KR20130111969A - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

(식 중, R³ 은 -CH₂-, -O-, -CONH-, -NHCO-, -COO-, -OCO- 및 -NH- 로 이루어지는 군에서 선택되는 기를 나타낸다. R⁴ 는 단결합, 또는 탄소수 1 ∼ 10 의 알킬렌을 나타낸다. R⁵ 는 단결합, -CH₂-, -O- 또는 -NH- 를 나타낸다. R⁶ 은 1 개 혹은 복수의 고리로 구성되고, 적어도 1 개의 방향 고리를 말단에 갖는 탄소수 5 ∼ 18 의 2 가 유기기를 나타낸다. R⁷ 은 수소 원자, 메틸기 등이다)Even if baking below 200 degreeC provides the material for liquid crystal aligning film which does not generate | occur | produce film peeling or a scratch at the time of rubbing, and obtains favorable liquid-crystal orientation, and the novel diamine used for it.
A liquid crystal aligning agent containing at least one polymer selected from the group consisting of a polyamic acid and a polyimide obtained by dehydrating and closing the polyamic acid, wherein the diamine component contains a diamine represented by the following formula [3]: .
(Formula 1)

Wherein R ³ represents a group selected from the group consisting of -CH _2- , -O-, -CONH-, -NHCO-, -COO-, -OCO- and -NH-. R ⁴ represents a single bond, Or alkylene having 1 to 10 carbon atoms, R ⁵ represents a single bond, -CH _2- , -O- or -NH- R ⁶ is composed of one or a plurality of rings, and at least one aromatic ring; the two carbon atoms of 5 to 18 having at its end represents an organic group. R ⁷ is a hydrogen atom, a methyl group, etc.)

Description

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

This invention relates to the liquid crystal aligning agent used when producing a liquid crystal aligning film, the liquid crystal aligning film obtained from this liquid crystal aligning agent, and the liquid crystal display element which has this liquid crystal aligning film, and novel diamine suitable for them.

In liquid crystal display elements used in liquid crystal televisions, liquid crystal monitors, liquid crystal displays of portable devices, and the like, polyimide-based liquid crystal alignment films are most often used because of their excellent productivity and excellent chemical and thermal durability. This polyimide liquid crystal aligning film is produced by apply | coating the solution of polyimide or the solution of the polyamic acid which is a polyimide precursor to a board | substrate, and baking at the temperature of about 200-250 degreeC normally.

The baking process at the time of manufacturing a polyimide-type liquid crystal aligning film is a process which requires especially high temperature among the processes of manufacturing a liquid crystal display element, and aimed at the use of a plastic substrate until now, and the request from the heat resistance which a color filter has For the reason of reduction of energy cost, etc., the polyimide-type liquid crystal aligning film material which can be baked at 200 degrees C or less is proposed (for example, refer patent document 1).

Usually, after a polyimide-type liquid crystal aligning film is baked, orientation processing is performed by the method of what is called rubbing rubbed with cloth, such as cotton, nylon, and rayon. In recent years, as a substitute for this rubbing, an alignment treatment method for irradiating polarized ultraviolet rays or the like, a liquid crystal display element with a vertical alignment mode that does not require alignment treatment, and the like have also been developed, and some of them have been put into practical use. However, also at present, the alignment treatment by rubbing occupies an important position in the process of manufacturing the liquid crystal alignment film.

In recent years, the lack of the mechanical strength of the film | membrane with respect to a rubbing process at the time of baking a polyimide-type liquid crystal aligning film at low temperature becomes a problem. That is, when a rubbing process is performed, a flaw generate | occur | produces on the surface of a liquid crystal aligning film, or a part of film | membrane peels from a board | substrate. In low temperature baking, since the film | membrane intensity | strength is insufficient compared with normal baking temperature, the problem by this rubbing process becomes a more serious problem. About the liquid crystal aligning film which improves the rubbing tolerance at the time of low temperature baking, the method of using specific tetracarboxylic dianhydride for the raw material of a polyamic acid (for example, refer patent document 2), the method of using an additive (for example, (Refer patent document 3), the method of using the diamine which introduce | transduced the acrylic acid residue at the terminal of a side chain (for example, refer patent document 4), etc. are proposed.

Japanese Patent Laid-Open No. 5-158047 Japanese Unexamined Patent Publication No. 2000-298279 Japanese Unexamined Patent Publication No. 2002-357831 Japanese Laid-Open Patent Publication 2008-203332

The subject of this invention is also possible to provide the material for a liquid crystal aligning film which does not generate | occur | produce film peeling or a scratch at the time of rubbing even if baking at 200 degrees C or less, and also obtains favorable liquid crystal alignability, and can produce also at baking of 200 degrees C or less, and rubbing It is possible to provide a liquid crystal aligning film which does not cause film peeling or scratches at the time and obtains a good liquid crystal alignment property, and which can be applied to a substrate having a relatively low heat resistance such as a plastic substrate and a reduction in energy cost at the time of manufacture. It is providing the liquid crystal display element, and providing the new diamine suitable for them.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors used the diamine component containing the diamine which has a specific structure containing a novel diamine compound before this application, and, even if baking at 200 degrees C or less, favorable liquid-crystal orientation It found that the liquid crystal aligning film which is obtained and which does not generate | occur | produce a film peeling or a scratch at the time of rubbing was obtained, and came to complete this invention. That is, this invention makes the following a summary.

1. It selects from the group which consists of a polyamic acid obtained by dehydrating and ring-closing the polyamic acid obtained by superposing | polymerizing-reacting the diamine component shown by following formula [1] and the tetracarboxylic dianhydride component shown by following formula [2]. A liquid crystal aligning agent containing at least 1 type of polymer used, The diamine component represented by following formula [3] contains in the said diamine component, The liquid crystal aligning agent characterized by the above-mentioned.

[Formula 1]

(2)

(3)

In the formula, R ³ represents a group selected from the group consisting of -CH _2- , -O-, -CONH-, -NHCO-, -COO-, -OCO- and -NH-. R ⁴ represents a single bond Or alkylene having 1 to 10 carbon atoms, and one or a plurality of -CH ₂ -of the alkylene may be substituted with -CF _2- , and when any of the following groups are not adjacent to each other, And these groups may be substituted; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-.

R ⁵ represents a single bond, -CH _2- , -O- or NH-. R ⁶ is composed of one or a plurality of rings, represents a divalent organic group having 5 to 18 carbon atoms having at least one aromatic ring at the terminal, and the ring may be a carbon ring or a heterocyclic ring, or one or a plurality of rings. The hydrogen atom of may be substituted with the fluorine atom. R ⁷ is a hydrogen atom, a methyl group or a trifluoromethyl group)

2. In this formula R ³ in [3], -O- or -COO- is, the liquid crystal alignment according to the item 1.

3. Liquid crystal aligning agent of said 1 or 2 whose R < ⁴ > in Formula [3] is C1-C4 alkylene.

4. Liquid crystal aligning agent in any one of said 1-3 whose R < ⁵ > in Formula [3] is -O-.

5. Liquid crystal aligning agent in any one of said 1-4 whose R < ⁶ > in Formula [3] is 1, 4- phenylene group.

6. The liquid crystal aligning agent in any one of said 1-5 whose R < ⁷ > in Formula [3] is a methyl group.

7. Liquid crystal aligning agent in any one of said 1-6 in which 30 mol% or more of diamine represented by said formula [3] is contained in the diamine component shown by Formula [1].

8. Liquid crystal orientation in any one of said 1-7 in which tetracarboxylic dianhydride which has alicyclic structure in R < ₂ > of Formula [2] is contained in the tetracarboxylic dianhydride component shown by Formula [2]. My.

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

10. The liquid crystal aligning film obtained by rubbing after apply | coating the liquid crystal aligning agent in any one of said 1-8 to a board | substrate, and baking at the temperature of 200 degrees C or less.

11. The liquid crystal display element which has a liquid crystal aligning film as described in said 9 or 10.

12. The diamine represented by following formula [3].

[Formula 4]

Wherein R ³ represents a group selected from the group consisting of -CH _2- , -O-, -CONH-, -NHCO-, -COO-, -OCO- and -NH-. R ⁴ represents a single bond Or alkylene having 1 to 10 carbon atoms, and one or a plurality of -CH ₂ -of the alkylene is -CF _2- ; May be substituted, and when any of the groups illustrated below are not adjacent to each other, they may be substituted with these groups; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH -. R ⁵ is a single bond, -CH ₂ -, represents -O- or NH-. R ⁶ is composed of one or a plurality of rings, represents a divalent organic group having 5 to 18 carbon atoms having at least one aromatic ring at the terminal, and the ring may be a carbon ring or a heterocyclic ring, or one or a plurality of rings. The hydrogen atom of may be substituted with the fluorine atom. R ⁷ is a hydrogen atom, a methyl group or a trifluoromethyl group)

Even if the liquid crystal aligning agent of this invention is the baking temperature of 200 degrees C or less, a film peeling or a damage does not generate | occur | produce by a rubbing process, and the liquid crystal aligning film with favorable orientation of a liquid crystal can be obtained. Moreover, the liquid crystal aligning agent of this invention can obtain high reliability also in the liquid crystal display element using the orientation processing method which irradiates a polarized ultraviolet-ray, etc., or the orientation processing method which irradiates an ultraviolet-ray etc., applying a voltage.

Diamine shown by following formula [3] contains in the diamine used for manufacture of the liquid crystal aligning agent of this invention.

[Chemical Formula 5]

In the formula, R ³ represents a group selected from the group consisting of -CH _2- , -O-, -CONH-, -NHCO-, -COO-, -OCO- and -NH-. R ⁴ represents a single bond Or alkylene having 1 to 10 carbon atoms, and one or a plurality of -CH ₂ -of the alkylene may be substituted with -CF _2- , and when any of the following groups are not adjacent to each other, And these groups may be substituted; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-.

R ⁵ is a single bond, -CH ₂ - represents the, -O- or -NH-. R ⁶ is composed of one or a plurality of rings, represents a divalent organic group having 5 to 18 carbon atoms having at least one aromatic ring at the terminal, and the ring may be a carbon ring or a heterocyclic ring, or one or a plurality of rings. The hydrogen atom of may be substituted with the fluorine atom. R ⁷ is a hydrogen atom, a methyl group or a trifluoromethyl group)

R <^3> -R <^4> -R <^5> -R < ⁶ > in formula [3] is a spacer site | part in a side chain, and R <^3> represents the coupling group with the diamino benzene skeleton in this spacer site | part. This linking group is -CH _2- (ie methylene), -O- (ie ether), -CONH- (ie amide), -NHCO- (ie reverse amide), -COO- (ie Ester), -OCO- (ie, reverse ester), and -NH- (ie, amino). These bonding groups can be formed by conventional organic synthetic techniques, but from the viewpoint of ease of synthesis, -CH _2- , -O-, -COO-, -NHCO- or -NH- is preferable, and -O- or- COO- is more preferable.

R < ⁴ > in Formula [3] is a part used as the center of a spacer site | part, As a basic structure, it is a single bond or C1-C10 alkylene. However, arbitrary -CH ₂ -of this alkylene may be substituted by -CF _2- . Further, -CH ₂ is substituted - is, or may be a plurality of point may be a single spot. In addition, one or a plurality of -CH ₂ -of the alkylene may be substituted with these bonding groups when any of the bonding groups shown below are not adjacent to each other; -O-, -NHCO-, -CONH -, -COO-, -OCO-, -NH-, -NHCONH-, -NH. This means that R <^4> may include the structure called alkylene- its coupling group-alkylene. In addition, the R ³ -CH ₂ - when the, ends of the side of the R ³ and R ⁴ may be a means that the combiner. Similarly, R ⁵ -CH ₂ - when the, ends of the side of the R ⁵ R ⁴ are means that may be the coupler. Therefore, when R ³ is -CH ₂ -and R ⁵ is -CH _2- , R ⁴ is a structure called its bond group-alkylene-the bond group, and R ⁴ is a structure called any of the bond groups. It means to be. Further, -CH ₂ -substituted by the linking group may be one point, or may be a plurality of points unless the linking groups are adjacent to each other. It is preferable that R <^4> is C1-C6 alkylene, and it is especially preferable that it is C4-C4 alkylene.

R < ⁵ > in Formula [3] represents a coupling group with R <^6> in a spacer site | part. A combiner, a single bond, -CH ₂ -, but selected from -O- and -NH-, is preferably -O-.

R < ⁶ > in Formula [3] consists of one or some ring, and represents the C5-C18 divalent organic group which has at least 1 aromatic ring at the terminal. The ring may be a carbon ring or a hetero ring. As a structure of such an organic group, although the following structures are specifically mentioned, it is not limited to this. In addition, one or a plurality of hydrogen atoms in the ring may be substituted with a fluorine atom.

[Formula 6]

[Formula 7]

Further, to improve the reactivity of the acrylic group and a methacrylic group (i.e., -OC (= O) -CH = CH 2 or -OC (= O) -C (= CH 2) substituent represented by -CH _3), It is preferable that the acryl group or methacryl group is couple | bonded with the aromatic ring. From such a viewpoint, as R <^6> , a 1, 4- phenylene group etc. are preferable, for example.

Although R < ⁷ > in Formula [3] is a hydrogen atom, a methyl group, or a trifluoromethyl group, it is preferable that it is a methyl group.

In said Formula [3], the bonding position of two amino groups on a benzene ring is not specifically limited. Two amino groups are the position of 2,3-, the position of 2,4-, the position of 2,5-, the position of 2,6-, the position of 3,4- with respect to the substituent which has an acrylate structure at the terminal. And 3,5-positions, preferably 2,4- or 3,5-positions.

&Lt; Synthesis method of diamine compound &gt;

Although the method of synthesize | combining the diamine compound shown by said Formula [3] is not specifically limited, For example, it can obtain by reducing the nitro group of the dinitro compound represented by following formula [4] and converting into an amino group.

[Formula 8]

(R <^3> , R <^4> , R <^5> , R <^6> and R <^7> in formula [4] are synonymous with the definition of Formula [3].

When reducing the said dinitro compound, reduction is performed using a catalyst such that the terminal double bonds are not hydrogenated. It is preferable to use zinc, tin, tin chloride, iron, etc. in ammonium chloride, hydrogen chloride, etc. in solvents, such as ethyl acetate, toluene, tetrahydrofuran, a dioxane, and alcohol type | system | groups, for a reduction reaction.

The dinitro compound represented by said formula [4] is a method of combining the dinitro compound containing -R ⁶ -R ⁵ -R ⁴ -R ³ through an ester bond with respect to a methacrylic acid compound or an acrylic acid compound, etc. You can get it. Examples, R ⁶ is a hydroxyl group (-OH) the dinitro compound and acrylic compound, acrylic acid or a compound containing the substituted -R ⁶ -R ⁵ -R ⁴ -R ³ by the DCC (N, N'- Dicyclohexylcarbodiimide) or a method of reacting with a condensing agent such as EDC (1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride), or R ⁶ represents a hydroxyl group (-OH And a dinitro compound containing -R ⁶ -R ⁵ -R ⁴ -R ³ substituted with) and an acrylic acid chloride compound or an acrylic acid chloride compound in the presence of a base.

The dinitro compound containing -R ⁶ -R ⁵ -R ⁴ -R ³ binds an alcohol compound containing -R ⁶ via R ⁵ to a dinitrobenzene compound containing -R ⁴ -R ³ . The method can be obtained. For example, R ⁵ of the carbon bond (-CH ₂ -) of cases, R ⁴ R ⁵ is an end portion of the dinitro benzene compound containing a halide and -R ⁴ -R ^3, R ⁶ -R ⁵ The method of synthesize | combining this oxidized and the alcohol compound which has an unsaturated bond using a hex reaction or a sonogashi cross coupling reaction, etc. are mentioned.

If R ⁵ is an ether bond (-O-) has, R ⁴ is the reaction of the two groups bonded to the hydroxy-dinitrobenzene compound and R ⁶ containing halogenated -R ⁴ -R ³ diol compound in the presence of an alkali The method of making it come can be mentioned.

R ⁵ is a method of reacting an alcohol compound having an amino group in the case of amino bond (-NH-), dinitrobenzene compound and R ⁶ containing the R ⁴ is an -R ⁴ -R ³ halide under alkaline presence Can be.

The dinitrobenzene compound containing -R ⁴ -R ³ can be obtained by, for example, bonding -R ⁴ to R in dinitrobenzene via R ³ .

For example, when R <^3> is an amide bond (-CONH-), the method of making dinitrobenzene acid chloride and the amino compound containing R <^4> react in alkali presence is mentioned. Moreover, when R <^3> is a reverse amide bond (-HNCO-), the method of making amino group containing dinitrobenzene and the acid chloride containing R <^4> react in alkali presence is mentioned.

When R <^3> is an ester bond (-COO-), the method of making dinitrobenzene acid chloride and the alcohol compound containing R <^4> react in alkali presence is mentioned. Moreover, when R <^3> is a reverse ester bond (-OCO-), the method of making hydroxy group containing dinitrobenzene and the acid chloride containing R <^4> react in alkali presence is mentioned.

When R <^3> is an ether bond (-O-), the method of making halogen group containing dinitrobenzene and the alcohol compound containing R <^4> react in alkali presence is mentioned.

When R <^3> is an amino bond (-NH-), the method of making halogen group containing dinitrobenzene and the amino compound containing R <^4> react in alkali presence is mentioned.

In the case where R ³ is a carbon bond (-CH _2- ), a halogen group-containing dinitrobenzene and a compound having an unsaturated bond by oxidizing the terminal of the R ³ side of R ⁴ -R ³ are subjected to a hex reaction or a sonogashira cross-coupling. The method of using a ring reaction is mentioned.

As said dinitro benzene acid chloride, 3, 5- dinitro benzoic acid chloride, 3, 5- dinitro benzoic acid, 2, 4- dinitro benzoic acid chloride, 3, 5- dinitro benzyl chloride, 2, 4- di Nitrobenzyl chloride and the like. Moreover, 2, 4- dinitro aniline, 3, 5- dinitro aniline, 2, 6- dinitro aniline etc. are mentioned as an amino group containing nitrobenzene. Examples of the nitro group-containing nitrobenzene include 2,4-dinitrophenol, 3,5-dinitrophenol, 2,6-dinitrophenol and the like. Examples of the halogen-containing dinitrobenzene include 2,4-dinitrofluorobenzene, 3,5-dinitrofluorobenzene, 2,6-dinitrofluorobenzene, 2,4-dinitroiodobenzene, 3, 5-dinitro iodobenzene, 2,6-dinitro iodobenzene, and the like.

The liquid crystal aligning agent of this invention is obtained by dehydrating and ring-closing the polyamic acid obtained by superposing | polymerizing-reacting the diamine component shown by said Formula [1], and the tetracarboxylic dianhydride component shown by said Formula [2], and this polyamic acid. As a liquid crystal aligning agent containing the at least 1 sort (s) of polymer chosen from the group which consists of polyimides, the diamine represented by said formula [3] is contained in the said diamine component.

In the diamine component, one type of diamine represented by Formula [3] may be sufficient and two or more types may be mixed.

In the diamine component represented by the formula [1] used for the polymerization reaction of a polyamic acid, the content rate of the diamine represented by Formula [3] is not specifically limited, but 10 mol from a viewpoint of suppressing film peeling and rubbing damage at the time of rubbing. It is preferable that it is% or more, More preferably, it is 30 mol% or more. Diamine represented by Formula [3] may be sufficient as 100 mol% of a diamine component.

When the content rate of the diamine represented by Formula [3] is less than 100 mol%, the structure and composition of the remaining diamine component are not specifically limited. When the specific example of diamine components other than the diamine shown by Formula [3] is shown, the diamine which is a divalent organic group which R < ₁ > in Formula [1] shows in the following table is mentioned, These may be one type and use two or more types together You may also

When using some of the diamine R ₁ is a B-83 ~ B-104 in the diamine component, it is possible to increase the pretilt angle of the liquid crystal when the liquid crystal alignment film.

The structure and composition of the tetracarboxylic dianhydride component represented by formula [2] used for the polymerization reaction of a polyamic acid are not specifically limited, One type of compound may be used and two or more types of compounds may be used together. Represents a specific example of the compound, there is a 4 indicating to the R ₂ of the formula [2] table include organic group-tetracarboxylic acid dianhydride.

When a tetracarboxylic acid dianhydride component, the R ₂ of the formula [2] with an organic group-tetracarboxylic acid dianhydride having an alicyclic structure, it is preferable because of the rubbing resistance it is further improved. At this time, the tetracarboxylic acid and the content of the of the total acid dianhydride component, equation [2] The organic group tetracarboxylic dianhydride R ₂ has a cycloaliphatic structure is at least 10 ㏖% preferably, more preferably Is 20 mol% or more, More preferably, it is 50 mol% or more, and 100 mol% may be sufficient. Examples of R ₂ having an alicyclic structure include A-1 to A-24 in the above table. As R <_2> which has alicyclic structure, A-1 of the said table is more preferable.

The polymerization reaction for obtaining a polyamic acid can be performed by mixing a diamine component and the tetracarboxylic dianhydride component in an organic solvent. The organic solvent at this time is not particularly limited as long as the resulting polyamic acid is dissolved. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone , N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, and the like. These may be used independently, and may mix and use. Moreover, even if it is a solvent which does not melt a polyamic acid, you may mix and use it with the said solvent in the range which does not precipitate the produced polyamic acid. Since water in the organic solvent inhibits the polymerization reaction of the polyamic acid and causes hydrolysis of the produced polyamic acid, it is preferable that the organic solvent is dehydrated and dried as much as possible.

As a method of mixing a tetracarboxylic dianhydride component and a diamine component in an organic solvent, the solution which disperse | distributed or dissolved the diamine component in the organic solvent is stirred, and the tetracarboxylic dianhydride component is disperse | distributed as it is or in an organic solvent. Or the method of dissolving and adding, the method of adding a diamine component to the solution which disperse | distributed or dissolved the tetracarboxylic dianhydride component in the organic solvent, the method of alternately adding the tetracarboxylic dianhydride component and a diamine component, etc. Can be mentioned. Moreover, when a tetracarboxylic dianhydride component or a diamine component consists of two or more types of compounds, it may carry out polymerization reaction in the state which mixed these several types of components previously, and may carry out polymerization reaction individually individually.

The temperature at the time of performing the polymerization reaction of a polyamic acid is -20-150 degreeC normally, Preferably it is 0-100 degreeC, More preferably, it is 10-80 degreeC. The higher the temperature, the faster the polymerization reaction is completed, but when the temperature is too high, a high molecular weight polyamic acid may not be obtained. In addition, the polymerization reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult, which is preferable. Preferably it is 1-50 mass%, More preferably, it is 5-30 mass%. The polymerization may be carried out at a high concentration in the initial stage, and then an organic solvent may be added.

The molecular weight of the obtained polyamic acid can be controlled by the molar ratio of the tetracarboxylic dianhydride component and diamine component used for a polymerization reaction, and molecular weight becomes large, so that this molar ratio is close to 1: 1. As for the molecular weight of the polyamic acid used by this invention or the polyimide obtained by dehydrating and ring-closing this polyamic acid, 2,000-200,000 are preferable at a weight average molecular weight from a viewpoint of handling ease and the characteristic stability at the time of using it as a liquid crystal aligning film, More preferably, it is 5,000-100,000.

The dehydration ring closure reaction (imidization reaction) for obtaining polyimide from a polyamic acid can be performed by stirring a polyamic acid in presence of a basic catalyst and an acid anhydride in an organic solvent. Pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. are mentioned as a basic catalyst at this time. Especially, pyridine is preferable because it has a basicity suitable for advancing reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Especially, since acetic anhydride becomes easy to refine | purify the obtained polyimide after completion | finish of imidation, it is preferable. As an organic solvent, the solvent used at the time of the polymerization reaction of the polyamic acid mentioned above can be used.

The imidation ratio of polyimide can be controlled by adjusting catalyst amount, reaction temperature, and reaction time. As quantity of a basic catalyst, 0.5-30 times mole of an amic acid group is preferable, More preferably, it is 2-20 times mole. Moreover, 1-50 times mole of an amic acid group is preferable, and, as for the quantity of an acid anhydride, More preferably, it is 3-30 times mole. The reaction temperature is preferably -20 to 250 ° C, more preferably 0 to 180 ° C. The imidation ratio of the polyimide used for the liquid crystal aligning agent of this invention does not need to be 100%, and may be what imidated partially.

The polyamic acid or polyimide obtained as described above can be recovered by adding the reaction solution to the stirred poor solvent, precipitating it, and filtering. Although it does not specifically limit as a poor solvent used at this time, Methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, etc. are mentioned.

The liquid crystal aligning agent of this invention can be obtained by melt | dissolving at least one polymer of the polyamic acid obtained by the above, or the polyimide which dehydrated-closed this polyamic acid in the organic solvent. Moreover, you may use the reaction solution of a polyamic acid or a polyimide as it is, or dilute with an organic solvent and use it.

The organic solvent used for dissolving the polymer or diluting the reaction solution is not particularly limited as long as the polymer component contained therein is dissolved. Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, and N-ethylpyrroli DON, N-vinylpyrrolidone, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, etc. are mentioned, These may be one type, or they may use in mixture of many types. do.

Moreover, even if it is a solvent which does not melt | dissolve a polymer component alone, if it is a range in which a polymer component does not precipitate, it can mix with the liquid crystal aligning agent of this invention. It is known that coating film uniformity improves at the time of apply | coating to a board | substrate by mixing suitably the solvent which has a low surface tension especially, It is used preferably also in the liquid crystal aligning agent of this invention. Specific examples of such a solvent include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, and 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-mono Ethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester, etc. Can be mentioned.

Although the solid content concentration of the liquid crystal aligning agent of this invention can be suitably changed with the thickness of the film to form, 1-10 mass% is preferable from a viewpoint of forming a uniform, defect-free thin film, and 3-8 mass% Is more preferable.

The liquid crystal aligning agent of this invention may contain the other polyamic acid and polyimide which superposed | polymerized separately in the range which does not impair the effect of this invention. Similarly, you may contain resin other than a polyamic acid and polyimide. In addition, in order to further improve the adhesiveness of the coating film to a board | substrate, you may add well-known additives, such as a silane coupling agent.

In this invention, the liquid crystal aligning agent of the said this invention is apply | coated to a board | substrate, it can dry and bake to make a film, and a liquid crystal aligning film is obtained by performing the orientation process by rubbing this film surface.

It will not specifically limit, if it is a thing with high transparency as a board | substrate which apply | coats a liquid crystal aligning agent, a glass substrate etc. can be used. In the reflective liquid crystal display element, only one substrate may be opaque, such as a silicon wafer, and the electrode in this case may use a material that reflects light such as aluminum.

As a coating method of a liquid crystal aligning agent, the spin coat method, the printing method, the inkjet method, etc. are mentioned, The transfer printing methods, such as flexographic printing, are industrially used widely from the viewpoint of productivity, The liquid crystal aligning agent of this invention It is also preferably used. Moreover, it is preferable to use a liquid crystal aligning agent after filtering with the membrane filter of 0.1 micrometer-1 micrometer of pore diameters.

Although the drying process after apply | coating a liquid crystal aligning agent is not necessarily required, when the time from application | coating to baking is not fixed for every board | substrate, or is not immediately baked after application | coating, it is preferable to include a drying process. The solvent should just be evaporated to the extent that a coating film shape does not deform | transform by conveyance of a board | substrate etc., and this drying is not specifically limited about the drying means. For example, the method of drying for 0.5 to 30 minutes, Preferably 1 to 5 minutes is taken on 50-150 degreeC, Preferably it is 80-120 degreeC hotplate.

Baking after apply | coating a liquid crystal aligning agent, Preferably it can carry out at arbitrary temperature of 100-350 degreeC. Moreover, even if baking the liquid crystal aligning agent of this invention is 200 degrees C or less, a favorable liquid crystal aligning film can be obtained. For example, a favorable liquid crystal aligning film can be obtained also in the baking temperature of 100 to 200 degreeC, and also 100 to 160 degreeC. This firing can be performed in a hot plate, a hot air circulation furnace, an infrared furnace, or the like.

When the thickness of the film after baking is too thick, it becomes disadvantageous in terms of 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.

Cotton, nylon, rayon etc. are mentioned as a material of the rubbing cloth used for a rubbing process.

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

As an example of liquid crystal cell preparation, a pair of board | substrates 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, and the other one side board | substrate is bonded together so that a liquid crystal aligning film surface may become inner side. And a method of sealing by injecting a liquid crystal under reduced pressure, or dropping a liquid crystal onto a liquid crystal alignment film surface on which a spacer is dispersed, and then bonding the substrate to perform sealing. The thickness of the spacer at this time becomes like this. Preferably it is 1-30 micrometers, More preferably, it is 2-10 micrometers.

Example

Although an Example is given to the following and this invention is demonstrated in more detail, the interpretation of this invention is not limited to these. In addition, the symbol and structure of the tetracarboxylic dianhydride and diamine used by the synthesis example are shown below.

[Chemical Formula 9]

[Formula 10]

The symbol of the organic solvent used in the Example etc. is as follows.

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

THF: Tetrahydrofuran

DMF: N, N-dimethylformamide

PhMe: Toluene

&Lt; Measurement of molecular weight of polymer &

The molecular weight of the polyimide or polyamic acid in the synthesis example was determined using the Shodex Corporation room temperature gel permeation chromatography (GPC) apparatus (GPC-101) and Shodex Corporation columns (KD-803, KD-805). It measured in the same way.

Column temperature: 50 ° C

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

Flow rate: 1.0 ml / min

Standard sample for calibration curve production: 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.

<Measurement of ¹ H-NMR>

Apparatus: Fourier transform type superconducting nuclear magnetic resonance apparatus (FT-NMR) INOVA-400 (manufactured by Varian) 400 MHz

Solvent: deuterated dimethylsulfoxide (DMSO-d ₆ ), deuterated chloroform (CDCl ₃ )

Standard substance: Tetramethylsilane (TMS)

Example 1 Synthesis of DA-1

[Formula 11]

Synthesis Example 1 Synthesis of Precursor DA-1-1 of DA-1

[Chemical Formula 12]

To a 500 ml three-necked flask, 56.8 g of 2,4-dinitrofluorobenzene, 300 ml of toluene, 137.0 g of 1,4-butanediol and 37.0 g of triethylamine were added, and the system was heated to 100 ° C. And stirred. 1N hydrochloric acid was added after completion | finish of reaction, and pH was 6-7. The organic layer was extracted with ethyl acetate, anhydrous magnesium sulfate was added to the organic layer, dehydrated and filtered, and then solvent distilled off using a rotary evaporator to give 69.9 g of the desired substance (yellow viscous). Obtained (yield 89%). The results of ¹ H-NMR measurement of the target product are shown below. From this result, the obtained solid confirmed that it was DA-1-1 of the objective. In addition, ¹ H-NMR means the nuclear magnetic resonance spectrum of the hydrogen atom in a molecule | numerator.

Synthesis Example 2 Synthesis of Precursor DA-1-2 of DA-1

[Chemical Formula 13]

38.43 g of DA-1-1, 350 ml of methylene chloride, 20.6 g of methanesulfonyl chloride and 37.9 g of triethylamine were added to a 500 ml three-neck flask, and the mixture was stirred at room temperature. After the completion of the reaction, the organic layer was extracted with ethyl acetate, anhydrous magnesium sulfate was added to the organic layer, dehydrated and filtered, and then solvent distilled off using a rotary evaporator to remove 48.8 g of the target substance (orange viscous). Obtained (yield 97%). The results of ¹ H-NMR measurement of the target product are shown below. From this result, the obtained solid confirmed that it was DA-1-2 of the objective.

Synthesis Example 3 Synthesis of Precursor DA-1-3 of DA-1

[Formula 14]

20.0 g of DA-1-2, 200 ml of dimethylformamide, 20.0 g of hydroquinone and 12.4 g of potassium carbonate were added to a 500 ml three-necked flask, and the system was heated to 80 ° C and stirred. 1N hydrochloric acid was added after completion | finish of reaction, and pH was 6-7. The organic layer was extracted with ethyl acetate, anhydrous magnesium sulfate was added to the organic layer, dehydrated and filtered, and then solvent distilled off using a rotary evaporator. The residue is washed with hot water and filtered to dissolve the filtrate in methanol and the insolubles are removed by filtration. The solvent was distilled off again using a rotary evaporator, and the residue was isolated by silica gel column chromatography (ethyl acetate: hexane = 1: 3 volume ratio) to obtain 16.2 g of the target substance (yellow solid) (yield) 77%). The result of having measured the target object by <^1> H-NMR is shown below. From this result, the obtained solid confirmed that it was DA-1-3 of the objective.

Synthesis Example 4 Synthesis of Precursor DA-1-4 of DA-1

[Formula 15]

To a 500 ml three-necked flask, 10.0 g of DA-1-3, 3.8 g of triethylamine, and 200 ml of THF were added. System inside was cooled, it was 0 degreeC, 3.9g of methacryloyl chloride was added, and it stirred at room temperature. After completion of the reaction, 50 ml of pure water was added and stirred. Then ethyl acetate was added to extract the organic layer. Anhydrous magnesium sulfate was added to the organic layer, followed by dehydration drying and filtration. Thereafter, the solvent was distilled off using a rotary evaporator Respectively. The residue was recrystallized using ethyl acetate / hexane = 2/8 to obtain 10.0 g of the target substance (yellow solid) (yield 84%). The result of having measured the target object by <^1> H-NMR is shown below. From this result, the obtained solid confirmed that it was DA-1-4 of the objective.

Synthesis Example 5 Synthesis of DA-1

[Chemical Formula 16]

To the 200 ml three-necked flask, 4.2 g of DA-1-4, 40 ml of tetrahydrofuran and 40 ml of pure water were added, the system was stirred, 13.2 g of tin chloride was added, and the system was heated to 70 ° C. Heated and stirred. After completion | finish of reaction, 200 ml of 5% sodium hydrogencarbonate aqueous solution was added, and pH was set to 7-8. 80 ml of ethyl acetate was added, the white precipitate was removed by filtration, the organic layer was extracted with ethyl acetate, anhydrous magnesium sulfate was added to the organic layer, dehydration dried and filtered, and then the solvent was distilled off using a rotary evaporator. Was carried out. The residue was recrystallized using ethyl acetate / hexane = 3/7 to obtain 1.0 g of the target product (white solid) (yield 30%). The result of having measured the target object by <^1> H-NMR is shown below. From this result, the obtained solid confirmed that it was DA-1 of the objective.

Example 2 Synthesis of DA-2

[Chemical Formula 17]

Synthesis Example 6 Synthesis of Precursor DA-2-1 of DA-2

[Chemical Formula 18]

To a 300 ml three-neck flask, 16.2 g of 3,5-dinitrobenzoyl chloride, 150 ml of tetrahydrofuran and 13.9 g of 4-bromo-1-butanol were added, followed by stirring at room temperature. After completion of the reaction, the organic layer was extracted with ethyl acetate, anhydrous magnesium sulfate was added to the organic layer, dehydrated and filtered, and then solvent distilled off using a rotary evaporator to obtain 23.0 g of the target substance (yellow viscous). Obtained (yield 95%). The result of having measured the target object by <^1> H-NMR is shown below. From this result, the obtained solid confirmed that it was DA-2-1 of the objective.

Synthesis Example 7 Synthesis of Precursor DA-2-2 of DA-2

[Chemical Formula 19]

To a 300 ml three-necked flask, 10.0 g of DA-2-1, 100 ml of dimethylformamide, 6.6 g of hydroquinone, 7.2 g of potassium iodide and 4.4 g of potassium carbonate were added, and the system was heated to 80 ° C. And stirred. 1N hydrochloric acid was added after completion | finish of reaction, and pH was 6-7. The organic layer was extracted with ethyl acetate, anhydrous magnesium sulfate was added to the organic layer, dehydrated and filtered, and then solvent distilled off using a rotary evaporator. The residue is washed with hot water and filtered to dissolve the filtrate in methanol and the insolubles are removed by filtration. The solvent was distilled off again using a rotary evaporator, and the residue was isolated by silica gel column chromatography (ethyl acetate: hexane = 1: 3 volume ratio) to obtain 5.7 g of the target substance (yellow solid) (yield) 53%). The result of having measured the target object by <^1> H-NMR is shown below. From this result, the obtained solid confirmed that it was DA-2-2 of the objective.

Synthesis Example 8 Synthesis of Precursor DA-2-3 of DA-2

[Chemical Formula 20]

To a 300 ml three-necked flask, 5.7 g of DA-2-2, 2.0 g of triethylamine and 100 ml of tetrahydrofuran were added. System inside was cooled, it was made 0 degreeC, 2.0 g of methacryloyl chloride was added, and it stirred at room temperature. After completion of the reaction, 50 ml of pure water was added and stirred. Then ethyl acetate was added to extract the organic layer. Anhydrous magnesium sulfate was added to the organic layer, followed by dehydration drying and filtration. Thereafter, the solvent was distilled off using a rotary evaporator Respectively. The residue was purified by silica gel column chromatography (ethyl acetate: hexane = 1: 3 volume ratio) to obtain 3.6 g of the target product (yellow solid) (yield 54%). The result of having measured the target object by <^1> H-NMR is shown below. From this result, the obtained solid confirmed that it was DA-2-3 of the objective.

Synthesis Example 9 Synthesis of DA-2

[Chemical Formula 21]

To a 200 ml three-necked flask, 3.6 g of DA-2-3, 30 ml of tetrahydrofuran and 30 ml of pure water were added, the system was stirred, 10.6 g of tin chloride was added, and the system was heated to 70 ° C. Heated and stirred. After completion | finish of reaction, 200 ml of 5% sodium hydrogencarbonate aqueous solution was added, and pH was set to 7-8. 80 ml of ethyl acetate was added, the white precipitate was removed by filtration, the organic layer was extracted with ethyl acetate, anhydrous magnesium sulfate was added to the organic layer, dehydration dried and filtered, and then the solvent was distilled off using a rotary evaporator. Was carried out. The residue was recrystallized using ethyl acetate / hexane = 3/7 to obtain 2.8 g of the target substance (white solid) (yield 93%). The result of having measured the target object by <^1> H-NMR is shown below. From this result, the obtained solid confirmed that it was DA-2 of the objective.

Example 3 Synthesis of DA-5

[Chemical Formula 22]

Synthesis Example 10 Synthesis of Precursor DA-5-1 of DA-5

(23)

To a 300 ml three-necked flask, 10.4 g of DA-2-1, 160 ml of acetone, 14.2 g of 4,4'-biphenol, 6.0 g of potassium iodide and 5.5 g of potassium carbonate were added, and the inside of the system was 50 Heated to &lt; RTI ID = 0.0 &gt; 1N hydrochloric acid was added after completion | finish of reaction, and pH was 6-7. The organic layer was extracted with ethyl acetate, anhydrous magnesium sulfate was added to the organic layer, dehydrated and filtered, and then solvent distilled off using a rotary evaporator. The residue is dissolved in isopropyl alcohol and the insolubles are removed by filtration. The solvent was distilled off again using a rotary evaporator, and the residue was recrystallized using isopropyl alcohol / hexane = 1/2 to obtain 6.2 g of the target substance (reddish brown solid) (yield 46%). ). The result of having measured the target object by <^1> H-NMR is shown below. From this result, the obtained solid confirmed that it was DA-5-1 of the objective.

Synthesis Example 11 Synthesis of Precursor DA-5-2 of DA-5

&Lt; EMI ID =

6.0 g of DA-5-1, 1.3 g of triethylamine, and 120 ml of tetrahydrofuran were added to a 300 ml three-neck flask. System inside was cooled, it was made 0 degreeC, 2.7 g of methacryloyl chloride was added, and it stirred at room temperature. After completion of the reaction, 50 ml of pure water was added and stirred, ethyl acetate was added to extract the organic layer, anhydrous magnesium sulfate was added to the organic layer, dehydration dried and filtered, and then solvent distillation was removed using a rotary evaporator. The residue was recrystallized using ethyl acetate / hexane = 1/9 to obtain 5.5 g of the target substance (yellow solid) (yield 79%). The result of having measured the target object by <^1> H-NMR is shown below. From this result, the obtained solid confirmed that it was DA-5-2 of the objective.

Synthesis Example 12 Synthesis of DA-5

(25)

To a 200 ml three-necked flask, 5.2 g of DA-5-2, 50 ml of tetrahydrofuran and 50 ml of pure water were added, the system was stirred, 13.3 g of tin chloride was added, and the system was heated to 70 ° C. Heated and stirred. After completion | finish of reaction, the 5% sodium hydrogencarbonate aqueous solution was added, and pH was set to 7-8. 80 ml of ethyl acetate was added, the white precipitate was removed by filtration, the organic layer was extracted with ethyl acetate, anhydrous magnesium sulfate was added to the organic layer, dehydration dried and filtered, and then the solvent was distilled off using a rotary evaporator. Was carried out. The residue was recrystallized using ethyl acetate / hexane = 3/7 to obtain 2.8 g of the target substance (yellow white solid) (yield 87%). The result of having measured the target object by <^1> H-NMR is shown below. From this result, the obtained solid confirmed that it was DA-5 of the objective.

Example 4 Synthesis of DA-6

(26)

Synthesis Example 13 Synthesis of Precursor DA-6-1 of DA-6

(27)

To a 300 ml three-necked flask, 11.2 g of DA-2-1, 180 ml of acetone, 7.7 g of 4,4'-dihydroxybenzophenone, 6.5 g of potassium iodide and 4.6 g of potassium carbonate were added, The inside was heated to 50 ° C. and stirred. 1N hydrochloric acid was added after completion | finish of reaction, and pH was 6-7. The organic layer was extracted with ethyl acetate, anhydrous magnesium sulfate was added to the organic layer, dehydrated and filtered, and then solvent distilled off using a rotary evaporator. The residue is dissolved in isopropyl alcohol and the insolubles are removed by filtration. The solvent was distilled off again using a rotary evaporator, and the residue was recrystallized using isopropyl alcohol / hexane = 1/1 to obtain 6.2 g of the target substance (yellow solid) (yield 50%). ). The result of having measured the target object by <^1> H-NMR is shown below. From this result, the obtained solid confirmed that it was DA-6-1 of the objective.

Synthesis Example 14 Synthesis of Precursor DA-6-2 of DA-6

(28)

5.8 g of DA-6-1, 1.6 g of triethylamine, and 60 mL of tetrahydrofuran were added to a 300 mL three neck flask. System inside was cooled, it was made 0 degreeC, 2.5 g of methacryloyl chloride was added, and it stirred at room temperature. After completion of the reaction, 50 ml of pure water was added and stirred, ethyl acetate was added to extract the organic layer, anhydrous magnesium sulfate was added to the organic layer, dehydration dried and filtered, and then solvent distillation was removed using a rotary evaporator. The residue was purified by silica gel column chromatography (ethyl acetate: hexane = 1: 4 volume ratio) to obtain 5.6 g of the target substance (yellow white solid) (yield 85%). The result of having measured the target object by <^1> H-NMR is shown below. From this result, the obtained solid confirmed that it was DA-6-2 of the objective.

Synthesis Example 15 Synthesis of DA-6

[Formula 29]

To a 200 ml three-necked flask, 5.5 g of DA-6-2, 50 ml of tetrahydrofuran and 50 ml of pure water were added, the system was stirred, 13.3 g of tin chloride was added, and the system was heated to 70 ° C. Heated and stirred. After completion | finish of reaction, the 5% sodium hydrogencarbonate aqueous solution was added, and pH was set to 7-8. 80 ml of ethyl acetate was added, the white precipitate was removed by filtration, the organic layer was extracted with ethyl acetate, anhydrous magnesium sulfate was added to the organic layer, dehydration dried and filtered, and then the solvent was distilled off using a rotary evaporator. Was carried out. The residue was recrystallized using ethyl acetate / hexane = 1/9 to obtain 2.8 g of the desired substance (yellow viscous solid) (yield 84%). The result of having measured the target object by <^1> H-NMR is shown below. From this result, the obtained solid confirmed that it was DA-6 of the objective.

Example 5 Synthesis of DA-7

(30)

Synthesis Example 16 Synthesis of Precursor DA-7-1 of DA-7

(31)

To a 300 ml three-necked flask, 7.7 g of p- (trans-4-hydroxycyclohexyl) phenol, 4.4 g of triethylamine and 100 ml of tetrahydrofuran were added. System inside was cooled, it was made 0 degreeC, 4.4 g of methacryloyl chloride was added, and it stirred at room temperature. After completion of the reaction, 50 ml of pure water was added and stirred, ethyl acetate was added to extract the organic layer, anhydrous magnesium sulfate was added to the organic layer, dehydration dried and filtered, and then solvent distillation was removed using a rotary evaporator. The residue was recrystallized using ethyl acetate / hexane = 1/9 to obtain 7.5 g of the target substance (white solid) (yield 72%). The result of having measured the target object by <^1> H-NMR is shown below. From this result, the obtained solid confirmed that it was DA-7-1 of the objective.

Synthesis Example 17 Synthesis of Precursor DA-7-2 of DA-7

(32)

To a 300 ml three-neck flask, 5.2 g of DA-7-1, 2.0 g of triethylamine and 50 ml of tetrahydrofuran were added. System inside was cooled, it was made 0 degreeC, 4.6g of 3, 5- dinitro benzoyl chlorides were added, and it stirred at room temperature. After completion of the reaction, 50 ml of pure water was added and stirred. Then ethyl acetate was added to extract the organic layer. Anhydrous magnesium sulfate was added to the organic layer, followed by dehydration drying and filtration. Thereafter, the solvent was distilled off using a rotary evaporator Respectively. The residue was purified by silica gel column chromatography (ethyl acetate: hexane = 1: 4 volume ratio) to obtain 6.8 g of the target product (white solid) (yield 75%). The result of having measured the target object by <^1> H-NMR is shown below. From this result, the obtained solid confirmed that it was DA-7-2 of the objective.

Synthesis Example 18 Synthesis of DA-7

(33)

To the 200 ml three-necked flask, 6.8 g of DA-7-2, 60 ml of tetrahydrofuran and 60 ml of pure water were added, the system was stirred, 19.9 g of tin chloride was added, and the system was heated to 70 ° C. Heated and stirred. After completion | finish of reaction, the 5% sodium hydrogencarbonate aqueous solution was added, and pH was set to 7-8. 80 ml of ethyl acetate was added, the white precipitate was removed by filtration, the organic layer was extracted with ethyl acetate, anhydrous magnesium sulfate was added to the organic layer, dehydration dried and filtered, and then the solvent was distilled off using a rotary evaporator. Was carried out. The residue was recrystallized using ethyl acetate / hexane = 1/9 to obtain 5.8 g of the desired substance (white solid) (yield 98%). The result of having measured the target object by <^1> H-NMR is shown below. From this result, the obtained solid confirmed that it was DA-7 of the objective.

Example 6 Synthesis of Liquid Crystal Alignment Agent

1.94 g (0.0099 mol) of CBDA and 3.84 g (0.01 mol) of DA-2 were made to react in NMP23.14g for 16 hours at room temperature, and the polyamic-acid solution (PAA-1) was prepared. The number average molecular weight of this polyamic acid was about 5000, and the weight average molecular weight was about 8000. NMP and BCS were added and stirred to 10 g of this polyamic-acid solution, and it prepared to be 6 mass% of polyamic acid (PAA-1), 74 mass% of NMP, and 20 mass% of BCS, and then the membrane of 1 micrometer of pore diameters It filtered under pressure by the filter and obtained the liquid crystal aligning agent.

Example 7 Synthesis of Liquid Crystal Aligner

1.76 g (0.009 mol) of CBDA and 4.60 g (0.01 mol) of DA-5 were made to react in NMP 36.10g for 16 hours at room temperature, and the polyamic-acid solution (PAA-4) was prepared. The number average molecular weight of this polyamic acid was about 10000, and the weight average molecular weight was about 80000. NMP and BCS were added and stirred to 10 g of this polyamic-acid solution, and it prepared to be 6 mass% of polyamic acid (PAA-4), 74 mass% of NMP, and 20 mass% of BCS, and then the membrane of 1 micrometer of pore diameters It filtered under pressure by the filter and obtained the liquid crystal aligning agent.

Example 8 Synthesis of Liquid Crystal Alignment

1.94 g (0.099 mol) of CBDA and 4.60 g (0.01 mol) of DA-6 were made to react in NMP27.31g for 16 hours at room temperature, and the polyamic-acid solution (PAA-5) was prepared. The number average molecular weight of this polyamic acid was about 20000, and the weight average molecular weight was about 200000. NMP and BCS were added and stirred to 10 g of this polyamic-acid solution, and it prepared to be 6 mass% of polyamic acid (PAA-5), 74 mass% of NMP, and 20 mass% of BCS, and then the membrane of 1 micrometer of pore diameters It filtered under pressure by the filter and obtained the liquid crystal aligning agent.

Example 9 Synthesis of Liquid Crystal Aligner

1.94 g (0.099 mol) of CBDA and 3.94 g (0.01 mol) of DA-7 were made to react in NMP 33.35g for 16 hours at room temperature, and the polyamic-acid solution (PAA-6) was prepared. The number average molecular weight of this polyamic acid was about 7000, and the weight average molecular weight was about 30000. NMP and BCS were added and stirred to 10 g of this polyamic-acid solution, and it prepared to be 6 mass% of polyamic acid (PAA-6), 74 mass% of NMP, and 20 mass% of BCS, and then the membrane of 1 micrometer of pore diameters It filtered under pressure by the filter and obtained the liquid crystal aligning agent.

(Comparative Example 1) Synthesis of liquid crystal aligning agent

1.94 g (0.0099 mol) of CBDA and 2.64 g (0.01 mol) of DA-3 were made to react in NMP18.34g for 16 hours at room temperature, and the polyamic-acid solution (PAA-2) was prepared. The number average molecular weight of this polyamic acid was about 22000, and the weight average molecular weight was about 62000. NMP and BCS were added and stirred to 10 g of this polyamic-acid solution, and it prepared to be 6 mass% of polyamic acid (PAA-2), 74 mass% of NMP, and 20 mass% of BCS, and then the membrane of 1 micrometer of pore diameters It filtered under pressure by the filter and obtained the liquid crystal aligning agent.

(Comparative Example 2) Synthesis of liquid crystal aligning agent

1.86 g (0.095 mol) of CBDA and 1.08 g (0.01 mol) of DA-4 were made to react in NMP16.68g for 16 hours at room temperature, and the polyamic-acid solution (PAA-3) was prepared. The number average molecular weight of this polyamic acid was about 8000, and the weight average molecular weight was about 18000. NMP and BCS were added and stirred to 10 g of this polyamic-acid solution, and it prepared to be 6 mass% of polyamic acid (PAA-3), 74 mass% of NMP, and 20 mass% of BCS, and then the membrane of 1 micrometer of pore diameters It filtered under pressure by the filter and obtained the liquid crystal aligning agent.

About the liquid crystal aligning agent prepared in said Examples 6-9 and Comparative Examples 1 and 2, the board | substrate with a liquid crystal aligning film was produced as follows.

<Evaluation of rubbing resistance>

The liquid crystal aligning agent was spin-coated to the glass substrate with a transparent electrode, and it dried for 70 second on the 70 degreeC hotplate, and then baked on the 120 degreeC hotplate for 10 minutes, and formed the coating film of 100 nm in film thickness. This coated film surface was rubbed on the conditions of the roll rotation speed 1000rpm, the roll advancing speed 50mm / sec, and 0.5 mm of pushing amount using the rayon cloth with the rubbing apparatus of roll diameter 120mm, and the board | substrate with a liquid crystal aligning film was obtained. The obtained liquid crystal aligning film surface was observed with the confocal laser microscope, and the following evaluation was performed. Below, the evaluation result of rubbing tolerance is shown.

(Circle): Grinding debris and rubbing scratches are not observed.

Δ: Grinding debris and rubbing scratches are observed.

X: The film was peeled off or a rubbing scratch was visually observed.

Industrial availability

Since the liquid crystal aligning agent of this invention can obtain the liquid crystal aligning film which the orientation of a liquid crystal is uniform, and there is no orientation defect, the cost accompanying baking of an alignment film can be reduced, and let alone a glass substrate, the liquid crystal display element using a plastic substrate, etc. It can also use preferably.

In addition, the JP Patent application 2010-148647, the claim, and all the content of the abstract for which it applied on June 30, 2010 are referred here, and it takes in as an indication of the specification of this invention.

Claims (13)

At least selected from the group consisting of a polyamic acid obtained by polymerizing a diamine component represented by the following formula [1] and a tetracarboxylic dianhydride component represented by the following formula [2] and a polyimide obtained by dehydrating and closing the polyamic acid: As a liquid crystal aligning agent containing 1 type of polymers, the diamine represented by following formula [3] is contained in the said diamine component, The liquid crystal aligning agent characterized by the above-mentioned.
[Formula 1]

(2)

(3)

In the formula, R ³ represents a group selected from the group consisting of -CH _2- , -O-, -CONH-, -NHCO-, -COO-, -OCO- and -NH-. R ⁴ represents a single bond Or alkylene having 1 to 10 carbon atoms, and one or a plurality of -CH ₂ -of the alkylene may be substituted with -CF _2- , and when any of the following groups are not adjacent to each other, And these groups may be substituted; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-.
R ⁵ is a single bond, -CH ₂ -, represents -O- or NH-. R ⁶ is composed of one or a plurality of rings, represents a divalent organic group having 5 to 18 carbon atoms having at least one aromatic ring at the terminal, and the ring may be a carbon ring or a heterocyclic ring, or one or a plurality of rings. The hydrogen atom of may be substituted with the fluorine atom. R ⁷ is a hydrogen atom, a methyl group or a trifluoromethyl group) The method of claim 1,
Equation [3] R ³ is a liquid crystal orientation, -O- or -COO- in. 3. The method according to claim 1 or 2,
The liquid crystal aligning agent whose R < ⁴ > in Formula [3] is C1-C4 alkylene. The method according to any one of claims 1 to 3,
The liquid crystal aligning agent whose R < ⁵ > in Formula [3] is -O-. The method according to any one of claims 1 to 4,
The liquid crystal aligning agent whose R < ⁶ > in Formula [3] is a 1, 4- phenylene group. 6. The method according to any one of claims 1 to 5,
The liquid crystal aligning agent whose R < ⁷ > in Formula [3] is a methyl group. 7. The method according to any one of claims 1 to 6,
The liquid crystal aligning agent in which the diamine represented by the said Formula [3] contains 30 mol% or more in the diamine component shown by Formula [1]. The method according to any one of claims 1 to 7,
The liquid crystal aligning agent in which the tetracarboxylic dianhydride which has alicyclic structure is contained in R < ₂ > of Formula [2] in the tetracarboxylic dianhydride component shown by Formula [2]. A liquid crystal alignment film obtained from the liquid crystal aligning agent according to any one of claims 1 to 8. The liquid crystal aligning film obtained by rubbing after apply | coating the liquid crystal aligning agent in any one of Claims 1-8 to a board | substrate, and baking at the temperature of 200 degrees C or less. The liquid crystal display element which has a liquid crystal aligning film of Claim 9 or 10. Diamine represented by following formula [3].
[Chemical Formula 4]

Wherein R ³ represents a group selected from the group consisting of -CH _2- , -O-, -CONH-, -NHCO-, -COO-, -OCO- and -NH-. R ⁴ represents a single bond, Or alkylene having 1 to 10 carbon atoms, and one or a plurality of -CH ₂ -of the alkylene may be substituted with -CF _2- , and when any of the groups illustrated below are not adjacent to each other, It may be substituted by these groups; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-.
R ⁵ represents a single bond, -CH _2- , -O- or NH-. R ⁶ is composed of one or a plurality of rings, represents a divalent organic group having 5 to 18 carbon atoms having at least one aromatic ring at the terminal, and the ring may be a carbon ring or a heterocyclic ring, or one or a plurality of rings. The hydrogen atom of may be substituted with the fluorine atom. R ⁷ is a hydrogen atom, a methyl group or a trifluoromethyl group) The diamine represented by following formula DA1, formula DA2, formula DA5, formula DA6, or formula DA7.
[Chemical Formula 5]