WO2021028960A1 - Colored resin composition, cured product, and laminate - Google Patents

Abstract

[Problem] To provide: a colored resin composition which includes a polyimide compound that is highly soluble in an organic solvent and from which a cured product having excellent adhesion to a polyimide film substrate can be formed; and a cured product formed using said colored resin composition. [Solution] A colored resin composition according to the present invention comprises (A) an organic solvent-soluble polyimide compound, (B) a colorant, and (C) an organic solvent, the colored resin composition being characterized in that the (A) organic solvent-soluble polyimide compound is obtained by imidizing a polyimide precursor composed of reaction components including: (A-1) a diamine compound represented by general formula (1); (A-2) at least one among a diamine compound having at least one among a carboxyl group and a hydroxyl group, and a diamine compound having a siloxane bond; and (A-3) an acid anhydride.

Description

Colored resin composition, cured product and laminate

The present invention relates to a colored resin composition, and a cured product and a laminate formed by using the colored resin composition.

Polyimide compounds are widely used in various fields because they have excellent properties such as high heat resistance and dimensional stability. For example, in recent years, glass substrates such as cover glasses provided in organic EL display devices have been used. , It is being studied to change to a resin film (hereinafter referred to as a polyimide film) base material containing a polyimide compound and to impart flexibility to these.

Further, the organic EL display device or the like is provided with a metal wiring in the ITO film pattern formed in the image display area and the peripheral portion thereof, and further, a cover is provided so that the metal wiring is not visually recognized by the user. A shielding portion is provided on the inner peripheral portion of the glass.

This shielding portion is composed of a cured product formed by applying a colored resin composition containing a resin material and a coloring agent to the inner peripheral portion of the cover glass and drying it.
In recent years, in order to impart higher flexibility to organic EL display devices and the like, the glass base material has been changed to a polyimide film base material, and a resin material contained in a colored resin composition used for forming a shielding portion. However, the use of polyimide compounds is being considered.

Normally, a polyimide compound has low solubility in an organic solvent, and when a cured product is to be formed, the polyimide compound is dissolved in an organic solvent as a precursor (polyamic acid), coated, and then heated at a high temperature to form a ring. It was necessary to carry out a chemical dehydration reaction (polyimide).
Here, Patent Document 1 proposes the use of an organic solvent-soluble polyimide compound in order to solve the problem caused by high-temperature heating during the formation of a cured product.

Patent Document 1: Japanese Unexamined Patent Publication No. 2007-12990

Nowadays, the present inventors have adhered to a polyimide film substrate in a cured product formed by using a colored resin composition containing a conventionally known organic solvent-soluble polyimide compound as disclosed in Patent Document 1. I noticed a new issue that was not enough and there was room for improvement.
The present invention has been made to solve such a problem, and its main purpose is to form a cured product containing a polyimide compound having high solubility in an organic solvent and having excellent adhesion to a polyimide film substrate. It is to provide a colored resin composition which can be made.
Another object of the present invention is to provide a cured product and a laminate formed by using the colored resin composition.

As a result of diligent research toward the realization of the above object, the present inventors have completed an invention having the following contents as a gist.
That is, the colored resin composition of the present invention
(A) Organic solvent-soluble polyimide compound and
(B) Colorant and
(C) A colored resin composition containing an organic solvent.
The organic solvent-soluble polyimide compound (A) is
(A-1) The diamine compound represented by the following general formula (1) and
(A-2) A diamine compound having at least one of a carboxyl group and a hydroxyl group, and at least one of a diamine compound having a siloxane bond.
(A-3) It is characterized in that it is an imidized polyimide precursor composed of a reaction component containing an acid anhydride.

(In the above general formula (1),
Any of R ₁ to R ₄ is selected from an aromatic group having 6 to 10 carbon atoms, a phenoxy group having 6 to 10 carbon atoms, a benzyl group having 6 to 10 carbon atoms, and a benzyloxy group having 6 to 10 carbon atoms. , Other R ₁ to R ₄ are hydrogen atoms. )

In one embodiment, the (A) organic solvent-soluble polyimide compound contains a diamine compound having at least one of a carboxyl group and a hydroxyl group as a reaction component (A-2).
The diamine compound having at least one of a carboxyl group and a hydroxyl group is represented by the following general formula (2) or (3).

(In the above general formulas (2) and (3), R ₅ is selected from a divalent organic group or a single bond, and n is an integer of 1 to 10, preferably 1 to 5.
Further, R ₆ is independently selected from COOH or OH, o is an integer of 0 to 4, and the diamine compound represented by the general formula (2) has at least one R _6. ,
In the above general formula (3), p is an integer of 1 to 4. )

In one embodiment, the (A) organic solvent-soluble polyimide compound contains a diamine compound having a siloxane bond as a reaction component (A-2).
The diamine compound having a siloxane bond is represented by the following general formula (4).

(In the above general formula (4), R ₇ to R ₁₂ are alkyl groups or phenyl groups.
q and r are independently integers of 1 to 10, and s is an integer of 0 to 10. )

In one embodiment, the organic solvent is an aromatic carboxylic acid ester.

In one embodiment, the (A) organic solvent-soluble polyimide compound contains both a diamine compound having at least one of a carboxyl group and a hydroxyl group and a diamine compound having a siloxane bond as a reaction component (A-2).

The cured product of the present invention is characterized by being formed by using the above-mentioned colored resin composition.

The laminate of the present invention is characterized by including a polyimide film base material and a layer made of a cured product formed by using the colored resin composition.

According to the present invention, a colored resin composition capable of forming a cured product without requiring excessive heating and forming a cured product having good adhesion to a polyimide film substrate can be obtained. Can be provided.
Further, according to the present invention, it is possible to provide a cured product and a laminate formed by using the colored resin composition.

[Colored resin composition]
The colored resin composition of the present invention is characterized by containing (A) an organic solvent-soluble polyimide compound, (B) a colorant, and (C) an organic solvent.
In addition, the colored resin composition of the present invention may contain an antifoaming agent.

Hereinafter, various materials contained in the colored resin composition of the present invention will be described in detail.

[(A) Organic solvent-soluble polyimide compound]
The organic solvent-soluble polyimide compound is composed of (A-1) a diamine compound represented by the following general formula (1), (A-2) a diamine compound having at least one of a carboxyl group and a hydroxyl group, and a diamine compound having a siloxane bond. A polyimide precursor (polyamic acid) composed of a reaction component containing at least one of them and (A-3) acid anhydride is dehydrated and ring-closed to be polyimideized.
Such an organic solvent-soluble polyimide compound is highly soluble in an organic solvent and does not need to be contained in the colored resin composition in the state of a polyimide precursor (polyamic acid). Therefore, in the formation of the cured product, it is not necessary to excessively heat for the dehydration ring closure reaction, and the cured product can be formed by volatilizing the organic solvent in the colored resin composition by drying, and the polyimide film can be formed. It is possible to effectively prevent discoloration of the resin. Further, the cured product formed by using the colored resin composition containing such an organic solvent-soluble polyimide compound exhibits excellent adhesion to the polyimide film base material.

The content of the organic solvent-soluble polyimide compound in the colored resin composition is preferably 15% by mass or more and 35% by mass or less, and more preferably 20% by mass or more and 30% by mass or less. By setting the content of the organic solvent-soluble polyimide compound in the colored resin composition within the above numerical range, the adhesion of the cured product formed by using the colored resin composition containing the organic solvent-soluble polyimide compound to the polyimide film substrate can be improved. Can be improved further. In addition, the moldability of the colored resin composition of the present invention can be improved. In particular, when screen printing is used for forming the cured product, the release property of the colored resin composition can be remarkably improved.

In the organic solvent-soluble polyimide compound, the constituent ratio of the constituent unit derived from the diamine compound represented by the general formula (1) and the constituent unit derived from the diamine compound having at least one of a carboxyl group and a hydroxyl group is based on mol%. It is preferably 1: 1 to 1: 4, and more preferably 1: 1 to 1: 3. By setting the composition ratio within the above numerical range, the solubility of the organic solvent-soluble polyimide compound in the organic solvent can be effectively improved. In addition, the adhesion of the cured product formed by using the colored resin composition containing the organic solvent-soluble polyimide compound to the polyimide film substrate can be effectively improved. Further, the coefficient of thermal expansion of this cured product can be effectively improved.

In the organic solvent-soluble polyimide compound, the structural unit derived from the diamine compound represented by the general formula (1) and the structural unit derived from the diamine compound having a siloxane bond are 1: 1 to 1 on a mol% basis. : 4 is preferable, and 1: 1 to 1: 3 is more preferable. By setting the content ratio within the above numerical range, the solubility of the organic solvent-soluble polyimide compound in the organic solvent can be effectively improved. In addition, the adhesion of the cured product formed by using the colored resin composition containing the organic solvent-soluble polyimide compound to the polyimide film substrate can be effectively improved. Furthermore, the coefficient of thermal expansion of this cured product can be effectively improved.

Further, it is preferable that the organic solvent-soluble polyimide compound contains both a diamine compound having at least one of a carboxyl group and a hydroxyl group and a diamine compound having a siloxane bond as a reaction component (A-2). Thereby, the adhesion of the cured product formed by using the colored resin composition containing the organic solvent-soluble polyimide compound to the polyimide film substrate can be more effectively improved.
In this case, in this organic solvent-soluble polyimide compound, a structural unit derived from a diamine compound represented by the general formula (1), a diamine compound having at least one of a carboxyl group and a hydroxyl group, and a structural unit derived from a diamine compound having a siloxane bond. The composition ratio of and is preferably 1: 1 to 1: 6 on a molar% basis, and more preferably 1: 1 to 1: 5. By setting the composition ratio within the above numerical range, the solubility of the organic solvent-soluble polyimide compound in the organic solvent can be effectively improved. In addition, the adhesion of the cured product formed by using the colored resin composition containing the organic solvent-soluble polyimide compound to the polyimide film substrate can be effectively improved. Further, the coefficient of thermal expansion of this cured product can be effectively improved.
When the organic solvent-soluble polyimide compound contains both a diamine compound having at least one of a carboxyl group and a hydroxyl group and a diamine compound having a siloxane bond as the reaction component (A-2), the organic solvent-soluble polyimide compound is used. In the compound, the constituent ratio of the constituent unit derived from the diamine compound having at least one of a carboxyl group and the hydroxyl group and the constituent unit derived from the diamine compound having a siloxane bond is preferably 4: 1 to 1: 4. More preferably, it is 3: 2 to 2: 3. By setting the composition ratio within the above numerical range, the adhesion of the cured product formed by using the colored resin composition containing the organic solvent-soluble polyimide compound to the polyimide film substrate can be more effectively improved.

The weight average molecular weight (Mw) of the organic solvent-soluble polyimide compound is preferably 30,000 or more and 100,000 or less, more preferably 33,000 or more and 80,000 or less, and 33,000 or more. It is particularly preferably 50,000 or less. By setting the Mw of the organic solvent-soluble polyimide compound within the above numerical range, the moldability of the colored resin composition of the present invention can be improved. In particular, when screen printing is used for forming the cured product, the release property of the colored resin composition can be remarkably improved.
In the present invention, Mw means a value measured by gel permeation chromatography using polystyrene as a standard substance, and is measured by a method based on JIS K 7252-1 (published in 2008).

[Diamine compound represented by the general formula (1)]
The organic solvent-soluble polyimide compound constituting the colored resin composition of the present invention contains a diamine compound represented by the following general formula (1) as a reaction component at the time of synthesis. Thereby, the solubility of the organic solvent-soluble polyimide compound in the organic solvent can be effectively improved. Further, the coefficient of thermal expansion of the cured product formed by using the colored resin composition containing the organic solvent-soluble polyimide compound can be effectively improved.

In the general formula _(1), any one of R 1 ~ _{R 4} are preferably either _{R 1} or _{R 3,} particularly preferably is _{R 3,} aromatic groups having 6 to 10 carbon atoms, 6 carbon atoms It is selected from a phenoxy group having a phenoxy group of about 10 and a benzyl group having 6 to 10 carbon atoms and a benzyloxy group having 6 to 10 carbon atoms, and the other groups R ₁ to R ₄ are hydrogen atoms.
The aromatic group having 6 to 10 carbon atoms includes a phenyl group, a trill group, a methylphenyl group, a dimethylphenyl group, an ethylphenyl group, a diethylphenyl group, a propylphenyl group, a butylphenyl group, a fluorophenyl group, and a pentafluorophenyl group. , Chlorphenyl group, bromophenyl group, methoxyphenyl group, dimethoxyphenyl group, ethoxyphenyl group, diethoxyphenyl group, methoxybenzyl group, dimethoxybenzyl group, ethoxybenzyl group, diethoxybenzyl group, aminophenyl group, aminobenzyl group , Nitrophenyl group, nitrobenzyl group, cyanophenyl group, cyanobenzyl group, phenethyl group, phenylpropyl group, phenylamino group, diphenylamino group, biphenyl group, naphthyl group and the like.
Examples of the phenoxy group having 6 to 10 carbon atoms include a methylphenoxy group, an ethylphenoxy group, a propylphenoxy group, a dimethylphenoxy group, a diethylphenoxy group, a methoxyphenoxy group, an ethoxyphenoxy group and a dimethoxyphenoxy group.
Examples of the benzyl group having 6 to 10 carbon atoms include a benzyl group, a methylbenzyl group, an ethylbenzyl group, a propylbenzyl group, a dimethylbenzyl group, a methoxybenzyl group, an ethoxybenzyl group and a methoxybenzyl group.
As the benzyloxy group having 6 to 10 carbon atoms, the methylbenzyloxy group includes a benzyloxy group, a betylbenzyloxy group, an ethylbenzyloxy group, a propylbenzyloxy group, a dimethylbenzyloxy group, a methoxybenzyloxy group and an ethoxy. Examples include the benzyloxy group.
Among the above, from the viewpoint of further improving the effect of the diamine compound represented by the above general formula (1), an aromatic group having 6 to 10 carbon atoms is more preferable, and a phenyl group, a tolyl group, a methylphenyl group, and the like. A dimethylphenyl group, an ethylphenyl group and a diethylphenyl group are more preferable, and a phenyl group is particularly preferable.

The following compounds are mentioned as a particularly preferable embodiment of the diamine compound represented by the general formula (1).

In the organic solvent-soluble polyimide compound, when the total content of the constituent units derived from the diamine component is 100 mol parts, the constituent ratio of the diamine compound represented by the above general formula (1) is 15 mol parts or more and 60 mol parts. It is preferably 18 mol parts or more, and more preferably 55 mol parts or less. By setting such a numerical range, the effect of the diamine compound represented by the above-mentioned general formula (1) can be further improved. In addition, the adhesion of the cured product formed by using the colored resin composition of the present invention to the polyimide film substrate can be further improved.

[Diamine compound having at least one of a carboxyl group and a hydroxyl group]
In one embodiment, the organic solvent-soluble polyimide compound constituting the colored resin composition of the present invention contains a diamine compound having at least one of a carboxyl group and a hydroxyl group as a reaction component at the time of synthesis. Thereby, the adhesiveness of the cured product formed by using the colored resin composition of the present invention to the polyimide film base material can be effectively improved.

In one embodiment, the diamine compound having at least one of a carboxyl group and a hydroxyl group is represented by the following general formula (2).

In the above general formula (2), R ₅ is a divalent organic group or a single bond, and n is an integer of 1 to 10, preferably 1 to 5.
Further, R ₆ is independently selected from COOH or OH, o is an integer of 0 to 4, and the diamine compound represented by the general formula (2) has at least one R ₆ .

The following compounds are mentioned as a particularly preferable embodiment of the diamine compound having at least one of a carboxyl group and a hydroxyl group represented by the general formula (2).

In one embodiment, the diamine compound having at least one of a carboxyl group and a hydroxyl group is represented by the following general formula (3).

In the above general formula (3), R ₅ is a divalent organic group or a single bond, and p is an integer of 1 to 4.

The following compounds are mentioned as a particularly preferable embodiment of the diamine compound having at least one of a carboxyl group and a hydroxyl group represented by the general formula (3).

In the organic solvent-soluble polyimide compound, when the total content of the constituent units derived from the diamine component is 100 mol parts, the constituent ratio of the diamine compound having at least one of a carboxyl group and a hydroxyl group is 30 mol parts or more and 85 mol parts or less. It is more preferably 33 mol parts or more and 60 mol parts or less, and further preferably 35 mol parts or more and 45 mol parts or less. By setting such a numerical range, the adhesion of the cured product formed by using the colored resin composition of the present invention to the polyimide film substrate can be further improved. Further, the solubility of the organic solvent-soluble polyimide compound in the organic solvent can be effectively improved. Further, the coefficient of thermal expansion of the cured product formed by using the colored resin composition containing the organic solvent-soluble polyimide compound can be effectively improved.

[Diamine compound with siloxane bond]
In one embodiment, the organic solvent-soluble polyimide compound constituting the colored resin composition of the present invention contains a diamine compound having a siloxane bond as a reaction component during synthesis. Thereby, the adhesiveness of the cured product formed by using the colored resin composition of the present invention to the polyimide film base material can be effectively improved.

In one embodiment, the diamine compound having a siloxane bond is represented by the following general formula (4).

In the above general formula (4), R ₇ to R ₁₂ are alkyl groups or phenyl groups. From the viewpoint of obtaining excellent adhesion to the polyimide film substrate in the cured product, an alkyl group is preferable, and the number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 6. It is more preferably 1 to 3.
Further, q and r are independently selected from integers of 1 to 10. From the viewpoint of polymerization reactivity, it is preferably 1 to 6, and more preferably 1 to 3. s is selected from an integer from 0 to 10. From the viewpoint of polymerization reactivity, it is preferably 0 to 6, and more preferably 0 to 2.

The following compounds are mentioned as a particularly preferable embodiment of the diamine compound having a siloxane bond represented by the general formula (4).

In the organic solvent-soluble polyimide compound, when the total content of the constituent units derived from the diamine component is 100 mol parts, the constituent ratio of the diamine compound having a siloxane bond is preferably 30 mol parts or more and 60 mol parts or less. , 35 mol parts or more, more preferably 55 mol parts or less. By setting such a numerical range, the adhesion of the cured product formed by using the colored resin composition of the present invention to the polyimide film substrate can be further improved. Further, the solubility of the organic solvent-soluble polyimide compound in the organic solvent can be effectively improved. Further, the coefficient of thermal expansion of the cured product formed by using the colored resin composition containing the organic solvent-soluble polyimide compound can be effectively improved.

[Acid anhydride]
The organic solvent-soluble polyimide compound constituting the colored resin composition of the present invention can be used as a reaction component during synthesis, and examples of the acid anhydride include pyromellitic anhydride, 2,2'-bis [4- (3). , 4-Dicarboxyphenoxy) propanoic acid dianhydride], 4,4'-oxydiphthalic acid dianhydride, biphenyl-3,4,3', 4'-tetracarboxylic acid dianhydride, benzophenone-3,4 3', 4'-Tetracarboxylic Acid Dianhydride, Diphenylsulfon-3,4,3', 4'-Tetracarboxylic Acid Dianhydride, 4,4'-(2,2-hexafluoroisopropyridene) diphthalic acid Dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene diacid anhydride, 4,4'-(4,4'-isopropyridene diphenoxy) diphthalic anhydride, 2,3,6 , 7-Naphthalenetetracarboxylic acid 2,3: 6,7-dianhydride, bis (1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid) 1,4-phenylene, butane-1, 2,3,4-Tetracarboxylic acid dianhydride, Pentan-1,2,4,5-Tetracarboxylic acid dianhydride, Cyclobutane-1,2,3,4-Tetracarboxylic acid dianhydride, 1,2 , 3,4-Tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, octahydrobiphenylene-4a, 8b: 4b, 8a-tetracarboxylic acid dianhydride, cyclopentane-1,2, 3,4-Tetracarboxylic acid dianhydride, cyclohexane-1,2,4,5-tetracarboxylic acid dianhydride, cyclohexa-1-ene-2,3,5,6-tetracarboxylic acid dianhydride, 3 -Ethylcyclohexa-1-ene-3- (1,2), 5,6-tetracarboxylic hydride, 1-methyl-3-ethylcyclohexane-3- (1,2), 5,6-tetra Carboxyl dianhydride, 1-methyl-3-ethylcyclohexa-1-ene-3- (1,2), 5,6-tetracarboxylic hydride, 1-ethylcyclohexane-1- (1,2) ), 3,4-Tetracarboxylic acid dianhydride, 1-propylcyclohexane-1- (2,3), 3,4-Tetracarboxylic acid dianhydride, 1,3-dipropylcyclohexane-1- (2,3) 3), 3- (2,3) -Tetracarboxylic acid dianhydride, Dicyclohexyl-3,4,3', 4'-Tetracarboxylic acid dianhydride, Bicyclo [2.2.1] heptane-2,3 , 5,6-Tetracarboxylic Acid Dianhydride, 1-propylcyclohexane-1- (2) , 3), 3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-1- (2,3), 3- (2,3) -tetracarboxylic dianhydride, bicyclo [2. 2.2] Octane-2,3,5,6-tetracarboxylic dianhydride, Bicyclo [2.2.2] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, Octahydro-3H, 3''H-dispyro [4,7-methanoisobenzofuran-5,1'-cyclopentane-3', 5''-[4,7] methanoisobenzofuran] -1,1'', 2', 3,3'' (4H, 4''H) -pentaone, 3- (carboxymethyl) -1,2,4-cyclopentanetricarboxylic acid 1,4: 2,3-dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 4- (2,5-dioxotetrahydroxy-3-yl) -1,2,3 Examples thereof include 4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride.
Among these, from the viewpoint of the solubility of the organic solvent-soluble polyimide compound in the organic solvent, the adhesion of the cured product to the polyimide film substrate, and the coefficient of thermal expansion, 2,2'-bis [4- (3,4-) Dicarboxyphenoxy) propanoic dianhydride] and 4,4'-oxydiphthalic dianhydride are preferred. By using such an acid anhydride, the adhesion of the cured product formed by using the colored resin composition of the present invention to the polyimide film can be further improved. Further, the solubility of the organic solvent-soluble polyimide compound in the organic solvent can be effectively improved.

[Other polymerization components]
The organic solvent-soluble polyimide compound constituting the colored resin composition of the present invention may contain other reaction components as reaction components at the time of synthesis as long as the characteristics of the present invention are not impaired.
Other polymerization components include 4,4'-bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, and bis. [4- (3-Aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1, 1,1,3,3,3-hexafluoropropane, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 3,3'-diaminodiphenyl ether, 3 , 4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfoxide, 3,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfoxide , 3,3'-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′-diamino Benzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (4) -Aminophenoxy) phenyl] ethane, 1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] propane, 1,2-bis [ 4- (4-Aminophenoxy) phenyl] propane, 1,3-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1, 1-bis [4- (4-aminophenoxy) phenyl] butane, 1,3-bis [4- (4-aminophenoxy) phenyl] butane, 1,4-bis [4- (4-aminophenoxy) phenyl] Butane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane, 2,3-bis [4- (4-aminophenoxy) phenyl] butane, 2- [4- (4-aminophenoxy) phenyl] -2- [4- (4-Aminophenoxy) -3-methylphenyl] propane, 2,2-bis [4- (4-Aminophenoki) Shi) -3-methylphenyl] propane, 2- [4- (4-aminophenoxy) phenyl] -2- [4- (4-aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (4-Aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoro Propane, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-) Aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfoxide, bis [4 -(4-Aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,3-bis [4- (4- (4- (4-)4-) Aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 4,4'-bis [ (3-Aminophenoxy) Benzoyl] Benzene, 1,1-bis [4- (3-aminophenoxy) phenyl] propane, 1,3-bis [4- (3-aminophenoxy) phenyl] propane, 3,4' -Diaminodiphenyl sulfide, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, bis [4- (3-aminophenoxy) phenyl] Methan, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, bis [4- (3-aminophenoxy) phenyl] Sulfoxide, 4,4'-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether, 4,4'-bis [4- ( 4-Amino-α, α-dimethylbenzyl) phenoxy] Benzenephenone, 4,4'-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, bis [4- {4- (4) -Aminophenoxy) Phenoxy} phenyl] sul Hong, 1,4-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] Benzene, 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-fluorophenoxy) -Α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-methylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino) -6-Cyanophenoxy) -α, α-Dimethylbenzyl] Benzene, 3,3'-diamino-4,4'-diphenoxybenzophenone, 4,4'-diamino-5,5'-diphenoxybenzophenone, 3, 4'-diamino-4,5'-diphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 4,4'-diamino-5-phenoxybenzophenone, 3,4'-diamino-4-phenoxybenzophenone, 3,4'-diamino-5'-phenoxybenzophenone, 3,3'-diamino-4,4'-dibiphenoxybenzophenone, 4,4'-diamino-5,5'-dibiphenoxybenzophenone, 3,4'- Diamino-4,5'-dibiphenoxybenzophenone, 3,3'-diamino-4-biphenoxybenzophenone, 4,4'-diamino-5-biphenoxybenzophenone, 3,4'-diamino-4-biphenoxybenzophenone, 3,4'-Diamino-5'-biphenoxybenzophenone, 1,3-bis (3-amino-4-phenoxybenzoyl) benzene, 1,4-bis (3-amino-4-phenoxybenzoyl) benzene, 1, 3-Bis (4-amino-5-phenoxybenzoyl) benzene, 1,4-bis (4-amino-5-phenoxybenzoyl) benzene, 1,3-bis (3-amino-4-biphenoxybenzoyl) benzene, 1,4-Bis (3-amino-4-biphenoxybenzoyl) benzene, 1,3-bis (4-amino-5-biphenoxybenzoyl) benzene, 1,4-bis (4-amino-5-biphenoxy) Benoxyl) benzene, 2,6-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzonitrile and some or all of the hydrogen atoms on the aromatic ring in the above aromatic diamine are halogen. An atom, an alkyl or alkoxyl group having 1 to 3 carbon atoms, a cyano group, or an alkyl group or alkoxyl halide having 1 to 3 carbon atoms in which a part or all of the hydrogen atoms of the alkyl group or alkoxyl group are substituted with halogen atoms. 4,4'-Methylenebis (cyclohexylamine), isophoronediamine, trans-1,4-diaminocyclohexane, cis-1,4-diaminocyclohexane, 1,4-cyclohexanebis (methylamine), such as aromatic diamine substituted with a group. , 2,5-bis (aminomethyl) bicyclo [2,2,1] heptane, 2,6-bis (aminomethyl) bicyclo [2,2,1] heptane, 3,8-bis (aminomethyl) tricyclo [ 5,2,1,0] Decane, 1,3-diaminoadamantan, 2,2-bis (4-aminocyclohexyl) propane, 2,2-bis (4-aminocyclohexyl) hexafluoroppropane, 1,3- Propanediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine Such as aliphatic diamines.

The organic solvent-soluble polyimide compound constituting the colored resin composition of the present invention can be synthesized by a conventionally known method. Specifically, it can be obtained by reacting a diamine compound with an acid anhydride to obtain a polyimide precursor (polyamic acid), and then performing a cyclization dehydration reaction to convert it into a polyimide compound.
The synthesis of the organic solvent-soluble polyimide compound can be carried out in an organic solvent described later.
During the cyclization dehydration reaction, an imidization catalyst may be used, for example, methylamine, ethylamine, trimethylamine, triethylamine, propylamine, tripropylamine, butylamine, tributylamine, tert-butylamine, hexylamine, triethanolamine, etc. N, N-dimethylethanolamine, N, N-diethylethanolamine, triethylenediamine, N-methylpyrrolidin, N-ethylpyrrolidin, aniline, benzylamine, toluidine, trichloroaniline, pyridine, colidin, lutidine, picolin, quinoline, isoquinolin , Valerolactone and the like can be used.
If necessary, an azeotropic dehydrating agent such as toluene, xylene, or ethylcyclohexane, and an acid catalyst such as acetic anhydride, propionic anhydride, butyric anhydride, and benzoic anhydride can be used.
Further, a sealing agent such as benzoic acid, phthalic anhydride, or hydrogenated phthalic anhydride can be used.

[(B) Colorant]
The colored resin composition of the present invention contains at least one colorant.
The colorant may be a pigment or a dye, but a pigment is preferable from the viewpoint of heat resistance and light resistance of the cured product formed by the colored resin composition of the present invention. Further, the pigment may be an organic pigment or an inorganic pigment. Further, the pigment and the dye may be used in combination.

The colorant is not particularly limited, and a conventionally known colorant can be appropriately used. However, a shielding portion provided with an organic EL display device or the like on a cured product formed by the colored resin composition of the present invention. When applied to, it is preferable to use a black colorant or a white colorant.
Examples of the black colorant include carbon black, iron tetraoxide, titanium oxide, copper manganese black, copper chromium black and cobalt black, cyanine black and aniline black.
Further, in the present invention, the black colorant also includes a colorant obtained by mixing a plurality of colorants to make them black.
Examples of the white colorant include titanium oxide, barium carbonate, zirconium oxide, calcium carbonate, zinc white, antimony white and zinc sulfide.

The content of the colorant in the colored resin composition is preferably 80 parts by mass or more and 200 parts by mass or less, preferably 100% by mass or more, with respect to 100 parts by mass of the organic solvent-soluble polyimide compound constituting the colored resin composition. , 150% by mass or less is more preferable.
By setting the content of the colorant in the colored resin composition within the above numerical range, the colored resin composition of the present invention can obtain excellent handleability in the coating step, and the cured product formed after heating can be obtained. , It is possible to provide a shielding property applied to a shielding portion provided in an organic EL display device or the like.

[(C) Organic solvent]
As the organic solvent, for example, a lactone-based organic solvent, an ester-based organic solvent, an ether-based organic solvent, a ketone-based organic solvent, an alcohol-based organic solvent, and the like can be used. Among these, a lactone-based organic solvent and an ester-based organic solvent can be used. Organic solvents are preferred.
The lactone-based organic solvent is preferably γ-butyrolactone, and the ester-based organic solvent is preferably an aromatic carboxylic acid ester, more preferably alkyl benzoate, and particularly preferably methyl benzoate or ethyl benzoate.
Such an organic solvent can satisfactorily dissolve the organic solvent-soluble polyimide compound contained in the colored resin composition of the present invention, and the interface between the cured product formed by the colored resin composition and the polyimide film base material. It is possible to prevent the whitening phenomenon caused by the erosion of the organic solvent. In addition, the storage stability of the colored resin composition and the continuous printability in screen printing can be effectively improved.
The colored resin composition of the present invention may contain two or more kinds of organic solvents.

The content of the organic solvent in the colored resin composition is preferably 210 parts by mass or more and 550 parts by mass or less, and 250 parts by mass or more and 400 parts by mass or less with respect to 100 parts by mass of the organic solvent-soluble polyimide compound. Is preferable. By setting the content of the organic solvent in the colored resin composition within the above numerical range, the organic solvent-soluble polyimide compound can be satisfactorily dissolved and the moldability of the colored resin composition of the present invention can be improved. it can.

[Defoamer]
In one embodiment, the colored resin composition of the present invention may contain an antifoaming agent. Examples of the defoaming agent include silicone resin, polydimethylsiloxane, silicone oil and fluorine compound.

The content of the defoaming agent in the colored resin composition is preferably 0.1% by mass or more and 10% by mass or less, and more preferably 0.5% by mass or more and 5% by mass or less. By setting the content of the defoaming agent in the colored resin composition within the above numerical range, a good cured product without residual voids or poor appearance such as repellent can be obtained.

[Other materials]
The colored resin composition may contain a polyimide compound other than the organic solvent-soluble polyimide compound and a precursor (polyamic acid) of the organic solvent-soluble polyimide compound as long as the characteristics of the present invention are not impaired.

Further, as long as the characteristics of the present invention are not impaired, the colored resin composition comprises a pigment dispersant, a thickener, an oxygen remover, a fluorescent whitening agent, a surfactant, an antioxidant, a plasticizer, a flame retardant, and an antistatic agent. Additives such as inhibitors, leveling agents, and antibacterial agents can be included.

[Cured product]
The cured product of the present invention is formed by using the above-mentioned colored resin composition, and has high adhesion to a polyimide film base material.
The shape of the cured product is not particularly limited, and it is preferable to change the shape as appropriate depending on the intended use. For example, a film-shaped cured product can be used.

The coefficient of thermal expansion of the cured product is preferably less than 50 ppm / ° C.
In the present invention, the coefficient of thermal expansion of the cured product is such that the cured product is subjected to a thermomechanical analyzer (manufactured by TA Instruments Japan, TMA'Q400) at a temperature rise temperature of 10 ° C./min at room temperature to 370 ° C. Refers to the average coefficient of thermal expansion from 500 ° C to 250 ° C.

The cured product of the present invention can be produced by applying a colored resin composition on a substrate such as a polyimide film and drying it.
Examples of the coating method of the colored resin composition include a screen printing method, a gravure printing method, a spin coating method, an inkjet method, a spray coating method, a slit coating method, a dispenser coating method, a dropping method, and the like. The screen printing method is particularly preferable because the shape of the coating film can be easily formed.
The drying temperature of the colored resin composition is preferably 80 to 200 ° C., which can prevent discoloration of the coating film made of the colored resin composition.

[Laminate]
The laminate of the present invention is characterized by including a polyimide film base material and a layer made of a cured product formed by using the colored resin composition.

The thickness of the polyimide film base material is preferably 10 μm or more and 120 μm or less, and preferably 20 μm or more and 100 μm or less. By setting the thickness of the polyimide film base material within the above numerical range, it is possible to obtain a laminate having good adhesion and high flexibility.

The thickness of the layer made of the cured product formed by using the colored resin composition is preferably 1 μm or more and 500 μm or less, and preferably 3 μm or more and 20 μm or less. By setting the layer made of the cured product formed by using the colored resin composition within the above numerical range, a laminated body having a shielding property and excellent adhesion can be obtained.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples.

(Example 1: Synthesis of polyimide compound A)
4.57 g (15 mmol) of (2-phenyl-4-aminophenyl) -4-aminobenzoate (PHBAAB) represented by the following formula in a 500 ml separable flask equipped with a nitrogen introduction tube and a stirrer, according to the following formula. 4.29 g (15 mmol) of 4,4'-diamino-3,3'-dicarboxydiphenylmethane (MBAA) represented by the following formula, 2,2'-bis [4- (3,4-di) represented by the following formula. Carboxyphenoxy) propanoic acid dianhydride] (BPADA) 15.61 g (30 mmol), methyl benzoate 94.64 g, pyridine 0.47 g (6 mmol), toluene 10 g, and in a nitrogen atmosphere at 180 ° C. A solution of 20% by mass of polyimide compound A was obtained by reacting for 4 hours while removing toluene from the system on the way. No precipitation of the synthesized polyimide compound A was observed in this polyimide solution.
The composition ratios of PHBAAB, MBAA and BPADA in the polyimide compound A are as shown in Table 1.
The weight average molecular weight of the polyimide compound A was measured in accordance with JIS K 7252-1 (issued in 2008) and found to be 48,000.

A polyimide solution containing polyimide compound A and methyl benzoate, carbon black, and an antifoaming agent were mixed at the blending ratios shown in Table 2 to obtain the colored resin composition A of the present invention.

(Example 2: Synthesis of polyimide compound B)
In a 500 ml separable flask equipped with a nitrogen introduction tube and a stirrer, 4.57 g (15 mmol) of PHBAAB, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6FAP) 5 represented by the following formula. .49 g (15 mmol), BPADA 15.61 g (30 mmol), methyl benzoate 94.64 g, pyridine 0.47 g (6 mmol), and toluene 10 g were added, and toluene was added to the system at 180 ° C. in a nitrogen atmosphere. A solution of 20% by weight of polyimide compound B was obtained by reacting with the mixture for 4 hours. No precipitation of the synthesized polyimide compound B was observed in this polyimide solution.
The composition ratios of PHBAAB, 6FAP and BPADA in the polyimide compound B are as shown in Table 1.
The weight average molecular weight of the polyimide compound B was measured and found to be 48,000.

A polyimide solution containing polyimide compound B and methyl benzoate, carbon black, and an antifoaming agent were mixed at the blending ratios shown in Table 2 to obtain the colored resin composition B of the present invention.

(Example 3: Synthesis of polyimide compound C)
PHBAAB 4.57 g (15 mmol), 3,5-diaminobenzoic acid (DABz) 2.28 g (15 mmol), BPADA 15.61 g in a 500 ml separable flask equipped with a nitrogen introduction tube and a stirrer. (30 mmol), 94.64 g of methylbenzoate, 0.47 g (6 mmol) of pyridine, and 10 g of toluene were added and reacted at 180 ° C. under a nitrogen atmosphere for 4 hours while removing toluene from the system. A 20 wt% solution of the polyimide compound C was obtained. No precipitation of the synthesized polyimide compound was observed in this polyimide solution.
The composition ratios of PHBAAB, DABz and BPADA in the polyimide compound C are as shown in Table 1.
Moreover, when the weight average molecular weight of the polyimide compound C was measured, it was 43,000.

A polyimide solution containing polyimide compound C and methyl benzoate, carbon black, and an antifoaming agent were mixed at the blending ratios shown in Table 2 to obtain the colored resin composition C of the present invention.

(Example 4: Synthesis of polyimide compound D)
PHBAAB 4.57 g (15 mmol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane (PAM-E) 3 represented by the following formula in a 500 ml separable flask equipped with a nitrogen introduction tube and a stirrer. .73 g (15 mmol), BPADA 15.61 g (30 mmol), methyl benzoate 94.64 g, pyridine 0.47 g (6 mmol), and toluene 10 g were added, and toluene was added to the system at 180 ° C. in a nitrogen atmosphere. A polyimide solution of 20% by weight of the polyimide compound D was obtained by reacting with the mixture for 4 hours. No precipitation of the synthesized polyimide compound was observed in this polyimide solution.
The composition ratios of PHBAAB, PAM-E and BPADA in the polyimide compound D are as shown in Table 1.
Moreover, when the weight average molecular weight of the polyimide compound D was measured, it was 38,000.

The polyimide compound D, the methyl benzoate polyimide solution, carbon black, and the defoaming agent were mixed at the blending ratios shown in Table 2 to obtain the colored resin composition D of the present invention.

(Example 5: Synthesis of polyimide compound E)
PHBAAB 1.82 g (6 mmol), MBAA 3.44 g (12 mmol), PAM-E 2.98 g (12 mmol) in a 500 ml separable flask equipped with a nitrogen introduction tube and a stirrer, represented by the following formula 4, 9.31 g (30 mmol) of 4'-oxydiphthalic acid anhydride (ODPA), 94.64 g of methyl benzoate, 0.47 g (6 mmol) of pyridine, and 10 g of toluene were added, and toluene was added in the middle at 180 ° C. under a nitrogen atmosphere. Was reacted for 4 hours while removing the residue from the system to obtain a 20 wt% solution of the polyimide compound E. No precipitation of the synthesized polyimide compound was observed in this polyimide solution.
The composition ratios of PHBAAB, MBAA, PAM-E and ODPA in the polyimide compound E are as shown in Table 1.
The weight average molecular weight of the polyimide compound E was measured and found to be 39,000.

A polyimide solution containing a polyimide compound E and methyl benzoate, carbon black, and an antifoaming agent were mixed at the blending ratios shown in Table 2 to obtain the colored resin composition E of the present invention.

(Example 6: Synthesis of polyimide compound F)
PHBAAB 1.82 g (6 mmol), 6FAP 4.40 g (12 mmol), PAM-E 2.98 g (12 mmol), ODPA 9.31 g (30 mmol), in a 500 ml separable flask equipped with a nitrogen introduction tube and a stirrer. 94.64 g of methyl benzoate, 0.47 g (6 mmol) of pyridine, and 10 g of toluene were added and reacted at 180 ° C. under a nitrogen atmosphere for 4 hours while removing toluene from the system to 20% by weight of polyimide. A solution of compound F was obtained. No precipitation of the synthesized polyimide compound was observed in this polyimide solution.
The composition ratios of PHBAAB, 6FAP, PAM-E and ODPA in the polyimide compound F are as shown in Table 1.
The weight average molecular weight of the polyimide compound F was measured and found to be 43,000.

A polyimide solution containing a polyimide compound F and methyl benzoate, carbon black, and an antifoaming agent were mixed at the blending ratios shown in Table 2 to obtain the colored resin composition F of the present invention.

(Example 7: Synthesis of polyimide compound G)
PHBAAB 1.82 g (6 mmol), 6FAP 5.49 g (15 mmol), DABz 1.37 g (9 mmol), ODPA 9.31 g (30 mmol), methyl benzoate in a 500 ml separable flask equipped with a nitrogen introduction tube and a stirrer. 94.64 g, 0.47 g (6 mmol) of pyridine, and 10 g of toluene were added and reacted at 180 ° C. under a nitrogen atmosphere for 4 hours while removing toluene from the system on the way to obtain 20% by weight of the polyimide compound G. A solution was obtained. No precipitation of the synthesized polyimide compound was observed in this polyimide solution.
The composition ratios of PHBAAB, 6FAP, DABz and ODPA in the polyimide compound G are as shown in Table 1.
Moreover, when the weight average molecular weight of the polyimide compound G was measured, it was 43,000.

A polyimide solution containing a polyimide compound G and methyl benzoate, carbon black, and an antifoaming agent were mixed at the blending ratios shown in Table 2 to obtain the colored resin composition G of the present invention.

(Comparative Example 1: Synthesis of Polyimide Compound a)
In the synthesis of the early-stage polyimide compound A, without using PHBAAB, MBAA was 8.59 g (30 mmol) and BPADA was 15.61 g (30 mmol), and polyimide compound a was synthesized in the same manner as in Example 1. The polyimide compound a was not dissolved in methyl benzoate and was in a precipitated state.
The composition ratios of MBAA and BPADA in the polyimide compound a are as shown in Table 1.

(Comparative Example 2: Synthesis of Polyimide Compound b)
In the synthesis of the early-stage polyimide compound A, without using MBAA, PHBAAB was 9.12 g (30 mmol) and BPADA was 15.61 g (30 mmol), and the polyimide compound b was synthesized in the same manner as in Example 1. The polyimide compound b was in a state of being dissolved in methyl benzoate.
The composition ratios of PHBAAB and BPADA in the polyimide compound b are as shown in Table 1.
The weight average molecular weight of the polyimide compound b was measured and found to be 49,000.

A polyimide solution containing a polyimide compound b and methyl benzoate, carbon black, and an antifoaming agent were mixed at the blending ratios shown in Table 2 to obtain a colored resin composition b.

(Comparative Example 3: Synthesis of Polyimide Compound c)
In the synthesis of the early polyimide compound A, 3.42 g (15 mmol) of 4-aminophenyl-4-aminobenzoate (APAB) represented by the following chemical formula was used instead of PHBAAB, and 4.56 g (15 mmol) of MBAA was used. ), The polyimide compound c was synthesized in the same manner as in Example 1 in which BPADA was expressed as 15.61 g (30 mmol). The polyimide compound c was not dissolved in methyl benzoate and was in a precipitated state.
The composition ratios of APAB, MBAA and BPADA in the polyimide compound c are as shown in Table 1.

<< Adhesion evaluation >>
A polyimide film (manufactured by Koron Co., Ltd.) having a thickness of 50 μm was prepared. The colored resin compositions obtained in the above Examples and Comparative Examples were applied to the surface of this polyimide film and dried by heating at 100 ° C. to form a cured film.
The adhesion of the cured film was confirmed in accordance with JIS K 5600-5-6.
Specifically, a single-edged blade is used to make 100-square grid-like cuts in the cured film at 1 mm intervals, then "cellotape" (registered trademark) is attached, and then the cellophane tape (registered trademark) is peeled off. , The state of the cured film was visually confirmed and evaluated based on the following evaluation criteria. The evaluation results are summarized in Table 3.
(Evaluation criteria)
⊚: High adhesion was confirmed with no peeling of the cured film.
〇: It was confirmed that the corners of the trout were peeled off slightly.
X: Peeling of the corners of the squares was confirmed, or peeling of one or more squares was confirmed.

<< Evaluation of coefficient of thermal expansion >>
The cured film prepared in the above adhesion evaluation was cut into a test piece having a length of 100 mm, a width of 100 mm, and a thickness of 15 μm. The coefficient of linear thermal expansion of this test piece was measured using a thermomechanical analyzer (manufactured by TA Instruments Japan, TMA'Q400).
Specifically, after mounting the test piece on a thermomechanical analyzer, measurements were taken from room temperature to 370 ° C. under a nitrogen atmosphere (nitrogen flow rate: 100 mL / min) at a heating rate of 10 ° C./min.
Next, the average coefficient of linear thermal expansion in the range of 50 ° C. to 250 ° C. was calculated and evaluated according to the following evaluation criteria. The evaluation results are summarized in Table 3.
(Evaluation criteria)
◯: The average coefficient of linear thermal expansion was less than 50 ppm / ° C.
X: The average coefficient of linear thermal expansion was 50 ppm / ° C. or higher.

Claims (7)

1. (A) Organic solvent-soluble polyimide compound and
   (B) Colorant and
   (C) A colored resin composition containing an organic solvent.
   The organic solvent-soluble polyimide compound (A) is
   (A-1) The diamine compound represented by the following general formula (1) and
   (A-2) A diamine compound having at least one of a carboxyl group and a hydroxyl group, and at least one of a diamine compound having a siloxane bond.
   (A-3) A colored resin composition, which is an imidized polyimide precursor composed of a reaction component containing an acid anhydride.
   

   

   (In the above general formula (1),
   Any of R ₁ to R ₄ is selected from an aromatic group having 6 to 10 carbon atoms, a phenoxy group having 6 to 10 carbon atoms, a benzyl group having 6 to 10 carbon atoms, and a benzyloxy group having 6 to 10 carbon atoms. , Other R ₁ to R ₄ are hydrogen atoms. )
2. The organic solvent-soluble polyimide compound (A) contains a diamine compound having at least one of the carboxyl group and the hydroxyl group as the reaction component (A-2).
   The colored resin composition according to claim 1, wherein the diamine compound having at least one of a carboxyl group and a hydroxyl group is represented by the following general formula (2) or (3).
   

   

   

   (In the above general formulas (2) and (3), R ₅ is selected from a divalent organic group or a single bond, and n is an integer of 1 to 10, preferably 1 to 5.
   Further, R ₆ is independently selected from COOH or OH, o is an integer of 0 to 4, and the diamine compound represented by the general formula (2) has at least one R _6. ,
   In the above general formula (3), p is an integer of 1 to 4. )
3. The organic solvent-soluble polyimide compound (A) contains the diamine compound having a siloxane bond as the reaction component (A-2).
   The colored resin composition according to claim 1 or 2, wherein the diamine compound having a siloxane bond is represented by the following general formula (4).
   

   

   (In the above general formula (4), R ₇ to R ₁₂ are alkyl groups or phenyl groups.
   q and r are independently integers of 1 to 10, and s is an integer of 0 to 10. )
4. The colored resin composition according to any one of claims 1 to 3, wherein the organic solvent is an aromatic carboxylic acid ester.
5. The organic solvent-soluble polyimide compound (A) contains, as a reaction component (A-2), both a diamine compound having at least one of the carboxyl group and the hydroxyl group and the diamine compound having the siloxane bond. The colored resin composition according to any one of 4.
6. A cured product, which is formed by using the colored resin composition according to any one of claims 1 to 5.
7. A laminate characterized by comprising a polyimide film base material and a layer made of a cured product formed by using the colored resin composition according to any one of claims 1 to 5.