TW202007711A - Curable compositions, cured film, and color filter substrate - Google Patents

Abstract

The present invention relates to a curable composition, a cured film and a color filter substrate. The curable composition comprises an imide compound (A), a polyfunctional carboxyl compound (B), and a polyfunctional epoxy compound (C), wherein the imide compound (A) is a reaction product using an anhydride (a1) having a polymerizable double bond and an alkoxysilyl compound (a2) having an amino group as essential raw materials, the polyfunctional carboxyl compound (B) is a compound having three or more carboxyl groups per molecule, and the polyfunctional epoxy compound (C) is a compound having three or more epoxy groups per molecule. The curable composition of the present invention has low viscosity and high planarity. By using the curable composition of the present invention, a cured film having high transparency, heat resistance and photo-alignment can be obtained.

Description

Curable composition, cured film, and color filter substrate

The present invention relates to a curable composition that provides a color filter protective film having optical alignment, a cured film formed from the curable composition, and a color filter substrate including the cured film.

A color filter substrate is included in a display element for color display or the like. The color filter substrate includes red (R), green (G), and blue (B) color bodies or a black matrix for preventing color mixing, and there is a step difference on the surface of the color filter substrate. In order to make the cell gap of the liquid crystal display element uniform within the plane, or to make the thickness of the optical functional film formed on the color filter substrate uniform, a method of flattening the step of the surface of the color filter substrate is used. Functional color filter protection film. In addition, in order to control the alignment direction of the liquid crystal molecules in the liquid crystal display element, or when the polymerizable liquid crystal composition is used to form the optical functional film, the alignment direction of the polymerizable liquid crystal molecules is controlled. Alignment film with the function of controlling the alignment direction. In order to achieve a thinner or lighter liquid crystal display element, a color filter protective film that has both the two functions performed by the two films and has an alignment property has been developed.

Examples of the color filter protective film with alignment are the color filter protective film with friction alignment described in Patent Document 1 and the color filter protective film with optical alignment described in Patent Document 2. The composition providing the former protective film is a hardening composition containing polyimide and an epoxy compound, and the alignment treatment method of the former protective film is the friction method. The composition for providing the latter protective film is a hardening composition containing a polymer having a photo-alignment group such as a cinnamyl group and a cross-linking group such as an epoxy group and a cross-linking component such as polyester amide acid, and the alignment of the latter The treatment is performed using linearly polarized ultraviolet irradiation. Up to now, in order to improve the display quality of liquid crystal display elements, the alignment process has been promoted to replace the friction method, which causes static electricity due to direct contact with the film, with non-contact linearly polarized ultraviolet irradiation, and to seek color filters with optical alignment A film protection film and a composition for providing the color filter protection film.

However, in order to cope with the recent demands for lower power consumption and longer life of display elements, the color filter protective film with optical alignment described in Patent Document 2 is required to improve both characteristics. The first is to improve the transparency of the protective film for the purpose of improving the light transmittance of the liquid crystal display element. The second type is the improvement of the heat resistance of the protective film (the reduction in the amount of thermal weight loss during additional heating) for the purpose of reducing the influence on the other members of the liquid crystal display element caused by the degassing from the protective film.

In addition, as a composition used in the formation of a color filter protective film having optical alignment, it is considered to use a composition for an optical alignment film (for example, Patent Document 3). However, the composition for a photo-alignment film described in Patent Document 3 has high viscosity (the coating film obtained by coating the composition and removing the composition with a solvent is easily sticky). Therefore, there is a problem in that, when forming a color filter protective film having photo-alignment, a foreign substance adheres; or an operator's finger touches the surface of the coating film to cause a trace. Furthermore, there is a problem in that the composition for a photo-alignment film is formed into a film thickness (for example, 100 nm) that is used as a general photo-alignment film, and the flatness is poor even when it is used as a general color filter. When the film thickness of the sheet protective film (for example, 1.5 μm) is formed, the flatness is also poor, and the display quality of the liquid crystal display element is low.

Based on the above, it is expected to develop a curable composition that provides a cured film with high transparency, heat resistance, and high optical alignment, has low viscosity, and has high planarity. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 9-230364 [Patent Document 2] Japanese Patent Laid-Open No. 2014-84355 [Patent Document 3] Japanese Patent Laid-Open No. 2015-49419

[Problems to be solved by the invention] The present invention provides a curable composition that provides a cured film with high transparency, heat resistance, and high optical alignment, low viscosity, and high planarity, a cured film obtained from the curable composition, and including the cured film Film of color filter substrate. [Technical means to solve the problem]

The inventors of the present invention conducted intensive studies to solve the above problems, and as a result, they found that the above objects can be achieved by the following curable composition and a cured film obtained by curing the curable composition, and completed the present invention. , The curable composition includes an amide imine compound (A), a multifunctional carboxyl compound (B), and a multifunctional epoxy compound (C), and in the curable composition, the amide imine compound (A) is The reaction product using an acid anhydride (a1) having a polymerizable double bond and an alkoxysilane group compound (a2) having an amino group as essential raw materials, and a polyfunctional carboxyl compound (B) having three or more carboxyl groups per molecule Compound, the multifunctional epoxy compound (C) is a compound having three or more epoxy groups per molecule.

[1] A curable composition comprising an amide imine compound (A), a polyfunctional carboxyl compound (B) and a polyfunctional epoxy compound (C), and in the curable composition, The amide imine compound (A) is a reaction product derived from an acid anhydride (a1) having a polymerizable double bond and an alkoxysilane group compound (a2) having an amino group as necessary raw materials, The multifunctional carboxyl compound (B) is a compound having three or more carboxyl groups per molecule, The multifunctional epoxy compound (C) is a compound having three or more epoxy groups per molecule.

[2] The curable composition according to [1], wherein the total of the amide imine compound (A), the polyfunctional carboxyl compound (B), and the polyfunctional epoxy compound (C) In an amount of 100% by weight, the amide imine compound (A) is 5% to 80% by weight; In the total amount of 100% by weight of the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C), the polyfunctional carboxyl compound (B) is 20% to 80% by weight.

[3] The curable composition according to item [1], wherein the total of the amide imine compound (A), the polyfunctional carboxyl compound (B), and the polyfunctional epoxy compound (C) In an amount of 100% by weight, the amide imine compound (A) is 15% to 60% by weight; In the total amount of 100% by weight of the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C), the polyfunctional carboxyl compound (B) is 40% to 75% by weight.

式（1）中，R¹ 及R² 分別獨立地為氫或碳數1～5的烷基。

式（2）中，R³ 為氫或碳數1～5的烷基。[4] The curable composition according to any one of [1] to [3], wherein the acid anhydride (a1) having a polymerizable double bond is selected from a compound represented by the following formula (1) and At least one of the compounds represented by the following formula (2).

In formula (1), R ¹ and R ² are each independently hydrogen or a C 1-5 alkyl group.

In formula (2), R ³ is hydrogen or a C 1-5 alkyl group.

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

[6] The hardenable composition according to any one of [1] to [5], wherein the alkoxysilane group compound (a2) having an amino group is selected from 3-aminopropyltrimethoxysilane , At least one of 3-aminopropyltriethoxysilane, 4-aminophenyltrimethoxysilane and 4-aminophenyltriethoxysilane.

[7] The curable composition according to any one of [1] to [6], wherein the polyfunctional carboxyl compound (B) is a tetracarboxylic dianhydride, a diamine, and a polyhydric hydroxyl compound. The raw material of polyester amide acid.

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

[9] A color filter substrate including the cured film according to item [8]. [Effect of invention]

The curable composition of a preferred embodiment of the present invention is a curable composition that provides a cured film with high transparency, heat resistance, and high optical alignment, and has low viscosity and high planarization. The cured film obtained from the curable composition can be used as a color filter protective film. Since the cured film has high transparency, the curable composition has high flatness and the viscosity of the curable composition is low, when forming a cured film, adhesion of foreign matter is reduced, so when 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 cured film has high heat resistance, the display element including the cured film has little influence on other members caused by outgassing from the cured film. In addition, since the cured film has high optical alignment, alignment control of liquid crystal molecules can be performed without using an alignment film.

In this specification, in order to show one or both of "acrylic acid" and "methacrylic acid", it is sometimes expressed as "(meth)acrylic acid". Similarly, in order to indicate one or both of "acrylate" and "methacrylate", it is sometimes expressed as "(meth)acrylate", in order to indicate "acryloyloxy" and "methacryloyl" One or both of "oxy" is sometimes expressed as "(meth)acryloyloxy".

<1. The curable composition of the present invention> The curable composition of the present invention is characterized by containing an amide imine 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 amide imine compound (A), the polyfunctional carboxyl compound (B), and the polyfunctional epoxy compound (C). In order to obtain a hardened film with high optical alignment, the imidate compound (A), the amide imide compound (A), the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C) are 100% by weight of the amide imine compound (A). The compounding ratio is preferably 5% by weight or more, and more preferably 15% by weight or more. In order to obtain a hardenable composition with low viscosity and high flatness, the acetylene compound (A), the polyfunctional carboxyl compound (B), and the polyfunctional epoxy compound (C) are contained in 100% by weight The compounding ratio of the amine compound (A) is preferably 80% by weight or less, and more preferably 60% by weight or less. In order to obtain a cured film with high heat resistance and high optical alignment, the compounding rate of the polyfunctional carboxyl compound (B) in 100% by weight of the total amount of the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C) is preferably: 20% by weight to 80% by weight, more preferably 40% by weight to 75% by weight.

In this specification, the amide imine compound (A), the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C) are sometimes collectively expressed as "main components", and the amide imine compound (A) is sometimes referred to as The total amount of polyfunctional carboxyl compound (B) and polyfunctional epoxy compound (C) is expressed as "main component amount".

<1-1. Acetylene imine compound (A)> The amide imine compound (A) used in the present invention is a reaction product derived from an acid anhydride (a1) having a polymerizable double bond and an alkoxysilane group compound (a2) having an amino group as necessary raw materials.

Regarding the raw material of the amide imine compound (A), the preferable content ratio of the acid anhydride (a1) having a polymerizable double bond and the alkoxysilane group compound (a2) having an amino group is the acid anhydride (a1) having a polymerizable double bond The molar ratio (anhydride group/amino group) of the amino group of the acid anhydride group and the alkoxysilane group compound (a2) having an amino group is 0.8 or more and 1.2 or less, and the more preferable content ratio is 0.9 or more and 1.1 or less. If it is the content ratio, the exposure amount required to have photoalignment is small.

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

In consideration of the ease of obtaining raw materials and the solubility of the obtained imide compound (A) in a solvent, the preferred acid anhydride (a1) having a polymerizable double bond is a compound represented by the following formula (1) and the following The compound represented by the formula (2).

式（1）中，R¹ 及R² 分別獨立地為氫或碳數1～5的烷基。

In formula (1), R ¹ and R ² are each independently hydrogen or a C 1-5 alkyl group.

式（2）中，R³ 為氫或碳數1～5的烷基。

In formula (2), R ³ is hydrogen or a C 1-5 alkyl group.

In the formula (1), R ¹ and R ² are each independently preferably hydrogen or methyl; more preferably, both R ¹ and R ² are hydrogen (the compound represented by formula (1) is maleic anhydride) and R ^{One of 1} and R ² is hydrogen and the other is methyl (the compound represented by formula (1) is citraconic anhydride).

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

The acid anhydride (a1) having a polymerizable double bond is particularly preferably citraconic anhydride. Regarding citraconic anhydride, when producing the imidate compound (A), the reactivity of the polymerizable double bond is low and the imidate compound (A) is easily produced.

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

Specific examples of the alkoxysilane group compound (a2) having an amino group are 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyl diethoxysilane, 4-aminophenyltrimethoxysilane, 4-aminophenyltriethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane And 3-(2-aminoethylamino)propyltriethoxysilane. One or more of these compounds can be used.

In consideration of reactivity and ease of obtaining raw materials, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, and 3- The aminopropylmethyl diethoxysilane is more preferably 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane.

<1-1-3. Synthesis method of amide imine compound (A)> The reaction method of the amide imine compound (A) is not particularly limited, but it is preferably a reaction in a solution using a solvent. In this specification, the solvent used in the synthesis to obtain the amide imine compound (A) is simply expressed as "synthetic solvent". The acid anhydride (a1) having a polymerizable double bond and the alkoxysilane group compound (a2) having an amino group are easily reacted by being stirred in a solution at room temperature and generate an amidic acid. The temperature of the system rises due to the heat of reaction when the amide acid is produced, so it is easy to control the temperature in the system by proceeding in the solution.

Thereafter, the amide acid is heated and imidate, thereby obtaining the imidate compound (A). The obtained imide compound (A) has a group containing a polymerizable double bond and an imide structure, and has an unreacted alkoxysilyl group.

The heating temperature at the time of imidization is 60°C to 150°C, preferably 80°C to 130°C. Alkali catalysts can also be added as amide imidization catalysts. Examples of basic catalysts are pyridine, triethylamine, trimethylamine, tributylamine and trioctylamine. In addition, for the purpose of suppressing the polymerization of the photopolymerizable group initiated in the reaction, a polymerization inhibitor may be used in combination. Examples of polymerization inhibitors are 2,2,6,6-tetramethylpyridin-1-oxy, 4-hydroxy-2,2,6,6-tetramethylpyridin-1-oxy, Triphenyltetrazyl (verdazyl), p-methoxyphenol, hydroquinone and dibutylhydroxytoluene.

The synthesis solvent is not particularly limited as long as it can dissolve the acid anhydride (a1) having a polymerizable double bond as a raw material, the alkoxysilane group compound (a2) having an amino group, and the amide imine compound (A). By selecting a solvent having a hydroxyl group as the synthesis solvent, the synthesis reaction of the amide imine compound (A) can reduce the reaction rate of the hydrolysis condensation of the alkoxysilane group.

In addition to selecting a solvent having a hydroxyl group as the synthesis solvent, the concentration of the raw material during the synthesis or the heating temperature is also adjusted, so that when the amide imine compound (A) is synthesized, the alkoxysilane group can be hydrolyzed and condensed. The reaction rate is controlled.

In the synthesis, if the raw materials are used in a high concentration and heated at a high temperature, the amide acid generated in the initial reaction itself functions as an acid catalyst and is generated by the imidate of the amide acid Water initiates the hydrolysis reaction of the alkoxysilane group, so the molecular weight can be increased. The heating temperature during the reaction is preferably 100°C to 150°C. In addition, an acid catalyst such as water and formic acid is added, and further heating is performed to distill off the low boiling point component, thereby further increasing the molecular weight.

<1-1-4. Specific examples of synthetic solvents> Specific examples of synthetic solvents are glycol 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"), Monoethers of glycol compounds such as butanediol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether body; 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 Diether body of glycol compounds such as alcohol diethyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether; 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 Monoether monoesters of glycol compounds such as esters, butylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate body; Diesters of glycol 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; Methyl methoxyacetate, ethyl methoxyacetate, methyl 3-methoxypropionate (hereinafter abbreviated as "MMP"), ethyl 3-ethoxypropionate, ethyl 3-ethoxypropionate Monoether monoesters of monohydroxy carboxylic acid compounds such as esters and methyl 4-methoxybutyrate; Diesters of dicarboxylic acid compounds such as dimethyl succinate and diethyl succinate; Monoamide body of monocarboxylic acid compounds such as N,N-dimethylacetamide, N,N-dimethylpropylamide; Dialkyl ketone compounds such as methyl isobutyl ketone, methyl n-butyl ketone, diethyl ketone, ethyl isobutyl ketone, diisobutyl ketone, and di-n-butyl ketone; Cyclic ether compounds such as hexamethylene oxide and 1,4-dioxane; β-propiolactone, γ-butyrolactone, δ-valerolactone and other cyclic ester compounds; Cyclic amide compounds such as 2-pyrrolidone and N-methyl-2-pyrrolidone; and Cyclic ketone compounds such as cyclopentanone (hereinafter abbreviated as "CPN"), cyclohexanone, and cycloheptanone. One or more of these compounds can be used.

Among the specific examples of these synthetic solvents, in terms of high solubility of the amide imine compound (A), monoethers of glycol compounds, diethers of glycol compounds, and monoethers of glycol compounds are preferred Ester body and monoether monoester body of monohydroxy carboxylic acid compound.

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

The weight average molecular weight in this specification is a value converted from polystyrene calculated by gel permeation chromatography (Gel Permeation Chromatography, GPC) (column temperature: 35°C, flow rate: 1 mL/min). Standard polystyrene uses polystyrene with a molecular weight of 645 to 132,900 (for example, Agilent Technologies' polystyrene calibration kit (PL2010-0102), and the column uses PLgel MIXED-D (Trade name, Agilent Technologies, Inc.), can be measured using tetrahydrofuran as the mobile phase. In addition, the weight average molecular weight of the commercial item in this specification is the value described in a catalog.

<1-2. Multifunctional 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 preferable polyfunctional carboxyl compound (B) is polyester amide acid obtained by reacting tetracarboxylic dianhydride (b11), diamine (b12) and polyhydroxy compound (b13) as essential raw materials and reacting them. (B1). The raw material of the compound is easily obtained or the production of the compound is easy, and the curable composition containing the compound has good compatibility with the amide imine compound (A) and the polyfunctional epoxy compound (C).

<1-2-1. Polyesteramide (B1)> The polyester amide acid (B1) used in the present invention is a reaction product obtained by reacting tetracarboxylic dianhydride (b11), diamine (b12), and polyhydroxy compound (b13) as necessary raw materials. Furthermore, in addition to these components, one or more kinds selected from monohydric alcohol (b14) and styrene-maleic anhydride copolymer (b15) may be added to the raw material.

The method of adding polyester amide acid (B1) to the curable composition of the present invention may directly add the solution after the polymerization reaction, or may concentrate the solution to take out the solid content, thereby adding only the solid content.

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

Specific examples of aromatic tetracarboxylic dianhydride are 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride , 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ash tetracarboxylic dianhydride, 2,2',3,3' -Diphenyl sulfone tetracarboxylic dianhydride, 2,3,3',4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride , 2,2',3,3'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,2-[bis(3, 4-dicarboxyphenyl)] hexafluoropropane dianhydride and ethylene glycol bis (dehydrated trimellitate); specific examples of alicyclic tetracarboxylic dianhydride are cyclobutane tetracarboxylic dianhydride, methyl Cyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride and cyclohexane tetracarboxylic dianhydride; specific examples of aliphatic tetracarboxylic dianhydride are ethane tetracarboxylic dianhydride and butane tetracarboxylic acid Acid dianhydride.

Among these tetracarboxylic dianhydrides, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, ethylene glycol bis (dehydrated trimellitate) and butane tetracarboxylic dianhydride, more preferably 3,3 ',4,4'-diphenylbenzene tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride and butane tetracarboxylic dianhydride. The cured film obtained from the curable composition containing polyester amide acid (B1) is high in transparency, and the polyester amide acid (B1) is composed of one or more kinds selected from these tetracarboxylic dianhydrides Raw materials obtained.

The tetracarboxylic dianhydride (b11) may be used alone or in combination of two or more.

＜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 ash and 3,4'-diaminodiphenyl ash; with four Specific examples of the diamines of each benzene ring are bis[4-(4-aminophenoxy)phenyl] phenanthrene, bis[4-(3-aminophenoxy)phenyl] phenanthrene, bis[3-(4 -Aminophenoxy)phenyl] phenanthrene, [4-(4-aminophenoxy)phenyl][3-(4-aminophenoxy)phenyl] phenanthrene, [4-(3-aminophenoxy Group) phenyl][3-(4-aminophenoxy)phenyl] benzene and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane.

Among these diamines, 3,3′-diaminodiphenylbenzene is preferred. The polyester amide acid (B1) obtained from the raw material containing the diamine has good solubility in solvents.

The diamine (b12) may be used alone or in combination of two or more.

<1-2-1-3. Polyhydroxy compound (b13)> Specific examples of the polyhydric hydroxy compound (b13) used in the present invention are ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol with a weight average molecular weight of 1,000 or less, propylene glycol, and diethylene glycol. Propylene glycol, 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-pentanediol, 2,4-pentanediol, 1,2-pentanetriol, 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 Alcohol, 3,6-octanediol, 1,2,8-octanetriol, 1,2-nonandiol, 1,9-nonandiol, 1,2,9-nonanetriol, 1,2- Decanediol, 1,10-decanediol, 1,2,10-decanetriol, 1,2-dodecanediol, 1,12-dodecanediol, glycerin, trimethylolpropane, Pentaerythritol, dipentaerythritol, bisphenol A, bisphenol S, bisphenol F, diethanolamine and triethanolamine.

Among these compounds, preferred are ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8-octanediol The alcohol is more preferably 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. The polyester amide acid (B1) obtained from one or more raw materials selected from these compounds has good solubility in solvents.

The polyhydric hydroxy compound (b13) may be used alone or in combination of two or more.

＜1-2-1-4. Monohydric alcohol (b14)＞ In the synthesis of polyester amide acid (B1), in addition to tetracarboxylic dianhydride (b11), diamine (b12), and polyhydroxy compound (b13), a monohydric alcohol (b14) may be further reacted.

Specific examples of the monohydric alcohol (b14) are methanol, ethanol, 1-propanol, isopropanol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, Dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, phenol, borneol (borneol), maltol (maltol), linalool (Linalool), terpineol (terpineol), dimethylbenzyl methanol, 3-ethyl-3-hydroxymethyloxetane.

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

The monohydric alcohol (b14) may be used alone or in combination of two or more.

<1-2-1-5. Styrene-maleic anhydride copolymer (b15)> In the synthesis of polyester amide acid (B1), in addition to tetracarboxylic dianhydride (b11), diamine (b12) and polyhydroxy compound (b13), styrene-maleic anhydride copolymer (b15) can also be used React.

By adding the styrene-maleic anhydride copolymer (b15), the compatibility of the polyester amide acid (B1) with respect to the multifunctional epoxy compound (C) can be improved. The molar ratio of styrene/maleic anhydride is 0.5 to 4, preferably 1 to 3, specifically, more preferably about 1, about 2 or about 3, further preferably about 1 or about 2, and particularly preferably about 1.

Specific examples of commercially available products of styrene-maleic anhydride copolymer (b15) are SMA1000, SMA2000, and SMA3000 (all are trade names, Chuan Crude Oil Chemical Co., Ltd.). Among these specific examples, SMA1000 having good solubility in solvents is preferable.

The styrene-maleic anhydride copolymer (b15) may be used alone or in combination of two or more.

<1-2-1-6. Polymerization method of polyester amide acid (B1)> The polyester amide acid (B1) used in the present invention can be produced by a known polymerization method (for example, described in Japanese Patent Laid-Open No. 2015-163685). A preferred polymerization method is solution polymerization using a solvent (hereinafter referred to as "polymerization solvent") used in the polymerization reaction.

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

Examples of the multifunctional epoxy compound (C) used in the present invention are Phenol novolac epoxy compound, cresol novolac epoxy compound, bisphenol A novolac epoxy compound, biphenyl polyfunctional epoxy compound, polyfunctional epoxy compound with a siloxane bond site, 2-[4-(2,3-epoxypropyloxy)phenyl]-2-[4-[1,1-bis[4-(2,3-epoxypropyloxy)phenyl]ethyl ]Phenyl]propane, 1,3-bis[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-[4-[1-[4-(2,3 -Glycidoxy)phenyl]-1-methylethyl]phenyl]ethyl]phenoxy]-2-propanol and α-2,3-glycidoxyphenyl-w- Hydropoly[2-(2,3-glycidoxy)benzylidene-2,3-glycidoxyoxyphenylene] and other compounds with more than three glycidyl ether groups; Compounds having three or more glycidyl groups, such as homopolymers of glycidyl methacrylate, copolymers of glycidyl methacrylate and polymerizable compounds other than glycidyl methacrylate, and the like; and 1,2-epoxy-4-(2-oxepropyl) cyclohexane adducts of 2,2-bis(hydroxymethyl)-1-butanol have three or more oxygen heterocycles Propyl compounds.

A curable composition containing a compound having three or more glycidyl ether groups provides a cured film with good heat resistance, and a curable composition containing a compound having three or more glycidyl ester groups when the burning temperature is low A cured film with good chemical resistance is also provided, and a curable composition containing a compound having three or more oxetanyl groups provides a cured film with good UV resistance.

Among the compounds having three or more glycidyl ether groups, bisphenol A novolac-type epoxy compounds and 2-[4-(2,3-epoxypropoxy) that provide cured films with particularly good heat resistance are particularly preferred )Phenyl]-2-[4-[1,1-bis[4-(2,3-epoxypropoxy)phenyl]ethyl]phenyl]propane, 1,3-bis[4-[ 1-[4-(2,3-epoxypropyloxy)phenyl]-1-[4-[1-[4-(2,3-epoxypropyloxy)phenyl]-1-methyl Ethyl]phenyl]ethyl]phenoxy]-2-propanol and α-2,3-glycidoxy phenyl-w-hydropoly[2-(2,3-glycidoxy) ) Benzylidene-2,3-glycidoxyphenylene].

Specific examples of commercially available products of phenol novolac epoxy compounds are EPPN-201 (trade name, Nippon Kayaku Co., Ltd.) and jER 152, jER 154 (both trade names, Mitsubishi Chemical Co., Ltd.); cresol Specific examples of commercially available products of novolac epoxy compounds are EOCN-102S, EOCN-103S, EOCN-104S, and EOCN-1020 (all are trade names, Nippon Kayaku Co., Ltd.); bisphenol A novolac type ring Specific examples of commercially available products of oxygen compounds are jER 157S65 and jER 157S70 (both trade names, Mitsubishi Chemical Corporation); specific examples of commercially available products of biphenyl type polyfunctional epoxy compounds are NC-3000 and NC- 3000-L, NC-3000-H, NC-3100 (all are trade names, Nippon Kayaku Co., Ltd.); a specific example of a commercially available product of a polyfunctional epoxy compound having a siloxane bond site is Court Oslo (COATOSIL) MP200 (trade name, Japan Momentive Performance Materials Japan Co., Ltd.), Conpoceran (Conpoceran) SQ506 (trade name, Arakawa Chemical Co., Ltd.), ES-1023 (trade name , Shin-Etsu Chemical Industry Co., Ltd.); contains 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-(2,3-ring Oxypropyloxy)phenyl]ethyl]phenyl]propane and 1,3-bis[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-[4- Specific examples of commercially available products of [1-[4-(2,3-epoxypropoxy)phenyl]-1-methylethyl]phenyl]ethyl]phenoxy]-2-propanol TECHMORE VG3101L (trade name, Printec Co., Ltd.); α-2,3-epoxypropoxyphenyl-w-hydropoly[2-(2,3- Specific examples of commercially available products of glycidoxy)benzylidene-2,3-glycidoxyoxyphenylene] are EPPN-501H and EPPN-502H (all are trade names, Nippon Kayaku Co., Ltd. ); A specific example of a homopolymer of glycidyl methacrylate is MARPROOF G-01100 (trade name, Nippon Oil Co., Ltd.); 2,2-bis(hydroxymethyl)-1- A specific example of a commercially available product of 1,2-epoxy-4-(2-oxepropyl)cyclohexane adduct of butanol is EHPE3150 (trade name, Daicel Co., Ltd.) .

<1-4. Additives (D)> The curable composition of the present invention may further contain additives (D). From the viewpoint of improving the characteristics of the curable composition of the present invention, such as coating uniformity, adhesion, stability, chemical resistance, and low-temperature curability, additives arbitrarily added to the curable composition of the present invention may be added (D).

Examples of additives (D) are anionic, cationic, nonionic and fluorine-based surfactants; silicone resin-based coating improvers; silane-based coupling agents and other adhesion improvers; sodium polyacrylate and other anti-agglomeration Agents; acrylic, styrene, polyethyleneimine, and urethane polymer dispersants; hindered phenolic antioxidants; epoxy compounds other than polyfunctional epoxy compounds (C), melamine compounds, and Cross-linking agents such as diazide compounds; photoacid generators; polyfunctional (meth)acrylate compounds; and photopolymerization initiators.

<1-4-1. Surfactant> From the viewpoint of further improving coating uniformity, the curable composition of the present invention may further contain a surfactant. Specific examples of surfactants are Polyflow No. 75, Polyflow No. 90, and Polyflow No. 95 (all are trade names, Kyoeisha Chemical Co., Ltd. Co., Ltd.), DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISE DISPERBYK-166, DISPERBYK-170, DISPERBYK-180, DISPERBYK-181, DISPERBYK-181, DISPERBYK -182, BYK-300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-342, BYK-346, BYK-361N, BYK-UV3500, BYK-UV3570 (all are trade names, Japanese Gram Chemical (BYK Chemie Japan) Co., Ltd.), KP-341, KP-368, KF-96-50CS, KF-50-100CS (all trade names, Shin-Etsu Chemical Industry Co., Ltd.), Surflon (Surflon ) S611 (trade name, AGC Seimi Chemical), Ftergent 222F, Ftergent 208G, Ftergent 251, Ftergent 251, Ftergent 710FL, Fujit ( Ftergent) 710FM, Ftergent 710FS, Ftergent 601AD, Ftergent 650A, FTX-218 (all trade names, Neos Co., Ltd.), Megafac F-171, Megafac F-177, Megafac F-410, Megafac F-430, Megafac F-444, Megafac F-472SF, Mega (Megafac) F-475, Megafac F-477, Megafac F-552, Megafac F-553, Megafac F-554, Megafac F -555, Megafac F-556, Megafac F-558, Megafac F-559, Megafac R-94, Megafac RS-75 , Megafac RS-72-K, Megafac RS-76-NS, Megafac DS-21 (all trade names, DIC Co., Ltd.), Digotun (TEGO Twin) 4000, TEGO Twin 4100, TEGO Flow 370, TEGO Glide 440, TEGO Glide 450, Tegola TEGO Rad 2200N (all trade names, Evonik Degussa Japan Co., Ltd.), fluoroalkyl benzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether , Fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerol tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethyl ammonium salt, fluoroalkyl sulfamate , Polyoxyethylene nonylphenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, Polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan lauric acid Ester, sorbitan palmitate, sorbitan stearate, sorbitan 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 surfactants can be used.

Specific examples of these surfactants are selected from BYK-306, BYK-342, BYK-346, KP-341, KP-368, Surflon S611, Ftergent 710FL, Fujit (Ftergent) 710FM, Ftergent 710FS, Ftergent 650A, Megafac F-477, Megafac F-556, Megafac RS-72-K, Megafa (Megafac) DS-21, TEGO Twin 4000, fluoroalkyl benzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl sulfonate, fluoroalkyl tri At least one of methyl ammonium salt and fluoroalkyl sulfamate is preferable because it has a large effect of improving the uniformity of application of the curable composition.

The addition amount of the surfactant in the curable composition of the present invention is preferably 0.01 to 0.1 parts by weight relative to 100 parts by weight of the main component.

<1-4-2. Adhesion improver> From the viewpoint of further improving the adhesion of the formed cured film to the substrate, the curable composition of the present invention may further contain an adhesion improving agent. Examples of the adhesion improving agent are silane-based coupling agents, aluminum-based coupling agents, and titanate-based coupling agents other than the amide imine compound (A). Specific examples of the silane-based coupling agent other than the amide imine compound (A) are 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane (for example, Sila-Ace S510; trade name, JNC Co., Ltd.), 2-(3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane (for example, Sila-Ace S530; trade name, JNC Co., Ltd.), 3-trimethoxysilylpropyl methacrylate (for example, Sila-Ace S710; trade name, JNC Co., Ltd., 3-mercaptopropyltrimethoxysilane (for example, Sila-Ace S810; trade name, (JNC) Co., Ltd., the specific example of the aluminum-based coupling agent is aluminum acetoxydiisopropoxide, and the specific example of the titanate-based coupling agent is tetraisopropylbis(dioctyl) Phosphite) titanate. One or more of these adhesion improving agents can be used.

Among the specific examples of these adhesion-improving agents, 3-glycidoxypropyltrimethoxysilane and 3-trimethoxysilylpropylmethacrylate have a large effect of improving the adhesion of the cured film to the substrate , So preferred.

The addition amount of the adhesion improving agent in 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.

<1-4-3. Anti-agglomerating agent> From the viewpoint of being compatible with a solvent to prevent aggregation, the curable composition of the present invention may further contain an anti-agglomeration agent. The anti-agglomeration agent is used to be compatible with the solvent to prevent aggregation. Specific examples of the anti-agglomerating agent arbitrarily added to the hardenable composition of the present invention are DISPERBYK-145, DISPERBYK-161, DISPERBYK- 162, DISPERBYK -163, DISPERBYK -164, DISPERBYK -182, DISPERBYK -184, DISPERBYK DISPERBYK-185, DISPERBYK-2163, DISPERBYK-2164, BYK-220S, DISPERBYK-191, DISPERBYK (191 DISPERBYK)-199, DISPERBYK-2015 (all trade names, BYK Chemie Japan Co., Ltd.), FTX-218, Ftergent 710FM, Ftergent ) 710FS (both trade names, Neos Co., Ltd.), Floren (Flowlen) G-600 and Floren (Flowlen) G-700 (both trade names, Kyoeisha Chemical Co., Ltd. the company). One or more of these anti-agglomerating agents can be used.

<1-4-4. Antioxidant> From the viewpoint of preventing yellowing of the cured film when exposed to high temperature, the curable composition of the present invention may further contain an antioxidant. Specific examples of antioxidants are Irganox 1010, Irganox 1010FF, Irganox 1035, Irganox 1035FF, Irganox (Irganox) 1076, Irganox 1076FD, Irganox 1098, Irganox 1135, Irganox 1135, Irganox 1330, Irganox (Irganox) 1726, Irganox 1425WL, Irganox 1520L, Irganox 245, Irganox 245FF, Irganox (Irganox) 259, Irganox 3114, Irganox 565, Irganox 565DD (all are trade names, BASF Japan) Co., Ltd. ), ADK STAB (ADK STAB) AO-20, ADK STAB (ADK STAB) AO-30, ADK STAB (ADK STAB) AO-50, ADK STAB (ADK STAB) AO-60 and ADK STAB AO-80 (both trade names, ADEKA Co., Ltd.). One or more of these antioxidants can be used.

Specific examples of these antioxidants are preferably Irganox 1010 and ADK STAB AO-60.

The addition amount of the antioxidant in the curable composition of the present invention is preferably 0.01 to 5 parts by weight relative to 100 parts by weight of the main component.

<1-4-5. Crosslinking agent> From the viewpoint of improving heat resistance, chemical resistance, film surface uniformity, flexibility, flexibility, and elasticity, the curable composition of the present invention may further contain rings other than the polyfunctional epoxy compound (C) Oxygen compounds, melamine compounds and diazide compounds and other cross-linking agents.

Examples of epoxy compounds other than the multifunctional epoxy compound (C) are bisphenol A epoxy compounds, bisphenol F epoxy compounds, biphenyl difunctional epoxy compounds, and disiloxanes having a siloxane bond site. Compounds with two glycidyl ether groups such as functional epoxy compounds; diglycidyl terephthalate, diglycidyl phthalate and 1,2-cyclohexanedicarboxylic acid diglycidyl ester have two A glycidyl ester group; and 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate and other compounds with two alicyclic epoxy groups. One or more of these compounds can be used.

Specific examples of commercially available products of bisphenol A-type epoxy compounds are jER 828, jER 1004, and jER 1009 (all trade names, Mitsubishi Chemical Corporation); specific examples of commercially available products of bisphenol F-type epoxy compounds JER 806, jER 4005P (both trade names, Mitsubishi Chemical Corporation); specific examples of commercially available products of biphenyl type bifunctional epoxy compounds are jER YX4000, jER YX4000H, jER YL6121H (both trade names, Mitsubishi) Chemical Co., Ltd.); a specific example of a commercially available product of a difunctional epoxy compound having a siloxane bond site is TSL9906 (trade name, Momentive Performance Materials Japan Co., Ltd.); p-benzene Specific examples of commercially available products of diglycidyl dicarboxylate are Denacol EX-711 (trade name, Nagase chemteX Co., Ltd.); the market of diglycidyl phthalate Specific examples of products sold are Denacol EX-721 (trade name, Nagase chemteX Co., Ltd.); 3',4'-epoxycyclohexylmethyl-3,4-cyclo A specific example of a commercially available product of oxycyclohexane carboxylic acid ester is Celloxide 2021P (trade name, Daicel Co., Ltd.).

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

<1-4-6. Photoacid generator> From the viewpoint of patterning by exposure and development, the curable composition of the present invention may further contain a photoacid generator. Examples of photoacid generators are 1,2-quinonediazide compounds.

Specific examples of 1,2-quinonediazide compounds are 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate and 2,3,4-trihydroxy Benzophenone-1,2-naphthoquinonediazide-5-sulfonate (for example, trade name, NT-200, Toyo Synthetic Chemical Industry), 2,4,6-trihydroxybenzophenone-1 ,2-naphthoquinonediazide-4-sulfonate, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate; 2,2',4 ,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,2',4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone Diazide-5-sulfonate, 2,3,3',4-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,3',4 -Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide- 4-sulfonate, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate; bis(2,4-dihydroxyphenyl)methane -1,2-naphthoquinonediazide-4-sulfonate, bis(2,4-dihydroxyphenyl)methane-1,2-naphthoquinonediazide-5-sulfonate, bis(p-hydroxy Phenyl)methane-1,2-naphthoquinonediazide-4-sulfonate, bis(p-hydroxyphenyl)methane-1,2-naphthoquinonediazide-5-sulfonate; tri(p-hydroxy Phenyl)methane-1,2-naphthoquinonediazide-4-sulfonate, tris(p-hydroxyphenyl)methane-1,2-naphthoquinonediazide-5-sulfonate, 1,1, 1-Tris(p-hydroxyphenyl)ethane-1,2-naphthoquinonediazide-4-sulfonate, 1,1,1-tris(p-hydroxyphenyl)ethane-1,2-naphthoquinone Diazide-5-sulfonate; bis(2,3,4-trihydroxyphenyl)methane-1,2-naphthoquinonediazide-4-sulfonate, bis(2,3,4-tris Hydroxyphenyl)methane-1,2-naphthoquinonediazide-5-sulfonate, 2,2-bis(2,3,4-trihydroxyphenyl)propane-1,2-naphthoquinonediazide -4-sulfonate, 2,2-bis(2,3,4-trihydroxyphenyl)propane-1,2-naphthoquinonediazide-5-sulfonate; 1,1,3-tri( 2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonate, 1,1,3-tris(2,5-di Methyl-4-hydroxyphenyl)-3-phenylpropane-1,2-naphthoquinonediazide-5-sulfonate, 4,4'-[1-[4-[1-[4-hydroxyl Phenyl]-1-methylethyl]phenyl]ethylene]bisphenol-1,2-naphthoquinonediazide-4-sulfonate, 4,4'-[1-[4-[1 -[4-Hydroxyphenyl]-1-methylethyl]phenyl]ethylene]bisphenol-1,2-naphthoquinonediazide-5-sulfonate; bis(2,5-dimethyl Yl-4-hydroxyphenyl)-2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonate, bis(2,5-dimethyl-4-hydroxybenzene Yl)-2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonate, 3,3,3',3'-tetramethyl-1,1'-spirobiindene-5 ,6,7,5',6',7'-hexanol-1,2-naphthoquinonediazide-4-sulfonate, 3,3,3',3'-tetramethyl-1,1 '-Spirobiindene-5,6,7,5',6',7'-hexanol-1,2-naphthoquinonediazide-5-sulfonate; 2,2,4-trimethyl- 7,2',4'-trihydroxyflavan-1,2-naphthoquinonediazide-4-sulfonate and 2,2,4-trimethyl-7,2',4'-trihydroxy yellow Alkane-1,2-naphthoquinonediazide-5-sulfonate. One or more of these photoacid generators can be used.

The addition amount of the photoacid generator in the curable composition of the present invention is preferably 1 part by weight to 20 parts by weight relative to 100 parts by weight of the main component.

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

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 are ethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,3-butane Glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, tri Ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate ) Acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, ethylene oxide modified bisphenol A di(meth)acrylate 2. Di(meth)acrylates of glycol compounds such as ethylene oxide modified bisphenol F di(meth)acrylate and ethylene oxide modified bisphenol S di(meth)acrylate; Di(meth)acrylate body of triol compounds such as glycerin acrylate methacrylate, glycerin di(meth)acrylate and ethoxylated isocyanurate diacrylate; Di(meth)acrylate bodies 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(meth)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 Alcohol-modified tetrapropylene glycol di(meth)acrylate, epichlorohydrin modified polypropylene glycol di(meth)acrylate, (meth)acrylic adduct of bisphenol A epoxy compound, bisphenol F ring (Meth)acrylic acid adducts of oxygen compounds (meth)acrylic acid adducts and (meth)acrylic acid adducts of bisphenol S-type epoxy compounds. One or more of these compounds can be used.

Specific examples of compounds having three or more (meth)acryloyl groups per molecule are trimethylolpropane tri(meth)acrylate, trimethylolpropane ethylene oxide (EO) Tri(meth)acrylate, trimethylolpropane propylene oxide (Propylene Oxide, PO) modified tri(meth)acrylate, glycerin tri(meth)acrylate, glycerin EO modified tri(methyl) ) Acrylate, glycerol PO modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethoxylated isocyanurate tri(meth)acrylate and e-caprolactone modified tri- (2-(meth)acryloyloxyethyl) isocyanurate and other trifunctional (meth)acrylate compounds; Di-trimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol alkoxy tetra (meth) acrylate and di Glycerol EO modified tetrafunctional (meth)acrylate compounds such as tetraacrylate; Pentaerythritol penta(meth)acrylate and other pentafunctional (meth)acrylate compounds; Hexafunctional (meth)acrylate compounds such as dipentaerythritol hexaacrylate; and Multifunctional (meth)acrylate compound with carboxyl groups. One or more of these compounds can be used.

Specific examples of commercially available products of trimethylolpropane triacrylate as trifunctional acrylate compounds are NK ester (NK ESTER) TMPT (trade name, Shin Nakamura Chemical Industry Co., Ltd.), TMPTA (trade name, contest Luonuosi (Daicel Allnex) Co., Ltd. and Aronix (Aronix) M-309 (trade name, East Asia Synthetic Co., Ltd.); Specific examples of commercially available products of trimethylolpropane EO modified triacrylate are TMPEOTA (trade name, Daicel Allnex Co., Ltd.), Aronix M-350, Yarrow Nice (Aronix) M-360 (both trade names, East Asia Synthetic Co., Ltd.); Specific examples of commercially available products of trimethylolpropane PO modified triacrylate are EBECRYL 135 (trade name, Daicel Allnex Co., Ltd.), Aronix (Aronix) ) M-310, Aronix M-321 (both trade names, East Asia Synthetic Co., Ltd.); A specific example of a commercially available product of glycerin PO modified triacrylate is OTA 480 (trade name, Daicel Allnex Co., Ltd.); A specific example of a commercially available product of ethoxylated isocyanurate triacrylate is NK ester (NK ESTER) A-9300 (trade name, Shin Nakamura Chemical Industry Co., Ltd.); A specific example of a commercially available product of e-caprolactone modified tri-(2-acryloyloxyethyl) isocyanurate is NK ester (NK ESTER) A-9300-1CL (trade name, Shin Nakamura Chemical Industrial Co., Ltd.).

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

Specific examples of commercially available products of di-trimethylolpropane tetraacrylate as tetrafunctional acrylate compounds are NK ester (NK ESTER) AD-TMP (trade name, Shin Nakamura Chemical Industry Co., Ltd.), Aibo EBECRYL 140 and EBECRYL 1142 (both trade names, Daicel Allnex Co., Ltd.), Aronix M-408 (trade name, East Asia Synthesizer) Co., Ltd.); A specific example of a commercially available product of ethoxylated pentaerythritol tetraacrylate is NK ester (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 (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 Allnex Co., Ltd.); A specific example of a commercially available product of diglycerin EO modified tetraacrylate is Aronix M-460 (trade name, East Asia Synthetic Co., Ltd.).

Specific examples of commercially available products of dipentaerythritol hexaacrylate as hexafunctional acrylate compounds are NK ester (NK ESTER) A-DPH (trade name, Shin Nakamura Chemical Industry Co., Ltd.) and DPHA (trade name, Daicel) Daicel Allnex Co., Ltd.).

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

A specific example of a commercially available product of a mixture of ethoxylated isocyanurate triacrylate as a trifunctional acrylate compound and ethoxylated isocyanurate diacrylate as a difunctional acrylate compound is Aronis. (Aronix) M-315 (3% to 13% by weight) (trade name, East Asia Synthetic Co., Ltd., content list in parentheses is the content rate of ethoxylated isocyanurate diacrylate in the mixture Record the value).

Specific examples of commercially available products of a mixture of pentaerythritol triacrylate as a trifunctional acrylate compound and pentaerythritol tetraacrylate as a tetrafunctional acrylate compound are PETIA, PETRA, and PETA (all are trade names, Daicel Onos ( Daicel Allnex Co., Ltd.), Aronix M-306 (65% to 70% by weight), Aronix M-305 (55% to 63% by weight) and Aronix ( Aronix) M-450 (less than 10% by weight) (all are trade names; East Asia Synthetic Co., Ltd., the content rate in parentheses is listed in the catalogue of the content rate of pentaerythritol triacrylate in the mixture).

A specific example of a commercially available product of a mixture of dipentaerythritol pentaacrylate as a pentafunctional acrylate and dipentaerythritol hexaacrylate as a hexafunctional acrylate is Aronix M-403 (50% by weight to 60% by weight) ), Aronix M-400 (40% by weight to 50% by weight), Aronix M-402 (30% by weight to 40% by weight), Aronix M-404 ( 30% by weight to 40% by weight), Aronix M-406 (25% by weight to 35% by weight) and Aronix M-405 (10% by weight to 20% by weight) (trade name, East Asia Synthetic Co., Ltd., the content rate in parentheses is the cataloged value of the content rate of pentaerythritol pentaacrylate in the mixture).

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

<1-4-8. Photopolymerization initiator> From the viewpoint of improving low-temperature curability, the curable composition of the present invention may further contain a photopolymerization initiator. In the case of adding a photopolymerization initiator, the sintering temperature can be reduced by using an ultraviolet irradiation step in combination with a polyfunctional (meth)acrylate compound.

Specific examples of the photopolymerization initiator are benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropyl oxa Anthrone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylbenzeneacetone, 2-hydroxy-2-methyl-4'-iso Propyl phenylacetone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-benzene Acetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one (for example, trade name, Yanjia 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., 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isoamyl ester, 4,4'-bis( Tert-butylperoxycarbonyl)benzophenone, 3,4,4'-tris(tert-butylperoxycarbonyl)benzophenone, 1,2-octanedione, 1-(4-(benzene Thio)phenyl]-2-(O-benzyl oxime) (for example, trade name, Irgacure OXE01, BASF Japan Co., Ltd.), ethyl ketone, 1-[9 -Ethyl-6-(2-methylbenzyl)-9H-oxazol-3-yl]-1-(O-acetyl oxime) (for example, trade name, Irgacure OXE02 , BASF Japan Co., Ltd., Irgacure OXE03 (trade name, BASF Japan Co., Ltd.), 1,2-propanedione, 1-[4-[4- (2-Hydroxyethoxy)phenylthio]phenyl]-2-(O-acetyl oxime) (for example, trade name, Adeka Arkls) NCI-930, Addico (ADEKA) Co., Ltd., Adeka Arkls NCI-831 (trade name, ADEKA Co., Ltd.), Adeka Optomer N- 1919 (trade name, ADEKA Corporation), 2,4,6-trimethylbenzyl diphenylphosphine oxide, 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'-methoxystyryl)-4,6 -Bis(trichloromethyl)-s-triazine, 2-(4'-pentyloxystyryl )-4,6-bis(trichloromethyl)-s-triazine, 4-[p-N,N-bis(ethoxycarbonylmethyl)]-2,6-bis(trichloromethyl)- S-triazine, 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(4'-methyl Oxyphenyl)-s-triazine, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 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'-tetra(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) oxazole, 3,6-bis(2-methyl-2-morpholino Propionyl)-9-n-dodecyl oxazole, 1-hydroxycyclohexyl phenyl ketone and bis(η ⁵ -2,4-cyclopentadien-1-yl)-bis(2,6-di Fluoro-3-(1H-pyrrol-1-yl)-phenyl) titanium. One or more of these photopolymerization initiators can be used.

Among the specific examples of these photopolymerization initiators, if selected from 1,2-octanedione, 1-[4-(phenylthio)phenyl]-2-(O-benzoyl oxime) and 1 ,2-propanedione,1-[4-[4-(2-hydroxyethoxy)phenylthio]phenyl]-2-(O-acetyl oxime) more than one, it can be less The amount of exposure shows the effect of improving the low temperature curability of the curable composition. The addition amount of the photopolymerization initiator suitable for expressing the effect is 0.1 to 5 parts by weight relative to 100 parts by weight of the main component.

<1-5. Solvent added arbitrarily in the curable composition> In addition to the polymerization solvent, a solvent may be added to the curable composition of the present invention. The solvent arbitrarily added to the curable composition of the present invention (hereinafter referred to as "dilution solvent (E)") is preferably a soluble imide compound (A), polyfunctional carboxyl compound (B), and polyfunctional epoxy Compound (C) solvent. When the hardening composition contains the additive (D), the solvent (E) for dilution is preferably a solvent that can further dissolve the additive (D).

The specific example of the dilution solvent (E) is the same as the solvent described as the specific example of the reaction solvent. One or more of these solvents can be used.

<1-6. Preservation of the curable composition> When the curable composition of the present invention is stored in a light-shielded range in the range of -30°C to 25°C, the composition has good stability over time, which is preferable. More preferably, it is stored at -20°C to 5°C.

<2. Cured film obtained from curable composition> The curable composition of the present invention can be obtained by mixing an amide imine compound (A), a polyfunctional carboxyl compound (B) and a polyfunctional epoxy compound (C), and further selectivity according to the target characteristics Adding additives (D) and dilution solvents (E), these compounds are uniformly mixed and dissolved.

By applying the curable composition obtained in the above manner to the surface of the substrate, when the curable composition contains the solvent for the composition, the solvent for the composition is further removed through a heating step, a depressurization step, etc., thereby Coating film can be formed. Specific examples of the method of applying the curable composition to the surface of the substrate are spin coating, roll coating, dipping, and slit coating. A specific example of using the heating step to remove the solvent for the composition is pre-baking using a hot plate and an oven. The pre-baking conditions vary depending on the type of ingredients and the mixing ratio. Usually, the temperature is 70°C to 150°C, if it is a hot plate, it is 1 to 5 minutes, and if it is an oven, it is 5 to 15 minutes.

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

When the polyfunctional (meth)acrylate compound and the photopolymerization initiator as an additive (D) are added to the curable composition, in addition to heat curing by heat treatment, ultraviolet irradiation may be used in combination. Light hardening. In this 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, because it does not affect the photodimerization reaction after forming the hardened film. Furthermore, the ultraviolet rays used in the photo-hardening may be polarized ultraviolet rays or unpolarized ultraviolet rays.

The cured film obtained in this way undergoes three-dimensional crosslinking caused by the condensation of the alkoxysilane group of the amide imide compound (A), and the carboxyl group of the multifunctional carboxyl compound (B) and the multifunctional epoxy compound (C) The three-dimensional crosslinking caused by the epoxy reaction. In addition, regarding the condensation of the alkoxysilyl group of the amide imine compound (A), the carboxyl group of the polyfunctional carboxyl compound (B) functions as a catalyst for increasing the rate of the condensation reaction. Therefore, the obtained cured film has high heat resistance and high resistance to the solvent in the polymerizable liquid crystal composition described later.

In addition, there is a group having a polymerizable double bond of an imide compound (A) and an imide structure in the obtained cured film. The group having a polymerizable double bond and an imidate structure is irradiated with linearly polarized ultraviolet light (wavelength example is 313 nm), and double bonds arranged in a direction parallel to the polarization direction of the linearly polarized ultraviolet light cause a photodimerization reaction, Thus, the liquid crystal alignment ability is given to the cured film, and thus the obtained cured film has optical alignment.

Similarly, a cured film obtained from a curable composition containing a polymer having a cinnamyl group and an epoxy group and a polyfunctional carboxyl compound described in Conventional Document 2 is also three-dimensionally cross-linked and has optical alignment.

However, regarding the curable composition of the present invention and the curable composition described in Conventional Document 2, the compound having a photo-alignment property differs from the other components in the main component in crosslinkability.

The crosslinkable group of the amide imide compound (A) contained in the curable composition of the present invention, which is a photo-alignable compound, is an alkoxysilyl group, so the crosslinkable groups of other components in the main component The crosslinkability with the carboxyl group of the polyfunctional carboxyl compound (B) and the epoxy group of the polyfunctional epoxy compound (C) is low.

On the other hand, the epoxy group, which is a crosslinkable group of a polymer having a cinnamoyl group and an epoxy group, which is a compound having a photo-alignment contained in the curable composition described in Conventional Document 2, is the main component. The crosslinkability of other components of the compound is high in crosslinkability with the carboxyl group of the multifunctional carboxyl compound.

Therefore, when the curable composition of the present invention is cured, the hindrance of photoalignment caused by the crosslinking of the compound having photoalignment and the other components of the main component is small, and this is described in Conventional Document 2 When the curable composition is cured, the photo-alignment caused by the cross-linking of the compound having photo-alignment and other components in the main component is greatly hindered. Therefore, regarding the curable composition of the present invention, even when the compounding ratio of the component having photo-alignment is low, the obtained cured film may have photo-alignment. Therefore, when the curable composition containing no photoalignment component is compared with the curable composition added with photoalignment component, the addition of the photoalignment component can be suppressed. Degradation of characteristics other than optical alignment.

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

Since the curable composition of the present invention has high flatness, the step of the surface of the color filter substrate is reduced by including the cured film. Therefore, when a color filter substrate including the cured film of the present invention is used in a display element, the display quality of the display element is high. [Example]

Next, the present invention will be specifically described through Synthesis Examples, Comparative Synthesis Examples, Examples, and Comparative Examples, but the invention is not limited to these Examples.

The compounds used in Synthesis Examples, Comparative Synthesis Examples, Examples, and Comparative Examples are described in advance for each component.

Anhydride with polymerizable double bond (a1): a1-1: citraconic anhydride a1-2: Maleic anhydride a1-3: Itaconic anhydride Alkoxy silane compounds with amino groups (a2): a2-1: 3-aminopropyltriethoxysilane (hereinafter abbreviated as "APTS") Synthetic solvents used in the synthesis of amide imine compounds (A): EDM, PGME Polymerization inhibitor used in the synthesis of amide imine compound (A): Dibutylhydroxytoluene (hereinafter abbreviated as "BHT")

Tetracarboxylic dianhydride (b11): b11-1: Butane tetracarboxylic dianhydride (trade name, Rikacid BT-100, New Japan Physical and Chemical Corporation, hereinafter referred to as "BT-100") b11-2: 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (hereinafter abbreviated as "ODPA") Diamine (b12): b12-1: 3,3'-diaminodiphenyl ash (hereinafter abbreviated as "DDS") Polyhydroxy compound (b13): b13-1: 1,4-butanediol Monohydric alcohol (b14): b14-1: benzyl alcohol Styrene-maleic anhydride copolymer (b15): b15-1: SMA1000 (trade name, Sichuan Crude Oil Chemical Co., Ltd.) Polymerization solvent used in the reaction of polyester amide acid (B1): MMP, PGMEA

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

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

Solvent for dilution (E): E-1: PGME E-2: PGBE E-3: EDM E-4: PGMEA E-5: MMP E-6: CPN

First, a solution containing the amide imine compound (A) (Synthesis Example 1 to Synthesis Example 3) was synthesized as follows.

[Synthesis Example 1] Synthesis of solution containing amide imine compound (A-1) In a 500 mL four-necked flask including a thermometer, a stirrer, a raw material charging inlet, and a nitrogen gas inlet, citraconic anhydride, which is an acid anhydride (a1) having a polymerizable double bond, and alkoxy, which has an amino group, are charged with the following weights The APTS of the silane-based compound (a2) and EDM as a synthesis solvent were heated in an oil bath set at 130°C for 3 hours, and then aged at 145°C for 2 hours, and the low-boiling components were distilled off under normal pressure . Citraconic anhydride 64.51 g APTS 127.49 g EDM 48.00 g The reaction liquid was cooled to 30° C. or lower to obtain a solution containing an amide imine 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 dry weight method. As a result of these, the weight average molecular weight was 2,150, and the solid content concentration was 78% by weight. In addition, the molar ratio (anhydride group/amino group) of the amino group of the acid anhydride (a1) having a polymerizable double bond and the amino group of the alkoxysilane group compound (a2) charged as raw materials was 1.0.

[Synthesis Example 2] Synthesis of solution containing amide imine compound (A-2) In a 200 mL four-necked flask including a thermometer, a stirrer, a raw material charging inlet, and a nitrogen gas inlet, maleic anhydride, which is an acid anhydride (a1) having a polymerizable double bond, and alkoxy, which has an amino group, are charged with the following weights The APTS of the silane-based compound (a2), BHT as a polymerization inhibitor, and EDM as a synthesis solvent are heated in an oil bath set at 100°C for 3 hours, and then set at 120°C for 2 hours, and at normal pressure Next, the low boiling point components are distilled off. Maleic anhydride 10.00 g APTS 22.58 g BHT 0.0163 g EDM 21.72 g The reaction liquid was cooled to 30° C. or lower to obtain a solution containing an amide imine 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 dry weight method. As a result of these, the weight average molecular weight was 2,850, and the solid content concentration was 58% by weight. In addition, the molar ratio (acid anhydride group/amino group) of the acid anhydride group of the acid anhydride (a1) having a polymerizable double bond and the amino group of the alkoxysilane group compound (a2) having an amino group charged as raw materials was 1.0.

[Synthesis Example 3] Synthesis of solution containing amide imine compound (A-3) In a 200 mL four-necked flask including a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet, itaconic anhydride, which is an acid anhydride (a1) having a polymerizable double bond, and alkoxy, which has an amino group, are charged with the following weights The APTS of the silane-based compound (a2), BHT as a polymerization inhibitor, and PGME as a synthesis solvent were heated in an oil bath set at 100°C for 3 hours, and then set at 120°C for 2 hours, and at normal pressure Next, the low boiling point components are distilled off. Itaconic anhydride 8.00 g APTS 15.80 g BHT 0.0119 g PGME 23.81 g The reaction liquid was cooled to 30° C. or lower to obtain a solution containing an amide imine 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 dry weight method. As a result of these, the weight average molecular weight was 1,100, and the solid content concentration was 49% by weight. In addition, the molar ratio (acid anhydride group/amino group) of the acid anhydride group of the acid anhydride (a1) having a polymerizable double bond and the amino group of the alkoxysilane group compound (a2) having an amino group charged as raw materials was 1.0.

Using a raw material containing tetracarboxylic dianhydride, diamine, and polyhydroxy compound, a solution containing polyester amide acid was synthesized as follows (Synthesis Example 4 and Synthesis Example 5).

[Synthesis Example 4] Synthesis of a solution containing polyester amide acid (B1-1) In a 1,000 mL four-necked flask including a thermometer, stirrer, raw material inlet, and nitrogen inlet, 604.80 g of PGMEA as the solvent used in the synthesis reaction and 34.47 g of BT as the tetracarboxylic dianhydride -100, 164.11 g of SMA1000 as a styrene-maleic anhydride copolymer, 50.17 g of benzyl alcohol as a monohydroxy compound, and 10.45 g of 1,4-butanediol as a polyhydroxy compound under a dry nitrogen gas flow And it was stirred at 130°C for 3 hours. Thereafter, the solution after the reaction was cooled to 25°C, and 10.80 g of DDS as a diamine and 25.20 g of PGMEA were added, stirred at 20°C to 30°C for 2 hours, and then stirred at 115°C for 1 hour, and After cooling to 30° C. or lower, a light yellow transparent solution containing polyester amidic acid (B1-1) with a solid content concentration of 30% by weight was obtained. The weight average molecular weight measured by GPC was 10,000.

[Synthesis Example 5] Synthesis of a solution containing polyester amide acid (B1-2) In a 1,000 mL four-necked flask including a thermometer, stirrer, raw material inlet and nitrogen inlet, 446.96 g of MMP as the solvent used in the synthesis reaction and 31.93 g of 1,4 as the polyhydroxy compound -Butanediol, 25.54 g of benzyl alcohol as a monohydroxy compound, and 183.20 g of ODPA as a tetracarboxylic dianhydride were stirred at 130° C. for 3 hours under a stream of dry nitrogen. Thereafter, the solution after the reaction was cooled to 25°C, and 29.33 g of DDS as a diamine and 183.04 g of MMP were added, stirred at 20°C to 30°C for 2 hours, and then stirred at 115°C for 1 hour, and It cooled to 30 degreeC or less, and obtained the solution containing the polyester amidic acid (B1-2) with a pale yellow transparent solid content concentration of 30 weight%. In addition, the weight average molecular weight measured by GPC was 4,200.

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

[Synthesis Example 6] Synthesis of a solution containing a polymer (Z-1) having a cinnamyl group and an epoxy group Into a 500 mL four-necked flask including a thermometer, a stirrer, a raw material inlet and a nitrogen inlet, 135.00 g of 2-acrylic acid-2-{4-[(1E )-3-methoxy-3- pendant-1-propen-1-yl]phenoxy}ethyl=2-methyl ester, 15.00 g of methacrylic acid as a polymerizable compound having an epoxy group Glycidyl ester, 15.00 g of 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator, and 50.00 g of CPN as a reaction solvent, heated at a polymerization temperature of 90°C Polymerization took place in 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 cinnamyl group and an epoxy group with a solid content concentration of 25% by weight. In addition, the weight average molecular weight measured by GPC was 6,400.

[Example 1] The solution containing the amide imide compound (A-1) obtained in Synthesis Example 1 as the solution containing the amide imide compound (A) was used as the solution containing the polyfunctional carboxyl group at the ratio (unit: g) described in Table 1. The solution containing the compound amide acid (B1-1) obtained in Synthesis Example 4 of the solution of the compound (B), 157S70 as the multifunctional epoxy compound (C), and PGBE as the solvent for dilution (E) , EDM and PGMEA are mixed and dissolved, and filtered with a membrane filter (0.2 μm) to obtain a hardening composition.

Proportion of the imidate compound (A) in the total amount of acetimidate compound (A), polyfunctional carboxy compound (B) and polyfunctional epoxy compound (C) 100% by weight (unit:% by weight, in the table "100×(A)/[(A)+(B)+(C)]") is shown in Table 1.

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

Table 1

表中的（A-1）、（A-2）、（A-3）、（B1-1）、（B1-2）及（Z-1）為溶液的重量。Table 1 (continued)

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

In addition, the total amount of the solvent contained in the curable composition of Example 1 is PGBE which is the reaction solvent contained in the solution containing the amide imine compound (A-1), and the dilution solvent (E) The total amount of EDM, PDMA, and PGMEA was prepared by the above-mentioned procedure so that the solid content concentration became approximately 25% by weight. The same also applies to Examples and Comparative Examples after Example 2.

[Fabrication of glass substrate with cured 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, thereby obtaining a substrate with a coating film. Furthermore, post-baking in an oven at 230° C. for 30 minutes, a substrate with a cured film having a cured film thickness of approximately 1.5 μm was obtained. Hereinafter, the obtained substrate with a cured film is expressed as "glass substrate with a cured film".

[Viscosity evaluation] The stickiness of the coating film of the substrate with the coating film was confirmed. The non-sticky (non-sticky) case is evaluated as sticky "◎", the non-sticky but residual fingerprint when pressed strongly is evaluated as sticky "○", and the sticky case is evaluated as sticky " ×", the liquid state is evaluated as the viscosity "××". Table 1 shows the evaluation results.

[Measurement of light transmittance] Use a UV-visible near-infrared spectrophotometer V-670 (trade name, Japan Spectroscopy Co., Ltd.), and set a glass substrate on which the hardened film is not formed on the reference side of the ultraviolet-visible near-infrared spectrophotometer and set the obtained on the sample side For a glass substrate with a cured film, the transmittance of only the cured film at a wavelength of light of 400 nm was measured. Table 1 shows the measured values.

[Evaluation of transparency] The case where the light transmittance is 99.0% or more is evaluated as transparency "◎", the case where 97.0% or more and less than 99.0% is evaluated as transparency "○", and the case where less than 97.0% is evaluated as transparency "×" ". Table 1 shows the evaluation results.

[Calculation of 5% weight loss temperature] A powdery sample for measurement was cut out from the obtained cured film of the glass substrate with a cured film. The temperature dependence of the thermal weight loss rate of the obtained sample was measured using a differential thermal balance Thermo plus EVO TG-DTA 8120 (trade name, Rigaku Corporation). The temperature was heated from a room temperature at a temperature increase rate of 10°C/min, and the temperature at which the weight reduction rate became 5% based on the thermal weight reduction rate of 100°C was calculated as the “5% weight reduction temperature”. Table 1 shows the calculated values.

[Evaluation of heat resistance] The case where the 5% weight loss temperature is 310°C or higher is evaluated as heat resistance “◎”, the case where the temperature is 290°C or higher and less than 310°C is evaluated as heat resistance “○”, and the case where the temperature is less than 290°C is evaluated as heat resistance "×". Table 1 shows the evaluation results.

[Preparation of polymerizable liquid crystal composition] The polymerizable liquid crystal composition used in the evaluation was prepared as follows. Add 5.0 g of Paliocolor LC242 (trade name, BASF Japan Co., Ltd.), 0.25 g of IRGACURE 907 (trade name, BASF Japan) Co., Ltd. ), 0.0050 g of BYK361N (trade name, BYK Chemie Japan) Co., Ltd. and toluene as an organic solvent are prepared in such a way that the organic solvent is 85% by weight as a whole, and are uniformly mixed and dissolved. Let the said composition be a polymerizable liquid crystal composition (PLC-1).

[Fabrication of glass substrate with optical function film] The light irradiated by the ultra-high pressure mercury lamp is converted into linear polarized light through a filter and a wire grid polarizing plate that cut off light below 300 nm, and is converted into 313 nm The obtained glass substrate with a cured film was irradiated with 500 mJ/cm ² .

Then, 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 cooling the substrate to room temperature, the entire line of an ultra-high pressure mercury lamp of 300 mJ/cm ^{2 was} irradiated in 365 nm conversion, and the polymerizable liquid crystal composition was photohardened to fix the alignment. Hereinafter, the obtained substrate is expressed as "glass substrate with optical functional film".

[Evaluation of optical alignment] The obtained glass substrate with an optical function film was sandwiched between two linear polarizers in a crossed (crossed nicols) state, and the backlight was illuminated from below and observed. The light and dark display without alignment defects (no light leakage) is evaluated as light alignment "◎", and the light and dark display can be displayed as a whole, but the partial alignment defects are observed as light alignment "○", and the other The situation is evaluated as the optical alignment "×". Table 1 shows the evaluation results.

[Manufacture of color filter substrate with cured film] The glass substrate was changed to a color filter substrate, and otherwise, a color filter substrate with a cured film was obtained according to a method of manufacturing a glass substrate with a cured film. Here, the color filter substrate used in the experiment is a substrate including red (R), green (G), and blue (B) color bodies and a black matrix for preventing color mixing on a glass substrate, and the maximum step difference is 0.60 μm～0.65 μm.

[Calculation of flattening rate] In the preparation of a color filter substrate with a cured film, the maximum step difference (set to "TIR ₀ ") of the color filter substrate before applying the curable composition was measured, After the color filter substrate with a cured film was produced, the maximum step difference (set to "TIR ₁ ") of the obtained color filter substrate with a cured film was measured. Based on the two maximum order differences obtained, the flattening rate = 100% × [(TIR ₀ )-(TIR ₁ )]/(TIR ₀ ) is calculated. Table 1 shows the calculated values.

[Evaluation of flatness] The case where the flattening rate is 50% or more is evaluated as the flattening property "○", and the case where the flattening rate is less than 50% is evaluated as the flattening property "×". Table 1 shows the evaluation results.

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

The viscosity was evaluated according to the method of Example 1, the transparency was evaluated based on the measured value of light transmittance, the heat resistance was evaluated based on the calculated value of 5% weight loss temperature, and the optical alignment was evaluated, based on the calculated value of the flattening rate To evaluate flatness. Table 1 shows the respective measured values, calculated values, and evaluation results. However, the rotation speed when spin-coating the curable composition on the glass substrate is adjusted so that the thickness of the cured film becomes approximately 1.5 μm.

From the results shown in Table 1, it is clear that the curable compositions of Examples 1 to 11 have low viscosity and excellent flatness, and the transparency, heat resistance and transparency of the cured film obtained from the curable composition Excellent optical alignment. On the other hand, the cured film obtained from the curable composition of Comparative Example 1 containing no amide imine compound (A) had poor optical alignment. The curable composition described in Comparative Example 2 without the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C) had high viscosity and poor flatness. In addition, the transparency and the transparency of the cured film obtained from the curable compositions of Comparative Examples 3 and 4 comprising the polyfunctional carboxyl compound (B) and the polymer (Z) having a cinnamyl group and an epoxy group Poor heat resistance.

[Industry availability] The curable composition of the present invention has low viscosity and excellent flatness, and the cured film obtained from the curable composition of the present invention has excellent transparency, heat resistance, and optical alignment, and thus can be used as a color with optical alignment Filter protection film.

no

no

Claims (9)

A hardening composition comprising an amide imine compound (A), a polyfunctional carboxyl compound (B) and a polyfunctional epoxy compound (C), and The amide imine compound (A) is a reaction product derived from an acid anhydride (a1) having a polymerizable double bond and an alkoxysilane group compound (a2) having an amino group as necessary raw materials, The multifunctional carboxyl compound (B) is a compound having three or more carboxyl groups per molecule, The multifunctional epoxy compound (C) is a compound having three or more epoxy groups per molecule. The curable composition as described in item 1 of the patent application scope, wherein the total amount of the amide imine compound (A), the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C) 100% by weight, the amide imine compound (A) is 5% to 80% by weight; In the total amount of 100% by weight of the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C), the polyfunctional carboxyl compound (B) is 20% to 80% by weight. The curable composition as described in item 1 of the patent application scope, wherein the total amount of the amide imine compound (A), the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C) 100% by weight, the amide imine compound (A) is 15% to 60% by weight; In the total amount of 100% by weight of the polyfunctional carboxyl compound (B) and the polyfunctional epoxy compound (C), the polyfunctional carboxyl compound (B) is 40% to 75% by weight. The curable composition as described in any one of the first to third patent claims, wherein the acid anhydride (a1) having a polymerizable double bond is selected from a compound represented by the following formula (1) and At least one of the compounds represented by the following formula (2);

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

In formula (2), R ³ is hydrogen or a C 1-5 alkyl group. The curable composition as described in any one of the first to fourth patent applications, wherein the acid anhydride (a1) having a polymerizable double bond is selected from maleic anhydride, citraconic anhydride and itaconic anhydride At least one of them. The hardenable composition according to any one of claims 1 to 5 of the patent application, wherein the alkoxysilane group compound (a2) having an amino group is selected from 3-aminopropyltrimethoxysilane , At least one of 3-aminopropyltriethoxysilane, 4-aminophenyltrimethoxysilane and 4-aminophenyltriethoxysilane. The curable composition as described in any one of the patent application items 1 to 6, wherein the polyfunctional carboxyl compound (B) is a tetracarboxylic dianhydride, diamine, and polyhydroxy compound are required The raw material of polyester amide acid. A cured film obtained by curing the curable composition according to any one of claims 1 to 7 of the patent application. A color filter substrate including the cured film as described in item 8 of the patent application.