KR102234876B1 - Liquid-crystal orientation treatment agent, liquid-crystal orientation film, and liquid-crystal display element - Google Patents

Abstract

A liquid crystal aligning agent, a liquid crystal aligning film and a liquid crystal display element that can achieve a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time, suppress a decrease in voltage retention, and obtain a liquid crystal aligning film with quick relaxation of accumulated residual charge Provides. The liquid crystal aligning agent containing the following (A) component and (B) component. Component (A): A polymer containing at least one of a polyimide precursor and a polyimide obtained by reacting a diamine component containing a diamine compound having a side chain structure of formula [1] and a tetracarboxylic acid component. Component (B): A polymer containing at least one of a polyimide precursor and a polyimide obtained by reacting a diamine component not containing a diamine compound having a side chain structure represented by formula [1] and a tetracarboxylic acid component. (Y ¹ , Y ² , Y ³ are single bonds, alkylene, etc.; Y ⁴ and Y ⁵ are divalent cyclic groups such as benzene rings; n is an integer of 0 to 4; Y ⁶ is an alkyl group having 1 to 18 carbon atoms, etc. )

Description

A liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element {LIQUID-CRYSTAL ORIENTATION TREATMENT AGENT, LIQUID-CRYSTAL ORIENTATION FILM, AND LIQUID-CRYSTAL DISPLAY ELEMENT}

The present invention relates to a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element used for a liquid crystal display element.

A liquid crystal display element is currently widely used as a display device realizing a thin and light weight. Usually, a liquid crystal aligning film is used in a liquid crystal display element in order to determine an alignment state of a liquid crystal.

As one of the characteristics required for the liquid crystal aligning film, there is a control of the so-called pretilt angle of the liquid crystal in which the orientation tilt angle of the liquid crystal molecules with respect to the substrate surface is maintained at an arbitrary value. It is known that the size of the pretilt angle can be changed by selecting the structure of the polyimide constituting the liquid crystal alignment film. Even in the technique of controlling the pretilt angle by the structure of the polyimide, the method of using a diamine having a side chain as a part of the polyimide raw material can control the pretilt angle according to the use ratio of the diamine. It is relatively easy to obtain a pretilt angle, and is useful as a means of increasing the pretilt angle (see, for example, Patent Document 1). In addition, the diamine component for increasing the pretilt angle of the liquid crystal has been studied to improve the stability and process dependence of the pretilt angle. As the side chain structure, a cyclic structure such as a phenyl group or a cyclohexyl group is used. It is proposed to contain (for example, see Patent Document 2).

In addition, from the viewpoints of suppressing a decrease in the contrast of the liquid crystal display device and reducing an afterimage phenomenon as a result of the high definition of the liquid crystal display device, the liquid crystal alignment film used also has a high voltage retention rate, or accumulation when a DC voltage is applied. The characteristic that the charge is small or that the charge accumulated by the DC voltage is relieved quickly is becoming increasingly important.

In the polyimide liquid crystal alignment film, the time until the afterimage generated by the DC voltage disappears is short, and in addition to polyamic acid or imide group-containing polyamic acid, a liquid crystal aligning agent containing a tertiary amine of a specific structure is used. What was used (for example, see Patent Document 3) or a liquid crystal aligning agent containing a soluble polyimide in which a specific diamine having a pyridine skeleton is used as a raw material (for example, see Patent Document 4) is known. have. In addition, the voltage retention rate is high and the time until the afterimage generated by the DC voltage disappears is short, and in addition to polyamic acid or its imidized polymer, compounds containing one carboxylic acid group in the molecule, and one in the molecule It is known that a liquid crystal aligning agent containing a very small amount of a compound selected from a compound containing a carboxylic anhydride group and a compound containing one tertiary amino group in a molecule (see, for example, Patent Document 5).

Japanese Laid-Open Patent Publication No. Hei 2-282726 Japanese Laid-Open Patent Publication No. Hei 9-278724 Japanese Patent Application Laid-Open No. Hei 9-316200 Japanese Laid-Open Patent Publication No. Hei 10-104633 Japanese Laid-Open Patent Publication No. Hei 8-76128

The liquid crystal alignment film is also used to control the angle of the liquid crystal with respect to the substrate, that is, the pretilt angle of the liquid crystal. In particular, in VA (Vertical Alignment) mode or PSA (Polymer Sustained Alignment) mode, since it is necessary to vertically align the liquid crystal, the liquid crystal alignment film has the ability to vertically align the liquid crystal (also referred to as vertical alignment or high pretilt angle). ) Is required. Moreover, not only a high vertical alignment property but also the stability of a liquid crystal aligning film is becoming important. In particular, in order to obtain high luminance, a liquid crystal display device that uses a backlight with a large amount of heat and a large amount of light irradiation, for example, in a car navigation system or a large TV, is often used or left in an environment exposed to high temperature and light irradiation for a long time. have. Under such severe conditions, when the vertical orientation is deteriorated, problems such as initial display characteristics are not obtained or non-uniformity occurs in display.

Further, with regard to the voltage retention, which is one of the electrical characteristics of a liquid crystal display element, high stability under the above severe conditions is also required. That is, when the voltage retention is lowered by irradiation of light from the backlight, an afterimage defect (also referred to as a line afterimage), which is one of the display defects of the liquid crystal display element, tends to occur, and a highly reliable liquid crystal display element cannot be obtained. Therefore, in addition to having good initial characteristics, the liquid crystal aligning film is required that the voltage retention does not decrease well even after exposure to light irradiation for a long time. In addition, also for surface afterimages, which are another afterimage defect, there is a demand for a liquid crystal alignment film in which residual charges accumulated by a DC voltage are quickly relieved by irradiation of light from a backlight.

Therefore, the present invention can exhibit a stable pretilt angle even after exposure to high temperature and light irradiation for a long time, and also suppresses a decrease in voltage retention even after exposure to light irradiation for a long time, and accumulates by direct current voltage. It is an object of the present invention to provide a liquid crystal aligning agent in which a liquid crystal aligning film in which residual charge relaxation is quick is obtained.

In addition, an object of the present invention is to provide a liquid crystal alignment film having the above characteristics, and a liquid crystal display device provided with the liquid crystal alignment film.

As a result of intensive research, the present inventor found out that a liquid crystal aligning agent having two polymers having a specific structure is very effective in order to achieve the above object, and came to complete the present invention.

That is, the present invention has the following summary.

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

Component (A): At least one polymer selected from the group consisting of a polyimide precursor and a polyimide obtained by reacting a diamine component containing a diamine having a structure represented by the following formula [1] with a tetracarboxylic acid component.

Component (B): At least one type of polymer selected from the group consisting of a polyimide precursor and a polyimide obtained by reacting a diamine component not containing a diamine having a structure represented by the following formula [1] with a tetracarboxylic acid component.

[Formula 1]

(Y ¹ represents a single bond, -(CH ₂ ) _a- (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO-, or OCO-. Y ² is a single bond or (CH ₂ ) _b -represents (b is an integer of 1 to 15) Y ³ is a single bond, -(CH ₂ ) _c- (c is an integer of 1 to 15), -O-, -CH ₂ Represents O-, -COO- or OCO- Y ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton, and the ring any hydrogen atom of an alkyl group having 1 to 3 on the sentence, a fluorine-containing alkyl group having 1 to 3 carbon atoms, an alkoxyl group, having 1 to 3, may be substituted 1 to 3 carbon atoms a fluorine-containing alkoxy group or a fluorine atom. Y ⁵ is Represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring, and a heterocycle, and any hydrogen atom on these cyclic groups contains an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, and a fluorine having 1 to 3 carbon atoms It may be substituted with an alkyl group, a C1-C3 fluorine-containing alkoxyl group, or a fluorine atom. n represents an integer of 0-4. Y ⁶ is a C1-C18 alkyl group, a C1-C18 fluorine-containing alkyl group, a C1 It represents an alkoxyl group of to 18 or a fluorine-containing alkoxyl group of 1 to 18 carbon atoms.)

2. The liquid crystal aligning agent according to the above 1, wherein the diamine having a structure represented by the above formula [1] is represented by the following formula [1a]. Formula (1a) (in, Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , n, Y ⁶ and m represent the same meanings as above.

[Formula 2]

3. A polyimide precursor obtained by reacting a diamine component containing a diamine and a tetracarboxylic acid component in which the component (B) has at least one substituent selected from a carboxyl group (COOH group) and a hydroxyl group (OH group) And at least one type of polymer selected from the group consisting of polyimide.

4. Said 1, 2, or 3, wherein the component (A) is a polymer used for a diamine component containing a diamine having at least one substituent selected from a carboxyl group (COOH group) and a hydroxyl group (OH group). The liquid crystal aligning agent described in.

5. The liquid crystal aligning agent according to the above 3 or 4, wherein the diamine having at least one substituent selected from the carboxyl group and the hydroxyl group is represented by the following formula [2a].

[Formula 3]

(A ¹ represents at least one substituent selected from the following formulas [2a-1] and [2a-2], and m1 represents an integer of 1 to 4).

[Formula 4]

(d represents the integer of 0-4, e represents the integer of 0-4).

6. The liquid crystal aligning agent according to any one of the above 1 to 5, wherein the polymer of the component (A) and the component (B) is a polymer in which a diamine represented by the following formula [3a] is used for the diamine component.

[Formula 5]

(B ¹ is -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON(CH ₃ )- or N(CH ₃ ) Represents CO- B ² represents a single bond, an alkylene having 1 to 20 carbon atoms, a non-aromatic ring or an aromatic ring B ³ represents a single bond, -O-, -NH-, -N(CH ₃ )- , -CONH-, -NHCO-, -COO-, -OCO-, -CON(CH ₃ )-, N(CH ₃ )CO-, or -O(CH ₂ ) _m2- (m2 is an integer from 1 to 5 B ⁴ represents a nitrogen-containing heterocycle, n1 represents an integer of 1 to 4, and when n1 is 2 or more, -B ¹ -B ² -B ³ -B ⁴ may be the same as or different from each other do).

7. The liquid crystal orientation according to 6 ^{, wherein B 1} in the formula [3a] is -O-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCO- or CON(CH _{3 )-} Treatment agent.

^{8. The liquid crystal aligning agent according to the above 6 or 7 wherein B 2} in the formula [3a] is a single bond, an alkylene having 1 to 5 carbon atoms, a cyclohexane ring, or a benzene ring.

^{9. According to any one of 6 to 8 above, wherein B 3} in the formula [3a] is a single bond, -O-, -OCO-, or O(CH ₂ ) _2- (m2 is an integer of 1 to 5). Liquid crystal aligning agent.

^{10. The liquid crystal aligning agent in any one of said 6-9 whose B 4} in said formula [3a] is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, or a pyrimidine ring.

^{11. B 1} in the above formula [3a] represents -CONH-, B ² represents an alkylene having 1 to 5 carbon atoms, B ³ represents a single bond, and B ⁴ represents an imidazole ring or a pyridine ring, The liquid crystal aligning agent according to said 6 in which n1 is 1.

12. In any one of the above 1 to 11, wherein the tetracarboxylic acid component in at least one of the component (A) and the component (B) contains a tetracarboxylic dianhydride represented by the following formula [4]. The described liquid crystal aligning agent.

[Formula 6]

(Z ¹ is a group selected from the following formula [4a]-formula [4k]).

[Formula 7]

(Z ² to Z ⁵ each independently represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and Z ⁶ and Z ⁷ each independently represent a hydrogen atom or a methyl group)

13. The liquid crystal aligning agent in any one of said 1-12 containing at least 1 type of solvent among N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butyrolactone.

14. The liquid crystal aligning agent in any one of said 1 to 13 containing at least 1 type of solvent selected from following formula [D-1]-formula [D-3].

[Formula 8]

(D ¹ represents an alkyl group having a carbon number of 1 to 3, D ² represents an alkyl group having a carbon number of 1 to 3, D ³ represents an alkyl group having from 1 to 4 carbon atoms).

15. At least one solvent selected from 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether and dipropylene glycol dimethyl ether The liquid crystal aligning agent in any one of said 1-14 containing.

16. A crosslinkable compound having at least one substituent selected from the group consisting of an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group in the liquid crystal aligning agent, a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group And at least one crosslinkable compound selected from a crosslinkable compound having a polymerizable unsaturated bond.

17. A liquid crystal aligning film obtained from the liquid crystal aligning agent in any one of said 1-16.

18. A liquid crystal aligning film obtained by printing the liquid crystal aligning agent according to any one of the above 1 to 16 by an ink jet method.

19. A liquid crystal display device having the liquid crystal alignment film according to 17 or 18 above.

20. A liquid crystal composition containing a polymerizable compound that has a liquid crystal layer between a pair of substrates with electrodes and is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, and the electrode The liquid crystal alignment film according to the above 17 or 18 used for a liquid crystal display device manufactured through a step of polymerizing the polymerizable compound while applying a voltage therebetween.

21. A liquid crystal alignment film comprising a liquid crystal layer formed between a pair of substrates with electrodes, and containing a polymerizable group that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, and the The liquid crystal aligning film according to the above 17 or 18 used for a liquid crystal display device manufactured through a step of polymerizing the polymerizable group while applying a voltage between electrodes.

22. A liquid crystal display device having the liquid crystal alignment film according to 20 or 21 above.

Liquid crystal having two polymers of at least one polymer selected from polyimide precursors and polyimides containing a specific structure of the present invention, and at least one polymer selected from polyimide precursors and polyimides not containing a specific structure The alignment treatment agent can obtain a liquid crystal alignment film capable of expressing a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time. Further, even after exposure to light irradiation for a long period of time, a liquid crystal alignment film can be obtained that suppresses a decrease in voltage retention and relieves residual charges accumulated by a direct current voltage quickly. Therefore, a liquid crystal display element having a liquid crystal aligning film obtained from the liquid crystal aligning agent of the present invention is excellent in reliability, and can be preferably used for a large-screen, high-definition liquid crystal television or the like.

The liquid crystal aligning agent of this invention contains the following (A) component and (B) component.

Component (A): Selected from polyimide precursors and polyimides obtained by reacting a diamine component containing a diamine compound having a side chain structure (also referred to as a specific side chain structure) represented by the above formula [1] and a tetracarboxylic acid component A polymer containing at least any one of (also referred to as a specific polymer (A)).

Component (B): containing at least one selected from a polyimide precursor and a polyimide obtained by reacting a diamine component not containing a diamine compound having a side chain structure represented by the above formula [1] and a tetracarboxylic acid component Polymer (also referred to as specific polymer (B)).

The liquid crystal aligning agent of this invention contains the following (A) component and (B) component among them. In that case, it is preferable to use the diamine compound which has a specific side chain structure only for (A) component.

Component (A): A polymer containing at least any one selected from a polyimide precursor and a polyimide obtained by reacting a diamine component and a tetracarboxylic acid component.

Component (B): A polymer containing at least any one selected from a polyimide precursor and a polyimide obtained by reacting a diamine component and a tetracarboxylic acid component.

The specific side chain structure represented by formula [1] contained in the specific polymer (A) of the present invention has at least one group selected from a benzene ring, a cyclohexyl ring and a heterocycle, or a steroid skeleton at the side chain portion. It has a C17-C51 divalent organic group. The side chain structures of these rings and organic groups show a rigid structure compared to the side chain structure of a long chain alkyl group, which is a conventional technique in which the liquid crystal is vertically aligned. Thereby, the liquid crystal aligning film obtained from the liquid crystal aligning agent which has a specific side chain structure can obtain high and stable vertical alignment of a liquid crystal as compared with that of the side chain structure of a conventional long chain alkyl group.

In addition, the specific side chain structure is more stable against light such as ultraviolet rays than the side chain structure of a conventional long chain alkyl group. Therefore, even if the specific side chain structure is exposed to light irradiation for a long period of time, the voltage retention rate is lowered, and the decomposition product of the side chain component which accumulates residual electric charge by direct current voltage can be suppressed.

In addition, the liquid crystal aligning agent of this invention is a liquid crystal aligning agent which has a specific polymer (A) and a specific polymer (B), and a specific polymer (B) does not contain a specific side chain structure. Therefore, the liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention can suppress the accumulation|storage of residual electric charge by a DC voltage from the point that the quantity of the side chain component which increases the volume resistance of a liquid crystal aligning film becomes small.

In this way, according to the liquid crystal aligning agent of the present invention, a liquid crystal aligning film capable of expressing a stable pretilt angle can be obtained even after being exposed to high temperature and light irradiation for a long time. Further, even after exposure to light irradiation for a long period of time, a liquid crystal alignment film can be obtained that suppresses a decrease in voltage retention and relieves residual charges accumulated by a direct current voltage quickly.

<Specific side chain structure>

The specific polymer (A) of the present invention is at least selected from a polyimide precursor and a polyimide obtained by reacting a diamine component containing a diamine compound having a specific side chain structure represented by the following formula [1] and a tetracarboxylic acid component. It is a polymer containing either one.

[Formula 9]

(In formula [1], ^{the definitions of Y 1} , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , and n are as described above)

In formula [1], Y ¹ _{is a single bond, -(CH 2} ) _a- (a is an integer of 1 to 15), -O-, especially from the viewpoint of availability of raw materials and ease of synthesis. -CH ₂ O- or COO- is preferred. More preferable ones are a single bond, -(CH ₂ ) _a- (a is an integer of 1 to 10), -O-, -CH ₂ O-, or COO-. Y ² is particularly preferably a single bond or (CH ₂ ) _b- (b is an integer of 1 to 10). Y ³ is particularly preferably a single bond, -(CH ₂ ) _c- (c is an integer of 1 to 15), -O-, -CH ₂ O-, or COO- from the viewpoint of ease of synthesis. . More preferable ones are a single bond, -(CH ₂ ) _c- (c is an integer of 1 to 10), -O-, -CH ₂ O-, or COO-. Y ⁴ is preferably an organic group having 17 to 51 carbon atoms having a benzene ring, a cyclohexane ring, or a steroid skeleton from the viewpoint of ease of synthesis. Y ⁵ is particularly preferably a benzene ring or a cyclohexane ring. Among them, 0 to 3 are preferable from the viewpoint of availability of raw materials and ease of synthesis. More preferable thing is 0-2. Y ⁶ is preferably a C 1 to C 18 alkyl group, a C 1 to C 10 fluorine-containing alkyl group, a C 1 to C 18 alkoxyl group, or a C 1 to C 10 fluorine-containing alkoxyl group. More preferably, it is a C1-C12 alkyl group or a C1-C12 alkoxyl group. Particularly preferably, they are a C1-C9 alkyl group or a C1-C9 alkoxyl group.

^{As a preferable combination of Y 1} , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in the formula [1], pages 13 to 13 of WO2011/132751 (published on October 27, 2011)- Combinations similar to (2-1) to (2-629) shown in Tables 6 to 47 on page 34 can be mentioned. Further, by reading the table, each of International Publication, there is Y ¹ ~ Y ⁶ of the present invention shown as Y1 ~ Y6, Y1 ~ Y6 is replaced with Y ¹ ~ Y ^6. In addition, in (2-605) to (2-629) published in each table of the international publication, the organic group having 17 to 51 carbon atoms having a steroid skeleton in the present invention has a steroid skeleton having 12 to 25 carbon atoms. Although shown as an organic group, an organic group having 12 to 25 carbon atoms having a steroid skeleton is replaced by an organic group having 17 to 51 carbon atoms having a steroid skeleton.

Among them, (2-25)-(2-96), (2-145)-(2-168), (2-217)-(2-240), (2-268)-(2-315) , (2-364) to (2-387), (2-436) to (2-483), or a combination of (2-603) to (2-615) is preferable. Particularly preferred combinations are (2-49) to (2-96), (2-145) to (2-168), (2-217) to (2-240), (2-603) to (2- 606), (2-607) to (2-609), (2-611), (2-612) or (2-624).

<Specific polymer (A)·Specific polymer (B)>

The specific polymer (A) and the specific polymer (B) contain at least any one selected from a polyimide precursor and a polyimide (collectively referred to as a polyimide polymer) obtained by reacting a diamine component and a tetracarboxylic acid component. It is a polymer.

The polyimide precursor is a structure represented by the following formula [A].

[Formula 10]

(R ¹ is a tetravalent organic group, R ² is a divalent organic group, A ¹ and A ² represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, each of which may be the same or different, and A ³ and A ⁴ Represents a hydrogen atom, an alkyl group or an acetyl group having 1 to 5 carbon atoms, each may be the same or different, and n2 represents a positive integer)

As the diamine component, it is a diamine compound having two primary or secondary amino groups in the molecule, and as the tetracarboxylic acid component, a tetracarboxylic acid compound, a tetracarboxylic dianhydride, a tetracarboxylic acid dihalide compound , A tetracarboxylic acid dialkyl ester compound or a tetracarboxylic acid dialkyl ester dihalide compound.

The polyimide polymer of the present invention is obtained relatively simply by using a tetracarboxylic dianhydride represented by the following formula [B] and a diamine compound represented by the following formula [C] as raw materials, according to the following formula [D]. A polyamic acid composed of the structural formula of the shown repeating unit or a polyimide obtained by imidating the polyamic acid is preferable. Especially, it is preferable to use a polyimide for a specific polymer (A) and a specific polymer (B) from the point of physical and chemical stability of a liquid crystal aligning film.

[Formula 11]

(R ¹ and R ² have the same meaning as defined in formula [A])

[Formula 12]

(R ¹ , R ² and n2 have the same meaning as defined in formula [A])

In addition, in the polymer of formula [D] obtained above by a conventional synthesis method, an alkyl group having 1 to 8 carbon atoms of ^{A 1} and A ^{2 represented by formula [A] and A 3} and A ^{4 represented by formula [A]} It is also possible to introduce a C1-C5 alkyl group or an acetyl group.

The specific polymer (A) is a polyimide polymer obtained using a diamine component containing a diamine compound having a specific side chain structure. In that case, as the diamine compound having a specific side chain structure, it is preferable to use a diamine compound (also referred to as a specific side chain type diamine compound) represented by the following formula [1a].

[Formula 13]

In formula [1a], Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , and n are the same as each definition in the above formula [1], and each preferred definition is also the same. Do.

Moreover, ^{preferable combinations of Y 1} , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n are also the same as those described for the above formula [1]. In addition, m is an integer of 1-4. Preferably, it is an integer of 1.

Specifically, the structure represented by the following formula [1a-1]-formula [1a-31] is mentioned, for example.

[Formula 14]

(R ¹ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ -or CH ₂ OCO-, and R ² is a C1-C22 linear or branched alkyl group, a C1-C22 alkyl group, 22 linear or branched alkoxyl group, C1-C22 linear or branched fluorine-containing alkyl group or fluorine-containing alkoxyl group)

[Formula 15]

(R ³ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -or CH ₂ -, and R ⁴ Is a C1-C22 linear or branched alkyl group, a C1-C22 linear or branched alkoxyl group, a C1-C22 linear or branched fluorine-containing alkyl group or a fluorine-containing alkoxyl group)

[Formula 16]

(R ⁵ is -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, -CH ₂ -, -O- Or NH-, and R ⁶ is a fluorine group, cyano group, trifluoromethane group, nitro group, azo group, formyl group, acetyl group, acetoxy group or hydroxyl group)

[Formula 17]

(R ⁷ is a linear or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomers of 1,4-cyclohexylene are trans isomers, respectively)

[Formula 18]

(R ⁸ is a linear or branched alkyl group having 3 to 12 carbon atoms, and the cis-trans isomers of 1,4-cyclohexylene are trans isomers, respectively)

[Formula 19]

(A ₄ is a linear or branched alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, A ₃ is a 1,4-cyclohexylene group or a 1,4-phenylene group, and A ₂ is an oxygen atom or COO-* (however, the bond hand given ``*'' is bonded to A <sub>3</sub> ), A <sub>1</sub> is an oxygen atom or COO-* (however, the bond hand given ``*'' is bonded to (CH ₂ )a ₂₎ In addition, 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 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

In the formulas [1a-1] to [1a-31], the diamine compound having a particularly preferable structure is formula [1a-1] to formula [1a-6], and formula [1a-9] to formula [1a-13] Or it is a formula [1a-22]-a formula [1a-31].

It is preferable that the specific side chain type diamine compound in a specific polymer (A) is 10 mol% or more and 80 mol% or less of the whole diamine component. Particularly preferred are 10 mol% or more and 70 mol% or less.

The specific side-chain diamine compound is based on characteristics such as solubility in a solvent of a specific polymer (A) and coating properties of a liquid crystal aligning agent, alignment properties of a liquid crystal in the case of a liquid crystal aligning film, a voltage retention rate, and an accumulated charge. It is also possible to use types or a mixture of two or more.

It is preferable to use another diamine compound (it is also called a specific 2nd diamine compound) together with a specific side-chain type diamine compound for the diamine component at the time of manufacturing a specific polymer (A) and a specific polymer (B).

Among them, it is preferable to use a diamine compound having at least one substituent selected from a carboxyl group (COOH group) and a hydroxyl group (OH group).

Specifically, it is preferable to use a diamine compound represented by the following formula [2a].

[Formula 25]

In formula [2a], A ¹ represents a substituent having at least one structure selected from the following formulas [2a-1] and [2a-2]. Among them, a substituent having a structure represented by formula [2a-1] is preferable.

In formula [2a], m1 represents the integer of 1-4. Among them, 1 is preferable.

[Formula 26]

In formula [2a-1], d represents the integer of 0-4. Especially, 0 or 1 is preferable.

In formula [2a-2], e represents the integer of 0-4. Especially, 0 or 1 is preferable.

More specifically, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2 ,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, or 3,5-diaminobenzoic acid. Among them, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid or 3,5-diaminobenzoic acid is preferable.

Moreover, as a specific 2nd diamine compound, the diamine compound represented by following formula [2b-1]-formula [2b-4] can also be used.

[Formula 27]

(A ¹ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- or N(CH ₃ ) CO- is represented, m ¹ and m ² each represent an integer of 0 to 4, and m ¹ + m ² represents an integer of 1 to 4, in formula [2b-2], m ³ and m ⁴ Each represents an integer of 1 to 5, in formula [2b-3], A ² represents a linear or branched alkyl group having 1 to 5 carbon atoms, m ⁵ represents an integer of 1 to 5, formula [2b-4 ] In, A ³ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -O-, -CO -, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- or N (CH ₃ ) CO- is represented, and m ⁶ represents the integer of 1 to 4)

The specific second diamine compound may be used for the diamine component of any polyimide polymer among the specific polymer (A) or the specific polymer (B), and the diamine of the specific polymer of both the specific polymer (A) and the specific polymer (B) It can also be used for ingredients. Especially, it is preferable to use only a diamine component of a specific polymer (A), or use only a diamine component of a specific polymer (B).

It is preferable that the specific 2nd diamine compound is 10 mol% or more of the whole diamine component. Especially, 20 mol% or more is preferable, and 30 mol% or more is especially preferable.

The specific 2nd diamine compound is solubility in a solvent of a specific polymer (A) and a specific polymer (B), coating property of a liquid crystal aligning agent, alignment property of a liquid crystal in the case of a liquid crystal aligning film, voltage retention, accumulated charge, etc. Depending on the characteristics, one type or a mixture of two or more may be used.

As the diamine component of the specific polymer (A) and the specific polymer (B) of the present invention, a diamine compound represented by the following formula [3a] together with a specific side-chain diamine compound and a specific second diamine compound (specific third diamine compound It is preferable to use).

[Formula 28]

In formula [3a], B ¹ is -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON(CH ₃ )- Or N(CH ₃ )CO-. Among them, -O-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON(CH ₃ )- or N(CH ₃ )CO- synthesizes a diamine compound. It is preferable because it is easy to do. Particularly preferred are -O-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCO- or CON(CH ₃ )-. More preferred is -O-, -CONH- or CH ₂ O-.

In formula [3a], B ² represents a single bond, an alkylene group having 1 to 20 carbon atoms, a non-aromatic ring or an aromatic ring.

The C1-C20 alkylene group may be linear or may be branched. Moreover, you may have an unsaturated bond. In particular, an alkylene group having 1 to 10 carbon atoms is preferable.

Specific examples of the non-aromatic ring include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, and a cyclododecane ring. , Cyclotridecane ring, Cyclotetradecane ring, Cyclopentadecane ring, Cyclohexadecane ring, Cycloheptadecane ring, Cyclooctadecane ring, Cyclononadecane ring, Cycloic acid ring, Tricycloeic acid ring, Tricyclodeco An acid ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring, or an adamantane ring. Among them, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring, or an adamantane ring is preferable.

Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an azulene ring, an indene ring, a fluorene ring, an anthracene ring, a phenanthrene ring, or a phenalene ring. Among them, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, a fluorene ring, or an anthracene ring is preferable.

^{Preferred B 2} in the formula [3a] includes a single bond, an alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring, and an adamane. It is a carbon ring, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, a fluorene ring, or an anthracene ring. Especially, a single bond, a C1-C5 alkylene group, a cyclohexane ring, or a benzene ring is preferable.

In formula [3a], B ³ is a single bond, -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -COO-, -OCO-, -CON(CH ₃ ) -Or N(CH ₃ )CO-, -O(CH ₂ ) _m2- (m2 is an integer of 1 to 5). Among them, a single bond, -O-, -COO-, -OCO-, or O(CH ₂ ) _m2- (m2 is an integer of 1 to 5) is preferable, and particularly preferable is a single bond, -O-, -OCO- or O(CH ₂ ) _m2- (m2 is an integer of 1 to 5).

In formula [3a], B ⁴ is a nitrogen-containing heterocycle, and is a heterocycle containing at least one structure selected from the following formulas [a], [b] and [c].

[Formula 29]

(In formula [c], Z represents a C1-C5 alkyl group)

More specifically, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thia Diazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzoimidazole ring, cinnoline ring, phenanthroline ring, indole ring, And a quinoxaline ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring, or an acridine ring. Among them, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, or a benzoimidazole ring is preferable, and in particular Preferred are a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring or a pyrimidine ring.

Moreover, it is preferable that B ³ in Formula [3a] is bonded with a substituent not adjacent to Formula [a], Formula [b], and Formula [c] contained in B ^4.

^{Preferred combinations of B 1} , B ² , B ³ and B ⁴ in formula [3a] are as shown in Tables 1 to 31 below. In addition, X ¹ , X ² , X ³ and X ⁴ in Tables 1 to 31 shall be read by replacing them with ^{B 1} , B ² , B ³ and B ⁴ , respectively.

In formula [3a], n1 is an integer of 1 to 4, and preferably 1 or 2 in terms of reactivity with a tetracarboxylic acid component.

^{Particularly preferable combination of B 1} , B ² , B ³ , B ⁴ and n1 in formula [3a] is that ^{B 1} represents -CONH-, B ² represents an alkyl group having 1 to 5 carbon atoms, and B ^{3 represents} It represents a single bond, B ⁴ represents an imidazole ring or a pyridine ring, and n1 represents a diamine compound.

The bonding position of two amino groups (-NH _{2) in formula [3a] is not limited.} Specifically, with respect to the bonding group (B ¹ ) of the side chain, 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 or 3, Five positions are mentioned. Among them, from the viewpoint of reactivity when synthesizing a polyamic acid, positions 2 and 4, positions 2 and 5, or positions 3 and 5 are preferable. If the ease in synthesizing a diamine compound is also taken into account, the positions 2 and 4 or the positions 2 and 5 are more preferable.

The specific third diamine compound may be used for the diamine component of any polyimide polymer among the specific polymer (A) or the specific polymer (B), and the diamine of the specific polymer of both the specific polymer (A) and the specific polymer (B) It can also be used for ingredients. Especially, when a specific 2nd diamine compound is used for a diamine component for a specific polymer (A), it is preferable to use a specific 3rd diamine compound for a diamine component of a specific polymer (B). Moreover, when using a specific 2nd diamine compound for a diamine component for a specific polymer (B), it is preferable to use a specific 3rd diamine compound for a diamine component of a specific polymer (A). That is, for each specific polymer, it is preferable to separately use a specific second diamine compound and a specific third diamine compound for the diamine component.

It is preferable that the specific 3rd diamine compound is 5 mol% or more of the whole diamine component. Especially, 10 mol% or more is preferable, and 15 mol% or more is especially preferable.

The specific third diamine compound is the solubility of the specific polymer (A) and the specific polymer (B) in the solvent, the coating property of the liquid crystal aligning agent, the alignment of the liquid crystal in the case of a liquid crystal aligning film, the voltage retention rate, the accumulated charge, etc. Depending on the characteristics, one type or a mixture of two or more may be used.

As the diamine component of the specific polymer (A) and the specific polymer (B), as long as the effect of the present invention is not impaired, together with a specific side chain diamine compound, a specific second diamine compound, and a specific third diamine compound, other A diamine compound (also referred to as another diamine compound) can also be used.

As other diamine compounds, specifically, 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, m-phenylenediamine, p-phenylenediamine, 4,4'-diamino Biphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 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'-trifluoro Methyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobi Phenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 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-aminophenyl)silane, dimethyl- Bis(4-aminophenyl)silane, dimethyl-bis(3-aminophenyl)silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 4,4'-diaminodiphenylamine, 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'-diamino Benzophenone, 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-ami) Nophenyl)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) Si) benzene, 4,4'-[1,4-phenylenebis(methylene)]dianiline, 4,4'-[1,3-phenylenebis(methylene)]dianiline, 3,4'-[ 1,4-phenylenebis(methylene)]dianiline, 3,4'-[1,3-phenylenebis(methylene)]dianiline, 3,3'-[1,4-phenylenebis(methylene) ]Daniline, 3,3'-[1,3-phenylenebis(methylene)]Daniline, 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) terephthalate, bis (3-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N,N' -(1,4-phenylene)bis(4-aminobenzamide), 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) terephthalamide, 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-amid Nophenyl)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, 1,3-bis(4-aminophenoxy) Si) 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-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy) Hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-bis(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-bis(4-aminophenoxy)decane, 1,10-bis(3-aminophenoxy)decane, 1,11-bis(4-aminophenoxy)undecane, 1,11-bis(3-aminophenoxy)undecane, 1,12-bis( 4-aminophenoxy)dodecane, 1,12-bis(3-aminophenoxy)dodecane, bis(4-aminocyclohexyl)methane, 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-diaminoundecane or 1,12-diaminododecane, and the like.

Moreover, as another diamine compound, the diamine compound represented by the following formula [D1]-formula [DA25] can also be used.

[Formula 30]

[Chemical Formula 31]

[Formula 32]

(A ¹ represents a C1-C22 alkyl group or a fluorine-containing alkyl group)

[Formula 33]

[Formula 34]

[Formula 35]

(A ¹ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or NH-, and A ² is a C1-C22 linear or A branched alkyl group or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms)

[Chemical Formula 36]

(p represents the integer of 1-10)

[Chemical Formula 37]

[Formula 38]

(m represents the integer of 0-3, n represents the integer of 1-5)

[Chemical Formula 39]

Other diamine compounds may be used for the diamine component of any polyimide polymer among the specific polymer (A) or the specific polymer (B), and the diamine component of the specific polymer of both the specific polymer (A) and the specific polymer (B) Can also be used for

In addition, other diamine compounds are the solubility of the specific polymer (A) and the specific polymer (B) in the solvent, the coating property of the liquid crystal aligning agent, the alignment property of the liquid crystal in the case of a liquid crystal alignment film, the voltage retention rate, the accumulated charge, etc. Depending on the characteristics of, one type or two or more types may be used in combination.

As the tetracarboxylic acid component for producing the specific polymer (A) and the specific polymer (B), that is, these polyimide polymers, tetracarboxylic dianhydride represented by the following formula [4] (specific tetracarboxylic acid Dianhydride) is preferably used. In that case, not only the specific tetracarboxylic dianhydride represented by the formula [4], but also the tetracarboxylic acid derivative thereof, a tetracarboxylic acid, a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound, or a tetracarboxylic acid di An alkyl ester dihalide compound can also be used.

[Formula 40]

(Z ¹ is a group having a structure selected from the following formulas [4a] to [4k])

[Formula 41]

The formula ^{[4a], Z 2 ~ Z} 5 is may be a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, respectively, be the same or different.

In formula [4g], Z ⁶ and Z ⁷ represent a hydrogen atom or a methyl group, and may be the same or different, respectively.

^{In Z 1} in the formula [4], in terms of ease of synthesis and ease of polymerization reactivity when preparing a polymer, formulas [4a], [4c], [4d], [4e], and [4f] ], tetracarboxylic dianhydride having a structure represented by formula [4g] or formula [4k], and tetracarboxylic acid derivatives thereof are preferred. More preferable ones are those of the structure represented by formula [4a], formula [4e], formula [4f], formula [4g] or formula [4k], and particularly preferred ones are formula [4e], formula [4f], and formula [ 4g] or of the formula [4k].

In the polyimide polymer of the present invention, other tetracarboxylic acid components other than the specific tetracarboxylic dianhydride may be used as long as the effect of the present invention is not impaired.

Examples of other tetracarboxylic acid components include tetracarboxylic acid compounds, tetracarboxylic dianhydrides, tetracarboxylic acid dihalide compounds, tetracarboxylic acid dialkyl ester compounds, or tetracarboxylic acid dialkyl ester dihalide compounds shown below. Can be mentioned.

That is, as other tetracarboxylic acid components, pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic 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 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-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'-diphenylsulfonetetracarboxylic acid, 3,4, 9,10-perylenetetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid.

In the tetracarboxylic acid component in the specific polymer (A) and the specific polymer (B), it is preferable that the specific tetracarboxylic dianhydride in each specific polymer is 10 mol% or more of the tetracarboxylic acid component. . Especially, 20 mol% or more is preferable, and 30 mol% or more is especially preferable. All of the tetracarboxylic acid components may be specific tetracarboxylic dianhydrides.

Specific tetracarboxylic dianhydride and other tetracarboxylic acid components are the solubility of the specific polymer (A) and the specific polymer (B) in the solvent, the coating properties of the liquid crystal aligning agent, and the liquid crystal in the case of a liquid crystal aligning film One type or two or more types may be used in combination, depending on characteristics such as orientation, voltage retention, and accumulated charge.

<Method for producing specific polymer (A) and specific polymer (B)>

The specific polymer (A) in the present invention is composed of a polyimide precursor and a polyimide obtained by reacting a diamine component containing a diamine compound having a specific side chain structure represented by the above formula [1] and a tetracarboxylic acid component. It is at least one type of polymer selected from the group. In that case, as a diamine compound which has a specific side chain structure, it is preferable to use the specific side chain type diamine compound represented by the said formula [1a].

Further, in the specific polymer (A), together with a specific side-chain diamine compound, a diamine compound having at least one substituent selected from a carboxyl group and a hydroxyl group, and/or a specific third diamine represented by the above formula [3a] You may use a compound together. In that case, it is preferable to use a specific second diamine compound represented by the above formula [2a] for the diamine compound having at least one type of substituent selected from a carboxyl group and a hydroxyl group.

In the case of using a specific second diamine compound in combination, the specific side chain diamine compound is preferably 10 to 80 mol%, and the specific second diamine compound is preferably 10 to 90 mol%, with respect to 100 mol% of the total diamine component. . More preferably, the specific side chain diamine compound is 10 to 80 mol%, and the specific second diamine compound is 20 to 70 mol%.

In the case of using a specific third diamine compound in combination, the specific side chain diamine compound is preferably 10 to 80 mol%, and the specific third diamine compound is preferably 10 to 90 mol% with respect to 100 mol% of the total diamine component. . More preferably, the specific side chain diamine compound is 10 to 80 mol%, and the specific third diamine compound is 20 to 70 mol%.

The ratio of use when a specific second diamine compound and a specific third diamine compound are used in combination is 10 to 80 mol% of the specific side chain diamine compound, and 10 to 80 mol% of the specific second diamine compound with respect to 100 mol% of the total diamine component. 80 mol% and the specific third diamine compound are preferably 10 to 80 mol%. More preferably, the specific side chain diamine compound is 10 to 80 mol%, the specific second diamine compound is 20 to 70 mol%, and the specific third diamine compound is 20 to 70 mol%. In this invention, it is preferable to use a specific 3rd diamine compound together for a specific polymer (A).

The specific polymer (B) in the present invention is selected from the group consisting of a polyimide precursor and a polyimide obtained by reacting a diamine component and a tetracarboxylic acid component not containing a diamine compound having a specific side chain structure in the diamine component. Is at least one type of polymer. In that case, it is preferable to use a diamine compound which has at least 1 type of substituent selected from a carboxyl group and a hydroxyl group for a specific polymer (B). A more preferable thing is a specific 2nd diamine compound represented by said formula [2a].

It is preferable that the ratio of use of the specific 2nd diamine compound is 10 mol% or more with respect to 100 mol% of all the diamine components, as mentioned above. A more preferable thing is 20 mol% or more, A particularly preferable thing is 30 mol% or more.

Moreover, a specific 2nd diamine compound and a specific 3rd diamine compound can also be used together for a specific polymer (B). In that case, the specific second diamine compound is preferably 10 to 80 mol%, and the specific third diamine compound is preferably 10 to 80 mol% with respect to 100 mol% of the total diamine component. More preferably, the specific second diamine compound is 20 to 70 mol%, and the specific third diamine compound is 20 to 70 mol%.

In the present invention, the method for producing the specific polymer (A) and the specific polymer (B), that is, these polyimide polymers is not particularly limited. Usually, it is obtained by reacting a diamine component and a tetracarboxylic acid component. In general, by reacting at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic dianhydride and derivatives of the tetracarboxylic acid and a diamine component consisting of one or a plurality of diamine compounds. And a method of obtaining a polyamic acid. Specifically, a method of polycondensing a tetracarboxylic dianhydride and a primary or secondary diamine compound to obtain a polyamic acid, and a dehydration polycondensation reaction of a tetracarboxylic acid and a primary or secondary diamine compound to obtain a polyamide A method of obtaining an acid or a method of obtaining a polyamic acid by reacting a tetracarboxylic acid dihalide with a primary or secondary diamine compound is used.

In order to obtain an alkyl polyamic acid ester, a method of polycondensing a tetracarboxylic acid obtained by dialkyl esterification of a carboxylic acid group and a primary or secondary diamine compound, a tetracarboxylic acid dihalide obtained by dialkyl esterification of a carboxylic acid group A method of reacting with a primary or secondary diamine compound or a method of converting the carboxyl group of a polyamic acid into an ester is used.

In order to obtain a polyimide, a method of subjecting the polyamic acid or polyamic acid alkyl ester to ring closure to form a polyimide is used.

The reaction of the diamine component and the tetracarboxylic acid component is usually carried out with the diamine component and the tetracarboxylic acid component in an organic solvent. The organic solvent used at that time is not particularly limited as long as the produced polyimide precursor is dissolved. Below, although the specific example of the organic solvent used for reaction is given, it is not limited to these examples.

For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide or And 1,3-dimethyl-imidazolidinone.

Moreover, when the solvent solubility of a polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formula [D-1]-formula [D A solvent represented by -3] can be used.

[Formula 42]

(D ¹ represents an alkyl group having a carbon number of 1 to 3, D ² represents an alkyl group having a carbon number of 1 to 3, D ³ represents an alkyl group having from 1 to 4 carbon atoms).

These may be used individually or may be mixed and used. Moreover, even if it is a solvent which does not dissolve a polyimide precursor, you may use it, mixing with the said solvent as long as the produced|generated polyimide precursor does not precipitate. Moreover, since moisture in an organic solvent inhibits a polymerization reaction and furthermore causes hydrolysis of the produced polyimide precursor, it is preferable to use a dehydration-dried organic solvent.

When reacting a diamine component and a tetracarboxylic acid component in an organic solvent, a solution obtained by dispersing or dissolving the diamine component in an organic solvent is stirred, and the tetracarboxylic acid component is added as it is or by dispersing or dissolving it in an organic solvent. Conversely, a method of adding a diamine component to a solution in which a tetracarboxylic acid component is dispersed or dissolved in an organic solvent, a method of alternately adding a diamine component and a tetracarboxylic acid component, etc. are mentioned. You can use it. In addition, in the case of reacting using a plurality of diamine components or tetracarboxylic acid components, respectively, the reaction may be carried out in a premixed state, or individually sequentially reacted, or individually reacted low molecular weight substances are mixed and reacted to form a polymer. You can do it. The polymerization temperature in that case can be selected from -20°C to 150°C, but is preferably in the range of -5°C to 100°C. Further, the reaction can be carried out at an arbitrary concentration, but if the concentration is too low, it becomes difficult to obtain a polymer having a high molecular weight, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult. Therefore, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial reaction is carried out at a high concentration, and then, an organic solvent can be added.

In the polymerization reaction of the polyimide precursor, the ratio of the total number of moles of the diamine component and the total number of moles of the tetracarboxylic acid component is preferably from 0.8 to 1.2. Similar to a conventional polycondensation reaction, the closer this molar ratio is to 1.0, the greater the molecular weight of the resulting polyimide precursor.

The polyimide of the present invention is a polyimide obtained by cyclizing the polyimide precursor described above, and in this polyimide, the cyclization rate of the amic acid group (also referred to as the imidation rate) is not necessarily 100%. It can be arbitrarily adjusted accordingly. In particular, in the present invention, since a decrease in the voltage retention rate after exposure to light irradiation for a long time can be suppressed, the specific polymer (A) is 30 to 100%, and the specific polymer (B) is 30 to 100%. desirable. More preferably, the specific polymer (A) is 40 to 90%, and the specific polymer (B) is 40 to 90%. It is particularly preferable that the specific polymer (A) is 50 to 85%, and the specific polymer (B) is 50 to 85%.

As a method of imidizing the polyimide precursor, thermal imidization in which the solution of the polyimide precursor is heated as it is, or catalytic imidization in which a catalyst is added to the solution of the polyimide precursor is exemplified.

When the polyimide precursor is thermally imidized in a solution, the temperature is from 100°C to 400°C, preferably from 120°C to 250°C, and it is preferable to carry out while removing water generated by the imidation reaction to the outside of the system.

The catalytic imidization of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to the solution of the polyimide precursor and stirring at -20 to 250°C, preferably 0 to 180°C. The amount of the basic catalyst is 0.5 to 30 mole times, preferably 2 to 20 mole times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mole times, preferably 3 to 30 mole times of the amic acid group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and the like. Among them, pyridine is preferable because it has a suitable basicity 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 preferable because purification after completion of the reaction becomes easy. The imidation rate by catalytic imidization can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

When the generated polyimide precursor or polyimide is recovered from the polyimide precursor or the reaction solution of polyimide, the reaction solution may be added to a solvent to precipitate. As a solvent used for precipitation, methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water, etc. are mentioned. The polymer injected into the solvent and precipitated may be collected by filtration and then dried at room temperature or heated under normal pressure or reduced pressure. Further, by re-dissolving the polymer recovered by precipitation in an organic solvent and repeating the operation of reprecipitation recovery 2 to 10 times, impurities in the polymer can be reduced. Examples of the solvent at this time include alcohols, ketones, hydrocarbons, and the like, and when three or more solvents selected from these are used, the efficiency of purification is further increased, and therefore, it is preferable.

The molecular weight of the polyimide-based polymer of the present invention is 5,000 to a weight average molecular weight measured by GPC (Gel Permeation Chromatography) when considering the strength of the liquid crystal alignment film obtained therefrom, workability at the time of forming the liquid crystal alignment film, and coating film properties. It is preferable to set it as 1,000,000, More preferably, it is 10,000-150,000.

<Liquid crystal orientation treatment agent>

The liquid crystal aligning agent of this invention is a coating solution for forming a liquid crystal aligning film (it is also called a resin film), and is a coating solution for forming a liquid crystal aligning film containing a specific polymer (A), a specific polymer (B), and a solvent.

It is preferable that the ratio of the specific polymer (A) and the specific polymer (B) in the liquid crystal aligning agent is 10 to 900 parts by mass of the specific polymer (B) with respect to 100 parts by mass of the specific polymer (A). More preferably, the specific polymer (B) is 20 to 800 parts by mass. Particularly preferably, the specific polymer (B) is 30 to 700 parts by mass.

All of the polymer components in the liquid crystal aligning agent of the present invention may be the specific polymer (A) and the specific polymer (B) of the present invention, or other polymers other than that may be mixed. In that case, the content of other polymers other than the above is 0.5 parts by mass to 15 parts by mass, preferably 1 to 10 parts by mass based on 100 parts by mass of the total of the specific polymer (A) and the specific polymer (B). to be. Examples of other polymers other than those described above include a cellulose polymer, an acrylic polymer, a methacrylic polymer, polystyrene, polyamide, or polysiloxane.

From the viewpoint of forming a uniform liquid crystal alignment film by application of the solvent in the liquid crystal aligning agent of the present invention, it is preferable that the content of the solvent in the liquid crystal aligning agent is 70 to 99.9 mass%. This content can be appropriately changed according to the film thickness of the target liquid crystal aligning film.

The solvent used for the liquid crystal aligning agent of the present invention is not particularly limited as long as it is a solvent (also referred to as a good solvent) that dissolves the specific polymer (A) and the specific polymer (B). Although specific examples of the good solvent are given below, it is not limited to these examples.

For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone.

Among them, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butyrolactone.

Moreover, when the solubility of a specific polymer (A) and a specific polymer (B) in a solvent is high, it is preferable to use the solvent represented by the said formula [D-1]-formula [D-3].

It is preferable that the good solvent in the liquid crystal aligning agent of this invention is 10-100 mass% of the whole solvent contained in a liquid crystal aligning agent. Especially, 20 to 90 mass% is preferable. A more preferable thing is 30 to 80 mass %.

As the liquid crystal aligning agent of the present invention, a solvent (also referred to as a poor solvent) that improves the coating properties and surface smoothness of the liquid crystal aligning film when the liquid crystal aligning agent is applied can be used as long as the effect of the present invention is not impaired. have. Below, although a specific example of a poor solvent is given, it is not limited to these examples.

For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, Isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1- Butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methyl Cyclohexanol, 3-methylcyclohexanol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl Ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl Acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2-(methoxymethoxy) ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2-( Hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1-(butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether , Dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol di Acetate, diethylene glycol monoethyl ether acetate T, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, lactic acid Ethyl, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3- Ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl, 3-methoxypropionate butyl, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactate isoamyl ester, or The solvent etc. which are represented by said formula [D-1]-formula [D-3] are mentioned.

Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, or the above formula [ It is preferable to use the solvent represented by D-1]-Formula [D-3].

It is preferable that these poor solvents are 1 to 70 mass% of the whole solvent contained in a liquid crystal aligning agent. Especially, 1 to 60 mass% is preferable. More preferably, it is 5 to 60 mass %.

In the liquid crystal alignment treatment agent of the present invention, a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group, and a crosslinking having at least one substituent selected from the group consisting of a lower alkoxyalkyl group It is preferable to introduce a sexual compound or a crosslinkable compound having a polymerizable unsaturated bond. It is necessary to have two or more of these substituents and polymerizable unsaturated bonds in the crosslinkable compound.

As a crosslinkable compound having an epoxy group or an isocyanate group, for example, bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene , Tetraglycidyl-m-xylenediamine, tetraglycidyl-1,3-bis(aminoethyl)cyclohexane, tetraphenylglycidyletherethane, triphenylglycidyletherethane, bisphenolhexafluoroaceto 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, tetraglycidylmethaxylenediamine, 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-epoxypro)) Foxy)phenyl)-1-(4-(1-(4-(2,3-epoxypropoxy)phenyl)-1-methylethyl)phenyl)ethyl)phenoxy)-2-propanol.

The crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [4A].

[Formula 43]

Specifically, crosslinkable compounds represented by formulas [4a] to [4k] disclosed in items 58 to 59 of WO2011/132751 (published on October 27, 2011) can be mentioned.

As a crosslinkable compound having a cyclocarbonate group, it is a crosslinkable compound which has at least two cyclocarbonate groups represented by the following formula [5A].

[Formula 44]

Specifically, crosslinkable compounds represented by formulas [5-1] to [5-42] published in items 76 to 82 of International Publication WO2012/014898 (published on Feb. 2, 2012) are exemplified.

As a crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group, for example, an amino resin having at least one substituent selected from a hydroxyl group and an alkoxyl group, for example For example, a melamine resin, a urea resin, a guanamine resin, a glycoluril-formaldehyde resin, a succinylamide-formaldehyde resin, or an ethyleneurea-formaldehyde resin may be mentioned. Specifically, a melamine derivative, a benzoguanamine derivative, or a glycoluril in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group or both can be used. This melamine derivative or 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 one triazine ring.

Examples of such melamine derivatives or benzoguanamine derivatives include commercially available MX-750 in which an average of 3.7 methoxymethyl groups per triazine ring is substituted, and MW in which an average of 5.8 methoxymethyl groups per triazine ring is substituted. -30 (above, manufactured by Sanwa Chemical) or Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712 and other methoxymethylated melamines, Cymel 235, 236, 238, 212, 253 , Methoxymethylated butoxymethylated melamine such as 254, butoxymethylated melamine such as Cymel 506, 508, methoxymethylated isobutoxymethylated melamine containing carboxyl groups such as Cymel 1141, methoxymethylated ethoxymethylated such as Cymel 1123 Benzoguanamine, methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, and methoxymethylated ethoxymethylated benzoguanamine containing carboxyl groups such as Cymel 1125-80 Namin (above, manufactured by Mitsui Cyanamide Co., Ltd.) is mentioned. Further, examples of the glycoluril include butoxymethylolated glycoluril such as Cymel 1170, methylolated glycoluril such as Cymel 1172, and methoxymethylolated glycoluril such as Powder Link 1174.

As a benzene or phenolic compound having a hydroxyl group or an alkoxyl group, for example, 1,3,5-tris(methoxymethyl)benzene, 1,2,4-tris(isopropoxymethyl)benzene, 1 ,4-bis(sec-butoxymethyl)benzene or 2,6-dihydroxymethyl-p-tert-butylphenol, and the like.

More specifically, international publication WO2011/132751. The crosslinkable compound represented by formula [6-1]-formula [6-48] published on page 62-page 66 of (2011.10.27 publication) is mentioned.

As a crosslinkable compound having a polymerizable unsaturated bond, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, tri(meth)acrylate ) A crosslinkable compound having three polymerizable unsaturated groups in a molecule, such as acryloyloxyethoxytrimethylolpropane or glycerin polyglycidyl ether poly(meth)acrylate, and 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)acrylic Rate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid A crosslinkable compound having two polymerizable unsaturated groups in a molecule such as diglycidyl ester di(meth)acrylate or hydroxypivalate neopentyl glycol di(meth)acrylate, and 2-hydroxyethyl(meth)acrylic Rate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy- 2-hydroxypropylphthalate, 3-chloro-2-hydroxypropyl (meth)acrylate, glycerin mono (meth)acrylate, 2-(meth)acryloyloxyethylphosphate ester or N-methylol (meth) A crosslinkable compound having one polymerizable unsaturated group such as acrylamide in the molecule can be mentioned.

Moreover, a compound represented by the following formula [7A] can also be used.

[Formula 45]

(In formula [7A], E ₁ is a group selected from the group consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring, and a phenanthrene ring. And E ₂ represents a group selected from the following formulas [7a] and [7b], and n represents an integer of 1 to 4).

[Formula 46]

The compound is an example of a crosslinkable compound, and is not limited thereto. Moreover, the number of crosslinkable compounds used for the liquid crystal aligning agent of this invention may be 1 type, and may combine 2 or more types.

It is preferable that content of the crosslinkable compound in the liquid-crystal aligning agent of this invention is 0.1-150 mass parts with respect to 100 mass parts of all polymer components. In order to allow the crosslinking reaction to proceed to exhibit the desired effect, 0.1 to 100 parts by mass is more preferable, and in particular, 1 to 50 parts by mass is most preferable based on 100 parts by mass of all polymer components.

The liquid crystal aligning agent of this invention can use a compound which improves the uniformity of the film thickness and surface smoothness of a liquid crystal aligning film when the liquid crystal aligning agent is applied, as long as the effect of this invention is not impaired.

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

More specifically, for example, Ftop EF301, EF303, EF352 (above, manufactured by Tochem Products), Megapac F171, F173, R-30 (above, manufactured by Dai Nippon Ink), Florade FC430, FC431 ( As mentioned above, Sumitomo 3M company make), Asahigard AG710, Suflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, Asahi Glass company make), etc. are mentioned. The ratio of use of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of all polymer components contained in the liquid crystal aligning agent.

Further, in the liquid crystal aligning agent of the present invention, as a compound which promotes charge transfer in the liquid crystal aligning film to promote charge dropout of the device, published on pages 69 to 73 of WO2011/132751 (published on October 27, 2011). A nitrogen-containing heterocyclic amine compound represented by formula [M1] to formula [M156] can also be added. Although this amine compound may be added directly to a liquid crystal aligning agent, it is preferable to add after setting it as a solution of concentration 0.1 mass%-10 mass %, preferably 1 mass%-7 mass% with a suitable solvent. As this solvent, if it is an organic solvent which dissolves the specific polymer (A) and the specific polymer (B) mentioned above, it will not specifically limit.

In the liquid crystal aligning agent of the present invention, in addition to the above poor solvent, a crosslinkable compound, a compound that improves the uniformity or surface smoothness of the film thickness of a resin film or a liquid crystal aligning film, and a compound that promotes charge dropout, the effects of the present invention are impaired. If it is not within the range, a dielectric material or a conductive material for the purpose of changing electrical properties such as dielectric constant and conductivity of the liquid crystal alignment film may be added.

<Liquid crystal alignment film/liquid crystal display element>

The liquid crystal aligning agent of the present invention can be used as a liquid crystal aligning film by performing alignment treatment by rubbing treatment or light irradiation after coating and firing on a substrate. Moreover, in the case of a vertical alignment use etc., it can be used as a liquid crystal aligning film without alignment treatment. The substrate used at this time is not particularly limited as long as it is a substrate having high transparency, and in addition to a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate may 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 driving a liquid crystal is formed. In addition, in a reflective liquid crystal display device, an opaque substrate such as a silicon wafer can be used as long as it is only on one substrate, and a material that reflects light such as aluminum can also be used as an electrode in this case.

The application method of the liquid crystal aligning agent is not particularly limited, but industrially, a method performed by screen printing, offset printing, flexo printing, inkjet method, or the like is common. Other coating methods include a dip method, a roll coater method, a slit coater method, a spinner method, or a spray method, and may be used depending on the purpose.

After applying the liquid crystal aligning agent on the substrate, by a heating means such as a hot plate, a heat circulation type oven or an IR (infrared ray) type oven, depending on the solvent used for the liquid crystal aligning agent, 30 to 300° C., preferably Can be set as a liquid crystal aligning film by evaporating the solvent at a temperature of 30 to 250°C. If the thickness of the liquid crystal aligning film after firing is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Therefore, it is preferably 5 to 300 nm, more preferably 10 It is-100 nm. When the liquid crystal is horizontally aligned or obliquely aligned, the sintered liquid crystal alignment film is treated by rubbing or polarized ultraviolet irradiation.

In the liquid crystal display device of the present invention, after obtaining a substrate with a liquid crystal aligning film from the liquid crystal aligning agent of the present invention by the above-described method, a liquid crystal cell is produced by a known method to obtain a liquid crystal display device.

As a manufacturing method of a liquid crystal cell, a pair of substrates on which a liquid crystal alignment film was formed is prepared, spacers are scattered on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside, and the other substrate is bonded together.合), a method of injecting a liquid crystal under reduced pressure to seal, or a method of attaching and sealing a substrate after dropping the liquid crystal on the surface of the liquid crystal aligning film on which the spacers are scattered, and the like can be exemplified.

In addition, the liquid crystal aligning agent of the present invention comprises a liquid crystal layer between a pair of substrates with electrodes, and contains a polymerizable compound that is polymerized by at least one of active energy rays and heat between the pair of substrates. It is also preferably used for a liquid crystal display device manufactured through a step of polymerizing a polymerizable compound by at least one of irradiation and heating of an active energy ray while disposing a liquid crystal composition and applying a voltage between the electrodes. Here, as the active energy ray, ultraviolet rays are preferable. As ultraviolet rays, the wavelength is 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120°C, preferably 60 to 80°C. In addition, ultraviolet rays and heating may be performed at the same time.

The liquid crystal display device described above controls the pretilt of liquid crystal molecules by the PSA (Polymer Sustained Alignment) method. In the PSA system, a small amount of a photopolymerizable compound, such as a photopolymerizable monomer, is mixed in a liquid crystal material, and after assembling a liquid crystal cell, UV light is applied to the photopolymerizable compound while applying a predetermined voltage to the liquid crystal layer. Etc. are irradiated, and the pretilt of the liquid crystal molecules is controlled by the resulting polymer. Since the alignment state of the liquid crystal molecules when the polymer is formed is stored even after removing the voltage, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field or the like formed in the liquid crystal layer. Moreover, since the PSA system does not require rubbing treatment, it is suitable for formation of a vertically aligned liquid crystal layer in which it is difficult to control pretilt by rubbing treatment.

That is, in the liquid crystal display device of the present invention, after obtaining a substrate with a liquid crystal aligning film from a liquid crystal aligning agent by the above-described method, a liquid crystal cell is prepared, and a polymerizable compound is polymerized by at least one of irradiation with ultraviolet rays and heating. By doing so, it can be said that the orientation of liquid crystal molecules is controlled.

To give an example of manufacturing a liquid crystal cell of the PSA method, a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers are scattered on the liquid crystal alignment film of one substrate, and the surface of the liquid crystal alignment film is inside, and the other substrate is A method of bonding and sealing by injecting a liquid crystal under reduced pressure, or a method of bonding and sealing a substrate after dropping the liquid crystal on the surface of the liquid crystal alignment film on which the spacers are scattered are mentioned.

In the liquid crystal, a polymerizable compound that is polymerized by heat or ultraviolet irradiation is mixed. Examples of the polymerizable compound include compounds having one or more polymerizable unsaturated groups such as an acrylate group and a methacrylate group in a molecule. In that case, 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. If the amount of the polymerizable compound is less than 0.01 parts by mass, the polymerizable compound is not polymerized and the alignment of the liquid crystal cannot be controlled. If the amount is more than 10 parts by mass, the amount of unreacted polymerizable compounds increases, resulting in a residual image property of the liquid crystal display device. It is lowered.

After manufacturing the liquid crystal cell, the polymerizable compound is polymerized by irradiating heat or ultraviolet rays while applying an alternating current or direct current voltage to the liquid crystal cell. Thereby, the alignment of the liquid crystal molecules can be controlled.

In addition, the liquid crystal aligning agent of the present invention comprises a liquid crystal layer between a pair of substrates provided with an electrode, and contains a polymerizable group that is polymerized by at least one of active energy rays and heat between the pair of substrates. It is preferable to use also for a liquid crystal display device manufactured through a step of disposing a liquid crystal alignment layer and applying a voltage between the electrodes, that is, in the SC-PVA mode. Here, as the active energy ray, ultraviolet rays are preferable. As ultraviolet rays, the wavelength is 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120°C, preferably 60 to 80°C. In addition, ultraviolet rays and heating may be performed at the same time.

In order to obtain a liquid crystal aligning film containing a polymerizable group polymerized from at least one of active energy rays and heat, a method of adding a compound containing this polymerizable group to a liquid crystal aligning agent, or a method of using a polymer component containing a polymerizable group Can be mentioned.

To give an example of manufacturing a liquid crystal cell in SC-PVA mode, prepare a pair of substrates on which the liquid crystal alignment film of the present invention is formed, and disperse spacers on the liquid crystal alignment film on one side of the substrate, so that the liquid crystal alignment film surface is inside. , A method of bonding the other substrates and sealing by injecting a liquid crystal under reduced pressure, or a method of bonding and sealing the substrates after dropping liquid crystal onto the liquid crystal alignment film surface on which the spacers are scattered.

After manufacturing the liquid crystal cell, the alignment of the liquid crystal molecules can be controlled by irradiating heat or ultraviolet rays while applying an alternating current or direct current voltage to the liquid crystal cell.

As described above, by using the liquid crystal aligning agent of the present invention, it is possible to provide a liquid crystal aligning film capable of expressing a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time. Further, even after being exposed to high temperature and light irradiation for a long time, it is possible to obtain a liquid crystal alignment film in which a decrease in voltage retention is suppressed and residual charges accumulated by a direct current voltage are relieved quickly. In particular, the liquid crystal aligning agent of the present invention becomes useful for a liquid crystal aligning film of a liquid crystal display element using a PSA mode or an SC-PVA mode. Therefore, the liquid crystal display device manufactured using the liquid crystal aligning agent of the present invention has excellent reliability, and can be preferably used for large-sized liquid crystal televisions, small and medium-sized car navigation systems, smartphones, and the like.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In addition, the abbreviations used below are as follows.

(Specific side chain type diamine compound)

A1: 1,3-diamino-4-[4-(trans-4-n-heptylcyclohexyl)phenoxy]benzene

A2: 1,3-diamino-5-[4-(trans-4-n-heptylcyclohexyl)phenoxymethyl]benzene

A3: 1,3-diamino-4-{4-[trans-4-(trans-4-n-pentylcyclohexyl)cyclohexyl]phenoxy}benzene

A4: Diamine compound represented by the following formula [A4]

[Chemical Formula 47]

[Formula 48]

(Specific second diamine compound)

B1: 3,5-diaminobenzoic acid (specific second diamine compound having a carboxyl group (COOH group))

[Formula 49]

(Specific tertiary diamine compound)

C1: Diamine compound represented by the following formula [C1]

C2: Diamine compound represented by the following formula [C2]

[Formula 50]

(Other diamine compounds)

D1: p-phenylenediamine

D2: m-phenylenediamine

D3: 1,3-diamino-4-octadecyloxybenzene

[Formula 51]

(Specific tetracarboxylic dianhydride)

E1: 1,2,3,4-cyclobutanetetracarboxylic dianhydride

E2: Bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride

E3: Tetracarboxylic dianhydride represented by the following formula [E3]

E4: Tetracarboxylic dianhydride represented by the following formula [E4]

E5: Tetracarboxylic dianhydride represented by the following formula [E5]

[Formula 52]

<Crosslinkable compound introduced into a liquid crystal orientation treatment agent>

M1: crosslinkable compound represented by the following formula [M1]

[Chemical Formula 53]

<Solvent used in the present invention>

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

γ-BL: γ-butyrolactone

BCS: Ethylene glycol monobutyl ether

PB: Propylene glycol monobutyl ether

EC: Diethylene glycol monoethyl ether

DME: Dipropylene glycol dimethyl ether

"Measurement of molecular weight of polyimide polymer"

The molecular weight of the polyimide precursor and the polyimide in the synthesis example is a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) (made by Showa Electric Corporation), a column (KD-803, KD-805) (Shodex Corporation). Production) was used, and it measured as follows.

Column temperature: 50 °C

Eluent: N,N'-dimethylformamide (as additive, lithium bromide-hydrate (LiBr H ₂ O) is 30 mmol/L (liter), phosphoric acid/anhydrous crystal (o-phosphoric acid) is 30 mmol/L , Tetrahydrofuran (THF) is 10 ml/ℓ)

Flow rate: 1.0 ml/min

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

"Measurement of imidation ratio of polyimide"

The imidation ratio of the polyimide in the synthesis example was measured as follows. 20 mg of the polyimide powder was put into an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Scientific Co., Ltd.)), and deuterated dimethyl sulfoxide (DMSO-d6, 0.05% by mass TMS (tetramethylsilane) was mixed Product) (0.53 ml) was added, and ultrasonic waves were added to dissolve completely. A 500 MHz proton NMR was measured for this solution with an NMR measuring device (JNW-ECA500) (manufactured by Nippon Electronics Datum). For the imidation rate, a proton derived from a structure that does not change before and after imidation is determined as a reference proton, and the peak integrated value of this proton and the proton peak derived from the NH group of the amic acid appearing in the vicinity of 9.5 ppm to 10.0 ppm. It was calculated|required by the following formula using the value.

Imidation rate (%) = (1-α·x/y) × 100

In the above formula, x is the integrated value of the proton peak derived from the NH group of the amic acid, y is the integrated value of the peak of the reference proton, and α is the NH of the amic acid in the case of polyamic acid (imidation ratio is 0%). It is the ratio of the number of reference protons to 1 group proton.

"Synthesis of polyimide polymer"

<Synthesis Example 1>

E1 (5.21 g, 26.6 mmol), A1 (5.12 g, 13.5 mmol) and B1 (2.05 g, 13.5 mmol) were mixed in NEP (37.1 g), and reacted at 40° C. for 8 hours, and resin solid content concentration A 25 mass% polyamic acid solution (1) was obtained. Mn (number average molecular weight) of this polyamic acid was 25,800, and Mw (weight average molecular weight) was 86,900.

<Synthesis Example 2>

E2 (3.22 g, 12.9 mmol), A2 (4.62 g, 11.7 mmol), B1 (1.78 g, 11.7 mmol) and D1 (0.28 g, 2.60 mmol) were mixed in NEP (24.8 g), and 80 After reacting at °C for 5 hours, E1 (2.52 g, 12.9 mmol) and NEP (12.4 g) were added, followed by reaction at 40 °C for 6 hours, and a polyamic acid solution (2) having a resin solid content concentration of 25% by mass Got it. Mn of this polyamic acid was 23,100 and Mw was 76,400.

<Synthesis Example 3>

After NEP was added to the polyamic acid solution (2) (30.0 g) obtained in Synthesis Example 2 and diluted to 6% by mass, acetic anhydride (3.95 g) and pyridine (2.40 g) were added as an imidation catalyst, and 70 g It was made to react at C for 3.5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (3). The imidation ratio of this polyimide was 75 %, Mn was 21,100 and Mw was 57,500.

<Synthesis Example 4>

E2 (1.31 g, 5.23 mmol), A3 (3.44 g, 7.94 mmol), C1 (2.57 g, 10.6 mmol) and D2 (0.86 g, 7.94 mmol) were mixed in NMP (24.5 g), and 80 After reacting at °C for 5 hours, E1 (4.10 g, 20.9 mmol) and NMP (12.3 g) were added and reacted at 40 °C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

After NMP was added to the obtained polyamic acid solution (30.0 g) and diluted to 6% by mass, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as an imidation catalyst, and reacted at 80°C for 3.5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (4). The imidation ratio of this polyimide was 80 %, Mn was 15,900 and Mw was 43,800.

<Synthesis Example 5>

E2 (1.23 g, 4.91 mmol), A2 (3.92 g, 9.94 mmol), C2 (2.58 g, 9.94 mmol) and D2 (0.54 g, 4.97 mmol) were mixed in NMP (24.2 g), and 80 After reacting at°C for 5 hours, E1 (3.85 g, 19.6 mmol) and NMP (12.1 g) were added, followed by reaction at 40°C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

After NMP was added to the obtained polyamic acid solution (30.0 g) and diluted to 6% by mass, acetic anhydride (3.85 g) and pyridine (2.50 g) were added as an imidation catalyst, and reacted at 60°C for 2 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (5). The imidation ratio of this polyimide was 55 %, Mn was 16,900 and Mw was 46,900.

<Synthesis Example 6>

E2 (2.55 g, 10.2 mmol), A4 (2.55 g, 5.17 mmol), B1 (0.39 g, 2.58 mmol), C2 (3.35 g, 12.9 mmol) and D2 (0.56 g, 5.17 mmol) After mixing in NEP (24.8 g) and reacting at 80° C. for 5 hours, E1 (3.00 g, 15.3 mmol) and NEP (12.4 g) were added and reacted at 40° C. for 6 hours, and the resin solid content concentration was 25 A polyamic acid solution of mass% was obtained.

After NEP was added to the obtained polyamic acid solution (30.5 g) and diluted to 6% by mass, acetic anhydride (3.95 g) and pyridine (2.55 g) were added as an imidation catalyst, and reacted at 60°C for 3 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (6). The imidation ratio of this polyimide was 61 %, Mn was 16,000 and Mw was 44,800.

<Synthesis Example 7>

E2 (3.40 g, 13.6 mmol), B1 (4.19 g, 27.6 mmol) and D1 (0.74 g, 6.89 mmol) were mixed in NEP (24.7 g) and reacted at 80°C for 5 hours, then E1 ( 4.00 g, 20.4 mmol) and NEP (12.3 g) were added and reacted at 40° C. for 6 hours to obtain a polyamic acid solution (7) having a resin solid content concentration of 25% by mass. Mn of this polyamic acid was 27,500 and Mw was 90,100.

<Synthesis Example 8>

After NEP was added to the polyamic acid solution (7) (30.0 g) obtained in Synthesis Example 7 and diluted to 6% by mass, acetic anhydride (4.40 g) and pyridine (3.30 g) were added as an imidation catalyst, and 80 It was made to react at C for 3.5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (8). The imidation ratio of this polyimide was 80 %, Mn was 23,400 and Mw was 64,500.

<Synthesis Example 9>

E2 (3.96 g, 15.8 mmol), B1 (4.14 g, 27.2 mmol), C1 (0.39 g, 1.60 mmol) and D2 (0.35 g, 3.20 mmol) were mixed in NEP (24.2 g), and 80 After reacting at°C for 5 hours, E1 (3.10 g, 15.8 mmol) and NEP (12.1 g) were added, followed by reaction at 40°C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

After NEP was added to the obtained polyamic acid solution (30.0 g) and diluted to 6% by mass, acetic anhydride (4.00 g) and pyridine (2.50 g) were added as an imidation catalyst, and reacted at 60°C for 2 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (9). The imidation ratio of this polyimide was 53 %, Mn was 19,900 and Mw was 55,100.

<Synthesis Example 10>

E3 (5.90 g, 26.3 mmol), A2 (4.21 g, 10.7 mmol), B1 (0.41 g, 2.67 mmol) and D2 (1.44 g, 13.3 mmol) were mixed in NMP (35.9 g), and 40 The reaction was carried out at°C for 8 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

After NMP was added to the obtained polyamic acid solution (30.0 g) and diluted to 6% by mass, acetic anhydride (4.50 g) and pyridine (3.35 g) were added as an imidation catalyst, and reacted at 80°C for 3.5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (10). The imidation ratio of this polyimide was 81 %, Mn was 18,200 and Mw was 51,600.

<Synthesis Example 11>

E3 (5.50 g, 24.5 mmol), A4 (2.45 g, 4.97 mmol), B1 (0.19 g, 1.24 mmol), C2 (3.54 g, 13.7 mmol) and D2 (0.54 g, 4.97 mmol) It mixed in NMP (36.7 g) and made to react at 40 degreeC for 8 hours, and obtained the polyamic acid solution of 25 mass% of resin solid content concentration.

After NMP was added to the obtained polyamic acid solution (30.5 g) and diluted to 6% by mass, acetic anhydride (3.90 g) and pyridine (2.60 g) were added as an imidation catalyst, and reacted at 60°C for 3.5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (11). The imidation ratio of this polyimide was 65 %, Mn was 18,500 and Mw was 50,200.

<Synthesis Example 12>

E3 (7.50 g, 33.5 mmol), B1 (3.61 g, 23.7 mmol), C1 (0.41 g, 1.69 mmol) and D1 (0.92 g, 8.47 mmol) were mixed in NMP (37.3 g), and 40 The reaction was carried out at°C for 8 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

After NMP was added to the obtained polyamic acid solution (30.0 g) and diluted to 6% by mass, acetic anhydride (4.20 g) and pyridine (3.10 g) were added as an imidation catalyst, and reacted at 80°C for 2.5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (12). The imidation ratio of this polyimide was 75 %, Mn was 19,800 and Mw was 53,900.

<Synthesis Example 13>

E4 (5.21 g, 17.3 mmol), A1 (4.60 g, 12.1 mmol), B1 (0.67 g, 4.39 mmol) and D1 (0.59 g, 5.49 mmol) were mixed in NEP (23.8 g), and 80 After reacting at°C for 6 hours, E1 (0.85 g, 4.33 mmol) and NEP (11.9 g) were added, followed by reacting at 40°C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

After NEP was added to the obtained polyamic acid solution (30.0 g) and diluted to 6% by mass, acetic anhydride (3.80 g) and pyridine (2.50 g) were added as an imidation catalyst, and reacted at 60°C for 2 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (13). The imidation ratio of this polyimide was 55 %, Mn was 16,800 and Mw was 45,300.

<Synthesis Example 14>

E4 (3.29 g, 11.0 mmol), A2 (3.51 g, 8.88 mmol), C1 (1.61 g, 6.66 mmol), C2 (1.15 g, 4.44 mmol) and D2 (0.24 g, 2.22 mmol) After mixing in NMP (23.9 g) and reacting at 80° C. for 6 hours, E1 (2.15 g, 11.0 mmol) and NMP (12.0 g) were added and reacted at 40° C. for 6 hours, resulting in a resin solid content concentration of 25 A polyamic acid solution of mass% was obtained.

After NMP was added to the obtained polyamic acid solution (30.1 g) and diluted to 6% by mass, acetic anhydride (4.20 g) and pyridine (3.15 g) were added as an imidation catalyst, and reacted at 80°C for 2.5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (14). The imidation ratio of this polyimide was 73 %, Mn was 15,900 and Mw was 43,800.

<Synthesis Example 15>

E5 (4.30 g, 20.3 mmol), A3 (3.89 g, 8.98 mmol), C2 (1.33 g, 5.13 mmol) and D2 (1.25 g, 11.6 mmol) were mixed in NMP (23.5 g), and 80 After reacting at°C for 6 hours, E1 (0.99 g, 5.07 mmol) and NMP (11.8 g) were added, followed by reaction at 40°C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

After NMP was added to the obtained polyamic acid solution (30.0 g) and diluted to 6% by mass, acetic anhydride (3.85 g) and pyridine (2.40 g) were added as an imidation catalyst, and reacted at 60°C for 2 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (15). The imidation ratio of this polyimide was 51 %, Mn was 15,700 and Mw was 44,500.

<Synthesis Example 16>

E5 (2.95 g, 13.9 mmol), A2 (3.71 g, 9.39 mmol), B1 (0.36 g, 2.35 mmol), C1 (1.14 g, 4.70 mmol), C2 (1.22 g, 4.70 mmol) and D1 (0.25 g, 2.35 mmol) was mixed in NEP (23.9 g) and reacted at 80° C. for 6 hours, then E2 (2.32 g, 9.27 mmol) and NEP (11.9 g) were added, at 80° C. The reaction was carried out for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

After NMP was added to the obtained polyamic acid solution (30.0 g) and diluted to 6% by mass, acetic anhydride (4.20 g) and pyridine (3.20 g) were added as an imidation catalyst, and reacted at 80°C for 2 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (16). The imidation ratio of this polyimide was 68 %, Mn was 15,500 and Mw was 45,100.

<Synthesis Example 17>

E5 (4.10 g, 19.3 mmol), B1 (4.47 g, 29.4 mmol) and D2 (0.35 g, 3.26 mmol) were mixed in NMP (24.3 g) and reacted at 80° C. for 6 hours, then E2 ( 3.22 g, 12.9 mmol) and NMP (12.1 g) were added and reacted at 80°C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

After NMP was added to the obtained polyamic acid solution (30.0 g) and diluted to 6% by mass, acetic anhydride (4.20 g) and pyridine (3.20 g) were added as an imidation catalyst, and reacted at 80°C for 2.5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (17). The imidation ratio of this polyimide was 73 %, Mn was 16,200 and Mw was 48,100.

<Synthesis Example 18>

E2 (2.85 g, 11.4 mmol), A1 (2.20 g, 5.77 mmol) and B1 (3.51 g, 23.1 mmol) were mixed in NEP (23.8 g) and reacted at 80° C. for 5 hours, then E1 ( 3.35 g, 17.1 mmol) and NEP (11.9 g) were added and reacted at 40° C. for 6 hours to obtain a polyamic acid solution (18) having a resin solid content concentration of 25% by mass. Mn of this polyamic acid was 24,800 and Mw was 80,200.

<Synthesis Example 19>

After NEP was added to the polyamic acid solution (18) (30.0 g) obtained in Synthesis Example 18 and diluted to 6% by mass, acetic anhydride (4.40 g) and pyridine (3.35 g) were added as an imidation catalyst, and 80 It was made to react at C for 3.5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (19). The imidation ratio of this polyimide was 79 %, Mn was 18,400 and Mw was 47,200.

<Synthesis Example 20>

E2 (3.25 g, 13.0 mmol), B1 (1.80 g, 11.9 mmol), D1 (0.28 g, 2.60 mmol) and D3 (4.46 g, 11.9 mmol) were mixed in NMP (24.7 g), and 80 After reacting at°C for 5 hours, E1 (2.55 g, 13.0 mmol) and NMP (12.4 g) were added, followed by reaction at 40°C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

After NMP was added to the obtained polyamic acid solution (30.0 g) and diluted to 6% by mass, acetic anhydride (4.20 g) and pyridine (3.20 g) were added as an imidation catalyst, and reacted at 80°C for 3 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (20). The imidation ratio of this polyimide was 75 %, Mn was 14,600 and Mw was 41,200.

The polyimide polymers are shown in Tables 32 to 34.

"Production of liquid crystal orientation treatment agent"

In Examples 1 to 20 and Comparative Examples 1 to 7 to be described below, a production example of a liquid crystal aligning agent is described. Moreover, this liquid crystal aligning agent was used also for evaluation.

The obtained liquid-crystal aligning agent is shown to Tables 35-37. In addition, the following *1 to *5 in Tables 35 to 37 respectively represent the following meanings.

*1: The introduced amount (parts by mass) of the specific polymer (A) relative to 100 parts by mass of all polymers is shown.

*2: The amount (parts by mass) of the specific polymer (B) introduced relative to 100 parts by mass of all polymers is shown.

*3: The introduced amount (part by mass) of each solvent relative to 100 parts by mass of all solvents is shown.

*4: The ratio occupied by all the polymers in the liquid crystal aligning agent is shown.

*5: The ratio occupied by all the polymers in the liquid crystal aligning agent is shown.

Using the liquid crystal aligning agent obtained in Examples and Comparative Examples, as follows: "Evaluation of inkjet coating property of liquid crystal aligning agent", "Production of liquid crystal cell and evaluation of pretilt angle (normal cell)", "Voltage retention rate Evaluation (normal cell)", "evaluation of relaxation of residual charge (normal cell)", and "production of liquid crystal cell and evaluation of liquid crystal orientation (PSA cell)" were performed.

"Evaluation of inkjet coating properties of liquid crystal orientation treatment agent"

The liquid crystal aligning agent (4) obtained in Example 4, the liquid crystal aligning agent (7) obtained in Example 7, the liquid crystal aligning agent (10) obtained in Example 10, the liquid crystal aligning agent (13) obtained in Example 13, and Examples The liquid crystal aligning agent (18) obtained in 18 was pressure-filtered with a membrane filter having a pore diameter of 1 µm to evaluate ink jet coating properties. HIS-200 (manufactured by Hitachi Plant Technology Co., Ltd.) was used for the inkjet applicator. The coating was applied on an ITO (indium tin oxide) evaporated substrate cleaned with pure water and IPA, with a coating area of 70 × 70 mm, a nozzle pitch of 0.423 mm, a scan pitch of 0.5 mm, a coating speed of 40 mm/sec, and a coating. Temporary drying was carried out on a hot plate at 70°C for 5 minutes, and the time from to the temporary drying was 60 seconds.

The coating film properties of the substrate with the obtained liquid crystal alignment film were confirmed. Specifically, the coating film was visually observed under a sodium lamp to confirm the presence or absence of a pinhole. As a result, even in the liquid crystal aligning film obtained in any Example, a pinhole was not observed on the coating film, and a liquid crystal aligning film excellent in coating film properties was obtained.

"Production of liquid crystal cell and evaluation of pretilt angle (normal cell)"

The liquid crystal aligning agent obtained in Examples and Comparative Examples was pressure-filtered with a membrane filter having a pore diameter of 1 µm to produce a liquid crystal cell (normal cell). This solution was spin-coated on the ITO side of a substrate (100 mm long × 100 mm wide, 0.7 mm thick) with a 100 × 100 mm ITO electrode washed with pure water and IPA, and then on a hot plate at 100° C. for 5 minutes, Heat treatment was carried out at 230° C. for 30 minutes in a thermally circulating clean oven to obtain an ITO substrate with a polyimide liquid crystal aligning film having a film thickness of 100 nm. In addition, the liquid-crystal aligning agent (4) obtained in Example 4, the liquid-crystal aligning agent (7) obtained in Example 7, the liquid-crystal aligning agent (10) obtained in Example 10, the liquid-crystal aligning agent (13) obtained in Example 13, and The liquid crystal aligning agent (18) obtained in Example 18 produced a substrate with a liquid crystal aligning film under the same conditions as the above-described "evaluation of inkjet coatability of the liquid crystal aligning agent", and then 230 in a heat circulation type clean oven. It heat-processed at degreeC for 30 minutes, and obtained the ITO board|substrate with the polyimide liquid crystal aligning film of 100 nm in film thickness.

The coated film surface of this ITO substrate was rubbed using a rayon cloth with a rubbing apparatus having a roll diameter of 120 mm under conditions of a roll rotation speed of 1000 rpm, a roll advance speed of 50 mm/sec, and a press fit amount of 0.1 mm.

Two ITO substrates with the obtained liquid crystal alignment film were prepared, and a 6 µm spacer was sandwiched therebetween with the liquid crystal alignment film surface as the inner side, and the circumference was adhered with a sealing agent to prepare an empty cell. MLC-6608 (manufactured by Merck Japan) was injected into this empty cell by a vacuum injection method, and the injection port was sealed to obtain a liquid crystal cell (normal cell).

Next, the pretilt angle of this liquid crystal cell (normal cell) was measured. The pretilt angle measured the liquid crystal cell after performing an isotropic treatment (heat treatment at 95°C for 5 minutes) of liquid crystal, and then heat treatment (heat treatment at 120°C for 5 hours).

Further, after isotropic treatment was performed on the liquid crystal cell produced under the same conditions as above, the liquid crystal cell after irradiation with ultraviolet rays of 10 J/cm 2 in terms of 365 nm was also measured. In addition, the pretilt angle was measured at room temperature using PAS-301 (manufactured by ELSICON). In addition, irradiation of ultraviolet rays was performed using the table-top type UV curing apparatus (HCT3B28HEX-1) (made by Senlite).

Evaluation is for the pretilt angle after isotropic treatment of the liquid crystal (also referred to as after Iso treatment), after heat treatment (also referred to as after high temperature treatment) and after irradiation with ultraviolet rays (also referred to as after ultraviolet irradiation) The smaller the angle change, the better it was (Tables 38 to 40 show the values of the pretilt angle after Iso treatment, after high temperature treatment, and after UV irradiation).

Tables 38 to 40 show the results obtained in Examples and Comparative Examples.

"Evaluation of voltage retention (normal cell)"

The voltage retention was evaluated using the liquid crystal cell (normal cell) produced under the same conditions as the above-described "production of a liquid crystal cell and evaluation of pretilt angle (normal cell)". Specifically, to the liquid crystal cell (normal cell) obtained by the above method, a voltage of 1 V was applied at a temperature of 80° C. for 60 μs, and the voltage after 50 ms was measured, and the voltage retention rate ( It was calculated as VHR). In addition, the measurement was performed with the setting of Voltage: ±1 V, Pulse Width: 60 μs, and Flame Period: 50 ms using a voltage retention rate measuring device (VHR-1, manufactured by Toyo Technica).

In addition, the liquid crystal cell in which the voltage retention was measured immediately after the above liquid crystal cell was manufactured was irradiated with UV rays of 50 J/cm 2 in terms of 365 nm using a table-top UV curing device (HCT3B28HEX-1, manufactured by Senlite). Then, the voltage retention was measured under the same conditions as above.

As for the evaluation, the value of the voltage retention rate immediately after liquid crystal cell production was high, and the decrease in the value after ultraviolet irradiation with respect to the value of the voltage retention rate immediately after liquid crystal cell production was made better (Tables 41 to 43 show liquid crystal cells). The value of VHR immediately after production and after ultraviolet irradiation is shown). Tables 41 to 43 show the results obtained in Examples and Comparative Examples.

"Evaluation of residual charge relaxation (normal cell)"

Using the liquid crystal cell (normal cell) manufactured under the same conditions as the above-described "production of liquid crystal cell and evaluation of pretilt angle (normal cell)", evaluation of relaxation of residual electric charges was performed. Specifically, after applying a DC voltage of 10 V to the liquid crystal cell for 30 minutes and short-circuiting for 1 second, the potential generated in the liquid crystal cell was measured for 1800 seconds. Among them, the value of the residual charge after 50 seconds was used to evaluate the relaxation of the residual charge. In addition, for the measurement, a 6254 type liquid crystal physical property evaluation device (manufactured by Toyo Technica) was used.

In addition, to the liquid crystal cell in which the residual electric charge has been measured immediately after the above liquid crystal cell is manufactured, a tabletop UV curing device (HCT3B28HEX-1) (manufactured by Senlite) is used to irradiate UV rays of 30 J/cm 2 in terms of 365 nm. Then, the residual charge was measured under the same conditions as above.

The evaluation was made better as the value of the residual charge immediately after liquid crystal cell production and after ultraviolet irradiation was smaller (Tables 41 to 43 show the value of VHR immediately after liquid crystal cell production and after ultraviolet irradiation). Tables 41 to 43 show the results obtained in Examples and Comparative Examples.

"Production of liquid crystal cell and evaluation of liquid crystal orientation (PSA cell)"

The liquid crystal aligning agent (2) obtained in Example 2, the liquid crystal aligning agent (3) obtained in Example 3, the liquid crystal aligning agent (9) obtained in Example 9, the liquid crystal aligning agent (11) obtained in Example 11, and Examples The liquid crystal aligning agent (14) obtained in 14 was pressure-filtered with a membrane filter having a pore diameter of 1 µm, and production of a liquid crystal cell and evaluation of liquid crystal orientation (PSA cell) were performed. This solution was cleaned with pure water and IPA, and a substrate with an ITO electrode with a pattern spacing of 20 µm of 10 × 10 mm (40 mm in length × 30 mm in width, 0.7 mm in thickness) and a 10 × 40 mm ITO in the center Spin coat on the ITO surface of the electrode-attached substrate (40 mm long × 30 mm wide, 0.7 mm thick), heat treated on a hot plate at 100°C for 5 minutes, and heat-treated at 230°C for 30 minutes in a thermally circulating clean oven. A polyimide coating film having a film thickness of 100 nm was obtained.

The substrate to which the liquid crystal alignment film was attached was combined with the liquid crystal alignment film surface as the inner side, a 6 µm spacer was sandwiched therebetween, and the periphery was bonded with a sealing agent to produce an empty cell. 100 mass% of the nematic liquid crystal (MLC-6608) of the polymerizable compound (1) represented by the following formula to a nematic liquid crystal (MLC-6608) (manufactured by Merck Japan) in this empty cell by a vacuum injection method The liquid crystal obtained by mixing 0.3% by mass of the polymerizable compound (1) was injected, and the injection port was sealed to obtain a liquid crystal cell.

[Chemical Formula 54]

While applying a voltage of 5 V AC to the obtained liquid crystal cell, a metal halide lamp having an illuminance of 60 mW was used to cut a wavelength of 350 nm or less, and irradiation with ultraviolet rays of 20 J/cm 2 in terms of 365 nm was performed, and the liquid crystal was A liquid crystal cell (PSA cell) in which the orientation direction was controlled was obtained. When the liquid crystal cell was irradiated with ultraviolet rays, the temperature in the irradiation device was 50°C.

The response speed of the liquid crystal before ultraviolet irradiation of this liquid crystal cell and after ultraviolet irradiation was measured. The response speed measured T90 → T10 from 90% transmittance to 10% transmittance.

In the PSA cell obtained in an example, it was confirmed that the orientation direction of the liquid crystal was controlled because the response speed of the liquid crystal cell after ultraviolet irradiation became faster than the liquid crystal cell before ultraviolet irradiation. In addition, in all liquid crystal cells, it was confirmed that the liquid crystal was uniformly oriented by observation with a polarization microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation).

<Example 1>

The polyamic acid solution (1) (5.00 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 1 and the polyamic acid solution (7) (3.30 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 7 were NEP ( 13.3 g), BCS (9.80 g), EC (3.30 g) and M1 (0.21 g) were added, followed by stirring at 25°C for 6 hours to obtain a liquid crystal aligning agent (1). Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Example 2>

To the polyamic acid solution (2) (6.50 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 2 and the polyamic acid solution (7) (2.80 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 7 (2.80 g) 14.9 g) and BCS (14.5 g) were added, and it stirred at 25 degreeC for 4 hours, and the liquid-crystal aligning agent (2) was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Example 3>

NEP (17.2 g) was added to the polyimide powder (3) (1.00 g) obtained in Synthesis Example 3 and the polyimide powder (8) (1.00 g) obtained in Synthesis Example 8, followed by stirring at 70° C. for 24 hours to dissolve. . PB (14.1 g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and the liquid-crystal aligning agent (3) was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Example 4>

NEP (19.2 g) was added to the polyimide powder (3) (0.65 g) obtained in Synthesis Example 3 and the polyimide powder (8) (0.65 g) obtained in Synthesis Example 8, followed by stirring at 70° C. for 24 hours to dissolve. . BCS (7.20 g) and PB (10.8 g) were added to this solution, followed by stirring at 40° C. for 4 hours to obtain a liquid crystal aligning agent (4). Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Example 5>

NMP (18.5 g) was added to the polyimide powder (4) (1.65 g) obtained in Synthesis Example 4 and the polyimide powder (8) (0.71 g) obtained in Synthesis Example 8, followed by stirring at 70° C. for 24 hours to dissolve. . BCS (18.5 g) and M1 (0.12 g) were added to this solution, and it stirred at 40 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (5). Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Example 6>

NMP (2.96 g) and NEP (4.48 g) were added to the polyimide powder (5) (0.95 g) obtained in Synthesis Example 5, followed by stirring at 70° C. for 24 hours to dissolve. PB (7.44 g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

On the other hand, NMP (4.44 g) and NEP (6.72 g) were added to the polyimide powder (9) (1.43 g) obtained in Synthesis Example 9, followed by stirring at 70°C for 24 hours to dissolve. PB (11.2 g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

The two solutions obtained above were mixed, and it stirred at 25 degreeC for 4 hours, and the liquid-crystal aligning agent (6) was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Example 7>

To the polyimide powder (5) (0.45 g) obtained in Synthesis Example 5 and the polyimide powder (9) (1.05 g) obtained in Synthesis Example 9 were added NMP (4.10 g) and NEP (20.7 g), at 70°C. It was stirred and dissolved for 24 hours. PB (16.5 g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and the liquid-crystal aligning agent (7) was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Example 8>

NMP (21.5 g) was added to the polyimide powder (5) (0.75 g) obtained in Synthesis Example 5 and the polyimide powder (17) (1.75 g) obtained in Synthesis Example 17, followed by stirring at 70° C. for 24 hours to dissolve. . BCS (13.7 g), DME (3.90 g), and M1 (0.25 g) were added to this solution, followed by stirring at 40° C. for 6 hours to obtain a liquid crystal aligning agent (8). Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Example 9>

NEP (11.8 g) was added to the polyimide powder (6) (1.25 g) obtained in Synthesis Example 6, followed by stirring at 70°C for 24 hours to dissolve. BCS (1.98 g) and PB (5.89 g) were added to this solution, followed by stirring at 40° C. for 4 hours to obtain a solution.

On the other hand, NEP (9.60 g) was added to the polyimide powder (12) (1.02 g) obtained in Synthesis Example 12, followed by stirring at 70° C. for 24 hours to dissolve. BCS (1.62 g) and PB (4.81 g) were added to this solution, followed by stirring at 40°C for 4 hours to obtain a solution.

The two solutions obtained above were mixed, M1 (0.07 g) was added there, and it stirred at 40 degreeC for 4 hours, and the liquid-crystal aligning agent (9) was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Example 10>

NMP (19.0 g) and γ-BL (3.80 g) were added to the polyimide powder (6) (0.55 g) obtained in Synthesis Example 6 and the polyimide powder (12) (0.83 g) obtained in Synthesis Example 12, and 70 It was stirred and dissolved at C for 24 hours. PB (15.2 g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and the liquid-crystal aligning agent (10) was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Example 11>

NMP (3.40 g) and NEP (17.0 g) were added to the polyimide powder (10) (0.65 g) obtained in Synthesis Example 10 and the polyimide powder (8) (1.52 g) obtained in Synthesis Example 8, and at 70°C It was stirred and dissolved for 24 hours. BCS (3.40 g) and PB (10.2 g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and the liquid-crystal aligning agent (11) was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Example 12>

NEP (16.6 g) and γ-BL (3.70 g) were added to the polyimide powder (11) (1.65 g) obtained in Synthesis Example 11 and the polyimide powder (12) (0.71 g) obtained in Synthesis Example 12, followed by 70 g. It was stirred and dissolved at C for 24 hours. PB (16.6 g) and M1 (0.24 g) were added to this solution, and it stirred at 40 degreeC for 6 hours, and obtained the liquid-crystal aligning agent (12). Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Example 13>

NMP (3.90 g) and NEP (15.6 g) were added to the polyimide powder (11) (0.85 g) obtained in Synthesis Example 11 and the polyimide powder (12) (0.57 g) obtained in Synthesis Example 12, and at 70°C It was stirred and dissolved for 24 hours. PB (19.5 g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (13). Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Example 14>

NMP (7.50 g) and NEP (3.75 g) were added to the polyimide powder (13) (1.20 g) obtained in Synthesis Example 13, followed by stirring at 70° C. for 24 hours to dissolve. BCS (3.75 g) and DME (3.75 g) were added to this solution, followed by stirring at 40° C. for 4 hours to obtain a solution.

On the other hand, NMP (7.50 g) and NEP (3.75 g) were added to the polyimide powder (9) (1.20 g) obtained in Synthesis Example 9, followed by stirring at 70° C. for 24 hours to dissolve. BCS (3.75 g) and DME (3.75 g) were added to this solution, followed by stirring at 40° C. for 4 hours to obtain a solution.

The two solutions obtained above were mixed, and it stirred at 25 degreeC for 4 hours, and the liquid-crystal aligning agent (14) was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Example 15>

NMP (5.70 g) and NEP (15.1 g) were added to the polyimide powder (14) (1.45 g) obtained in Synthesis Example 14 and the polyimide powder (8) (0.97 g) obtained in Synthesis Example 8, and at 70°C It was stirred and dissolved for 24 hours. PB (17.0 g) and M1 (0.07 g) were added to this solution, and it stirred at 40 degreeC for 6 hours, and the liquid-crystal aligning agent (15) was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Example 16>

To the polyimide powder (15) (1.75 g) obtained in Synthesis Example 15 and the polyimide powder (9) (0.44 g) obtained in Synthesis Example 9 were added NMP (6.90 g) and NEP (13.7 g), at 70°C It was stirred and dissolved for 24 hours. PB (13.7 g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and the liquid-crystal aligning agent (16) was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Example 17>

To the polyimide powder (16) (0.65 g) obtained in Synthesis Example 16 and the polyimide powder (17) (1.52 g) obtained in Synthesis Example 17 were added NMP (11.9 g) and NEP (6.80 g), at 70°C. It was stirred and dissolved for 24 hours. BCS (15.3 g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (17). Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Example 18>

NEP (11.6 g) and γ-BL (5.80 g) were added to the polyimide powder (16) (0.35 g) obtained in Synthesis Example 16 and the polyimide powder (17) (1.05 g) obtained in Synthesis Example 17, and 70 It was stirred and dissolved at C for 24 hours. PB (21.2 g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (18). Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Example 19>

NMP (7.80 g) and NEP (13.7 g) were added to the polyimide powder (16) (0.75 g) obtained in Synthesis Example 16 and the polyimide powder (8) (1.75 g) obtained in Synthesis Example 8, and at 70°C It was stirred and dissolved for 24 hours. PB (13.7 g), EC (3.90 g), and M1 (0.13 g) were added to this solution, followed by stirring at 40° C. for 6 hours to obtain a liquid crystal aligning agent (19). Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Example 20>

NEP (15.7 g) was added to the polyamic acid solution (2) (1.88 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 2 and the polyimide powder (17) (0.50 g) obtained in Synthesis Example 17, and 70 It was stirred and dissolved at C for 24 hours. BCS (7.40 g) and PB (7.40 g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (20). Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Comparative Example 1>

NEP (15.2 g) and BCS (14.9 g) were added to the polyamic acid solution (2) (9.50 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 2, and stirred at 25°C for 4 hours, and a liquid crystal aligning agent (21) was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Comparative Example 2>

NEP (14.4 g) and BCS (14.1 g) were added to the polyamic acid solution (7) (9.00 g) having a resin solid content concentration of 25 mass% obtained in Synthesis Example 7 and stirred at 25° C. for 4 hours, and a liquid crystal aligning agent (22) was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Comparative Example 3>

NEP (19.4 g) was added to the polyimide powder (3) (2.25 g) obtained in Synthesis Example 3, followed by stirring at 70°C for 24 hours to dissolve. PB (15.9 g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and the liquid-crystal aligning agent (23) was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Comparative Example 4>

NEP (19.0 g) was added to the polyimide powder (8) (2.20 g) obtained in Synthesis Example 8, and it was stirred and dissolved at 70 degreeC for 24 hours. PB (15.5 g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and the liquid-crystal aligning agent (24) was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Comparative Example 5>

To the polyamic acid solution (2) (7.00 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 2 and the polyamic acid solution (18) (3.00 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 18 (3.00 g) 16.0 g) and BCS (15.7 g) were added, and it stirred at 25 degreeC for 4 hours, and the liquid-crystal aligning agent (25) was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Comparative Example 6>

NEP (18.1 g) was added to the polyimide powder (3) (1.05 g) obtained in Synthesis Example 3 and the polyimide powder (19) (1.05 g) obtained in Synthesis Example 19, followed by stirring at 70° C. for 24 hours to dissolve. . PB (14.8 g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and the liquid-crystal aligning agent (26) was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Comparative Example 7>

NEP (17.2 g) was added to the polyimide powder (20) (1.00 g) obtained in Synthesis Example 20 and the polyimide powder (8) (1.00 g) obtained in Synthesis Example 8, followed by stirring at 70° C. for 24 hours to dissolve. . PB (14.1 g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and the liquid-crystal aligning agent (27) was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that it was a uniform solution.

<Evaluation of liquid crystal orientation treatment agent>

Using each of the liquid crystal aligning agents each obtained in Examples 1 to 20 and Comparative Examples 1 to 7 described above, "Production of liquid crystal cell and evaluation of pretilt angle (normal cell)", "evaluation of voltage retention (normal cell)" "And "evaluation of relaxation of residual charge (normal cell)" were performed. In addition, about each liquid crystal aligning agent obtained in Examples 4, 7, 10, 13, 18, respectively, the evaluation of the inkjet coatability was also performed.

The results of these evaluations are put together in Tables 39 to 43 below and shown.

As can be seen from the above results, the liquid crystal aligning agent of the Example exhibited a stable pretilt angle even if the liquid crystal cell was subjected to high-temperature treatment and ultraviolet irradiation compared to the comparative example. Furthermore, even when irradiation with ultraviolet rays is applied, a decrease in the voltage retention is suppressed, and the residual charge accumulated by the DC voltage is quickly alleviated. That is, the liquid crystal aligning agent of the present invention becomes a liquid crystal aligning film capable of expressing a stable pretilt angle even after exposure to high temperature and light irradiation for a long time, and suppresses a decrease in voltage retention even after exposure to light irradiation for a long time. In addition, it becomes a liquid crystal aligning film in which the relaxation of residual charges accumulated by the DC voltage is quick.

Specifically, comparison of Examples of a liquid crystal aligning agent using a specific polymer (A) and a specific polymer (B) and Examples of a liquid crystal aligning agent using only one of them, that is, Example 2 and Comparative Example 1 Or a comparison of Comparative Example 2, a comparison of Example 3 and Comparative Example 3 or Comparative Example 4. In Comparative Examples 1 and 3 using only these specific polymers (A), compared to the corresponding Examples, the variation of the pretilt angle after high-temperature treatment and ultraviolet irradiation was large, and the voltage retention rate was significantly lowered for these treatments. And the value of the residual charge also increased. Among them, in particular, the decrease in voltage retention was large. Moreover, in Comparative Example 2 and Comparative Example 4, the liquid crystal was not aligned vertically.

Further, Examples of the liquid crystal aligning agent using the specific polymer (A) and the specific polymer (B), and the specific side chain type diamine having a specific polymer (A) and a specific side chain structure represented by the above formula [1] It is a comparison of a comparative example of a liquid crystal aligning agent using a polymer using a compound, that is, a comparison between Example 2 and Comparative Example 5, and a comparison between Example 3 and Comparative Example 6. Compared to the corresponding examples, these comparative examples had a large variation in the pretilt angle after high-temperature treatment and ultraviolet irradiation, and with respect to these treatments, the voltage retention rate was significantly lowered, and the residual charge value was also increased. In particular, the voltage retention was lowered and the value of the residual charge was large.

In addition, a comparison of Examples of a liquid crystal aligning agent using a specific polymer (A) and a specific polymer (B), and a comparative example of a polymer having a conventional side chain structure and a liquid crystal aligning agent using a specific polymer (B), that is, It is a comparison between Example 3 and Comparative Example 7. Compared with Example 3, the variation of the pretilt angle after the high-temperature treatment and ultraviolet irradiation was large in Comparative Example 7, and the voltage retention was significantly lowered and the residual charge value was also increased with respect to these treatments. In particular, the width of change in the pretilt angle after UV irradiation was large.

Industrial applicability

The liquid crystal aligning agent of the present invention can provide a liquid crystal aligning film capable of expressing a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time. Further, even after exposure to light irradiation for a long period of time, it is possible to provide a liquid crystal aligning film in which a decrease in voltage retention is suppressed and residual charges accumulated by a DC voltage are quickly relieved. In addition, a liquid crystal display device having the above liquid crystal alignment layer and a liquid crystal alignment treatment agent capable of providing the above liquid crystal alignment layer can be provided.

Therefore, a liquid crystal display element having a liquid crystal aligning film obtained from the liquid crystal aligning agent of the present invention has excellent reliability, and can be preferably used for a large-screen and high-definition liquid crystal television, etc., and a TN element, an STN element, a TFT liquid crystal element, in particular It is useful for vertically aligned liquid crystal display devices.

Moreover, the liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention is useful also for a liquid crystal display element which needs to be irradiated with ultraviolet rays when manufacturing a liquid crystal display element. That is, a liquid crystal composition comprising a liquid crystal layer formed between a pair of substrates with electrodes, and containing a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, A liquid crystal display device manufactured through a process of polymerizing the polymerizable compound while applying a voltage between the electrodes, further comprising a liquid crystal layer between a pair of substrates with electrodes, and between the pair of substrates It is also useful for a liquid crystal display device manufactured by disposing a liquid crystal alignment film containing a polymerizable group that is polymerized by at least one of an active energy ray and heat, and polymerizing the polymerizable group while applying a voltage between the electrodes.

In addition, the specification of Japanese Patent Application No. 2013-182352, the scope of claims, and the entire contents of the abstract for which it applied on September 3, 2013 are cited here and taken as an indication of the specification of the present invention.

Claims (28)

It contains the following (A) component and (B) component, and further contains at least two solvents of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether And a solvent of propylene glycol monobutyl ether is contained in one of them.
Component (A): At least one polymer selected from the group consisting of a polyimide precursor and a polyimide obtained by reacting a diamine component containing a diamine having a structure represented by the following formula [1] with a tetracarboxylic acid component.
Component (B): At least one type of polymer selected from the group consisting of a polyimide precursor and a polyimide obtained by reacting a diamine component not containing a diamine having a structure represented by the following formula [1] with a tetracarboxylic acid component.

(Y ¹ represents a single bond, -(CH ₂ ) _a- (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO-, or OCO-. Y ² is a single bond or (CH ₂ ) _b -represents (b is an integer of 1 to 15) Y ³ is a single bond, -(CH ₂ ) _c- (c is an integer of 1 to 15), -O-, -CH ₂ Represents O-, -COO- or OCO- Y ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton, and the ring any hydrogen atom of an alkyl group having 1 to 3 on the sentence, a fluorine-containing alkyl group having 1 to 3 carbon atoms, an alkoxyl group, having 1 to 3, may be substituted 1 to 3 carbon atoms a fluorine-containing alkoxy group or a fluorine atom. Y ⁵ is Represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring, and a heterocycle, and any hydrogen atom on these cyclic groups contains an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, and a fluorine having 1 to 3 carbon atoms It may be substituted with an alkyl group, a C1-C3 fluorine-containing alkoxyl group, or a fluorine atom. n represents an integer of 0-4. Y ⁶ is a C1-C18 alkyl group, a C1-C18 fluorine-containing alkyl group, a C1 It represents an alkoxyl group of to 18 or a fluorine-containing alkoxyl group of 1 to 18 carbon atoms.) The method of claim 1,
The liquid crystal aligning agent which diamine which has a structure represented by said formula [1] is represented by following formula [1a].

(Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , n and Y ⁶ represent the same meanings as above, and m is an integer of 1 to 4). The method of claim 1,
Polyimide precursor and polyimide obtained by reacting a diamine component containing a diamine having at least one substituent selected from a carboxyl group (COOH group) and a hydroxyl group (OH group) and a tetracarboxylic acid component as the component (B) A liquid crystal aligning agent which is at least 1 type of polymer selected from the group consisting of mids. The method of claim 1,
The liquid crystal aligning agent which is a polymer used for the diamine component containing the said (A) component further a diamine which has at least 1 type of substituent selected from carboxyl group (COOH group) and hydroxyl group (OH group). The method of claim 3,
The liquid crystal aligning agent represented by the following formula [2a] by diamine which has at least 1 type of substituent selected from the said carboxyl group and a hydroxyl group.

(A ¹ represents at least one substituent selected from the following formulas [2a-1] and [2a-2], and m1 represents an integer of 1 to 4).

(d represents the integer of 0-4, e represents the integer of 0-4). The method of claim 1,
The liquid crystal aligning agent which is a polymer in which the polymer of the said (A) component and (B) component used the diamine represented by following formula [3a] for a diamine component.

(B ¹ is -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON(CH ₃ )- or N(CH ₃ ) Represents CO- B ² represents a single bond, an alkylene having 1 to 20 carbon atoms, a non-aromatic ring or an aromatic ring B ³ represents a single bond, -O-, -NH-, -N(CH ₃ )- , -CONH-, -NHCO-, -COO-, -OCO-, -CON(CH ₃ )-, N(CH ₃ )CO-, or -O(CH ₂ ) _m2- (m2 is an integer from 1 to 5 B ⁴ represents a nitrogen-containing heterocycle, n1 represents an integer of 1 to 4, and when n1 is 2 or more, -B ¹ -B ² -B ³ -B ⁴ may be the same as or different from each other do). The method of claim 6,
^{B 1} in the above formula [3a] is -O-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCO- or CON(CH ₃ )-. The method of claim 6,
^{B 2} in the formula [3a] is a single bond, an alkylene having 1 to 5 carbon atoms, a cyclohexane ring, or a benzene ring. The method of claim 6,
^{The liquid crystal aligning agent in which B 3} in said formula [3a] is a single bond, -O-, -OCO-, or -O(CH ₂ ) _m2- (m2 is an integer of 1-5). The method of claim 6,
^{B 4} in the formula [3a] is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, or a pyrimidine ring. The method of claim 6,
In the formula [3a], B ¹ represents -CONH-, B ² represents an alkylene having 1 to 5 carbon atoms, B ³ represents a single bond, B ⁴ represents an imidazole ring or a pyridine ring, and n1 represents One liquid crystal aligning agent. The method of claim 1,
The liquid crystal aligning agent in which the tetracarboxylic acid component in at least one of said (A) component and (B) component contains tetracarboxylic dianhydride represented by following formula [4].

(Z ¹ is a group selected from the following formula [4a]-formula [4k]).

(Z ² to Z ⁵ each independently represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and Z ⁶ and Z ⁷ each independently represent a hydrogen atom or a methyl group) The method of claim 1,
A liquid crystal aligning agent containing at least 1 type of solvent selected from following formula [D-1]-formula [D-3].

(D ¹ represents an alkyl group having a carbon number of 1 to 3, D ² represents an alkyl group having a carbon number of 1 to 3, D ³ represents an alkyl group having from 1 to 4 carbon atoms). The method of claim 1,
In the liquid crystal aligning agent, a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group, and A liquid crystal aligning agent containing at least one type of crosslinkable compound selected from crosslinkable compounds having a polymerizable unsaturated bond. A liquid crystal aligning film obtained from the liquid crystal aligning agent in any one of Claims 1-14. A liquid crystal aligning film obtained by printing the liquid crystal aligning agent according to any one of claims 1 to 14 by an ink jet method. A liquid crystal display device comprising the liquid crystal aligning film according to claim 15. A liquid crystal display device comprising the liquid crystal alignment film according to claim 16. The method of claim 15,
It has a liquid crystal layer between a pair of substrates with electrodes, and a liquid crystal composition containing a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, and between the electrodes A liquid crystal alignment layer used in a liquid crystal display device manufactured through a process of polymerizing the polymerizable compound while applying a voltage. The method of claim 16,
It has a liquid crystal layer between a pair of substrates with electrodes, and a liquid crystal composition containing a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, and between the electrodes A liquid crystal alignment layer used in a liquid crystal display device manufactured through a process of polymerizing the polymerizable compound while applying a voltage. The method of claim 15,
A liquid crystal alignment layer comprising a liquid crystal layer formed between a pair of substrates with electrodes, and containing a polymerizable group that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, and between the electrodes A liquid crystal alignment layer used in a liquid crystal display device manufactured through a process of polymerizing the polymerizable group while applying a voltage to the polymerizable group. The method of claim 16,
A liquid crystal alignment layer comprising a liquid crystal layer formed between a pair of substrates with electrodes, and containing a polymerizable group that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, and between the electrodes A liquid crystal alignment layer used in a liquid crystal display device manufactured through a process of polymerizing the polymerizable group while applying a voltage to the polymerizable group. A liquid crystal display device comprising the liquid crystal alignment film according to claim 19. A liquid crystal display device comprising the liquid crystal alignment film according to claim 20. A liquid crystal display device comprising the liquid crystal alignment film according to claim 21. A liquid crystal display device comprising the liquid crystal alignment film according to claim 22. delete delete