JP2022113632A - Polyamic acid and thermocurable composition using the same, cured film and liquid crystal display element - Google Patents

Abstract

To provide: a polyamic acid that is soluble in a mild solvent and a thermocurable composition using the same, a cured film and a liquid crystal display element; a thermocurable composition which uses the polyamic acid and has orientation ability with respect to a liquid crystal and a polymerizable liquid crystal and has flattening ability with respect to a substrate; a cured film which is composed of the thermocurable composition and gives high transmittance and high voltage retention; and an electronic component such as a liquid crystal display element and a solid-state imaging device having the cured film.SOLUTION: A polyamic acid is provided which is obtained by reacting an aliphatic tetracarboxylic acid dianhydride represented by formula (1) with raw material including aliphatic diamine that is at least one selected from the group consisting of 1,3- bisaminomethylcyclohexane and bis(aminomethyl)norbornane. A thermocurable composition uses the polyamic acid. In the formula (1), R1, R2, R3 and R4 are each independently H, CH3 or F.SELECTED DRAWING: None

Description

The present invention provides a polyamic acid that is soluble in a mild solvent, a thermosetting composition containing the polyamic acid that suppresses the erosion of color filters, and the thermosetting composition that has alignment ability and flattening ability. The present invention relates to a cured film and electronic components having the cured film, such as a liquid crystal display device and a solid-state imaging device.

A liquid crystal display device is provided with a retardation film in order to widen the viewing angle, adjust the image color tone, and the like. As such a retardation film, a stretched polymer film or a coating-type cured film made of a polymerizable liquid crystal composition is used. A coating-type cured film made of a polymerizable liquid crystal composition makes it possible to make a liquid crystal display device thinner and improve display quality by making the retardation film thinner and improving durability as compared with a conventional polymer film.

A retardation film using a polymerizable liquid crystal is obtained by coating a polymerizable liquid crystal composition solution on a substrate having an alignment film subjected to alignment treatment, aligning the polymerizable liquid crystal composition, and then applying the polymerizable liquid crystal composition. (Patent Document 1). A rubbing method, a photo-alignment method, and the like are known as alignment treatment methods. As the alignment film for polymerizable liquid crystal (polymerizable liquid crystal alignment film), an alignment film for drive liquid crystal (liquid crystal alignment film) can be used. Henceforth, in this specification, a liquid crystal aligning film and a polymerizable liquid crystal aligning film may be collectively called an alignment film.

Most of the compositions for liquid crystal alignment films are compositions containing polyimide and its precursor polyamic acid. Polyimide and its precursor polyamic acid are poorly soluble in organic solvents. Therefore, N-methyl-2-pyrrolidone (hereinafter referred to as "NMP") having high polarity is used as a solvent for the composition for liquid crystal alignment films.

On the other hand, a color filter substrate is used as one method for colorizing liquid crystal display elements. In recent years, finer pigments and dyes have come to be used in order to cope with the widening of the color gamut of color display. Since these finely divided pigments and dyes are easily eluted into highly polar cyclic amide compounds such as NMP, they have low resistance to the solvent in the composition for liquid crystal alignment film. A color filter that has been corroded by a solvent causes color change or color loss, thereby deteriorating the performance of the color filter, and as a result, the display quality of the liquid crystal display element is degraded.

Color filters composed of pixels such as R (red), G (green), and B (blue) used in liquid crystal display elements have different coating film thicknesses for each of the above RGB colors, resulting in unevenness on the surface. appear. If the surface unevenness is large, the display quality of the liquid crystal display element is degraded. For these reasons, a transparent protective film (hereinafter referred to as an "overcoat film") is provided in order to suppress the solvent erosion of the color filter and flatten the surface unevenness.

With the spread of liquid crystal display devices, there is a demand for reduction in manufacturing costs such as shortening of the manufacturing process, and development of materials that provide multiple functions to one coating film layer is required. When the above two-layer film structure of the alignment film and the overcoat film is made into a single layer film, the single layer film should have both the function of the alignment film and the function of the overcoat film, that is, the alignment ability and the flattening ability. is required. In addition, since the solution of the composition is directly applied onto the color filter when forming the monolayer film, a composition containing a reduced or no solvent that is highly corrosive to the underlying color filter is required. It has been demanded.

On the other hand, there are very few reports on compositions having both alignment ability and flattening ability. A thermosetting composition comprising an aromatic polyamic acid has been reported (Patent Document 2), but there is room for improvement in the flatness and voltage holding ratio of the cured film obtained from the composition.

JP 2007-148098 A Chinese Patent Application Publication No. 112194793

To provide a polyamic acid soluble in a mild solvent. Another object of the present invention is to provide a thermosetting composition that uses the polyamic acid of the present invention and has an ability to align liquid crystals and polymerizable liquid crystals and an ability to flatten a substrate. A further object of the present invention is to provide a cured film comprising the thermosetting composition of the present invention and having a high transmittance and a high voltage holding ratio. An electronic component such as a liquid crystal display device and a solid-state imaging device having the cured film is provided.

As a result of intensive studies to solve the above problems, the present inventors have found that by reacting a raw material containing an aliphatic tetracarboxylic dianhydride having a specific structure and an aliphatic diamine having a specific structure, a mild solvent It has been found that a soluble polyamic acid is obtained. By using the polyamic acid of the present invention, in the thermosetting composition, it is possible not only to reduce the amount of solvent highly corrosive to the underlying color filter, but also not to use such a solvent at all. became. Furthermore, by using the thermosetting composition of the present invention, it was found that a cured film having both the functions of an alignment film and an overcoat film and having a satisfactory high transmittance and a high voltage holding ratio can be obtained. I completed the present invention. As used herein, the term "mild solvent" refers to a solvent composition in which the content of a cyclic amide compound such as NMP, which is highly corrosive to the underlying color filter, is 5% by weight or less in the total solvent, and which is highly corrosive to the color filter. Including the case of a low single solvent.

式（１）中、Ｒ^１、Ｒ^２、Ｒ^３、およびＲ^４はそれぞれ独立に、Ｈ、ＣＨ_３、またはＦである。
［２］ 前記原料が、さらに末端封止剤を含む、項１に記載のポリアミド酸（Ａ）。
［３］ 項１または２に記載のポリアミド酸（Ａ）と、溶剤（Ｂ２）を含む熱硬化性組成物。
［４］ さらに、硬化剤（Ｃ）を含む、項３に記載の熱硬化性組成物。
［５］ さらに、重合性二重結合を有する化合物、界面活性剤、密着性向上剤、および酸化防止剤からなる群から選択された少なくとも１種の添加剤（Ｄ）を含む、項３または４に記載の熱硬化性組成物。
［６］ 項３～５のいずれか１項に記載の熱硬化性組成物を硬化させて得られる硬化膜。
［７］ 項６に記載の硬化膜を、液晶配向膜、重合性液晶配向膜、および透明保護膜の少なくとも１つとして有する液晶表示素子。 The present invention includes the following configurations.
[1] A polyamic acid obtained by reacting a raw material containing a tetracarboxylic dianhydride and a diamine,
In the tetracarboxylic dianhydride, the content of the aliphatic tetracarboxylic dianhydride represented by formula (1) is 90 mol% or more, and in the diamine, 1,3-bisaminomethylcyclohexane and bis Polyamic acid (A), wherein the content of at least one aliphatic diamine selected from the group consisting of (aminomethyl)norbornane is 90 mol% or more.

In 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 contains a terminal blocking agent.
[3] A thermosetting composition comprising the polyamic acid (A) according to Item 1 or 2 and a solvent (B2).
[4] The thermosetting composition according to Item 3, further comprising a curing agent (C).
[5] Item 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 The thermosetting composition according to .
[6] A cured film obtained by curing the thermosetting composition according to any one of Items 3 to 5.
[7] A liquid crystal display device comprising 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.

The polyamic acid of the present invention has a specific structure and is soluble in mild solvents. Since the thermosetting composition of the present invention contains the above-mentioned specific polyamic acid, it does not contain NMP in the solvent, or even if it contains it, it is contained in a very small amount, so it is possible to suppress the corrosion of the substrate during film formation. be. In addition, the resulting cured film can have a high transmittance and a high voltage holding ratio. Furthermore, since the cured film made of this composition has the ability to align liquid crystals and polymerizable liquid crystals and has the ability to flatten the substrate, it can be used both as an alignment film and an overcoat film.

1. Polyamic acid (A) of the present invention
Polyamic acid (A) of the present invention is a polymer obtained by reacting raw materials containing tetracarboxylic dianhydride and diamine.

1-1. Tetracarboxylic dianhydride In the present invention, a tetracarboxylic dianhydride is used as a raw material for obtaining polyamic acid (A). Tetracarboxylic dianhydrides include aliphatic tetracarboxylic dianhydrides and aromatic tetracarboxylic dianhydrides. From the viewpoint of imparting good solubility, the polyamic acid (A) of the present invention has a content of the aliphatic tetracarboxylic dianhydride represented by the formula (1) in the raw material tetracarboxylic dianhydride. It is characterized by being 90 mol % or more.

式（１）中、Ｒ^１、Ｒ^２、Ｒ^３、およびＲ^４はそれぞれ独立に、Ｈ、ＣＨ_３、またはＦである。

In formula (1), R ¹ , R ² , R ³ and R ⁴ are each independently H, CH ₃ or F.

More preferably, the content of the compound represented by formula (1) is 95 mol % or more in the starting tetracarboxylic dianhydride.

Of the aliphatic tetracarboxylic dianhydrides represented by formula (1), 1,2,3,4-butanetetracarboxylic dianhydride in which R ¹ to R ⁴ are hydrogen is preferred because it is inexpensive. used for

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

Specific examples of aliphatic tetracarboxylic dianhydrides that can be used in combination include cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride and ethane. A tetracarboxylic dianhydride is mentioned.

Specific examples of aromatic tetracarboxylic dianhydrides that can be used in combination include 3,3′,4,4′-diphenyl ether tetracarboxylic dianhydride, 4,4′-sulfonyldiphthalic anhydride, 3,3′, 4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, pyromellitic anhydride, 1,4-bis(3,4-dicarboxyphenoxy ) benzene dianhydride, p-phenylenebis(trimellitate anhydride), and 4,4′-(hexafluoroisopropylidene)diphthalic anhydride.

1-2. Diamine In the present invention, a diamine is used as a raw material for obtaining the polyamic acid (A). Diamines include aliphatic diamines and aromatic diamines. From the viewpoint of imparting good solubility, the polyamic acid (A) of the present invention contains at least one selected from the group consisting of 1,3-bisaminomethylcyclohexane and bis(aminomethyl)norbornane in the raw material diamine. The content of the aliphatic diamine is 90 mol% or more.

The content of at least one aliphatic diamine selected from the group consisting of 1,3-bisaminomethylcyclohexane and bis(aminomethyl)norbornane is more preferably 95 mol % or more in the raw material 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 present polyamic acid (A) can be maintained. The diamine used in combination may be either an aliphatic diamine or an aromatic diamine. From the viewpoint of voltage holding ratio, it is preferable to use an aliphatic diamine together. From the viewpoint of heat resistance and high refractive index, it is preferable to use an aromatic diamine together.

Examples of aliphatic diamines that 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-tetramethyldisiloxane may be mentioned.

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

1-3. Ratio of tetracarboxylic dianhydride and diamine Polyamic acid (A) used in the present invention is synthesized by reacting tetracarboxylic dianhydride and diamine. If the molar difference between the tetracarboxylic dianhydride and the diamine used is large, the molecular weight of the polymer will not increase and the amount of residual monomer will increase, leading to deterioration in display characteristics when forming a liquid crystal display device. Therefore, the ratio of tetracarboxylic dianhydride and diamine in the raw material is such that the tetracarboxylic dianhydride is X mol and the diamine is Y mol, and the relationship of 0.8 ≤ X / Y ≤ 1.2 is established. ratio. More preferably, 0.9≤X/Y≤1.1, still more preferably 0.95≤X/Y≤1.05.

1-4. Terminal blocker The polyamic acid (A) of the present invention may contain a terminal blocker as a raw material. Terminal capping agents include monohydroxy compounds, monoamine compounds or acid anhydrides.

When at least one of a monohydroxy compound and a monoamine compound is used as a terminal blocking agent, the acid anhydride group at the terminal of the polyamic acid can be blocked, and when an acid anhydride is used as the terminal blocking agent, polyamic acid The terminal amino group of can be blocked. The polyamic acid (A) obtained by terminal blocking improves the storage stability of the thermosetting composition.

Specific examples of monohydroxy compounds include benzyl alcohol, methanol, ethanol, 1-propanol, isopropyl alcohol, allyl alcohol, borneol, linalool, terpineol, and 3-ethyl-3-hydroxymethyloxetane. One or more of these can be used.

Propylene glycol monomethyl ether, ethylene glycol monobutyl ether, etc., which will be described later in the section of solvents, are monohydroxy compounds. It is useful as a solvent for use in curable compositions. When used as a solvent during the synthesis of polyamic acid (A), some of it may react like a terminal blocking agent, but in this specification, it is not included in the terminal blocking agent and is used as a solvent. handle.

Among these, benzyl alcohol and 3-ethyl-3-hydroxymethyloxetane are more preferred.

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

Specific examples of monoamine compounds include aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine and dibutylamine, cyclohexylamine and dicyclohexylamine. alicyclic monoamines such as aniline, toluidine, diphenylamine, aromatic monoamines such as naphthylamine, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldi ethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane Aminosilanes such as silane, p-aminophenylmethyldiethoxysilane, m-aminophenyltrimethoxysilane, and m-aminophenylmethyldiethoxysilane can be mentioned. One or more of these can be used.

Among these, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, aniline, 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane are preferred.

The content of the monoamine compound in the raw material composition is preferably 0.01 to 20 mol parts, more preferably 0.01 to 10 mol parts, relative to 100 mol parts of the total amount of the tetracarboxylic dianhydride and the diamine. 0.01 to 5 molar parts are more preferred.

Specific examples of acid anhydrides include phthalic anhydride, trimellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride. , succinic anhydride, dodecenyl succinic anhydride. One or more of these can be used.

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

The content of the acid anhydride in the raw material composition is preferably 0.01 to 20 mol parts, more preferably 0.01 to 10 mol parts, per 100 mol parts of the total amount of the tetracarboxylic dianhydride and the diamine. , 0.01 to 5 mol parts is more preferable.

1-5. Solvent (B1) used for synthesis reaction of polyamic acid (A)
Polyamic acid (A) can be synthesized by reacting a tetracarboxylic dianhydride, a diamine, and, if necessary, a terminal blocker in a solvent. The solvent used in the synthesis reaction for obtaining the polyamic acid (A) may be hereinafter referred to as 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, and 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, γ-butyrolactone, NMP, N,N-dimethylpropionamide, N,N-dimethylisobutyramide , N,N-diethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylpropionamide, N-methylpropionamide, and dimethyl carbonate. can. One or more of these can be used.

Among these, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene from the viewpoint of the solubility of the polyamic acid and the erosion of the resulting thermosetting composition to the substrate during application. 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,N-dimethylisobutyramide, N, N-diethylacetamide, N,N-diethylformamide and N,N-diethylpropionamide are preferred.

From the viewpoint of handleability, the solvent may be left as it is to form a polyamic acid solution or gel. It is preferable to use the polyamic acid solution in the preparation of the thermosetting composition from the standpoint of shortening the production time. In such a case, the reaction solvent preferably does not contain NMP in order to suppress corrosiveness to the substrate. Depending on the structure of the polyamic acid, it is conceivable to use NMP for the purpose of increasing its solubility. In that case, considering the erosion of the substrate, the content of NMP is preferably 5% by weight or less in the total reaction solvent.

From the point of view of transportation, the solvent may be removed to produce polyamic acid solids or powders thereof. A reprecipitation method is convenient for taking out the polyamic acid solid matter from the polyamic acid solution containing the reaction solvent. When using the polyamic acid solid obtained by using the reprecipitation method for the preparation of the thermosetting composition, NMP may be used as the reaction solvent. The method for obtaining polyamic acid solids by reprecipitation is as follows.

For the reprecipitation method, a poor solvent that hardly dissolves polyamic acid is used. A polyamic acid solution is added to a large excess of poor solvent to precipitate and recover polyamic acid. The collected precipitate is dried under reduced pressure to evaporate the solvent to obtain a polyamic acid solid. Poor solvents include methanol, acetone, methyl alcohol, water and the like. For details, reference can be made to International Publication No. 2004/053583, Japanese Unexamined Patent Application Publication No. 2005-336246, and the like.

After obtaining the polyamic acid solid substantially free of the NMP used as the reaction solvent in this way, it is dissolved in the solvent (B2) used in the thermosetting composition of the present invention, which will be described later, to obtain the thermosetting polymer of the present invention. Compositions can be prepared.

1-6. Method for Synthesizing Polyamic Acid (A) The order of addition of raw materials to the reaction system is not particularly limited. When the end capping reaction is performed using the above-mentioned monohydroxy compound, monoamine compound, and acid anhydride, after reacting the tetracarboxylic dianhydride and the diamine, the temperature of the reaction system is cooled to 40° C. or less. and reacted at 10 to 40° C. 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. Within these ranges, the solubility, alignment ability and flatness are good.

As described above, the polyamic acid in the present invention is a polymer obtained by reacting raw materials containing tetracarboxylic dianhydride and diamine. In the present specification, a polyamic acid includes a form in which a part thereof is cyclodehydrated to form a polyimide in the reaction process.

2. Thermosetting Composition of the Present Invention The thermosetting composition of the present invention is a thermosetting composition containing a polyamic acid (A) and a solvent (B2).

2-1. Solvent (B2) used for thermosetting composition
The solvent (B2) used in the thermosetting composition of the present invention is preferably a solvent capable of dissolving the polyamic acid (A), the curing agent (C), the additive (D) and the like. Further, a solvent that has low erosion to the underlying color filter is preferable.

In the case where the polyamic acid solution is used in the thermosetting composition without taking out the polyamic acid solids from the polyamic acid solution obtained in the synthesis of the polyamic acid (A), the reaction contained in the polyamic acid solution Solvent (B1) is also included in solvent (B2).

Specific examples of the solvent (B2) include 4-hydroxy-2-butanone, diacetone alcohol, 2-butanone, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, ethyl lactate, methyl hydroxyacetate, ethyl hydroxyacetate, hydroxy Butyl acetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, 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, 2 -propyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, 2-methoxy-2-methylpropionate methyl acid, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 4-hydroxy- 4-methyl-2-pentanone, 1,4-butanediol, cyclopentanone, cyclohexanone, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, γ-butyrolactone, N,N-dimethylisobutyramide, N,N-diethylacetamide, N,N-diethylformamide, N,N-diethylpropionamide, 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, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monoethyl ether acetate, propylene diethylene glycol monopropyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diprolylene Glycol monomethyl ether, diprolylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, tripropylene glycol dimethyl ether, polyethylene glycol with a weight average molecular weight of 1,000 or less, polypropylene glycol with a weight average molecular weight of 1,000 or less, weight average molecular weight Polydipropylene glycol with a weight average molecular weight of 1,000 or less, polytripropylene glycol with a weight average molecular weight of 1,000 or less, and polytetrapropylene glycol with a weight average molecular weight of 1,000 or less can be mentioned. One or more of these can be used.

Among these, cyclopentanone, cyclohexanone, γ-butyrolactone, N,N-dimethylisobutyramide, N,N-diethylacetamide, N,N-diethylformamide, N,N-diethylpropionamide, ethylene glycol monobutyl ether, propylene It is preferably selected from glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether.

Cyclopentanone, cyclohexanone, γ-butyrolactone, N,N-dimethylisobutyramide, N,N-diethylacetamide, N,N-diethylformamide, and N,N-diethylpropionamide when more emphasis is placed on solubility It is preferable to select and use one or more of the first group solvents consisting of

A second group consisting of ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether when more emphasis is placed on applicability and less erosion on color filters. It is more preferable to select and use one or more of the solvents.

When the balance between solubility and applicability is emphasized, it is more preferable to select one or more of the first group solvent and the second group solvent, and mix and use them.

It is preferable that the solvent (B2) does not contain NMP in order to suppress corrosion of the substrate. NMP may be used for the purpose of increasing the solubility of polyamic acid. In that case, the content of NMP in the total solvent is preferably 5% by weight or less.

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

2-2. Curing agent (C)
The thermosetting composition of the present invention may further contain a curing agent (C). It is assumed that the addition of a curing agent causes a cross-linking reaction during the process of curing the thermosetting composition. Therefore, the resulting cured film can be prevented from being scraped off by rubbing in the rubbing step to be performed later. In addition, higher heat resistance can be expected by cross-linking.

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

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

Examples of compounds having two or more functional groups per molecule that react with carboxyl groups include bisphenol A-type epoxy compounds, bisphenol F-type epoxy compounds, glycidyl ether-type epoxy compounds, glycidyl ester-type epoxy compounds, biphenyl-type epoxy compounds, and phenol novolak-type compounds. Epoxy compounds, cresol novolak-type epoxy compounds, bisphenol A novolac-type epoxy compounds, aliphatic polyglycidyl ether compounds, cycloaliphatic epoxy compounds, epoxy compounds having siloxane binding sites, glycidylamine-type epoxy compounds, etc. 2 per molecule Compounds having the above epoxy groups, compounds having two or more oxazoline groups per molecule, and polymers having two or more of at least one of epoxy groups and oxazoline groups per molecule can be mentioned.

Specific examples of compounds having two or more epoxy groups per molecule include jER 828, jER 1004, and jER 1009 (all trade names; Mitsubishi Chemical Corporation), which are bisphenol A type epoxy compounds, and bisphenol F type epoxy compounds. jER 806 and jER 4005P (both trade names; Mitsubishi Chemical Corporation), glycidyl ether type epoxy compounds TECHMORE VG3101L (trade name; Printec Co., Ltd.), EHPE3150 (trade name; Daicel Co., Ltd.) , EPPN-501H, EPPN-502H (both trade names; Nippon Kayaku Co., Ltd.), jER 1032H60 (trade name; Mitsubishi Chemical Co., Ltd.), Denacol EX-721 (trade name; Nagase ChemteX Co., Ltd.), diglycidyl 1,2-cyclohexanedicarboxylate (trade name; Tokyo Chemical Industry Co., Ltd.), biphenyl-type epoxy compounds jER YX4000, jER YX4000H, jER YL6121H (all trade names; Mitsubishi Chemical Co., Ltd.), NC-3000, NC-3000-L, NC-3000-H, NC-3100 (all trade names; Nippon Kayaku Co., Ltd.), EPPN-201 (product Name: Nippon Kayaku Co., Ltd.), jER 152, jER 154 (both trade names: Mitsubishi Chemical Co., Ltd.), cresol novolac type epoxy compounds EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (both trade names; Nippon Kayaku Co., Ltd.), jER 157S65 and jER 157S70, which are bisphenol A novolak epoxy compounds (both trade names; Mitsubishi Chemical Corporation), and Celoxide 2021P, which is a cycloaliphatic epoxy compound. , Celoxide 3000, Epolead GT401 (both trade names; Daicel Co., Ltd.), 1,3-bis[2-(3,4-epoxycyclohexyl)ethyl]tetramethyldisiloxane (which is an epoxy compound having a siloxane bond site) ( Product name: Gelest Inc. Polated), TSL9906 (product name: Momentive Performance Materials Japan LLC), COATOSIL MP200 (product name: Momentive Performance Materials Japan LLC), Composelan SQ5 06 (trade name; Arakawa Chemical Co., Ltd.), ES-1023 (trade name; Shin-Etsu Chemical Co., Ltd.), N,N,N',N'-tetraglycidyl-4,4 which is a glycidylamine type epoxy compound '-diaminodiphenylmethane, Sumiepoxy ELM-434 (trade name; Sumitomo Chemical Co., Ltd.), and Sumiepoxy ELM-100 (trade name; Sumitomo Chemical Co., Ltd.).

A specific example of a compound having two or more oxazoline groups per molecule is 2,2'-(1,3-phenylene)bis-(2-oxazoline).

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

2-3. Additive (D)
Various additives (D) can be added to the thermosetting composition of the present invention in order to improve film properties such as flatness, scratch resistance, coating uniformity and adhesion. The additive (D) mainly includes a compound having a polymerizable double bond, a surfactant, an adhesion improver such as a silane coupling agent, and an antioxidant.

2-3-1. Compound Having Polymerizable Double Bond A compound having a polymerizable double bond may be used in the thermosetting composition of the present invention. 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.

Among the compounds having a polymerizable double bond, specific examples of compounds having two polymerizable double bonds per molecule 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 Glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, epichlorohydrin-modified propylene glycol di(meth)acrylate, epichlorohydrin-modified dipropylene glycol di(meth)acrylate, epichlorohydrin-modified tripropylene glycol di(meth)acrylate, epichlorohydrin-modified tetra Propylene 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 (meth)acrylates, methoxylated cyclohexyl di(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol hydroxypivalate di(meth)acrylate, caprolactone-modified neopentyl glycol hydroxypivalate di(meth)acrylate, stearin acid-modified pentaerythritol di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, bis[(meth)acryloxyneopentylglycol]adipate, bisphenol A di(meth)acrylate, ethylene oxide-modified bisphenol A di(meth)acrylate, Bisphenol F di(meth)acrylate, ethyleneoxy de-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-butylene glycol di(meth) Acrylates, dicyclopentanyl diacrylate, ethylene oxide-modified phosphate di(meth)acrylate, caprolactone/ethylene oxide-modified phosphate di(meth)acrylate, epichlorohydrin-modified phthalate di(meth)acrylate, tetrabromobisphenol A di(meth)acrylate , triglycerol di(meth)acrylate, neopentyl glycol-modified trimethylolpropane di(meth)acrylate, and isocyanuric acid ethylene oxide-modified diacrylate.

Among the compounds having polymerizable double bonds, specific examples of compounds having 3 or more polymerizable double bonds per molecule include trimethylolpropane tri(meth)acrylate and 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 phosphate tri(meth)acrylate, caprolactone/ethylene oxide-modified phosphate tri(meth)acrylate, caprolactone-modified tris[(meth)acryloxyethyl]isocyanurate, ditrimethylolpropane tetra( meth)acrylate, diglycerin tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, and alkyl-modified dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, alkyl-modified dipentaerythritol penta(meth)acrylate Acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, isocyanuric acid ethylene oxide-modified triacrylate, and carboxyl group-containing polyfunctional (meth)acrylate can be mentioned.

As the compound having a polymerizable double bond, the above compounds may be used alone, or two or more of them may be mixed and used.

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

The content of the compound having a polymerizable double bond is the polyamic acid (A ) is 1 to 60 parts by weight per 100 parts by weight. It is preferably 1 to 20 parts by weight when more emphasis is placed on the orientation ability.

2-3-2. Surfactant To the thermosetting composition of the present invention, an anionic, cationic, nonionic, fluorine-based or silicon-based leveling agent/surfactant may be added in order to improve coating uniformity.

Specific examples of surfactants include Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (both trade names; Kyoeisha Chemical Co., Ltd.), Disperbyk-161, Disperbyk-162, Disperbyk-163, Disperbyk-164, Disperbyk-166, Disperbyk-170, Disperbyk-180, Disperbyk-181, Disperbyk-182, BYK-300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-342, BYK-346, BYK-361N, BYK-3560, BYK-UV3500, BYK-UV3570 (all trade names: BYK-Chemie Japan Co., Ltd.), KP-341, KP-368, KP-96-50CS, KP-50-100CS (all trade names; Shin-Etsu Chemical Co., Ltd.), Surflon S611 (trade name; AGC Seimi Chemical ( Ltd.), Futergent 222F, Futergent 208G, Futergent 251, Futergent 710FL, Futergent 710FM, Futergent 710FS, Futergent 601AD, Futergent 650A, FTX-218 (all trade names; Neos Co., Ltd.) , Megafuck F-410, Megafuck F-430, Megafuck F-444, Megafuck F-472SF, Megafuck F-475, Megafuck F-477, Megafuck F-552, Megafuck F-553, Mega Fac F-554, Megafac F-555, Megafac F-556, Megafac F-558, Megafac F-559, Megafac R-94, Megafac RS-75, Megafac RS-72-K, Mega Fac RS-76-NS, Megafac DS-21 (both trade names; DIC Corporation), TEGO Twin 4000, TEGO Twin 4100, TEGO Flow 370, TEGO Flow 375, TEGO Glide 440, TEGO Glide 450, TEGO Rad 2200N (both trade names; Evonik Japan Co., Ltd.), fluoroalkylbenzenesulfonate, fluoroalkylcarboxylate, fluoroalkylpolyoxyethylene ether, fluoroalkylammonium iodide, fluoroalkylbetaine, fluoroalkylsulfonate, di Glycerin tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl tri methylammonium salt, fluoroalkylaminosulfonate, 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 laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate ate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkyl benzene sulfonate, and alkyl diphenyl ether disulfonic acid Mention may be made of salt. One or more of these can be used.

Among these, from the viewpoint of high coating uniformity, BYK-306, BYK-342, BYK-346, BYK-361N, BYK-3560, KP-341, Surflon S611, Futergent 710FL, Futergent 710FM, Futergent 710FS , Futergent 650A, Megafac F-477, Megafac F-556, Megafac RS-72-K, Megafac DS-21, TEGO Twin 4000, TEGO Flow 375, Fluoroalkylbenzenesulfonate, Fluoroalkylcarboxylate , fluoroalkylpolyoxyethylene ethers, fluoroalkylsulfonates, fluoroalkyltrimethylammonium salts, and fluoroalkylaminosulfonates are preferred.

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 weight of the thermosetting composition.

2-3-3. Adhesion Improver The thermosetting composition of the present invention contains an adhesion improver such as a silane-based, aluminum-based or titanate-based coupling agent from the viewpoint of further improving the adhesion between the cured film to be formed and the substrate. may further contain.

Specific examples of adhesion improvers include 3-glycidyloxypropyldimethylethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. Examples include silane-based coupling agents such as silane and 3-mercaptopropyltrimethoxysilane, aluminum-based coupling agents such as acetoalkoxyaluminum diisopropylate, and titanate-based coupling agents such as tetraisopropylbis(dioctylphosphite) titanate. be able to.

Among these, 3-glycidyloxypropyltrimethoxysilane 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 contains a phenol antioxidant, a phosphorus antioxidant, a sulfur antioxidant, from the viewpoint of improving transparency and preventing yellowing of the cured film when exposed to high temperatures. Antioxidants such as antioxidants and amine antioxidants may further be contained. Among these, phenolic antioxidants are preferred from the viewpoint of stability.

Specific examples of phenolic antioxidants include tert-butylhydroquinone, butylhydroxytoluene, ANTAGE SP (trade name; Kawaguchi Chemical Industry Co., Ltd.), pentaerythritol tetrakis[3-(3,5-di-tert-butyl- 4-hydroxyphenyl)propionate], thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate, N,N'-(hexane-1,6-diyl)bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanamide], ethylenebis(oxyethylene)bis -(3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], Octyl-3,5-di-tert-butyl-4-hydroxy-hydro cinnamic acid, 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 (, 1,1,3-tris(2-methyl-4-hydroxy- 5-tert-butylphenyl)butane, 4,4′-butylidenebis(6-tert-butyl-3-methylphenol), 2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert acrylate) -butyl-5-methylbenzyl)phenyl, 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, 2,2′-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)propanoa [items] can be mentioned.

Among these, from the viewpoint of thermal stability, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylene bis [3-(3,5-di-tert-butyl -4-hydroxyphenyl)propionate] is more preferred. From the viewpoint of solubility, butylhydroxytoluene and octyl-3,5-di-tert-butyl-4-hydroxy-hydrocalcinic acid 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, per 100 parts by weight of polyamic acid (A).

2-4. Preparation of thermosetting composition
The thermosetting composition of the present invention comprises a polyamic acid (A), a solvent (B2), and optionally a curing agent (C), a compound having a polymerizable double bond, a surfactant, and an adhesion improver. , antioxidants, and other additives are selected and added, and they are uniformly mixed and dissolved.

2-5. Storage of Thermosetting Composition The thermosetting composition of the present invention is preferably stored at -30° C. to 25° C. because the composition has good stability over time. -20°C to 10°C is more preferred.

3. Cured Film Obtained from Thermosetting Composition The thermosetting composition prepared as described above is coated on a substrate surface by a conventionally known coating method such as a spin coating method, a roll coating method, a dipping method, and a slit coating method. can be applied to form a coating film. Next, this coating film is preliminarily baked on a hot plate, an oven, or the like, and then subjected to main baking to harden the coating film, whereby a cured film can be obtained. It is also preferable to add a step of partially removing the solvent by reducing the pressure before the calcination. Then, alignment ability is imparted by performing an alignment treatment using a rubbing method. Rubbing can be performed by a known method.

The calcination conditions vary depending on the type and blending ratio of each component, but are generally 1 to 15 minutes on a hot plate at 60 to 100° C. or in an oven. The main baking conditions vary depending on the type and blending ratio of each component, but are usually on a hot plate at 120 to 250° C. or in an oven for 5 to 90 minutes.

When the thermosetting composition contains a curing agent, a cross-linking 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 cured film is very tough.

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

EXAMPLES Next, the present invention will be specifically described by synthesis examples, examples and comparative examples, but the present invention is not limited by these examples.

For the abbreviations used in the examples, the corresponding compound names, trade names, etc. are described below.
<Solvent>
GBL: γ-butyrolactone ECa: diethylene glycol monoethyl ether acetate BCS: ethylene glycol monobutyl ether PGME: propylene glycol monomethyl ether EDM: diethylene glycol ethyl methyl ether 3MP: methyl 3-methoxypropionate <tetracarboxylic dianhydride>
BT-100: 1,2,3,4-butanetetracarboxylic dianhydride (Likacid BT-100; trade name; Shin Nippon Chemical Co., Ltd.)
ODPA: 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride <diamine>
DDS: 4,4'-diaminodiphenylsulfone 1,3-BAC: 1,3-bisaminomethylcyclohexane NBDA: bis(aminomethyl)norbornane (trade name; Mitsui Chemicals Fine Co., Ltd.)
BAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]propane <end blocking agent>
BzOH: benzyl alcohol TMA: trimellitic anhydride <curing agent>
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; Toagosei Co., Ltd.)
M402: Dipentaerythritol pentaacrylate (Aronix M-402; trade name; Toagosei Co., Ltd.)
S510: 3-glycidyloxypropyltrimethoxysilane (Sila Ace S510; trade name; JNC Corporation)
BHT: Butyl hydroxytoluene F-477: Megafac F-477 (trade name; DIC Corporation)
TEGO Flow 375: TEGO Flow 375 (trade name; Evonik Japan Co., Ltd.)
BYK-3560: BYK-3560 (trade name; BYK-Chemie Japan Co., Ltd.)
BYK-361N: BYK-361N (trade name; BYK-Chemie Japan Co., Ltd.)
DS-21: Megafac DS-21 (trade name; DIC Corporation)

Abbreviations of measurement items in the examples are shown below.
Mw: weight average molecular weight Mn: number average molecular weight DOP: flattening ratio

The Mw and Mn of the polyamic acid were measured by the GPC method using a 2695 separation module/2414 differential refractometer (manufactured by Waters), and were determined by polystyrene conversion. The resulting polyamic acid was diluted with a phosphoric acid-DMF mixed solution (phosphoric acid/DMF=0.6/100: weight ratio) so that the polyamic acid concentration was about 1% by weight. HSPgel RT MB-M (manufactured by Waters) was used as a column, and the mixed solution was used as a developing agent, and measurement was performed under conditions of a column temperature of 50° C. and a flow rate of 0.40 mL/min. As standard polystyrene, TSK standard polystyrene manufactured by Tosoh Corporation was used.

Next, the apparatus and analysis conditions used in the examples are shown.
<GPC>
Apparatus: Waters 2695 separation module/2414 differential refractometer Solvent: phosphoric acid-DMF mixed solution (phosphoric acid/DMF=0.6/100 weight ratio)
Flow rate: 0.40 mL/min
Column temperature: 50°C
Column used: HSPgel RT MB-M manufactured by Waters
Standard sample for calibration curve: TSK standard polystyrene <spinner> manufactured by Tosoh Corporation
Apparatus: MS-A150 manufactured by Mikasa Co., Ltd.
<Viscosity measurement>
Apparatus: E-type viscometer "TV-22" (trade name) manufactured by Toki Sangyo Co., Ltd.
Measurement method: According to JIS C 2103 Section 5.3.
Measurement temperature: 25°C
<Film thickness measurement>
Apparatus: KLA-Tencor Japan Co., Ltd. stylus type film thickness gauge P-16 (trade name)
Measurement method: Measured at three locations, and the average value was taken as the film thickness.
<Transmittance measurement>
Apparatus: UV-visible spectrophotometer V-670 (trade name) manufactured by JASCO Corporation
<Voltage holding rate measurement>
Apparatus: Model 6254 liquid crystal physical property evaluation apparatus manufactured by Toyo Technica Co., Ltd. (trade name)
Pulse voltage gate width: 60 μs
Frequency: 3Hz
Peak value: 1V
Measurement temperature: 60°C

[Synthesis of polyamic acid]
[Synthesis Example 1] Synthesis of polyamic acid (A1) BT-100 (27.94 g; 141.02 mmol), 1,3- BAC (20.06 g; 141.02 mmol) and GBL (144.00 g) were added at room temperature. The reaction vessel was heated in an oil bath maintained at 85° C. for 2 hours, and it was confirmed that the contents in the reaction vessel were dissolved. After cooling to room temperature, BCS (48.00 g) was added and stirred at 85° C. for 5 hours. After cooling to room temperature, a uniform, transparent solution of polyamic acid (A1) having a solid concentration of 20.0% was obtained. Polyamic acid (A1) has an Mw of 10,700 and an Mn of 9,900. This solution (hereinafter referred to as SA1) was used as it was for preparing a thermosetting composition.

[Synthesis Example 2] Synthesis of polyamic acid (A2) Tetracarboxylic dianhydride and diamine were combined with BT-100 (27.46 g; 138.60 mmol) and 1,3-BAC (9.86 g; 69.31 mmol). The reaction was carried out in the same manner as in Synthesis Example 1, except that NBDA (10.69 g; 69.30 mmol) was used. After cooling to room temperature, a homogeneous, transparent solution of polyamic acid (A2) with a solids concentration of 20.0% was obtained. Polyamic acid (A2) has an Mw of 11,700 and an Mn of 10,800. This solution (hereinafter referred to as SA2) was used as it was for preparing a thermosetting composition.

[Synthesis Example 3] Synthesis of polyamic acid (A3) Except for changing tetracarboxylic dianhydride and diamine to BT-100 (26.99 g; 136.22 mmol) and NBDA (21.01 g; 136.20 mmol) A reaction was carried out in the same manner as in Synthesis Example 1. After cooling to room temperature, a homogeneous, transparent solution of polyamic acid (A3) with a solids concentration of 20.0% was obtained. Polyamic acid (A3) has an Mw of 15,300 and an Mn of 13,000. This solution (hereinafter referred to as SA3) was used as it was for preparing a thermosetting composition.

[Synthesis Example 4] Synthesis of polyamic acid (A4) In a 500 mL four-necked separable flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, BT-100 (41.91 g; 211.53 mmol), 1,3- BAC (30.09 g; 211.53 mmol) and GBL (126.00 g) were added at room temperature. The reaction vessel was heated in an oil bath maintained at 110° C. for 2 hours, and it was confirmed that the contents in the reaction vessel were dissolved. After cooling to room temperature, PGME (42.00 g) was added and stirred at 110° C. for 5 hours. After cooling to room temperature, a uniform, transparent solution of polyamic acid (A4) having a solid concentration of 30.0% was obtained. Polyamic acid (A4) has an Mw of 11,200 and an Mn of 10,400. This solution (hereinafter referred to as SA4) was used as it was for preparing a thermosetting composition.

[Synthesis Example 5] Synthesis of polyamic acid (A5) Tetracarboxylic dianhydride and diamine were combined with BT-100 (41.55 g; 209.66 mmol), 1,3-BAC (22.37 g; 157.26 mmol). The reaction was carried out in the same manner as in Synthesis Example 4, except that NBDA (8.09 g; 52.44 mmol) was used. After cooling to room temperature, a homogeneous, transparent solution of polyamic acid (A5) with a solids concentration of 30.0% was obtained. Polyamic acid (A5) has an Mw of 11,000 and an Mn of 10,300. This solution (hereinafter referred to as SA5) was used as it was for preparing a thermosetting composition.

[Synthesis Example 6] Synthesis of polyamic acid (A6) Tetracarboxylic dianhydride and diamine were combined with BT-100 (41.18 g; 207.84 mmol) and 1,3-BAC (14.78 g; 103.90 mmol). The reaction was carried out in the same manner as in Synthesis Example 4, except that NBDA (16.03 g; 103.92 mmol) was used. After cooling to room temperature, a homogeneous, transparent solution of polyamic acid (A6) with a solids concentration of 30.0% was obtained. Polyamic acid (A6) has an Mw of 11,100 and an Mn of 10,400. This solution (hereinafter referred to as SA6) was used as it was for preparing a thermosetting composition.

[Synthesis Example 7] Synthesis of polyamic acid (A7) Tetracarboxylic dianhydride and diamine were combined with BT-100 (40.83 g; 206.08 mmol) and 1,3-BAC (7.33 g; 51.53 mmol). The reaction was carried out in the same manner as in Synthesis Example 4, except that NBDA (23.84 g; 154.54 mmol) was used. After cooling to room temperature, a homogeneous, transparent solution of polyamic acid (A7) with a solids concentration of 30.0% was obtained. Polyamic acid (A7) has an Mw of 11,000 and an Mn of 10,400. This solution (hereinafter referred to as SA7) was used as it was for preparing a thermosetting composition.

[Synthesis Example 8] Synthesis of polyamic acid (A8) Tetracarboxylic dianhydride and diamine were changed to BT-100 (40.48 g; 204.31 mmol) and NBDA (31.52 g; 204.33 mmol) A reaction was carried out in the same manner as in Synthesis Example 4. After cooling to room temperature, a homogeneous, transparent solution of polyamic acid (A8) with a solids concentration of 30.0% was obtained. Polyamic acid (A8) has an Mw of 11,000 and an Mn of 10,300. This solution (hereinafter referred to as SA8) was used as it was for preparing a thermosetting composition.

[Synthetic Example 9] Synthesis of polyamic acid (A9) BAC (14.44 g; 101.51 mmol), NBDA (15.66 g; 101.52 mmol) and GBL (126.00 g) were added at room temperature. The reaction vessel was heated in an oil bath maintained at 110° C. for 2 hours, and it was confirmed that the contents in the reaction vessel were dissolved. After cooling to room temperature, PGME (42.00 g) was added and stirred at 110° C. for 5 hours. After cooling to room temperature, BzOH (0.88 g; 8.14 mmol) was added, the reaction was stirred for 2 hours at room temperature, and a uniform transparent solution of polyamic acid (A9) with a solid concentration of 30.0% was prepared. Obtained. Polyamic acid (A9) has an Mw of 11,100 and an Mn of 10,300. This solution (hereinafter referred to as SA9) was used as it was for preparing a thermosetting composition.

[Synthesis Example 10] Synthesis of polyamic acid (A10) Tetracarboxylic dianhydride and diamine were changed to BT-100 (40.34 g; 203.60 mmol), NBDA (30.79 g; 199.60 mmol), and the terminal A reaction was carried out in the same manner as in Synthesis Example 9, except that the sealing agent was changed to BzOH (0.86 g; 7.95 mmol). A uniform, transparent solution of polyamic acid (A10) having a solid concentration of 30.0% was obtained. Polyamic acid (A10) has an Mw of 11,000 and an Mn of 10,300. This solution (hereinafter referred to as SA10) was used as it was for preparing a thermosetting composition.

[Synthesis Example 11] Synthesis of polyamic acid (A11) Tetracarboxylic dianhydride and diamine were combined with BT-100 (41.10 g; 207.44 mmol), 1,3-BAC (14.46 g; 101.65 mmol). A reaction was carried out in the same manner as in Synthesis Example 9, except that NBDA (15.68 g; 101.65 mmol) was used and the terminal blocking agent was changed to aniline (0.76 g; 8.16 mmol). A uniform, transparent solution of polyamic acid (A11) having a solid concentration of 30.0% was obtained. Polyamic acid (A11) has an Mw of 10,700 and an Mn of 10,000. This solution (hereinafter referred to as SA11) was used as it was for preparing a thermosetting composition.

[Synthesis Example 12] Synthesis of polyamic acid (A12) Tetracarboxylic dianhydride and diamine were changed to BT-100 (40.41 g; 203.96 mmol), NBDA (30.85 g; 199.99 mmol), and the terminal A reaction was carried out in the same manner as in Synthesis Example 9, except that the sealing agent was changed to aniline (0.74 g; 7.94 mmol). A uniform, transparent solution of polyamic acid (A12) having a solid concentration of 30.0% was obtained. Polyamic acid (A12) has an Mw of 11,400 and an Mn of 10,600. This solution (hereinafter referred to as SA12) was used as it was for preparing a thermosetting composition.

[Synthesis Example 13] Synthesis of polyamic acid (A13) Tetracarboxylic dianhydride and diamine were combined with BT-100 (40.40 g; 203.91 mmol), 1,3-BAC (14.79 g; 103.97 mmol). A reaction was carried out in the same manner as in Synthesis Example 9, except that NBDA (16.04 g; 103.98 mmol) was used and the terminal blocking agent was changed to TMA (1.54 g; 8.02 mmol). A uniform, transparent solution of polyamic acid (A13) having a solid concentration of 30.0% was obtained. Polyamic acid (A13) has an Mw of 11,200 and an Mn of 10,400. This solution (hereinafter referred to as SA13) was used as it was for preparing a thermosetting composition.

[Synthesis Example 14] Synthesis of polyamic acid (A14) Tetracarboxylic dianhydride and diamine were changed to BT-100 (39.71 g; 200.42 mmol), NBDA (31.54 g; 204.46 mmol), and the terminal A reaction was carried out in the same manner as in Synthesis Example 9, except that the sealing agent was changed to TMA (1.54 g; 8.02 mmol). A uniform, transparent solution of polyamic acid (A14) having a solid concentration of 30.0% was obtained. Polyamic acid (A14) has an Mw of 11,100 and an Mn of 10,300. This solution (hereinafter referred to as SA14) was used as it was for preparing a thermosetting composition.

[Synthesis Example 15] Synthesis of polyamic acid (A15) Tetracarboxylic dianhydride and diamine were mixed with BT-100 (36.44 g; 183.90 mmol), ODPA (6.34 g; 20.43 mmol), NBDA (31. 52 g; After cooling to room temperature, a homogeneous, transparent solution of polyamic acid (A15) with a solids concentration of 30.0% was obtained. Polyamic acid (A15) has an Mw of 9,200 and an Mn of 8,900. This solution (hereinafter referred to as SA15) was used as it was for preparing a thermosetting composition.

[Comparative Synthesis Example 1] Synthesis of polyamic acid (A16) ODPA (26.66 g; 85.94 mmol) and DDS (21.34 g) were added to a 500 mL four-necked separable flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube. ; 85.94 mmol) and GBL (144.00 g) were added at room temperature and stirred for 1 hour to confirm that the contents in the reaction vessel had dissolved. ECa (48.00 g) was added, the reaction vessel was stirred in an oil bath maintained at 80° C. for an additional hour, cooled to room temperature, and homogenous, transparent polyamic acid (A16 ) was obtained. Polyamic acid (A16) has an Mw of 8,200 and an Mn of 3,100. This solution (hereinafter referred to as SA16) was used as it was for preparing a thermosetting composition.

[Comparative Synthesis Example 2] Synthesis of polyamic acid (A17) Tetracarboxylic dianhydride and diamine were mixed with ODPA (14.82 g; 47.77 mmol), BT-100 (9.46 g; 47.75 mmol), DDS (23 .72 g; 95.53 mmol), and the reaction was carried out in the same manner as in Comparative Synthesis Example 1 except that the solvent was changed to GBL (126.00 g) and BCS (42.00 g). After cooling to room temperature, a homogeneous, transparent solution of polyamic acid (A17) with a solids concentration of 20.0% was obtained. Polyamic acid (A17) has an Mw of 31,100 and an Mn of 22,000. This solution (hereinafter referred to as SA17) was used as it was for preparing a thermosetting composition.

[Comparative Synthesis Example 3] Synthesis of polyamic acid (A18) Tetracarboxylic dianhydride and diamine, BT-100 (31.95 g; 161.26 mmol), DDS (40.05 g; 161.29 mmol), solvent GBL (126.00 g) and BCS (42.00 g) were used for the same reaction as in Comparative Synthesis Example 2. After cooling to room temperature, a homogeneous, transparent solution of polyamic acid (A18) with a solids concentration of 20.0% was obtained. Polyamic acid (A18) has an Mw of 21,400 and an Mn of 8,100. This solution (hereinafter referred to as SA18) was used as it was for preparing a thermosetting composition.

[Comparative Synthesis Example 4] Synthesis of polyamic acid (A19) Except for changing tetracarboxylic dianhydride and diamine to BT-100 (15.63 g; 78.89 mmol) and BAPP (32.37 g; 78.85 mmol) was reacted in the same manner as in Comparative Synthesis Example 2. After cooling to room temperature, a homogeneous, transparent solution of polyamic acid (A19) with a solids concentration of 20.0% was obtained. Polyamic acid (A19) has an Mw of 21,300 and an Mn of 16,000. This solution (hereinafter referred to as SA19) was used as it was for preparing a thermosetting composition.

[Comparative Synthesis Example 5] Synthesis of polyamic acid (A20) In a 500 mL four-necked separable flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, ODPA (18.78 g; 60.54 mmol), BT-100 (12 .00 g; 60.57 mmol), 1,3-BAC (17.22 g; 121.05 mmol) and GBL (144.00 g) were added at room temperature and the reaction vessel was stirred in an oil bath maintained at 85° C. for 2 hours. did. It was confirmed that the contents in the reaction vessel had dissolved. The temperature was returned to room temperature, BCS (48.00 g) was added, and the mixture was further stirred in an oil bath maintained at 85°C for 5 hours. Since precipitates were generated during cooling, the desired polyamic acid (A20) could not be obtained.

[Comparative Synthesis Example 6] Synthesis of polyamic acid (A21) Tetracarboxylic dianhydride and diamine were mixed with ODPA (18.23 g; 58.76 mmol), BT-100 (11.64 g; 58.75 mmol) and NBDA (18 13 g; could not get

[Comparative Synthesis Example 7] Synthesis of polyamic acid (A22) Tetracarboxylic dianhydride and diamine were mixed with BT-100 (31.42 g; 158.58 mmol), ODPA (12.30 g; 39.64 mmol), NBDA (30 .58 g; After cooling to room temperature, a homogeneous, transparent solution of polyamic acid (A22) with a solids concentration of 30.0% was obtained. Polyamic acid (A22) has an Mw of 9,400 and an Mn of 9,000. This solution (hereinafter referred to as SA22) was used as it was for preparing a thermosetting composition.

Tables 1-1 to 1-3 show the tetracarboxylic dianhydrides, diamines, terminal blocking agents used in each synthesis, the reaction solvent used, the solubility of the resulting polyamic acid, Mw, Mn, Mw /Mn. The numbers in square brackets in Tables 1-1 to 1-3 represent the molar fractions of the raw materials introduced. For example, in the case of Synthesis Example 1, each raw material was weighed and added so that 100 mol % of diamine 1,3-BAC would be 100 mol % with respect to 100 mol % of tetracarboxylic dianhydride. In the solubility column, 〇 indicates that uniform and transparent polyamic acid was obtained, and × indicates that the content did not dissolve and polymer was not obtained, or polyamic acid did not dissolve due to precipitation. was described.

[Preparation of thermosetting composition]
[Preparation Example 1]
After mixing and dissolving polyamic acid solution (SA1) (10.0000 g), 1,3-PBO (0.0600 g), F-477 (0.0092 g), BCS (12.2445 g) and GBL (39.0705 g) A composition 1 was obtained by filtering through a fluororesin membrane filter (0.5 μm).

[Preparation Example 2]
Preparation and filtration were carried out in the same manner as in Preparation Example 1, except that the polyamic acid solution (SA1) was changed to the polyamic acid solution (SA2) to obtain a composition 2.

[Preparation Example 3]
Preparation and filtration were performed in the same manner as in Preparation Example 1, except that the polyamic acid solution (SA1) was changed to the polyamic acid solution (SA3) to obtain composition 3.

[Preparation Example 4]
Preparation and filtration were carried out in the same manner as in Preparation Example 1, except that the polyamic acid solution (SA1) was changed to the polyamic acid solution (SA4) to obtain a composition 4.

[Preparation Example 5]
Preparation and filtration were carried out in the same manner as in Preparation Example 1, except that the polyamic acid solution (SA1) was changed to the polyamic acid solution (SA5) to obtain composition 5.

[Preparation Example 6]
Preparation and filtration were carried out in the same manner as in Preparation Example 1, except that the polyamic acid solution (SA1) was changed to the polyamic acid solution (SA6) to obtain composition 6.

[Preparation Example 7]
Preparation and filtration were carried out in the same manner as in Preparation Example 1, except that the polyamic acid solution (SA1) was changed to the polyamic acid solution (SA7) to obtain composition 7.

[Preparation Example 8]
Preparation and filtration were carried out in the same manner as in Preparation Example 1, except that the polyamic acid solution (SA1) was changed to the polyamic acid solution (SA8) to obtain composition 8.

[Preparation Example 9]
Preparation and filtration were carried out in the same manner as in Preparation Example 1, except that the polyamic acid solution (SA1) was changed to the polyamic acid solution (SA9) to obtain composition 9.

[Preparation Example 10]
Preparation and filtration were carried out in the same manner as in Preparation Example 1, except that the polyamic acid solution (SA1) was changed to the polyamic acid solution (SA10) to obtain composition 10.

[Preparation Example 11]
Preparation and filtration were carried out in the same manner as in Preparation Example 1, except that the polyamic acid solution (SA1) was changed to the polyamic acid solution (SA11) to obtain composition 11.

[Preparation Example 12]
Polyamic acid solution (SA8) (10.0000 g), 1,3-PBO (0.0600 g), F-477 (0.0561 g), PGME (12.5117 g), GBL (31.7552 g) and EDM (7. 9388 g) were mixed and dissolved, and the mixture was filtered through a fluororesin membrane filter (0.5 μm) to obtain composition 12.

[Preparation Example 13]
Prepared in the same manner as in Preparation Example 12 except that the additive F-477 was changed to TEGO Flow 375 (0.0092 g) and the solvent was changed to PGME (12.2445 g), GBL (31.2564 g) and EDM (7.8141 g). After filtration, composition 13 was obtained.

[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 (0.0278 g) and the solvent was changed to BCS (12.3504 g) and GBL (39.3176 g). 14 was obtained.

[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 (0.0278 g), 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 (0.0278 g), to obtain composition 16.

[Preparation Example 17]
Polyamic acid solution (SA8) (10.0000 g), TGDDE (0.6000 g), F-477 (0.0101 g), S510 (0.1500 g), BHT (0.0600 g), BCS (13.9596 g) and GBL (43.0725 g) were mixed and dissolved, and then filtered through a fluororesin membrane filter (0.5 μm) to obtain composition 17.

[Preparation Example 18]
Polyamic acid solution (SA8) (10.0000 g), 1,3-PBO (0.1500 g), M208 (0.3000 g), F-477 (0.0106 g), BHT (0.0600 g), BCS (14. 8172 g) and GBL (45.0735 g) were mixed and dissolved, and filtered through a fluororesin membrane filter (0.5 μm) to obtain composition 18.

[Preparation Example 19]
Preparation and filtration were carried out in the same manner as in Preparation Example 18, except that additive M208 was changed to M402 (0.3000 g), and composition 19 was obtained.

[Preparation Example 20]
Polyamic acid solution (SA6) (10.0000 g), 1,3-PBO (0.1500 g), F-477 (0.0106 g), S510 (0.1500 g), BHT (0.0600 g), PGME (13. 9596 g) and GBL (43.0725 g) were mixed and dissolved, and then filtered through a fluororesin membrane filter (0.5 μm) to obtain composition 20.

[Preparation Example 21]
Polyamic acid solution (SA6) (10.0000 g), TGDDE (0.1500 g), F-477 (0.0101 g), S510 (0.1500 g), BHT (0.0600 g), PGME (13.9596 g) and GBL (43.0725 g) were mixed and dissolved, and then filtered through a fluororesin membrane filter (0.5 μm) to obtain composition 21.

[Preparation Example 22]
Polyamic acid solution (SA6) (10.0000 g), 1,3-PBO (0.1500 g), M208 (0.3000 g), F-477 (0.0106 g), BHT (0.0600 g), PGME (14. 8172 g) and GBL (45.0735 g) were mixed and dissolved, and filtered through a fluororesin membrane filter (0.5 μm) to obtain composition 22.

[Preparation Example 23]
Preparation and filtration were carried out in the same manner as in Preparation Example 22, except that additive M208 was changed to M402 (0.3000 g), to obtain composition 23.

[Preparation Example 24]
After mixing and dissolving polyamic acid solution (SA15) (10.0000 g), 1,3-PBO (0.0600 g), F-477 (0.0092 g), PGME (14.8172 g) and GBL (39.0705 g) A composition 24 was obtained by filtering through a fluororesin membrane filter (0.5 μm).

[Comparative Preparation Example 1]
Polyamic acid solution (SA16) (10.0000 g), 1,3-PBO (0.0400 g), F-477 (0.0061 g), BCS (4.7059 g), GBL (14.1176 g) and 3MP (11. 9565 g) were mixed and dissolved, and the mixture was filtered through a fluororesin membrane filter (0.5 μm) to obtain composition 25.

[Comparative Preparation Example 2]
Preparation and filtration were carried out in the same manner as in Comparative Preparation Example 1, except that the polyamic acid solution (SA16) was changed to the polyamic acid solution (SA17) to obtain composition 26.

[Comparative Preparation Example 3]
Preparation and filtration were carried out in the same manner as in Comparative Preparation Example 1, except that the polyamic acid solution (SA16) was changed to the polyamic acid solution (SA18) to obtain composition 27.

[Comparative Preparation Example 4]
Preparation and filtration were carried out in the same manner as in Comparative Preparation Example 1, except that the polyamic acid solution (SA16) was changed to the polyamic acid solution (SA19) to obtain composition 28.

[Comparative Preparation Example 5]
After mixing and dissolving polyamic acid solution (SA22) (10.0000 g), 1,3-PBO (0.0600 g), F-477 (0.0092 g), PGME (14.8172 g) and GBL (39.0705 g) A composition 29 was obtained by filtering through a fluororesin membrane filter (0.5 μm).

The components and proportions 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.

[Example 1] to [Example 24], [Comparative Example 1] to [Comparative Example 5]
Each of Compositions 1 to 29 obtained in the above preparation examples was subjected to various evaluations as follows.

<Transmittance measurement>
The thermosetting composition was coated on a Corning glass substrate "EAGLE XG" (trade name, thickness 0.7 mm) by adjusting the number of revolutions so that the film thickness was about 1.5 μm using a spin coater. applied. Next, the substrate coated with the composition was dried on a hot plate at 60°C for 3 minutes and then baked in an oven at 230°C for 30 minutes to prepare a test substrate having a cured film for transmittance measurement. , transmittance measurements were performed. The transmittance was evaluated for values at transmission wavelengths of 400 nm and 313 nm. At a transmission wavelength of 400 nm, a transmittance of 90% or more was indicated by ◯, and a transmittance of less than 90% was indicated by x. At a transmission wavelength of 313 nm, a transmittance of 80% or more was indicated by ◯, and a transmittance of less than 80% was indicated by x. The results are shown in Tables 3-1 to 3-5.

<Flatness evaluation>
The thermosetting composition was applied onto a color filter substrate (a substrate having patterned colored bodies of three colors of R, G, and B on a glass substrate) whose maximum level difference had been measured in advance. A spin coater was used for coating, and the number of revolutions was adjusted so that the film thickness was about 1.5 μm. Next, the substrate coated with the composition was dried on a hot plate at 60°C for 3 minutes and then baked in an oven at 230°C for 30 minutes to prepare a test substrate having a cured film for flatness evaluation. . The maximum step was measured for the resulting test substrate. Here, the maximum step is the maximum value of the surface steps of the substrate, and corresponds to the film thickness difference between the thickest and thinnest portions of the substrate.
Flatness was evaluated by flattening ratio (DOP). DOP was calculated as follows. The color filter substrate without cured film used had a maximum level difference of 1.0 μm.

DOP (%) = (t1-t2)/t2 x 100

t1 (μm): maximum step of color filter substrate without cured film t2 (μm): maximum step of test substrate with cured film

It can be said that the closer the planarization rate is to 100%, the better the planarity. A flattening rate of less than 60% was rated x, 60% or more and less than 70% was rated Δ, and 70% or more was rated ◯. The results are shown in Tables 3-1 to 3-5.

<Orientation evaluation>
A polymerizable liquid crystal composition solution used for evaluation was prepared in advance as follows.
20.00 g of Paliocolor LC242 (trade name; BASF Japan Ltd.), 1.00 g of IRGACURE907 (trade name; BASF Japan Ltd.), 0.020 g of BYK-361N, and toluene as a solvent are added. is adjusted to 85% by weight of the total, and mixed and dissolved uniformly. This composition is designated as a polymerizable liquid crystal composition solution (PLC-1).

Another cured film for transmittance measurement was prepared according to the above-described method for preparing a cured film for transmittance measurement. The obtained cured film for transmittance measurement was subjected to a rubbing treatment using a rubbing apparatus equipped with a rayon rubbing cloth YA-18-R (trade name; Yoshikawa Kako Co., Ltd.). The rubbing speed is 60 mm/sec and the roller rotation speed is 1,000 rpm. Next, a polymerizable liquid crystal composition solution (PLC-1) was applied onto the substrate with a spin coater, dried on a hot plate at 80° C. for 1 minute, and irradiated with 300 mJ/cm ² using an ultra-high pressure mercury lamp. gone. The exposure amount is a value measured using a 365 nm illuminance meter without using a cut filter and a polarizing plate. Furthermore, by post-baking in an oven at 230° C. for 30 minutes, a test substrate having a cured film for evaluation of orientation was prepared, and orientation was evaluated.

The obtained test substrate having the cured film for evaluation of orientation was sandwiched between two linear polarizing plates in the orthogonal (crossed Nicols) state in a direction parallel to the polarizing plates, and the optical anisotropy was measured while maintaining the direction parallel to the polarizing plates. Observation was performed by rotating the glass substrate with the body and irradiating the backlight from below. Rotate the test substrate having a cured film for evaluation of orientation and determine that there is orientation if light and darkness are observed, and indicate 〇 in Tables 3-1 to 3-5. It was determined that the compound had no orientation, and was marked with x in Tables 3-1 to 3-5.

<Voltage holding rate evaluation>
The thermosetting composition was applied to two glass substrates with ITO electrodes by a spinner method. After the coated substrate was dried by heating at 60° C. for 3 minutes, it was heat-treated in an oven at 230° C. for 30 minutes. A cured film having a thickness of about 100 nm formed by this heat treatment was rubbed (indentation: 0.3 mm, stage feed speed: 60 m/s, rotation speed: 1000 rpm, 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° C. for 30 minutes. After spraying a gap agent of 7 μm on one of the cured films, two substrates with cured films were placed facing each other so that the film surfaces of the cured films faced each other and the rubbing directions were anti-parallel. It was sealed with a curing agent to prepare an anti-parallel cell with a gap of 7 μm. A liquid crystal composition (LC-1) was injected into this cell, and the injection port was sealed with a photocurable sealant. Then, heat treatment was performed at 110° C. for 30 minutes to prepare a liquid crystal display element for voltage holding rate measurement.

（物性値）
Δε（誘電率異方性）：５．１
Δｎ（屈折率異方性）：０．０９３ The liquid crystal composition (LC-1) used was a composition obtained by mixing the following liquid crystal compounds in the stated weight ratio.

(Liquid crystal composition (LC-1))

(physical property value)
Δε (dielectric anisotropy): 5.1
Δn (refractive index anisotropy): 0.093

A voltage holding ratio (VHR) was measured using the obtained liquid crystal display element. The closer the voltage holding ratio value is to 100%, the better. A value of the voltage holding ratio of less than 70% was rated as x, a value of 70% or more and less than 90% was rated as Δ, and a value of 90% or more was rated as ◯. The results are shown in Tables 3-1 to 3-5.

Comparative Synthesis Examples 5 and 6 in Table 1-3 are difficult to dissolve in a mild solvent that does not contain NMP, and it was found that the raw material composition (combination and ratio of raw materials) of the present invention exhibits excellent solubility. rice field.

Comparative Synthesis Examples 1 to 4 yielded polyamic acids that were soluble in NMP-free mild solvents. However, as can be seen by comparing Tables 3-1 to 3-4 with Table 3-5, the properties such as transmittance and flatness are inferior to those of the cured film of the present invention. It was found that the cured film of the present invention not only exhibited stable alignment ability for liquid crystals or polymerizable liquid crystals, but also had much higher transmittance, especially at 313 nm, than the comparative example. It was also found that the flatness and voltage holding ratio were excellent.

ADVANTAGE OF THE INVENTION According to this invention, the cured film which has the high transmittance|permeability and the high voltage retention which has planarization ability and alignment ability can be provided.

Claims (7)

A polyamic acid obtained by reacting a raw material containing a tetracarboxylic dianhydride and a diamine,
In the tetracarboxylic dianhydride, the content of the aliphatic tetracarboxylic dianhydride represented by formula (1) is 90 mol% or more, and in the diamine, 1,3-bisaminomethylcyclohexane and bis Polyamic acid (A), wherein the content of at least one aliphatic diamine selected from the group consisting of (aminomethyl)norbornane is 90 mol% or more.

In formula (1), R ¹ , R ² , R ³ and R ⁴ are each independently H, CH ₃ or F. The polyamic acid (A) according to claim 1, wherein the raw material further contains a terminal blocking agent. A thermosetting composition comprising the polyamic acid (A) according to claim 1 or 2 and a solvent (B2). 4. A thermosetting composition according to claim 3, further comprising a curing agent (C). Furthermore, 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, according to claim 3 or 4. thermosetting composition. A cured film obtained by curing the thermosetting composition according to any one of claims 3 to 5. A liquid crystal display device 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.