CN114790287A

CN114790287A - Polyamic acid, and thermosetting composition, cured film and liquid crystal display element using same

Info

Publication number: CN114790287A
Application number: CN202111147026.5A
Authority: CN
Inventors: 安井平; 藤马佐知子; 渡边尚树
Original assignee: JNC Corp
Current assignee: JNC Corp
Priority date: 2021-01-25
Filing date: 2021-09-28
Publication date: 2022-07-26
Also published as: JP2022113632A

Abstract

The invention provides a polyamic acid soluble in a mild solvent, and a thermosetting composition, a cured film and a liquid crystal display element using the same. Also provided is a thermosetting composition using the polyamic acid of the present invention, which has alignment ability for liquid crystal and polymerizable liquid crystal, and planarization ability for a substrate. Further, a cured film comprising the thermosetting composition of the present invention and having a high transmittance and a high voltage holding ratio is provided. An electronic component such as a liquid crystal display element or a solid-state imaging element having the cured film is provided. The polyamic acid is obtained by reacting raw materials including an aliphatic tetracarboxylic dianhydride having a specific structure and an aliphatic diamine having a specific structure. And a thermosetting composition using the polyamic acid.

Description

Polyamic acid, and thermosetting composition, cured film and liquid crystal display element using same

Technical Field

The present invention relates to a polyamic acid soluble in a mild solvent, a thermosetting composition containing the polyamic acid, which suppresses the corrosiveness to a color filter, a cured film having both alignment capability and planarization capability, which contains the thermosetting composition, and an electronic component such as a liquid crystal display element or a solid-state imaging element having the cured film.

Background

A liquid crystal display device is provided with a retardation film for the purpose of widening a viewing angle, adjusting a color tone of an image, and the like. As such a retardation film, an extended polymer film or a coating-type cured film containing a polymerizable liquid crystal composition can be used. The coating type cured film containing the polymerizable liquid crystal composition can realize thinning of a liquid crystal display device and improvement of display quality by making the retardation film thinner and improving durability as compared with conventional polymer films.

A retardation film using a polymerizable liquid crystal is formed by applying a polymerizable liquid crystal composition solution onto a substrate having an alignment film subjected to an alignment treatment, aligning the polymerizable liquid crystal composition, and then polymerizing the polymerizable liquid crystal composition (patent document 1). As a method of alignment treatment, a rubbing method, a photo-alignment method, and the like are known. As the alignment film for polymerizable liquid crystal (polymerizable liquid crystal alignment film), an alignment film for driving liquid crystal (liquid crystal alignment film) can be used. Hereinafter, in the present specification, the liquid crystal alignment film and the polymerizable liquid crystal alignment film are collectively referred to as an alignment film.

Many of the compositions for liquid crystal alignment films include polyimide or polyamic acid as a precursor thereof. Polyimide or its precursor polyamic acid is insufficient in solubility in an organic solvent. Therefore, N-methyl-2-pyrrolidone (hereinafter referred to as "NMP") having high polarity is used as a solvent of the composition for a liquid crystal alignment film.

On the other hand, as one of colorization methods of a liquid crystal display element, a color filter substrate is used. In recent years, in order to cope with the widening of color gamut of color display, micronized pigments or dyes have been used. These fine pigments or dyes are easily eluted into a highly polar cyclic amide compound such as NMP, and therefore have low resistance to a solvent in a composition for a liquid crystal alignment film. The color filter corroded by the solvent is changed in color or discolored, and the performance of the color filter is deteriorated, and as a result, the display quality of the liquid crystal display element is deteriorated.

In addition, a color filter including pixels of R (red), G (green), B (blue), and the like used in a liquid crystal display element has a coating film with a different thickness for each of the RGB colors, and exhibits a level difference on the surface. If the surface level difference is large, the display quality of the liquid crystal display element is degraded. Accordingly, a transparent protective film (hereinafter referred to as an "overcoat film") is provided to suppress solvent attack on the color filter and to planarize the surface level difference.

As liquid crystal display devices have become widespread, reduction in manufacturing cost, such as reduction in manufacturing processes, is required, and development of materials having a plurality of functions in one coating layer is required. In the case where the double-layer structure of the alignment film and the overcoat film is a single-layer film, the single-layer film needs to have both functions of the alignment film and the overcoat film, i.e., an alignment ability and a planarization ability. In addition, since a solution of the composition is directly applied to the color filter when the single layer film is formed, a composition in which the content of a solvent having high corrosiveness to the color filter as a base is controlled or the solvent is not contained is required.

On the other hand, there are few reports on a composition having both orientation ability and planarization ability. Although a thermosetting composition containing an aromatic polyamic acid has been reported (patent document 2), a cured film obtained from the composition has room for improvement in flatness and voltage holding ratio.

[ Prior art documents ]

[ patent document ]

[ patent document 1] Japanese patent laid-open No. 2007-148098

[ patent document 2] specification of Chinese patent application publication No. 112194793

Disclosure of Invention

[ problems to be solved by the invention ]

A polyamic acid soluble in a mild solvent is provided. Also provided is a thermosetting composition using the polyamic acid of the present invention, which has alignment ability for liquid crystal and polymerizable liquid crystal, and planarization ability for a substrate. Further, a cured film comprising the thermosetting composition of the present invention and having a high transmittance and a high voltage holding ratio is provided. An electronic component such as a liquid crystal display element or a solid-state imaging element having the cured film is provided.

[ means for solving the problems ]

As a result of diligent research directed toward solving the above problems, the present inventors have found that a polyamic acid soluble in a mild solvent can be obtained by reacting a raw material containing an aliphatic tetracarboxylic dianhydride having a specific structure and an aliphatic diamine having a specific structure. By using the polyamic acid of the present invention, the amount of the solvent used in the thermosetting composition, which is highly aggressive to the underlying color filter, can be suppressed, and the solvent can be completely eliminated. Further, the present inventors have found that a cured film having both functions of an alignment film and an overcoat film and having a satisfactory high transmittance and a high voltage holding ratio can be obtained by using the thermosetting composition of the present invention, and have completed the present invention. In the present specification, the mild solvent refers to a solvent composition in which the content of a cyclic amide compound such as NMP, which is highly aggressive to a color filter as a base, is 5 wt% or less in all solvents, and includes a case of a single solvent which is low in aggressive to a color filter.

The present invention includes the following configurations.

[1] A polyamic acid (A) obtained by reacting a raw material comprising a tetracarboxylic dianhydride and a diamine, and

the tetracarboxylic dianhydride contains 90 mol% or more of an aliphatic tetracarboxylic dianhydride represented by the formula (1), and contains 90 mol% or more of at least one aliphatic diamine selected from the group consisting of 1, 3-bisaminomethylcyclohexane and bis (aminomethyl) norbornane.

In the formula (1), R ¹ 、R ² 、R ³ And R ⁴ Are each independently H, CH ₃ Or F.

[2] The polyamic acid (A) according to item 1, wherein the raw material further comprises an end capping agent.

[3] A thermosetting composition comprising the polyamic acid (A) according to item 1 or item 2 and a solvent (B2).

[4] The thermosetting composition according to item 3, further comprising a curing agent (C).

[5] The thermosetting composition according to item 3 or item 4, further comprising at least one additive (D) selected from the group consisting of a compound having a polymerizable double bond, a surfactant, an adhesion improver and an antioxidant.

[6] A cured film obtained by curing the thermosetting composition according to any one of items 3 to 5.

[7] A liquid crystal display element having the cured film according to item 6 as at least one of a liquid crystal alignment film, a polymerizable liquid crystal alignment film, and a transparent protective film.

[ Effect of the invention ]

The polyamic acid of the present invention has a specific structure and is soluble in a mild solvent. The thermosetting composition of the present invention contains the specific polyamic acid, and therefore does not contain NMP in a solvent or contains a very small amount of NMP, and therefore can suppress the corrosion to a substrate during film formation. In addition, the obtained cured film can have high transmittance and high voltage holding ratio. Further, the cured film containing the composition has an ability to align a liquid crystal and a polymerizable liquid crystal, or has an ability to planarize a substrate, and thus can be used as both an alignment film and an overcoat film.

Detailed Description

1. Polyamic acid (A) of the present invention

The polyamic acid (a) of the present invention is a polymer obtained by reacting a raw material containing a tetracarboxylic dianhydride and a diamine.

1-1 tetracarboxylic acid dianhydride

In the present invention, as a raw material for obtaining the polyamic acid (a), tetracarboxylic dianhydride is used. Examples of the tetracarboxylic acid dianhydride include aliphatic tetracarboxylic acid dianhydride and aromatic tetracarboxylic acid dianhydride. In the polyamic acid (a) of the present invention, the content of the aliphatic tetracarboxylic dianhydride represented by the formula (1) in the raw tetracarboxylic dianhydride is 90 mol% or more from the viewpoint of imparting good solubility.

The content of the compound represented by formula (1) is more preferably 95 mol% or more in the raw material tetracarboxylic dianhydride.

Among the aliphatic tetracarboxylic dianhydrides represented by the formula (1), R is preferably used from the viewpoint of low cost ¹ ～R ⁴ 1,2, 3, 4-butanetetracarboxylic dianhydride which is hydrogen.

Any tetracarboxylic dianhydride can be used in combination within a range in which the effect of the polyamic acid (a) can be maintained. The tetracarboxylic dianhydride used in combination may be any of aliphatic tetracarboxylic dianhydrides and aromatic tetracarboxylic dianhydrides. From the viewpoint of voltage holding ratio, it is preferable to use an aliphatic tetracarboxylic dianhydride in combination. From the viewpoint of heat resistance and high refractive index, it is preferable to use an aromatic tetracarboxylic dianhydride in combination.

Specific examples of the aliphatic tetracarboxylic acid dianhydride which can be used in combination include: cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride and ethanetetracarboxylic dianhydride.

Specific examples of the aromatic tetracarboxylic dianhydrides to be used in combination include: 3, 3 ', 4, 4' -diphenyl ether tetracarboxylic dianhydride, 4, 4 '-sulfonyl diphthalic anhydride, 3', 4, 4 '-biphenyltetracarboxylic dianhydride, 3', 4, 4 '-benzophenonetetracarboxylic dianhydride, pyromellitic anhydride, 1, 4-bis (3, 4-dicarboxyphenoxy) benzoic dianhydride, p-phenylenebis (trimellitic anhydride) and 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride.

1-2-diamines

In the present invention, as a raw material for obtaining polyamic acid (a), diamine is used. The diamine includes an aliphatic diamine and an aromatic diamine. In the polyamic acid (a) of the present invention, the content of the aliphatic diamine, which is at least one selected from the group consisting of 1, 3-bisaminomethylcyclohexane and bis (aminomethyl) norbornane, in the raw material diamine is 90 mol% or more from the viewpoint of imparting good solubility.

The content of the aliphatic diamine which is at least one selected from the group consisting of 1, 3-bisaminomethylcyclohexane and bis (aminomethyl) norbornane is more preferably 95 mol% or more in the raw diamine.

Bis (aminomethyl) norbornane is an isomeric mixture of 2, 5-bis (aminomethyl) norbornane and 2, 6-bis (aminomethyl) norbornane.

Any diamine can be used in combination as long as the effect of the polyamic acid (A) can be maintained. The diamine used in combination may be any of an aliphatic diamine and an aromatic diamine. From the viewpoint of voltage holding ratio, it is preferable to use an aliphatic diamine in combination. From the viewpoint of heat resistance and high refractive index, it is preferable to use an aromatic diamine in combination.

Examples of aliphatic diamines which can be used in combination include: 1, 2-bisaminomethylcyclohexane, 1, 4-bisaminomethylcyclohexane, 1-amino-3-aminomethyl-3, 5, 5-trimethylcyclohexane and 1, 3-bis (3-aminopropyl) -1, 1,3, 3-tetramethylbicyclohexane.

Examples of aromatic diamines which may be used in combination include: 4, 4 '-diaminodiphenyl sulfone, 1, 3-diaminobenzene, 2, 4-diaminotoluene, 4' -diaminodiphenylmethane, 4 '-diaminodiphenyl ether, 3' -dimethyl-4, 4 '-diaminobiphenyl, 2' -bis (trifluoromethyl) -4, 4 '-diaminobiphenyl, 3, 7-diamino-dimethyldibenzothiophene-5, 5' -dioxide, 4 '-diaminobenzophenone, 3' -diaminobenzophenone, 4 '-bis (4-aminophenyl) sulfide, 9-bis (4-aminophenyl) fluorene, 2, 4' -diaminodiphenyl ether, 3 '-diaminodiphenyl ether, 4' -bis (4-aminophenyl) sulfide, and their salts, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, 4, 4 '-bis (4-aminophenoxy) biphenyl, 4, 4' -bis (3-aminophenoxy) biphenyl, 2-bis [4- (4-aminophenoxy) phenyl ] propane, bis [4- (4-aminophenoxy) phenyl ] sulfone, bis [4- (3-aminophenoxy) phenyl ] sulfone, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 3 '-dihydroxy-4, 4' -diaminobiphenyl and 3, 3 ', 4, 4' -tetraaminobiphenyl.

1-3 ratio of tetracarboxylic dianhydride to diamine

The polyamic acid (a) used in the present invention is synthesized by reacting tetracarboxylic dianhydride and diamine. If the difference in the number of moles between the tetracarboxylic dianhydride and the diamine used is large, the molecular weight of the polymer does not increase, and the amount of the residual monomer increases, resulting in a decrease in the display characteristics when forming the liquid crystal display device. Therefore, the ratio of the tetracarboxylic dianhydride to the diamine in the raw material is preferably set to a ratio such that the relationship of 0.8. ltoreq. X/Y. ltoreq.1.2 holds for X moles of the tetracarboxylic dianhydride and Y moles of the diamine. More preferably 0.9. ltoreq. X/Y. ltoreq.1.1, still more preferably 0.95. ltoreq. X/Y. ltoreq.1.05.

1-4. end capping agent

The polyamic acid (a) of the present invention may contain an end-capping agent in the raw material. Examples of the end-capping agent include monohydroxy compounds, monoamine compounds, and acid anhydrides.

When at least one of a monohydroxy compound and a monoamine compound is used as the end-capping agent, an acid anhydride group at the end of the polyamic acid can be capped, and when an acid anhydride is used as the end-capping agent, an amino group at the end of the polyamic acid can be capped. The polyamic acid (a) obtained by capping these terminals improves the storage stability of the thermosetting composition.

Specific examples of the monohydroxy compound include: benzyl alcohol, methanol, ethanol, 1-propanol, isopropanol, allyl alcohol, borneol (borneel), linalool (linalool), terpineol (terpineol), and 3-ethyl-3-hydroxymethyloxetane. More than one of these may be used.

In the case of the solvent, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, and the like, which will be described later, are monohydroxy compounds, but have an appropriate boiling point, and therefore are excellent in coatability and low in the corrosiveness to substrates, and therefore are useful as solvents for use in the thermosetting composition of the present invention. When the polyamic acid (a) is used as a solvent in the synthesis, a part thereof may react like a capping agent, but the reaction is not included in the capping agent but treated as a solvent in the present specification.

Among these, benzyl alcohol and 3-ethyl-3-hydroxymethyl oxetane are more preferable.

The content of the monohydroxy compound in the raw material composition is preferably 0.01 to 20 parts by mole, more preferably 0.01 to 10 parts by mole, and still more preferably 0.01 to 5 parts by mole, relative to 100 parts by mole of the total amount of the tetracarboxylic dianhydride and the diamine.

Specific examples of the monoamine compound include: aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine; aminosilanes such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p-aminophenylmethyldiethoxysilane, m-aminophenyltrimethoxysilane and m-aminophenylmethyldiethoxysilane. More than one of these may be used.

Of these, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, aniline, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane are preferable.

The content of the monoamine compound in the raw material composition is preferably 0.01 to 20 parts by mole, more preferably 0.01 to 10 parts by mole, and still more preferably 0.01 to 5 parts by mole, based on 100 parts by mole of the total amount of the tetracarboxylic dianhydride and the diamine.

Specific examples of the acid anhydride include: phthalic anhydride, trimellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, dodecenylsuccinic anhydride. More than one of these may be used.

Among these, trimellitic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride are preferable.

The content of the acid anhydride in the raw material composition is preferably 0.01 to 20 parts by mole, more preferably 0.01 to 10 parts by mole, and still more preferably 0.01 to 5 parts by mole, based on 100 parts by mole of the total amount of the tetracarboxylic dianhydride and the diamine.

1-5. solvent (B1) used in the Synthesis reaction of Polyamic acid (A)

The polyamic acid (a) can be synthesized by reacting tetracarboxylic dianhydride with diamine and, if necessary, a capping agent in a solvent. The solvent used in the synthesis reaction for obtaining the polyamic acid (a) is hereinafter sometimes referred to as a reaction solvent (B1).

Specific examples of the reaction solvent (B1) include: 4-hydroxy-2-butanone, diacetone alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, ethyl lactate, cyclopentanone, cyclohexanone, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, tripropylene glycol dimethyl ether, gamma-butyrolactone, NMP, N-dimethylpropionamide, N-dimethylisobutylamide, N-diethylacetamide, N-dimethylformamide, N-dimethylbutylacetamide, ethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dimethyl ether, 3-diethyl ether, 3-methyl ether, 3-methoxypropionate, 3-ethoxypropionate, 3-methoxybutyl acetate, ethyl lactate, cyclohexanone, and/or tripropylene glycol dimethyl ether, N, N-diethylformamide, N-dimethylacetamide, N-diethylpropionamide, N-methylpropionamide, and dimethyl carbonate. More than one of these may be used.

Of these, from the viewpoint of solubility of polyamic acid and erodibility to a substrate when coating the obtained thermosetting composition, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, tripropylene glycol dimethyl ether, γ -butyrolactone, N-dimethyl isobutyramide, N-diethylacetamide, N-diethylformamide, and N, N-diethylacrylamide are preferable.

From the viewpoint of handling, the solvent may be left as it is to be used to prepare a polyamic acid solution or a gel. For shortening the production time, it is preferable to use the polyamic acid solution in the preparation of the thermosetting composition. In this case, in order to suppress the corrosiveness to the substrate, the reaction solvent preferably does not contain NMP. Depending on the structure of the polyamic acid, it may be considered to use NMP for the purpose of improving solubility. In this case, the content of NMP is preferably 5 wt% or less in the entire reaction solvent in view of the aggressiveness to the substrate.

From the viewpoint of transportation, the solvent may be removed to prepare a polyamic acid solid or a powder thereof. The reprecipitation method is simple when the polyamic acid solid matter is extracted from the polyamic acid solution containing the reaction solvent. When the solid polyamic acid obtained by the reprecipitation method is used for the preparation of a thermosetting composition, NMP may be used as the reaction solvent. The method for obtaining the polyamic acid solid material by the reprecipitation method is as follows.

The reprecipitation method uses a poor solvent which hardly dissolves polyamic acid. A polyamic acid solution is added to a large excess amount of a poor solvent to precipitate and recover the polyamic acid. The recovered precipitate was dried under reduced pressure to evaporate the solvent, and a polyamic acid solid was obtained. Examples of the poor solvent include methanol (methanol), acetone, methanol (methyl alcoho1), and water. For details, reference may be made to International publication No. 2004/053583, Japanese patent laid-open No. 2005-336246 and the like.

In this way, after the polyamic acid solid content substantially free of NMP used as the reaction solvent is obtained, the polyamic acid solid content can be dissolved in a solvent (B2) used in the thermosetting composition of the present invention described later, thereby preparing the thermosetting composition of the present invention.

1-6 Synthesis method of Polyamic acid (A)

The order of addition of the raw materials to the reaction system is not particularly limited. In the case of using the monohydroxy compound, the monoamine compound, and the acid anhydride for the end-capping reaction, the tetracarboxylic dianhydride and the diamine are reacted with each other, and then the reaction system is cooled to a temperature of 40 ℃ or lower and added thereto, and the reaction is carried out at 10 to 40 ℃ for 0.1 to 12 hours.

The weight average molecular weight of the obtained polyamic acid (A) is preferably 1,000 to 200,000, more preferably 2,000 to 50,000. When the molecular weight is within these ranges, the solubility, the orientation ability and the flatness are good.

As described above, the polyamic acid in the present invention is a polymer obtained by reacting raw materials including tetracarboxylic dianhydride and diamine. In the present specification, a form in which a part of the reaction step is dehydrated and cyclized to form a polyimide is also included in the polyamic acid.

2. The thermosetting composition of the present invention

The thermosetting composition of the present invention comprises polyamic acid (a) and solvent (B2).

2-1. solvent for thermosetting composition (B2)

The solvent (B2) used in the thermosetting composition of the present invention is preferably a solvent in which the polyamic acid (a), the curing agent (C), the additive (D), and the like are soluble. In addition, a solvent having low corrosiveness to the base color filter is preferable.

In addition, in the case where the polyamic acid solid material is used in the thermosetting composition in the state of the polyamic acid solution without taking out the polyamic acid solid material from the polyamic acid solution obtained by the synthesis of polyamic acid (a), the reaction solvent (B1) contained in the polyamic acid solution is also contained in the solvent (B2).

Specific examples of the solvent (B2) include: 4-hydroxy-2-butanone, diacetone alcohol, 2-butanone, ethyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl glycolate, ethyl glycolate, butyl glycolate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxopropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, Ethyl 2-ethoxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, 4-hydroxy-4-methyl-2-pentanone, 1, 4-butanediol, cyclopentanone, cyclohexanone, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, gamma-butyrolactone, N-dimethyl isobutylamide, N-diethylacetamide, N-diethylformamide, N-methyl-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, ethyl 1, 4-butanediol, cyclopentanone, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, gamma-butyrolactone, N-dimethyl isobutylamide, N-diethylacetamide, N-diethylformamide, N-methyl-2-hydroxy-2-methylpropionate, ethyl 2-methyl-hydroxy-2-methyl propionate, ethyl-2-methyl propionate, 1-4-hydroxy-4-methyl propionate, 1-butanediol, 4-methyl propionate, and methyl propionate, N, N-diethyl propionamide, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, tripropylene glycol dimethyl ether, polyethylene glycol having a weight average molecular weight of 1,000 or less, polyethylene glycol, propylene glycol, dipropylene glycol monomethyl ether, propylene glycol, ethylene glycol, propylene glycol, and the like, Polypropylene glycol having a weight average molecular weight of 1,000 or less, and polypropylene glycol having a weight average molecular weight of 1,000 or less. More than one of these may be used.

Of these, preferred are those selected from cyclopentanone, cyclohexanone, γ -butyrolactone, N-dimethyl isobutyl amide, N-diethyl acetamide, N-diethyl formamide, N-diethyl propionamide, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether.

When importance is attached to solubility, it is preferable to select and use one or more solvents of the first group including cyclopentanone, cyclohexanone, γ -butyrolactone, N-dimethyl isobutyl amide, N-diethyl acetamide, N-diethyl formamide, and N, N-diethyl propionamide.

When importance is attached to the coatability and the low-corrosiveness to the color filter, it is more preferable to select and use at least one of the second group of solvents including ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether.

When importance is attached to the balance between solubility and coatability, it is more preferable to mix one or more solvents selected from the first group of solvents and the second group of solvents.

In order to suppress the aggressivity to the substrate, NMP is preferably not contained in the solvent (B2). For the purpose of improving the solubility of polyamic acid, it is conceivable to use NMP. In this case, the NMP content is preferably 5 wt% or less in the entire solvent.

The content of the solvent (B2) is preferably 60 to 99% by weight based on the total amount of the thermosetting composition. More preferably 70 to 96 wt%.

2-2 hardening agent (C)

The thermosetting composition of the present invention may further contain a curing agent (C). It is assumed that the addition of the curing agent causes a crosslinking reaction in the process of curing the thermosetting composition. Thus, the obtained hardened film can suppress the abrasion of the film due to friction in the subsequent rubbing step. Further, a higher heat resistance can be expected by crosslinking.

The curing agent (C) is not particularly limited as long as it is a compound having two or more functional groups reactive with a carboxyl group in one molecule.

Examples of functional groups which react with carboxyl groups are epoxy groups and oxazoline groups.

As the compound having two or more functional groups reactive with a carboxyl group per molecule, there can be mentioned: a bisphenol a-type epoxy compound, a bisphenol F-type epoxy compound, a glycidyl ether-type epoxy compound, a glycidyl ester-type epoxy compound, a biphenyl-type epoxy compound, a phenol novolac-type epoxy compound, a cresol novolac-type epoxy compound, a bisphenol a novolac-type epoxy compound, an aliphatic polyglycidyl ether compound, a cyclic aliphatic epoxy compound, an epoxy compound having a siloxane bonding site, a glycidyl amine-type epoxy compound, and the like, a compound having two or more epoxy groups per molecule, a compound having two or more oxazoline groups per molecule, and a polymer having at least one of two or more epoxy groups and an oxazoline group per molecule.

Specific examples of the compound having two or more epoxy groups per molecule include: jER 828, jER 1004, and jER 1009 (all trade names; Mitsubishi chemical (strand)) as bisphenol A type epoxy compounds; jER 806 and jER 4005P (both trade names; Mitsubishi chemical (Strand)) which are bisphenol F type epoxy compounds; teckmo (TECHMORE) VG3101L (trade name; Printec (Printec) (Strand)), EHPE3150 (trade name; cellophane (Daicel) (Strand)), EPPN-501H, EPPN-502H (both trade names; Nippon Chemicals (Strand)), jER 1032H60 (trade name; Mitsubishi Chemicals (Strand)); danacol (Denacol) EX-721 (trade name; tradename; tokyo chemical industry, stock)) as a glycidyl ester type epoxy compound; jER YX4000, jER YX4000H, jER YL6121H (all trade names; Mitsubishi chemical (stock)), NC-3000-L, NC-3000-H, NC-3100 (all trade names; Japan Chemicals (stock)), which are biphenyl type epoxy compounds; EPPN-201 (trade name; Japan Chemicals (stock)), jER 152, jER 154 (both trade names; Mitsubishi chemical (stock)) as a phenol novolak-type epoxy compound; EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (all trade names; Japan Chemicals (thigh)); jER 157S65, jER 157S70 (both trade names; Mitsubishi chemical (jet.)) as bisphenol A novolak-type epoxy compounds; cyrocide 2021P, Cyrocide 3000, Ebolide GT401 (trade name; Daicel (thigh)), which are cyclic aliphatic epoxy compounds; 1, 3-bis [2- (3, 4-epoxycyclohexyl) ethyl ] tetramethyldisiloxane (trade name; quick Incorporated), TSL9906 (trade name; Japanese advanced Performance Materials Japan, Ltd.), Coomassie (COATASIL) MP200 (trade name; Japanese advanced Performance Materials Japan, Ltd.), Marseiran (Conporaran) 506 (trade name; crude Sichuan chemical (stock)), ES-1023 (trade name; shin-Etsu chemical (stock)); n, N '-tetraglycidyl-4, 4' -diaminodiphenylmethane, sumitoxico (sumiooxy) ELM-434 (trade name; sumitox chemical (stock)), sumitox (sumitoxy) ELM-100 (trade name; sumitox chemical (stock)), which is a glycidyl amine type epoxy compound.

Specific examples of the compound having two or more oxazoline groups per molecule include 2, 2' - (1, 3-phenylene) bis- (2-oxazoline).

The amount of the curing agent (C) added is preferably 0.5 to 60 parts by weight, more preferably 1 to 30 parts by weight, based on 100 parts by weight of the polyamic acid (a).

2-3. additive (D)

Various additives (D) can be added to the thermosetting composition of the present invention to improve film properties such as flatness, scratch resistance, coating uniformity, and adhesiveness. Examples of the additive (D) include an adhesion improver such as a compound having a polymerizable double bond, a surfactant and a silane coupling agent, and an antioxidant.

2-3-1. Compounds having polymerizable double bond

In the thermosetting composition of the present invention, a compound having a polymerizable double bond can also be used. The compound having a polymerizable double bond used in the thermosetting composition of the present invention is not particularly limited as long as it has two or more polymerizable double bonds per molecule.

Specific examples of the compound having two polymerizable double bonds per molecule in the compound having a polymerizable double bond include: ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, epichlorohydrin-modified ethylene glycol di (meth) acrylate, epichlorohydrin-modified diethylene glycol di (meth) acrylate, epichlorohydrin-modified triethylene glycol di (meth) acrylate, epichlorohydrin-modified tetraethylene glycol di (meth) acrylate, epichlorohydrin-modified polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, epichlorohydrin-modified propylene glycol di (meth) acrylate, epichlorohydrin-modified dipropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, propylene glycol di (acrylate, propylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, propylene glycol acrylate, epichlorohydrin-modified tripropylene glycol di (meth) acrylate, epichlorohydrin-modified tetrapropylene glycol di (meth) acrylate, epichlorohydrin-modified polypropylene glycol di (meth) acrylate, glycerol acrylate methacrylate, glycerol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, epichlorohydrin-modified 1, 6-hexanediol di (meth) acrylate, methoxylated cyclohexyl di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalyl acetate di (meth) acrylate, caprolactone-modified hydroxypivalyl acetate di (meth) acrylate, stearic acid-modified pentaerythritol di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, bis [ (meth) acryloyloxy neopentyl glycol ] adipate, allylated cyclohexyldi (meth) acrylate, poly (meth) acrylate, Bisphenol A di (meth) acrylate, ethylene oxide-modified bisphenol A di (meth) acrylate, bisphenol F di (meth) acrylate, ethylene oxide-modified bisphenol F di (meth) acrylate, bisphenol S di (meth) acrylate, ethylene oxide-modified bisphenol S di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, dicyclopentanyl diacrylate, ethylene oxide-modified di (meth) acrylate phosphate, caprolactone-ethylene oxide-modified di (meth) acrylate phosphate, epichlorohydrin-modified di (meth) acrylate phthalate, tetrabromobisphenol a di (meth) acrylate, tripropylene triol di (meth) acrylate, neopentyl glycol-modified trimethylolpropane di (meth) acrylate, and ethylene isocyanurate-modified diacrylate.

Specific examples of the compound having three or more polymerizable double bonds per molecule in the compound having a polymerizable double bond include: trimethylolpropane tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, propylene oxide-modified trimethylolpropane tri (meth) acrylate, epichlorohydrin-modified trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, epichlorohydrin-modified glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, ethylene oxide-modified phosphoric acid tri (meth) acrylate, caprolactone-modified tris [ (meth) acryloyloxyethyl ] isocyanurate, di-trimethylolpropane tetra (meth) acrylate, diglycerol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate and alkyl-modified dipentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, and alkyl-modified dipentaerythritol tetra (meth) acrylate, Dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, ethylene oxide isocyanurate-modified triacrylate, and carboxyl-containing polyfunctional (meth) acrylate.

The compound having a polymerizable double bond may be used alone or in combination of two or more.

Among the compounds having a polymerizable double bond, from the viewpoint of flatness and scratch resistance, it is preferably selected from the group consisting of ethylene oxide-modified bisphenol F di (meth) acrylate, ethylene oxide isocyanurate-modified diacrylate, ethylene oxide isocyanurate-modified triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and carboxyl group-containing polyfunctional (meth) acrylate.

From the viewpoint of balance among flatness, heat resistance, and alignment ability with respect to liquid crystal and polymerizable liquid crystal, the content of the compound having a polymerizable double bond is 1 to 60 parts by weight based on 100 parts by weight of the polyamic acid (a) in the thermosetting composition of the present invention. When importance is attached to the orientation ability, the amount is preferably 1 to 20 parts by weight.

2-3-2. surfactant

The thermosetting composition of the present invention may contain an anionic, cationic, nonionic, fluorine-based or silicon-based leveling agent or surfactant to improve coating uniformity.

Specific examples of the surfactant include: polyflow No.75, Polyflow No.90, Polyflow No.95 (trade names; Kyoho chemical Co., Ltd.); disperbyk (Disperbyk) -161, Disperbyk (Disperbyk) -162, Disperbyk (Disperbyk) -163, Disperbyk (Disperbyk) -164, Disperbyk (Disperbyk) -166, Disperbyk (Disperbyk) -170, Disperbyk (Disperbyk) -180, Disperbyk (Disperbyk) -181, Disperbyk (Disperbyk) -182, Bib (BK) -300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-346, BYK-361N, BYK-60, BYK-UV3500, BYK-UV3570 (all trade names of BYK chemistry (Japan) (Jathigh)); KP-341, KP-368, KP-96-50CS, KP-50-100CS (all trade names; shin-Etsu chemical industry (stock)); shafu Long (Surflon) S611 (trade name; AGC Qingmei Chemical (AGC Seimi Chemical) (thigh)); forget (Ftergent)222F, Forget (Ftergent)208G, Forget (Ftergent)251, Forget (Ftergent)710FL, Forget (Ftergent)710FM, Forget (Ftergent)710FS, Forget (Ftergent)601AD, Forget (Ftergent)650A, FTX-218 (both trade names; Nioos (Neos) (stock)); meijia method (Megafac) F-410, Meijia method (Megafac) F-430, Meijia method (Megafac) F-444, Meijia method (Megafac) F-472SF, Meijia method (Megafac) F-475, Meijia method (Megafac) F-477, Meijia method (Megafac) F-552, Meijiafac method (Megafac) F-553, Meijiafac method (Megafac) F-554, Meijiafac method (Megafac) F-555, Meijiafac method (Megafac) F-556, Meijiafac (Megafac) F-558, Meijiafac method (Megafac) F-559, Meijiafa (Megafac) R-94, Meijiafac method (Megafac fac) RS-75, Meijiafac method (Megafac) RS-72-K, Meijiafac method (Megafac) F-76, Meijiafac method (Megafac) RS-76, Meijiafac (DS) (trade names, Meijiafac) (product names) (21 DS) (Meijiadic); digotun (TEGO Twin)4000, Digotun (TEGO Twin)4100, Digovero (TEGO Flow)370, Digovero (TEGO Flow)375, Digoglyde (TEGO Glide)440, Digoglyde (TEGO Glide)450, Digoglyde (TEGO Rad)2200N (all trade names; Nippon Windo (Evonik Japan) (stock)); fluoroalkyl benzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglyceryl tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethyl ammonium salt, fluoroalkyl sulfamate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene lauryl amine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, fluoroalkyl iodide, fluoroalkyl betaine, and fluoroalkyl betaine, Polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate and alkyl diphenyl ether disulfonate. More than one of these may be used.

Of these, BYK-306, BYK-342, BYK-346, BYK-361N, BYK-3560, KP-341, salofuron (Surflon) S611, Forgelite (Ftergent)710FL, Forgelite (Ftergent)710FM, Forgelite (Ftergent)710FS, Ftergent (Ftergent)650A, Meijia (Megafac) F-477, Meijia (Megafac) F-556, Meijia (Megafac) RS-72-K, Meijiafa (Megafac) DS-21, Digago (TEGO Twin)4000, DigaFlow (TEGO) 375, fluoroalkyl benzene sulfonate, fluoroalkyl polyoxyethylene ether, fluoroalkyl trimethyl ammonium salt, and fluoroalkyl aminosulfonate are preferable from the viewpoint of high coating uniformity.

The content of the surfactant in the thermosetting composition of the present invention is preferably 0.005 to 1% by weight based on the total amount of the thermosetting composition.

2-3-3 adhesion improver

From the viewpoint of further improving the adhesion between the formed cured film and the substrate, the thermosetting composition of the present invention may further contain an adhesion improving agent such as a silane-based, aluminum-based, or titanate-based coupling agent.

Specific examples of the adhesion improver include: silane-based coupling agents such as 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane; aluminum coupling agents such as aluminum acetyl alkoxy diisopropoxide; and titanate coupling agents such as tetraisopropylbis (dioctyl phosphite) titanate.

Of these, 3-glycidoxypropyltrimethoxysilane is preferred.

The content of the adhesion improver is preferably 0.01 to 10% by weight based on the total amount of the thermosetting composition.

2-3-4 antioxidant

The thermosetting composition of the present invention may further contain an antioxidant such as a phenol antioxidant, a phosphorus antioxidant, a sulfur antioxidant, or an amine antioxidant, from the viewpoint of improving transparency and preventing yellowing of the cured film when exposed to high temperatures. Among them, a phenol-based antioxidant is preferable from the viewpoint of stability.

Specific examples of the phenolic antioxidant include: t-butylhydroquinone, butylhydroxytoluene, ANTAGE (ANTAGE) SP (trade name; Sichuan chemical industry (Strand)), pentaerythrityl tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], thiodiethylene bis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], octadecyl-3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, N' - (hexane-1, 6-diyl) bis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionamide ], ethylene bis (oxyethylene) bis- (3- (5-t-butyl-4-hydroxy-m-tolyl) propionate, methyl ethyl-p-butoxide, methyl-p-butoxide, ethyl-p-butoxide, N-butyl-1, 6-diyl) bis (3, 5-di-t-butyl-4-hydroxy-m-tolyl) propionate, N-butyl-4-hydroxy-p-propoxide, N-butyl-hydroxy-p-butoxide, N-butyl-hydroxy-p, 1, 6-hexanediol bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], octyl-3, 5-di-tert-butyl-4-hydroxy-hydrocinnamate, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, 4, 6-bis (dodecylthiomethyl) -o-cresol, 4, 6-bis (octylthiomethyl) -o-cresol, 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 4' -butylidenebis (6-tert-butyl-3-methylphenol), 2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5- Methylbenzyl) phenylacrylate, 1,3, 5-tris [ [4- (1, 1-dimethylethyl) -3-hydroxy-2, 6-dimethylphenyl ] methyl ] -1, 3, 5-triazine-2, 4, 6- (1H, 3H, 5H) -trione, 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -1, 3, 5-triazine-2, 4, 6- (1H, 3H, 5H) -trione, 4- [ [4, 6-bis (octylthio) -1, 3, 5-triazin-2-yl ] amino ] -2, 6-di-tert-butylphenol, 2 '-dimethyl-2, 2' - (2, 4, 8, 10-tetraoxaspiro [5.5] undecane-3, 9-diyl) dipropane-1, 1' -diyl bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ].

Among them, pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and thiodiethylene bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] are more preferable from the viewpoint of thermal stability. From the viewpoint of solubility, butylhydroxytoluene and octyl-3, 5-di-tert-butyl-4-hydroxy-hydrocinnamate are more preferable.

The content of the antioxidant is preferably 0.01 to 5.0 parts by weight, more preferably 0.05 to 2.0 parts by weight, based on 100 parts by weight of the polyamic acid (a).

2-4 preparation of thermosetting composition

The thermosetting composition of the present invention can be obtained by: the polyamic acid (a), the solvent (B2), and further, if necessary, additives (D) such as a curing agent (C), a compound having a polymerizable double bond, a surfactant, an adhesion improver, an antioxidant, and other additives are selectively added and uniformly mixed and dissolved.

2-5 storage of the thermosetting composition

The thermosetting composition of the present invention is preferably stored at-30 to 25 ℃ because the composition has good stability with time. More preferably from-20 ℃ to 10 ℃.

3. Cured film obtained from thermosetting composition

The thermosetting composition prepared in the above manner can be applied to the surface of a substrate by a conventionally known coating method such as a spin coating method, a roll coating method, a dipping method, and a slit coating method to form a coating film. Next, the coating film may be subjected to primary baking in a hot plate, an oven, or the like, and then subjected to primary baking for curing the coating film, thereby obtaining a cured film. Before the temporary calcination, it is also preferable to add a step of removing a part of the solvent by reducing the pressure. Next, an alignment treatment is performed by using a rubbing method to impart an alignment ability. The rubbing can be performed by a known method.

The temporary calcination conditions vary depending on the kind and blending ratio of each component, and are usually carried out on a hot plate at 60 to 100 ℃ or in an oven for 1 to 15 minutes. The conditions for the main calcination vary depending on the kind and blending ratio of each component, and the calcination is usually carried out on a hot plate at 120 to 250 ℃ or in an oven for 5 to 90 minutes.

When the thermosetting composition contains a curing agent, a crosslinking reaction occurs between the carboxyl group of the polyamic acid and the epoxy group or oxazoline group of the curing agent in the main baking step. Therefore, the obtained hardened film is very tough.

The cured film of the present invention has an ability to align a liquid crystal and a polymerizable liquid crystal by alignment treatment, and is excellent in transparency, flatness, and voltage holding ratio. Therefore, the film has the functions of both the alignment film and the overcoat film, and can be used as both the coating film layers. The coating layer can be used to manufacture a liquid crystal display element or a solid-state imaging element.

[ examples ]

The present invention will be specifically described below with reference to synthesis examples, examples and comparative examples, but the present invention is not limited to these examples at all.

The abbreviations described in the examples are as follows, and the corresponding compound names, trade names, and the like.

< solvent >

GBL: gamma-butyrolactone

ECa: diethylene glycol monoethyl ether acetate

BCS: ethylene glycol monobutyl ether

PGME: propylene glycol monomethyl ether

EDM: diethylene glycol ethyl methyl ether

3 MP: 3-Methoxypropionic acid methyl ester

< tetracarboxylic dianhydride >

BT-100: 1,2, 3, 4-butanetetracarboxylic dianhydride (Rikacid) BT-100, trade name; Xinri physicochemical (Strand)

ODPA: 3, 3 ', 4, 4' -Diphenyl Ether tetracarboxylic dianhydride

< diamine >

DDS: 4, 4' -diaminodiphenyl sulfone

1, 3-BAC: 1, 3-bisaminomethylcyclohexane

NBDA: bis (aminomethyl) norbornane (trade name; Mitsui Fine chemistry (Strand))

BAPP: 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane

< end capping agent >

BzOH: benzyl alcohol

TMA: trimellitic anhydride

< hardener >

1, 3-PBO: 2, 2' - (1, 3-phenylene) bis- (2-oxazoline)

TGDDE: n, N, N ', N ' -tetraglycidyl-4, 4 ' -diaminodiphenylmethane

< additive >

M208: ethylene oxide-modified bisphenol F diacrylate (Aronix M-208; trade name; Toyo Synthesis (Strand))

M402: dipentaerythritol pentaacrylate (Aronix M-402; trade name; Toyo Synthesis (Strand))

S510: 3-glycidoxypropyltrimethoxysilane (Sila-Ace) S510; trade name; Jienzhi (JNC) (Strand)

BHT: butylated hydroxytoluene

F-477: meijiafa (Megafac) F-477 (trade name; Di love Bio (DIC) (stock))

TEGO Flow 375: digaofolo (TEGO Flow)375 (trade name; Nippon winning money)

BYK-3560: ByK (BYK) -3560 (trade name; Nippon Bik chemical (Strand))

BYK-361N: ByK-361N (trade name; Nippon Bik chemical (stock))

DS-21: meijiafa (Megafac) DS-21 (trade name; Di love student (DIC) (stock))

The abbreviations of the measurement items in the examples are shown below.

Mw: weight average molecular weight

Mn: number average molecular weight

DOP: planarization rate

The Mw and Mn of the polyamic acid are determined by: the measurement was performed by a Gel Permeation Chromatography (GPC) method using a 2695 separation module 2414 differential refractometer (manufactured by Waters), and was converted into polystyrene. The obtained polyamic acid was diluted with a mixed solution of phosphoric acid and Dimethylformamide (DMF) (phosphoric acid/DMF 0.6/100: weight ratio) so that the concentration of the polyamic acid became about 1 wt%. The column was measured using HSPgel RT MB-M (manufactured by Waters) at a column temperature of 50 ℃ and a flow rate of 0.40mL/min, using the mixed solution as a developing solvent. As the standard polystyrene, TSK standard polystyrene manufactured by Tosoh (Strand) was used.

Next, the apparatus and analysis conditions used in the examples are shown.

＜GPC＞

The device comprises the following steps: 2695 Split Module-2414 differential refractometer manufactured by Waters corporation

Solvent: phosphoric acid-DMF mixed solution (phosphoric acid/DMF ═ 0.6/100: weight ratio)

Flow rate: 0.40mL/min

Temperature of the pipe column: 50 deg.C

Using a pipe column: HSPgel RT MB-M manufactured by Waters corporation

Calibration curve standard: TSK Standard polystyrene manufactured by Tosoh

< rotator (spinner) >

The device comprises the following steps: MS-A150 manufactured by Mikasa (Mikasa) (Strand)

< measurement of viscosity >

The device comprises the following steps: e-type viscometer "TV-22" (trade name) manufactured by eastern industries (Ltd.)

The determination method comprises the following steps: according to Japanese Industrial Standards (JIS) C21035.3.

Measuring temperature: 25 deg.C

< measurement of film thickness >

The device comprises the following steps: stylus type film thickness meter P-16 (trade name) manufactured by Nippon Kogyo (KLA-Tencor Japan)

The determination method comprises the following steps: three sites were measured, and the average value was defined as the film thickness.

< measurement of transmittance >

The device comprises the following steps: ultraviolet-visible spectrophotometer V-670 (trade name) manufactured by Japan Spectroscopy (Strand)

< determination of Voltage holding ratio >

The device comprises the following steps: liquid Crystal physical Property evaluation device 6254 model (trade name) manufactured by Toyo science Corporation

Pulse voltage gate width: 60 mu s

Frequency: 3Hz

Peak value: 1V

Measuring temperature: 60 ℃ C

[ Synthesis of Polyamic acid ]

Synthesis example 1 Synthesis of Polyamic acid (A1)

BT-100(27.94 g; 141.02mmol), 1,3-BAC (20.06 g; 141.02mmol) and GBL (144.00g) were placed in a 500mL four-neck separable flask equipped with a thermometer, stirrer and nitrogen inlet at room temperature. The reaction vessel was heated in an oil bath maintained at 85 ℃ for 2 hours, and it was confirmed that the contents in the reaction vessel were dissolved. After cooling to room temperature, BCS (48.00g) was added, followed by stirring at 85 ℃ for 5 hours. After cooling to room temperature, a uniform and transparent solution of polyamic acid (A1) having a solid content concentration of 20.0% was obtained. Polyamic acid (A1) had a Mw of 10,700 and a Mn of 9,900. The solution (hereinafter referred to as SA1) was used directly for the preparation of a thermosetting composition.

Synthesis example 2 Synthesis of Polyamic acid (A2)

The reaction was carried out in the same manner as in Synthesis example 1 except that the tetracarboxylic dianhydride and diamine were changed to BT-100(27.46 g; 138.60mmol), 1,3-BAC (9.86 g; 69.31mmol) and NBDA (10.69 g; 69.30 mmol). After cooling to room temperature, a uniform and transparent solution of polyamic acid (A2) having a solid content concentration of 20.0% was obtained. Polyamic acid (A2) had a Mw of 11,700 and a Mn of 10,800. The solution (hereinafter referred to as SA2) was used directly for the preparation of a thermosetting composition.

Synthesis example 3 Synthesis of Polyamic acid (A3)

A reaction was carried out in the same manner as in Synthesis example 1 except that the tetracarboxylic dianhydride and the diamine were changed to BT-100(26.99 g; 136.22mmol) and NBDA (21.01 g; 136.20 mmol). After cooling to room temperature, a uniform and transparent solution of polyamic acid (A3) having a solid content concentration of 20.0% was obtained. Polyamic acid (A3) had a Mw of 15,300 and a Mn of 13,000. The solution (hereinafter referred to as SA3) was used directly for the preparation of a thermosetting composition.

Synthesis example 4 Synthesis of Polyamic acid (A4)

BT-100(41.91 g; 211.53mmol), 1,3-BAC (30.09 g; 211.53mmol) and GBL (126.00g) were placed in a 500mL four-neck separable flask equipped with a thermometer, a stirrer and a nitrogen inlet tube at room temperature. The reaction vessel was heated in an oil bath maintained at 110 ℃ for 2 hours, and it was confirmed that the contents in the reaction vessel were dissolved. After cooling to room temperature, PGME (42.00g) was added, followed by stirring at 110 ℃ for 5 hours. After cooling to room temperature, a uniform and transparent solution of polyamic acid (A4) having a solid content concentration of 30.0% was obtained. Polyamic acid (A4) had an Mw of 11,200 and an Mn of 10,400. The solution (hereinafter referred to as SA4) was used directly for the preparation of a thermosetting composition.

Synthesis example 5 Synthesis of Polyamic acid (A5)

Synthesis example 4 was repeated in the same manner with the exception that the tetracarboxylic dianhydride and diamine were changed to BT-100(41.55 g; 209.66mmol), 1,3-BAC (22.37 g; 157.26mmol) and NBDA (8.09 g; 52.44 mmol). After cooling to room temperature, a uniform and transparent solution of polyamic acid (A5) having a solid content concentration of 30.0% was obtained. Polyamic acid (A5) had an Mw of 11,000 and an Mn of 10,300. The solution (hereinafter referred to as SA5) was used directly for the preparation of a thermosetting composition.

Synthesis example 6 Synthesis of Polyamic acid (A6)

Synthesis example 4 was repeated in the same manner with the exception that the tetracarboxylic dianhydride and diamine were changed to BT-100(41.18 g; 207.84mmol), 1,3-BAC (14.78 g; 103.90mmol) and NBDA (16.03 g; 103.92 mmol). After cooling to room temperature, a uniform and transparent solution of polyamic acid (a6) having a solid content concentration of 30.0% was obtained. Polyamic acid (A6) had an Mw of 11,100 and an Mn of 10,400. The solution (hereinafter referred to as SA6) was used directly for the preparation of a thermosetting composition.

Synthesis example 7 Synthesis of Polyamic acid (A7)

Synthesis example 4 was repeated in the same manner with the exception that the tetracarboxylic dianhydride and the diamine were changed to BT-100(40.83 g; 206.08mmol), 1,3-BAC (7.33 g; 51.53mmol) and NBDA (23.84 g; 154.54 mmol). After cooling to room temperature, a uniform and transparent solution of polyamic acid (a7) having a solid content concentration of 30.0% was obtained. Polyamic acid (A7) had an Mw of 11,000 and an Mn of 10,400. The solution (hereinafter referred to as SA7) was used directly for the preparation of a thermosetting composition.

Synthesis example 8 Synthesis of Polyamic acid (A8)

A reaction was carried out in the same manner as in Synthesis example 4 except that the tetracarboxylic dianhydride and the diamine were changed to BT-100(40.48 g; 204.31mmol) and NBDA (31.52 g; 204.33 mmol). After cooling to room temperature, a uniform and transparent solution of polyamic acid (A8) having a solid content concentration of 30.0% was obtained. Polyamic acid (A8) had an Mw of 11,000 and an Mn of 10,300. The solution (hereinafter referred to as SA8) was used directly for the preparation of a thermosetting composition.

Synthesis example 9 Synthesis of Polyamic acid (A9)

BT-100(41.03 g; 207.09mmol), 1,3-BAC (14.44 g; 101.51mmol), NBDA (15.66 g; 101.52mmol) and GBL (126.00g) were placed in a 500mL four-neck separable flask equipped with a thermometer, a stirrer and a nitrogen inlet tube at room temperature. The reaction vessel was heated in an oil bath maintained at 110 ℃ for 2 hours, and it was confirmed that the contents in the reaction vessel were dissolved. After cooling to room temperature, PGME (42.00g) was added, followed by stirring at 110 ℃ for 5 hours. After cooling to room temperature, BzOH (0.88 g; 8.14mmol) was added and further reaction and stirring were carried out at room temperature for 2 hours, a uniform and transparent solution of polyamic acid (A9) having a solid content of 30.0% was obtained. Polyamic acid (A9) had an Mw of 11,100 and an Mn of 10,300. The solution (hereinafter referred to as SA9) was used directly for the preparation of a thermosetting composition.

Synthesis example 10 Synthesis of Polyamic acid (A10)

A reaction was carried out in the same manner as in Synthesis example 9 except that the tetracarboxylic dianhydride and the diamine were changed to BT-100(40.34 g; 203.60mmol) and NBDA (30.79 g; 199.60mmol), and the end-capping agent was changed to BzOH (0.86 g; 7.95 mmol). A uniform transparent polyamic acid (A10) solution having a solid content concentration of 30.0% was obtained. Polyamic acid (A10) had an Mw of 11,000 and an Mn of 10,300. The solution (hereinafter referred to as SA10) was used directly for the preparation of a thermosetting composition.

Synthesis example 11 Synthesis of Polyamic acid (A11)

Synthesis example 9 was repeated in the same manner with the exception that the tetracarboxylic dianhydride and the diamine were changed to BT-100(41.10 g; 207.44mmol), 1,3-BAC (14.46 g; 101.65mmol) and NBDA (15.68 g; 101.65mmol), and the end-capping agent was changed to aniline (0.76 g; 8.16 mmol). A uniform transparent polyamic acid (A11) solution having a solid content concentration of 30.0% was obtained. Polyamic acid (A11) had an Mw of 10,700 and an Mn of 10,000. The solution (hereinafter referred to as SA11) was used directly for the preparation of a thermosetting composition.

Synthesis example 12 Synthesis of Polyamic acid (A12)

The reaction was carried out in the same manner as in Synthesis example 9 except that the tetracarboxylic dianhydride and diamine were changed to BT-100(40.41 g; 203.96mmol) and NBDA (30.85 g; 199.99mmol), and the end-capping agent was changed to aniline (0.74 g; 7.94 mmol). A uniform and transparent polyamic acid (A12) solution having a solid content of 30.0% was obtained. Polyamic acid (A12) had an Mw of 11,400 and an Mn of 10,600. The solution (hereinafter referred to as SA12) was used directly for the preparation of a thermosetting composition.

Synthesis example 13 Synthesis of Polyamic acid (A13)

Synthesis example 9 was repeated in the same manner with the exception that the tetracarboxylic dianhydride and diamine were changed to BT-100(40.40 g; 203.91mmol), 1,3-BAC (14.79 g; 103.97mmol) and NBDA (16.04 g; 103.98mmol), and the end-capping agent was changed to TMA (1.54 g; 8.02 mmol). A uniform transparent polyamic acid (A13) solution having a solid content concentration of 30.0% was obtained. Polyamic acid (A13) had an Mw of 11,200 and an Mn of 10,400. The solution (hereinafter referred to as SA13) was used directly for the preparation of a thermosetting composition.

Synthesis example 14 Synthesis of Polyamic acid (A14)

The reaction was carried out in the same manner as in Synthesis example 9 except that the tetracarboxylic dianhydride and diamine were changed to BT-100(39.71 g; 200.42mmol) and NBDA (31.54 g; 204.46mmol), and the end-capping agent was changed to TMA (1.54 g; 8.02 mmol). A uniform transparent polyamic acid (A14) solution having a solid content concentration of 30.0% was obtained. The Mw of the polyamic acid (A14) was 11,100 and the Mn was 10,300. The solution (hereinafter referred to as SA14) was used directly for the preparation of a thermosetting composition.

Synthesis example 15 Synthesis of Polyamic acid (A15)

Reactions were carried out in the same manner as in Synthesis example 8 except that the amounts of the tetracarboxylic dianhydride and the diamine were changed to BT-100(36.44 g; 183.90mmol), ODPA (6.34 g; 20.43mmol) and NBDA (31.52 g; 204.33 mmol). After cooling to room temperature, a uniform and transparent solution of polyamic acid (A15) having a solid content concentration of 30.0% was obtained. Polyamic acid (A15) had a Mw of 9,200 and a Mn of 8,900. The solution (hereinafter referred to as SA15) was used directly for the preparation of a thermosetting composition.

Comparative Synthesis example 1 Synthesis of Polyamic acid (A16)

ODPA (26.66 g; 85.94mmol), DDS (21.34 g; 85.94mmol) and GBL (144.00g) were placed in a 500mL four-necked separable flask equipped with a thermometer, a stirrer and a nitrogen inlet at room temperature, and stirred for 1 hour to confirm dissolution of the contents in the reaction vessel. ECa (48.00g) was added, and the reaction vessel was stirred in an oil bath maintained at 80 ℃ for further 1 hour and cooled to room temperature to obtain a uniform and transparent solution of polyamic acid (a16) having a solid content of 20.0%. Polyamic acid (A16) had an Mw of 8,200 and an Mn of 3,100. The solution (hereinafter referred to as SA16) was used directly for the preparation of a thermosetting composition.

Comparative Synthesis example 2 Synthesis of Polyamic acid (A17)

The reaction was carried out in the same manner as in comparative Synthesis example 1 except that the tetracarboxylic dianhydride and diamine were changed to ODPA (14.82 g; 47.77mmol), BT-100(9.46 g; 47.75mmol) and DDS (23.72 g; 95.53mmol), and the solvent was changed to GBL (126.00g) and BCS (42.00 g). After cooling to room temperature, a uniform and transparent solution of polyamic acid (A17) having a solid content concentration of 20.0% was obtained. Polyamic acid (A17) had a Mw of 31,100 and a Mn of 22,000. The solution (hereinafter referred to as SA17) was used directly for the preparation of a thermosetting composition.

Comparative Synthesis example 3 Synthesis of Polyamic acid (A18)

The reaction was carried out in the same manner as in comparative Synthesis example 2 except that the tetracarboxylic dianhydride and diamine were changed to BT-100(31.95 g; 161.26mmol) and DDS (40.05 g; 161.29mmol), and the solvent was changed to GBL (126.00g) and BCS (42.00 g). After cooling to room temperature, a uniform and transparent solution of polyamic acid (A18) having a solid content concentration of 20.0% was obtained. Polyamic acid (A18) had an Mw of 21,400 and an Mn of 8,100. The solution (hereinafter referred to as SA18) was used directly for the preparation of a thermosetting composition.

Comparative Synthesis example 4 Synthesis of Polyamic acid (A19)

The reaction was carried out in the same manner as in comparative Synthesis example 2 except that the tetracarboxylic dianhydride and diamine were changed to BT-100(15.63 g; 78.89mmol) and BAPP (32.37 g; 78.85 mmol). After cooling to room temperature, a uniform and transparent solution of polyamic acid (a19) having a solid content concentration of 20.0% was obtained. Polyamic acid (A19) had a Mw of 21,300 and a Mn of 16,000. The solution (hereinafter referred to as SA19) was used directly for the preparation of a thermosetting composition.

Comparative Synthesis example 5 Synthesis of Polyamic acid (A20)

ODPA (18.78 g; 60.54mmol), BT-100(12.00 g; 60.57mmol), 1,3-BAC (17.22 g; 121.05mmol) and GBL (144.00g) were charged into a 500mL four-neck separable flask equipped with a thermometer, stirrer and nitrogen inlet at room temperature, and the reaction vessel was stirred in an oil bath maintained at 85 ℃ for 2 hours. Dissolution of the contents of the reaction vessel was confirmed. After returning to room temperature, BCS (48.00g) was added, and the mixture was stirred in an oil bath maintained at 85 ℃ for 5 hours. Since precipitates were generated upon cooling, the target polyamic acid (a20) could not be obtained.

Comparative Synthesis example 6 Synthesis of Polyamic acid (A21)

The reaction was carried out in the same manner as in comparative Synthesis example 5 except that the tetracarboxylic dianhydride and diamine were changed to ODPA (18.23 g; 58.76mmol), BT-100(11.64 g; 58.75mmol) and NBDA (18.13 g; 117.53mmol), but precipitates were generated upon cooling in the same manner as in comparative Synthesis example 5, and thus the objective polyamic acid (A21) could not be obtained.

Comparative Synthesis example 7 Synthesis of Polyamic acid (A22)

The reaction was carried out in the same manner as in comparative Synthesis example 2 except that the amounts of the tetracarboxylic dianhydride and diamine were changed to BT-100(31.42 g; 158.58mmol), ODPA (12.30 g; 39.64mmol) and NBDA (30.58 g; 198.22 mmol). After cooling to room temperature, a uniform and transparent solution of polyamic acid (a22) having a solid content concentration of 30.0% was obtained. Polyamic acid (A22) had an Mw of 9,400 and an Mn of 9,000. The solution (hereinafter referred to as SA22) was used directly for the preparation of a thermosetting composition.

The tetracarboxylic dianhydride, diamine, end-capping agent, reaction solvent used, solubility of the obtained polyamic acid, Mw, Mn, Mw/Mn used in each synthesis, and the like are shown in tables 1-1 to 1-3. In tables 1-1 to 1-3, the numbers in brackets indicate the mole fraction of the charged raw material. For example, in the case of synthesis example 1, each raw material was metered and charged so that the diamine 1,3-BAC was 100 mol% based on 100 mol% of the tetracarboxylic dianhydride. In the column of solubility, the case where uniform and transparent polyamic acid was obtained was described as "o", and the case where the content was not dissolved and no polymer was obtained, or the case where polyamic acid was not dissolved due to precipitation was described as "x".

[ preparation of thermosetting composition ]

[ preparation example 1]

A polyamic acid solution (SA1) (10.0000g), 1, 3-PBO (0.0600g), F-477(0.0092g), BCS (12.2445g), and GBL (39.0705g) were mixed and dissolved, and then filtered through a fluororesin membrane filter (0.5 μm), thereby obtaining composition 1.

[ preparation example 2]

Composition 2 was obtained by filtration in the same manner as in preparation example 1, except that the polyamic acid solution (SA1) was changed to the polyamic acid solution (SA 2).

[ preparation example 3]

Composition 3 was obtained by performing filtration in the same manner as in preparation example 1, except that the polyamic acid solution (SA1) was changed to a polyamic acid solution (SA 3).

[ preparation example 4]

Composition 4 was obtained by the same method as in preparation example 1 except that the polyamic acid solution (SA1) was changed to the polyamic acid solution (SA 4).

[ preparation example 5]

Composition 5 was obtained by filtration in the same manner as in preparation example 1, except that the polyamic acid solution (SA1) was changed to the polyamic acid solution (SA 5).

[ preparation example 6]

Composition 6 was obtained by filtration in the same manner as in preparation example 1, except that the polyamic acid solution (SA1) was changed to the polyamic acid solution (SA 6).

[ preparation example 7]

Composition 7 was obtained by filtration in the same manner as in preparation example 1, except that the polyamic acid solution (SA1) was changed to the polyamic acid solution (SA 7).

[ preparation example 8]

Composition 8 was obtained by the same method as in preparation example 1 except that the polyamic acid solution (SA1) was changed to the polyamic acid solution (SA 8).

[ preparation example 9]

Composition 9 was obtained by filtration in the same manner as in preparation example 1, except that the polyamic acid solution (SA1) was changed to the polyamic acid solution (SA 9).

[ preparation example 10]

Composition 10 was obtained by performing filtration in the same manner as in preparation example 1, except that the polyamic acid solution (SA1) was changed to a polyamic acid solution (SA 10).

[ preparation example 11]

Composition 11 was obtained by filtration in the same manner as in preparation example 1, except that the polyamic acid solution (SA1) was changed to the polyamic acid solution (SA 11).

[ preparation example 12]

A polyamic acid solution (SA8) (10.0000g), 1, 3-PBO (0.0600g), F-477(0.0561g), PGME (12.5117g), GBL (31.7552g), and EDM (7.9388g) were mixed and dissolved, and then filtered through a fluororesin membrane filter (0.5 μm), thereby obtaining composition 12.

[ preparation example 13]

Composition 13 was obtained by filtration in the same manner as in preparation example 12 except that additive F-477 was changed to DugaVeroFlow 375(0.0092g), and the solvent was changed to PGME (12.2445g), GBL (31.2564g) and EDM (7.8141 g).

[ preparation example 14]

Preparation and filtration were carried out in the same manner as in preparation example 12 except that the additive F-477 was changed to BYK-3560(0.0278g) and the solvent was changed to BCS (12.3504g) and GBL (39.3176g), to obtain composition 14.

[ preparation example 15]

Preparation and filtration were carried out in the same manner as in preparation example 14 except that the additive BYK-3560 was changed to BYK-361N (0.0278g), so as to obtain composition 15.

[ preparation example 16]

Preparation and filtration were carried out in the same manner as in preparation example 14 except that the additive BYK-3560 was changed to DS-21(0.0278g), so as to obtain composition 16.

[ preparation example 17]

A polyamic acid solution (SA8) (10.0000g), TGDDE (0.6000g), F-477(0.0101g), S510(0.1500g), BHT (0.0600g), BCS (13.9596g), and GBL (43.0725g) were mixed and dissolved, and then filtered through a fluororesin membrane filter (0.5 μm), thereby obtaining composition 17.

[ preparation example 18]

A polyamic acid solution (SA8) (10.0000g), 1, 3-PBO (0.1500g), M208(0.3000g), F-477(0.0106g), BHT (0.0600g), BCS (14.8172g), and GBL (45.0735g) were mixed and dissolved, and then filtered through a fluororesin membrane filter (0.5 μ M), thereby obtaining composition 18.

[ preparation example 19]

Composition 19 was obtained by preparing and filtering in the same manner as in preparation example 18, except that the additive M208 was changed to M402(0.3000 g).

[ preparation example 20]

A polyamic acid solution (SA6) (10.0000g), 1, 3-PBO (0.1500g), F-477(0.0106g), S510(0.1500g), BHT (0.0600g), PGME (13.9596g), and GBL (43.0725g) were mixed and dissolved, and then filtered through a fluororesin membrane filter (0.5 μm), thereby obtaining composition 20.

[ preparation example 21]

A polyamic acid solution (SA6) (10.0000g), TGDDE (0.1500g), F-477(0.0101g), S510(0.1500g), BHT (0.0600g), PGME (13.9596g), and GBL (43.0725g) were mixed and dissolved, and then filtered through a fluororesin membrane filter (0.5 μm), thereby obtaining composition 21.

[ preparation example 22]

A polyamic acid solution (SA6) (10.0000g), 1, 3-PBO (0.1500g), M208(0.3000g), F-477(0.0106g), BHT (0.0600g), PGME (14.8172g), and GBL (45.0735g) were mixed and dissolved, and then filtered through a fluororesin membrane filter (0.5 μ M), thereby obtaining composition 22.

[ preparation example 23]

Composition 23 was obtained by conducting preparation and filtration in the same manner as in preparation example 22, except that additive M208 was changed to M402(0.3000 g).

[ preparation example 24]

A polyamic acid solution (SA15) (10.0000g), 1, 3-PBO (0.0600g), F-477(0.0092g), PGME (14.8172g), and GBL (39.0705g) were mixed and dissolved, and then filtered through a fluororesin membrane filter (0.5 μm), thereby obtaining composition 24.

Comparative preparation example 1

A polyamic acid solution (SA16) (10.0000g), 1, 3-PBO (0.0400g), F-477(0.0061g), BCS (4.7059g), GBL (14.1176g) and 3MP (11.9565g) were mixed and dissolved, followed by filtration through a fluororesin membrane filter (0.5 μm), whereby a composition 25 was obtained.

Comparative preparation example 2

Composition 26 was obtained by filtration in the same manner as in comparative preparation example 1, except that the polyamic acid solution (SA16) was changed to the polyamic acid solution (SA 17).

Comparative preparation example 3

Composition 27 was obtained by filtration in the same manner as in comparative preparation example 1, except that the polyamic acid solution (SA16) was changed to the polyamic acid solution (SA 18).

Comparative preparation example 4

Composition 28 was obtained by performing filtration in the same manner as in comparative preparation example 1, except that the polyamic acid solution (SA16) was changed to a polyamic acid solution (SA 19).

Comparative preparation example 5

A polyamic acid solution (SA22) (10.0000g), 1, 3-PBO (0.0600g), F-477(0.0092g), PGME (14.8172g), and GBL (39.0705g) were mixed and dissolved, and then filtered through a fluororesin membrane filter (0.5 μm), thereby obtaining a composition 29.

The components and their ratios of compositions 1 to 29 obtained in preparation examples 1 to 24 and comparative preparation examples 1 to 5 are shown in tables 2-1 to 2-3.

[ tables 2 to 3]

Unit: g

[ examples 1] to [ example 24] and [ comparative examples 1] to [ comparative example 5]

The compositions 1 to 29 obtained in the preparation examples were each subjected to various evaluations in the following manner.

< measurement of transmittance >

The thermosetting composition was applied to a glass substrate "easy height (EAGLE) XG" (trade name, thickness 0.7mm) manufactured by Corning, inc, by adjusting the rotation speed so that the film thickness became about 1.5 μm using a spin coater. Subsequently, the substrate coated with the composition was dried on a hot plate at 60 ℃ for 3 minutes, and then fired in an oven at 230 ℃ for 30 minutes to prepare a test substrate having a cured film for transmittance measurement, and the transmittance was measured. The transmittance was evaluated by the values at transmission wavelengths of 400nm and 313 nm. At a transmission wavelength of 400nm, a transmittance of 90% or more was evaluated as "O", and a transmittance of less than 90% was evaluated as "X". A transmittance at a transmission wavelength of 313nm was evaluated as "O" when 80% or more was observed, and "X" when less than 80% was observed. The results are shown in tables 3-1 to 3-5.

< evaluation of flatness >

The thermosetting composition was applied to a color filter substrate (a substrate having R, G, B three-color pattern-shaped colored bodies on a glass substrate) in which the maximum level difference was measured in advance. The spin coater was used for coating, and the rotation speed was adjusted so that the film thickness became about 1.5 μm. Subsequently, the substrate coated with the composition was dried on a hot plate at 60 ℃ for 3 minutes, and then fired in an oven at 230 ℃ for 30 minutes, thereby producing a test substrate having a cured film for flatness evaluation. The maximum step was measured for the obtained test substrate. Here, the maximum level difference is the maximum value of the level difference on the surface of the substrate, and corresponds to the difference in film thickness between the portion having the thickest film thickness and the portion having the thinnest film thickness on the substrate.

The flatness was evaluated as the flattening ratio (DOP). DOP was calculated as follows. In addition, a substrate having a maximum step of 1.0 μm was used as the color filter substrate without the cured film.

DOP(％)＝(t1-t2)/t2×100

t1(μm): maximum step of color filter substrate without hardening film

t2(μm): maximum step of test substrate with hardened film

The closer the planarization rate is to 100%, the more excellent the planarization is. The flattening ratio was evaluated as ×, 60% or more and less than 70% as Δ, and 70% or more as ≈. The results are shown in tables 3-1 to 3-5.

< evaluation of orientation >

The polymerizable liquid crystal composition solution used in the evaluation was prepared in advance in the following manner.

20.00g of Paliorca LC242 (trade name; BASF Japan) (Strand)), 1.00g of Irgacure 907 (trade name; BASF Japan) (Strand)), 0.020g of BYK-361N (Bristoseh) and toluene as a solvent were added thereto, and the mixture was uniformly mixed and dissolved so that the solvent became 85 wt% of the whole. The composition was used as a polymerizable liquid crystal composition solution (PLC-1).

In accordance with the above-described method for producing a cured film for transmittance measurement, a single cured film for transmittance measurement is produced. The obtained cured film for transmittance measurement was subjected to rubbing treatment using a rubbing apparatus equipped with a rayon rubbing cloth YA-18-R (trade name; Giagawa chemical). The rubbing speed was 60 mm/sec, and the roller rotation speed was 1,000 rpm. Subsequently, a polymerizable liquid crystal composition solution (PLC-1) was applied onto the substrate by a spin coater, dried on a hot plate at 80 ℃ for 1 minute, and then applied to a thickness of 300mJ/cm using an extra-high pressure mercury lamp ² And (4) irradiating. The exposure amount was measured by using a 365nm illuminometer without using a cut-off filter and a polarizing plate. Further, a test substrate having a cured film for evaluating orientation was prepared by baking the substrate in an oven at 230 ℃ for 30 minutes, and the orientation was evaluated.

The test substrate having the cured film for orientation evaluation obtained was sandwiched between two linear polarizing plates in an orthogonal (cross nicol) state in an orientation parallel to the polarizing plates, and the glass substrate with the optically anisotropic material was rotated while maintaining the orientation parallel to the polarizing plates, and was observed by irradiating a backlight from below. A test substrate having a cured film for evaluating alignment properties was rotated, and the presence of alignment properties was judged when light and dark were visible, and the presence of alignment properties was judged as O in tables 3-1 to 3-5, and the absence of light and dark was judged as no alignment properties of a polymerizable liquid crystal compound, and the absence of alignment properties was X in tables 3-1 to 3-5.

< evaluation of Voltage holding ratio >

The thermosetting composition was applied to two glass substrates each having an Indium Tin Oxide (ITO) electrode by a spinner method. The coated substrate was dried by heating at 60 ℃ for 3 minutes, and then heat-treated in an oven at 230 ℃ for 30 minutes. The cured film having a film thickness of about 100nm formed by the heat treatment was subjected to rubbing treatment (indentation: 0.3mm, stage transfer speed: 60m/s, rotation speed: 1000rpm, rubbing cloth: YA-18-R (rayon)). Subsequently, the substrate with the cured film was ultrasonically cleaned in ultrapure water for 5 minutes and dried in an oven at 120 ℃ for 30 minutes. After a7 μm gap agent was applied to one of the cured films, two substrates with cured films were placed in opposition to each other so that the film surfaces of the cured films were opposed to each other and the rubbing direction was antiparallel, and then sealed with an epoxy curing agent to produce an antiparallel cell having a gap of 7 μm. The cell was filled with a liquid crystal composition (LC-1), and the filling opening was sealed with a photocurable sealant. Then, the resultant was subjected to heat treatment at 110 ℃ for 30 minutes to prepare a liquid crystal display device for measuring a voltage holding ratio.

The liquid crystal composition (LC-1) used was a mixture of the liquid crystal compounds shown below at the weight ratios described below.

(liquid Crystal composition (LC-1))

(physical Property value)

Δ ∈ (dielectric constant anisotropy): 5.1

Δ n (refractive index anisotropy): 0.093

Using the obtained liquid crystal display element, a Voltage Holding Ratio (VHR) was measured. The closer the value of the voltage holding ratio is to 100%, the better it is. The value of the voltage holding ratio was evaluated as ×, 70% or more and less than 90% as Δ, and 90% or more as ≈. The results are shown in tables 3-1 to 3-5.

[ Table 3-1]

[ tables 3-2]

[ tables 3 to 3]

[ tables 3 to 4]

[ tables 3 to 5]

As a result of the comparative synthesis examples 5 and 6 in tables 1 to 3 being difficult to dissolve in a mild solvent containing no NMP, it was found that the raw material composition (combination and ratio of raw materials) of the present invention exhibited excellent solubility.

In comparative synthesis examples 1 to 4, polyamic acid dissolved in a mild solvent containing no NMP was obtained. However, when tables 3-1 to 3-4 are compared with tables 3-5, it is understood that the properties such as transmittance and flatness are inferior to those of the cured film of the present invention. It is understood that the cured film of the present invention not only exhibits stable alignment ability with respect to liquid crystal or polymerizable liquid crystal, but also has a transmittance at 313nm, which is much higher than that of the comparative example. Further, it was found that the flatness and the voltage holding ratio were also excellent.

[ industrial applicability ]

According to the present invention, a cured film having both planarization ability and alignment ability, and having high transmittance and high voltage holding ratio can be provided.

Claims

1. A polyamic acid (A) obtained by reacting a raw material comprising a tetracarboxylic dianhydride and a diamine, and

wherein the tetracarboxylic dianhydride has a content of an aliphatic tetracarboxylic dianhydride represented by the formula (1) of 90 mol% or more, and the diamine has a content of at least one aliphatic diamine selected from the group consisting of 1, 3-bisaminomethylcyclohexane and bis (aminomethyl) norbornane of 90 mol% or more,

2. The polyamic acid (a) according to claim 1, wherein the raw material further comprises an end capping agent.

3. A thermosetting composition comprising the polyamic acid (A) according to claim 1 or 2 and a solvent (B2).

4. The thermosetting composition according to claim 3, further comprising a curing agent (C).

5. The thermosetting composition according to claim 3 or 4, further comprising at least one additive (D) selected from the group consisting of a compound having a polymerizable double bond, a surfactant, an adhesion improver and an antioxidant.

6. A cured film obtained by curing the thermosetting composition according to any one of claims 3 to 5.

7. A liquid crystal display element comprising the cured film according to claim 6 as at least one of a liquid crystal alignment film, a polymerizable liquid crystal alignment film, and a transparent protective film.