TWI649362B - Composition, liquid crystal alignment treatment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Abstract

The present invention is to provide a composition containing the component (A): the following formula [A]: (In the formula, X ¹ and X ² each independently represent a C 1-3 alkyl group, X ³ and X ⁴ each independently represent a C 1-3 alkyl group) The solvent shown; and (B) Ingredient: At least one polymer selected from the precursors of amide imide and polyimide.

Description

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

The present invention relates to a composition for forming a polyimide film, a liquid crystal alignment treatment agent used in the manufacture of a liquid crystal display element, a liquid crystal alignment film obtained by the liquid crystal alignment treatment agent, and a liquid crystal obtained by using the liquid crystal alignment film Invention of display element.

Films formed from organic materials, such as polymer materials, focus on ease of formation or insulating properties, etc., and have been widely used as interlayer insulating films or protective films in electronic devices. Among them, in a liquid crystal display element widely known as a display device, an organic film formed of an organic material is used as a liquid crystal alignment film.

In recent years, the use of liquid crystal display elements in large-screen LCD TVs or high-definition mobile devices (display parts of digital cameras or portable phones) has been widely used. Along with this, when compared with the past, the substrate used in it will be larger, and the unevenness of the substrate will become larger. However, even in these situations, from the viewpoint of display characteristics, the liquid crystal alignment film is required to have a uniform coating film for a large substrate or step. In the manufacturing process of the liquid crystal alignment film, polyamic acid or Solvent soluble polyimide (also known as polyimide) and other polyimide-based polymers (also known as resins) liquid crystal alignment treatment agent is applied to the substrate, the industry generally uses Flexo (Flexo) ) Printing method or inkjet coating method. At this time, in the solvent of the liquid crystal alignment treatment agent, in addition to N-methyl-2-pyrrolidone (also known as NMP) or γ-butane which has a solvent (also known as a good solvent) having excellent solubility in the resin In addition to lactone (also known as γ-BL), etc., from the viewpoint of improving the coating properties of the liquid crystal alignment film, it is also possible to mix ethylene glycol monobutyl ether, etc. with a solvent having a low resin solubility (also known as a poor solvent) (For example, Patent Document 1).

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2-37324

In addition to liquid crystal alignment films, polyimide-based organic films (also known as polyimide films) are also widely used as interlayer insulating films or protective films in electronic devices. The same is true for liquid crystal alignment films, which can be formed by a composition (also called a coating solution) containing a solution of polyimide or a solution of a polyimide precursor. Therefore, in other electronic devices, there is also a need to improve the coating properties of the polyimide film. That is, when the coating properties of the polyimide film are improved, defects accompanying coating can be effectively suppressed.

Also, using "obtained from a diamine compound having a side chain The liquid crystal alignment treatment agent obtained from "polyamic acid or polyimide" has a high hydrophobicity of the side chain part, so the coating property of the liquid crystal alignment film tends to be reduced. In particular, there may be a case where uniform coating properties cannot be obtained, that is, a case where sand holes occur along with splashing, and when used as a liquid crystal display element, this part will form a display defect. Therefore, when a uniform coating film property is to be obtained, it is necessary to have a large amount of a poor solvent to expand the wettability for the coating solution applied to the substrate. However, the poor solvent has a relatively poor ability to dissolve polyamic acid or polyimide, so when mixed in a large amount, there will be a problem of resin precipitation.

In addition, in recent years, liquid crystal display elements have been used more often in conjunction with mobile devices such as smartphones or portable phones. However, in these applications, in order to ensure the largest possible display surface, etc. The sealing agent used between the substrates mostly exists near the end of the liquid crystal alignment film. Therefore, if the coating property of the end of the liquid crystal alignment film is deteriorated, that is, the end of the liquid crystal alignment film fails to form a straight line, or the end of the liquid crystal is arched, the liquid crystal alignment film and the sealing will be reduced The adhesion (also known as adhesion) effect between the agents will reduce the display characteristics or reliability of the liquid crystal display element.

In addition, in the composition using polyimide or liquid crystal alignment treatment agent, the NMP or γ-BL of these solvents used has a high boiling point, so it is used to fabricate polyimide films such as interlayer insulating films or protective films In the case of liquid crystal alignment films, sintering at high temperature must be performed. Therefore, from the viewpoint of reducing the energy cost, in the production of these polyimide films and liquid crystal alignment films, it is often sought to enable sintering at low temperatures.

Therefore, the present invention aims to provide a composition having the above-mentioned characteristics. That is, an object of the present invention is to provide a composition capable of suppressing the generation of sand holes caused by splashing when forming a polyimide film, and to provide a composition having excellent coating properties at the ends. Even if low-temperature sintering is performed, the composition of the polyimide film can be produced for the purpose.

Also, when providing a liquid crystal alignment treatment agent using the composition of the present invention, when forming a liquid crystal alignment film, the generation of sand holes caused by splashing can be suppressed, and the coating properties of the ends are also Excellent liquid crystal alignment treatment agent. In particular, even when a liquid crystal alignment treatment agent obtained using "polyamide acid or polyimide obtained by using a diamine compound having a side chain" is used, a liquid crystal alignment treatment agent having these excellent characteristics can be provided. In addition, there is provided a liquid crystal alignment treatment agent having excellent electrical characteristics, particularly voltage retention (also referred to as VHR) in a liquid crystal display element even when sintering at the time of producing a liquid crystal alignment film is at a low temperature.

In addition, there is provided a polyimide film obtained from the foregoing composition, a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent, and a display device having the liquid crystal alignment film.

The present inventors have conducted intensive studies and found that a composition containing a solvent having a specific structure and at least one polymer selected from a polyimide precursor or polyimide is extremely important for achieving the above object Effective, thus completing the present invention.

That is, the present invention has the following main contents.

(1) A composition characterized by containing (A) component: a solvent represented by the following formula [A]: (In the formula, X ¹ and X ² each independently represent an alkyl group having 1 to 3 carbon atoms, X ³ and X ⁴ each independently represent an alkyl group having 1 to 3 carbon atoms); and (B) component: composed of polyacrylamide At least one polymer selected from imine precursor and polyimide.

(2) The composition as described in (1) above, wherein the solvent of the aforementioned component (A) is a solvent represented by the following formula [A-1]:

(3) The composition as described in (1) or (2) above, wherein the component (B) is at least one selected from the structures having the following formula [1-1] and formula [1-2] A diamine compound with a structure of at least one polymer selected from polyimide precursor and polyimide used as part of the raw material: (In the formula, Y ¹ represents a single bond,-(CH ₂ ) _a- (a is an integer from 1 to 15), -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON (CH ₃ )-, -N (CH ₃ ) CO-, -COO- and -OCO- selected at least one kind of bonding group, Y ² represents a single bond or-(CH ₂ ) _b- (b is 1 ~ 15 Integer), Y ³ represents at least 1 selected from single bonds,-(CH ₂ ) _c- (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- and -OCO- The bonding group of the species, Y ⁴ represents a divalent cyclic group of at least one ring selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent ring having a carbon number of 17 to 51 having a cholesterol skeleton Organic group, any hydrogen atom on the aforementioned cyclic group can be substituted by C 1-3 alkyl group, C 1-3 alkoxy group, C 1-3 fluoroalkyl group, C 1 ~ 3 is substituted with a fluorine-containing alkoxy group or a fluorine atom, and Y ⁵ represents a bivalent cyclic group of at least one kind of ring selected from a benzene ring, a cyclohexane ring, and a heterocyclic ring. Any hydrogen atom can be substituted by C 1-3 alkyl, C 1-3 alkoxy, C 1-3 fluorinated alkyl, C 1-3 fluorinated alkoxy or fluorine Substituted by atoms, n represents an integer of 0 ~ 4, Y ⁶ represents an alkyl group with a carbon number of 1-22, carbon At least one selected from alkenyl groups having 2 to 22 carbon atoms, fluoroalkyl groups having 1 to 22 carbon atoms, alkoxy groups having 1 to 22 carbon atoms, and fluoroalkoxy groups having 1 to 22 carbon atoms; 4] -Y ⁷ -Y ⁸ [1-2] (wherein, Y ⁷ represents a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON (CH ₃ )-, -N (CH ₃ ) CO-, -COO- and -OCO- selected at least one kind of bonding group, Y ⁸ represents a C 8-22 alkyl group or a C 6-18 fluorine-containing alkyl group) .

(4) The composition as described in (3) above, wherein the diamine compound having the structure represented by the above formula [1-1] and formula [1-2] is a diamine compound represented by the following formula [1a]: (In the formula, Y represents at least one structure selected from the structures shown in the above formula [1-1] and formula [1-2], and m represents an integer of 1 to 4).

(5) The composition according to any one of (1) to (4) above, wherein the polymer of the component (B) is at least one selected from a carboxyl group (COOH group) and a hydroxyl group (OH group) A diamine compound of one kind of substituent is used as a part of the raw material, and at least one kind of polymer selected from a polyimide precursor and a polyimide is obtained.

(6) The composition as described in (5) above, wherein the diamine compound having a carboxyl group and a hydroxyl group is a diamine compound represented by the following formula [2a]: {In the formula, A represents a substituent of at least one structure selected from the following formula [2-1] and formula [2-2]: [Chem 7] -(CH ₂ ) _a -COOH [2-1] -(CH ₂ ) _b -OH [2-2] (In formula [2-1], a represents an integer of 0 ~ 4, in formula [2-2], b represents an integer of 0 ~ 4), m represents 1 ~ 4 integer}.

(7) The composition according to any one of (1) to (6) above, wherein the polymer of the component (B) is a diamine compound represented by the following formula [3a] as a part of the raw material At least one type of polymer selected from polyimide precursors and polyimide is used: (In the formula, B ¹ represents -O-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON (CH ₃ )-and -N (CH ₃ ) CO- selected at least one kind of bonding group, B ² represents a divalent group consisting of a single bond, an aliphatic hydrocarbon having 1 to 20 carbon atoms, and a divalent non-aromatic cyclic hydrocarbon At least one type selected from the group of divalent groups and aromatic hydrocarbons, B ³ represents 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 is an integer from 1 to 5) at least one type of bonding selected Group, B ⁴ represents a nitrogen-containing heterocyclic group, n represents an integer from 1 to 4).

(8) The composition as described in (7) above, wherein B ¹ in the above formula [3a] represents -CONH-, B ² represents an alkylene group having 1 to 5 carbon atoms, B ³ represents a single bond, and B ⁴ represents Imidazolyl or pyridyl, n represents a diamine compound of 1.

(9) The composition according to any one of (1) to (8) above, wherein the polymer of the component (B) is the following formula [4]: {In the formula, Z is at least one selected from the polyimide precursor and the polyimide used from the tetracarboxylic acid compounds represented by the following formula [4a] to formula [4k] as part of the raw material Of polymers: (In formula [4a], Z ¹ to Z ⁴ each independently represent a hydrogen atom, a methyl group, a chlorine atom or a phenyl group, and in formula [4g], Z ⁵ and Z ⁶ each independently represent a hydrogen atom or a methyl group) The basis of at least one selected structure}.

(10) The composition according to any one of (1) to (9) above, wherein the polymer of the component (B) is at least one selected from polyalkylamide and polyimide Of polymers.

(11) The composition according to any one of (1) to (10) above, wherein the component (C) contains N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone And at least one solvent selected from γ-butyrolactone.

(12) The composition according to any one of (1) to (11) above, wherein (D) component contains 1-hexanol, cyclohexanol, 1,2-ethylene glycol, 1,2- Propylene glycol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, and at least one solvent selected from the solvents represented by the following formula [D-1] to formula [D-3]: (In formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms, in formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms, in formula [D-3], D ³ represents an alkyl group having 1 to 4 carbon atoms).

(13) The composition according to any one of (1) to (12) above, which contains a crosslinking property having an epoxy group, an isocyanate group, a glycidyl group or a cyclic carbonate group Compounds, cross-linkable compounds with at least one substituent selected from the group consisting of hydroxy, hydroxyalkyl, and lower alkoxyalkyl, and cross-linkable compounds with polymerizable unsaturated bonds, selected At least one crosslinkable compound.

(14) The composition according to any one of (1) to (13) above, wherein the component (A) is 5 to 70% by mass of the total solvent contained in the composition.

(15) The composition according to any one of (11) to (14) above, wherein the (C) component is 40 to 80% by mass of the total solvent contained in the composition.

(16) The composition according to any one of (12) to (15) above, wherein the (D) component is 1 to 50% by mass of the total solvent contained in the composition.

(17) The composition according to any one of (1) to (16) above, wherein the component (B) is 0.1% by mass to 30% by mass in the composition.

(18) A polyimide film, characterized by the above (1) ~ Those obtained by the composition of any one of (17) above.

(19) A liquid crystal alignment treatment agent characterized by being obtained from the composition of any one of (1) to (17) above.

(20) A liquid crystal alignment film characterized by using the liquid crystal alignment treatment agent of (19) above.

(21) A liquid crystal alignment film characterized by using the liquid crystal alignment treatment agent of (19) above by an inkjet method.

(22) A liquid crystal display device characterized by having the liquid crystal alignment film of (20) or (21) above.

(23) The liquid crystal alignment film according to the above (20) or (21), which is used between a pair of substrates provided with electrodes, has a liquid crystal layer, and is arranged between the pair of substrates via active energy rays and heat At least one of the polymerized compound-containing liquid crystal compositions polymerized is a liquid crystal display element produced by the step of continuously applying a voltage between the electrodes to polymerize the polymerizable compound.

(24) A liquid crystal display device characterized by having the liquid crystal alignment film of (23) above.

(25) The liquid crystal alignment film according to the above (20) or (21), which is used between a pair of substrates provided with electrodes and has a liquid crystal layer, and between the pair of substrates, is arranged to pass active energy rays and heat At least one of the polymerized group-containing liquid crystal alignment films polymerized is a liquid crystal display element produced by continuously applying a voltage between the electrodes to polymerize the polymerizable group.

(26) A liquid crystal display element characterized by having the above (25) The liquid crystal alignment film.

The composition of the present invention containing a solvent having a specific structure and at least one polymer selected from a polyimide precursor or polyimide can suppress the accompanying splash when forming a polyimide film The formation of sand holes caused by bullets, and the polyimide film with excellent coating properties at the end can also be produced. At the same time, even under low temperature sintering, polyimide film can be produced.

In addition, when the liquid crystal alignment treatment agent of the composition of the present invention is used, it is possible to provide the formation of a liquid crystal alignment film, which can suppress the occurrence of sand holes caused by splashing. In addition, the coating properties of the ends are also Excellent liquid crystal alignment treatment agent. In particular, when a liquid crystal alignment treatment agent using "polyamic acid or polyimide obtained by using a diamine compound having a side chain" is used, a liquid crystal alignment treatment agent having these excellent characteristics can also be provided. In addition, even if the sintering at the time of producing the liquid crystal alignment film is a low-temperature treatment, it is possible to provide a liquid crystal alignment treatment agent having excellent electrical characteristics, particularly excellent voltage retention (VHR) in the liquid crystal display element.

In addition, when the composition of the present invention is used as a liquid crystal alignment treatment agent, the formation of sand holes caused by splashing can be suppressed, and in addition, a liquid crystal alignment film having excellent coating properties at the ends can be provided. In particular, when a liquid crystal alignment treatment agent using "polyamic acid or polyimide obtained using a diamine compound having a side chain" is used, a liquid crystal alignment film having these excellent characteristics can also be provided. In addition, even when the sintering at the time of manufacturing the liquid crystal alignment film is low In a warm state, it is also possible to provide a liquid crystal alignment film having excellent electrical characteristics, particularly excellent voltage retention (VHR) in a liquid crystal display element. Therefore, the liquid crystal display device having the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention is one with excellent reliability, and is suitable for large-screen and high-definition LCD TVs or small and medium-sized car navigation systems or smartphone Wait.

(a) ‧‧‧Polyimide film (liquid crystal alignment film)

(b) ‧‧‧ chromium vapor-deposited substrate

[Fig. 1] A diagram showing that the end of a polyimide film coated with a glass substrate is linear.

[Fig. 2] A diagram showing that the end of the polyimide film coated with a glass substrate is in an expanded state.

[Forms for carrying out the invention]

Hereinafter, the present invention will be described in detail.

The present invention is a composition containing the following components (A) and (B), a liquid crystal alignment treatment agent, a liquid crystal alignment film obtained using the liquid crystal alignment treatment agent, and a liquid crystal display element having the liquid crystal alignment film.

(A) Ingredient: A solvent (also called a specific solvent) represented by the following formula [A].

(In formula [A], X ¹ and X ² each independently represent an alkyl group having 1 to 3 carbon atoms, and X ³ and X ⁴ each independently represent an alkyl group having 1 to 3 carbon atoms).

(B) Ingredients: at least one kind of polymer (also called specific polymer) selected from polyimide precursor and polyimide.

The specific solvent of the present invention can be used as long as it can dissolve polyimide precursors and polyimide-based polymers such as polyimide-based polymers (also known as good solvents). In addition, it also has an improved polyimide The coating effect of amine film and liquid crystal alignment film. That is, the specific solvent of the present invention generally has a lower surface tension as the solvent when compared with the NMP used as a good solvent, and the coating solution as the specific solvent is not as good as the coating without using it Compared with the solution, it has a higher wettability of the coating solution for the substrate. In this way, when used as a polyimide film and a liquid crystal alignment film, the linearity of the ends of these films can be improved. In addition, because of the higher wettability of the coating solution for the substrate, the occurrence of sand holes caused by splashing can also be suppressed.

In addition, the specific solvent of the present invention generally has a lower boiling point when compared with NMP or γ-BL used as a good solvent. Therefore, the sintering at the time of producing the polyimide film and the liquid crystal alignment film can also be performed at a low temperature. Therefore, in particular, even when the sintering at the time of manufacturing the liquid crystal alignment film is in a low temperature state, a liquid crystal alignment film with excellent VHR in the liquid crystal display element can be produced.

In addition, the component (B) of the present invention is a polymer selected from at least one type of polyimide precursor or polyimide. Among them, the composition of the present invention is used as a liquid crystal alignment treatment agent to produce a liquid crystal alignment film In the form, a polyimide precursor having at least one type of side chain (also collectively referred to as a specific side chain structure) selected from the structures represented by the following formula [1-1] and formula [1-2] is used. At least one kind of polymer (also referred to as specific polymer) selected from polyimide or polyimide is preferred.

(In formula [1-1], Y ¹ represents a single bond,-(CH ₂ ) _a- (a is an integer from 1 to 15), -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON (CH ₃ )-, -N (CH ₃ ) CO-, -COO- and -OCO- selected at least one kind of bonding group, Y ² represents a single bond or-(CH ₂ ) _b- (b Is an integer from 1 to 15), Y ³ represents a single bond,-(CH ₂ ) _c- (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- and -OCO- At least one kind of bonding group, Y ⁴ represents a divalent cyclic group of at least one kind of ring selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a carbon number of 17 to 51 having a cholesterol skeleton Divalent organic group, any hydrogen atom on the aforementioned cyclic group can be substituted by C 1-3 alkyl group, C 1-3 alkoxy group, C 1-3 fluoroalkyl group, carbon Substituted by fluorine-containing alkoxy groups or fluorine atoms of numbers 1 to 3, Y ⁵ represents a divalent cyclic group of at least one kind of ring selected from the group consisting of benzene ring, cyclohexane ring and heterocycle. Any hydrogen atom on the base can be substituted by C 1-3 alkyl, C 1-3 alkoxy, C 1-3 fluorinated alkyl, C 1-3 fluorinated alkoxy substituted with a fluorine atom or a group, n-represents an integer of 0 to 4, Y ⁶ represents an alkyl group of 1 to 22 carbon atoms, the carbon Alkenyl group of 2 to 22 carbon atoms of the fluorinated alkyl group having 1 to 22 carbon atoms of an alkoxy group having 1 to 22 carbon atoms and a fluorine-containing group having 1 to 22 of the selected at least one kind of).

[ Chem . 14] -Y ⁷ -Y ⁸ [1-2] (In formula [1-2], Y ⁷ represents a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-,- CON (CH ₃ )-, -N (CH ₃ ) CO-, -COO- and -OCO- selected at least one kind of bonding group, Y ⁸ represents an alkyl group having 8 to 22 carbon atoms or 6 to 6 carbon atoms 18 of fluorine-containing alkyl).

Among them, the specific side chain structure represented by the aforementioned formula [1-1] is a divalent cyclic group having a benzene ring, a cyclohexyl ring or a heterocyclic ring in the side chain portion, or a carbon number of 17 to 51 having a cholesterol skeleton 2-valent organic radical. The divalent cyclic groups of these benzene rings, cyclohexyl rings or heterocycles, or the divalent organic groups with a carbon number of 17 to 51 having a cholesterol skeleton, show a rigid structure. In this way, the thermal stability of the side chain portion can be improved, and the decomposition of the side chain portion caused by sintering when the liquid crystal alignment film is produced can be suppressed, and a liquid crystal alignment film having excellent VHR can be obtained.

From the above points, it is known that the composition of the present invention containing a specific solvent and at least one polymer selected from a polyimide precursor or polyimide is a type that can form excellent coating properties, and even The sintering at low temperature can also form the composition of polyimide film.

In addition, the liquid crystal alignment treatment agent obtained by the composition of the present invention can produce a liquid crystal alignment film having excellent coating properties. In addition, even when the sintering at the time of manufacturing the liquid crystal alignment film is in a low temperature state, a liquid crystal alignment film having excellent VHR in the liquid crystal display element can be obtained. Therefore, when the liquid crystal alignment film is used, a highly reliable liquid crystal with excellent display characteristics can be provided Liquid crystal display element.

In addition, the composition of the present invention containing a specific solvent and at least one polymer selected from a polyimide precursor or polyimide having a specific side chain structure represented by the aforementioned formula [1-1] The liquid crystal alignment treatment agent exhibits a better effect than the aforementioned effect, that is, even when the sintering at the time of production of the liquid crystal alignment film is in a low temperature state, a liquid crystal alignment film with excellent VHR in the liquid crystal display element can be obtained. Therefore, when this liquid crystal alignment film is used, a highly reliable liquid crystal display element with more excellent display characteristics can be improved.

Hereinafter, the embodiments of the present invention will be described in more detail.

<Specific solvent>

The specific solvent of the present invention is a solvent represented by the following formula [A].

In formula [A], X ¹ and X ² each independently represent an alkyl group having 1 to 3 carbon atoms (for example, methyl, ethyl, propyl, or isopropyl), preferably methyl or ethyl, Particularly preferred is methyl.

In formula [A], X ³ and X ⁴ each independently represent an alkyl group having 1 to 3 carbon atoms (for example, methyl, ethyl, propyl, or isopropyl), preferably methyl or ethyl, Particularly preferred is methyl.

Specifically, for example, those represented by the following formula [A-1] Better.

The amount of the specific solvent of the present invention can improve the above-mentioned expanded wettability of the coating solution on the substrate, and preferably accounts for 5 to 80% by mass of the entire solvent contained in the composition and the liquid crystal alignment treatment agent. Among them, 5 to 75% by mass is better. It is preferably 5 to 70% by mass, and more preferably 10 to 60% by mass.

Among the total solvents in the composition and the liquid crystal alignment treatment agent, the greater the amount of the specific solvent of the present invention, the effect of the present invention is to increase the wettability of the coating solution to the substrate and to obtain Polyimide film and liquid crystal alignment film with excellent coating properties.

<Specific polymer>

The specific polymer of the component (B) of the present invention is at least one polymer selected from a polyimide precursor and a polyimide (also collectively referred to as a polyimide-based polymer). Among them, the polyimide-based polymer of the present invention is preferably a polyimide precursor or polyimide obtained by reacting a diamine component and a tetracarboxylic acid component.

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

(In formula [a], R ¹ is a tetravalent organic group, R ² is a divalent organic group, A ¹ and A ² each independently represent a hydrogen atom or a C 1-5 alkyl group, A ³ and A ⁴ , each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an acetyl group, and n represents a positive integer).

Examples of the aforementioned diamine component include diamine compounds having two primary or secondary amine groups in the molecule.

In addition, the tetracarboxylic acid component includes, for example, a tetracarboxylic acid compound, a tetracarboxylic dianhydride, a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound, or a tetracarboxylic acid dialkyl ester dihalide compound. .

To prepare the polyamido acids in which A ¹ and A ² in the formula [a] are hydrogen atoms, the diamine compound having two primary or secondary amine groups in the molecule can be combined with the tetracarboxylic acid compound or It can be prepared by reacting tetracarboxylic anhydride.

To prepare polyalkyl amides in which A ¹ and A ² in the formula [a] are alkyl groups having 1 to 5 carbon atoms, the aforementioned diamine compound, tetracarboxylic acid dihalide compound, and tetracarboxylic acid can be used It can be prepared by reacting a dialkyl acid compound or a tetracarboxylic acid dialkyl ester dihalide compound. In addition, in the polyamic acid obtained by the above method, an alkyl group having 1 to 5 carbon atoms may be introduced into A ¹ and A ² represented by formula [a].

The polyimide-based polymer of the present invention has the following At least one kind of diamine compound with a specific side chain structure selected from the structures represented by formula [1-1] and formula [1-2] is used as a part of the raw material from a polyimide precursor and a polyimide At least one polymer selected from amines is preferred.

In formula [1-1], Y ¹ represents a single bond,-(CH ₂ ) _a- (a is an integer from 1 to 15), -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON (CH ₃ )-, -N (CH ₃ ) CO-, -COO- and -OCO- selected at least one kind of bonding group. Among them, from the viewpoint of easy availability or synthesis of raw materials, single bonds,-(CH ₂ ) _a- (a is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- are preferred . More preferably, it is a single bond,-(CH ₂ ) _a- (a is an integer from 1 to 10), -O-, -CH ₂ O-, or -COO-.

In formula [1-1], Y ² represents a single bond or-(CH ₂ ) _b- (b is an integer of 1 to 15). Among them, a single bond or-(CH ₂ ) _b- (b is an integer of 1-10) is preferred.

In formula [1-1], Y ³ represents a single bond,-(CH ₂ ) _c- (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- and -OCO- At least one kind of bonding group selected. Among them, from the viewpoint of easy synthesis, single bond,-(CH ₂ ) _c- (c is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- is preferred. More preferably, it is a single bond,-(CH ₂ ) _c- (c is an integer from 1 to 10), -O-, -CH ₂ O-, or -COO-.

In formula [1-1], Y ⁴ is a divalent cyclic group of at least one kind of ring selected from a benzene ring, a cyclohexane ring, and a heterocyclic ring, and any hydrogen atom on these cyclic groups, It can be substituted by C 1-3 alkyl group, C 1-3 alkoxy group, C 1-3 fluorinated alkyl group, C 1-3 fluorinated alkoxy group or fluorine atom. In addition, Y ⁴ is a divalent organic group selected from organic groups having a carbon number of 17 to 51 having a cholesterol skeleton. Among them, from the viewpoint of easy synthesis, a divalent cyclic group having a benzene ring or cyclohexane ring, or a divalent organic group having a carbon number of 17 to 51 having a cholesterol skeleton is preferred.

In formula [1-1], Y ⁵ represents a divalent cyclic group of at least one kind of ring selected from a benzene ring, a cyclohexane ring, and a heterocyclic ring, and any hydrogen atom on these cyclic groups, It can be substituted by C 1-3 alkyl group, C 1-3 alkoxy group, C 1-3 fluorinated alkyl group, C 1-3 fluorinated alkoxy group or fluorine atom. Among them, benzene ring or cyclohexane ring is preferred.

In formula [1-1], n represents an integer of 0 to 4. Among them, from the viewpoint of easy availability or synthesis of raw materials, 0 to 3 is preferable. The better is 0 ~ 2.

In formula [1-1], Y ⁶ represents an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a fluorine-containing alkyl group having 1 to 22 carbon atoms, and an alkoxy group having 1 to 22 carbon atoms. And at least one selected from fluorine-containing alkoxy groups having 1 to 22 carbon atoms. Among them, the alkyl group having 1 to 18 carbon atoms, the alkenyl group having 2 to 18 carbon atoms, the fluorine-containing alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 18 carbon atoms or the carbon atom having 1 to 10 Fluoroalkoxy is preferred. More preferably, it is an alkyl group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons or an alkoxy group having 1 to 12 carbons. Particularly preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.

In the formula [1-1], the preferred combination of Y ¹ to Y ⁶ and n can be exemplified by Table 6 to Table 47 on pages 13 to 34 of pages 13/1341 of the International Publication No. 2011/132751 (published on 2011.10.27) The revealed (2-1) ~ (2-629) are the same combination and so on. In addition, in the tables in the International Publication, relative to Y ¹ to Y ⁶ in the present invention, they are represented by Y1 to Y6, but Y1 to Y6 and Y ¹ to Y ⁶ can be replaced with each other by equivalents. In addition, (2-605) to (2-629) disclosed in the tables of the International Open Gazette, in the present invention, represent an organic group having a carbon number of 17 to 51 having a cholesterol skeleton, and a carbon number having a cholesterol skeleton of 12 to 12 The organic group of 25, so the organic group with a carbon number of 12 to 25 having a cholesterol skeleton can be replaced with the organic group with a carbon number of 17 to 51 having a cholesterol skeleton according to the present invention.

[化 19] -Y ⁷ -Y ⁸ [1-2]

In formula [1-2], Y ^{7 is} composed of a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON (CH ₃ )-, -N (CH ₃ ) CO-, -COO- and -OCO- selected at least one bonding group. Among them, a single bond, -O-, -CH ₂ O-, -CONH-, -CON (CH ₃ )-or -COO- is preferred. More preferably, it is a single bond, -O-, -CONH- or -COO-.

In formula [1-2], Y ⁸ represents a C 8-22 alkyl group or a C 6-18 fluorine-containing alkyl group. Among them, the alkyl group having 8 to 18 carbon atoms is preferred.

For the specific side chain structure of the present invention, from the viewpoint of obtaining a highly stable liquid crystal vertical alignment, it is preferable to use the structure shown in formula [1-1].

The method for introducing a specific polymer into a specific side chain structure of the present invention is not particularly limited, and it is preferable to use a diamine compound having a specific side chain structure as a diamine component user.

Specifically, for example, it is preferable to use a diamine compound (also referred to as a specific side chain type diamine compound) represented by the following formula [1a]. at this time, A diamine compound in which the amine group in the following formula [1a] is a secondary amine group can also be used.

In formula [1a], Y represents at least one structure selected from the structures shown in the above formula [1-1] and formula [1-2]. In addition, Y in formula [1a] represents a preferable combination of Y ¹ to Y ⁶ and n in the case of formula [1-1], and is the same as described above, for example.

In formula [1a], m represents an integer of 1-4. Among them, 1 is better.

Specific examples of the specific side chain type diamine compound of the present invention are, for example, the diamine compounds represented by the following formula [1a-1] to formula [1a-34], and further, for example, these amine groups are secondary amine groups The diamine compound.

(In formula [1a-1] to formula [1a-3], R ¹ , R ³ and R ⁵ each independently represent -O-, -OCH _2- , -CH ₂ O-, -COOCH ₂ -or -CH ₂ OCO-, formula [1a-1] to formula [1a-3], R ² , R ⁴ and R ⁶ each independently represent a linear or branched alkyl group with a carbon number of 1 to 22, and a carbon number of 1 to 22 straight-chain or branched alkoxy groups, straight-chain or branched fluorine-containing alkyl groups having 1 to 22 carbon atoms or fluorine-containing alkoxy groups having 1 to 22 carbon atoms).

(In formula [1a-4] to formula [1a-6], R ¹ , R ³ and R ⁵ each independently represent -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -,- CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -or -CH _2- , in formula [1a-4] to formula [1a-6], R ² , R ⁴ and R ⁶ each independently represent the carbon number Straight-chain or branched alkyl group of 1-22, straight-chain or branched alkoxy group with carbon number 1-22, straight-chain or branched fluoroalkyl group with carbon number 1-22 or carbon number 1 22 of fluorine-containing alkoxy groups).

(In formula [1a-7] and formula [1a-8], R ¹ and R ³ independently represent -COO-, -OCO-, -CONH-, -NHCO-, -COOCH _2- , -CH ₂ OCO -, -CH ₂ O-, -OCH _2- , -CH _2- , -O- or -NH-, R ² and R ⁴ each independently represent a fluoro group, a cyano group, a trifluoromethyl group, a nitro group, an azo Group, methyl acetyl group, acetyl group, acetyl group or hydroxy group).

(In formula [1a-9] and formula [1a-10], R ¹ and R ² each independently represent a straight-chain or branched alkyl group having 3 to 12 carbon atoms, and a 1,4-cyclohexyl group- Trans isomers are, respectively, trans isomers).

(In formula [1a-11] and formula [1a-12], R ¹ and R ² each independently represent a linear or branched alkyl group having 3 to 12 carbon atoms, and a 1,4-cyclohexyl group- Trans isomers are, respectively, trans isomers).

(In formula [1a-13], A ₄ is a C 3-20 linear or branched alkyl group substituted by a fluorine atom, and A ₃ is 1,4-cyclohexyl or 1,4-phenylene , A ₂ is an oxygen atom or -COO- * (where the bond marked "*" is bonded to A ₃ ), A ₁ is an oxygen atom or -COO- * (where the bond marked "*" The bond is (CH ₂ ) a ₂ ). In addition, a ₁ is an integer of 0 or 1, a ₂ is an integer of 2 to 10, and a ₃ is an integer of 0 or 1.)

(In formula [1a-32] to formula [1a-35], A ¹ to A ⁴ each independently represent an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group).

In the aforementioned formulas [1a-1] to [1a-21] and [1a-24] to [1a-35], the specific side chain type diamine compound of particularly excellent structure is, formula [1a-1] to formula [1a -6], formula [1a-9] ~ formula [1a-13] or formula [1a-24] ~ formula [1a-31].

The specific side chain type diamine in the specific polymer of the present invention The compound is preferably 10 mol% or more and 80 mol% or less with respect to the entire diamine component. Tejia is more than 10 mol% and less than 70 mol%.

The specific side chain type diamine compound of the present invention incorporates the solubility of the specific polymer of the present invention in a solvent, the coating properties of the composition and the liquid crystal alignment treatment agent, the alignment of the liquid crystal in the case of the liquid crystal alignment film, For characteristics such as voltage retention rate and accumulated charge, one type may be used or two or more types may be used in combination.

Among the specific polymers of the present invention, a diamine compound having at least one substituent selected from a carboxyl group (COOH group) and a hydroxyl group (OH group) is preferably used as the diamine component.

Specifically, for example, those using the diamine compound represented by the following formula [2a] are preferred. In this case, a diamine compound in which the amine group in the following formula [2a] is a secondary amine group can also be used.

In formula [2a], A represents a substituent of at least one structure selected from the following formula [2-1] and formula [2-2].

[化 34] -(CH ₂ ) _a -COOH [2-1]-(CH ₂ ) _b -OH [2-2]

In formula [2-1], a represents an integer of 0 to 4.

In formula [2-2], b represents an integer of 0 ~ 4.

In formula [2a], m represents an integer of 1-4.

More specifically, for example, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6 -Diamine Resorcinol, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid or 3,5-diaminobenzoic acid, etc. Among them, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid or 3,5-diaminobenzoic acid is preferred.

In addition, diamine compounds represented by the following formula [2a-1] to formula [2a-4] and diamine compounds in which these amine groups are secondary amine groups can also be used.

(In formula [2a-1], A ¹ represents a single bond, -CH _2- , -C ₂ H _4- , -C (CH ₃ ) _2- , -CF _2- , -C (CF ₃ ) _2- , -O-, -CO-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH _2- , -COO-, -OCO-, -CON (CH ₃ )-and -N (CH ₃ ) CO- selected at least one kind of bonding group, m ¹ and m ² , each independently represents an integer of 0 ~ 4, and m ¹ + m ² represents 1 ~ 4 Integer, in formula [2a-2], m ³ and m ⁴ each independently represent an integer of 1 ~ 5, in formula [2a-3], A ² represents a linear or branched alkyl group having 1 to 5 carbon atoms, m ⁵ represents an integer of 1 ~ 5. In formula [2a-4], A ³ and A ⁴ each independently represent a single bond, -CH _2- , -C ₂ H _4- , -C (CH ₃ ) ₂ -,- CF _2- , -C (CF ₃ ) _2- , -O-, -CO-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON (CH ₃ )-and -N (CH ₃ ) CO- selected at least one kind of bonding group, m ⁶ represents an integer of 1 ~ 4).

In the specific polymer of the present invention, a diamine compound having at least one kind of substituent selected from a carboxyl group (COOH group) and a hydroxyl group (OH group), with respect to the entire diamine component, is at least 10 mole% 80 Mole% or less is preferred. Tejia is more than 10 mol% and less than 70 mol%.

The diamine compound of the present invention having at least one substituent selected from a carboxyl group (COOH group) and a hydroxyl group (OH group) is compounded with the solubility of the specific polymer of the present invention in solvents, composition and liquid crystal alignment treatment In the case of the coating properties of the agent, the alignment properties of the liquid crystal in the case of the liquid crystal alignment film, the voltage retention rate, the accumulated charge and other characteristics, one type may be used or two or more types may be used in combination.

In the specific polymer of the present invention, it is preferable to use a diamine compound having a nitrogen-containing heterocyclic ring represented by the following formula [3a] and these diamine compounds having secondary amine groups.

In formula [3a], B ¹ represents -O-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON (CH ₃ ) -And-N (CH ₃ ) CO- selected at least one kind of bonding group. Among them, -O-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON (CH ₃ )-or -N (CH ₃ ) CO- are easy to synthesize From the viewpoint of a diamine compound, it is preferable. More preferred are -O-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, or -CON (CH ₃ )-. Particularly preferred is -O-, -CONH- or -CH ₂ O-.

In formula [3a], B ² represents a single bond, a divalent radical of an aliphatic hydrocarbon having 1 to 20 carbon atoms, a divalent radical of a non-aromatic cyclic hydrocarbon, and a divalent radical of an aromatic hydrocarbon At least one of them. The divalent base of the aliphatic hydrocarbon having 1 to 20 carbon atoms may be linear or branched. In addition, it may have an unsaturated bond. Among them, alkylene having 1 to 10 carbon atoms is preferred. In addition, specific examples of the non-aromatic hydrocarbon include cyclopropyl ring, cyclobutane ring, cyclopentane ring, cyclohexyl ring, cycloheptane ring, cyclooctane ring, cyclonon ring, cyclodecane ring, cycloundecyl ring , Ring twelve, ring thirteen, ring fourteen, ring fifteen, ring sixteen, ring seventeen, ring eighteen, ring nineteen, ring twenty (icosene), three Eicosene ring, docosane ring, bicycloheptane ring, decahydronaphthalene ring, norbornene ring or adamantane ring, etc. Among them, cyclopropyl ring, cyclobutane ring, cyclopentane ring, cyclohexyl ring, cycloheptane ring, norbornene ring or adamantane ring are preferred. Specific examples of the aromatic hydrocarbon group include benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, stilbene ring, anthracene ring, phenanthrene ring, and phlebo ring. Among them, benzene ring, naphthalene ring, tetrahydronaphthalene ring, stilbene ring or anthracene ring is preferred.

In formula [3a], preferred B ² is a single bond, an alkylene group having 1 to 10 carbon atoms, or a cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring , A bivalent group of at least one ring selected from norbornene ring, adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, stilbene ring and anthracene ring Among them, a single bond, an alkylene group having 1 to 5 carbon atoms, or a divalent group of a cyclohexane ring or a benzene ring is preferred.

In formula [3a], B ³ represents a single bond, -O-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -COO-, -OCO-, -CON (CH ₃ )-, -N (CH ₃ ) CO- and -O (CH ₂ ) _m- (m is an integer from 1 to 5) at least one kind of bonding group selected. Among them, single bond, -O-, -COO-, -OCO- or -O (CH ₂ ) _m- (m is an integer of 1 to 5) is preferred. More preferably, it is a single bond, -O-, -OCO-, or -O (CH ₂ ) _m- (m is an integer from 1 to 5).

In formula [3a], B ⁴ is a nitrogen-containing heterocyclic group, which is a structure containing at least one selected from the following formula [3a-1], formula [3a-2] and formula [3a-3] Of heterocyclic bases.

(In formula [3a-3], Z ¹¹ represents an alkyl group having 1 to 5 carbon atoms).

More specifically, for example, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, Purine ring, thiadiazole ring, ta Ring, pyrazoline ring, three Ring, pyrazolidine ring, triazole ring, pyridine Ring, benzimidazole ring, cinnoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine (phenothiazine) ring, oxadiazole ring or acridine ring, etc. Among them, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, ta Ring, three Ring, triazole ring, pyridine Ring or benzimidazole ring is preferred. More preferred are pyrrole ring, imidazole ring, pyrazole ring, pyridine ring or pyrimidine ring. In addition, B ³ in formula [3a] is bonded to a ring atom that is not adjacent to the structures of formula [3a-1], formula [3a-2] and formula [3a-3] contained in B ⁴ Better.

In formula [3a], n is an integer from 1 to 4 From the viewpoint of partial reactivity, 1 or 2 is preferable.

In formula [3a], the particularly preferred combination of B ¹ to B ⁴ and n is that B ¹ represents -CONH-, B ² represents an alkylene group having 1 to 5 carbon atoms, B ³ represents a single bond, and B ⁴ represents an imidazole ring Or a pyridine ring, n represents a diamine compound of 1.

The bonding position of the two amine groups (-NH ₂ ) in formula [3a] is not particularly limited. Specifically, for example, with respect to the bonding group (-B ^1- ) of the side chain, it is 2,3 position, 2,4 position, 2,5 position, 2,6 on the benzene ring Position, 3,4 position or 3,5 position, etc. Among them, from the viewpoint of the reactivity when synthesizing polyamic acid, the position of 2,4, the position of 2,5, or the position of 3,5 is preferable. Coupled with the ease of synthesis of the diamine compound, the 2,4 position or the 2,5 position is preferred.

In the specific polymer of the present invention, the diamine compound having the nitrogen-containing heterocyclic ring represented by the aforementioned formula [3a] is preferably 10 mol% or more and 80 mol% or less of the entire diamine component. Tejia is more than 10 mol% and less than 70 mol%.

The diamine compound of the present invention having the nitrogen-containing heterocyclic ring represented by the aforementioned formula [3a], in combination with the solubility of the specific polymer of the present invention in solvents, the composition and the coating properties of the liquid crystal alignment treatment agent, is used as a liquid crystal alignment film In the case of characteristics such as alignment, voltage retention, and accumulated charge of the liquid crystal, one type may be used or two or more types may be used in combination.

The specific polymer of the present invention can use other diamine compounds represented by the following formula [a-1] to formula [a-13] and these amine groups as long as the effects of the present invention are not impaired A diamine compound with a secondary amine group.

(In formula [a-1], A ¹ and A ³ independently represent -COO-, -OCO-, -CONH-, -NHCO-, -CH _2- , -O-, -CO-, and -NH -At least one selected bonding group, A ² represents a linear or branched alkyl group having 1 to 22 carbon atoms, or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms, In formula [a-2], A ⁴ and A ⁶ independently represent -COO-, -OCO-, -CONH-, -NHCO-, -CH _2- , -O-, -CO-, and -NH- At least one selected bonding group, A ⁵ represents a linear or branched alkyl group having 1 to 22 carbon atoms, or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms).

(In formula [a-3], A ¹ and A ³ independently represent -COO-, -OCO-, -CONH-, -NHCO-, -CH _2- , -O-, -CO-, and -NH -At least one selected bonding group, A ² represents a linear or branched alkyl group having 1 to 22 carbon atoms, or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms, In formula [a-4], A ⁴ and A ⁶ independently represent -COO-, -OCO-, -CONH-, -NHCO-, -CH _2- , -O-, -CO-, and -NH- At least one selected bonding group, A ⁵ represents a linear or branched alkyl group having 1 to 22 carbon atoms, or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms).

(In formula [a-5], A ¹ and A ³ independently represent -COO-, -OCO-, -CONH-, -NHCO-, -CH _2- , -O-, -CO-, and -NH -At least one selected bonding group, A ² represents a linear or branched alkyl group having 1 to 22 carbon atoms, or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms, In formula [a-6], A ⁴ and A ⁶ independently represent -COO-, -OCO-, -CONH-, -NHCO-, -CH _2- , -O-, -CO-, and -NH- At least one selected bonding group, A ⁵ represents a linear or branched alkyl group having 1 to 22 carbon atoms, or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms).

(In formula [a-7], p represents an integer of 1-10).

(In formula [a-12], R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and in formula [a-13], n represents an integer of 1 to 10).

In addition, as other diamine compounds, the following diamine compounds and those in which the amine groups are secondary amine groups can also be used.

Specifically, for example, p-phenylene diamine, 2,3,5,6-tetramethyl-p-phenylene diamine, 2,5-dimethyl-p-phenylene diamine Amine, m-phenylene diamine, 2,4-dimethyl-m-phenylene diamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 4,4'-di Aminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3 ' -Dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diamino Biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2 ' -Diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-di Aminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'- Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonamide Diphenylamine, 3,3'-sulfonyldiphenylamine, bis (4-aminophenyl) silane, bis (3- (Aminophenyl) silane, di Methyl-bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine, 4 , 4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diamine Diphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, N-methyl (3,3'-diaminodiphenyl) amine, N-methyl (3,4 '-Diaminodiphenyl) amine, N-methyl (2,2'-diaminodiphenyl) amine, N-methyl (2,3'-diaminodiphenyl) amine, 4 , 4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2 '-Diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis (4-aminophenyl) ethane, 1,2-bis (3-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,3-bis (3- Aminophenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4-bis (3-aminophenyl) butane, bis (3,5-diethyl 4-amino-4-aminophenyl) methane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4 -Aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, 1,3-bis (4-aminophenoxy ), Benzene, 4,4 '-[1,4-phenylene bis (methylidene)] diphenylamine, 4,4'-[1,3-phenylene bis (methylidene)] diphenylamine, 3,4 '-[1,4-phenylene bis (methylidene)] diphenylamine, 3,4'-[1,3-phenylene bis (methylidene)] diphenylamine, 3,3 ' -[1,4-Phenylbis (methyl)) diphenylamine, 3,3 '-[1,3-Phenylbis (methyl)] diphenylamine, 1,4-Phenylbis [(4-Aminophenyl) Formaldehyde], 1,4-Extenyl Bis [(3-Aminophenyl) Formaldehyde], 1,3-Extenyl Bis [(4-Aminophenyl) Formaldehyde ], 1,3-phenylene bis [(3-aminophenyl) formaldehyde], 1,4-phenylene bis (4-aminobenzoate), 1,4-phenylene Bis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), Bis (4-aminophenyl) terephthalate, bis (3-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis ( 3-aminophenyl) isophthalate, N, N '-(1,4-phenylene) bis (4-aminobenzylamide), N, N'-(1,3- Phenylene) bis (4-aminobenzylamide), N, N '-(1,4-phenylene) bis (3-aminobenzylamine), N, N'-(1, 3-Phenylphenyl) bis (3-aminobenzamide), N, N'-bis (4-aminophenyl) p-xylylenediamine, N, N'-bis (3-amino) Phenyl) p-xylylenediamine, N, N'-bis (4-aminophenyl) m-xylylenediamine, N, N'-bis (3-aminophenyl) m-xylylenediamide Amine, 9,10-bis (4-aminophenyl) anthracene, 4,4'-bis (4-aminophenoxy) diphenyl sulfone, 2,2'-bis [4- (4-amine Phenoxy) phenyl] propane, 2,2'-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2'-bis (4-aminophenyl) hexa Fluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2'-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2'-bis (4-aminophenyl) propane 2,2'-bis (3-aminophenyl) propane, 2,2'-bis (3-amino-4-methylphenyl) propane, 1,3-bis (4-aminophenoxy ) Propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,4-bis (3-aminophenoxy) Butane, 1,5-bis (4-aminophenoxy) pentane, 1,5-bis (3-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) ) Hexane, 1,6-bis (3-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 1,7- (3-aminophenoxy) ) Heptane, 1,8-bis (4-aminophenoxy) octane, 1,8-bis (3-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) Group) nonane, 1,9-bis (3-aminophenoxy) nonane, 1,10- (4-aminophenoxy) decane, 1,10- (3-aminophenoxy ) Decane, 1,11- (4-aminophenoxy) undecane, 1,11- (3-aminophenoxy) undecane Aromatic diamine compounds such as alkane, 1,12- (4-aminophenoxy) dodecane, 1,12- (3-aminophenoxy) dodecane, bis (4-amino ring Alicyclic diamine compounds such as hexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5 -Diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10 -Aliphatic diamine compounds such as diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, etc.

The other diamine compounds of the present invention incorporate the solubility of the specific polymer of the present invention in solvents, the coating properties of the composition and the liquid crystal alignment treatment agent, the alignment of the liquid crystal in the case of the liquid crystal alignment film, and the voltage retention ratio , Characteristics such as accumulated charge, you can use 1 type or mix 2 or more types.

To prepare the specific polymer of the present invention, that is, the tetracarboxylic acid component of these polyimide-based polymers, it is preferred to use the tetracarboxylic dianhydride represented by the following formula [4]. In this case, not only the tetracarboxylic dianhydride represented by the formula [4] but also tetracarboxylic acid, tetracarboxylic dihalide compound, tetracarboxylic dialkyl ester compound or tetracarboxylic dicarboxylic acid derivative of the tetracarboxylic acid derivative Alkyl ester dihalide compounds (tetracarboxylic dianhydride and its derivatives represented by formula [4] are also collectively referred to as specific tetracarboxylic acid components).

(In formula [4], Z represents at least one structure selected from the structures shown in the following formula [4a] to formula [4k]).

In formula [4a], Z ¹ to Z ⁴ each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom, or a phenyl group.

In formula [4g], Z ⁵ and Z ⁶ each independently represent a hydrogen atom or a methyl group.

In Z in formula [4], from the viewpoints of the ease of synthesis or the ease of polymerization reactivity when manufacturing a polymer, the formula [4a], formula [4c] to formula [4g] or formula [4k] Tetracarboxylic dianhydride and its tetracarboxylic acid derivatives of the structure shown are preferred. More preferred is the structure shown in formula [4a] or formula [4e] ~ formula [4g]. Particularly preferred are tetracarboxylic dianhydrides and their tetracarboxylic acid derivatives of the structure shown in [4a], formula [4e] or formula [4f].

The specific tetracarboxylic acid component in the specific polymer of the present invention is preferably 1 mol% to 100 mol% in 100 mol% of all tetracarboxylic acid components. Among them, 5 mol% to 95 mol% is better. The better ones are 20 mol% to 80 mol%.

The specific tetracarboxylic acid component of the present invention, in combination with the solubility of the specific polymer of the present invention in solvents, the coating properties of the composition and the liquid crystal alignment treatment agent, the alignment of the liquid crystal in the case of the liquid crystal alignment film, and the voltage retention rate, When accumulating characteristics such as electric charges, one type may be used or two or more types may be used in combination.

In the specific polymer of the present invention, tetracarboxylic acid components other than the specific tetracarboxylic acid component can be used as long as the effect of the present invention is not impaired. Other tetracarboxylic acid components include, for example, the following tetracarboxylic acid compounds, tetracarboxylic dianhydrides, tetracarboxylic acid dihalide compounds, tetracarboxylic acid dialkyl ester compounds or tetracarboxylic acid dialkyl ester dihalides Compounds etc.

That is, other tetracarboxylic acid components include, for example, 1,2,5,6-naphthalene tetracarboxylic acid, 1,4,5,8-naphthalene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid , 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4-biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ', 4,4'-benzophenone tetracarboxylic acid, bis (3,4-dicarboxyphenyl) ash, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-di Carboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) di Methylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis (3,4-dicarboxyphenyl) pyridine, 3,3 ', 4,4'-diphenylbenzene tetracarboxylic acid, 3,4,9,10-perylene tetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutane Tetracarboxylic acid, etc.

The other tetracarboxylic acid components of the present invention, in combination with the solubility of the specific polymer of the present invention in solvents, the coating properties of the composition and the liquid crystal alignment treatment agent, the liquid crystal alignment film in the case of the liquid crystal alignment film, and the voltage retention For characteristics such as the rate and the accumulated charge, one type may be used or two or more types may be used in combination.

<Manufacturing method of specific polymer>

In the present invention, the method for producing specific polymers, that is, the production of these polyimide-based polymers is not particularly limited. Generally, it can be obtained by reacting the diamine component with the tetracarboxylic acid component. Generally speaking, the diamine component formed by combining at least one kind of tetracarboxylic acid component selected from the group consisting of tetracarboxylic dianhydride and its derivatives with one or more diamine compounds Carrying out the reaction to prepare the method of polyamide. Specifically, for example, a method of producing polyamic acid by polycondensing a tetracarboxylic dianhydride with a primary or secondary diamine compound, or using a tetracarboxylic acid with a primary or secondary diamine compound A method of producing polyamic acid by dehydration polycondensation reaction or a method of polycondensing tetracarboxylic acid dihalide with a primary or secondary diamine compound to produce polyamic acid.

In order to obtain a polyalkyl amide, for example, a method of polycondensing a tetracarboxylic acid obtained by esterifying a carboxylic acid dialkyl with a primary or secondary diamine compound, using a carboxylic acid dialkyl ester The method of polycondensing the obtained tetracarboxylic acid dihalide and the primary or secondary diamine compound or the method of converting the carboxyl group of the polyamic acid into an ester.

When polyimide is to be produced, for example, a method of forming a polyimide by ring-closing the aforementioned polyamic acid or polyalkyl amide can be used.

The reaction of the diamine component and the tetracarboxylic acid component is usually carried out by making the diamine component and the tetracarboxylic acid component in a solvent. The solvent used at this time may also use the specific solvent of the present invention, but it is not particularly limited as long as it can dissolve the produced polyimide precursor solvent. The following are specific examples of the solvents used in the reaction, but they are not limited to these examples.

For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidine Ketone or γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide or 1,3-dimethyl-tetrahydroimidazolone, etc. In addition, when the polyimide precursor has high solvent solubility, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following formula [D -1] ~ Solvent shown in formula [D-3].

(In formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms, in formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms, in formula [D-3], D ³ represents an alkyl group having 1 to 4 carbon atoms).

These solvents may be used alone or in combination. In addition, even if it is a solvent that does not dissolve the polyimide precursor, it may be mixed with the aforementioned solvent as long as the produced polyimide precursor is not precipitated within a range. In addition, the moisture in the solvent will hinder the polymerization reaction, and it is the cause of the hydrolysis of the polyimide precursor produced, so the solvent is preferably dehydrated and dried.

When the diamine component and the tetracarboxylic acid component are reacted in a solvent, for example, the solution obtained by dispersing or dissolving the diamine component in the solvent is stirred to disperse or dissolve the tetracarboxylic acid component or The method of adding by solvent, or the method of dispersing or dissolving the tetracarboxylic acid component in the solution obtained by the solvent, adding the diamine component, or the method of adding the diamine component and the tetracarboxylic acid component to each other, etc. Use any of these method. In addition, when a plurality of diamine components or tetracarboxylic acid components are used to carry out the reaction, the reaction may be carried out in a mixed state first, or the reaction may be sequentially performed individually, or the low The molecular weight body may be mixed to form a polymer. The polymerization temperature at this time can be selected from any temperature of -20 ° C to 150 ° C, but it is preferably in the range of -5 ° C to 100 ° C. In addition, the reaction can be carried out at any concentration, but if the concentration is too low, it will not be easy to produce high molecular weight polymers, and if the concentration is too high, the viscosity of the reaction solution will be too high to make uniform stirring difficult. Therefore, it is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass. The reaction may be carried out at a high concentration in the initial stage, and then, a solvent may be added.

In the polymerization reaction of the polyimide precursor, the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. It is the same as the normal polycondensation reaction. The closer the molar ratio is to 1.0, the larger the molecular weight of the polyimide precursor produced.

The polyimide of the present invention is a polyimide obtained by ring-closing the aforementioned polyimide precursor. In this polyimide, the ring-closing rate of the amide acid group (also referred to as the imidate rate) It does not have to be 100%, and it can be adjusted arbitrarily according to the purpose or purpose.

The method of imidizing the polyimide precursor, for example, directly heating the solution of the polyimide precursor to make it thermally imidized or adding a catalyst to the solution of the polyimide precursor Catalysts such as imidization.

In the case where the polyimide precursor is thermally imidized in solution, its temperature is 100 ° C to 400 ° C, preferably 120 ° C to 250 ° C, and the water produced by the imidization reaction is continued Excluded from reaction It is better to proceed outside the system.

The catalyst of the polyimide precursor is imidized. For example, in the solution of the polyimide precursor, an alkaline catalyst and an acid anhydride are added, and the temperature is -20 ° C ~ 250 ° C, preferably 0 ° C ~ Stir at 180 ° C. The amount of the alkaline catalyst is 0.5 mole times to 30 mole times of the amide acid group, preferably 2 mole times to 20 mole times, and the amount of the anhydride is 1 mole times to 50 mole times of the amide acid group Molar times, preferably 3 mole times to 30 mole times. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine can preferably maintain a moderate basicity during the reaction, and the like is preferred. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic dianhydride. Among these, when acetic anhydride is used, it is preferably purified after the completion of the reaction. When the catalyst is imidized, the imidization rate can be controlled by adjusting the amount of catalyst, reaction temperature and reaction time.

In the case of recovering the generated polyimide precursor or polyimide from the reaction solution of the polyimide precursor or polyimide, it is sufficient to put the reaction solution in a solvent to precipitate it. Examples of the solvent used for precipitation include methanol, ethanol, isopropanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. The polymer deposited by the solvent for precipitation can be recovered by filtration, and then dried under normal pressure or reduced pressure at normal temperature or under heating. In addition, the polymer after precipitation recovery can be re-dissolved in the solvent 2 to 10 times and re-precipitated and recovered to reduce impurities in the polymer. The solvent at this time may be, for example, alcohols, ketones, or hydrocarbons. When using more than three types of solvents selected from these contents, the efficiency of purification can be further improved. good.

<Composition‧Liquid crystal alignment treatment agent>

The composition of the present invention and the liquid crystal alignment treatment agent using the same are coating solutions used for forming polyimide films and liquid crystal alignment films (also collectively referred to as resin coatings), which are used to form specific solvents and contain specific polymers The coating solution used for the resin coating.

For the specific polymer of the present invention, any of polyimide-based polymers such as polyamic acid, polyalkyl amide and polyimide can be used. Among them, polyalkyl amide or polyimide is preferred. More preferably, it is polyimide.

All the polymer components in the composition of the present invention and the liquid crystal alignment treatment agent may be all the specific polymers of the present invention. In this case, the specific polymer of the present invention may use two or more types of blends. In addition, the specific polymer may be obtained by mixing with other polymers. Other polymers include, for example, cellulose-based polymers, acrylic polymers, methacrylic polymers, polystyrene, polyamide, polysiloxane, and the like. At this time, the content of the other polymers is 0.5 to 30 parts by mass relative to 100 parts by mass of the specific polymer of the present invention. Among them, 1 to 20 parts by mass is better.

In addition, in the case where the composition of the present invention is used as a liquid crystal alignment treatment agent to form a liquid crystal alignment film, a specific polymer having a specific side chain structure represented by the aforementioned formula [1-1] of the present invention is used as the specific polymer The better. Among them, the use of "use has a specific side chain structure shown in formula [1-1] The specific polymer obtained by the specific side chain type diamine compound represented by the formula [1a] is preferred. In particular, for a TN (Twisted Nematic) mode or a VA (Vertical Alignment) mode, etc., a liquid crystal alignment film in which a pretilt angle of liquid crystal is a necessary mode is preferably a specific polymer using a specific side chain type diamine compound. In this case, a specific polymer using a specific side chain type diamine compound may be used in combination with a specific polymer not using a specific side chain type diamine compound. In this case, the content of the specific polymer without using the specific side chain type diamine compound is preferably 10 to 300 parts by mass relative to 100 parts by mass of the specific polymer using the specific side chain type diamine compound. Among them, 20 to 200 parts by mass is better.

The solvent in the composition of the present invention and the liquid crystal alignment treatment agent can form a uniform resin film by coating, and the content of the solvent is preferably 70 to 99.9% by mass. This content can be appropriately changed in accordance with the film thickness of the polyimide film and the liquid crystal alignment film as the purpose.

In addition, the solvent at this time may be all the specific solvent of the present invention, and may be used together with a solvent that can dissolve the specific polymer of the present invention, that is, a good solvent. The following will list specific examples of good solvents, but not limited to these contents.

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

Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyl lactone (the above, also referred to as (C) component) is preferably used.

These (C) components are preferably 1 to 70% by mass of the total solvent contained in the composition and the liquid crystal alignment treatment agent. Among them, 5 to 65% by mass is better. It is preferably 5 to 60% by mass, and more preferably 10 to 60% by mass.

When the aforementioned good solvent is blended with the solubility of the specific polymer of the present invention in the solvent, the composition and the coating properties of the liquid crystal alignment treatment agent, one kind or two or more kinds may be used in combination.

The composition and liquid crystal alignment treatment agent of the present invention, without impairing the scope of the effects of the present invention, can also be used as an organic solvent that can improve the coating properties or surface smoothness of the resin coating when coating the composition and liquid crystal alignment treatment agent , That is, poor solvent. The following is a specific example of a poor solvent, but it is not limited to these contents.

For example, ethanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol Alcohol, isoamyl alcohol, tert-pentanol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1 -Methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2-ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol , 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl -1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butane Oxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentane Ketone, 2-hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2- Ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propyl carbonate, ethyl carbonate, 2- (methoxymethoxy) ethanol, ethylene glycol Monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2- (hexyl oxo) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1- (butoxy) Ethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate , Ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol Monobutyl ether acetate, 2- (2-ethoxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol Monoethyl ether, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, propylene acetate Methyl ketoate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isolactic lactate Amyl ester or the solvent represented by the aforementioned formula [D-1] to formula [D-3], etc.

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 formula [D -1] The solvent represented by formula [D-3] (the above, also referred to as (D) component) is preferred.

These (D) components are based on the composition and liquid crystal alignment treatment agent. It is preferably 10 to 80% by mass of the total contained solvent. Among them, 10 to 70% by mass is better. It is preferably 20 to 70% by mass, and more preferably 20 to 60% by mass.

When the aforementioned poor solvent is combined with the solubility of the specific polymer of the present invention in the solvent, the composition and the coating properties of the liquid crystal alignment treatment agent, one type or two or more types may be used in combination.

In the composition and liquid crystal alignment treatment agent of the present invention, a crosslinkable compound having an epoxy group, an isocyanate group, a propylene oxide group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group are introduced A crosslinkable compound of at least one kind of substituent selected from the group or a crosslinkable compound having a polymerizable unsaturated bond is preferably introduced. These substituents or polymerizable unsaturated bonds must have two or more in the crosslinkable compound.

Crosslinkable compounds with epoxy or isocyanate groups, for example, diphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetra Glycidylaminodiphenyl ester, tetraglycidyl-m-xylenediamine, tetraglycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenylglycidyl ether ethane, triphenyl Glycidyl ether ethane, diphenol hexafluoroacetone diglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy) -1-trifluoromethyl-2,2,2- Trifluoromethyl) benzene, 4,4-bis (2,3-epoxypropoxy) octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidylmethylxylenediamine, 2 -(4- (2,3-epoxypropoxy) phenyl) -2- (4- (1,1-bis (4- (2,3-epoxypropoxy) phenyl) ethyl Yl) phenyl) propane or 1,3-bis (4- (1- (4- (2,3-epoxypropoxy) phenyl) -1- (4- (1- (4- (2,3-epoxypropoxy) phenyl) -1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol and the like.

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

Specifically, for example, the cross-linkable compounds represented by the formula [4a] to the formula [4k] disclosed in Items 58 to 59 of International Publication No. 2011/132751 (published on October 27, 2011) are listed.

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

Specifically, the cross-linkable compounds shown in Formula [5-1] to Formula [5-42] disclosed in Items 76 to 82 of International Publication No. 2012/014898 (published on 2012.2.2) can be cited. Wait.

Cross-linkable compounds having at least one substituent selected from the group consisting of hydroxy and alkoxy groups, for example, amine-based resins having hydroxy or alkoxy groups, for example, melamine resin, urea resin, qua Resin, acetylene urea-formaldehyde resin, succinylamide-formaldehyde resin or ethylene urea-formaldehyde resin, etc. Specifically, for example, melamine derivatives and benzoxazines in which the hydrogen atom of the amine group is substituted with methylol or alkoxymethyl or both can be used. Derivatives, or acetylene urea. The melamine derivative or benzox Derivatives can exist in the form of dimers or trimers. Of these, every three The ring is preferably one having 3 to 6 hydroxymethyl groups or alkoxymethyl groups on average.

The melamine derivatives or benzox Examples of derivatives include, for example, each of the three commercially available products Ring, MX-750 substituted by an average of 3.7 methoxymethyl groups, each three Ring, MW-30 (above, manufactured by Sanwa Chemical Co., Ltd.) or CYMEL 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc. substituted with an average of 5.8 methoxymethyl groups Methoxymethylated melamine, CYMEL 235, 236, 238, 212, 253, 254, etc. Methoxymethylated butoxymethylated melamine, CYMEL 506, 508 etc. butoxymethylated melamine, CYMEL Methoxymethylated isobutoxymethylated melamine containing carboxyl group such as 1141, methoxymethylated ethoxymethylated benzoxabene such as CYMEL 1123 , CYMEL 1123-10 and other methoxymethylated butoxymethylated benzox , CYMEL 1128 and other butoxymethylated benzoxa , CYMEL 1125-80 and other carboxyl-containing methoxymethylated ethoxymethylated benzox (Above, manufactured by Mitsui Cyanamide Co., Ltd.), etc. Examples of acetylene urea include butoxymethylated acetylene urea such as CYMEL 1170, hydroxymethylated acetylene urea such as CYMEL 1172, and methoxymethylated acetylene urea such as POWERLINK 1174.

Benzene or phenolic compounds with hydroxyl or alkoxy groups, for example, 1,3,5-ginseng (methoxymethyl) benzene, 1,2,4-ginseng (isopropoxymethyl) benzene, 1, 4-bis (sec-butoxymethyl) benzene or 2,6-dihydroxymethyl-p-tert-butylphenol, etc.

More specifically, the crosslinkability as shown in the formula [6-1] to formula [6-48] disclosed in pages 62 to 66 of International Publication No. 2011/132751 (published on 2011.10.27) can be cited. Compounds etc.

Examples of crosslinkable compounds having polymerizable unsaturated bonds include three trimethylolpropane tri (meth) acrylates, pentaerythritol tri (meth) acrylates, and dipentaerythritol penta (methyl) ) A crosslinkable compound of a polymerizable unsaturated group such as acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane or glycerol polyglycidyl ether poly (meth) acrylate, and Such as having 2 ethylene glycol di (meth) acrylates, diethylene glycol di (meth) acrylates, tetraethylene glycol di (meth) acrylates, polyethylene glycol di (meth) in the molecule Acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide di Phenol A type di (meth) acrylate, oxypropylene diphenol type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, Pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) propylene Crosslinkable compounds of polymerizable unsaturated groups such as acid esters, diglycidyl phthalate di (meth) acrylate or hydroxytert-valeric acid neopentyl glycol di (meth) acrylate, etc. , With one 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2- Phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl benzoate, 3-chloro-2-hydroxypropyl (methyl) Crosslinking of polymerizable unsaturated groups such as acrylate, glycerol mono (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate or N-methylol (meth) acrylamide Sex compounds.

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

(In formula [7A], E ¹ represents at least one selected from cyclohexane ring, dicyclohexane ring, benzene ring, biphenyl ring, triphenyl ring, naphthalene ring, stilbene ring, anthracene ring and phenanthrene ring , E ² represents the base selected by the following formula [7a] or formula [7b], n represents an integer of 1 ~ 4).

The above compound is an example of a crosslinkable compound, but it is not limited to this content. In addition, the crosslinkable compound used in the composition of the present invention and the liquid crystal alignment treatment agent may be only one type, or a combination of two or more types.

In the composition and liquid crystal alignment treatment agent of the present invention, the content of the crosslinkable compound is preferably 0.1 to 150 parts by mass relative to 100 parts by mass of the entire polymer component. Among them, from the viewpoint of achieving the intended effect by performing the cross-linking reaction, it is preferably 0.1 to 100 parts by mass relative to 100 parts by mass of the entire polymer component. Better is 1 quality ~ 50 parts by mass.

The composition and liquid crystal alignment treatment agent of the present invention can also be used when coating the composition and liquid crystal alignment treatment agent within a range that does not impair the effects of the present invention, and can improve the film thickness uniformity or surface smoothness of the resin coating Of compounds.

Compounds that can improve the film thickness uniformity or surface smoothness of the resin coating include, for example, fluorine-based surfactants, polysiloxane-based surfactants, and aprotic surfactants.

More specifically, for example, F-TOP EF301, EF303, EF352 (above, manufactured by Dow Chemical Process Co., Ltd.), Magnesium F171, F173, R-30 (above, manufactured by Dainippon Paint Co., Ltd.), FLUORAD FC430 , FC431 (above, manufactured by Sumitomo 3M Corporation), ASAHIGARD AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass), etc.

The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass relative to 100 parts by mass of all polymer components contained in the composition and the liquid crystal alignment treatment agent .

In addition, in the composition of the present invention and the liquid crystal alignment treatment agent, a compound that promotes charge movement in the resin film to promote dissociation of charge of the element can be added to page 69 of International Publication No. 2011/132751 (published on 2011.10.27) The nitrogen-containing heterocyclic amine compounds represented by formula [M1] to formula [M156] disclosed on page 73. The amine compound may be directly added to the composition and the liquid crystal alignment treatment agent, and may be dissolved in a suitable solvent as a concentration A solution of 0.1% by mass to 10% by mass, preferably 1% by mass to 7% by mass, is preferably added afterwards. The solvent is not particularly limited as long as it can dissolve the above-mentioned specific polymer.

The composition and liquid crystal alignment treatment agent of the present invention, in addition to the compound that can improve the film thickness uniformity or surface smoothness of the above-mentioned poor solvent, crosslinkable compound, resin coating, and the compound that promotes charge dissociation, do not impair the effects of the present invention Within the range, a dielectric or conductive substance may be added for the purpose of changing the electrical characteristics such as the dielectric constant and conductivity of the resin film.

<Polyimide film>

The composition of the present invention can be used as a polyimide film after being coated on a substrate and sintered. The substrate used at this time may be a plastic substrate such as a glass substrate, a silicon wafer, an acrylic substrate, a polycarbonate substrate, or a PET (polyethylene terephthalate) substrate according to the intended device. In addition, a polyimide film can also be used as a thin film substrate. The coating method of the composition is not particularly limited, and industrially, the dipping method, roll coating method, slot coating method, spin method, spray method, screen printing, lithographic printing, Flexo printing or inkjet method. These can be used appropriately according to their purpose.

After the composition is coated on the substrate, the solvent can be evaporated at 50 to 300 ° C, preferably 80 to 250 ° C by using heating means such as a hot plate, a thermal cycle oven or an IR (infrared) oven. A polyimide film is formed. In the case of using the composition obtained by the specific solvent of the present invention, a polyimide film can be produced even at a temperature of 200 ° C or lower. After sintering The thickness of the polyimide film can be adjusted to 0.01 ~ 100μm according to the purpose.

<Liquid crystal alignment film and liquid crystal display element>

The liquid crystal alignment treatment agent of the composition of the present invention can be used as a liquid crystal alignment film after being coated on a substrate, sintered, and subjected to alignment treatment such as rubbing treatment or light irradiation. Moreover, in the case of vertical alignment applications such as VA mode, it can be used as a liquid crystal alignment film even without alignment treatment. The substrate used at this time is not particularly limited as long as it has a high transparency. In addition to the glass substrate, for example, an acrylic substrate, a polycarbonate substrate, or PET (polyethylene terephthalate) can also be used Acid ester) plastic substrates such as substrates. From the viewpoint of simplification of the manufacturing process, it is preferable to form a substrate on which an ITO (indium tin oxide) electrode or the like used for liquid crystal driving is formed. In addition, in the reflective liquid crystal display element, as long as it is a single-sided substrate, an opaque substrate such as a silicon wafer may also be used. In this case, for example, a material that reflects light such as aluminum may also be used.

The coating method of the liquid crystal alignment treatment agent is not particularly limited, and industrially, it is generally a method performed using screen printing, lithographic printing, flexo printing, or inkjet method. Other coating methods include, for example, a dipping method, a roll coating method, a slit coating method, a spin method, and a spray method, etc., which may be appropriately used according to the purpose.

After the liquid crystal alignment treatment agent is coated on the substrate, a heating plate, a thermal cycle oven, or an IR (infrared) oven or other heating means can be used to make the solvent used with the liquid crystal alignment treatment agent at 30 to 300 ° C. Preferably, the solvent is evaporated at a temperature of 30 to 250 ° C to form a liquid crystal alignment film. In the case of using the liquid-crystal alignment treatment agent of the specific solvent of this invention, a liquid-crystal alignment film can be produced even at the temperature of 200 degrees C or less. The thickness of the liquid crystal alignment film after sintering is unfavorable from the viewpoint of power consumption of the liquid crystal display element when it is too thick. When it is too thin, the reliability of the liquid crystal display element will be reduced, so it is preferably 5 to 300 nm, more preferably 10 ~ 150mm. When the liquid crystal is horizontally or obliquely aligned, the sintered liquid crystal alignment film can be subjected to rubbing or polarized ultraviolet irradiation.

The liquid crystal display device of the present invention is a liquid crystal cell manufactured as a liquid crystal display element by a well-known method after preparing a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention according to the aforementioned method.

The manufacturing method of the liquid crystal cell may include, for example, first preparing a pair of substrates forming a liquid crystal alignment film, and spreading spacers on the liquid crystal alignment film of the single-sided substrate, with the liquid crystal alignment film surface as the inner side, and the other single It is a method of bonding the substrates on the side and injecting the liquid crystal under reduced pressure, and then sealing, or on the liquid crystal alignment film surface of the spacer, after the liquid crystal is dropped, the substrates are bonded and sealed.

In addition, the liquid crystal alignment treatment agent of the present invention is suitable for use. A liquid crystal layer is provided between a pair of substrates provided with electrodes, and is disposed between a pair of substrates to be polymerizable via at least one of active energy rays and heat. The liquid crystal composition of the polymerizable compound is a liquid crystal display device produced by the step of polymerizing the polymerizable compound by irradiating at least one of active energy rays and heating while continuously applying a voltage between the electrodes. Among them, the active energy ray is preferably ultraviolet. The wavelength of UV is 300 ~ 400nm, It is preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. In addition, ultraviolet irradiation and heating may be performed simultaneously.

The aforementioned liquid crystal display device is a type that can control the pretilt angle of liquid crystal molecules through a PSA (Polymer Sustained Alignment) method. In the PSA method, a small amount of photopolymerizable compound, such as a photopolymerizable monomer, can be mixed into the liquid crystal material, and after combining the liquid crystal cell, the photopolymerizable compound can be irradiated with ultraviolet rays to the liquid crystal layer under a specific voltage. The pre-tilt angle of liquid crystal molecules is controlled by the generated polymer. The alignment state of the liquid crystal molecules when the polymer is generated is remembered even after the voltage is removed, so the pretilt angle of the liquid crystal molecules can be adjusted by controlling the electric field formed by the liquid crystal layer. In addition, in the PSA method, since no rubbing treatment is required, it is suitable for forming a vertical alignment type liquid crystal layer that is not easy to control the pretilt angle by rubbing treatment.

That is, the liquid crystal display element of the present invention is a substrate with a liquid crystal alignment film prepared from the liquid crystal alignment treatment agent of the present invention according to the aforementioned method, a liquid crystal cell is fabricated, and the polymerization is terminated by at least one of ultraviolet irradiation and heating until polymerization It can polymerize and control the alignment of liquid crystal molecules.

An example of manufacturing a liquid crystal cell of the PSA method will be described, that is, for example, a pair of substrates on which a liquid crystal alignment film is formed, and a spacer is spread on the liquid crystal alignment film of a single-sided substrate, with the liquid crystal alignment film facing inward The method is to stick the other one-sided substrate, inject the liquid crystal under reduced pressure and then seal, or drop the liquid crystal alignment film surface with the spacer dispersed into the liquid crystal, and then stick the substrate to seal.

In the liquid crystal, a polymerizable compound that is polymerized by heat or ultraviolet irradiation can be mixed. The polymerizable compound is, for example, a compound having one or more polymerizable unsaturated groups such as an acrylate group or a methacrylate group in the molecule. At this time, the polymerizable compound is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass relative to 100 parts by mass of the liquid crystal component. When the polymerizable compound is less than 0.01 parts by mass, the polymerizable compound will not be polymerized and the alignment of the liquid crystal cannot be controlled. When it is more than 10 parts by mass, the unreacted polymerizable compound is excessive, which may cause the afterimage characteristics of the liquid crystal display element reduce.

After the liquid crystal cell is prepared, the polymerizable compound can be polymerized by applying heat or ultraviolet rays while continuously applying an AC or DC voltage to the liquid crystal cell. In this way, 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 for a liquid crystal layer between a pair of substrates having electrodes, and between the pair of substrates, a content polymerizable via at least one of active energy rays and heat is disposed The polymerizable liquid crystal alignment film is preferably a liquid crystal display device produced by applying a voltage between electrodes, that is, the SC-PVA mode. Among them, the active energy ray is preferably ultraviolet. The wavelength of 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, preferably 60 to 80 ° C. In addition, ultraviolet irradiation and heating may be performed simultaneously.

The method for producing a liquid crystal alignment film containing a polymerizable group polymerized by at least one of active energy rays and heat includes, for example, a method of adding a compound containing this polymerizable group to a liquid crystal alignment treatment agent, Or a method of using a polymer component containing a polymerizable group.

An example of manufacturing the liquid crystal cell of the SC-PVA mode may include, for example, preparing a pair of substrates on which the liquid crystal alignment film of the present invention is formed, spreading spacers on the liquid crystal alignment film of the single-sided substrate, with the liquid crystal alignment film facing inward The method is to stick another one-sided substrate, inject liquid crystal under reduced pressure and seal it, or after the liquid crystal alignment film surface of the spacer is dropped into liquid crystal, and then the method of bonding and sealing the substrate.

After the liquid crystal cell is fabricated, the liquid crystal cell can be continuously applied with AC or DC voltage, and the alignment of the liquid crystal molecules can be controlled by heat or ultraviolet radiation.

As described above, the liquid crystal alignment treatment agent of the present invention can form a liquid crystal alignment film having excellent coating properties. In addition, even when the sintering at the time of manufacturing the liquid crystal alignment film is in a low temperature state, it can be obtained as a liquid crystal display element The electrical characteristics of VHR are excellent liquid crystal alignment films. Therefore, the liquid crystal display device having the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention is suitable for large-screen and high-definition LCD TVs or small and medium-sized car navigation systems or smart phones, with excellent reliability. Wait.

[Example]

The present invention will be described in more detail with examples below, but the present invention is not limited to this content.

"Abbreviations used in the synthesis examples, examples and comparative examples of the present invention"

The abbreviations used in Synthesis Examples, Examples, and Comparative Examples are shown below.

<Monomer used for producing the polyimide-based polymer of the present invention> (Specific side chain type diamine compound of the present invention)

A1: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene (having a specific side chain structure represented by formula [1-1] of the present invention The specific side chain type diamine compound)

A2: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxymethyl] benzene (having a specific side of formula [1-1] of the present invention (Chain structure specific side chain type diamine compound)

A3: 1,3-diamino-4- {4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy} benzene (having the formula [1 of the present invention -1] The specific side chain type diamine compound shown in the specific side chain structure)

A4: diamine compound represented by the following formula [A4] (specific side chain type diamine compound having a specific side chain structure represented by formula [1-1] of the present invention)

A5: 1,3-diamino-4-octadecyloxybenzene (specific side chain type diamine compound having a specific side chain structure represented by formula [1-2] of the present invention)

(Diamine compound represented by formula [2a] of the present invention)

B1: 3,5-diaminobenzoic acid (diamine compound having a carboxyl group (COOH group) represented by formula [2a] of the present invention)

(Diamine compound represented by formula [3a] of the present invention)

C1: a diamine compound represented by the following formula [C1] (a diamine compound having a nitrogen-containing heterocyclic ring represented by the formula [3a] of the present invention)

C2: a diamine compound represented by the following formula [C2] (a diamine compound having a nitrogen-containing heterocyclic ring represented by the formula [3a] of the present invention)

(Other diamine compounds)

D1: p-phenylene diamine

D2: m-phenylene diamine

(Specific tetracarboxylic acid composition)

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

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

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

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

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

<Crosslinkable compound used in the present invention>

K1: Crosslinkable compound represented by the following formula [K1]

<Specific solvent of the present invention>

S1: Solvent represented by the following formula [S1] (specific solvent represented by the formula [A-1] of the present invention)

<Other solvents>

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

γ-BL: γ-butyrolactone

BCS: ethylene glycol monobutyl ether

PB: Propylene glycol monobutyl ether

EC: Diethylene glycol monoethyl ether

DME: Dipropylene glycol dimethyl ether

"Determination of the molecular weight of the polyimide polymer of the present invention"

The molecular weights of the polyimide precursor and polyimide in the synthesis example are the room temperature gel permeation chromatography (GPC) device (GPC-101) (manufactured by Showa Denko) and the column (KD-803) , KD-805) (manufactured by Shodex), and measured in the following manner.

Column temperature: 50 ℃

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

Flow rate: 1.0ml / min

Standard samples for making calibration lines: 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 (Made by the experimental company).

"Determination of the Amidation Rate of the Polyimide of the Invention"

The imidization ratio of polyimide in the synthesis example was measured in the following manner. Add 20 mg of polyimide powder to NMR (nuclear magnetic resonance) sample tube (NMR sampling standard test tube, 5 (manufactured by Kusano Scientific Co., Ltd.)) was added heavy dimethyl sulfoxide (DMSO-d ₆ , 0.05% by mass TMS (tetramethylsilane) mixed product) (0.53 ml), and ultrasonic waves were applied to completely dissolve it. This solution was measured for a 500 MHz proton NMR using an NMR measuring machine (JNW-ECA500) (manufactured by JEOL DATUM Corporation). The imidization rate is determined based on the protons generated by the unchanged structure before and after imidization as the reference protons. It is the peak integration value using the protons, and it is caused by the amide acid occurring near 9.5 ppm to 10.0 ppm. The total value of the proton peak generated by the NH group is obtained according to the following formula.

Amidification rate (%) = (1-α‧x / y) × 100

In the above formula, x is the integrated peak value of protons generated from the NH group of the amidic acid, y is the integrated peak value of the reference proton, and α is the polyamic acid (acid imidization rate is 0%). NH relative to 1 amide acid Matrix protons, the ratio of the number of reference protons.

"Synthesis of Polyimide-based Polymers of the Invention" <Synthesis Example 1>

Mix E1 (5.21g, 26.6mmol), A1 (5.12g, 13.5mmol) and B1 (2.05g, 13.5mmol) in S1 (37.1g), and react at 40 ° C for 8 hours to obtain a resin solid content concentration of 25% by mass of polyamic acid solution (1). The number average molecular weight of this polyamide was 25,800 and the weight average molecular weight was 86,900.

<Synthesis Example 2>

E2 (3.40g, 13.6mmol), B1 (4.19g, 27.6mmol) and D1 (0.74g, 6.89mmol) were mixed in S1 (24.7g), after reacting at 80 ° C for 5 hours, E1 (4.00g) was added , 20.4mmol) and S1 (12.3g), at 40 ℃, 6 hours of reaction, to obtain a resin solid content concentration of 25% by mass of polyamic acid solution (2). The number average molecular weight of this polyamide was 26,200, and the weight average molecular weight was 86,400.

<Synthesis Example 3>

To the polyamic acid solution (2) (30.0 g) obtained according to the synthesis method of Synthesis Example 2, after adding NMP to dilute to 6% by mass, add acetic anhydride (3.95 g) and pyridine as the amide imidization catalyst (2.50g), react at 60 ° C for 2 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C After drying, polyimide powder (3) is obtained. The polyimide has an imidization ratio of 53%, a number average molecular weight of 22,100, and a weight average molecular weight of 60,900.

<Synthesis Example 4>

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

NEP was added to the obtained polyamic acid solution (30.0 g), diluted to 6% by mass, and then acetic anhydride (4.40 g) and pyridine (3.30 g) as an imidization catalyst were added and reacted at 80 ° C 3.5 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain polyimide powder (4). The polyimide has an imidization rate of 80%, a number average molecular weight of 19,900, and a weight average molecular weight of 55,100.

<Synthesis Example 5>

E2 (3.22g, 12.9mmol), A2 (4.62g, 11.7mmol), B1 (1.78g, 11.7mmol) and D1 (0.28g, 2.60mmol) were mixed in S1 (24.8g) and reacted at 80 ° C After 5 hours, E1 (2.52g, 12.9mmol) and S1 (12.4g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution (5) with a resin solid content concentration of 25% by mass. Polyamide Has a number average molecular weight of 20,900 and a weight average molecular weight of 72,100.

<Synthesis Example 6>

To the polyamic acid solution (5) (30.0 g) obtained according to the synthesis method of Synthesis Example 5, after adding NMP to dilute to 6% by mass, acetic anhydride (3.95 g) and pyridine as the amide imidization catalyst were added (2.40g), reacted at 70 ° C for 3.5 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain polyimide powder (6). The polyimide had an imidization ratio of 73%, a number average molecular weight of 19,900, and a weight average molecular weight of 53,900.

<Synthesis Example 7>

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

To the obtained polyamic acid solution (30.0 g), after adding NMP to dilute to 6% by mass, acetic anhydride (4.50 g) and pyridine (3.30 g) as an imidization catalyst were added and reacted at 80 ° C 3.5 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain polyimide powder (7). The polyimide has an imidization rate of 80% and a number average molecular weight of 15,900, weight average molecular weight is 43,800. .

<Synthesis Example 8>

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

To the obtained polyamic acid solution (30.0g), after adding NMP to dilute to 6% by mass, acetic anhydride (3.85g) and pyridine (2.50g) as an imidization catalyst were added and reacted at 60 ° C 2 hour. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain polyimide powder (8). The polyimide had an imidization ratio of 55%, a number average molecular weight of 16,900, and a weight average molecular weight of 46,900.

<Synthesis Example 9>

E2 (2.55g, 10.2mmol), A4 (2.55g, 5.17mmol), B1 (0.39g, 2.58mmol), C2 (3.35g, 12.9mmol) and D2 (0.56g, 5.17mmol) in NEP (24.8g ), Mixed at 80 ° C for 5 hours, added E1 (3.00g, 15.3mmol) and NEP (12.4g), and reacted at 40 ° C for 6 hours to obtain polyacrylamide with a resin solid content concentration of 25% by mass Amino acid solution.

To the obtained polyamic acid solution (30.5g), add NEP dilute After releasing to 6% by mass, acetic anhydride (3.95g) and pyridine (2.55g) as an amide imidization catalyst were added and reacted at 60 ° C for 3 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain polyimide powder (9). The polyimide has an imidization rate of 61%, a number average molecular weight of 16,000, and a weight average molecular weight of 44,800.

<Synthesis Example 10>

Mix E2 (1.20g, 4.78mmol), A5 (3.65g, 9.69mmol), C2 (2.51g, 9.69mmol) and D2 (0.52g, 4.84mmol) in NMP (23.3g) and react at 80 ℃ After 5 hours, E1 (3.75 g, 19.1 mmol) and NMP (11.6 g) were added and reacted at 40 ° C. for 6 hours to obtain a polyamic acid solution with a resin solid content concentration of 25% by mass.

To the obtained polyamic acid solution (30.0g), after adding NMP to dilute to 6% by mass, acetic anhydride (3.80g) and pyridine (2.55g) as an imidization catalyst were added at 60 ° C. React for 2 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain polyimide powder (10). The polyimide has an imidization rate of 56%, a number average molecular weight of 16,200, and a weight average molecular weight of 48,100.

<Synthesis Example 11>

Mix E3 (7.50g, 33.5mmol), B1 (3.61g, 23.7mmol), C1 (0.41g, 1.69mmol) and D1 (0.92g, 8.47mmol) in NMP (37.3g) Combine and react at 40 ° C for 8 hours to obtain a polyamic acid solution with a resin solid content concentration of 25% by mass.

NMP was added to the obtained polyamic acid solution (30.0g) and diluted to 6% by mass, then acetic anhydride (4.20g) and pyridine (3.10g) as an imidization catalyst were added and reacted at 80 ° C for 2.5 hour. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain polyimide powder (11). The polyimide has an imidization rate of 75%, a number average molecular weight of 19,800, and a weight average molecular weight of 53,900.

<Synthesis Example 12>

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

NMP was added to the obtained polyamic acid solution (30.0 g), diluted to 6% by mass, then acetic anhydride (4.50 g) and pyridine (3.35 g) as an imidization catalyst were added, and reacted at 80 ° C for 3.5 hour. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain polyimide powder (12). The polyimide had an imidization rate of 81%, a number average molecular weight of 18,200, and a weight average molecular weight of 51,600.

<Synthesis Example 13>

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

NMP was added to the obtained polyamic acid solution (30.5g), diluted to 6% by mass, then acetic anhydride (3.90g) and pyridine (2.60g) as an imidization catalyst were added, and reacted at 60 ° C 3.5 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain polyimide powder (13). The polyimide has an imidization rate of 65%, a number average molecular weight of 18,500, and a weight average molecular weight of 50,200.

<Synthesis Example 14>

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

To the obtained polyamic acid solution (30.0g), after adding NEP to dilute to 6% by mass, acetic anhydride (3.80g) and pyridine (2.50g) as an imidization catalyst were added and reacted at 60 ° C. 2 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain polyimide powder End (14). The polyimide has an imidization rate of 55%, a number average molecular weight of 16,800, and a weight average molecular weight of 45,300.

<Synthesis Example 15>

Combine E4 (3.29g, 11.0mmol), A2 (3.51g, 8.88mmol), C1 (1.61g, 6.66mmol), C2 (1.15g, 4.44mmol) and D2 (0.24g, 2.22mmol) in NMP (23.9g) ), Mixed at 80 ° C for 6 hours, added E1 (2.15g, 11.0mmol) and NMP (12.0g), and reacted at 40 ° C for 6 hours to obtain polyacrylamide with a resin solid content concentration of 25% by mass Amino acid solution.

To the obtained polyamic acid solution (30.1g), after adding NMP to dilute to 6% by mass, acetic anhydride (4.20g) and pyridine (3.15g) as an imidization catalyst were added and reacted at 80 ° C 2.5 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain polyimide powder (15). The polyimide had an imidization rate of 73%, a number average molecular weight of 15,900, and a weight average molecular weight of 43,800.

<Synthesis Example 16>

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

To the obtained polyamic acid solution (30.0g), after adding NMP to dilute to 6% by mass, acetic anhydride (3.85g) and pyridine (2.40g) as an imidization catalyst were added at 60 ° C. React for 2 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain polyimide powder (16). The polyimide has an imidization rate of 51%, a number average molecular weight of 15,700, and a weight average molecular weight of 44,500.

<Synthesis Example 17>

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

To the obtained polyamic acid solution (30.0g), after adding NMP to dilute to 6% by mass, acetic anhydride (4.20g) and pyridine (3.20g) as an imidization catalyst were added and reacted at 80 ° C 2.5 hours. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain polyimide powder (17). The polyimide has an imidization rate of 73%, a number average molecular weight of 16,200, and a weight average molecular weight of 48,100.

<Synthesis Example 18>

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

To the obtained polyamic acid solution (30.0g), after adding NMP to dilute to 6% by mass, acetic anhydride (4.20g) and pyridine (3.20g) as an imidization catalyst were added and reacted at 80 ° C 2 hour. This reaction solution was poured into methanol (460 ml), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain polyimide powder (18). The polyimide had an imidization ratio of 68%, a number average molecular weight of 15,500, and a weight average molecular weight of 45,100.

<Synthesis Example 19>

E2 (3.10g, 12.4mmol), B1 (3.82g, 25.1mmol) and D1 (0.68g, 6.28mmol) were mixed in NMP (22.5g). After reacting at 80 ° C for 5 hours, E1 (3.65g) was added , 18.6mmol) and NMP (11.3g), at 40 ℃, 6 hours of reaction, to obtain a resin solid content concentration of 25% by mass of polyamic acid solution (19). The number average molecular weight of this polyamide was 27,900, and the weight average molecular weight was 88,900.

<Synthesis Example 20>

Combine E2 (3.13g, 12.5mmol), A2 (4.49g, 11.4mmol), B1 (1.73g, 11.4mmol) and D1 (0.27g, 2.53mmol) in NMP (24.2g) After mixing for 5 hours at 80 ° C, E1 (2.45g, 12.5mmol) and NMP (12.1g) were added and reacted at 40 ° C for 6 hours to obtain polyamidoamine with a resin solid concentration of 25% by mass Acid solution (20). The number average molecular weight of this polyamide was 22,200, and the weight average molecular weight was 76,900.

The polyimide-based polymers of the present invention are shown in Table 1 and Table 2.

"Manufacture of the composition of the present invention and liquid crystal alignment treatment agent"

The following Examples 1 to 20 and Comparative Examples 1 to 4 are examples of manufacturing compositions disclosed. In addition, these compositions are also used as evaluation agents for liquid crystal alignment treatment agents.

The composition and liquid crystal alignment treatment agent of the present invention are shown in Tables 3 to 5.

Using the composition and liquid crystal alignment treatment agent obtained in the examples and comparative examples of the present invention, "printability evaluation of the composition and liquid crystal alignment treatment agent (evaluation of sand holes)" and "printing of the composition and liquid crystal alignment treatment agent" Property evaluation (evaluation of coating film end), "evaluation of voltage retention (VHR) (general cell)", "evaluation of inkjet coatability of liquid crystal alignment treatment agent", "production of liquid crystal cell and liquid crystal Alignment evaluation (PSA cell) "and" Fabrication of liquid crystal cell and evaluation of liquid crystal alignment (SC-PVA Unit cell) ".

"Evaluation of printability of composition and liquid crystal alignment treatment agent (evaluation of shakong)"

Using the compositions obtained according to the methods of the examples and comparative examples of the present invention, the evaluation of polyimide membrane sand holes was carried out. Specifically, for example, these compositions are pressure-filtered using a membrane filter with a pore size of 1 μm, and printed on an unwashed Cr vapor-deposited substrate (length 100 mm × width 100 mm, thickness 1.0 mm). The printing machine is a simple printing machine S15 (manufactured by Japan Photographic Printing Co., Ltd.), the printing area is 80 x 80 mm relative to the center of the substrate, the printing pressure is 0.2 mm, and the disposable substrate is 5 pieces. From printing to pre-drying The time was 90 seconds, the pre-drying was performed on a hot plate at 70 ° C for 5 minutes, and the main sintering was performed in a heat-circulating dust-free oven at 160 ° C for 15 minutes.

Subsequently, the number of sand holes attached to the obtained polyimide film-attached substrate was confirmed. Specifically, for example, the substrate with the polyimide film attached will be visually observed under a sodium lamp, and the number of sand holes on the polyimide film will be calculated. In addition, the smaller the number of sand holes, the less precipitates in the composition, and the better in this evaluation.

Tables 6 to 8 indicate the number of sand holes obtained in the examples and comparative examples.

In addition, the compositions obtained in Examples and Comparative Examples of the present invention can be used for liquid crystal alignment treatment agents. Therefore, the evaluation of the sand holes of the polyimide film of the composition obtained in the examples and comparative examples of the present invention can be suitably used as the evaluation of the sand holes of the liquid crystal alignment film.

"Evaluation of printability of composition and liquid crystal alignment treatment agent (evaluation of coating film end)"

Using the polyimide film-attached substrate obtained from the aforementioned "evaluation of the printability of the composition and liquid crystal alignment treatment agent (evaluation of sand holes)", the coating film end of the polyimide film was evaluated, that is, polyimide Evaluation of the linearity of the end of the imine membrane (also known as linearity evaluation) and the evaluation of the swelling of the end of the polyimide membrane (also known as the evaluation of swelling).

The linearity of the end of the polyimide film was evaluated by using an optical microscope to observe the polyimide film at the right end with respect to the printing direction. More specifically, for example, the difference between (1) and (2) in FIG. 1 of the polyimide film image obtained by observation using an optical microscope magnification of 25 times, that is, the length of A in FIG. 1 is measured. At this time, all the portraits of the polyimide film can obtain the same magnification. The shorter the length of A, the better the linearity of the end of the polyimide film.

The evaluation of the swelling at the end of the polyimide film was performed using an optical microscope to observe the polyimide film at the right end with respect to the printing direction. Specifically, for example, observation using an optical microscope magnification of 25 times, and the length of B in FIG. 2 of the obtained polyimide film portrait are measured. At this time, all the polyimide film images can get the same magnification. The shorter the length of B, the better the expansion of the end of the polyimide film.

In Table 6 to Table 8, the length of A and the length of B obtained in Examples and Comparative Examples are disclosed.

In addition, the composition of the examples and comparative examples of the present invention It can be used for liquid crystal alignment treatment agent. Therefore, the evaluation of the coating film end of the polyimide film obtained in this example and the comparative example is also used as the evaluation of the coating film end of the liquid crystal alignment film.

"Evaluation of Voltage Retention Rate (VHR) (General Cell)"

Using the liquid crystal alignment treatment agents obtained in Examples and Comparative Examples of the present invention, the voltage retention rate (VHR) was evaluated. Specifically, for example, after these liquid crystal alignment treatment agents are pressure-filtered using a membrane filter with a pore size of 1 μm, they are spin-coated on an auxiliary membrane washed with pure water and IPA (isopropyl alcohol). On the ITO surface of the substrate with an ITO electrode (40mm in length x 30mm in width and 0.7mm in thickness), heat treatment at 160 ° C for 15 minutes in a heat-circulating dust-free oven at 80 ° C for 3 minutes on a hot plate, An ITO substrate with a liquid crystal alignment film with a film thickness of 100 nm was obtained. A rubbing device with a roller diameter of 120 mm was used for the coating film surface of the ITO substrate, and a chemical fiber cloth was used to perform rubbing treatment under the conditions of roller rotation number: 300 rpm, roller travel speed: 20 mm / sec, and extrusion amount: 0.4 mm.

Prepare two ITO substrates with the prepared liquid crystal alignment film, combine the liquid crystal alignment film facing inwards with a spacer of 6 μm, and print the ultraviolet curing type sealer. Next, after bonding the substrate on the other side face-to-face with the liquid crystal alignment film, a curing treatment of an ultraviolet curing type sealing agent is performed to produce an empty cell. Specifically, for example, using a metal halide lamp with an illuminance of 60 mW, blocking a wavelength of 310 nm or less, irradiating 5 J / cm ² of ultraviolet light converted to a wavelength of 365 nm, and then performing 120 ° C. in a thermal cycle type dust-free oven. After 60 minutes of heat treatment, an empty cell was prepared. The nematic liquid crystal is injected into this empty cell using a reduced pressure injection method to produce a liquid crystal cell (general cell).

In addition, the liquid crystal alignment treatment agent (2) to the liquid crystal alignment treatment agent (4) obtained by the method of Example 2 to Example 4, the liquid crystal alignment treatment agent (12) obtained by the method of Example 12, and the example The liquid crystal alignment treatment agent (19) obtained by the method of 19, the liquid crystal alignment treatment agent (21) obtained by the method of Comparative Example 1 and the liquid crystal alignment treatment agent (22) obtained by the method of Comparative Example 2, The liquid crystal uses MLC-2003 (made by Marc Japan).

In addition, in the liquid crystal cell using the liquid crystal alignment agent obtained in Examples and Comparative Examples other than the foregoing, MLC-6608 (manufactured by Mark Japan) was used as the liquid crystal.

At a temperature of 80 ° C, a voltage of 1 V was applied for 60 μs to the resulting liquid crystal cell, the voltage after 50 ms was measured, and the result of calculating how much the voltage could be retained was regarded as the voltage retention rate (VHR). In addition, the measurement was performed using a voltage retention measurement device (VHR-1) (manufactured by Dongyang Technology Co., Ltd.) under the settings of Voltage: ± 1 V, Pulse Width: 60 μs, and Flame Period: 50 ms.

In addition, after storing the liquid crystal cell after the VHR measurement in a high-temperature bath at a temperature of 80 ° C. for 720 hours, the VHR measurement was performed again under the same conditions as above (also referred to as after high-temperature bath storage).

It is evaluated that the value of VHR immediately after the production of the liquid crystal cell is added, and the value of the VHR immediately after the production of the liquid crystal cell is smaller, the smaller the number of reductions in the value of VHR after storage in the high-temperature bath is better.

In Table 9 to Table 11, the values of the voltage retention rate (VHR) obtained in the examples and comparative examples are indicated.

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

Using the liquid crystal alignment treatment agent (4) obtained by the method of Example 4 of the present invention, the liquid crystal alignment treatment agent (7) obtained by the method of Example 7, and the liquid crystal alignment treatment agent (15) obtained by the method of Example 15, Evaluation of inkjet coatability. Specifically, for example, the liquid crystal alignment treatment agent is subjected to pressure filtration using a membrane filter with a pore size of 1 μm, and the inkjet coater uses HIS-200 (manufactured by Hitachi Machinery Technology Co., Ltd.), which is purified by pure water and IPA-cleaned ITO (indium tin oxide) vapor-deposited substrate with a coating area of 70 × 70 mm, a nozzle pitch of 0.423 mm, a scanning pitch of 0.5 mm, a coating speed of 40 mm / sec, and a coating time to pre-drying of 60 Seconds, pre-drying is performed on a hot plate at 70 ° C for 5 minutes, and formal sintering is performed in a heat-circulating dust-free oven at 160 ° C for 15 minutes.

Observe the obtained substrate with liquid crystal alignment film under sodium lamp, and calculate the result of the number of sand holes on the liquid crystal alignment film. It is known that no matter how the liquid crystal alignment film obtained in any embodiment, the number of sand holes is less than 5 . Furthermore, in any of the embodiments, a liquid crystal alignment film having excellent uniform coating properties can be produced.

In addition, using the obtained substrate with a liquid crystal alignment film, the VHR (general unit cell) evaluation was performed according to the conditions of the aforementioned "voltage retention rate (VHR) evaluation (general unit cell)".

"Fabrication of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)"

Using the liquid crystal alignment treatment agent (6) obtained by the method of Example 6 of the present invention, the liquid crystal alignment treatment agent (9) obtained by the method of Example 9, and the liquid crystal alignment treatment agent (14) obtained by the method of Example 14, Production of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell). Specifically, for example, the liquid crystal alignment treatment agent is subjected to pressure filtration using a membrane filter with a pore size of 1 μm, and spin-coated on a center washed with pure water and IPA with a 10 × 10 mm pattern interval of 20 μm After the ITO electrode substrate (length 40mm × 30mm, thickness 0.7mm) and the ITO surface of the substrate with a 10 × 40mm ITO electrode in the center (length 40mm × 30mm, thickness 0.7mm), and then 80 on the heating plate ℃, 3 minutes, heat cycle type dust-free oven 160 ℃, 15 minutes heat treatment, and the substrate with liquid crystal alignment film with a film thickness of 100nm was prepared.

The substrates with the liquid crystal alignment film are combined with a 6 μm spacer sandwiched with the liquid crystal alignment film facing inward, and the surrounding is adhered with a sealant to make an empty cell. In this empty cell, the polymerizable compound (1) represented by the following formula is 100% by mass with respect to the nematic liquid crystal (MLC-6608) by a reduced pressure injection method, and the polymerizable compound (1) is 0.3 mass % The liquid crystal obtained by mixing is injected into a nematic liquid crystal (MLC-6608) (manufactured by Mark Japan), and the injection port is sealed to produce a liquid crystal cell.

To the obtained liquid crystal cell, using a metal halide lamp with an illuminance of 60mW while continuously applying an alternating voltage of 5V, blocking a wavelength below 350nm, irradiating ultraviolet light 20J / cm ² converted to 365nm, the alignment direction of the resulting liquid crystal is controlled The liquid crystal cell (PSA cell). When the ultraviolet ray is used to irradiate the liquid crystal cell, the temperature in the irradiation device is 50 ° C.

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

Regardless of the PSA cell obtained in any of the examples, the response speed of the liquid crystal cell after the ultraviolet irradiation is faster when compared with the liquid crystal cell before the ultraviolet irradiation. The result shows that the alignment direction of the liquid crystal is affected by controller. In addition, regardless of any liquid crystal cell, observation results using a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) confirmed that the liquid crystals were uniformly aligned.

"Fabrication of liquid crystal cell and evaluation of liquid crystal alignment (SC-PVA cell)"

Using the liquid crystal alignment treatment agent (6) obtained by the method of Example 6 of the present invention, the liquid crystal alignment treatment agent (9) obtained by the method of Example 9, and the liquid crystal alignment treatment agent (14) obtained by the method of Example 14, Production of liquid crystal cell and evaluation of liquid crystal alignment (SC-PVA cell). Specifically, examples For example, the aforementioned polymerizable compound (1) is added to these liquid crystal alignment treatment agents in an amount of 2% by mass with respect to 100% by mass of the total polymer component in the liquid crystal alignment treatment agent, and stirred at 25 ° C. 4 hour. Thereafter, the obtained liquid crystal alignment treatment agent was subjected to pressure filtration using a membrane filter with a pore size of 1 μm, and was spin-coated on an ITO electrode with a pattern spacing of 10 × 10 mm and a pitch of 20 μm washed with pure water and IPA. The ITO surface of the substrate (40mm in length × 30mm in width and 0.7mm in thickness) and the ITO surface of the substrate (40mm in length × 30mm in width and 0.7mm in thickness) with an ITO electrode of 10 × 40mm in the center, at 80 ° C for 3 minutes on a hot plate After heat treatment at 160 ° C for 15 minutes in a heat-circulating dust-free oven, a substrate with a liquid crystal alignment film with a film thickness of 100 nm is obtained.

The substrates with the liquid crystal alignment film are combined with a 6 μm spacer sandwiched with the liquid crystal alignment film facing inward, and the surrounding is adhered with a sealant to make an empty cell. This empty cell was injected into a nematic liquid crystal (MLC-6608) (manufactured by Mark Japan) by a method of reduced pressure injection, and the injection port was sealed to produce a liquid crystal cell.

To the obtained liquid crystal cell, using a metal halide lamp with an illuminance of 60mW while continuously applying an alternating voltage of 5V, blocking a wavelength below 350nm, irradiating ultraviolet light 20J / cm ² converted to 365nm, the alignment direction of the resulting liquid crystal is controlled The liquid crystal cell (SC-PVA cell). When the ultraviolet ray is used to irradiate the liquid crystal cell, the temperature in the irradiation device is 50 ° C.

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

Regardless of the SC-PVA cell obtained in any example, the response speed of the liquid crystal cell after the ultraviolet irradiation is faster when compared with the liquid crystal cell before the ultraviolet irradiation. The result is known. Confirm the alignment direction of the liquid crystal For those under control. In addition, regardless of any liquid crystal cell, observation results using a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) confirmed that the liquid crystals were uniformly aligned.

<Example 1>

S1 (8.17g), K1 (0.18g), NEP (3.92g) and S1 (8.17g), K1 (0.18g), and NEP (3.92g) were added to the polyamic acid solution (1) (10.0g) with a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 1. PB (19.6g) was stirred at 25 ° C for 8 hours to obtain composition (1). In this composition, it was confirmed that there was no abnormality such as turbidity or precipitates, but a homogeneous solution. In addition, this composition (1) is also used for evaluation of the liquid crystal alignment treatment agent (1).

Using the obtained composition (1) and liquid crystal alignment treatment agent (1), "evaluation of the printability of the composition and liquid crystal alignment treatment agent (evaluation of sand holes)" and "evaluation of the printability of the composition and liquid crystal alignment treatment agent" (Evaluation of coating film end) "and" Evaluation of voltage retention rate (VHR) (general cell) ".

<Example 2>

To the polyamic acid solution (2) (10.5g) with a resin solid content concentration of 25% by mass obtained according to the synthesis method of Synthesis Example 2, S1 (16.8g) and BCS (16.4g) were added and stirred at 25 ° C After 4 hours, the composition (2) was obtained. In this composition, it was confirmed that there was no abnormality such as turbidity or precipitates, but a uniform solution liquid. In addition, the composition (2) is also used for evaluation of the liquid crystal alignment treatment agent (2).

Using the obtained composition (2) and liquid crystal alignment treatment agent (2), "evaluation of the printability of the composition and liquid crystal alignment treatment agent (evaluation of sand holes)" and "evaluation of the printability of the composition and liquid crystal alignment treatment agent" (Evaluation of coating film end) "and" Evaluation of voltage retention rate (VHR) (general cell) ".

<Example 3>

To the polyimide powder (3) (1.60 g) obtained by the synthesis method of Synthesis Example 3, S1 (13.8 g) was added and stirred at 70 ° C for 24 hours to dissolve. To this solution, BCS (11.3g) was added and stirred at 40 ° C for 3 hours to obtain a composition (3). In this composition, it was confirmed that there was no abnormality such as turbidity or precipitates, but a homogeneous solution. In addition, this composition (3) is also used for evaluation of the liquid crystal alignment treatment agent (3).

Using the obtained composition (3) and liquid crystal alignment treatment agent (3), "evaluation of the printability of the composition and liquid crystal alignment treatment agent (evaluation of sand holes)" and "evaluation of the composition and liquid crystal alignment treatment agent printability ( "Evaluation of coating film ends" and "Evaluation of voltage retention (VHR) (general cell)".

<Example 4>

To the polyimide powder (4) (1.70 g) obtained by the synthesis method of Synthesis Example 4, S1 (14.1 g) and NEP (9.37 g) were added, followed by stirring at 70 ° C for 24 hours to dissolve. To this solution, BCS (9.37g) and PB (14.1g) were added and stirred at 40 ° C for 3 hours to obtain a composition (4). This composition Among the materials, it was confirmed that no abnormalities such as turbidity or precipitates were found, but a homogeneous solution. In addition, this composition (4) is also used for evaluation of the liquid crystal alignment treatment agent (4).

Using the obtained composition (4) and liquid crystal alignment treatment agent (4), "evaluation of the printability of the composition and liquid crystal alignment treatment agent (evaluation of sand hole)" and "voltage retention rate (VHR) evaluation (general crystal Cell) "and" Evaluation of Inkjet Coating Properties of Liquid Crystal Alignment Treatment Agent ".

<Example 5>

To the polyamic acid solution (5) (10.0g) with a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 5, S1 (14.0g) and BCS (17.7g) were added and stirred at 25 ° C 4 Hour, the composition (5). In this composition, it was confirmed that there was no abnormality such as turbidity or precipitates, but a homogeneous solution. In addition, this composition (5) is also used for evaluation of the liquid crystal alignment treatment agent (5).

Using the obtained composition (5) and liquid crystal alignment treatment agent (5), "evaluation of the printability of the composition and liquid crystal alignment treatment agent (evaluation of sand holes)" and "evaluation of the printability of the composition and liquid crystal alignment treatment agent (Evaluation of coating film end) "and" Evaluation of voltage retention rate (VHR) (general cell) ".

<Example 6>

To the polyimide powder (6) (1.70 g) obtained by the synthesis method of Synthesis Example 6, S1 (14.7 g) was added and stirred at 70 ° C for 24 hours to dissolve. To this solution, add BCS (12.0g) and stir at 40 ° C for 3 In hours, the composition (6) is obtained. In this composition, it was confirmed that there was no abnormality such as turbidity or precipitates, but a homogeneous solution. In addition, this composition (6) is also used for evaluation of the liquid crystal alignment treatment agent (6).

Using the obtained composition (6) and liquid crystal alignment treatment agent (6), "evaluation of the printability of the composition and liquid crystal alignment treatment agent (evaluation of sand holes)" and "evaluation of the printability of the composition and liquid crystal alignment treatment agent" (Evaluation of coating film end), "Evaluation of voltage retention rate (VHR) (general cell)", "Fabrication of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)" and "Evaluation of liquid crystal cell Production and evaluation of liquid crystal alignment (SC-PVA cell) ".

<Example 7>

To the polyimide powder (6) (1.65 g) obtained by the synthesis method of Synthesis Example 6, S1 (9.10 g) and NEP (13.7 g) were added, and stirred at 70 ° C for 24 hours to dissolve. To this solution, PB (22.8g) was added and stirred at 40 ° C for 3 hours to obtain a composition (7). In this composition, it was confirmed that there was no abnormality such as turbidity or precipitates, but a homogeneous solution. In addition, this composition (7) is also used for evaluation of the liquid crystal alignment treatment agent (7).

Using the obtained composition (7) and liquid crystal alignment treatment agent (7), "evaluation of the printability of the composition and liquid crystal alignment treatment agent (evaluation of sand holes)" and "voltage retention rate (VHR) evaluation (general crystal Cell) "and" Evaluation of Inkjet Coating Properties of Liquid Crystal Alignment Treatment Agent ".

<Example 8>

To the polyimide powder (7) (1.60 g) obtained by the synthesis method of Synthesis Example 7, S1 (6.27 g) and NEP (7.52 g) were added and stirred at 70 ° C for 24 hours to dissolve. To this solution, BCS (2.51g) and PB (8.77g) were added and stirred at 40 ° C for 3 hours to obtain a composition (8). In this composition, it was confirmed that there was no abnormality such as turbidity or precipitates, but a homogeneous solution. In addition, this composition (8) is also used for evaluation of the liquid crystal alignment treatment agent (8).

Using the obtained composition (8) and liquid crystal alignment treatment agent (8), "evaluation of the printability of the composition and liquid crystal alignment treatment agent (evaluation of sand holes)" and "evaluation of the printability of the composition and liquid crystal alignment treatment agent" (Evaluation of coating film end) "and" Evaluation of voltage retention rate (VHR) (general cell) ".

<Example 9>

To the polyimide powder (8) (1.60 g) obtained by the synthesis method of Synthesis Example 8, S1 (7.52 g) and NMP (5.01 g) were added and stirred at 70 ° C for 24 hours to dissolve. To this solution, PB (10.0g) and DME (2.51g) were added and stirred at 40 ° C for 5 hours to obtain a composition (9). In this composition, it was confirmed that there was no abnormality such as turbidity or precipitates, but a homogeneous solution. In addition, this composition (9) is also used for evaluation of the liquid crystal alignment treatment agent (9).

Using the obtained composition (9) and liquid crystal alignment treatment agent (9), "evaluation of the printability of the composition and liquid crystal alignment treatment agent (evaluation of sand holes)" and "evaluation of the printability of the composition and liquid crystal alignment treatment agent" (Evaluation of coating film end) '', `` Evaluation of voltage retention rate (VHR) (general cell) '', "Fabrication of liquid crystal cells and evaluation of liquid crystal alignment (PSA cell)" and "Fabrication of liquid crystal cells and evaluation of liquid crystal alignment (SC-PVA cell)".

<Example 10>

To the polyimide powder (9) (1.65 g) obtained by the synthesis method of Synthesis Example 9, S1 (10.3 g) and NEP (7.76 g) were added, followed by stirring at 70 ° C for 24 hours to dissolve. To this solution, PB (6.46g) and EC (1.29g) were added and stirred at 40 ° C for 3 hours to obtain a composition (10). In this composition, it was confirmed that there was no abnormality such as turbidity or precipitates, but a homogeneous solution. In addition, this composition (10) is also used for evaluation of the liquid crystal alignment treatment agent (10).

Using the obtained composition (10) and liquid crystal alignment treatment agent (10), "evaluation of the printability of the composition and liquid crystal alignment treatment agent (evaluation of sand holes)" and "evaluation of the printability of the composition and liquid crystal alignment treatment agent" (Evaluation of coating film end) "and" Evaluation of voltage retention rate (VHR) (general cell) ".

<Example 11>

To the polyimide powder (10) (1.60 g) obtained by the synthesis method of Synthesis Example 10, S1 (3.76 g) and NEP (10.0 g) were added, followed by stirring at 70 ° C for 24 hours to dissolve. To this solution, BCS (11.3g) was added and stirred at 40 ° C for 3 hours to obtain a composition (11). In this composition, it was confirmed that there was no abnormality such as turbidity or precipitates, but a homogeneous solution. Again, this group The finished product (11) is also used for evaluation of the liquid crystal alignment treatment agent (11).

Using the obtained composition (11) and liquid crystal alignment treatment agent (11), "evaluation of the printability of the composition and liquid crystal alignment treatment agent (evaluation of sand holes)" and "evaluation of the printability of the composition and liquid crystal alignment treatment agent" (Evaluation of coating film end) "and" Evaluation of voltage retention rate (VHR) (general cell) ".

<Example 12>

To the polyimide powder (11) (1.70 g) obtained by the synthesis method of Synthesis Example 11, S1 (5.33 g) and γ-BL (13.3 g) were added, followed by stirring at 70 ° C for 24 hours to dissolve. To this solution, BCS (7.99g) was added and stirred at 40 ° C for 3 hours to obtain a composition (12). In this composition, it was confirmed that there was no abnormality such as turbidity or precipitates, but a homogeneous solution. In addition, this composition (12) is also used for evaluation of a liquid crystal alignment treatment agent (12).

Using the obtained composition (12) and liquid crystal alignment treatment agent (12), "evaluation of the printability of the composition and liquid crystal alignment treatment agent (evaluation of sand holes)" and "evaluation of the printability of the composition and liquid crystal alignment treatment agent" (Evaluation of coating film end) "and" Evaluation of voltage retention rate (VHR) (general cell) ".

<Example 13>

To the polyimide powder (12) (1.65 g) obtained by the synthesis method of Synthesis Example 12, S1 (7.76 g) and NMP (5.17 g) were added, followed by stirring at 70 ° C for 24 hours to dissolve. In this solution, add BCS (5.17g) and PB (7.76g), and stirred at 40 ° C for 3 hours to obtain a composition (13). In this composition, it was confirmed that there was no abnormality such as turbidity or precipitates, but a homogeneous solution. In addition, this composition (13) is also used for evaluation of the liquid crystal alignment treatment agent (13).

Using the obtained composition (13) and liquid crystal alignment treatment agent (13), "evaluation of the printability of the composition and liquid crystal alignment treatment agent (evaluation of sand holes)" and "evaluation of the printability of the composition and liquid crystal alignment treatment agent" (Evaluation of coating film end) "and" Evaluation of voltage retention rate (VHR) (general cell) ".

<Example 14>

To the polyimide powder (13) (1.60 g) obtained by the synthesis method of Synthesis Example 13, S1 (5.01 g) and NEP (7.52 g) were added, followed by stirring at 70 ° C for 24 hours to dissolve. To this solution, PB (12.5g) was added and stirred at 40 ° C for 3 hours to obtain a composition (14). In this composition, it was confirmed that there was no abnormality such as turbidity or precipitates, but a homogeneous solution. In addition, this composition (14) is also used for evaluation of the liquid crystal alignment treatment agent (14).

Using the obtained composition (14) and liquid crystal alignment treatment agent (14), "evaluation of the printability of the composition and liquid crystal alignment treatment agent (evaluation of sand holes)" and "evaluation of the printability of the composition and liquid crystal alignment treatment agent" (Evaluation of coating film end), "Evaluation of voltage retention rate (VHR) (general cell)", "Fabrication of liquid crystal cell and evaluation of liquid crystal alignment (PSA cell)" and "Evaluation of liquid crystal cell Production and evaluation of liquid crystal alignment (SC-PVA cell) ".

<Example 15>

To the polyimide powder (13) (1.70 g) obtained by the synthesis method of Synthesis Example 13, S1 (4.69 g) and γ-BL (18.8 g) were added, followed by stirring at 70 ° C for 24 hours to dissolve. To this solution, BCS (9.37g) and PB (14.1g) were added and stirred at 40 ° C for 3 hours to obtain a composition (15). In this composition, it was confirmed that there was no abnormality such as turbidity or precipitates, but a homogeneous solution. In addition, this composition (15) is also used for evaluation of the liquid crystal alignment treatment agent (15).

Using the obtained composition (15) and liquid crystal alignment treatment agent (15), "evaluation of the printability of the composition and liquid crystal alignment treatment agent (evaluation of sand hole)" and "voltage retention rate (VHR) evaluation (general crystal Cell) "and" Evaluation of Inkjet Coating Properties of Liquid Crystal Alignment Treatment Agent ".

<Example 16>

To the polyimide powder (14) (1.60 g) obtained by the synthesis method of Synthesis Example 14, S1 (12.5 g) and NEP (2.51 g) were added, followed by stirring at 70 ° C for 24 hours to dissolve. To this solution, K1 (0.08g) and BCS (10.0g) were added and stirred at 40 ° C for 5 hours to obtain a composition (16). In this composition, it was confirmed that there was no abnormality such as turbidity or precipitates, but a homogeneous solution. In addition, this composition (16) is also used for evaluation of the liquid crystal alignment treatment agent (16).

Using the obtained composition (16) and liquid crystal alignment treatment agent (16), "evaluation of the printability of the composition and liquid crystal alignment treatment agent (Sha Kong "Evaluation", "Evaluation of the printability of the composition and liquid crystal alignment treatment agent (evaluation of the coating film end)" and "Evaluation of the voltage retention rate (VHR) (general cell)".

<Example 17>

To the polyimide powder (15) (1.60 g) obtained by the synthesis method of Synthesis Example 15, S1 (15.0 g) and γ-BL (2.51 g) were added and stirred at 70 ° C for 24 hours to dissolve. To this solution, K1 (0.08g), BCS (2.51g) and PB (5.01g) were added, and the mixture was stirred at 40 ° C for 5 hours to obtain a composition (17). In this composition, it was confirmed that there was no abnormality such as turbidity or precipitates, but a homogeneous solution. In addition, this composition (17) is also used for evaluation of the liquid crystal alignment treatment agent (17).

Using the obtained composition (17) and liquid crystal alignment treatment agent (17), "evaluation of the printability of the composition and liquid crystal alignment treatment agent (evaluation of sand holes)" and "evaluation of the printability of the composition and liquid crystal alignment treatment agent" (Evaluation of coating film end) "and" Evaluation of voltage retention rate (VHR) (general cell) ".

<Example 18>

To the polyimide powder (16) (1.70 g) obtained by the synthesis method of Synthesis Example 16, S1 (2.66 g) and NEP (10.7 g) were added, followed by stirring at 70 ° C for 24 hours to dissolve. To this solution, BCS (5.33g) and PB (7.99g) were added and stirred at 40 ° C for 3 hours to obtain a composition (18). In this composition, it was confirmed that there was no abnormality such as turbidity or precipitates, but a uniform solution liquid. In addition, this composition (18) is also used for evaluation of the liquid crystal alignment treatment agent (18).

Using the obtained composition (18) and liquid crystal alignment treatment agent (18), "evaluation of the printability of the composition and liquid crystal alignment treatment agent (evaluation of sand holes)" and "evaluation of the printability of the composition and liquid crystal alignment treatment agent" (Evaluation of coating film end) "and" Evaluation of voltage retention rate (VHR) (general cell) ".

<Example 19>

To the polyimide powder (17) (1.60 g) obtained by the synthesis method of Synthesis Example 17, S1 (8.77 g) and NMP (5.01 g) were added and stirred at 70 ° C for 24 hours to dissolve. To this solution, BCS (8.77g) and EC (2.51g) were added, and stirred at 40 ° C for 3 hours to obtain a composition (19). In this composition, it was confirmed that there was no abnormality such as turbidity or precipitates, but a homogeneous solution. In addition, this composition (19) is also used for evaluation of the liquid crystal alignment treatment agent (19).

Using the obtained composition (19) and liquid crystal alignment treatment agent (19), "evaluation of the printability of the composition and liquid crystal alignment treatment agent (evaluation of sand holes)" and "evaluation of the printability of the composition and liquid crystal alignment treatment agent" (Evaluation of coating film end) "and" Evaluation of voltage retention rate (VHR) (general cell) ".

<Example 20>

Polyimide powder obtained by the synthesis method of Synthesis Example 18 (18) To (1.60g), S1 (10.0g) and NEP (3.76g) were added and stirred at 70 ° C for 24 hours to dissolve. To this solution, BCS (3.76g) and PB (7.52g) were added and stirred at 40 ° C for 3 hours to obtain a composition (20). In this composition, it was confirmed that there was no abnormality such as turbidity or precipitates, but a homogeneous solution. In addition, this composition (20) is also used for evaluation of the liquid crystal alignment treatment agent (20).

Using the obtained composition (20) and liquid crystal alignment treatment agent (20), "evaluation of the printability of the composition and liquid crystal alignment treatment agent (evaluation of sand holes)" and "evaluation of the printability of the composition and liquid crystal alignment treatment agent" (Evaluation of coating film end) "and" Evaluation of voltage retention rate (VHR) (general cell) ".

<Comparative Example 1>

To the polyamic acid solution (19) (10.0g) with a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 19, NMP (16.0g) and BCS (15.7g) were added and stirred at 25 ° C 4 In hours, the composition (21) is obtained. In this composition, it was confirmed that there was no abnormality such as turbidity or precipitates, but a homogeneous solution. In addition, this composition (21) is also used for evaluation of a liquid crystal alignment treatment agent (21).

Using the obtained composition (21) and liquid crystal alignment treatment agent (21), "evaluation of the printability of the composition and liquid crystal alignment treatment agent (evaluation of sand holes)" and "evaluation of the printability of the composition and liquid crystal alignment treatment agent" (Evaluation of coating film end) "and" Evaluation of voltage retention rate (VHR) (general cell) ".

<Comparative Example 2>

To the polyimide powder (3) (1.70 g) obtained by the synthesis method of Synthesis Example 3, NMP (14.7 g) was added and stirred at 70 ° C for 24 hours to dissolve. To this solution, BCS (12.0g) was added and stirred at 40 ° C for 3 hours to obtain a composition (22). In this composition, it was confirmed that there was no abnormality such as turbidity or precipitates, but a homogeneous solution. In addition, this composition (22) is also used for evaluation of the liquid crystal alignment treatment agent (22).

Using the obtained composition (22) and liquid crystal alignment treatment agent (22), "evaluation of the printability of the composition and liquid crystal alignment treatment agent (evaluation of sand holes)" and "evaluation of the printability of the composition and liquid crystal alignment treatment agent" (Evaluation of coating film end) "and" Evaluation of voltage retention rate (VHR) (general cell) ".

<Comparative Example 3>

To the polyamic acid solution (20) (10.5g) with a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 20, NMP (14,7g) and BCS (18.5g) were added and stirred at 25 ° C After 4 hours, the composition (23) was obtained. In this composition, it was confirmed that there was no abnormality such as turbidity or precipitates, but a homogeneous solution. In addition, this composition (23) is also used for evaluation of the liquid crystal alignment treatment agent (23).

Using the obtained composition (23) and liquid crystal alignment treatment agent (23), "evaluation of the printability of the composition and liquid crystal alignment treatment agent (evaluation of sand holes)" and "evaluation of the printability of the composition and liquid crystal alignment treatment agent" (Tu "Evaluation of membrane end)" and "Evaluation of voltage retention rate (VHR) (general cell)".

<Comparative Example 4>

To the polyimide powder (6) (1.65 g) obtained by the synthesis method of Synthesis Example 6, NMP (14.2 g) was added and stirred at 70 ° C for 24 hours to dissolve. To this solution, BCS (11.6g) was added and stirred at 40 ° C for 3 hours to obtain a composition (24). In this composition, it was confirmed that there was no abnormality such as turbidity or precipitates, but a homogeneous solution. In addition, this composition (24) is also used for evaluation of the liquid crystal alignment treatment agent (24).

Using the obtained composition (24) and liquid crystal alignment treatment agent (24), "evaluation of the printability of the composition and liquid crystal alignment treatment agent (evaluation of sand holes)" and "evaluation of the printability of the composition and liquid crystal alignment treatment agent" (Evaluation of coating film end) "and" Evaluation of voltage retention rate (VHR) (general cell) ".

From the above results, it can be seen that the polyimide film obtained from the composition of the examples of the present invention shows a uniform coating without occurrence of sand holes when compared with the polyimide film obtained from the composition of the comparative example. In addition, the end of the polyimide film has a high degree of linearity, and the expanded state of the end is also small. Specifically, for example, a composition using a specific solvent of the (A) component of the present invention is compared with a composition not using the component, that is, the comparison between Example 2 and Comparative Example 1, Example 3 and Comparative Example Comparison of 2, comparison between Example 5 and Comparative Example 3, and comparison between Example 6 and Comparative Example 4. In these comparative examples, when compared with the corresponding examples, it is known that the number of sand holes in the polyimide film is more, and the coating film property of the coating film end of the polyimide film is also Poor results. In addition, the compositions of these examples were also evaluated as liquid crystal alignment treatment agents, and the results of the examples using these compositions were also used as results of liquid crystal alignment treatment agents.

In addition, when the liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent of the composition of the present invention is compared with the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the comparative example, it is known that even when the liquid crystal alignment film is produced, the sintering is at a low temperature state At this time, the voltage retention ratio (also called VHR) in the liquid crystal display element is also a better result. Specifically, for example, using the present invention (A) The liquid crystal alignment treatment agent of the specific solvent of the component is compared with the liquid crystal alignment treatment agent not using the component, that is, the comparison between Example 2 and Comparative Example 1, the comparison between Example 3 and Comparative Example 2, and the implementation Comparison between Example 5 and Comparative Example 3 and between Example 6 and Comparative Example 4. Among these comparative examples, when compared with the corresponding examples, it is found that the VHR value is a lower value. In particular, not only the value immediately after the production of the liquid crystal cell, but also the value after storage in the high-temperature bath is a lower value, that is, it is confirmed that the decrease in VHR with the high temperature appears to be more drastic.

[Industrial utility]

When the composition of the present invention forms a polyimide film, a polyimide film that suppresses the generation of sand holes caused by splashing and has excellent coating properties at the end can be prepared. At this time, even if low-temperature sintering is performed, a polyimide film can be produced.

In addition, when the composition of the present invention is used as a liquid crystal alignment treatment agent, a liquid crystal alignment film that suppresses the generation of sand holes caused by splashing and has excellent coating film properties at the ends can be obtained. In addition, even when the sintering at the time of manufacturing the liquid crystal alignment film is in a low temperature state, a liquid crystal alignment film having excellent electrical characteristics, particularly excellent voltage retention (also referred to as VHR) can be formed in the liquid crystal display element. Therefore, the liquid crystal display device having the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention is one with excellent reliability and can be applied to a large-screen and high-definition LCD TV or a small and medium-sized car navigation system or smartphone Etc., and for TN elements, STN elements, TFT liquid crystal elements, especially VA Vertical alignment type liquid crystal display elements such as mode, PSA mode and SC-PVA mode are useful.

Claims (23)

A composition characterized by containing (A) component: a solvent represented by the following formula [A]:

(In the formula, X ¹ and X ² each independently represent an alkyl group having 1 to 3 carbon atoms, X ³ and X ⁴ each independently represent an alkyl group having 1 to 3 carbon atoms); and (B) component: having a carboxyl group (COOH group) and hydroxyl group (OH group) selected at least one kind of substituent diamine compound as a part of the raw material used for the polymerization of at least one selected from the polyimide precursor and polyimide Among them, the component (A) is 5 to 70% by mass of the entire solvent contained in the composition, and the component (B) is 0.1 to 30% by mass of the composition. The composition of claim 1, wherein the solvent of the aforementioned component (A) is a solvent represented by the following formula [A-1]:

The composition of claim 1 or claim 2, wherein the component (B) is a structure having at least one structure selected from the structures shown in the following formula [1-1] and formula [1-2] At least one polymer selected from polyimide precursor and polyimide used as a part of the raw material of the diamine compound:

(In the formula, Y ¹ represents a single bond,-(CH ₂ ) _a- (a is an integer from 1 to 15), -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON (CH ₃ )-, -N (CH ₃ ) CO-, -COO- and -OCO- selected at least one kind of bonding group, Y ² represents a single bond or-(CH ₂ ) _b- (b is 1 ~ 15 Integer), Y ³ represents at least one of single bond,-(CH ₂ ) _c- (c is an integer of 1 ~ 15), -O-, -CH ₂ O-, -COO- and -OCO- Bonding group, Y ⁴ represents a divalent cyclic group of at least one ring selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group with a carbon number of 17 to 51 having a cholesterol skeleton , Any hydrogen atom on the aforementioned cyclic group can be substituted by a C 1-3 alkyl group, a C 1-3 alkoxy group, a C 1-3 fluorinated alkyl group, a C 1 to 3 Substituted with a fluorine-containing alkoxy group or a fluorine atom, Y ⁵ represents a bivalent cyclic group of at least one kind of ring selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, any of these cyclic groups Hydrogen atom can be affected by C 1-3 alkyl group, C 1-3 alkoxy group, C 1-3 fluorinated alkyl group, C 1-3 fluorinated alkoxy group or fluorine atom Substitution, n represents an integer of 0 ~ 4, Y ⁶ represents an alkyl group having a carbon number of 1-22, a carbon number of 2-22 At least one selected from the group consisting of alkenyl group, fluorine-containing alkyl group having 1 to 22 carbon atoms, alkoxy group having 1 to 22 carbon atoms and fluorine-containing alkoxy group having 1 to 22 carbon atoms; [ Chem . 4] -Y ⁷ -Y ⁸ [1-2] (wherein, Y ⁷ represents a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON (CH ₃ )-, -N (CH ₃ ) At least one bonding group selected from CO-, -COO- and -OCO-, Y ⁸ represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms). The composition of claim 3, wherein the diamine compound having the structure represented by the aforementioned formula [1-1] and formula [1-2] is a diamine compound represented by the following formula [1a]:

(In the formula, Y represents at least one structure selected from the structures shown in the above formula [1-1] and formula [1-2], and m represents an integer of 1 to 4). The composition according to claim 1, wherein the diamine compound having a carboxyl group and a hydroxyl group is a diamine compound represented by the following formula [2a]:

{In the formula, A represents a substituent of at least one structure selected from the following formula [2-1] and formula [2-2], and m represents an integer of 1 to 4: [化 7] -(CH ₂ ) _a -COOH [2-1]-(CH ₂ ) _b -OH [2-2] (In formula [2-1], a represents an integer of 0 ~ 4, in formula [2-2], b represents 0 ~ Integer of 4)}. The composition according to claim 1 or claim 2, wherein the polymer of the aforementioned component (B) is a polyimide precursor which is a diamine compound represented by the following formula [3a] used as part of the raw material And at least one polymer selected from polyimide:

(In the formula, B ¹ represents -O-, -NH-, -N (CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON (CH ₃ )-and -N (CH ₃ ) CO- selected at least one kind of bonding group, B ² represents a divalent group consisting of a single bond, an aliphatic hydrocarbon having 1 to 20 carbon atoms, and a divalent non-aromatic cyclic hydrocarbon At least one type selected from the group of divalent groups and aromatic hydrocarbons, B ³ represents 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 is an integer from 1 to 5) at least one type of bonding selected Group, B ⁴ represents a nitrogen-containing heterocyclic group, n represents an integer from 1 to 4). The composition of claim 6, wherein B ¹ in the above formula [3a] represents -CONH-, B ² represents an alkylene group having 1 to 5 carbon atoms, B ³ represents a single bond, and B ⁴ represents imidazolyl or pyridine Radical, n represents a diamine compound of 1. The composition according to claim 1 or claim 2, wherein the polymer of the aforementioned (B) component is a polyimide precursor which is a tetracarboxylic acid component represented by the following formula [4] used as part of the raw material At least one type of polymer selected from polyimide and polyimide:

{In the formula, Z represents the base of at least one structure selected from the following formula [4a] to formula [4k]:

(In formula [4a], Z ¹ to Z ⁴ each independently represent a hydrogen atom, a methyl group, a chlorine atom or a phenyl group, and in formula [4g], Z ⁵ and Z ⁶ each independently represent a hydrogen atom or a methyl group)} . The composition of claim 1 or claim 2, wherein the polymer of the aforementioned component (B) is at least one polymer selected from polyalkylamide and polyimide. The composition according to claim 1 or claim 2, which contains at least one selected from N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and γ-butyrolactone The solvent is (C) component. The composition according to claim 1 or claim 2, which contains 1-hexanol, cyclohexanol, 1,2-ethylene glycol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether , Dipropylene glycol dimethyl ether and at least one solvent selected from the solvents represented by the following formula [D-1] to formula [D-3] as the component (D):

(In formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms, in formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms, in formula [D-3], D ³ represents an alkyl group having 1 to 4 carbon atoms). The composition according to claim 1 or claim 2, wherein the composition contains a cross-linkable compound having an epoxy group, an isocyanate group, a glycidyl group or a cyclic carbonate group, and has a hydroxyl group, a hydroxyalkyl group At least one cross-linkable compound selected from the group consisting of a lower alkoxyalkyl group and at least one cross-linkable compound selected from the cross-linkable compounds having a polymerizable unsaturated bond. The composition of claim 10, wherein the component (C) is 40 to 80% by mass of the total solvent contained in the composition. The composition of claim 11, wherein the component (D) is 1 to 50% by mass of the total solvent contained in the composition. A polyimide film characterized by a composition derived from any one of claim 1 to claim 14. A liquid crystal alignment treatment agent characterized in that it is obtained from the composition of any one of claim 1 to claim 14. A liquid crystal alignment film characterized by using the liquid crystal alignment treatment agent of claim 16. A liquid crystal alignment film characterized by using the liquid crystal alignment treatment agent of claim 16, obtained by the inkjet method. A liquid crystal display element characterized by having the liquid crystal alignment film of claim 17 or claim 18. The liquid crystal alignment film according to claim 17 or claim 18, which is used between a pair of substrates provided with electrodes and has a liquid crystal layer, and between the pair of substrates, the arrangement can be polymerized via at least one of active energy rays and heat The liquid crystal composition containing a polymerizable compound is a liquid crystal display device obtained by continuously applying a voltage between the electrodes to polymerize the polymerizable compound. A liquid crystal display device characterized by having the liquid crystal alignment film of claim 20. The liquid crystal alignment film according to claim 17 or claim 18, which is used between a pair of substrates provided with electrodes and has a liquid crystal layer, and between the pair of substrates, the arrangement can be polymerized via at least one of active energy rays and heat The liquid crystal alignment film containing a polymerizable group is obtained by continuously applying a voltage between the electrodes to polymerize the polymerizable group. A liquid crystal display element characterized by having the liquid crystal alignment film of claim 22.