TWI678385B - Liquid crystal alignment treatment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Abstract

The present invention provides a liquid crystal alignment film capable of suppressing a decrease in voltage holding ratio, without display unevenness occurring near a frame of a liquid crystal display element, a liquid crystal display element having the liquid crystal alignment film, and a liquid crystal alignment film capable of forming the liquid crystal alignment film. Liquid crystal alignment treatment agent.

The liquid crystal alignment treatment agent of the present invention contains the following (A) component, (B) component, and (C) component.

(A) Component: Polyfluorene obtained by reacting a diamine component having a structure represented by the following formula [1] and a diamine component having a structure represented by the following formula [2] and a tetracarboxylic acid component An amine precursor or a polyimide obtained by subjecting the polyimide precursor to amidation.

(B) component: a polyimide precursor obtained by reacting a diamine component containing a diamine having a structure represented by the following formula [2] with a tetracarboxylic acid component or subjecting the polyimide precursor to polyimide Aminated polyimide.

(C): Polyimide precursor obtained by reacting a diamine component having a diamine having at least one type of substituent selected from the group consisting of a carboxyl group (COOH group) and a hydroxyl group (OH group) and a tetracarboxylic acid component. Polyimide precursor Polyimide polyimide.

(X¹表示單鍵等，X²表示單鍵等，X³表示單鍵等，X⁴表示苯環等，X⁵表示苯環等，n表示0~4之整數，X⁶表示碳數1~18之烷基等。)

(X ¹ represents a single bond, etc., X ² represents a single bond, etc., X ³ represents a single bond, etc., X ⁴ represents a benzene ring, etc., X ⁵ represents a benzene ring, etc., n represents an integer from 0 to 4, and X ⁶ represents a carbon number of 1 ~ 18 alkyl, etc.)

-W ¹ -W ² -W ³ -W ⁴ [2] (W ¹ represents -O-. W ² represents a single bond. W ³ represents a single bond. W ⁴ represents a nitrogen-containing aromatic heterocyclic ring.)

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 obtained from the liquid crystal alignment treatment agent, and a liquid crystal display element using the liquid crystal alignment film.

Liquid crystal display elements are used to realize thin and lightweight display devices, and are currently widely used. Generally, this liquid crystal display element uses a liquid crystal alignment film in order to determine the alignment state of the liquid crystal.

The liquid crystal alignment film is used to control the alignment state of the liquid crystal. However, with the high definition of liquid crystal display elements, it is required to suppress display defects caused by a decrease in the contrast of the liquid crystal display elements or long-term use. For these reasons, a liquid crystal alignment film using polyimide has been proposed to improve the alignment of liquid crystals, and it is not easy to cause display defects in the peripheral portion of the liquid crystal display screen. A liquid crystal alignment film using a liquid crystal alignment treatment agent added with an alkoxysilane compound (See Patent Documents 1 and 2).

In addition, with the high definition of liquid crystal display elements, from the viewpoint of suppressing the decrease in contrast of the liquid crystal display elements or the reduction of afterimages, the liquid crystal alignment film used here has a high voltage retention rate and a direct current. The characteristics such as a low accumulated charge at the time of compressing, or a relaxation and a rapid accumulation of the charge due to the DC voltage are becoming important.

In the polyimide-based liquid crystal alignment film, the shorter period of time after which the afterimage caused by the DC voltage disappears is used. In addition to polyimide or polyimide containing a polyimide group, a material containing a specific structure is used. A liquid crystal alignment treatment agent for a tertiary amine (for example, refer to Patent Document 3) or a liquid crystal alignment treatment agent containing a soluble polyfluorene imine using a specific diamine having a pyridine skeleton or the like (see Patent Document 4), etc. Known.

In addition, the voltage holding rate is high, and the time until the afterimage caused by the DC voltage disappears is short. For example, in addition to polyamic acid or its imidized polymer, a small amount of A liquid crystal alignment treatment agent selected from a compound having one carboxylic acid group, a compound containing one carboxylic anhydride group in the molecule, and a compound containing one tertiary amine group in the molecule (see Patent Document 5) is known. .

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 61-171762

[Patent Document 2] Japanese Patent Application Laid-Open No. 11-119226

[Patent Document 3] Japanese Unexamined Patent Publication No. 9-316200

[Patent Document 4] Japanese Patent Laid-Open No. 10-104633

[Patent Document 5] Japanese Unexamined Patent Publication No. 8-76128

In recent years, liquid crystal display elements have been used for mobile applications such as smart phones and mobile phones. For these applications, in order to ensure as many display surfaces as possible, the width of the sealant used between the substrates of the liquid crystal display element must be narrower than before. In addition, for the reasons described above, it is required that the drawing position of the sealant be a position that contacts the end portion of the liquid crystal alignment film with weak adhesiveness to the sealant, or an upper portion of the liquid crystal alignment film. In this case, water is easily mixed between the sealant and the liquid crystal alignment film due to use under high temperature and high humidity conditions, and display unevenness occurs near the frame of the liquid crystal display element. Therefore, it is required to improve the adhesion between the sealant and the liquid crystal alignment film, and to suppress such display unevenness.

In addition, the voltage holding ratio, which is one of the electrical characteristics of a liquid crystal display element, is also required to have high stability under severe conditions as described above. That is, when the voltage holding ratio is lowered by the light from the backlight, afterimage failure (also called line afterimage), which is one of the display defects of the liquid crystal display element, is likely to occur, and a liquid crystal display element with high reliability cannot be obtained. Therefore, in addition to the good initial characteristics of the liquid crystal alignment film, it is required that the voltage holding ratio is not easily reduced even after being exposed to light for a long time, for example. In addition, for another surface afterimage with a poor afterimage, a liquid crystal alignment film with a rapid relaxation of the residual charge accumulated by the DC voltage by irradiation with backlight light is also required.

Therefore, an object of the present invention is to provide a liquid crystal alignment film having both of the above characteristics. That is, it is an object of the present invention to provide an adhesive that can improve the adhesion between a sealant and a liquid crystal alignment film. A liquid crystal alignment film that suppresses occurrence of display unevenness near a frame of a liquid crystal display element. In addition, an object of the present invention is to provide a liquid crystal alignment film that can suppress a decrease in voltage holding ratio even after being exposed to light for a long period of time, and that the residual charge accumulated by a DC voltage can be quickly alleviated.

The present invention also provides a liquid crystal display element having the liquid crystal alignment film, and a liquid crystal alignment treatment agent capable of providing the liquid crystal alignment film.

As a result of careful study by the present inventors, it was found that a liquid crystal alignment treatment agent containing three polymers having a specific structure can very effectively achieve the above-mentioned object, and completed the present invention.

That is, the present invention has the following technical features.

(1) A liquid crystal alignment treatment agent containing the following (A) component, (B) component, and (C) component,

(A) Component: Polyfluorene obtained by reacting a diamine component having a structure represented by the following formula [1] and a diamine component having a structure represented by the following formula [2] and a tetracarboxylic acid component An amine precursor or a polyimide obtained by subjecting the polyimide precursor to amidation.

(B) component: a polyimide precursor obtained by reacting a diamine component containing a diamine having a structure represented by the following formula [2] with a tetracarboxylic acid component or subjecting the polyimide precursor to polyimide Aminated polyimide.

(C): Polyimide precursor obtained by reacting a diamine component having a diamine having at least one type of substituent selected from the group consisting of a carboxyl group (COOH group) and a hydroxyl group (OH group) and a tetracarboxylic acid component. Polyimide precursor Polyimide polyimide.

However, the diamine component in the polymer of at least one of the components (A), (B), and (C) contains a diamine having a structure represented by the following formula [4].

(X¹表示選自由單鍵、-(CH₂)_a-(a為1~15之整數)、-O-、-CH₂O-、-COO-及-OCO-所成群之至少1種之鍵結基(bonding group)。X²表示單鍵或-(CH₂)_b-(b為1~15之整數)。X³表示選自由單鍵、-(CH₂)_c-(c為1~15之整數)、-O-、-CH₂O-、-COO-及-OCO-所成群之至少1種。X⁴表示選自由苯環、環己烷環及雜環所成群之至少1種之2價環狀基、或具有類固醇骨架之碳數17~51之2價有機基，前述環狀基上之任意的氫原子可被碳數1~3之烷基、碳數1~3之烷氧基、碳數1~3之含氟之烷基、碳數1~3之含氟之烷氧基或氟原子所取代。X⁵表示選自由苯環、環己烷環及雜環所成群之至少1種的環狀基，此等之環狀基上之任意的氫原子可被碳數1~3之烷基、碳數1~3之烷氧基、碳數1~3之含氟之烷基、碳數1~3之含氟之烷氧基或氟原子所取代。n表示0~4之整數。X⁶表示選自由碳數1~18之烷基、碳數1~18之含氟之烷基、碳數1~18之烷氧基及碳數1~18之含氟之烷氧基所 成群之至少1種)[化2]-W ¹ -W ² -W ³ -W ⁴ [2](W¹表示選自由-O-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-CH₂O-、-OCO-、-CON(CH₃)-及-N(CH₃)CO-所成群之至少1種的鍵結基。W²表示選自由單鍵、碳數1~20之伸烷基、及非芳香族環及芳香族環所成群之至少1種。W³表示選自由單鍵、-O-、-NH-、-N(CH₃)-、-CONH-、-NHCO-、-COO-、-OCO-、-CON(CH₃)-、-N(CH₃)CO-及-O(CH₂)_m-(m表示1~5之整數)所成群之至少1種。W⁴表示含氮之芳香族雜環)

(X ¹ represents at least one selected from the group consisting of a single bond,-(CH ₂ ) _a- (a is an integer from 1 to 15), -O-, -CH ₂ O-, -COO-, and -OCO- Bonding group. X ² represents a single bond or-(CH ₂ ) _b- (b is an integer from 1 to 15). X ³ represents a group selected from a single bond,-(CH ₂ ) _c- (c is an integer of 1 to 15), - O -, - CH 2 O -, - COO- -OCO- and at least one of the groups of selected from the group consisting .X ⁴ represents a benzene ring, a cyclohexane ring, and the heterocyclic groups At least one kind of divalent cyclic group, or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton, and any hydrogen atom on the aforementioned cyclic group may be an alkyl group or carbon number of 1 to 3 carbon atoms Substituted by alkoxy groups 1 to 3, fluorine-containing alkyl groups having 1 to 3 carbon atoms, fluorine-containing alkoxy groups having 1 to 3 carbon atoms or fluorine atoms. X ⁵ represents a group selected from benzene rings and cyclohexane rings. And at least one type of cyclic group formed by a heterocyclic ring, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and carbon number Substituted by a fluorine-containing alkyl group of 1 to 3, a fluorine-containing alkoxy group or a fluorine atom of 1 to 3 carbon atoms. N represents an integer of 0 to 4. X ⁶ represents a group selected from alkyl groups of 1 to 18 carbon atoms, C1-C18 fluorine-containing alkyl, C1-C18 Alkoxy and at least one group of fluorine-containing alkoxy having 1 to 18 carbons) [Chemical 2] -W ¹ -W ² -W ³ -W ⁴ [2] (W ¹ represents a group selected from- O-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON (CH ₃ )-, and -N (CH ₃ ) CO- At least one type of bonding group in a group. W ² represents at least one type selected from the group consisting of a single bond, an alkylene group having 1 to 20 carbon atoms, and a non-aromatic ring and an aromatic ring. W ³ represents an optional group. Free single bond, -O-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -COO-, -OCO-, -CON (CH ₃ )-, -N (CH ₃ ) CO- and -O (CH ₂ ) _m- (m represents an integer of 1 to 5) at least one group. W ⁴ represents a nitrogen-containing aromatic heterocyclic ring)

(2) The liquid crystal alignment treatment agent according to the above item (1), wherein the diamine having the structure represented by the aforementioned formula [1] is used only for the diamine component in the aforementioned (A) component.

(3) The liquid crystal alignment treatment agent according to the above item (1), wherein the proportion of the diamine having the structure represented by the aforementioned formula [1] in the component (A) described above with respect to the entire diamine component (mole%) When it is set to 1.0, the diamine in the component (B) having the structure represented by the formula [1] is larger than that of the entire diamine component. The usage ratio (mol%) is a ratio of 0.01 to 0.8.

(4) The liquid crystal alignment treatment agent according to the above item (1) or (3), wherein the use ratio of the diamine having the structure represented by the formula [1] in the component (A) to the entire diamine component ( When the mole ratio (mol%) is 1.0, the use ratio (mol%) of the diamine having the structure represented by the formula [1] in the (C) component to the entire diamine component is 0.01 to 0.3.

(5) The liquid crystal alignment treatment agent according to any one of the above items (1) to (4), wherein the liquid crystal alignment treatment agent has at least one substituent selected from the group consisting of the carboxyl group (COOH group) and the hydroxyl group (OH group). Diamine is used only for the diamine component in said (C) component.

(6) The liquid crystal alignment treatment agent according to any one of the items (1) to (5), wherein the diamine having the structure represented by the aforementioned formula [4] is used only as the diamine component in the aforementioned (A) component .

(X表示前述式[1]表示之構造。n1表示1~4之整數)。 (7) The liquid crystal alignment treatment agent according to any one of the items (1) to (6), wherein the diamine having the structure represented by the aforementioned formula [1] is represented by the following formula [1a],

(X represents the structure represented by the aforementioned formula [1]. N1 represents an integer of 1 to 4).

(W表示前述式[2]表示之構造。p1表示1~4之整數)。 (8) The liquid crystal alignment treatment agent according to any one of items (1) to (7) above, wherein the diamine having the structure represented by the aforementioned formula [2] is represented by the following formula [2a],

(W represents the structure represented by the aforementioned formula [2]. P1 represents an integer of 1 to 4).

(Y表示以下述式[3-1]或式[3-2]表示之構造。m1表示1~4之整數)

(a及b各自表示0~4之整數)。 (9) The liquid crystal alignment treatment agent according to any one of the items (1) to (8), wherein the diamine having at least one kind of substituent selected from the group consisting of a carboxyl group and a hydroxyl group is represented by the following formula [3a ] Means,

(Y represents a structure represented by the following formula [3-1] or [3-2]. M1 represents an integer of 1 to 4)

(a and b each represent an integer of 0 to 4).

(q1表示1~8之整數)。 (10) The liquid crystal alignment treatment agent according to any one of items (1) to (9) above, wherein the diamine having a structure represented by the aforementioned formula [4] is represented by the following formula [4a-1],

(q1 represents an integer from 1 to 8).

(Z表示選自由下述式[5a]~式[5k]表示之構造所成群之至少1種)

(Z¹~Z⁴各自獨立表示選自由氫原子、甲基、氯原子及苯環所成群之至少1種，Z⁵及Z⁶各自獨立表示氫原子或甲基)。 (11) The liquid crystal alignment treatment agent according to any one of the items (1) to (10), wherein the tetracarboxylic acid component in the components (A), (B), and (C) contains the following formula [ 5] tetracarboxylic dianhydride,

(Z represents at least one selected from the group consisting of the structures represented by the following formulas [5a] to [5k])

(Z ¹ to Z ⁴ each independently represent at least one selected from the group consisting of a hydrogen atom, a methyl group, a chlorine atom, and a benzene ring, and Z ⁵ and Z ⁶ each independently represent a hydrogen atom or a methyl group).

(12) The liquid crystal alignment treatment agent according to any one of the items (1) to (11), which contains a material selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butane. At least one solvent in which the esters are grouped.

(D¹表示碳數1~3之烷基。D²表示碳數1~3之烷基。D³表示碳數1~4之烷基)。 (13) The liquid crystal alignment treatment agent according to any one of (1) to (12) above, which contains a liquid crystal alignment treatment agent selected from the group consisting of 1-hexanol, cyclohexanol, 1,2-ethylene glycol, and 1,2-propylene glycol. Propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, and at least one solvent grouped by a solvent represented by the following formula [D1] to [D3],

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

(14) The liquid crystal alignment treatment agent according to any one of the above items (1) to (13), wherein the liquid crystal alignment treatment agent contains: a material selected from the group consisting of an epoxy group, an isocyanate group, an oxetanyl group, and a cyclocarbonic acid; A crosslinkable compound having at least one group grouped by an ester group, a crosslinkable compound having at least one group selected from a group consisting of a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group, or a polymerizable compound A crosslinkable compound of a saturated bond group.

(15) A liquid crystal alignment film obtained from the liquid crystal alignment treatment agent according to any one of the items (1) to (14) above.

(16) A liquid crystal alignment film obtained by applying the liquid crystal alignment treatment agent according to any one of the items (1) to (14) above by an inkjet method.

(17) A liquid crystal display element having the liquid crystal alignment film as described in the item (15) or (16) above.

(18) The liquid crystal alignment film according to the item (15) or (16) above, which is formed by having a liquid crystal layer between a pair of substrates provided with electrodes, and an active energy ray is arranged between the pair of substrates. A liquid crystal composition of a polymerizable compound polymerized by at least one of heat and heat is a liquid crystal display device produced by a step of polymerizing the polymerizable compound by applying a voltage between the electrodes.

(19) A liquid crystal display element having the liquid crystal alignment film according to the item (18) above.

(20) The liquid crystal alignment film according to the item (15) or (16) above, which is formed by having a liquid crystal layer between a pair of substrates provided with electrodes, and an active energy ray is disposed between the pair of substrates. The polymerizable group liquid crystal alignment film polymerized by at least one of heat and heat, is a liquid crystal display device manufactured by the step of polymerizing the polymerizable group by applying a voltage between the electrodes.

(21) A liquid crystal display element having the liquid crystal alignment film according to the item (20) above.

The liquid crystal alignment treatment agent of the present invention can obtain a liquid crystal alignment film which can improve the adhesion between the sealant and the liquid crystal alignment film, and can suppress the occurrence of display unevenness near the frame of the liquid crystal display element under high temperature and high humidity conditions. In addition, a liquid crystal alignment film can be obtained which can suppress a decrease in the voltage holding ratio even after being irradiated with light for a long period of time, and can quickly reduce the residual charge accumulated by the DC voltage.

According to the present invention, although a mechanism for obtaining a liquid crystal display element having the above-mentioned excellent characteristics is not clear, it can be estimated as follows.

The specific structure (1) in the specific polymer (A) is a divalent organic group having 17 to 51 carbon atoms having a benzene ring, a cyclohexane ring, a heterocyclic ring, or a steroid skeleton. These ring and organic group side-chain structures are more rigid than conventional long-chain alkyl groups in which liquid crystals are vertically aligned, and have a stable structure against light such as ultraviolet rays. Therefore, compared with the prior art, the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent having a specific side chain structure can reduce the voltage holding ratio even when exposed to light, and can suppress the accumulation of residual charges due to DC voltage. Decomposition of side chain components.

In addition, the specific structure (4) of the specific diamine (4) generates a radical by irradiation of ultraviolet rays. Therefore, through the hardening step of the sealant when manufacturing the liquid crystal display element, that is, the ultraviolet irradiation step, radicals that promote the hardening of the sealant are also generated from the liquid crystal alignment film, which can further improve the hardening of the sealant and the sealant and liquid crystal Adhesiveness of the alignment film.

In addition, the nitrogen-containing heterocyclic system possessed by the specific structure (2) in the specific polymers (A) and (B) is due to the electrostatic property of the carboxyl group or the hydroxyl group in the specific polymer (C), salt formation, hydrogen bonding, and the like. Interact and combine, so in Between the nitrogen-containing aromatic heterocyclic ring and the carboxyl group or the hydroxyl group, the charge movement becomes easy to occur. Thereby, the moving charge can efficiently move the intra- and inter-molecules of the polyimide-based polymer, and the residual charges accumulated due to the DC voltage can be quickly alleviated. Therefore, a liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention has excellent reliability.

[Form of Implementing Invention]

In this manual, "part" and "%" mean "mass part" and "mass%" respectively unless otherwise stated.

<Specific diamine (1)>

The specific diamine (1) is a diamine having a specific structure of the following formula [1].

X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and n are as defined above, but each of them is preferably the following.

X ^{1 is} preferably a single bond,-(CH ₂ ) _a- (a is an integer of 1 to 15), -O-, -CH ₂ O-, or -COO from the viewpoint of availability of raw materials or ease of synthesis. -. More preferably, it is a single bond,-(CH ₂ ) _a- (a is an integer from 1 to 10), -O-, -CH ₂ O-, or -COO-.

X ^{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, X 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 from 1 to 10), -O-, -CH ₂ O-, or -COO-.

From the viewpoint of ease of synthesis, X ⁴ is preferably a benzene ring, a cyclohexane ring, or an organic group having 17 to 51 carbon atoms having a steroid skeleton.

X ^{5 is} preferably a benzene ring or a cyclohexane ring.

X ^{6 is} preferably an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 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 1 to 10 carbon atoms Its fluorine-containing alkoxy group. More preferably, it is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. Particularly preferred are alkyl groups having 1 to 9 carbon atoms, alkenyl groups having 2 to 12 carbon atoms or alkoxy groups having 1 to 9 carbon atoms.

From the viewpoint of availability of raw materials or ease of synthesis, n is preferably 0 to 3. More preferably, it is 0 to 2.

Preferred combinations of X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and n include, for example, Tables 6 to Tables on pages 13 to 34 of International Publication WO2011 / 132751 (published on 2011.10.27) The same combinations as (2-1) to (2-629) described in 47. In the tables of International Publications, X ¹ to X ⁶ in the present invention are represented by Y1 to Y6, but Y1 to Y6 can be interpreted as X ¹ to X ⁶ . In addition, in (2-605) to (2-629) disclosed in the tables of the International Publication, the organic group having a carbon number of 17 to 51 in the present invention and the carbon number of 12 to 25 having a steroid skeleton in the present invention The organic group represents, but the organic group having a carbon number of 12 to 25 having a steroid skeleton can be interpreted as an organic group having a carbon number of 17 to 51 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) , (2-603) ~ (2-615) or (2-624). 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).

The specific diamine (1) is particularly preferably a diamine represented by the following formula [1a].

X represents a structure represented by the aforementioned formula [1]. The detailed and preferred combinations of X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , and n in formula [1a] are as described in the formula [1].

n1 represents an integer from 1 to 4. Among them, an integer of 1 is preferred.

Specifically, for example, Formulas [2-1] to [2-6], [2-9] to Formulas described in pages 15 to 19 of International Publication WO2013 / 125595 (published 2013.8.29) can be listed. [2-31] diamine. Further, according to International Publication WO2013 / 125595 of the formula [2-1] to the formula [2-3], and R ₂ in the formula [2-4] to Formula [2-6] is selected from the group consisting of R ₄ represents At least one of a group consisting of 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 and a fluorine-containing alkoxy group having 1 to 18 carbon atoms . In addition, A ₄ in Formula [2-13] represents a linear or branched alkyl group having 3 to 18 carbon atoms. In addition, R _{3 in} Formulas [2-4] to [2-6] represents at least one selected from the group consisting of -O-, -CH ₂ O-, -COO-, and -OCO-.

Among them, the preferred diamine exhibits a stable pretilt angle, can reduce the unevenness of liquid crystal alignment generated by the ODF method, and has a high effect of suppressing the decrease in voltage holding ratio even after being exposed to long-term light irradiation. Formula [2-1] to Formula [2-6], Formula [2-9] to Formula [2-13], or Formula [2-22] to Formula [2-31] described in International Publication WO2013 / 125595 Of the diamine.

The use ratio of the specific diamine (1) is preferably the following use ratio from the viewpoint described above. The specific polymer (A) is preferably 10 to 70 mole% with respect to the entire diamine component. More preferably, it is 15 to 70 mol%, and particularly good is 20 to 60 mol%. The specific polymer (B) is preferably 0 to 40 mole% with respect to the entire diamine component. More preferably, it is 0 to 30 mole%, and particularly preferably, it is 0 to 25 mole%. The specific polymer (C) is preferably 0 to 20 mole%. More preferably, it is 0 to 10 mole%.

In addition, the specific diamine (1) may be used singly or as a mixture for the characteristics of the solubility of the polyfluorene-imide polymer in a solvent, the liquid crystal alignment property when used as a liquid crystal alignment film, and the optical characteristics of a liquid crystal display element. Use more than 2 types.

<Specific diamine (2)>

The specific diamine (2) in the present invention is a diamine having a specific structure (2) represented by the following formula [2].

[ Chem . 14] -W ¹ -W ² -W ³ -W ⁴ [2]

W ¹ , W ² , W ³ and W ⁴ are as defined above, and each of them is preferably the following.

W ^{1 is} preferably -O-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON (CH ₃ )-or -N (CH ₃ ) CO-. From the viewpoint of ease of synthesis, -O-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, or -CON (CH ₃ )-is more preferable. Particularly preferred is -O-, -CONH- or -CH ₂ O-.

W ² represents at least one selected from the group consisting of a single bond, an alkylene group having 1 to 20 carbon atoms, a non-aromatic ring, and an aromatic ring.

The alkylene group having 1 to 20 carbon atoms may be linear or branched. Moreover, it may have an unsaturated bond. Among them, an alkylene group having 1 to 10 carbon atoms is preferable from the viewpoint of easy synthesis.

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, and a cyclodecane ring. , Cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, ring Nonadecane ring, icosene ring, eicosene ring, docosane ring, dicycloheptane ring, decahydronaphthalene ring, norbornene ring And adamantane ring. Among them, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring or an adamantane ring are more preferable.

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

W ^{2 has} a single bond, an alkylene group with a carbon number of 1 to 10, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring, an adamantane ring, and benzene. Rings, naphthalene rings, tetrahydronaphthalene rings, fluorene rings or anthracene rings are preferred. Among them, from the viewpoint of ease of synthesis and the easing of residual charge accumulated by a DC voltage caused by exposure to long-term light irradiation, a single bond, an alkylene group having 1 to 5 carbon atoms, and cyclohexyl are preferred. Alkanes or benzene rings.

W ^{3 is} preferably a single bond, -O-, -COO-, -OCO-, or -O (CH ₂ ) _m- (m represents an integer of 1 to 5). From the viewpoint of easy synthesis, a single bond, -O-, -OCO-, or -O (CH ₂ ) _m- (m represents an integer of 1 to 5) is more preferred.

W ⁴ represents a nitrogen-containing aromatic heterocyclic ring, and is selected from heterocyclic rings having at least one structure grouped by the following formula [a], formula [b], and formula [c].

(Z表示碳數1~5之烷基。)

(Z represents an alkyl group having 1 to 5 carbon atoms.)

More specific examples include a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, an isoquinoline ring, a carbazole ring, and a purine. Ring, thiadiazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzoimidazole ring, pyrene A phthaloline ring, a phenanthroline ring, an indole ring, a quinoxaline ring, a benzothiazole ring, a phenothiazine ring, an oxadiazole ring, an 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, a benzimidazole ring, or a benzimidazole ring is preferable. From the viewpoint that the residual charge accumulated in the DC voltage caused by exposure to long-term light irradiation is relaxed and becomes faster, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, or a pyrimidine ring is more preferable. Particularly preferred is an imidazole ring or a pyridine ring.

Further, it is preferable that W ³ in the formula [2] is bonded to a substituent not adjacent to the formula [a], the formula [b], and the formula [c] included in W ⁴ .

The combinations of W ¹ , W ² , W ³ , and W ⁴ in Formula [2a] are shown in Tables 1 to 31 below.

Among these, (a-43) ~ (a-49), (a-57) ~ (a-63), (a-218) ~ (a-224), (a-232) ~ (a- 238), (a-323) ~ (a-329), (a-337) ~ (a-343), (a-428) ~ (a-434), or (a-442) ~ (a-448) Of combination. From the viewpoint of easing the relaxation of the residual charge accumulated by the DC voltage after prolonged exposure to light, it is more preferably (a-44), (a-45), (a-58), or (a-59) Of combination.

The specific diamine (2) is particularly preferably a diamine represented by the following formula [2a].

式[2a]中，W表示前述式[2]表示之構造。又，式[2a]中之W¹、W²、W³、及W⁴之詳細及較佳的組合如前述式[2]所記載。p1表示1~4之整數。其中，由合成之容易度的觀點，較佳為1。

In the formula [2a], W represents a structure represented by the aforementioned formula [2]. The detailed and preferred combinations of W ¹ , W ² , W ³ , and W ⁴ in Formula [2a] are as described in Formula [2]. p1 represents an integer from 1 to 4. Among these, 1 is preferable from the viewpoint of the ease of synthesis.

The use ratio of the specific diamine (2) is preferably the following use ratio from the viewpoint described above. The specific polymer (A) is preferably 1 to 60 mole% with respect to the entire diamine component. More preferably, it is 5 to 50 mole%, and particularly preferably, it is 10 to 50 mole%. The specific polymer (B) is preferably 5 to 100 mole% with respect to the entire diamine component. More preferably, it is 10 to 95 mole%, and particularly preferably, it is 15 to 95 mole%. The specific polymer (C) is preferably 0 to 20 mole%. More preferably, it is 0 to 10 mole%, and particularly preferably, it is 0 mole%.

In addition, specific diamine (2) blended with a polyfluorene-imide-based polymer can be used alone or in combination as a solvent for liquid solubility, liquid crystal alignment when used as a liquid crystal alignment film, and optical characteristics of a liquid crystal display device. 2 More than one kind of use.

<Specific diamine (3)>

The specific diamine (3) in the present invention is a diamine having at least one kind of substituent selected from the group consisting of a carboxyl group (COOH group) and a hydroxyl group (OH group).

Specifically, it is preferable to use a diamine represented by the following formula [3a].

式[3a]中，Y表示下述式[3-1]或式[3-2]表示之構造。

In the formula [3a], Y represents a structure represented by the following formula [3-1] or [3-2].

m1 represents an integer from 1 to 4.

式[3-1]中，a表示0~4之整數。其中，從原料之取得性或合成之容易度的觀點，較佳為0或1之整數。

In the formula [3-1], a represents an integer of 0 to 4. Among them, an integer of 0 or 1 is preferred from the viewpoint of availability of raw materials or ease of synthesis.

In Formula [3-2], b represents an integer of 0 to 4. Among them, an integer of 0 or 1 is preferred from the viewpoint of availability of raw materials or ease of synthesis.

More specifically, for example, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4, 6-diaminoresorcinol, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, and the like.

Among them, 2,4-diaminophenol, 3,5 are preferred from the viewpoint of suppressing a decrease in the voltage retention rate after exposure to long-term light irradiation and the relaxation and quickening of the residual charge accumulated by the DC voltage. -Diaminophenol, 3,5-diaminobenzyl alcohol or 3,5-diaminobenzoic acid.

The proportion of the specific diamine (3) used is more than The following use ratios are preferred. It is preferably 0 to 20 mole% relative to the entire diamine component. More preferably, it is 0 to 10 mole%, and particularly preferably, it is 0 mole%. The specific polymer (B) is preferably 0 to 20 mole% with respect to the entire diamine component. More preferably, it is 0 to 10 mole%, and particularly preferably, it is 0 mole%. The specific polymer (C) is preferably 40 to 100 mole%. More preferably, it is 50 to 100 mol%, and particularly good is 60 to 100 mol%.

In addition, specific diamines (3) and polyfluorene-imide-based polymers can be used singly or in combination with a solvent such as a liquid crystal alignment film, a liquid crystal alignment film, and optical characteristics of a liquid crystal display device. More than one kind of use.

<Specific diamine (4)>

The specific diamine (4) in the present invention is a diamine having a specific structure (4) represented by the following formula [4].

More specifically, it is preferable to use a diamine represented by the following formula [4a-1].

(q1表示1~8之整數。)

(q1 represents an integer from 1 to 8.)

The use ratio of the specific diamine (4) is to improve the adhesion between the sealant and the liquid crystal alignment film, and to suppress the occurrence of display unevenness near the frame of the liquid crystal display element under high temperature and high humidity conditions, so the following is preferred. Use ratio. The specific polymer (A) is preferably 1 to 50 mole% with respect to the entire diamine component. More preferably, it is 5 to 40 mol%, and particularly good is 5 to 30 mol%. The specific polymer (B) is preferably 0 to 20 mole% with respect to the entire diamine component. More preferably, it is 0 to 10 mole%, and particularly preferably, it is 0 mole%. The specific polymer (C) is preferably 0 to 20 mole%. More preferably, it is 0 to 10 mole%, and particularly preferably, it is 0 mole%.

In addition, the specific diamine (4) blended with a polyfluorene-imide-based polymer has solubility in a solvent, liquid crystal alignment properties when used as a liquid crystal alignment film, and optical characteristics of a liquid crystal display element. One type or a mixture of two types can be used. More than one kind of use.

<Specific polymer (A) ~ Specific polymer (C)>

The specific polymer (A), the specific polymer (B), and the specific polymer (C) in the present invention each represent the polymer of the above-mentioned (A) component, (B) component, and (C) component. An imine precursor or polyimide (collectively referred to as a polyimide-based polymer). These are polyimide precursors and polyimide obtained by reacting a diamine component with a tetracarboxylic acid component.

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

(R¹表示4價有機基。R²表示2價有機基。A¹及A²各自獨立表示氫原子或碳數1~8之烷基。A³及A⁴各自獨立表示氫原子、碳數1~5之烷基或乙醯基。nA表示正之整數)。

(R ¹ represents a tetravalent organic group. R ² represents a divalent organic group. A ¹ and A ² each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. A ³ and A ⁴ each independently represent a hydrogen atom and a carbon number Alkyl or ethanoyl from 1 to 5. nA represents a positive integer).

Examples of the diamine component include diamines having two primary or secondary amine groups in the molecule. Examples of the tetracarboxylic acid component include tetracarboxylic acid, tetracarboxylic dianhydride, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, and tetracarboxylic acid dialkyl ester dihalide.

The polyfluorene-imide-based polymer can be obtained easily by using a tetracarboxylic dianhydride represented by the following formula [B] and a diamine represented by the following formula [C] as raw materials. The polyamidic acid constituted by the structural formula of the repeating unit represented by the formula [D], or the polyamidoimide that polyimides the polyamidic acid. Among these, polyimide-based polymers are preferably polyimide from the viewpoint of physical and chemical stability of the liquid crystal alignment film.

(R¹及R²係與前述式[A]所定義者相同意義。)

(R ¹ and R ² have the same meanings as defined by the aforementioned formula [A].)

(R¹、R²及nA係與式[A]所定義者相同意義。)

(R ¹ , R ² and nA have the same meanings as defined by formula [A].)

In addition, a general synthetic method may also be adopted. In the polymer of the formula [D] obtained above, an alkyl group having 1 to 8 carbon atoms of A ¹ and A ² represented by the formula [A] and a compound represented by the formula [A] may be introduced. A ³ and A ^{4 have} 1 to 5 carbon or alkyl groups.

The specific polymers (A), (B), and (C) may use other diamines in addition to the aforementioned specific diamines, as long as the effects of the present invention are not impaired.

Specific examples include diamines represented by the following formulas [D1] to [D6].

In addition, for example, other diamines described in pages 19 to 23 of International Publication WO2013 / 125595 (published 2013.8.29) and the formulas [DA1] to [DA12] described in pages 23 to 24 of the same publication can be cited. ] And diamines represented by formulas [DA15] to [DA20], and diamines represented by formulas [DA27] and [DA28] described on page 26 of the same publication.

Other diamines may be used for the diamine component of the specific polymer of any one of the specific polymers (A), (B), and (C), may be used for the diamine component of all these specific polymers, or The diamine component of any particular polymer.

In addition, other diamine-compounded polyimide-based polymers can be used alone or as a mixture of two or more characteristics such as the solubility in solvents, the liquid crystal alignment properties when used as a liquid crystal alignment film, and the optical characteristics of liquid crystal display elements. use.

As the tetracarboxylic acid component in the polymer of at least any one of the specific polymers (A), (B), and (C), a tetracarboxylic dianhydride (also referred to as a specific Tetracarboxylic acid component). It is more preferable to use a specific tetracarboxylic acid component for all the specific polymers.

式[5]中，Z表示選自由前述式[5a]~式[5k]所示構造所成之群之至少1種之結構。

In the formula [5], Z represents at least one structure selected from the group consisting of the structures shown in the formulas [5a] to [5k].

Z in the formula [5] is preferably from the viewpoints of ease of synthesis or ease of polymerization reactivity at the time of manufacturing a polymer, and is preferably represented by the formula [5a], [5c], [5d], or [5e] ], [5f], [5g], or [5k]. More preferred is the structure shown by Formula [5a], [5e], [5f], [5g], or [5k]. Particularly preferred is a structure shown by Formula [5e], [5f], [5g], or [5k].

The use ratio of the specific tetracarboxylic acid component is relative to all the tetracarboxylic acid components. It is preferably 1 mol% or more. More preferably, it is 5 mol% or more. Particularly preferred is 10 mol% or more. From the viewpoint of suppressing a decrease in voltage holding rate after exposure to long-term light irradiation, the most preferable is 10 to 90 mol%.

When a tetracarboxylic acid component having a structure represented by the above formula [5e], [5f], [5g], or [5k] is used, the use amount is set to the total of the tetracarboxylic acid components. At least 20 mol%, the desired effect can be obtained. It is preferably at least 30 mol%. The entire tetracarboxylic acid component may be a tetracarboxylic acid component having a structure represented by the formula [5e], [5f], [5g], or [5k].

In all the specific polymers, a tetracarboxylic acid component other than the specific tetracarboxylic acid component can be used as long as the effect of the present invention is not impaired.

Specifically, for example, International Publication WO2013 / 125595 (2013.8.29 publication) Other tetracarboxylic acid components described on pages 27 to 28. In addition, the specific tetracarboxylic acid component and other tetracarboxylic acid components are mixed with each other, and one type or a mixture of two or more types can be used.

The specific polymer (A) in the present invention is a polyimide precursor obtained by reacting a diamine component of a specific diamine (1) and a specific diamine (2) with a tetracarboxylic acid component, or a polyimide Ammonium precursors are polyimines which are imidized.

In this case, the proportion of the specific diamine (1) and the specific diamine (2) used (containing) in the entire diamine component is as follows. That is, the specific diamine (1) is preferably 10 to 70 mole% with respect to the entire diamine component. More preferably, it is 15 to 70 mol%, and particularly good is 20 to 60 mol%. The specific diamine (2) is preferably 1 to 60 mole% with respect to the entire diamine component. More preferably, it is 5 to 50 mole%, and particularly preferably, it is 10 to 50 mole%. It is also specific that the diamine (3) improves the adhesion between the sealant and the liquid crystal alignment film, and can suppress the occurrence of display unevenness near the frame of the liquid crystal display element under high temperature and high humidity conditions. Compared with the entire diamine component, It is preferably 0 to 20 mole%. More preferably, it is 0 to 10 mole%, and particularly preferably, it is 0 mole%, that is, a specific diamine (3) is not used.

The specific polymer (B) is a polyimide precursor obtained by reacting a diamine component containing a specific diamine (2) with a tetracarboxylic acid component, or a polymer obtained by subjecting the polyimide precursor to polyimide醯 imine. At this time, the use ratio (mole%) of the specific diamine (2) in the entire diamine component is as follows. That is, the specific diamine (2) is preferably 5 to 100 mole% with respect to the entire diamine component. More preferably, it is 10 to 95 mole%, and particularly preferably, it is 15 to 95 mole%. The specific diamine (1) is preferably 0 to 40 mole% relative to the entire diamine component. Better 0 to 30 mole%, particularly preferred is 0 to 25 mole%. However, the specific diamine (1) in the specific polymer (B) is used in proportion to the entire diamine component (mol%) when the specific diamine (1) in the specific polymer (A) is used (mol When the ear%) is 1.0, the ratio becomes a usage ratio (mole%) of less than 1.0. In this case, when the ratio is 0, that is, when the diamine component of the specific polymer (B) does not use the specific diamine (1), the decrease in the voltage holding ratio after long-term exposure to light is suppressed. From the viewpoint of easing the relaxation of the residual electric charge accumulated in the DC voltage, it is preferable. When the specific polymer (B) uses the specific diamine (1), the ratio is preferably 0.01 to 0.9. It is more preferably 0.01 to 0.8, and particularly preferably 0.05 to 0.7.

The specific diamine (3) is preferably 0 to 20 mole% with respect to the entire diamine component. More preferably, it is 0 to 10 mol%. From the viewpoint of improving the adhesion between the sealant and the liquid crystal alignment film, under the conditions of high temperature and high humidity, it can suppress the occurrence of display unevenness near the frame of the liquid crystal display element. Mol%, that is, the specific diamine (3) is not used as the diamine component of the specific polymer (B).

The specific polymer (C) is a polyimide precursor obtained by reacting a diamine component containing a specific diamine (3) and a tetracarboxylic acid component, or a polymer obtained by subjecting the polyimide precursor to polyimide醯 imine. In this case, the specific diamine (3) used in the entire diamine component (mole%) is as follows. That is, the specific diamine (3) is preferably 40 to 100 mole% with respect to the entire diamine component. More preferably, it is 50 to 100 mol%, and particularly good is 60 to 100 mol%. The specific diamine (1) is preferably 0 to 20 mole% with respect to the entire diamine component. More preferably, it is 0 to 10 mole%. But the specific diamine (1) in the specific polymer (C) The usage ratio (mol%) with respect to the entire diamine component is when the usage ratio (mol%) of the specific diamine (1) in the specific polymer (A) is 1.0. Ratio (mol%). At this time, when the ratio is 0, that is, when the diamine component of the specific polymer (C) does not use the specific diamine (1), the reduction in the voltage holding ratio after long-term exposure to light is suppressed. From the viewpoint of easing the relaxation of the residual electric charge accumulated in the DC voltage, it is preferable. When the specific polymer (C) uses the specific diamine (1), the ratio is preferably 0.01 to 0.4. It is more preferably 0.01 to 0.3, and particularly preferably 0.01 to 0.2.

The specific diamine (3) is preferably 0 to 20 mole% with respect to the entire diamine component. More preferably, it is 0 to 10 mol%. From the viewpoint of suppressing a decrease in the voltage retention rate after long-term exposure to light and the relaxation and acceleration of the residual charge accumulated by the DC voltage, it is more preferably 0 mol%. That is, the specific diamine (3) is not used for the diamine component of the specific polymer (C).

In the present invention, the diamine component in the polymer of at least one of the specific polymers (A), (B), and (C) contains the specific diamine (4). The diamine at this time is preferably a diamine represented by the aforementioned formula [4a-1]. The specific diamine (4) is preferably used for specific polymers from the viewpoint of improving the adhesion between the sealant and the liquid crystal alignment film, and suppressing the occurrence of display unevenness near the frame of the liquid crystal display element under high temperature and high humidity conditions. (A). At this time, the use ratio of the specific diamine (4) in the specific polymer (A) is preferably 1 to 50 mole% relative to the entire diamine component. More preferably, it is 5 to 40 mole%, and particularly preferably, it is 5 to 30 mole%. When the specific polymer (B) is used, it is preferably from 0 to 20 mole%, more preferably from 0 to 10 mole% relative to the entire diamine component. In addition, make When used for a specific polymer (C), 0-20 mole% is preferable with respect to the whole diamine component, More preferably, it is 0-10 mole%.

The specific polymers (A), (B), and (C) of the present invention are generally obtained by reacting a diamine component and a tetracarboxylic acid component. In general, for example, a diamine component formed from at least one type of tetracarboxylic acid component selected from the group consisting of tetracarboxylic dianhydride and its derivative of tetracarboxylic acid and one or more types of diamines can be cited. A method of reacting to obtain polyamic acid. Specifically, a method of polycondensing a tetracarboxylic dianhydride and a diamine of class 1 or 2 to obtain a polyphosphonic acid can be used, and a dehydration polycondensation reaction of a tetracarboxylic acid and a diamine of class 1 or 2 can be used. A method of obtaining a polyamic acid, or a method of reacting a tetracarboxylic acid dihalide with a first- or second-order diamine to obtain a polyamino acid.

In order to obtain a polyalkylamino acid alkyl ester, the following method can be used: a method of polycondensing a tetracarboxylic acid having a dialkyl esterified carboxylic acid group and a diamine of a first or second order, and a carboxylic acid group; A method in which a dialkyl esterified tetracarboxylic acid dihalide is reacted with a first or second order diamine, or a method in which a carboxyl group of a polyamic acid is converted into an ester.

In order to obtain polyimide, the following method can be used, and the method of subjecting the said polyamidic acid or a polyalkylamic acid alkyl ester to ring closure can be used as a polyimide.

The reaction of the diamine component and the tetracarboxylic acid component is usually carried out in an organic solvent. The organic solvent used at this time is not particularly limited as long as it can dissolve the generated polyfluorene imide precursor. Specific examples of the organic solvent used in the following reaction can be listed, but are not limited to these examples.

Examples include N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone. Ketones, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylmethylene, 1,3-dimethyl-imidazolinone, and the like. 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 can be used. [D-1] to a solvent represented by the formula [D-3].

(D¹表示碳數1~3之烷基。D²表示碳數1~3之烷基。D³表示碳數1~4之烷基)。

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

These can be used alone or in combination. Moreover, even if it is a solvent which cannot dissolve a polyfluorene imide precursor, as long as the produced | generated polyfluorene imide precursor does not precipitate, it can mix with the said organic solvent and use. In addition, the water in the organic solvent will hinder the polymerization reaction and even cause the hydrolysis of the resulting polyimide precursor. Therefore, it is preferable to use a dehydration method for the organic solvent.

When the diamine component and the tetracarboxylic acid component are reacted in an organic solvent, for example, a solution obtained by dispersing or dissolving the diamine component in an organic solvent is stirred, and the tetracarboxylic acid component is added or dispersed in this state. Or a method of dissolving in an organic solvent and then adding it. Conversely, a method of adding a diamine component to a solution in which a tetracarboxylic acid component is dispersed and dissolved in an organic solvent, a method of adding a diamine component and a tetracarboxylic acid component alternately Wait, can Use any of these methods. In the case where the diamine component and the tetracarboxylic acid component are respectively reacted by using a plurality of types, the reaction may be performed in a state of being mixed in advance, or the reactions may be sequentially performed separately, or the low-molecular weight bodies of the respective reactions may be mixed. A polymer may be used.

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, although the reaction can be carried out at an arbitrary concentration, when the concentration is too low, it is not easy to obtain a polymer with a high molecular weight, and when the concentration is too high, it is difficult to perform uniform stirring because the viscosity of the reaction solution is too high. Therefore, it is preferably 1 to 50%, and more preferably 5 to 30%. The polymerization reaction is performed at a high concentration in the initial stage, and then, an organic solvent may be added.

In the polymerization reaction of the polyimide precursor, the ratio of the total mole number of the diamine component to the total mole number of the tetracarboxylic acid component is preferably 0.8 to 1.2. As with the usual polymerization reaction, the closer this mole ratio is to 1.0, the larger the molecular weight of the polyfluorene imide precursor produced.

Polyimide is a polyimide obtained by subjecting the aforementioned polyimide precursor to ring closure. The ring closure rate (also known as the amidation rate) of the amido group is not necessarily 100%. Any adjustment. Among them, in the present invention, all the specific polymers are preferably polyimide in which the polyimide precursor is fluorinated.

The ratio of amidine imidation at this time is preferably as follows. That is, the specific polymer (A) is preferably 50 to 90%. More preferably, it is 55 to 90%, and particularly good is 60 to 90%. The specific polymer (B) is preferably 50 to 95%. It is more preferably 55 to 95%, and particularly preferably 60 to 95%. The specific polymer (C) is preferably 50 to 90%. More preferably, it is 60 to 90%, and particularly good is 60 to 80%.

Examples of the method for fluorinating a polyfluorene imide precursor include, for example, heating the fluorene with a polyfluorene precursor solution in a heated state, or adding a catalyst to the polyfluorene imide precursor solution. The catalyst is the method of imidization. The temperature at which the polyfluorene imine precursor is thermally fluorinated in the solution is 100 ° C to 400 ° C, preferably 120 ° C to 250 ° C, and the water generated by the fluorene imidization reaction is discharged. Outside the reaction system, it is preferable to perform the reaction.

Catalyst for polyimide precursors: imidization is added to the solution of the polyimide precursors. The basic catalyst and acid anhydride are added, and the mixture is stirred at -20 to 250 ° C, preferably 0 to 180 ° C. Come on. The amount of 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. Ear times.

Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferred because it has appropriate basicity when the reaction is performed. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, when acetic anhydride is used, purification is facilitated after the completion of the reaction, which is preferable. The rate of catalyst imidization can be controlled by adjusting the amount of catalyst, reaction temperature and reaction time.

In the case where the polyfluorene imide precursor or the polyfluorene imide reaction solution is used to recover the generated polyfluorene imide precursor or the polyfluorene imide, the reaction solution may be put into a solvent to cause precipitation. Examples of the solvent used for the precipitation include methanol, ethanol, isopropanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. Put the precipitated polymer into the solvent and recover it by filtration. Dry under pressure or reduced pressure at room temperature or under heating. In addition, when the polymer after the precipitation recovery is re-dissolved in an organic solvent, and the operation of the re-precipitation recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the solvent at this time include alcohols, ketones, and hydrocarbons. When three or more types of solvents selected in this manner are used, purification efficiency can be further improved, which is preferable.

The molecular weight of the polyimide-based polymer is determined by GPC (GelPermeation Chromatography) method, taking into account the strength of the liquid crystal alignment film obtained, the workability during the formation of the liquid crystal alignment film, and the coating performance. The molecular weight is preferably 5,000 to 1,000,000. Among them, 10,000 to 150,000 is preferred.

As mentioned above, all the specific polymers in the present invention show stable vertical stability after being exposed to light for a long period of time at high temperature and long-term exposure to light. The polyfluorene imide obtained by subjecting the aforementioned polyfluorene imide precursor to a catalyst hydrazone is preferred. The hydrazone imidization ratio at this time is preferably in the above range.

<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 forms a coating for a liquid crystal alignment film containing specific polymers (A), (B), (C) and a solvent. Cloth solution.

The use (contain) ratio of the specific polymers (A), (B), and (C) in the liquid crystal alignment treatment agent is preferably as follows. That is, with respect to 100 parts of the specific polymer (A), the specific polymer (B) is preferably 30 to 300 parts, and the specific polymer (C) is preferably 60 to 500 parts. More preferably, the specific polymer (B) is 50 to 250 Parts, the specific polymer (C) is 100 to 350 parts, particularly preferably the specific polymer (B) is 50 to 200 parts, and the specific polymer (C) is 100 to 300 parts.

All of the polymer components in the liquid crystal alignment treatment agent may be all specific polymers, or polymers other than these may be mixed. At this time, the content of the other polymers is preferably 0.5 to 15 parts with respect to 100 parts of the entire specific polymer. More preferably, it is 1 to 10 servings. Examples of other polymers include cellulose-based polymers, acrylic polymers, methacrylic polymers, polystyrene, polyamines, and polysiloxanes.

The content of the solvent in the liquid crystal alignment treatment agent is preferably 70 to 99.9% from the viewpoint of forming a uniform liquid crystal alignment film by coating. This content can be appropriately changed depending on the film thickness of the liquid crystal alignment film for the purpose.

The solvent used for the liquid crystal alignment treatment agent is not particularly limited as long as it is a solvent (also referred to as a good solvent) that dissolves all the specific polymers. Specific examples of good solvents are listed below, but they are not limited to these.

For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylsulfine, γ-butane Lactone, 1,3-dimethyl-imidazolinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, and the like.

Among these, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone is preferably used.

In addition, when the solubility of a specific polymer in a solvent is high, it is preferable to use a solvent represented by the aforementioned formulas [D-1] to [D-3].

The good solvent in the liquid crystal alignment treatment agent is preferably 10 to 100% of the total solvent contained in the liquid crystal alignment treatment agent. More preferably, it is 20 to 90%. Particularly good is 30 ~ 80%.

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

Specifically, for example, the weak solvents described in pages 35 to 37 of International Publication WO2013 / 125595 (published 2013.8.29) can be cited.

Among them, 1-hexanol, cyclohexanol, 1,2-ethylene glycol, 1,2-propylene glycol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, or the aforementioned Solvents represented by the formulas [D-1] to [D-3] are preferred.

These weak solvents are preferably 1 to 70% of the total solvent contained in the liquid crystal alignment treatment agent. More preferably, it is 1 to 60%. Especially good is 5 ~ 60%.

In the liquid crystal alignment treatment agent, as long as the effect of the present invention is not impaired, it is preferable to introduce a crosslinkable compound selected from the group consisting of an epoxy group, an isocyanate group, an oxetanyl group, and a cyclic carbonate group, It is selected from the group consisting of a crosslinkable compound consisting of a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group, or a crosslinkable compound having a polymerizable unsaturated bond group (collectively referred to as a specific crosslinkable compound). In this case, these groups must have two or more in the compound.

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include, for example, International Publication WO2013 / 125595 (Published 2013.8.29) The crosslinkable compound having an epoxy group or an isocyanate group as described on pages 37 to 38.

Specific examples of the crosslinkable compound having an oxetanyl group include crosslinkability represented by formulas [4a] to [4k] described in International Publication WO2011 / 132751, pages 58 to 59. Compound.

Specific examples of the crosslinkable compound having a cyclic carbonate group include cross-sections represented by formulas [5-1] to [5-42] described in International Publication WO2012 / 014898, pages 76 to 82.联 性 bonding compound.

A crosslinkable compound having at least one type of group selected from the group consisting of a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group, and specifically, for example, International Publication 2013/125595 (2013.8.29) The melamine derivatives or benzoguanamine derivatives described in pages 39 to 40, and the formulas [6-1] to formula [6-1] described in pages 62 to 66 of International Publication WO2011 / 132751 (published on 2011.10.27) 6-48].

Specific examples of the crosslinkable compound having a polymerizable unsaturated bond include, for example, the crosslinkability of a polymerizable unsaturated bond described in pages 40 to 41 of International Publication WO2013 / 125595 (published on 2013.8.29). Compound.

The content of the specific crosslinkable compound in the liquid crystal alignment treatment agent is preferably 0.1 to 100 parts with respect to 100 parts of the entire polymer component. In order to perform the crosslinking reaction and exhibit the effect of the purpose, it is more preferably 0.1 to 50 parts. Particularly good is 1 to 30 servings.

In the liquid crystal alignment treatment agent of the present invention, in order to promote the charge transfer in the liquid crystal alignment film and the charge elimination of the element, an international company can be added. The nitrogen-containing heterocyclic amine represented by the formulas [M1] to [M156] described in the publications WO2011 / 132751 (published on 2011.10.27) on pages 69 to 73. This amine can be directly added to the liquid crystal alignment treatment agent, but it is better to add it after forming a solution with a concentration of 0.1 to 10%, preferably 1 to 7% with an appropriate solvent. This solvent is not particularly limited as long as it is an organic solvent that dissolves a specific polymer.

As long as the liquid crystal alignment treatment agent does not impair the effect of the present invention, a compound that improves the uniformity of the film thickness or the surface smoothness of the liquid crystal alignment film when the liquid crystal alignment treatment agent is applied can be used. In addition, a compound or the like that improves the adhesion between the liquid crystal alignment film and the substrate may be used.

Examples of the compound that improves the uniformity or surface smoothness of the liquid crystal alignment film include, for example, a fluorine-based surfactant, a polysiloxane-based surfactant, and an anionic surfactant. Specifically, for example, the surfactants described in pages 42 to 43 of International Publication WO2013 / 125595 (publication 2013.8.29) can be cited.

The use amount of these surfactants is preferably 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the entire polymer component contained in the liquid crystal alignment treatment agent.

Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include, for example, a compound containing a functional silane or a compound containing an epoxy group. Specific examples include compounds described in pages 43 to 44 of International Publication WO2013 / 125595 (published on 2013.8.29).

The use ratio of the compound adhered to the substrate is 100% of the total polymer content of the liquid crystal alignment treatment agent. Parts, preferably 0.1 to 30 parts. More preferably, it is 1 to 20 servings. When it is less than 0.1 part, the adhesion improvement effect cannot be expected. When it exceeds 30 parts, the storage stability of the liquid crystal alignment treatment agent may be deteriorated.

In addition to the compounds other than those mentioned above, the liquid crystal alignment treatment agent may add a dielectric body or a conductive substance for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film within a range that does not impair the effects of the present invention.

<Liquid crystal alignment film. Liquid crystal display element>

The liquid crystal alignment treatment agent of the present invention is coated on a substrate, and after sintering, it is subjected to alignment treatment by rubbing treatment or light irradiation, etc., and can be used as a liquid crystal alignment film. Moreover, in the case of vertical alignment applications, etc., it can also be used as a liquid crystal alignment film without alignment treatment. The substrate used at this time is not particularly limited as long as it is a substrate with high transparency. 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 manufacturing process, it is preferable to use a substrate formed with an ITO (Indium Tin Oxide) electrode for liquid crystal driving. Moreover, in a reflective liquid crystal display element, if it is only a single-sided substrate, an opaque substrate such as a silicon wafer may be used. In this case, an electrode that reflects light may also be used.

The application method of the liquid crystal alignment treatment agent is not particularly limited, and industrially, it is generally screen printing, lithography, flexo printing, inkjet method, and the like. Other coating methods include, for example, a dipping method, a roll coating method, a slit coating method, a spin coater method, and a spray method. These methods can be used according to the purpose.

After the liquid crystal alignment treatment agent is coated on the substrate, Heating means such as circulating oven, IR (infrared) oven, etc., combined with the solvent used in the liquid crystal alignment treatment agent, evaporate the solvent at a temperature of 30 to 300 ° C, preferably 30 to 250 ° C, and can be used as a liquid crystal alignment film. If the thickness of the sintered liquid crystal alignment film is too thick, it is disadvantageous from the viewpoint of power consumption of the liquid crystal display element. If it is too thin, the reliability of the liquid crystal display element may be reduced. Therefore, it is preferably 5 to 300 nm. It is preferably 10 to 100 nm. When the liquid crystal is aligned horizontally or obliquely, the sintered liquid crystal alignment film can be subjected to rubbing or polarized ultraviolet irradiation.

The liquid crystal display element of the present invention can be prepared as a liquid crystal display element by a known method after a substrate with a liquid crystal alignment film is prepared from the liquid crystal alignment treatment agent of the present invention by the method described above.

A method for manufacturing a liquid crystal cell includes, for example, preparing a pair of substrates having a liquid crystal alignment film, and dispersing a spacer on the liquid crystal alignment film of a single-sided substrate, so that the liquid crystal alignment film surface becomes the inner side, so as to fit the substrate on the other side. A method of sealing after injecting the liquid crystal, or a method of dropping the liquid crystal onto the liquid crystal alignment film surface on which the spacers are dispersed, and then bonding the substrate to the sealing method are examples.

The liquid crystal alignment treatment agent of the present invention is also preferably used in a liquid crystal display element, that is, formed by having a liquid crystal layer between a pair of substrates provided with electrodes, and disposed between the pair of substrates. A liquid crystal composition of a polymerizable compound polymerized by at least one of an active energy ray and heat, a voltage is applied between the electrodes, and the polymerizable compound is polymerized by at least one of irradiation and heating of the active energy ray. The obtained liquid crystal display element. Among them, ultraviolet rays are preferred as the active energy rays. Of UV The wavelength is 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Moreover, ultraviolet rays and heating may be performed simultaneously.

The above-mentioned liquid crystal display element controls a pretilt angle of liquid crystal molecules by a PSA (Polymer Sustained Alignment) mode. In the PSA mode, a small amount of a photopolymerizable compound, such as a photopolymerizable monomer, is mixed in a liquid crystal material. After the liquid crystal cell is combined, a specific voltage is applied to the liquid crystal layer, and the photopolymerizable compound is irradiated with ultraviolet rays or the like. The pretilt angle of the liquid crystal molecules is controlled by the generated polymer. Because the alignment state of the liquid crystal molecules when the polymer is generated, there will also be memory after the voltage is removed, so the pretilt angle of the liquid crystal molecules can be adjusted by controlling the electric field formed in the liquid crystal layer. In the PSA mode, since rubbing treatment is unnecessary, it is also suitable for forming a liquid crystal layer of a vertical alignment type in which a pretilt angle is difficult to control by rubbing treatment. That is, in the liquid crystal display element of the present invention, after a substrate with a liquid crystal alignment film is prepared from a liquid crystal alignment treatment agent through the method described above, a liquid crystal cell is produced, and at least one of ultraviolet radiation and heating is used to make the polymerizable polymer. Compounds polymerize and control the alignment of liquid crystal molecules.

An example of a method for manufacturing a liquid crystal cell in the PSA mode is shown below. That is, the liquid crystal when the liquid crystal cell is produced by the above-mentioned production method is mixed with a polymerizable compound polymerized by heat or ultraviolet irradiation. Examples of the polymerizable compound include compounds having one or more polymerizable unsaturated groups such as an acrylate group or a methacrylate group in the molecule. At this time, the polymerizable compound is preferably 0.01 to 10 parts, more preferably 0.1 to 5 parts by mass based on 100 parts of the liquid crystal component. Polymerizable compound When it is 0.01 parts, the polymerizable compound does not polymerize, and it becomes impossible to control the alignment of the liquid crystal. When it exceeds 10 parts, the amount of unreacted polymerizable compounds increases, which reduces the afterimage characteristics of the liquid crystal display element. After the liquid crystal cell is produced, an alternating current or a direct current voltage is applied to the liquid crystal cell, and at the same time, heat or radiation is applied to polymerize the polymerizable compound. Thereby, the alignment of the liquid crystal molecules can be controlled.

In addition, the liquid crystal alignment treatment agent of the present invention can also be used in a liquid crystal display element, that is, an SC-PVA mode. The liquid crystal display element is formed by having a liquid crystal layer between a pair of substrates having electrodes. A liquid crystal display element containing a polymerizable group polymerized by at least one of active energy rays and heat is disposed between the substrates, and a liquid crystal display element is produced by applying a voltage between the electrodes. Among them, ultraviolet rays are preferred as the active energy rays. The wavelength of the ultraviolet rays is 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, and more preferably 60 to 80 ° C. Moreover, ultraviolet rays and heating may be performed simultaneously.

In order to obtain a liquid crystal alignment film containing a polymerizable group polymerized by at least one of active energy rays and heat, for example, a method for adding a compound containing the polymerizable group to a liquid crystal alignment treatment agent, or using Method for polymer component containing polymerizable group.

When an example of producing a liquid crystal cell in the SC-PVA mode is listed, it is as follows, for example. That is, a liquid crystal cell is manufactured according to the above-mentioned manufacturing method. Then, an AC or DC voltage is applied to the liquid crystal cell, and the orientation of the liquid crystal molecules can be controlled by heat or ultraviolet rays.

As described above, by using the liquid crystal alignment treatment agent of the present invention, it is possible to provide an improved adhesiveness between the sealant and the liquid crystal alignment film, and to suppress the occurrence of display unevenness near the frame of the liquid crystal display element under the conditions of high temperature and high humidity. Liquid crystal alignment film. In addition, the present invention provides a liquid crystal alignment film capable of suppressing a decrease in voltage retention even after prolonged exposure to light and reducing the residual charge accumulated by a DC voltage. Therefore, the liquid crystal display element produced using the liquid crystal alignment treatment agent of the present invention has excellent reliability, and can be suitably used for large-sized liquid crystal televisions, small and medium-sized car navigation systems, and smart phones. In particular, the liquid crystal alignment treatment agent of the present invention can be used for a liquid crystal alignment film using a liquid crystal display element of VA mode, PSA mode, and SC-PVA mode.

[Example]

The following examples illustrate the present invention in more detail, but the present invention is not limited to these. The abbreviations of the compounds used below are as shown below.

(Specific diamine (1))

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

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

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

(Specific diamine (2))

(Specific diamine (3))

C1: 3,5-diaminobenzoic acid

(Specific diamine (4))

(Other diamines)

E1: p-phenylenediamine, E2: m-phenylenediamine

E3: 1,3-diamino-4-octadecyloxybenzene

(Specific tetracarboxylic dianhydride)

F1: 1,2,3,4-cyclobutane tetracarboxylic dianhydride

F2: Bicyclic [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride

(Crosslinkable compound)

(Solvent)

NMP: N-methyl-2-pyrrolidone, NEP: N-ethyl-2-pyrrolidone, γ-BL: γ-butyrolactone, BCS: ethylene glycol monobutyl ether, PB: propylene glycol monobutyl ether, DME: Dipropylene glycol dimethyl ether, DPM: Dipropylene glycol monomethyl ether

"Molecular weight measurement of polyimide polymers"

A normal temperature gel permeation chromatography (GPC) device (GPC-101, manufactured by Showa Denko Corporation) and a column (KD-803, KD-805, manufactured by Shodex) were used for measurement as described below.

Column temperature: 50 ℃

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

Flow rate: 1.0ml / min

Standard samples for the preparation of calibration curves: 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) (polymer Experimental company).

"Measurement of the polyimide-based imidization rate of polyfluorene-based polymers"

5(草野科學公司製))中，添加重氫化二甲基亞碸(DMSO-d6，0.05%TMS(四甲基矽烷)混合品)(0.53ml)，施以超音波使其完全溶解。將此溶液使用NMR測定機(JNW-ECA500、日本電子數據公司製)測定於500MHz之質子NMR。醯亞胺化率係以來自醯亞胺化前後未變化之構造之質子作為基準質子來決定，其係使用此質子之波峰積算值與出現於9.5~10.0ppm附近之來自醯胺酸之NH基之質子波峰積算值，依下式而求得。 Put 20 mg of polyfluorene imine powder into an NMR (nuclear magnetic resonance) sample tube (NMR standard sampling tube,

5 (manufactured by Kusano Science Co., Ltd.), deuterated dimethyl sulfene (DMSO-d6, 0.05% TMS (tetramethylsilane) mixed product) (0.53 ml) was added, and ultrasonic waves were applied to completely dissolve. This solution was measured for a proton NMR at 500 MHz using an NMR measuring machine (JNW-ECA500, manufactured by Japan Electronics Data Corporation). The hydrazone imidization rate is determined by using protons from structures that have not changed before and after hydrazone imidization as the reference protons. It uses the integrated peak value of this proton and the NH group from hydrazone that appears near 9.5 to 10.0 ppm. The proton peak integrated value can be obtained according to the following formula.

醯 imidization rate (%) = (1-α.x / y) × 100 (x is the integrated value of the proton peak derived from the NH group of fluoramic acid, y is the integrated value of the peak value of the reference proton, and α is polyamine In the case of an acid (amidation ratio of 0%), the ratio of the number of reference protons to the number of NH matrix protons of one amidine).

"Synthesis of Polyimide Polymers" <Synthesis example 1>

F2 (2.04g, 8.15mmol), A1 (2.52g, 6.62mmol), B1 (1.20g, 4.95mmol), D1 (0.55g, 1.66mmol) and E1 (0.36g, 3.33mmol) in NMP (16.5g ) And mixed at 80 ° C for 5 hours, then F1 (1.60 g, 8.16 mmol) and NMP (8.26 g) were added, and the mixture was reacted at 40 ° C for 6 hours to obtain a concentration (meaning a resin solid content concentration. The same applies hereinafter). ) Is a 25% polyamic acid solution.

To the obtained polyamidic acid solution (30.0 g), NMP was added to dilute to 6%, and then acetic anhydride (4.50 g) and pyridine (3.30 g) were added as the phosphonium imidization catalyst, and reacted at 80 ° C. 4 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (1). This polyfluorene imine has an imidization ratio of 80%, a number average molecular weight (Mn) of 16,200, and a weight average molecular weight (Mw) of 45,300.

<Synthesis example 2>

F2 (2.04g, 8.15mmol), A3 (2.15g, 4.97mmol), B1 (1.20g, 4.95mmol), D1 (1.09g, 3.30mmol) and E1 (0.36g, 3.33mmol) in NMP (16.9g ) And mixed at 80 ° C for 5 hours, F1 (1.60 g, 8.16 mmol) and NMP (8.44 g) were added and reacted at 40 ° C for 6 hours to obtain a 25% polyamine solution.

To the obtained polyamidic acid solution (30.0 g), NMP was added to dilute to 6%, and then acetic anhydride (4.50 g) and pyridine as the phosphonium imidization catalyst were added. (3.30 g), and reacted at 80 ° C for 3.5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyfluoreneimide powder (2). The polyimide has a hydrazone imidization rate of 75%, Mn of 15,800, and Mw of 43,700.

<Synthesis example 3>

F2 (0.83g, 3.32mmol), A2 (2.32g, 5.88mmol), B1 (1.22g, 5.04mmol), D1 (0.83g, 2.51mmol) and E1 (0.36g, 3.33mmol) in NEP (16.3g ), Mixed and reacted at 80 ° C for 5 hours, then added F1 (2.60g, 13.3mmol) and NEP (8.16g), and reacted at 40 ° C for 6 hours to obtain a 25% polyamine solution.

To the obtained polyamidic acid solution (30.0 g), NEP was added to dilute to 6 mass%, and then acetic anhydride (4.50 g) and pyridine (3.30 g) were added as the imidization catalyst, and reacted at 80 ° C for 3 hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (3). The polyimide has an imidization ratio of 70%, Mn of 15,900, and Mw of 43,800.

<Synthesis example 4>

F2 (2.04g, 8.15mmol), A4 (1.60g, 3.25mmol), B1 (1.40g, 5.78mmol), D1 (1.09g, 3.30mmol) and E1 (0.36g, 3.33mmol) was mixed in NMP (16.2g), and after reacting at 80 ° C for 5 hours, F1 (1.60g, 8.16mmol) and NMP (8.12g) were added and reacted at 40 ° C for 6 hours. A 25% polyamic acid solution was obtained.

After adding NMP to the obtained polyamidic acid solution (30.0g) and diluting it to 6%, acetic anhydride (4.50g) and pyridine (3.30g) were added as the imidization catalyst, and reacted at 80 ° C for 2.5 hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyfluoreneimide powder (4). The polyimide has an imidization ratio of 65%, Mn of 14,500, and Mw of 40,900.

<Synthesis example 5>

F3 (3.50g, 15.6mmol), A2 (2.50g, 6.34mmol), B1 (1.15g, 4.75mmol), D1 (1.05g, 3.18mmol) and E1 (0.17g, 1.57mmol) in NEP (25.1g ) And mixed at 40 ° C. for 8 hours to obtain a 25% polyamine solution.

After adding NEP to the obtained polyphosphonic acid solution (30.0 g) and diluting it to 6 mass%, acetic anhydride (4.50 g) and pyridine (3.30 g) were added 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 filtered off. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimide powder (5). The polyimide has a fluorene imidation rate of 70%, Mn of 18,300, and Mw of 49,400.

<Synthesis example 6>

F4 (2.45g, 8.16mmol), A2 (1.96g, 4.97mmol), B1 (1.40g, 5.78mmol), D1 (0.82g, 2.48mmol) and E1 (0.36g, 3.33mmol) in NMP (17.2g ), Mixed and reacted at 80 ° C for 5 hours, then added F1 (1.60g, 8.16mmol) and NMP (8.58g), and reacted at 40 ° C for 6 hours to obtain a 25% polyamic acid solution.

NMP was added to the obtained polyamic acid solution (30.0 g) to dilute to 6%, and then acetic anhydride (4.50 g) and pyridine (3.30 g) were added as the imidization catalyst, and reacted at 80 ° C for 3.5. hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (6). The polyimide has a hydrazone imidization rate of 75%, Mn of 15,600, and Mw of 43,200.

<Synthesis example 7>

F2 (0.83g, 3.32mmol), A1 (2.56g, 6.73mmol), B1 (1.22g, 5.04mmol), D1 (0.55g, 1.66mmol) and E2 (0.36g, 3.33mmol) in NMP (16.3g ) And mixed at 80 ° C. for 5 hours, F1 (2.60 g, 13.3 mmol) and NMP (8.12 g) were added and reacted at 40 ° C. for 6 hours to obtain a 25% polyamine solution.

NMP was added to the obtained polyamic acid solution (30.0g) and diluted to After 6%, acetic anhydride (4.50 g) and pyridine (3.30 g) were added as sulfonium imidization catalysts, and reacted at 80 ° C for 3.5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyfluoreneimide powder (7). The polyimide has a hydrazone imidization ratio of 75%, Mn of 17,000, and Mw of 44,200.

<Synthesis example 8>

F2 (3.06g, 12.2mmol), A1 (2.52g, 6.62mmol), B2 (0.64g, 2.47mmol), D1 (0.55g, 1.66mmol) and E2 (0.63g, 5.83mmol) in NEP (16.4g ) And mixed at 80 ° C. for 5 hours, then F1 (0.80 g, 4.08 mmol) and NEP (8.19 g) were added and reacted at 40 ° C. for 6 hours to obtain a 25% polyamine solution.

To the obtained polyamidic acid solution (30.0 g), NEP was added to dilute to 6 mass%, and then acetic anhydride (4.50 g) and pyridine (3.30 g) were added as the phosphonium imidization catalyst, and reacted at 80 ° C for 3.5. hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyfluoreneimide powder (8). The polyimide has a hydrazone imidization rate of 75%, Mn of 16,300, and Mw of 44,300.

<Synthesis example 9>

F2 (2.17g, 8.67mmol), A1 (2.67g, 7.02mmol), B1 (1.28g, 5.28mmol) and E1 (0.57g, 5.27mmol) were mixed in NMP (16.8g). After reacting at 80 ° C for 5 hours, F1 (1.70g, 8.67mmol) and NMP (8.39g) were added. , And reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a concentration of 25%.

After adding NMP to the obtained polyamidic acid solution (30.0g) and diluting it to 6%, acetic anhydride (4.50g) and pyridine (3.30g) were added as the imidization catalyst, and reacted at 80 ° C for 4 hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (9). The polyimide has an imidization ratio of 80%, Mn of 17,500, and Mw of 47,200.

<Synthesis example 10>

F2 (2.04g, 8.15mmol), B1 (1.20g, 4.95mmol), E1 (0.36g, 3.33mmol) and E3 (1.87g, 4.97mmol) were mixed in NMP (16.3g), and reacted at 80 ° C After 5 hours, F1 (1.60 g, 8.16 mmol) and NMP (8.16 g) were added, and the mixture was reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a concentration of 25%.

NMP was added to the obtained polyamic acid solution (30.0 g) to dilute to 6%, and then acetic anhydride (4.50 g) and pyridine (3.30 g) were added as the imidization catalyst, and reacted at 80 ° C for 3.5. hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyfluoreneimide powder (10). The polyimide has an imidization ratio of 75%, Mn of 15,800, and Mw of 42,500.

<Synthesis example 11>

F2 (0.89g, 3.56mmol), A1 (1.38g, 3.63mmol) and B1 (3.50g, 14.4mmol) were mixed in NMP (17.2g), and after reacting at 80 ° C for 5 hours, F1 (2.80g) was added , 14.3 mmol) and NMP (8.57 g), and reacted at 40 ° C. for 6 hours to obtain a 25% polyamine solution.

To the obtained polyamidic acid solution (30.0 g), NMP was added to dilute to 6%, and then acetic anhydride (4.50 g) and pyridine (3.30 g) were added as the phosphonium imidization catalyst, and reacted at 80 ° C. 5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (11). The polyimide has a fluorene imidation rate of 90%, Mn of 17,800, and Mw of 46,900.

<Synthesis example 12>

F2 (0.96g, 3.84mmol), A1 (1.47g, 3.86mmol), B1 (1.88g, 7.76mmol) and E1 (0.84g, 7.77mmol) were mixed in NMP (16.3g) and reacted at 80 ° C After 5 hours, F1 (3.00 g, 15.3 mmol) and NMP (8.15 g) were added, and the mixture was reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a concentration of 25%.

To the obtained polyamidic acid solution (30.0 g), NMP was added to dilute to 6%, and then acetic anhydride (4.50 g) and pyridine as the phosphonium imidization catalyst were added. (3.30 g), and reacted at 80 ° C for 3.5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (12). The polyimide has an imidization ratio of 75%, Mn of 18,600, and Mw of 48,300.

<Synthesis Example 13>

F2 (2.30 g, 9.19 mmol), B1 (4.05 g, 16.7 mmol) and E2 (0.20 g, 1.85 mmol) were mixed in NMP (16.7 g), and after reacting at 80 ° C for 5 hours, F1 (1.80 g) was added , 9.18 mmol) and NMP (8.35 g), and reacted at 40 ° C. for 6 hours to obtain a 25% polyamic acid solution.

After adding NMP to the obtained polyamidic acid solution (30.0g) and diluting it to 6%, acetic anhydride (4.50g) and pyridine (3.30g) were added as the imidization catalyst, and reacted at 80 ° C for 2.5 hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (13). The polyimide has an imidization ratio of 65%, Mn of 22,100, and Mw of 53,400.

<Synthesis Example 14>

F2 (2.55g, 10.2mmol), A1 (1.57g, 4.13mmol), B1 (1.07g, 4.13mmol) and E2 (1.34g, 12.4mmol) were mixed in NMP (17.1g) and reacted at 80 ° C After 5 hours, add F1 (2.00 g, 10.2 mmol) and NMP (8.54 g) were reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a concentration of 25%.

NMP was added to the obtained polyamic acid solution (30.0 g) to dilute to 6%, and then acetic anhydride (4.50 g) and pyridine (3.30 g) were added as the imidization catalyst, and reacted at 80 ° C for 3.5. hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyfluoreneimide powder (14). The polyimide has a hydrazone imidization rate of 75%, Mn of 17,900, and Mw of 46,500.

<Synthesis Example 15>

F2 (2.81g, 11.2mmol) and C1 (3.46g, 22.7mmol) were mixed in NMP (16.9g), and after reacting at 80 ° C for 5 hours, F1 (2.20g, 11.2mmol) and NMP (8.46g) were added. ), And reacted at 40 ° C. for 6 hours to obtain a 25% concentration polyamic acid solution.

NMP was added to the obtained polyamic acid solution (30.0 g) to dilute to 6%, and then acetic anhydride (4.50 g) and pyridine (3.30 g) were added as the imidization catalyst, and reacted at 80 ° C for 3.5. hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (15). The polyimide has a hydrazone imidization rate of 75%, Mn of 21,800, and Mw of 52,100.

<Synthesis example 16>

F2 (2.81g, 11.2mmol), C1 (2.94g, 19.3mmol) and E2 (0.37g, 3.42mmol) were mixed in NMP (16.6g), and after reacting at 80 ° C for 5 hours, F1 (2.20g) was added , 11.2 mmol) and NMP (8.31 g), and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a concentration of 25%.

After adding NMP to the obtained polyamidic acid solution (30.0g) and diluting it to 6%, acetic anhydride (4.50g) and pyridine (3.30g) as the phosphonium imidization catalyst were added and reacted at 80 ° C for 3 hours. hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyfluoreneimide powder (16). The polyimide has a fluorene imidization rate of 70%, Mn of 23,200, and Mw of 54,200.

<Synthesis example 17>

F5 (2.30 g, 10.8 mmol), C1 (2.84 g, 18.7 mmol) and E2 (0.36 g, 3.33 mmol) NEP (16.4 g) were mixed and reacted at 80 ° C for 5 hours. F1 (2.30 g, 10.8 mmol) and NEP (8.21 g), and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution having a concentration of 25%.

After adding NEP to the obtained polyamidic acid solution (30.0g) and diluting it to 6%, acetic anhydride (4.50g) and pyridine (3.30g) as the phosphonium imidization catalyst were added, and the reaction was performed at 80 ° C for 3 hours. . This reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyfluoreneimide powder (17). The polyimide has an imidization ratio of 70%, Mn of 20,500, and Mw of 51,800.

<Synthesis example 18>

F2 (2.04g, 8.15mmol), A1 (2.52g, 6.62mmol), B1 (1.20g, 4.95mmol), C1 (0.50g, 3.29mmol) and D1 (0.55g, 1.66mmol) in NMP (16.8g ) And mixed at 80 ° C for 5 hours, F1 (1.60g, 8.16mmol) and NMP (8.41g) were added, and the mixture was reacted at 40 ° C for 6 hours to obtain a 25% polyamine solution.

After adding NMP to the obtained polyamidic acid solution (30.0g) and diluting it to 6%, acetic anhydride (4.50g) and pyridine (3.30g) were added as the imidization catalyst, and reacted at 80 ° C for 4 hour. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyfluorene imine powder (18). The polyimide has an imidization ratio of 81%, Mn of 15,300, and Mw of 41,600.

Tables 32 and 33 show the polyimide-based polymers obtained in each synthesis example.

"Evaluation of Inkjet Coating Property of Liquid Crystal Alignment Treatment Agent"

The liquid crystal alignment treatment agents obtained in Examples 3 and 8 described later were used to evaluate the inkjet coating properties. Specifically, these liquid crystal alignment treatment agents are subjected to pressure filtration using a membrane filter with a pore size of 1 μm, and the substrate with an ITO (indium tin oxide) electrode is washed with pure water and IPA (isopropanol). (100mm in height × 100mm in width, 0.7mm in thickness) on the ITO surface with a coating area of 70 × 70mm, a nozzle pitch of 0.423mm, a scanning pitch of 0.5mm, and a coating speed of 40mm / sec. cloth. At this time, HIS-200 (manufactured by Hitachi Equipment Technology) was used as the inkjet coater. The time from the application to the pre-drying was 60 seconds, and the pre-drying was performed on a hot plate under the conditions of 70 ° C. and 5 minutes.

The coating film surface of the substrate with the liquid crystal alignment film obtained above was visually observed to evaluate the coating property. Specifically, the coating film surface was visually observed under a sodium lamp, and the presence or absence of pinholes was confirmed. As a result, it was confirmed that the liquid crystal alignment film obtained in any of the examples had no pinholes on the coating film surface, and a liquid crystal alignment film having excellent coating film properties could be obtained.

`` Evaluation of display unevenness near the border of a liquid crystal cell (general cell) ''

The liquid crystal alignment treatment agents obtained in the examples and comparative examples described later were filtered under pressure using a membrane filter with a pore size of 1 μm, and were spin-coated on a substrate with ITO electrodes (40 mm in height and 30 mm in width) washed with pure water and IPA. , Thickness 0.7mm), heat treatment on a hot plate at 100 ° C for 5 minutes, heat cycle type cleaning oven at 230 ° C, heat treatment 30 Minutes, an ITO substrate with a liquid crystal alignment film with a film thickness of 100 nm was obtained. In addition, the liquid crystal alignment treatment agent of Example 3 and Example 8 was made into a substrate under the same conditions as the above "Evaluation of the inkjet coating property of the liquid crystal alignment treatment agent", and then a thermal cycle type cleaning oven was used at 230 ° C. Heat treatment was performed for 30 minutes to form an ITO substrate with a liquid crystal alignment film having a film thickness of 100 nm.

Next, the coated surface of this substrate was rubbed using a friction device with a roller diameter of 120 mm, using artificial fiber cloth, under the conditions that the roller rotation number was 1000 rpm, the roller travel speed was 50 mm / sec, and the pushing amount was 0.1 mm. deal with.

Then, two substrates after the rubbing treatment were prepared so that the coating film surface became the inside, and a spacer of 6 μm was held together, and then a sealant was used to create an empty cell. MLC-6608 (manufactured by Mok. Japan) was injected into the empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell.

Using the obtained liquid crystal cell, the display unevenness characteristics near the frame of the liquid crystal cell were evaluated. Specifically, using a polarizing plate and a backlight, the liquid crystal alignment near the sealant was evaluated by visual observation. As a result, all the liquid crystal cells obtained in the examples and comparative examples showed uniform liquid crystal alignment.

Then, the liquid crystal cell was stored in a constant temperature and humidity tank at a temperature of 80 ° C. and a humidity of 90% RH for 144 hours, and the alignment of the liquid crystal near the sealant was evaluated under the same conditions as above. The evaluation was performed after the liquid crystal alignment disorder was not found in the vicinity of the sealant after storage in a constant temperature and humidity tank, and the evaluation was more excellent (good expressions in Tables 37 to 39).

`` Evaluation of Voltage Holding Rate (General Cell) ''

The voltage retention rate was evaluated using a liquid crystal cell produced under the same conditions as the aforementioned "Evaluation of Display Unevenness Characteristics Near a Frame of a Liquid Crystal Cell (General Cell)". Specifically, at a temperature of 80 ° C., a voltage of 1 V is applied to the liquid crystal cell obtained by the above method for 60 μs, the voltage after 50 ms is measured, and the voltage retention rate (also referred to as VHR) is used to calculate how much the voltage can be maintained. The measurement was performed using a voltage holding ratio measuring device (VHR-1, manufactured by Dongyang Technology Co., Ltd.) under the settings of Voltage: ± 1V, Pulse Width: 60 μs, and Flame Period: 50 ms.

In addition, using a desk-type UV curing device (HCT3B28HEX-1, manufactured by CENLITE), a liquid crystal cell was prepared for the liquid crystal cell and the voltage retention ratio was measured. The liquid crystal cell was irradiated with ultraviolet rays converted into 365 nm at 50 J / cm ² and the above. Under the same conditions, the voltage holding ratio was measured.

In this evaluation, the value of the voltage retention rate after the production of the liquid crystal cell is high. In addition, compared to the value of the voltage retention rate after the production of the liquid crystal cell (also referred to as the initial stage), the value after ultraviolet irradiation (also referred to as ultraviolet The smaller the decrease after irradiation), the better in this evaluation. Tables 37 to 39 show the values of each VHR.

"Assessment of Reduction of Residual Charge (General Cell)"

The relaxation of the residual charge was evaluated using a liquid crystal cell prepared under the same conditions as the aforementioned "Evaluation of Display Unevenness Characteristics Near a Frame of a Liquid Crystal Cell (General Cell)". Specifically, for a liquid crystal cell, a DC voltage of 10V is applied. After adding for 30 minutes and making the short circuit for 1 second, the potential occurring in the liquid crystal cell was measured at 1800 seconds. The value of the residual charge after 50 seconds was used to evaluate the relaxation of the residual charge. For the measurement system, a 6254 type liquid crystal physical property evaluation device (manufactured by Toyo Technology Co., Ltd.) was used.

In addition, using a desktop UV curing device (HCT3B28HEX-1, manufactured by CENLITE), the above-mentioned liquid crystal cell was made into a liquid crystal cell after measuring the residual charge, and then irradiated with ultraviolet rays of 30 J / cm ² converted at 365 nm, as described above. Under the conditions, the residual charge was measured.

In this evaluation, the smaller the decrease in the value after liquid crystal cell fabrication (also referred to as the initial stage) and the value of the residual charge after ultraviolet irradiation (also referred to as after ultraviolet irradiation), the more excellent in this evaluation. Tables 37 to 39 show the values of the respective residual charges.

`` Creation of Liquid Crystal Cells and Evaluation of Liquid Crystal Orientation (PSA Cells) ''

The liquid crystal alignment treatment agents obtained in Examples 3 and 9 described later were used to prepare a liquid crystal cell and evaluate the liquid crystal alignment (PSA cell). Specifically, these liquid crystal alignment treatment agents are subjected to pressure filtration using a membrane filter with a pore size of 1 μm, and the center after washing with pure water and IPA is attached with a 10 × 10 mm pattern interval of 20 μm with ITO. Rotate the ITO electrode substrate (40mm × 30mm horizontal, 0.7mm in thickness) and the ITO surface of the substrate with ITO electrode (40mm × 30mm horizontal, 0.7mm in thickness) attached to the center with 10 × 40mm ITO. Coated, heat-treated on a hot plate at 100 ° C for 5 minutes, and heat-treated in a thermal cycle cleaning oven at 230 ° C for 30 minutes to obtain a film with a thickness of 100 nm. ITO substrate for liquid crystal alignment film. In addition, the liquid crystal alignment treatment agent of Example 3 was made into a substrate under the same conditions as the above "Evaluation of the inkjet coating property of the liquid crystal alignment treatment agent", and then was heat-treated at 230 ° C for 30 minutes in a thermal cycle type cleaning oven An ITO substrate with a liquid crystal alignment film with a film thickness of 100 nm was formed.

Next, with these two substrates, a coating film surface was placed inside, and a spacer of 6 μm was held together, and then a sealant was used to form an empty cell. The nematic liquid crystal (Nematic) (MLC-6608, manufactured by Mok. Japan Co., Ltd.) was 100% of a nematic liquid crystal (MLC-6608, manufactured by Mok. Japan) with respect to nematic liquid crystal by a reduced pressure injection method. A liquid crystal mixed with 0.3% of the polymerizable compound (1) is injected into the empty cell, and the injection port is sealed to obtain a liquid crystal cell.

For the obtained liquid crystal cell, while applying a voltage of AC5V, a metal halide lamp with an illuminance of 60mW was used to remove the wavelength below 350nm, and the ultraviolet light converted to 365nm was converted to 20J / cm ^{2 to} obtain a liquid crystal crystal with controlled alignment direction of the liquid crystal. Cell. The temperature in the irradiation device when the liquid crystal cell was irradiated with ultraviolet rays was 50 ° C.

Then, the response speed of the liquid crystal of the liquid crystal cell before and after ultraviolet irradiation was measured. Response speed is measured from 90% transmission to transmission T90 → T10 at a rate of 10%.

Compared with the liquid crystal cell before ultraviolet irradiation, any liquid crystal cell has a faster response speed after the ultraviolet irradiation, so it is confirmed that the alignment direction of the liquid crystal is controlled. Moreover, each liquid crystal cell was observed with a polarizing microscope (ECLIPSE E600WPOL, manufactured by NIKON Corporation), and it was confirmed that the liquid crystals are uniformly aligned.

<Example 1>

NEP (3.92 g) was added to the polyimide powder (1) (0.50 g) obtained in Synthesis Example 1, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (3.92 g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

Further, NEP (5.88 g) was added to the polyfluorene imine powder (11) (0.75 g) obtained in Synthesis Example 11, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (5.88 g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

Further, NEP (9.79 g) was added to the polyfluorene imine powder (15) (1.25 g) obtained in Synthesis Example 15, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (9.79 g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

The three solutions obtained above were mixed and stirred at 40 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (1). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Example 2>

NEP (3.92 g) was added to the polyfluorene imide powder (2) (0.50 g) obtained in Synthesis Example 2, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (2.35 g) and PB (1.57 g) were added to this solution, and stirred at 40 ° C for 4 hours to obtain a solution.

Further, NEP (5.88 g) was added to the polyfluorene imine powder (11) (0.75 g) obtained in Synthesis Example 11, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (3.53 g) and PB (2.35 g) were added to this solution, and stirred at 40 ° C for 4 hours to obtain a solution.

Further, NEP (9.79 g) was added to the polyfluorene imine powder (15) (1.25 g) obtained in Synthesis Example 15, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (5.88g) and PB (3.92g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

The three solutions obtained above were mixed and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment agent (2). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Example 3>

Polyimide powder (3) (0.30 g) obtained in Synthesis Example 3, polyimide powder (11) (0.45 g) obtained in Synthesis Example 11, and polyimide powder (15) obtained in Synthesis Example 15 (0.75 g) was added with NEP (16.5 g) and γ-BL (4.18 g), and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (8.27g), PB (8.27g), and DME (4.14g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (3). This LCD alignment process No abnormalities such as turbidity or precipitation were observed in the agent, and it was confirmed that the agent was a uniform solution.

<Example 4>

NMP (6.27 g) was added to the polyfluorene imine powder (4) (0.80 g) obtained in Synthesis Example 4, and the mixture was stirred at 70 ° C. for 24 hours to be dissolved. BCS (5.02 g) and DME (1.25 g) were added to this solution, and stirred at 40 ° C for 4 hours to obtain a solution.

Further, NMP (6.27 g) was added to the polyfluorene imine powder (13) (0.80 g) obtained in Synthesis Example 13, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (5.02 g) and DME (1.25 g) were added to this solution, and stirred at 40 ° C for 4 hours to obtain a solution.

Further, NMP (8.36 g) was added to the polyfluorene imine powder (15) (1.07 g) obtained in Synthesis Example 15, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (6.68 g) and DME (1.67 g) were added to this solution, and stirred at 40 ° C for 4 hours to obtain a solution.

The three solutions obtained above were mixed and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (4). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Example 5>

NEP (7.52 g) was added to the polyfluorene imine powder (5) (0.80 g) obtained in Synthesis Example 5, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Add BCS (2.51g) and PB (2.51g) to this solution, and stir at 40 ° C for 4 hours. In time, a solution was obtained.

Further, NEP (7.52 g) was added to the polyfluorene imine powder (11) (0.80 g) obtained in Synthesis Example 11, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (2.51 g) and PB (2.51 g) were added to this solution, and stirred at 40 ° C for 4 hours to obtain a solution.

Further, NEP (10.0 g) was added to the polyfluorene imine powder (15) (1.07 g) obtained in Synthesis Example 15, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (3.34g) and PB (3.34g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

The three solutions obtained above were mixed and stirred at 40 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (5). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Example 6>

Polyimide powder (6) (0.50 g) obtained in Synthesis Example 6, polyimide powder (11) (0.75 g) obtained in Synthesis Example 11, and polyimide powder (15) obtained in Synthesis Example 15. (1.25 g) was added with NEP (21.5 g), and the mixture was stirred at 70 ° C for 24 hours to be dissolved. PB (17.6 g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (6). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Example 7>

Added to polyimide powder (7) (0.80 g) obtained in Synthesis Example 7 NMP (3.76 g) and NEP (3.76 g) were stirred at 70 ° C for 24 hours to dissolve them. BCS (2.51 g) and PB (2.51 g) were added to this solution, and stirred at 40 ° C for 4 hours to obtain a solution.

Further, NMP (3.76 g) and NEP (3.76 g) were added to the polyfluorene imine powder (11) (0.80 g) obtained in Synthesis Example 11, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (2.51 g) and PB (2.51 g) were added to this solution, and stirred at 40 ° C for 4 hours to obtain a solution.

Further, NMP (5.02 g) and NEP (5.02 g) were added to the polyfluorene imine powder (15) (1.07 g) obtained in Synthesis Example 15, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (3.34g) and PB (3.34g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

The three solutions obtained above were mixed and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (7). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Example 8>

Polyimide powder (8) (0.30 g) obtained in Synthesis Example 8, polyimide powder (11) (0.45 g) obtained in Synthesis Example 11, and polyimide powder (15) obtained in Synthesis Example 15. (0.75 g) was added to NEP (12.4 g) and γ-BL (6.21 g), and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (8.27g) and PB (14.5g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (8). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Example 9>

NEP (5.09 g) was added to the polyfluorene imine powder (1) (0.50 g) obtained in Synthesis Example 1, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (1.18 g) and PB (1.57 g) were added to this solution, and stirred at 40 ° C for 4 hours to obtain a solution.

Further, NEP (7.64 g) was added to the polyfluorene imine powder (12) (0.75 g) obtained in Synthesis Example 12, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (1.76 g) and PB (2.35 g) were added to this solution, and stirred at 40 ° C for 4 hours to obtain a solution.

Further, NEP (12.7 g) was added to the polyfluorene imide powder (15) (1.25 g) obtained in Synthesis Example 15, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (2.94 g) and PB (3.92 g) were added to this solution, and stirred at 40 ° C for 4 hours to obtain a solution.

The three solutions obtained above were mixed and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (9). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Example 10>

NEP (4.70 g) was added to the polyfluorene imide powder (5) (0.50 g) obtained in Synthesis Example 5, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. PB (3.13 g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

Further, NEP (7.05 g) was added to the polyfluorene imine powder (13) (0.75 g) obtained in Synthesis Example 13, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. PB (4.70 g) was added to this solution, and the mixture was stirred at 40 ° C for 4 hours to obtain a solvent. liquid.

Further, NEP (11.8 g) was added to the polyfluorene imine powder (15) (1.25 g) obtained in Synthesis Example 15, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. PB (7.83 g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

The three solutions obtained above were mixed and stirred at 40 ° C. for 4 hours to obtain a liquid crystal alignment treatment agent (10). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Example 11>

NEP (4.70 g) was added to the polyimide powder (1) (0.50 g) obtained in Synthesis Example 1, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (0.78 g) and PB (2.35 g) were added to this solution, and stirred at 40 ° C for 4 hours to obtain a solution.

Further, NEP (7.05 g) was added to the polyfluorene imine powder (14) (0.75 g) obtained in Synthesis Example 14, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (1.18 g) and PB (3.53 g) were added to this solution, and stirred at 40 ° C for 4 hours to obtain a solution.

Further, NEP (11.8 g) was added to the polyfluorene imine powder (15) (1.25 g) obtained in Synthesis Example 15, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (1.96g) and PB (5.88g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

The three solutions obtained above were mixed and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (11). In this liquid crystal alignment treatment agent, No abnormality such as turbidity or precipitation was found, and it was confirmed that the solution was a homogeneous solution.

<Example 12>

NMP (6.27 g) was added to the polyfluorene imine powder (1) (0.80 g) obtained in Synthesis Example 1, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (2.51 g) and PB (3.76 g) were added to this solution, and stirred at 40 ° C for 4 hours to obtain a solution.

Further, NMP (4.18 g) was added to the polyfluorene imine powder (11) (0.53 g) obtained in Synthesis Example 11, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (1.67 g) and PB (2.51 g) were added to this solution, and stirred at 40 ° C for 4 hours to obtain a solution.

Further, NMP (10.4 g) was added to the polyfluorene imine powder (16) (1.33 g) obtained in Synthesis Example 16, and the mixture was stirred at 70 ° C. for 24 hours to be dissolved. BCS (4.18 g) and PB (6.27 g) were added to this solution, and stirred at 40 ° C for 4 hours to obtain a solution.

The three solutions obtained above were mixed, M1 (0.19 g) was further added, and the mixture was stirred at 40 ° C. for 6 hours to obtain a liquid crystal alignment treatment agent (12). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Example 13>

Polyimide powder (1) (0.80 g) obtained in Synthesis Example 1, polyimide powder (11) (0.80 g) obtained in Synthesis Example 11, and polyimide powder (17) obtained in Synthesis Example 17 (1.07g) was added with NEP (20.9g), and stirred at 70 ° C Let it dissolve for 24 hours. BCS (8.36g) and PB (12.5g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (13). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Example 14>

Polyimide powder (1) (0.80 g) obtained in Synthesis Example 1, polyimide powder (11) (0.80 g) obtained in Synthesis Example 11, and polyimide powder (17) obtained in Synthesis Example 17 (1.07 g) was added with NEP (20.9 g), and the mixture was stirred at 70 ° C for 24 hours to be dissolved. PB (12.5 g) and DPM (8.36) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (23). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Comparative example 1>

NEP (19.6 g) was added to the polyfluorene imine powder (1) (2.50 g) obtained in Synthesis Example 1, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (19.6g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (14). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Comparative example 2>

NEP (19.6 g) was added to the polyfluorene imine powder (11) (2.50 g) obtained in Synthesis Example 11, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. Dissolve here BCS (19.6 g) was added to the solution and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (15). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Comparative example 3>

NEP (19.6 g) was added to the polyfluorene imide powder (15) (2.50 g) obtained in Synthesis Example 15, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (19.6g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (16). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Comparative Example 4>

NEP (10.2 g) was added to the polyfluorene imine powder (1) (1.30 g) obtained in Synthesis Example 1, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (10.2 g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

Further, NEP (10.2 g) was added to the polyfluorene imine powder (11) (1.30 g) obtained in Synthesis Example 11, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (10.2 g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

The two solutions obtained above were mixed and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (17). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Comparative example 5>

NEP (10.2 g) was added to the polyfluorene imine powder (1) (1.30 g) obtained in Synthesis Example 1, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (10.2 g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

Further, NEP (10.2 g) was added to the polyfluorene imine powder (15) (1.30 g) obtained in Synthesis Example 15, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (10.2 g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

The two solutions obtained above were mixed and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (18). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Comparative Example 6>

NEP (10.2 g) was added to the polyimide powder (11) (1.30 g) obtained in Synthesis Example 11, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (10.2 g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

Further, NEP (10.2 g) was added to the polyfluorene imine powder (15) (1.30 g) obtained in Synthesis Example 15, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (10.2 g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

The two solutions obtained above were mixed and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (19). In this liquid crystal alignment treatment agent, No abnormality such as turbidity or precipitation was found, and it was confirmed that the solution was a homogeneous solution.

<Comparative Example 7>

NEP (3.92 g) was added to the polyfluorene imine powder (9) (0.50 g) obtained in Synthesis Example 9, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (3.92 g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

Further, NEP (5.88 g) was added to the polyfluorene imine powder (11) (0.75 g) obtained in Synthesis Example 11, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (5.88 g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

Further, NEP (9.79 g) was added to the polyfluorene imine powder (15) (1.25 g) obtained in Synthesis Example 15, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (9.79 g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

The three solutions obtained above were mixed and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (20). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Comparative Example 8>

NMP (3.92 g) was added to the polyfluorene imide powder (10) (0.50 g) obtained in Synthesis Example 10, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (2.35 g) and PB (1.57 g) were added to this solution, and stirred at 40 ° C for 4 hours to obtain a solution.

Further, NMP (5.88 g) was added to the polyfluorene imine powder (11) (0.75 g) obtained in Synthesis Example 11, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (3.53 g) and PB (2.35 g) were added to this solution, and stirred at 40 ° C for 4 hours to obtain a solution.

Further, NMP (9.79 g) was added to the polyfluorene imine powder (15) (1.25 g) obtained in Synthesis Example 15, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (5.88g) and PB (3.92g) were added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the solution.

The three solutions obtained above were mixed and stirred at 40 ° C for 4 hours to obtain a liquid crystal alignment treatment agent (21). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

<Comparative Example 9>

NEP (19.6 g) was added to the polyimide powder (18) (2.50 g) obtained in Synthesis Example 18, and the mixture was stirred at 70 ° C for 24 hours to be dissolved. BCS (19.6g) was added to this solution, and it stirred at 40 degreeC for 4 hours, and obtained the liquid-crystal aligning agent (22). In this liquid crystal alignment treatment agent, no abnormal phenomenon such as turbidity or precipitation was found, and it was confirmed that this was a uniform solution.

Tables 34 to 36 show the composition ratios of the liquid crystal alignment treatment agents obtained in the examples and comparative examples, the polyimide-based polymers used, and the solid content concentration (%).

In the table, * 1 indicates the content (parts) of the specific polymer (A) when 100 parts of the total polymer is used, and * 2 indicates the content of the specific polymer (B) when 100 parts of the total polymer is used. Content (parts), * 3 means relative to all When the polymer is 100 parts, the content (parts) of the specific polymer (C), and * 4 means the content (parts) of other polymers when the total polymer is 100 parts.

* 5 indicates the content ratio (solid content concentration) of the entire polymer in the liquid crystal alignment treatment agent.

In the following Tables 37 to 39, * 1 indicates that the liquid crystal cell has a disorder of the alignment of the liquid crystal near the sealant, and * 2 indicates that in the liquid crystal cell, the width from the sealant to 0.5 cm is found in the liquid crystal cell. Match Anisotropic disorder (compared to * 1, the width of the disorder of liquid crystal alignment is wider), * 3 indicates the area of the liquid crystal cell with a width from the sealant to 1.0cm, and the disorder of liquid crystal alignment is found Phenomenon (compared to * 2, the width of the disorder phenomenon of liquid crystal alignment is wider).

From the above results, it is understood that when the liquid crystal alignment treatment agent of the example is compared with the liquid crystal alignment treatment agent of the comparative example, the liquid crystal cell is not found near the sealant even if it is stored in a high temperature and high humidity tank for a long time. Disorders. In addition, even if the liquid crystal cell is irradiated with ultraviolet rays, a decrease in the voltage holding ratio can be suppressed, and a rapid relaxation of the residual charge accumulated by the DC voltage is achieved.

That is, when the examples using the three types of specific polymers (A), (B), and (C) are compared with the comparative example using only one of them, the liquid crystal alignment treatment agent of the comparative example cannot satisfy the present invention. The full effect. Specifically, Example 1 is compared with Comparative Example 1, Comparative Example 2, or Comparative Example 3. In addition, Examples 1 and 4, Comparative Example 4, Comparative Example 5, or Comparative Example 6 The comparison is the same. In addition, when Example 1 using the specific diamine (4) was compared with Comparative Example 7 which was not used, the liquid crystal alignment treatment agent of the comparative example could not satisfy all the effects of the present invention.

In addition, when comparing Example 2 using a specific diamine (1) with Comparative Example 8 using a conventional diamine having an alkyl-type side chain structure, the liquid crystal alignment treatment agent of the comparative example cannot satisfy all of the present invention. effect.

In addition, when comparing Example 1 with Comparative Example 9 using all polyimide powders of the specific diamines (1), (2), (3), and (4), the liquid crystal alignment treatment agent of the comparative example cannot be used. All the effects of the present invention are satisfied. In particular, the occurrence of display unevenness near the frame of the liquid crystal cell and the value of the residual charge after ultraviolet irradiation become large.

[Industrial availability]

A liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is one having excellent reliability, and can be applied to large-screen and high-definition liquid crystal televisions. It can be used for TN elements, STN elements, TFT liquid crystal elements, especially Liquid crystal display element of vertical alignment type.

In addition, the entire contents of the specification, the scope of patent application, and the abstract of Japanese Patent Application No. 2014-262604 filed on December 25, 2014 are incorporated herein, and are incorporated herein by reference.

Claims (21)

A liquid crystal alignment treatment agent containing the following (A) component, (B) component, and (C) component, (A) component: a diamine having a structure represented by the following formula [1], and having the following A polyfluorene imide precursor obtained by reacting a diamine component of a structured diamine and a tetracarboxylic acid component represented by formula [2] or a polyfluorene imine obtained by subjecting the polyfluorene imine precursor to imidization, B) Component: a polyimide precursor containing a diamine component of a diamine having a structure represented by the following formula [2] and a tetracarboxylic acid component, or a polyimide precursor obtained by reacting the polyimide precursor Poly (fluorene) imide, (C): Reaction of a diamine component containing a diamine having at least one kind of substituent selected from the group consisting of a carboxyl group (COOH group) and a hydroxyl group (OH group) and a tetracarboxylic acid component The obtained polyfluorene imide precursor or the polyfluorine imidized with the polyfluorene imide precursor, but at least one of the components (A), (B), and (C) is polymerized The diamine component contains diamine having a structure represented by the following formula [4], (X ¹ represents at least one selected from the group consisting of a single bond,-(CH ₂ ) _a- (a is an integer of 1-15), -O-, -CH ₂ O-, -COO-, and -OCO- X ² represents a single bond or-(CH ₂ ) _b- (b is an integer from 1 to 15), X ³ represents a single bond,-(CH ₂ ) _c- (c is from 1 to 15 integer), - O -, - CH 2 O -, - COO- -OCO- and at least one of the groups, X ⁴ represents a group selected consisting of a benzene ring, a cyclohexane ring, and the heterocyclic groups of at least one A bivalent cyclic group or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton. Any hydrogen atom on the aforementioned cyclic group may be an alkyl group having 1 to 3 carbon atoms and an alkyl group having 1 to 3 carbon atoms. Alkoxy, fluorine-containing alkyl group having 1 to 3 carbon atoms, fluorine-containing alkoxy group having 1 to 3 carbon atoms or fluorine atom, X ⁵ represents a group selected from benzene ring, cyclohexane ring and heterocyclic ring At least one type of cyclic group in a group. Any hydrogen atom on these cyclic groups may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or 1 to 3 carbon atoms. Substituted by a fluorine-containing alkyl group, a fluorine-containing alkoxy group or a fluorine atom having 1 to 3 carbon atoms, n represents an integer of 0 to 4, and X ⁶ represents a group selected from an alkyl group having 1 to 18 carbon atoms and 1 to 3 carbon atoms. Fluorine-containing alkyl group of 18, alkoxy group of 1 to 18 carbons and carbon At least one of the groups of fluorine-containing alkoxy groups of 1 to 18) [Chemical 2] -W ¹ -W ² -W ³ -W ⁴ [2] (W ¹ represents a group selected from -O-, -NH -, -N (CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON (CH ₃ )-, and -N (CH ₃ ) CO- are at least 1 W ² represents at least one member selected from the group consisting of a single bond, an alkylene group having 1 to 20 carbon atoms, and a non-aromatic ring and an aromatic ring, and W ³ represents a member selected from a single bond,- O-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -COO-, -OCO-, -CON (CH ₃ )-, -N (CH ₃ ) CO- and -O (CH ₂ ) _m- (m represents an integer of 1 to 5) at least one group, and W ⁴ represents a nitrogen-containing aromatic heterocyclic ring) For example, the liquid crystal alignment treatment agent according to item 1 of the patent application scope, in which the diamine having the structure represented by the aforementioned formula [1] is used only as the diamine component in the aforementioned (A) component. For example, the liquid crystal alignment treatment agent in the first patent application range, wherein the use ratio (mole%) of the diamine having the structure represented by the aforementioned formula [1] in the aforementioned (A) component to the entire diamine component is set to At 1.0, the use ratio (mole%) of the diamine having the structure represented by the formula [1] in the component (B) to the entire diamine component is a ratio of 0.01 to 0.8. For example, the liquid crystal alignment treatment agent in the scope of claims 1 or 3, in which the proportion of the diamine in the component (A) having the structure represented by the aforementioned formula [1] is used relative to the entire diamine component (mole%) When it is set to 1.0, the use ratio (mole%) of the diamine which has the structure represented by said formula [1] in the said (C) component with respect to the whole diamine component is 0.01-0.3. For example, the liquid crystal alignment treatment agent according to any one of claims 1 to 3, wherein the diamine having at least one substituent selected from the group consisting of the aforementioned carboxyl group (COOH group) and hydroxyl group (OH group) is only used A diamine component used in the component (C). For example, in the liquid crystal alignment treatment agent according to any one of claims 1 to 3, a diamine having a structure represented by the aforementioned formula [4] is used only for the diamine component in the aforementioned (A) component. For example, the liquid crystal alignment treatment agent according to any one of claims 1 to 3, wherein the diamine having the structure represented by the aforementioned formula [1] is represented by the following formula [1a], (X represents the structure represented by the aforementioned formula [1], and n1 represents an integer of 1 to 4). For example, the liquid crystal alignment treatment agent according to any one of claims 1 to 3, wherein the diamine having the structure represented by the aforementioned formula [2] is represented by the following formula [2a], (W represents the structure represented by the aforementioned formula [2], and p1 represents an integer of 1 to 4). For example, the liquid crystal alignment treatment agent according to any one of claims 1 to 3, wherein the diamine having at least one substituent selected from the group consisting of a carboxyl group and a hydroxyl group is represented by the following formula [3a], (Y represents a structure represented by the following formula [3-1] or [3-2], and m1 represents an integer of 1 to 4) (a and b each represent an integer of 0 to 4). For example, the liquid crystal alignment treatment agent according to any one of claims 1 to 3, wherein the diamine having a structure represented by the aforementioned formula [4] is represented by the following formula [4a-1], (q1 represents an integer from 1 to 8). For example, the liquid crystal alignment treatment agent according to any one of claims 1 to 3, wherein the tetracarboxylic acid component in the components (A), (B), and (C) contains the following formula [5] Tetracarboxylic dianhydride, (Z represents at least one selected from the group consisting of the structures represented by the following formulas [5a] to [5k]) (Z ¹ to Z ⁴ each independently represent at least one selected from the group consisting of a hydrogen atom, a methyl group, a chlorine atom, and a benzene ring, and Z ⁵ and Z ⁶ each independently represent a hydrogen atom or a methyl group). For example, the liquid crystal alignment treatment agent according to any one of claims 1 to 3, which contains a group selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butyrolactone. At least 1 kind of solvent. For example, the liquid crystal alignment treatment agent according to any one of claims 1 to 3, which contains a liquid crystal alignment treatment agent selected from the group consisting of 1-hexanol, cyclohexanol, 1,2-ethylene glycol, 1,2-propylene glycol, and propylene glycol monobutylene. Ethers, ethylene glycol monobutyl ethers, dipropylene glycol dimethyl ethers, and at least one solvent grouped by solvents represented by the following formulas [D1] to [D3], (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 according to any one of claims 1 to 3, wherein the liquid crystal alignment treatment agent contains: a material selected from the group consisting of an epoxy group, an isocyanate group, an oxetanyl group, and a cyclocarbonate group. A crosslinkable compound having at least one type of group, a crosslinkable compound having at least one type selected from the group consisting of a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group, or a polymerizable unsaturated bond group Crosslinkable compound. A liquid crystal alignment film is obtained from a liquid crystal alignment treatment agent according to any one of claims 1 to 14. A liquid crystal alignment film is obtained by applying the liquid crystal alignment treatment agent according to any one of claims 1 to 14 of the scope of patent application by an inkjet method. A liquid crystal display element is provided with a liquid crystal alignment film as described in claim 15 or 16. For example, the liquid crystal alignment film with the scope of patent application No. 15 or 16 is used to have a liquid crystal layer between a pair of substrates having electrodes, and the arrangement between the pair of substrates includes at least active energy rays and heat. The liquid crystal composition of the polymerizable compound that is polymerized by one is a liquid crystal display device produced by the step of polymerizing the polymerizable compound by applying a voltage between the electrodes. A liquid crystal display element is provided with a liquid crystal alignment film as in item 18 of the scope of patent application. For example, the liquid crystal alignment film with the scope of patent application No. 15 or 16 is used to form a liquid crystal layer between a pair of substrates provided with electrodes. At least one polymerizable liquid crystal alignment film polymerized is a liquid crystal display device manufactured by a step of polymerizing the polymerizable group by applying a voltage between the electrodes. A liquid crystal display element is provided with a liquid crystal alignment film according to item 20 of the patent application.