KR101518092B1 - 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 1,4-페닐렌 또는 1,4-시클로헥실렌이고, X₂ 는 탄소수 3 ∼ 12 의 알킬기, 탄소수 3 ∼ 12 의 알콕시기, 탄소수 3 ∼ 12 의 플루오로알킬기 또는 탄소수 3 ∼ 12 의 플루오로알콕시기이다)A liquid crystal alignment treatment agent characterized by containing the following component (A) and the following component (B).
Component (A): Polyimide having a carboxyl group in the molecule of the polymer in which a polyamic acid having a structural formula of a repeating unit represented by the following formula [1] is imidized.
(B): An amine compound having one primary amino group and one nitrogen-containing aromatic heterocyclic ring in the molecule, and the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group.
[Chemical Formula 1]

(In the formula [1], R ₁ is a tetravalent organic group and R ₂ is a divalent organic group containing the following formula [2]
(2)

(Wherein X ₁ is 1,4-phenylene or 1,4-cyclohexylene, X ₂ is an alkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, a fluorine atom having 3 to 12 carbon atoms A fluoroalkyl group or a fluoroalkoxy group having 3 to 12 carbon atoms)

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment treatment agent, and a liquid crystal display element using the same. BACKGROUND ART [0002]

The present invention relates to a liquid crystal alignment treatment agent used in producing a liquid crystal alignment film, and a liquid crystal display element using the same.

As a liquid crystal alignment film of a liquid crystal display element at present, a so-called polyimide-based liquid crystal (hereinafter referred to as " liquid crystal alignment layer ") obtained by applying and firing a liquid crystal alignment treatment agent (also referred to as liquid crystal aligning agent) containing a solution of a polyimide precursor or a solution of soluble polyimide as a main component An orientation film is mainly used.

One of the properties required for a liquid crystal alignment film is so-called pre-tilt angle control of a liquid crystal in which the alignment tilt angle of the liquid crystal molecules with respect to the substrate surface is maintained at an arbitrary value. It is known that the size of the pretilt angle can be changed by selecting the structure of the polyimide constituting the liquid crystal alignment film.

Among techniques for controlling the pretilt angle by the structure of polyimide, in the method of using a diamine having a side chain as a part of a polyimide raw material, since the pretilt angle is increased according to the use ratio of the diamine, It is relatively easy to control by an angle and is useful as means for increasing the pre-tilt angle. As a side chain structure of a diamine for increasing the pretilt angle of a liquid crystal, it has been proposed to include a cyclic structure such as a steroid skeleton (see, for example, Patent Document 1) and a phenyl group or a cyclohexyl group 2). Further, diamines having three or four such ring structures in the side chain have been proposed (see, for example, Patent Document 3).

On the other hand, when a solution of a polyamic acid or a solution of a solvent-soluble polyimide is applied to a substrate in a process of manufacturing a liquid crystal alignment film, it is generally practiced by flexography or the like industrially, Butyl cellosolve or the like is mixed with N-methyl-2-pyrrolidone or? -Butyrolactone, which has excellent solubility of the polymer, for the purpose of forming a uniform and defect-free thin film. However, a solvent such as butyl cellosolve has a problem that the ability to dissolve polyamic acid or polyimide is poor, so that precipitation occurs when mixed in a large amount (see, for example, Patent Document 4). This problem is particularly pronounced in solutions of solvent-soluble polyimides. In addition, the polyimide obtained by using the diamine having the side chain as described above tends to lower the coating uniformity of the solution. Therefore, it is necessary to increase the mixing amount of the coating property improving solvent such as butyl cellosolve , And the mixing allowable amount of such a solvent is also an important property of the polyimide.

In addition, from the viewpoint of suppressing a decrease in contrast of a liquid crystal display element and reducing a residual image phenomenon with the liquid crystal display element becoming finer and finer, the liquid crystal alignment film used therein has a higher voltage holding ratio, It is becoming increasingly important that the amount of accumulated charge when applied is low and that the residual charge accumulated by the DC voltage is fast.

In a polyimide-based liquid crystal alignment film, a liquid crystal alignment agent containing a tertiary amine having a specific structure in addition to a polyamic acid or an imide group-containing polyamic acid, (See, for example, Patent Document 5), and a liquid crystal aligning agent containing a soluble polyimide in which a specific diamine having a pyridine skeleton or the like is used as a raw material (see, for example, Patent Document 6) . In addition, a compound having one carboxylic acid group in the molecule in addition to polyamic acid and its imidized polymer, such as a compound having a high voltage holding ratio and a short time until the afterimage generated by the DC voltage disappears, A liquid crystal aligning agent using a liquid crystal aligning agent containing a very small amount of a compound containing a carboxylic acid anhydride group and a compound containing one tertiary amino group in the molecule (see, for example, Patent Document 7) is known.

However, in recent years, a liquid crystal display device having a large screen and a large screen has been widely put to practical use, and the liquid crystal display device for such use has a problem in that, There is a demand for characteristics that are more stringent and can endure long-term use in a severe use environment. Therefore, the liquid crystal alignment film used therefor needs to have higher reliability than that of the conventional liquid crystal alignment film. The liquid crystal alignment film is also excellent in the initial characteristics. For example, after the liquid crystal alignment film is exposed for a long time at a high temperature, It is required to maintain good properties even after exposure.

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

The present invention has the property of increasing the pre-tilt angle of the liquid crystal when the liquid crystal alignment film is used, and it is possible to orient the liquid crystal vertically even with a small use ratio, and also to mix the poor solvent with the liquid for the liquid crystal alignment treatment agent The liquid crystal alignment treatment agent does not cause precipitation well even when the liquid crystal alignment treatment agent is used. In addition to these characteristics, it is also possible to provide a liquid crystal display device capable of suppressing the decrease of the voltage holding ratio even after the backlight has been exposed to the ultraviolet ray for a long time, and the residual charge accumulated by the DC voltage is quickly alleviated even after a long- And a liquid crystal alignment treatment agent capable of obtaining an alignment film. And further to provide a liquid crystal display device with high reliability that can withstand long-term use in a severe use environment.

As a result of intensive research to achieve the above object, the present inventors have found a novel liquid crystal alignment treatment agent which achieves this. The present invention is based on this finding, and has the following points.

(1) A liquid crystal alignment treatment agent characterized by containing the following component (A) and the following component (B).

Component (A): Polyimide having a carboxyl group in the molecule of the polymer in which a polyamic acid having a structural formula of a repeating unit represented by the following formula [1] is imidized.

(B): An amine compound having one primary amino group and one nitrogen-containing aromatic heterocyclic ring in the molecule, and the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group.

[Chemical Formula 1]

(In the formula [1], R ₁ is a tetravalent organic group and R ₂ is a divalent organic group containing the following formula [2]

(2)

(Wherein X ₁ is 1,4-phenylene or 1,4-cyclohexylene, X ₂ is an alkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, a fluorine atom having 3 to 12 carbon atoms A fluoroalkyl group having 3 to 12 carbon atoms, or a fluoroalkoxy group having 3 to 12 carbon atoms)

(2) The liquid crystal alignment treating agent according to the above (1), wherein R ₂ in the formula [1] is a divalent organic group containing the following formula [3].

(3)

(In the formula [3], n is an integer of 2 to 11, and the cis-trans isomer of 1,4-cyclohexylene is a trans isomer)

(3) The liquid crystal alignment treatment agent according to (1), wherein R ₂ in the formula [1] is a divalent organic group containing the following formula [4].

[Chemical Formula 4]

(In the formula [4], n is an integer of 2 to 11, and the cis-trans isomer of 1,4-cyclohexylene is a trans isomer)

(4) The polyimide film according to the above (1), wherein the component (A) is a polymer obtained by imidizing a polyamic acid having a structural formula of a repeating unit represented by the formula [1], wherein the carboxyl group content of the polymer is 0.1 to 3 The liquid crystal alignment treatment agent described in any one of (1) to (3) above.

(5) The polymer (A) is a polymer obtained by imidizing a polyamic acid having a structural formula in which a part of the repeating unit of the repeating unit represented by the formula [1] has a unit represented by the following formula [5] (1) to (4), wherein the amount of the carboxyl group of the polymer is 0.1 to 3 as an average value to the repeating unit of the 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 and R ₄ has a carboxyl group)

(6) The liquid crystal alignment treating agent according to any one of (1) to (5), wherein the component (B) is an amine compound represented by the following formula [6].

[Chemical Formula 6]

(In the formula [6], 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 heterocyclic ring)

(7) The liquid crystal alignment treating agent according to any one of (1) to (5), wherein the component (B) is an amine compound represented by the following formula [7].

(7)

(Wherein Y ₃ represents a divalent aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group having 1 to 10 carbon atoms, Y ₄ represents a single bond, -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)

(8) The liquid crystal alignment treating agent according to (7), wherein component (B) is an amine compound comprising a combination of Y ₃ , Y ₄ and Y ₅ in formula [7]

Y ₃ represents 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, a cyclooctane ring, A cyclopentadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cyclooctadecane ring, a cyclododecane ring, a cyclotetradecane ring, a cyclotetradecane ring, a cyclotetradecane ring, a cyclopentadecane ring, a cyclohexadecane ring, Is selected from the group consisting of a decane ring, a cyclohexanoic acid ring, a tricycloicoic acid ring, a tricyclodecanoic 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-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-, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, A cycloheptadecane ring, a cycloheptadecane ring, a cyclohexadecane ring, a cycloheptadecane ring, a cyclohexadecane ring, a cyclohexadecane ring, a cycloheptadecane ring, a cyclohexadecane ring, a cyclohexadecane ring, a cyclohexadecane ring, A cyclohexadecane ring, a cyclohexadecane ring, a cyclooctadecane ring, a cyclooctadecane ring, a cyclononadecane ring, a cyclooctanoic ring, a tricycloicoic acid ring, a tricyclodecanoic acid ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring, Naphthalene ring, tetrahydronaphthalene ring, azul ring A thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazine ring, an imidazole ring, an imidazole ring, an oxazole ring, a thiazole ring, A carbazole ring, a pyridine ring, a thiadiazole ring, a pyridazine ring, a triazine ring, a pyrazolidine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, a benzoimidazole ring, An oxadiazole ring, an oxidine ring, a piperazine ring, a piperidine ring, a dioxane ring, an oxadiazole ring, an oxadiazole ring, an oxadiazole ring, an oxidine ring, an oxazole ring, a piperazine ring, A ring and a morpholine ring;

Y ₅ is selected from the group consisting of a pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, A pyrimidine ring, a pyrazoline ring, a pyrazoline ring, a triazine ring, a pyrazolidine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, a benzimidazole ring, a chinoline ring, a phenanthroline ring, A ring selected from the group consisting of a ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring and an acridine ring.

(9) The liquid crystal composition according to any one of the above items (1) to (8), which contains 0.01 to 2 molar times of the component (B) relative to 1 mol of the carboxyl group contained in the polyimide of the component (A) Orientation treatment agent.

(10) The liquid crystal alignment treatment agent according to any one of (1) to (9), which is obtained by mixing a polyimide of component (A) and an organic solvent containing an amine compound of component (B) under heating.

(11) A liquid crystal alignment film obtained from the liquid crystal alignment treatment agent described in any one of (1) to (10) above.

(12) A liquid crystal display element having the liquid crystal alignment film according to (11) above.

The liquid crystal alignment treatment agent of the present invention can be obtained by a comparatively simple method. Further, the liquid crystal alignment treatment agent of the present invention has a property of increasing the pretilt angle of the liquid crystal when the liquid crystal alignment film is formed, and the liquid crystal can be aligned vertically even with a small use ratio. Further, even when a poor solvent is mixed with the coating liquid of the liquid crystal alignment treatment agent, precipitation hardly occurs. In addition, it is possible to obtain a liquid crystal alignment film having a high voltage holding ratio and a high relaxation of the residual charge accumulated by a direct current voltage even after a long time exposure at a high temperature.

Further, the liquid crystal display element having the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is excellent in reliability, and can be preferably used for a liquid crystal television of a large screen and a large screen.

The liquid crystal alignment treatment agent of the present invention is a polymer obtained by imidizing a polyamic acid having a structural unit of the repeating unit represented by the above formula [1], which is a component (A), and a polyimide having a carboxyl group in the molecule (hereinafter, (Hereinafter sometimes referred to as a specific polyimide), and (B) an amine compound having one amino group and one nitrogen-containing aromatic heterocyclic ring in the molecule, and the amino group is bonded to an aliphatic hydrocarbon group or a nonaromatic cyclic hydrocarbon group (Hereinafter sometimes referred to as a specific amine compound). In the present specification, the above-mentioned amino group (-NH ₂ ) has the same meaning as the primary amino group, and is hereinafter also referred to as a primary amino group.

The specific polyimide in the liquid crystal alignment treatment agent of the present invention is a specific diamine (hereinafter sometimes referred to as a specific diamine) having a substituent having a property of increasing the pretilt angle on the side chain. Therefore, when this specific diamine is used, the obtained liquid crystal alignment treatment agent can orient the liquid crystal vertically even with a small usage ratio. By lowering the use ratio, the solubility of the organic solvent in the polymer is increased, and precipitation does not occur even when a poor solvent is mixed in the coating liquid of the liquid crystal alignment treatment agent.

In the liquid crystal alignment treatment agent of the present invention, the amino group in the specific amine compound forms a salt with the carboxyl group in the specific polyimide, or the amide bond in the specific polyimide accompanies desorption of water or alcohol to the carboxyl group or carboxy ester group , It is considered that a bonding reaction involving the ring opening of the imide group is carried out with respect to the imide group in the specific polyimide. Further, it is considered that the amino group forming the salt with the carboxyl group in the specific polyimide forms an amide bond by elimination of water by the baking process in the production of the liquid crystal alignment film. As a result, it is considered that, despite the simple means of mixing the liquid crystal alignment treatment agent of the present invention in an organic solvent, among the obtained liquid crystal alignment films, a specific amine compound and a specific polyimide are efficiently bonded.

On the other hand, the nitrogen-containing aromatic heterocyclic ring in the specific amine compound functions as an electron hopping site due to its conjugated structure, thereby promoting the charge transfer in the obtained liquid crystal alignment film. When the liquid crystal alignment film is formed, the nitrogen-containing aromatic heterocyclic ring and the carboxyl group in the specific polyimide are linked by electrostatic interaction such as salt formation or hydrogen bonding, so that the carboxyl group in the specific polyimide and the nitrogen-containing aromatic heterocyclic ring in the specific amine compound Charge transfer occurs. Further, since this specific amine compound is chemically bonded to the specific polyimide, the charge transferred to the nitrogen-containing aromatic heterocyclic ring moiety can efficiently move within the polyimide molecule or between the molecules.

In view of the above, the liquid crystal alignment treatment agent of the present invention has a property of increasing the pretilt angle of the liquid crystal when the liquid crystal alignment film is used, and the liquid crystal can be aligned vertically even with a small use ratio. Further, even when a poor solvent is mixed with the coating liquid of the liquid crystal alignment treatment agent, precipitation hardly occurs. In addition, it is possible to obtain a liquid crystal alignment film having a high voltage holding ratio and a high relaxation of the residual charge accumulated by a direct current voltage even after a long time exposure at a high temperature.

≪ Component (A) / specific polyimide >

In the present invention, the specific polyimide as the component (A) is a polymer obtained by imidizing a polyamic acid having a structural formula of a repeating unit represented by the formula [1], and if the polymer has a carboxyl group in the molecule, And is not particularly limited. The polyimide is preferably a polymer obtained by imidizing a polyamic acid having a structural formula of a repeating unit represented by the formula [1], because the polyimide is relatively easily obtained by using a tetracarboxylic acid dianhydride and a diamine as raw materials.

[Chemical Formula 8]

(In the formula [1], R ₁ is a tetravalent organic group and R ₂ is a divalent organic group containing the following formula [2]

[Chemical Formula 9]

In the formula [2], X ₁ is 1,4-phenylene or 1,4-cyclohexylene. The ring of 1,4-phenylene or 1,4-cyclohexylene may optionally have a substituent. X ₂ represents an alkyl group having 3 to 12 carbon atoms, preferably 3 to 6 carbon atoms, a fluoroalkyl group having 3 to 12 carbon atoms, preferably 3 to 6 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, preferably 3 to 6 carbon atoms, 3 to 12, preferably 3 to 6 fluoroalkoxy groups. The alkyl group, fluoroalkyl group, alkoxy group and fluoroalkoxy group may be linear or branched, but are preferably linear, and may have an appropriate substituent.

The benzene ring of the main chain in the formula [2] is bonded to the -NH- of the polymer of the formula [1], and the bonding position at which the -NH- in the benzene ring is bonded is not limited. Specific examples include, as shown in formula [8] of the following formula with respect to the Z ₁ of [2], 2, 3 position, 2, 4-position, 2, 5-position, 2, 6-position, 3, and 4, and positions of 3 and 5, respectively. Among them, positions 2 and 4, positions 2 and 5, positions 3 and 5 are preferable from the viewpoint of reactivity when synthesizing polyamic acid. When the ease of diamine synthesis is also taken into account, positions 2 and 4 or positions 2 and 5 are preferred.

[Chemical formula 10]

Among the formula [2], the structure represented by the following formulas [3] and [4], in which X ₁ is 1,4-trans-cyclohexylene, is preferable in view of the effect of increasing the pretilt angle of the liquid crystal Do. In particular, the structure represented by the formula [3] is more preferable since the effect is excellent.

(11)

In the formula [3], n is an integer of 2 to 11, preferably an integer of 2 to 6, and the cis-trans isomer of 1,4-cyclohexylene is a trans isomer.

[Chemical Formula 12]

In the formula [4], n is an integer of 2 to 11, preferably n is an integer of 2 to 6, and the cis-trans isomer of 1,4-cyclohexylene is a trans isomer.

Preferable specific examples of the structure represented by the formula [2] of the present invention can be represented by the following formulas [9] to [12]. Each of n in the formulas [9] to [12] is independently preferably an integer of 2 to 11, particularly preferably an integer of 2 to 6. The cis-trans isomers of 1,4-cyclohexylene in the formulas [9] to [12] are trans isomers, respectively.

[Chemical Formula 13]

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

[Chemical Formula 14]

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

The method for producing the diamine represented by the formula [13] is not particularly limited, but preferred methods include the following methods.

[Chemical Formula 15]

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

, Synthesizing a dinitro compound of the formula [14], reducing the nitro group by a conventional method, and converting the nitro group into an amino group.

The dinitro compound of the formula [14] can be obtained by a reaction between a hydroxyl group-containing compound represented by the following formula [15] and dinitrochlorobenzene.

[Chemical Formula 16]

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

Specific polyimides containing the structures of formulas [3], [4] and [9] to [12] can also be obtained by the same method as described above.

In the formula [1], each of R ₁ and R ₂ may be a single kind or a combination of plural kinds of different repeating units having different R ₁ and R ₂ , respectively.

For the purpose of increasing the pretilt angle of the liquid crystal, it is preferable to use at least 1 mol% of the structure of the formula [2]. For the purpose of orienting the liquid crystal vertically, it is preferably used in an amount of 10 mol% or more, more preferably 15 mol% or more. The same applies to specific polyimides containing the structures of formulas [3], [4], and [9] to [12].

The specific polyimide can be obtained by controlling the imidization rate when the polyamic acid is imidized to usually less than 100%.

The specific polyimide may include a polyimide acid imidized with a repeating unit having a structural unit represented by the following formula [5] in the structural formula of the repeating unit represented by the formula [1].

[Chemical Formula 17]

(In the formula [5], R ₃ is a tetravalent organic group, R ₄ is a divalent organic group, and at least one of R ₃ and R ₄ has a carboxyl group)

At this time, the imidization rate may be 100%.

The imidization rate of the specific polyimide is preferably 20% or more, more preferably 40% or more, because a high voltage holding ratio is obtained.

The average value of the carboxyl group in the specific polyimide to the repeating unit of the structural formula as the polyimide is preferably 0.1 to 4, more preferably 0.3 to 3, and particularly preferably 2 to 5, in view of the effect of the present invention being efficiently obtained. 0.5 to 2.5. The repeating unit at this time is also a unit containing an amidic acid group which is not imidized. For example, in the case of a polyimide obtained by imidizing a polyamic acid having a repeating unit represented by the formula [1], when the imidization rate is less than 100%, the combination of the structures of the following formulas [16a] to [16d] The repeating unit in the case of calculating the amount of the carboxyl group in the above includes all of the formulas [16a] to [16d].

[Chemical Formula 18]

In the present invention, the amount of the carboxyl group in the specific polyimide (hereinafter also referred to as the average value of the carboxyl groups) is obtained as the sum of P in the following (i) and Q in (ii).

(I) an average value of repeating units of a structural formula as a polyimide of a carboxyl group derived from an imidized amide acid: P

(Ii) the average value of the carboxyl groups contained in R ₃ and R ₄ of the formula [5] to the repeating units of the structural formula as the polyimide: Q

The P in the above (i) can be calculated from the following equation (1) using the imidization rate (z). In addition, the imidization rate z is obtained from, for example, " measurement of imidization rate "

P = 2 x (1 - z / 100) (1)

On the other hand, Q in the above (ii) represents an average value of the carboxyl groups contained in R ₃ of formula [5] to the repeating units of the structural formula as polyimide: Q ₁ and the ratio of the carboxyl groups contained in R ₄ to the polyimide And the average value of repeating units: Q ₂ .

Each of R ₃ and R ₄ is a tetracarboxylic acid dianhydride residue (R ₃ ) or a diamine residue (R ₄ ), which is a part or all of raw materials used to obtain a specific polyimide.

Therefore, the above-mentioned Q ₁ is calculated by using the molar fraction of the tetracarboxylic acid dianhydride represented by the following formula [V1] in the total molar amount of the tetracarboxylic acid dianhydride used for obtaining the specific polyimide, (3).

[Chemical Formula 19]

Q ₁ =? ₁ ? W ₁ / W ₂ (3)

Here, β ₁ represents the number of carboxyl groups contained in R ₃ , W ₁ represents the molar amount of the tetracarboxylic acid dianhydride of the formula [V1], and W ₂ represents the total molar amount of the tetracarboxylic acid dianhydride.

The above-mentioned Q ₂ is calculated from the following formula (4) using the molar fraction of the diamine represented by the following formula [V2] in the total molar amount of the diamine used for obtaining the specific polyimide.

[Chemical Formula 20]

Q ₂ =? ₂ x W ₃ / W ₄ (4)

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

Thus, the amount of the carboxyl group is obtained by the following formula (5).

The amount of the carboxyl group in the specific polyimide

= P + Q ₁ + Q ₂

= 2 × (1 - z / 100) + β 1 × W 1 / W 2 + β 2 × W 3 / W 4 (5)

In the present invention, the adjustment of the amount of the carboxyl group in the specific polyimide is carried out,

(1) means for adjusting by controlling the imidization rate,

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

. The means (1) and (2) may be used in combination.

From the viewpoint of the degree of freedom of choice of R ₁ and R _{2 in} the formula [1], the means of (1) is preferable. From the viewpoint of the degree of freedom of selection of the imidization ratio of the specific polyimide, the means of (2) is preferable. From the viewpoint that the possibility that the specific amine compound is eliminated or the polyimide chain is broken by the imidization reaction by the firing step in the production of the liquid crystal alignment film is small, the means of (2) is preferable.

When the amount of the carboxyl group in the specific polyimide is adjusted by the means of (1), R ₁ and R ₂ in the formula [1] are not particularly limited. In addition, R ₁ and R ₂ are each formula may be either one kinds in the (1), each having a different structure of the R ₁ and R _2, It may be a combination of plural kinds different as a repeating unit.

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

[Chemical Formula 21]

[Chemical Formula 22]

Among them, A-6, A-16, A-18 to A-22, A-25, A-37 and A-38 are preferable because polyimide having a high imidization rate has high solubility in an organic solvent.

When 10 mol% or more of R _{1 has} an alicyclic structure or an aliphatic structure such as A-1 to A-25, the voltage holding ratio is preferably improved. Particularly, it is preferable that two types of R _{1 selected} from A-1, A-16 and A-19 are used together because a liquid crystal orientation film with a higher charge relaxation can be obtained.

In the formula [1], R ₂ may contain an organic group other than the structure represented by the formula [2]. Specific examples thereof are as follows.

(23)

≪ EMI ID =

(25)

(26)

(27)

(28)

(In the B-112 and B-113, Q is -COO-, -OCO-, -CONH-, -NHCO-, -CH 2 - represent any of, -O-, -CO-, -NH-)

When the amount of the carboxyl group in the specific polyimide is adjusted by the means of (2) above, the structure is not particularly limited as long as it has a carboxyl group in either R ₃ or R ₄ . Further, the preferable number of carboxyl groups R ₃ and R ₄ each 0-2 (where, R ₃ or R ₄ is of either has at least one carboxyl group) to the.

From the viewpoints of ease of synthesis of polyimide and availability of raw materials, it is preferable that R ₄ has a carboxyl group. Examples of R ₄ having a carboxyl group include B-102 to B-113. At this time, R ₄ having a carboxyl group may be one kind or two or more kinds may be used in combination. When R ₄ has a carboxyl group, the structure of R ₃ is not particularly limited, and specific examples include A-1 to A-45.

≪ Production method of specific polyimide &

The production method of the specific polyimide used as the component (A) used in the present invention is not particularly limited, but generally, a tetracarboxylic acid component consisting of one or more kinds selected from a tetracarboxylic acid and a derivative thereof, A method of synthesizing a polyamic acid having a structural unit of a repeating unit represented by the formula [1] by reacting a diamine component comprising one or more kinds of diamine compounds and then imidizing the polyamic acid to form a polyimide do.

At this time, the obtained polyamic acid can be made into a homopolymer (homopolymer) or a copolymer (copolymer) by appropriately selecting the tetracarboxylic acid component and the diamine component as raw materials.

As used herein, the tetracarboxylic acid and its derivative are tetracarboxylic acid, tetracarboxylic acid dihalide or tetracarboxylic acid dianhydride. Among them, the tetracarboxylic acid dianhydride is preferred because of its high reactivity with the diamine compound.

Specific examples of the method for producing a specific polyimide will be described below.

For example, a tetracarboxylic acid component containing at least one tetracarboxylic acid dianhydride represented by the formula [17] and a diamine compound containing at least one member selected from a diamine compound represented by the formula [18] May be subjected to a polycondensation reaction in an organic solvent such as N-methylpyrrolidone, N, N'-dimethylacetamide, N, N'-dimethylformamide or? -Butyrolactone to obtain a polyamic acid.

[Chemical Formula 29]

R ₁ in the formula [17] is the same as that in the formula [1].

(30)

R ₂ in the formula [18] is the same as that in the formula [1].

At that time, the reaction temperature may be any temperature between -20 ° C and 150 ° C, preferably between -5 ° C and 100 ° C.

The ratio of the total number of moles of the compound constituting the tetracarboxylic acid component to 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 the molar ratio is to 1.0, the larger the degree of polymerization of the resulting polymer.

In order to obtain a polyamic acid having a unit represented by the formula [5] in a part or all of the repeating unit in the structural unit of the repeating unit represented by the formula [1], a tetracarboxylic acid dianhydride having a carboxyl group in R ₁ , / Or a diamine having a carboxyl group in R < ₂ > may be used.

As a method of imidizing polyamic acid, thermal imidization by heating and catalyst imidization using a catalyst are common, but the catalyst imidization, in which the imidization reaction proceeds at a relatively low temperature, Is not preferable.

The catalyst imidization can be carried out by stirring the polyamic acid in an organic solvent in the presence of a basic catalyst and an acid anhydride. The reaction temperature in this case is -20 to 250 ° C, preferably 0 to 180 ° C. When the reaction temperature is higher, the imidization proceeds rapidly, but when the reaction temperature is too high, the molecular weight of the polyimide may be lowered. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amide group, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to 30 moles, of the amide group. If the amount of the basic catalyst or the acid anhydride is small, the reaction does not proceed sufficiently, and if it is excessively large, it becomes difficult to completely remove the catalyst after completion of the reaction. Examples of the basic catalyst used in this case include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, pyridine is preferred because it has a basicity suitable for promoting the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like. Of these, use of acetic anhydride is preferable since the purification after completion of the reaction is facilitated. The organic solvent is not limited as long as it dissolves polyamic acid. Examples thereof include N, N'-dimethylformamide, N, N'-dimethylacetamide, N-methyl- N-methyl caprolactam, dimethyl sulfoxide, tetramethyl urea, dimethyl sulfone, hexamethyl sulfoxide,? -Butyrolactone, and the like. The imidization rate by the catalyst imidization can be controlled by adjusting the catalyst amount, the reaction temperature, and the reaction time.

The resulting polyimide is obtained by charging the reaction solution into a poor solvent and recovering the resulting precipitate. The poor solvent to be used is not particularly limited, and examples thereof include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, . The polyimide precipitated by charging into a poor solvent may be filtered and then converted into a powder at normal temperature or reduced pressure at room temperature or by heating and drying. The polyimide may be further purified by repeating the operation of dissolving the polyimide powder in an organic solvent and re-precipitating the solution twice to 10 times. When the impurities are not completely removed by one settling recovery operation, it is preferable to carry out this purification step.

The molecular weight of the specific polyimide used in the present invention is not particularly limited, but is preferably 2,000 to 200,000, more preferably 4,000 to 50,000, in terms of weight average molecular weight, from the viewpoints of ease of handling and stability of characteristics when formed into a film . The molecular weight was determined by GPC (Gel Permeation Chromatography).

<Component (B) / specific amine compound>

The specific amine compound (B) used in the present invention is an amine compound having one amino group and one nitrogen-containing aromatic heterocyclic ring in the molecule, and the amino group is bonded to a divalent aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group.

Since this specific amine compound has only one amino group contained in the molecule, the possibility that problems such as precipitation and gelation of the polymer occur during preparation of the liquid crystal alignment treatment agent and storage of the liquid crystal alignment agent can be avoided.

The primary amino group contained in a specific amine compound is preferably bonded to a divalent aliphatic hydrocarbon group or a nonaromatic hydrocarbon group containing no aromatic hydrocarbon within the molecule from the viewpoint of ease of salt formation or coupling reaction with a specific polyimide It needs to be.

Specific examples of the aliphatic hydrocarbon group include a linear alkylene group, an alkylene group having a branched structure, and a divalent hydrocarbon group having an unsaturated bond. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 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 cyclododecane ring, a cyclododecane ring, a cyclododecane ring, a cyclododecane ring, a cyclododecane ring, a cyclotodecane ring, a cyclotetradecane ring, a cyclopentadecane ring, a cyclohexadecane ring, a cycloheptadecane ring, , A tricyclodecanoic acid ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring, an adamantane ring, and the like. Preferably a ring of 3 to 20 carbon atoms, more preferably a ring of 3 to 15 carbon atoms, and more preferably a ring of non-aromatic cyclic hydrocarbon group of 3 to 10 carbon atoms.

The nitrogen-containing aromatic heterocyclic ring contained in the specific amine compound is preferably an aromatic cyclic ring having at least one, preferably one to four, structures selected from the following formulas [20a], [20b] and [ More preferably 1 to 4 carbon atoms.

(31)

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

Specific examples of the nitrogen-containing aromatic heterocyclic ring include 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 pyrimidine ring, a pyrimidine ring, a pyrimidine ring, a pyrazine ring, a pyrimidine ring, a pyrimidine ring, a pyrimidine ring, a pyrimidine ring, a pyrimidine ring, An indole ring, a quinoxaline ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring, an acridine ring and the like. The carbon atom of these nitrogen-containing aromatic heterocyclic rings may have a substituent containing a hetero atom.

The specific amine compound more preferable is an amine compound represented by the following formula [6].

(32)

(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 heterocyclic ring)

In the formula [6], Y ₁ is not particularly limited as long as it is a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group.

The preferable Y ₁ in the formula [6] is a divalent organic group having one kind selected from an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms. Examples of the non-aromatic cyclic hydrocarbon group include the structures described above. More preferably an aliphatic hydrocarbon group having 1 to 15 carbon atoms such as 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 cyclododecane ring, a cyclotridecane ring, a cyclotetradecane ring, a norbornene ring, an adamantane ring and the like. And particularly preferably a linear or branched alkyl 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 preferably -O-, -NH-, -CO-O-, -O-CO- , -S (O) -CO-NH- , -NH-CO-, -CO-, -S-, 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 ring-shaped A hydrogen atom bonded to any carbon atom may be substituted with a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic hydrocarbon group, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a heterocyclic ring, A fluorine atom or a hydroxyl group.

Specific examples of the bivalent cyclic hydrocarbon group include benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, phenalene ring, cyclopropane ring, A cyclopentane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclododecane ring, a cyclododecane ring, a cyclododecane ring, a cyclotetradecane ring, a cyclotetradecane ring, A cyclohexadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cyclooctadecane ring, a cyclooctadecane ring, a cyclooctadecane ring, a cyclooctadecane ring, a cyclohexadecane ring, a tricyclohexane ring, a tricyclodecanoic ring, a bicycloheptane ring, a decahydronaphthalene ring, Nangrene, and adamantane rings.

Specific examples of the divalent heterocyclic ring include 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 thiadiazole ring, a pyridazine ring, a pyrazoline ring, a triazine ring, a pyrazolidine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, a benzimidazole ring, a chinolin ring, a phenanthrene 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 the formula [6] is a nitrogen-containing aromatic heterocyclic ring and is an aromatic ring containing at least one structure selected from the formulas [20a], [20b] and [20c] Type hydrocarbons. Specific examples thereof include the structures described above. Of these, preferred are 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, phthalazine ring are preferable.

The nitrogen-containing aromatic in view of the heterocyclic ring and ease of electrostatic interaction, such as salt formation, or hydrogen bonding of the carboxyl group of the specific polyimide, Y ₁ is a formula that is contained in Y ₂ [20a], formula [20b] or a group represented by the formula Is preferably bonded to a substituent which is not adjacent to [20c].

The carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y ₂ in formula [6] may have a halogen atom and / or a substituent of an organic group, and the organic group may be a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom You can.

Expression combination of preferred Y ₁ and Y ₂ according to [6], Y ₁ is a divalent having one type of compound selected from aliphatic hydrocarbon groups and non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms having 1 to 20 U equipment, Y ₂ is a pyrrole ring, utilizing 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, a benzoimidazole ring, a quinoxaline A ring, an azepine ring, a diazepine ring, a naphthyridine ring, a phenazine ring, and a phthalazine ring. The carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y ₂ may have a substituent group of a halogen atom and / or an organic group, and the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom.

A more preferable specific amine compound is an amine compound represented by the following formula [7].

(33)

(Wherein Y ₃ is a divalent aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group having 1 to 10 carbon atoms, Y ₄ is a single bond, -O-, -NH-, -S-, -SO ₂ - 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 the formula [7] is a divalent aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group having 1 to 10 carbon atoms. 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, A cyclopentadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cyclooctadecane ring, a cyclooctadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, A naphthalene ring, a nonadecane ring, a cyclohexanoic acid ring, a tricycloic acid ring, a tricyclodecanoic acid ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring, an adamantane ring and the like. More preferably a linear or branched alkylene group having 1 to 10 carbon atoms, 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 cyclododecane ring, a cyclotridecane ring, a cyclotetradecane ring, a norbornene ring or an adamantane ring. And particularly preferably a linear or branched alkylene group having 1 to 10 carbon atoms.

-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 - (CF 3) 2, -C -, -C (CH 3) 2 -, -Si (CH ₃ ) ₂ -, -O-Si (CH ₃ ) ₂ -, -Si (CH ₃ ) ₂ -O-, -O-Si (CH ₃ ) ₂ -O- and a divalent cyclic hydrocarbon group And a hydrogen atom bonded to any carbon atom may be substituted with a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic hydrocarbon group, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a heterocyclic ring, a fluorine atom Or a hydroxyl group. The cyclic hydrocarbon group and the heterocyclic ring referred to herein are the same as those defined for Y ₁ in the formula [6].

Y ₄ in the formula [7] is a single bond, -O-, -NH-, -S-, -SO ₂ - or a divalent organic group having 1 to 19 carbon atoms. The divalent organic group having 1 to 19 carbon atoms is a divalent organic group having 1 to 19 carbon atoms and may contain an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, or the like.

Specific examples of Y ₄ include 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-, a cyclopropane ring, a cyclobutane ring, And examples thereof include a cyclohexane ring, a cyclohexane ring, a cycloheptane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cyclododecane ring, a cyclododecane ring, a cyclotridecane ring, a cyclotetradecane ring, a cyclopentadecane ring, A cycloheptadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cyclooctadecane ring, a cyclononadecane ring, a cyclooctane ring, Ring, benzene ring, naphthalene ring, tetrahydronaphthalene A heterocyclic ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, an imidazole ring, an imidazole ring, an imidazole ring, A pyrimidine ring, a pyrazoline ring, a pyrazoline ring, an isoquinoline ring, a carbazole ring, a pyridine ring, a thiadiazole ring, a pyridazine ring, a triazine ring, a pyrazolidine ring, a triazole ring, A benzothiazole ring, a phenothiazine ring, an oxadiazole ring, an acridine ring, an oxazole ring, a piperazine ring, a piperidine ring, a pyrrolidine ring, a pyrrolidine ring, A ring, a dioxane ring, a morpholine ring and the like.

And Y ₄ may contain two or more kinds thereof. As specific examples of these two or more species,

And the like.

Y ₅ in the formula [7] is a nitrogen-containing aromatic heterocyclic ring and is the same as the definition of Y _{2 in} the formula [6], and therefore, Y ₅ is the same as defined in Y ₂ . Specific examples thereof include the same structure as Y ₂ described above. Of these, preferred are pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, benzoimidazole ring, quinoxaline ring, An azepine ring, a diazepine ring, a naphthyridine ring, a phenazine ring, or a phthalazine ring are preferable.

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 Is preferably bonded to a carbon atom not adjacent to [20c].

The carbon atom of the nitrogen-containing aromatic heterocyclic ring represented by Y &lt; ₅ &gt; in the formula [7] may have a halogen atom and / or a substituent group of an organic group and the organic group may contain a hetero atom such as an oxygen atom, You can.

Preferred combinations of Y _3, Y ₄ and Y ₅ in the formula [7], Y ₃ is straight-chain having 1 to 10 carbon atoms or a branched alkylene group, a cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring , A cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cyclododecane ring, a cyclododecane ring, a cyclotridecane ring, a cyclotetradecane ring, a norbornene ring or an adamantane ring, Y ₄ A straight chain or branched alkylene group having 1 to 10 carbon atoms,

A cyclopentane ring, a cyclopentane ring, a cyclopentane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cyclododecane ring, a cyclododecane ring, a norbornene ring, A heterocyclic ring, a phenanthrene ring, or a phenalene ring, Y ₅ is a pyrrole ring, an imidazole ring, a pyrazole ring, a benzene ring, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an azulene ring, an indene ring, a fluorene ring, A pyrimidine ring, a pyrimidine ring, a pyridazine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, a benzimidazole ring, a quinoxaline ring, Or a phthalazine ring. The carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y &lt; ₅ &gt; may have a substituent group of a halogen atom and / or an organic group, and the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom.

A more preferable combination of Y ₃ , Y ₄ and Y _{5 in} the formula [7] is that Y ₃ is a linear or branched alkylene group having 1 to 5 carbon atoms, a cyclopropane ring, a cyclobutane ring and a cyclopentane ring, A cyclic heptane ring, a norbornene ring or an adamantane ring, Y ₄ is a single bond, a linear or branched alkylene group having 1 to 5 carbon atoms,

A cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring, an adamantane ring, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an azulene ring, an indene ring, a fluorene ring Wherein 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, an anthracene ring, a phenanthrene ring, Benzimidazole ring, benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, naphthyridine ring, phenazine ring, or phthalazine ring. The carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y &lt; ₅ &gt; may have a substituent group of a halogen atom and / or an organic group, and the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom.

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

A cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring, an adamantane ring, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, a fluorene ring or an anthracene ring, Y _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 benzoimidazole ring. The carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y &lt; ₅ &gt; may have a substituent group of a halogen atom and / or an organic group, and the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom.

A particularly preferable combination of Y ₃ , Y ₄ and Y _{5 in} the formula [7] is that Y ₃ is a linear or branched alkylene group having 1 to 5 carbon atoms, a cyclobutane ring or a cyclohexane ring, Y ₄ is a single bond -O-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -CH (OH) -, a benzene ring, a naphthalene ring, a fluorene ring and an anthracene ring, Y &lt; ₅ &gt; is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring or a pyrimidine ring. The carbon atom of the nitrogen-containing aromatic heterocyclic ring of Y &lt; ₅ &gt; may have a substituent group of a halogen atom and / or an organic group, and the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom.

Specific examples of the specific amine compound used in the present invention include M1 to M156.

(34)

(35)

(36)

(37)

(38)

[Chemical Formula 39]

More preferred compounds include M6 to M8, M10, M16 to M21, M31 to M36, M40 to M45, M47 to M57, M59 to M63, M68, M69, M72 to M82, M95 to M98, M100 to M103, M125, M128 to M137, M139 to M143, and M149 to M156. More preferably, 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 to M136, M139, M140, M143, M150, M152 to M156.

&Lt; Liquid crystal alignment treatment agent &

The liquid crystal alignment treatment agent of the present invention is usually obtained by mixing the specific polyimide as the component (A) and the specific amine compound as the component (B) in an organic solvent. The specific polyimide to be mixed and the specific amine compound may be each one kind or a plurality of kinds may be used in combination.

As a mixing method, a reaction solution (a solution of a specific polyimide) in which a polyamic acid which is a precursor of a specific polyimide is imidized may be used. Usually, a solution obtained by dissolving a specific polyimide powder obtained by purification in an organic solvent And a specific amine compound is added to the solution. The organic solvent to be used at this time is not particularly limited as long as it is a solvent for dissolving the specific polyimide. Specific examples of such organic solvents are given below.

Examples of the solvent include N, N'-dimethylformamide, N, N'-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, , N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, gamma -butyrolactone, 1,3-dimethyl-imidazolidinone, dipentene, Methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone and the like . These solvents may be used by mixing two or more kinds.

Or may be heated for the purpose of accelerating dissolution of a specific polyimide when the specific polyimide is dissolved in an organic solvent. If the heating temperature is excessively high, the molecular weight of the polyimide may be lowered, so that the temperature is preferably 30 to 100 ° C. The concentration of the specific polyimide solution is not particularly limited, but is easily mixed with a specific amine compound. Therefore, the specific polyimide concentration in the solution is preferably from 1 to 20 mass%, more preferably from 3 to 15 mass% Particularly preferably 3 to 10% by mass.

The specific amine compound may be directly added to the solution of the specific polyimide described above, but it is preferable to add the solution after adjusting the concentration of the solution to 0.1 to 10% by mass with an appropriate solvent. Examples of the solvent include a solvent for the specific polyimide described above.

It is preferable to heat the specific polyimide and the specific amine compound after mixing them in an organic solvent. By heating, the ratio of the specific amine compound already bonded to the specific polyimide in the state of the liquid crystal alignment treatment agent is increased, and the charge can be moved more efficiently when the liquid crystal alignment film is formed. The temperature in the case of heating after mixing is preferably 10 to 100 占 폚, more preferably 20 to 80 占 폚.

The amount of the specific amine compound to be used is preferably 0.01 to 2 moles per one mole of the carboxyl group contained in the specific polyimide because the effect of the present invention is efficiently obtained and the stability of the liquid crystal alignment treatment agent is not impaired, More preferably 0.05 to 1 mole times, and particularly preferably 0.08 to 0.8 mole times.

The liquid crystal alignment treatment agent of the present invention may contain, as other components, other than the specific polyimide or specific amine compound, a solvent or a compound which improves the uniformity of the film thickness or the surface smoothness when the liquid crystal alignment treatment agent is applied, And the like. The other components may be added during the mixing of the specific polyimide and the specific amine compound, or may be added to the mixed solution later.

Specific examples of the solvent for improving the uniformity of the film thickness and the surface smoothness include the following.

Examples of the solvent include isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl But are not limited to, carbitol acetate, carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, Monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl Ether, dipropylene glycol monopro Methyl 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 Propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, lactic acid, methyl lactate, isobutylene, amyl acetate, butyl butylate, butyl ether, diisobutyl ketone, methylcyclohexene, Ethyl acetate, methyl acetate, ethyl acetate, n-butyl acetate, propyleneglycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, Methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2 - propanol, 1-phenoxy 2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- -Ethoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, n-propyl lactate, n-butyl lactate, and lactic acid diisobutyl ester.

These solvents may be used alone or in combination. When such a solvent is used, it is preferably 5 to 80 mass%, and more preferably 20 to 60 mass%, of the total solvent contained in the liquid crystal alignment treatment agent.

Examples of the compound that improves film thickness uniformity and surface smoothness include fluorinated surfactants, silicone surfactants, and nonionic surfactants.

More specifically, for example, EFTA EF301, EF303 and EF352 (manufactured by TOKEM PRODUCTS CO., LTD.), Megafac F171, F173 and R-30 (manufactured by Dainippon Ink and Chemicals, Inc.), FLORAD FC430 and FC431 manufactured by Sumitomo 3M ), Asahi Guard AG710, Surplon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.). The proportion of these surfactants to be used is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass based on 100 parts by mass of the component (A) contained in the liquid crystal alignment treatment agent.

Specific examples of the compound which improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy (2-aminoethyl) Aminopropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N- Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- 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-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl ) Cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane and the like.

When a compound for improving adhesion to these substrates is used, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the specific polyimide component contained in the liquid crystal alignment treatment agent. If the amount is less than 0.1 part by mass, the effect of improving the adhesion can not be expected, and if it is more than 30 parts by mass, the alignment property of the liquid crystal may be deteriorated.

The liquid crystal alignment treatment agent of the present invention may contain a polymer component other than the specific polyimide or a dielectric substance or a conductive substance for the purpose of changing electric characteristics such as dielectric constant and conductivity of the liquid crystal alignment film as long as the effects of the present invention are not impaired. , And further a crosslinkable compound for the purpose of increasing the hardness and density of the film when it is made into a liquid crystal alignment film may be added.

The concentration of the solid content in the liquid crystal alignment treatment agent of the present invention can be appropriately changed according to the thickness of the desired liquid crystal alignment film. In order to form a coating film without defects and to obtain an appropriate film thickness as the liquid crystal alignment film, To 20% by mass, and more preferably 2% by mass to 10% by mass.

<Liquid Crystal Alignment Film / Liquid Crystal Display Device>

The liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film without rubbing treatment, light irradiation or the like, or without orientation treatment in a vertical alignment application, after being applied and baked on a substrate. At this time, the substrate to be used is not particularly limited as long as it is a substrate having high transparency, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used. It is preferable to use a substrate on which an ITO electrode or the like for liquid crystal driving is formed from the viewpoint of simplifying the process. In the reflection type liquid crystal display device, if it is only one substrate, it may be opaque such as a silicon wafer. In this case, a material that reflects light such as aluminum may be used as the electrode in this case.

The method of applying the liquid crystal alignment treatment agent is not particularly limited, but is generally industrially carried out by screen printing, offset printing, flexographic printing, inkjet or the like. Examples of other application methods include dip, roll coater, slit coater, and spinner, and these may be used depending on the purpose.

After the liquid crystal alignment treatment agent is applied onto the substrate, the solvent can be evaporated by heating means such as a hot plate at 50 to 300 ° C, preferably 80 to 250 ° C to form a coating film. When the thickness of the coated film after firing is too large, the power consumption of the liquid crystal display element is disadvantageously deteriorated. When the thickness is too thin, the reliability of the liquid crystal display element may be deteriorated. Therefore, the thickness is preferably 5 to 300 nm, more preferably 10 to 100 Nm. When the liquid crystal is horizontally oriented or tilted, the coated film after firing is treated by rubbing, polarized ultraviolet irradiation, or the like.

In the liquid crystal display element of the present invention, a substrate with a liquid crystal alignment film is obtained from the liquid crystal aligning agent of the present invention by the above-described technique, and then a liquid crystal cell is produced by a known method to obtain a liquid crystal display element.

For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, a spacer is dispersed on the liquid crystal alignment film of the one-side substrate, the liquid crystal alignment film surface is made inward, A method in which a liquid crystal is injected under reduced pressure and sealed, or a method in which a liquid crystal is dropped on the surface of a liquid crystal alignment film on which a spacer is dispersed, and then the substrate is sealed by sealing. The thickness of the spacer at this time is preferably 1 to 30 占 퐉, more preferably 2 to 10 占 퐉.

As described above, the liquid crystal display device manufactured using the liquid crystal alignment treatment agent of the present invention is excellent in reliability, and can be preferably used for a large-screen liquid crystal television with a large screen.

Example

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the interpretation of the present invention is not limited to these examples.

Explanation of the abbreviations used in this embodiment.

(Tetracarboxylic acid dianhydride)

CBDA: 1,2,3,4-Cyclobutane tetracarboxylic acid dianhydride

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

(40)

(Diamine)

DBA: 3,5-diaminobenzoic acid

PBCH5DAB: 1,3-diamino-4- {trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy}

BPCH5DAB: 1,3-diamino-4- {4- [4- (trans-4-n-pentylcyclohexyl) phenyl] phenoxy}

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

(41)

(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

(42)

(Comparative compound)

Py: Pyridine

AP: 3-aminopyridine

HA: Hexylamine

(43)

(Organic solvent)

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

&Lt; Measurement of molecular weight of polyimide &

The molecular weight of the polyimide in Synthesis Example was measured using a room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., a column (KD-803, KD-805) Respectively.

Column temperature: 50 ° C

Eluent: N, N'- dimethylformamide (lithium bromide as an additive-hydrate (LiBr · H ₂ O) is 30 m㏖ / ℓ, phosphoric acid anhydrous crystal (o- phosphoric acid) is 30 m㏖ / ℓ, tetrahydrofuran (THF) of 10 ml / l)

Flow rate: 1.0 ml / min

Standard samples for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight: about 9,000,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation; and polyethylene glycol (molecular weight about 12,000, 4,000, 1,000) manufactured by Polymer Laboratories.

&Lt; Measurement of imidization rate &

The imidization rate of the polyimide in the synthesis example was measured as follows. 20 mg of the polyimide powder was placed in an NMR sample tube (NMR sampling tube standard 5 manufactured by Kusano Scientific Co., Ltd.), 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d ₆ , 0.05% TMS mixture) was added, . This solution was subjected to proton NMR measurement at 500 MHz using an NMR measuring instrument (JNW-ECA500) manufactured by Nippon DATUM Co., The proton derived from the structure in which the imidation rate does not change before and after the imidation is determined as the reference proton and the proton peak integrated value derived from the NH group of the amic acid, which appears in the vicinity of 9.5 to 10.0 ppm, By using the following formula.

·x/y) × 100Imidization rate (%) = (1 -

X / y) x 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 integrated value derived from the NH group of amic acid, y is the peak integrated value of the reference proton,

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

&Lt; Calculation method of carboxyl group amount >

Was calculated by the method described above.

&Lt; Synthesis Example 1 &

BODA (14.11 g, 56.3 mmol), DBA (9.15 g, 60.1 mmol) and PBCH5DAB (6.53 g, 15.0 mmol) as a side chain diamine were mixed in NMP (740 g) and reacted at 80 ° C for 5 hours Then, CBDA (3.23 g, 16.5 mmol) and NMP (56.0 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution.

NMP was added to the polyamic acid solution (30.0 g) to dilute to 6 mass%, acetic anhydride (3.79 g) and pyridine (2.94 g) were added as an imidization catalyst and reacted at 80 ° C for 3 hours. The reaction solution was poured into methanol (408 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (A). The imidization ratio of the polyimide was 40%, the number average molecular weight was 17,300, and the weight average molecular weight was 46,800. The amount of the carboxyl group in the polyimide is 2.00 relative to the repeating unit.

&Lt; Synthesis Example 2 &

BPCH5DAB (2.38 g, 5.54 mmol) as a side chain diamine was mixed in NMP (26.2 g) and reacted at 80 ° C for 5 hours Then, CBDA (1.19 g, 6.07 mmol) and NMP (20.0 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution.

NMP was added to the polyamic acid solution (30.0 g) to dilute to 6 mass%, acetic anhydride (3.74 g) and pyridine (2.89 g) were added as an imidization catalyst and reacted at 80 ° C for 3 hours. The reaction solution was poured into methanol (410 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (B). The imidization ratio of the polyimide was 41%, the number average molecular weight was 18,300, and the weight average molecular weight was 49,200. The amount of the carboxyl group in the polyimide is 1.98 relative to the repeating unit.

&Lt; Synthesis Example 3 &

BODA (33.87 g, 135.3 mmol), DBA (19.23 g, 126.3 mmol) and PBCH5DAB (23.53 g, 54.1 mmol) as a side chain diamine were mixed in NMP (185.0 g) and reacted at 80 ° C for 5 hours Then, CBDA (8.62 g, 43.9 mmol) and NMP (155.8 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution.

To this polyamic acid solution (100.2 g) was added NMP and diluted to 6 mass%. Acetic anhydride (10.82 g) and pyridine (8.34 g) were added as an imidization catalyst and reacted at 80 ° C for 3 hours. The reaction solution was poured into methanol (1300 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (C). The imidization ratio of the polyimide was 45%, the number average molecular weight was 19,100, and the weight average molecular weight was 50,800. The amount of the carboxyl group in the polyimide is 1.80 relative to the repeating unit.

&Lt; Synthesis Example 4 &

NMP was added to the polyamide acid solution (251.2 g) obtained in Synthesis Example 3 to dilute it to 6 mass%, acetic anhydride (53.91 g) and pyridine (41.8 g) were added as an imidation catalyst, Lt; / RTI &gt; This reaction solution was poured into methanol (3200 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (D). The imidization ratio of the polyimide was 80%, the number average molecular weight was 15,200, and the weight average molecular weight was 45,500. The amount of the carboxyl group in the polyimide is 1.10 relative to the repeating unit.

&Lt; Synthesis Example 5 &

PCH7DAB (6.09 g, 16 mmol) as a side chain diamine was mixed in NMP (131 g) and reacted at 80 占 폚 for 5 hours to obtain a mixture of BODA (15.0 g, 60 mmol), DBA (9.74 g, Then, CBDA (3.88 g, 19.8 mmol) and NMP (30 g) were added and reacted at 40 ° C for 3 hours to obtain a polyamic acid solution.

To this polyamic acid solution (10.0 g) was added NMP and diluted to 6 mass%. Acetic anhydride (1.27 g) and pyridine (0.98 g) were added as an imidization catalyst and reacted at 80 ° C for 3 hours. The reaction solution was poured into methanol (140 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (E). The imidization ratio of the polyimide was 46%, the number average molecular weight was 20,200, and the weight average molecular weight was 62,500. The amount of the carboxyl group in the polyimide is 1.88 relative to the repeating unit.

&Lt; Synthesis Example 6 &

PCH7DAB (152.2 g, 400 mmol) as a side chain diamine was mixed in NMP (1290 g) and reacted at 80 占 폚 for 5 hours to obtain a mixture of BODA (150.1 g, 600 mmol), DBA (60.9 g, Then, CBDA (38.8 g, 198 mmol) and NMP (320 g) were added and reacted at 40 ° C for 3 hours to obtain a polyamic acid solution.

To this polyamic acid solution (101.2 g) was added NMP and diluted to 6 mass%. Acetic anhydride (21.3 g) and pyridine (16.5 g) were added as an imidization catalyst and reacted at 90 ° C for 3 hours. This reaction solution was poured into methanol (13005 ml), and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (F). The imidization ratio of the polyimide was 81%, the number average molecular weight was 20,400, and the weight average molecular weight was 63,000. The amount of the carboxyl group in the polyimide is 0.88 relative to the repeating unit.

&Lt; Example 1 >

NMP (12.0 g) was added to the polyimide powder (A) (2.12 g) obtained in Synthesis Example 1 and dissolved by stirring at 70 占 폚 for 40 hours. To this solution was added a 10 mass% NMP solution of 3-AMP (0.64 g, 0.064 g as 3-AMP), NMP (4.41 g) and BCS (15.9 g) and the mixture was stirred at 50 캜 for 15 hours, To obtain a treating agent [1]. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.

&Lt; Production of liquid crystal cell &

The liquid crystal alignment treatment agent [1] obtained above was spin-coated on the ITO surface of the substrate with 3 × 4 cm ITO electrodes and baked at 80 ° C. for 5 minutes and at 210 ° C. in a hot air circulating oven for 1 hour to obtain a film having a thickness of 100 nm A polyimide coating film was prepared.

This substrate with a liquid crystal alignment film was rubbed under the conditions of a roll diameter of 120 mm, a rubbing apparatus of rayon cloth at a revolution of 300 rpm, a roll advancing speed of 20 mm / sec, and a press-in amount of 0.3 mm to obtain a substrate with a liquid crystal alignment film.

Two sheets of the liquid crystal alignment film-attached substrates were prepared, and a bead spacer of 6 mu m was dispersed on the liquid crystal alignment film side of the sheet, and then a sealant was printed thereon. One other substrate was laminated so that the liquid crystal alignment film surface was inward and the rubbing direction was opposite, and then the sealant was cured to prepare an empty cell. A nematic liquid crystal cell with an anti-parallel orientation was obtained by vacuum injection into this open cell.

&Lt; Evaluation of Pretilt Angle >

The pre-tilt angle of the liquid crystal cell prepared above was measured at room temperature using a pre-tilt angle measuring apparatus (model: PAS-301 manufactured by ELSICON). The results are shown in Table 1 below.

The liquid crystal cell produced in the same manner as above was observed by a polarization microscope except that the rubbing treatment was not performed, and it was confirmed that the liquid crystal was uniformly vertically aligned.

&Lt; Evaluation of voltage holding ratio &

A voltage of 4 V was applied to the liquid crystal cell after the pretilt angle measurement at a temperature of 80 캜 for 60 탆 and the voltage after 16.67 ㎳ and after 1667 ㎳ was measured to calculate the voltage holding ratio. The results are shown in Table 2 below.

&Lt; Evaluation of relaxation of residual charge >

After applying a DC voltage of 10 V for 30 minutes to the liquid crystal cell after the measurement of the voltage holding ratio and short-circuiting for 1 second, the potential generated in the liquid crystal cell was measured for 1,800 seconds. Then, residual charges after 50 seconds and after 1000 seconds were measured. A 6254-type liquid crystal physical property evaluation device manufactured by Toyo Technica Co., Ltd. was used for the measurement. The results are shown in Table 3 below.

&Lt; Evaluation after leaving at high temperature >

After the measurement of the residual charge, the liquid crystal cell was left in a high-temperature bath set at 100 DEG C for 7 days, and then the voltage holding ratio and the residual charge were measured. The results are shown in Tables 2 and 3 below.

&Lt; Evaluation of voltage holding ratio after ultraviolet irradiation >

A voltage of 4 V was applied to the liquid crystal cell prepared above at a temperature of 80 占 폚 for 60 占 퐏 and the voltage after 16.67 ms and 1667 ms was measured to calculate the voltage holding ratio. After measurement, the liquid crystal cell was irradiated with ultraviolet rays having an irradiation dose of 10 J / cm 2 at 365 nm by a tabletop UV curing device (HCT3 B28 HEX-1 (manufactured by Sensen special light source) Were measured. The results are shown in Table 4 below.

&Lt; Example 2 >

NMP (11.4 g) was added to the polyimide powder (B) (2.02 g) obtained in Synthesis Example 2 and dissolved by stirring at 70 占 폚 for 40 hours. To this solution was added a 10 mass% NMP solution of 3-AMP (0.61 g, 0.061 g as 3-AMP), NMP (4.21 g) and BCS (15.2 g), and the mixture was stirred at 50 캜 for 15 hours, To obtain a treating agent [2]. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.

Using the obtained liquid crystal alignment treatment agent [2], a liquid crystal cell was prepared in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 1 below. The liquid crystal cell produced in the same manner as in Example 1 except that the rubbing treatment was not performed was observed with a polarization microscope, and it was confirmed that the liquid crystal was uniformly vertically aligned.

Using the liquid crystal cell prepared in the same manner as in Example 1, evaluation of the voltage holding ratio, evaluation of relaxation of residual charge, evaluation after leaving at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Tables 2, 3 and 4 below.

&Lt; Example 3 >

NMP (11.4 g) was added to the polyimide powder (C) (2.01 g) obtained in Synthesis Example 3 and dissolved by stirring at 70 占 폚 for 40 hours. To this solution was added a 10 mass% NMP solution of 3-AMP (0.60 g, 0.060 g as 3-AMP), NMP (4.18 g) and BCS (15.1 g) To obtain a treating agent [3]. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.

Using the obtained liquid crystal alignment treatment agent [3], a liquid crystal cell was prepared in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 1 below. The liquid crystal cell produced in the same manner as in Example 1 except that the rubbing treatment was not performed was observed with a polarization microscope, and it was confirmed that the liquid crystal was uniformly vertically aligned.

Using the liquid crystal cell prepared in the same manner as in Example 1, evaluation of the voltage holding ratio, evaluation of relaxation of residual charge, evaluation after leaving at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Tables 2, 3 and 4 below.

<Example 4>

NMP (11.2 g) was added to the polyimide powder (C) (1.98 g) obtained in Synthesis Example 3 and dissolved by stirring at 70 占 폚 for 40 hours. To this solution was added a 10 mass% NMP solution of 3-AMP (1.98 g, 0.20 g as 3-AMP), NMP (2.87 g) and BCS (14.9 g) and stirred at 50 占 폚 for 15 hours, To obtain a treating agent [4]. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.

Using the obtained liquid crystal alignment treatment agent [4], a liquid crystal cell was prepared in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 1 below. The liquid crystal cell produced in the same manner as in Example 1 except that the rubbing treatment was not performed was observed with a polarization microscope, and it was confirmed that the liquid crystal was uniformly vertically aligned.

Using the liquid crystal cell prepared in the same manner as in Example 1, evaluation of the voltage holding ratio, evaluation of relaxation of residual charge, evaluation after leaving at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Tables 2, 3 and 4 below.

&Lt; Example 5 >

NMP (11.3 g) was added to the polyimide powder (D) (2.00 g) obtained in Synthesis Example 4 and dissolved by stirring at 70 占 폚 for 40 hours. To this solution was added a 10 mass% NMP solution of 3-AMP (0.60 g, 0.060 g as 3-AMP), NMP (4.16 g) and BCS (15.0 g) and the mixture was stirred at 50 占 폚 for 15 hours, To obtain a treating agent [5]. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.

Using the obtained liquid crystal alignment treatment agent [5], a liquid crystal cell was prepared in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 1 below. The liquid crystal cell produced in the same manner as in Example 1 except that the rubbing treatment was not performed was observed with a polarization microscope, and it was confirmed that the liquid crystal was uniformly vertically aligned.

Using the liquid crystal cell prepared in the same manner as in Example 1, evaluation of the voltage holding ratio, evaluation of relaxation of residual charge, evaluation after leaving at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Tables 2, 3 and 4 below.

&Lt; Example 6 >

NMP (11.3 g) was added to the polyimide powder (D) (2.00 g) obtained in Synthesis Example 4 and dissolved by stirring at 70 占 폚 for 40 hours. To this solution was added a 10 mass% NMP solution of 3-AMP (1.00 g, 0.10 g as 3-AMP), NMP (3.80 g) and BCS (15.0 g) and the mixture was stirred at 50 占 폚 for 15 hours, To obtain a treating agent [6]. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.

Using the obtained liquid crystal alignment treatment agent [6], a liquid crystal cell was prepared in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 1 below. The liquid crystal cell produced in the same manner as in Example 1 except that the rubbing treatment was not performed was observed with a polarization microscope, and it was confirmed that the liquid crystal was uniformly vertically aligned.

Using the liquid crystal cell prepared in the same manner as in Example 1, evaluation of the voltage holding ratio, evaluation of relaxation of residual charge, evaluation after leaving at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Tables 2, 3 and 4 below.

&Lt; Example 7 >

NMP (12.5 g) was added to the polyimide powder (D) (2.21 g) obtained in Synthesis Example 4 and dissolved by stirring at 70 占 폚 for 40 hours. To this solution was added a 10 mass% NMP solution of 3-AMP (1.55 g, 0.16 g as 3-AMP), NMP (3.80 g) and BCS (16.6 g) and stirred at 50 캜 for 15 hours, A treating agent [7] was obtained. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.

Using the obtained liquid crystal alignment treatment agent [7], a liquid crystal cell was prepared in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 1 below. The liquid crystal cell produced in the same manner as in Example 1 except that the rubbing treatment was not performed was observed with a polarization microscope, and it was confirmed that the liquid crystal was uniformly vertically aligned.

Using the liquid crystal cell prepared in the same manner as in Example 1, evaluation of the voltage holding ratio, evaluation of relaxation of residual charge, evaluation after leaving at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Tables 2, 3 and 4 below.

&Lt; Example 8 >

NMP (11.3 g) was added to the polyimide powder (D) (2.00 g) obtained in Synthesis Example 4 and dissolved by stirring at 70 占 폚 for 40 hours. To this solution was added a 10 mass% NMP solution of 3-AMP (2.00 g, 0.20 g as 3-AMP), NMP (2.90 g) and BCS (15.0 g) and the mixture was stirred at 50 캜 for 15 hours, A treating agent [8] was obtained. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.

Using the obtained liquid crystal alignment treatment agent [8], a liquid crystal cell was prepared in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 1 below. The liquid crystal cell produced in the same manner as in Example 1 except that the rubbing treatment was not performed was observed with a polarization microscope, and it was confirmed that the liquid crystal was uniformly vertically aligned.

Using the liquid crystal cell prepared in the same manner as in Example 1, evaluation of the voltage holding ratio, evaluation of relaxation of residual charge, evaluation after leaving at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Tables 2, 3 and 4 below.

&Lt; Example 9 >

NMP (11.5 g) was added to the polyimide powder (D) (2.03 g) obtained in Synthesis Example 4 and dissolved by stirring at 70 占 폚 for 40 hours. To this solution was added a 10 mass% NMP solution of 4-AMP (1.42 g, 0.14 g as 4-AMP), NMP (3.49 g) and BCS (15.2 g) and stirred at 50 占 폚 for 15 hours, To obtain a treating agent [9]. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.

Using the obtained liquid crystal alignment treatment agent [9], a liquid crystal cell was prepared in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 1 below. The liquid crystal cell produced in the same manner as in Example 1 except that the rubbing treatment was not performed was observed with a polarization microscope, and it was confirmed that the liquid crystal was uniformly vertically aligned.

Using the liquid crystal cell prepared in the same manner as in Example 1, evaluation of the voltage holding ratio, evaluation of relaxation of residual charge, evaluation after leaving at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Tables 2, 3 and 4 below.

&Lt; Example 10 >

NMP (11.3 g) was added to the polyimide powder (D) (2.00 g) obtained in Synthesis Example 4 and dissolved by stirring at 70 占 폚 for 40 hours. To this solution was added a 10 mass% NMP solution of AEP (1.40 g) (0.14 g as AEP), NMP (3.44 g) and BCS (15.0 g) and the mixture was stirred at 50 ° C for 15 hours, &Lt; / RTI &gt; No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.

Using the obtained liquid crystal alignment treatment agent [10], a liquid crystal cell was prepared in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 1 below. The liquid crystal cell produced in the same manner as in Example 1 except that the rubbing treatment was not performed was observed with a polarization microscope, and it was confirmed that the liquid crystal was uniformly vertically aligned.

Using the liquid crystal cell prepared in the same manner as in Example 1, evaluation of the voltage holding ratio, evaluation of relaxation of residual charge, evaluation after leaving at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Tables 2, 3 and 4 below.

&Lt; Example 11 >

NMP (11.4 g) was added to the polyimide powder (D) (2.00 g) obtained in Synthesis Example 4 and dissolved by stirring at 70 占 폚 for 40 hours. The liquid crystal alignment treatment agent [11] was added to this solution by adding an API 10 mass% NMP solution (1.40 g) (0.14 g as API), NMP (3.44 g) and BCS (15.1 g) &Lt; / RTI &gt; No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.

Using the obtained liquid crystal alignment treatment agent [11], a liquid crystal cell was prepared in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 1 below. The liquid crystal cell produced in the same manner as in Example 1 except that the rubbing treatment was not performed was observed with a polarization microscope, and it was confirmed that the liquid crystal was uniformly vertically aligned.

Using the liquid crystal cell prepared in the same manner as in Example 1, evaluation of the voltage holding ratio, evaluation of relaxation of residual charge, evaluation after leaving at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Tables 2, 3 and 4 below.

&Lt; Example 12 >

NMP (11.6 g) was added to the polyimide powder (D) (2.04 g) obtained in Synthesis Example 4 and dissolved by stirring at 70 占 폚 for 40 hours. To this solution was added a 10 mass% NMP solution of 2-AMMP (1.43 g, 0.14 g as 2-AMMP), NMP (3.51 g) and BCS (15.3 g) and the mixture was stirred at 50 占 폚 for 15 hours, To obtain a treating agent [12]. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.

Using the obtained liquid crystal alignment treatment agent [12], a liquid crystal cell was prepared in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 1 below. The liquid crystal cell produced in the same manner as in Example 1 except that the rubbing treatment was not performed was observed with a polarization microscope, and it was confirmed that the liquid crystal was uniformly vertically aligned.

Using the liquid crystal cell prepared in the same manner as in Example 1, evaluation of the voltage holding ratio, evaluation of relaxation of residual charge, evaluation after leaving at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Tables 2, 3 and 4 below.

&Lt; Comparative Example 1 &

NMP (11.9 g) was added to the polyimide powder (C) (2.10 g) obtained in Synthesis Example 3 and dissolved by stirring at 70 占 폚 for 40 hours. NMP (4.94 g) and BCS (15.9 g) were added to this solution and stirred at 50 占 폚 for 15 hours to obtain a liquid crystal alignment treatment agent [13]. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.

Using the obtained liquid crystal alignment treatment agent [13], a liquid crystal cell was prepared in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 1 below. The liquid crystal cell produced in the same manner as in Example 1 except that the rubbing treatment was not performed was observed with a polarization microscope, and it was confirmed that the liquid crystal was uniformly vertically aligned.

Using the liquid crystal cell prepared in the same manner as in Example 1, evaluation of the voltage holding ratio, evaluation of relaxation of residual charge, evaluation after leaving at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Tables 2, 3 and 4 below.

&Lt; Comparative Example 2 &

NMP (11.8 g) was added to the polyimide powder (D) (2.08 g) obtained in Synthetic Example 4 and dissolved by stirring at 70 占 폚 for 40 hours. NMP (4.89 g) and BCS (15.6 g) were added to this solution, and the mixture was stirred at 50 占 폚 for 15 hours to obtain a liquid crystal alignment treating agent [14]. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.

Using the obtained liquid crystal alignment treatment agent [14], a liquid crystal cell was prepared in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 1 below. The liquid crystal cell produced in the same manner as in Example 1 except that the rubbing treatment was not performed was observed with a polarization microscope, and it was confirmed that the liquid crystal was uniformly vertically aligned.

Using the liquid crystal cell prepared in the same manner as in Example 1, evaluation of the voltage holding ratio, evaluation of relaxation of residual charge, evaluation after leaving at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Tables 2, 3 and 4 below.

&Lt; Comparative Example 3 &

NMP (11.3 g) was added to the polyimide powder (E) (2.00 g) obtained in Synthesis Example 5 and dissolved by stirring at 70 占 폚 for 40 hours. NMP (4.71 g) and BCS (15.0 g) were added to this solution and stirred at 50 占 폚 for 15 hours to obtain a liquid crystal alignment treatment agent [15]. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.

Using the obtained liquid crystal alignment treatment agent [15], a liquid crystal cell was prepared in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 1 below. The liquid crystal cell produced in the same manner as in Example 1 except that the rubbing treatment was not performed was observed with a polarization microscope, and it was confirmed that the liquid crystal was uniformly vertically aligned.

Using the liquid crystal cell prepared in the same manner as in Example 1, evaluation of the voltage holding ratio, evaluation of relaxation of residual charge, evaluation after leaving at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Tables 2, 3 and 4 below.

&Lt; Comparative Example 4 &

NMP (11.3 g) was added to the polyimide powder (D) (2.00 g) obtained in Synthesis Example 4 and dissolved by stirring at 70 占 폚 for 40 hours. To this solution was added a 10 mass% NMP solution (1.40 g) of Py (0.14 g as Py), NMP (3.44 g) and BCS (15.2 g), and stirred at 50 ° C for 15 hours to obtain a liquid crystal alignment treatment agent [ &Lt; / RTI &gt; No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.

Using the obtained liquid crystal alignment treatment agent [16], a liquid crystal cell was prepared in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 1 below. The liquid crystal cell produced in the same manner as in Example 1 except that the rubbing treatment was not performed was observed with a polarization microscope, and it was confirmed that the liquid crystal was uniformly vertically aligned.

Using the liquid crystal cell prepared in the same manner as in Example 1, evaluation of the voltage holding ratio, evaluation of relaxation of residual charge, evaluation after leaving at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Tables 2, 3 and 4 below.

&Lt; Comparative Example 5 &

NMP (11.2 g) was added to the polyimide powder (D) (1.98 g) obtained in Synthesis Example 4 and dissolved by stirring at 70 占 폚 for 40 hours. To this solution was added a 10 mass% NMP solution of AP (1.39 g) (0.14 g as AP), NMP (3.41 g) and BCS (14.9 g) and stirred at 50 ° C for 15 hours to obtain a liquid crystal alignment treatment agent [ &Lt; / RTI &gt; No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.

Using the obtained liquid crystal alignment treatment agent [17], a liquid crystal cell was prepared in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 1 below. The liquid crystal cell produced in the same manner as in Example 1 except that the rubbing treatment was not performed was observed with a polarization microscope, and it was confirmed that the liquid crystal was uniformly vertically aligned.

Using the liquid crystal cell prepared in the same manner as in Example 1, evaluation of the voltage holding ratio, evaluation of relaxation of residual charge, evaluation after leaving at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Tables 2, 3 and 4 below.

&Lt; Comparative Example 6 >

NMP (11.3 g) was added to the polyimide powder (D) (2.00 g) obtained in Synthesis Example 4 and dissolved by stirring at 70 占 폚 for 40 hours. To this solution was added a 10 mass% NMP solution (1.40 g) of HA (0.14 g as HA), NMP (3.44 g) and BCS (15.0 g), and the mixture was stirred at 50 占 폚 for 15 hours, &Lt; / RTI &gt; No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.

Using the obtained liquid crystal alignment treatment agent [18], a liquid crystal cell was prepared in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 1 below. The liquid crystal cell produced in the same manner as in Example 1 except that the rubbing treatment was not performed was observed with a polarization microscope, and it was confirmed that the liquid crystal was uniformly vertically aligned.

Using the liquid crystal cell prepared in the same manner as in Example 1, evaluation of the voltage holding ratio, evaluation of relaxation of residual charge, evaluation after leaving at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Tables 2, 3 and 4 below.

&Lt; Comparative Example 7 &

NMP (11.4 g) was added to the polyimide powder (E) (2.01 g) obtained in Synthesis Example 5 and dissolved by stirring at 70 占 폚 for 40 hours. To this solution was added a 10 mass% NMP solution of 3-AMP (0.60 g, 0.06 g as 3-AMP), NMP (4.18 g) and BCS (15.1 g) and the mixture was stirred at 50 占 폚 for 15 hours, To obtain a treating agent [21]. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.

Using the obtained liquid crystal alignment treatment agent [19], a liquid crystal cell was prepared in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 1 below. The liquid crystal cell produced in the same manner as in Example 1 except that the rubbing treatment was not performed was observed with a polarizing microscope, and as a result, the liquid crystal was not vertically aligned.

Using the liquid crystal cell prepared in the same manner as in Example 1, evaluation of the voltage holding ratio, evaluation of relaxation of residual charge, evaluation after leaving at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Tables 2, 3 and 4 below.

&Lt; Comparative Example 8 >

NMP (11.4 g) was added to the polyimide powder (F) (2.01 g) obtained in Synthesis Example 6 and dissolved by stirring at 70 占 폚 for 40 hours. To this solution was added a 10 mass% NMP solution of 3-AMP (1.41 g, 0.14 g as 3-AMP), NMP (3.46 g) and BCS (15.1 g) and the mixture was stirred at 50 占 폚 for 15 hours, To obtain a treating agent [20]. No abnormality such as turbidity or precipitation was observed in this liquid crystal alignment treatment agent, and it was confirmed that the resin component was uniformly dissolved.

Using the obtained liquid crystal alignment treatment agent [20], a liquid crystal cell was prepared in the same manner as in Example 1, and the pretilt angle was evaluated. The results are shown in Table 1 below. The liquid crystal cell produced in the same manner as in Example 1 except that the rubbing treatment was not performed was observed with a polarization microscope, and it was confirmed that the liquid crystal was uniformly vertically aligned.

Using the liquid crystal cell prepared in the same manner as in Example 1, evaluation of the voltage holding ratio, evaluation of relaxation of residual charge, evaluation after leaving at high temperature, and evaluation of voltage holding ratio after ultraviolet irradiation were performed. The results are shown in Tables 2, 3 and 4 below.

Industrial availability

The liquid crystal alignment treatment agent of the present invention has a property of increasing the pretilt angle of the liquid crystal when it is a liquid crystal alignment film and can orient the liquid crystal vertically even with a small use ratio, Precipitation does not occur well. In addition to these characteristics, it is also possible to provide a liquid crystal display device capable of suppressing the decrease of the voltage holding ratio even after the backlight has been exposed to the ultraviolet ray for a long time, the charge retained rate is high and the charge accumulated by the DC voltage is quickly alleviated even after long- It is possible to provide a liquid crystal alignment treatment agent capable of obtaining an alignment film. As a result, it is useful for TN devices, STN devices, TFT liquid crystal devices, and vertically aligned liquid crystal display devices.

The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2007-340890 filed on December 28, 2007 are hereby incorporated herein by reference as the disclosure of the present invention.

Claims (13)

A liquid crystal alignment treatment agent characterized by containing the following component (A) and the following component (B).
Component (A): Polyimide having a carboxyl group in the molecule of the polymer in which a polyamic acid having a structural formula of a repeating unit represented by the following formula [1] is imidized.
(B): An amine compound having one primary amino group and one nitrogen-containing aromatic heterocyclic ring in the molecule, and the primary amino group is bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group.
[Chemical Formula 1]

(In the formula [1], R ₁ is a tetravalent organic group and R ₂ is a divalent organic group containing the following formula [2]
(2)

(Wherein X ₁ is 1,4-phenylene or 1,4-cyclohexylene, X ₂ is an alkyl group having 3 to 12 carbon atoms, an alkoxy group having 3 to 12 carbon atoms, a fluorine atom having 3 to 12 carbon atoms A fluoroalkyl group or a fluoroalkoxy group having 3 to 12 carbon atoms) The method according to claim 1,
X ₂ in the formula [2] is an alkyl group of 3 to 6 carbon atoms, an alkoxy group of 3 to 6 carbon atoms, a fluoroalkyl group of 3 to 6 carbon atoms, or a fluoroalkoxy group of 3 to 6 carbon atoms. The method according to claim 1,
A liquid crystal alignment treatment agent wherein R ₂ in the formula [1] is a divalent organic group containing the following formula [3].
(3)

(In the formula [3], n is an integer of 2 to 11, and the cis-trans isomer of 1,4-cyclohexylene is a trans isomer) The method according to claim 1,
A liquid crystal alignment treating agent wherein R ₂ in the formula [1] is a divalent organic group containing the following formula [4].
[Chemical Formula 4]

(In the formula [4], n is an integer of 2 to 11, and the cis-trans isomer of 1,4-cyclohexylene is a trans isomer) 5. The method according to any one of claims 1 to 4,
(A) is a polymer in which a polyamic acid having a structural formula of a repeating unit represented by the formula [1] is imidized, and the amount of the carboxyl group contained in the polymer is 0.1 to 3 Orientation treatment agent. 5. The method according to any one of claims 1 to 4,
(A) is a polymer obtained by imidizing a polyamic acid having a structural formula in which a part of the repeating unit of the repeating unit represented by the formula [1] has a unit represented by the following formula [5], and the polymer Is 0.1 to 3 in terms of the average value of the repeating units of the 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 and R ₄ has a carboxyl group) 5. The method according to any one of claims 1 to 4,
(B) is an amine compound represented by the following formula [6].
[Chemical Formula 6]

(In the formula [6], 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 heterocyclic ring) 8. The method of claim 7,
(B) is an amine compound represented by the following formula [7].
(7)

(Wherein Y ₃ represents a divalent aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group having 1 to 10 carbon atoms, Y ₄ represents a single bond, -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) 9. The method of claim 8,
And the component (B) is an amine compound comprising a combination of Y ₃ , Y ₄ and Y ₅ of the formula [7] selected from the groups or rings described below, respectively.
Y ₃ represents 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, a cyclooctane ring, A cyclopentadecane ring, a cycloheptadecane ring, a cycloheptadecane ring, a cyclooctadecane ring, a cyclododecane ring, a cyclotetradecane ring, a cyclotetradecane ring, a cyclotetradecane ring, a cyclopentadecane ring, a cyclohexadecane ring, Is selected from the group consisting of a decane ring, a cyclohexanoic acid ring, a tricycloicoic acid ring, a tricyclodecanoic acid ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring and an adamantane ring;
Y ₄ represents a single bond, -O-, -NH-, -S-, -SO ₂ -, a hydrocarbon group having 1 to 19 carbon atoms, -CO-O-, -O-CO-, -CO- _{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-, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, A cycloheptadecane ring, a cycloheptadecane ring, a cyclohexadecane ring, a cycloheptadecane ring, a cyclohexadecane ring, a cyclohexadecane ring, a cycloheptadecane ring, a cyclohexadecane ring, a cyclohexadecane ring, a cyclohexadecane ring, A cyclohexadecane ring, a cyclohexadecane ring, a cyclooctadecane ring, a cyclooctadecane ring, a cyclononadecane ring, a cyclooctanoic ring, a tricycloicoic acid ring, a tricyclodecanoic acid ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring, Naphthalene ring, tetrahydronaphthalene ring, azul ring A thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazine ring, an imidazole ring, an imidazole ring, an oxazole ring, a thiazole ring, A carbazole ring, a pyridine ring, a thiadiazole ring, a pyridazine ring, a triazine ring, a pyrazolidine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, a benzoimidazole ring, An oxadiazole ring, an oxidine ring, a piperazine ring, a piperidine ring, a dioxane ring, an oxadiazole ring, an oxadiazole ring, an oxadiazole ring, an oxidine ring, an oxazole ring, a piperazine ring, A ring and a morpholine ring;
Y ₅ represents 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 carbazole ring, A pyrimidine ring, a pyrazoline ring, a pyrazoline ring, a triazine ring, a pyrazolidine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, a benzimidazole ring, a chinoline ring, a phenanthroline ring, A ring selected from the group consisting of a ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring and an acridine ring. 5. The method according to any one of claims 1 to 4,
(B) is contained in an amount of 0.01 to 2 molar times relative to 1 mol of the carboxyl group of the polyimide of the component (A). 5. The method according to any one of claims 1 to 4,
A liquid crystal alignment treatment agent obtained by mixing a polyimide of component (A) and an organic solvent containing an amine compound of component (B) under heating. A liquid crystal alignment film obtained from the liquid crystal alignment treatment agent according to any one of claims 1 to 4. A liquid crystal display element having the liquid crystal alignment film according to claim 12.