KR20130109095A - Liquid crystal alignment treatment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

단, X₁ 은, -O-, -NH-, -N(CH₃)-, -CONH-, -NHCO-, -CH₂O-, -COO-, -OCO-, -CON(CH₃)- 또는 N(CH₃)CO- 이고, X₂ 는, 탄소수 1 ∼ 5 의 알킬렌기이고, X₃ 은 식 [1a] 로 나타내는 구조이고, n 은 1 ∼ 4 의 정수이다.Provided is a liquid crystal aligning film in which a drop in voltage retention is suppressed even when exposed to sufficient solvent resistance and light irradiation. A liquid crystal aligning film is obtained using the diamine compound shown by Formula [2].
(Formula 1)

Provided that X ₁ is -O-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -COO-, -OCO-, -CON (CH ₃ ) - or N (CH ₃₎ CO-, X ₂ is an alkylene group having a carbon number of 1 ~ 5, X ₃ is a structure represented by the formula [1a], n is an integer from 1-4.

Description

Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element {LIQUID CRYSTAL ALIGNMENT TREATMENT AGENT, LIQUID CRYSTAL ALIGNMENT FILM, AND LIQUID CRYSTAL DISPLAY ELEMENT}

The present invention is a diamine compound, a polymer such as a polyimide precursor or a polyimide obtained by using the diamine compound, a liquid crystal alignment agent containing the polymer, a liquid crystal alignment film obtained from this liquid crystal alignment agent and a liquid crystal display element using the liquid crystal alignment layer. It is about.

The liquid crystal aligning film is a structural member of the liquid crystal display element widely used as a display device, and plays a role which orientates a liquid crystal in a fixed direction. The main liquid crystal aligning film currently used industrially is formed with the liquid-crystal aligning agent which consists of a solution of polyamic acid (also called polyamic acid) or polyimide which is a polyimide precursor. Specifically, after apply | coating and heating a liquid-crystal aligning agent to a board | substrate, the orientation process for orientating a liquid crystal in parallel or inclining with respect to a board | substrate surface is performed. Although the surface extending | stretching process by rubbing is mentioned as an orientation process, In addition, the orientation process using the anisotropic optical reaction by polarized ultraviolet irradiation etc. is proposed.

In addition to the role of orienting the liquid crystal in a certain direction, the liquid crystal alignment film has a role of controlling the pretilt angle of the liquid crystal. Moreover, in recent years, while a liquid crystal display element becomes high functional and its use range expands further, the liquid crystal aligning film is request | required the performance and reliability for suppressing the display defect of a liquid crystal display element and realizing high display quality.

For example, although the above-mentioned rubbing process is performed by rubbing the surface of a liquid crystal aligning film with cloth, from the point of countermeasures of a foreign material, etc., the degree of shaving by a rubbing process is slight in a liquid crystal aligning film, ie, rubbing tolerance High (high mechanical strength) is required. Patent Document 1 describes that a polyimide-based liquid crystal alignment treatment agent contains a compound having two or more epoxy groups in a molecule for the purpose of improving rubbing resistance.

Japanese Patent Application Laid-Open No. 9-146100

In the manufacturing process of the liquid crystal panel which comprises a liquid crystal display element, the washing process which wash | cleans a liquid crystal aligning film with water or an organic solvent in order to remove the trace amount of cutting waste which arose in a rubbing process, and the impurity which adhered to the liquid crystal aligning film at the time of baking have. In this case, the liquid crystal aligning film does not melt | dissolve with respect to these washing | cleaning liquids, especially an organic solvent, ie, a thing with high solvent tolerance is necessary. When a liquid crystal aligning film melt | dissolves in a washing | cleaning liquid, the liquid crystal aligning film of predetermined film thickness will no longer be obtained and it is difficult to implement | achieve the high display quality in a liquid crystal display element.

Moreover, with the recent high performance of the liquid crystal display element, a liquid crystal display element is used for the liquid crystal television which is high in a big screen, an on-vehicle use, for example, a car navigation system, a meter panel, etc. In such a use, in order to obtain high brightness, a backlight with a large amount of heat generation may be used. In this case, high stability to light from the backlight is required. In particular, when the voltage retention, which is one of the electrical characteristics, is lowered by light irradiation from the backlight, afterimage defects (line afterimages), which are one of the display defects of the liquid crystal display element, are likely to occur, thereby providing high reliability liquid crystal display elements. You will not be able to get it. Therefore, in a liquid crystal aligning film, the characteristic which voltage retention does not fall well is calculated | required also after being exposed to light irradiation for a long time in addition to the favorable initial characteristic.

An object of this invention is to provide the liquid crystal aligning film which has the said characteristic. That is, the objective of this invention is the liquid crystal aligning agent which has sufficient solvent tolerance in the washing | cleaning process in a liquid crystal panel manufacturing process, and the liquid crystal aligning film which can obtain the liquid crystal aligning film in which the fall of voltage retention was suppressed even when exposed to light irradiation, Furthermore, An object is to provide the liquid crystal display element provided with the outstanding display quality using this liquid-crystal aligning agent.

Moreover, the objective of this invention is also providing the polyimide precursor, polyimide which comprise the said liquid-crystal aligning agent, and the diamine compound for obtaining these polyimide precursors and polyimides.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching, this inventor acquired the following knowledge and came to complete this invention. That is, by using the diamine compound of a specific structure, the polyimide precursor which has a characteristic structure was obtained, and it discovered that the polyimide which has a characteristic structure is obtained by imidating this polyimide precursor.

And the liquid-crystal aligning agent containing the at least one of these polyimide precursors and polyimide is preferable for forming a liquid crystal aligning film, and the obtained liquid-crystal aligning film is very effective in achieving the objective of this invention mentioned above. Figured out. The diamine compound of the specific structure mentioned above contains the novel compound which is not published in the literature.

This invention has the following summary.

1. A liquid-crystal aligning agent containing at least 1 polymer chosen from the group which consists of a polyimide precursor which has a cyclocarbonate group, and the polyimide which imidated this polyimide precursor.

2. Said cyclocarbonate group is said liquid crystal aligning agent of 1 which exists in terminal of side chain of said polyimide precursor and said polyimide.

3. The liquid-crystal aligning agent as described in said 1 or 2 in which the side chain which has the said cyclocarbonate group is represented by following formula [1].

[Formula 1]

(X ₁ is —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —COO—, —OCO—, —CON (CH ₃ ) — Or N (CH ₃ ) CO-, X ₂ is an alkylene group having 1 to 5 carbon atoms, and X ₃ is a structure represented by the following formula [1a]:

(2)

4. The said polyimide precursor and said polyimide are liquid-crystal aligning agents in any one of said 1-3 which is a polymer which uses the diamine compound shown by following formula [2] as a raw material.

(3)

(X ₁ is —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —COO—, —OCO—, —CON (CH ₃ ) — Or N (CH ₃ ) CO-, X ₂ is an alkylene group having 1 to 5 carbon atoms, X ₃ is a structure represented by the following formula [1a], and n is an integer of 1 to 4)

[Formula 4]

5. Furthermore, the liquid-crystal aligning agent in any one of said 1-4 containing the base which has a primary amino group and nitrogen containing heterocyclic ring in molecular structure.

6. Said base is said liquid-crystal aligning agent of said 5 which is at least 1 compound chosen from group which consists of 3-aminopropylimidazole and 3-picorylamine.

7. The liquid-crystal aligning agent in any one of said 1-6 containing the organic solvent which melt | dissolves the said polyimide precursor and polyimide, and that organic solvent contains a 5-80 mass% poor solvent in a liquid-crystal aligning agent.

8. Liquid crystal aligning film obtained from liquid-crystal aligning agent in any one of said 1-7.

9. It arrange | positions the liquid crystal composition which has a liquid crystal layer between a pair of board | substrates provided with an electrode, and contains the polymeric compound superposed | polymerized by at least one of an active energy ray and a heat between said pair of board | substrates, and The liquid crystal aligning film of said 8 used for the liquid crystal display element manufactured through the process of superposing | polymerizing the said polymeric compound, applying a voltage between electrodes.

10. The liquid crystal display element which has the liquid crystal aligning film of 9 said.

11. A liquid crystal composition comprising a liquid crystal layer between an electrode and a pair of substrates provided with the liquid crystal alignment film, and containing a polymerizable compound polymerizing at least one of active energy rays and heat between the pair of substrates. And the said liquid crystal display element manufactured through the process of superposing | polymerizing the said polymeric compound, applying a voltage between the said electrodes.

12. The diamine compound characterized by the following formula [2].

[Chemical Formula 5]

(X ₁ is —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —COO—, —OCO—, —CON (CH ₃ ) — Or N (CH ₃ ) CO-, X ₂ is an alkylene group having 1 to 5 carbon atoms, X ₃ is a structure represented by the following formula [1a], and n is an integer of 1 to 4)

[Formula 6]

13. The polyimide precursor obtained by making the diamine component containing the diamine compound of said 12 react with an acid dianhydride component.

14. The polyimide precursor according to 13 above, wherein the diamine component further contains a diamine compound represented by the following Formula [3].

[Formula 7]

(Y ₁ is a single bond,-(CH ₂ ) _a- (a is an integer from 1 to 10), -O-, -CH ₂ O-, -COO-, and 2 selected from the group consisting of -OCO- Y ₂ is a single bond or a divalent organic group selected from (CH ₂ ) _b − (b is an integer of 1 to 10), and Y ₃ is a single bond, — (CH ₂ ) _c. (c is an integer of 1 to 10), -O-, -CH ₂ O-, -COO-, and -OCO-. A divalent organic group selected from the group consisting of Y ₄ represents a benzene ring and a cyclo. As a cyclic group chosen from the group which consists of a hexyl ring and a heterocyclic ring, arbitrary hydrogen atoms on these cyclic groups are a C1-C3 alkyl group, a C1-C3 alkoxyl group, a C1-C3 fluorine-containing alkyl group, C1-C1 - a divalent organic group selected from organic groups having a carbon number of 12 to 25 having a fluorine-containing alkoxy group or a fluorine-substituted divalent organic group which is, or steroid skeleton of 3. Y ₅ Is a cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring and a hetero ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, or having 1 to 3 carbon atoms. a fluorine-containing alkyl group, having 1 to 3 fluorine-containing alkoxy group or a divalent organic group which is a fluorine atom may be substituted, n is an integer of 0 ~ 4. Y ₆ is an alkyl group having 1 to 18 carbon atoms, having 1 to 18 carbon atoms Fluorine-containing alkyl group, a C1-C18 alkoxyl group, or a C1-C18 fluorine-containing alkoxyl group, m is an integer of 1-4)

15. The polyimide precursor according to the above-mentioned 13 or 14, wherein the acid dianhydride component is tetracarboxylic dianhydride represented by the following formula [4].

[Formula 8]

(Z ₁ is a tetravalent organic group having 4 to 13 carbon atoms and further has a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms)

16. The said liquid-crystal aligning agent as described in said 15 whose Z <_1> in the said tetracarboxylic dianhydride is an organic group of any structure of following formula [4a]-formula [4j].

[Chemical Formula 9]

(In formula [4a], Z <_2> -Z <_5> is respectively independently group chosen from a hydrogen atom, a methyl group, a chlorine atom, or a benzene ring, and in formula [4g], Z <_6> , Z <_7> is respectively independent. Is a hydrogen atom or a methyl group)

17. The polyimide obtained by dehydrating and ring-closing the polyimide precursor in any one of said 13-15.

The liquid crystal aligning film obtained using the liquid-crystal aligning agent of this invention has sufficient solvent tolerance in the washing | cleaning process in a liquid crystal panel manufacturing process, and the fall of voltage retention is suppressed even if it exposes to irradiation of light. Moreover, the liquid crystal display element which has this liquid crystal aligning film has the outstanding display quality.

Moreover, according to this invention, the novel diamine compound which is a raw material of the said liquid-crystal aligning agent is provided, The polyimide precursor and polyimide manufactured from a diamine compound are also provided.

The liquid-crystal aligning agent of this invention contains the polyimide precursor which has a cyclocarbonate group, and at least one in the polyimide obtained by dehydrating and ring-closing this polyimide precursor. Here, it is preferable that a cyclocarbonate group is located in the side chain terminal of a polyimide precursor and a polyimide, respectively.

Specifically, the liquid-crystal aligning agent of this invention contains the polyimide precursor which has a side chain of following formula [1], and at least one in the polyimide obtained by dehydrating and ring-closing this polyimide precursor.

[Formula 10]

Formula [1], X ₁ is, -O- (ether bond), -NH- (amino _{bond), -N (CH 3) -} ( amino methylated bond), -CONH- (amide bond), -NHCO- (Reverse amide bond), -CH ₂ O- (methylene ether bond), -COO- (ester bond), -OCO- (reverse ester bond), -CON (CH ₃ )-(N-methylated amide bond) and N (CH ₃₎ a linking group selected from the group consisting of CO- (N- methylation reverse amide bond). X ₁ is -O-, -NH-, -CONH-, -NHCO-, -CON (CH ₃ )-, -CH ₂ O-, -COO in terms of easy synthesis of raw materials and relatively easy availability. -Or OCO-. More preferably _{-O-, -CONH-, -CON (CH 3} ) -, -CH 2 O- or a COO-.

In formula [1], X <_2> is C1-C5, Preferably it is an alkylene group of 1-3.

In formula [1], X <_3> represents a cyclocarbonate group. Specifically, X ₃ is preferably a structure represented by the following formula [1a].

[Formula 11]

The cyclocarbonate group present at the end of the side chain in the formula [1] reacts with at least one of the carboxyl group and the hydroxyl group under heating to form a structure in which the polymer is crosslinked. Thereby, it can be set as the liquid crystal aligning film which is excellent in solvent tolerance and also excellent in stability with respect to light irradiation, such as a backlight.

Moreover, when a cyclocarbonate group is located in the side chain edge part of Formula [1], the liquid crystal aligning film which has high growth and toughness with the structure of high crosslinking density is obtained. Thereby, since the elongation of a polymer is hardly impaired at the time of rubbing, high rubbing tolerance is realizable. Moreover, since the cyclocarbonate group in a side chain edge can advance a crosslinking reaction efficiently, even if a crosslinkable compound is added, the residual of the unreacted crosslinkable compound which causes the characteristic fall of a liquid crystal display element etc. is reduced. You can also

Thus, the liquid crystal aligning film obtained from the said liquid-crystal aligning agent is excellent in solvent tolerance in the manufacturing process of a liquid crystal panel, and voltage retention is not largely reduced by the influence of light irradiation by a backlight. Moreover, since rubbing tolerance is also excellent, the liquid crystal display element excellent in display quality is obtained by applying this liquid crystal aligning film.

Hereinafter, the diamine compound of the specific structure used for the liquid-crystal aligning agent of this invention is demonstrated in detail. The liquid-crystal aligning agent of this invention can contain another component in addition to a polyimide precursor and a polyimide, Preferably, it is comprised containing a basic compound as a base, another diamine compound, etc ..

<Specific diamine compound>

The liquid-crystal aligning agent of this invention is a polyimide precursor obtained by reaction of a diamine component and tetracarboxylic dianhydride, and the polyimide obtained by dehydrating and ring-closing this polyimide precursor (in this specification, when these are generically called a specific polymer, There is). It is preferable that the diamine component contains the diamine compound (it calls also a specific diamine compound in this specification) represented by following formula [2].

[Chemical Formula 12]

In formula [2], X <_1> , X <_2> and X <_3> have the same definition as the case in the said Formula [1]. In formula [2], n is an integer of 1-4, Preferably n is an integer of 1-2, More preferably, n is 1.

The bonding position of two amino groups (-NH ₂ ) in Formula [2] is not limited. Specifically, with respect to the side chain linking group (X ₁ ), 2, 3 positions, 2, 4 positions, 2, 5 positions, 2, 6 positions, 3, 4 positions, 3, The position of 5 is mentioned. Especially, the position of 2, 4, the position of 2, 5, the position of 3, 5 are preferable from a viewpoint of the reactivity at the time of synthesize | combining a polyamic acid.

Preferred combinations of X ₁ , X ₂ , X ₃ and n in formula [2] are as shown by combination numbers (2-1) to (2-15) shown in Table 1.

[Table 1]

<The synthesis method of a specific diamine compound>

Although the method of manufacturing the specific diamine compound shown by Formula [2] is not specifically limited, What is shown below is mentioned as a preferable method.

As an example, the specific diamine compound of this invention is obtained by synthesize | combining the dinitro body represented by following formula [2A], reducing a nitro group again, and converting into an amino group.

[Chemical Formula 13]

There is no restriction | limiting in particular in the method of reducing a dinitro group, Usually, palladium-carbon, platinum oxide, raninickel, platinum black, rhodium-alumina, or platinum sulfide carbon is used as a catalyst, ethyl acetate, toluene, tetrahydrofuran In a solvent such as a dioxane or an alcohol solvent, there is a method performed by hydrogen gas, hydrazine, hydrogen chloride, or the like. In addition, X <_1> , X <_2> , X <_3> and n in Formula [2A] are the same as the definition in Formula [2] in the said specific diamine compound.

Formula [2A] di knitted Roche is, through a X ₂ and combined with X ₁ and X ₃ in. Then, in addition to via a X ₁ a method of bonding and the dinitrophenyl portion, via the connecting X ₁ dinitrophenyl portion And X ₂ may be bonded to each other, followed by bonding to X ₃ .

These bonding groups can be formed by appropriately selecting and using a known method in organic synthesis. For example, when X ₁ is an ether or methylene ether bond, as a method of forming it, in addition to a method of reacting a corresponding dinitro group-containing halogen derivative with a hydroxyl group derivative containing X ₂ and X ₃ in the presence of alkali And a dinitro group-containing hydroxyl group derivative and a halogen-substituted derivative containing X ₂ and X ₃ are reacted in the presence of alkali.

Moreover, when X <_1> is an amino bond, the method of making the corresponding dinitro group containing halogen derivative and the amino group substituted derivative containing X <_2> and X <_3> react in alkali presence is mentioned.

In the case of X ₁ is an amide bond, and a method of reacting an amino group-containing substituents to the corresponding dinitro group-containing acid chloride to the body, X ₂ and X ₃ under the presence of an alkali.

Moreover, when X <_1> is a reverse amide bond, the method of making the corresponding dinitro group containing amino group substituent and the acid chloride body containing X <_2> and X <_3> react in alkali presence is mentioned.

Moreover, when X <_1> is an ester bond, the method of making the corresponding dinitro group containing acid chloride body, and the hydroxyl group substituted derivative containing X <_2> and X <_3> react in alkali presence is mentioned.

Moreover, when X <_1> is a reverse ester bond, the method of making the corresponding dinitro-group containing hydroxyl group derivative and the acid chloride body containing X <_2> and X <_3> react in alkali presence is mentioned.

Specific examples of the dinitro group-containing halogen derivative and the dinitro group-containing derivative include 3,5-dinitrochlorobenzene, 2,4-dinitrochlorobenzene, 2,4-dinitrofluorobenzene, and 3,5- Dinitrobenzoic acid chloride, 3,5-dinitrobenzoic acid, 2,4-dinitrobenzoic acid chloride, 2,4-dinitrobenzoic acid, 3,5-dinitrobenzylchloride, 2,4-dinitrobenzylchloride, 3, 5-dinitrobenzyl alcohol, 2,4-dinitrobenzyl alcohol, 2,4-dinitroaniline, 3,5-dinitroaniline, 2,6-dinitroaniline, 2,4-dinitrophenol, 2, 5-dinitrophenol, 2,6-dinitrophenol, 2,4-dinitrophenylacetic acid, etc. are mentioned. Considering the method of obtaining a raw material, ease, reactivity, etc., 1 type or multiple types can be selected and used out of these.

<Basic compound>

It is preferable that the liquid-crystal aligning agent of this invention contains a basic compound as a base in order to advance the crosslinking reaction of the cyclocarbonate group which a polyimide precursor and a polyimide have. About the kind of basic compound, if there is sufficient basicity in order to advance crosslinking reaction of a cyclocarbonate group, it will not specifically limit.

Specific examples thereof include alkali amine compounds such as sodium hydroxide and potassium hydroxide or hydroxides of alkaline earth metals, inorganic amine compounds such as ammonia, and organic amine compounds such as pyridine and triethylamine. Especially, an organic amine compound is preferable at the point of the electrical characteristic of a liquid crystal aligning film.

As an example of an organic amine compound, the nitrogen containing heterocyclic amine compound shown by following formula [M1]-a formula [M156] is mentioned more specifically.

Although these amine compounds may be added directly to the solution of a specific polymer, it is preferable to add, after making into the solution of density | concentration 0.1-10 mass%, Preferably 1-7 mass% with a suitable solvent. It will not specifically limit, if it is an organic solvent in which the specific polymer of this invention is dissolved.

[Formula 14]

[Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

As a more preferable organic amine compound, M6, M7, M16, M17, M20, M35, M36, M40, M49, M50, M60-M62, M69, M70, M76, M118-M121, M135, or M140 are mentioned. . More preferably, they are M6, M16, M17, M35, M36, M40, M49, M50, M60, M61, M118, M120, M121, or M140. Most preferred is M6, M17, M35, M40, M61, or M118.

The basic compound contained in the liquid-crystal aligning agent of this invention may be one type, and may be combined two or more types.

It is preferable that content of the basic compound in the liquid-crystal aligning agent of this invention is 0.1-100 mass parts with respect to 100 mass parts of specific polymers, and promotes reaction with the carboxylic acid group and hydroxyl group contained in a polyamic acid or a polyimide. In order not to make it or reduce the orientation of a liquid crystal, More preferably, it is 0.1-50 mass parts, Especially, it is 1-30 mass parts.

<Polyimide Precursor and Polyimide>

In this invention, a specific polymer is at least 1 sort (s) of polymer chosen from the group which consists of a polyimide precursor and polyimide.

Since a specific polymer is obtained comparatively simply by polycondensing the diamine component represented by following formula [A] and the tetracarboxylic dianhydride component represented by following formula [B], it is poly which has a repeating unit represented by following formula [C] Amic acid, Furthermore, the polyimide which imidated this polyamic acid is preferable.

[Chemical Formula 20]

In formula [B], R <_1> is a divalent organic group and R <_2> represents a tetravalent organic group.

[Chemical Formula 21]

In formula [C], R <_1> , R <_2> is synonymous with what was defined by Formula [A] and Formula [B], and R <_1> , R <_2> may respectively be one type and may combine different multiple types. N represents a positive integer.

The polyimide precursor and polyimide of this invention are obtained using the diamine component and the acid dianhydride component containing the said specific diamine compound. Such a diamine component can contain the diamine compound (it is also called a specific side chain type diamine compound in this specification) represented by following formula [3].

[Chemical Formula 22]

Equation [3], Y ₁ is a single _{bond, - (CH 2) a -} 2 is (a is an integer of 1 to 15), selected from -O-, -CH ₂ O-, -COO- or OCO- It is an organic group. Among these, a single bond, is preferred because (a is an integer of 1 ~ 15), -O-, -CH 2 O- or COO- is the synthesis of the side chain structure is easy - (CH _{2) a.} More preferably a single _{bond, - (CH 2) a -} (a is an integer of 1 to 10), it is -O-, -CH ₂ O- or COO-.

Equation [3], Y ₂ represents a single bond or (CH _{2) b} - is a divalent organic group selected from (b is an integer of 1 to 15). Among these, a single bond or (CH _{2) b} - is preferred (b is an integer of 1-10).

In the formula _[3], Y 3 represents a single _{bond, - (CH 2) c -} 2 is (c is an integer of 1 to 15), selected from -O-, -CH ₂ O-, -COO- or OCO- It is an organic group. Among them, a single bond, are preferred because of (c is an integer of 1 ~ 15), -O-, -CH 2 O-, -COO- or OCO- is easy to synthesis - (CH _{2) c.} More preferably a single _{bond, - (CH 2) c -} (c is an integer of 1 to 10), is -O-, -CH ₂ O-, -COO- or OCO-.

In formula [3], Y <_4> is a cyclic group chosen from the group which consists of a benzene ring, a cyclohexyl ring, and a hetero ring, and arbitrary hydrogen atoms on these cyclic groups are a C1-C3 alkyl group, C1-C3 Oil having 12 to 25 carbon atoms having a divalent organic group which may be substituted with a group selected from the group consisting of an alkoxyl group, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, and a fluorine atom. It is a divalent organic group chosen from an apparatus. Especially, the C12-C25 organic group which has a benzene ring, a cyclohexyl ring, or a steroid structure is preferable.

Y <_5> is a cyclic group chosen from the group which consists of a benzene ring, a cyclohexyl ring, and a heterocyclic ring in formula [3], The arbitrary hydrogen atoms on these cyclic groups are a C1-C3 alkyl group, C1-C3 It is a divalent organic group which may be substituted by what is selected from the group which consists of an alkoxyl group, a C1-C3 fluorine-containing alkyl group, a C1-C3 fluorine-containing alkoxyl group, and a fluorine atom. Especially, a benzene ring or a cyclohexyl ring is preferable.

In formula [3], Y <_6> is C1-C18, Preferably it is 1-12, More preferably, it is an alkyl group of 1-9, C1-C18, Preferably it is 1-12, More preferably, it is 1-12 9 fluorine-containing alkyl group, 1 to 18 carbon atoms, preferably 1 to 12, more preferably 1 to 9 alkoxyl group, or 1 to 18 carbon atoms, preferably 1 to 12, more preferably 1 to 9 It is a fluorine-containing alkoxyl group.

In formula [3], n is an integer of 0-4. Preferably it is an integer of 0-2. Moreover, m is an integer of 1-4. Preferably it is an integer of 1-2.

Preferred combinations of Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₅ , Y ₆ and n in formula [3] are as shown in Tables 2 to 43.

[Table 2]

[Table 3]

[Table 4]

[Table 5]

TABLE 6

[Table 7]

[Table 8]

TABLE 9

[Table 10]

[Table 11]

[Table 12]

[Table 13]

[Table 14]

[Table 15]

[Table 16]

TABLE 17

[Table 18]

[Table 19]

[Table 20]

[Table 21]

[Table 22]

[Table 23]

[Table 24]

[Table 25]

[Table 26]

[Table 27]

[Table 28]

[Table 29]

[Table 30]

[Table 31]

[Table 32]

[Table 33]

[Table 34]

[Table 35]

[Table 36]

[Table 37]

[Table 38]

[Table 39]

[Table 40]

[Table 41]

[Table 42]

[Table 43]

The specific side chain type diamine compound represented by Formula [3] is a structure shown by following formula [3-1]-formula [3-31] more specifically.

(23)

Formula [3-1] - formula [3-3] of, R _{1 is, -O-, -OCH 2 -, -CH} 2 O-, -COOCH 2 -, or represents a -CH ₂ OCO-, R ₂ Is a C1-C22 alkyl group, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group.

&Lt; EMI ID =

Formula [3-4] - formula [3-6] of, R _{3 is, -COO-, -OCO-, -COOCH 2 -} , -CH 2 OCO-, -CH 2 O-, -OCH 2 - or CH ₂ -represents and R ₄ is a C1-C22 alkyl group, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.

(25)

Formula [3-7] and the formula [3-8] of, R _{5 is, -COO-, -OCO-, -COOCH 2 -} , -CH 2 OCO-, -CH 2 O-, -OCH 2 -, - CH ₂ -or O-, and R ₆ is a fluorine group, cyano group, trifluoromethane group, nitro group, azo group, formyl group, acetyl group, acetoxy group or hydroxyl group.

(26)

In formula [3-9] and formula [3-10], R <_7> is a C3-C12 alkyl group and the cis-trans isomerization of 1, 4- cyclohexylene is a trans isomer, respectively.

(27)

In formula [3-11] and formula [3-12], R <_8> is a C3-C12 alkyl group and the cis-trans isomerization of 1, 4- cyclohexylene is a trans isomer, respectively.

(28)

In formula [3-13], A <_4> is a C3-C20 alkyl group which may be substituted by the fluorine atom, A <_3> is a 1, 4- cyclohexylene group or a 1, 4- phenylene group, A <_2> is , An oxygen atom or COO- * (wherein the bond to which "*" has been attached is combined with A ₃ ), and A ₁ represents an oxygen atom or COO- * (wherein the bond to which "*" is given is (CH ₂₎ ) a ₂ ) A ₁ is an integer of 0 or 1, a ₂ is an integer of 2 to 10, and a ₃ is an integer of 0 or 1).

[Formula 29]

(30)

(31)

(32)

(33)

<Other diamine compound>

Although the polyimide precursor of this invention can be obtained using the specific diamine compound shown by Formula [2], unless the effect of this invention is impaired, the specific side chain type diamine compound shown by said Formula [3], and In addition, another diamine compound can be used together. Specific examples of such other diamine compounds are given below.

For example, p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl -m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5 -Diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diamino ratio Phenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy 4,4 ' -Diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diamino Biphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-dia Minodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylme Ethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2 ' -Diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldianiline, 3,3'-sulfonyldianiline, bis (4-aminophenyl) silane, bis (3-amino Phenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4,4'-thiodaniline, 3,3'-thiodaniline, 4,4'-dia Minodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N -Methyl (4,4'-diaminodiphenyl) amine, N-methyl (3,3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (2,2'-diaminodiphenyl) amine, N-methyl (2,3'-diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3 , 4'-diaminoben Phenone, 1,4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7- Diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis ( 4-aminophenyl) ethane, 1,2-bis (3-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, 1,4- Bis (4-aminophenyl) butane, 1,4-bis (3-aminophenyl) butane, bis (3,5-diethyl-4-aminophenyl) methane, 1,4-bis (4-aminophenoxy) Benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4- Aminobenzyl) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4 '-[1,4-phenylenebis (methylene)] dianiline, 4,4'-[1,3-phenyl Renbis (methylene)] dianiline, 3,4 '-[1,4-phenylenebis (methylene)] dianiline, 3,4 '-[1,3-phenylenebis (methylene)] dianiline, 3,3'-[1,4-phenylenebis (methylene)] dianiline, 3,3 '-[1,3- Phenylenebis (methylene)] dianiline, 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis [(3-aminophenyl) methanone], 1,3- Phenylenebis [(4-aminophenyl) methanone], 1,3-phenylenebis [(3-aminophenyl) methanone], 1,4-phenylenebis (4-aminobenzoate), 1,4 -Phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), bis (4-aminophenyl) tere Phthalate, bis (3-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N, N '-(1,4-phenylene) bis (4-amino Benzamide), N, N '-(1,3-phenylene) bis (4-aminobenzamide), N, N'-(1,4-phenylene) bis (3-aminobenzamide), N, N '-(1,3-phenylene) bis (3-aminobenzamide), N, N'-bis (4-aminophenyl) Lephthalamide, N, N'-bis (3-aminophenyl) terephthalamide, N, N'-bis (4-aminophenyl) isophthalamide, N, N'-bis (3-aminophenyl) isophthalamide , 9,10-bis (4-aminophenyl) anthracene, 4,4'-bis (4-aminophenoxy) diphenylsulfone, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane , 2,2'-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2'-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis (3- Aminophenyl) hexafluoropropane, 2,2'-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2'-bis (4-aminophenyl) propane, 2,2'-bis (3 -Aminophenyl) propane, 2,2'-bis (3-amino-4-methylphenyl) propane, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, 1,3-bis (4-aminophenoxy ) Propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,4-bis (3-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,5-bis (3-ami Phenoxy) pentane, 1,6-bis (4-aminophenoxy) hexane, 1,6-bis (3-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 1,7 -(3-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,8-bis (3-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) Nonane, 1,9-bis (3-aminophenoxy) nonane, 1,10- (4-aminophenoxy) decane, 1,10- (3-aminophenoxy) decane, 1,11- (4-amino Aromatics such as phenoxy) undecane, 1,11- (3-aminophenoxy) undecane, 1,12- (4-aminophenoxy) dodecane and 1,12- (3-aminophenoxy) dodecane Alicyclic diamines such as diamine, bis (4-aminocyclohexyl) methane and bis (4-amino-3-methylcyclohexyl) methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5 -Diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11- Aliphatic diamines such as diaminoundecane and 1,12-diaminododecane; .

Moreover, as another diamine compound, what has an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, or a heterocyclic ring in the diamine side chain, or the thing which has a macrocyclic substituent which consists of these, etc. are mentioned. Specifically, the diamine shown by the following formula [DA1]-a formula [DA12] can be illustrated.

(34)

A <_1> is a C1-C22 alkyl group or fluorine-containing alkyl group in a formula [DA1]-a formula [DA5].

(35)

Formula [DA6] ~ formula [DA11] of, A ₂ is, -COO-, -OCO-, -CONH-, -NHCO- , -CH 2 -, represents a -O-, -CO- or NH-, A ₃ represents a C1-C22 alkyl group or a fluorine-containing alkyl group.

(36)

P is an integer of 1-10 in a formula [DA12]. Furthermore, unless the effect of this invention is impaired, the diamine compound shown by following formula [DA13]-a formula [DA20] can also be used.

[Formula 37]

M is an integer of 0-3 in a formula [DA17], and n is an integer of 1-5 in a formula [DA20].

Moreover, unless the effect of this invention is impaired, the diamine compound which has a carboxyl group in the molecule | numerator shown by following formula [DA21]-a formula [DA24] can also be used.

(38)

Formula [DA21] of a, m ₁ is an integer of 1 to 4, the formula [DA22] of, A ₄ is a single _{bond, -CH 2 -, -C 2 H} 4 -, -C (CH 3) 2 -, -CF _2- , -C (CF ₃ )-, -O-, -CO-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON (CH ₃ )-or N (CH ₃ ) CO-. m <_2> and m <_3> show the integer of 0-4, respectively, and m <_2> + m <_3> shows the integer of 1-4. M <_4> and m <_5> are the integers of 1-5 in a formula [DA23], A <_5> is a C1-C5 linear or branched alkyl group in a formula [DA24], and m <_6> is an integer of 1-5. to be. In formula [DA25], A ₆ is a single bond, -CH _2- , -C ₂ H _4- , -C (CH ₃ ) _2- , -CF _2- , -C (CF ₃ )-, -O- , -CO-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH _2- , -COO-, -OCO-, -CON (CH ₃ ) Or N (CH ₃ ) CO-, m ₇ is an integer of 1 to 4;

The said specific side chain type diamine compound and other diamine compound can also be used 1 type or in mixture of 2 or more types according to the characteristics, such as liquid crystal alignability, voltage retention, and an accumulated charge, when it sets as a liquid crystal aligning film.

&Lt; Tetracarboxylic acid dianhydride &gt;

The polyimide precursor in this invention is obtained by reaction of a diamine component and the tetracarboxylic-acid component. Below, the specific example of the tetracarboxylic-acid component is given.

In order to obtain the specific polymer of this invention, it is preferable to use tetracarboxylic dianhydride (it is also called specific tetracarboxylic dianhydride in this specification) represented by following formula [4] as a raw material part.

[Chemical Formula 39]

In formula [4], Z <_1> is a C4-C13 tetravalent organic group, and also has a C4-C10, Preferably it is a 4-6 non-aromatic cyclic hydrocarbon group.

Preferable specific examples of Z ₁ are represented by the following formulas [4a] to [4j].

[Formula 40]

Z <_2> -Z <_5> is group chosen from a hydrogen atom, a methyl group, a chlorine atom, and a benzene ring in formula [4a], and may be same or different, respectively.

In formula [4g], Z <_6> , Z <_7> is a hydrogen atom or a methyl group, and may be same or different, respectively.

In formula [4], the particularly preferable structure of Z ₁ is formula [4a], formula [4c], formula [4d], formula [4e], formula [4f] or formula [4g] from the polymerization reactivity and the ease of synthesis. ] to be.

In this invention, as long as the effect of this invention is not impaired, other tetracarboxylic dianhydride other than specific tetracarboxylic dianhydride can be used. As other tetracarboxylic dianhydride, the tetracarboxylic dianhydride of the tetracarboxylic acid shown below is mentioned. Specific examples thereof include pyromellitic acid, 2,3,6,7-naphthalene tetracarboxylic acid, 1,2,5,6-naphthalene tetracarboxylic acid, 1,4,5,8- Naphthalenetetracarboxylic acid, 2,3,6,7-anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid , 2,3,3 ', 4-biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3', 4,4'-benzophenonetetracarboxylic acid, bis (3, 4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro Rho-2,2-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4 , 5-pyridinetetracarboxylic acid, 2,6-bis (3,4-dicarboxyphenyl) pyridine, 3,3 ', 4,4'-diphenylsulfontetracarboxylic acid, 3,4,9,10 Perylenetetracarboxylic acid, 1,3-diphenyl-1,2,3,4- Clobutanetetracarboxylic acid, oxydiphthaltetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4 , 5-cyclohexanetetracarboxylic acid, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2,3,4- Cyclobutanetetracarboxylic acid, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cycloheptanetetracarboxylic acid, 2,3,4,5 -Tetrahydrofurantetracarboxylic acid, 3,4-dicarboxy-1-cyclohexylsuccinic acid, 2,3,5-tricarboxycyclopentylacetic acid, 3,4-dicarboxy-1,2,3,4-tetra Hydro-1-naphthalenesuccinic acid, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid, bicyclo [4,3,0] nonane-2,4,7,9- Tetracarboxylic acid, bicyclo [4,4,0] decane-2,4,7,9-tetracarboxylic acid, bicyclo [4,4,0] decane-2,4,8,10-tetracar Acid, tricyclo- [6.3.0.0 <2,6>]-undecane-3, 5,9,11-tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4 -Tetrahydrinaphthalene-1,2-dicarboxylic acid, bicyclo [2,2,2] octo-7-ene-2,3,5,6-tetracarboxylic acid, 5- (2,5- Dioxotetrahydrofuryl) -3-methyl-3-cyclohexane-1,2-dicarboxylic acid, tetracyclo [6,2,1,1,0,2,7] dodeca-4,5,9 , 10-tetracarboxylic acid, 3,5,6-tricarboxynorbornane-2: 3,5: 6-dicarboxylic acid or 1,2,4,5-cyclohexanetetracarboxylic acid Can be.

In this invention, one type or two types or more can be selected and used out of the said tetracarboxylic dianhydride in consideration of characteristics, such as liquid crystal alignability, voltage holding | maintenance characteristic, and accumulated charge.

&Lt; Specific polymer &

The liquid-crystal aligning agent of this invention contains at least one in the polyimide which imidated the polyimide precursor which has a cyclocarbonate group, and this polyimide precursor. In this invention, a polyimide precursor and polyimide may be named generically and a specific polymer.

A polyimide precursor is a structure shown by following formula [A].

(41)

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

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

(42)

(In formula [B] and formula [C], R <_1> and R <_2> is synonymous with what was defined by formula [A].).

(43)

In the present invention, a method of synthesizing a specific polymer is not particularly limited. Usually, it is obtained by making a diamine component and the tetracarboxylic-acid component react. Generally, the polyamic acid is obtained by making at least 1 sort (s) of tetracarboxylic-acid component selected from the group which consists of tetracarboxylic acid and its derivative (s), and the diamine component which consists of 1 type or multiple types of diamine compound react. Specifically, there are a method of polycondensation of a tetracarboxylic acid dianhydride and a diamine component to obtain a polyamic acid, a method of obtaining a polyamic acid by dehydration polycondensation reaction of a tetracarboxylic acid and a diamine component or a method in which a tetracarboxylic acid dihalide and a diamine To obtain a polyamic acid.

In order to obtain a polyamic-acid alkylester, the method of polycondensing the tetracarboxylic acid and the diamine component which dialkyl-esterified the carboxylic acid group, and polycondensed the tetracarboxylic-acid dihalide and the diamine component which dicarboxylic-esterified the carboxylic acid group Or a method of converting a carboxyl group of a polyamic acid into an ester is used.

In order to obtain a polyimide, the method of closing the said polyamic acid or polyamic-acid alkylester to make a polyimide is used.

As the ratio of the cyclocarbonate group in a specific polymer increases, the characteristic of the liquid crystal aligning film obtained using the liquid-crystal aligning agent comprised containing this specific polymer becomes favorable. Specifically, the solvent resistance in the liquid crystal panel manufacturing process is excellent, and the rubbing resistance also becomes good. In addition, the fall of the voltage retention is suppressed also with the irradiation of light by the backlight.

When introduce | transducing a cyclocarbonate group into a specific polymer using a specific diamine compound, the specific diamine compound is 1 mol% or more in a diamine component, Furthermore, mol% or more, from a point which raises characteristics, such as said solvent tolerance, more preferable More preferably 10 mol% or more. Moreover, it is also possible that 100 mol% of a diamine component is a specific diamine compound. However, from a viewpoint of maintaining uniform applicability | paintability at the time of apply | coating a liquid-crystal aligning agent, 80 mol% or less of the diamine component is preferable, More preferably, it is 40 mol% or less.

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

The organic solvent used for the reaction of the diamine component and the tetracarboxylic acid component is not particularly limited as long as the produced polyamic acid is dissolved. Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine and dimethyl sulfone , Hexamethyl sulfoxide, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl iso amyl ketone, methyl isopropyl ketone, methyl cell Rhosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene Glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoa Tate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol Monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate Butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, Propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, pro acetate Lenglycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxy Propyl propionate, butyl 3-methoxypropionate, diglyme, or 4-hydroxy-4-methyl-2-pentanone. These may be used independently, or may mix and use them. Moreover, the solvent which does not melt a polyimide precursor may be sufficient, and if it is a range in which the produced polyamic acid does not precipitate, you may mix and use it with the said solvent. In addition, since water in an organic solvent inhibits a polymerization reaction and causes hydrolysis of the produced | generated polyimide precursor, it is preferable to use what dehydrated the organic solvent.

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

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

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

The polyimide of this invention is obtained by dehydrating and ring-closing said polyimide precursor. This polyimide is useful as a polymer for obtaining a liquid crystal aligning film.

In the polyimide of the present invention, the dehydration ring closure rate (imidization rate) of the polyimide precursor is not necessarily 100%, and may be adjusted in the range of 45 to 85%, for example, depending on the use or purpose. .

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

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

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

Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like, and among them, pyridine is preferable in view of having a basicity suitable for advancing the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like, and among them, acetic anhydride is preferred in view of ease of purification after completion of the reaction. The imidation ratio by catalyst imidation can be controlled by adjusting catalyst amount, reaction temperature, and reaction time.

When recovering the produced polyimide precursor or polyimide from the reaction solution of the polyimide precursor or the polyimide, the reaction solution may be thrown into the poor solvent and precipitated. Examples of the poor solvent used for the precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene or water. The polymer precipitated by being poured into the poor solvent can be dried by normal temperature or heating under normal pressure or reduced pressure after filtration and recovery. Moreover, the impurity in a polymer can be reduced when the polymer which precipitated and collect | recovered is re-dissolved in an organic solvent, and repeats the operation of reprecipitation recovery 2 to 10 times. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons, and the like, and the use of three or more kinds of poor solvents selected from these is preferable because the efficiency of purification is further enhanced.

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

&Lt; Liquid crystal alignment treatment agent &

The liquid-crystal aligning agent of this invention is a coating liquid for forming a liquid crystal aligning film, and is a solution obtained by melt | dissolving the resin component for forming the resin film which is a liquid crystal aligning film in an organic solvent. This resin component contains at least 1 sort (s) of polymer chosen from the specific polymer mentioned above. 1-20 mass% is preferable, as for content of the resin component in a liquid-crystal aligning agent, More preferably, it is 3-15 mass%, Especially preferably, it is 3-10 mass%.

In this invention, all of the resin component contained in a liquid-crystal aligning agent may be a specific polymer. Moreover, in addition to a specific polymer, you may use the other polyimide precursor or polyimide which does not have a cyclocarbonate group. Furthermore, polymers other than a polyimide precursor and a polyimide, specifically, an acrylic polymer, a methacryl polymer, polystyrene, a polyamide, etc. are mentioned. Content of another specific polymer can be 0.5-15 mass%, Preferably it is 1-10 mass%.

When making an organic solvent contain in the liquid-crystal aligning agent of this invention, from a viewpoint of forming a uniform thin film by application | coating, 70-99 mass% is preferable and 80-99 mass% of content of an organic solvent is more preferable. . This content can be suitably changed with the film thickness of a liquid crystal aligning film. It will not specifically limit, if it is an organic solvent in which the specific polymer mentioned above is dissolved as an organic solvent in that case. More specifically, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethyl-2-py Ralidone, N-vinylpyrrolidone, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl Nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme or 4-hydroxy-4-methyl-2-pentanone. These may be used alone or in combination.

The liquid-crystal aligning agent of this invention is a crosslinkable compound which has an epoxy group, an isocyanate group, or an oxetane group, and also at least 1 chosen from the group which consists of a hydroxyl group and an alkoxyl group, unless the effect of this invention is impaired. You may introduce | transduce the crosslinkable compound which has a substituent of a species, and also the crosslinkable compound which has a polymerizable unsaturated bond.

As a crosslinkable compound which has an epoxy group or an isocyanate group, it is bisphenol acetone glycidyl ether, a phenol novolak epoxy resin, a cresol novolak epoxy resin, triglycidyl isocyanurate, tetraglycidyl amino diphenylene, for example. , Tetraglycidyl-m-xylenediamine, tetraglycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenylglycidyl ether ethane, triphenylglycidyl ether ethane, bisphenol hexafluoroacet Diglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis ( 2,3-epoxypropoxy) octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidylmethylylenediamine, 2- (4- (2,3-epoxypropoxy) phenyl) -2- (4- (1,1-bis (4- (2,3-epoxypropoxy) phenyl) ethyl) phenyl) propane or 1,3-bis (4- (1- (4- (2,3-epoxyprop Foxy) phenyl) -1- (4 -(1- (4- (2,3-epoxypropoxyphenyl) -1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol and the like.

As a crosslinkable compound which has an oxetane group, the crosslinkable compound which has at least two oxetane groups represented by following formula [5] is mentioned.

(44)

Specifically, it is a crosslinking | crosslinked compound shown by following formula [5-1]-formula [5-11].

[Chemical Formula 45]

(46)

[Formula 47]

As a crosslinkable compound which has at least 1 sort (s) of substituent chosen from the group which consists of a hydroxyl group and an alkoxyl group, For example, Amino resin which has a hydroxyl group or an alkoxyl group, For example, Melamine resin, Urea resin, Guanamine resin, glycoluril-formaldehyde resin, succinylamide formaldehyde resin, or ethylene urea-formaldehyde resin, etc. are mentioned.

As this crosslinking | crosslinked compound, the melamine derivative, the benzoguanamine derivative, glycoluril, etc. which the hydrogen atom of the amino group substituted by the methylol group or the alkoxymethyl group or both can be used, for example. At this time, a melamine derivative and a benzoguanamine derivative may exist as a dimer or a trimer. It is preferable that these have an average of 3 or more and 6 or less of methylol groups or alkoxymethyl groups per triazine ring.

Examples of such a melamine derivative or benzoguanamine derivative include MX-750 in which a methoxymethyl group is substituted in an average of 3.7 methoxymethyl groups per one triazine ring of a commercial product, MW having an average of 5.8 methoxymethyl groups per triazine ring -30 (manufactured by Sanwa Chemical Co.), methoxymethylated melamine such as Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, Cymel 235, 236, 238, 212, 253 , 254 and the like, butoxymethylated melamines such as Cymel 506 and 508, carboxyl-containing methoxymethylated isobutoxymethylated melamines such as Cymel 1141, and methoxymethylated ethoxymethylated melamines such as Cymel 1123 Methoxymethylated butoxymethylated benzoguanamine such as benzoguanamine, Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, carboxyl-containing methoxymethylated methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80, Namin it can be given (or more, produced by Mitsui between Ana Mid), and the like. Examples of the glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylolated glycoluril such as Cymel 1172, and methoxymethylolated glycoluril such as PowderLink 1174.

As a benzene which has a hydroxyl group or an alkoxyl group, or a phenolic compound, For example, 1,3,5- tris (methoxymethyl) benzene, 1,2, 4- tris (isopropoxymethyl) benzene, 1, 4-bis (sec-butoxymethyl) benzene, 2, 6- dihydroxymethyl- p-tert- butylphenol, etc. are mentioned.

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

(48)

(49)

(50)

(51)

(52)

As a crosslinkable compound which has a polymerizable unsaturated bond, trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tri (meth) acryloyl Crosslinking | crosslinked compound which has three polymerizable unsaturated groups in a molecule | numerator, such as oxyethoxy trimethylol propane and glycerol polyglycidyl ether poly (meth) acrylate, Furthermore, ethylene glycol di (meth) acrylate, diethylene glycol di ( Meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) Acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide bisphenol Type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) Polymeric unsaturated, such as acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl ester di (meth) acrylate, and hydroxy pivar acid neopentyl glycol di (meth) acrylate Crosslinkable compound which has two groups in a molecule, Furthermore, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy 2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylic Late, 2- (meth) acryloyl jade The crosslinking | crosslinked compound which has one polymerizable unsaturated group, such as a cyethyl phosphate ester and N-methylol (meth) acrylamide in a molecule | numerator, etc. are mentioned.

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

(53)

In formula [7], A <_1> is group chosen from a cyclohexyl ring, a bicyclohexyl ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring, or a phenanthrene ring, A ₂ is group chosen from following formula [7a] or formula [7b], and n is an integer of 1-4.

[Formula 54]

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

It is preferable that content of a crosslinking | crosslinked compound is 0.1-150 mass parts with respect to 100 mass parts of resin components in a liquid-crystal aligning agent, and a crosslinking reaction advances, and in order to express a desired effect, and not to reduce the orientation of a liquid crystal. More preferably, it is 0.1-100 mass parts, Especially 1-50 mass parts.

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

(55)

(56)

(57)

(58)

[Chemical Formula 59]

(60)

Moreover, the liquid-crystal aligning agent of this invention is an organic solvent (also called a poor solvent) and a compound which improves the film thickness uniformity and surface smoothness at the time of apply | coating a liquid-crystal aligning agent, unless the effect of this invention is impaired. The compound which improves the adhesiveness of a liquid crystal aligning film and a board | substrate can be used.

The following are mentioned as a specific example of the poor solvent which improves the uniformity and surface smoothness of a film thickness. Examples of the solvent include isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl But are not limited to, carbitol acetate, carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, Monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl Ether, dipropylene glycol monopro Fill ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, di Isobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, lactic acid Ethyl, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3- Ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol , 1-phenoxy -2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2- Solvents having a low surface tension such as ethoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester or lactic acid isoamyl ester. These poor solvents may be used by one type, and may be used in mixture of multiple types. When using the above poor solvent, it is preferable that the addition amount is 5-80 mass% of the whole solvent contained in a liquid-crystal aligning agent, More preferably, it is 20-60 mass%.

As a compound which improves the uniformity and surface smoothness of a film thickness, a fluorine type surfactant, a silicone type surfactant, or a nonionic surfactant etc. are mentioned. More specifically, for example, F-top EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), Megapack F171, F173, R-30 (manufactured by Dainippon Ink, Inc.), Furard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.) ), Asahi Guard AG710, Saflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.), etc. are mentioned. The use ratio of these surfactant becomes like this. Preferably it is 0.01-2 mass parts with respect to 100 mass parts of the resin component contained in a liquid-crystal aligning agent, More preferably, it is 0.01-1 mass part.

As a specific example of the compound which improves the adhesiveness of a liquid crystal aligning film and a board | substrate, what is a functional silane containing compound and an epoxy group containing compound shown next is mentioned. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy (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- -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3- Aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 Tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl ) Cyclohexane or N, N, N ', N'- tetraglycidyl-4,4'- diamino diphenylmethane, etc. are mentioned.

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

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

<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 after being applied and baked on a substrate and subjected to an orientation treatment by rubbing treatment, light irradiation, or the like. Moreover, in the case of a vertical alignment use, it can use as a liquid crystal aligning film even without an orientation processing. It will not specifically limit, if it is a board | substrate with high transparency as a board | substrate used at this time, In addition to a glass substrate, plastic substrates, such as an acryl substrate and a polycarbonate board | substrate, etc. can also be used. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO electrode or the like for liquid crystal driving is formed. In the reflective liquid crystal display element, an opaque substrate such as a silicon wafer can also be used as long as the substrate on one side, and a material that reflects light such as aluminum can be used as the electrode in this case.

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

After apply | coating a liquid-crystal aligning agent on a board | substrate, a solvent can be evaporated at 50-300 degreeC, Preferably 80-250 degreeC by heating means, such as a hotplate, and it can be set as a coating film. When the thickness of the coating film after baking is too thick, it becomes disadvantageous in terms of the power consumption of a liquid crystal display element, and when too thin, the reliability of a liquid crystal display element may fall, Preferably it is 5-300 nm, More preferably, it is 10 -100 nm. When the liquid crystal is horizontally oriented or tilted, the coated film after firing is subjected to rubbing, polarized ultraviolet irradiation, or the like.

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

As a manufacturing method of a liquid crystal cell, a pair of board | substrate with which a liquid crystal aligning film was formed is prepared, a spacer is spread | dispersed on the liquid crystal aligning film of a single side board | substrate, so that a liquid crystal aligning film surface may become inward, and another other board | substrate is bonded together (貼And the method of inject | pouring and sealing a liquid crystal under reduced pressure, or the method of bonding and sealing a board | substrate after bonding a liquid crystal to the liquid crystal aligning film surface which spread | dispersed the spacer, etc. can be illustrated.

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

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

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

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

The liquid crystal is mixed with a polymerizable compound which is polymerized by irradiation with heat or ultraviolet rays. Examples of the polymerizable compound include a compound having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in the molecule. At that time, the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the liquid crystal component. When the polymerizable compound is less than 0.01 part by mass, the polymerizable compound is not polymerized and the orientation of the liquid crystal cannot be controlled. When the polymerizable compound is more than 10 parts by mass, the unreacted polymerizable compound is increased and the afterimage property of the liquid crystal display element is increased. Degrades.

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

By passing through the process illustrated above, the liquid crystal display element of this invention is obtained. Since these liquid crystal display elements use the alignment film of this invention as a liquid crystal aligning film, they become excellent in reliability and can be used suitably for a high definition liquid crystal television etc. in a big screen.

Example

Examples will be described below. In addition, this invention is limited to these and is not interpreted.

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

&Lt; Tetracarboxylic acid dianhydride &gt;

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

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

(61)

<Specific diamine compound>

B-1: The diamine compound synthesize | combined in Example 1

[Formula 62]

<Other diamine compound>

B-2: 3, 5- diamino benzoic acid

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

(63)

<Base>

C-1: 3 aminopropylimidazole

C-2 ： 3 aminopyridine

<Organic solvent>

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

PGMEA: Propylene glycol monomethyl ether acetate

PGME: Propylene glycol monomethyl ether

IPA: Isopropyl Alcohol

DMSO: Dimethyl sulfoxide

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

<Measurement of Molecular Weight of Polyamic Acid and Polyimide>

As a molecular weight of a polyamic acid and a polyimide, the Showa Denko normal-temperature gel permeation chromatography (GPC) apparatus (GPC-101) and the Shodex company column (KD-803, KD-805) were used. The measurement conditions are as follows.

Column temperature: 50 ° C

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

Flow rate: 1.0 ml / min

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

&Lt; Measurement of imidization rate &

20 mg of polyimide powder was put into an NMR sample tube (Kusano Scientific Co., Ltd., NMR sampling tube standard φ 5), 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS (tetramethylsilane) mixed product) was added, Ultrasonic was added to complete dissolution. About this solution, the proton NMR of 500 MHz was measured using the NMR measuring device (JNW-ECA500) by the Japan Electronic Datum company. The imidation ratio determines the proton derived from the structure which does not change before and after imidation as a reference proton, the peak integrated value of this proton, and the proton peak integrated value derived from the NH group of the amic acid appearing around 9.5-10.0 ppm. It calculated | required by following formula (1) using.

Imidation ratio (%) = (1- (alpha) x / y) x100 ... (One)

In said Formula (1), x is a proton peak integrated value derived from NH group of an amic acid, y is a peak integrated value of a reference proton, (alpha) is an amide in the case of polyamic acid (imidization ratio of 0%). The ratio of the number of reference protons to one NH group protons in the acid.

Next, the synthesis example of the specific diamine compound of this invention is shown. In addition, ¹ H-NMR means the nuclear magnetic resonance spectrum of the hydrogen atom in a molecule | numerator in a synthesis example, and shows the spectral data of the obtained compound.

Example 1.

Synthesis of Diamine Compound

&Lt; EMI ID =

The synthesis of the diamine compound (B-1) was carried out according to the above synthesis scheme. Specifically, a tetrahydrofuran (400 g) solution of compound (302) (21.51 g, 182.2 mmol) and triethylamine (18.44 g, 182.2 mmol) is cooled to 10 ° C. or less and the compound ( 301) (40.00 g, 173.5 mmol) solution of tetrahydrofuran (200 g) was added dropwise while paying attention to heat generation. After completion of the dropwise addition, the reaction temperature was raised to 23 ° C. and reaction was again performed. After confirming completion of the reaction by HPLC (high performance liquid chromatography), the reaction solution was poured into distilled water (4.8 L), the precipitated solid was filtered and washed with water, and then dispersed and washed with methanol (324 g) to give a compound (303). Was obtained (amount: 48.65 g, yield: 90%).

¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 9.03 (1H, t), 8.87 (2H, d), 5.24-5.19 (1H, m), 4.67-4.57 (3H, m), 4.47 (1H , dd).

A mixture of compound 303 (40.00 g, 128.1 mmol), 5% palladium carbon (functional, 4.0 g, 10 wt%), and 1,4-dioxane (600 g) was added at 23 ° C. in the presence of hydrogen. Stirred. After completion | finish of reaction, after filtering a catalyst with celite, the solvent was distilled off by the evaporator and oily crude was obtained. Ethyl acetate (200 g) was added to the obtained crude product, and crystallization was carried out while heating and stirring, followed by filtration and drying to obtain a diamine compound (B-1) as a white solid (amount: 17.45 g, yield: 54%).

¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 6.42 (2H, d), 6.04 (1H, t), 5.14-5.09 (1H, m), 5.03 (4H, br s), 4.62 (1H, t), 4.50 (1H, doublet), 4.39-4.32 (2H, m).

Example 2.

<Synthesis of Polyamic Acid 1>

N-2 for A-2 (7.86 g, 31.4 mmol), B-3 (5.62 g, 12.9 mmol), B-2 (1.96 g, 12.9 mmol), and B-1 (2.79 g, 11.0 mmol) After mixing in (57.1 g) and reacting at 80 ° C for 5 hours, A-1 (1.05 g, 5.51 mmol) and NMP (20.1 g) were added, and the mixture was reacted at 55 ° C for 6 hours to give a polyamic acid ( The solution (concentration 20.0 mass%) of A) was obtained. The number average molecular weight of this polyamic acid (A) was 25,528, and the weight average molecular weight was 97,025.

Example 3.

<Synthesis 1 of polyimide>

After adding NMP to the solution of polyamic acid (A) obtained in Example 2 (25.0 g) and diluting to 6 mass%, acetic anhydride (4.88 g) and pyridine (1.51 g) were added as an imidation catalyst, It reacted at 100 degreeC for 2 hours. The reaction solution was filtered with methanol (314 g), and the resulting precipitate was separated by filtration. Methanol wash | cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the powder of polyimide (B) was obtained. The imidation ratio of this polyimide (B) was 77%, the number average molecular weight was 18,898 and the weight average molecular weight was 102,005.

NMP18.8g was added to 3.85 g of powders of a polyimide (B), and it stirred for 30 hours and was made to melt | dissolve at 70 degreeC, and obtained the polyimide (B) solution.

Example 4.

<Preparation 1 of the liquid-crystal aligning agent>

NMP, the C-1 NMP solution, and BCS were added to the polyimide (B) solution obtained in Example 3, and it stirred at 50 degreeC for 20 hours, 6 mass% of polyimides, 0.3 mass% of C-1, NMP was prepared so that 48.7 mass% and BCS might be 45 mass%. It filtered under pressure with the membrane filter of 1 micrometer of pore diameters, and obtained the liquid-crystal aligning agent.

Example 5.

<Synthesis 2 of polyamic acid>

N-2 for A-2 (8.29 g, 33.0 mmol), B-3 (5.93 g, 13.6 mmol), B-2 (2.96 g, 19.4 mmol), and B-1 (1.47 g, 5.84 mmol) After mixing in (58.8g) and making it react at 80 degreeC for 5 hours, A-1 (1.14g, 5.81 mmol) and NMP (20.3g) are added, it is made to react at 55 degreeC for 6 hours, and the polyamic acid ( The solution (concentration 20.0 mass%) of C) was obtained. The number average molecular weight of this polyamic acid (C) was 24,325, and the weight average molecular weight was 82,359.

Example 6.

<Synthesis 2 of polyimide>

In the same manner as in Example 3, NMP was added to the solution (25.0 g) of the polyamic acid (C) obtained in Example 5, and diluted to a concentration of 6 mass%, followed by acetic anhydride (5.02 g) as the imidization catalyst. And pyridine (1.55 g) were added and reacted at 100 degreeC for 2 hours. The reaction solution was poured into methanol (314 g), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the powder of polyimide (D). The imidation ratio of this polyimide (D) was 77%, the number average molecular weight was 20,405 and the weight average molecular weight was 82,988.

NMP18.6g was added to 3.82 g of powders of a polyimide (D), and it stirred for 30 hours and was made to melt | dissolve at 70 degreeC, and obtained the polyimide (D) solution.

Example 7.

<Preparation 2 of the liquid-crystal aligning agent>

In the same manner as in Example 4, NMP, a C-1 NMP solution, and BCS were added to the polyimide (D) solution obtained in Example 6, and stirred at 50 ° C. for 20 hours. The polyimide was 6% by mass and C- 1 was prepared to be 0.3 mass%, NMP was 48.7 mass%, and BCS was 45 mass%. It filtered under pressure with the membrane filter of 1 micrometer of pore diameters, and obtained the liquid-crystal aligning agent.

Example 8.

<Preparation 3 of a liquid-crystal aligning agent>

NMP and C-2 NMP solution and BCS were added to the polyimide (B) solution obtained in Example 3, and it stirred at 50 degreeC for 15 hours, 6 mass% of polyimides, 0.3 mass% of C-1, NMP was prepared so that 48.7 mass% and BCS might be 45 mass%. It filtered under pressure with the membrane filter of 1 micrometer of pore diameters, and obtained the liquid-crystal aligning agent.

Example 9.

<Preparation 4 of a liquid-crystal aligning agent>

NMP and the C-2 NMP solution and BCS were added to the polyimide (D) solution obtained in Example 6, and it stirred at 50 degreeC for 20 hours, 6 mass% of polyimides, 0.3 mass% of C-1, and NMP Was prepared to be 48.7% by mass and BCS to 45% by mass. It filtered under pressure with the membrane filter of 1 micrometer of pore diameters, and obtained the liquid-crystal aligning agent.

Example 10.

<Preparation 5 of the liquid-crystal aligning agent>

NMP and BCS were added and stirred to the polyimide solution (B) solution obtained in Example 3, and it prepared so that 6 mass% of polyimide, 48.7 mass%, and BCS may be 45 mass%. It filtered under pressure with the membrane filter of 1 micrometer of pore diameters, and obtained the liquid-crystal aligning agent.

Example 11.

<Preparation 6 of the liquid-crystal aligning agent>

NMP, the C-2 NMP solution, and BCS were added and stirred to the solution of the polyamic acid (A) obtained in Example 2, 6 mass% of polyimide, 0.3 mass% of C-2, and 48.7 mass of NMP. % And BCS were prepared so that it might be 45 mass%. It filtered under pressure with the membrane filter of 1 micrometer of pore diameters, and obtained the liquid-crystal aligning agent.

Example 12.

<Preparation 7 of a liquid-crystal aligning agent>

NMP and C-2 NMP solution and BCS were added to the polyamic acid (C) solution obtained in Example 5, and it stirred, The polyamic acid (C) was 6 mass%, C-2 was 0.3 mass%, NMP Was prepared to be 48.7% by mass and BCS to 45% by mass. It filtered under pressure with the membrane filter of 1 micrometer of pore diameters, and obtained the liquid-crystal aligning agent.

Example 13.

<Preparation 8 of a liquid-crystal aligning agent>

NMP and BCS were added and stirred to the solution of the polyamic acid (A) obtained in Example 2, and it prepared so that 6 mass% of polyimide, 48.7 mass%, and BCS may be 45 mass%. It filtered under pressure with the membrane filter of 1 micrometer of pore diameters, and obtained the liquid-crystal aligning agent.

Below, the polyamic acid, a polyimide, and a liquid-crystal aligning agent as a comparative example are shown.

Comparative Example 1

A-2 (41.7 g, 166 mmol), B-3 (29.7 g, 68.3 mmol) and B-2 (19.4 g, 12.7 mmol) were mixed in NMP (290 g) and 5 hours at 80 ° C. After reacting, A-1 (5.57g, 28.4 mmol) and NMP (93.0g) were added and reacted at 55 degreeC for 6 hours, and the solution (concentration 20.0 mass%) of polyamic acid (E) was obtained. The number average molecular weight of this polyamic acid (E) was 24,513, and the weight average molecular weight was 79,705.

Comparative Example 2

In the same manner as in Example 3, after adding NMP to the solution of polyamic acid (E) obtained in Comparative Example 1 (75.0 g) and diluting it to 6 mass%, acetic anhydride (15.55 g), as an imidization catalyst, And pyridine (4.82 g) were added and reacted at 100 ° C for 2 hours. The reaction solution was poured into methanol (946 g), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the powder of polyimide (F). The imidation ratio of this polyimide (F) was 77%, the number average molecular weight was 19,377 and the weight average molecular weight was 53,171.

NMP56.6g was added to 11.6 g of powder of a polyimide (F), and it stirred for 30 hours and was made to melt | dissolve at 70 degreeC, and obtained the polyimide (F) solution.

Comparative Example 3

In the same manner as in Example 4, to the polyimide (F) solution obtained in Comparative Example 2, NMP, an NMP solution of C-1, and BCS were added and stirred at 50 ° C. for 20 hours, where the polyimide was 6% by mass and C -1 was prepared to be 0.3 mass%, NMP was 48.7 mass%, and BCS was 45 mass%. It filtered under pressure with the membrane filter of 1 micrometer of pore diameters, and obtained the liquid-crystal aligning agent.

Comparative Example 4

NMP and the C-2 NMP solution and BCS were added to the polyimide (F) solution obtained by the comparative example 2, and it stirred at 50 degreeC for 20 hours, 6 mass% of polyimides, 0.3 mass% of C-2, and NMP Was prepared to be 48.7% by mass and BCS to 45% by mass. It filtered under pressure with the membrane filter of 1 micrometer of pore diameters, and obtained the liquid-crystal aligning agent.

Comparative Example 5

NMP and BCS were added and stirred to the polyimide (F) solution obtained by the comparative example 2, and it prepared so that 6 mass% of polyimide, 48.7 mass% of NMP, and 45 mass% of BCS may be sufficient. It filtered under pressure with the membrane filter of 1 micrometer of pore diameters, and obtained the liquid-crystal aligning agent.

Comparative Example 6

NMP and C-2 NMP solution and BCS were added to the polyamic acid (E) solution obtained by the comparative example 1, and it stirred, 6 mass% of polyimides, 0.3 mass% of C-2, and 48.7 mass% of NMP. And BCS were prepared so that it might be 45 mass%. It filtered under pressure with the membrane filter of 1 micrometer of pore diameters, and obtained the liquid-crystal aligning agent.

Comparative Example 7.

NMP and BCS were added and stirred to the polyamic acid (E) solution obtained by the comparative example 1, and it prepared so that 6 mass% of polyamic acid (E), 48.7 mass%, and BCS may be 45 mass%. It filtered under pressure with the membrane filter of 1 micrometer of pore diameters, and obtained the liquid-crystal aligning agent.

Table 44 shows the liquid-crystal aligning agent which is an Example, and the liquid-crystal aligning agent of a comparative example.

[Table 44]

Next, the liquid-crystal aligning agent of the said Example was evaluated, comparing with the comparative example. First, the method of evaluation is demonstrated.

<Evaluation of solvent tolerance>

Solvent resistance was evaluated by examining the residual film rate after solvent immersion. Specifically, after spin-coating a liquid-crystal aligning agent to the glass substrate in which the ITO electrode was formed, and drying it for 5 minutes on an 80 degreeC hotplate, it bakes for 30 minutes in 230 degreeC hot-air circulation type oven, and has a film thickness of 100 nm. The coating film of was formed. The board | substrate with which this liquid crystal aligning film was formed was immersed in NMP of 23 degreeC for 1 minute, and the residual film ratio was calculated | required according to the following formula | equation. In formula (2), a is the film thickness after dipping and b is the film thickness before dipping.

Residual film ratio (%) = (a / b) × 100. (2)

<Evaluation of Electrical Characteristics and UV Resistance>

After spin-coating a liquid-crystal aligning agent on the glass substrate in which the ITO electrode was formed, and drying for 5 minutes on a 80 degreeC hotplate, baking for 30 minutes in 230 degreeC hot-air circulation type oven, and forming the coating film of film thickness 100, The board | substrate with which the liquid crystal aligning film was formed was obtained. Two board | substrates with this liquid crystal aligning film were prepared, and after spread | dispersing a 6 micrometers spacer on one liquid crystal aligning film surface, the sealing compound was printed from on this. Subsequently, after bonding the other board | substrate and liquid crystal aligning film surface facing each other, the sealing compound was hardened and the empty cell was produced. Liquid crystal MLC-6608 (made by Merck Japan) was injected into this empty cell by the pressure reduction injection method, the injection hole was sealed, and the liquid crystal cell of the vertical orientation was obtained.

The voltage of 1 V was applied to the said liquid crystal cell at the temperature of 80 degreeC, the voltage after 50 ms was measured, and how much voltage was hold | maintained was calculated as voltage retention. Moreover, UV light (ultraviolet light) was irradiated to the liquid crystal cell after voltage retention measurement, and it carried out similarly to the above, and measured voltage retention again. The irradiation energy was calculated based on the irradiation intensity at 350 nm. The evaluation results are summarized in Table 45.

[Table 45]

As shown in the evaluation result of Table 45, in the said residual film ratio evaluation, the liquid crystal aligning film obtained from the liquid-crystal aligning agent of the Example showed high residual film ratio in both, and it turned out that it was excellent in solvent tolerance. On the other hand, the liquid crystal aligning film obtained from the liquid-crystal aligning agent which is a comparative example showed the low residual film ratio, and it turned out that solvent tolerance was remarkably inferior compared with an Example.

The result of having performed evaluation of solvent tolerance using solvents other than NMP is also shown. The same evaluation as the residual film rate evaluation using the NMP described above using IPA as the solvent and the same evaluation as the residual film rate evaluation using the above described NMP using PGMEA resulted in the remaining of the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the example. The film rate was 100% in either case. In addition, the residual film ratio of the liquid crystal aligning film obtained from the liquid-crystal aligning agent of the comparative example was 100% in any case.

When evaluation similar to the residual film rate evaluation using said NMP was performed using PGME, the residual film rate of the liquid crystal aligning film obtained from the liquid-crystal aligning agent of the Example was 100%. Moreover, each residual film ratio of the liquid crystal aligning film obtained from the liquid-crystal aligning agent of Comparative Examples 3-5 was 100%. On the other hand, the residual film rate of the liquid crystal aligning film of Comparative Example 6 was 30%, and the residual film rate of the liquid crystal aligning film of Comparative Example 7 was 5%.

Comparative Examples 6 and 7 are liquid-crystal aligning agents containing polyamic acid, and Examples 11-13 are liquid-crystal aligning agents containing polyamic acid. About the liquid crystal aligning film obtained from the liquid-crystal aligning agent of Examples 11-13, when PGME used the same evaluation as the residual film rate evaluation using said NMP, residual film rate shows 100% as a high value. Therefore, in an Example, even if it contains a polyamic acid and comprises a liquid-crystal aligning agent, it turns out that it shows high solvent tolerance.

From the above evaluation result, it turns out that the liquid crystal aligning film obtained from the liquid-crystal aligning agent of the Example has very excellent solvent tolerance, and the superiority with respect to the prior art is exhibited clearly with respect to the solvent with especially high solubility.

Next, electrical characteristics will be described. The liquid crystal cell using the liquid-crystal aligning agent of an Example shows the high voltage retention more than 90% in all, and it turns out that it is excellent in an electrical characteristic.

About UV tolerance, the voltage retention of the liquid crystal cell using the liquid-crystal aligning agent of Examples 11-13 becomes high value exceeding 79% even after UV irradiation, and is 90% in another Example other than these, Very high voltage retention exceeding

As mentioned above, it turns out that the liquid crystal cell which has a liquid crystal aligning film obtained from the liquid-crystal aligning agent of an Example has the outstanding electrical property and UV tolerance.

On the other hand, in the case of the liquid-crystal aligning agent which is a comparative example, in the comparative example 6, it turns out that the voltage retention of the liquid crystal cell after UV irradiation is 70.8%, and in comparative example 7, it is a low value with 74.6%. Moreover, also in any comparative example, when 50J UV light is irradiated, it turns out that a voltage retention does not show a high value exceeding 90%.

From the above evaluation results, the liquid crystal aligning film obtained using the liquid-crystal aligning agent from the polyamic acid and polyimide obtained using the diamine compound of this invention is excellent in solvent tolerance, and can suppress the fall of the voltage retention by light irradiation. I can see.

Industrial availability

The liquid crystal aligning film of this invention has sufficient solvent tolerance in the washing | cleaning process in a liquid crystal panel manufacturing process, and even if it exposes to irradiation of light, the fall of voltage retention is suppressed, and the liquid crystal display element which has this liquid crystal aligning film has the outstanding display quality, It can be used suitably for a high definition liquid crystal television etc. in a big screen.

In addition, all the content of the JP Patent application 2010-133337, a claim, drawing, and the abstract for which it applied on June 10, 2010 is referred here, and it is taken as a part of indication of the specification of this invention.

Claims (17)

At least one polymer chosen from the group which consists of a polyimide precursor which has a cyclocarbonate group, and the polyimide which imidated this polyimide precursor is contained, The liquid-crystal aligning agent characterized by the above-mentioned. The said cyclocarbonate group is a liquid-crystal aligning agent of Claim 1 which exists in the side chain terminal of the said polyimide precursor and the said polyimide. The liquid crystal aligning agent of Claim 1 or 2 in which the side chain which has the said cyclocarbonate group is represented by following formula [1].
[Formula 1]

(X ₁ is —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —COO—, —OCO—, —CON (CH ₃ ) — Or N (CH ₃ ) CO-, X ₂ is an alkylene group having 1 to 5 carbon atoms, and X ₃ is a structure represented by the following formula [1a]:
(2)

The said polyimide precursor and the said polyimide are liquid crystal aligning agents of any one of Claims 1-3 which are polymers which use the diamine compound shown by following formula [2] as a raw material.
(3)

(X ₁ is —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —COO—, —OCO—, —CON (CH ₃ ) — Or N (CH ₃ ) CO-, X ₂ is an alkylene group having 1 to 5 carbon atoms, X ₃ is a structure represented by the following formula [1a], and n is an integer of 1 to 4)
[Chemical Formula 4]

The liquid crystal aligning agent according to any one of claims 1 to 4, further comprising a base having a primary amino group and a nitrogen-containing heterocyclic ring in its molecular structure. The liquid crystal aligning agent according to claim 5, wherein the base is at least one compound selected from the group consisting of 3-aminopropylimidazole and 3-picorylamine. The liquid crystal of any one of Claims 1-6 containing the organic solvent which melt | dissolves the said polyimide precursor and a polyimide, and this organic solvent contains 5-80 mass% poor solvent in a liquid-crystal aligning agent. Orientation treatment agent. The liquid crystal aligning film obtained from the liquid-crystal aligning agent as described in any one of Claims 1-7. The liquid crystal composition of Claim 8 which has a liquid crystal layer between a pair of board | substrates provided with an electrode, and contains the polymeric compound which superposes | polymerizes with at least one of an active energy ray and a heat between said pair of board | substrates. It arrange | positioned and a liquid crystal aligning film used for the liquid crystal display element manufactured through the process of superposing | polymerizing the said polymeric compound, applying a voltage between the said electrodes. The liquid crystal display element which has a liquid crystal aligning film of Claim 9. The method according to claim 10, comprising a liquid crystal layer between the electrode and the pair of substrates provided with the liquid crystal alignment film, and containing a polymerizable compound polymerizing at least one of active energy rays and heat between the pair of substrates. A liquid crystal display device manufactured by disposing a liquid crystal composition and polymerizing the polymerizable compound while applying a voltage between the electrodes. A diamine compound characterized by the following formula [2].
[Chemical Formula 5]

(X ₁ is —O—, —NH—, —N (CH ₃ ) —, —CONH—, —NHCO—, —CH ₂ O—, —COO—, —OCO—, —CON (CH ₃ ) — Or N (CH ₃ ) CO-, X ₂ is an alkylene group having 1 to 5 carbon atoms, X ₃ is a structure represented by the following formula [1a], and n is an integer of 1 to 4)
[Chemical Formula 6]

The polyimide precursor obtained by making the diamine component containing the diamine compound of Claim 12, and an acid dianhydride component react. The polyimide precursor of Claim 13 in which the said diamine component contains the diamine compound further represented by following formula [3].
(7)

(Y ₁ is a single bond,-(CH ₂ ) _a- (a is an integer from 1 to 10), -O-, -CH ₂ O-, -COO-, and 2 selected from the group consisting of -OCO- Y ₂ is a single bond or a divalent organic group selected from (CH ₂ ) _b − (b is an integer of 1 to 10), and Y ₃ is a single bond, — (CH ₂ ) _c. (c is an integer of 1 to 10), -O-, -CH ₂ O-, -COO-, and -OCO-. A divalent organic group selected from the group consisting of Y ₄ represents a benzene ring and a cyclo. As a cyclic group chosen from the group which consists of a hexyl ring and a heterocyclic ring, arbitrary hydrogen atoms on these cyclic groups are a C1-C3 alkyl group, a C1-C3 alkoxyl group, a C1-C3 fluorine-containing alkyl group, C1-C1 - a divalent organic group selected from organic groups having a carbon number of 12 to 25 having a fluorine-containing alkoxy group or a fluorine-substituted divalent organic group which is, or steroid skeleton of 3. Y ₅ Is a cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring and a hetero ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, or having 1 to 3 carbon atoms. a fluorine-containing alkyl group, having 1 to 3 fluorine-containing alkoxy group or a divalent organic group which is a fluorine atom may be substituted, n is an integer of 0 ~ 4. Y ₆ is an alkyl group having 1 to 18 carbon atoms, having 1 to 18 carbon atoms Fluorine-containing alkyl group, a C1-C18 alkoxyl group, or a C1-C18 fluorine-containing alkoxyl group, m is an integer of 1-4) The polyimide precursor of Claim 13 or 14 whose said acid dianhydride component is tetracarboxylic dianhydride represented by following formula [4].
[Chemical Formula 8]

(Z ₁ is a tetravalent organic group having 4 to 13 carbon atoms and further has a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms) The liquid-crystal aligning agent of Claim 15 whose Z <_1> in the said tetracarboxylic dianhydride is an organic group of any structure of following formula [4a]-a formula [4j].
[Chemical Formula 9]

(In formula [4a], Z <_2> -Z <_5> is respectively independently group chosen from a hydrogen atom, a methyl group, a chlorine atom, or a benzene ring, and in formula [4g], Z <_6> , Z <_7> is respectively independent. Is a hydrogen atom or a methyl group) The polyimide obtained by dehydrating and ring-closing the polyimide precursor in any one of Claims 13-15.