TWI628232B - Liquid crystal alignment treatment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Abstract

The invention provides a liquid crystal alignment treatment agent and a liquid crystal alignment agent for forming a liquid crystal alignment film that can find a stable pretilt angle, suppress a decrease in voltage retention rate, and accelerate and alleviate the accumulated residual charge even after being exposed to high temperature and light irradiation for a long time. Film and liquid crystal display element.

This liquid crystal alignment treatment agent contains the following (A) component and (B) component.

(A) Component: Polymerization of at least one of polyimide precursor and polyimide containing a diamine component containing a diamine compound having a branched structure of formula [1] and reacting with a tetracarboxylic acid component Thing.

(B) Component: at least one of polyimide precursors and polyimide containing a diamine component that does not contain a diamine compound having a branched structure represented by formula [1], and a reaction with a tetracarboxylic acid component Polymer on one side.

(Y ¹ , Y ² , Y ³ are single bonds, alkylene groups, etc .; Y ⁴ , Y ⁵ are bivalent cyclic groups such as benzene rings; n is an integer from 0 to 4; Y ⁶ is a carbon number of 1 ~ 18 alkyl, etc.).

Description

Liquid crystal alignment treatment agent, liquid crystal alignment film and liquid crystal display element

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

Liquid crystal display elements are currently widely used to realize thin and lightweight displays. In order to determine the alignment state of liquid crystal in a general liquid crystal display element, a liquid crystal alignment film is used.

One of the characteristics required for a liquid crystal alignment film is that the alignment tilt angle of the liquid crystal molecules with respect to the substrate surface can be maintained at an arbitrary value, and the so-called pretilt angle of the liquid crystal can be controlled. It is known that the magnitude of the pretilt angle can be changed by selecting the structure of the polyimide used for the liquid crystal alignment film. Even if it is a technique for controlling the pretilt angle through the structure of polyimide, the method of using a branched diamine as a part of the raw material of the polyimide can also control the pretilt angle according to the proportion of the diamine used, so It is easier to obtain the intended pretilt angle, and it is suitable to increase the pretilt angle (for example, refer to Patent Document 1). In addition, regarding the diamine component for increasing the pretilt angle of liquid crystals, a structure for improving the stability and step dependence of the pretilt angle has been reviewed, and it has been proposed to use a cyclic structure such as phenyl and cyclohexyl as its branch chain. For structure (for example, refer to Patent Document 2).

In addition, with the high definition of liquid crystal display elements, it is of secondary importance to suppress the liquid crystal display elements from reducing the contrast and reducing the afterimage development. Even the liquid crystal alignment film used has a high voltage retention rate and reduces the application. The characteristics of accumulating electric charges at a DC voltage or accelerating and alleviating the electric charges accumulated by a DC voltage are becoming important.

Regarding polyimide-based liquid crystal alignment films, it is known to shorten the time required for the afterimage to disappear by a DC voltage. For example, in addition to polyimide or polyimide containing polyimide, In addition, a liquid crystal alignment treatment agent containing a tertiary amine with a specific structure (for example, refer to Patent Document 3), and a liquid crystal alignment treatment agent containing a soluble polyfluorene imide containing a specific diamine having a pyridine skeleton as a raw material. (For example, refer to Patent Document 4). In addition, it is known to increase the voltage holding ratio and shorten the time required for the afterimage to disappear after the DC voltage is applied. For example, in addition to polyamic acid and its imidized polymer, it contains a very small amount of A liquid crystal alignment treatment agent selected from a compound containing one carboxylic acid group in the molecule, a compound containing one carboxylic acid anhydride group in the molecule, and a compound containing one tertiary amine group in the molecule (for example, refer to a patent Reference 5).

Prior art literature Patent literature

Patent Document 1: Japanese Unexamined Patent Publication No. 2-282726

Patent Document 2: Japanese Unexamined Patent Publication No. 9-278724

Patent Document 3: Japanese Unexamined Patent Publication No. 9-316200

Patent Document 4: Japanese Unexamined Patent Publication No. 10-104633

Patent Document 5: Japanese Unexamined Patent Publication No. 8-76128

The liquid crystal alignment film is also used to control the angle of the liquid crystal relative to the substrate, that is, the pretilt angle of the liquid crystal. Especially VA (Vertical Alignment) mode or PSA (Polymer Sustained Alignment) mode, etc., need to align the liquid crystal vertically, so the liquid crystal alignment film is required to have the ability to align the liquid crystal vertically (also called vertical alignment or high pretilt angle). In addition to the high vertical alignment, the liquid crystal alignment film is also important relative to its stability. In particular, a liquid crystal display element, such as a car navigation system or a large television, which uses a backlight that increases the amount of heat to obtain high brightness and has a large amount of light exposure, is used or placed in an environment exposed to long periods of high temperature and light exposure. Under such severe conditions, vertical alignment is reduced, and there are problems such that initial display characteristics cannot be obtained, and speckles occur during display.

Further, regarding the voltage holding ratio, which is one of the electrical characteristics of the liquid crystal display element, high stability is also required under the severe conditions described above. That is, the voltage holding ratio is lowered by the light irradiation from the backlight, so that sintering failure (also referred to as wire sintering), which is one of the display failures of liquid crystal display elements, easily occurs, and a highly reliable liquid crystal display element cannot be obtained. Therefore, in addition to the good initial characteristics of the liquid crystal alignment film, it is also required that it is not easy to reduce the voltage holding ratio even after being exposed to long-term light irradiation. In addition, it is also required to accelerate and alleviate the residual charge accumulated by the DC voltage due to the light irradiation from the backlight with respect to the sintering of another poorly sintered surface.

Therefore, the object of the present invention is to provide a stable pretilt angle that can be found even after being exposed to long-term high temperature and light irradiation. In addition, even after being exposed to long-term light irradiation, the voltage retention rate can be suppressed from decreasing and accelerated. Liquid crystal alignment treatment agent for liquid crystal alignment film that alleviates residual charge accumulated by DC voltage.

Another object of the present invention is to provide a liquid crystal alignment film having the above-mentioned characteristics, and a liquid crystal display element provided with the liquid crystal alignment film.

After intensive research by the inventors, it was found that a liquid crystal alignment treatment agent having two polymers having a specific structure is extremely effective in achieving the above-mentioned object and completed the present invention.

That is, this invention has the following summary.

A liquid crystal alignment treatment agent comprising the following components (A) and (B), (A): a diamine component containing a diamine having a structure represented by the following formula [1], Polyimide precursors obtained by reacting with a tetracarboxylic acid component and at least one polymer selected from the group consisting of polyimide, component (B): which does not contain a compound represented by the following formula [1] A diamine component of a diamine having a structure, a polyimide precursor obtained by reacting with a tetracarboxylic acid component, and at least one polymer selected from the group consisting of polyimide,

(Y ¹ represents a single bond,-(CH ₂ ) _a- (a is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or OCO-; Y ² represents a single bond or ( CH ₂ ) _b- (b is an integer from 1 to 15); Y ³ represents a single bond,-(CH ₂ ) _c- (c is an integer from 1 to 15), -O-, -CH ₂ O-,- COO- or OCO-; Y ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring, and a heterocyclic ring, or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton. Any hydrogen atom on the base can be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and a fluorine-containing alkyl group having 1 to 3 carbon atoms. Alkoxy or fluorine atom substitution; Y ⁵ represents a bivalent cyclic group selected from benzene ring, cyclohexane ring and heterocyclic ring, and any hydrogen atom on these cyclic groups may be 1 to 3 carbon atoms Substituted by alkyl group, alkoxy group having 1 to 3 carbon atoms, fluorine-containing alkyl group having 1 to 3 carbon atoms, fluorine-containing alkoxy group having 1 to 3 carbon atoms or fluorine atom substitution; n represents an integer of 0 to 4 ; Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms).

2. The liquid crystal alignment treatment agent according to the above 1, wherein the diamine having the structure represented by the formula [1] is represented by the following formula [1a], and Y ¹ , Y ² , and Y in the formula (1a) ^{3, Y 4, Y 5,} n, Y ⁶ and m are the same as previously defined.

3. The liquid crystal alignment treatment agent according to 1 or 2 above, wherein The component (B) is a polyimide obtained by reacting a diamine component containing a diamine having a substituent selected from at least one of a carboxyl group (COOH group) and a hydroxyl group (OH group) with a tetracarboxylic acid component. A polymer of at least one selected from the group consisting of a precursor and a polyimide.

4. The liquid crystal alignment treatment agent according to the above 1, 2 or 3, wherein the component (A) is a diamine component and further contains one having at least one selected from a carboxyl group (COOH group) and a hydroxyl group (OH). Polymers of substituted diamines.

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

(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).

[Chem. 4]-(CH ₂ ) _d -COOH [2a-1]-(CH ₂ ) _e -OH [2a-2]

(d represents an integer from 0 to 4, and e represents an integer from 0 to 4.)

6. The liquid crystal alignment treatment agent according to any one of the above 1 to 5, wherein the polymer of the component (A) and the component (B) is a diamine component using a diamine represented by the following formula [3a] Polymer (B ¹ represents -O-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON (CH ₃ )-or N (CH ₃ ) CO-; B ² represents a single bond, an alkylene group 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 1 ~ 5 An integer); B ⁴ represents a nitrogen-containing heterocyclic ring; n1 represents an integer of 1 to 4; when n1 is 2 or more, -B ¹ -B ² -B ³ -B ⁴ may be the same or different).

7. The liquid crystal alignment treatment agent according to the above 6, wherein B ¹ in the formula [3a] is -O-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCO- or CON (CH ₃ )-.

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

9. The liquid crystal alignment treatment agent according to any one of 6 to 8, wherein B ³ in the formula [3a] is a single bond, -O-, -OCO-, or O (CH ₂ ) _2- ( m2 is an integer from 1 to 5).

10. The liquid crystal alignment treatment agent according to any one of 6 to 9, wherein B ⁴ in the formula [3a] is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, or a pyrimidine ring.

11. The liquid crystal alignment treatment agent according to the above 6, wherein B ¹ in the formula [3a] represents -CONH-, B ² represents an alkylene group having 1 to 5 carbon atoms, B ³ represents a single bond, and B ⁴ Represents an imidazole ring or a pyridine ring, and n1 is 1.

12. The liquid crystal alignment treatment agent according to any one of 1 to 11 above, wherein the tetracarboxylic acid component of at least one of the (A) component and (B) component is a component represented by the following formula [4] Tetracarboxylic dianhydride,

(Z ¹ is a base selected from the following formulas [4a] to [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).

13. The liquid crystal alignment treatment agent according to any one of 1 to 12 above, which contains a solvent of at least one of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butyrolactone.

14. The liquid crystal alignment treatment agent according to any one of 1 to 13 above, which contains at least one solvent selected from the following formulas [D-1] to [D-3],

(D ¹ represents an alkyl group having 1 to 3 carbon atoms, D ² represents an alkyl group having 1 to 3 carbon atoms, and D ³ represents an alkyl group having 1 to 4 carbon atoms).

15. The liquid crystal alignment treatment agent according to any one of 1 to 14 above, which contains 1-hexanol, cyclohexanol, 1,2-ethylene glycol, 1,2-propylene glycol, and propylene glycol monobutyl ether. A solvent of at least one selected from the group consisting of ethylene glycol monobutyl ether and dipropylene glycol dimethyl ether.

16. The liquid crystal alignment treatment agent according to any one of the above 1 to 15, wherein the liquid crystal alignment treatment agent contains a crosslinkable compound having an epoxy group, an isocyanate group, a propylene oxide group, or a cyclic carbonate group. A cross-linkable compound having at least one selected from the group consisting of a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group; and a cross-linkable compound having a polymerizable unsaturated bond At least one crosslinkable compound.

17. A liquid crystal alignment film obtained from the liquid crystal alignment treatment agent according to any one of 1 to 16 above.

18. A liquid crystal alignment film obtained by printing the liquid crystal alignment treatment agent according to any one of 1 to 16 by an inkjet printing method.

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

20. The liquid crystal alignment film according to 17 or 18 above, which is used A liquid crystal layer is provided between a pair of substrates provided with electrodes, and a liquid crystal composition containing a polymerizable compound polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, and a voltage is applied to the electrodes. A liquid crystal display device produced by the step of simultaneously polymerizing the polymerizable compound.

21. The liquid crystal alignment film according to the above 17 or 18, which is composed of a liquid crystal layer used between a pair of substrates provided with electrodes, and contains a polymerizable group which is polymerized by at least one of active energy rays and heat. The liquid crystal alignment film is a liquid crystal display device produced by a step of polymerizing the polymerizable group while applying a voltage between the pair of substrates while applying a voltage between the electrodes.

22. A liquid crystal display element comprising the liquid crystal alignment film according to 20 or 21 above.

The polymer having at least one selected from among polyfluorene imide precursors containing a specific structure and polyamimine according to the present invention, and from among polyfluorene imide precursors and polyfluorene containing no specific structure The liquid crystal alignment treatment agent for the two polymers of at least one polymer is a liquid crystal alignment film with a stable pretilt angle that can be found even after being exposed to high temperature and light irradiation for a long time. In addition, a liquid crystal alignment film capable of suppressing a decrease in the voltage holding rate even after being exposed to long-term light irradiation and accelerating and alleviating the residual charge accumulated by the DC voltage can be obtained. Therefore, a liquid crystal display device having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention has excellent reliability. It is suitable for large-screen and high-definition LCD TVs.

Embodiment of the invention

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

(A) Component: Polyfluorene imide obtained by reacting a diamine component containing a diamine compound having a branched structure (also referred to as a specific branched structure) represented by the above formula [1] with a tetracarboxylic acid component A polymer (also referred to as a specific polymer (A)) selected from at least one of a precursor and a polyimide.

(B) Component: a polyimide precursor and a polyimide obtained by reacting a diamine component that does not contain a diamine compound having a branched structure represented by the above formula [1] and reacting with a tetracarboxylic acid component A polymer selected from at least one of them (also referred to as a specific polymer (B)).

The liquid crystal alignment treatment agent of the present invention further contains the following (A) component and (B) component, and it is preferable that only the (A) component is a diamine compound having a specific branched structure.

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

(B) Component: A polymer containing at least one selected from the group consisting of a polyimide precursor and a polyimide obtained by a reaction between a diamine component and a tetracarboxylic acid component.

The specific polymer (A) of the present invention is represented by the formula [1] The specific branched chain structure shown is a branched site having at least one selected from a benzene ring, a cyclohexyl ring, and a heterocyclic ring, or a bivalent organic group having 17 to 51 carbon atoms having a steroid skeleton. The branched structures of these rings and organic groups are more rigid when compared to the branched structures of the long-chain alkyl groups of the prior art in which liquid crystals are vertically aligned. Therefore, a liquid crystal alignment film obtained from a liquid crystal alignment treatment agent having a specific branched structure can obtain a more stable vertical alignment of the liquid crystal when compared with a branched structure of a long chain alkyl group.

Moreover, when a specific branched structure is compared with the branched structure of the previous long-chain alkyl group, it is more stable with respect to light, such as an ultraviolet-ray. Therefore, even if the specific branched chain structure is exposed to long-term light irradiation, it is possible to suppress a decrease in the voltage holding ratio, and to suppress the decomposition of branched chain components that accumulate residual charges due to a DC voltage.

The liquid crystal alignment treatment agent of the present invention is a liquid crystal alignment treatment agent having a specific polymer (A) and a specific polymer (B), and the specific polymer (B) does not contain a specific branched structure. Therefore, the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention can reduce the content of the branched chain components that can increase the volume resistance of the liquid crystal alignment film, and suppress the residual charge accumulated by the direct current.

Therefore, the liquid crystal alignment treatment agent of the present invention can be obtained, and even after being exposed to high temperature and light irradiation for a long time, a stable liquid crystal alignment film with a pretilt angle can be found. In addition, even after being exposed to long-term light irradiation, it is possible to suppress the decrease in the voltage holding ratio and accelerate and reduce the residual charge accumulated by the DC voltage.

<Specific branch chain structure>

The specific polymer (A) of the present invention is At least one selected from the group consisting of a diamine component of a diamine compound having a specific branched chain structure represented by the following formula [1], and a polyimide precursor obtained by reacting with a tetracarboxylic acid component, and polyimide polymer.

(In the formula [1], the definitions of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n are the same as above).

In the formula [1], Y ¹ is preferably a single bond,-(CH ₂ ) _a- (a is an integer of 1 to 15), -O-, -CH from the viewpoint of availability of raw materials and ease of synthesis. ₂ O- or COO-. More preferably, it is a single bond,-(CH ₂ ) _a- (a is an integer of 1 to 10), -O-, -CH ₂ O-, or COO-. Y ^{2 is} preferably a single bond or (CH ₂ ) _b- (b is an integer from 1 to 10). From the viewpoint of ease of synthesis, Y ³ is preferably a single bond,-(CH ₂ ) _c- (c is an integer of 1 to 15), -O-, -CH ₂ O-, or COO-. More preferably, it is a single bond,-(CH ₂ ) _c- (c is an integer of 1 to 10), -O-, -CH ₂ O-, or COO-. From the viewpoint of ease of synthesis, Y ⁴ is preferably a benzene ring, a cyclohexane ring, or an organic group having 17 to 51 carbon atoms having a steroid skeleton. Y ^{5 is} preferably a benzene ring or a cyclohexane ring. From the viewpoint of availability of raw materials and ease of synthesis, n is preferably 0 to 3. More preferably, it is 0 to 2. Y ^{6 is} preferably an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 10 carbon atoms. More preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. Particularly preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.

In the formula [1], a preferred combination of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n is, for example, as shown in pages 13 to 34 of International Publication WO 2011/132751 (published on 2011.10.27). The same combinations as (2-1) to (2-629) disclosed in Tables 6 to 47 on the page. In the tables of the International Publication, Y ¹ to Y ⁶ of the present invention are represented by Y ¹ to Y ⁶ , and Y ¹ to Y ⁶ can be interpreted as Y ¹ to Y ⁶ . Further, in (2-605) to (2-629) disclosed in the tables of the International Publication, the organic group having 17 to 51 carbon atoms having a steroid skeleton of the present invention is represented as having 12 to 6 carbon atoms having a steroid skeleton. The organic group of 25, and the organic group of 12 to 25 carbons having a steroid skeleton can be interpreted as the organic group of 17 to 51 carbons having a steroid skeleton.

Among them, (2-25) ~ (2-96), (2-145) ~ (2-168), (2-217) ~ (2-240), (2-268) ~ (2-315) ), (2-364) ~ (2-387), (2-436) ~ (2-483), or (2-603) ~ (2-615). The best combination is (2-49) ~ (2-96), (2-145) ~ (2-168), (2-217) ~ (2-240), (2-603) ~ (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) include a polyimide precursor and a polyimide (also collectively referred to as a polyimide polymer) obtained by reacting a diamine component and a tetracarboxylic acid component. A polymer selected from at least one of the above).

The polyfluorene imide precursor refers to a structure represented by the following formula [A].

(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, which may be the same or different from each other, and A ³ and A ⁴ represent A hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an ethynyl group may be the same as or different from each other, and n2 represents a positive integer).

The diamine component is a diamine compound having two primary or secondary amine groups in the molecule, and a tetracarboxylic acid component such as a tetracarboxylic acid compound, a tetracarboxylic dianhydride, a tetracarboxylic dihalide compound, and a tetracarboxylic acid di An alkyl ester compound or a dialkyl tetracarboxylic acid dihalide compound.

The polyfluorene imide polymer of the present invention is preferably made from a tetracarboxylic dianhydride represented by the following formula [B] and a diamine compound represented by the following formula [C] as raw materials, and is preferable for reasons of simpler production. The polyamidic acid formed by the structural formula of the repeating unit represented by the following formula [D], or the polyamidoimide obtained by polyimidating this polyamidic acid. Among them, the specific polymer (A) and the specific polymer (B) are preferably polyimide from the viewpoint of the physical and chemical stability of the liquid crystal alignment film.

(R ¹ and R ² are the same as defined in formula [A]).

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

Further, in a general synthesis method, an alkyl group having 1 to 8 carbon atoms of A ¹ and A ² represented by the formula [A], and 1 to 5 carbon atoms of A ³ and A ⁴ represented by the formula [A] can be used. The alkyl group or acetamidine group is introduced into the polymer of the formula [D] obtained above.

The specific polymer (A) is a polyfluorene-imide-based polymer obtained by using a diamine component containing a diamine compound having a specific branched structure. In this case, the diamine compound having a specific branched structure is preferably a diamine compound (also referred to as a specific branched diamine compound) represented by the following formula [1a].

In the formula [1a], Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ^6, and n are each the same as the definition of the above formula [1], and their preferred definitions are also the same.

The preferred combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ^6, and n are also the same as those described in the above formula [1]. In addition, m is an integer of 1 to 4. It is preferably an integer of 1.

Specific examples are the structures represented by the following formulas [1a to 1] to [1a-31].

(R ¹ represents -O-, -OCH _2- , -CH ₂ O-, -COOCH ₂ -or CH ₂ OCO-, and R ² is a linear or branched alkyl group having 1 to 22 carbon atoms and carbon number. 1 to 22 linear or branched alkoxy groups, 1 to 22 carbon straight or branched chain fluorine-containing alkyl groups or fluorine-containing alkoxy groups).

(R ³ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH _2- , -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -or CH _2- , and R ⁴ is carbon Linear or branched alkyl group having 1 to 22 carbon atoms, linear or branched alkoxy group having 1 to 22 carbon atoms, linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms Or fluorine-containing alkoxy).

(R ⁵ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH _2- , -CH ₂ OCO-, -CH ₂ O-, -OCH _2- , -CH _2- , -O- Or NH-, and R ⁶ is fluoro, cyano, trifluoromethyl, nitro, azo, formamyl, ethenyl, ethenyloxy, or hydroxy).

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

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

(A ₄ is a linear or branched alkyl group having 3 to 20 carbon atoms which may be substituted by a fluorine atom, A ₃ is 1,4-cyclohexyl or 1,4-phenylene, and A ₂ is an oxygen atom Or COO- ＊ (again, the bond system with "*" is bonded to A ₃ ), A ₁ is an oxygen atom or COO- ＊ (again, the bond system with "*" is connected to (CH ₂ ) a ₂ bond). Also, 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.).

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

The specific branched diamine compound of the specific polymer (A) is preferably 10 mol% or more and 80 mol% or less of the entire diamine component. Particularly preferred is 10 mol% to 70 mol%.

The specific branched diamine compound can respond to the solubility of the specific polymer (A) with respect to the solvent, the coating property of the liquid crystal alignment treatment agent, the alignment property of the liquid crystal when used as a liquid crystal alignment film, the voltage holding ratio, and the accumulated charge, etc. Characteristics, use one or two or more mixed.

When the specific polymer (A) and the specific polymer (B) are produced, the diamine component is preferably used together with a specific branched diamine compound and another diamine compound (also referred to as a specific second diamine compound). .

Among them, the carboxyl group (COOH group) and hydroxyl group are used. A diamine compound of at least one selected from the group (OH group).

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

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

In the formula [2a], m1 represents an integer of 1 to 4. Among them, 1 is preferred.

[Chem. 26]-(CH ₂ ) _d -COOH [2a-1]-(CH ₂ ) _e -OH [2a-2]

In the formula [2a-1], d represents an integer of 0 to 4. Among them, 0 or 1 is preferred.

In the formula [2a-2], e represents an integer of 0 to 4. Among them, 0 or 1 is preferred.

More specifically, for example, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diamino group Resorcinol, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, or 3,5-diaminobenzoic acid. Among them, 2,4-diaminobenzoic acid and 2,5-diaminobenzoic acid are preferred. Acid or 3,5-diaminobenzoic acid.

The specific second diamine compound may be a diamine compound represented by the following formulas [2b-1] to [2b-4].

(A ¹ represents 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-, 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 represent 1 to 5 Integer, in the 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, and in the formula [2b-4], A ³ represents a single bond Junction, -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-, m ⁶ represents an integer of 1 to 4).

Specific second diamine compounds can be used for specific polymers (A) or The diamine component of any of the polyfluorene-imide-based polymers of the specific polymer (B) may be a diamine component of a specific polymer that can be used for both the specific polymer (A) and the specific polymer (B). Among these, it is preferable to use only the diamine component of a specific polymer (A), or to use only the diamine component of a specific polymer (B).

The specific second diamine compound is preferably 10 mol% or more of the entire diamine component. Among them, more than 20 mol% is preferred, and particularly preferred is more than 30 mol%.

The specific second diamine compound can respond to the solubility of the specific polymer (A) and the specific polymer (B) with respect to the solvent, the coating property of the liquid crystal alignment treatment agent, the alignment property of the liquid crystal when used as a liquid crystal alignment film, The voltage holding ratio and the stored charge can be used singly or in combination of two or more kinds.

The diamine component of the specific polymer (A) and the specific polymer (B) of the present invention is preferably a combination of a specific branched diamine compound and a specific second diamine compound, and the following formula [3a] Represents a diamine compound (also referred to as a specific third diamine compound).

In Formula [3a], B ¹ represents -O-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON (CH ₃ )- Or N (CH ₃ ) CO-. Among these, it is preferable to easily synthesize a diamine compound -O-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON (CH ₃ )-or N (CH ₃ ) CO -. Particularly preferred is -O -, - NH -, - CONH -, - NHCO -, - CH 2 O -, - OCO- or CON (CH ₃₎ -. More preferably -O -, - CONH-, or CH ₂ O-.

In the 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 alkylene group having 1 to 20 carbon atoms may be linear or branched. Moreover, it may have an unsaturated bond. Particularly preferred is an alkylene group having 1 to 10 carbon atoms.

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, and a ring eleven Alkanes, cyclododecanes, cyclotridecanes, cyclotetradecanes, cyclopentadecans, cyclohexadecanes, cycloheptadecans, cyclooctadecanes, cyclononadecanes , Cycloeicosane ring, tricyclic eicosane ring, tricyclic, dicycloheptane ring, decalin ring, norbornene ring or adamantane ring, etc. Among them, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring or an adamantane ring are preferred.

Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, a fluorene ring, an indene ring, a fluorene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among them, a benzene ring, a naphthalene ring, a tetralin ring, a fluorene ring, or an anthracene ring is preferred.

B ² in formula [3a] is preferably 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, or norbornyl. Ethene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, fluorene ring or anthracene ring. Among them, a single bond, an alkylene group having 1 to 5 carbon atoms, a cyclohexane ring or a benzene ring is preferred.

In formula [3a], B ³ represents 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 from 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 preferred, and a single bond, -O-, -OCO is particularly preferred -Or O (CH ₂ ) _m2- (m2 is an integer from 1 to 5).

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

(In the formula [c], Z represents an alkyl group having 1 to 5 carbon atoms).

More specifically, for example, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiazole Azole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazidine ring, triazole ring, pyrazine ring, benzimidazole ring (benzoimidazole ring), perylene ring, phenanthroline ring, Indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring or acridine ring and the like. 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, and a benzimidazole ring (benzoimidazole ring) are preferred, and particularly preferred It is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring or a pyrimidine ring.

In addition, in formula [3a], B ^{3 is} preferably bonded to a substituent which is not adjacent to formula [a], formula [b], and formula [c] contained in B ⁴ .

The preferred combinations of B ¹ , B ² , B ³ and B ⁴ in formula [3a] are shown in Tables 1 to 31 below. In addition, in Tables 1 to 31, X ¹ , X ² , X ³ and X ⁴ can be interpreted as B ¹ , B ² , B ³ and B ^{4 respectively} .

In the formula [3a], n1 is an integer of 1 to 4, and from the viewpoint of reactivity with a tetracarboxylic acid component, 1 or 2 is preferable.

The particularly preferred combination of B ¹ , B ² , B ³ , B ⁴ and n1 in formula [3a] is: B ¹ represents -CONH-, B ² represents an alkyl group having 1 to 5 carbon atoms, and B ³ represents a single bond , B ⁴ represents an imidazole ring or a pyridine ring, and n1 represents a diamine compound of 1.

The bonding position of the two amine groups (-NH ₂ ) in the formula [3a] is not limited. Specifically, for example, the position of 2,3 on the benzene ring with respect to the branched bonding group (B ¹ ), the position of 2,4, the position of 2,5, the position of 2,6, the position of 3,4 or 3 , The position of 5. Among them, from the viewpoint of reactivity when synthesizing polyamic acid, the positions of 2, 4 and 2, 5 or 3 and 5 are preferred. In addition, the ease of synthesizing the diamine compound is more preferably a position of 2,4 or a position of 2,5.

The specific third diamine compound can be used in the diamine component of the polyimide-based polymer of either the specific polymer (A) or the specific polymer (B), and can also be used in the specific polymer (A). And specific aggregations (B) in the diamine component of the specific polymer on both sides. When the diamine component of the specific polymer (A) is a specific second diamine compound, the specific third diamine compound is preferably used for the diamine component of the specific polymer (B). When the diamine component of the specific polymer (B) is a specific second diamine compound, the specific third diamine compound is preferably a diamine component used in the specific polymer (A). That is, it is preferable that the specific second diamine compound and the specific third diamine compound are each used for a diamine component with respect to each specific polymer.

The specific third diamine compound is preferably 5 mol% or more of the entire diamine component. Among them, more than 10 mol% is preferred, and particularly preferred is more than 15 mol%.

The specific third diamine compound can respond to the solubility of the specific polymer (A) and the specific polymer (B) with respect to the solvent, the coating property of the liquid crystal alignment treatment agent, the alignment property of the liquid crystal when used as a liquid crystal alignment film, The characteristics of the voltage holding rate and the stored charge can be used singly or in combination of two or more kinds.

As long as the diamine component of the specific polymer (A) and the specific polymer (B) does not impair the effect of the present invention, a specific branched diamine compound, a specific second diamine compound, and a specific third Diamine compounds, and other diamine compounds (also known as other diamine compounds).

Specific examples of other diamine compounds include 2,4-dimethyl-m-phenylene diamine, 2,6-diamino toluene, m-phenylene diamine, p-phenylene diamine, 4, 4'-diaminobiphenyl, 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'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4 ' -Diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminobiphenyl Methane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diamine Diphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-di Amino diphenyl ether, 2,3'-diamino diphenyl ether, 4,4'-sulfohydrazine diphenylamine, 3,3'-sulfohydrazine diphenylamine, bis (4-aminophenyl) silane , Bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4,4'-thiodiphenylamine , 3,3'-thiodiphenylamine, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2 2,2'-diaminodiphenylamine, 2,3'-diaminodiamine Amino, 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'-Diaminobenzophenone, 1,4-Diaminonaphthalene, 2,2 ' -Diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1 , 8-Diaminonaphthalene, 2,5-Diaminonaphthalene, 2,6-Diaminonaphthalene, 2,7-Diaminonaphthalene, 2,8-Diaminonaphthalene, 1,2-bis ( 4-aminophenyl) ethane, 1,2-bis (3-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,3-bis (3-amine Phenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4-bis (3-aminophenyl) butane, Bis (3,5-diethyl-4-aminophenyl) methane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene , 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, 1,3- Bis (4-aminophenoxy) benzene, 4,4 '-[1,4-phenylenebis (methylene)] diphenylamine, 4,4'-[1,3-phenylenebis ( Methylene)] diphenylamine, 3,4 '-[1,4-phenylene bis (methylene)] diphenylamine, 3,4'-[1,3-phenylene bis (methylene) ] Diphenylamine, 3,3 '-[1,4-phenylenebis (methylene)] diphenylamine, 3,3'-[1,3-phenylenebis (methylene)] diphenylamine, 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis [(3-aminophenyl) methanone], 1,3-phenylenebis [(4-aminophenyl) methanone], 1,3-phenylphenylbis [(3-aminophenyl) methanone], 1,4-phenylphenylbis (4-aminobenzoic acid) Esters), 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) Group) isophthalate, bis (3-aminophenyl) m-xylylene Acid ester, N, N '-(1,4-phenylene) bis (4-aminophenylhydrazine), N, N'-(1,3-phenylene) bis (4-aminophenylhydrazone) Amine), N, N '-(1,4-phenylene) bis (3-aminophenylhydrazone), N, N'-(1,3-phenylene) bis (3-aminophenylhydrazone) Amine), N, N'-bis (4-aminophenyl) p-xylylenediamine, N, N'-bis (3-aminophenyl) p-xylylenediamine, N, N'- Bis (4-aminophenyl) m-xylylenediamine, N, N'-bis (3-aminophenyl) m-xylylenediamine, 9,10-bis (4-aminophenyl) Anthracene, 4,4'-bis (4-aminophenoxy) diphenylphosphonium, 2,2'-bis [4- (4-aminophenoxy) phenyl] propane, 2,2'- Bis [4- (4-aminophenoxy) phenyl] hexafluoro Propane, 2,2'-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2'-bis (3-amino- 4-methylphenyl) hexafluoropropane, 2,2'-bis (4-aminophenyl) propane, 2,2'-bis (3-aminophenyl) propane, 2,2'-bis ( 3-amino-4-methylphenyl) propane, 1,3-bis (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1,4- Bis (4-aminophenoxy) butane, 1,4-bis (3-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,5 -Bis (3-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) undec Alkane, 1,11-bis (3-aminophenoxy) undecane, 1,12-bis (4-aminophenoxy) dodecane, 1,12-bis (3-aminophenoxy) ) Dodecane, bis (4-aminocyclohexyl) methyl , 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.

As the other diamine compounds, diamine compounds represented by the following formulas [D1] to [DA25] can be used.

(A ¹ represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group).

(A ¹ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH _2- , -O-, -CO- or NH-, and A ² represents a linear or branched carbon having 1 to 22 carbon atoms. Chain alkyl or linear or branched fluorine-containing alkyl having 1 to 22 carbon atoms).

(p represents an integer from 1 to 10).

(m represents an integer from 0 to 3, and n represents an integer from 1 to 5.)

Other diamine compounds can be used in the diamine component of the polyfluorene-imide polymer of either the specific polymer (A) or the specific polymer (B), and can also be used in the specific polymer (A) and the specific polymerization. (B) in the diamine component of the specific polymer on both sides.

In addition, other diamine compounds may respond to the solubility of the specific polymer (A) and the specific polymer (B) in a solvent, the coating property of a liquid crystal alignment treatment agent, the alignment property of a liquid crystal when used as a liquid crystal alignment film, and a voltage. Retention rate, accumulated charge, and other characteristics are used in combination of one kind or two or more kinds.

It is preferable to use the tetracarboxylic dianhydride represented by the following formula [4] to prepare the specific polymer (A) and the specific polymer (B), that is, the tetracarboxylic acid component for the polyfluorene-based polymer. (Specific tetracarboxylic dianhydride). In this case, in addition to the specific tetracarboxylic dianhydride represented by the formula [4], a tetracarboxylic acid, a tetracarboxylic dihalide compound, a tetracarboxylic dialkyl ester compound, or a tetracarboxylic acid of the tetracarboxylic acid derivative may be used. Dialkyl ester dihalide.

(Z ^{1 is a base selected} from the following formulas [4a] to [4k]).

In the formula [4a], Z ² to Z ⁵ represent a hydrogen atom, a methyl group, a chlorine atom, or a benzene ring, and may 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.

Z ¹ in the formula [4] is preferably a formula [4a], a formula [4c], a formula [4d], a formula [4e], from the viewpoints of ease of synthesis and ease of polymerization reactivity when manufacturing a polymer. A tetracarboxylic dianhydride having a structure represented by Formula [4f], Formula [4g], or Formula [4k] and a tetracarboxylic acid derivative thereof. More preferably, it is a structure represented by Formula [4a], [4e], [4f], [4g], or [4k], and particularly preferably [4e], [4f], or [4g]. Or something of formula [4k].

The polyfluorene-imide polymer of the present invention may use other tetracarboxylic acid components other than the specific tetracarboxylic dianhydride, as long as the effect of the present invention is not impaired.

Other tetracarboxylic acid components include the following tetracarboxylic acid compounds, tetracarboxylic dianhydrides, tetracarboxylic dihalide compounds, tetracarboxylic acid dialkyl ester compounds, or tetracarboxylic acid dialkyl ester dihalogen compounds.

That is, other tetracarboxylic acid components such as pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid Carboxylic acid, 2,3,6,7-anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3 ', 4'-Biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3', 4,4'-benzophenone tetracarboxylic acid, bis (3,4-dicarboxyl Phenyl) fluorene, 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-dicarboxybenzene ) Pyridine, 3,3 ', 4,4'-diphenylfluorenetetracarboxylic acid, 3,4,9,10-fluorenetetracarboxylic acid or 1,3-diphenyl-1,2,3,4 -Cyclobutane tetracarboxylic acid.

The tetracarboxylic acid component of the specific polymer (A) and the specific polymer (B) is preferably such that the specific tetracarboxylic dianhydride of each specific polymer is 10 mol% or more of the tetracarboxylic acid component. Among them, more than 20 mol% is preferred, and particularly preferred is more than 30 mol%. The tetracarboxylic acid components may all be specific tetracarboxylic dianhydrides.

The specific tetracarboxylic dianhydride and other tetracarboxylic acid components can be used in accordance with the solubility of the specific polymer (A) and the specific polymer (B) in a solvent, the coating property of a liquid crystal alignment treatment agent, and the liquid crystal alignment film. Liquid crystals have characteristics such as alignment, voltage retention, and accumulated charge, and are used by mixing one or two or more kinds.

<Production method of specific polymer (A) and specific polymer (B)>

The specific polymer (A) of the present invention is a polyimide precursor obtained by reacting a diamine component containing a diamine compound having a specific branched structure represented by the aforementioned formula [1] with a tetracarboxylic acid component, and A polymer of at least one selected from the group consisting of polyimide. In this case, the diamine compound having a specific branched structure is preferably a specific branched diamine compound represented by the formula [1a].

In the specific polymer (A), a specific branched diamine compound may be used in combination with a diamine compound having at least one selected from a carboxyl group and a hydroxyl group, and / or a specific compound represented by the formula [3a]. Third diamine compound. In this case, it has at least one selected from a carboxyl group and a hydroxyl group. The diamine compound is preferably a specific second diamine compound represented by the aforementioned formula [2a].

When the specific second diamine compound is used in combination, the specific branched diamine compound is preferably 100-80 mol% with respect to 100 mol% of the total diamine component, and the specific second diamine compound is 10 ~ 90 mol%. More preferably, the specific branched diamine compound is 10 to 80 mol%, and the specific second diamine compound is 20 to 70 mol%.

When using a specific tertiary diamine compound in combination, the specific branched diamine compound is preferably 10 to 80 mol% relative to 100 mol% of the total diamine component, and the specific tertiary diamine compound is 10 ~ 90 mol%. More preferably, the specific branched diamine compound is 10 to 80 mol%, and the specific third diamine compound is 20 to 70 mol%.

When the specific second diamine compound and the specific third diamine compound are used in combination, the specific branched chain diamine compound is preferably 10 to 80 mol% relative to 100 mol% of the total diamine component. The specific second diamine compound is 10 to 80 mole%, and the specific third diamine compound is 10 to 80 mole%. More preferably, the specific branched 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 the present invention, the specific polymer (A) is preferably a combination of a specific third diamine compound.

The specific polymer (B) of the present invention is a polyimide precursor and polyimide obtained by reacting a diamine component that does not contain a diamine compound having a specific branched structure with a diamine component and reacting with a tetracarboxylic acid component. A polymer of at least one selected from the group. In this case, the specific polymer (B) is preferably, A diamine compound having at least one selected from a carboxyl group and a hydroxyl group is used. More preferably, it is a specific second diamine compound represented by the said Formula [2a].

The use ratio of the specific second diamine compound is, for example, as described above, preferably 100 mol% or more with respect to 100 mol% of the entire diamine component. More preferably, it is 20 mol% or more, and particularly preferable is 30 mol% or more.

The specific polymer (B) may be used in combination with a specific second diamine compound and a specific third diamine compound. In this case, it is preferable that the specific second diamine compound is 10 to 80 mol%, and the specific third diamine compound is 10 to 80 mol% relative to 100 mol% of the entire diamine component. More preferably, the specific second diamine compound is 20 to 70 mole%, and the specific third diamine compound is 20 to 70 mole%.

The method for producing the specific polymer (A) and the specific polymer (B) in the present invention, that is, the polyfluorene-based polymer is not particularly limited. Generally, it is obtained by reacting a diamine component and a tetracarboxylic acid component. Generally, for example, reacting at least one tetracarboxylic acid component selected from the group consisting of a tetracarboxylic dianhydride and a derivative of the tetracarboxylic acid with a diamine component formed from one or more kinds of diamine compounds, Method for obtaining polyamic acid. Specifically, the method can be obtained by polycondensing a tetracarboxylic dianhydride with a primary or secondary diamine compound to obtain polyamidonic acid, or by dehydrating polycondensation reaction between a tetracarboxylic acid and a primary or secondary diamine compound. A method of polyamidic acid or a method of obtaining a polyamidic acid by reacting a tetracarboxylic dihalide with a primary or secondary diamine compound.

It can be used in the production of polyalkylamino alkyl esters. Polytetracarboxylic acid obtained by esterifying a carboxylic acid group with a dialkyl group is polycondensed with a primary or secondary diamine compound. A method of reacting, a method of reacting a tetracarboxylic dihalide obtained by esterifying a carboxylic acid group with a dialkyl group and a primary or secondary diamine compound, or a method of converting a carboxyl group of a polyamic acid into an ester.

In the production of polyimide, a method of obtaining a polyimide by ring-closing the polyamic acid or a polyalkylamic acid alkyl ester can be used.

The reaction of the diamine component and the tetracarboxylic acid component is generally performed by reacting the diamine component and the tetracarboxylic acid component in an organic solvent. The organic solvent used in this case is not particularly limited as long as it can dissolve the produced polyimide precursor. Specific examples of the organic solvent used for the reaction will be given below, but the invention is not limited to these examples.

For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylformamide Alkylidene or 1,3-dimethyl-imidazolinone.

When the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formula [ D-1] to a solvent represented by the formula [D-3].

(D ¹ represents an alkyl group having 1 to 3 carbon atoms, D ² represents an alkyl group having 1 to 3 carbon atoms, and D ³ represents an alkyl group having 1 to 4 carbon atoms).

These can be used alone or in combination. In addition, even if the solvent of the polyimide precursor cannot be dissolved, the generated polyimide is not precipitated. Within the scope of the precursor, it can be used in combination with the above solvents. In addition, the water in the organic solvent hinders the polymerization reaction and causes the produced polyimide precursor to be hydrolyzed. Therefore, it is preferable to use a dehydrated organic solvent as the organic solvent.

A method for reacting a diamine component with a tetracarboxylic acid component in an organic solvent is, for example, a method in which the diamine component is dispersed or dissolved in an organic solvent while stirring, and the tetracarboxylic acid component is directly dispersed or dissolved in an organic solvent and added, Alternatively, a method in which a diamine component is added to a solution obtained by dispersing or dissolving a tetracarboxylic acid component in an organic solvent or a method in which a diamine component and a tetracarboxylic acid component are alternately added may be used. In addition, when a plurality of diamine components and a tetracarboxylic acid component are each reacted, the reaction may be performed in a state of being mixed in advance, the reactions may be sequentially performed in each case, or the low molecular weight substances obtained by the respective reactions may be mixed to obtain a polymer. The polymerization temperature at this time can be selected from any temperature of -20 ° C to 150 ° C, but is preferably in the range of -5 ° C to 100 ° C. In addition, the reaction can be performed at any concentration, but when the concentration is too low, it is difficult to obtain a polymer with a high molecular weight, and when the concentration is too high, the viscosity of the reaction solution is excessively increased, and it is difficult to uniformly stir. Therefore, it is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass. The reaction can be performed at a high concentration in the initial stage, and an organic solvent is added thereafter.

In the polymerization reaction of the polyimide precursor, the total molar number of the diamine component and the total molar number of the tetracarboxylic acid component is preferably 0.8 to 1.2. Like the general polycondensation reaction, when the molar ratio is approximately 1.0, the molecular weight of the resulting polyfluorene imine precursor can be increased.

The polyimide of the present invention is a polyimide obtained by ring closure of the aforementioned polyimide precursor, and the ring closure ratio of the amino acid group in the polyimide (also It is called imidization ratio, but it is not required to be 100%, and it can be adjusted arbitrarily according to use or purpose. Among them, in the present invention, from the viewpoint of suppressing a decrease in the voltage retention rate after exposure to long-term light irradiation, the specific polymer (A) is preferably 30 to 100%, and the specific polymer (B) is 30 to 100%. More preferably, the specific polymer (A) is 40 to 90%, and the specific polymer (B) is 40 to 90%. Particularly preferred is that the specific polymer (A) is 50 to 85%, and the specific polymer (B) is 50 to 85%.

The method for making the polyfluorene imide precursor be fluorinated, for example, directly heating the solution of the polyfluorene imide precursor by thermal hydration, or adding a catalyst to the catalyst of the polyfluorene imide precursor solution Imidization.

The temperature at which the polyimide precursor is thermally imidized in the solution is 100 ° C to 400 ° C, preferably 120 ° C to 250 ° C, and the water generated by the imidization reaction is excluded from the system. good.

The catalyst of polyimide precursor can be imidized by adding basic catalyst and acid anhydride to the solution of polyimide precursor, and stirring at -20 ~ 250 ℃, preferably 0 ~ 180 ℃ get on. The amount of the alkaline catalyst is 0.5 to 30 mol times of the amino acid group, preferably 2 to 20 mol times, and the amount of the acid anhydride is 1 to 50 mol times of the amino acid group, preferably 3 to 30 mol times. 30 mol times. Basic catalysts, such as pyridine, triethylamine, trimethylamine, tributylamine, or trioctylamine, etc., among which pyridine is preferred to have moderate alkalinity during the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, acetic anhydride is preferably used for purification after the reaction is completed. The rate of ammonium imidization through catalyst imidization can be controlled by adjusting the amount of catalyst, reaction temperature and reaction time.

When the polyfluorene imide precursor or polyfluorene imine is recovered from the polyfluorene imide precursor or the polyfluorene imide reaction solution, the reaction solution can be put into a solvent to precipitate. The solvent used for the precipitation is, for example, methanol, ethanol, isopropanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water, and the like. After the polymer precipitated by adding the solvent is filtered and recovered, the polymer can be dried at normal temperature or under reduced pressure. In addition, repeating the operation of re-dissolving the polymer recovered by precipitation 2 to 10 times in an organic solvent and re-precipitating and recovering can reduce impurities in the polymer. At this time, solvents such as alcohols, ketones, or hydrocarbons are used. When three or more solvents selected from these are used, the purification efficiency can be further improved.

In consideration of the molecular weight of the polyfluorene imide polymer of the present invention, the weight average molecular weight measured by GPC (Gel Permeation Chromatography) method is preferred when considering the strength of the obtained liquid crystal alignment film, the workability during the formation of the liquid crystal alignment film, and the coating properties. It is 5,000 to 1,000,000, and more preferably 10,000 to 150,000.

<Liquid crystal alignment treatment agent>

The liquid crystal alignment treatment agent of the present invention is a coating solution for forming a liquid crystal alignment film (also referred to as a resin film), and a coating for forming a liquid crystal alignment film containing a specific polymer (A), a specific polymer (B), and a solvent. Cloth solution.

The ratio of the specific polymer (A) and the specific polymer (B) in the liquid crystal alignment treatment agent is preferably 10 to 900 parts by mass with respect to 100 parts by mass of the particular polymer (B). More preferably, the specific polymer (B) is 20 to 800 parts by mass, particularly preferably, the specific polymer (B) is 30 ~ 700 parts by mass.

All the polymer components in the liquid crystal alignment treatment agent of the present invention may be all the specific polymer (A) and the specific polymer (B) of the present invention, and other polymers may be mixed. At this time, the content of the other polymer is 0.5 to 15 parts by mass, and preferably 1 to 10 parts by mass based on 100 parts by mass of the specific polymer (A) and the specific polymer (B) in total. The other polymers include, for example, a cellulose polymer, an acrylic polymer, a methacrylic polymer, polyfluorene, polyamine, or silicone.

The solvent in the liquid crystal alignment treatment agent of the present invention is from the viewpoint of forming a uniform liquid crystal alignment film by coating, and the content of the solvent in the liquid crystal alignment treatment agent is preferably 70 to 99.9% by mass. The content can be appropriately changed according to the film thickness of the liquid crystal alignment film according to the purpose.

The solvent used for the liquid crystal alignment treatment agent of the present invention may be a solvent (also referred to as a good solvent) capable of dissolving the specific polymer (A) and the specific polymer (B), and is not particularly limited. Specific examples of good solvents are given below, but are not limited to these examples.

For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylmethylene, γ- Butyrolactone, 1,3-dimethyl-imidazolinone, methyl ethyl ketone, cyclohexanone, cycloheptanone, 4-hydroxy-4-methyl-2-heptanone, and the like.

Among these, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butyrolactone are preferably used.

When the solubility of the specific polymer (A) and the specific polymer (B) with respect to a solvent is high, it is preferable to use the above formulas [D-1] to [D-3] The solvent shown.

The good solvent in the liquid crystal alignment treatment agent of the present invention is preferably 10 to 100% by mass of the entire solvent contained in the liquid crystal alignment treatment agent. Among them, 20 to 90% by mass is preferable, and 30 to 80% by mass is more preferable.

As long as the liquid crystal alignment treatment agent of the present invention does not impair the effect of the present invention, a solvent (also referred to as a weak solvent) for improving the coating property and surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied can be used. Specific examples of weak solvents are given below, but are not limited to these examples.

For example, ethanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol Alcohol, isoamyl alcohol, tert-pentanol, 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-methylcyclohexanol, 3-methylcyclohexanol, 1,2-ethylene glycol, 1,2-propylene glycol, 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-ethylhexylethyl Acid ester, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, butyl carbonate, 2- (methoxymethoxy) Based) ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisopentyl 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, diethylene glycol monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethylene glycol Acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, acetic acid Propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3- Ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid , Butyl 3-methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate or the aforementioned formulas [D-1] ~ [D-3] The solvent and the like.

Among these, 1-hexanol, cyclohexanol, 1,2-ethylene glycol, 1,2-propylene glycol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, and diethylene glycol dimethyl ether are preferably used. Or the solvent represented by said formula [D-1]-formula [D-3].

These weak solvents are preferably 1 to 70% by mass of the entire solvent contained in the liquid crystal alignment treatment agent. Among them, 1 to 60% by mass is more preferable, and 5 to 60% by mass is more preferable.

The liquid crystal alignment treatment agent of the present invention is preferably one having Cross-linking compound of epoxy group, isocyanate group, propylene oxide group or cyclic carbonate group, cross-linking having at least one selected from the group consisting of hydroxyl group, hydroxyalkyl group and lower alkoxyalkyl group Crosslinkable compounds, or crosslinkable compounds with polymerizable unsaturated bonds. These substituents or polymerizable unsaturated bonds need to be two or more in the crosslinkable compound.

Crosslinkable compounds having epoxy or isocyanate groups such as bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl trimeric isocyanate, tetraglycidylamine group Diphenylene ester, tetraglycidyl-m-xylylenediamine, tetraglycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenylglycidyl ether ethane, triphenylglycidyl Glyceryl ether ethane, bisphenol hexafluoroacetamidine diglycidyl ether, 1,3-bis (1- (2,3-glycidoxy) -1-trifluoromethyl-2,2,2-tris Fluoromethyl) benzene, 4,4-bis (2,3-glycidoxy) octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl-m-xylylenediamine, 2- (4- (2,3-glycidoxy) phenyl) -2- (4- (1,1-bis (4- (2,3-glycidoxy) phenyl) ethyl) benzene Yl) propane or 1,3-bis (4- (1- (4- (2,3-glycidoxy) phenyl) -1- (4- (1- (4- (2,3-cyclo Oxypropoxy) phenyl) -1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol and the like.

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

Specifically, for example, the crosslinkable compounds represented by formulas [4a] to [4k] disclosed in items 58 to 59 of International Publication WO2011 / 132751 (published on 2011.10.27).

The crosslinkable compound having a cyclic carbonate group is a crosslinkable compound having at least two cyclic carbonate groups represented by the following formula [5A].

Specifically, for example, the cross-linkable compounds represented by the formulas [5-1] to [5-42] disclosed in items 76 to 82 of International Publication WO2012 / 014898 (published on 2012.2.2).

A crosslinkable compound having at least one selected from the group consisting of a hydroxyl group and an alkoxy group, such as an amine-based resin having at least one selected from the group consisting of a hydroxyl group and an alkoxy group, such as a melamine resin. , Urea resin, guanoamine resin, glycoluril-formaldehyde resin, succinylpyramine-formaldehyde resin, or ethyl urea-formaldehyde resin, etc. Specifically, a melamine derivative, a benzoguanamine derivative, or a glycoluril may be used in which the hydrogen atom of the amine group is substituted with methylol or alkoxymethyl or both. The melamine derivative or benzoguanamine derivative may exist as a dimer or a trimer. These are preferably 3 to 6 on average per triazine ring Of methylol or alkoxymethyl.

Such melamine derivatives or benzoguanamine derivatives, for example, MX-750 substituted with an average of 3.7 methoxymethyl groups per triazine ring on the market, and an average of 5.8 per triazine ring Methoxymethyl substituted MW-30 (above manufactured by Sanwa Chemical Co., Ltd.), or methoxymethyl 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc. Methoxymethylated butylated methylated melamine, semyl 235, 236, 238, 212, 253, 254, etc. melamine, butoxymethylated melamine 506, 508, etc. Melamine, methionized isobutoxy methylated melamine containing carboxyl like 1141, melamine, methoxymethylated ethoxymethylated benzoguanamine like melamine, 1123 like semyl, semyl 1123-10 methoxymethylated butoxymethylated benzoguanamine, semyl 1128 butoxymethylated benzoguanamine, semyl 1125-80 containing carboxyl groups Methoxymethylated ethoxymethylated benzoguanamine (the above is made by Mitsui Saina). Examples of glycoluril include butoxymethylated glycoluril, such as 1170, and methylolated glycoluril, such as 1170, and methoxymethylolated glycoluril, like 1174.

Benzene or phenolic compounds having a hydroxyl or alkoxy group such as 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, for example, the crosslinkable compounds represented by the formulas [6-1] to [6-48] disclosed on pages 62 to 66 of International Publication WO2011 / 132751 (published on 2011.10.27).

Crosslinkable compounds having polymerizable unsaturated bonds such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri (methyl) ) Cross-linking compounds having 3 polymerizable unsaturated groups in the molecule such as propylene ethoxyethoxytrimethylolpropane or glycerol polyglycidyl ether poly (meth) acrylate, for example, 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, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylic acid Ester, propylene oxide bisphenol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol di (meth) acrylate, ethyl Diethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl bis ( Cross-linking compound having two polymerizable unsaturated groups in the molecule such as acrylate) or hydroxytrimethylacetic acid neopentyl glycol di (meth) acrylate, or 2-hydroxyethyl (meth) acrylic acid Ester, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (methyl) Acrylic acid 2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, 2- (meth) acrylic acid A crosslinkable compound having one polymerizable unsaturated group in the molecule such as phosphoric acid phosphate ester or N-hydroxymethyl (meth) acrylamide.

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

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

The said compound is an example of a crosslinkable compound, It is not limited to these. The crosslinkable compound used in the liquid crystal alignment treatment agent of the present invention may be one type or a combination of two or more types.

In the liquid crystal alignment treatment agent of the present invention, the content of the crosslinkable compound is preferably 0.1 to 150 parts by mass relative to 100 parts by mass of the entire polymer component. In order to perform the crosslinking reaction to find the desired effect, it is more preferably 0.1 to 100 parts by mass, and most preferably 1 to 50 parts by mass, relative to 100 parts by mass of the entire polymer component.

As long as the liquid crystal alignment treatment agent of the present invention does not impair the effect of the present invention, a compound for improving the uniformity of the film thickness and surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied can be used.

Compounds for improving the uniformity and surface smoothness of the liquid crystal alignment film, such as fluorine-based surfactants and polysiloxane-based surfactants Agents, non-ionic surfactants, etc.

More specifically, Jeffrey EF301, EF303, EF352 (the above are manufactured by Teckem), Megan F171, F173, R-30 (the above are manufactured by Dainippon Ink), Flora FC430, FC431 (the above are (Made by Sumitomo 3M), Assassi AG710, Saffron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (the above are made by Asahi Glass Co., Ltd.), etc. The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass, relative to 100 parts by mass of all polymer components contained in the liquid crystal alignment treatment agent.

In addition, the liquid crystal alignment treatment agent of the present invention may add a compound for promoting charge movement in the liquid crystal alignment film and accelerating charge release of the device, for example, the formulas disclosed in pages 69 to 73 of International Publication WO2011 / 132751 (published on 2011.10.27) [ M1] to a nitrogen-containing heterocyclic amine compound represented by the formula [M156]. The amine compound can be directly added to the liquid crystal alignment treatment agent, but it is preferably added in a solution having a concentration of 0.1% to 10% by mass, preferably 1% to 7% by mass, with an appropriate solvent. The solvent may be any organic solvent that can dissolve the specific polymer (A) and the specific polymer (B).

The liquid crystal alignment treatment agent of the present invention, in addition to the above-mentioned weak solvent, crosslinkable compound, a compound for improving the uniformity and surface smoothness of the film thickness of the resin film or the liquid crystal alignment film, and a compound for promoting charge release, does not damage the present invention. Within the scope of the effect, a dielectric body or a conductive substance for changing the electrical characteristics such as the dielectric constant and conductivity of the liquid crystal alignment film may be added.

<Liquid crystal alignment film, liquid crystal display element>

The liquid crystal alignment treatment agent of the present invention is coated on a substrate and subjected to an alignment treatment such as rubbing treatment or light irradiation after firing, and can be used as a liquid crystal alignment film. When used for vertical alignment applications, it can be used as a liquid crystal alignment film even without alignment treatment. The substrate used at this time is not particularly limited, 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 simplifying the steps, it is preferable to use a substrate for forming an ITO electrode or the like for liquid crystal driving. In the reflective liquid crystal display element, an opaque substrate such as a silicon wafer can be used for only one side substrate, and an electrode capable of reflecting light such as aluminum can be used for the electrode at this time.

The application method of the liquid crystal alignment treatment agent is not particularly limited, and is generally industrially performed by screen printing, offset printing, flexible printing, or inkjet printing. Other coating methods such as a dipping method, a roll coating method, a gap coating method, a spin coating method, or a spray method can be used depending on the purpose.

After applying the liquid crystal alignment treatment agent to the substrate, the heating method such as a hot plate, a thermal cycle type oven, or an IR (infrared) type oven is preferably 30 to 300 ° C. according to the solvent used for the liquid crystal alignment treatment agent. The solvent was evaporated at a temperature of 30 to 250 ° C to obtain a liquid crystal alignment film. The thickness of the liquid crystal alignment film after firing is 5 to 300 nm, and more preferably 10 to 100 nm, because it is not good for the power consumption of the liquid crystal display element when it is too thick, and the reliability of the liquid crystal display element is reduced when it is too thin. In order to make the liquid crystal horizontal alignment or oblique alignment, the calcined liquid crystal alignment film is rubbed or illuminated. Processing such as polarized ultraviolet radiation.

The liquid crystal display element of the present invention is obtained by using the liquid crystal alignment treatment agent of the present invention to obtain a substrate with a liquid crystal alignment film by the above method, and then fabricating a liquid crystal cell as a liquid crystal display element by a known method.

The manufacturing method of the liquid crystal cell is, for example, preparing a pair of substrates forming a liquid crystal alignment film, dispersing a distance adjusting object on the liquid crystal alignment film of a single substrate, bonding the other substrate with the liquid crystal alignment film surface inside, and then injecting under reduced pressure. A method of reseal the liquid crystal, or a method of bonding the substrate and reseal the liquid crystal by dripping the liquid crystal on the liquid crystal alignment film surface of the distance-adjusting object.

In addition, the liquid crystal alignment treatment agent of the present invention is preferably configured by having a liquid crystal layer between a pair of substrates provided with electrodes, and disposing a liquid crystal composition containing a polymerizable compound polymerized by at least one of active energy rays and heat. A liquid crystal display element produced by applying a voltage between electrodes between a pair of substrates and polymerizing a polymerizable compound by at least one of irradiating active energy rays and heating. The active energy ray is preferably ultraviolet. The wavelength of the ultraviolet rays is 300 to 400 nm, preferably 310 to 360 nm. When polymerization is performed by heating, the heating temperature is 40 to 120 ° C, and preferably 60 to 80 ° C. Moreover, ultraviolet rays and heating can be performed simultaneously.

The liquid crystal display element is a substance that controls the pretilt of liquid crystal molecules by a PSA (Poly Sustained Alignment) method. In the PSA method, a small amount of a photopolymerizable compound, such as a photopolymerizable monomer, is mixed into a liquid crystal material. After assembling a liquid crystal cell, ultraviolet light or the like is irradiated to the photopolymerizable compound while a certain voltage is applied to the liquid crystal layer. Polymer to control the pretilt of liquid crystal molecules. After removing the voltage The alignment state of the liquid crystal molecules when the polymer is formed can still be memorized, so the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field and the like formed in the liquid crystal layer. In addition, the PSA method does not require rubbing treatment, and is therefore suitable for forming a liquid crystal layer of a vertical alignment type in which pretilt is difficult to control by rubbing treatment.

That is, the liquid crystal display element of the present invention may be obtained by obtaining a substrate with a liquid crystal alignment film from a liquid crystal alignment treatment agent by the method described above, preparing a liquid crystal cell, and polymerizing a polymerizable compound by irradiating at least one of ultraviolet rays and heating. An object that controls the alignment of liquid crystal molecules.

As an example of making a PSA-type liquid crystal cell, that is, prepare a pair of substrates forming a liquid crystal alignment film, disperse the spacers on the liquid crystal alignment film of a single-sided substrate, and attach the other substrate with the liquid crystal alignment film surface as the inner side. A method of injecting liquid crystal under reduced pressure and resealing, or a method of attaching a substrate to a liquid crystal by dripping liquid crystals on the surface of the liquid crystal alignment film on which the distance-adjusting objects are dispersed, and then sealing.

A polymerizable compound polymerized by heat or ultraviolet radiation is mixed in the liquid crystal. The polymerizable compound is, for example, a compound having one or more polymerizable unsaturated groups such as an acrylate group or a methacrylate group in the molecule. In this case, the polymerizable compound is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass based on 100 parts by mass of the liquid crystal component. When the polymerizable compound is less than 0.01 parts by mass, the polymerizable compound cannot be polymerized and the liquid crystal alignment cannot be controlled. When the polymerizable compound is more than 10 parts by mass, the sintering characteristics of the liquid crystal display element are reduced due to the unreacted polymerizable compound.

After the liquid crystal cell is manufactured, an AC or DC voltage is applied to the liquid crystal cell, and at the same time, a polymerizable compound is polymerized by irradiating heat or ultraviolet rays. This can control the alignment of the liquid crystal molecules.

In addition, the liquid crystal alignment treatment agent of the present invention is suitable for a liquid crystal alignment film comprising a liquid crystal layer between a pair of substrates provided with electrodes, and a liquid crystal alignment film containing a polymerizable group polymerized by at least one of active energy rays and heat. The SC-PVA mode is a liquid crystal display device manufactured by applying a voltage between electrodes between the aforementioned pair of substrates. The active energy ray is preferably ultraviolet. The wavelength of the ultraviolet rays is 300 to 400 nm, preferably 310 to 360 nm. When polymerization is performed by heating, the heating temperature is 40 to 120 ° C, and preferably 60 to 80 ° C. Moreover, ultraviolet rays and heating can be performed simultaneously.

A method for producing a liquid crystal alignment film containing a polymerizable group polymerized by at least one of active energy ray and heat, such as a method of adding a compound containing the polymerizable group to a liquid crystal alignment treatment agent, or using a polymer containing a polymerizable group Material composition method.

Take an example of making a liquid crystal cell in the SC-PVA mode, that is, prepare a pair of substrates forming the liquid crystal alignment film of the present invention, and disperse the spacers on the liquid crystal alignment film of the unilateral substrate, and attach the liquid crystal alignment film as the inner After one substrate is placed, the liquid crystal is injected under reduced pressure and resealed, or the liquid crystal is dropped on the surface of the liquid crystal alignment film on which the distance-adjuster is dispersed, and then the substrate is sealed again.

After the liquid crystal cell is manufactured, the AC or DC voltage is applied to the liquid crystal cell and at the same time it is irradiated with heat or ultraviolet rays to control the alignment of the liquid crystal molecules.

As described above, the liquid crystal alignment treatment agent of the present invention can be used to provide a liquid crystal alignment film with a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time. It is also possible to obtain a liquid crystal alignment film capable of suppressing a decrease in the voltage holding ratio even after being exposed to a long-term high temperature and light irradiation, and quickly mitigating the residual charge accumulated by a DC voltage. Especially the liquid of the present invention The crystal alignment treatment agent is suitable for a liquid crystal alignment film using liquid crystal display elements of PSA mode and SC-PVA mode. Therefore, the liquid crystal display element produced by using the liquid crystal alignment treatment agent of the present invention is a substance having excellent reliability, and is suitable for large-scale liquid crystal televisions, small and medium-sized car navigation systems, and smart phones.

Examples

The present invention will be described in more detail with reference to the following examples, but is not limited thereto. The symbols used below are as follows.

(Specific branched 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-heptylcyclohexyl) cyclohexyl] phenoxy} benzene

A4: a diamine compound represented by the following formula [A4]

(Specific second diamine compound)

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

(Specific tertiary diamine compound)

C1: a diamine compound represented by the following formula [C1]

C2: a diamine compound represented by the following formula [C2]

(Other diamine compounds)

D1: p-phenylene diamine

D2: m-phenylene diamine

D3: 1,3-diamino-4-octadecyloxybenzene

(Specific tetracarboxylic dianhydride)

E1: 1,2,3,4-cyclobutane tetracarboxylic 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]

<Crosslinkable compound introduced into liquid crystal alignment treatment agent>

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

<Solvents 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

[Determination of molecular weight of polyfluorene-based polymer]

In the synthesis examples, the molecular weights of the polyimide precursors and polyimide were measured using a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko Corporation) and column (KD-803, KD-805). (Manufactured by Shodex), and measured by the following method.

Column temperature: 50 ℃

Eluent: N, N'-dimethylformamide (additives: lithium bromide-hydrate (LiBr-H ₂ O) 30mmol / L (liter), phosphoric anhydride crystal (o-phosphoric acid) 30mmol / L, and tetrahydrofuran (THF) 10ml / L)

Flow rate: 1.0ml / min

Standard samples for calibration line production: TSK standard polyethylene oxide (molecular weight: approximately 900,000, 150,000, 100,000, and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight: approximately 12,000, 4,000, and 1,000) (wave Freeman Corporation).

"Determination of Polyimide Imidation Rate"

The fluorene imidation rate of polyfluorene imine in the synthesis example was measured by the following method. Put 20 mg of polyfluorene imine powder into an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, In 5 (manufactured by Kusano Science Co., Ltd.), deuterated dimethylsulfinium (DMSO-d6, 0.05% by mass TMS (tetramethylsilane) mixed product) (0.53 ml) was added, and then an ultrasonic wave was applied to completely dissolve it. A 500 MHz proton NMR of this solution was measured using an NMR measuring machine (JNW-ECA500) (manufactured by Nippon Dendam Co., Ltd.). The hydrazone imidization rate is determined by using protons from structures that have not changed before and after hydrazone as the reference protons. The peak value of the protons and the NH groups from the NH group derived from sulfamic acid appear in the vicinity of 9.5 ppm to 10.0 ppm. The proton peak integrated value is obtained by the following formula.

醯 Imidization rate (%) = (1-α.x / y) × 100

In the above formula, x is an integrated value of a proton peak derived from an NH group of amidine, y is an integrated peak value of a reference proton, and α is a polyamic acid (amidation ratio of 0%) relative to amidine Proportion of the number of reference protons per NH matrix proton.

`` Synthetic polyfluorene-based polymer '' <Synthesis example 1>

E1 (5.21g, 26.6mmol), A1 (5.12g, 13.5mmol) and B1 (2.05g, 13.5mmol) were mixed with NEP (37.1g), and then reacted at 40 ° C for 8 hours to obtain a resin solid content concentration of 25 mass % Polyamic acid solution (1). The polyamic acid had a Mn (number average molecular weight) of 25,800 and a Mw (weight average molecular weight) of 86,900.

<Synthesis example 2>

E2 (3.22g, 12.9mmol), A2 (4.62g, 11.7mmol), B1 (1.78g, 11.7mmol) and D1 (0.28g, 2.60mmol) were mixed in NEP (24.8g), and then reacted at 80 ° C for 5 After 1 hour, E1 (2.52 g, 12.9 mmol) and NEP (12.4 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution (2) having a resin solid content concentration of 25% by mass. The polyamic acid had Mn of 23,100 and Mw of 76,400.

<Synthesis example 3>

NEP was added to the polyamidic acid solution (2) (30.0 g) obtained in Synthesis Example 2 and diluted to 6 mass%, and then acetic anhydride (3.95 g) and pyridine (2.40 g) were used as the phosphonium imidization catalyst. The reaction was carried out at 70 ° C for 3.5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol and then dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (3). The polyimide has a hydrazone imidization ratio of 75%, Mn of 21,100, and Mw of 57,500.

<Synthesis example 4>

E2 (1.31g, 5.23mmol), A3 (3.44g, 7.94mmol), C1 (2.57g, 10.6mmol), and D2 (0.86g, 7.94mmol) were mixed in NMP (24.5g), and then reacted at 80 ° C for 5 After 1 hour, 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.

NMP was added to the obtained polyfluorenic acid solution (30.0g) and diluted to 6% by mass, and then acetic anhydride (4.50g) and pyridine (3.30g) were added as the phosphonium imidization catalyst, and the reaction was carried out at 80 ° C for 3.5. hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol, and then dried under reduced pressure at 100 ° C. to obtain a polyimide powder (4). The polyimide has a fluorene imidation ratio of 80%, Mn of 15,900, and Mw of 43,800.

<Synthesis example 5>

E2 (1.23g, 4.91mmol), A2 (3.92g, 9.94mmol), C2 (2.58g, 9.94mmol), and D2 (0.54g, 4.97mmol) were mixed in NMP (24.2g), and then reacted at 80 ° C for 5 After 1 hour, E1 (3.85 g, 19.6 mmol) and NMP (12.1 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 adding NMP to the obtained polyamidic acid solution (30.0g) and diluting it to 6 mass%, acetic anhydride (3.85g) and pyridine (2.50g) were added as the phosphonium imidization catalyst, and reacted at 60 ° C. 2 hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was collected by filtration. Wash this with methanol After the precipitate was dried under reduced pressure at 100 ° C., a polyimide powder (5) was obtained. The polyimide has an imidization ratio of 55%, Mn of 16,900, and Mw of 46,900.

<Synthesis example 6>

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

After adding NEP to the obtained polyamidic acid solution (30.5g) and diluting it to 6% by mass, acetic anhydride (3.95g) and pyridine (2.55g) were added as the phosphonium imidization catalyst, and reacted at 60 ° C for 3 hours. hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol, and then dried under reduced pressure at 100 ° C. to obtain a polyimide powder (6). The polyimide has a fluorene imidization rate of 61%, Mn of 16,000, and Mw of 44,800.

<Synthesis example 7>

After mixing E2 (3.40 g, 13.6 mmol), B1 (4.19 g, 27.6 mmol) and D1 (0.74 g, 6.89 mmol) in NEP (24.7 g), the reaction was performed at 80 ° C for 5 hours, and then E1 (4.00 g, 20.4mmol) and NEP (12.3g), reacted at 40 ° C for 6 hours, the resin solid content concentration was 25% by mass polyamic acid solution (7). The polyamic acid had Mn of 27,500 and Mw of 90,100.

<Synthesis example 8>

NEP was added to the polyamidic acid solution (7) (30.0 g) obtained in Synthesis Example 7 and diluted to 6 mass%, and then acetic anhydride (4.40 g) and pyridine (3.30 g) were used as the phosphonium imidization catalyst. The reaction was carried out at 80 ° C for 3.5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol, and then dried under reduced pressure at 100 ° C. to obtain a polyimide powder (8). The polyimide has an imidization ratio of 80%, Mn of 23,400, and Mw of 64,500.

<Synthesis example 9>

E2 (3.96g, 15.8mmol), B1 (4.14g, 27.2mmol), C1 (0.39g, 1.60mmol), and D2 (0.35g, 3.20mmol) were mixed in NEP (24.2g), and then reacted at 80 ° C for 5 After 1 hour, E1 (3.10 g, 15.8 mmol) and NEP (12.1 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 adding NEP to the obtained polyamidic acid solution (30.0g) and diluting it to 6% by mass, acetic anhydride (4.00g) and pyridine (2.50g) as the phosphonium imidization catalyst were added and reacted at 60 ° C. 2 hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol, and then dried under reduced pressure at 100 ° C. to obtain a polyimide powder (9). The polyimide has a fluorinated imidization rate of 53%, Mn of 19,900, and Mw of 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 then reacted at 40 ° C. 8 A polyamic acid solution having a resin solid content concentration of 25% by mass was obtained for hours.

After adding NMP to the obtained polyamidic acid solution (30.0g) and diluting to 6% by mass, acetic anhydride (4.50g) and pyridine (3.35g) were added as the phosphonium imidization catalyst, and the reaction was carried out at 80 ° C for 3.5. hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol, and then dried under reduced pressure at 100 ° C. to obtain a polyimide powder (10). The polyimide has a fluorene imidization ratio of 81%, Mn of 18,200, and Mw of 51,600.

<Synthesis example 11>

E3 (5.50g, 24.5mmol), A4 (2.45g, 4.97mmol), B1 (0.19g, 1.24mmol) and C2 (3.54g, 13.7mmol) and D2 (0.54g, 4.97) were mixed in NMP (36.7g) mmol), and then reacted at 40 ° C. for 8 hours to obtain a polyamic acid solution having a resin solid content concentration of 25% by mass.

After adding NMP to the obtained polyamidic acid solution (30.5g) and diluting it to 6 mass%, acetic anhydride (3.90g) and pyridine (2.60g) were added as the phosphonium imidization catalyst, and the reaction was carried out at 60 ° C for 3.5. hour. Throw the reaction solution It was poured into methanol (460 ml), and the resulting precipitate was collected by filtration. The precipitate was washed with methanol, and then dried under reduced pressure at 100 ° C. to obtain a polyimide powder (11). The polyimide has a fluorene imidization rate of 65%, Mn of 18,500, and Mw of 50,200.

<Synthesis example 12>

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

After adding NMP to the obtained polyamidic acid solution (30.0g) and diluting it to 6 mass%, acetic anhydride (4.20g) and pyridine (3.10g) were added as the phosphonium imidization catalyst, and the reaction was carried out at 80 ° C for 2.5 hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol, and then dried under reduced pressure at 100 ° C. to obtain a polyimide powder (12). The polyimide has a hydrazone imidization rate of 75%, Mn of 19,800, and Mw of 53,900.

<Synthesis Example 13>

E4 (5.21g, 17.3mmol), A1 (4.60g, 12.1mmol), B1 (0.67g, 4.39mmol), and D1 (0.59g, 5.49mmol) were mixed in NEP (23.8g), and then reacted at 80 ° C. 6 After 1 hour, E1 (0.85 g, 4.33 mmol) and NEP (11.9 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 adding NEP to the obtained polyamidic acid solution (30.0g) and diluting to 6% by mass, acetic anhydride (3.80g) and pyridine (2.50g) were added as the phosphonium imidization catalyst, and reacted at 60 ° C. hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol, and then dried under reduced pressure at 100 ° C. to obtain a polyimide powder (13). The polyimide has a fluorene imidation rate of 55%, Mn of 16,800, and Mw of 45,300.

<Synthesis Example 14>

E4 (3.29g, 11.0mmol), A2 (3.51g, 8.88mmol), C1 (1.61g, 6.66mmol), C2 (1.15g, 4.44mmol) and D2 (0.24g, 2.22) were mixed in NMP (23.9g) After reacting at 80 ° C for 6 hours, E1 (2.15g, 11.0mmol) and NMP (12.0g) were added, and the reaction was conducted at 40 ° C for 6 hours to obtain a polyamine solution having a resin solid content concentration of 25% by mass. .

NMP was added to the obtained polyamidic acid solution (30.1 g) and diluted to 6% by mass, and then acetic anhydride (4.20 g) and pyridine (3.15 g) were added as the phosphonium imidization catalyst, and the reaction was performed at 80 ° C for 2.5. hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol and then dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (14). The polyimide has a fluorene imidation rate of 73%, Mn of 15,900, and Mw of 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 reacted at 80 ° C. 6 After 1 hour, E1 (0.99 g, 5.07 mmol) and NMP (11.8 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.

NMP was added to the obtained polyamidic acid solution (30.0g) and diluted to 6% by mass, and then acetic anhydride (3.85g) and pyridine (2.40g) were added as the phosphonium imidization catalyst, and reacted at 60 ° C. 2 hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol, and then dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (15). The polyimide has a fluorinated imidization rate of 51%, Mn of 15,700, and Mw of 44,500.

<Synthesis example 16>

E5 (2.95g, 13.9mmol), A2 (3.71g, 9.39mmol), B1 (0.36g, 2.35mmol), C1 (1.14g, 4.70mmol), C2 (1.22g, 4.70) were mixed in NEP (23.9g) mmol) and D1 (0.25g, 2.35mmol), reacted at 80 ° C for 6 hours, then added E2 (2.32g, 9.27mmol) and NEP (11.9g), and reacted at 80 ° C for 6 hours. 25% by mass polyamic acid solution.

NMP was added to the obtained polyfluorenic acid solution (30.0g) and diluted to 6% by mass, and then acetic anhydride (4.20g) and pyridine (3.20g) were used as the phosphonium imidization catalyst, and reacted at 80 ° C. 2 hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was collected by filtration. Wash this with methanol The precipitate was dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (16). The polyimide has a fluorene imidation ratio of 68%, Mn of 15,500, and Mw of 45,100.

<Synthesis example 17>

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

After adding NMP to the obtained polyamidic acid solution (30.0g) and diluting to 6% by mass, acetic anhydride (4.20g) and pyridine (3.20g) were added as the phosphonium imidization catalyst, and the reaction was carried out at 80 ° C for 2.5 hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol, and then dried under reduced pressure at 100 ° C. to obtain a polyimide powder (17). This polyfluorene imine has a sulfonium imidization ratio of 73%, Mn of 16,200, and Mw of 48,100.

<Synthesis example 18>

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

<Synthesis example 19>

The polyamine solution (18) (30.0 g) obtained by adding Synthesis Example 18 to NEP was diluted to 6% by mass, and then acetic anhydride (4.40 g) and pyridine (3.35 g) were used as the phosphonium imidization catalyst. The reaction was carried out at 80 ° C for 3.5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol, and then dried under reduced pressure at 100 ° C to obtain a polyimide powder (19). The polyimide has a fluorene imidation ratio of 79%, Mn of 18,400, and Mw of 47,200.

<Synthesis example 20>

E2 (3.25g, 13.0mmol), B1 (1.80g, 11.9mmol), D1 (0.28g, 2.60mmol), and D3 (4.46g, 11.9mmol) were mixed in NMP (24.7g) and reacted at 80 ° C for 5 After 1 hour, E1 (2.55 g, 13.0 mmol) and NMP (12.4 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.

NMP was added to the obtained polyfluorenic acid solution (30.0g) and diluted to 6% by mass, and then acetic anhydride (4.20g) and pyridine (3.20g) were used as the phosphonium imidization catalyst, and reacted at 80 ° C for 3 hours. hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was collected by filtration. The precipitate was washed with methanol and then dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (20). The polyfluorene imine has a hydrazone imidation ratio of 75%, Mn of 14,600, and Mw of 41,200.

The polyfluorene-based polymers are shown in Tables 32 to 34.

[Manufacturing liquid crystal alignment treatment agent]

The following Examples 1 to 20 and Comparative Examples 1 to 7 are examples of manufacturing liquid crystal alignment treatment agents. The liquid crystal alignment treatment agent is also used for evaluation.

The obtained liquid crystal aligning agent is shown in Table 35-Table 37. The following * 1 to * 5 in Tables 35 to 37 each indicate the following definitions.

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

* 2: The introduction amount (parts by mass) of the specific polymer (B) relative to 100 parts by mass of the entire polymer.

* 3: The amount of each solvent introduced (100 parts by mass) relative to 100 parts by mass of the entire solvent.

＊ 4: The proportion of all polymers in the liquid crystal alignment treatment agent.

＊ 5: The proportion of all polymers in the liquid crystal alignment treatment agent.

Using the liquid crystal alignment treatment agents obtained in the examples and comparative examples, the following "Evaluation of inkjet printing coating of liquid crystal alignment treatment agents" was performed Properties "," Making a liquid crystal cell and evaluating a pretilt angle (general cell) "," Evaluating a voltage retention rate (general cell) "," Evaluating the mitigation of residual charge (general cell) ", and" Making a liquid crystal cell and evaluating liquid crystal alignment ( PSA unit) ".

"Evaluating the inkjet printing coatability of liquid crystal alignment treatment agents"

The liquid crystal alignment treatment agent (4) obtained in Example 4; the liquid crystal alignment treatment agent (7) obtained in Example 7; the liquid crystal alignment treatment agent (10) obtained in Example 10; After the liquid crystal alignment treatment agent (13) obtained in Example 13 and the liquid crystal alignment treatment agent (18) obtained in Example 18, the inkjet printing coatability was evaluated. The inkjet printing coater used was HIS-200 (manufactured by Hitachi Equipment Technology Co., Ltd.). The coating was performed on an ITO (indium tin oxide) evaporation substrate washed with pure water and IPA. The coating area was 70 × 70mm, the nozzle pitch was 0.423mm, the scanning pitch was 0.5mm, and the coating speed was 40 mm / sec. The time from coating to calcination drying was 60 seconds, and calcination drying was performed at 70 ° C for 5 minutes on a hot plate.

The coating property of the obtained substrate with a liquid crystal alignment film was confirmed. Specifically, visual observation was performed under a sodium lamp to confirm the presence or absence of pinholes. As a result, there were no pinholes in the coating film of the liquid crystal alignment film obtained in any of the examples, and a liquid crystal alignment film having excellent coating film properties was obtained.

"Making LCD Cells and Evaluating Pretilt Angle (General Units)"

The liquid crystal alignment treatment agents obtained in the examples and comparative examples were pressure-filtered using a membrane filter having a pore size of 1 μm, and then a liquid crystal cell (general cell) was produced. This solution was spin-coated on the ITO surface of a 100 × 100mm substrate (100mm × 100mm in width and 0.7mm in thickness) with an ITO electrode washed with pure water and IPA. A heat treatment was performed at 230 ° C for 30 minutes in a thermal cycle type aseptic oven for 30 minutes to obtain an ITO substrate with an agglomerated polyimide liquid crystal alignment film having a film thickness of 100 nm. In addition, the liquid crystal alignment treatment agent (4) obtained in Example 4 and the liquid crystal alignment treatment agent (7) obtained in Example 7 were used under the same conditions as the above "evaluating the inkjet printing coatability of the liquid crystal alignment treatment agent". The liquid crystal alignment treatment agent (10) obtained in Example 10, the liquid crystal alignment treatment agent (13) obtained in Example 13, and the liquid crystal alignment treatment agent (18) obtained in Example 18 were used to prepare a substrate with a liquid crystal alignment film, and then subjected to thermal cycling. In an aseptic oven at 230 ° C. for 30 minutes, an ITO substrate with agglomerated fluorene imine liquid crystal alignment film with a film thickness of 100 nm was obtained.

A friction device with a roll diameter of 120 mm was used to rub the coated film surface of the ITO substrate under conditions of rayon cloth, roll revolutions of 1000 rpm, roll travel speed of 50 mm / sec, and push-in amount of 0.1 mm.

Two obtained ITO substrates with a liquid crystal alignment film were prepared, and a 6 μm distance adjuster was held so that the liquid crystal alignment film surface was inside. After the combination, a sealant was used to join the surroundings to make an empty cell. MLC-6608 (Merco) was injected into the empty cell by a reduced pressure injection method, and a liquid crystal cell (general cell) was obtained after the injection port was sealed.

Next, the pretilt angle of the liquid crystal cell (general cell) was measured. Advance The inclination angle was obtained after the liquid crystal cell was subjected to the isotopic treatment of the liquid crystal (heat treatment at 95 ° C for 5 minutes), and the liquid crystal cell after the heat treatment (heat treatment at 120 ° C for 5 hours) was measured.

In addition, a liquid crystal cell prepared under the same conditions as described above was subjected to an in-situ treatment, and then the liquid crystal cell was irradiated with ultraviolet rays of 10 J / cm ² at 365 nm conversion. The pretilt angle was measured at room temperature using PAS-301 (manufactured by ELSICON). Ultraviolet irradiation is performed using a desktop UV curing device (HCT3B28HEX-1) (specially made first).

The evaluation method is based on the pretilt angle of the liquid crystal after the parity treatment (also called the Iso treatment), the heat treatment (also called the high temperature treatment), and the pretilt angle after the ultraviolet irradiation (also called the ultraviolet irradiation). Those with relatively small changes are considered good (Tables 38 to 40 show values of the pretilt angle after Iso treatment, after high temperature treatment, and after ultraviolet irradiation).

Tables 38 to 40 show the results obtained in the marked examples and comparative examples.

`` Evaluation of voltage holding ratio (general unit) ''

The voltage holding ratio was evaluated using a liquid crystal cell (general cell) manufactured under the same conditions as the above-mentioned "producing a liquid crystal cell and evaluating a pretilt angle (general cell)". Specifically, at a temperature of 80 ° C, a voltage of 1V at 60 μs is applied to the liquid crystal cell (general cell) obtained by the above method, the voltage after 50ms is measured, and then how much voltage can be maintained as the voltage retention rate (referred to as VHR) )use. The measurement was performed using a voltage holding ratio measuring device (VHR-1, manufactured by Toyo Technology Co., Ltd.), and the voltage was set to Voltage: ± 1V, Pulse Width: 60μs, and Flame Period: 50ms. Row.

In addition, using a desktop UV curing device (HCT3B28HEX-1, first manufactured by special company), 50 J / cm ² of ultraviolet light converted at 365 nm was irradiated onto the liquid crystal cell immediately after measuring the voltage holding ratio after the production of the liquid crystal cell, and then The voltage holding ratio was measured under the same conditions as above.

The evaluation method is that the value of the voltage holding ratio measured immediately after the liquid crystal cell is made is high, and the value of the voltage holding ratio measured immediately after the liquid crystal cell is made, the smaller the value after the ultraviolet irradiation is, the better. (Tables 41 to 43 show the VHR values immediately after the production of the liquid crystal cell and after the ultraviolet irradiation). Tables 41 to 43 show the results obtained in the examples and comparative examples.

"Assessment of Reduction of Residual Charges (General Unit)"

The liquid crystal cell (general cell) produced under the same conditions as the above-mentioned "producing a liquid crystal cell and evaluating the pretilt angle (general cell)" was used to evaluate the relaxation of the residual charge. Specifically, a DC voltage of 10 V was applied to the liquid crystal cell for 30 minutes and then short-circuited for 1 second, and then the potential generated in the liquid crystal cell was measured for 1800 seconds. The residual charge value after 50 seconds was used to evaluate the relaxation of the residual charge. In the measurement, a 6254 type liquid crystal physical property evaluation device (manufactured by Toyo Technology Co., Ltd.) was used.

In addition, using a desk-type UV curing device (HCT3B28HEX-1) (manufactured by Toray Co., Ltd.), 30 J / cm ² of ultraviolet light converted at 365 nm was irradiated onto the liquid crystal cell immediately after the above-mentioned production of the liquid crystal cell was measured for residual charge. The residual charge was measured under the same conditions as above.

The evaluation method is that the smaller the residual charge value measured immediately after the liquid crystal cell is manufactured and after the irradiation with ultraviolet rays is regarded as good (Tables 41 to 43 show the VHR values immediately after the liquid crystal cell is manufactured and after ultraviolet rays are irradiated). Tables 41 to 43 show the results obtained in the examples and comparative examples.

"Making a liquid crystal cell and evaluating liquid crystal alignment (PSA cell)"

The liquid crystal alignment treatment agent (2) obtained in Example 2, the liquid crystal alignment treatment agent (3) obtained in Example 3, the liquid crystal alignment treatment agent (9) obtained in Example 9, and the pressure were filtered through a membrane filter with a pore size of 1 μm. After the liquid crystal alignment treatment agent (11) obtained in Example 11 and the liquid crystal alignment treatment agent (14) obtained in Example 14, a liquid crystal cell was prepared and the liquid crystal alignment property (PSA cell) was evaluated. This solution was spin-coated on a substrate (length 40mm × width 30mm, thickness 0.7mm) with a 10 × 10mm pattern interval ITO electrode at the center and a 10 × 40mm ITO electrode at the center after washing with pure water and IPA. After the ITO surface of the substrate (length 40mm × width 30mm, thickness 0.7mm), heat treatment was performed on the hot plate at 100 ° C. for 5 minutes and 230 ° C. for 30 minutes in a thermal cycle type aseptic oven to obtain a film thickness of 100 nm. Polyimide coating film.

With the liquid crystal alignment film surface as the inner side, the substrate with the liquid crystal alignment film was held by a 6 μm distance adjusting combination, and then the surrounding cells were made with a sealant to make empty cells, and the nematic liquid crystal (MLC- 6608) (Mercury Japan Co., Ltd.), a polymerizable compound (1) having a polymerizable compound (1) represented by the following formula in an amount of 0.3% by mass relative to 100% by mass of nematic liquid crystal (MLC-6608) The resulting liquid crystal is injected into the empty sheet In the cell, a liquid crystal cell is obtained after the injection port is sealed.

While applying an AC voltage of 5V to the obtained liquid crystal cell, a metal halide lamp with an illuminance of 60mW was used to cut off a wavelength of less than 350nm and irradiate 20J / cm ² of ultraviolet light at 365nm conversion to obtain a liquid crystal with controlled orientation direction of the liquid crystal. Unit (PSA unit). When the liquid crystal cell was irradiated with ultraviolet rays, the temperature inside the irradiation device was 50 ° C.

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

The PSA cell obtained in any of the embodiments is a comparison of the liquid crystal cell before ultraviolet radiation, and the response speed of the liquid crystal cell after ultraviolet radiation is faster, so it is confirmed that the alignment direction of the liquid crystal is controlled. In addition, each of the liquid crystal cells was observed with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation), and it was confirmed that the liquid crystals were uniformly aligned.

<Example 1>

NEP (13.3 g), BCS (9.80 g), EC (3.30 g), and M1 (0.21 g) were added to a polyamic acid solution (1) (5.00 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 1. And tree obtained in Synthesis Example 7 In a polyamic acid solution (7) (3.30 g) having a fat solid content concentration of 25% by mass, it was stirred at 25 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (1). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<Example 2>

NEP (14.9 g) and BCS (14.5 g) were added to the polyamic acid solution (2) (6.50 g) of the resin solid content concentration of 25% by mass obtained in Synthesis Example 2 and the resin solid content concentration of 25 masses by the synthesis example 7 In a polyamic acid solution (7) (2.80 g) in%, it was stirred at 25 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (2). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be 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, and stirred at 70 ° C. for 24 hours. Let it dissolve. PB (14.1 g) was added to the solution, and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (3). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be 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) obtained in Synthesis Example 8. (0.65 g), the solution was stirred at 70 ° C for 24 hours to be dissolved. BCS (7.20 g) and PB (10.8 g) were added to the solution and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (4). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be 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, and stirred at 70 ° C. for 24 hours. Let it dissolve. BCS (18.5 g) and M1 (0.12 g) were added to the solution, and stirred at 40 ° C. for 6 hours to obtain a liquid crystal alignment treatment agent (5). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<Example 6>

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

Further, NMP (4.44 g) and NEP (6.72 g) were added to the polyfluorene imine powder (9) (1.43 g) obtained in Synthesis Example 9, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. PB (11.2 g) was added to the solution, and the solution was stirred at 40 ° C for 4 hours.

The two solutions obtained above were mixed and stirred at 25 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (6). The liquid crystal alignment treatment agent did not appear turbid and separated. An abnormality was detected and it was confirmed to be a homogeneous solution.

<Example 7>

NMP (4.10 g) and NEP (20.7 g) were added 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, It was stirred at 70 ° C for 24 hours to dissolve it. PB (16.5 g) was added to the solution, and stirred at 40 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (7). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be 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, and stirred at 70 ° C. for 24 hours. Let it dissolve. BCS (13.7 g), DME (3.90 g), and M1 (0.25 g) were added to the solution, and stirred at 40 ° C. for 6 hours to obtain a liquid crystal alignment treatment agent (8). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<Example 9>

NEP (11.8 g) was added to the polyfluorene imine powder (6) (1.25 g) obtained in Synthesis Example 6, and stirred at 70 ° C. for 24 hours to dissolve it. BCS (1.98 g) and PB (5.89 g) were added to the solution, and the solution was stirred at 40 ° C for 4 hours.

Further, NEP (9.60 g) was added to the polyfluorene imine powder (12) (1.02 g) obtained in Synthesis Example 12, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (1.62 g) and PB (4.81 g) were added to the solution, and the solution was stirred at 40 ° C for 4 hours to obtain a solution.

After mixing the two solutions obtained above, M1 (0.07 g) was added and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (9). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be 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. The solution was stirred at 70 ° C for 24 hours to be dissolved. PB (15.2 g) was added to the solution and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (10). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be 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, It was stirred at 70 ° C for 24 hours to dissolve it. BCS (3.40 g) and PB (10.2 g) were added to the solution, and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (11). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be 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. The solution was stirred at 70 ° C for 24 hours to be dissolved. PB (16.6 g) and M1 (0.24 g) were added to the solution, and stirred at 40 ° C. for 6 hours to obtain a liquid crystal alignment treatment agent (12). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be 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, It was stirred at 70 ° C for 24 hours to dissolve it. PB (19.5 g) was added to the solution, and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (13). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<Example 14>

NMP (7.50 g) and NEP (3.75 g) were added to the polyfluorene imine powder (13) (1.20 g) obtained in Synthesis Example 13, and stirred at 70 ° C for 24 hours to dissolve. BCS (3.75 g) and DME (3.75 g) were added to the solution, and the solution was stirred at 40 ° C for 4 hours.

Further, NMP (7.50 g) and NEP (3.75 g) were added to the polyfluorene imine powder (9) (1.20 g) obtained in Synthesis Example 9, and stirred at 70 ° C for 24 hours to dissolve. Add BCS (3.75g) and DME (3.75g) to the The solution was stirred at 40 ° C for 4 hours to obtain a solution.

The two solutions obtained above were mixed and stirred at 25 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (14). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be 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, It was stirred at 70 ° C for 24 hours to dissolve it. PB (17.0 g) and M1 (0.07 g) were added to the solution and stirred at 40 ° C. for 6 hours to obtain a liquid crystal alignment treatment agent (15). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<Example 16>

NMP (6.90g) and NEP (13.7g) were added to the polyfluorene imine powder (15) (1.75g) obtained in Synthesis Example 15 and the polyfluorene imine powder (9) (0.44g) obtained in Synthesis Example 9, It was stirred at 70 ° C for 24 hours to dissolve it. PB (13.7 g) was added to the solution and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (16). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<Example 17>

NMP (11.9 g) and NEP (6.80 g) were added to the polyimide powder (16) (0.65 g) obtained in Synthesis Example 16 and the polymer obtained in Synthesis Example 17 The amidine imine powder (17) (1.52 g) was dissolved by stirring at 70 ° C for 24 hours. BCS (15.3 g) was added to the solution and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (17). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be 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. The solution was stirred at 70 ° C for 24 hours to be dissolved. PB (21.2 g) was added to the solution, and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (18). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be 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, It was stirred at 70 ° C for 24 hours to dissolve it. PB (13.7g), EC (3.90g) and M1 (0.13g) were added to the solution, and stirred at 40 ° C for 6 hours to obtain a liquid crystal alignment treatment agent (19). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<Example 20>

NEP (15.7 g) was added to the resin solid content obtained in Synthesis Example 2 The 25% by mass polyamine solution (2) (1.88 g) and the polyimide powder (17) (0.50 g) obtained in Synthesis Example 17 were stirred at 70 ° C for 24 hours to be dissolved. BCS (7.40 g) and PB (7.40 g) were added to the solution, and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (20). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<Comparative example 1>

NEP (15.2g) and BCS (14.9g) were added to the 25% by mass polyamic acid solution (2) (9.50g) of the resin solid content concentration obtained in Synthesis Example 2, and stirred at 25 ° C for 4 hours to obtain a liquid crystal alignment. Treatment agent (21). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<Comparative example 2>

NEP (14.4 g) and BCS (14.1 g) were added to a polyamic acid solution (7) (9.00 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 7, and stirred at 25 ° C for 4 hours to obtain a liquid crystal alignment. Treatment agent (22). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<Comparative example 3>

NEP (19.4 g) was added to the polyfluorene imine powder (3) (2.25 g) obtained in Synthesis Example 3, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Will PB (15.9 g) was added to the solution, and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (23). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<Comparative Example 4>

NEP (19.0 g) was added to the polyfluorene imine powder (8) (2.20 g) obtained in Synthesis Example 8, and stirred at 70 ° C for 24 hours to dissolve. PB (15.5 g) was added to the solution and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (24). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<Comparative example 5>

NEP (16.0 g) and BCS (15.7 g) were added to a polyamic acid solution (2) (7.00 g) having a resin solid content concentration of 25% by mass obtained in Synthesis Example 2 and a resin solid content concentration of 25 masses obtained in Synthesis Example 18. The polyamic acid solution (18) (3.00 g) was stirred at 25 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (25). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be 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, and stirred at 70 ° C for 24 hours. Let it dissolve. PB (14.8g) was added to the solution, and stirred at 40 ° C for 4 hours to obtain a liquid crystal compound. 向 处理 剂 (26). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be 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, and stirred at 70 ° C. for 24 hours. Let it dissolve. PB (14.1 g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (27). This liquid crystal alignment treatment agent did not exhibit abnormalities such as turbidity and precipitation, and was confirmed to be a uniform solution.

<Evaluation of liquid crystal alignment treatment agent>

Using the liquid crystal alignment treatment agents obtained in the above Examples 1 to 20 and Comparative Examples 1 to 7, respectively, "producing a liquid crystal cell and evaluating a pretilt angle (general cell)", "evaluating a voltage holding ratio (general cell)", and "evaluating residual Ease of Charge (General Unit) ". The liquid crystal alignment treatment agents obtained in Examples 4, 7, 10, 13, and 18 were evaluated for inkjet printing coatability.

The evaluation results are shown in Table 39 to Table 43 below.

From the above results, it is known that in the comparative example of the liquid crystal alignment treatment agent of the example, the liquid crystal cell is subjected to high-temperature treatment and ultraviolet irradiation. Line, you can also get a stable pre-tilt angle. In addition, even when the ultraviolet rays are irradiated, the decrease in the voltage holding ratio can be suppressed, and the residual charge accumulated by the DC voltage can be accelerated and relaxed. That is, the liquid crystal alignment treatment agent of the present invention can form a liquid crystal alignment film in which a stable pretilt angle is found even after being exposed to long-term high temperature and light irradiation, and can be formed even after being exposed to long-term light irradiation. The liquid crystal alignment film having a reduced voltage holding ratio and accelerating and alleviating the residual charge accumulated by the DC voltage.

Specifically, the embodiment using the liquid crystal alignment treatment agent of the specific polymer (A) and the specific polymer (B) is compared with the embodiment where the liquid crystal alignment treatment agent of any of these is not used, that is, Comparative Example 2 Compared with Comparative Example 1 or Comparative Example 2, Example 3 and Comparative Example 3 or Comparative Example 4 were compared. These comparative examples 1 and 3 using only the specific polymer (A), when comparing the corresponding examples, the pretilt angle is greatly changed after high temperature treatment and ultraviolet irradiation, and the voltage retention is greatly reduced compared to these treatments. Rate, and increase the value of residual charge. Among them, the voltage holding ratio is significantly reduced. In Comparative Examples 2 and 4, the liquid crystals were not vertically aligned.

In addition, an example using the liquid crystal alignment treatment agent of the specific polymer (A) and the specific polymer (B) of the example is compared with the use of the specific polymer (A) and the specific branched chain having the formula [1]. A comparative example of a liquid crystal alignment treatment agent for a polymer of a specific branched-chain diamine compound having a structure, that is, Comparative Example 2 and Comparative Example 5, and Comparative Example 3 and Comparative Example 6. When these comparative examples are compared with the corresponding examples, the pretilt angle is greatly changed after high-temperature treatment and ultraviolet irradiation, and the voltage retention rate is greatly reduced and the value of the residual charge is increased relative to these treatments. Especially lower The voltage holding rate and the value of increasing the residual charge.

In addition, an example in which the liquid crystal alignment treatment agent using the specific polymer (A) and the specific polymer (B) was compared with the liquid crystal alignment treatment agent using the polymer having the conventional branched structure and the specific polymer (B) was compared. Comparative example, that is, Example 3 and Comparative Example 7 are compared. When Comparative Example 7 is compared with Example 3, the pretilt angle is significantly changed after high-temperature treatment and ultraviolet irradiation, and the voltage retention ratio is reduced and the value of the residual charge is increased relative to these treatments. In particular, the pretilt angle after UV irradiation is greatly reduced.

Industrial use possibility

The liquid crystal alignment treatment agent of the present invention can provide a liquid crystal alignment film with a stable pretilt angle even after being exposed to high temperature and light irradiation for a long time. Furthermore, it is possible to provide a liquid crystal alignment film capable of suppressing a decrease in the voltage holding rate even after being exposed to long-term light irradiation, and accelerating and alleviating the residual charge accumulated by the DC voltage. In addition, a liquid crystal display device having the liquid crystal alignment film, and a liquid crystal alignment treatment agent for the liquid crystal alignment film can be provided.

Therefore, the liquid crystal display element having the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is a substance having excellent reliability, and is suitable for large-screen and high-definition liquid crystal televisions. It is suitable for TN elements, STN elements, and TFT liquid crystal elements. , Especially vertical alignment type liquid crystal display elements.

The liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is also applicable to a liquid crystal display element that needs to be irradiated with ultraviolet rays when a liquid crystal display element is produced. That is, for a pair of substrates with electrodes It has a liquid crystal layer in between, and a liquid crystal composition containing a polymerizable compound polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, and the polymerizability is polymerized while a voltage is applied to the electrodes. The liquid crystal display element produced by the compound step and a pair of electrodes provided with a liquid crystal layer between the substrates are arranged through a liquid crystal alignment film containing a polymerizable group polymerized by at least one of active energy rays and heat. The liquid crystal display element manufactured by the step of polymerizing the polymerizable group while applying a voltage between the electrodes between a pair of substrates is also applicable.

The entire contents of the specification, patent application scope, and abstract of Japanese Patent Application No. 2013-182352, filed on September 3, 2013, are incorporated in the description of the present invention.

Claims (22)

A liquid crystal alignment treatment agent, which is characterized by containing the following component (A) and component (B), (A) component: a diamine component containing a diamine having a structure represented by the following formula [1], and Polyimide precursors obtained by the reaction of carboxylic acid components and at least one polymer selected from the group consisting of polyimide, component (B): a component that does not contain a structure represented by the following formula [1] A diamine component of a diamine, a polyimide precursor obtained by reacting with a tetracarboxylic acid component, and at least one polymer selected from the group consisting of polyimide, but (A) component and (B) component None of which has a photoreactive side chain including at least one selected from the group consisting of methacrylfluorenyl, acrylfluorenyl, vinyl, allyl, coumarin, styryl, and cinnamyl; Y ¹ represents a single bond,-(CH ₂ ) _a- (a is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or OCO-; Y ² represents a single bond or (CH ₂ ) _b- (b is an integer from 1 to 15); Y ³ represents a single bond,-(CH ₂ ) _c- (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO -Or OCO-; Y ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring, and a heterocyclic ring, or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton, and the aforementioned ring Any hydrogen atom on the base can be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, and a fluorine-containing alkyl group having 1 to 3 carbon atoms. Oxygen or fluorine atom substitution; Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups may be 1 to 3 carbon atoms Substituted by alkyl group, alkoxy group having 1 to 3 carbon atoms, fluorine-containing alkyl group having 1 to 3 carbon atoms, fluorine-containing alkoxy group having 1 to 3 carbon atoms or fluorine atom substitution; n represents an integer of 0 to 4 ; Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. The liquid crystal alignment treatment agent according to claim 1, wherein the diamine having the structure represented by the aforementioned formula [1] is represented by the following formula [1a], Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , n, Y ⁶ and m represent the same definitions as described above. The liquid crystal alignment treatment agent according to claim 1, wherein the component (B) is a diamine component composed of a diamine having at least one selected from a carboxyl group (COOH group) and a hydroxyl group (OH group), A polyimide precursor obtained by reacting with a tetracarboxylic acid component and a polymer of at least one selected from the group consisting of polyimide. In the liquid crystal alignment treatment agent according to claim 1, wherein the component (A) is a diamine component, a diamine containing a diamine having at least one selected from a carboxyl group (COOH group) and a hydroxyl group (OH group) is used. polymer. In the liquid crystal alignment treatment agent according to claim 3 or 4, wherein the diamine having a substituent selected from at least one of the carboxyl group and the hydroxyl group is represented by the following formula [2a], A ¹ represents at least one substituent selected from the following formulas [2a-1] and [2a-2]; m1 represents an integer of 1 to 4, and [Chem 4]-(CH ₂ ) _d -COOH [ 2a-1]-(CH ₂ ) _e -OH [2a-2] d represents an integer from 0 to 4; e represents an integer from 0 to 4. The liquid crystal alignment treatment agent according to claim 1, wherein the polymer of the components (A) and (B) is a polymer of a diamine component using a diamine represented by the following formula [3a], B ¹ represents -O-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON (CH ₃ )-, or N (CH ₃ ) CO-; B ² represents a single bond, an alkylene group 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 1 to 5 (Integer); B ⁴ represents a nitrogen-containing heterocyclic ring; n1 represents an integer of 1 to 4; when n1 is 2 or more, -B ¹ -B ² -B ³ -B ⁴ may be the same or different. The liquid crystal alignment treatment agent according to claim 6, wherein B ¹ in the foregoing formula [3a] is -O-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, or CON ( CH ₃ )-. The liquid crystal alignment treatment agent according to claim 6, wherein B ² in the foregoing formula [3a] is a single bond, an alkylene group having 1 to 5 carbon atoms, a cyclohexane ring, or a benzene ring. For example, the liquid crystal alignment treatment agent of claim 6, wherein B ³ in the foregoing formula [3a] is a single bond, -O-, -OCO-, or O (CH ₂ ) _m2- (m2 is an integer from 1 to 5) . The liquid crystal alignment treatment agent according to claim 6, wherein B ⁴ in the foregoing formula [3a] is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, or a pyrimidine ring. For example, the liquid crystal alignment treatment agent of claim 6, wherein B ¹ in the foregoing formula [3a] represents -CONH-, B ² represents an alkylene group having 1 to 5 carbon atoms, B ³ represents a single bond, and B ⁴ represents an imidazole ring Or pyridine ring, n1 is 1. The liquid crystal alignment treatment agent according to claim 1, wherein the tetracarboxylic acid component of at least one of the components (A) and (B) is a tetracarboxylic dianhydride represented by the following formula [4], Z ^{1 is a base selected} from the following formulas [4a] to [4k], Z ² to Z ⁵ each independently represent a hydrogen atom, a methyl group, a chlorine atom, or a benzene ring; Z ⁶ and Z ⁷ each independently represent a hydrogen atom or a methyl group. The liquid crystal alignment treatment agent according to claim 1, which contains a solvent of at least one of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and γ-butyrolactone. For example, the liquid crystal alignment treatment agent of claim 1, which contains at least one solvent selected from the following formulas [D-1] to [D-3], D ¹ represents an alkyl group having 1 to 3 carbon atoms, D ² represents an alkyl group having 1 to 3 carbon atoms, and D ³ represents an alkyl group having 1 to 4 carbon atoms. For example, the liquid crystal alignment treatment agent of claim 1, which contains 1-hexanol, cyclohexanol, 1,2-ethylene glycol, 1,2-propylene glycol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, and A solvent of at least one selected from dipropylene glycol dimethyl ether. The liquid crystal alignment treatment agent according to claim 1, wherein the liquid crystal alignment treatment agent contains a crosslinkable compound having an epoxy group, an isocyanate group, an propylene oxide group, or a cyclic carbonate group, A crosslinkable compound of at least one selected from the group consisting of lower alkoxyalkyl groups, and a crosslinkable compound of at least one selected from the crosslinkable compounds having a polymerizable unsaturated bond. A liquid crystal alignment film is obtained from the liquid crystal alignment treatment agent according to any one of claims 1 to 16. A liquid crystal alignment film is obtained by printing the liquid crystal alignment treatment agent according to any one of claims 1 to 16 by an inkjet printing method. A liquid crystal display element having a liquid crystal alignment film as claimed in claim 17 or 18. For example, the liquid crystal alignment film of claim 17 or 18 is used for disposing a liquid crystal composition containing a polymerizable compound polymerized by at least one of active energy rays and heat through a liquid crystal layer between a pair of substrates provided with electrodes. A liquid crystal display device produced by the step of polymerizing the polymerizable compound while applying a voltage between the pair of substrates between the electrodes. For example, the liquid crystal alignment film of claim 17 or 18 is composed of a liquid crystal layer having a liquid crystal layer between a pair of substrates provided with electrodes. The liquid crystal alignment film contains a polymerizable group polymerized by at least one of active energy rays and heat. A film is disposed between the pair of substrates, and a liquid crystal display device manufactured by the step of polymerizing the polymerizable group while applying a voltage between the electrodes. A liquid crystal display element having a liquid crystal alignment film as claimed in claim 20 or 21.