KR102465496B1 - A liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element - Google Patents

Abstract

The diamine containing the tetracarboxylic acid which contains tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride represented by following formula (1) in the ratio of 10:90-90:10, and the diamine represented by following formula (2) The at least 1 sort(s) of polymer and organic solvent chosen from the polyamic acid obtained using and the imidation polymer of this polyamic acid are contained, The liquid crystal aligning agent characterized by the above-mentioned.

Description

A liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element

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

DESCRIPTION OF RELATED ART Conventionally, liquid crystal devices are widely used as display parts, such as a personal computer, a mobile phone, and a television receiver. The liquid crystal device includes, for example, a liquid crystal layer sandwiched between an element substrate and a color filter substrate, a pixel electrode and a common electrode for applying an electric field to the liquid crystal layer, an alignment film for controlling alignment of liquid crystal molecules in the liquid crystal layer, and a pixel A thin film transistor (TFT) that switches an electric signal supplied to the electrode is provided. As a driving method of liquid crystal molecules, a vertical electric field system such as a TN system and a VA system, and a transverse electric field system such as an IPS system and a fringe field switching (hereinafter referred to as FFS) system are known (for example, Patent Document 1).

On the other hand, in recent years, since the economical efficiency in a production process is also very important for a liquid crystal display element and an organic electroluminescent element, the recycle use of a device substrate is calculated|required. That is, after forming a liquid crystal aligning film from a liquid crystal aligning agent, when a defect occurs by inspecting alignment, etc., it is required to be able to easily perform a rework process of removing the liquid crystal aligning film from the substrate and recovering the substrate, have. However, the liquid crystal aligning film obtained from the liquid crystal aligning agent proposed conventionally was made to insolubilize in the organic solvent etc. rather after a post-baking, and was aimed at reducing film|membrane decrease. Moreover, even if it applies the structure of the liquid crystal aligning agent which rework property has been examined so far to the structure of the liquid crystal aligning agent for transverse electric fields as it is, it cannot necessarily be said that the desired objective is achieved, In a liquid crystal aligning agent, it is again It was necessary to actually evaluate the quality of reworkability and to review the optimal composition structure.

Japanese Laid-Open Patent Publication No. 2013-167782

An object of this invention is to provide the liquid crystal aligning agent from which the liquid crystal aligning film excellent in rework property is obtained.

As a result of the present inventors earnestly examining in order to solve the said subject, the polyamic acid and polyamic acid obtained from the tetracarboxylic acid containing specific aromatic tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride, and diamine which have a specific structure By using the imidation polymer of a mixed acid, it discovered that the liquid crystal aligning film excellent in rework property was obtained, and completed this invention.

In this way, this invention is based on said knowledge, and has the following summary.

1. A tetracarboxylic dianhydride component containing tetracarboxylic dianhydride represented by the following formula (1) and an aliphatic tetracarboxylic dianhydride in a ratio of 10:90 to 90:10, and the following formula (2) The polyamic acid obtained using the diamine component containing the diamine shown, and the at least 1 sort(s) of polymer chosen from the imidation polymer of this polyamic acid, and an organic solvent are contained, The liquid crystal aligning agent characterized by the above-mentioned.

[Formula 1]

(in formula (1), i is 0 or 1, X is a single bond, an ether bond, carbonyl, an ester bond, phenylene, a linear alkylene having 1 to 20 carbon atoms, 2 to 20 carbon atoms a group consisting of branched alkylene, cyclic alkylene having 3 to 12 carbon atoms, sulfonyl, amide bond, or a combination thereof, wherein alkylene having 1 to 20 carbon atoms is selected from an ester bond and an ether bond may be interrupted by a bond, and the carbon atoms of phenylene and alkylene may be substituted with one or more identical or different substituents selected from a halogen atom, a cyano group, an alkyl group, a haloalkyl group, an alkoxy group and a haloalkoxy group. do.

In formula (2), Y ₁ is a divalent organic group having at least one structure selected from the group consisting of an amino group, an imino group, and a nitrogen-containing heterocyclic ring, or an amino group in which a thermal leaving group is substituted on a nitrogen atom. , an imino group and a divalent organic group selected from a nitrogen-containing heterocyclic ring, and B ₁ and B ₂ are each independently a hydrogen atom, or an optionally substituted alkyl group, alkenyl group, or alkynyl group having 1 to 10 carbon atoms.)

2. 10-100 mol% in said tetracarboxylic dianhydride component is tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride represented by said Formula (1), Liquid crystal aligning agent of 1 characterized by the above-mentioned .

3. 10-100 mol% in the said diamine component is diamine of Formula (2), The liquid crystal aligning agent of 1 or 2 characterized by the above-mentioned.

4. Liquid crystal aligning agent in any one of 1-3 whose Y< ₁ > in Formula (2) is at least 1 type chosen from the structure of following formula (YD-1) - (YD-5).

[Formula 2]

(In the formula (YD-1), A ₁ is a nitrogen atom-containing heterocyclic ring having 3 to 15 carbon atoms, and Z ₁ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. In -2), W ₁ is a hydrocarbon group having 1 to 10 carbon atoms, A ₂ is a monovalent organic group having 3 to 15 carbon atoms having a nitrogen atom-containing heterocyclic ring, or di substituted with an aliphatic group having 1 to 6 carbon atoms. In the formula (YD-3), W ₂ is a divalent organic group having 6 to 15 carbon atoms and having 1 to 2 benzene rings, and W ₃ is alkylene or biphenyl having 2 to 5 carbon atoms. Ren, Z ₂ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a benzene ring, or a thermally leaving group, and a is an integer of 0 to 1. In the formula (YD-4), A ₃ is 3 to 15 carbon atoms. In the formula (YD-5), A ₄ is a nitrogen atom-containing heterocyclic ring having 3 to 15 carbon atoms, and W ₅ is an alkylene having 2 to 5 carbon atoms.)

5. A ₁ , A ₂ , A ₃ , and A ₄ described in formulas (YD-1), (YD-2), (YD-4), and (YD-5) are pyrrolidine, pyrrole, imi The liquid crystal aligning agent of 4 which is at least 1 type chosen from the group which consists of dazole, pyrazole, oxazole, thiazole, piperidine, piperazine, pyridine, pyrazine, indole, benzimidazole, quinoline, and isoquinoline.

6. Y ₁ in formula (2) is at least one selected from the group consisting of divalent organic groups having structures of the following formulas (YD-6) to (YD-21), 1 to 5 The liquid crystal aligning agent as described in.

[Formula 3]

(In formula (YD-17), h is an integer of 1-3, and in formulas (YD-14) and (YD-21), j is an integer of 1-3.)

7. Y ₁ in formula (2) is at least one selected from the group consisting of divalent organic groups having the structures of formulas (YD-14) and (YD-18), in 6 The liquid crystal aligning agent described.

8. Liquid crystal aligning agent in any one of 1-7 whose tetracarboxylic dianhydride represented by said Formula (1) is 3,3',4,4'- biphenyl tetracarboxylic dianhydride.

9. The liquid crystal according to any one of 1 to 8, wherein the aliphatic tetracarboxylic dianhydride is bicyclo[3.3.0]octane 2,4,6,8-tetracarboxylic acid 2,4:6,8 dianhydride. Orienting agent.

10. The liquid crystal aligning film obtained by apply|coating and baking the liquid crystal aligning agent in any one of 1-9.

11. A liquid crystal display element provided with the liquid crystal aligning film of 10.

The liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention is excellent in rework property.

The liquid crystal aligning agent of this invention contains the diamine containing the tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride containing tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride which are represented by following formula (1), and diamine represented by following formula (2) It is characterized by containing the at least 1 sort(s) of polymer and organic solvent chosen from the polyamic acid obtained using a component, and the imidation polymer of this polyamic acid.

[Formula 4]

In the formula (1), i is 0 or 1, X is a single bond, an ether bond, carbonyl, an ester bond, phenylene, a linear alkylene having 1 to 20 carbon atoms, 2 to 20 carbon atoms a group consisting of branched alkylene, cyclic alkylene having 3 to 12 carbon atoms, sulfonyl, an amide bond, or a combination thereof, wherein the alkylene having 1 to 20 carbon atoms is selected from an ester bond and an ether bond It may be interrupted by a bond, and the carbon atoms of phenylene and alkylene may be substituted with one or more identical or different substituents selected from a halogen atom, a cyano group, an alkyl group, a haloalkyl group, an alkoxy group and a haloalkoxy group. .

In formula (2), Y ₁ is a divalent organic group having at least one structure selected from the group consisting of an amino group, an imino group, and a nitrogen-containing heterocyclic ring, or an amino group in which a thermal leaving group is substituted on a nitrogen atom. , an imino group and a divalent organic group selected from a nitrogen-containing heterocyclic ring, and B ₁ and B ₂ are each independently a hydrogen atom or an optionally substituted C1-C10 alkyl group, alkenyl group, or alkynyl group.

Hereinafter, each constituent requirement will be described in detail.

<Tetracarboxylic acid dianhydride component>

Although the following compounds are mentioned as tetracarboxylic dianhydride represented by said Formula (1), It is not limited to these.

[Formula 5]

(In the formula, q represents an integer of 1 to 20.)

Among the tetracarboxylic dianhydrides represented by these formula (1), since the rework property improvement effect is high, in Formula (1), i is 1 tetracarboxylic dianhydride, ie, two or more benzene rings. The tetracarboxylic dianhydride which has is preferable, and (1-2)-(1-11) is preferable in the said specific example, and since it contains a biphenyl structure and has a rigid structure, Formula ( 3,3',4,4'-biphenyltetracarboxylic dianhydride represented by 1-5) is particularly preferable.

As a specific aliphatic tetracarboxylic dianhydride used by this invention, the tetracarboxylic dianhydride represented by following formula (3) is mentioned.

[Formula 6]

In the formula, X ₁ is any of the following (X-1) to (X-28).

[Formula 7]

[Formula 8]

[Formula 9]

In the formula (X-1), R ₃ to R ₆ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, more preferably a hydrogen atom or a methyl group.

Among the above, (X-1) to (X-20) are preferable in that they do not contain an aromatic moiety, and (X-10) is most preferable in that it is particularly difficult to thermally imidate.

When the total amount of tetracarboxylic dianhydride and aliphatic dianhydride represented by Formula (1) in the whole tetracarboxylic dianhydride component used for manufacture of (A) component of this invention is too small, this invention No effect is obtained. Therefore, as for the total amount of tetracarboxylic dianhydride and aliphatic dianhydride represented by Formula (1), 10-100 mol% is preferable with respect to 1 mol of all the tetracarboxylic dianhydride, More preferably, 50- It is 100 mol%, More preferably, it is 80-100 mol%.

Although the content ratio of the tetracarboxylic dianhydride and aliphatic acid dianhydride represented by Formula (1) is a ratio used as 10:90-90:10, Preferably it is 20:80-80:20, More preferably, it is 40 It is a ratio used as :60-60:40, Especially preferably, it is 46:54-54:46, It is most preferable that it is substantially equivalent.

Although tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride represented by Formula (1) may each be used independently and may use plurality together, tetracarboxylic acid represented by Formula (1) also in that case As for dianhydride and aliphatic tetracarboxylic dianhydride, it is preferable to use said preferable quantity as a total.

The polyamic acid contained in the liquid crystal aligning agent of this invention uses tetracarboxylic dianhydride represented by following formula (4) other than tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride represented by Formula (1), also be

[Formula 10]

In Formula (4), X is a tetravalent organic group, and the structure is not specifically limited. If a specific example is given, the structure of following formula (X-31) - (X-36) is mentioned.

[Formula 11]

<Diamine component>

The diamine component used for manufacture of the liquid crystal aligning agent of this invention contains the diamine of said Formula (2). In formula (2), Y ₁ is a divalent organic group having at least one structure selected from the group consisting of an amino group, an imino group, and a nitrogen-containing heterocyclic ring, or an amino group in which a thermal leaving group is substituted on a nitrogen atom. , an imino group and a divalent organic group selected from a nitrogen-containing heterocyclic ring, and B ₁ and B ₂ are each independently a hydrogen atom or an optionally substituted C1-C10 alkyl group, alkenyl group, or alkynyl group.

Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group, a decyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the alkenyl group include those in which one or more CH-CH structures present in the above alkyl group are substituted with a C=C structure, and more specifically, a vinyl group, an allyl group, a 1-propenyl group, and an isopropane group. phenyl group, 2-butenyl group, 1,3-butadienyl group, 2-pentenyl group, 2-hexenyl group, cyclopropenyl group, cyclopentenyl group, cyclohexenyl group, etc. are mentioned. Examples of the alkynyl group include those in which one or more CH ₂ -CH ₂ structures present in the above alkyl group are substituted with a C≡C structure, and more specifically, an ethynyl group, 1-propynyl group, 2-propynyl group and the like.

As long as said alkyl group, an alkenyl group, and an alkynyl group are C1-C10 as a whole, they may have a substituent, Furthermore, they may form ring structure with a substituent. In addition, the formation of a ring structure by a substituent means that substituents or a substituent and a part of parental skeleton couple|bond to form a ring structure.

Examples of the substituent include a halogen group, a hydroxyl group, a thiol group, a nitro group, an aryl group, an organooxy group, an organothio group, an organosilyl group, an acyl group, an ester group, a thioester group, a phosphoric acid ester group, an amide group, an alkyl group. , an alkenyl group, and an alkynyl group are mentioned.

A fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned as a halogen group which is a substituent.

A phenyl group is mentioned as an aryl group which is a substituent. The other substituent mentioned above may further substitute by this aryl group.

As an organooxy group which is a substituent, the structure represented by O-R can be shown. This R may be the same or different, and can illustrate the alkyl group, alkenyl group, alkynyl group, aryl group, etc. which were mentioned above. These R may be further substituted with the above-mentioned substituents. Specific examples of the alkyloxy group include a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, and an octyloxy group.

As an organothio group which is a substituent, the structure represented by -S-R can be shown. As this R, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, etc. which were mentioned above can be illustrated. These R may be further substituted with the above-mentioned substituents. Specific examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, and an octylthio group.

As an organosilyl group which is a substituent, the structure represented by -Si-(R) ₃ can be shown. This R may be the same or different, and can illustrate the alkyl group, alkenyl group, alkynyl group, aryl group, etc. which were mentioned above. These R may be further substituted with the above-mentioned substituents. Specific examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a tripentylsilyl group, a trihexylsilyl group, a pentyldimethylsilyl group, and a hexyldimethylsilyl group. can

As an acyl group which is a substituent, the structure represented by -C(O)-R can be shown. As this R, the above-mentioned alkyl group, alkenyl group, aryl group, etc. can be illustrated. These R may be further substituted with the above-mentioned substituents. Specific examples of the acyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, and a benzoyl group.

As an ester group which is a substituent, the structure represented by -C(O)O-R or -OC(O)-R can be shown. As this R, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, etc. which were mentioned above can be illustrated. These R may be further substituted with the above-mentioned substituents.

As a thioester group which is a substituent, the structure represented by -C(S)O-R or -OC(S)-R can be shown. As this R, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, etc. which were mentioned above can be illustrated. These R may be further substituted with the above-mentioned substituents.

As a phosphate ester group which is a substituent, the structure represented by -OP(O)-(OR) ₂ can be shown. This R may be the same or different, and can illustrate the alkyl group, alkenyl group, alkynyl group, aryl group, etc. which were mentioned above. These R may be further substituted with the above-mentioned substituents.

As an amide group as a substituent, a structure represented by -C(O)NH ₂ , or -C(O)NHR, -NHC(O)R, -C(O)N(R) ₂ , -NRC(O)R can represent This R may be the same or different, and can illustrate the alkyl group, alkenyl group, alkynyl group, aryl group, etc. which were mentioned above. These R may be further substituted with the above-mentioned substituents.

As an aryl group which is a substituent, the thing similar to the above-mentioned aryl group is mentioned. The other substituent mentioned above may further substitute by this aryl group.

As an alkyl group which is a substituent, the thing similar to the above-mentioned alkyl group is mentioned. The other substituent mentioned above may further substitute by this alkyl group.

As an alkenyl group which is a substituent, the thing similar to the above-mentioned alkenyl group is mentioned. The other substituent mentioned above may further substitute by this alkenyl group.

As an alkynyl group which is a substituent, the thing similar to the above-mentioned alkynyl group is mentioned. The other substituent mentioned above may further substitute by this alkynyl group.

In general, since introducing a bulky structure may reduce the reactivity of the amino group and the liquid crystal orientation, as B ₁ and B ₂ , a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent is more preferable. and a hydrogen atom, a methyl group or an ethyl group is particularly preferable.

As a structure of Y< ₁ > in Formula (2), it has at least 1 type of structure selected from the group which consists of an amino group, an imino group, and a nitrogen-containing heterocyclic ring, or the amino group which the thermal leaving property group substituted on the nitrogen atom. , if it has at least 1 type of structure chosen from an imino group and a nitrogen-containing heterocyclic ring, the structure will not be specifically limited. Darely, if the specific example is exemplified, a divalent compound having at least one structure selected from the group consisting of an amino group, an imino group, and a nitrogen-containing heterocyclic ring represented by the following formulas (YD-1) to (YD-5) and organic groups.

[Formula 12]

In the formula (YD-1), A ₁ is a nitrogen atom-containing heterocyclic ring having 3 to 15 carbon atoms, and Z ₁ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.

In the formula (YD-2), W ₁ is a hydrocarbon group having 1 to 10 carbon atoms, and A ₂ is a monovalent organic group having 3 to 15 carbon atoms having a nitrogen atom-containing heterocyclic ring, or an aliphatic group having 1 to 6 carbon atoms. It is a substituted disubstituted amino group.

In the formula (YD-3), W ₂ is a divalent organic group having 6 to 15 carbon atoms and having 1 to 2 benzene rings, W ₃ is alkylene or biphenylene having 2 to 5 carbon atoms, and Z ₂ is a hydrogen atom, a C1-C5 alkyl group, a benzene ring, or a thermal-leaving group, and a is the integer of 0-1.

In formula (YD-4), _A3 is a C3-C15 nitrogen atom containing heterocyclic ring.

In the formula (YD-5), A ₄ is a nitrogen atom-containing heterocyclic ring having 3 to 15 carbon atoms, and W ₅ is an alkylene having 2 to 5 carbon atoms.)

A heterocyclic ring containing 3 to 15 carbon atoms of A ₁ , A ₂ , A ₃ , and A ₄ of formulas (YD-1), (YD-2), (YD-4), and (YD-5) is not particularly limited as long as it has a known structure. Among them, pyrrolidine, pyrrole, imidazole, pyrazole, oxazole, thiazole, piperidine, piperazine, pyridine, pyrazine, indole, benzimidazole, quinoline, isoquinoline, and carbazole are mentioned, Piperazine, piperidine, indole, benzimidazole, imidazole, carbazole, and pyridine are more preferred.

Further, the thermal leaving group may be a substituent that does not detach at room temperature and is replaced with a hydrogen atom by detaching when the alignment film is fired, and specific examples thereof include a tert-butoxycarbonyl group and a 9-fluorenylmethoxycarbonyl group.

Moreover, as a specific example of Y2 in Formula (2), the _divalent organic group which has a nitrogen atom represented by following formula (YD-6) - (YD-52) is mentioned, Charge accumulation by alternating current drive , the formulas (YD-14) to (YD-21) are more preferable, and (YD-14) and (YD-18) are particularly preferable.

[Formula 13]

In formulas (YD-14) and (YD-21), j is an integer of 0-3.

[Formula 14]

In formulas (YD-24), (YD-25), (YD-28) and (YD-29), j is an integer of 0 to 3. In formula (YD-17), h is an integer of 1-3.

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

(In formula (YD-50), m and n are each an integer of 1 to 11, and m+n is an integer of 2 to 12.)

It is preferable that the ratio of the diamine represented by Formula (2) in the polyamic acid of this invention and the imidation polymer of a polyamic acid is 10-100 mol% with respect to 1 mol of all diamines, More preferably, 30-100 It is mol%, More preferably, it is 50-100 mol%.

Although the polyamic acid which is (A) component of this invention, and the diamine represented by Formula (2) in the imidation polymer of a polyamic acid may be used independently and may use plurality together, also in that case, it is Formula (2) As for the diamine shown, it is preferable to use said preferable quantity as a total.

The polyamic acid contained in the liquid crystal aligning agent of this invention may use the diamine represented by following formula (5) other than the diamine represented by said Formula (2). Y ₂ in following formula (5) is a divalent organic group, The structure is not specifically limited, Two or more types may be mixed. If the specific example is dared to show, the following (Y-1) - (Y-49) and (Y-57) - (Y-97) will be mentioned.

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

[Formula 25]

[Formula 26]

[Formula 27]

[Formula 28]

[Formula 29]

In the imidation polymer of the polyamic acid and polyamic acid which are (A) component which are contained in the liquid crystal aligning agent of this invention WHEREIN: Since the effect of this invention may be impaired when the ratio of the diamine represented by Formula (5) increases, , which is not preferable. Therefore, as for the ratio of the diamine represented by Formula (5), 0-90 mol% is preferable with respect to 1 mol of all diamines, More preferably, it is 0-50 mol%, More preferably, it is 0-20 mol%.

<Method for producing polyamic acid>

The polyamic acid which is a polyimide precursor used for this invention is compoundable by the method shown below.

Specifically, tetracarboxylic dianhydride and diamine are synthesized by reacting them in the presence of an organic solvent at -20 to 150°C, preferably 0 to 70°C, for 30 minutes to 24 hours, preferably for 1 to 12 hours. can do.

The organic solvent used for the above reaction is preferably N,N-dimethylformamide, N-methyl-2-pyrrolidone, γ-butyrolactone or the like from the viewpoint of monomer and polymer solubility, and these are one or two types. You may mix and use the above.

From a viewpoint that precipitation of a polymer does not occur easily and a high molecular weight body is easy to obtain, 1-30 mass % is preferable, and, as for the density|concentration of a polymer, 5-20 mass % is more preferable.

The polyamic acid obtained by making it above can precipitate and collect|recover a polymer by inject|pouring into a poor solvent, stirring a reaction solution well. Moreover, after performing precipitation several times and washing|cleaning with a poor solvent, the powder of the refined polyamic acid can be obtained by normal temperature or heat-drying. Although the poor solvent is not specifically limited, Water, methanol, ethanol, 2-propanol, hexane, a butyl cellosolve, acetone, toluene, etc. are mentioned, Water, methanol, ethanol, 2-propanol, etc. are preferable.

<Method for producing polyimide>

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

When manufacturing a polyimide from a polyamic acid, chemical imidation which adds a catalyst to the solution of the said polyamic acid obtained by reaction of a diamine component and tetracarboxylic dianhydride is simple. Chemical imidization is preferable because the imidation reaction proceeds at a relatively low temperature, and the molecular weight reduction of the polymer does not easily occur during the imidization process.

Chemical imidation can be performed by stirring the polymer to be imidated in presence of a basic catalyst and an acid anhydride in an organic solvent. As the organic solvent, a solvent used in the polymerization reaction described above may be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferable because it has a suitable basicity for advancing the reaction. Further, examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, acetic anhydride is preferably used because purification after completion of the reaction becomes easy.

The temperature at the time of imidation reaction is -20-140 degreeC, Preferably it is 0-100 degreeC, and can carry out reaction time in 1-100 hours. The quantity of a basic catalyst is 0.5-30 times mole of a polyamic-acid group, Preferably it is 2-20 times mole, and the quantity of an acid anhydride is 1-50 times mole of a polyamic-acid group, Preferably it is 3-30 times mole. The imidation rate of the polymer obtained is controllable by adjusting a catalyst amount, temperature, and reaction time.

Since the catalyst etc. which added remain in the solution after imidation reaction of a polyamic acid, by the means described below, it collect|recovers the obtained imidation polymer, melt|dissolves again in an organic solvent, and setting it as the liquid crystal aligning agent of this invention desirable.

A polymer can be deposited by injecting|pouring into a poor solvent, stirring well the solution of the polyimide obtained by making it above. Precipitation is carried out several times, washed with a poor solvent, and then dried at room temperature or heat to obtain a purified polymer powder.

Although the said poor solvent is not specifically limited, Methanol, 2-propanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, etc. are mentioned, Methanol, ethanol , 2-propanol, acetone, and the like are preferred.

<Liquid crystal aligning agent>

The liquid crystal aligning agent used for this invention has the form of the solution which the polymer component melt|dissolved in the organic solvent. As for the molecular weight of a polymer, 2,000-500,000 are preferable in a weight average molecular weight, More preferably, it is 5,000-300,000, More preferably, it is 10,000-100,000. Moreover, the number average molecular weight becomes like this. Preferably it is 1,000-250,000, More preferably, it is 2,500-150,000, More preferably, it is 5,000-50,000.

Although the density|concentration of the polymer of the liquid crystal aligning agent used for this invention can be suitably changed according to thickness setting of the coating film to be formed, it is preferable that it is 1 mass % or more from the point of forming a uniform and defect-free coating film, and the solution It is preferable to set it as 10 mass % or less from the point of storage stability. A particularly preferable concentration of the polymer is 2 to 8% by mass.

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

Moreover, as for the organic solvent contained in a liquid crystal aligning agent, it is common to use the mixed solvent which used together the solvent which improves the applicability|paintability at the time of apply|coating a liquid crystal aligning agent, and the surface smoothness of a coating film in addition to the above solvents, Also in the liquid crystal aligning agent of this invention, such a mixed solvent is used suitably. Although the specific example of the organic solvent used together is given below, it is not limited to these examples.

For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, Isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1- Butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methyl Cyclohexanol, 3-methylcyclohexanol, 2,6-dimethyl-4-heptanol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1 ,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, diisopropyl ether , dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol Diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-hep Tanone, 4-heptanone, 2,6-dimethyl-4-heptanone, 4,6-dimethyl-2-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2- Ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2-(methoxymethoxy) ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2 -(Hexyloxy)ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monobutyl ether, 1-(butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-( 2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, Acetate propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-methoxy methyl propionate, 3-ethoxy ethyl propionate, 3-ethoxy methyl ethyl ethyl propionate, 3-methoxy ethyl propionate, 3-ethoxy propionic acid, 3- Methoxypropionic acid, 3-methoxypropionate propyl, 3-methoxypropionate butyl, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester, the following formula [D-1 ] to [D-3], and the like.

[Formula 30]

In formula [D- ¹ ], D1 represents a C1-C3 alkyl group, in formula [D- ² ], D2 represents a C1-C3 alkyl group, In formula [D- ³ ], D3 represents a C1-C4 alkyl group.

Among them, preferred combinations of solvents include N-methyl-2-pyrrolidone, γ-butyrolactone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone and propylene glycol monobutyl ether. Butyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone and diethylene Glycoldiethyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether, 2,6-dimethyl-4-heptanone, N-methyl-2-pyrrolidone and γ- Butyrolactone, propylene glycol monobutyl ether, diisopropyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and 2,6-dimethyl-4-heptanol, N- methyl-2-pyrrolidone, γ-butyrolactone, dipropylene glycol dimethyl ether, and the like. The kind and content of such a solvent are suitably selected according to the coating apparatus of a liquid crystal aligning agent, application|coating conditions, application|coating environment, etc.

Moreover, in order to raise the mechanical strength of a film|membrane, you may add the following additives to the liquid crystal aligning agent of this invention.

[Formula 31]

[Formula 32]

It is preferable that these additives are 0.1-30 mass parts with respect to 100 mass parts of the polymer component contained in a liquid crystal aligning agent. If it is less than 0.1 mass part, an effect cannot be anticipated, and since the orientation of a liquid crystal is reduced when it exceeds 30 mass parts, More preferably, it is 0.5-20 mass parts.

In the liquid crystal aligning agent of this invention, as long as it is a range in which the effect of this invention is not impaired other than the above, polymers other than the polymer of this invention, the objective of changing electrical properties, such as dielectric constant and electroconductivity of a liquid crystal aligning film, or a conductive material , a silane coupling agent for the purpose of improving the adhesion between the liquid crystal aligning film and the substrate, the crosslinking compound for the purpose of increasing the hardness and density of the film when it is used as a liquid crystal aligning film, and furthermore, the imidization of the polyamic acid when firing the coating film efficiently You may add an imidation accelerator etc. for the purpose of advancing.

<Liquid crystal alignment film>

<Method for Producing Liquid Crystal Alignment Film>

The liquid crystal aligning film of this invention is a film|membrane obtained by apply|coating the said liquid crystal aligning agent to a board|substrate, drying and baking. The substrate on which the liquid crystal aligning agent of the present invention is applied is not particularly limited as long as it is a substrate with high transparency, and plastic substrates such as glass substrates, silicon nitride substrates, acrylic substrates, and polycarbonate substrates can be used, and ITO electrodes for driving liquid crystals It is preferable from the point of simplification of a process to use the board|substrate on which the back was formed. In the reflective liquid crystal display element, an opaque material such as a silicon wafer can be used as long as it is only a one-side substrate, and a material that reflects light such as aluminum can also be used for the electrode in this case.

As a coating method of the liquid crystal aligning agent of this invention, the spin coating method, the printing method, the inkjet method, etc. are mentioned. The drying after apply|coating the liquid crystal aligning agent of this invention, and a baking process can select arbitrary temperature and time. Usually, in order to fully remove the organic solvent to contain, it is made to dry at 50 degreeC - 120 degreeC for 1 minute - 10 minutes, and after that, it bakes at 150 degreeC - 300 degreeC for 5 minutes - 120 minutes. Although the thickness of the coating film after baking is not specifically limited, Since reliability of a liquid crystal display element may fall when it is too thin, it is 5-300 nm, Preferably it is 10-200 nm.

As a method of orientating the obtained liquid crystal aligning film, the rubbing method, the photo-alignment processing method, etc. are mentioned. The rubbing process can be performed using an existing rubbing apparatus. Cotton, nylon, rayon, etc. are mentioned as a material of the rubbing cloth at this time. Generally, as conditions of a rubbing process, the conditions of 300-2000 rpm rotation speed, 5-100 mm/s of feed rates, and 0.1-1.0 mm of press-in amount are used. Thereafter, residues generated by rubbing are removed by ultrasonic cleaning using pure water, alcohol, or the like.

As a specific example of the photo-alignment treatment method, the coating film surface is irradiated with radiation deflected in a certain direction, and in some cases, further heat treatment at a temperature of 150 to 250 ° C., a method of imparting liquid crystal alignment ability. can be heard As the radiation, ultraviolet rays and visible rays having a wavelength of 100 nm to 800 nm can be used. Among these, the ultraviolet-ray which has a wavelength of 100 nm - 400 nm is preferable, and what has a wavelength of 200 nm - 400 nm is especially preferable. Moreover, in order to improve liquid-crystal orientation, you may irradiate a radiation, heating a coating-film board|substrate at 50-250 degreeC. 1-10,000 mJ/cm<2> is preferable and, as for the irradiation amount of the said radiation, 100-5,000 mJ/cm<2> is especially preferable. The liquid crystal aligning film manufactured as mentioned above can orientate a liquid crystal molecule stably in a fixed direction.

Since higher anisotropy can be provided so that the extinction ratio of the polarized ultraviolet-ray is high, it is preferable. Specifically, 10:1 or more is preferable and, as for the extinction ratio of the ultraviolet-ray polarized on a straight line, 20:1 or more is more preferable.

In the above, the film irradiated with polarized radiation may be contact-treated with a solvent containing at least one selected from water and organic solvents.

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

From the viewpoint of versatility and safety, at least one selected from the group consisting of water, 2-propanol, 1-methoxy-2-propanol and ethyl lactate is more preferable. Water, 2-propanol, and a mixed solvent of water and 2-propanol are particularly preferred.

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

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

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

As heating temperature, 150-300 degreeC is preferable. A higher temperature promotes the reorientation of molecular chains, but an excessively high temperature may accompany decomposition of the molecular chains. Therefore, as heating temperature, 180-250 degreeC is more preferable, and 200-230 degreeC is especially preferable.

If the heating time is too short, the effect of molecular chain reorientation may not be obtained, and if too long, the molecular chain may be decomposed, so 10 seconds to 30 minutes are preferable, and 1 minute to 10 minutes are more preferable do.

Moreover, the obtained liquid crystal aligning film can melt|dissolve in a rework material easily, and becomes a film|membrane excellent in rework property.

The solvent used for rework includes the following: glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and propylene glycol monomethyl ether Glycol esters, such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and propylene glycol propyl ether acetate; Glycols, such as diethylene glycol, propylene glycol, butylene glycol, hexylene glycol ; Alcohols such as methanol, ethanol, 2-propanol, and butanol; Ketones such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and γ-butyrolactone; 2-hydroxypropionate methyl; 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, methyl 3-methoxypropionate, 3-E Esters such as ethyl oxypropionate, 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide and N -amides such as methyl-2-pyrrolidone.

As a rework material, while containing basic components, such as ethanolamine, in the said solvent, it is preferable that the rust inhibitor is contained so that this alkalinity may not damage other members, such as an electrode. As a maker that provides such a rework material, Korea's Homyung Industrial Co., Ltd., KPX Chemical, etc. are mentioned.

After rework heats the rework material illustrated above at room temperature or 30 degreeC - 100 degreeC, 1 second - 1000 second of the board|substrate with a liquid crystal aligning film therein, Preferably rework is 30 second - 500 second immersion Alternatively, after the rework material is sprayed in a shower type, the liquid is removed and washed with an alcohol solvent or pure water. In addition, the temperature of the rework liquid at the time of rework is preferably a low temperature from a viewpoint of work efficiency etc., Usually, it is room temperature - 60 degreeC, More preferably, it is room temperature - 40 degreeC.

<Liquid crystal display element>

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

As an example of the method for manufacturing a liquid crystal cell, a liquid crystal display device having a passive matrix structure will be described as an example. Moreover, the liquid crystal display element of the active matrix structure in which switching elements, such as a TFT (Thin Film Transistor) was formed in each pixel part which comprises an image display may be sufficient.

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

Next, on each board|substrate, the liquid crystal aligning film of this invention is formed by said method.

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

Next, liquid-crystal material is inject|poured in the space surrounded by 2 sheets of board|substrates and sealing agent through the opening part formed in the sealing compound. After that, this opening is sealed with an adhesive. A vacuum injection method may be used for injection|pouring, and the method which utilized the capillary phenomenon in air|atmosphere may be used. Next, a polarizing plate is installed. A pair of polarizing plates are affixed to the surface on the opposite side to the liquid-crystal layer of 2 sheets of board|substrates specifically,. By passing through the above process, the liquid crystal display element of this invention is obtained.

In the present invention, as the sealing agent, for example, an epoxy group, an acryloyl group, a methacryloyl group, a hydroxyl group, an allyl group, a resin that is cured by heating having a reactive group such as an acetyl group is used. . In particular, it is preferable to use a cured resin system having reactive groups of both an epoxy group and a (meth)acryloyl group.

You may mix|blend an inorganic filler with the sealing compound of this invention for the purpose of adhesiveness and the improvement of moisture resistance. The inorganic filler that can be used is not particularly limited, but specifically, spherical silica, fused silica, crystalline silica, titanium oxide, titanium black, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate , calcium sulfate, mica, talc, clay, alumina, magnesium oxide, zirconium oxide, aluminum hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos, etc. and spherical silica, fused silica, crystalline silica, titanium oxide, titanium black, silicon nitride, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, and calcium silicate. , aluminum silicate. You may use said inorganic filler in mixture of 2 or more types.

Since this liquid crystal display element is using the liquid crystal aligning film obtained by the manufacturing method of the liquid crystal aligning film of this invention as a liquid crystal aligning film, it becomes the thing excellent in rework property, and it is a large screen, and it can utilize it suitably for a high-definition liquid crystal television etc.

Example

Hereinafter, the detailed content of the manufacturing method of the present invention will be described with reference to the experimental method and results obtained by examining the composition and mixing ratio of the raw materials, and Examples, which are typical manufacturing methods. In addition, this invention is not limited to these Examples.

Explanation of abbreviations used in this embodiment

(organic solvent)

NMP: N-methyl-2-pyrrolidone

GBL: γ-butyrolactone

BCS: Butyl Cellosolve

Acid dianhydride (A): following formula (A)

Acid dianhydride (B): the following formula (B)

Acid dianhydride (C): the following formula (C)

Acid dianhydride (D): the following formula (D)

DA-1: the following formula (DA-1)

DA-2: following formula (DA-2)

DA-3: the following formula (DA-3)

DA-4: following formula (DA-4)

DA-5: following formula (DA-5)

[Formula 33]

Below, the measurement of a viscosity, the measurement of an imidation rate, evaluation of rework property, manufacture of a liquid crystal cell, and the method of charge relaxation characteristic evaluation are written in.

[Measurement of viscosity]

In the synthesis example, the viscosity of the polyamic acid ester and polyamic acid solution was measured using an E-type viscometer TV-25H (manufactured by Toki Sangyo Co., Ltd.), sample amount 1.1 ml, CORD-1 (1°34', R24), temperature 25 Measured at °C.

[Evaluation of reworkability]

The liquid crystal aligning agent of this invention was apply|coated to the ITO board|substrate by spin coat application|coating. After drying for 1 minute 30 second on a 60 degreeC hotplate, 230 degreeC hot-air circulation type oven performed baking for 20 minutes, and the coating film with a film thickness of 100 nm was formed. Then, after immersing the manufactured board|substrate in the rework material (HM-R20) heated to 55 degreeC for 300 second and developing, it washed with running water for 20 second with ultrapure water. Then, the thing which air-blowed and the liquid crystal aligning film completely lose|disappeared was made into (circle) and the thing which remain|survives was made into x. The obtained result is shown in Table 3 about the case where the predetermined temperature of the rework liquid was 35 degreeC and 55 degreeC.

(Comparative polymerization example 1)

A 50 ml four-neck flask equipped with a stirring device was made into a nitrogen atmosphere, 2.55 g of (DA-1) and 0.96 g of (DA-4) were taken, 25.7 g of NMP was added, and the mixture was stirred while sending nitrogen at 23°C. was dissolved in After adding 3.00g of acid dianhydride (C), adding 11.2g of NMP further, stirring this diamine solution, and stirring at 23 degreeC in nitrogen atmosphere for 2 hours, stirring this diamine solution, 0.77g of acid dianhydride (D) After addition, 4.4g of NMP was further added, and it stirred at 23 degreeC in nitrogen atmosphere for 2 hours. Then, it stirred at 50 degreeC for 16 hours, and obtained the polyamic-acid solution (PAA-1). The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 358 cps.

(Comparative polymerization example 2)

A 50 ml four-neck flask equipped with a stirring device was made into a nitrogen atmosphere, 2.55 g of (DA-1) and 0.46 g of (DA-2) were taken, 22.3 g of NMP was added, and the mixture was stirred while sending nitrogen at 23°C. was dissolved in After adding 2.00 g of acid dianhydride (C), further adding 6.3 g of NMP, and stirring this diamine solution at 23 degreeC in nitrogen atmosphere, stirring this diamine solution, 1.51 g of acid dianhydride (D) In addition, 8.5g of NMP was added, and it stirred at 23 degreeC in nitrogen atmosphere for 2 hours. Then, it stirred at 50 degreeC for 16 hours, and obtained the polyamic-acid solution (PAA-2). The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 333 cps.

(Comparative polymerization example 3)

A 50 ml four-neck flask equipped with a stirring device was made into a nitrogen atmosphere, 2.55 g of (DA-1) and 0.46 g of (DA-2) were taken, 22.3 g of NMP was added, and the mixture was stirred while sending nitrogen at 23°C. was dissolved in While stirring this diamine solution, 4.5g of acid dianhydride (A) is added, 20.5g of NMPs are further added, and after stirring at 23 degreeC in nitrogen atmosphere for 2 hours, it stirs at 50 degreeC for 16 hours, polya A mixed acid solution (PAA-3) was obtained. The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 350 cps.

(Comparative polymerization example 4)

A 50 ml four-neck flask equipped with a stirring device was made into a nitrogen atmosphere, 2.55 g of (DA-1) and 0.49 g of (DA-2) were taken, 22.3 g of NMP was added, and the mixture was stirred while sending nitrogen at 23°C. was dissolved in After adding 3.00g of acid dianhydride (C), adding 12.0g of NMP further, stirring this diamine solution, and stirring at 23 degreeC in nitrogen atmosphere for 2 hours, stirring this diamine solution, 0.72g of acid dianhydride (D) After addition, 4.1g of NMP was further added, and it stirred at 23 degreeC in nitrogen atmosphere for 2 hours. Then, it stirred at 50 degreeC for 16 hours, and obtained the polyamic-acid solution (PAA-4). The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 333 cps.

(Polymerization Example 1)

A 50 ml four-neck flask equipped with a stirring device was made into a nitrogen atmosphere, 2.55 g of (DA-1) and 0.78 g of (DA-5) were taken, 24.4 g of NMP was added, and the mixture was stirred while sending nitrogen at 23°C. was dissolved in After adding 1.75g of acid dianhydride (B), further adding 4.3g of NMP, and stirring this diamine solution at 23 degreeC in nitrogen atmosphere, stirring this diamine solution, 1.41g of acid dianhydride (D) 8.0g of NMP was further added, and it stirred at 23 degreeC in nitrogen atmosphere for 2 hours. Then, it stirred at 50 degreeC for 16 hours, and obtained the polyamic-acid solution (PAA-5). The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 240 cps.

(Polymerization Example 2)

A 50 ml four-neck flask equipped with a stirring device was made into a nitrogen atmosphere, 2.55 g of (DA-1) and 0.49 g of (DA-2) were taken, 22.3 g of NMP was added, and the mixture was stirred while sending nitrogen at 23°C. was dissolved in After adding 2.35g of acid dianhydride (A), further adding 8.3g of NMP, and stirring this diamine solution at 23 degreeC in nitrogen atmosphere, stirring this diamine solution, 1.80g of acid dianhydride (C) After addition, 10.2g of NMP was further added, and it stirred at 23 degreeC in nitrogen atmosphere for 2 hours. Then, it stirred at 70 degreeC for 16 hours, and obtained the polyamic-acid solution (PAA-6). The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 380 cps.

(Polymerization Example 3)

A 50 ml four-necked flask with a stirring device was made into a nitrogen atmosphere, 2.55 g of (DA-1) and 0.63 g of (DA-3) were taken, 23.4 g of NMP was added, and the mixture was stirred while sending nitrogen at 23°C. was dissolved in After adding 2.35g of acid dianhydride (A), adding 8.0g of NMP further, stirring this diamine solution, and stirring at 23 degreeC in nitrogen atmosphere for 2 hours, stirring this diamine solution, 1.80g of acid dianhydride (C) After addition, 10.2g of NMP was further added, and it stirred at 23 degreeC in nitrogen atmosphere for 2 hours. Then, it stirred at 70 degreeC for 16 hours, and obtained the polyamic-acid solution (PAA-7). The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 350 cps.

(Polymerization Example 4)

A 50 ml four-necked flask with a stirring device was made into a nitrogen atmosphere, 2.55 g of (DA-1) and 0.95 g of (DA-4) were taken, 25.7 g of NMP was added, and the mixture was stirred while sending nitrogen at 23°C. was dissolved in After adding 2.35g of acid dianhydride (A), adding 7.5g of NMP further, stirring this diamine solution, stirring this diamine solution, and stirring at 23 degreeC in nitrogen atmosphere for 2 hours, 1.80g of acid dianhydride (C) After addition, 10.2g of NMP was further added, and it stirred at 23 degreeC in nitrogen atmosphere for 2 hours. Then, it stirred at 70 degreeC for 16 hours, and obtained the polyamic-acid solution (PAA-8). The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 365 cps.

(Polymerization Example 5)

A 50 ml four-neck flask equipped with a stirring device was made into a nitrogen atmosphere, 2.55 g of (DA-1) and 0.78 g of (DA-5) were taken, 24.4 g of NMP was added, and the mixture was stirred while sending nitrogen at 23°C. was dissolved in After adding 2.35g of acid dianhydride (A), adding 7.8g of NMP further, stirring this diamine solution, and stirring at 23 degreeC in nitrogen atmosphere for 2 hours, stirring this diamine solution, 1.80g of acid dianhydride (C) After addition, 10.2g of NMP was further added, and it stirred at 23 degreeC in nitrogen atmosphere for 2 hours. Then, it stirred at 70 degreeC for 16 hours, and obtained the polyamic-acid solution (PAA-9). The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 389 cps.

(Polymerization Example 6)

A 50 ml four-neck flask equipped with a stirring device was made into a nitrogen atmosphere, 2.55 g of (DA-1) and 0.49 g of (DA-2) were taken, 22.3 g of NMP was added, and the mixture was stirred while sending nitrogen at 23°C. was dissolved in After adding 2.35g of acid dianhydride (A), adding 8.3g of NMP further, stirring this diamine solution, and stirring at 23 degreeC in nitrogen atmosphere for 2 hours, stirring this diamine solution, 1.41g of acid dianhydride (D) 8.0g of NMP was further added, and it stirred at 23 degreeC in nitrogen atmosphere for 2 hours. Then, it stirred at 70 degreeC for 16 hours, and obtained the polyamic-acid solution (PAA-10). The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 321 cps.

(Polymerization Example 7)

A 50 ml four-neck flask equipped with a stirring device was made into a nitrogen atmosphere, 2.55 g of (DA-1) and 0.49 g of (DA-2) were taken, 22.3 g of NMP was added, and the mixture was stirred while sending nitrogen at 23°C. was dissolved in After adding 1.41g of acid dianhydride (A), adding 2.9g of NMP further, stirring this diamine solution, and stirring at 23 degreeC in nitrogen atmosphere for 2 hours, stirring this diamine solution, 1.41g of acid dianhydride (B) 7.9 g of NMP was further added, and it stirred at 23 degreeC in nitrogen atmosphere for 2 hours. Then, 1.00g of acid dianhydride (C) was added, 5.7g of NMPs were further added, and it stirred at 23 degreeC in nitrogen atmosphere for 2 hours. Then, it stirred at 70 degreeC for 16 hours, and obtained the polyamic-acid solution (PAA-11). The viscosity in the temperature of 25 degreeC of this polyamic-acid solution was 365 cps.

(Comparative Examples 1 to 4)

15.0 g of the polyamic acid solution obtained by the comparative synthesis example is fractionated to the 50 ml Erlenmeyer flask with a stirrer, 11.25 g of NMP, and 11.25 g of BCS are added, and it stirs with a magnetic stirrer for 2 hours, and liquid crystal aligning agent of Table 1 (A-1) to (A-4) were obtained.

(Examples 1 to 7)

15.0 g of the polyamic acid solution obtained in the synthesis example was fractionated to the 50 ml Erlenmeyer flask containing a stirrer, 11.25 g of NMP, and 11.25 g of BCS were added, and it stirred with a magnetic stirrer for 2 hours, and liquid crystal aligning agent of Table 2 ( B-1) to (B-7) were obtained.

The liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention reduces the charge accumulation by asymmetry of alternating current drive in the liquid crystal display element of an IPS drive system or an FFS drive system, and relaxation|relief of the residual electric charge accumulate|stored by DC voltage Since it is fast, the liquid crystal display element of the IPS drive method and FFS drive method excellent in an afterimage characteristic is obtained. Therefore, it is especially useful as a liquid crystal aligning film of the liquid crystal display element of an IPS drive system or an FFS drive system, or a liquid crystal television.

Claims (11)

A tetracarboxylic dianhydride component containing tetracarboxylic dianhydride represented by the following formula (1) and an aliphatic tetracarboxylic dianhydride in a molar ratio of 10:90 to 90:10 and a tetracarboxylic dianhydride component represented by the following formula (2) The at least 1 type of polymer and organic solvent chosen from the imidation polymer of the polyamic acid obtained using the diamine component containing diamine, and this polyamic acid, The liquid crystal aligning agent characterized by the above-mentioned.

(The tetracarboxylic dianhydride represented by Formula (1) is 3,3',4,4'- biphenyltetracarboxylic dianhydride.
In the formula (2), Y ₁ is at least one selected from the group consisting of a divalent organic group having the structures of the following formulas (YD-14) and (YD-18), in the formula (YD-14), j is an integer of 1 to 3, and B ₁ and B ₂ are each independently a hydrogen atom or an optionally substituted C1-C10 alkyl group, alkenyl group, or alkynyl group.)

The method of claim 1,
10-100 mol% in the said tetracarboxylic dianhydride component is tetracarboxylic dianhydride and aliphatic dianhydride represented by the said Formula (1), The liquid crystal aligning agent characterized by the above-mentioned. The method of claim 1,
10-100 mol% in the said diamine component is diamine of Formula (2), The liquid crystal aligning agent characterized by the above-mentioned. The method of claim 1,
The liquid crystal aligning agent whose said aliphatic tetracarboxylic dianhydride is bicyclo [3.3.0] octane 2,4,6,8-tetracarboxylic acid 2,4:6,8 dianhydride. The liquid crystal aligning film obtained by apply|coating and baking the liquid crystal aligning agent in any one of Claims 1-4. A liquid crystal display element provided with the liquid crystal aligning film of Claim 5. delete delete delete delete delete