JP6841048B2 - Polyimide - Google Patents

Description

The present invention is excellent in alkali solubility, solvent solubility, storage stability, and heat resistance, and is suitably used as a resin for a photosensitive resin composition (resist) used in the production of semiconductor integrated circuits, printed wiring boards, liquid crystal panels, and the like. Regarding polyimides that can be.

Resists used in the manufacture of semiconductor integrated circuits, printed wiring boards, liquid crystal panels, etc. include positive resists and negative resists. The difference between the two is that in the positive resist, the exposed area is removed by the developing process and the unexposed area remains as a layer on the substrate, whereas in the negative resist, the exposed area remains as a relief structure.

Conventionally, acrylic resins have been used as these resist resins, but in recent years, resist resins have been changed to polyimide in order to improve heat resistance and the like.
Further, as the developing solution, there are an organic solvent-based developing solution and an alkaline aqueous solution, but in recent years, an alkaline aqueous solution has come to be used in order to reduce the environmental load.

Polyimide has various excellent properties such as heat resistance, flame retardancy, flexibility, electrical properties, and chemical resistance, but it is sparingly soluble in organic solvents and insoluble in alkaline aqueous solutions. A polyamic acid (polyamic acid), which is a polyimide precursor, has both solvent solubility and alkali solubility, but the polyamic acid has drawbacks that it is inferior in storage stability and has a high curing temperature.

Patent Document 1 describes 3,3', 4,4'-bicyclohexanetetracarboxylic dianhydride (H-BPDA) or 1,2,4,5 as the polyimide used for the alkali-developable polyimide resin composition. -A phenolic hydroxyl group formed by polycondensing a tetracarboxylic dianhydride containing cyclohexanetetracarboxylic dianhydride (H-PMDA) as an essential component and a diamine compound containing a diamine compound having a phenolic hydroxyl group as an essential component. Containing polyimides have been proposed. However, according to the studies by the present inventors, the polyimide obtained from the diamine component having a phenolic hydroxyl group and 3,3', 4,4'-bicyclohexanetetracarboxylic acid dianhydride has sufficient solubility in an alkaline aqueous solution. Rather, there is a risk that undissolved residue will occur during alkaline development.

Patent Document 2 describes, as a photosensitive resin composition having excellent storage stability and capable of water-based development, an acrylic-modified soluble polyimide containing a polymerizable functional group and containing a carboxyl group and / or a hydroxyl group. Although described, there is no specific example of a polyimide having both a carboxyl group and a phenolic hydroxyl group, and an aromatic tetracarboxylic acid dianhydride is used as the tetracarboxylic acid dianhydride. According to the study by the present inventors, in the case of a polyimide using an aromatic tetracarboxylic dianhydride, the higher the imidization rate, the poorer the solubility in an organic solvent, and the imidization rate at the time of production becomes lower. Stable production becomes difficult because it affects solvent solubility.

Japanese Patent No. 5530363 Japanese Unexamined Patent Publication No. 2004-325980

The alkali solubility of resists used in the manufacture of semiconductor integrated circuits, printed wiring boards, liquid crystal panels, etc. is not as high as it is, but it is suitable for the composition and temperature of the alkaline developer used, workability in the manufacturing process, and required characteristics. It is desirable that it is alkali-soluble. However, conventionally, although a polyimide having been provided with alkali solubility has been proposed, there is no problem of controlling the degree of alkali solubility, and no device for controlling alkali solubility has been made.

An object of the present invention is to provide a polyimide which is excellent in alkali solubility, solvent solubility, storage stability and heat resistance, and whose alkali solubility can be easily controlled according to the required degree of alkali solubility.

As a result of diligent studies to solve the above problems, the present inventors have selected residues derived from 3,3', 4,4'-bicyclohexanetetracarboxylic dianhydride as tetracarboxylic acid residues. We have found that a polyimide containing, as a diamine residue, a residue derived from a diamine compound having a phenolic hydroxyl group and a residue derived from a diamine compound having a carboxyl group can solve the above-mentioned problems. The invention was completed.

That is, the gist of the present invention is as follows.

[1] A tetracarboxylic acid residue derived from 3,3', 4,4'-bicyclohexanetetracarboxylic acid dianhydride and a diamine residue derived from a diamine compound having a phenolic hydroxyl group (hereinafter, "" A polyimide containing a "phenolic hydroxyl group-containing diamine residue") and a diamine residue derived from a diamine compound having a carboxyl group (hereinafter referred to as "carboxyl group-containing diamine residue").

[2] The phenolic hydroxyl group-containing diamine residue and the carboxyl group-containing diamine residue are mixed in a mol ratio of phenolic hydroxyl group-containing diamine residue: carboxyl group-containing diamine residue = 1: 0.1 to 150. The polyimide according to [1].

[3] The phenolic hydroxylamine-containing diamine residue is a diamine residue derived from an aromatic diamine compound having two phenolic hydroxyl groups, and the carboxyl group-containing diamine residue is a monocyclic aromatic having a carboxyl group. The polyimide according to [1] or [2], which is a diamine residue derived from a diamine compound.

[4] The OH equivalent based on the phenolic hydroxyl group-containing diamine residue is 300 to 30,000 g / eq. The polyimide according to any one of [1] to [3], wherein the acid value based on the carboxyl group-containing diamine residue is 20 to 150 mg-KOH / g.

The polyimide of the present invention is excellent in alkali solubility, solvent solubility, storage stability, and heat resistance, and its alkali solubility can be easily controlled according to the required degree of alkali solubility.
Such a polyimide of the present invention can be suitably used as a resist resin used in the manufacture of semiconductor integrated circuits, printed wiring boards, liquid crystal panels and the like.

Hereinafter, embodiments of the present invention will be described in detail, but the description of each constituent requirement described below is a representative example of the embodiment of the present invention, and the present invention is limited thereto as long as the gist thereof is not exceeded. It is not something that is done.

The polyimide of the present invention contains a tetracarboxylic acid residue derived from 3,3', 4,4'-bicyclohexanetetracarboxylic dianhydride (hereinafter, may be abbreviated as "H-BPDA"). , A diamine residue derived from a diamine compound having a phenolic hydroxyl group (hereinafter, referred to as "phenolic hydroxyl group-containing diamine residue"), and a diamine residue derived from a diamine compound having a carboxyl group (hereinafter, "" It is characterized by containing at least a carboxyl group-containing diamine residue.
That is, since the polyimide of the present invention is a polyimide rather than a polyamic acid, it is excellent in storage stability and heat resistance, and is a tetracarboxylic derived from H-BPDA, which is an alicyclic tetracarboxylic dianhydride. By including the acid residue, an alicyclic structure is introduced into the polyimide skeleton, and the polyimide skeleton has excellent solvent solubility, storage stability, and heat resistance. Further, since it contains a phenolic hydroxyl group-containing diamine residue and a carboxyl group-containing diamine residue, alkali solubility can be easily imparted and its control can be easily performed.

As a method for producing polyimide, as shown in the following reaction formula (I), a polyimide precursor (polyamic acid, polyamic acid) is produced by a polycondensation reaction between a tetracarboxylic acid dianhydride and a diamine compound. Then, there are a method of forming a polyimide by a dehydration ring closing reaction of this polyimide precursor and a method of directly producing a polyimide from a tetracarboxylic acid dianhydride and a diisocyanate compound as shown in the following reaction formula (II). , The polyimide of the present invention may be produced by any method.

Therefore, in the present invention, the "phenolic hydroxyl group-containing diamine residue" is not limited to the "diamine residue derived from the diamine compound having a phenolic hydroxyl group", but is derived from the "diisocyanate compound having a phenolic hydroxyl group". It may be a "diamine residue". Similarly, the "carboxyl group-containing diamine residue" is not limited to "diamine residue derived from a diamine compound having a carboxyl group", but is also "diamine residue derived from a diamine compound having a carboxyl group". You may.
Examples of the diisocyanate compound used in the production of the polyimide of the present invention include compounds in which "diamine" is replaced with "diisocyanate" among the names of diamine compounds exemplified below.

[Tetracarboxylic acid residue]
<H-BPDA residue>
The polyimide of the present invention is a residue derived from 3,3', 4,4'-bicyclohexanetetracarboxylic dianhydride (H-BPDA) represented by the following structural formula as a tetracarboxylic acid residue (hereinafter, hereafter. It may be referred to as "H-BPDA residue") as an essential component.

When the polyimide of the present invention contains an H-BPDA residue, an alicyclic structure is introduced into the polyimide skeleton, and it can be made excellent in solvent solubility, storage stability, and heat resistance.

<Other tetracarboxylic acid residues>
The polyimide of the present invention may contain only the above H-BPDA residue as a tetracarboxylic acid residue, and is a tetracarboxylic acid derived from the H-BPDA residue and another tetracarboxylic dianhydride. It may contain a residue (hereinafter, may be referred to as "another tetracarboxylic acid residue").

The other tetracarboxylic dianhydride is a residue derived from a tetracarboxylic dianhydride other than H-BPDA, and the tetracarboxylic dianhydride other than H-BPDA is an aromatic tetracarboxylic dianhydride. Examples thereof include dianhydride and aliphatic tetracarboxylic dianhydride.

Examples of the aromatic tetracarboxylic dianhydride include tetracarboxylic dianhydride having one aromatic ring in one molecule, tetracarboxylic dianhydride having two or more independent aromatic rings in one molecule, and 1 Examples thereof include tetracarboxylic dianhydride having a condensed aromatic ring in the molecule.

Among these, tetracarboxylic dianhydride having one aromatic ring in one molecule or tetracarboxylic dianhydride having one aromatic ring in one molecule tends to be easy to control the viscosity at the time of production, improve solvent solubility, and improve coating flexibility. A tetracarboxylic dianhydride having two or more independent aromatic rings in one molecule is preferable, and a tetracarboxylic dianhydride having two or more independent aromatic rings in one molecule is particularly preferable.

Examples of the tetracarboxylic dianhydride having one aromatic ring in one molecule include pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride and the like.

Examples of the tetracarboxylic dianhydride having two or more independent aromatic rings in one molecule include 1,1-bis (2,3-dicarboxyphenyl) ethanedianhydride and bis (2,3-di). Carboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4) -Dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-) Dicarboxyphenyl) ether dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic dianhydride, 4,4'- Oxydiphthalic dianhydride, 4,4- (p-phenylenedioxy) diphthalic dianhydride, 4,4- (m-phenylenedioxy) diphthalic dianhydride, 2,2', 6,6'- Examples thereof include biphenyltetracarboxylic dianhydride.

Examples of the tetracarboxylic acid dianhydride having a condensed aromatic ring in one molecule include 1,2,5,6-naphthalenedicarboxylic acid dianhydride, 1,4,5,8-naphthalenedicarboxylic acid dianhydride, 2, 3,6,7-naphthalenedicarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2,3,6,7-anthracenetetracarboxylic acid dianhydride, 1,2,7 , 8-Phenantrene tetracarboxylic acid dianhydride and the like.

Examples of the aliphatic tetracarboxylic dianhydride include an alicyclic tetracarboxylic dianhydride other than H-BPDA and a chain aliphatic tetracarboxylic dianhydride.

Examples of the alicyclic tetracarboxylic acid dianhydride include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2 and 3. , 4,5-Cyclohexanetetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 5- (2,5-dioxotetrahydro) Frill) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, tricyclo [6.4.0.0 (2,7)] dodecane-1,8: 2,7-tetracarboxylic acid dianhydride Bicyclo [2.2.2] Oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, 4- (2,5-dioxo tetrahydrofuran-3-yl) -1,2 , 3,4-Tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, 1,1'-bicyclohexane-3,3', 4,4'-tetracarboxylic acid dianhydride and the like.

Examples of the chain aliphatic tetracarboxylic acid dianhydride include ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride and the like. Can be mentioned.

Examples of the tetracarboxylic dianhydride other than H-BPDA include silicone-based tetracarboxylic dianhydride and, for example, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3. , 3-Hexafluoropropane dianhydride (also known as 4,4'-(hexafluoroisopropyridene) -diphthalic acid dianhydride), 2,2-bis (2,3-dicarboxyphenyl) -1,1,1 1,3,3,3-Hexafluoropropane dianhydride, 2,2'-bis (trifluoromethyl) -4,4', 5,5'-biphenyltetracarboxylic dianhydride, 4,4'- (Hexafluorotrimethylethylene) diphthalic dianhydride, 4,4'-(octafluorotetramethylene) diphthalic acid dianhydride, 2,2'-bis (trifluoromethyl) -4,4', 5,5' -Biphenyltetracarboxylic dianhydride, 4,4'-(hexafluorotrimethylethylene) diphthalic acid dianhydride, 4,4'-(octafluorotetramethylene) diphthalic acid dianhydride, 2,2-bis (3) , 4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropanedianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3 3,3-Hexafluoropropanedianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropanedianhydride, 2,2-bis A tetracarboxylic dianhydride containing a fluorine atom such as (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropanedianhydride can also be used.

When the polyimide of the present invention contains the above-mentioned other tetracarboxylic acid residues, the other tetracarboxylic acid residues may be only one kind or may contain two or more kinds.

<Content ratio of H-BPDA residue>
In the polyimide of the present invention, in order to surely obtain the above effect by containing the H-BPDA residue as the tetracarboxylic acid residue, the ratio of the H-BPDA residue to the total tetracarboxylic acid residue contained in the polyimide is It is preferably 10 mol% or more, particularly preferably 30 mol% or more, and particularly preferably 50 to 100 mol%.

[Diamine residue]
The polyimide of the present invention is characterized by containing a phenolic hydroxyl group-containing diamine residue and a carboxyl group-containing diamine residue as diamine residues.

When the polyimide of the present invention contains a phenolic hydroxyl group-containing diamine residue and a carboxyl group-containing diamine residue as diamine residues, alkali solubility is imparted and the degree of alkali solubility can be controlled. ..

That is, the introduction of the carboxyl group-containing diamine residue imparts remarkably good alkali solubility. The phenolic hydroxyl group-containing diamine residue also contributes to alkali solubility as compared with the diamine residue derived from the diamine compound containing no phenolic hydroxyl group or carboxyl group, but the degree is lower than that of the carboxyl group-containing diamine residue. Therefore, in the case of a polyimide containing both a phenolic hydroxyl group-containing diamine residue and a carboxyl group-containing diamine residue, the degree of alkali solubility can be easily controlled according to the application by adjusting the content ratio. It becomes.

<Phenolic hydroxyl group-containing diamine residue>
The phenolic hydroxyl group-containing diamine residue is a residue derived from a diamine compound having a phenolic hydroxyl group, and the diamine compound having the phenolic hydroxyl group includes at least two amino groups and at least one amino group in one molecule. There is no particular limitation as long as it is a compound having a phenolic hydroxyl group, but from the viewpoint of solubility control and production stability, an aromatic diamine having two amino groups and two phenolic hydroxyl groups in one molecule is preferable. Examples thereof include compounds, which may be compounds having a fluorine atom. Specifically, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxybiphenyl. , 3,3'-diamino-4,4'-dihydroxybenzophenone, 2,2-bis (3-amino-4-hydroxyphenyl) methane, 2,2-bis (3-amino-4-hydroxyphenyl) ethane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 9,9'-bis (3-amino-4-hydroxy) Examples thereof include 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 2,2-bis (3-amino-4). -Hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 9,9'-bis (3-amino-4-hydroxyphenyl) fluorene are preferred, 2,2-bis (3-Amino-4-hydroxyphenyl) Propane, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 2,2-bis (3) -Amino-4-hydroxyphenyl) Hexafluoropropane is particularly preferred.

The polyimide of the present invention may contain a residue derived from a diamine compound having one kind of phenolic hydroxyl group as a phenolic hydroxyl group-containing diamine residue, and a diamine compound having two or more kinds of phenolic hydroxyl groups. It may contain residues derived from.

<Carboxyl group-containing diamine residue>
The carboxyl group-containing diamine residue is a residue derived from a diamine compound having a carboxyl group, and examples of the diamine compound having a carboxyl group include 3,5-diaminobenzoic acid and 3,4-diaminobenzoic acid. Monocyclic compounds such as 1,3-diamino-4,6-dicarboxybenzene, 1,2-diamino-4,6-dicarboxybenzene, 1,3-diamino-4,5-dicarboxybenzene, 3,3 Carboxybiphenyl compounds such as'-diamino-4,4'-dicarboxybiphenyl, 4,4'-diamino-2,2', 5,5'-tetracarboxybiphenyl, 4,4'-diamino-3,3' Carboxydiphenylalkane such as −dicarboxydiphenylmethane, 3,3'-diamino-4,4'-dicarboxydiphenylmethane, carboxydiphenyl ether such as 4,4'-diamino-2,2', 5,5'-tetracarboxydiphenyl ether Compounds, diphenylsulfone compounds such as 3,3'-diamino-4,4'-dicarboxydiphenylsulfone, bis (hydroxy) such as 2,2-bis [4- (4-amino-3-carboxyphenyl) phenyl] propane Examples thereof include phenoxy) biphenyl compounds and bis [(carboxyphenoxy) phenyl] sulfone compounds such as 2,2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] sulfone, and solubility control and production stability. From the viewpoint of improving heat resistance, preferably 3,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 1,3-diamino-4,6-dicarboxybenzene, 1,2-diamino-4,6- Monocyclic compounds such as dicarboxybenzene and 1,3-diamino-4,5-dicarboxybenzene, that is, monocyclic aromatic diamine compounds having a carboxyl group, more preferably diaminobenzoic acid (3,5-). Diaminobenzoic acid).

The polyimide of the present invention may contain a residue derived from a diamine compound having one kind of carboxyl group as a carboxyl group-containing diamine residue, and is derived from a diamine compound having two or more kinds of carboxyl groups. Residues may be included.

<Other diamine residues>
The polyimide of the present invention may contain only the above-mentioned phenolic hydroxyl group-containing diamine residue and carboxyl group-containing diamine residue as diamine residues, and may contain only the above-mentioned phenolic hydroxyl group-containing diamine residue and carboxyl group-containing diamine residue. It may contain residues derived from the group and other diamine compounds (hereinafter, may be referred to as "other diamine residues").

The other diamine residues are residues derived from a diamine compound other than the diamine compound having a phenolic hydroxyl group and the diamine compound having a carboxyl group, and the diamine compound having the phenolic hydroxyl group and the diamine compound having a carboxyl group. Examples of the diamine compound other than the above include aromatic diamine compounds and aliphatic diamine compounds.

Examples of the aromatic diamine compound include a diamine compound having one aromatic ring in one molecule, a diamine compound having two or more independent aromatic rings in one molecule, and a diamine compound having a condensed aromatic ring in one molecule. Can be mentioned. Among these, a diamine compound having one aromatic ring in one molecule or a diamine compound having two or more independent aromatic rings is preferable, and two or more independent aromatic rings are preferable from the viewpoint of facilitating viscosity control during production. A diamine compound having a ring is particularly preferable.

Examples of the diamine compound having one aromatic ring in one molecule include 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine and the like.

Examples of the amine compound having two or more independent aromatic rings in one molecule include 4,4'-(biphenyl-2,5-diylbisoxy) bisaniline, 4,4'-diaminodiphenyl ether, and 3,4'. −Diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, bis (4- (4-aminophenoxy) phenyl) sulfone, 2,2-bis ( 4- (4-Aminophenoxy) phenyl) propane, bis (4- (3-aminophenoxy) phenyl) sulfone, 1,3-bis (4-aminophenoxy) neopentane, 4,4'-diamino-3,3' -Dimethylbiphenyl, 4,4'-diamino-2,2'-dimethylbiphenyl (also known as 3,3'-dimethylbenzidine), 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-diamino Diphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, N- (4-aminophenoxy) -4-aminobenzamine, bis (3-aminophenyl) sulfone, norbornandiamine and the like. Be done. Among them, from the viewpoint of solubility, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, (4- (4-aminophenoxy) phenyl) sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'- Diaminodiphenyl sulfone, 2,2-bis (4- (4-aminophenoxy) phenyl) propane and the like are preferable.

Examples of the diamine compound having a condensed aromatic ring in one molecule include 4,4'-(9-fluorenylidene) dianiline, 2,7-diaminofluorene, 1,5-diaminonaphthalene, and 3,7-diamino-2,8-. Examples thereof include dimethyldibenzothiophene 5,5-dioxide.

Examples of the aliphatic diamine compound include an alicyclic diamine compound and a chain aliphatic diamine compound.

Examples of the alicyclic diamine compound include 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,4-diaminocyclohexane, and 4,4'-methylenebis (cyclohexylamine). Examples thereof include 4,4'-methylenebis (2-methylcyclohexylamine).

Examples of the chain aliphatic diamine compound include 1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-hexamethylenediamine, and 1,5-. Examples thereof include diaminopentane, 1,10-diaminodecane, 1,2-diamino-2-methylpropane, 2,3-dimethyl-2,3-butanediamine, 2-methyl-1,5-diaminopentane and the like.

Among these, an alicyclic diamine compound is preferable from the viewpoint of heat resistance, and 1,4-diaminocyclohexane or 1,3-bis (aminomethyl) cyclohexane is particularly preferable.

Other diamine compounds include silicone-based diamine compounds, 4-fluoro-1,2-phenylenediamine, 4-fluoro-1,3-phenylenediamine, 3-trifluoromethyl-1,5-phenylenediamine, 4-. Trifluoromethyl-1,5-phenylenediamine, 4-trifluoromethyl-1,2-phenylenediamine, 2-trifluoromethyl-1,4-phenylenediamine, 2,2'-bis (trifluoromethyl) -4 , 4'-diaminobiphenyl, 4,4'-diamino-2- (trifluoromethyl) diphenyl ether, 4,4'-diamino-2,2'-(trifluoromethyl) biphenyl, 4,4'-diamino-2 -Methyl-2'-trifluoromethylbiphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- {4-amino-2- (trifluoromethyl) ) Phenoxy} phenyl] Hexafluoropropane, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2 -Bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2-bis {4- (4-aminophenoxy) -3,5-dibromophenyl} hexa Examples thereof include diamine compounds containing a fluorine atom such as fluoropropane.

When the polyimide of the present invention contains the above-mentioned other diamine residues, the other diamine residues may be only one kind or may contain two or more kinds.

<Content ratio of phenolic hydroxyl group-containing diamine residue and carboxyl group-containing diamine residue>
The polyimide of the present invention can surely obtain the above effect by containing a phenolic hydroxyl group-containing diamine residue and a carboxyl group-containing diamine residue as diamine residues, and in addition, the phenolic hydroxyl group in all diamine residues contained in the polyimide. The total ratio of the contained diamine residue and the carboxyl group-containing diamine residue is preferably 30 mol% or more, particularly preferably 40 mol% or more, and particularly preferably 50 to 100 mol%.

Further, in order to facilitate control of alkali solubility by having both a phenolic hydroxyl group-containing diamine residue and a carboxyl group-containing diamine residue, the phenolic hydroxyl group-containing diamine residue contained in the polyimide of the present invention can be used. The ratio of the carboxyl group-containing diamine residue is preferably phenolic hydroxyl group-containing diamine residue: carboxyl group-containing diamine residue = 1: 0.1 to 150 in mol ratio, and this mol ratio is 1: 0.25. More preferably, it is ~ 100.

[Molecular weight]
The weight average molecular weight (Mw) of the polyimide of the present invention is not particularly limited, but the polystyrene-equivalent weight average molecular weight is usually 1000 or more, preferably 3000 or more, and more preferably 5000 or more. Further, it is usually 200,000 or less, preferably 180,000 or less, and more preferably 150,000 or less. When the weight average molecular weight is in the above range, solvent solubility, composition viscosity, and the like tend to be easy to handle in ordinary manufacturing equipment, which is preferable. The polystyrene-equivalent weight average molecular weight of polyimide can be determined by gel permeation chromatography (GPC).

The number average molecular weight (Mn) of the polyimide of the present invention is not particularly limited, but the polystyrene-equivalent number average molecular weight is usually 500 or more, preferably 1000 or more, and more preferably 2500 or more. Further, it is usually 100,000 or less, preferably 90,000 or less, and more preferably 80,000 or less. When the number average molecular weight is in the above range, solvent solubility, composition viscosity, and the like tend to be easy to handle in ordinary manufacturing equipment, which is preferable. The polystyrene-equivalent number average molecular weight can be determined by the same method as the weight average molecular weight.

The molecular weight distribution (PDI: weight average molecular weight / number average molecular weight (Mw / Mn)) of the polyimide of the present invention is usually 1 or more, preferably 1.1 or more, and more preferably 1.2 or more. Further, it is usually 10 or less, preferably 9 or less, and more preferably 8 or less. When the molecular weight distribution is in the above range, a film having excellent uniformity, smoothness, etc. tends to be obtained, for example, when used as a resist.

[OH equivalent / acid value]
The polyimide of the present invention has an OH equivalent of 300 to 30,000 g / eq based on a phenolic hydroxyl group-containing diamine residue. The acid value based on the carboxyl group-containing diamine residue is preferably in the range of 20 to 150 mg-KOH / g.

When the OH equivalent and the acid value are within the above ranges, excellent alkali solubility and its controllability can be obtained.

The OH equivalent of polyimide can be calculated from the molecular weight and molar ratio of the constituent residues, and the OH equivalent was also determined in this way in the examples described later. Further, the acid value of polyimide can be obtained by calculation from the molecular weight and molar ratio of the constituent residues, and the acid value was also obtained in this way in the examples described later.

[Alkali-soluble / solvent-soluble]
The polyimide of the present invention is excellent in alkali solubility, and exhibits alkali solubility of, for example, 0.1% by mass or more at room temperature (23 ° C.) in a 0.05 M potassium hydroxide aqueous solution. For example, the dissolution concentration can be appropriately adjusted in the range of 0.1 to 30% by mass.

The polyimide of the present invention is also excellent in solvent solubility, and for example, exhibits a solubility of 5% by mass or more at room temperature (25 ° C.) in a solvent or the like used for producing a polyimide precursor described later. ..

[Polyimide manufacturing method]
The polyimide of the present invention uses at least 3,3', 4,4'-bicyclohexanetetracarboxylic dianhydride (H-BPDA) as a raw material for tetracarboxylic dianhydride, and at least a phenolic hydroxyl group as a raw material for a diamine compound. It can be produced according to a conventional method except that a diamine compound having a diamine compound and a diamine compound having a carboxyl group are used. As described above, a diisocyanate compound may be used instead of the diamine compound.

The method for producing a polyimide of the present invention includes a method of producing a polyimide precursor from a tetracarboxylic dianhydride and a diamine compound and imidizing the polyimide precursor to obtain a polyimide, and a method of directly producing a polyimide from a tetracarboxylic dianhydride and a diamine compound. There is a way to do it.

When the polyimide precursor is imidized to produce a polyimide, the imidization ratio is not particularly limited, but the higher the imidization ratio, the more preferable, and usually 80% or more, particularly 90 to 100%.

<Method of producing polyimide via polyimide precursor>
(Manufacturing of polyimide precursor)
In the polyimide precursor of the present invention, a tetracarboxylic acid dianhydride that requires H-BPDA is reacted with a diamine compound that requires a diamine compound having a phenolic hydroxyl group and a diamine compound having a carboxyl group in a solvent. can get. The method for reacting the tetracarboxylic dianhydride and the diamine compound in a solvent is not particularly limited. Further, the order of addition and the method of addition of the tetracarboxylic dianhydride and the diamine compound are not particularly limited. For example, a polyimide precursor can be obtained by sequentially adding a tetracarboxylic dianhydride and a diamine compound to a solvent and stirring at an appropriate temperature.

The amount of the diamine compound is usually 0.7 mol or more, preferably 0.8 mol or more, and usually 1.3 mol or less, preferably 1.2 mol or less, relative to 1 mol of tetracarboxylic dianhydride. is there. By setting the diamine compound in such a range, the yield of the obtained polyimide precursor tends to be improved.

The concentrations of the tetracarboxylic dianhydride and the diamine compound in the reaction solution can be appropriately set according to the reaction conditions and the viscosity of the obtained polyimide precursor.

The total concentration of the tetracarboxylic dianhydride and the diamine compound is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, based on the total amount of the reaction solution containing the tetracarboxylic dianhydride, the diamine compound and the solvent. It is usually 70% by mass or less, preferably 50% by mass or less. If the concentrations of the tetracarboxylic dianhydride and the diamine compound are not too low, the molecular weight tends to be extended. Further, if this concentration is not too high, the viscosity does not become too high, and the reaction solution tends to be easily agitated.

The temperature at which the tetracarboxylic dianhydride and the diamine compound are reacted in the solvent is not particularly limited as long as the reaction proceeds, but is usually 0 ° C. or higher, preferably 20 ° C. or higher, and usually 120 ° C. or lower. It is preferably 100 ° C. or lower.
The reaction time is usually 1 hour or more, preferably 2 hours or more, usually 100 hours or less, preferably 42 hours or less. By carrying out under such conditions, it tends to be possible to obtain a polyimide precursor at low cost and in good yield.
The pressure during the reaction may be normal pressure, pressurization or depressurization. The atmosphere may be in the air or in an inert atmosphere.

The solvent used for reacting the tetracarboxylic dianhydride and the diamine compound is not particularly limited. For example, hydrocarbon solvents such as hexane, cyclohexane, heptane, benzene, toluene, xylene, mecitylene, anisole; halogenation of carbon tetrachloride, methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, fluorobenzene and the like. Hydrocarbon solvent; ether solvent such as diethyl ether, tetrahydrofuran, 1,4-dioxane, methoxybenzene; ketone solvent such as acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Glycol-based solvents such as glycol dimethyl ether, diethylene glycol dimethyl ether and propylene glycol monomethyl ether acetate; amide-based solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; Solvents; heterocyclic solvents such as pyridine, picolin, lutidine, quinoline, isoquinoline; phenolic solvents such as phenol and cresol; lactone solvents such as γ-butyrolactone, γ-valerolactone, δ-valerolactone; and the like. .. These solvents may be used alone or in any ratio and combination of two or more.

The obtained polyimide precursor may be used as it is for the next imidization, or may be added to a poor solvent to precipitate it in a solid state before use.

The poor solvent to be used is not particularly limited and may be appropriately selected depending on the type of polyimide precursor, but an ether solvent such as diethyl ether and diisopropyl ether; a ketone solvent such as acetone, methyl ethyl ketone, isobutyl ketone and methyl isobutyl ketone; methanol, Alcohol-based solvents such as ethanol and isopropyl alcohol; and the like. Above all, an alcohol solvent is preferable because a precipitate can be efficiently obtained, a boiling point is low, and drying tends to be easy. These solvents may be used alone or in any ratio and combination of two or more.

(Immidization of polyimide precursor)
A polyimide can be obtained by dehydrating and cyclizing the polyimide precursor obtained by the above method or the like in the presence of a solvent. The imidization can be carried out by using any conventionally known method, and examples thereof include thermal imidization in which thermal cyclization is performed, chemical imidization in which chemical cyclization is performed, and the like. These imidization reactions may be carried out individually or in combination of two or more.

<Heating imidization>
Examples of the solvent for imidizing the polyimide precursor include the same solvent used in the reaction for obtaining the polyimide precursor. The solvent used for producing the polyimide precursor and the solvent used for producing the polyimide may be the same or different.
In this case, the water generated by imidization inhibits the ring closure reaction and may be discharged to the outside of the system. The concentration of the polyimide precursor during the imidization reaction is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, and usually 70% by mass or less, preferably 40% by mass or less. By performing in this range, the production efficiency tends to be high, and the solution viscosity tends to be easy to produce.

The imidization reaction temperature is not particularly limited, but is usually 50 ° C. or higher, preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and usually 300 ° C. or lower, preferably 280 ° C. or lower, more preferably 250 ° C. or lower. It is preferable to carry out in this range because the imidization reaction proceeds efficiently and reactions other than the imidization reaction tend to be suppressed.
The pressure during the reaction may be normal pressure, pressurization, or depressurization. The atmosphere may be in the air or in an inert atmosphere.

Further, as an imidization accelerator for promoting imidization, a compound having a function of enhancing nucleophile and electrophile can be added. Specifically, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, triethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, triethylenediamine, N-methylpyrrolidin, N-ethylpyrrolidin. , N-Methylpiperidin, N-ethylpiperidine, imidazole, pyridine, quinoline, isoquinoline and other tertiary amine compounds; acetic acid, 4-hydroxyphenylacetic acid, 3-hydroxybenzoic acid, N-acetylglycine, N-benzoylglycine and the like. Aldehyde compounds; polyvalent phenolic compounds such as 3,5-dihydroxyacetophenone, methyl 3,5-dihydroxybenzoate, pyrogallol, methyl gallate, ethyl gallate, naphthalene-1,6-diol; 2-hydroxypyridine, 3-hydroxy Pyridine, 4-hydroxypyridine, 4-pyridinemethanol, N, N-dimethylaminopyridine, nicotine aldehyde, isonicotin aldehyde, picolin aldehyde, picolin aldehyde oxime, nicotine aldehyde oxime, isonicotin aldehyde oxime, ethyl picolinate, ethyl nicotinate , Ethyl isonicotinate, nicotine amide, isonicotinamide, 2-hydroxynicotinic acid, 2,2'-dipyridyl, 4,4'-dipyridyl, 3-methylpyridazine, quinoline, isoquinolin, phenanthroline, 1,10-phenanthroline, Heterocyclic compounds such as imidazole, benzimidazole, 1,2,4-triazole; and the like.

Of these, at least one selected from the group consisting of tertiary amine compounds, carboxylic acid compounds and heterocyclic compounds is preferable, and at least one selected from the group consisting of triethylamine, imidazole and pyridine controls the reaction rate. It is more preferable because it tends to be easy. These compounds may be used alone or in any ratio and combination of two or more.

The amount of the imidization accelerator used is usually 0.01 mol% or more, preferably 0.1 mol% or more, more preferably 1 mol% or more, based on the carboxyl group of the polyimide precursor. Further, it is preferably 50 mol% or less, and more preferably 10 mol% or less. When the amount of the imidization accelerator used is in the above range, the imidization reaction tends to proceed efficiently.
Further, the timing of adding the imidization accelerator can be appropriately adjusted, and may be before the start of heating or during heating. Further, it may be added in a plurality of times.

<Chemical imidization>
A polyimide can be obtained by chemically imidizing a polyimide precursor with a dehydration condensing agent in the presence of a solvent.

Examples of the solvent used in the chemical imidization include the same solvents as those used in the reaction for obtaining the polyimide precursor described above.

Examples of the dehydration condensing agent include N, N-2 substituted carbodiimides such as N, N-dicyclohexylcarbodiimide and N, N-diphenylcarbodiimide; acid anhydrides such as acetic anhydride and trifluoroacetic anhydride; thionyl chloride, tosyl chloride and the like. Chloride; acetyl chloride, acetyl bromide, propionyl iodide, acetyl fluoride, propionyl chloride, propionyl bromide, propionyl iodide, propionyl fluoride, isobutyryl chloride, isobutyryl bromide, isobutyryl iodide, isobuchi Lilfluoride, n-butyryl chloride, n-butyryl bromide, n-butyryl iodide, n-butyryl fluoride, mono-, di-, tri-chloroacetyl chloride, mono-, di-, tri- Bromoacetyl chloride, mono-, di-, tri-iodoacetyl chloride, mono-, di-, tri-fluoroacetyl chloride, chloroacetic anhydride, phenylphosphonic dichloride, thionyl chloride, thionyl bromide, thionyliodide, thionylfluo Halogen compounds such as rides; phosphorus compounds such as phosphorus trichloride, triphenyl phosphite, and diethyl phosphate cyanide; and the like.

Of these, acid anhydrides and halogenated compounds are preferable, and acid anhydrides are particularly preferable because the imidization reaction tends to proceed efficiently. These compounds may be used alone or in any ratio and combination of two or more.

The amount of these dehydration condensing agents used is usually 0.1 mol or more, preferably 0.2 mol or more, and usually 1.0 mol or less, preferably 0.9 mol or less, with respect to 1 mol of the polyimide precursor. By setting the amount of the dehydration condensing agent used within this range, imidization can be performed efficiently.

The concentration of the polyimide precursor in the reaction solution during the imidization reaction is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, and usually 70% by mass or less, preferably 40% by mass or less. .. Within this range, the production efficiency can be increased, and the solution viscosity tends to be easy to produce.

The imidization reaction temperature is not particularly limited, but is usually 0 ° C. or higher, preferably 10 ° C. or higher, and more preferably 20 ° C. or higher. Further, it is usually 150 ° C. or lower, preferably 130 ° C. or lower, and more preferably 100 ° C. or lower. It is preferable to carry out the imidization reaction in this range because the imidization reaction tends to proceed efficiently. Further, it is preferable because side reactions other than the imidization reaction are suppressed.
The pressure during the reaction may be normal pressure, pressurization or depressurization. The atmosphere may be in the air or in an inert atmosphere.

Further, as a catalyst for promoting imidization, an imidization accelerator such as the above-mentioned tertiary amine compound can be added in the same manner as for heat imidization.

<Method of producing polyimide from tetracarboxylic dianhydride and diamine compound>
A polyimide can be directly obtained from a tetracarboxylic dianhydride and a diamine compound by using a conventionally known method. This method carries out the process from the synthesis of the poimide precursor to the imidization without stopping the reaction or isolating the precursor.

The order and method of adding the tetracarboxylic dianhydride and the diamine compound are not particularly limited. For example, the temperature at which the tetracarboxylic dianhydride and the diamine compound are added in order to the solvent and the reaction until imidization proceeds. Polyimide can be obtained by stirring with.

The amount of the diamine compound is usually 0.7 mol or more, preferably 0.8 mol or more, and usually 1.3 mol or less, preferably 1.2 mol or less, with respect to 1 mol of the tetracarboxylic dianhydride. By setting the amount of the diamine compound in such a range, the yield of the obtained polyimide tends to be improved.

The concentrations of the tetracarboxylic dianhydride and the diamine compound in the reaction solution can be appropriately set according to the respective conditions and the viscosity during the polymerization.
The total concentration of the tetracarboxylic dianhydride and the diamine compound in the reaction solution is not particularly set, but is usually 1% by mass or more, preferably 5% by mass or more, and usually 70% by mass or less, preferably 40% by mass. It is as follows. When the concentration in the reaction solution is in an appropriate range, the molecular weight tends to be extended and stirring tends to be easy.

Examples of the solvent used in this reaction include the same solvents as those used in the reaction for obtaining the polyimide precursor.

Further, when the polyimide is obtained from the tetracarboxylic acid dianhydride and the diamine compound, heating imidization and / or chemical imidization can be adopted as in the case of obtaining the polyimide from the polyimide precursor, and heating in this case can be adopted. The reaction conditions for imidization and chemical imidization are the same as described above.

The obtained polyimide may be used as it is, or may be used by adding it to a poor solvent to precipitate the polyimide in a solid state and then redissolving it in another solvent.

The poor solvent at this time is not particularly limited and may be appropriately selected depending on the type of polyimide. For example, an ether solvent such as diethyl ether and diisopropyl ether; a ketone solvent such as acetone, methyl ethyl ketone, isobutyl ketone and methyl isobutyl ketone; Alcohol-based solvents such as methanol, ethanol and isopropyl alcohol; and the like. Above all, an alcohol solvent such as isopropyl alcohol is preferable because a precipitate can be efficiently obtained, the boiling point is low, and drying tends to be easy. These solvents may be used alone or in any ratio and combination of two or more.

Examples of the solvent for redissolving polyimide include hydrocarbon solvents such as hexane, cyclohexane, heptane, benzene, toluene, xylene, mesitylene, and anisole; N, N-dimethylformamide, N, N-dimethylacetamide, and N. -Amid solvent such as methyl-2-pyrrolidone; Aproton solvent such as dimethyl sulfoxide; Glycol solvent such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate; And so on. Of these, anisole, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, ethylene glycol dimethyl ether, and ethylene glycol monomethyl ether are particularly preferable. These solvents may be used alone or in any ratio and combination of two or more.

[Use]
The polyimide of the present invention is excellent in alkali-soluble, solvent-soluble, storage stability, and heat resistance, and because of its excellent alkali-soluble property, it can be suitably used as an alkali-developable resist resin.

When the polyimide of the present invention is used as a resist used in the manufacture of semiconductor integrated circuits, printed wiring boards, liquid crystal panels, etc., an anion regenerating agent, a photoacid generator, an alkali dissolution accelerator, a photocrosslinking agent, etc., as necessary. Is used as a photosensitive composition containing the above.
The photosensitive resin composition may further contain additives such as a coupling agent, a plasticizer, another film-forming resin, a surfactant, a stabilizer, and a leveling agent.

Suitable solvents for the production of resist solutions are, in principle, all solvents in which the non-volatile components of the photoresist, such as polyimide and photoacid generators and other additives, are sufficiently soluble and do not irreversibly react with these components. is there. Suitable solvents are, for example, aprotic polar solvents such as N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, butyrolactone, cyclohexanone, diacetoxyethylene glycol, sulfoxide, tetramethylurea, N, N-dimethylacetamide, Dimethylformamide, dimethyl sulfoxide, acetonitrile, diglyme, phenol, cresol, toluene, methylene chloride, chloroform, tetrahydrofuran, dioxane, acetone and the like.

In order to form an image with the photosensitive resin composition using the polyimide of the present invention, a photoresist layer is formed on the substrate by using a resist solution in which the photosensitive resin composition is dissolved in a solvent as described above. As the substrate, any of organic substances such as resin, inorganic substances, metals and the like may be used.

The formation of the resist layer on the substrate is usually performed by dipping, spraying, roll coating or spin coating. At this time, a film can be formed to a desired thickness by adjusting the viscosity, solid content concentration, spin coating rate, and the like of the resist solution. For example, a layer and relief structure having a layer thickness of 0.1 to 500 μm, preferably 1 to 100 μm is formed. In the case of a thin layer or an insulating layer in a multi-layer circuit, it may be about 1 to 50 μm. After applying the resist to the substrate, it is usually pre-dried at 50 to 120 ° C., exposed to a desired pattern, and then subjected to alkaline development.

Examples of the alkali of the alkaline developing solution used here include sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, ammonium hydrogencarbonate, tetramethylammonium hydroxide, and the like. Tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, N-methyldietanolamine, N-ethyldietanolamine, N, N-dimethylethanolamine, triethanolamine, triisopropanolamine, triisopropyl Examples include amines.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded.

In the following, the abbreviations for the raw materials used are as follows.
ABA: 3,5-diaminobenzoic acid BAPA: 2,2-bis (3-amino-4-hydroxyphenyl) propane 6F-BAPA: 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane H -BPDA: 3,3', 4,4'-bicyclohexanetetracarboxylic dianhydride DMAc: N, N-dimethylacetamide

The evaluation method of the obtained polyimide is as follows.
[Alkali soluble]
At room temperature (23 ° C.), a polyimide solution was added to 5 g of a 0.05 M potassium hydroxide aqueous solution so that the resin solid content was 5 mg, and the mixture was stirred for 2 hours, visually observed, and evaluated according to the following criteria. Although DMAc is contained in the polyimide solution, it does not significantly affect the evaluation of alkali solubility because the amount of DMAc is very small with respect to the amount of the potassium hydroxide aqueous solution.
◯: Completely dissolved without remaining undissolved, and good alkali solubility.
Δ: Partially dissolved and slightly inferior in alkali solubility.
X: Does not dissolve and is poorly soluble in alkali.

[Heat-resistant]
After applying the polyimide solution to the glass substrate and firing at 350 ° C. for 30 minutes, the polyimide film obtained by peeling from the glass substrate is measured by a thermogravimetric / differential thermal amount simultaneous measuring device (TG-DTA) and the weight is reduced by 5%. The temperature (Td _5% ) was evaluated as the heat resistant temperature.
The _{higher the Td 5%,} the more preferable.

[Example 1]
ABA: 5.71 g (0.037 mol), BAPA: 9.69 g (0.037 mol), in a four-necked flask equipped with a reflux nitrogen gas introduction tube, a cooler, a Dean-Stark aggregator filled with toluene, and a stirrer. H-BPDA: 22.51 g (0.073 mol), DMAc: 114 g, and toluene: 22.7 g were added, and the mixture was heated under reflux in an oil bath at 190 ° C. for 12 hours. Then, toluene was distilled off at normal pressure to obtain a polyimide solution 1.
The obtained polyimide solution 1 was evaluated for alkali solubility, and the results are shown in Table 1.
_{Moreover, when Td 5%} was measured for this polyimide solution 1, it was confirmed that it had high heat resistance of 402 ° C.

[Example 2]
ABA of Example 1 was changed to 14.91 g (0.098 mol), H-BPDA was changed to 30.02 g (0.098 mol), DMAc was changed to 137 g, toluene was changed to 27.4 g, and 6F- instead of BAPA. Polyimide solution 2 was obtained in the same manner as in Example 1 except that 0.73 g (0.002 mol) of BAPA was used.
The obtained polyimide solution 2 was evaluated for alkali solubility, and the results are shown in Table 1.

[Comparative Example 1]
Except that BAPA of Example 1 was changed to 18.08 g (0.07 mol), H-BPDA was changed to 21.01 g (0.069 mol), DMAc was changed to 117 g, toluene was changed to 23.5 g, and ABA was not added. Obtained a polyimide solution 3 in the same manner as in Example 1.
The obtained polyimide solution 3 was evaluated for alkali solubility, and the results are shown in Table 1.

Table 1 shows the acid value and OH equivalent of each polyimide.

From Table 1, it can be seen that the polyimides of Examples 1 and 2 containing the H-BPDA residue, the phenolic hydroxyl group-containing diamine residue, and the carboxyl group-containing diamine residue are excellent in alkali solubility.
Further, as can be seen from the results of Example 1, the polyimide of the present invention containing the H-BPDA residue is also excellent in heat resistance.
On the other hand, the polyimide of Comparative Example 1 does not contain a carboxyl group-containing diamine residue and is inferior in alkali solubility.

Claims (3)

A tetracarboxylic acid residue derived from 3,3', 4,4'-bicyclohexanetetracarboxylic dianhydride, and
Aromatic diamine residues derived from diamine compounds having two phenolic hydroxyl groups (hereinafter referred to as "phenolic hydroxyl group-containing diamine residues"),
A polyimide containing a diamine residue derived from a monocyclic aromatic diamine compound having a carboxyl group (hereinafter, referred to as "carboxyl group-containing diamine residue"). Claim that the phenolic hydroxyl group-containing diamine residue and the carboxyl group-containing diamine residue are contained in a molar ratio of phenolic hydroxyl group-containing diamine residue: carboxyl group-containing diamine residue = 1: 0.1 to 150. The polyimide according to 1. The OH equivalent based on the phenolic hydroxyl group-containing diamine residue is 300 to 30,000 g / eq. The polyimide according to claim 1 or 2 , wherein the acid value based on the carboxyl group-containing diamine residue is 20 to 150 mg-KOH / g.