KR102259997B1 - Composition, treatment agent for liquid crystal alignment, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

In the present invention, component (A): following formula [A]: (wherein, X ¹ and X ² each independently represent an alkyl group having 1 to 3 carbon atoms, and X ³ and X ⁴ are each independently , a C1-C3 alkyl group is represented); and (B) component: a polyimide precursor and a composition containing at least one polymer selected from polyimide.

Description

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

This invention relates to the liquid-crystal aligning agent used in manufacture of the composition used for formation of a polyimide film, and a liquid crystal display element, the liquid crystal aligning film obtained from this liquid-crystal aligning agent, and the liquid crystal display element using this liquid crystal aligning film.

BACKGROUND ART Films made of organic materials such as polymer materials have attracted attention for ease of formation, insulating performance, and the like, and are widely used as interlayer insulating films, protective films, and the like in electronic devices. Especially, in the liquid crystal display element well-known as a display device, the organic film which consists of an organic material is used as a liquid crystal aligning film.

BACKGROUND ART In recent years, liquid crystal display elements have been widely put to practical use in large-screen liquid crystal televisions and high-definition mobile applications (display parts of digital cameras and mobile phones). In connection with it, the size of the board|substrate used compared with the prior art is enlarged, Furthermore, the unevenness|corrugation of a board|substrate level|step difference is large. Also in such a situation, it has been calculated|required that a liquid crystal aligning film is uniformly coated with respect to a large board|substrate and a level|step difference from the point of a display characteristic. The process of preparation of this liquid crystal aligning film WHEREIN: When apply|coating the liquid-crystal aligning agent using polyimide-type polymers (it is also mentioned resin), such as a polyamic acid and a solvent-soluble polyimide (it is also mentioned a polyimide) to a board|substrate, industrial In general, it is carried out by a flexographic printing method, an inkjet coating method, or the like. In that case, in the solvent of a liquid-crystal aligning agent, N-methyl-2-pyrrolidone (it is also mentioned NMP) which is a solvent (it is also mentioned a positive solvent) excellent in the solubility of resin, or γ-butyrolactone (γ-BL) In addition to) etc., in order to improve the coating-film property of a liquid crystal aligning film, the ethylene glycol monobutyl ether etc. which are a low solvent (it is also called a poor solvent) of resin are mixed (for example, refer patent document 1). .

Japanese Laid-Open Patent Publication No. 2-37324

The polyimide-type organic film (it is also mentioned a polyimide film) is widely used other than a liquid crystal aligning film, for the interlayer insulating film, a protective film, etc. in an electronic device. It is possible to form from the composition (it is also mentioned a coating solution) containing the solution of the polyamic acid which is a polyimide precursor, or a polyimide similarly to the case of a liquid crystal aligning film. And also in another electronic device, it is calculated|required to improve the coating-film property of a polyimide film. That is, the improvement of the coating-film property of a polyimide film becomes effective in order to suppress the defect which arises with application|coating.

Moreover, since the hydrophobicity of a side chain site|part is high, the liquid-crystal aligning agent using the polyamic acid obtained using the diamine compound which has a side chain, and a polyimide, there exists a tendency for the coating-film property of a liquid crystal aligning film to fall. In particular, when uniform coating-film property is not obtained, ie, when a pinhole accompanying repelling generate|occur|produces and it is set as a liquid crystal display element, that part turns into a display defect. Therefore, in order to obtain uniform coating-film property, it is necessary to increase the mixing amount of the poor solvent with high wettability of the application solution with respect to a board|substrate. However, since a poor solvent is inferior in the ability to dissolve a polyamic acid and a polyimide, there exists a problem that resin precipitation generate|occur|produces when mixed in large quantities.

In addition, in recent years, liquid crystal display elements are being used exclusively for mobile applications such as smart phones and mobile phones. In these applications, in order to secure as many display surfaces as possible, the liquid crystal display element is used for bonding between substrates. A sealing compound exists in the position adjacent to the edge part of a liquid crystal aligning film. Therefore, when the coating-film property of the edge part of a liquid crystal aligning film falls, that is, when the edge part of a liquid crystal aligning film is not a straight line, or when the edge part is a mounted state, adhesion|attachment of a liquid crystal aligning film and a sealing compound (it is also called adhesion) The effect becomes low and the display characteristic and reliability of a liquid crystal display element are reduced.

Furthermore, in the composition or liquid-crystal aligning agent using a polyimide, since the boiling point of NMP and (gamma)-BL which are solvents used for them is high, when producing polyimide films, such as an interlayer insulating film and a protective film, and a liquid crystal aligning film, at high temperature firing is required. Therefore, when producing these polyimide films and a liquid crystal aligning film from the point of reduction of energy cost, baking at low temperature is calculated|required.

Then, an object of this invention is to provide the composition which has the said characteristic. That is, the objective of this invention is providing the composition which can suppress generation|occurrence|production of the pinhole accompanying repelling, and is excellent also in the coating-film property of the edge part, when forming a polyimide film. In that case, it also aims to become a composition which can produce a polyimide film also by baking at low temperature.

Moreover, the liquid-crystal aligning agent using the composition of this invention WHEREIN: When forming a liquid crystal aligning film, generation|occurrence|production of the pinhole accompanying repelling can be suppressed, and the liquid-crystal aligning agent excellent also in the coating-film property of the edge part is provided. In particular, even if it is a liquid-crystal aligning agent using the polyamic acid obtained using the diamine compound which has a side chain, and a polyimide, it exists in providing the liquid-crystal aligning agent excellent in these characteristics. Furthermore, even if baking at the time of producing a liquid crystal aligning film is low temperature, it exists in providing the liquid-crystal aligning agent excellent in the electrical characteristic in a liquid crystal display element, especially voltage retention (it is also mentioned VHR).

In addition, it exists in providing the liquid crystal display element which has the polyimide film obtained from said composition, the liquid crystal aligning film obtained from said liquid-crystal aligning agent, and said liquid crystal aligning film.

As a result of earnest research, the present inventors found that a composition containing a solvent having a specific structure and at least one polymer selected from a polyimide precursor or a polyimide is very effective for achieving the above object, came to the conclusion of the invention.

That is, this invention has the following summary.

(1) (A) component: the following formula [A]:

[Formula 1]

a solvent represented by (wherein, 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); and

(B) Component: The composition containing the at least 1 sort(s) of polymer chosen from a polyimide precursor and a polyimide.

(2) The solvent of the component (A) is the following formula [A-1]:

[Formula 2]

The composition according to the above (1), which is a solvent represented by

(3) The component (B) is the following formula [1-1] and formula [1-2]:

[Formula 3]

(Wherein, Y ¹ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- and -OCO- represent at least one bonding group selected from, Y ² is a single bond or -(CH ₂ ) _b - (b is 1 to 15 is an integer of), and Y ³ is a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- and -OCO- represents at least one bonding group, Y ⁴ is a divalent cyclic group of at least one ring selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a C17-C51 divalent organic group having a steroid skeleton; , any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom; Y ⁵ represents a divalent cyclic group of at least one ring selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and arbitrary hydrogen atoms on these cyclic groups are an alkyl group having 1 to 3 carbon atoms, or an alkoxyl group having 1 to 3 carbon atoms. , a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom may be substituted, n represents an integer of 0 to 4, Y ⁶ is an alkyl group having 1 to 22 carbon atoms, 2 to carbon atoms at least one selected from a 22 alkenyl group, a C1-C22 fluorine-containing alkyl group, a C1-C22 alkoxyl group, and a C1-C22 fluorine-containing alkoxyl group);

[Formula 4]

(Wherein, Y ⁷ is a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- and - represents at least one bonding group selected from OCO-, and 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 according to the above (1) or (2), which is a polyimide precursor and at least one polymer selected from polyimide in which a diamine compound having at least one structure selected from the structure represented by is used as a part of the raw material.

(4) The diamine compound which has a structure shown by said Formula [1-1] and Formula [1-2] following Formula [1a]:

[Formula 5]

(In formula, Y represents at least 1 sort(s) of structure chosen from the structure shown by the said Formula [1-1] and Formula [1-2], and m represents the integer of 1-4)

The composition according to the above (3), which is a diamine compound represented by

(5) Polyimide precursor and polyimide in which the polymer of the component (B) uses a diamine compound having at least one substituent selected from a carboxyl group (COOH group) and a hydroxyl group (OH group) as a part of the raw material The composition as described in any one of said (1) - said (4) which is at least 1 type of polymer chosen.

(6) The diamine compound having a carboxyl group and a hydroxyl group is represented by the following formula [2a]:

[Formula 6]

{wherein, A is the following formulas [2-1] and [2-2]:

[Formula 7]

(in formula [2-1], a represents the integer of 0-4, and in formula [2-2], b represents the integer of 0-4) represents the substituent of the at least 1 structure selected from, and m represents an integer of 1 to 4}

The composition according to the above (5), which is a diamine compound represented by

(7) The polymer of the component (B) is the following formula [3a]:

[Formula 8]

(Wherein, B ¹ is -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON(CH ₃ )- and - Represents at least one bonding group selected from N(CH ₃ ^{)CO—, B 2} is a single bond, a divalent group of an aliphatic hydrocarbon having 1 to 20 carbon atoms, a divalent group of a non-aromatic cyclic hydrocarbon, and 2 of an aromatic hydrocarbon represents at least one selected from a valent group, and B ³ is 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 of 1 to 5) represents at least one bonding group selected from, and B ⁴ is nitrogen-containing Said (1) - said (6) which are at least 1 sort(s) of polymer selected from the polyimide precursor and polyimide which used the diamine compound represented by a heterocyclic group and n represents the integer of 1-4 for a part of a raw material. The composition as described in any one of.

^{(8) B 1} in the formula [3a] represents -CONH-, B ² represents an alkylene group having 1 to 5 carbon atoms, B ³ represents a single bond, and B ⁴ represents an imidazolyl group or a pyridyl group The composition according to the above (7), wherein n is a diamine compound representing 1.

(9) The polymer of the component (B) is the following formula [4]:

[Formula 9]

{wherein, Z is the following formula [4a] to formula [4k]:

[Formula 10]

(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 the formula [4g], Z ⁵ and Z ⁶ are each independently a hydrogen atom or represents a group having at least one structure selected from the group consisting of)

The composition according to any one of (1) to (8), which is at least one polymer selected from a polyimide precursor and a polyimide in which the tetracarboxylic acid compound represented by is used as a part of the raw material.

(10) The composition according to any one of (1) to (9), wherein the polymer of the component (B) is at least one type of polymer selected from polyamic acid alkyl esters and polyimides.

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

(12) as component (D), 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether and The following formulas [D-1] to [D-3]:

[Formula 11]

(In the formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms, in the formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms, and in the formula [D-3], D ³ represents a C1-C4 alkyl group)

The composition according to any one of (1) to (11), comprising at least one solvent selected from the solvents represented by .

(13) In the composition, a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group, and a crosslinkable compound having at least one substituent selected from the group consisting of a lower alkoxyalkyl group and at least one crosslinkable compound selected from crosslinkable compounds having a polymerizable unsaturated bond. The composition according to any one of (1) to (12) above.

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

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

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

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

(18) A polyimide film obtained from the composition according to any one of (1) to (17).

(19) Liquid-crystal aligning agent obtained from the composition in any one of said (1) - said (17).

(20) The liquid crystal aligning film obtained using the liquid-crystal aligning agent as described in said (19).

(21) A liquid crystal aligning film obtained by the inkjet method using the liquid-crystal aligning agent as described in said (19).

(22) The liquid crystal display element which has a liquid crystal aligning film as described in said (20) or said (21).

(23) A liquid crystal composition having a liquid crystal layer between a pair of substrates provided with electrodes and comprising a polymerizable compound that polymerizes by at least one of an active energy ray and heat is disposed between the pair of substrates; The liquid crystal aligning film as described in said (20) or said (21) characterized by the above-mentioned (20) or said (21) being used for the liquid crystal display element manufactured through the process of polymerizing the said polymeric compound while applying a voltage between the said electrodes.

(24) It has the liquid crystal aligning film as described in said (23), The liquid crystal display element characterized by the above-mentioned.

(25) A liquid crystal aligning film having a liquid crystal layer between a pair of substrates provided with an electrode and comprising a polymerizable group that polymerizes by at least one of an active energy ray and heat is disposed between the pair of substrates, The liquid crystal aligning film as described in said (20) or said (21) characterized by the above-mentioned (20) or said (21) being used for the liquid crystal display element manufactured through the process of polymerizing the said polymeric group, applying a voltage between electrodes.

(26) It has the liquid crystal aligning film as described in said (25), The liquid crystal display element characterized by the above-mentioned.

The composition containing the solvent having a specific structure of the present invention and at least one polymer selected from a polyimide precursor or polyimide can suppress the occurrence of pinholes accompanying repelling when forming a polyimide film, The polyimide film excellent also in the coating film property of the edge part can be produced. In that case, a polyimide film|membrane can be produced also by baking at low temperature.

Moreover, the liquid-crystal aligning agent using the composition of this invention WHEREIN: When forming a liquid crystal aligning film, generation|occurrence|production of the pinhole accompanying repelling can be suppressed, and the liquid-crystal aligning agent excellent also in the coating-film property of the edge part is provided. In particular, even if it is a liquid-crystal aligning agent using the polyamic acid obtained using the diamine compound which has a side chain, and a polyimide, it exists in providing the liquid-crystal aligning agent excellent in these characteristics. Furthermore, even if baking at the time of producing a liquid crystal aligning film is low temperature, it exists in providing the liquid-crystal aligning agent excellent in the electrical characteristic in a liquid crystal display element, especially voltage retention (VHR).

Moreover, by using the composition of this invention as a liquid-crystal aligning agent, generation|occurrence|production of the pinhole accompanying repelling can be suppressed and the liquid crystal aligning film excellent also in the coating-film property of the edge part can be provided. Even if it is a liquid-crystal aligning agent using the polyamic acid and polyimide obtained especially using the diamine compound which has a side chain, the liquid crystal aligning film excellent in these characteristics can be provided. Furthermore, even if baking at the time of producing a liquid crystal aligning film is low temperature, the liquid crystal aligning film excellent in the electrical characteristic in a liquid crystal display element, especially voltage retention (VHR) can be provided. Therefore, the liquid crystal display element which has a liquid crystal aligning film obtained from the liquid-crystal aligning agent of this invention becomes a thing excellent in reliability, and it is a large screen, and it can use suitably for a high-definition liquid crystal television, a small and medium-sized car navigation system, a smart phone, etc.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which showed the linearity of the edge part of the polyimide film apply|coated to the glass substrate.
2 is a view showing mounting of an end of a polyimide film applied to a glass substrate.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

This invention is a liquid crystal display element which has the liquid-crystal aligning film obtained using the composition containing following (A) component and (B) component, a liquid-crystal aligning agent, this liquid-crystal aligning agent, Furthermore, this liquid crystal aligning film.

(A) Component: The solvent (it is also mentioned a specific solvent) shown by a following formula [A].

[Formula 12]

(In formula [A], X ¹ and X ² each independently represent a C1-C3 alkyl group, and X ³ and X ⁴ each independently represent a C1-C3 alkyl group).

(B) component: at least 1 sort(s) of polymer chosen from a polyimide precursor and a polyimide (it is also mentioned a specific polymer).

The specific solvent of this invention can be used as a solvent (it is also mentioned a good solvent) which can melt|dissolve polyimide-type polymers, such as a polyimide precursor and a polyimide, Furthermore, the effect which improves the coating film property of a polyimide film and a liquid crystal aligning film there is also That is, the specific solvent of the present invention has a low surface tension as a solvent compared to NMP, which is usually used as a good solvent, so that the coating solution using the specific solvent is more resistant to the substrate than the coating solution not using it. The wetting and diffusivity of the coating solution for the skin is increased. Thereby, when it is set as a polyimide film and a liquid crystal aligning film, the linearity of the edge part of these films|membrane becomes high. Moreover, generation|occurrence|production of the pinhole accompanying repelling can also be suppressed by the wet-diffusion property of the application|coating solution with respect to a board|substrate becoming high.

Moreover, the specific solvent of this invention has a low boiling point compared with NMP and (gamma)-BL which are normally used as a good solvent. Therefore, baking at the time of producing a polyimide film and a liquid crystal aligning film can be performed at low temperature. Therefore, even if baking at the time of especially producing a liquid crystal aligning film is low temperature, the liquid crystal aligning film excellent in VHR in a liquid crystal display element can be obtained.

In addition, (B) component of this invention is an at least 1 sort(s) of polymer chosen from a polyimide precursor or a polyimide. Especially, when using the composition of this invention for a liquid-crystal aligning agent and producing a liquid crystal aligning film, the at least 1 sort(s) of side chain chosen from the structure shown by following formula [1-1] and formula [1-2] It is preferable to use the at least 1 sort(s) of polymer (it is also mentioned a specific polymer) chosen from the polyimide precursor or polyimide which has (it is also mentioned a specific side chain structure collectively).

[Formula 13]

(in formula [1-1], Y ¹ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -CONH-, -NHCO- , -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- and -OCO- represent at least one bonding group selected from, Y ² is a single bond or -(CH ₂ ) _b - ( b is an integer of 1 to 15), Y ³ is a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO-, and represents at least one bonding group selected from -OCO-, Y ⁴ is a divalent cyclic group of at least one ring selected from a benzene ring, a cyclohexane ring, and a heterocyclic ring, or a C17-C51 steroid skeleton represents a divalent organic group, and any hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. may be substituted, Y ⁵ represents a divalent cyclic group of at least one ring selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, or 1 carbon atom It may be substituted with a -3 alkoxyl group, a C1-C3 fluorine-containing alkyl group, a C1-C3 fluorine-containing alkoxyl group, or a fluorine atom, n represents an integer of 0-4, Y ⁶ is a C1-C22 at least one selected from an alkyl group, a C2-C22 alkenyl group, a C1-C22 fluorine-containing alkyl group, a C1-C22 alkoxyl group, and a C1-C22 fluorine-containing alkoxyl group).

[Formula 14]

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

Especially, the specific side chain structure shown by said Formula [1-1] has a benzene ring, a cyclohexyl ring, or a heterocyclic divalent cyclic group, or steroid skeleton in a side chain part, C17-C51 divalent organic have a flag These divalent cyclic groups of a benzene ring, a cyclohexyl ring, or a heterocyclic ring, or a C17-C51 divalent organic group which has a steroid skeleton shows a rigid structure. Thereby, stability with respect to the heat|fever of a side chain site|part improves, decomposition|disassembly of the side chain site|part by baking at the time of producing a liquid crystal aligning film is suppressed, and the liquid crystal aligning film excellent in VHR can be obtained.

In view of the above, the composition containing the specific solvent of the present invention and at least one polymer selected from a polyimide precursor or polyimide has excellent coating properties and can form a polyimide film even by firing at a low temperature. become a composition.

Moreover, the liquid-crystal aligning agent obtained from the composition of this invention can obtain the liquid crystal aligning film excellent in coating-film property. Moreover, even if baking at the time of producing a liquid crystal aligning film is low temperature, the liquid crystal aligning film excellent in VHR in a liquid crystal display element can be obtained. Therefore, the highly reliable liquid crystal display element excellent in a display characteristic can be provided by using this liquid crystal aligning film.

In addition, the liquid-crystal aligning agent obtained from the composition containing the at least 1 sort(s) of polymer chosen from the polyimide precursor or polyimide which has the specific solvent of this invention, and the specific side chain structure shown by said Formula [1-1] is said more Even if the effect of, ie, baking at the time of producing a liquid crystal aligning film is low temperature, the liquid crystal aligning film excellent in VHR in a liquid crystal display element can be obtained. Therefore, by using this liquid crystal aligning film, the highly reliable liquid crystal display element which is more excellent in a display characteristic can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in more detail.

<Specific solvent>

The specific solvent of this invention is a solvent shown by a following formula [A].

[Formula 15]

In formula [A], X ¹ and X ² each independently represent an alkyl group having 1 to 3 carbon atoms (eg, a methyl group, an ethyl group, a propyl group or an isopropyl group), preferably a methyl group or an ethyl group , particularly preferably a methyl group.

In formula [A], X ³ and X ⁴ each independently represent an alkyl group having 1 to 3 carbon atoms (eg, a methyl group, an ethyl group, a propyl group or an isopropyl group), preferably a methyl group or an ethyl group , particularly preferably a methyl group.

Specifically, it is preferable to represent with a following formula [A-1].

[Formula 16]

It is preferable that the quantity of the specific solvent of this invention is 5-80 mass % of the whole solvent contained in a composition and a liquid-crystal aligning agent, in order to improve the wet-diffusion property of the coating solution with respect to the board|substrate mentioned above more. Especially, 5-75 mass % is preferable. More preferably, it is 5-70 mass %, More preferably, it is 10-60 mass %.

In the whole solvent in a composition and a liquid-crystal aligning agent, the polyimide film and liquid crystal aligning film excellent in the effect of this invention, ie, the wet diffusion of the coating solution with respect to a board|substrate, become high, so that there is much quantity of the specific solvent of this invention in a composition and liquid-crystal aligning agent can be obtained

<Specific Polymer>

The specific polymer which is (B) component of this invention is at least 1 sort(s) of polymer chosen from a polyimide precursor and a polyimide (it is generically called a polyimide-type polymer). Especially, it is preferable that the polyimide-type polymer of this invention is a polyimide precursor or polyimide obtained by making a diamine component and a tetracarboxylic-acid component react.

A polyimide precursor is a structure shown by a following formula [a].

[Formula 17]

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

As said diamine component, the diamine compound which has two primary or secondary amino groups in a molecule|numerator is mentioned.

Moreover, as said tetracarboxylic-acid component, a tetracarboxylic-acid compound, tetracarboxylic dianhydride, a tetracarboxylic-acid dihalide compound, a tetracarboxylic-acid dialkyl ester compound, or a tetracarboxylic-acid dialkyl ester dihalide compound is mentioned can

Formula [a] in the A ¹ and A ² is a hydrogen atom in order to obtain a polyamic acid, and a diamine compound having two primary or amino groups of the second class in a molecule, a tetracarboxylic acid compound or a tetracarboxylic acid anhydride can be obtained by reacting

Formula [a] in order of A ¹ and A ² to obtain a polyamide acid alkyl ester group having 1 to 5 carbon atoms, said diamine compound and a tetracarboxylic dihydrazide halide compound, a tetracarboxylic acid di-alkyl ester compound or tetracarboxylic It can obtain by making an acid dialkyl ester dihalide compound react. Moreover, a C1-C5 alkyl group can also be introduce|transduced into ^A<1> and A<^2> shown by a formula [a] to the polyamic acid obtained by the said method.

The polyimide-type polymer of this invention used the diamine compound which has at least 1 sort(s) of specific side chain structure chosen from the structure shown by following formula [1-1] and formula [1-2] for a part of a raw material polyimide It is preferable that it is at least 1 sort(s) of polymer chosen from a precursor and a polyimide.

[Formula 18]

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

Formula [1-1] in, Y ² represents a single bond or - represents a (b is an integer of _{1 ~ 15) - (CH 2} ) b. Among these, a single bond or - (CH _{2) b} - a (b is an integer of 1 to 10) are preferred.

In formula [1-1], Y ³ is a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- and -OCO- At least 1 type of bonding group selected is shown. Among these, a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, or -COO- is preferable from the point of synthesis easiness. More preferable are a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -CH ₂ O-, or -COO-.

In formula [1-1], Y ⁴ is a divalent cyclic group of at least one ring selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms. , a C1-C3 alkoxyl group, a C1-C3 fluorine-containing alkyl group, a C1-C3 fluorine-containing alkoxyl group, or a fluorine atom may be substituted. Further, Y ⁴ may be a divalent organic group selected from an organic group having a steroid skeleton and having 17 to 51 carbon atoms. Especially, a C17-C51 divalent organic group which has a bivalent cyclic group of a benzene ring or a cyclohexane ring, or a steroid skeleton from the point of synthesis|combination easiness is preferable.

In formula [1-1], Y ⁵ represents a divalent cyclic group of at least one ring selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atoms on these cyclic groups are alkyl groups having 1 to 3 carbon atoms. , a C1-C3 alkoxyl group, a C1-C3 fluorine-containing alkyl group, a C1-C3 fluorine-containing alkoxyl group, or a fluorine atom may be substituted. Among them, a benzene ring or a cyclohexane ring is preferable.

In formula [1-1], n represents the integer of 0-4. Especially, the point of the availability of a raw material and the easiness of a synthesis|combination to 0-3 are preferable. More preferably, it is 0-2.

In formula [1-1], Y<^6> is a C1-C22 alkyl group, a C2-C22 alkenyl group, a C1-C22 fluorine-containing alkyl group, a C1-C22 alkoxyl group, and a C1-C22 fluorine containing. At least 1 sort(s) chosen from an alkoxyl group is shown. Especially, a C1-C18 alkyl group, a C2-C18 alkenyl group, a C1-C10 fluorine-containing alkyl group, a C1-C18 alkoxyl group, or a C1-C10 fluorine-containing alkoxyl group is preferable. More preferably, they are a C1-C12 alkyl group, a C2-C12 alkenyl group, or a C1-C12 alkoxyl group. Especially preferably, they are a C1-C9 alkyl group or a C1-C9 alkoxyl group.

Expression in a desired combination of Y ¹ - Y ⁶ and n in [1-1] is shown on Table 6 and Table 47 on pages 13 to 34 page of International Publication No. 2011/132751 (published 27/10/2011) The combination similar to (2-1)-(2-629) is mentioned. Further, by reading the table, each of International Publication, there is Y ¹ ~ Y ⁶ in the present invention, shown as Y1 ~ Y6, Y1 ~ Y6 is changed as Y ¹ ~ Y ^6. In addition, in (2-605)-(2-629) published in each table|surface of International Publication, the C17-C51 organic group which has a steroid skeleton in this invention has a C12-C25 steroid skeleton Although shown as an organic group, a C12-C25 organic group which has a steroid skeleton shall be read interchangeably as a C17-C51 organic group which has a steroid skeleton.

[Formula 19]

In formula [1-2], Y ⁷ is a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, - At least 1 type of bonding group selected from COO- and -OCO- is represented. Among them, a single bond, -O-, -CH ₂ O-, -CONH-, -CON(CH ₃ )-, or -COO- is preferable. More preferably, it is a single bond, -O-, -CONH-, or -COO-.

In the formula [1-2], Y ⁸ represents a fluorine-containing alkyl group of a carbon number of 8 to 22 carbon atoms or an alkyl group of 6 to 18. Especially, a C8-C18 alkyl group is preferable.

As a specific side chain structure of this invention, it is preferable to use the structure shown by Formula [1-1] from the point which can obtain the vertical alignment property of a high and stable liquid crystal.

Although there is no restriction|limiting in particular in the method of introduce|transducing the specific side chain structure of this invention into a specific polymer, It is preferable to use the diamine compound which has a specific side chain structure for a diamine component.

It is preferable to use the diamine compound (it is also mentioned a specific side chain type diamine compound) specifically, shown by a following formula [1a]. In that case, the diamine compound whose amino group in a following formula [1a] is a secondary amino group can also be used.

[Formula 20]

In formula [1a], Y shows the at least 1 sort(s) of structure chosen from the structure shown by said Formula [1-1] and Formula [1-2]. In addition, the formula Y ¹ ~ preferred combination of Y ⁶ and n in the case where the Y in [1a] shows the formula [1-1] is the same as above.

In formula [1a], m represents the integer of 1-4. Especially, 1 is preferable.

In the specific example of the specific side chain type diamine compound of this invention, the diamine compound shown, for example by a following formula [1a-1] - a formula [1a-34], and the diamine compound whose amino group is a secondary amino group can be heard

[Formula 21]

(Formula [1a-1] in ~ formula ^{[1a-3], R 1} , R 3 and R ⁵ are, each _{independently, -O-, -OCH 2 -, -CH} 2 O-, -COOCH 2 - , or -CH ₂ OCO- is represented, and in formulas [1a-1] to [1a-3], R ² , R ⁴ and R ⁶ are each independently a linear or branched alkyl group having 1 to 22 carbon atoms; It represents a C1-C22 linear or branched alkoxyl group, a C1-C22 linear or branched fluorine-containing alkyl group, or a C1-C22 fluorine-containing alkoxyl group).

[Formula 22]

(In formulas [1a-4] to [1a-6], R ¹ , R ³ and R ⁵ are each independently -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ - , -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ - or -CH ₂ ^{-, wherein R 2} , R ⁴ and R ⁶ are in the formulas [1a-4] to [1a-6], each independently a C1-C22 linear or branched alkyl group, a C1-C22 linear or branched alkoxyl group, a C1-C22 linear or branched fluorine-containing alkyl group, or a C1-C22 represents a fluorine-containing alkoxyl group).

[Formula 23]

(In formulas [1a-7] and [1a-8], R ¹ and R ³ are each independently -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, -CH ₂ -, -O- or -NH- represents, R ² and R ⁴ are each independently a fluorine group, a cyano group, trifluoro represents a methyl group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group or a hydroxyl group).

[Formula 24]

(In formulas [1a-9] and [1a-10], R ¹ and R ² each independently represent a linear or branched alkyl group having 3 to 12 carbon atoms, and cis-trans isomers, respectively, are trans isomers).

[Formula 25]

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

[Formula 26]

(In the formula [1a-13], A ₄ is a linear or branched alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, and A ₃ is a 1,4-cyclohexylene group or a 1,4-phenylene group and A ₂ is an oxygen atom or -COO-* (however, the bond to which “*” is attached is bonded to A ₃ ), A ₁ is an oxygen atom or -COO-* (provided that “*” is attached to the bond The hand _{binds to (CH 2} )a ₂ )). In addition, a ₁ is an integer of 0 or 1, a ₂ is an integer of 2 to 10, and a ₃ is an integer of 0 or 1).

[Formula 27]

[Formula 28]

[Formula 29]

[Formula 30]

[Chemical Formula 31]

[Formula 32]

(In the formula [1a-32] ~ formula ^{[1a-35], A 1} ~ A 4 are, each independently, an alkyl group or a fluorine-containing alkyl group having a carbon number of 1-22, respectively).

In said formula [1a-1] - [1a-21], [1a-24] - [1a-35], the specific side chain type diamine compound of a especially preferable structure is a formula [1a-1] - a formula [1a- 6], a formula [1a-9] - a formula [1a-13], or a formula [1a-24] - a formula [1a-31].

It is preferable that the specific side chain type diamine compounds in the specific polymer of this invention are 10 mol% or more of the whole diamine component and 80 mol% or less. Especially preferably, it is 10 mol% or more and 70 mol% or less.

The specific side chain type diamine compound of this invention is the solubility to the solvent of the specific polymer of this invention, the applicability|paintability of a composition and a liquid-crystal aligning agent, the orientation of the liquid crystal in setting it as a liquid crystal aligning film, voltage retention, accumulation|storage charge, etc. Depending on the characteristics, one type or a mixture of two or more types may be used.

It is preferable that it is the polymer which used for the diamine component the diamine compound which has at least 1 sort(s) of substituent chosen from a carboxyl group (COOH group) and a hydroxyl group (OH group) in the specific polymer of this invention.

It is preferable to use the diamine compound specifically, shown by a following formula [2a]. In that case, the diamine compound whose amino group in a following formula [2a] is a secondary amino group can also be used.

[Formula 33]

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

[Formula 34]

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

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

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

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

Moreover, the diamine compound shown by a following formula [2a-1] - a formula [2a-4] and the diamine compound whose amino group is a secondary amino group can also be used.

[Formula 35]

(in formula [2a-1], A ¹ is a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON( CH ₃ )- and at least one bonding group selected from _{-N(CH 3} ^{)CO-, m 1} and m ² each independently represent an integer of 0 to 4, and m ¹ + m ² are An integer of 1 to 4 is shown, in formula [2a-2], m ³ and m ⁴ are each independently an integer of 1 to 5, and in formula [2a-3], A ² has 1 to 5 carbon atoms represents a linear or branched alkyl group of, m ⁵ represents an integer of 1 to 5, in formula [2a-4], A ³ and A ⁴ are each independently 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- represents at least one bonding group selected from , m ⁶ represents an integer of 1 to 4).

The diamine compound having at least one substituent selected from a carboxyl group (COOH group) and a hydroxyl group (OH group) in the specific polymer of the present invention is preferably 10 mol% or more and 80 mol% or less of the total diamine component. . Especially preferably, it is 10 mol% or more and 70 mol% or less.

The diamine compound which has at least 1 sort(s) of substituent chosen from the carboxyl group (COOH group) and hydroxyl group (OH group) of this invention with respect to the solvent of the specific polymer of this invention, the applicability|paintability of a composition and a liquid-crystal aligning agent, According to characteristics, such as the orientation of a liquid crystal in the case of setting it as a liquid crystal aligning film, voltage retention, and accumulated electric charge, you can also use it 1 type or in mixture of 2 or more types.

It is preferable to use for the specific polymer of this invention the diamine compound which has a nitrogen-containing heterocyclic ring shown by a following formula [3a], and the diamine compound whose amino group is a secondary amino group.

[Chemical Formula 36]

In formula [3a], B ¹ is -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON(CH ₃ )- and at least one bonding group selected from -N(CH _{3 )CO-.} Among them, -O-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO- is a diamine compound It is preferable because it is easy to synthesize|combine. More preferable are -O-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, or -CON(CH ₃ )-. Particularly preferred are -O-, -CONH- or -CH ₂ O-.

Formula [3a] of, B ² represents at least one kind selected from a single bond, a divalent group, and the divalent aromatic hydrocarbon divalent group, non-aromatic cyclic hydrocarbon of the aliphatic hydrocarbon group of 1 to 20 carbon atoms. The divalent group of the C1-C20 aliphatic hydrocarbon may be linear or may be branched. Moreover, you may have an unsaturated bond. Especially, a C1-C10 alkylene group is preferable. Further, specific examples of the non-aromatic hydrocarbon include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, a cyclodo Decane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosan ring, tricycloeicosane ring, tri and a cyclodeconic acid ring, a bicycloheptane ring, a decahydronaphthalene ring, a norbornene ring or an adamantane ring. Among these, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring, or an adamantane ring is preferable. Specific examples of the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an azulene ring, an indene ring, a fluorene ring, an anthracene ring, a phenanthrene ring or a phenalene ring. Among them, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, a fluorene ring, or an anthracene ring is preferable.

Expression roneun preferred B ² in [3a], a single bond, having from 1 to 10 carbon atoms in the alkylene group, or a cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, a norbornene ring, Oh It is a divalent group of at least 1 sort(s) of ring selected from a danthanane ring, a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, a fluorene ring, and an 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 preferable.

In formula [3a], B ³ is 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 of 1-5) represents at least 1 type of bonding group selected from. Among them, a single bond, -O-, -COO-, -OCO-, or -O(CH ₂ ) _m - (m is an integer of 1 to 5) is preferable. More preferably, it is a single bond, -O-, -OCO-, or -O(CH ₂ ) _m - (m is an integer of 1 to 5).

In formula [3a], B ⁴ is a nitrogen-containing heterocyclic group, and is a heterocyclic group containing at least one structure selected from the following formulas [3a-1], [3a-2] and [3a-3]. It is a ring of rings.

[Chemical Formula 37]

(In formula [3a-3], Z ¹¹ represents a C1-C5 alkyl group).

More specifically, a pyrrole ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a pyrazoline ring, an isoquinoline ring, a carbazole ring, a purine ring, a thia Diazole ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzoimidazole ring, cinnoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzo and a thiazole ring, a phenothiazine ring, an oxadiazole ring or an acridine ring. Among them, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring or a benzimidazole ring is preferable. More preferred are a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring or a pyrimidine ring. In addition, B ³ in formula [3a] is bonded to a ring atom not adjacent to the structure of formula [3a-1], formula [3a-2] and formula [3a-3] contained in B ^{4 ,} It is preferable to have

In formula [3a], n is an integer of 1-4, Preferably, it is 1 or 2 from a reactive point with a tetracarboxylic-acid component.

In the particularly preferred ^{combination of B 1} to B ⁴ and n in the ^{formula [3a], B 1} represents -CONH-, B ² represents an alkylene group having 1 to 5 carbon atoms, B ³ represents a single bond, B ⁴ is already represents an imidazole ring or a pyridine ring, n is a diamine compound represented by the first.

Coupled position of the two amino groups (-NH ₂₎ of the formula [3a] is not limited. Specifically, with respect to the bonding group (-B ¹ -) of the side chain, the position of 2, 3, the position of 2, 4, the position of 2, 5, the position of 2, 6, the position of 3 or 4 on the benzene ring, or Positions 3 and 5 are mentioned. Especially, from a reactive viewpoint at the time of synthesize|combining a polyamic acid, the position of 2, 4, the position of 2, 5, or the position of 3 and 5 is preferable. When the easiness at the time of synthesize|combining a diamine compound is also taken into consideration, the position of 2, 4 or the position of 2, 5 is more preferable.

It is preferable that the diamine compounds which have a nitrogen-containing heterocyclic ring shown by the said formula [3a] in the specific polymer of this invention are 10 mol% or more and 80 mol% or less of the whole diamine component. Especially preferably, it is 10 mol% or more and 70 mol% or less.

When the diamine compound which has a nitrogen-containing heterocyclic ring shown by said Formula [3a] of this invention sets it as the solubility to the solvent of the specific polymer of this invention, the applicability|paintability of a composition and a liquid-crystal aligning agent, a liquid crystal aligning film, According to characteristics, such as orientation, voltage retention, and accumulated electric charge, you may use 1 type or in mixture of 2 or more types.

In the specific polymer of this invention, unless the effect of this invention is impaired, as another diamine compound, the diamine compound shown by a following formula [a-1] - a formula [a-13], and these amino groups are 2 A diamine compound which is an amino group of a class can also be used.

[Formula 38]

(In formula [a-1], A ¹ and A ³ are each independently -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- and - represents at least one bonding group selected from NH-, 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 [a-2], A ⁴ and A ⁶ are each independently -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- and -NH- represents at least one bonding group selected from, and A ⁵ represents a C1-C22 linear or branched alkyl group, or a C1-C22 linear or branched fluorine-containing alkyl group).

[Chemical Formula 39]

(In formula [a-3], A ¹ and A ³ are each independently -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- and - represents at least one bonding group selected from NH-, 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 [a-4], A ⁴ and A ⁶ are each independently -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- and -NH- represents at least one bonding group selected from, and A ⁵ represents a C1-C22 linear or branched alkyl group, or a C1-C22 linear or branched fluorine-containing alkyl group).

[Formula 40]

(In formula [a-5], A ¹ and A ³ are each independently -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- and - represents at least one bonding group selected from NH-, 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 [a-6], A ⁴ and A ⁶ are each independently -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- and -NH- represents at least one bonding group selected from, and A ⁵ represents a C1-C22 linear or branched alkyl group, or a C1-C22 linear or branched fluorine-containing alkyl group).

[Formula 41]

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

[Formula 42]

[Formula 43]

(In formula [a-12], R<^1> represents a hydrogen atom or a C1-C5 alkyl group, and in formula [a-13], n represents the integer of 1-10).

In addition, as another diamine compound, the following diamine compound and the diamine compound whose amino group is a secondary amino group can also be used.

Specifically, p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl -m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'- Diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-dia Minobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'- Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfo Nyldianiline, 3,3'-sulfonyldianiline, bis(4-aminophenyl)silane, bis(3-aminophenyl)silane, dimethyl-bis(4-aminophenyl)silane, dimethyl-bis(3-aminophenyl) Silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodi Phenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, N-methyl (3,3'- Diaminodiphenyl)amine, N-methyl (3,4'-diaminodiphenyl)amine, N-methyl (2,2'-diaminodiphenyl)amine, N-methyl (2,3'-diamino) Diphenyl)amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'-diamino Benzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-dia Minonaphthalene, 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-aminophenyl)methane , 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4- Aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-[1,4-phenylenebis(methylene)]di Aniline, 4,4'-[1,3-phenylenebis(methylene)]dianiline, 3,4'-[1,4-phenylenebis(methylene)]dianiline, 3,4'-[1, 3-phenylenebis(methylene)]dianiline, 3,3'-[1,4-phenylenebis(methylene)]dianiline, 3,3'-[1,3-phenylenebis(methylene)]di Aniline, 1,4-phenylenebis[(4-aminophenyl)methanone], 1,4-phenylenebis[(3-aminophenyl)methanone], 1,3-phenylenebis[(4-amino) Phenyl)methanone], 1,3-phenylenebis[(3-aminophenyl)methanone], 1,4-phenylenebis(4-aminobenzoate), 1,4-phenylenebis(3-amino benzoate), 1,3-phenylenebis(4-aminobenzoate), 1,3-phenylenebis(3-aminobenzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl) ) terephthalate, bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate, N,N'-(1,4-phenylene)bis(4-aminobenzamide), N,N' -(1,3-phenylene)bis(4-aminobenzamide), N,N'-(1,4-phenylene)bis(3-aminobenzamide), N,N'-(1,3- Phenylene)bis(3-aminobenzamide), N,N'-bis(4-aminophenyl)terephthalamide, N,N'-bis(3-aminophenyl)terephthalamide, N,N'-bis(4 -Aminophenyl)isophthalamide, N,N'-bis(3-aminophenyl)isophthalamide, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy) Diphenylsulfone, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2 '-Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexa Fluoropropane, 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)nonane, 1,9-bis(3-aminophenoxy)nonane, 1,10-(4-aminophenoxy)decane, 1,10-(3-aminophenoxy)decane, 1,11-(4-aminophenoxy) ) Aromatic diamine compounds such as undecane, 1,11-(3-aminophenoxy)undecane, 1,12-(4-aminophenoxy)dodecane, and 1,12-(3-aminophenoxy)dodecane , alicyclic diamine compounds such as bis(4-aminocyclohexyl)methane and bis(4-amino-3-methylcyclohexyl)methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5 -Diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11- and aliphatic diamine compounds such as diaminoundecane and 1,12-diaminododecane.

Other diamine compounds of the present invention are properties such as solubility in the solvent of the specific polymer of the present invention, coating properties of a composition and a liquid-crystal aligning agent, the orientation of the liquid crystal in the case of forming a liquid crystal aligning film, voltage retention, and accumulated charge Accordingly, one type or a mixture of two or more types may be used.

It is preferable to use the tetracarboxylic dianhydride shown by a following formula [4] as a tetracarboxylic-acid component for producing the specific polymer of this invention, ie, these polyimide-type polymers. In that case, not only the tetracarboxylic dianhydride shown by Formula [4], but the tetracarboxylic acid which are this tetracarboxylic-acid derivative, the tetracarboxylic-acid dihalide compound, the tetracarboxylic-acid dialkyl ester compound, or the tetracarboxylic-acid dialkyl An ester dihalide compound can also be used (the tetracarboxylic dianhydride and its derivative(s) represented by Formula [4] are collectively named, and it is also called a specific tetracarboxylic-acid component).

[Formula 44]

(In formula [4], Z shows the at least 1 sort(s) of structure chosen from the structure shown by a following formula [4a] - a formula [4k]).

[Formula 45]

In the formulas ^{[4a], Z 1 ~ Z} 4 are, each independently, represent a hydrogen atom, a methyl group, an ethyl group, a chlorine atom or a phenyl group.

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

In Z in formula [4], from the point of the easiness of synthesis or the easiness of polymerization reactivity at the time of manufacturing a polymer, the tetra of a structure shown by a formula [4a], a formula [4c] - a formula [4g], or a formula [4k] Carboxylic acid dianhydride and its tetracarboxylic acid derivative are preferable. A more preferable thing is a thing of a structure shown by a formula [4a] or a formula [4e] - a formula [4g]. Especially preferable are tetracarboxylic dianhydride of the structure shown by [4a], a formula [4e], or a formula [4f], and its tetracarboxylic acid derivative.

It is preferable that the specific tetracarboxylic-acid component in the specific polymer of this invention is 1 mol% - 100 mol% in 100 mol% of all the tetracarboxylic-acid components. Especially, 5 mol% - 95 mol% are preferable. More preferably, they are 20 mol% - 80 mol%.

The specific tetracarboxylic acid component of this invention is the solubility to the solvent of the specific polymer of this invention, the applicability|paintability of a composition and a liquid-crystal aligning agent, the orientation of the liquid crystal in the case of setting it as a liquid crystal aligning film, voltage retention, accumulation|storage charge, etc. Depending on the characteristics, one type or a mixture of two or more types may be used.

Unless the effect of this invention is impaired for the specific polymer of this invention, other tetracarboxylic-acid components other than a specific tetracarboxylic-acid component can also be used. As another tetracarboxylic-acid component, the tetracarboxylic-acid compound shown below, tetracarboxylic dianhydride, a tetracarboxylic-acid dihalide compound, a tetracarboxylic-acid dialkyl ester compound, or a tetracarboxylic-acid dialkyl ester dihalide compound can be heard

That is, as the other tetracarboxylic acid component, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,5,6-anthracenetetra Carboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4-biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3 ,3',4,4'-benzophenonetetracarboxylic acid, bis(3,4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4- Dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethylsilane , bis(3,4-dicarboxyphenyl)diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxyphenyl)pyridine, 3,3', 4,4'-diphenylsulfonetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid, etc. can be heard

The other tetracarboxylic-acid component of this invention is the solubility with respect to the solvent of the specific polymer of this invention, the applicability|paintability of a composition and a liquid-crystal aligning agent, the orientation of the liquid crystal in setting it as a liquid crystal aligning film, voltage retention, accumulated electric charge, etc. Depending on the characteristics, one type or a mixture of two or more types may be used.

<Production method of specific polymer>

In this invention, the method for producing a specific polymer, ie, these polyimide-type polymers, is not specifically limited. Usually, it is obtained by making a diamine component and a tetracarboxylic-acid component react. In general, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic dianhydride and derivatives of tetracarboxylic acid is reacted with a diamine component composed of one or more diamine compounds. , a method for obtaining polyamic acid. Specifically, a method of polycondensing tetracarboxylic dianhydride and a primary or secondary diamine compound to obtain polyamic acid, a polyamide by dehydration polycondensation of tetracarboxylic acid and primary or secondary diamine compound. A method of obtaining an acid or a method of obtaining a polyamic acid by polycondensing a tetracarboxylic acid dihalide and a primary or secondary diamine compound is used.

In order to obtain polyamic-acid alkylester, the method of polycondensing the tetracarboxylic acid which dialkylesterified the carboxylic acid group, and the primary or secondary diamine compound, the tetracarboxylic-acid dihalide which carried out the dialkylesterification of the carboxylic acid group. and a method of polycondensing a primary or secondary diamine compound or a method of converting a carboxyl group of a polyamic acid into an ester is used.

In order to obtain a polyimide, the method of ring-closing said polyamic acid or polyamic-acid alkylester to make a polyimide is used.

Reaction of a diamine component and a tetracarboxylic-acid component performs a diamine component and a tetracarboxylic-acid component in a solvent normally. As a solvent used in that case, although the specific solvent of this invention may be used, if the produced|generated polyimide precursor melt|dissolves, it will not specifically limit. Although the specific example of the solvent used for reaction is given below, it is not limited to these examples.

For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide or 1,3-dimethyl-imidazolidinone. Moreover, when the solvent solubility of a polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or a following formula [D-1] - a formula [ D-3] can be used.

[Formula 46]

(In the formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms, in the formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms, and in the formula [D-3], D ³ represents a C1-C4 alkyl group).

These solvents may be used independently and may be mixed and used. Moreover, even if it is a solvent in which a polyimide precursor is not dissolved, you may use it in the range in which the produced|generated polyimide precursor does not precipitate, mixing with the said solvent. Moreover, since moisture in a solvent inhibits a polymerization reaction and becomes a cause of hydrolyzing the produced|generated polyimide precursor further, it is preferable to use the solvent which carried out dehydration and drying.

When the diamine component and the tetracarboxylic acid component are reacted in a solvent, a solution obtained by dispersing or dissolving the diamine component in the solvent is stirred, and the tetracarboxylic acid component is added as it is or by dispersing or dissolving it in the solvent, and vice versa. The method of adding a diamine component to the solution which disperse|distributed or melt|dissolved a carboxylic acid component in a solvent, the method of adding a diamine component and a tetracarboxylic-acid component alternately, etc. are mentioned, Any of these methods may be used. In addition, in the case of reacting using a plurality of diamine components or tetracarboxylic acid components, respectively, they may be reacted in a pre-mixed state, may be individually and sequentially reacted, or individually reacted low molecular weight substances may be mixed and reacted. It is good also as a polymer. Although the polymerization temperature in that case can select arbitrary temperatures of -20 degreeC - 150 degreeC, Preferably it is the range of -5 degreeC - 100 degreeC. In addition, although the reaction can be carried out at any concentration, if the concentration is too low, it becomes difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult. Therefore, Preferably it is 1-50 mass %, More preferably, it is 5-30 mass %. In the initial stage of the reaction, it can be carried out at a high concentration, and then a solvent can be added.

In the polymerization reaction of a polyimide precursor, it is preferable that ratio of the total number of moles of a diamine component and the total number of moles of a tetracarboxylic-acid component is 0.8-1.2. As in a typical polycondensation reaction, the closer this molar ratio is to 1.0, the greater the molecular weight of the polyimide precursor produced.

The polyimide of the present invention is a polyimide obtained by ring closure of the above polyimide precursor, and in this polyimide, the ring closure rate of the amic acid group (also referred to as imidization rate) is not necessarily 100%, It can be adjusted arbitrarily according to

As a method of imidating a polyimide precursor, the thermal imidation which heats the solution of a polyimide precursor as it is, or catalyst imidation which adds a catalyst to the solution of a polyimide precursor is mentioned.

The temperature in the case of thermal imidation of a polyimide precursor in a solution is 100 degreeC - 400 degreeC, Preferably it is 120 degreeC - 250 degreeC, It is preferable to carry out, removing the water produced|generated by the imidation reaction to the outside of a system.

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

When collect|recovering the produced|generated polyimide precursor or polyimide from the reaction solution of a polyimide precursor or a polyimide, what is necessary is just to inject|throw-in a reaction solution to a solvent and just to precipitate. Examples of the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. The polymer precipitated by putting it in a solvent can be collected by filtration, and then dried under normal pressure or reduced pressure, at room temperature or by heating. Moreover, when the polymer which carried out precipitation collection|recovery is made to dissolve again in a solvent, and operation which carries out reprecipitation collection|recovery is repeated 2 times - 10 times, the impurity in a polymer can be decreased. Examples of the solvent at this time include alcohols, ketones, hydrocarbons, and the like, and the use of three or more solvents selected from these is preferable because the efficiency of purification further increases.

<Composition, liquid crystal aligning agent>

The composition of this invention and the liquid-crystal aligning agent using the same are a coating solution for forming a polyimide film and a liquid crystal aligning film (it is generically called a resin film), Comprising: Coating solution for forming the resin film containing a specific solvent and a specific polymer. to be.

Any polyimide-type polymer of a polyamic acid, polyamic-acid alkylester, and a polyimide may be used for the specific polymer of this invention. Especially, polyamic-acid alkylester or polyimide is preferable. More preferably, it is polyimide.

The specific polymer of this invention may be sufficient as all the polymer components in the composition of this invention, and a liquid-crystal aligning agent. In that case, you may mix and use 2 or more types of the specific polymer of this invention. Moreover, other polymers other than that may be mixed with a specific polymer. Examples of the other polymer include a cellulosic polymer, an acrylic polymer, a methacrylic polymer, polystyrene, polyamide, or polysiloxane. In that case, content of other polymers other than that is 0.5 mass part - 30 mass parts with respect to 100 mass parts of specific polymers of this invention. Especially, 1 mass part - 20 mass parts are preferable.

Moreover, when using the composition of this invention as a liquid-crystal aligning agent and forming a liquid crystal aligning film, it is preferable to use for a specific polymer the specific polymer which has the specific side chain structure shown by said Formula [1-1] of this invention. . Especially, it is preferable to use the specific polymer using the specific side chain type diamine compound shown by Formula [1a] which has the specific side chain structure shown by Formula [1-1]. It is preferable that it is a specific polymer using a specific side chain type diamine compound about the liquid crystal aligning film with respect to the mode especially requiring the pretilt angle of a liquid crystal, such as TN (Twisted Nematic) mode and VA (Vertical Alignment) mode. In addition, in that case, you may mix and use the specific polymer which used the specific side chain type diamine compound, and the specific polymer which does not use the specific side chain type diamine compound. In that case, it is preferable that content of the specific polymer which does not use a specific side chain type diamine compound is 10 mass parts - 300 mass parts with respect to 100 mass parts of specific polymers using a specific side chain type diamine compound. Especially, 20 mass parts - 200 mass parts are preferable.

It is preferable that content of a solvent is 70-99.9 mass % from a viewpoint of the solvent in the composition of this invention, and a liquid-crystal aligning agent forming a uniform resin film by application|coating. This content can be suitably changed according to the film thickness of the polyimide film made into the objective, and a liquid crystal aligning film.

In addition, as a solvent in that case, although the specific solvent of this invention may be sufficient as all, you may use the solvent which dissolves the specific polymer of this invention, ie, a good solvent, simultaneously. Although the specific example of a good solvent is given below, it is not limited to these examples.

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

Among them, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or γ-butyllactone (above (also referred to as component (C)).

It is preferable that these (C)components are 1-70 mass % of the whole solvent contained in a composition and a liquid-crystal aligning agent. Especially, 5-65 mass % is preferable. More preferably, it is 5-60 mass %, More preferably, it is 10-60 mass %.

According to the solubility with respect to the solvent of the specific polymer of this invention, a composition, and the applicability|paintability of a liquid-crystal aligning agent, the said good solvent can also be used 1 type or in mixture of 2 or more types.

For the composition and liquid-crystal aligning agent of this invention, unless the effect of this invention is impaired, the organic solvent which improves the coatability and surface smoothness of the resin film at the time of apply|coating a composition and a liquid-crystal aligning agent, ie, a poor solvent. It is also preferable Although the specific example of a poor solvent is given below, it is not limited to these examples.

For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, Isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1- Butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methyl Cyclohexanol, 3-methylcyclohexanol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl Ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl Acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2-(methoxymethoxy) ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2-( Hexyloxy) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1-(butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether , Dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol di Acetate, diethylene glycol monoethyl ether acetate 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, acetic acid Ethyl, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3- Methoxypropionic acid, 3-methoxypropionate propyl, 3-methoxybutylpropionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, or the above formulas [D-1] to [D] -3], and the like.

Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, or the formula [D-1 ] - it is preferable to use the solvent (it is also mentioned as (D)component) represented by a formula [D-3].

It is preferable that these (D)components are 10-80 mass % of the whole solvent contained in a composition and a liquid-crystal aligning agent. Especially, 10-70 mass % is preferable. More preferably, it is 20-70 mass %, More preferably, it is 20-60 mass %.

According to the solubility with respect to the solvent of the specific polymer of this invention, a composition, and the applicability|paintability of a liquid-crystal aligning agent, the said poor solvent can also be used 1 type or in mixture of 2 or more types.

The composition and liquid-crystal aligning agent of this invention have at least 1 type of substituent selected from the crosslinkable compound which has an epoxy group, an isocyanate group, an oxetane group, or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group. It is preferable to introduce a compound or a crosslinkable compound having a polymerizable unsaturated bond. It is necessary to have two or more of these substituents and a polymerizable unsaturated bond in a crosslinkable compound.

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenol acetone glycidyl ether, phenol novolak epoxy resin, cresol novolak epoxy resin, triglycidyl isocyanurate, tetraglycidyl aminodiphenylene , tetraglycidyl-m-xylenediamine, tetraglycidyl-1,3-bis(aminoethyl)cyclohexane, tetraphenylglycidyletherethane, triphenylglycidyletherethane, bisphenolhexafluoroaceto Diglycidyl ether, 1,3-bis(1-(2,3-epoxypropoxy)-1-trifluoromethyl-2,2,2-trifluoromethyl)benzene, 4,4-bis( 2,3-epoxypropoxy)octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl metaxylenediamine, 2-(4-(2,3-epoxypropoxy)phenyl)-2- (4-(1,1-bis(4-(2,3-epoxypropoxy)phenyl)ethyl)phenyl)propane or 1,3-bis(4-(1-(4-(2,3-epoxyprop and epoxy)phenyl)-1-(4-(1-(4-(2,3-epoxypropoxy)phenyl)-1-methylethyl)phenyl)ethyl)phenoxy)-2-propanol.

The crosslinkable compound which has an oxetane group is a crosslinkable compound which has at least two oxetane groups shown by a following formula [4A].

[Formula 47]

Specifically, the crosslinking|crosslinked compound shown by the formula [4a] - formula [4k] disclosed in the 58th - 59th paragraph of international publication 2011/132751 (2011.10.27 publication) is mentioned.

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

[Formula 48]

The crosslinking|crosslinked compound specifically, shown by Formula [5-1] - Formula [5-42] published in 76th-82nd of International Publication No. 2012/014898 (2012.2.2 publication) is mentioned.

Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include an amino resin having a hydroxyl group or an alkoxyl group, for example, a melamine resin, a urea resin, and guanamine resin, glycoluril-formaldehyde resin, succinylamide-formaldehyde resin, or ethyleneurea-formaldehyde resin. Specifically, a melamine derivative, a benzoguanamine derivative, or glycoluril in which the hydrogen atom of the amino group is substituted with a methylol group, an alkoxymethyl group, or both can be used. This melamine derivative or benzoguanamine derivative can also exist as a dimer or a trimer. It is preferable that these have an average of 3 or more and 6 or less of a methylol group or an alkoxymethyl group per triazine ring.

Examples of such melamine derivatives or benzoguanamine derivatives include MX-750, in which an average of 3.7 methoxymethyl groups are substituted per triazine ring, and 5.8 methoxymethyl groups per triazine ring are substituted on average. Methoxymethylated melamine such as MW-30 (above, manufactured by Sanwa Chemical) and Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, Cymel 235, 236, 238, 212 Methoxymethylated butoxymethylated melamine such as , 253 and 254, butoxymethylated melamine such as Cymel 506 and 508, carboxymethyl group-containing methoxymethylated isobutoxymethylated melamine such as Cymel 1141, and methoxymethylated such as Cymel 1123 Toxymethylated benzoguanamine, methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, carboxymethyl group-containing methoxymethylated ethoxymethylated such as Cymel 1125-80 Benzoguanamine (above, the Mitsui cyanamide make) is mentioned. Further, examples of glycoluril include butoxymethylation glycoluril such as Cymel 1170, methylolation glycoluril such as Cymel 1172, and methoxymethylolation glycoluril such as Powder Link 1174.

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

More specifically, the crosslinking|crosslinked compound shown by Formula [6-1] - Formula [6-48] published on page 62 - page 66 of International Publication No. 2011/132751 (published on October 27, 2011) is mentioned. .

Examples of the crosslinkable compound having a polymerizable unsaturated bond include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and tri(meth)acrylate. ) A crosslinkable compound having three polymerizable unsaturated groups in the molecule, such as acryloyloxyethoxytrimethylolpropane or glycerin polyglycidyl ether poly(meth)acrylate, and also ethylene glycol di(meth)acrylate, diethylene Glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide bisphenol A type di(meth)acrylate, propylene oxide bisphenol type di(meth)acrylate, 1,6-hexanediol di(meth) acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, A crosslinkable compound having two polymerizable unsaturated groups in the molecule, such as phthalic acid diglycidyl ester di (meth) acrylate or hydroxypivalate neopentyl glycol di (meth) acrylate, in addition to 2-hydroxyethyl (meth) ) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyl oxide Cy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate or N-methylol ( The crosslinkable compound etc. which have one polymerizable unsaturated group, such as meth)acrylamide, are mentioned in a molecule|numerator.

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

[Formula 49]

(In formula [7A], E ^{1 is at least one selected} from a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring, and a phenanthrene ring; and E ² represents group selected from the following formula [7a] or formula [7b], and n represents an integer of 1 to 4).

[Formula 50]

The compound is an example of a crosslinkable compound, but is not limited thereto. In addition, the number of the crosslinking|crosslinked compounds used for the composition of this invention, and a liquid-crystal aligning agent may be one, and may combine them two or more types.

It is preferable that content of the crosslinkable compound in the composition of this invention and a liquid-crystal aligning agent are 0.1 mass part - 150 mass parts with respect to 100 mass parts of all the polymer components. Especially, in order for a crosslinking reaction to advance and to express the objective effect, 0.1 mass part - 100 mass parts are preferable with respect to 100 mass parts of all polymer components. More preferably, they are 1 mass part - 50 mass parts.

As long as the effect of this invention is not impaired for the composition and liquid-crystal aligning agent of this invention, the compound which improves the uniformity of the film thickness of a resin film at the time of apply|coating a composition and a liquid-crystal aligning agent, and surface smoothness can be used.

As a compound which improves the uniformity of the film thickness of a resin film, and surface smoothness, a fluorochemical surfactant, silicone type surfactant, nonionic surfactant, etc. are mentioned.

More specifically, for example, F Top EF301, EF303, EF352 (above, manufactured by Tochem Products), Megapac F171, F173, R-30 (above, manufactured by Dainippon Ink), Fluorad FC430, FC431 ( As mentioned above, the Sumitomo 3M company make), Asahi Guard AG710, Sufflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, the Asahi Glass company make) etc. are mentioned.

To [ the usage ratio of these surfactant / 100 mass parts of all the polymer components contained in a composition and a liquid-crystal aligning agent ], Preferably they are 0.01 mass part - 2 mass parts, More preferably, they are 0.01 mass part - 1 mass part.

Moreover, in the composition and liquid-crystal aligning agent of this invention, it is a compound which accelerates|stimulates the electric charge transfer in a resin film, and accelerates|stimulates the charge omission of an element, To the 69 pages - 73 pages of international publication 2011/132751 (2011.10.27 publication) You can also add the nitrogen-containing heterocyclic amine compound shown by Formula [M1] - Formula [M156] listed. Although you may add this amine compound directly to a composition and a liquid-crystal aligning agent, it is 0.1 mass % - 10 mass % of density|concentrations with a suitable solvent, It is preferable to add, after setting it as the preferably 1 mass % - 7 mass % solution. As this solvent, if it is a solvent in which the specific polymer mentioned above is dissolved, it will not specifically limit.

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

<Polyimide film>

The composition of this invention can be used as a polyimide film|membrane, after apply|coating and baking on a board|substrate. As the substrate used at this time, a plastic substrate such as a glass substrate, a silicon wafer, an acrylic substrate, a polycarbonate substrate, or a PET (polyethylene terephthalate) substrate can also be used depending on the target device. Moreover, a polyimide film can also be used as a film board|substrate as it is. The coating method of the composition is not particularly limited, but industrially, a dip method, a roll coater method, a slit coater method, a spinner method, a spray method, a screen printing method, an offset printing method, a flexographic printing method, or an inkjet method. It is common. These may use these according to the objective.

After apply|coating a composition on a board|substrate, 50-300 degreeC, preferably 80-250 degreeC, with heating means, such as a hot plate, a heat circulation type oven, or IR (infrared) type oven, evaporates a solvent, and a polyimide film can be done with In the case of the composition using the specific solvent of the present invention, a polyimide film can be produced even at a temperature of 200°C or lower. The thickness of the polyimide film after baking can be adjusted to 0.01-100 micrometers according to the objective.

<Liquid crystal alignment film, liquid crystal display element>

After apply|coating and baking the liquid-crystal aligning agent using the composition of this invention on a board|substrate, it can orientate-process by a rubbing process, light irradiation, etc., and can be used as a liquid crystal aligning film. Moreover, in the case of vertical alignment uses, such as a VA mode, it can use as a liquid crystal aligning film without an orientation treatment. It will not specifically limit as a board|substrate used at this time, if it is a board|substrate with high transparency, In addition to a glass substrate, plastic substrates, such as an acrylic board|substrate, a polycarbonate board|substrate, or a PET (polyethylene terephthalate) board|substrate, etc. can be used. From a viewpoint of simplification of a process, it is preferable to use the board|substrate with which the ITO (indium tin oxide) electrode etc. for liquid-crystal drive were formed. In the reflective liquid crystal display device, an opaque substrate such as a silicon wafer can also be used as long as it is only a one-sided substrate, and a material that reflects light such as aluminum can be used as the electrode in this case.

Although the application method of a liquid-crystal aligning agent is not specifically limited, Industrially, the method of performing by screen printing, an offset printing, a flexographic printing, the inkjet method, etc. is common. As another coating method, there exist a dip method, the roll coater method, the slit coater method, the spinner method, the spray method, etc., You may use these according to the objective.

After apply|coating a liquid-crystal aligning agent on a board|substrate, it is 30-300 degreeC according to the solvent used for a liquid-crystal aligning agent by heating means, such as a hotplate, heat circulation type oven, or IR (infrared) type|mold oven, Preferably can evaporate a solvent at the temperature of 30-250 degreeC, and can be set as a liquid crystal aligning film. In the case of the liquid-crystal aligning agent using the specific solvent of this invention, a liquid crystal aligning film is producible also at the temperature of 200 degrees C or less. When the thickness of the liquid crystal aligning film after baking is too thick, it becomes disadvantageous from the point of power consumption of a liquid crystal display element, and since reliability of a liquid crystal display element may fall when too thin, Preferably it is 5-300 nm, More preferably is 10 to 150 nm. When a liquid crystal is horizontally orientated or diagonally aligned, the liquid crystal aligning film after baking is processed by rubbing, polarization|polarized-light ultraviolet irradiation, etc.

After the liquid crystal display element of this invention obtained the board|substrate with a liquid crystal aligning film from the liquid-crystal aligning agent of this invention by the said method, a liquid crystal cell was produced by a well-known method, and it was set as the liquid crystal display element.

As a manufacturing method of a liquid crystal cell, a pair of board|substrates with a liquid crystal aligning film are prepared, a spacer is spread|dispersed on the liquid crystal aligning film of one board|substrate, a liquid crystal aligning film surface is made inside, and the other board|substrate is bonded together, The method of injecting a liquid crystal under reduced pressure and sealing, or the method of bonding a board|substrate together and sealing after dripping a liquid crystal to the liquid crystal aligning film surface which disperse|distributed the spacer, etc. can be illustrated.

Moreover, the liquid-crystal aligning agent of this invention has a liquid-crystal layer between a pair of board|substrates with an electrode, and it contains a polymeric compound which superposes|polymerizes by at least one of an active energy ray and a heat|fever between a pair of board|substrates It is preferably used also for the liquid crystal display element manufactured through the process of superposing|polymerizing a polymeric compound by at least one of irradiation and heating of an active energy ray, arranging a liquid crystal composition and applying a voltage between electrodes. Here, as an active energy ray, an ultraviolet-ray is preferable. As an ultraviolet-ray, a wavelength is 300-400 nm, Preferably it is 310-360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120°C, preferably 60 to 80°C. Moreover, you may perform an ultraviolet-ray and a heating simultaneously.

Said liquid crystal display element controls the pretilt of a liquid crystal molecule by PSA(Polymer Sustained Alignment) system. In the PSA system, a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer, is mixed in a liquid crystal material, a liquid crystal cell is assembled, and then ultraviolet rays are applied to the photopolymerizable compound in a state where a predetermined voltage is applied to the liquid crystal layer. and the like, and the pretilt of the liquid crystal molecules is controlled by the resulting polymer. Since the alignment state of the liquid crystal molecules when the polymer is formed is memorized even after voltage is removed, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field or the like formed in the liquid crystal layer. Moreover, in the PSA system, since a rubbing process is not required, it is suitable for formation of the liquid-crystal layer of the vertically-aligned type in which it is difficult to control a pretilt by rubbing process.

That is, after the liquid crystal display element of this invention obtains the board|substrate with a liquid crystal aligning film from the liquid-crystal aligning agent of this invention by the said method, it produces a liquid crystal cell, and at least one of irradiation of an ultraviolet-ray, and a heating produces a polymeric compound. By superposing|polymerizing, it can be set as the thing to control the orientation of a liquid crystal molecule.

For an example of liquid crystal cell production of the PSA system, a pair of substrates with a liquid crystal aligning film are prepared, a spacer is dispersed on the liquid crystal aligning film of one substrate, the liquid crystal aligning film surface is inside, and the other substrate is After bonding, the method of injecting a liquid crystal under reduced pressure and sealing it, or the method of bonding a board|substrate together and sealing, after dripping a liquid crystal to the liquid crystal aligning film surface which disperse|distributed the spacer, etc. are mentioned.

A polymeric compound which superposes|polymerizes by heat|fever or ultraviolet irradiation is mixed with a liquid crystal. As a polymeric compound, the compound which has one or more polymerizable unsaturated groups, such as an acrylate group and a methacrylate group, in a molecule|numerator is mentioned. In that case, it is preferable that a polymeric compound is 0.01-10 mass parts with respect to 100 mass parts of a liquid crystal component, More preferably, it is 0.1-5 mass parts. When the amount of the polymerizable compound is less than 0.01 parts by mass, the polymerizable compound does not polymerize and the alignment control of the liquid crystal becomes impossible, and when it exceeds 10 parts by mass, the unreacted polymeric compound increases and the baking characteristics of the liquid crystal display element decrease. .

After producing a liquid crystal cell, a heat|fever or an ultraviolet-ray is irradiated and a polymeric compound is superposed|polymerized, applying the voltage of alternating current or direct current to a liquid crystal cell. Thereby, the orientation of liquid crystal molecules can be controlled.

In addition, the liquid-crystal aligning agent of this invention has a liquid-crystal layer between a pair of board|substrates provided with an electrode, and contains a polymeric group which superposes|polymerizes by at least one of an active energy ray and a heat|fever between the pair of board|substrates It is preferable to arrange|position a liquid crystal aligning film, and to use also for the liquid crystal display element manufactured through the process of applying a voltage between electrodes, ie, SC-PVA mode. Here, as an active energy ray, an ultraviolet-ray is preferable. As an ultraviolet-ray, a wavelength is 300-400 nm, Preferably it is 310-360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120°C, preferably 60 to 80°C. Moreover, you may perform an ultraviolet-ray and a heating simultaneously.

In order to obtain the liquid crystal aligning film containing the polymeric group which superposes|polymerizes from at least one of an active energy ray and a heat|fever, the method of adding the compound containing this polymeric group in a liquid-crystal aligning agent, the method of using the polymer component containing a polymeric group can be heard

To give an example of liquid crystal cell production in SC-PVA mode, prepare a pair of substrates on which the liquid crystal aligning film of the present invention is formed, and spread the spacers on the liquid crystal aligning film of one substrate, so that the liquid crystal aligning film surface is inside, The method of bonding the board|substrate of the other side, the method of inject|pouring and sealing a liquid crystal under reduced pressure, or the method of bonding and sealing a board|substrate, after dripping a liquid crystal to the liquid crystal aligning film surface which disperse|distributed the spacer, etc. are mentioned.

After producing a liquid crystal cell, the orientation of a liquid crystal molecule can be controlled by irradiating a heat|fever or an ultraviolet-ray, applying the voltage of alternating current or direct current to a liquid crystal cell.

As mentioned above, the liquid-crystal aligning agent of this invention becomes a liquid crystal aligning film excellent in coating-film property, Furthermore, even if baking at the time of producing a liquid crystal aligning film is low temperature, the liquid crystal aligning film excellent in VHR which is an electrical characteristic in a liquid crystal display element do. Therefore, the liquid crystal display element which has a liquid crystal aligning film obtained from the liquid-crystal aligning agent of this invention becomes a thing excellent in reliability, and it is a large screen, and it can use suitably for a high-definition liquid crystal television, a small and medium-sized car navigation system, a smart phone, etc.

Example

The present invention will be described in more detail below by way of Examples, but is not limited thereto.

"Abbreviations used in Synthesis Examples, Examples and Comparative Examples of the present invention"

The abbreviation used by the synthesis example, an Example, and a comparative example is as follows.

<Monomer for producing the polyimide-based polymer of the present invention>

(Specific side chain diamine compound of the present invention)

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

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

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

A4: The diamine compound (The specific side chain type diamine compound which has a specific side chain structure shown by Formula [1-1] of this invention) shown by a following formula [A4]

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)

[Formula 51]

[Formula 52]

[Formula 53]

(Diamine compound represented by Formula [2a] of this invention)

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

[Formula 54]

(Diamine compound represented by Formula [3a] of this invention)

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

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

[Formula 55]

(Other diamine compounds)

D1: p-phenylenediamine

D2: m-phenylenediamine

[Formula 56]

(Specific tetracarboxylic acid component)

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

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

E3: tetracarboxylic dianhydride represented by a following formula [E3]

E4: tetracarboxylic dianhydride represented by a following formula [E4]

E5: tetracarboxylic dianhydride represented by a following formula [E5]

[Formula 57]

<The crosslinkable compound used for this invention>

K1: A crosslinkable compound represented by the following formula [K1]

[Formula 58]

<Specific solvent of the present invention>

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

[Formula 59]

<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

"Measurement of the molecular weight of the polyimide-based polymer of the present invention”

The molecular weight of the polyimide precursor and the polyimide in the synthesis example was determined by a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko Co., Ltd.), a column (KD-803, KD-805) (Shodex Corporation). Manufacture) was used, and measurement was carried out as follows.

Column temperature: 50℃

Eluent: N,N-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr·H ₂ O) is 30 mmol/L (liter), phosphoric acid and anhydrous crystals (o-phosphoric acid) are 30 mmol/L, Tetrahydrofuran (THF) is 10 ml/L)

Flow rate: 1.0 ml/min

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

"Measurement of imidation rate of polyimide of the present invention"

The imidation ratio of the polyimide in a synthesis example was measured as follows. 20 mg of polyimide powder was placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, φ5 (manufactured by Kusano Scientific)), deuterated dimethyl sulfoxide (DMSO-d ₆ , 0.05 mass% TMS (tetramethylsilane)) mixture) (0.53 ml) was added, and ultrasonic wave was applied to dissolve completely. Proton NMR of 500 MHz was measured for this solution with the NMR measuring instrument (JNW-ECA500) (made by Nippon Electronics Datum). The imidation rate is determined by determining a proton derived from a structure that does not change before and after imidization as a reference proton, and the integrated peak of this proton and the proton peak derived from the NH group of the amic acid appearing in the vicinity of 9.5 ppm to 10.0 ppm. It calculated|required by the following formula using the value.

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

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

"Synthesis of polyimide-based polymer of the present invention"

<Synthesis Example 1>

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

<Synthesis Example 2>

E2 (3.40 g, 13.6 mmol), B1 (4.19 g, 27.6 mmol) and D1 (0.74 g, 6.89 mmol) were mixed in S1 (24.7 g) and reacted at 80° C. for 5 hours, followed by E1 ( 4.00 g, 20.4 mmol) and S1 (12.3 g) were added, and it was made to react at 40 degreeC for 6 hours, and the polyamic-acid solution (2) whose resin solid content concentration is 25 mass % was obtained. The number average molecular weight of this polyamic acid was 26,200, and the weight average molecular weight was 86,400.

<Synthesis Example 3>

After adding NMP to the polyamic acid solution (2) (30.0 g) obtained by the synthesis method of Synthesis Example 2 and diluting to 6 mass %, acetic anhydride (3.95 g) and pyridine (2.50 g) as an imidation catalyst were added It was added and it was made to react at 60 degreeC for 2 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder (3) was obtained. The imidation ratio of this polyimide was 53 %, the number average molecular weight was 22,100, and the weight average molecular weight was 60,900.

<Synthesis Example 4>

E2 (3.96 g, 15.8 mmol), B1 (4.14 g, 27.2 mmol), C1 (0.39 g, 1.60 mmol) and D2 (0.35 g, 3.20 mmol) were mixed in NEP (24.2 g), 80 After making it react at °C for 5 hours, E1 (3.10 g, 15.8 mmol) and NEP (12.1 g) were added, and it was made to react at 40 degreeC for 6 hours, and the polyamic-acid solution whose resin solid content concentration is 25 mass % was obtained.

After adding NEP to the obtained polyamic-acid solution (30.0g) and diluting to 6 mass %, acetic anhydride (4.40g) and pyridine (3.30g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3.5 hours. . This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (4). The imidation ratio of this polyimide was 80 %, the number average molecular weight was 19,900, and the weight average molecular weight was 55,100.

<Synthesis Example 5>

E2 (3.22 g, 12.9 mmol), A2 (4.62 g, 11.7 mmol), B1 (1.78 g, 11.7 mmol) and D1 (0.28 g, 2.60 mmol) are mixed in S1 (24.8 g), 80 After making it react at °C for 5 hours, E1 (2.52 g, 12.9 mmol) and S1 (12.4 g) are added, and it is made to react at 40 degreeC for 6 hours, and the polyamic acid solution (5) whose resin solid content concentration is 25 mass % got The number average molecular weight of this polyamic acid was 20,900, and the weight average molecular weight was 72,100.

<Synthesis Example 6>

After adding NMP to the polyamic acid solution (5) (30.0 g) obtained by the synthesis method of Synthesis Example 5 and diluting to 6 mass %, acetic anhydride (3.95 g) and pyridine (2.40 g) were added as an imidation catalyst. It was added and it was made to react at 70 degreeC for 3.5 hours. This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (6). The imidation ratio of this polyimide was 73 %, the number average molecular weight was 19,900, and the weight average molecular weight was 53,900.

<Synthesis Example 7>

E2 (1.31 g, 5.23 mmol), A3 (3.44 g, 7.94 mmol), C1 (2.57 g, 10.6 mmol) and D2 (0.86 g, 7.94 mmol) were mixed in NMP (24.5 g), 80 After making it react at °C for 5 hours, E1 (4.10 g, 20.9 mmol) and NMP (12.3 g) were added, and it was made to react at 40 degreeC for 6 hours, and the polyamic-acid solution whose resin solid content concentration is 25 mass % was obtained.

After adding NMP to the obtained polyamic-acid solution (30.0g) and diluting to 6 mass %, acetic anhydride (4.50g) and pyridine (3.30g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3.5 hours. . This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (7). The imidation ratio of this polyimide was 80 %, the number average molecular weight was 15,900, and the weight average molecular weight was 43,800.

<Synthesis Example 8>

E2 (1.23 g, 4.91 mmol), A2 (3.92 g, 9.94 mmol), C2 (2.58 g, 9.94 mmol) and D2 (0.54 g, 4.97 mmol) were mixed in NMP (24.2 g), 80 After making it react at °C for 5 hours, E1 (3.85 g, 19.6 mmol) and NMP (12.1 g) were added, and it was made to react at 40 degreeC for 6 hours, and the polyamic-acid solution whose resin solid content concentration is 25 mass % was obtained.

After adding NMP to the obtained polyamic-acid solution (30.0g) and diluting to 6 mass %, acetic anhydride (3.85g) and pyridine (2.50g) were added as an imidation catalyst, and it was made to react at 60 degreeC for 2 hours. . This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (8). The imidation ratio of this polyimide was 55 %, the number average molecular weight was 16,900, and the weight average molecular weight was 46,900.

<Synthesis Example 9>

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

After adding NEP to the obtained polyamic-acid solution (30.5g) and diluting to 6 mass %, acetic anhydride (3.95g) and pyridine (2.55g) were added as an imidation catalyst, and it was made to react at 60 degreeC for 3 hours. . This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (9). The imidation ratio of this polyimide was 61 %, the number average molecular weight was 16,000, and the weight average molecular weight was 44,800.

<Synthesis Example 10>

E2 (1.20 g, 4.78 mmol), A5 (3.65 g, 9.69 mmol), C2 (2.51 g, 9.69 mmol) and D2 (0.52 g, 4.84 mmol) were mixed in NMP (23.3 g), 80 After making it react at °C for 5 hours, E1 (3.75 g, 19.1 mmol) and NMP (11.6 g) were added, and it was made to react at 40 degreeC for 6 hours, and the polyamic-acid solution whose resin solid content concentration is 25 mass % was obtained.

After adding NMP to the obtained polyamic-acid solution (30.0g) and diluting to 6 mass %, acetic anhydride (3.80g) and pyridine (2.55g) were added as an imidation catalyst, and it was made to react at 60 degreeC for 2 hours. . This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (10). The imidation ratio of this polyimide was 56 %, the number average molecular weight was 16,200, and the weight average molecular weight was 48,100.

<Synthesis Example 11>

E3 (7.50 g, 33.5 mmol), B1 (3.61 g, 23.7 mmol), C1 (0.41 g, 1.69 mmol) and D1 (0.92 g, 8.47 mmol) were mixed in NMP (37.3 g), 40 It was made to react at °C for 8 hours, and the polyamic-acid solution whose resin solid content concentration is 25 mass % was obtained.

After adding NMP to the obtained polyamic-acid solution (30.0g) and diluting to 6 mass %, acetic anhydride (4.20g) and pyridine (3.10g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 2.5 hours. . This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (11). The imidation ratio of this polyimide was 75 %, the number average molecular weight was 19,800, and the weight average molecular weight was 53,900.

<Synthesis Example 12>

E3 (5.90 g, 26.3 mmol), A2 (4.21 g, 10.7 mmol), B1 (0.41 g, 2.67 mmol) and D2 (1.44 g, 13.3 mmol) were mixed in NMP (35.9 g), 40 It was made to react at °C for 8 hours, and the polyamic-acid solution whose resin solid content concentration is 25 mass % was obtained.

After adding NMP to the obtained polyamic-acid solution (30.0g) and diluting to 6 mass %, acetic anhydride (4.50g) and pyridine (3.35g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 3.5 hours. . This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder (12) was obtained. The imidation ratio of this polyimide was 81 %, the number average molecular weight was 18,200, and the weight average molecular weight was 51,600.

<Synthesis Example 13>

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

After adding NMP to the obtained polyamic-acid solution (30.5g) and diluting to 6 mass %, acetic anhydride (3.90g) and pyridine (2.60g) were added as an imidation catalyst, and it was made to react at 60 degreeC for 3.5 hours. . This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (13). The imidation ratio of this polyimide was 65 %, the number average molecular weight was 18,500, and the weight average molecular weight was 50,200.

<Synthesis Example 14>

E4 (5.21 g, 17.3 mmol), A1 (4.60 g, 12.1 mmol), B1 (0.67 g, 4.39 mmol) and D1 (0.59 g, 5.49 mmol) were mixed in NEP (23.8 g), 80 After making it react at °C for 6 hours, E1 (0.85 g, 4.33 mmol) and NEP (11.9 g) were added, and it was made to react at 40 degreeC for 6 hours, and the polyamic-acid solution whose resin solid content concentration is 25 mass % was obtained.

After adding NEP to the obtained polyamic-acid solution (30.0g) and diluting to 6 mass %, acetic anhydride (3.80g) and pyridine (2.50g) were added as an imidation catalyst, and it was made to react at 60 degreeC for 2 hours. . This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 degreeC, and the polyimide powder (14) was obtained. The imidation ratio of this polyimide was 55 %, the number average molecular weight was 16,800, and the weight average molecular weight was 45,300.

<Synthesis Example 15>

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

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

<Synthesis Example 16>

E5 (4.30 g, 20.3 mmol), A3 (3.89 g, 8.98 mmol), C2 (1.33 g, 5.13 mmol) and D2 (1.25 g, 11.6 mmol) were mixed in NMP (23.5 g), 80 After making it react at °C for 6 hours, E1 (0.99 g, 5.07 mmol) and NMP (11.8 g) were added, and it was made to react at 40 degreeC for 6 hours, and the polyamic-acid solution whose resin solid content concentration is 25 mass % was obtained.

After adding NMP to the obtained polyamic-acid solution (30.0g) and diluting to 6 mass %, acetic anhydride (3.85g) and pyridine (2.40g) were added as an imidation catalyst, and it was made to react at 60 degreeC for 2 hours. . This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (16). The imidation ratio of this polyimide was 51 %, the number average molecular weight was 15,700, and the weight average molecular weight was 44,500.

<Synthesis Example 17>

E5 (4.10 g, 19.3 mmol), B1 (4.47 g, 29.4 mmol) and D2 (0.35 g, 3.26 mmol) were mixed in NMP (24.3 g) and reacted at 80° C. for 6 hours, followed by E2 ( 3.22 g, 12.9 mmol) and NMP (12.1 g) were added, it was made to react at 80 degreeC for 6 hours, and the polyamic-acid solution whose resin solid content concentration is 25 mass % was obtained.

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

<Synthesis Example 18>

E5 (2.95 g, 13.9 mmol), A2 (3.71 g, 9.39 mmol), B1 (0.36 g, 2.35 mmol), C1 (1.14 g, 4.70 mmol), C2 (1.22 g, 4.70 mmol) and D1 (0.25 g, 2.35 mmol) was mixed in NEP (23.9 g) and reacted at 80° C. for 6 hours, after which E2 (2.32 g, 9.27 mmol) and NEP (11.9 g) were added, and at 80° C. It was made to react for 6 hours, and the polyamic-acid solution whose resin solid content concentration is 25 mass % was obtained.

After adding NMP to the obtained polyamic-acid solution (30.0g) and diluting to 6 mass %, acetic anhydride (4.20g) and pyridine (3.20g) were added as an imidation catalyst, and it was made to react at 80 degreeC for 2 hours. . This reaction solution was poured into methanol (460 ml), and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, and it dried under reduced pressure at 100 degreeC, and obtained polyimide powder (18). The imidation ratio of this polyimide was 68 %, the number average molecular weight was 15,500, and the weight average molecular weight was 45,100.

<Synthesis Example 19>

E2 (3.10 g, 12.4 mmol), B1 (3.82 g, 25.1 mmol) and D1 (0.68 g, 6.28 mmol) were mixed in NMP (22.5 g), and after reacting at 80 ° C. for 5 hours, E1 ( 3.65 g, 18.6 mmol) and NMP (11.3 g) were added, it was made to react at 40 degreeC for 6 hours, and the polyamic-acid solution (19) whose resin solid content concentration is 25 mass % was obtained. The number average molecular weight of this polyamic acid was 27,900, and the weight average molecular weight was 88,900.

<Synthesis Example 20>

E2 (3.13 g, 12.5 mmol), A2 (4.49 g, 11.4 mmol), B1 (1.73 g, 11.4 mmol) and D1 (0.27 g, 2.53 mmol) are mixed in NMP (24.2 g), 80 After making it react at °C for 5 hours, E1 (2.45 g, 12.5 mmol) and NMP (12.1 g) are added, and it is made to react at 40 degreeC for 6 hours, The polyamic acid solution (20) whose resin solid content concentration is 25 mass % got The number average molecular weight of this polyamic acid was 22,200, and the weight average molecular weight was 76,900.

The polyimide-based polymer of the present invention is shown in Tables 1 and 2.

"Production of the composition and liquid-crystal aligning agent of this invention"

In the following Examples 1 to 20 and Comparative Examples 1 to 4, preparation examples of the composition are described. Moreover, these compositions are used also for evaluation of a liquid-crystal aligning agent.

The composition and liquid-crystal aligning agent of this invention are shown to Table 3 - Table 5.

Using the composition and liquid-crystal aligning agent obtained by the Example and comparative example of this invention, "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a pinhole)", "evaluation of printability of a composition and a liquid-crystal aligning agent (coating film edge part) Evaluation)", "Evaluation of voltage retention (VHR) (normal cell)", "Evaluation of inkjet applicability of liquid crystal aligning agent", "Preparation of liquid crystal cell and evaluation of liquid crystal orientation (PSA cell)" and "production of liquid crystal cell" And evaluation of liquid-crystal orientation (SC-PVA cell)" was implemented.

"Evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a pinhole)"

Using the composition obtained by the method of the Example and comparative example of this invention, the pinhole of a polyimide film|membrane was evaluated. Specifically, these compositions were filtered under pressure with a membrane filter having a pore diameter of 1 µm, and printing was performed on an undefined Cr vapor deposition substrate (length 100 mm × width 100 mm, thickness 1.0 mm). A simple printing machine S15 type (manufactured by Nippon Photo Printing) was used as the printing machine, the printing area was in the range of 80 × 80 mm with respect to the center of the substrate, the printing pressure was 0.2 mm, and the yarn substrate was 5 sheets, from printing to temporary drying. time of 90 seconds, pre-drying was carried out on a hot plate at 70° C. for 5 minutes, and the main firing was carried out under the conditions of 160° C. for 15 minutes in a heat circulation type clean oven.

Then, the number of pinholes of the board|substrate on which the obtained polyimide film was formed was confirmed. Specifically, the substrate on which the polyimide film was formed was visually observed under a sodium lamp, and the number of pinholes on the polyimide film was counted. In addition, as the number of pinholes was small, there were few precipitates in a composition, and it was set as the thing excellent in this evaluation.

In Tables 6-8, the number of the pinholes obtained by the Example and the comparative example is shown.

Moreover, the composition obtained by the Example and comparative example of this invention can be used for a liquid-crystal aligning agent. Therefore, evaluation of the pinhole of the polyimide film of the composition obtained by the Example and the comparative example of this invention was made into evaluation of the pinhole of a liquid crystal aligning film.

"Evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of the coating-film edge part)"

Evaluation of the coating film edge part of a polyimide film using the board|substrate with a polyimide film obtained by said "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a pinhole)", that is, evaluation of the linearity of an edge part of a polyimide film (linearity) Evaluation of the mounting of the end of the polyimide film (also referred to as evaluation) and (also referred to as evaluation of mounting) were evaluated.

Evaluation of the linearity of the edge part of a polyimide membrane was performed by optical microscope observation of the polyimide membrane of a right edge part with respect to a printing direction. More specifically, the difference between (1) and (2) in FIG. 1 of the polyimide film image obtained by observing the magnification of an optical microscope at 25 times, ie, the length of A in FIG. 1, was measured. At that time, the images of all the polyimide films were obtained at the same magnification. It was set as the thing excellent in the linearity of the edge part of a polyimide film, so that the length of this A was short.

Evaluation of the mounting of the edge part of a polyimide film was performed by optical microscope observation of the polyimide film of a right edge part with respect to a printing direction. Specifically, the length of B in FIG. 2 of the polyimide film|membrane image obtained by the magnification of the optical microscope observing at 25 was measured. At that time, all the polyimide film images were obtained at the same magnification. It was set as the thing excellent in the mounting of the edge part of a polyimide film, so that the length of this B was short.

In Tables 6-8, the length of said A and the length of B obtained by an Example and a comparative example are shown.

Moreover, the composition obtained by the Example and comparative example of this invention can be used for a liquid-crystal aligning agent. Therefore, evaluation of the coating-film edge part of the polyimide film obtained by the present Example and the comparative example was also made into evaluation of the coating-film edge part of a liquid crystal aligning film.

"Evaluation of voltage retention (VHR) (normal cell)"

Voltage retention (VHR) was evaluated using the liquid-crystal aligning agent obtained by the Example and the comparative example of this invention. The board|substrate with the ITO electrode which filter-filtered these liquid-crystal aligning agents under pressure with the membrane filter with a pore diameter of 1 micrometer specifically specifically, wash|cleaned with pure water and IPA (isopropyl alcohol) (40 mm long x 30 mm, thickness 0.7mm) )), spin-coated on the ITO surface, and heat-treated on a hot plate at 80 ° C. for 3 minutes and at 160 ° C. for 15 minutes in a heat circulation type clean oven to obtain an ITO substrate with a liquid crystal aligning film having a film thickness of 100 nm. The coating film surface of this ITO substrate was rubbed with a rubbing device having a roll diameter of 120 mm, using a rayon cloth, under the conditions of roll rotation speed: 300 rpm, roll advancing speed: 20 mm/sec, and press-in amount: 0.4 mm. did.

Two ITO board|substrates with the obtained liquid crystal aligning film were prepared, the liquid crystal aligning film surface was turned inside, the 6 micrometers spacer was interposed, and it combined, and printed the ultraviolet curing sealing compound. Then, after bonding the other board|substrate and a liquid crystal aligning film surface to face each other, the process for hardening an ultraviolet curing sealing compound was performed, and the empty cell was obtained. Specifically, using a metal halide lamp with an illuminance of 60 mW, a wavelength of 310 nm or less is cut, and ultraviolet rays of 5 J/cm 2 in terms of 365 nm are irradiated, and then at 120° C. in a heat circulation type clean oven. It heat-processed for 60 minutes, and obtained the empty cell. A nematic liquid crystal was injected into this empty cell by the reduced pressure injection method, and the liquid crystal cell (normal cell) was obtained.

Moreover, the liquid-crystal orientation obtained by the method of the liquid-crystal aligning agent (2) - liquid-crystal aligning agent (4) obtained by the method of Examples 2 - 4, the liquid-crystal aligning agent (12) obtained by the method of Example 12, and Example 19 In the liquid crystal cell using the liquid-crystal aligning agent (21) obtained by the method of a processing agent (19), the method of the comparative example 1, and the liquid-crystal aligning agent (22) obtained by the method of the comparative example 2, it is MLC-2003 (Merck Japan make) for a liquid crystal. was used.

In addition, MLC-6608 (made by Merck Japan) was used for a liquid crystal for the liquid crystal cell using the liquid-crystal aligning agent obtained by the Example and the comparative example other than the above.

60 microseconds of 1V voltage was applied to the obtained liquid crystal cell under the temperature of 80 degreeC, the voltage 50 milliseconds later was measured, and how much the voltage was maintained was calculated as voltage retention (VHR). In addition, the measurement was performed using the voltage retention measuring apparatus (VHR-1) (made by Toyo Technica) by setting of Voltage:±1V, Pulse Width: 60 microseconds, and Flame Period: 50 milliseconds.

Moreover, the liquid crystal cell in which the measurement of VHR was completed was stored in the high temperature tank with a temperature of 80 degreeC for 720 hours, and VHR was measured (it is also mentioned after high temperature tank storage) on the conditions similar to the above again.

In addition to the value of VHR immediately after liquid crystal cell preparation, evaluation said that it was favorable, so that the fall of the value of VHR after storage in a high temperature tank was small with respect to the value of VHR immediately after liquid crystal cell preparation.

In Tables 9-11, the values of voltage retention (VHR) obtained in Examples and Comparative Examples are shown.

"Evaluation of the inkjet applicability|paintability of a liquid crystal aligning agent"

Inkjet coating using the liquid-crystal aligning agent (4) obtained by the method of Example 4 of this invention, the liquid-crystal aligning agent (7) obtained by the method of Example 7, and the liquid-crystal aligning agent (15) obtained by the method of Example 15 The sex was evaluated. ITO (indium oxide) which filtered these liquid-crystal aligning agents under pressure with the membrane filter of 1 micrometer of pore diameters specifically, wash|cleaned with pure water and IPA using HIS-200 (made by Hitachi Plant Technologies) for an inkjet applicator. Note) on the vapor deposition substrate, the application area is 70 × 70 mm, the nozzle pitch is 0.423 mm, the scan pitch is 0.5 mm, the application speed is 40 mm/sec, the time from application to temporary drying is 60 seconds, the preliminary drying is hot On the plate, the main firing was performed at 70°C for 5 minutes and at 160°C for 15 minutes in a heat circulation type clean oven.

As a result of visually observing the board|substrate with the obtained liquid crystal aligning film under a sodium lamp and counting the number of pinholes on a liquid crystal aligning film, the liquid crystal aligning film obtained in all the Examples had less than 5 pinholes. Moreover, in all the Examples, the liquid crystal aligning film excellent in coating-film uniformity was obtained.

Moreover, VHR (normal cell) was evaluated on the conditions of the said "evaluation (normal cell) of voltage retention (VHR)" using the obtained board|substrate with a liquid crystal aligning film.

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

A liquid-crystal cell using the liquid-crystal aligning agent (6) obtained by the method of Example 6 of this invention, the liquid-crystal aligning agent (9) obtained by the method of Example 9, and the liquid-crystal aligning agent (14) obtained by the method of Example 14 Preparation and evaluation of the liquid-crystal orientation (PSA cell) were performed. The substrate (length 40 mm x horizontal) in which the ITO electrode of 10 x 10 mm pattern spacing 20 micrometers was formed in the center which pressure-filtered these liquid-crystal aligning agents with the membrane filter of 1 micrometer of pore diameters specifically, and wash|cleaned with pure water and IPA. 30 mm, thickness 0.7 mm) and the ITO electrode of 10 × 40 mm in the center of the substrate (length 40 mm × width 30 mm, thickness 0.7 mm) spin-coated on the ITO surface, on a hot plate at 80 ° C. for 3 minutes, It heat-processed at 160 degreeC for 15 minute(s) by heat circulation type clean oven, and obtained the board|substrate with a liquid crystal aligning film with a film thickness of 100 nm.

The liquid crystal aligning film surface was turned inside, these board|substrates with a liquid crystal aligning film were combined, the 6 micrometers spacer was interposed, the periphery was adhere|attached with a sealing compound, and the empty cell was produced. Polymeric compound (1) represented by the following formula to nematic liquid crystal (MLC-6608) (made by Merck Japan) by a reduced pressure injection method into this empty cell, 100 of nematic liquid crystal (MLC-6608) The liquid crystal which mixed 0.3 mass % of polymeric compound (1) with respect to mass % was inject|poured, the injection port was sealed, and the liquid crystal cell was obtained.

[Formula 60]

A wavelength of 350 nm or less is cut using a metal halide lamp with an illuminance of 60 mW, applying the voltage of AC 5V to the obtained liquid crystal cell, 20 J/cm<2> ultraviolet irradiation is performed in conversion of 365 nm, and liquid crystal The liquid crystal cell (PSA cell) by which the orientation direction of was controlled was obtained. The temperature in the irradiation apparatus at the time of irradiating an ultraviolet-ray to a liquid crystal cell was 50 degreeC.

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

Compared with the liquid crystal cell before ultraviolet irradiation, the PSA cell obtained in a certain Example confirmed that the orientation direction of a liquid crystal was controlled by the point with which the response speed of the liquid crystal cell after ultraviolet irradiation became quick. Moreover, all the liquid crystal cells confirmed that the liquid crystal was orientating uniformly by observation with the polarizing microscope (ECLIPSE E600WPOL) (made by Nikon Corporation).

"Preparation of liquid crystal cell and evaluation of liquid crystal orientation (SC-PVA cell)"

A liquid-crystal cell using the liquid-crystal aligning agent (6) obtained by the method of Example 6 of this invention, the liquid-crystal aligning agent (9) obtained by the method of Example 9, and the liquid-crystal aligning agent (14) obtained by the method of Example 14 was performed and evaluation of the liquid-crystal orientation (SC-PVA cell) was performed. Specifically, 2 mass % of polymeric compound (1) shown above was added to these liquid-crystal aligning agents with respect to 100 mass % of all the polymer components in a liquid-crystal aligning agent, and it stirred at 25 degreeC for 4 hours. Then, the obtained liquid-crystal aligning agent was pressure-filtered with the membrane filter of 1 micrometer of pore diameters, and the board|substrate (40 mm in length x 30 in width) was formed in the center wash|cleaned with pure water and IPA with an ITO electrode of 10 x 10 mm and 20 micrometers of pattern intervals. mm, thickness 0.7 mm) and the ITO surface of a substrate (length 40 mm × width 30 mm, thickness 0.7 mm) formed with an ITO electrode of 10 × 40 mm in the center, spin-coated on a hot plate at 80° C. for 3 minutes, heat It heat-processed at 160 degreeC for 15 minute(s) by circulation type clean oven, and obtained the board|substrate with a liquid crystal aligning film with a film thickness of 100 nm.

The liquid crystal aligning film surface was turned inside, these board|substrates with a liquid crystal aligning film were combined, the 6 micrometers spacer was interposed, the periphery was adhere|attached with a sealing compound, and the empty cell was produced. The nematic liquid crystal (MLC-6608) (made by Merck Japan) was inject|poured into this empty cell by the reduced pressure injection method, the injection port was sealed, and the liquid crystal cell was obtained.

A wavelength of 350 nm or less is cut using a metal halide lamp with an illuminance of 60 mW, applying the voltage of AC 5V to the obtained liquid crystal cell, 20 J/cm<2> ultraviolet irradiation is performed in conversion of 365 nm, and liquid crystal The liquid crystal cell (SC-PVA cell) by which the orientation direction of was controlled was obtained. The temperature in the irradiation apparatus at the time of irradiating an ultraviolet-ray to a liquid crystal cell was 50 degreeC.

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

Compared with the liquid crystal cell before ultraviolet irradiation, the SC-PVA cell obtained in a certain Example confirmed that the orientation direction of a liquid crystal was controlled at the point with which the response speed of the liquid crystal cell after ultraviolet irradiation became quick. Moreover, all the liquid crystal cells confirmed that the liquid crystal was orientating uniformly by observation with the polarizing microscope (ECLIPSE E600WPOL) (made by Nikon Corporation).

<Example 1>

To the polyamic acid solution (1) (10.0 g) having a resin solid content concentration of 25 mass% obtained by the synthesis method of Synthesis Example 1, S1 (8.17 g), K1 (0.18 g), NEP (3.92 g) and PB (19.6 g) ) was added and stirred at 25°C for 8 hours to obtain a composition (1). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (1) was used for evaluation also as a liquid-crystal aligning agent (1).

Using the obtained composition (1) and the liquid-crystal aligning agent (1), "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a pinhole)", "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a coating-film edge part)" and "Evaluation of voltage retention (VHR) (normal cell)" were performed.

<Example 2>

S1 (16.8 g) and BCS (16.4 g) are added to the polyamic acid solution (2) (10.5 g) having a resin solid content concentration of 25 mass% obtained by the synthesis method of Synthesis Example 2, and stirred at 25°C for 4 hours , to obtain a composition (2). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (2) was used for evaluation also as a liquid-crystal aligning agent (2).

Using the obtained composition (2) and the liquid-crystal aligning agent (2), "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a pinhole)", "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a coating-film edge part)" and "Evaluation of voltage retention (VHR) (normal cell)" were performed.

<Example 3>

S1 (13.8g) was added to the polyimide powder (3) (1.60g) obtained by the synthesis method of the synthesis example 3, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. BCS (11.3 g) was added to this solution, and it stirred at 40 degreeC for 3 hours, and obtained the composition (3). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (3) was used for evaluation also as a liquid-crystal aligning agent (3).

Using the obtained composition (3) and the liquid-crystal aligning agent (3), "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a pinhole)", "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a coating-film edge part)" and "Evaluation of voltage retention (VHR) (normal cell)" were performed.

<Example 4>

S1 (14.1 g) and NEP (9.37 g) were added to the polyimide powder (4) (1.70 g) obtained by the synthesis method of the synthesis example 4, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. BCS (9.37 g) and PB (14.1 g) were added to this solution, and it stirred at 40 degreeC for 3 hours, and obtained the composition (4). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (4) was used for evaluation as a liquid-crystal aligning agent (4).

Using the obtained composition (4) and the liquid-crystal aligning agent (4), "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a pinhole)", "evaluation of voltage retention (VHR) (normal cell)" and "liquid crystal orientation Evaluation of the inkjet applicability|paintability of a processing agent" was implemented.

<Example 5>

S1 (14.0 g) and BCS (17.7 g) are added to a polyamic acid solution (5) (10.0 g) having a resin solid content concentration of 25 mass% obtained by the synthesis method of Synthesis Example 5, and stirred at 25°C for 4 hours , to obtain a composition (5). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (5) was used for evaluation also as a liquid-crystal aligning agent (5).

Using the obtained composition (5) and the liquid-crystal aligning agent (5), "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a pinhole)", "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a coating-film edge part)" and "Evaluation of voltage retention (VHR) (normal cell)" were performed.

<Example 6>

S1 (14.7g) was added to the polyimide powder (6) (1.70g) obtained by the synthesis method of the synthesis example 6, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. BCS (12.0g) was added to this solution, and it stirred at 40 degreeC for 3 hours, and obtained the composition (6). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (6) was used for evaluation also as a liquid-crystal aligning agent (6).

Using the obtained composition (6) and liquid-crystal aligning agent (6), "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a pinhole)", "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a coating-film edge part)" , "Evaluation of voltage retention (VHR) (normal cell)", "Preparation of liquid crystal cell and evaluation of liquid crystal orientation (PSA cell)" and "Preparation of liquid crystal cell and evaluation of liquid crystal orientation (SC-PVA cell)" were conducted did.

<Example 7>

S1 (9.10 g) and NEP (13.7 g) were added to the polyimide powder (6) (1.65 g) obtained by the synthesis method of the synthesis example 6, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. PB (22.8 g) was added to this solution, and it stirred at 40 degreeC for 3 hours, and obtained the composition (7). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (7) was used for evaluation as a liquid-crystal aligning agent (7).

Using the obtained composition (7) and liquid-crystal aligning agent (7), "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a pinhole)", "evaluation of voltage retention (VHR) (normal cell)" and "liquid crystal orientation Evaluation of the inkjet applicability|paintability of a processing agent" was implemented.

<Example 8>

S1 (6.27 g) and NEP (7.52 g) were added to the polyimide powder (7) (1.60 g) obtained by the synthesis method of the synthesis example 7, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. BCS (2.51 g) and PB (8.77 g) were added to this solution, and it stirred at 40 degreeC for 3 hours, and obtained the composition (8). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (8) was used for evaluation also as a liquid-crystal aligning agent (8).

Using the obtained composition (8) and liquid-crystal aligning agent (8), "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a pinhole)", "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a coating-film edge part)" and "Evaluation of voltage retention (VHR) (normal cell)" were performed.

<Example 9>

S1 (7.52g) and NMP (5.01g) were added to the polyimide powder (8) (1.60g) obtained by the synthesis method of the synthesis example 8, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. PB (10.0 g) and DME (2.51 g) were added to this solution, and it stirred at 40 degreeC for 5 hours, and obtained the composition (9). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (9) was used for evaluation also as a liquid-crystal aligning agent (9).

Using the obtained composition (9) and the liquid-crystal aligning agent (9), "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a pinhole)", "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of the coating-film edge part)" , "Evaluation of voltage retention (VHR) (normal cell)", "Preparation of a liquid crystal cell and evaluation of liquid crystal orientation (PSA cell)" and "Preparation of a liquid crystal cell and evaluation of liquid crystal orientation (SC-PVA cell)" were carried out did.

<Example 10>

S1 (10.3g) and NEP (7.76g) were added to the polyimide powder (9) (1.65g) obtained by the synthesis method of the synthesis example 9, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. PB (6.46 g) and EC (1.29 g) were added to this solution, and it stirred at 40 degreeC for 3 hours, and obtained the composition (10). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (10) was used for evaluation also as a liquid-crystal aligning agent (10).

Using the obtained composition (10) and the liquid-crystal aligning agent (10), "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a pinhole)", "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of the coating-film edge part)" and "Evaluation of voltage retention (VHR) (normal cell)" were performed.

<Example 11>

S1 (3.76 g) and NEP (10.0 g) were added to the polyimide powder (10) (1.60 g) obtained by the synthesis method of the synthesis example 10, and it stirred at 70 degreeC for 24 hours, and made it melt|dissolve. BCS (11.3 g) was added to this solution, and it stirred at 40 degreeC for 3 hours, and obtained the composition (11). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (11) was used for evaluation also as a liquid-crystal aligning agent (11).

Using the obtained composition (11) and the liquid-crystal aligning agent (11), "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a pinhole)", "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a coating-film edge part)" and "Evaluation of voltage retention (VHR) (normal cell)" were performed.

<Example 12>

S1 (5.33 g) and γ-BL (13.3 g) were added to polyimide powder (11) (1.70 g) obtained by the synthesis method of Synthesis Example 11, and stirred at 70°C for 24 hours to dissolve. BCS (7.99 g) was added to this solution, and it stirred at 40 degreeC for 3 hours, and obtained the composition (12). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (12) was used for evaluation also as a liquid-crystal aligning agent (12).

Using the obtained composition (12) and the liquid-crystal aligning agent (12), "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a pinhole)", "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a coating-film edge part)" and "Evaluation of voltage retention (VHR) (normal cell)" were performed.

<Example 13>

S1 (7.76 g) and NMP (5.17 g) were added to the polyimide powder (12) (1.65 g) obtained by the synthesis method of the synthesis example 12, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. BCS (5.17 g) and PB (7.76 g) were added to this solution, and it stirred at 40 degreeC for 3 hours, and obtained the composition (13). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (13) was used for evaluation also as a liquid-crystal aligning agent (13).

Using the obtained composition (13) and the liquid-crystal aligning agent (13), "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a pinhole)", "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a coating-film edge part)" and "Evaluation of voltage retention (VHR) (normal cell)" were performed.

<Example 14>

S1 (5.01 g) and NEP (7.52 g) were added to the polyimide powder (13) (1.60 g) obtained by the synthesis method of the synthesis example 13, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. PB (12.5 g) was added to this solution, and it stirred at 40 degreeC for 3 hours, and obtained the composition (14). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (14) was used for evaluation also as a liquid-crystal aligning agent (14).

Using the obtained composition (14) and the liquid-crystal aligning agent (14), "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a pinhole)", "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a coating-film edge part)" , "Evaluation of voltage retention (VHR) (normal cell)", "Preparation of liquid crystal cell and evaluation of liquid crystal orientation (PSA cell)" and "Preparation of liquid crystal cell and evaluation of liquid crystal orientation (SC-PVA cell)" were performed did.

<Example 15>

S1 (4.69 g) and γ-BL (18.8 g) were added to the polyimide powder (13) (1.70 g) obtained by the synthesis method of the synthesis example 13, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. BCS (9.37 g) and PB (14.1 g) were added to this solution, and it stirred at 40 degreeC for 3 hours, and obtained the composition (15). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (15) was used for evaluation as a liquid-crystal aligning agent (15).

Using the obtained composition (15) and the liquid-crystal aligning agent (15), "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a pinhole)", "evaluation of voltage retention (VHR) (normal cell)" and "liquid crystal orientation Evaluation of the inkjet applicability|paintability of a processing agent" was implemented.

<Example 16>

S1 (12.5 g) and NEP (2.51 g) were added to the polyimide powder (14) (1.60 g) obtained by the synthesis method of the synthesis example 14, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. To this solution, K1 (0.08 g) and BCS (10.0 g) were added, followed by stirring at 40°C for 5 hours to obtain a composition (16). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (16) was used for evaluation also as a liquid-crystal aligning agent (16).

Using the obtained composition (16) and the liquid-crystal aligning agent (16), "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a pinhole)", "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of the coating-film edge part)" and "Evaluation of voltage retention (VHR) (normal cell)" were performed.

<Example 17>

S1 (15.0 g) and γ-BL (2.51 g) were added to the polyimide powder (15) (1.60 g) obtained by the synthesis method of the synthesis example 15, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. To this solution, K1 (0.08 g), BCS (2.51 g) and PB (5.01 g) were added, followed by stirring at 40°C for 5 hours to obtain a composition (17). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (17) was used for evaluation also as a liquid-crystal aligning agent (17).

Using the obtained composition (17) and the liquid-crystal aligning agent (17), "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a pinhole)", "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a coating-film edge part)" and "Evaluation of voltage retention (VHR) (normal cell)" were performed.

<Example 18>

S1 (2.66 g) and NEP (10.7 g) were added to the polyimide powder (16) (1.70 g) obtained by the synthesis method of the synthesis example 16, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. BCS (5.33 g) and PB (7.99 g) were added to this solution, and it stirred at 40 degreeC for 3 hours, and obtained the composition (18). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (18) was used for evaluation also as a liquid-crystal aligning agent (18).

Using the obtained composition (18) and the liquid-crystal aligning agent (18), "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a pinhole)", "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a coating-film edge part)" and "Evaluation of voltage retention (VHR) (normal cell)" were performed.

<Example 19>

S1 (8.77 g) and NMP (5.01 g) were added to the polyimide powder (17) (1.60 g) obtained by the synthesis method of the synthesis example 17, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. BCS (8.77 g) and EC (2.51 g) were added to this solution, and it stirred at 40 degreeC for 3 hours, and obtained the composition (19). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (19) was used for evaluation also as a liquid-crystal aligning agent (19).

Using the obtained composition (19) and the liquid-crystal aligning agent (19), "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a pinhole)", "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a coating-film edge part)" and "Evaluation of voltage retention (VHR) (normal cell)" were performed.

<Example 20>

S1 (10.0 g) and NEP (3.76 g) were added to the polyimide powder (18) (1.60 g) obtained by the synthesis method of the synthesis example 18, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. BCS (3.76g) and PB (7.52g) were added to this solution, and it stirred at 40 degreeC for 3 hours, and obtained the composition (20). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (20) was used for evaluation also as a liquid-crystal aligning agent (20).

Using the obtained composition (20) and the liquid-crystal aligning agent (20), "Evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a pinhole)", "Evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a coating-film edge part)" and "Evaluation of voltage retention (VHR) (normal cell)" were performed.

<Comparative Example 1>

NMP (16.0 g) and BCS (15.7 g) are added to the polyamic acid solution (19) (10.0 g) having a resin solid content concentration of 25 mass% obtained by the synthesis method of Synthesis Example 19, and stirred at 25°C for 4 hours, , to obtain a composition (21). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (21) was used for evaluation also as a liquid-crystal aligning agent (21).

Using the obtained composition (21) and the liquid-crystal aligning agent (21), "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a pinhole)", "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a coating-film edge part)" and "Evaluation of voltage retention (VHR) (normal cell)" were performed.

<Comparative Example 2>

NMP (14.7g) was added to the polyimide powder (3) (1.70g) obtained by the synthesis method of the synthesis example 3, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. BCS (12.0g) was added to this solution, and it stirred at 40 degreeC for 3 hours, and obtained the composition (22). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (22) was used for evaluation also as a liquid-crystal aligning agent (22).

Using the obtained composition (22) and the liquid-crystal aligning agent (22), "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a pinhole)", "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a coating-film edge part)" and "Evaluation of voltage retention (VHR) (normal cell)" were performed.

<Comparative Example 3>

NMP (14.7 g) and BCS (18.5 g) are added to a polyamic acid solution (20) (10.5 g) having a resin solid content concentration of 25 mass% obtained by the synthesis method of Synthesis Example 20, and stirred at 25°C for 4 hours , to obtain a composition (23). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (23) was used for evaluation also as a liquid-crystal aligning agent (23).

Using the obtained composition (23) and the liquid-crystal aligning agent (23), "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a pinhole)", "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a coating-film edge part)" and "Evaluation of voltage retention (VHR) (normal cell)" were performed.

<Comparative Example 4>

NMP (14.2g) was added to the polyimide powder (6) (1.65g) obtained by the synthesis method of the synthesis example 6, and it stirred at 70 degreeC for 24 hours, and was made to melt|dissolve. BCS (11.6g) was added to this solution, and it stirred at 40 degreeC for 3 hours, and obtained the composition (24). Abnormalities, such as turbidity and generation|occurrence|production of a precipitate, were not seen in this composition, and it was confirmed that it is a uniform solution. In addition, this composition (24) was used for evaluation also as a liquid-crystal aligning agent (24).

Using the obtained composition (24) and the liquid-crystal aligning agent (24), "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a pinhole)", "evaluation of the printability of a composition and a liquid-crystal aligning agent (evaluation of a coating-film edge part)" and "Evaluation of voltage retention (VHR) (normal cell)" were performed.

*1: The introduction amount (part by mass) of the specific solvent with respect to 100 parts by mass of all solvents is shown.

*2: The introduction amount (part by mass) of other solvents with respect to 100 parts by mass of all solvents is shown.

*3: The ratio (mass %) for all the polymers in a composition and a liquid-crystal aligning agent is shown.

*1: The introduction amount (part by mass) of the specific solvent with respect to 100 parts by mass of all solvents is shown.

*2: The introduction amount (part by mass) of other solvents with respect to 100 parts by mass of all solvents is shown.

*3: The ratio (mass %) for all the polymers in a composition and a liquid-crystal aligning agent is shown.

*1: The introduction amount (part by mass) of the specific solvent with respect to 100 parts by mass of all solvents is shown.

*2: The introduction amount (part by mass) of other solvents with respect to 100 parts by mass of all solvents is shown.

*3: The ratio (mass %) for all the polymers in a composition and a liquid-crystal aligning agent is shown.

As can be seen from the above results, the polyimide film obtained from the composition of the Example of the present invention exhibits a uniform coating property in which pinholes do not occur, compared to the polyimide film obtained from the composition of the comparative example, and the polyimide film The linearity of the end of the film was high, and the mounting of the end was small. Specifically, a composition using a specific solvent as component (A) of the present invention is compared with a composition not using it, that is, a comparison between Example 2 and Comparative Example 1, a comparison between Example 3 and Comparative Example 2, It is a comparison of Example 5 and Comparative Example 3 and a comparison of Example 6 and Comparative Example 4. In these comparative examples, compared with the corresponding Example, the number of pinholes on the polyimide film was large, and the coating-film property of the coating-film edge part of a polyimide film|membrane also brought the result bad. In addition, since the composition of these Examples was used for evaluation also as a liquid-crystal aligning agent, the result of the Example using these compositions was made into the result of a liquid-crystal aligning agent.

Moreover, compared with the liquid crystal aligning film obtained from the liquid-crystal aligning agent of a comparative example, the liquid crystal aligning film obtained from the liquid-crystal aligning agent using the composition of this invention is low temperature even if baking at the time of producing a liquid crystal aligning film is low temperature, the voltage retention (VHR) in a liquid crystal display element. Also called), this excellent result was obtained. Comparison of the liquid-crystal aligning agent using the specific solvent which is the (A) component of this invention, and the liquid-crystal aligning agent which does not use it specifically, ie, comparison of Example 2 and Comparative Example 1, Example 3 and comparative example It is a comparison of 2, a comparison of Example 5 and Comparative Example 3, and a comparison of Example 6 and Comparative Example 4. In these comparative examples, the value of VHR was low compared with the corresponding Example. In particular, not only the value immediately after liquid crystal cell preparation, but also the value after high temperature tank storage was low, ie, the fall of VHR accompanying high temperature was a large result.

Industrial applicability

When the composition of this invention forms a polyimide film, generation|occurrence|production of the pinhole accompanying repelling can be suppressed, and the polyimide film excellent also in the coating-film property of the edge part can be obtained. In that case, a polyimide film|membrane can be produced also by baking at low temperature.

Moreover, when the composition of this invention is used for a liquid-crystal aligning agent, generation|occurrence|production of the pinhole accompanying repelling can be suppressed and the liquid crystal aligning film excellent also in the coating-film property of the edge part can be obtained. Furthermore, even if baking at the time of producing a liquid crystal aligning film is low temperature, it turns into the liquid crystal aligning film excellent in the electrical characteristic in a liquid crystal display element, especially voltage retention (it is also mentioned VHR). Therefore, the liquid crystal display element which has a liquid crystal aligning film obtained from the liquid-crystal aligning agent of this invention becomes a thing excellent in reliability, and it can use suitably for a large-screen, high-definition liquid crystal television, a small and medium-sized car navigation system, a smart phone, etc., TN element , STN element, TFT liquid crystal element, especially, it is useful for vertical alignment type liquid crystal display elements, such as VA mode, PSA mode, and SC-PVA mode.

Claims (26)

(A) Component: the following formula [A]:
[Formula 1]

a solvent represented by (wherein, 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) component: at least 1 sort(s) of polymer chosen from a polyimide precursor and a polyimide; and
(C) A composition comprising as a component at least one solvent selected from N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, wherein the component (A) is a solvent contained in the composition It is 5-70 mass % of the whole, provided that the said (A) component is 60 mol% or more of the whole solvent contained in a composition, The composition except the case. The method of claim 1,
The solvent of the component (A) is the following formula [A-1]:
[Formula 2]

A composition that is a solvent represented by . The method of claim 1,
The component (B) has the following formulas [1-1] and [1-2]:
[Formula 3]

(Wherein, Y ¹ is a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- and -OCO- represent at least one bonding group selected from, Y ² is a single bond or -(CH ₂ ) _b - (b is 1 to 15 is an integer of), and Y ³ is a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- and -OCO- represents at least one bonding group, Y ⁴ is a divalent cyclic group of at least one ring selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a C17-C51 divalent organic group having a steroid skeleton; , any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom; Y ⁵ represents a divalent cyclic group of at least one ring selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and arbitrary hydrogen atoms on these cyclic groups are an alkyl group having 1 to 3 carbon atoms, or an alkoxyl group having 1 to 3 carbon atoms. , a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom may be substituted, n represents an integer of 0 to 4, Y ⁶ is an alkyl group having 1 to 22 carbon atoms, 2 to carbon atoms at least one selected from a 22 alkenyl group, a C1-C22 fluorine-containing alkyl group, a C1-C22 alkoxyl group, and a C1-C22 fluorine-containing alkoxyl group);
[Formula 4]

(Wherein, Y ⁷ is a single bond, -O-, -CH ₂ O-, -CONH-, -NHCO-, -CON(CH ₃ )-, -N(CH ₃ )CO-, -COO- and - represents at least one bonding group selected from OCO-, and 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 which is at least 1 type of polymer chosen from the polyimide precursor and polyimide which used for a part the diamine compound which has at least 1 type of structure selected from the structure represented by. The method of claim 3,
The diamine compound which has a structure shown by said Formula [1-1] and Formula [1-2] is following Formula [1a]:
[Formula 5]

(In formula, Y represents the at least 1 sort(s) of structure chosen from the structure shown by said Formula [1-1] and Formula [1-2], and m represents the integer of 1-4).
A composition which is a diamine compound represented by The method of claim 1,
At least one selected from polyimide precursors and polyimides in which the polymer of component (B) uses a diamine compound having at least one substituent selected from a carboxyl group (COOH group) and a hydroxyl group (OH group) as a part of the raw material A composition that is a polymer of a species. The method of claim 5,
The diamine compound having a carboxyl group and a hydroxyl group has the following formula [2a]:
[Formula 6]

{wherein, A is the following formulas [2-1] and [2-2]:
[Formula 7]

(in formula [2-1], a represents the integer of 0-4, and in formula [2-2], b represents the integer of 0-4) represents the substituent of the at least 1 structure selected from, and m represents an integer of 1 to 4}
A composition which is a diamine compound represented by The method of claim 1,
The polymer of the component (B) has the following formula [3a]:
[Formula 8]

(Wherein, B ¹ is -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON(CH ₃ )- and - Represents at least one bonding group selected from N(CH ₃ ^{)CO—, B 2} is a single bond, a divalent group of an aliphatic hydrocarbon having 1 to 20 carbon atoms, a divalent group of a non-aromatic cyclic hydrocarbon, and 2 of an aromatic hydrocarbon represents at least one selected from a valent group, and B ³ is 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 of 1 to 5) represents at least one bonding group selected from, and B ⁴ is nitrogen-containing It represents a heterocyclic group, and n represents the integer of 1-4)
The composition which is at least 1 sort(s) of polymer chosen from the polyimide precursor and polyimide which used the diamine compound represented by a part of a raw material. The method of claim 7,
^{B 1} in the formula [3a] represents -CONH-, B ² represents an alkylene group having 1 to 5 carbon atoms, B ³ represents a single bond, B ⁴ represents an imidazolyl group or a pyridyl group, n The composition which is a diamine compound which represents this 1. The method of claim 1,
The polymer of the component (B) has the following formula [4]:
[Formula 9]

{wherein, Z is the following formula [4a] to formula [4k]:
[Formula 10]

(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 the formula [4g], Z ⁵ and Z ⁶ are each independently a hydrogen atom or represents a methyl group)
represents a group having at least one structure selected from }
The composition which is at least 1 sort(s) of polymer selected from the polyimide precursor and polyimide which used the tetracarboxylic-acid component represented by for a part of a raw material. The method of claim 1,
The composition in which the polymer of the said (B) component is at least 1 sort(s) of polymer chosen from polyamic-acid alkylester and a polyimide. The method of claim 1,
(D) As the component, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether and the following formulas [D-1] - Formula [D-3]:
[Formula 11]

(In the formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms, in the formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms, and in the formula [D-3], D ³ represents a C1-C4 alkyl group)
A composition containing at least one solvent selected from the solvents represented by The method of claim 1,
In the composition, a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group, and polymerization A composition comprising at least one crosslinkable compound selected from crosslinkable compounds having a sexually unsaturated bond. The method of claim 1,
The composition in which the said (C) component is 10-80 mass % of the whole solvent contained in a composition. The method of claim 11,
The composition in which the said (D) component is 1-50 mass % of the whole solvent contained in a composition. The method of claim 1,
The composition in which the said (B) component is 0.1 mass % - 30 mass % in a composition. The polyimide film obtained from the composition in any one of Claims 1-15. The liquid-crystal aligning agent obtained from the composition in any one of Claims 1-15. The liquid crystal aligning film obtained using the liquid-crystal aligning agent of Claim 17. The liquid crystal aligning film obtained by the inkjet method using the liquid-crystal aligning agent of Claim 17. The liquid crystal display element which has the liquid crystal aligning film of Claim 18. The method of claim 18,
A liquid crystal composition having a liquid crystal layer between a pair of substrates provided with electrodes and comprising a polymerizable compound that polymerizes by at least one of an active energy ray and heat is disposed between the pair of substrates, between the electrodes A liquid crystal aligning film, characterized in that it is used in a liquid crystal display device manufactured through a process of polymerizing the polymerizable compound while applying a voltage to the . It has the liquid crystal aligning film of Claim 21, The liquid crystal display element characterized by the above-mentioned. The method of claim 18,
A liquid crystal aligning film having a liquid crystal layer between a pair of substrates provided with an electrode and comprising a polymerizable group that polymerizes by at least one of an active energy ray and heat is disposed between the pair of substrates, between the electrodes A liquid crystal aligning film used in a liquid crystal display device manufactured through a process of polymerizing the polymerizable group while applying a voltage. It has the liquid crystal aligning film of Claim 23, The liquid crystal display element characterized by the above-mentioned. delete delete

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