JP7017126B2 - Curable composition - Google Patents

Description

The present invention relates to a curable composition that provides a color filter protective film having photoalignment, a cured film thereof, and a color filter substrate provided with the cured film.

The color filter substrate is provided in a display element for color display and the like. The color filter substrate is provided with R (red), G (green) and B (blue) colored bodies and a black matrix for preventing color mixing, and there is a step on the surface of the color filter substrate. A color that has the function of flattening the steps on the surface of the color filter substrate in order to equalize the cell gap of the liquid crystal display element in the plane and to equalize the film thickness of the optical functional film formed on the color filter substrate. A filter protective film is used. Further, in order to control the orientation direction of the liquid crystal molecules in the liquid crystal display element and to control the orientation direction of the polymerizable liquid crystal molecules when forming an optical functional film using the polymerizable liquid crystal composition, the liquid crystal is used. An alignment film having a function of controlling the orientation direction of the molecule is provided. In order to reduce the thickness and weight of the liquid crystal display element, an oriented color filter protective film having two functions performed by each of these two films has been developed.

Examples of the color filter protective film having orientation are the color filter protective film having rubbing orientation described in Patent Document 1 and the color filter protective film having photoorientity described in Patent Document 2. The former composition for providing a protective film is a curable composition containing a polyimide and an epoxy compound, and the former protective film orientation treatment method is a rubbing method. The composition that provides the latter protective film is a curable composition containing a polymer having a photo-oriented group such as a cinnamoyl group and a cross-linking group such as an epoxy group, and a cross-linking component that is polyesteramidic acid, and the latter orientation. The treatment is by irradiation with linearly polarized ultraviolet rays. In recent years, in order to improve the display quality of liquid crystal display elements, the alignment processing process is being replaced from the rubbing method, which causes static electricity due to direct contact with the film, to non-contact linearly polarized ultraviolet irradiation. , A color filter protective film having photo-orientation and a composition for providing the same are required.

However, in order to meet the needs for low power consumption and long life for display elements in recent years, the color filter protective film having photoalignment described in Patent Document 2 is required to have two characteristics improved. .. The first is to improve the transparency of the protective film for the purpose of improving the light transmission of the liquid crystal display element. The second is to improve the heat resistance of the protective film (reduce the amount of heat weight reduction during additional heat), with the aim of reducing the effect of degassing from the protective film on other members of the liquid crystal display element. be.

Further, as a composition used for forming a color filter protective film having photo-alignment property, it is conceivable to use a composition for a photo-alignment film (for example, Patent Document 3). However, the composition for a photoalignment film described in Patent Document 3 has high tackiness (the coating film obtained by applying the composition and removing the solvent for the composition tends to be sticky). Therefore, there is a problem that foreign matter adheres when the color filter protective film having photoalignment is formed, or the surface of the coating film is touched by an operator's finger to leave a mark. Further, when this composition for a photoalignment film is formed with a film thickness (for example, 100 nm) used as a normal photoalignment film, the flattening property is poor, and the film thickness used as a normal color filter protective film (for example, for example). Even when it is formed at 1.5 μm), there is a problem that the flatness is poor and the display quality of the liquid crystal display element is low.

From the above, the development of a curable composition which provides a cured film having high transparency, heat resistance and photoorientity, has low tackiness and high flattening property is awaited.

Japanese Patent Application Laid-Open No. 9-230364 JP-A-2014-84355 JP 2015-49419

To provide a curable composition having a cured film having high transparency, heat resistance and photoalignment, low tackiness and high flattening property, a cured film obtained from the cured film, and a color filter substrate provided with the cured film. ..

As a result of diligent studies to solve the above problems, the present inventors have obtained a curable composition containing an imide compound (A), a polyfunctional carboxyl compound (B) and a polyfunctional epoxy compound (C), which is an imide compound. (A) is a reaction product using an acid anhydride (a1) having a polymerizable double bond and an alkoxysilyl compound (a2) having an amino group as essential raw materials, and a polyfunctional carboxyl compound (B) per molecule. A curable composition which is a compound having three or more carboxyl groups, and the polyfunctional epoxy compound (C) is a compound having three or more epoxy groups per molecule, and a cured film obtained by curing the curable composition. As a result, it was found that the above object can be achieved, and the present invention has been completed.

[1] A curable composition containing an imide compound (A), a polyfunctional carboxyl compound (B) and a polyfunctional epoxy compound (C);
The imide compound (A) is a reaction product from a raw material that requires an acid anhydride (a1) having a polymerizable double bond and an alkoxysilyl compound (a2) having an amino group.
The polyfunctional carboxyl compound (B) is a compound having three or more carboxyl groups per molecule.
A curable composition, wherein the polyfunctional epoxy compound (C) is a compound having three or more epoxy groups per molecule.

[2] The imide compound (A) is 5 to 80% by weight in the total amount of 100% by weight of the imide compound (A), the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C);
Item 2. Curability according to item [1], wherein the polyfunctional carboxyl compound (B) is 20 to 80% by weight in a total amount of 100% by weight of the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C). Composition.

[3] The imide compound (A) is 15 to 60% by weight in the total amount of 100% by weight of the imide compound (A), the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C);
Item 2. Curability according to item [1], wherein the polyfunctional carboxyl compound (B) is 40 to 75% by weight in the total amount of 100% by weight of the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C). Composition.

式（１）中、Ｒ^１及びＲ^２はそれぞれ独立に水素又は炭素数１～５のアルキル基である。

式（２）中、Ｒ^３は水素又は炭素数１～５のアルキル基である。 [4] The acid anhydride (a1) having a polymerizable double bond is at least one selected from the compound represented by the following formula (1) and the compound represented by the following formula (2). The curable composition according to any one of [1] to [3].

In formula (1), R ¹ and R ² are independently hydrogen or an alkyl group having 1 to 5 carbon atoms, respectively.

In formula (2), R ³ is hydrogen or an alkyl group having 1 to 5 carbon atoms.

[5] The acid anhydride (a1) having a polymerizable double bond is at least one selected from maleic acid anhydride, citraconic acid anhydride and itaconic acid anhydride, [1] to [4]. The curable composition according to any one of the above items.

[6] The alkoxysilyl compound (a2) having an amino group is selected from 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-aminophenyltrimethoxysilane, and 4-aminophenyltriethoxysilane. The curable composition according to any one of [1] to [5], which is at least one thereof.

[7] The item according to any one of [1] to [6], wherein the polyfunctional carboxyl compound (B) is a polyesteramide acid containing a tetracarboxylic dianhydride, a diamine and a polyvalent hydroxy compound as essential raw materials. The curable composition according to description.

[8] A cured film obtained by curing the curable composition according to any one of [1] to [7].

[9] A color filter substrate provided with the cured film according to item [8].

The curable composition according to a preferred embodiment of the present invention is a curable composition that gives a cured film having high transparency, heat resistance and photoalignment, and has low tackiness and high flattening property. The cured film obtained from the curable composition can be used as a color filter protective film. The cured film has high transparency, the curable composition has high flattening property, and the curable composition has low tackiness, so that the adhesion of foreign matter is reduced when the cured film is formed. When the cured film is used as a color filter protective film, the display quality of the liquid crystal display element is high. Since the heat resistance of the cured film is high, the display element provided with the cured film has little influence on other members due to degassing from the cured film. Further, since the cured film has high photo-orientation, it is possible to control the orientation of the liquid crystal molecules without using the alignment film.

In the present specification, it may be referred to as "(meth) acrylic" to indicate one or both of "acrylic" and "methacrylic". Similarly, it may be referred to as "(meth) acrylate" to indicate one or both of "acrylate" and "methacrylate", and to indicate one or both of "acryloxy" and "methacryloxy". It may be written as "(meth) acrylicoxy".

<1. Curable composition of the present invention>
The curable composition of the present invention is a curable composition comprising an imide compound (A), a polyfunctional carboxyl compound (B) and a polyfunctional epoxy compound (C).

In the curable composition of the present invention, there are preferable compounding ratios of the imide compound (A), the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C). In order to obtain a cured film having high photoalignment, the blending ratio of the imide compound (A) in the total amount of 100% by weight of the imide compound (A), the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C) is 100% by weight. Is preferably 5% by weight or more, and more preferably 15% by weight or more. In order to obtain a curable composition having low tackiness and high flattening property, the imide in 100% by weight of the total amount of the imide compound (A), the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C). The compounding ratio of the compound (A) is preferably 80% by weight or less, more preferably 60% by weight or less. In order to obtain a cured film having high heat resistance and high photoalignment, the polyfunctional carboxyl compound (B) is blended in 100% by weight of the total amount of the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C). The ratio is preferably 20 to 80% by weight, more preferably 40 to 75% by weight.

In the present specification, the imide compound (A), the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C) may be collectively referred to as "main component", and the imide compound (A) and the polyfunctional carboxyl are used. The total amount of the compound (B) and the polyfunctional epoxy compound (C) may be referred to as "main component amount".

<1-1. Imid compound (A)>
The imide compound (A) used in the present invention is a reaction product from a raw material that requires an acid anhydride (a1) having a polymerizable double bond and an alkoxysilyl compound (a2) having an amino group.

With respect to the raw material of the imide compound (A), the preferable content ratio of the acid anhydride (a1) having a polymerizable double bond and the alkoxysilyl compound (a2) having an amino group is the acid anhydride having a polymerizable double bond (a2). The molar ratio (acid anhydride group / amino group) of the amino group of the acid anhydride group of a1) and the alkoxysilyl compound (a2) having an amino group is 0.8 or more and 1.2 or less, which is a more preferable content ratio. Is 0.9 or more and 1.1 or less. With this content ratio, the amount of exposure required to have photoalignment is small.

<1-1-1. Acid anhydride with polymerizable double bond (a1)>
In the present invention, an acid anhydride (a1) having a polymerizable double bond is used as a raw material for obtaining the imide compound (A).

Considering the availability of raw materials and the solubility of the obtained imide compound (A) in a solvent, the acid anhydride (a1) having a preferable polymerizable double bond is a compound represented by the following formula (1). And the compound represented by the following formula (2).

式（１）中、Ｒ^１及びＲ^２はそれぞれ独立に水素又は炭素数１～５のアルキル基である。

In formula (1), R ¹ and R ² are independently hydrogen or an alkyl group having 1 to 5 carbon atoms, respectively.

式（２）中、Ｒ^３は水素又は炭素数１～５のアルキル基である。

In formula (2), R ³ is hydrogen or an alkyl group having 1 to 5 carbon atoms.

In the above formula (1), it is preferable that R ¹ and R ² are independently hydrogen or methyl groups, respectively; both R ¹ and R ² are hydrogen (the compound represented by the formula (1) is It is more preferable that one of R ¹ and R ² is hydrogen and the other is a methyl group (the compound represented by the formula (1) is citraconic acid anhydride). ..

In the above formula (2), R ³ is preferably hydrogen or a methyl group; more preferably R ³ is hydrogen (the compound represented by the formula (2) is itaconic acid anhydride).

It is particularly preferable that the acid anhydride (a1) having a polymerizable double bond is a citraconic acid anhydride. Citraconic acid anhydride has low reactivity of the polymerizable double bond at the time of producing the imide compound (A), and the production of the imide compound (A) is easy.

<1-1-2. Alkoxysilyl compound having an amino group (a2)>
In the present invention, an alkoxysilyl compound (a2) having an amino group is used as a raw material for obtaining the imide compound (A).

Specific examples of the alkoxysilyl compound (a2) having an amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4--. Aminophenyltrimethoxysilane, 4-aminophenyltriethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, and 3- (2-aminoethylamino) propyltriethoxysilane. One or more of these can be used.

Considering the reactivity and the availability of raw materials, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, and 3-aminopropylmethyldiethoxysilane are preferable, and 3-aminopropylmethyldiethoxysilane is preferable. Aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane are more preferred.

<1-1-3. Method for synthesizing imide compound (A)>
The reaction method of the imide compound (A) is not particularly limited, but the reaction in a solution using a solvent is preferable. In the present specification, the solvent used for the synthesis for obtaining the imide compound (A) is simply referred to as "synthetic solvent". The acid anhydride (a1) having a polymerizable double bond and the alkoxysilyl compound (a2) having an amino group are easily reacted by stirring in a solution at room temperature to produce an amide acid. Since the temperature inside the system rises due to the heat of reaction when producing amic acid, it becomes easier to control the temperature inside the system by performing it in a solution.

Then, the amic acid is heated to imidize to obtain the imide compound (A). The obtained imide compound (A) has a group having a polymerizable double bond and an imide structure, and has an unreacted alkoxysilyl group.

The heating temperature for imidization is 60 to 150 ° C, preferably 80 to 130 ° C. A base catalyst may be added as an imidization catalyst. Examples of base catalysts are pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Further, a polymerization inhibitor may be used in combination for the purpose of suppressing the polymerization of the photopolymerizable group induced during this reaction. Examples of polymerization inhibitors are 2,2,6,6-tetramethylpiperidinyl-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1-oxyl, triphenylfeldadyl. , P-Methylphenol, hydroquinone, and dibutylhydroxytoluene.

The synthetic solvent is not particularly limited as long as it can dissolve the acid anhydride (a1) having a polymerizable double bond, the alkoxysilyl compound (a2) having an amino group, and the imide compound (A), which are raw materials. By selecting a solvent having a hydroxyl group as the synthetic solvent, it is possible to reduce the reaction rate of hydrolysis condensation of the alkoxysilyl moiety when synthesizing the imide compound (A).

In addition to selecting a solvent having a hydroxyl group as the synthetic solvent, by adjusting the concentration of the raw material and the heating temperature at the time of synthesis, the reaction rate of hydrolysis condensation of the alkoxysilyl moiety when synthesizing the imide compound (A) It is possible to control.

When the raw material is used at a high concentration in the synthesis and heated at a high temperature, the amic acid itself produced in the first reaction acts as an acid catalyst, and the alkoxysilyl group is hydrolyzed by the water produced by the imidization of the amid acid. Since it induces a reaction, it is possible to improve the molecular weight. The heating temperature during this reaction is preferably 100 to 150 ° C. Further, it is possible to further improve the molecular weight by adding an acid catalyst such as water and formic acid and further heating to distill off the low boiling point.

<1-1-4. Specific examples of synthetic solvents>
Specific examples of the synthetic solvent include diol compounds such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, and triethylene glycol;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (hereinafter abbreviated as "PGME"), propylene glycol monoethyl ether, propylene glycol monobutyl ether (hereinafter abbreviated as "PGBE"), butylene glycol Monoether form of diol compound such as monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether;
Diether of diol compounds such as ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether (hereinafter abbreviated as "EDM"), diethylene glycol butyl methyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, and triethylene glycol dimethyl ether. body;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (hereinafter abbreviated as "PGMEA"), propylene glycol monoethyl ether acetate, butylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether Monoether monoesters of diol compounds such as acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate;
Diesters of diol compounds such as ethylene glycol diacetate and propylene glycol diacetate;
Monoesters of monocarboxylic acid compounds such as butyl acetate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate;
Of monohydroxycarboxylic acid compounds such as methyl methoxyacetate, ethyl methoxyacetate, methyl 3-methoxypropionate (hereinafter abbreviated as "MMP"), ethyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 4-methoxybutyrate, etc. Monoether monoester;
Diesters of dicarboxylic acid compounds such as dimethyl succinate and diethyl succinate;
A monoamide compound of a monocarboxylic acid compound such as N, N-dimethylacetamide, N, N-dimethylpropionic acid;
Dialkyl ketone compounds such as methyl isobutyl ketone, methyl normal butyl ketone, diethyl ketone, ethyl isobutyl ketone, diisobutyl ketone, dinormal butyl ketone;
Cyclic ether compounds such as hexamethylene oxide and 1,4-dioxane;
Cyclic ester compounds such as β-propiolactone, γ-butyrolactone, δ-valerolactone;
Cyclic amide compounds such as 2-pyrrolidone and N-methyl-2-pyrrolidone;
Further, it is a cyclic ketone compound such as cyclopentanone (hereinafter abbreviated as “CPN”), cyclohexanone, and cycloheptanone. One or more of these can be used.

Among the specific examples of these polymerization solvents, the monoether compound of the diol compound, the diether compound of the diol compound, the monoether monoester compound of the diol compound, and the monoether monoester compound of the monohydroxycarboxylic acid compound are imide compounds (A). ) Is highly soluble and preferable.

<1-1-5. Molecular weight of imide compound (A)>
The weight average molecular weight of the obtained imide compound (A) is preferably 500 to 500,000, more preferably 1,000 to 50,000. Within these ranges, the compatibility of the imide compound (A) with the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C) becomes good.

The weight average molecular weight in the present specification is a value in terms of polystyrene obtained by the GPC method (column temperature: 35 ° C., flow rate: 1 mL / min). Standard polystyrene is polystyrene with a molecular weight of 645 to 132,900 (for example, polystyrene calibration kit PL2010-0102 from Agilent Technologies, Inc.), and PLgel MIXED-D (trade name, Agilent Technologies, Inc.) is used for the column. It can be measured using silicide as the mobile phase. In addition, the weight average molecular weight of the commercial product in this specification is a value published in the catalog.

<1-2. Polyfunctional carboxyl compound (B)>
The polyfunctional carboxyl compound (B) used in the present invention is a compound having three or more carboxyl groups per molecule.

An example of a preferred polyfunctional carboxyl compound (B) is a polyesteramidic acid (B1) obtained by reacting a tetracarboxylic acid dianhydride (b11), a diamine (b12), and a polyvalent hydroxy compound (b13) as essential raw materials. ). This compound is easy to obtain a raw material and produce a compound, and the curable composition containing the compound has good compatibility with the imide compound (A) and the polyfunctional epoxy compound (C).

<1-2-1. Polyester amidoic acid (B1)>
The polyesteramide acid (B1) used in the present invention is a reaction product obtained by reacting a tetracarboxylic dianhydride (b11), a diamine (b12), and a polyvalent hydroxy compound (b13) as essential raw materials. be. Further, in addition to these, one or more selected from the monohydric alcohol (b14) and the styrene-maleic anhydride copolymer (b15) may be added to the raw material.

In the method of adding the polyesteramidic acid (B1) to the curable composition of the present invention, the solution after the polymerization reaction may be added as it is, or the solution may be concentrated to remove the solid content and only the solid content may be added. ..

<1-2-1-1. Tetracarboxylic dianhydride (b11)>
Examples of the tetracarboxylic acid dianhydride (b11) used in the present invention are aromatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, and aliphatic tetracarboxylic acid dianhydride.

Specific examples of aromatic tetracarboxylic acid dianhydrides include 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2', 3,3'-benzophenone tetracarboxylic acid dianhydride, 2 , 3,3', 4'-benzophenone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 2,2', 3,3'-diphenylsulfone tetracarboxylic Acid dianhydride, 2,3,3', 4'-diphenylsulfone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic acid dianhydride, 2,2', 3,3 '-Diphenyl ether tetracarboxylic acid dianhydride, 2,3,3', 4'-diphenyl ether tetracarboxylic acid dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride , And ethylene glycol bis (anhydrotrimeritate); specific examples of alicyclic tetracarboxylic acid dianhydrides include cyclobutanetetracarboxylic acid dianhydride, methylcyclobutanetetracarboxylic acid dianhydride, cyclopentanetetracarboxylic acid. Acid dianhydride and cyclohexanetetracarboxylic acid dianhydride; specific examples of the aliphatic tetracarboxylic acid dianhydride are ethanetetracarboxylic acid dianhydride and butanetetracarboxylic acid dianhydride.

Among these, 3,3', 4,4'-diphenyl sulfone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic acid dianhydride, 2,2- [bis (3,) 4-Dicarboxyphenyl)] Hexafluoropropane dianhydride, ethylene glycol bis (anhydrotrimethylate), and butanetetracarboxylic acid dianhydride are preferred, with 3,3', 4,4'-diphenyl sulfone tetracarboxylic. Acid dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic acid dianhydride, and butane tetracarboxylic acid dianhydride are more preferred. A cured film obtained from a curable composition containing a polyesteramidic acid (B1) obtained from a raw material containing one or more selected from these has high transparency.

As the tetracarboxylic dianhydride (b11), the above compounds may be used alone, or two or more of them may be mixed and used.

<1-2-1-2. Diamine (b12)>
Examples of the diamine (b12) used in the present invention are a diamine having two benzene rings and a diamine having four benzene rings.

Specific examples of diamines having two benzene rings are 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, and 3,4'-diaminodiphenyl sulfone; diamines having four benzene rings. Specific examples are bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [3- (4-aminophenoxy) phenyl] sulfone, [4- ( 4-Aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] sulfone, [4- (3-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] sulfone, and 2,2-bis [4- (4-Aminophenoxy) phenyl] Hexafluoropropane.

Among these, 3,3'-diaminodiphenyl sulfone is preferable. The polyester amidoic acid (B1) obtained from the raw material containing this has good solubility in a solvent.

As the diamine (b12), the above compounds may be used alone, or two or more of them may be mixed and used.

<1-2-1-3. Multivalent hydroxy compound (b13)>
Specific examples of the polyvalent hydroxy compound (b13) used in the present invention include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a weight average molecular weight of 1,000 or less, propylene glycol, dipropylene glycol, and tripropylene. Glycol, tetrapropylene glycol, polypropylene glycol with a weight average molecular weight of 1,000 or less, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentane Diol, 2,4-Pentylene Diol, 1,2,5-Pentane Triol, 1,2-hexanediol, 1,6-Hexanediol, 2,5-hexanediol, 1,2,6-Hexanetriol, 1, 2-Heptanediol, 1,7-Heptanediol, 1,2,7-Heptanetriol, 1,2-octanediol, 1,8-octanediol, 3,6-octanediol, 1,2,8-octanetriol , 1,2-Nonandiol, 1,9-Nonandiol, 1,2,9-Nonantriol, 1,2-Decandiol, 1,10-Decandiol, 1,2,10-Decantriol, 1,2 -Dodecanediol, 1,12-dodecanediol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, bisphenol A, bisphenol S, bisphenol F, diethanolamine, and triethanolamine.

Among these, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol are preferable, and 1, 4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are more preferred. The polyester amic acid (B1) obtained from a raw material containing one or more selected from these has good solubility in a solvent.

As the multivalent hydroxy compound (b13), the above-mentioned compound may be used alone, or two or more of them may be mixed and used.

<1-2-1-4-1 Alcohol (b14)>
For the synthesis of polyesteramidic acid (B1), a monohydric alcohol (b14) may be further reacted in addition to the tetracarboxylic acid dianhydride (b11), a diamine (b12), and a polyvalent hydroxy compound (b13). ..

Specific examples of the monohydric alcohol (b14) include methanol, ethanol, 1-propanol, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and the like. Dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, phenol, borneol, maltor, linalol, terpineol, dimethylbenzyl carbinol, 3-ethyl-3-hydroxymethyloxetane Is.

Among these, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyloxetane are preferable, and benzyl alcohol is more preferable. The polyester amic acid (B1) obtained from a raw material containing one or more selected from these has good compatibility with the polyfunctional epoxy compound (C).

As the monohydric alcohol (b14), the above compounds may be used alone, or two or more of them may be mixed and used.

<1-2-1-5. Styrene-maleic anhydride copolymer (b15)>
For the synthesis of polyesteramidic acid (B1), in addition to tetracarboxylic acid dianhydride (b11), diamine (b12), and polyvalent hydroxy compound (b13), a styrene-maleic acid anhydride copolymer (b15) is used. It may be reacted.

By adding the styrene-maleic anhydride copolymer (b15), the compatibility of the polyesteramidic acid (B1) with the polyfunctional epoxy compound (C) can be improved. The molar ratio of styrene / maleic anhydride is 0.5-4, preferably 1-3, specifically about 1, about 2 or about 3, more preferably about 1 or about 2. About 1 is particularly preferable.

Specific examples of commercially available products of the styrene-maleic anhydride copolymer (b15) are SMA1000, SMA2000, and SMA3000 (all trade names, Kawahara Yuka Co., Ltd.). Among these, SMA1000, which has good solubility in a solvent, is preferable.

As the styrene-maleic anhydride copolymer (b15), the above compounds may be used alone or in combination of two or more.

<1-2-1-6. Polymerization method of polyester amic acid (B1)>
The polyester amidoic acid (B1) used in the present invention is produced by a known polymerization method (for example, described in JP-A-2015-163685). A preferred polymerization method is solution polymerization using a solvent used for the polymerization reaction (hereinafter referred to as "polymerization solvent").

<1-3. Polyfunctional epoxy compound (C)>
The polyfunctional epoxy compound (C) used in the present invention is a compound having three or more epoxy groups per molecule.

An example of the polyfunctional epoxy compound (C) used in the present invention is
Phenol novolak type epoxy compound, cresol novolak type epoxy compound, bisphenol A novolak type epoxy compound, biphenyl type polyfunctional epoxy compound, polyfunctional epoxy compound with siloxane binding site, 2- [4- (2,3-epoxypropoxy) phenyl ] -2- [4- [1,1-bis [4- (2,3-epoxypropoxy) phenyl] ethyl] phenyl] propane, 1,3-bis [4- [1- [4- (2,3) -Epoxypropoxy) phenyl] -1- [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol, and α-2, A compound having three or more glycidyl ether groups such as 3-epoxypropoxyphenyl-ω-hydropoly [2- (2,3-epoxypropoxy) benziliden-2,3-epoxypropoxyphenylene];
Compounds having three or more glycidyl ester groups, such as homopolymers of glycidyl methacrylate, copolymers of glycidyl methacrylate and polymerizable compounds other than glycidyl methacrylate; and
It is a compound having three or more oxylanyl groups such as 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol.

A curable composition containing a compound having 3 or more glycidyl ether groups gives a cured film having good heat resistance, and a curable composition containing a compound having 3 or more glycidyl ester groups gives a cured film having good heat resistance, even when the firing temperature is low. A curable composition containing a compound having three or more oxylanyl groups gives a cured film having good chemical resistance, and gives a cured film having good UV resistance.

Among compounds having three or more glycidyl ether groups, a bisphenol A novolak type epoxy compound that gives a cured film having particularly good heat resistance, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2,3-epoxypropoxy) phenyl] ethyl] phenyl] propane, 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl]- 1- [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol, and α-2,3-epoxypropoxyphenyl-ω -Hydropoly [2- (2,3-epoxypropoxy) benziliden-2,3-epoxypropoxyphenylene] is particularly preferred.

Specific examples of commercially available phenol novolac type epoxy compounds are EPPN-201 (trade name, Nippon Kayaku Co., Ltd.) and jER 152, 154 (both trade names, Mitsubishi Chemical Co., Ltd.); cresol novolac type epoxy. Specific examples of commercially available compounds are EOCN-102S, 103S, 104S, 1020 (all trade names, Nippon Kayaku Co., Ltd.); specific examples of commercially available bisphenol A novolak type epoxy compounds are jER 157S65, 157S70 (trade name, Mitsubishi Chemical Co., Ltd.); Specific examples of commercially available biphenyl-type polyfunctional epoxy compounds are NC-3000, NC-3000-L, NC-3000-H, NC-3100 (any of them). COATOSIL MP200 (trade name, Momentive Performance Materials Japan GK), Composelan SQ506, as a specific example of a commercially available polyfunctional epoxy compound having a siloxane binding site. (Product name, Arakawa Chemical Co., Ltd.), ES-1023 (Product name, Shinetsu Chemical Industry Co., Ltd.); 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1, 1-bis [4- (2,3-epoxypropoxy) phenyl] ethyl] phenyl] propane, and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- Specific examples of commercially available products containing [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol are TECHMORE VG3101L (trade name, Printech Co., Ltd.); Specific examples of commercially available products of α-2,3-epoxypropoxyphenyl-ω-hydropoly [2- (2,3-epoxypropoxy) benziliden-2,3-epoxypropoxyphenylene] are EPPN-501H, 502H (trade name, Nippon Kayaku Co., Ltd.); a specific example of a homopolymer of glycidyl methacrylate is Marproof G-01100 (trade name, Nikko Co., Ltd.); 2, A specific example of a commercially available product of a 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct of 2-bis (hydroxymethyl) -1-butanol is EHPE3150 (trade name, Daicel Co., Ltd.).

<1-4. Additive (D)>
The curable composition of the present invention may further contain the additive (D). The additive (D) arbitrarily added to the curable composition of the present invention has the characteristics of the curable composition of the present invention such as coating uniformity, adhesion, stability, chemical resistance, and low temperature curability. It is added from the viewpoint of improving.

Examples of the additive (D) are anionic, cationic, nonionic, and fluorine-based surfactants; silicone resin-based coatability improvers; adhesion improvers such as silane-based coupling agents; sodium polyacrylates. Anti-aggregation agents such as: Acrylic, styrene-based, polyethyleneimine-based, and urethane-based polymer dispersants; Antioxidants such as hindered phenols; Epoxy compounds other than polyfunctional epoxy compound (C), melamine compounds, etc. And a cross-linking agent such as a bisazide compound; a photoacid generator; a polyfunctional (meth) acrylate compound; and a photopolymerization initiator.

<1-4-1. Surfactant>
The curable composition of the present invention may further contain a surfactant from the viewpoint of further improving coating uniformity. Specific examples of the surfactant include Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (trade name, Kyoeisha Chemical Co., Ltd.), DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-166, DISPERBYK-170, DISPERBYK-180, DISPERBYK-181, DISPERBYK-182 -300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-342, BYK-346, BYK-361N, BYK-UV3500, BYK-UV3570 (all trade names, Big Chemie Japan Co., Ltd.) , KP-341, KP-368, KF-96-50CS, KF-50-100CS (trade name, Shin-Etsu Chemical Industry Co., Ltd.), Surflon S611 (trade name, AGC Seimi Chemical Co., Ltd.), Footer Gent 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-171 , Mega Fuck F-177, Mega Fuck F-410, Mega Fuck F-430, Mega Fuck F-444, Mega Fuck F-472SF, Mega Fuck F-475, Mega Fuck F-477, Mega Fuck F-552, Mega Fuck F-553, Mega Fuck F-554, Mega Fuck F-555, Mega Fuck F-556, Mega Fuck F-558, Mega Fuck F-559, Mega Fuck R-94, Mega Fuck RS-75, Mega Fuck RS -72-K, Megafuck RS-76-NS, Megafuck DS-21 (all trade names, DIC Co., Ltd.), TEGO Twin 4000, TEGO Twin 4100, TEGO Flow 370, TEGO Glide 440, TEGO Glide 450, TEGO Rad 2200N, (trade name, Ebonic Degusa Japan Co., Ltd.), Fluoroalkylbenzene sulfonate, Fluoroalkylcarboxylate, Fluoroalkylpolyoxyethylene ether, Fluoroalkylammonium iodide, Fluoroalkylbetaine, Fluoroalkylsulfonate , Diglycerin tetrakis (fluoroalkyl polyoxyethylene ether), F Luoloalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tri Decyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate , Solbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate, and alkyl Diphenyl ether disulfonate. One or more of these can be used.

Among the specific examples of these surfactants, BYK-306, BYK-342, BYK-346, KP-341, KP-368, Surflon S611, Footergent 710FL, Footergent 710FM, Footergent 710FS, Footergent 650A, Megafuck F-477, Megafuck F-556, Megafuck RS-72-K, Megafuck DS-21, TEGO Twin 4000, Fluoroalkylbenzene Sulfonate, Fluoroalkylcarboxylate, Fluoroalkylpolyoxyethylene ether, Fluoro At least one selected from an alkyl sulfonate, a fluoroalkyltrimethylammonium salt, and a fluoroalkylaminosulfonate is preferable because it has a great effect of enhancing the coating uniformity of the curable composition.

The amount of the surfactant added to the curable composition of the present invention is preferably 0.01 to 0.1 parts by weight with respect to 100 parts by weight of the main component.

<1-4-2. Adhesion improver>
The curable composition of the present invention may further contain an adhesion improver from the viewpoint of further improving the adhesion of the formed cured film to the substrate. Examples of the adhesion improving agent are silane-based coupling agents, aluminum-based coupling agents, and titanate-based coupling agents other than the imide compound (A). Specific examples of the silane coupling agent other than the imide compound (A) include 3-glycidyloxypropyldimethylethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, and 3-glycidyloxypropyltrimethoxysilane (for example, Silaace S510; Product name, JNC Co., Ltd.), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (eg, Sila Ace S530; trade name, JNC Co., Ltd.), 3-trimethoxysilylpropyl methacrylate (eg, Sila Ace S710; product) , JNC Co., Ltd.), 3-mercaptopropyltrimethoxysilane (eg, Sila Ace S810; trade name, JNC Co., Ltd.), and specific examples of aluminum-based coupling agents are acetalkoxyaluminum diisopropyrate and titanate. A specific example of the coupling agent of the system is tetraisopropylbis (dioctylphosphite) titanate. One or more of these can be used.

Among the specific examples of these adhesion improvers, 3-glycidyloxypropyltrimethoxysilane and 3-trimethoxysilylpropylmethacrylate are preferable because they have a large effect of improving the adhesion of the cured film to the substrate.

The amount of the adhesion improver added to the curable composition of the present invention is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the main component amount.

<1-4-3. Anti-coagulation agent ＞
The curable composition of the present invention may further contain an antiaggregating agent from the viewpoint of blending with a solvent and preventing aggregation. Anti-aggregation agents are used to blend with the solvent and prevent aggregation. Specific examples of the antiaggregating agent arbitrarily added to the curable composition of the present invention include DISPERBYK-145, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-182, DISPERBYK-184, DISPERBYK. -185, DISPERBYK-2163, DISPERBYK-2164, BYK-220S, DISPERBYK-191, DISPERBYK-199, DISPERBYK-2015 (all trade names, Big Chemie Japan Co., Ltd.), FTX-218, Footergent 710FM, Footergent 710FS (Product name, Neos Co., Ltd.), Floren G-600, and Floren G-700 (trade name, Kyoeisha Chemical Co., Ltd.). One or more of these can be used.

<1-4-4. Antioxidant>
The curable composition of the present invention may further contain an antioxidant from the viewpoint of preventing yellowing when the cured film is exposed to a high temperature. Specific examples of the antioxidant include, Irganox1010, Irganox1010FF, Irganox1035, Irganox1035FF, Irganox1076, Irganox1076FD, Irganox1098, Irganox1135, Irganox1330, Irganox1726, Irganox1425WL, Irganox1520L, Irganox245, Irganox245FF, Irganox259, Irganox3114, Irganox565, Irganox565DD (all trade names, BASF Japan Co., Ltd.), ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-50, ADK STAB AO-60, and ADK STAB AO-80 (all trade names, ADEKA Corporation). One or more of these can be used.

Among the specific examples of these antioxidants, Irganox 1010 and ADK STAB AO-60 are preferable.

The amount of the antioxidant added to the curable composition of the present invention is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the main component.

<1-4-5. Crosslinker>
The curable composition of the present invention is an epoxy compound other than the polyfunctional epoxy compound (C), a melamine compound, from the viewpoint of improving heat resistance, chemical resistance, in-film uniformity, flexibility, flexibility, and elasticity. , And a cross-linking agent such as a bisazido compound may be further contained.

Examples of the epoxy compound other than the polyfunctional epoxy compound (C) include glycidyl ether groups such as bisphenol A type epoxy compound, bisphenol F type epoxy compound, biphenyl type bifunctional epoxy compound, and bifunctional epoxy compound having a siloxane bond site. Compounds having two; compounds having two glycidyl ester groups such as terephthalic acid diglycidyl ester, phthalic acid diglycidyl ester, and diglycidyl 1,2-cyclohexanedicarboxylate; and 3', 4'-epoxycyclohexylmethyl-3, 4-Epoxycyclohexane A compound having two alicyclic epoxy groups such as carboxylate. One or more of these can be used.

Specific examples of commercially available bisphenol A type epoxy compounds are jER 828, 1004, 1009 (all trade names, Mitsubishi Chemical Co., Ltd.); specific examples of commercially available bisphenol F type epoxy compounds are jER 806, 4005P. (All are trade names, Mitsubishi Chemical Co., Ltd.); Specific examples of commercially available biphenyl-type bifunctional epoxy compounds are jER YX4000, YX4000H, YL6121H (all trade names, Mitsubishi Chemical Co., Ltd.); siloxane bond. A specific example of a commercial product of a bifunctional epoxy compound having a moiety is TSL9906 (trade name, Momentive Performance Materials Japan LLC); a specific example of a commercial product of terephthalic acid diglycidyl ester is Denacol EX-. 711 (trade name, Nagasechemtex Co., Ltd.); a specific example of a commercially available phthalic acid diglycidyl ester is Denacol EX-721 (trade name, Nagasechemtex Co., Ltd.); 3', 4'- A specific example of a commercially available product of epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate is Celoxide 2021P (trade name, Daicel Co., Ltd.).

The amount of the epoxy compound other than the polyfunctional epoxy compound (C) added to the curable composition of the present invention is preferably 1 to 20 parts by weight with respect to 100 parts by weight of the main component amount.

<1-4-6. Photoacid generator>
The curable composition of the present invention may further contain a photoacid generator from the viewpoint of enabling patterning by exposure and development. An example of a photoacid generator is a 1,2-quinonediazide compound.

Specific examples of the 1,2-quinone diazide compound include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone diazido-4-sulfonic acid ester and 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone diazide. -5-Sulfonate (eg, trade name, NT-200, Toyo Synthetic Chemical Industry), 2,4,6-trihydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,4,6 -Trihydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonate; 2,2', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,2', 4,4'-Tetrahydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester, 2,3,3', 4-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2, 3,3', 4-Tetrahydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonate; bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinone diazide-4-sulfonic acid ester, Bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinone diazide-5-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinone diazide-4-sulfonic acid ester, bis (p-) Hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester; tri (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1 , 2-Naftquinone diazide-5-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinone diazide-4-sulfonic acid ester, 1,1,1-tri (p-) Hydroxyphenyl) ethane-1,2-naphthoquinonediazide-5-sulfonate; bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,3) ， 4-Tori Hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2 , 2-Bis (2,3,4-trihydroxyphenyl) Propane-1,2-naphthoquinonediazide-5-sulfonic acid ester; 1,1,3-Tris (2,5-dimethyl-4-hydroxyphenyl)- 3-PhenylPropane-1,2-naphthoquinone diazide-4-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinone diazido- 5-Sulfonate, 4,4'-[1- [4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] Ethiliden] Bisphenol-1,2-naphthoquinonediazide-4-sulfonic acid ester , 4,4'-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester; bis (2, 5-Dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1 , 2-naphthoquinone diazide-5-sulfonate, 3,3,3', 3'-tetramethyl-1,1'-spirobiinden-5,6,7,5', 6', 7'-hexanol -1,2-naphthoquinone diazide-4-sulfonic acid ester, 3,3,3', 3'-tetramethyl-1,1'-spirobiinden-5,6,7,5', 6', 7' -Hexanol-1,2-naphthoquinone diazide-5-sulfonic acid ester; 2,2,4-trimethyl-7,2', 4'-trihydroxyflaban-1,2-naphthoquinone diazide-4-sulfonic acid ester, and 2,2,4-trimethyl-7,2', 4'-trihydroxyflaban-1,2-naphthoquinone diazide-5-sulfonic acid ester. One or more of these can be used.

The amount of the photoacid generator added to the curable composition of the present invention is preferably 1 to 20 parts by weight with respect to 100 parts by weight of the main component amount.

<1-4-7. Polyfunctional (meth) acrylate compound>
The curable composition of the present invention may further contain a polyfunctional (meth) acrylate compound from the viewpoint of improving scratch resistance.

Examples of polyfunctional (meth) acrylate compounds are compounds having two (meth) acryloyl groups per molecule and compounds having three or more (meth) acryloyl groups per molecule.

Specific examples of compounds having two (meth) acryloyl groups per molecule include ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,3-butanediol di (meth) acrylate. Neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di ( Meta) 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, ethylene oxide-modified bisphenol Di (meth) acrylates of diol compounds such as A-di (meth) acrylate, ethylene oxide-modified bisphenol F di (meth) acrylate, and ethylene oxide-modified bisphenol S di (meth) acrylate;
Di (meth) acrylates of triol compounds such as glycerol acrylate methacrylates, glycerol di (meth) acrylates, and ethoxylated isocyanuric acid diacrylates;
Di (meth) acrylates of bisphenol compounds such as bisphenol A di (meth) acrylate, bisphenol F di (meth) acrylate, and bisphenol S di (meth) acrylate; and
Epichlorohydrin-modified ethylene glycol di (meth) acrylate, epichlorohydrin-modified 1,6-hexanediol di (meth) acrylate, epichlorohydrin-modified diethylene glycol di (meth) acrylate, epichlorohydrin-modified triethylene glycol di (meth) acrylate, epichlorohydrin-modified tetraethylene glycol di. (Meta) acrylate, epichlorohydrin-modified polyethylene 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, (meth) acrylic acid adduct of bisphenol A type epoxy compound, (meth) acrylic acid adduct of bisphenol F type epoxy compound, and bisphenol S type. Addition of (meth) acrylic acid of a diepoxy compound such as a (meth) acrylic acid adduct of an epoxy compound. One or more of these can be used.

Specific examples of compounds having three or more (meth) acryloyl groups per molecule include trimethylolpropane tri (meth) acrylate, trimethylolpropane EO-modified tri (meth) acrylate, and trimethylolpropane PO-modified tri (meth) acrylate. Gglycerol tri (meth) acrylate, glycerol EO modified tri (meth) acrylate, glycerol PO modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, and ε-caprolactone modified tris- A trifunctional (meth) acrylate compound such as (2- (meth) acryloxyethyl) isocyanurate;
Four-functional (meth) acrylates such as ditrimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol alkoxytetra (meth) acrylate, and diglycerin EO-modified tetra acrylate. ) Acrylate compound;
A pentafunctional (meth) acrylate compound such as dipentaerythritol penta (meth) acrylate;
Hexafunctional (meth) acrylate compounds such as dipentaerythritol hexaacrylate; and
It is a polyfunctional (meth) acrylate compound having a carboxyl group. One or more of these can be used.

Specific examples of commercially available products of trimethylolpropane triacrylate, which is a trifunctional acrylate compound, include NK ester TMPT (trade name, Shin-Nakamura Chemical Industry Co., Ltd.), TMPTA (trade name, Daicel Ornex Co., Ltd.), and Aronix. M-309 (trade name h Toa Synthetic Co., Ltd.);
Specific examples of commercially available products of trimethylolpropane EO-modified triacrylate are TMPEOTA (trade name, Daicel Ornex Co., Ltd.), Aronix M-350, M-360 (trade name, Toagosei Co., Ltd.);
Specific examples of commercially available products of trimethylolpropane PO-modified triacrylate are EBECRYL 135 (trade name, Daicel Ornex Co., Ltd.), Aronix M-310, M-321 (trade name, Toagosei Co., Ltd.);
A specific example of a commercially available product of glycerol PO-modified triacrylate is OTA 480 (trade name, Dycel Ornex Co., Ltd.);
A specific example of a commercially available product of ethoxylated isocyanuric acid triacrylate is NK ester A-9300 (trade name, Shin-Nakamura Chemical Industry Co., Ltd.);
A specific example of a commercially available product of ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate is NK ester A-9300-1CL (trade name, Shin-Nakamura Chemical Industry Co., Ltd.).

A specific example of a commercially available product of trimethylolpropane trimethacrylate, which is a trifunctional methacrylate compound, is NK ester TMPT (trade name, Shin-Nakamura Chemical Industry Co., Ltd.).

Specific examples of commercially available products of ditrimethylol propanetetraacrylate, which is a tetrafunctional acrylate compound, are NK ester AD-TMP (trade name, Shin-Nakamura Chemical Industry Co., Ltd.), EBECRYL 140, and 1142 (all trade names, Daicel).・ Ornex Co., Ltd., Aronix M-408 (trade name, Toa Synthetic Co., Ltd.);
A specific example of a commercially available product of ethoxylated pentaerythritol tetraacrylate is NK ester ATM-35E (trade name, Shin Nakamura Chemical Industry Co., Ltd.);
A specific example of a commercially available product of pentaerythritol tetraacrylate is NK ester A-TMMT (trade name, Shin-Nakamura Chemical Industry Co., Ltd.);
A specific example of a commercially available product of pentaerythritol alkoxytetraacrylate is EBECRYL 40 (trade name, Daicel Ornex Co., Ltd.);
A specific example of a commercially available product of diglycerin EO-modified tetraacrylate is Aronix M-460 (trade name, Toagosei Co., Ltd.).

Specific examples of commercially available products of dipentaerythritol hexaacrylate, which is a hexafunctional acrylate compound, are NK ester A-DPH (trade name, Shin Nakamura Chemical Industry Co., Ltd.) and DPHA (trade name, Daicel Ornex Co., Ltd.). Is.

Specific examples of commercially available products of polyfunctional acrylate compounds having a carboxyl group are Aronix M-510 and M-520 (both trade names, Toagosei Co., Ltd.).

Specific examples of a commercially available mixture of the trifunctional acrylate compound ethoxylated isocyanuric acid triacrylate and the bifunctional acrylate compound ethoxylated isocyanuric acid diacrylate are Aronix M-315 (3 to 13% by weight) (commodity). Name, Toa Synthetic Co., Ltd., the content in parentheses is the value listed in the catalog for the content of ethoxylated isocyanuric acid diacrylate in the mixture).

Specific examples of commercially available mixtures of pentaerythritol triacrylate, which is a trifunctional acrylate compound, and pentaerythritol tetraacrylate, which is a tetrafunctional acrylate compound, are PETIA, PETRA, and PETA (all trade names, Daicel Ornex Co., Ltd.). Company), Aronix M-306 (65-70% by weight), M-305 (55-63% by weight), and M-450 (less than 10% by weight) (trade name, Toa Synthetic Co., Ltd., in parentheses) The content is the value listed in the catalog for the content of pentaerythritol triacrylate in the mixture).

Specific examples of commercial products of a mixture of dipentaerythritol pentaacrylate, which is a pentafunctional acrylate, and dipentaerythritol hexaacrylate, which is a hexafunctional acrylate, are Aronix M-403 (50-60% by weight) and M-400 (50-60% by weight). 40-50% by weight), M-402 (30-40% by weight), M-404 (30-40% by weight), M-406 (25-35% by weight), and M-405 (10-20% by weight). ) (Product name, Toagosei Co., Ltd., the content in parentheses is the value listed in the catalog for the content of pentaerythritol pentaacrylate in the mixture).

The amount of the polyfunctional (meth) acrylate compound added to the curable composition of the present invention is preferably 1 to 20 parts by weight with respect to 100 parts by weight of the main component amount.

<1-4-8. Photopolymerization Initiator>
The curable composition of the present invention may further contain a photopolymerization initiator from the viewpoint of improving the low temperature curability. When a photopolymerization initiator is added, it is possible to lower the firing temperature by performing an ultraviolet irradiation step in combination with a polyfunctional (meth) acrylate compound.

Specific examples of the photopolymerization initiator include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2. -Methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenylketone, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy -2-Phenylacetophenone, camphorquinone, benzanthron, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one (for example, trade name: Irgacure 907, BASF Japan Co., Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (for example, trade name: Irgacure 369, BASF Japan Co., Ltd.), ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid Isoamyl, 4,4'-di (t-butylperoxycarbonyl) benzophenone, 3,4,4'-tri (t-butylperoxycarbonyl) benzophenone, 1,2-octanedione, 1- [4- (phenylthio) phenyl ] -2- (O-benzoyloxime) (for example, trade name, Irgacure OXE01, BASF Japan Co., Ltd.), Etanon, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl). ] -1- (O-Acetyloxym) (for example, trade name, Irgacure OXE02, BASF Japan Co., Ltd.), Irgacure OXE03 (trade name, BASF Japan Co., Ltd.), 1,2-propanedione, 1- [4- [4- [ 4- (2-Hydroxyethoxy) Phenylthio] Phenyl] -2- (O-Acetyloxime) (for example, trade name, Adeca Arklus NCI-930, ADEKA Co., Ltd.), Adeca Arklus NCI-831 (trade name, stock). Company ADEKA), Adecaoptomer N-1919 (trade name, ADEKA Co., Ltd.), 2,4,6-trimethylbenzoyldiphenylphosphinoxide, 2- (4'-methoxystyryl) -4,6-bis (trichloromethyl) ) -S-Triazine, 2- (3', 4'-dimethoxystyryl ) -4,6-bis (trichloromethyl) -s-triazine, 2- (2', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2'-methoxy) Styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [p-N, N -Di (ethoxycarbonylmethyl)] -2,6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -s-triazine, 1,3- Bis (trichloromethyl) -5- (4'-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis ( 2-Chlorophenyl) -4,4', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4' , 5,5'-Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4', 5,5'-tetraphenyl-1,2'- Biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 3- (2-methyl-2-) Dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexylphenylketone, and bis (η ^5-2,4 -cyclopentadiene-1) -Il) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium. One or more of these can be used.

Among the specific examples of these photopolymerization initiators, 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) and 1,2-propanedione, 1- [4 -When one or more selected from [4- (2-hydroxyethoxy) phenylthio] phenyl] -2- (O-acetyloxime) is used, the effect of improving the low temperature curability of the curable composition is less. Expressed in quantity. The amount of the photopolymerization initiator added suitable for exhibiting this effect is 0.1 to 5 parts by weight with respect to 100 parts by weight of the main component amount.

<1-5. Solvents optionally added to the curable composition>
A solvent may be added to the curable composition of the present invention in addition to the polymerization solvent. The solvent arbitrarily added to the curable composition of the present invention (hereinafter referred to as “diluting solvent (E)”) is an imide compound (A), a polyfunctional carboxyl compound (B) and a polyfunctional epoxy compound (C). A solvent capable of dissolving the above is preferable. When the curable composition contains the above-mentioned additive (D), the diluting solvent (E) is preferably a solvent capable of further dissolving the additive (D).

The specific example of the diluting solvent (E) is the same as the solvent described as a specific example of the above-mentioned reaction solvent. One or more of these can be used.

<1-6. Preservation of curable composition>
When the curable composition of the present invention is stored in the light-shielded range of −30 ° C. to 25 ° C., the stability over time of the composition becomes good, which is preferable. It is more preferable to store at -20 ° C to 5 ° C.

<2. Cured film obtained from curable composition>
The curable composition of the present invention is a mixture of an imide compound (A), a polyfunctional carboxyl compound (B) and a polyfunctional epoxy compound (C), and depending on the desired properties, further an additive (D) and a dilution compound. It can be obtained by selecting and adding the solvent (E) and uniformly mixing and dissolving them.

By applying the curable composition obtained as described above to the surface of the substrate, when the curable composition contains a solvent for the composition, the solvent for the composition is further removed by a heating step, a depressurizing step, or the like. By doing so, a coating film can be formed. Specific examples of the method for applying the curable composition to the substrate surface are a spin coating method, a roll coating method, a dipping method, and a slit coating method. Specific examples of the removal of the composition solvent by the heating step are prebaking in a hot plate and an oven. The prebaking conditions vary depending on the type and mixing ratio of each component, but are usually 70 to 150 ° C., 1 to 5 minutes for a hot plate, and 5 to 15 minutes for an oven.

Finally, a cured film can be obtained by heat treatment at 100 to 250 ° C., preferably 120 to 230 ° C. for a hot plate for 5 to 60 minutes and an oven for 20 to 90 minutes in order to completely cure the coating film. can.

When a polyfunctional (meth) acrylate compound and a photopolymerization initiator are added to the curable composition as the additive (D), photocuring by ultraviolet irradiation can be used in combination with thermosetting by heat treatment. In that case, the coating film before the heat treatment is irradiated with ultraviolet rays. The wavelength of the irradiated ultraviolet rays is preferably 350 nm or more so as not to affect the photodimerization reaction after the formation of the cured film. The ultraviolet rays used for this photocuring may be polarized ultraviolet rays or unpolarized ultraviolet rays.

The cured film thus obtained is three-dimensionally crosslinked by condensation of the alkoxysilyl group of the imide compound (A), and the carboxyl group of the polyfunctional carboxyl compound (B) and the epoxy group of the polyfunctional epoxy compound (C). Three-dimensional cross-linking by the reaction proceeds. In particular, with respect to the condensation of the alkoxysilyl group of the imide compound (A), the carboxyl group of the polyfunctional carboxyl compound (B) also cures as a catalyst for accelerating the condensation reaction rate, so that three-dimensional crosslinking is likely to proceed. Therefore, the obtained cured film has high heat resistance and high resistance to the solvent in the polymerizable liquid crystal composition described later.

Further, in the obtained cured film, a group having a polymerizable double bond and an imide structure of the imide compound (A) is present. When the group having the polymerizable double bond and the imide structure is irradiated with linearly polarized ultraviolet rays (the example of the wavelength is 313 nm), the double bonds arranged in the direction parallel to the polarization direction of the linearly polarized ultraviolet rays are photodimerized. The cured film is imparted with a liquid crystal alignment ability, so that the obtained cured film has photoalignment.

Similarly, the cured film obtained from the polymer having a cinnamoyle group and an epoxy group described in Prior Document 2 and the curable composition containing a polyfunctional carboxyl compound is also three-dimensionally crosslinked and has photo-orientation. Have.

However, the curable composition of the present invention and the curable composition described in Prior Document 2 differ in the crosslinkability between the compound having photoorientity and other components among the main components.

Since the crosslinkable group of the imide compound (A), which is a compound having photoorientation contained in the curable composition of the present invention, is an alkoxysilyl group, the crosslinkable group of another component among the main components is related to the crosslinkable group. , The carboxyl group of the polyfunctional carboxyl compound (B) and the epoxy group of the polyfunctional epoxy compound (C) have low crosslinkability.

On the other hand, the cinnamoyl group, which is a compound having photoorientation contained in the curable composition described in Prior Document 2, and the epoxy group, which is a crosslinkable group of the polymer having an epoxy group, are other components among the main components. The crosslinkability of the polyfunctional carboxyl compound is high with the carboxyl group of the polyfunctional carboxyl compound.

For these reasons, when the curable composition of the present invention is cured, the inhibition of photo-orientation due to cross-linking of the compound having photo-orientation and other components among the main components is small, whereas the above-mentioned Document 2 describes it. When the described curable composition is cured, the inhibition of photo-orientation by cross-linking the compound having photo-orientation and other components among the main components is large. Therefore, in the curable composition of the present invention, the obtained cured film can have photo-alignment even when the blending ratio of the components having photo-orientation is low. Therefore, when a curable composition that does not contain a component having photo-orientation and a curable composition to which a component having photo-orientation is added are compared, characteristics other than the photo-orientation due to the addition of the component having photo-orientation. The decrease can be suppressed.

<3. Color filter substrate with a cured film obtained from a curable composition>
The color filter substrate provided with the cured film of the present invention is a color filter substrate in which the cured film of the present invention is formed on a colored body of the color filter substrate.

Since the curable composition of the present invention has high flattening property, the step on the surface of the color filter substrate is reduced by providing the cured film. Therefore, when the color filter substrate provided with the cured film of the present invention is used for the display element, the display quality of the display element is high.

Next, the present invention will be specifically described with reference to synthetic examples, comparative synthetic examples, examples, and comparative examples, but the present invention is not limited to these examples.

The compounds used in the synthesis example, the comparative synthesis example, the example, and the comparative example are described for each component.

Acid anhydride with a polymerizable double bond (a1):
a1-1: Citraconic acid anhydride a1-2: Maleic acid anhydride a1-3: Itaconic acid anhydride An alkoxysilyl compound (a2) having an amino group:
a2-1: 3-Aminopropyltriethoxysilane (hereinafter abbreviated as "APTS")
Synthetic solvent used for the synthesis of imide compound (A):
EDM, PGME
Polymerization inhibitor used for the synthesis of imide compound (A):
Dibutylhydroxytoluene (hereinafter abbreviated as "BHT")

Tetracarboxylic dianhydride (b11):
b11-1: Butanetetracarboxylic dianhydride (trade name, Ricacid BT-100, Shin Nihon Rika Co., Ltd., hereinafter abbreviated as "BT-100")
b11-2: 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride (hereinafter abbreviated as "ODPA")
Diamine (b12):
b12-1: 3,3'-diaminodiphenyl sulfone (hereinafter abbreviated as "DDS")
Multivalent hydroxy compound (b13):
b13-1: 1,4-butanediol
Monohydric alcohol (b14):
b14-1: Benzyl alcohol
Styrene-maleic anhydride copolymer (b15):
b15-1: SMA1000 (trade name, Kawahara Yuka Co., Ltd.)
Polymerization solvent used for the reaction of polyester amic acid (B1):
MMP, PGMEA

Polyfunctional epoxy compound (C):
C-1: jER 157S70 (trade name, Mitsubishi Chemical Corporation, hereinafter abbreviated as "157S70"), which is a compound having three or more glycidyl ether groups.
C-2: PGMEA solution of homopolymer of glycidyl methacrylate, which is a compound having 3 or more glycidyl ester groups (solid content concentration 50% by weight, weight average molecular weight 3,000, hereinafter referred to as "PGMA3000").
C-3: EHPE3150 (trade name, Daicel Co., Ltd.), which is a compound having three or more oxylanyl groups.

Additive (D):
D-1: ADK STAB AO-60, a hindered phenolic antioxidant (trade name, ADEKA CORPORATION, hereinafter abbreviated as "AO-60").

Diluting solvent (E):
E-1: PGME
E-2: PGBE
E-3: EDM
E-4: PGMEA
E-5: MMP
E-6: CPN

First, a solution containing the imide compound (A) was synthesized as shown below (Synthesis Examples 1 to 3).

[Synthesis Example 1] Synthesis of a solution containing an imide compound (A-1) A 500 mL four-necked flask equipped with a thermometer, a stirrer, a raw material charging port and a nitrogen gas inlet has a polymerizable double bond. Citraconic anhydride as the acid anhydride (a1), APTS as the alkoxysilyl compound (a2) having an amino group, and EDM as the synthetic solvent are charged in the following weights and heated in an oil bath set at 130 ° C. for 3 hours. Further, the low boiling point was distilled off at normal pressure while aging at 145 ° C. for 2 hours.
Citraconic acid anhydride 64.51g
APTS 127.49g
EDM 48.00g
The reaction solution was cooled to 30 ° C. or lower to obtain a solution containing the imide compound (A-1). A part of the solution was sampled, the weight average molecular weight was measured by GPC analysis, and the solid content concentration was measured by the dry weight method. As a result, the weight average molecular weight was 2,150 and the solid content concentration was 78% by weight. The molar ratio of the acid anhydride group of the acid anhydride (a1) having a polymerizable double bond and the amino group of the alkoxysilyl compound (a2) having an amino group (acid anhydride group / amino group) prepared as a raw material. Is 1.0.

[Synthesis Example 2] Synthesis of a solution containing an imide compound (A-2) A 200 mL four-necked flask equipped with a thermometer, a stirrer, a raw material charging port and a nitrogen gas inlet has a polymerizable double bond. An oil bath set at 100 ° C. with maleic anhydride as the acid anhydride (a1), APTS as the alkoxysilyl compound (a2) having an amino group, BHT as the polymerization inhibitor, and EDM as the synthetic solvent in the following weights. The low boiling point was distilled off at normal pressure while aging at 120 ° C. for 2 hours.
Maleic anhydride 10.00g
APTS 22.58g
BHT 0.0163g
EDM 21.72g
The reaction solution was cooled to 30 ° C. or lower to obtain a solution containing the imide compound (A-2). A part of the solution was sampled, the weight average molecular weight was measured by GPC analysis, and the solid content concentration was measured by the dry weight method. As a result, the weight average molecular weight was 2,850 and the solid content concentration was 58% by weight. The molar ratio of the acid anhydride group of the acid anhydride (a1) having a polymerizable double bond and the amino group of the alkoxysilyl compound (a2) having an amino group (acid anhydride group / amino group) prepared as a raw material. Is 1.0.

[Synthesis Example 3] Synthesis of solution containing imide compound (A-3) A 200 mL four-necked flask equipped with a thermometer, a stirrer, a raw material charging port and a nitrogen gas inlet has a polymerizable double bond. An oil bath set at 100 ° C. with itaconic acid anhydride as the acid anhydride (a1), APTS as the alkoxysilyl compound (a2) having an amino group, BHT as the polymerization inhibitor, and PGME as the synthetic solvent in the following weights. The low boiling point was distilled off at normal pressure while aging at 120 ° C. for 2 hours.
Itaconic acid anhydride 8.00g
APTS 15.80g
BHT 0.0119g
PGME 23.81g
The reaction solution was cooled to 30 ° C. or lower to obtain a solution containing the imide compound (A-3). A part of the solution was sampled, the weight average molecular weight was measured by GPC analysis, and the solid content concentration was measured by the dry weight method. As a result, the weight average molecular weight was 1,100 and the solid content concentration was 49% by weight. The molar ratio of the acid anhydride group of the acid anhydride (a1) having a polymerizable double bond and the amino group of the alkoxysilyl compound (a2) having an amino group (acid anhydride group / amino group) prepared as a raw material. Is 1.0.

Using a raw material containing a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound, a solution containing a polyesteramide acid was synthesized as shown below (Synthesis Examples 4 and 5).

[Synthesis Example 4] Synthesis of a solution containing polyesteramidic acid (B1-1) Used for a synthesis reaction in a 1,000 mL four-mouthed flask equipped with a thermometer, a stirrer, a raw material charging port and a nitrogen gas inlet. 604.80 g of PGMEA as a solvent, 34.47 g of BT-100 as a tetracarboxylic acid dianhydride, 164.11 g of SMA-1000 as a styrene-maleic acid anhydride copolymer, and 50. 17 g and 10.45 g of 1,4-butanediol as a polyvalent hydroxy compound were charged, and the mixture was stirred at 130 ° C. for 3 hours under a dry nitrogen stream. Then, the solution after the reaction was cooled to 25 ° C., 10.80 g of DDS and 25.20 g of PGMEA were added as diamine, and the mixture was stirred at 20 to 30 ° C. for 2 hours, then stirred at 115 ° C. for 1 hour, 30 ° C. or lower. A solution containing polyesteramidic acid (B1-1) having a solid content concentration of 30% by weight, which was pale yellow and transparent, was obtained. The weight average molecular weight measured by GPC was 10,000.

[Synthesis Example 5] Synthesis of a solution containing polyesteramidic acid (B1-2) Used for a synthesis reaction in a 1,000 mL four-mouthed flask equipped with a thermometer, a stirrer, a raw material charging port and a nitrogen gas inlet. 446.96 g of MMP as a solvent, 31.93 g of 1,4-butanediol as a polyvalent hydroxy compound, 25.54 g of benzyl alcohol as a monohydroxy compound, and 183.20 g of ODPA as a tetracarboxylic acid dianhydride were charged and dried. The mixture was stirred at 130 ° C. for 3 hours under a nitrogen stream. Then, the solution after the reaction was cooled to 25 ° C., 29.33 g of DDS and 183.04 g of MMP were added as diamine, and the mixture was stirred at 20 to 30 ° C. for 2 hours, then stirred at 115 ° C. for 1 hour, 30 ° C. or lower. A solution containing polyesteramidic acid (B1-2) having a solid content concentration of 30% by weight, which was pale yellow and transparent, was obtained. The weight average molecular weight measured by GPC was 4,200.

Using a raw material containing a polymerizable compound having a cinnamoyle group and a polymerizable compound having an epoxy group, a solution containing a polymer (Z) having a cinnamoyle group and an epoxy group was synthesized as shown below (Synthesis Example 6). ).

[Synthesis Example 6] Synthesis of a solution containing a polymer (Z-1) having a cinnamoyl group and an epoxy group In a 500 mL four-mouthed flask equipped with a thermometer, a stirrer, a raw material charging port and a nitrogen gas inlet. As a polymerizable compound having a cinnamoyl group, 135.00 g of 2-{4-[(1E) -3-methoxy-3-oxoprope-1-en-1-yl] phenoxy} ethyl = 2-methylprope-2-enoate, 15.00 g of glycidyl methacrylate as a polymerizable compound having an epoxy group, 15.00 g of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator, and 50.00 g of CPN as a reaction solvent were charged, 90. Polymerization was carried out by heating at a polymerization temperature of ° C. for 2 hours. The solution after the reaction was cooled to 30 ° C. or lower to obtain a solution containing a polymer (Z-1) having a cinnamoyle group and an epoxy group having a solid content concentration of 25% by weight. The weight average molecular weight measured by GPC was 6,400.

[Example 1]
The solution containing the imide compound (A-1) obtained in Synthesis Example 1 as the solution containing the imide compound (A), and the polyesteramide obtained in Synthesis Example 4 as the solution containing the polyfunctional carboxyl compound (B). A solution containing an acid (B1-1), 157S70 as a polyfunctional epoxy compound (C), and PGBE, EDM, and PGMEA as a diluting solvent (E) are mixed and dissolved at the ratios (units: g) shown in Table 1. , Filtered with a solvent filter (0.2 μm) to obtain a curable composition.

The ratio of the imide compound (A) to 100% by weight of the total amount of the imide compound (A), the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C) (unit: weight%, in the table "100 × (A)) / [(A) + (B) + (C)] ”) is shown in Table 1.

The ratio of the polyfunctional carboxyl compound (B) to 100% by weight of the total amount of the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C) (unit: weight%, in the table "100 × (B) / [(B) ) + (C)] ”) is shown in Table 1.

表中の（Ａ－１）、（Ａ－２）、（Ａ－３）、（Ｂ１－１）、Ｂ１－２）、及び（Ｚ－１）は溶液の重量である。

In the table, (A-1), (A-2), (A-3), (B1-1), B1-2), and (Z-1) are the weights of the solution.

The total amount of the solvent contained in the curable composition of Example 1 is EDM, which is a reaction solvent contained in the solution containing the imide compound (A-1), and PGBE, EDM and PGBE, EDM of the diluting solvent (E). It is the total amount of PGMEA, and was prepared so that the solid content concentration was about 25% by weight in this step. The same applies to Examples 2 and below and Comparative Examples.

[Manufacturing of glass substrate with hardened film]
The obtained curable composition was spin-coated on a glass substrate at 800 rpm for 10 seconds and prebaked on a hot plate at 80 ° C. for 3 minutes to obtain a substrate with a coating film. Further, by post-baking in an oven at 230 ° C. for 30 minutes, a substrate with a cured film having a film thickness of about 1.5 μm was obtained. Hereinafter, the obtained substrate with a cured film will be referred to as a “glass substrate with a cured film”.

[Tackiness evaluation]
The stickiness of the coating film on the above-mentioned coated substrate was confirmed. If there is no tack (not sticky), the tackiness is "◎", if it is not sticky but fingerprints remain when pressed strongly, the tackiness is "○", if it is sticky, the tackiness is "×", and if it is liquid, it is tacky. The sex was evaluated as "XX". The evaluation results are shown in Table 1.

[Measurement of light transmittance]
Using an ultraviolet-visible near-infrared spectrophotometer V-670 (trade name, JASCO Corporation), a glass substrate without a cured film is installed on the reference side of the ultraviolet-visible-near-infrared spectrophotometer, and the sample side. By installing the glass substrate with the cured film obtained in the above, the light transmittance of the light of the cured film alone at a wavelength of 400 nm was measured. The measured values are shown in Table 1.

[Evaluation of transparency]
Transparency "◎" when the light transmittance is 99.0% or more, transparency "○" when the light transmittance is 97.0% or more and less than 99.0%, and transparency "×" when the light transmittance is less than 97.0%. I evaluated it. The evaluation results are shown in Table 1.

[Calculation of 5% weight loss temperature]
A powdery sample for measurement was carved from the cured film of the obtained glass substrate with a cured film. Using a differential thermal balance Thermo plus EVO TG-DTA 8120 (trade name, Rigaku Co., Ltd.), the temperature dependence of the thermal weight reduction rate of the obtained sample was measured. It was heated from room temperature at a heating rate of 10 ° C./min, and a "5% weight loss temperature" was calculated, which is a temperature at which the weight loss rate is 5% based on the thermogravimetric loss rate of 100 ° C. The calculated values are shown in Table 1.

[Evaluation of heat resistance]
When the 5% weight loss temperature was 310 ° C. or higher, it was evaluated as heat resistance "⊚", when it was 290 ° C. or higher and lower than 310 ° C., it was evaluated as heat resistance "◯", and when it was lower than 290 ° C., it was evaluated as heat resistance "x". The evaluation results are shown in Table 1.

[Preparation of polymerizable liquid crystal composition]
The polymerizable liquid crystal composition used for the evaluation was prepared as follows. Pario Color LC242 (trade name, BASF Japan Co., Ltd.) 5.0 g, IRGACURE907 (trade name, BASF Japan Co., Ltd.) 0.25 g, BYK361N (trade name, Big Chemie Japan Co., Ltd.) 0.0050 g, and organic Toluene is added as a solvent to prepare the organic solvent so that the total amount is 85% by weight, and the mixture is uniformly mixed and dissolved. This composition is referred to as a polymerizable liquid crystal composition (PLC-1).

[Manufacturing of glass substrate with optical functional film]
The light emitted from the ultrahigh-pressure mercury lamp was converted into linear polarization through a filter that cuts light of 300 nm or less and a wire grid polarizing plate, and the obtained glass substrate with a cured film was irradiated with 500 mJ / cm ² in terms of 313 nm.

Next, the polymerizable liquid crystal composition (PLC-1) was spin-coated on the substrate at a rotation speed of 1,300 rpm for 10 seconds and prebaked on a hot plate at 80 ° C. for 1 minute. After the substrate was cooled to room temperature, the entire line of the ultrahigh pressure mercury lamp was irradiated with 300 mJ / cm ² in terms of 365 nm to photo-cure the polymerizable liquid crystal composition and fix the orientation. Hereinafter, this obtained substrate will be referred to as a “glass substrate with an optical functional film”.

[Evaluation of photo-orientation]
The obtained glass substrate with an optical functional film was sandwiched between two linear polarizing plates in an orthogonal (cross Nicol) state, and the backlight was irradiated from below for observation. Photo-orientation is "◎" when light and dark display is possible without orientation defects (without light loss), and light-orientation "○" when light-dark display is possible almost entirely, but there are partial orientation defects. , The other cases were evaluated as photo-orientation "x". The evaluation results are shown in Table 1.

[Manufacturing of color filter substrate with cured film]
A color filter substrate with a cured film was obtained according to the method for producing a glass substrate with a cured film, except that the glass substrate was changed to a color filter substrate. Here, the color filter substrate used in the test is a substrate provided with R (red), G (green) and B (blue) colored bodies and a black matrix for preventing color mixing on a glass substrate, and has a maximum step. Is 0.60 μm to 0.65 μm.

[Calculation of flattening rate]
In the production of the color filter substrate with the cured film, the maximum step (referred to as "TIR ₀ ") of the color filter substrate before applying the curable composition was measured, and the curing obtained after the production of the color filter substrate with the cured film was performed. The maximum step (referred to as "TIR ₁ ") of the color filter substrate with a film was measured. From the two maximum steps obtained, flattening rate = 100% × [(TIR ₀ )-(TIR ₁ )] / (TIR ₀ ) was calculated. The calculated values are shown in Table 1.

[Evaluation of flatness]
When the flattening rate was 50% or more, the flattening property was evaluated as “◯”, and when the flattening rate was less than 50%, the flattening property was evaluated as “x”. The evaluation results are shown in Table 1.

[Examples 2 to 11 and Comparative Examples 1 to 4]
According to the method of Example 1, each component was mixed and dissolved at the ratio (unit: g) shown in Table 1 to obtain a curable composition. The ratio of the polyfunctional carboxyl compound (B) to the total amount of 100% by weight of the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C) is not described in Comparative Examples 2 to 4. In Comparative Examples 3 and 4, the ratio (unit) of the polymer (Z) having a cinnamoyle group and an epoxy group to 100% by weight of the total amount of the polyfunctional carboxyl compound (B) and the polymer (Z) having a cinnamoyle group and an epoxy group. :% by weight, "100 × (Z) / [(B) + (Z)]" is shown in Table 1).

According to the method of Example 1, the tackiness was evaluated, the transparency was evaluated from the measured value of the light transmittance, the heat resistance was evaluated from the calculated value of the 5% weight loss temperature, and the light orientation was evaluated. The flatness was evaluated from the calculated flattening rate. Table 1 shows each measured value, calculated value and evaluation result. However, the rotation speed when the curable composition was spin-coated on the glass substrate was adjusted so that the film thickness of the cured film was approximately 1.5 μm.

As is clear from the results shown in Table 1, the curable compositions of Examples 1 to 11 have low tackiness and excellent flattening property, and the cured film obtained from the curable composition has transparency and heat resistance. It has excellent properties and photoorientity. On the other hand, the cured film obtained from the curable composition of Comparative Example 1 containing no imide compound (A) has poor photoalignment. The curable composition according to Comparative Example 2 which does not contain the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C) has high tackiness and poor flattening property. Further, the cured film obtained from the curable compositions of Comparative Examples 3 and 4, which is a composition containing the polyfunctional carboxyl compound (B) and the polymer (Z) having a cinnamoyle group and an epoxy group, has transparency and heat resistance. Is defective.

The curable composition of the present invention has low tackiness and excellent flattening property, and the cured film obtained from the curable composition of the present invention has excellent transparency, heat resistance and photoalignment, and thus has photoalignment. It can be used as a color filter protective film.

Claims (9)

A curable composition comprising an imide compound (A), a polyfunctional carboxyl compound (B) and a polyfunctional epoxy compound (C);
The imide compound (A) is a reaction product from a raw material that requires an acid anhydride (a1) having a polymerizable double bond and an alkoxysilyl compound (a2) having an amino group.
The polyfunctional carboxyl compound (B) is a compound having three or more carboxyl groups per molecule.
A curable composition, wherein the polyfunctional epoxy compound (C) is a compound having three or more epoxy groups per molecule. The imide compound (A) is 5 to 80% by weight in the total amount of 100% by weight of the imide compound (A), the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C);
The curable composition according to claim 1, wherein the polyfunctional carboxyl compound (B) is 20 to 80% by weight in a total amount of 100% by weight of the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C). thing. The imide compound (A) is 15 to 60% by weight in the total amount of 100% by weight of the imide compound (A), the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C);
The curable composition according to claim 1, wherein the polyfunctional carboxyl compound (B) is 40 to 75% by weight in the total amount of 100% by weight of the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C). thing. Claim 1 that the acid anhydride (a1) having a polymerizable double bond is at least one selected from the compound represented by the following formula (1) and the compound represented by the following formula (2). The curable composition according to any one of 3 to 3.

In formula (1), R ¹ and R ² are independently hydrogen or an alkyl group having 1 to 5 carbon atoms, respectively.

In formula (2), R ³ is hydrogen or an alkyl group having 1 to 5 carbon atoms. One of claims 1 to 4, wherein the acid anhydride (a1) having a polymerizable double bond is at least one selected from maleic acid anhydride, citraconic acid anhydride and itaconic acid anhydride. The curable composition according to. At least the alkoxysilyl compound (a2) having an amino group is selected from 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-aminophenyltrimethoxysilane, and 4-aminophenyltriethoxysilane. The curable composition according to any one of claims 1 to 5, which is one. The curable composition according to any one of claims 1 to 6, wherein the polyfunctional carboxyl compound (B) is a polyesteramide acid containing a tetracarboxylic dianhydride, a diamine and a polyvalent hydroxy compound as essential raw materials. thing. A cured film obtained by curing the curable composition according to any one of claims 1 to 7. A color filter substrate provided with the cured film according to claim 8.