TWI837153B - Composition, cured product, preparing method for cured product, salt, and agent for aging-inhibition and improving film-forming property of composition for forming polyimide film - Google Patents

Abstract

The present invention provides a composition having excellent film-forming property and stability over time, a cured product of the composition, a method for producing a cured product using the composition, a salt, and an agent for inhibiting the change over time and improving the film-forming property of a composition for forming a polyimide film. The composition contains a salt represented by the following formula (1). (In the above formula, A represents a tetravalent organic group containing 1 or more alicyclic groups, and the n -COO ^- M ⁺ and (4-n) -COOH in the above formula are independently bonded to the above 1 or more alicyclic groups directly or via a linking group, M ⁺ represents a cation containing a nitrogen-containing heterocyclic ring, and n represents an integer of 1 to 4).

Description

Composition, cured product, method for producing cured product, salt, and agent for inhibiting temporal change of polyimide film-forming composition and improving film-forming property

The present invention relates to a composition suitable for forming a polyimide film, a cured product of the composition, a method for producing a cured product using the composition, a salt, and an agent for inhibiting temporal changes of the composition for forming a polyimide film and improving film-forming properties.

Polyimide resins are widely used as insulating materials or protective materials in electrical and electronic parts of various components or electronic substrates such as multi-layer wiring boards due to their excellent heat resistance, mechanical strength, insulation, and low dielectric constant.

Generally, polyimide resin is formed by heat treating a polyamide obtained by polymerizing a tetracarboxylic dianhydride component and a diamine component in a polar organic solvent. Based on this background, polyimide products for electronic materials are mostly supplied as a solution of a polyimide precursor such as polyamide. Specifically, when manufacturing electrical and electronic parts, a solution of a polyimide precursor is supplied to a portion where an insulating material or a protective material is to be formed by coating or injection, and then the solution of the polyimide precursor is heat treated to form an insulating material or a protective material.

The technical development of these polyimide resins is also actively carried out. For example, in Patent Document 1, a resin composition containing polyamide and alkaline nitrogen-containing compounds is disclosed for the purpose of improving film forming properties. [Prior Technical Document] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2018-58918

[Problems to be solved by the invention]

However, the inventors of the present invention have found that the resin composition containing polyamine and alkaline nitrogen-containing compounds will deteriorate over time after being prepared and left for several days. There is a need for a composition with excellent film-forming properties and stability over time.

The present invention is made in view of the problems of the above-mentioned prior art, and aims to provide a composition with excellent film-forming properties and stability over time, a cured product of the composition, a method for producing a cured product using the composition, a salt, and an agent for inhibiting the change over time and improving the film-forming properties of a composition for forming a polyimide film. [Means for solving the problem]

The inventors of the present invention have discovered that a composition comprising a salt of a carboxylic acid anion of a specific structure containing an alicyclic group and a nitrogen-containing heterocyclic cation has excellent film-forming properties and stability over time, thereby completing the present invention.

The first aspect of the present invention is a composition comprising a salt represented by the following formula (1): (In the above formula, A represents a tetravalent organic group containing 1 or more alicyclic groups, and the n -COO ^- M ⁺ and (4-n) -COOH in the above formula are independently bonded to the above 1 or more alicyclic groups directly or via a linking group, M ⁺ represents a cation containing a nitrogen-containing heterocyclic ring, and n represents an integer of 1 to 4).

The second aspect of the present invention is a cured product of the composition of the first aspect. The third aspect of the present invention is a method for producing a cured product, which comprises forming a film using the composition of the first aspect, and heating the film. The fourth aspect of the present invention is a salt represented by the following formula (1), (In the above formula, A represents a tetravalent organic group containing 1 or more alicyclic groups, and the n -COO ^- M ⁺ and (4-n) -COOH in the above formula are independently bonded to the above 1 or more alicyclic groups directly or via a linking group, M ⁺ represents a cation containing a nitrogen-containing heterocyclic ring, and n represents an integer of 1 to 4).

The fifth aspect of the present invention is a polyimide film-forming composition for suppressing temporal changes and enhancing film-forming properties, which comprises the salt of the fourth aspect. [Effect of the invention]

According to the present invention, a composition having excellent film-forming property and stability over time, a cured product of the composition, a method for producing the cured product using the composition, a salt, and an agent for inhibiting the change over time of a polyimide film-forming composition and improving film-forming property can be provided.

The following is a detailed description of the implementation of the present invention, but the present invention is not limited to the following implementation. It can be implemented with appropriate changes within the scope of the purpose of the present invention. In addition, in this specification, "~" means from above to below unless otherwise specified.

≪Composition≫ The composition of the first aspect includes a salt represented by the general formula (1). The salt can help improve film-forming properties and stability over time. In addition, the present invention is related to a salt represented by the general formula (1) and a composition for forming a polyimide film that inhibits changes over time and improves film-forming properties. The invention of the fourth aspect is a salt represented by the general formula (1). The invention of the fifth aspect is a composition for forming a polyimide film that inhibits changes over time and improves film-forming properties, comprising the salt of the fourth aspect.

<Salt> (Anion part) In the above formula (1), A represents a tetravalent organic group containing 1 or more alicyclic groups, and n -COO ^- M ⁺ and (4-n) -COOH in the above formula are independently bonded to the above 1 or more alicyclic groups directly or via a linking group. From the viewpoint of more surely achieving the effect of the present invention, n is preferably 2 or more and 4 or less, and more preferably 2 or 3. Examples of the above linking group include an alkylene group, an alkoxyene group, a cycloalkylene group or a cycloalkoxyene group, preferably an alkylene group or an alkoxyene group, and more preferably an alkylene group. Examples of the above alkylene group and the alkylene part of the above alkoxyene group include an alkylene group having 1 or more and less than 5 carbon atoms (preferably 1 or more and less than 3 carbon atoms, and more preferably 1 or 2 carbon atoms) which may have a substituent. Specific examples of the alkylene group include methylene, ethylene, propylene, butylene, pentylene, etc., preferably methylene, ethylene or propylene, more preferably methylene or ethylene. Examples of the cycloalkylene group and the cycloalkylene part of the cycloalkoxy group include cyclopentylene and cyclohexylene. In the above formula, the n -COO ^- M ⁺ and (4-n) -COOH groups are preferably directly bonded to the above one or more alicyclic groups. As the tetravalent organic group A, for example, a tetravalent organic group having 4 to 40 carbon atoms (preferably 5 to 30 carbon atoms, more preferably 6 to 25 carbon atoms, and even more preferably 6 to 20 carbon atoms) may or may not contain an aromatic group (e.g., a benzyl group, a naphthyl group, etc.) in addition to the above-mentioned 1 or 2 or more alicyclic groups, but preferably contains no aromatic group. In A, 1 or 2 or more alicyclic groups and the above-mentioned aromatic group may or may not be condensed. 1 or 2 or more alicyclic groups may or may not be linked by a spiro bond. The tetravalent organic group A may or may not contain a heteroatom (e.g., an oxygen atom, a sulfur atom, a nitrogen atom), a keto group (-CO-), or an unsaturated bond (e.g., a carbon-carbon double bond, a carbon-carbon triple bond) as a ring constituent atom. The tetravalent organic group A may or may not have a substituent.

The above-mentioned alicyclic group contained in the tetravalent organic group A may be monocyclic or polycyclic, for example, a monocyclic or polycyclic alicyclic group having 3 to 20 carbon atoms (preferably 4 to 15 carbon atoms, more preferably 5 to 12 carbon atoms, and even more preferably 6 to 10 carbon atoms), preferably a monocyclic or polycyclic alicyclic group having 3 to 20 members, more preferably a monocyclic or polycyclic alicyclic group having 4 to 18 members, even more preferably a monocyclic or polycyclic alicyclic group having 5 to 14 members, and particularly preferably a monocyclic or polycyclic alicyclic group having 6 to 10 members. The number of the above-mentioned alicyclic groups contained in the organic group A is preferably 1 to 6, more preferably 1 to 5. The above-mentioned alicyclic group may or may not contain a bridging group for intra-ring bridging, and an example of the above-mentioned bridging group is a divalent group having 1 to 5 carbon atoms (preferably 1 to 3 carbon atoms, more preferably 1 or 2 carbon atoms). Specific examples of alicyclic groups containing a bridging group include groups containing a bicyclo[2.2.1]heptane structure, etc. As the above-mentioned bridging group, an alkylene group, an ether bond (—O—), a thioether bond (—S—), a keto group or a divalent group composed of at least two of these groups are preferred, an alkylene group, an ether bond, a thioether bond or a divalent group composed of at least two of these groups are more preferred, an alkylene group, an ether bond, a thioether bond or a divalent group composed of at least two of these groups are further preferred, an alkylene group, an ether bond or a thioether bond are particularly preferred, and an alkylene group, an ether bond or a thioether bond is most preferred.

Examples of the alkylene group include an alkylene group having 1 to 5 carbon atoms (preferably 1 to 3 carbon atoms, more preferably 1 or 2 carbon atoms) which may have a substituent. Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, etc., preferably a methylene group, an ethylene group or a propylene group, more preferably a methylene group or an ethylene group.

The above-mentioned alicyclic group may or may not contain a heteroatom (e.g., oxygen atom, sulfur atom, nitrogen atom), a keto group, or an unsaturated bond (e.g., carbon-carbon double bond, carbon-carbon triple bond) as a ring-constituting atom. The above-mentioned alicyclic group may or may not have a substituent.

Examples of substituents that the tetravalent organic group A, the above-mentioned alicyclic group or the above-mentioned alkylene group may have include halogen atoms or organic groups. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms or iodine atoms. Examples of organic groups as substituents include organic groups with 1 to 10 carbon atoms. Preferred examples of organic groups include alkyl groups and alkoxy groups. Examples of the above-mentioned alkyl groups include alkyl groups with 1 to 10 carbon atoms. Specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc., preferably alkyl groups with 1 to 4 carbon atoms. Alkyl groups may have substituents. When the alkyl group has a substituent, examples of the substituent include halogen atoms, alkoxy groups, etc.

Examples of alkoxy groups include alkoxy groups having 1 to 10 carbon atoms. Specific examples of alkoxy groups include methoxy groups, ethoxy groups, propoxy groups, butoxy groups, hexyl groups, octyl groups, etc., preferably alkoxy groups having 1 to 4 carbon atoms. Alkoxy groups may have substituents. When alkoxy groups have substituents, examples of the substituents include halogen atoms, alkoxy groups, etc.

The above-mentioned quaternary organic group A may or may not be a residue obtained by removing two anhydride groups from tetracarboxylic dianhydride, and may or may not be a quaternary organic group including two identical or different alicyclic groups bonded to two selected from the group consisting of n -COO ^- M ⁺ and (4-n) -COOH in the above-mentioned formula (1). An example of a preferred embodiment of the above-mentioned quaternary organic group A is a quaternary group represented by the following formula (a2). (In the above formula (a2), ^Ra11 , ^Ra12 and ^Ra13 are each independently one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms and a fluorine atom, and m is an integer from 0 to 12.) In formula (a2), m is preferably 5 or less, more preferably 3 or less, from the viewpoint of easy purification of the raw material compound. Furthermore, from the viewpoint of chemical stability, m is preferably 1 or more, more preferably 2 or more. In formula (a2), m is particularly preferably 2 or 3.

Specific examples of the above-mentioned 4-valent organic group A are shown below, but the present invention is not limited thereto. In the following formula, * represents a direct bond to -COO ^- M ⁺ or -COOH, or represents a bond to a linking group bonded to -COO ^- M ⁺ or -COOH.

(Cation part) The cation M ⁺ containing a nitrogen-containing heterocyclic ring (M) in the above formula (1) is, for example, a cation containing a nitrogen-containing heterocyclic ring having 2 to 30 carbon atoms (preferably 2 to 20, more preferably 3 to 15, and more preferably 3 to 10) containing one or more nitrogen atoms (preferably 1 to 5, more preferably 2 to 4, and even more preferably 2 or 3). It can be any cation containing an aromatic or non-aromatic nitrogen-containing heterocyclic ring, and is preferably a cation containing an aromatic nitrogen-containing heterocyclic ring. The cation M ⁺ including the nitrogen-containing heterocyclic ring (M) may or may not contain a heteroatom (for example, an oxygen atom, a sulfur atom, etc.) other than the nitrogen atom as an atom constituting the ring, and may or may not have a substituent.

From the viewpoint of more surely achieving the effect of the present invention, the cation M ⁺ containing the nitrogen-containing heterocyclic ring (M) is preferably a cation represented by any one of the following formulas (2) to (11). (In formula (2), R ¹¹ independently represents a hydrogen atom or an organic group, and s represents an integer of 2 to 6.) Examples of the organic group in R ¹¹ include an alkyl group, a cycloalkyl group, an aryloxy group, and an aryl group. The above-mentioned alkyl group, the above-mentioned cycloalkyl group, the above-mentioned aryloxy group, and the above-mentioned aryl group may have a substituent. Examples of the substituent include halogen atoms such as fluorine, chlorine, bromine and iodine; cyano; nitro; alkoxy groups such as methoxy, ethoxy and t-butyloxy; aryloxy groups such as phenoxy and p-tolyloxy; acyloxy groups such as acetyloxy, propionyloxy and benzyloxy; alkoxycarbonyl groups such as methoxycarbonyl and butoxycarbonyl; aryloxycarbonyl groups such as phenoxycarbonyl; alkenyloxycarbonyl groups such as vinyloxycarbonyl and allyloxycarbonyl; acyl groups such as acetyl, benzyl, isobutyl, acryl, methacryl and methoxythioyl; alkylsulfanyl groups such as methylsulfanyl and t-butylsulfanyl; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl; methylamino and cyclopentyl groups. aliphatic secondary amine groups such as hexylamino; aliphatic tertiary amine groups such as dimethylamino, diethylamino, morpholinyl and piperidinyl; aromatic secondary amine groups such as phenylamino and p-toluidine; alkyl groups such as methyl, ethyl, t-butyl and dodecyl; aryl groups such as phenyl, p-tolyl, xylyl, cumene, naphthyl, anthracenyl and phenanthryl; hydroxyl; carboxyl; sulfonamido; formyl; hydroxyl; sulfonyl; methanesulfonyl; p-toluenesulfonyl; primary amine groups; nitroso; halogenated alkyl groups such as trifluoromethyl and trichloromethyl; trimethylsilyl; phosphinate; phosphonyl; alkylsulfonyl; arylsulfonyl; trialkylammonium; dimethylsirconium; triphenylbenzylphosphonium; etc. S is preferably an integer of 3 to 5, more preferably 3 or 4. (wherein, ^RH each independently represents a hydrogen atom or an alkyl group. ^R21 , ^R23 , ^R25 , ^R26 , ^R27 , ^R28 , ^R30 , ^R31 and ^R32 each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an alkenyl group or an alkynyl group. ^R22 , ^R24 and ^R29 each independently represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an alkynyl group. ^R21 to ^R32 each independently may be substituted by a halogen atom, a cyano group or a nitro group. ^R21 and ^R22 may be combined to form a ring. At least two ^R21s may be combined to form a ring. ^R23 and ^R24 may be combined to form a ring. Two R23s may be combined to form a ring. At least two ^R23s may be combined to form a ring. ^{(R 25} may be combined with each other to form a ring. At least two R ²⁶ may be combined with each other to form a ring. At least two R ²⁷ may be combined with each other to form a ring. R ²⁸ and R ²⁹ may be combined with each other to form a ring. At least two R ²⁸ may be combined with each other to form a ring. At least two R ³⁰ may be combined with each other to form a ring. At least two R ³¹ may be combined with each other to form a ring. At least two R ³² may be combined with each other to form a ring).

Examples of the halogen atom for R ²¹ to R ³² include fluorine atom, chlorine atom, bromine atom or iodine atom. The alkyl group for ^RH and R ²¹ to R ³² may be a straight chain alkyl group or a branched chain alkyl group. The number of carbon atoms in the alkyl group is not particularly limited. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5. Specific examples of the alkyl group for ^RH and ^R21 to ^R32 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, iso-pentyl, t-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethyl-n-hexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and n-eicosyl.

The cycloalkyl group for R ²¹ to R ³² is preferably a cycloalkyl group having 5 to 30 carbon atoms. Specific examples of the cycloalkyl group include cyclopentyl and cyclohexyl. The alkenyl group for R ²¹ to R ³² is preferably an alkenyl group having 2 to 10 carbon atoms. Specific examples of the alkenyl group include vinyl, allyl and styryl. The alkynyl group for R ²¹ to R ³² is preferably an alkynyl group having 2 to 10 carbon atoms. Specific examples of the alkynyl group include ethynyl, propynyl and propargyl.

In the composition of the first embodiment, the above salt may contain one kind alone or two or more kinds. The above salt may be produced by mixing and reacting (e.g., neutralization reaction) a tetracarboxylic acid compound in which the tetravalent organic group A in the above formula (1) is directly or via a linking group bonded to four -COOH groups with the above nitrogen-containing heterocyclic compound (M) under arbitrary conditions.

The content of the salt represented by the above formula (1) in the composition of the first aspect is not particularly limited, but relative to the entire composition of the first aspect, it is preferably 0.01 mass% to 80 mass%, more preferably 0.1 mass% to 50 mass%, more preferably 0.5 mass% to 30 mass%, and particularly preferably 1 mass% to 15 mass%. Moreover, relative to the entire composition of the first aspect (excluding the solvent), it is preferably 0.1 mass% to 80 mass%, more preferably 0.5 mass% to 70 mass%, and even more preferably 1 mass% to 60 mass%. Furthermore, the mass ratio of the above-mentioned salt to the mass of at least one resin precursor selected from the group consisting of the following monomer components consisting of a diamine component and a tetracarboxylic dianhydride component, polyamide and polyimide, or even the resin is preferably from 1 mass% to 50 mass%, more preferably from 5 mass% to 30 mass%, and even more preferably from 7 mass% to 20 mass%.

<Monomer components composed of free diamine components and tetracarboxylic dianhydride components, at least one resin precursor selected from the group consisting of polyamide and polyimide, and even resin> The composition of the first aspect, based on the viewpoint of more surely achieving the effect of the present invention, preferably further comprises monomer components composed of free diamine compounds and tetracarboxylic dianhydride, at least one resin precursor selected from the group consisting of polyamide (D) and polyimide, and even resin, and more preferably further comprises polyamide (D). Polyamide (D) is a resin precursor of polyimide generated when the composition is cured. Polyamide (D) can usually be obtained by condensing monomer components composed of tetracarboxylic dianhydride and diamine compounds. The polyamic acid may have a structural unit represented by the following formula (d1). (In formula (d1), D is a tetravalent organic group having 6 to 50 carbon atoms, and B is a divalent organic group).

Hereinafter, tetracarboxylic dianhydride and diamine compounds used for the production of polyamide (D) and a method for producing polyamide (D) will be described.

[Tetracarboxylic dianhydride] The tetracarboxylic dianhydride that generates the structural unit represented by formula (d1) is represented by the following formula (d1-1). The tetracarboxylic dianhydride represented by formula (d1-1) reacts with the diamine compound described later to obtain a polyamide (D) having the structural unit represented by formula (d1). The tetracarboxylic dianhydride may be used alone or in combination of two or more. (In formula (d1-1), D is a tetravalent organic group having 6 to 50 carbon atoms).

In formula (d1-1), D is a tetravalent organic group having 6 to 50 carbon atoms, and may have one or more substituents in addition to the two acid anhydride groups represented by -CO-O-CO- in formula (d1-1). Preferred examples of substituents are fluorine atoms, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, fluorinated alkyl groups having 1 to 6 carbon atoms, and fluorinated alkoxy groups having 1 to 6 carbon atoms. In addition to the acid anhydride groups represented by formula (d1-1), carboxyl groups and carbonate groups may also be contained. When the substituent is a fluorinated alkyl group or a fluorinated alkoxy group, it is preferably a perfluoroalkyl group or a perfluoroalkoxy group. The above substituents and the one or more substituents that the aromatic group described below may have on the aromatic ring may also be considered the same.

In formula (d1-1), D is a tetravalent organic group, and the lower limit of the number of carbon atoms is 6 and the upper limit is 50. The number of carbon atoms constituting D is preferably 8 or more, and more preferably 12 or more. Furthermore, the number of carbon atoms constituting D is more preferably 40 or less, and even more preferably 30. D may be an aliphatic group, an aromatic group, or a group combining these structures. D may contain a halogen atom, an oxygen atom, and a sulfur atom in addition to carbon atoms and hydrogen atoms. When D contains an oxygen atom, a nitrogen atom or a sulfur atom, the oxygen atom, nitrogen atom or sulfur atom may be contained in D as a group selected from a nitrogen-containing heterocyclic group, -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO ₂ -, -S-, and -SS-, and more preferably contained in D as a group selected from -O-, -CO-, -SO-, -SO ₂ -, -S-, and -SS-.

The tetracarboxylic dianhydride can be appropriately selected from tetracarboxylic dianhydrides that have been used as a synthetic raw material for polyamide. The tetracarboxylic dianhydride can be an aliphatic tetracarboxylic dianhydride or an aromatic tetracarboxylic dianhydride.

Examples of aliphatic tetracarboxylic dianhydrides include 2,2-bis(3,4-dicarboxy)propane dianhydride and bis(3,4-dicarboxy)methane dianhydride. In addition, aliphatic tetracarboxylic dianhydrides may contain an alicyclic structure. The alicyclic structure may be polycyclic. Examples of polycyclic alicyclic structures include bridged alicyclic structures such as bicyclo[2.2.1]heptane. For example, a bridged alicyclic structure may be condensed with other bridged alicyclic structures and/or non-bridged alicyclic structures, and a bridged alicyclic structure may be linked to other bridged alicyclic structures and/or non-bridged alicyclic structures via a screw bond. When aliphatic tetracarboxylic dianhydride is used, the composition tends to be easy to obtain a cured product having excellent transparency.

Furthermore, as the aliphatic group of D in the constituting formula (d1-1), a tetravalent group represented by the following formula (d2) can be used. When such a group is used, a polyimide film having transparency tends to be easily obtained. Furthermore, from the viewpoint of easy purification of the raw material compound, d in the formula (d2) is preferably 5 or less, and more preferably 3 or less. Furthermore, from the viewpoint of the excellent chemical stability of the raw material compound to obtain the structural unit represented by the formula (d1), d is preferably 1 or more, and more preferably 2 or more. d in the formula (d2) is particularly preferably 2 or 3. (In formula (d2), ^Rd11 , ^Rd12 and ^Rd13 are each independently one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms and a fluorine atom, and d is an integer of 0 to 12).

Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic dianhydride, 3,3',4,4'-oxybisphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, and 3,3',4,4'-diphenylsulfonatetetracarboxylic dianhydride.

The aromatic tetracarboxylic dianhydride may be, for example, a compound represented by the following general formula (d1-2) to (d1-4).

In the above formulae (d1-2) and (d1-3), ^Rd1 , ^Rd2 and ^Rd3 represent any one of an aliphatic group which may be substituted by a halogen group, an oxygen atom, a sulfur atom, an aromatic group separated by one or more divalent elements, or a divalent group formed by combining these. ^Rd2 and ^Rd3 may be the same or different. That is, ^Rd1 , ^Rd2 and ^Rd3 may include a carbon-carbon single bond, a carbon-oxygen-carbon ether bond or a halogen element (fluorine, chlorine, bromine, iodine), for example, 2,2-bis(3,4-dicarboxyphenoxy)propane dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, etc.

In the above formula (d1-4), ^Rd4 and ^Rd5 represent an aliphatic group which may be substituted with a halogen group, an aromatic group separated by one or more divalent elements, a halogen group, or a monovalent substituent formed by combining them, and they may be the same or different. Difluoropyromellitic dianhydride, dichloropyromellitic dianhydride, etc. may also be used.

Examples of tetracarboxylic dianhydrides for obtaining fluorinated polyimides containing fluorine in their molecular structure include (trifluoromethyl)pyromellitic dianhydride, bis(trifluoromethyl)pyromellitic dianhydride, bis(pentafluoropropyl)pyromellitic dianhydride, pentafluoroethylpyromellitic dianhydride, bis{3,5-bis(trifluoromethyl)phenoxy}pyromellitic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 5,5'-bis(trifluoromethyl)-3,3',4,4'-tetracarboxybiphenyl dianhydride, 2,2',5,5'-tetrakis(trifluoromethyl)-3,3',4,4'-tetracarboxybiphenyl dianhydride, 5,5'-bis(trifluoromethyl) -3,3',4,4'-tetracarboxy diphenyl ether dianhydride, 5,5'-bis(trifluoromethyl)-3,3',4,4'-tetracarboxy benzophenone dianhydride, bis{(trifluoromethyl)dicarboxyphenoxy}phthalic anhydride, bis{(trifluoromethyl)dicarboxyphenoxy}(trifluoromethyl)phthalic anhydride, bis(dicarboxyphenoxy)(trifluoromethyl)phthalic anhydride, bis(dicarboxyphenoxy)bis(trifluoromethyl)phthalic anhydride, bis(dicarboxyphenoxy)tetrakis(trifluoromethyl)phthalic anhydride, 2,2-bis{4-(3,4 dianhydride, bis{(trifluoromethyl)dicarboxyphenoxy}bis(trifluoromethyl)diphenyl dianhydride, bis{(trifluoromethyl)dicarboxyphenoxy}bis(trifluoromethyl)biphenyl dianhydride, bis{(trifluoromethyl)dicarboxyphenoxy}diphenyl ether dianhydride, bis(dicarboxyphenoxy)bis(trifluoromethyl)biphenyl dianhydride, difluoropyromellitic acid dianhydride, 1,4-bis(3,4-dicarboxytrifluorophenoxy)tetrafluorophthalic dianhydride, 1,4-bis(3,4-dicarboxytrifluorophenoxy)octafluorobiphenyl dianhydride, and the like.

As tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride is preferably used in consideration of the heat resistance, tensile elongation and chemical resistance of the obtained film or molded body, and 3,3',4,4'-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride are preferably used in consideration of the price and availability. In addition, acid chlorides and esters of tetracarboxylic acids having the same basic skeleton as these can also be used.

In the present embodiment, tetracarboxylic dianhydride may be used together with dicarboxylic anhydride. When these carboxylic anhydrides are used together, the properties of the obtained polyimide resin or the like containing an amide ring may be better. Examples of dicarboxylic anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, and the like.

[Diamine Compound] As the diamine compound, a compound represented by the following formula (d3-1) can be typically used. The diamine compound may be used alone or in combination of two or more. (In formula (d3-1), B represents a divalent organic group).

In formula (d3-1), B is a divalent organic group, and in addition to the two amino groups in formula (d3-1), it may also have one or more substituents. Preferred examples of substituents are fluorine atoms, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, fluorinated alkyl groups having 1 to 6 carbon atoms, fluorinated alkoxy groups having 1 to 6 carbon atoms, or hydroxyl groups. When the substituent is a fluorinated alkyl group or a fluorinated alkoxy group, it is preferably a perfluoroalkyl group or a perfluoroalkoxy group.

In formula (d3-1), the lower limit of the number of carbon atoms in the organic group as B is preferably 2, more preferably 6, and the upper limit is preferably 50, more preferably 30. B may be an aliphatic group, but is preferably an organic group containing one or more aromatic rings.

When B is an organic group containing one or more aromatic rings, the organic group may be one aromatic group itself, or may be a group in which two or more aromatic groups are bonded via aliphatic alkyl groups and halogenated aliphatic alkyl groups or a heteroatom containing oxygen atoms, sulfur atoms, nitrogen atoms, etc. Examples of the heteroatom bond containing oxygen atoms, sulfur atoms, nitrogen atoms, etc. contained in B are -CONH-, -NH-, -N=N-, -CH=N-, -COO-, -O-, -CO-, -SO-, -SO ₂ -, -S-, and -SS-, preferably -O-, -CO-, -SO-, -SO ₂ -, -S-, and -SS-.

The aromatic ring in B that is bonded to the amino group is preferably a benzene ring. When the ring in B that is bonded to the amino group is a condensed ring containing two or more rings, the ring in the condensed ring that is bonded to the amino group is preferably a benzene ring. In addition, the aromatic ring contained in B may also be an aromatic heterocyclic ring.

When B is an organic group containing an aromatic ring, the organic group is preferably at least one of the groups represented by the following formulae (21) to (24) from the viewpoint of heat resistance of a cured product formed using the resin composition. (In formulas (21) to (24), R ¹¹¹ represents one selected from the group consisting of a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, and a halogenated alkyl group having 1 to 4 carbon atoms. In formula (24), Q represents a 9,9'-fluorene group, or a group represented by the formula: -C ₆ H ₄ -, -CONH-C 6 H 4 -NHCO-, -NHCO-C ₆ H ₄ -CONH-, -OC 6 H 4 -CO-C 6 H 4 -O-, -OCO-C 6 H 4 -COO-, -OCO-C 6 H ₄ -C ₆ H ₄ -COO-, -OCO-C ₆ H ₄ -C ₆ H ₄ -COO-, -OCO-, -O-, -S-, -CO-, -CONH-, -SO ₂ -, -C(CF 3 ) 2 -, -C(CH 3 ) 2 -, -CH 2 -, -OC ₆ H ₄ -CO-C ₆ H ₄ -O-, -OCO-C 6 H 4 -COO-, -OCO-C 6 H 4 -C 6 H 4 -COO-, -OCO-, -O-, -S-, -CO-, -CONH-, -SO ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -CH ₂ -, -OC ₆ H _{-C 6} H ₄ -O-, -OC ₆ H ₄ -C(CF ₃ ) _{2 -C 6} H ₄ -O-, -OC ₆ H ₄ -SO ₂ -C ₆ H ₄ -O-, _{-C(CH 3 ) 2 -C 6 H 4 -C(CH 3 ) 2 - , -OC 10 H 6 -O- ,} -OC ₆ H ₄ -C ₆ H ₄ -O-, and -OC ₆ H ₄ -O-. In the examples of Q, -C ₆ H ₄ - is a phenylene group, preferably a m-phenylene group and a p-phenylene group, more preferably a p-phenylene group. Furthermore, -C ₁₀ H ₆ - is naphthalene-1,2-diyl, preferably naphthalene-1,4-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl and naphthalene-2,7-diyl, more preferably naphthalene-1,4-diyl and naphthalene-2,6-diyl).

R ¹¹¹ in formulas (21) to (24) is more preferably a hydrogen atom, a hydroxyl group, a fluorine atom, a methyl group, an ethyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom, a hydroxyl group or a trifluoromethyl group, from the viewpoint of heat resistance of the resulting cured product.

From the viewpoint of heat resistance of the resulting cured product, Q in formula (24) is preferably 9,9'-fluorene, _{-OC6H4 -O-} , -C( _CF3 ) _2- , -O-, -C( _CH3 ) _2- , _-CH2- , _-OC6H4 -C( _CH3 ) ₂ - _C6H4 -O-, or -CONH-, and particularly preferably _{-OC6H4 - O-} , -C( _CF3 ) _2- , _or -O-.

When an aromatic diamine is used as the diamine compound represented by formula (d3-1), the aromatic diamines shown below can be preferably used. That is, examples of aromatic diamines include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 3,4'-diaminodiphenylether, 3,3'-diaminodiphenylether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, )benzene, 1,3-bis(3-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)fluorene, 9,9-bis(4-amino-3-methylphenyl)fluorene, and 4,4-[1,4-phenylenebis(1-methylethane-1,1'-diyl)]diphenylamine, etc. Among them, p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, and 4,4'-diaminodiphenyl ether are particularly preferred in view of price, availability, and the like.

As B, a silicon-containing group which may have a chain aliphatic group and/or an aromatic ring may be used. As such a silicon-containing group, the following groups may be typically used.

From the viewpoint of further improving the mechanical properties of the obtained cured product, a group represented by the following formula (Si-1) can also be preferably used as B. (In formula (Si-1), ^R112 and ^R113 are independently a single bond or a methylene group, an alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms; ^R114 , ^R115 , ^R116 , and ^R117 are independently a group containing an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an amino group having 20 carbon atoms, a group represented by ^-OR118 ( ^R118 is a alkyl group having 1 to 20 carbon atoms), or an organic group containing one or more epoxide groups having 2 to 20 carbon atoms; and l is an integer from 3 to 50).

The alkylene group having 2 to 20 carbon atoms in ^R112 and ^R113 in the formula (Si-1) is preferably an alkylene group having 2 to 10 carbon atoms from the viewpoint of heat resistance and residual stress, such as dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene and the like.

As the cycloalkylene group having 3 to 20 carbon atoms in ^R112 and ^R113 in the formula (Si-1), a cycloalkylene group having 3 to 10 carbon atoms is preferably used from the viewpoint of heat resistance and residual stress, and examples thereof include a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, and the like. As the arylene group having 6 to 20 carbon atoms in ^R112 and ^R113 in the formula (Si-1), an aromatic group having 6 to 20 carbon atoms is preferably used from the viewpoint of heat resistance and residual stress, and examples thereof include a phenylene group and a naphthylene group.

As the alkyl group having 1 to 20 carbon atoms in ^R114 , ^R115 , ^R116 and ^R117 in the formula (Si-1), preferably, from the viewpoint of heat resistance and residual stress, an alkyl group having 1 to 10 carbon atoms is preferred, and specific examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, etc. As the cycloalkyl group having 3 to 20 carbon atoms in ^R113 , ^R115 , ^R116 and ^R117 in the formula (Si-1), preferably, from the viewpoint of heat resistance and residual stress, a cycloalkyl group having 3 to 10 carbon atoms is preferred, and specific examples include cyclopentyl, cyclohexyl, etc. As the aryl group having 6 to 20 carbon atoms in R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ and R ¹¹⁷ in the formula (Si-1), an aryl group having 6 to 12 carbon atoms is preferred from the viewpoint of heat resistance and residual stress, and specific examples include phenyl, tolyl, naphthyl, etc. As the group containing an amino group having 20 to less carbon atoms in R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ and R ¹¹⁷ in the formula (Si-1), an amino group, a substituted amino group (e.g., a bis(trialkylsilyl)amino group), etc. are exemplified. Examples of the group represented by ^-OR118 in ^R114 , ^R115 , ^R116 and ^R117 in formula (Si-1) include methoxy, ethoxy, propoxy, isopropoxy, butoxy, phenoxy, trialkoxy, naphthoxy, propenyloxy (e.g., allyloxy) and cyclohexyloxy. Among them, ^R114 , ^R115 , ^R116 and ^R117 are preferably methyl, ethyl, propyl or phenyl.

The group represented by the formula (Si-1) can be introduced by allowing a silicon-containing compound having amino groups at both ends to act on an acid anhydride. Specific examples of such silicon-containing compounds include methylphenyl polysilicone modified with amino groups at both ends (e.g., X-22-1660B-3 (number average molecular weight of about 4,400) and X-22-9409 (number average molecular weight of about 1,300) manufactured by Shin-Etsu Chemical Co., Ltd.), dimethyl polysilicone modified with amino groups at both ends (e.g., X-22-161A (number average molecular weight of about 1,600), X-22-161B (number average molecular weight of about 3,000) and KF8012 (number average molecular weight of about 4,400) manufactured by Shin-Etsu Chemical Co., Ltd.; BY16-835U (number average molecular weight of about 900) manufactured by Toray Dow Corning; and SILAPLANE FM3311 (number average molecular weight of about 1000) manufactured by JNC Corporation).

[Production method of polyamide (D)] Polyamide (D) having a structural unit represented by formula (d1) is typically a polymer obtained by reacting the tetracarboxylic dianhydride represented by formula (d1-1) and the diamine compound represented by formula (d3-1) in a solvent, or may be a polymer obtained by using one or more diamine compounds and/or tetracarboxylic dianhydrides. For example, it may be a polymer obtained by polycondensing a diamine compound and a mixture of two or more tetracarboxylic dianhydrides. In addition, polyamide (D) may be used alone or as a mixture of two or more.

The amount of tetracarboxylic dianhydride and diamine compound used in the synthesis of polyamide (D) is not particularly limited, but preferably 0.50 mol or more and 1.50 mol or less of diamine compound is used for 1 mol of tetracarboxylic dianhydride, more preferably 0.60 mol or more and 1.30 mol or less, and particularly preferably 0.70 mol or more and 1.20 mol or less. In addition, the weight average molecular weight of the obtained polyamide (D) can be appropriately set according to its use, but is, for example, 5000 or more, preferably 7500 or more, and more preferably 10000 or more. On the other hand, the weight average molecular weight of the obtained polyamide (D) is, for example, 100000 or less, preferably 80000 or less, and more preferably 75000 or less. The weight average molecular weight can be adjusted to the above value by adjusting the amount of tetracarboxylic dianhydride and diamine compound, or the reaction conditions such as solvent or reaction temperature.

The reaction of tetracarboxylic dianhydride and diamine compound is usually carried out in an organic solvent. The organic solvent used in the reaction of tetracarboxylic dianhydride and diamine compound is not particularly limited as long as it can dissolve tetracarboxylic dianhydride and diamine compound and does not react with tetracarboxylic dianhydride and diamine compound. The organic solvent may be used alone or in combination of two or more.

Examples of organic solvents used for the reaction of tetracarboxylic dianhydride and diamine compounds include nitrogen-containing polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N-methylcaprolactam and N,N,N',N'-tetramethylurea; dimethyl sulfoxide; acetonitrile; ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxane and tetrahydrofuran.

Among these organic solvents, nitrogen-containing polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N-methylcaprolactam and N,N,N',N'-tetramethylurea are preferred based on the solubility of the resulting polyamide (D) or polyimide resin.

The temperature at which the tetracarboxylic dianhydride and the diamine compound react is not particularly limited as long as the reaction can proceed well. Typically, the reaction temperature of the tetracarboxylic dianhydride and the diamine compound is preferably -5°C to 150°C, more preferably 0°C to 120°C, and particularly preferably 0°C to 70°C. The reaction time of the tetracarboxylic dianhydride and the diamine compound varies with the reaction temperature, but typically, it is preferably 1 hour to 50 hours, more preferably 2 hours to 40 hours, and particularly preferably 5 hours to 30 hours.

By the method described above, a solution containing polyamine (D) can be obtained. The solution containing polyamine (D) as described above can be used directly to prepare a composition, or a paste or solid of polyamine obtained by removing at least a portion of the solvent from the solution of polyamine (D) under reduced pressure at a low temperature that does not convert polyamine into polyimide resin can be used to prepare a resin composition.

The composition of the first embodiment, which further includes a monomer component composed of a free diamine compound and a tetracarboxylic dianhydride, at least one resin precursor selected from the group composed of polyamide (D) and polyimide, or even a resin, may also contain a carbonyl oxide compound (B1) having a -CO-O- bond in the molecule that is not equivalent to the salt represented by the above general formula (1). Specific examples of the carbonyl oxide compound (B1) include carboxylic acids, carboxylic acid esters, carboxylic acid anhydrides, and carbonates described in Japanese Patent Application Publication No. 2018-58918.

When the composition of the first aspect contains a carbonyl oxide compound (B1), the content of the carbonyl oxide compound (B1) is not particularly limited within the range not impairing the object of the present invention, but is preferably from 0.01 mass % to 30 mass %, more preferably from 0.05 mass % to 25 mass %, and particularly preferably from 0.2 mass % to 20 mass %, based on the total solid content of the composition (excluding the solvent).

(Solvent (S)) The composition of the first aspect preferably contains a solvent (S) in terms of coating properties. The composition may be a paste containing a solid or a solution, but a solution is preferred. The solvent (S) may be used alone or in combination of two or more. The type of the solvent (S) is not particularly limited within the scope not impairing the purpose of the present invention, and examples thereof include water, glycol monoethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, and diethylene glycol monophenyl ether; glycol diethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dipropyl ether; and glycol diethers such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, Phenyl ether acetate, diethylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate, etc. glycol monoacetates; diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monophenyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxy acetic acid esters; methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-propoxypropionate, propyl 3-methoxypropionate, isopropyl 3-methoxypropionate, ethyl ethoxylate, ethyl oxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl acetate, ethyl acetate, Esters such as esters, propyl acetate, isopropyl acetate, butyl acetate, isoamyl acetate, methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetylacetate, ethyl acetylacetate, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, and γ-butyrolactone; ethers such as diethyl ether, dipropyl ether, dibutyl ether, dihexyl ether, benzyl methyl ether, benzyl ethyl ether, and tetrahydrofuran; aromatics such as benzene, toluene, xylene, ethylbenzene, cresol, and chlorobenzene; aliphatic alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, n-hexanol, and cyclohexanol; glycols such as polyethylene glycol, ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; glycerol; etc. In addition, the solvent used for the reaction of the above-mentioned tetracarboxylic dianhydride and diamine compound can also be preferably used as a solvent in a composition comprising a monomer component composed of a free diamine compound and tetracarboxylic dianhydride, at least one resin precursor selected from the group composed of polyamide (D) and polyimide, or even the first state of the resin.

The solvent (S) may contain a compound (S1) represented by the following formula (5). (In formula (5), R ^S1 and R ^S2 are independently an alkyl group having 1 to 3 carbon atoms, and R ^S3 is a group represented by the following formula (5-1) or the following formula (5-2): In formula (5-1), R ^S4 is a hydrogen atom or a hydroxyl group, and R ^S5 and R ^S6 are each independently an alkyl group having 1 to 3 carbon atoms. In formula (5-2), R ^S7 and R ^S8 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

In the compound (S1) represented by the formula (5), specific examples of ^RS3 when the group represented by the formula (5-1) include N,N,2-trimethylpropionic acid amide, N-ethyl-N,2-dimethylpropionic acid amide, N,N-diethyl-2-methylpropionic acid amide, N,N,2-trimethyl-2-hydroxypropionic acid amide, N-ethyl-N,2-dimethyl-2-hydroxypropionic acid amide, and N,N-diethyl-2-hydroxy-2-methylpropionic acid amide.

In the compound (S1) represented by the formula (5), specific examples of ^RS3 when the group represented by the formula (5-2) include N,N,N',N'-tetramethylurea and N,N,N',N'-tetraethylurea.

Among the above-mentioned compounds (S1), N,N,2-trimethylpropionic acid amide and N,N,N',N'-tetramethylurea are particularly preferred.

When the composition includes a solvent (S), the content of the aforementioned compound (S1) in the solvent (S) is not particularly limited within the scope not impairing the purpose of the present invention. Relative to the mass of the solvent of the first embodiment of the composition further including a monomer component composed of a free diamine compound and a tetracarboxylic dianhydride, at least one resin precursor selected from the group composed of polyamide (D) and polyimide, or even a resin, the ratio of the compound (S1) relative to the total amount of the solvent (S) is typically preferably 70 mass % or more, more preferably 80 mass % or more, particularly preferably 90 mass % or more, and most preferably 100 mass %.

Examples of organic solvents that can be used together with compound (S1) include nitrogen-containing polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, hexamethylsulfonamide, and 1,3-dimethyl-2-imidazolidinone; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone; cyclic ethers such as dioxane and tetrahydrofuran; aromatic hydrocarbons such as toluene and xylene; and sulfoxides such as dimethyl sulfoxide.

The content of the solvent (S) in the composition is not particularly limited within the scope that does not impair the purpose of the present invention. The content of the solvent (S) in the composition is appropriately adjusted corresponding to the solid content in the composition. The solid content in the resin composition is, for example, in the range of 5 mass % to 99.9 mass %, preferably 5 mass % to 70 mass %, and more preferably 10 mass % to 60 mass %.

(Other components) The composition of the first aspect may contain various resins or additives as needed. Examples of resins include alkali-soluble resins or resins whose solubility in a developing solution (alkaline developing solution or solvent developing solution) increases by exposure or heating. The resin may or may not have an ethylenic unsaturated group. Examples of additives include colorants, dispersants, sensitizers, hardening accelerators, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomeration agents, thermal polymerization inhibitors, defoaming agents, surfactants, etc. When the composition of the first aspect includes a compound represented by the general formula (1), the resin content can be appropriately adjusted within a range of, for example, 10% to 90% by mass relative to the entire composition excluding the solvent, and is preferably 20% to 80% by mass. When the composition of the first aspect includes a polymer derived from a compound represented by the general formula (1), the resin content can be appropriately adjusted within a range of, for example, 1% to 90% by mass relative to the entire composition excluding the solvent, and is preferably 10% to 80% by mass. The amount of each additive added can be appropriately adjusted within a range of, for example, 0.001% to 60% by mass relative to the entire composition excluding the solvent of the first aspect, and is preferably 0.1% to 5% by mass.

The composition of the first aspect may be a thermosetting composition that hardens by heating, or may not be a thermosetting composition. When the composition of the first aspect is a thermosetting composition, the composition of the first aspect may contain additives or reinforcing materials such as a hardener, a hardening accelerator, a dehydration condensation agent, an antioxidant, a UV absorber, a flame retardant, a mold release agent, a plasticizer, a filler, and a reinforcing material as needed.

Furthermore, the composition of the first aspect may be a radiation-sensitive composition or may not be a radiation-sensitive composition. When the composition of the first aspect is a radiation-sensitive composition, it may be a negative radiation-sensitive composition that is insoluble in a developing liquid by exposure, or it may be a positive radiation-sensitive composition that is soluble in a developing liquid by exposure. Furthermore, the composition of the first aspect may be used as a processing liquid, etc. (for metal surface treatment, developing treatment, etching treatment, etc.). When the composition of the first aspect is a processing liquid composition, it preferably contains the above-mentioned solvent (S) in addition to the salt represented by formula (1). The treatment liquid composition may also contain any additives such as pH adjusters, surfactants, preservatives, viscosity adjusters, antioxidants, ultraviolet absorbers or colorants in amounts within the commonly used ranges.

(Preparation method of the composition of the first aspect) The composition of the first aspect can be prepared by mixing the above-mentioned components with a stirrer. In addition, the prepared composition of the first aspect can also be filtered using a membrane filter or the like to make it uniform.

(Application) The composition of the first aspect can be used as a protective film, interlayer insulating film, flat film, insulating film composition for forming electronic parts such as display elements, integrated circuit elements, solid-state imaging elements, etc., and can be used as a processing agent or sacrificial film composition in the manufacturing process of such electronic parts.

≪Cured material≫ The second-state cured material is a cured material of the first-state composition. The second-state cured material can be used as a protective film, interlayer insulating film, flattening film, or insulating film for electronic parts such as liquid crystal display devices, integrated circuit devices, and solid-state imaging devices.

When the cured product is a film, the thickness is preferably from 10 nm to 30,000 nm, more preferably from 50 nm to 1,500 nm, and even more preferably from 100 nm to 1,000 nm.

≪Method for producing a cured product≫ The method for producing a cured product of the third aspect includes forming a film by applying the composition of the first aspect (preferably on a substrate), and heating the film. (Film forming step) The method for forming a film by applying the composition of the first aspect is not particularly limited, but examples thereof include a coating method using a contact transfer type coating device such as a roll coater, a reverse roll coater, a rod coater, or a non-contact type coating device such as a rotary coater (rotary coating device), a curtain coater, etc. The coating film after the above coating is preferably dried (baked). The drying method is not particularly limited, and examples include (1) drying on a heating plate at a temperature of 70°C to 120°C, preferably 80°C to 100°C, for example, for 60 seconds to 20 minutes; (2) leaving at room temperature for several hours to several days; (3) placing in a warm air heater or infrared heater for several tens of minutes to several hours to remove the solvent, etc. After coating, the coating may be placed in a reduced pressure environment for the purpose of promoting degassing or removal of the solvent (S) from the coating. The vacuum degree of the reduced pressure environment is not particularly limited, but is preferably 300Pa or less, more preferably 150Pa or less, and more preferably 100Pa or less. The coating thickness is not particularly limited. Typically, the coating thickness is preferably 2 μm to 100 μm, more preferably 3 μm to 50 μm. The coating thickness can be appropriately controlled by the coating method or by adjusting the solid content concentration or viscosity of the resin composition.

The material of the substrate is not particularly limited as long as it does not cause thermal degradation or deformation when the coating is heated. The shape of the substrate is not particularly limited as long as it is a coating resin composition. Examples of the substrate include electronic components such as semiconductor components with electrodes or wiring to be insulated, intermediate products such as multi-layer wiring substrates, and various substrates. When the base is a substrate, examples of preferred substrate materials include glass; silicon; aluminum (Al); aluminum-silicon (Al-Si), aluminum-copper (Al-Cu), aluminum-silicon-copper (Al-Si-Cu) and other aluminum alloys; titanium (Ti); titanium-tungsten (Ti-W) and other titanium alloys; titanium nitride (TiN); tantalum (Ta); tungsten nitride (TaN); tungsten (W); tungsten nitride (WN); copper. In addition, when the coating is heated at a low temperature, a substrate with low heat resistance made of a resin such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT) can also be used.

(Heating step) The above-formed coating is preferably heated at a temperature of 70°C to 550°C. When heating the above-formed coating, the heating temperature is set, for example, at a temperature of 120°C to 500°C, preferably at a temperature of 150°C to 450°C. By heating the coating at a temperature within this range, thermal degradation or thermal decomposition of the generated polyimide can be suppressed, and a stable cured product can be generated. In addition, when the coating is heated at a high temperature, a large amount of energy is consumed or the high-temperature processing equipment is accelerated to deteriorate over time. Therefore, it is better to heat the coating at a lower temperature than that.

The heating time varies depending on the composition of the resin composition or the coating thickness, but the lower limit can be set to, for example, 5 minutes, preferably 10 minutes, and more preferably 20 minutes, and the upper limit can be set to, for example, 4 hours, preferably 3 hours, and more preferably 2.5 hours. In addition, from the perspective of reducing the yellowness of polyimide or more smoothly converting from polyamide to polyimide, the environment during heating (gas composition such as oxygen concentration) can also be adjusted, and a decompression step can be combined during heating or before and after heating. [Example]

The present invention is described in detail below based on embodiments, but the present invention is not limited to these embodiments.

[Synthesis Example 1] Synthesis of the salt represented by the above general formula (1) 1 (Preparation of tetracarboxylic dianhydride) According to the method described in Synthesis Example 1, Example 1 and Example 2 of International Publication No. 2011/099518, tetracarboxylic dianhydride represented by the following formula (CpODA: norbornene-2-spiro-α-cyclopenta-α'-spiro-2"-norbornene-5,5",6,6"-tetracarboxylic dianhydride) was prepared. (Ring-opening of tetracarboxylic dianhydride) Heat a 100 ml three-necked flask with a heating gun and dry it thoroughly. Next, replace the atmosphere in the thoroughly dried three-necked flask with nitrogen to create a nitrogen environment. Next, introduce 1.00 g (2.60 mmol) of the tetracarboxylic dianhydride (CpODA) into the three-necked flask, then add NMP (N-methylpyrrolidone) as a solvent and stir to obtain a solution. Next, add 10 ml of hydrochloric acid at a concentration of 1 mass % to the three-necked flask containing the solution while maintaining a nitrogen environment and stir for 1 hour. Then, pure water was added to the stirring solution to produce a white precipitate, which was filtered by vacuum to obtain 0.98 g (2.33 mmol) of a tetracarboxylic acid represented by the following formula as a solid. The measurement results of ¹ H-NMR (deuterated DMSO, 400 MHz) of the above tetracarboxylic acid are as follows. δ (ppm): 12.10-11.75 (OH, 4H), 2.90 (CH, 2H), 2.65 (CH2, 4H), 2.38 (CH, 2H), 2.18 (CH2, 4H), 1.92 (CH2, 2H), 1.78 (CH, 2H), 1.75-58 (CH, 2H), 1.15 (CH, 2H)

(Synthesis of diimidazole salt) 0.42 g (1.00 mmol) of the above tetracarboxylic acid and 0.14 g (2.00 mmol) of imidazole were introduced into a mortar and pressurized for 15 minutes to obtain the target diimidazole salt represented by the following formula (hereinafter sometimes referred to as "Compound 1") (yield 0.55 g, yield 98%, white solid). The results of ¹ H-NMR (deuterated DMSO, 400 MHz) of the above diimidazole salt are as follows. Cation δ (ppm): 7.01 (CH, 4H), 7.65 (CH, 2H) Anion δ (ppm): 2.90 (CH, 2H), 2.65 (CH, 2H), 2.40 (CH2, 2H), 2.20 (CH, 2H), 1.94 (CH2, 4H), 1.78 (CH, 2H), 1.75-1.58 (CH, 4H), 1.15 (CH, 2H)

[Synthesis Example 2] Synthesis of the salt represented by the above general formula (1) A diimidazole salt represented by the following formula (hereinafter sometimes referred to as "Compound 2") is obtained in the same manner as in the above (Synthesis of Diimidazole Salt) except that the tetracarboxylic acid represented by the above formula is used as the tetracarboxylic acid.

[Synthesis Example 3] Preparation of polyamide Heat a 30ml three-necked flask with a heating gun to make it fully dry. Next, replace the ambient gas in the three-necked flask with nitrogen and set the three-necked flask to a nitrogen environment. Add 0.90mmol of 4,4'-diaminophenylaniline (DABAN) to the three-necked flask, and then add N,N,N',N'-tetramethylurea (TMU). Stir the contents of the three-necked flask to obtain a slurry liquid in which aromatic diamine (DABAN) is dispersed in TMU. Next, 0.90 mmol of the tetracarboxylic dianhydride (CpODA) was added to the three-necked flask, and the contents of the flask were stirred at room temperature (25° C.) for 12 hours under a nitrogen atmosphere to obtain a reaction solution. In this way, a reaction solution (polyamide solution) containing 20.0% by mass of polyamide was prepared.

[Examples 1 and 2] (Preparation of the composition of Example 1) For the above-mentioned polyamine solution (polyamine concentration: 20.0 mass%), 0.9 g of the powder (Compound 1) obtained in Synthesis Example 1 was added and dissolved by strong stirring to prepare the composition of Example 1 (mixed solution for forming polyimide (varnish)) containing the above-mentioned solvent, the above-mentioned polyamine and the above-mentioned compound 1. In addition, in the mixed solution for forming polyimide obtained in this way, the total content of the above-mentioned polyamine and the above-mentioned compound 1 was 16.5 mass%.

(Preparation of the composition of Example 2) The composition of Example 2 (mixed solution (varnish) for forming polyimide) was prepared in the same manner as (Preparation of the composition of Example 1) except that the powder of the compound 1 obtained in Synthesis Example 1 was replaced with the powder of the compound 2 obtained in Synthesis Example 2.

(Preparation of the composition of Comparative Example 1) In addition, the composition of Comparative Example 1 (mixed solution (varnish) for forming polyimide) was prepared in the same manner as in Example 1, except that imidazole was used instead of the above-mentioned compound 1, that is, a composition containing the above-mentioned solvent, the above-mentioned polyamine acid and imidazole was prepared.

(Preparation of the composition of Comparative Example 2) In addition, the composition of Comparative Example 2 (mixed solution (varnish) for forming polyimide) was prepared in the same manner as Example 1, except that the above-mentioned compound 1 was not contained, that is, a composition containing the above-mentioned solvent and the above-mentioned polyamide acid was prepared.

(Polyimide film forming test) For the compositions of Examples 1 and 2 and Comparative Examples 1 and 2, the film forming properties were tested as follows. First, each composition was applied on a 100 mm × 100 mm glass substrate by rotation, and the pressure was reduced from atmospheric pressure to 50 Pa and dried (VCD). Once returned to atmospheric pressure, it was pre-baked on a heating plate at 80°C for 10 minutes under atmospheric pressure conditions, and post-baked at 360°C for 30 minutes in a nitrogen environment (sintering) to obtain a cured product (polyimide film) with a film thickness of 15 μm. For the polyimide film obtained in this way, the shape was visually observed to see if the film was well formed. In addition, the evaluation was based on the following criteria. ○: A roughly smooth film was observed, and no cracks were confirmed. ×: Film cracking was observed. The results are shown in Table 1 below.

(Temporal stability test) The compositions of Examples 1 and 2 and Comparative Examples 1 and 2 were subjected to temporal stability evaluation by gelation at the initial stage of preparation and after storage at 25°C for 7 days (○: no gelation, ×: gelation). The results are shown in Table 1.

From the results shown in Table 1, it can be understood that the composition of Comparative Example 1, which does not contain salt but contains imidazole, has excellent film-forming properties but poor stability over time. And the composition of Comparative Example 2, which does not contain salt or imidazole, has excellent stability over time but poor film-forming properties. On the other hand, the compositions of Examples 1 and 2 containing imidazole salts are both excellent in both film-forming properties and stability over time.

Claims (9)

A composition comprising a salt represented by the following formula (1):

(In the above formula, A represents a tetravalent organic group containing 1 or more alicyclic groups, and the n -COO ^- M ⁺ and (4-n) -COOH in the above formula are independently bonded to the above 1 or more alicyclic groups directly or via a linking group, M ⁺ represents a cation containing a nitrogen-containing heterocyclic ring, and the above cation is a cation represented by any one of the following formulas (2) to (11), and n represents an integer of 1 to 4).

(In formula (2), R ¹¹ independently represents a hydrogen atom or an organic group, and s represents an integer of 2 to 6),

(wherein, ^RH represents a hydrogen atom or an alkyl group, ^R21 , ^R23 , ^R25 , ^R26 , ^R27 , ^R28 , ^R30 , ^R31 and ^R32 represent independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an alkenyl group or an alkynyl group, ^R22 , ^R24 and ^R29 represent independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an alkynyl group, ^R21 to ^R32 may be independently substituted by a halogen atom, a cyano group or a nitro group, ^R21 and ^R22 may be bonded to each other to form a ring, at least two ^R21 may be bonded to each other to form a ring, ^R23 and ^R24 may be bonded to each other to form a ring, two R23 may be bonded to each other to form a ring, at least two ^R29 may be bonded to each other to form a ring, ^{R 25} may bond to each other to form a ring, at least two R ²⁶ may bond to each other to form a ring, at least two R ²⁷ may bond to each other to form a ring, R ²⁸ and R ²⁹ may bond to each other to form a ring, at least two R ²⁸ may bond to each other to form a ring, at least two R ³⁰ may bond to each other to form a ring, at least two R ³¹ may bond to each other to form a ring, and at least two R ³² may bond to each other to form a ring). The composition of claim 1, wherein the cation containing the nitrogen-containing heterocyclic ring is a cation represented by any one of the above formulas (2) to (9) and (11). The composition of claim 1 or 2 further comprises a monomer component composed of a free diamine component and a tetracarboxylic dianhydride component, and at least one resin precursor or resin selected from the group consisting of polyamide and polyimide. A hardened product of a composition as claimed in claim 1 or 2. A method for manufacturing a hardened material, comprising: applying the composition of claim 1 or 2 to form a film, and heating the film. A salt represented by the following formula (1),

(In the above formula, A represents a tetravalent organic group containing 1 or more alicyclic groups, and the n -COO ^- M ⁺ and (4-n) -COOH in the above formula are independently bonded to the above 1 or more alicyclic groups directly or via a linking group, M ⁺ represents a cation containing a nitrogen-containing heterocyclic ring, and the above cation is a cation represented by any one of the following formulas (2) to (11), and n represents an integer of 1 to 4).

(In formula (2), R ¹¹ independently represents a hydrogen atom or an organic group, and s represents an integer of 2 to 6),

(wherein, ^RH represents a hydrogen atom or an alkyl group, ^R21 , ^R23 , ^R25 , ^R26 , ^R27 , ^R28 , ^R30 , ^R31 and ^R32 represent independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an alkenyl group or an alkynyl group, ^R22 , ^R24 and ^R29 represent independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an alkynyl group, ^R21 to ^R32 may be independently substituted by a halogen atom, a cyano group or a nitro group, ^R21 and ^R22 may be bonded to each other to form a ring, at least two ^R21 may be bonded to each other to form a ring, ^R23 and ^R24 may be bonded to each other to form a ring, two R23 may be bonded to each other to form a ring, at least two ^R29 may be bonded to each other to form a ring, ^{R 25} may bond to each other to form a ring, at least two R ²⁶ may bond to each other to form a ring, at least two R ²⁷ may bond to each other to form a ring, R ²⁸ and R ²⁹ may bond to each other to form a ring, at least two R ²⁸ may bond to each other to form a ring, at least two R ³⁰ may bond to each other to form a ring, at least two R ³¹ may bond to each other to form a ring, and at least two R ³² may bond to each other to form a ring). As in claim 6, the aforementioned cation containing a nitrogen-containing heterocyclic ring is a cation represented by any one of the aforementioned formulas (2) to (9) and (11). A polyimide film-forming composition for suppressing temporal changes and enhancing film-forming properties, comprising a salt as described in claim 6. A use of the salt as claimed in claim 6 is to manufacture an agent for inhibiting the time-dependent change and enhancing the film-forming property of a composition for forming a polyimide film.