-crystal aligning agent in any one of said (1)-(5) whose quantity of the carboxyl group which this polymer has is 0.1-3 in average value with respect to the repeating unit of this polymer.

[Chemical Formula 5]

(Wherein, R ₃ is a tetravalent organic group, R ₄ is a divalent organic group, and at least one of R ₃ or R ₄ has a carboxyl group)

(7) The liquid-crystal aligning agent in any one of said (1)-(6) whose (B) component is an amine compound shown by following formula [6].

[Formula 6]

(In formula [6], Y <_1> is a divalent organic group which has an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and Y <_2> is a nitrogen-containing aromatic heterocyclic ring.)

(8) The liquid-crystal aligning agent in any one of said (1)-(6) whose (B) component is an amine compound shown by following formula [7].

[Formula 7]

(Wherein [7], Y ₃ is a divalent aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group having a carbon number of valence 1 ~ 10, Y ₄ represents a single bond, or -O-, -NH-, -S-, -SO _It is a bivalent or divalent organic group having 1 to 19 carbon atoms, and the total of the carbon atoms of Y ₃ and Y ₄ is 1 to 20. Y ₅ is a nitrogen-containing aromatic heterocyclic ring.)

(9) The liquid-crystal aligning agent as described in said (8) whose component (B) is an amine compound in which Y <_3> , Y <_4> and Y < ₅ > in Formula [7] are respectively chosen from the group or ring described below.

Stage, Y ₃ is a group having 1 to 10 carbon atoms in the straight-chain or branched alkylene group, having 1 to 10 carbon atoms of the unsaturated alkyl group, a cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, Cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotedecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclonona It is 1 type chosen from the group which consists of a decane ring, a cycloikoic acid ring, a tricyclo ecoic acid ring, a tricyclodecoic acid ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring, and an adamantane ring;

Y ₄ is a single bond, -O-, -NH-, -S-, -SO _2- , a hydrocarbon group having 1 to 19 carbon atoms, -CO-O-, -O-CO-, -CO-NH-,- NH-CO-, -CO-, -CF _2- , -C (CF ₃ ) _2- , -CH (OH)-, -C (CH ₃ ) _2- , -Si (CH ₃ ) _2- , -O -Si (CH ₃ ) _2- , -Si (CH ₃ ) ₂ -O-, -O-Si (CH ₃ ) ₂ -O-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cyclo Heptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotedecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, Cyclooctadecane ring, cyclononadecan ring, cycloicosan ring, tricycloecoic acid ring, tricyclodecoic acid ring, bicycloheptane ring, decahydronaphthalene ring, norbornene ring, adamantane ring, benzene ring, Naphthalene Ring, Tetrahydronaphthalene Ring, Azul Ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, penalene ring, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyra Sleepy ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, chi Nolin ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring, oxazole ring, piperazine ring, piperidine ring, dioxane It is 1 species chosen from the group which consists of a ring and a morpholine ring;

Y ₅ is pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole Ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, chinoline ring, phenanthroline ring, indole ring, quinoxaline It is 1 species chosen from the group which consists of a ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring, and an acridine ring.

(10) The liquid-crystal aligning agent in any one of said (1)-(9) which contains (B) component in the ratio of 0.01-2 mol double with respect to 1 mol amount of the carboxyl group which the polyimide of (A) component has. .

(11) The liquid-crystal aligning agent in any one of said (1)-(10) obtained by mixing under the heating the organic solvent containing the polyimide of (A) component and the amine compound of (B) component.

(12) The liquid crystal aligning film obtained from the liquid-crystal aligning agent in any one of said (1)-(11).

The liquid crystal display element which has a liquid crystal aligning film as described in said (12).

The liquid-crystal aligning agent of this invention can be obtained by a comparatively simple method. Moreover, the liquid-crystal aligning agent of this invention has the characteristic which enlarges the pretilt angle of a liquid crystal, when it is set as a liquid crystal aligning film, and can align a liquid crystal perpendicularly even with a small use ratio. Moreover, precipitation hardly arises even when a poor solvent is mixed with the coating liquid of a liquid-crystal aligning agent. Furthermore, the liquid crystal aligning film which has high voltage retention and quick relaxation of the residual electric charge accumulate | stored by DC voltage even after long time exposure under high temperature can be obtained.

Moreover, the liquid crystal display element which has the liquid crystal aligning film obtained from the liquid-crystal aligning agent of this invention becomes excellent in reliability, and can be used suitably for a high definition liquid crystal television etc.

The liquid-crystal aligning agent of this invention is a polymer which imidated the polyamic acid which has a structural formula of the repeating unit represented by said Formula [1] which is (A) component, The polyimide which has a carboxyl group in the molecule of this polymer (following, May be referred to as a specific polyimide), and (B) an amine compound having one amino group and a nitrogen-containing aromatic heterocyclic ring in its molecule, and wherein the amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. It is a liquid-crystal aligning agent containing (Hereinafter, it may be called a specific amine compound.). In the present specification, the above-described amino group (-NH ₂₎ is the same as primary amino groups, and also referred to as primary amino groups.

The specific polyimide in the liquid-crystal aligning agent of this invention uses for the raw material the specific diamine (henceforth called a specific diamine) which has a substituent which has the characteristic which enlarges a pretilt angle in a side chain. Therefore, when using this specific diamine, a liquid crystal can be orientated vertically also by the use ratio with few liquid-crystal aligning agents obtained. Moreover, by decreasing the use ratio, the organic solvent solubility of the polymer is increased, and precipitation does not occur well even when the poor solvent is mixed in the coating liquid of the liquid-crystal aligning agent.

In the liquid-crystal aligning agent of this invention, the amino group in a specific amine compound forms a salt with the carboxyl group in a specific polyimide, or has the amide bond accompanying desorption of water or alcohol with respect to the carboxyl group or carboxyester group in a specific polyimide, or It is thought that the coupling reaction with ring-opening of an imide group is performed with respect to the imide group in a specific polyimide. Moreover, the amino group which forms the carboxyl group and salt in a specific polyimide by the baking process at the time of manufacturing a liquid crystal aligning film is considered to form an amide bond by desorption of water. As a result, in the liquid crystal aligning film obtained, it is thought that the specific amine compound and the specific polyimide have couple | bonded efficiently in spite of the simple means of mixing in the organic solvent the liquid-crystal aligning agent of this invention.

On the other hand, since the nitrogen-containing aromatic heterocycle in a specific amine compound functions as an electron hopping site by the conjugated structure, it promotes charge transfer in the resulting liquid crystal alignment film. In addition, when a liquid crystal aligning film is used, the nitrogen-containing aromatic heterocycle and the carboxyl group in the specific polyimide are connected by electrostatic interaction such as salt formation or hydrogen bonding, so that the carboxyl group in the specific polyimide and the nitrogen-containing aromatic heterocycle in the specific amine compound are formed. The transfer of charges takes place at. Furthermore, since this specific amine compound is chemically bonded to a specific polyimide, the charges transferred to the nitrogen-containing aromatic heterocyclic moiety can efficiently move in or between the polyimide molecules.

By the above, when the liquid-crystal aligning agent of this invention is set as the liquid crystal aligning film, it has the characteristic which enlarges the pretilt angle of a liquid crystal, and can align a liquid crystal perpendicularly even with a small use ratio. Moreover, precipitation hardly arises even when a poor solvent is mixed with the coating liquid of a liquid-crystal aligning agent. Furthermore, the liquid crystal aligning film which has high voltage retention and quick relaxation of the residual electric charge accumulate | stored by DC voltage even after long time exposure under high temperature can be obtained.

<(A) component / specific polyimide>

In this invention, the specific polyimide which is (A) component is a polymer which imidated the polyamic acid which has a structural formula of the repeating unit represented by Formula [1], and if it is a polyimide which has a carboxyl group in the molecule of the polymer, the structure will be It is not specifically limited. Since this polyimide is obtained relatively simply by using tetracarboxylic dianhydride and diamine as a raw material, the polymer which imidated the polyamic acid which has a structural formula of a repeating unit represented by Formula [1] is preferable.

[Formula 8]

(In formula [1], R <_1> is tetravalent organic group and R <_2> is bivalent organic group containing following formula [2].)

[Formula 9]

In formula [2], X <_1> is phenylene, X <_2> is cyclohexylene or phenylene, and X <_3> is cyclohexylene. In phenylene or cyclohexylene, you may have a substituent as needed. X ₄ is 3 to 12 carbon atoms, preferably 3 to 6 alkyl groups, 3 to 12 carbon atoms, preferably 3 to 6 alkoxy groups, 3 to 12 carbon atoms, preferably 3 to 6 fluoroalkyl groups, or carbon atoms 3-12, Preferably they are 3-6 fluoroalkoxy groups. Although an alkyl group, a fluoroalkyl group, an alkoxy group, and a fluoroalkoxy group may be linear or branched type, a linear type is preferable and may have a suitable substituent.

The bonding position of the amino group in the benzene ring of the main chain in Formula [2] is not limited. As a specific example, with respect to Z < ₁ > in following formula [8], the position of 2, 3, the position of 2, 4, the position of 2, 5, the position of 2, 6, the position of 3, 4, 3 , 5 position. Especially, the position of 2, 4, the position of 2, 5, the position of 3, 5 are preferable from a viewpoint of the reactivity at the time of synthesize | combining a polyamic acid. In addition to the ease of diamine synthesis, the position of 2, 4 or the position of 2, 5 is preferable.

[Formula 10]

Among formula [2], 1,4-phenylene is preferable for X <_1> . In addition, X ₂ is preferably 1,4-phenylene or 1,4-cyclohexylene, more preferably 1,4-phenylene or 1,4-trans-cyclohexylene, particularly 1,4- Trans-cyclohexylene is preferred. Moreover, ₁ , 4- cyclohexylene is preferable and, as for X <_3> , ₁ , ₄ -trans-cyclohexylene is especially preferable.

Preferable specific examples of the structure represented by formula [2] of the present invention are as follows. Moreover, the integer of 2-11 is respectively preferable independently, and, as for n in following formula [9]-[12], the integer of 2-6 is especially preferable. In addition, the cis-trans isomer of 1, 4- cyclohexylene in a formula is a trans isomer, respectively.

[Formula 11]

The specific polyimide containing the structure of Formula [2] can be obtained by using the specific diamine shown by following formula [13] as a raw material.

[Formula 12]

(In formula [13], X ₁ , X ₂ , X ₃ and X ₄ are the same definitions as defined in formula [2].)

Although the method of manufacturing the diamine shown by Formula [13] is not specifically limited, The following method is mentioned as a preferable method.

[Formula 13]

(In formula [14], X ₁ , X ₂ , X ₃ and X ₄ are the same definitions as defined in formula [2].)

It is obtained by synthesize | combining the dinitro compound of Formula [14], and reducing a nitro group by a conventional method and converting into an amino group.

The dinitro compound of formula [14] can be obtained by reaction, such as a hydroxyl group containing compound and dinitrochlorobenzene shown by following formula [15].

[Formula 14]

(In formula [15], X ₁ , X ₂ , X ₃ and X ₄ are the same definitions as defined in formula [2].)

The specific polyimide containing the structure of Formula [3], [4], and [9]-[12] can also be obtained by the same method as the above.

In Formula [1], one type of R <_1> and R <_2> may respectively be different, and they may have different R <_1> and R <_2> , respectively, and may combine the multiple multiple types as a repeating unit.

It is preferable to use 1 mol% or more of the structure of Formula [2] for the purpose of enlarging the pretilt angle of a liquid crystal. It is preferable to use 10 mol% or more for the purpose of orienting a liquid crystal perpendicularly | vertically, More preferably, it is 15 mol% or more. The same also applies to the specific polyimide containing the structure of Formula [3], [4], and [9]-[12].

A specific polyimide can be obtained by controlling the imidation ratio at the time of imidating the said polyamic acid normally to less than 100%.

Moreover, a specific polyimide can also be obtained by imidating the polyamic acid containing the structural unit represented by following formula [5] in a repeating unit in the structural formula of the repeating unit represented by Formula [1].

[Formula 15]

(In formula [5], R <_3> is a tetravalent organic group, R <_4> is a divalent organic group, and at least one of R <_3> or R <_4> has a carboxyl group.)

In that case, 100% of the imidation ratio may be sufficient.

It is preferable that the imidation ratio of a specific polyimide is 20% or more, More preferably, it is 40% or more because a high voltage retention is obtained.

The amount of the carboxyl group in the specific polyimide is preferably 0.1 to 3, more preferably 0.3 to 2.0, particularly preferably 0.3 to 2.0 as an average value for the repeating unit of the structural formula as the polyimide, because the effect of the present invention is obtained efficiently. Preferably it is 0.5-1.8. The repeating unit in this case also combines the unit containing the unimidated amic acid group. For example, in the case of the polyimide obtained by imidating the polyamic acid which consists of a repeating unit represented by Formula [1], when the imidation ratio is less than 100%, it is a combination of the structure of following formula [16a]-[16d] Although what is comprised is conceivable, the repeating unit at the time of calculating the quantity of a carboxyl group mentioned above includes all of formula [16a]-[16d].

[Formula 16]

In this invention, the quantity (henceforth an average value of a carboxyl group) in a specific polyimide is calculated | required as the sum of P of following (i) and Q of (ii).

(Iii) Average value of repeating units of structural formulas as polyimides of carboxyl groups derived from unimidized amic acid: P

(Ii) Average value with respect to the repeating unit of the structural formula as a polyimide of the carboxyl group contained in R <_3> , R < ₄ > of said Formula [5]: Q

And P of said (i) can be computed from following formula (1) using imidation ratio (z). In addition, the imidation ratio (z) is calculated | required from <the measurement of the imidation ratio> mentioned later, for example.

P = 2 × (1-z / 100) (1)

On the other hand, Q of said (ii) is an average value with respect to the repeating unit of the structural formula as a polyimide of the carboxyl group contained in R < ₃ > of Formula [5]: Q <_1> and the carboxyl group contained in R <_4> of the structural formula as polyimide The average value for the repeating unit is obtained by the sum of Q ₂ .

Wherein the R _3, R ₄ are each a part or all of the raw materials used for obtaining the specific polyimide tetracarboxylic dianhydride moiety (R _3), the diamine moiety (R _4).

Therefore, the expression of the Q ₁ is to use a tetracarboxylic mole fraction of the acid dianhydride represented by the formula [V1] below in the total molar amount of the tetracarboxylic acid dianhydride used for obtaining the specific polyimide, It is calculated from (2).

[Formula 17]

(In formula [V1], R <_3> is the same as what was defined by formula [5].)

Q ₁ = β ₁ × W ₁ / W ₂ (2)

Herein, beta ₁ represents the number of carboxyl groups contained in R ₃ , W ₁ is a molar amount of tetracarboxylic dianhydride of formula [V1], and W ₂ represents a total molar amount of tetracarboxylic dianhydride.

Moreover, said Q <_2> is computed from following formula (3) using the mole fraction of the diamine shown by following formula [V2] in the total molar amount of the diamine used in order to obtain a specific polyimide.

[Formula 18]

(In formula [V2], R <_3> is the same as what was defined by formula [5].)

Q ₂ = β ₂ × W ₃ / W ₄ (3)

Here, β ₂ represents the number of carboxyl groups contained in R ₄ , W ₃ is the molar amount of the diamine represented by the formula [V2], and W ₄ represents the total molar amount of the diamine.

In this way, the quantity of a carboxyl group is calculated | required by following formula (4).

Amount of carboxyl group in specific polyimide

= P + Q ₁ + Q ₂

= 2 × (1-z / 100) + β_One × W_One/ W₂ + Β₂ × W₃/ W₄ (4)

In this invention, adjustment of the quantity of the carboxyl group in a specific polyimide,

(1) means for adjusting by controlling the imidation ratio,

(2) means for adjusting by the number of carboxyl groups contained in R ₃ or R ₄ of formula [5] and the ratio of formula [5] in the structural formula of the repeating unit represented by formula [1],

Any of these may be sufficient. Moreover, the means of (1) and (2) can also be used together.

The means of (1) is preferable from a viewpoint of the freedom of selection of R <_1> and R < ₂ > in Formula [1]. The means of (2) is preferable from a viewpoint of the freedom of selection of the imidation ratio of a specific polyimide. Moreover, the means of (2) is preferable from a viewpoint that there is little possibility that a specific amine compound will detach | desorb or a polyimide chain will be cut off by the imidation reaction by the baking process at the time of manufacturing a liquid crystal aligning film.

When adjusting the quantity of the carboxyl group in a specific polyimide by the means of said (1), R <_1> and R < ₂ > in Formula [1] are not specifically limited. In addition, R <_1> and R < ₂ > may be one type in formula [1], respectively, and may have a structure of R <_1> and R <_2> different from each other, and may combine the multiple multiple types as a repeating unit.

Give an embodiment of R ₁ in the formula (1) side is as follows.

[Formula 19]

[Formula 20]

Among them, A-6, A-16, A-18 to A-22, A-25, A-37 or A-38 are preferred because they have high solubility in organic solvents even in the case of polyimide having a high imidation ratio.

Moreover, when 10 mol% or more of R <_1> has alicyclic structure or aliphatic structure like A-1-A-25, since voltage retention improves, it is preferable. In particular, it is preferable to use two types of R <_{1> selected} from A-1, A-16, and A-19 together because a liquid crystal aligning film with faster relaxation of an electric charge can be obtained.

In the formula [1], R ₂ is may contain an organic group other than the structure represented by formula [2]. It is as follows if the specific example is given.

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

[Formula 25]

[Formula 26]

(In B-112 and B-113, Q represents any of -COO-, -OCO-, -CONH-, -NHCO-, -CH _2- , -O-, -CO-, -NH-)

When adjusting the amount of the carboxyl group of the specific polyimide by means of the above (2), R ₃ or R _4, if any that has a carboxyl group in its structure is not particularly limited. Moreover, as for the number of carboxyl groups, 0-2 pieces are preferable to R <_3> and R <_4> (however, either one of R <_3> or R <_4> has at least 1 carboxyl group) is preferable.

It is more preferable to have a carboxyl group in R <_4> from a viewpoint of the ease of synthesis of a polyimide, and the availability of a raw material. Examples of R ₄ having a carboxyl group include B-102 to B-113. At that time, R ₄ is a carboxyl group may be either one kinds or may, and in combinations of two or more. Moreover, when R <_4> has a carboxyl group, the structure of R <_3> is not specifically limited, A-1-A-45 is mentioned as a specific example.

<Method for Producing Specific Polyimide>

Although the manufacturing method of the specific polyimide which is (A) component used for this invention is not specifically limited, Generally, the tetracarboxylic-acid component which consists of 1 type or multiple types chosen from tetracarboxylic acid and its derivative (s), A method of reacting a diamine component composed of one or a plurality of diamine compounds to synthesize a polyamic acid having a structural formula of a repeating unit represented by formula [1], imidating the polyamic acid to form a polyimide is used. do.

In that case, the polyamic acid obtained can be set as a homopolymer (homopolymer) or a copolymer (copolymer) by selecting the tetracarboxylic-acid component and diamine component which are raw materials suitably.

Tetracarboxylic acid and its derivative (s) here are tetracarboxylic acid, tetracarboxylic-acid halide, or tetracarboxylic dianhydride. Especially, since tetracarboxylic dianhydride has high reactivity with a diamine compound, it is preferable.

The specific example of the manufacturing method of a specific polyimide is shown below.

For example, the diamine containing the tetracarboxylic-acid component containing at least 1 sort (s) chosen from the tetracarboxylic dianhydride represented by Formula [18], and the at least 1 sort (s) chosen from the diamine compound represented by Formula [19]. Polyamic acid can be obtained by making a component polycondensate in organic solvents, such as N-methylpyrrolidone, N, N'- dimethylacetamide, N, N'- dimethylformamide, and (gamma) -butyrolactone.

[Formula 27]

In addition, R < ₁ > in Formula [18] is the same as what was defined in Formula [1].

[Formula 28]

In addition, R < ₂ > in Formula [19] is the same as what was defined in Formula [1].

In that case, although reaction temperature can select arbitrary temperature of -20 degreeC-150 degreeC, Preferably it is the range of -5 degreeC-100 degreeC.

The ratio of the total number of moles of the compound constituting the tetracarboxylic acid component and the total number of moles of the diamine compound constituting the diamine component is preferably 0.8: 1 to 1.2: 1, particularly preferably 0.9: 1 to 1.1: 1. . The closer this molar ratio is to 1.0, the greater the degree of polymerization of the resulting polymer.

Moreover, in order to obtain the polyamic acid which has a unit represented by Formula [5] in one part or all part of a repeating unit in the structural formula of the repeating unit represented by Formula [1], the tetracarboxylic dianhydride which has a carboxyl group in R <_1> , and What is necessary is just to use the diamine which has a carboxyl group in R <_2> .

As a method of imidating a polyamic acid, thermal imidation by heating and catalyst imidation using a catalyst are common, but the molecular weight fall of the polyimide obtained by the catalyst imidation which the imidation reaction advances at comparatively low temperature is obtained It does not happen well and is preferable.

Catalyst imidation can be performed by stirring polyamic acid in presence of a basic catalyst and an acid anhydride in an organic solvent. The reaction temperature at this time is -20-250 degreeC, Preferably it is 0-180 degreeC. The higher the reaction temperature, the faster the imidization is. However, if the reaction temperature is too high, the molecular weight of the polyimide may decrease. The amount of the basic catalyst is 0.5 to 30 mole times, preferably 2 to 20 mole times, of the amic acid group, and the amount of acid anhydride is 1 to 50 mole times, preferably 3 to 30 mole times, of the amic acid group. If the amount of the basic catalyst or the acid anhydride is small, the reaction does not proceed sufficiently. If the amount is too high, it is difficult to completely remove the reaction after completion of the reaction. Pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. are mentioned as a basic catalyst used in this case, Especially, since pyridine has suitable basicity for advancing reaction, it is preferable. Moreover, acetic anhydride, trimellitic anhydride, a pyromellitic dianhydride, etc. are mentioned as acid anhydride, Especially, since acetic anhydride is used, since refinement | purification after completion | finish of reaction becomes easy, it is preferable. The organic solvent is not limited as long as the polyamic acid is dissolved, but examples thereof include N, N'-dimethylformamide, N, N'-dimethylacetamide, N-methyl-2-pyrrolidone, N-methyl caprolactam, dimethyl sulfoxide, tetramethylurea, dimethyl sulfone, hexamethyl sulfoxide, (gamma) -butyrolactone, etc. are mentioned. The imidation ratio by catalyst imidation can be controlled by adjusting catalyst amount, reaction temperature, and reaction time.

The produced polyimide is obtained by injecting the reaction solution into a poor solvent to recover the precipitate formed. The poor solvent used in that case is not specifically limited, For example, methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, etc. are mentioned. . The polyimide precipitated by being poured into the poor solvent can be filtrated and then dried at ordinary temperature or under reduced pressure to obtain a powder. If the polyimide powder is further dissolved in an organic solvent and reprecipitated 2 to 10 times, the polyimide may be purified. When impurities are not completely removed by one precipitation recovery operation, it is preferable to perform this purification step.

Although the molecular weight of the specific polyimide used for this invention is not specifically limited, From a viewpoint of the ease of handling and the stability of the characteristic at the time of film formation, 2,000-200,000 are preferable at a weight average molecular weight, More preferably, it is 4,000-50,000. . Molecular weight is calculated | required by GPC (gel permeation chromatography).

<(B) component / specific amine compound>

The specific amine compound which is (B) component used for this invention is an amine compound which has one amino group and nitrogen containing aromatic heterocyclic ring in a molecule | numerator, and the said amino group couple | bonded with the bivalent aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group.

Since this specific amine compound has only one amino group contained in the molecule, it is possible to avoid the possibility of problems such as precipitation of the polymer and gelation during preparation of the liquid crystal alignment agent or storage of the liquid crystal alignment agent.

The primary amino group contained in the specific amine compound is bound to a divalent aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group containing no aromatic hydrocarbon in the molecule from the viewpoint of ease of salt formation and binding reaction with the specific polyimide. You need to be.

As a specific example of an aliphatic hydrocarbon group, a linear alkylene group, the alkylene group which has a branched structure, the bivalent hydrocarbon group which has an unsaturated bond, etc. are mentioned. Carbon number of an aliphatic hydrocarbon group becomes like this. Preferably it is 1-20, More preferably, it is 1-15, More preferably, it is 1-10.

Specific examples of the divalent non-aromatic cyclic hydrocarbon group include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundane ring, Cyclododecane ring, Cyclotridecane ring, Cyclotedecane ring, Cyclopentadecan ring, Cyclohexadecane ring, Cycloheptadecane ring, Cyclooctadecane ring, Cyclononadecan ring, Cycloicosane ring, Tricycloeicoic acid ring , Tricyclodeco acid ring, bicycloheptane ring, decahydronaphthalene ring, norbornene ring, adamantane ring and the like. Preferably it is a ring which consists of 3-20 carbon atoms, More preferably, it is a ring which consists of 3-15 carbon atoms, More preferably, it is a non-aromatic cyclic hydrocarbon group of the ring which consists of 3-10 carbon atoms.

The nitrogen-containing aromatic heterocycle contained in the specific amine compound is an aromatic cyclic hydrocarbon containing at least one structure selected from the group consisting of the following formulas [20a], [20b] and [20c], more preferably Is 1-4.

[Formula 29]

(Wherein Z ₂ is a linear or branched alkyl group having 1 to 5 carbon atoms)

Specifically, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadia Sol ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, chinoline ring, phenanthroline ring, indole ring, quinox Saline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring, etc. are mentioned. In addition, the carbon atom of these nitrogen-containing aromatic heterocycles may have a substituent containing a hetero atom.

As a more preferable specific amine compound, it is an amine compound shown by following formula [6].

[Formula 30]

(Wherein Y ₁ is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and Y ₂ is a nitrogen-containing aromatic heterocycle)

In Formula [6], Y <_1> will not be specifically limited if it is a divalent organic group which has an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group.

Preferred Y ₁ in formula [6] is a divalent organic group having one kind selected from an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a nonaromatic cyclic hydrocarbon group having 3 to 20 carbon atoms. Examples of the non-aromatic cyclic hydrocarbon group include the structures described above. Y ₁ is more preferably an aliphatic hydrocarbon group having 1 to 15 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloound And a cann ring, a cyclododecane ring, a cyclotridecane ring, a cyclotetradecane ring, a norbornene ring and an adamantane ring. Y ₁ is particularly preferably a linear or branched alkylene group having 1 to 10 carbon atoms.

In addition, -CH ₂ -in any aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group not adjacent to the amino group contained in Y ₁ is -O-, -NH-, -CO-O-, -O-CO- , -CO-NH-, -NH-CO-, -CO-, -S-, -S (O) _2- , -CF _2- , -C (CF ₃ ) _2- , -C (CH ₃ ) ₂ -, -Si (CH ₃ ) _2- , -O-Si (CH ₃ ) _2- , -Si (CH ₃ ) ₂ -O-, -O-Si (CH ₃ ) ₂ -O-, divalent cyclic It may be substituted with a hydrocarbon group or a hetero ring. Moreover, the hydrogen atom couple | bonded with arbitrary carbon atoms may be substituted by the C1-C20 linear or branched alkylene group, a cyclic hydrocarbon group, a C1-C10 fluorine-containing alkyl group, a heterocyclic ring, a fluorine atom, and a hydroxyl group. .

Specific examples of the divalent cyclic hydrocarbon group include benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, phenylene ring, cyclopropane ring and cyclobutane Ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecan ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring , Cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecan ring, cycloic acid ring, tricycloecoic acid ring, tricyclodecoic acid ring, bicycloheptane ring, decahydronaphthalene ring, norbor Nene ring, an adamantane ring, etc. are mentioned.

Moreover, as a specific example of a bivalent hetero ring, a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, an isoquinoline ring, a carr Bazol ring, purine ring, thiadiazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzoimidazole ring, chinoline ring, phenan A troline ring, an indole ring, a quinoxaline ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring, an acridine ring and the like.

Y < ₂ > in Formula [6] is a nitrogen-containing aromatic heterocyclic ring, and contains the at least 1 structure chosen from the group which consists of Formula [20a], Formula [20b], and Formula [20c] similarly to the above-mentioned. Is an aromatic cyclic hydrocarbon. The structure mentioned above can be mentioned as the specific example. Among these, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, Azepine rings, diazepine rings, naphthyridine rings, phenazine rings, phthalazine rings are preferred.

In addition, Y ₁ is contained in Y ₂ in formulas [20a], [20b], and formulas from the viewpoint of ease of electrostatic interaction such as salt formation and hydrogen bonding of the nitrogen-containing aromatic heterocycle and the carboxyl group in the specific polyimide. It is preferable to combine with the substituent which is not adjacent to [20c].

In addition, the formula [6] Y ₂ is a nitrogen-containing carbon atom of the aromatic heterocyclic ring is optionally having a substituent, a halogen atom and / or an organic group, the organic group containing a hetero atom such as oxygen atom, sulfur atom, nitrogen atom You may also

Preferred combinations of Y ₁ and Y ₂ in formula [6] include ₂ having one kind selected from the group consisting of Y ₁ an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a nonaromatic cyclic hydrocarbon group having 3 to 20 carbon atoms. Is an organic group, Y ₂ is a pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring , Quinoxaline ring, azepine ring, diazepine ring, naphthyridine ring, phenazine ring or phthalazine ring. In addition, the carbon atom of the nitrogen-containing aromatic heterocycle of Y ₂ may have a substituent of a halogen atom and / or an organic group, and the organic group may contain hetero atoms, such as an oxygen atom, a sulfur atom, and a nitrogen atom.

As a more preferable specific amine compound, it is an amine compound shown by following formula [7].

[Formula 31]

(Wherein, Y ₃ is a divalent aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group of 1 to 10 carbon atoms, Y ₄ is a single bond or -O-, -NH-, -S-, -SO ₂ -or A divalent organic group having 1 to 19 carbon atoms, and the sum of the carbon atoms of Y ₃ and Y ₄ is 1 to 20. Y ₅ is a nitrogen-containing aromatic heterocyclic ring.)

Y < ₃ > in Formula [7] is a C1-C10 divalent aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group. Specific examples thereof include a linear or branched alkylene group having 1 to 10 carbon atoms, an unsaturated alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring and a cyclooctane ring , Cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotedecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclo Nonadecane ring, cycloicosic acid ring, tricycloecoic acid ring, tricyclodecoic acid ring, bicycloheptane ring, decahydronaphthalene ring, norbornene ring, adamantane ring and the like. More preferably, they are a C1-C10 linear or branched alkylene group, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, and a cycloound And a cann ring, a cyclododecane ring, a cyclotridecane ring, a cyclotedecane ring, a norbornene ring and an adamantane ring. Especially preferably, it is a C1-C10 linear or branched alkylene group.

-CH ₂ -in any aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group not adjacent to the amino group, included in Y ₃ , is -O-, -NH-, -CO-O-, -O-CO-,- CO-NH-, -NH-CO-, -CO-, -S-, -S (O) _2- , -CF _2- , -C (CF ₃ ) _2- , -C (CH ₃ ) _2- , -Si (CH ₃ ) _2- , -O-Si (CH ₃ ) _2- , -Si (CH ₃ ) ₂ -O-, -O-Si (CH ₃ ) ₂ -O-, divalent cyclic hydrocarbon group And a heterocyclic ring may be substituted. Moreover, the hydrogen atom couple | bonded with arbitrary carbon atoms may be substituted by the C1-C20 linear or branched alkyl group, a cyclic hydrocarbon group, a C1-C10 fluorine-containing alkyl group, a heterocyclic ring, a fluorine atom, and a hydroxyl group. The cyclic hydrocarbon group and heterocycle here are the same meaning as the definition described in Y < ₁ > in Formula [6].

₄ Y in the formula [7] represents a single bond, or _{-O-, -NH-, -S-, -SO 2} - or a divalent organic group having a carbon number of 1-19. This C1-C19 bivalent organic group is a divalent organic group which has 1-19 carbon atoms, and may contain the oxygen atom, the nitrogen atom, the sulfur atom, the silicon atom, etc. Specific examples of such Y ₄ are given below.

For example, a single bond, -O-, -NH-, -S-, -SO 2 -, a hydrocarbon group, having a carbon number of 1 ~ 19 -CO-O-, -O -CO-, -CO-NH-, -NH-CO-, -CO-, -CF _2- , -C (CF ₃ ) _2- , -CH (OH)-, -C (CH ₃ ) _2- , -Si (CH ₃ ) ₂ -,- O-Si (CH ₃ ) _2- , -Si (CH ₃ ) ₂ -O-, -O-Si (CH ₃ ) ₂ -O-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, Cycloheptane ring, Cyclooctane ring, Cyclononane ring, Cyclodecane ring, Cycloundecane ring, Cyclododecane ring, Cyclotridecane ring, Cyclotetradecane ring, Cyclopentadecane ring, Cyclohexadecane ring, Cycloheptadecane ring , Cyclooctadecane ring, cyclononadecan ring, cycloic acid ring, tricycloecoic acid ring, tricyclodecoic acid ring, bicycloheptane ring, decahydronaphthalene ring, norbornene ring, adamantane ring, benzene ring , Naphthalene ring, tetrahydronaphthalene ring, Zulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, penalene ring, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, Pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, Chinolin ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring, oxazole ring, piperazine ring, piperidine ring, di An oxane ring, a morpholine ring, etc. are mentioned. You may contain 2 or more types of these as Y <_4> .

As a specific example containing such 2 or more types,

Etc. can be mentioned.

Y < ₅ > in Formula [7] is a nitrogen containing aromatic heterocyclic ring, and is the same as that of the definition of Y < ₂ > in Formula [6]. As a specific example, there may be mentioned the same structure as the above-mentioned Y _2. Among these, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, Azepine rings, diazepine rings, naphthyridine rings, phenazine rings or phthalazine rings are preferred.

In addition, nitrogen containing in terms of ease of electrostatic interactions, such as aromatic heterocyclic rings and a particular polyimide salts of carboxyl groups and forming hydrogen bond in the, Y ₄ is that equation [20a], formula [20b] or a group represented by the formula contained in Y ₅ It is preferable to couple | bond with [20c] and the carbon atom which is not adjacent.

In addition, the formula Y ₅ is a carbon atom of the nitrogen-containing aromatic heterocyclic ring in [7], and may have a substituent of a halogen atom and / or an organic group, the organic group containing a hetero atom such as oxygen atom, sulfur atom, nitrogen atom You may also

In a preferable combination of Y ₃ , Y ₄ and Y ₅ in formula [7], Y ₃ is a C1-C10 linear or branched alkylene group, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring , Cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, norbornene ring or adamantane ring, Y ₄ A monovalent bond, a linear or branched alkylene group having 1 to 10 carbon atoms,

Cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononan ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, norbornene ring, adamantane Ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, phenylene ring, Y ₅ is pyrrole ring, imidazole ring, pyrazole ring, Pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzoimidazole ring, quinoxaline ring, azepine ring, diazepine ring, naphthyridine ring, phenazine Ring or phthalazine ring. In addition, the carbon atom of the nitrogen-containing aromatic heterocycle of Y ₅ may have a substituent of a halogen atom and / or an organic group, and the organic group may contain hetero atoms, such as an oxygen atom, a sulfur atom, and a nitrogen atom.

Equation [7] Y _3, Y ₄ and Y ₅ a more preferred combination of the can, Y ₃ are C 1 -C 5 straight-chain or branched alkylene group, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane Ring, cycloheptane ring, norbornene ring or adamantane ring, Y ₄ is a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms,

Cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene Ring, anthracene ring, phenanthrene ring or phenylene ring, Y ₅ is pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, Benzimidazole ring, benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, naphthyridine ring, phenazine ring or phthalazine ring. In addition, the carbon atom of the nitrogen-containing aromatic heterocycle of Y ₅ may have a substituent of a halogen atom and / or an organic group, and the organic group may contain hetero atoms, such as an oxygen atom, a sulfur atom, and a nitrogen atom.

In a more preferable combination of Y ₃ , Y ₄ and Y ₅ in formula [7], Y ₃ is a linear or branched alkylene group having 1 to 5 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, or cyclohexane Y ₄ is a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms,

Cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, fluorene ring or anthracene ring, Y ₅ is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring or a benzo imidazole ring. In addition, the carbon atom of the nitrogen-containing aromatic heterocycle of Y ₅ may have a substituent of a halogen atom and / or an organic group, and the organic group may contain hetero atoms, such as an oxygen atom, a sulfur atom, and a nitrogen atom.

A particularly preferred combination of Y _3, Y ₄ and Y ₅ in the formula [7], Y ₃ is a single bond 1 to 5 carbon atoms in the straight-chain or branched alkylene group, a cycloalkyl and butane ring or a cyclohexane ring, Y ₄ , -O-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -CH (OH)-, benzene ring, naphthalene ring, fluorene ring or anthracene ring, Y ₅ is a pyrrole ring, imidazole ring, pyrazole ring, pyridine ring or pyrimidine ring. In addition, the carbon atom of the nitrogen-containing aromatic heterocycle of Y ₅ may have a substituent of a halogen atom and / or an organic group, and the organic group may contain hetero atoms, such as an oxygen atom, a sulfur atom, and a nitrogen atom.

As a specific example of the specific amine compound used for this invention, the compound of M1-M156 is mentioned.

[Formula 32]

[Formula 33]

[Formula 34]

[Formula 35]

[Formula 36]

[Formula 37]

As a more preferable compound, M6-M8, M10, M16-M21, M31-M36, M40-M45, M47-M57, M59-M63, M68, M69, M72-M82, M95-M98, M100-M103, M108- M125, M128-M137, M139-M143, and M149-M156 can be mentioned. More preferable are M6 to M8, M16 to M20, M32 to M36, M40, M41, M44, M49 to M54, M59 to M62, M68, M69, M75 to M82, M100 to M103, M108 to M112, M114 to M116, M118 -M121, M125, M134-M136, M139, M140, M143, M150, M152-M156.

<Liquid crystal aligning agent>

The liquid-crystal aligning agent of this invention is obtained by mixing the specific polyimide which is above-mentioned (A) component, and the specific amine compound which is (B) component in an organic solvent normally. The specific polyimide and specific amine compound to mix may be one kind, respectively, and may use multiple types together.

As a mixing method, although you may use the reaction solution (solution of specific polyimide) which imidated the polyamic acid which is a precursor of a specific polyimide, Preferably the solution which melt | dissolved the powder of the specific polyimide obtained by refine | purifying in the organic solvent. The method of adding a specific amine compound to this is mentioned. The organic solvent used in that case will not be specifically limited if it is a solvent in which a specific polyimide is dissolved. Specific examples of such organic solvents are given below.

For example, N, N'-dimethylformamide, N, N'-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone , N-vinylpyrrolidone, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, dipentene, ethyl amyl ketone, Methylnonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone, and the like. . You may use these solvent in mixture of 2 or more types.

When dissolving a specific polyimide in an organic solvent, you may heat in order to accelerate dissolution of a specific polyimide. When the temperature to heat is too high, since the molecular weight of a polyimide may fall, the temperature of 30-100 degreeC is preferable. Although the density | concentration of a specific polyimide solution is not specifically limited, Since it is easy to mix uniformly with a specific amine compound, 1-20 mass% is preferable as a specific polyimide concentration in a solution, More preferably, it is 3-15 mass%, Especially preferably, it is 3-10 mass%.

Although a specific amine compound may be added directly to the solution of said specific polyimide, it is preferable to add, after making into solution of concentration 0.1-10 mass% with a suitable solvent preferably. As this solvent, the solvent of said specific polyimide is mentioned.

It is preferable to heat after mixing a specific polyimide and a specific amine compound in an organic solvent. By heating, the ratio of the specific amine compound and the specific polyimide which are already couple | bonded in the state of a liquid-crystal aligning agent increases, and when it is set as a liquid crystal aligning film, transfer of electric charge becomes possible more efficiently. As for the temperature in the case of heating after mixing, 10-100 degreeC is preferable, More preferably, it is 20-80 degreeC.

Content of the specific amine compound in the liquid-crystal aligning agent of this invention is added to 1 mol amount of the carboxyl group contained in a specific polyimide for the reason that the effect of this invention is obtained efficiently and does not impair stability of a liquid-crystal aligning agent. It is 0.01-2 mol times with respect to it, More preferably, it is 0.05-1 mol times, Especially preferably, it is 0.08-0.8 mol times.

In addition to the specific polyimide and the specific amine compound, the liquid-crystal aligning agent of the present invention is a solvent, a compound, a liquid crystal aligning film, and the adhesion between the substrate and the substrate to improve film thickness uniformity and surface smoothness when the liquid-crystal aligning agent is applied. You may contain the compound etc. to improve. Other components may be added in the middle of mixing the specific polyimide and the specific amine compound, or may be added later to these mixed solutions.

The following are mentioned as a specific example of the solvent which improves the uniformity and surface smoothness of a film thickness.

For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl Carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol Monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl Ether, dipropylene glycol monoprop Fill ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, di Isobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, lactic acid Ethyl, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3- Ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol , 1-phenoxy Cy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2 Solvents having low surface tension, such as ethoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, and lactic acid isoamyl ester.

One type of these solvents may be used, or two or more types may be mixed and used. When using the above solvent, it is preferable that it is 5-80 mass% of the whole solvent contained in a liquid-crystal aligning agent, More preferably, it is 20-60 mass%.

As a compound which improves the uniformity and surface smoothness of a film thickness, a fluorine-type surfactant, silicone type surfactant, nonionic surfactant, etc. are mentioned.

More specifically, for example, F-Top EF301, EF303, EF352 (manufactured by Tochem Products, Inc.), Megapak F171, F173, R-30 (manufactured by Dainippon Ink, Inc.), Florard FC430, FC431 (manufactured by Sumitomo 3M) ), Asahi Guard AG710, Suplon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.), etc. are mentioned. The use ratio of these surfactant becomes like this. Preferably it is 0.01-2 mass parts with respect to 100 mass parts of (A) 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 -Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidepropyltrimethoxysilane, 3-ureidepropyltriethoxysilane, N-ethoxy Carbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetri Amine, 10-trimethoxysilyl-1,4,7-triazadecan, 10-triethoxysilyl-1,4,7-triazadecan, 9-trimethoxysilyl-3,6-diazanyl Acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phen -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-diglycidylaminomethyl ) Cyclohexane, N, N, N ', N'- tetraglycidyl-4,4'- diamino diphenylmethane, etc. are mentioned.

It is preferable that the usage-amount of the compound which improves adhesiveness with these board | substrates is 0.1-30 mass parts with respect to 100 mass parts of specific polyimide components contained in a liquid-crystal aligning agent, More preferably, it is 1-20 mass parts. If it is less than 0.1 mass part, the effect of adhesive improvement cannot be expected, and when more than 30 mass parts, the orientation of a liquid crystal may worsen.

In the liquid-crystal aligning agent of this invention, in addition to the above, if it is a range in which the effect of this invention is not impaired, the dielectric material and electrically conductive substance for the purpose of changing the electrical components, such as polymer components other than specific polyimide, and the dielectric constant and electroconductivity of a liquid crystal aligning film, Furthermore, you may add the crosslinking | crosslinked compound of the objective which raises the hardness and the density of a film at the time of using as a liquid crystal aligning film.

Although the density | concentration of solid content in the liquid-crystal aligning agent of this invention can be changed suitably according to the film thickness of the liquid crystal aligning film made into the objective, for the reason that a coating film without a defect can be formed and an appropriate film thickness can be obtained as a liquid crystal aligning film. It is preferable to set it as 1-20 mass%, More preferably, it is 2-10 mass%.

<Liquid crystal aligning film, liquid crystal display element>

After apply | coating and baking on the board | substrate on a board | substrate, the liquid-crystal aligning agent of this invention can be used as a liquid-crystal aligning film, without performing an alignment process in a rubbing process, light irradiation, etc., or a vertical alignment use. Under the present circumstances, it will not specifically limit, if it is a board | substrate with high transparency as a board | substrate to be used, Plastic substrates, such as a glass substrate, an acryl substrate, and a polycarbonate board | substrate, etc. can be used. Moreover, it is preferable to use the board | substrate with which the ITO electrode etc. for liquid crystal drive were formed from a viewpoint of the simplification of a process. In the reflective liquid crystal display element, only an opaque one such as a silicon wafer can be used as long as it is a substrate on one side, and in this case, a material that reflects light such as aluminum can also be used.

Although the coating method of a liquid-crystal aligning agent is not specifically limited, Industrially, the method of performing by screen printing, offset printing, flexographic printing, an inkjet, etc. is common. Other coating methods include dips, roll coaters, slit coaters, spinners, and the like, which may be used depending on the purpose.

Baking after apply | coating a liquid-crystal aligning agent on a board | substrate can evaporate a solvent at 50-300 degreeC, Preferably it is 80-250 degreeC by heating means, such as a hotplate, and can 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 making a liquid crystal align horizontally or diagonally, the coating film after baking is processed by rubbing or polarized ultraviolet irradiation.

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

If an example of liquid crystal cell manufacture is given, a pair of board | substrate with which a liquid crystal aligning film was formed is prepared, a spacer is spread | dispersed on the liquid crystal aligning film of a single-sided substrate, so that a liquid crystal aligning film surface may become inward, and another other board | substrate is bonded together (貼And the method of sealing by injecting and sealing a liquid crystal under reduced pressure, or the method of bonding and sealing a board | substrate after dropping a liquid crystal on the liquid crystal aligning film surface which spread | dispersed the spacer, etc. can be illustrated. The thickness of the spacer at this time becomes like this. Preferably it is 1-30 micrometers, More preferably, it is 2-10 micrometers.

The liquid crystal display element manufactured using the liquid-crystal aligning agent of this invention as mentioned above becomes excellent in reliability, and can be used suitably for a high definition liquid crystal television etc ..

Example

Although an Example and a comparative example are given to the following and this invention is demonstrated in more detail, the interpretation of this invention is not limited to these Examples.

The description of the symbol used in a present Example is as follows.

(Tetracarboxylic dianhydride)

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

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

[Formula 38]

(Diamine)

DBA: 3,5-diaminobenzoic acid

m-PBCH5DABz: 1,3-diamino-5- {4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxymethyl} benzene

m-BPCH5DABz: 1,3-diamino-5- {4- [4- (trans-4-n-pentylcyclohexyl) phenyl] phenoxymethyl} benzene

p-PBCH5DABz: 1,4-diamino-5- {4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxymethyl} benzene

PCH7DAB: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene

[Formula 39]

(Specific amine compound)

3-AMP: 3-aminomethylpyridine

4-AMP: 4-aminomethylpyridine

AEP: 4- (2-aminoethyl) pyridine

API: 1- (3-aminopropyl) imidazole

2-AMMP: 2- (aminomethyl) -5-methylpyrazine

[Formula 40]

(Comparative compound)

Py: pyridine

AP: 3-aminopyridine

HA: hexylamine

[Formula 41]

(Organic solvent)

NMP: N-methyl-2-pyrrolidone

BCS: Butyl Cellosolve

<Measurement of molecular weight of polyimide>

The molecular weight of the polyimide in the synthesis example was a room temperature gel permeation chromatography (GPC) device (SSC-7200) manufactured by Senshu Scientific Co., Ltd., and a column (KD-803, KD-805) manufactured by Shodex Corporation as follows. Measured.

Column temperature: 50 ℃

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

Flow rate: 1.0 ml / min

Standard samples for calibration curve preparation: TSK standard polyethylene oxide (molecular weight of about 9000,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (molecular weight of about 12,000, 4,000, 1,000) manufactured by Polymer Laboratories.

<Measurement of imidation ratio>

The imidation ratio of the polyimide in a synthesis example was measured as follows. 20 mg of polyimide powder was placed in an NMR sample tube (NMR sampling tube standard φ 5 manufactured by Kusano Scientific Co., Ltd.), 0.53 mL of deuterated dimethyl sulfoxide (DMSO-d ₆ , 0.05% TMS mixed product) was added thereto, and ultrasonic wave was added thereto. Dissolved. The proton NMR of 500 MHz was measured for this solution by the NMR analyzer (JNW-ECA500) by the Nippon Electron Datum Co., Ltd. product. The imidation ratio determines the proton derived from the structure which does not change before and after imidization as a reference proton, and determines the peak integration value of this proton and the proton peak integration value derived from the NH group of amic acid which appears in the vicinity of 9.5-10.0 ppm. It calculated | required by the following formula using.

·x/y) × 100Imidation ratio (%) = (1-

X / y) × 100

는 폴리아믹산 (이미드화율이 0 ％) 의 경우에 있어서의 아믹산의 NH 기 프로톤 1 개에 대한 기준 프로톤의 개수 비율이다.In the above formula, x is the proton peak integration value derived from the NH group of amic acid, y is the peak integration value of a reference proton,

Is the number ratio of the reference protons to one NH group proton of the amic acid in the case of polyamic acid (imidization rate of 0%).

<Calculation method of carboxyl group amount>

It calculated by the method described above.

Synthesis Example 1

BODA (4.41 g, 17.6 mmol), DBA (2.86 g, 18.8 mmol), and m-PBCH5DABz (2.11 g, 4.70 mmol) as side chain diamines are mixed in NMP (23.0 g) and 5 at 80 ° C. After making it react for time, CBDA (1.01g, 5.15 mmol) and NMP (18.0g) were added, and it reacted at 40 degreeC for 6 hours, and obtained the polyamic-acid solution.

NMP was added to this polyamic acid solution (20.0 g), and it diluted to 6 mass%, acetic anhydride (2.53 g) and pyridine (1.96 g) were added as imidation catalyst, and it was made to react at 80 degreeC for 3 hours. . This reaction solution was poured into methanol (270 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (A). The imidation ratio of this polyimide was 40%, the number average molecular weight was 17,300 and the weight average molecular weight was 46,800. The quantity of the carboxyl group in this polyimide is 2.0 pieces with respect to a repeating unit.

Synthesis Example 2

BODA (32.28 g, 129.2 mmol), DBA (18.32 g, 120.4 mmol), and m-PBCH5DABz (23.16 g, 51.6 mmol) as side chain diamines were mixed in NMP (172.1 g) and 5 at 80 ° C. After reacting for time, CBDA (8.20 g, 42.0 mmol) and NMP (152.0 g) were added, and it reacted at 40 degreeC for 6 hours, and obtained the polyamic-acid solution.

NMP was added to this polyamic acid solution (150.0 g), and it diluted to 6 mass%, acetic anhydride (16.13 g) and pyridine (12.45 g) were added as imidation catalyst, and it was made to react at 80 degreeC for 3 hours. . This reaction solution was poured into methanol (1900 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (B). The imidation ratio of this polyimide was 80%, the number average molecular weight was 19,700 and the weight average molecular weight was 52,200. The quantity of the carboxyl group in this polyimide is 1.1 piece with respect to a repeating unit.

&Lt; Synthesis Example 3 &

After adding NMP to the polyamic-acid solution (30.2 g) obtained by the synthesis example 2, and diluting to 6 mass%, acetic anhydride (6.41 g) and triethylamine (2.27 g) are added as an imidation catalyst, and it is 100 It was made to react at 4 degreeC. Oxalic acid (2.82 g) was added to this reaction solution to neutralize it, and then charged in methanol (350 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (C). The imidation ratio of this polyimide was 98%, the number average molecular weight was 19,200 and the weight average molecular weight was 51,200. The quantity of carboxyl groups in this polyimide is 0.74 with respect to a repeating unit.

&Lt; Synthesis Example 4 &

BODA (3.90 g, 15.6 mmol), DBA (2.16 g, 14.2 mmol), and m-BPCH5DABz (2.65 g, 6.10 mmol) as side chain diamines were mixed in NMP (18.0 g) and 5 at 80 ° C. After making it react for time, CBDA (0.93g, 4.74 mmol) and NMP (14.4g) were added, and it reacted at 40 degreeC for 6 hours, and obtained the polyamic-acid solution.

NMP was added to this polyamic acid solution (30.0 g), and it diluted to 6 mass%, acetic anhydride (3.23 g) and pyridine (2.49 g) were added as imidation catalyst, and it was made to react at 80 degreeC for 3 hours. . This reaction solution was poured into methanol (380 ml), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (D). The imidation ratio of this polyimide was 82%, the number average molecular weight was 17,100 and the weight average molecular weight was 48,400. The quantity of the carboxyl group in this polyimide is 1.06 piece with respect to a repeating unit.

&Lt; Synthesis Example 5 &

BODA (3.28 g, 13.1 mmol), DBA (2.42 g, 15.9 mmol), and p-PBCH5DABz (2.26 g, 5.03 mmol) as side chain diamines were mixed in NMP (14.0 g) and 5 at 80 ° C. After making it react for time, CBDA (0.72g, 3.68 mmol) and NMP (11.3g) were added, and it reacted at 40 degreeC for 6 hours, and obtained the polyamic-acid solution.

NMP was added to this polyamic acid solution (30.1 g) and diluted to 6 mass%, acetic anhydride (3.22 g) and pyridine (2.51 g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3 hours. . This reaction solution was poured into methanol (380 ml), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (E). The imidation ratio of this polyimide was 80%, the number average molecular weight was 18,400 and the weight average molecular weight was 49,900. The quantity of the carboxyl group in this polyimide is 1.1 piece with respect to a repeating unit.

&Lt; Synthesis Example 6 &

PCH7DAB (6.09 g, 16.0 mmol) was mixed in NMP (131 g) as BODA (15.0 g, 60.0 mmol), DBA (9.74 g, 64.0 mmol), and side chain diamine, and reacted at 80 ° C for 5 hours. CBDA (3.88g, 19.8 mmol) and NMP (30g) were added after making it react, and it reacted at 40 degreeC for 3 hours, and obtained the polyamic-acid solution.

NMP was added to this polyamic acid solution (10.0g), and it diluted to 6 mass%, acetic anhydride (1.27g) and pyridine (0.98g) were added as imidation catalyst, and it was made to react at 80 degreeC for 3 hours. . This reaction solution was poured into methanol (140 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (F). The imidation ratio of this polyimide was 46%, the number average molecular weight was 20,200 and the weight average molecular weight was 62,500. The quantity of the carboxyl group in this polyimide is 1.88 piece with respect to a repeating unit.

Synthesis Example 7

PCH7DAB (152.2 g, 400 mmol) is mixed in NMP (1290 g) as BODA (150.1 g, 600 mmol), DBA (60.9 g, 400 mmol), and side chain diamine, and reacted at 80 ° C for 5 hours. CBDA (38.8g, 198 mmol) and NMP (320g) were added after making it react, and it reacted at 40 degreeC for 3 hours, and obtained the polyamic-acid solution.

NMP was added to this polyamic acid solution (101.2 g) and diluted to 6 mass%, acetic anhydride (21.3 g) and pyridine (16.5 g) were added as an imidation catalyst, and it was made to react at 90 degreeC for 3 hours. . This reaction solution was poured into methanol (1300 mL), and the obtained precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (G). The imidation ratio of this polyimide was 81%, the number average molecular weight was 20,400 and the weight average molecular weight was 63,000. The amount of carboxyl groups in this polyimide is 0.88 with respect to a repeating unit.

&Lt; Example 1 >

NMP (9.34g) was added to the polyimide powder (A) obtained by the synthesis example 1, and (1.65g), and it stirred for 40 hours and was made to melt | dissolve at 70 degreeC. 10 mass% NMP solution (0.50g) (0.050g as 3-AMP), NMP (3.43g), and BCS (12.5g) of 3-AMP were added to this solution, and liquid crystal aligning by stirring at 50 degreeC for 15 hours. Treatment agent [1] was obtained. Abnormalities, such as haze and precipitation, were not observed in this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

<Production of Liquid Crystal Cells>

The liquid-crystal aligning agent [1] obtained above was spin-coated to the ITO surface of the board | substrate with a 3 cm * 4 cm ITO electrode, and it baked at 80 degreeC for 5 minutes in 210 degreeC hot-air circulation type oven, and film thickness was 100 nm. Polyimide coating film was prepared.

The board | substrate with a liquid crystal aligning film was subjected to the rubbing process on the conditions of rotation speed 300rpm, the roll traveling speed 20mm / sec, and a press amount 0.3mm with the rubbing apparatus of roll diameter 120mm and the rayon cloth, and the board | substrate with a liquid crystal aligning film was obtained.

Two board | substrates with this liquid crystal aligning film were prepared, and after spread | dispersing a 6 micrometers bead spacer on the one liquid crystal aligning film surface, the sealing compound was printed from on. After attaching another board | substrate with the liquid crystal aligning film surface inside, and making a rubbing direction reverse, the sealing compound was hardened and the empty cell was manufactured. The nematic liquid crystal cell of antiparallel orientation was obtained by the pressure reduction injection method to this empty cell.

<Evaluation of Pretilt Angle>

The pretilt angle at room temperature was measured for the pretilt angle of the liquid crystal cell manufactured above using the pretilt angle measuring apparatus (Model: PAS-301 made from ELSICON). The results are shown in Table 2 described later.

Moreover, as a result of observing the liquid crystal cell manufactured similarly to the above except the rubbing process with the polarization microscope, it was confirmed that the liquid crystal was uniformly vertically aligned.

<Evaluation of Voltage Retention Rate>

A voltage of 4 V was applied to the liquid crystal cell after the pretilt angle measurement at a temperature of 80 ° C., and the voltage after 16.67 kV and after 1667 kV was measured, and the voltage retention was calculated as the voltage retention. The results are shown in Table 3 described later.

Mitigation Assessment of Residual Charge

DC voltage 10V was applied to the liquid crystal cell after voltage retention measurement for 30 minutes, and short-circuited for 1 second, and the electric potential generate | occur | produced in the liquid crystal cell was measured for 1800 second. And the residual electric charge after 50 second and 1000 second was measured. In addition, the Toyo Technica Co., Ltd. 6254 type liquid crystal physical property evaluation apparatus was used for the measurement. The results are shown in Table 4 described later.

<Evaluation after high temperature leaving>

After leaving the liquid crystal cell after residual charge measurement for 7 days in the high temperature tank set to 100 degreeC, voltage retention and residual charge were measured. The results are shown in Tables 3 and 4 described later.

<Evaluation of voltage retention after ultraviolet irradiation>

A voltage of 4 V was applied to the liquid crystal cell prepared above at a temperature of 80 ° C. at 60 Hz, and the voltages after 16.67 Hz and after 1667 Hz were measured, and the voltage retention was calculated as voltage retention. In addition, by a desk type UV curing device (HCT3 B28 HEX-1 (manufactured by Sen Special Light Source Co., Ltd.)) after the measurement, ultraviolet rays having a irradiation amount of 10 J / cm 2 at 365 nm were irradiated to the liquid crystal cell, under the same conditions. Retention rate was measured. The results are shown in Table 5 below.

<Example 2>

NMP (9.46g) was added to the polyimide powder (B) obtained by the synthesis example 2, and (1.67g), and it stirred for 40 hours and made it melt | dissolve at 70 degreeC. 10 mass% NMP solution (0.50g) (0.050g as 3-AMP), NMP (3.47g), and BCS (12.5g) of 3-AMP were added to this solution, and liquid crystal aligning by stirring at 50 degreeC for 15 hours. Treatment agent [2] was obtained. Abnormalities, such as haze and precipitation, were not observed in this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

Using the obtained liquid-crystal aligning agent [2], the liquid crystal cell was produced like Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. Moreover, as a result of observing the liquid crystal cell manufactured similarly to Example 1 with the polarizing microscope except having not performed the rubbing process, it was confirmed that the liquid crystal was uniformly vertically aligned.

Moreover, using the liquid crystal cell manufactured similarly to Example 1, evaluation of voltage retention, relaxation evaluation of residual electric charge, evaluation after high temperature standing, and voltage retention evaluation after ultraviolet irradiation were performed. The results are shown in Tables 3, 4 and 5 described later.

<Example 3>

NMP (9.34g) was added to the polyimide powder (B) obtained by the synthesis example 2, and (1.65g), and it stirred for 40 hours and was made to melt | dissolve at 70 degreeC. Liquid crystal orientation by adding 10 mass% NMP solution (0.83 g) (0.083 g as 3-AMP), NMP (3.14 g), and BCS (12.4 g) of 3-AMP to this solution, and stirring at 50 degreeC for 15 hours. Treatment agent [3] was obtained. Abnormalities, such as haze and precipitation, were not observed in this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

Using the obtained liquid-crystal aligning agent [3], the liquid crystal cell was produced like Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. Moreover, as a result of observing the liquid crystal cell manufactured similarly to Example 1 with the polarizing microscope except having not performed the rubbing process, it was confirmed that the liquid crystal was uniformly vertically aligned.

Moreover, using the liquid crystal cell manufactured similarly to Example 1, evaluation of voltage retention, relaxation evaluation of residual electric charge, evaluation after high temperature standing, and voltage retention evaluation after ultraviolet irradiation were performed. The results are shown in Tables 3, 4 and 5 described later.

<Example 4>

NMP (9.34g) was added to the polyimide powder (B) obtained by the synthesis example 2, and (1.65g), and it stirred for 40 hours and was made to melt | dissolve at 70 degreeC. 10 mass% NMP solution (1.16g) (0.116g as 3-AMP), NMP (2.84g), and BCS (12.4g) of 3-AMP were added to this solution, and liquid crystal aligning by stirring at 50 degreeC for 15 hours. Treatment agent [4] was obtained. Abnormalities, such as haze and precipitation, were not observed in this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

Using the obtained liquid-crystal aligning agent [4], the liquid crystal cell was produced like Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. Moreover, as a result of observing the liquid crystal cell manufactured similarly to Example 1 with the polarizing microscope except having not performed the rubbing process, it was confirmed that the liquid crystal was uniformly vertically aligned.

Moreover, using the liquid crystal cell manufactured similarly to Example 1, evaluation of voltage retention, relaxation evaluation of residual electric charge, evaluation after high temperature standing, and voltage retention evaluation after ultraviolet irradiation were performed. The results are shown in Tables 3, 4 and 5 described later.

<Example 5>

NMP (9.29g) was added to the polyimide powder (B) obtained by the synthesis example 2, and (1.64g), and it stirred for 40 hours and was made to melt | dissolve at 70 degreeC. Liquid crystal orientation by adding 10 mass% NMP solution (1.64 g) (0.164 g as 3-AMP), NMP (2.38 g), and BCS (12.3 g) of 3-AMP to this solution, and stirring at 50 degreeC for 15 hours. Treatment agent [5] was obtained. Abnormalities, such as haze and precipitation, were not observed in this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

Using the obtained liquid-crystal aligning agent [5], the liquid crystal cell was produced like Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. Moreover, as a result of observing the liquid crystal cell manufactured similarly to Example 1 with the polarizing microscope except having not performed the rubbing process, it was confirmed that the liquid crystal was uniformly vertically aligned.

Moreover, using the liquid crystal cell manufactured similarly to Example 1, evaluation of voltage retention, relaxation evaluation of residual electric charge, evaluation after high temperature standing, and voltage retention evaluation after ultraviolet irradiation were performed. The results are shown in Tables 3, 4 and 5 described later.

<Example 6>

NMP (9.34g) was added to the polyimide powder (B) obtained by the synthesis example 2, and (1.65g), and it stirred for 40 hours and was made to melt | dissolve at 70 degreeC. 10 mass% NMP solution of 4-AMP (1.16 g) (0.116 g as 4-AMP), NMP (2.84 g), and BCS (12.4 g) of 4-AMP were added to this solution, and the liquid crystal alignment was performed by stirring at 50 ° C for 15 hours. Treatment agent [6] was obtained. Abnormalities, such as haze and precipitation, were not observed in this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

Using the obtained liquid-crystal aligning agent [6], the liquid crystal cell was produced like Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. Moreover, as a result of observing the liquid crystal cell manufactured similarly to Example 1 with the polarizing microscope except having not performed the rubbing process, it was confirmed that the liquid crystal was uniformly vertically aligned.

Moreover, using the liquid crystal cell manufactured similarly to Example 1, evaluation of voltage retention, relaxation evaluation of residual electric charge, evaluation after high temperature standing, and voltage retention evaluation after ultraviolet irradiation were performed. The results are shown in Tables 3, 4 and 5 described later.

<Example 7>

NMP (9.41g) was added to the polyimide powder (B) obtained by the synthesis example 2, and (1.66g), and it stirred for 40 hours and made it melt | dissolve at 70 degreeC. A 10 mass% NMP solution (1.16 g) (0.116 g as AEP), NMP (2.86 g), and BCS (12.5 g) of AEP was added to the solution, followed by stirring at 50 ° C. for 15 hours to provide a liquid crystal aligning agent [7] Got. Abnormalities, such as haze and precipitation, were not observed in this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

Using the obtained liquid-crystal aligning agent [7], the liquid crystal cell was produced like Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. Moreover, as a result of observing the liquid crystal cell manufactured similarly to Example 1 with the polarizing microscope except having not performed the rubbing process, it was confirmed that the liquid crystal was uniformly vertically aligned.

Moreover, using the liquid crystal cell manufactured similarly to Example 1, evaluation of voltage retention, relaxation evaluation of residual electric charge, evaluation after high temperature standing, and voltage retention evaluation after ultraviolet irradiation were performed. The results are shown in Tables 3, 4 and 5 described later.

<Example 8>

NMP (9.34g) was added to the polyimide powder (B) obtained by the synthesis example 2, and (1.65g), and it stirred for 40 hours and was made to melt | dissolve at 70 degreeC. 10 mass% NMP solution (1.16 g) (0.116 g as API), NMP (2.84 g), and BCS (12.4 g) of API were added to this solution, and the liquid-crystal aligning agent was stirred for 15 hours at 50 degreeC [8] Got. Abnormalities, such as haze and precipitation, were not observed in this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

Using the obtained liquid-crystal aligning agent [8], the liquid crystal cell was produced like Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. Moreover, as a result of observing the liquid crystal cell manufactured similarly to Example 1 with the polarizing microscope except having not performed the rubbing process, it was confirmed that the liquid crystal was uniformly vertically aligned.

Moreover, using the liquid crystal cell manufactured similarly to Example 1, evaluation of voltage retention, relaxation evaluation of residual electric charge, evaluation after high temperature standing, and voltage retention evaluation after ultraviolet irradiation were performed. The results are shown in Tables 3, 4 and 5 described later.

Example 9

NMP (9.34g) was added to the polyimide powder (B) obtained by the synthesis example 2, and (1.65g), and it stirred for 40 hours and was made to melt | dissolve at 70 degreeC. Liquid crystal orientation by adding 10 mass% NMP solution (1.16g) (0.116g as 2-AMMP), NMP (2.84g), and BCS (12.4g) of 2-AMMP to this solution, and stirring at 50 degreeC for 15 hours. Treatment agent [9] was obtained. Abnormalities, such as haze and precipitation, were not observed in this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

Using the obtained liquid-crystal aligning agent [9], the liquid crystal cell was produced like Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. Moreover, as a result of observing the liquid crystal cell manufactured similarly to Example 1 with the polarizing microscope except having not performed the rubbing process, it was confirmed that the liquid crystal was uniformly vertically aligned.

Moreover, using the liquid crystal cell manufactured similarly to Example 1, evaluation of voltage retention, relaxation evaluation of residual electric charge, evaluation after high temperature standing, and voltage retention evaluation after ultraviolet irradiation were performed. The results are shown in Tables 3, 4 and 5 described later.

<Example 10>

NMP (9.29g) was added to the polyimide powder (C) obtained by the synthesis example 3, and (1.64g), and it stirred for 40 hours and was made to melt | dissolve at 70 degreeC. Liquid crystal orientation by adding 10 mass% NMP solution (1.64 g) (0.164 g as 3-AMP), NMP (2.38 g), and BCS (12.3 g) of 3-AMP to this solution, and stirring at 50 degreeC for 15 hours. Treatment agent [10] was obtained. Abnormalities, such as haze and precipitation, were not observed in this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

Using the obtained liquid-crystal aligning agent [10], the liquid crystal cell was produced like Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. Moreover, as a result of observing the liquid crystal cell manufactured similarly to Example 1 with the polarizing microscope except having not performed the rubbing process, it was confirmed that the liquid crystal was uniformly vertically aligned.

Moreover, using the liquid crystal cell manufactured similarly to Example 1, evaluation of voltage retention, relaxation evaluation of residual electric charge, evaluation after high temperature standing, and voltage retention evaluation after ultraviolet irradiation were performed. The results are shown in Tables 3, 4 and 5 described later.

<Example 11>

NMP (9.34g) was added to the polyimide powder (D) obtained by the synthesis example 4, and (1.65g), and it stirred for 40 hours and was made to melt | dissolve at 70 degreeC. Liquid crystal orientation by adding 10 mass% NMP solution (1.16 g) of 3-AMP (0.116 g as 3-AMP), NMP (2.85 g), and BCS (12.4 g) of 3-AMP to this solution, and stirring at 50 degreeC for 15 hours. Treatment agent [11] was obtained. Abnormalities, such as haze and precipitation, were not observed in this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

Using the obtained liquid-crystal aligning agent [11], the liquid crystal cell was produced like Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. Moreover, as a result of observing the liquid crystal cell manufactured similarly to Example 1 with the polarizing microscope except having not performed the rubbing process, it was confirmed that the liquid crystal was uniformly vertically aligned.

Moreover, using the liquid crystal cell manufactured similarly to Example 1, evaluation of voltage retention, relaxation evaluation of residual electric charge, evaluation after high temperature standing, and voltage retention evaluation after ultraviolet irradiation were performed. The results are shown in Tables 3, 4 and 5 described later.

<Example 12>

NMP (9.34g) was added to the polyimide powder (E) obtained by the synthesis example 5, and (1.65g), and it stirred for 40 hours and made it melt | dissolve at 70 degreeC. 10 mass% NMP solution (1.16g) (0.116g as 3-AMP), NMP (2.84g), and BCS (12.5g) of 3-AMP were added to this solution, and liquid crystal aligning by stirring at 50 degreeC for 15 hours. Treatment agent [12] was obtained. Abnormalities, such as haze and precipitation, were not observed in this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

Using the obtained liquid-crystal aligning agent [12], the liquid crystal cell was produced like Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. Moreover, as a result of observing the liquid crystal cell manufactured similarly to Example 1 with the polarizing microscope except having not performed the rubbing process, it was confirmed that the liquid crystal was uniformly vertically aligned.

Moreover, using the liquid crystal cell manufactured similarly to Example 1, evaluation of voltage retention, relaxation evaluation of residual electric charge, evaluation after high temperature standing, and voltage retention evaluation after ultraviolet irradiation were performed. The results are shown in Tables 3, 4 and 5 described later.

Comparative Example 1

NMP (9.34g) was added to the polyimide powder (B) obtained by the synthesis example 2, and (1.65g), and it stirred for 40 hours and was made to melt | dissolve at 70 degreeC. NMP (3.88g) and BCS (12.4g) were added to this solution, and the liquid-crystal aligning agent [13] was obtained by stirring at 50 degreeC for 15 hours. Abnormalities, such as haze and precipitation, were not observed in this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

Using the obtained liquid-crystal aligning agent [13], the liquid crystal cell was produced like Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. Moreover, as a result of observing the liquid crystal cell manufactured similarly to Example 1 with the polarizing microscope except having not performed the rubbing process, it was confirmed that the liquid crystal was uniformly vertically aligned.

Moreover, using the liquid crystal cell manufactured similarly to Example 1, evaluation of voltage retention, relaxation evaluation of residual electric charge, evaluation after high temperature standing, and voltage retention evaluation after ultraviolet irradiation were performed. The results are shown in Tables 3, 4 and 5 described later.

Comparative Example 2

NMP (9.24g) was added to the polyimide powder (C) obtained by the synthesis example 3, and (1.63g), and it stirred for 40 hours and made it melt | dissolve at 70 degreeC. NMP (3.83g) and BCS (12.2g) were added to this solution, and the liquid-crystal aligning agent [14] was obtained by stirring at 50 degreeC for 15 hours. Abnormalities, such as haze and precipitation, were not observed in this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

Using the obtained liquid-crystal aligning agent [14], the liquid crystal cell was produced like Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. Moreover, as a result of observing the liquid crystal cell manufactured similarly to Example 1 with the polarizing microscope except having not performed the rubbing process, it was confirmed that the liquid crystal was uniformly vertically aligned.

Moreover, using the liquid crystal cell manufactured similarly to Example 1, evaluation of voltage retention, relaxation evaluation of residual electric charge, evaluation after high temperature standing, and voltage retention evaluation after ultraviolet irradiation were performed. The results are shown in Tables 3, 4 and 5 described later.

Comparative Example 3

NMP (9.34g) was added to the polyimide powder (D) obtained by the synthesis example 4, and (1.65g), and it stirred for 40 hours and was made to melt | dissolve at 70 degreeC. NMP (3.88g) and BCS (12.3g) were added to this solution, and the liquid-crystal aligning agent [15] was obtained by stirring at 50 degreeC for 15 hours. Abnormalities, such as haze and precipitation, were not observed in this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

Using the obtained liquid-crystal aligning agent [15], the liquid crystal cell was produced like Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. Moreover, as a result of observing the liquid crystal cell manufactured similarly to Example 1 with the polarizing microscope except having not performed the rubbing process, it was confirmed that the liquid crystal was uniformly vertically aligned.

Moreover, using the liquid crystal cell manufactured similarly to Example 1, evaluation of voltage retention, relaxation evaluation of residual electric charge, evaluation after high temperature standing, and voltage retention evaluation after ultraviolet irradiation were performed. The results are shown in Tables 3, 4 and 5 described later.

<Comparative Example 4>

NMP (9.31g) was added to the polyimide powder (E) obtained by the synthesis example 5, and (1.65g), and it stirred for 40 hours and was made to melt | dissolve at 70 degreeC. NMP (3.88g) and BCS (12.4g) were added to this solution, and the liquid-crystal aligning agent [16] was obtained by stirring at 50 degreeC for 15 hours. Abnormalities, such as haze and precipitation, were not observed in this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

Using the obtained liquid-crystal aligning agent [16], the liquid crystal cell was produced like Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. Moreover, as a result of observing the liquid crystal cell manufactured similarly to Example 1 with the polarizing microscope except having not performed the rubbing process, it was confirmed that the liquid crystal was uniformly vertically aligned.

Moreover, using the liquid crystal cell manufactured similarly to Example 1, evaluation of voltage retention, relaxation evaluation of residual electric charge, evaluation after high temperature standing, and voltage retention evaluation after ultraviolet irradiation were performed. The results are shown in Tables 3, 4 and 5 described later.

Comparative Example 5

NMP (9.23g) was added to the polyimide powder (F) obtained by the synthesis example 6, and (1.63g), and it stirred for 40 hours and was made to melt | dissolve at 70 degreeC. NMP (3.83g) and BCS (12.2g) were added to this solution, and the liquid-crystal aligning agent [17] was obtained by stirring at 50 degreeC for 15 hours. Abnormalities, such as haze and precipitation, were not observed in this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

Using the obtained liquid-crystal aligning agent [17], the liquid crystal cell was produced like Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. Moreover, as a result of observing the liquid crystal cell manufactured similarly to Example 1 with the polarizing microscope except having not performed the rubbing process, it was confirmed that the liquid crystal was uniformly vertically aligned.

Moreover, using the liquid crystal cell manufactured similarly to Example 1, evaluation of voltage retention, relaxation evaluation of residual electric charge, evaluation after high temperature standing, and voltage retention evaluation after ultraviolet irradiation were performed. The results are shown in Tables 3, 4 and 5 described later.

Comparative Example 6

NMP (9.23g) was added to the polyimide powder (B) obtained by the synthesis example 2, and (1.63g), and it stirred for 40 hours and made it melt | dissolve at 70 degreeC. Py 10 mass% NMP solution (1.14 g) (0.114 g as Py), NMP (2.80 g), and BCS (12.3 g) were added to this solution, and the liquid-crystal aligning agent was stirred for 15 hours at 50 degreeC. Got. Abnormalities, such as haze and precipitation, were not observed in this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

Using the obtained liquid-crystal aligning agent [18], the liquid crystal cell was produced like Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. Moreover, as a result of observing the liquid crystal cell manufactured similarly to Example 1 with the polarizing microscope except having not performed the rubbing process, it was confirmed that the liquid crystal was uniformly vertically aligned.

Moreover, using the liquid crystal cell manufactured similarly to Example 1, evaluation of voltage retention, relaxation evaluation of residual electric charge, evaluation after high temperature standing, and voltage retention evaluation after ultraviolet irradiation were performed. The results are shown in Tables 3, 4 and 5 described later.

&Lt; Comparative Example 7 &

NMP (9.33g) was added to the polyimide powder (B) obtained by the synthesis example 2, and (1.65g), and it stirred for 40 hours and made it melt | dissolve at 70 degreeC. 10 mass% NMP solution (1.16 g) (0.116 g as AP), NMP (2.83 g), and BCS (12.3 g) of AP were added to this solution, and the liquid-crystal aligning agent was stirred for 15 hours at 50 ° C. Got. Abnormalities, such as haze and precipitation, were not observed in this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

Using the obtained liquid-crystal aligning agent [19], the liquid crystal cell was produced like Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. Moreover, as a result of observing the liquid crystal cell manufactured similarly to Example 1 with the polarizing microscope except having not performed the rubbing process, it was confirmed that the liquid crystal was uniformly vertically aligned.

Moreover, using the liquid crystal cell manufactured similarly to Example 1, evaluation of voltage retention, relaxation evaluation of residual electric charge, evaluation after high temperature standing, and voltage retention evaluation after ultraviolet irradiation were performed. The results are shown in Tables 3, 4 and 5 described later.

&Lt; Comparative Example 8 >

NMP (9.23g) was added to the polyimide powder (B) obtained by the synthesis example 2, and (1.63g), and it stirred for 40 hours and made it melt | dissolve at 70 degreeC. 10 mass% NMP solution of HA (1.14 g) (0.114 g as HA), NMP (2.78 g), and BCS (12.3 g) were added to the solution, followed by stirring at 50 ° C. for 15 hours to provide a liquid-crystal aligning agent [20] Got. Abnormalities, such as haze and precipitation, were not observed in this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

Using the obtained liquid-crystal aligning agent [20], the liquid crystal cell was produced like Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. Moreover, as a result of observing the liquid crystal cell manufactured similarly to Example 1 with the polarizing microscope except having not performed the rubbing process, it was confirmed that the liquid crystal was uniformly vertically aligned.

Moreover, using the liquid crystal cell manufactured similarly to Example 1, evaluation of voltage retention, relaxation evaluation of residual electric charge, evaluation after high temperature standing, and voltage retention evaluation after ultraviolet irradiation were performed. The results are shown in Tables 3, 4 and 5 described later.

&Lt; Comparative Example 9 &

NMP (9.34g) was added to the polyimide powder (F) obtained by the synthesis example 6, and (1.65g), and it stirred for 40 hours and made it melt | dissolve at 70 degreeC. 10 mass% NMP solution (0.50g) (0.05g as 3-AMP), NMP (3.43g), and BCS (12.4g) of 3-AMP were added to this solution, and liquid crystal aligning by stirring at 50 degreeC for 15 hours. Treatment agent [21] was obtained. Abnormalities, such as haze and precipitation, were not observed in this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

Using the obtained liquid-crystal aligning agent [21], the liquid crystal cell was produced like Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. Moreover, as a result of observing the liquid crystal cell manufactured similarly to Example 1 with the polarizing microscope except having not performed the rubbing process, the liquid crystal was not vertically aligned.

Moreover, using the liquid crystal cell manufactured similarly to Example 1, evaluation of voltage retention, relaxation evaluation of residual electric charge, evaluation after high temperature standing, and voltage retention evaluation after ultraviolet irradiation were performed. The results are shown in Tables 3, 4 and 5 described later.

&Lt; Comparative Example 10 &

NMP (9.34g) was added to the polyimide powder (G) obtained by the synthesis example 6, and (1.65g), and it stirred for 40 hours and was made to melt | dissolve at 70 degreeC. 10 mass% NMP solution (1.16g) (0.116g as 3-AMP), NMP (2.83g), and BCS (12.4g) of 3-AMP were added to this solution, and liquid crystal aligning by stirring at 50 degreeC for 15 hours. Treatment agent [22] was obtained. Abnormalities, such as haze and precipitation, were not observed in this liquid-crystal aligning agent, and it was confirmed that the resin component was melt | dissolving uniformly.

Using the obtained liquid-crystal aligning agent [22], the liquid crystal cell was produced like Example 1, and the pretilt angle was evaluated. The results are shown in Table 2 described later. Moreover, as a result of observing the liquid crystal cell manufactured similarly to Example 1 with the polarizing microscope except having not performed the rubbing process, it was confirmed that the liquid crystal was uniformly vertically aligned.

Moreover, using the liquid crystal cell manufactured similarly to Example 1, evaluation of voltage retention, relaxation evaluation of residual electric charge, evaluation after high temperature standing, and voltage retention evaluation after ultraviolet irradiation were performed. The results are shown in Tables 3, 4 and 5 described later.

When the liquid-crystal aligning agent of this invention is set as the liquid crystal aligning film, it has the characteristic which enlarges the pretilt angle of a liquid crystal, can align a liquid crystal perpendicularly even with a small use ratio, and is empty in the coating liquid of a liquid-crystal aligning agent. The precipitation hardly occurs even when the solvent is mixed. In addition to these characteristics, liquid crystals having a high voltage retention and a rapid relaxation of charges accumulated by DC voltage even after long-term exposure at high temperatures, and can suppress a drop in voltage retention even after long-term exposure to ultraviolet rays of the backlight. The liquid-crystal aligning agent from which an oriented film is obtained is obtained. Furthermore, it is possible to provide a highly reliable liquid crystal display element that can withstand long term use in an extreme use environment. As a result, it is useful for a TN element, an STN element, a TFT liquid crystal element, and also a vertically aligned liquid crystal display element.

In addition, the JP Patent application 2008-4992, the claim, and all the content of the abstract for which it applied on January 11, 2008 are referred here, and it introduces as an indication of the specification of this invention.

Claims (13)

The following (A) component and following (B) component are contained, The liquid-crystal aligning agent characterized by the above-mentioned.
(A) component: The polymer which imidated the polyamic acid which has a structural formula of the repeating unit represented by following formula [1], The polyimide which has a carboxyl group in the molecule | numerator in this polymer.
(B) Component: The amine compound which has one primary amino group and nitrogen containing aromatic heterocyclic ring in a molecule | numerator, and the said primary amino group couple | bonded with the aliphatic hydrocarbon group or the non-aromatic cyclic hydrocarbon group.
[Formula 1]

(In formula [1], R <_1> is tetravalent organic group and R <_2> is bivalent organic group containing following formula [2].)
(2)

(In formula [2], X <_1> is phenylene, X <_2> is cyclohexylene or phenylene, X <_3> is cyclohexylene. X <_4> is a C3-C12 alkyl group and a C3-C12 alkoxy group. , A fluoroalkyl group having 3 to 12 carbon atoms or a fluoroalkoxy group having 3 to 12 carbon atoms) The method of claim 1,
Formula X ₂ [2] is cyclohexyl, and xylene, or phenylene group, X ₄ is fluoroalkyl having 3 to 6 carbon atoms alkyl group, having 3 to 6 carbon atoms an alkoxy group, an alkyl group or a carbon number of 3-6 fluoroalkyl having 3 to 6 carbon atoms in the The liquid-crystal aligning agent which is an alkoxy group. The method of claim 1,
The liquid-crystal aligning agent whose R < ₂ > in Formula [1] is a divalent organic group containing following formula [3].
(3)

(In formula [3], n is an integer of 2-11. The cis-trans isomerization of 1, 4- cyclohexylene is a trans isomer.) The method of claim 1,
The liquid-crystal aligning agent whose R < ₂ > in Formula [1] is a divalent organic group containing following formula [4].
[Chemical Formula 4]

(In formula [4], n is an integer of 2-11. The cis-trans isomerization of 1, 4- cyclohexylene is a trans isomer.) The method according to any one of claims 1 to 4,
(A) A component is a polymer which imidated the polyamic acid which has a structural formula of the repeating unit represented by Formula [1], and the quantity of the carboxyl group which the polymer has is 0.1-3 in average value with respect to the repeating unit of this polymer. Treatment agent. 6. The method according to any one of claims 1 to 5,
(A) A component is a polymer which imidated the polyamic acid which has a structural formula in which one part or all part of a repeating unit has a unit represented by following formula [5] among the structural formulas of the repeating unit represented by said Formula [1], The amount of the carboxyl group which this polymer has is a liquid-crystal aligning agent which is 0.1-3 in an average value with respect to the repeating unit of this polymer.
[Chemical Formula 5]

(Wherein, R ₃ is a tetravalent organic group, R ₄ is a divalent organic group, and at least one of R ₃ or R ₄ has a carboxyl group) The method according to any one of claims 1 to 6,
The liquid-crystal aligning agent whose (B) component is an amine compound shown by following formula [6].
[Formula 6]

(In formula [6], Y <_1> is a divalent organic group which has an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group, and Y <_2> is a nitrogen-containing aromatic heterocyclic ring.) The method according to any one of claims 1 to 6,
The liquid-crystal aligning agent whose (B) component is an amine compound shown by following formula [7].
[Formula 7]

(Wherein [7], Y ₃ is a divalent aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group having a carbon number of valence 1 ~ 10, Y ₄ represents a single bond, or -O-, -NH-, -S-, -SO _It is a bivalent or divalent organic group having 1 to 19 carbon atoms, and the total of the carbon atoms of Y ₃ and Y ₄ is 1 to 20. Y ₅ is a nitrogen-containing aromatic heterocyclic ring.) The method of claim 8,
(B) A component is a liquid-crystal aligning agent whose Y <_3> , Y <_4> and Y < ₅ > in Formula [7] are an amine compound which consists of a combination chosen from the group or ring described below, respectively.
Stage, Y ₃ is a group having 1 to 10 carbon atoms in the straight-chain or branched alkylene group, having 1 to 10 carbon atoms of the unsaturated alkyl group, a cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, Cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotedecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclonona It is 1 type chosen from the group which consists of a decane ring, a cycloikoic acid ring, a tricyclo ecoic acid ring, a tricyclodecoic acid ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring, and an adamantane ring;
Y ₄ is a single bond, -O-, -NH-, -S-, -SO _2- , a hydrocarbon group having 1 to 19 carbon atoms, -CO-O-, -O-CO-, -CO-NH-,- NH-CO-, -CO-, -CF _2- , -C (CF ₃ ) _2- , -CH (OH)-, -C (CH ₃ ) _2- , -Si (CH ₃ ) _2- , -O -Si (CH ₃ ) _2- , -Si (CH ₃ ) ₂ -O-, -O-Si (CH ₃ ) ₂ -O-, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cyclo Heptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotedecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, Cyclooctadecane ring, cyclononadecan ring, cycloicosan ring, tricycloecoic acid ring, tricyclodecoic acid ring, bicycloheptane ring, decahydronaphthalene ring, norbornene ring, adamantane ring, benzene ring, Naphthalene Ring, Tetrahydronaphthalene Ring, Azul Ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, penalene ring, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyra Sleepy ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, chi Nolin ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring, oxazole ring, piperazine ring, piperidine ring, dioxane It is 1 species chosen from the group which consists of a ring and a morpholine ring;
Y ₅ is pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole Ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, chinoline ring, phenanthroline ring, indole ring, quinoxaline It is 1 species chosen from the group which consists of a ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring, and an acridine ring. The method according to any one of claims 1 to 9,
The liquid-crystal aligning agent containing (B) component in the ratio of 0.01-2 mol double quantity with respect to 1 mol amount of the carboxyl group which the polyimide of (A) component has. The method according to any one of claims 1 to 10,
The liquid-crystal aligning agent obtained by mixing under the heating the organic solvent containing the polyimide of (A) component and the amine compound of (B) component. The liquid crystal aligning film obtained from the liquid-crystal aligning agent as described in any one of Claims 1-11. The liquid crystal display element which has a liquid crystal aligning film of Claim 12.