JP7000682B2 - 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 manufacture of semiconductor integrated circuits, printed wiring boards, liquid crystal panels, and the like. With respect to the polyimide that can be.

Resists used in the manufacture of semiconductor integrated circuits, printed wiring boards, liquid crystal panels and the like 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 been used to reduce the environmental load.

Polyimide has various excellent properties such as heat resistance, flame retardancy, flexibility, electrical properties, and chemical resistance, but 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 the disadvantages of being inferior in storage stability and having a high curing temperature.

Patent Document 1 describes, as the polyimide used in the alkali-developable polyimide resin composition, 3,3', 4,4'-bicyclohexanetetracarboxylic acid dianhydride or 1,2,4,5-cyclohexanetetracarboxylic acid. A phenolic hydroxyl group-containing polyimide is proposed in which a tetracarboxylic acid dianhydride containing dianhydride as an essential component and a diamine compound containing a diamine compound having a phenolic hydroxyl group (aminophenol compound) as an essential component are subjected to a polycondensation reaction. ing. 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. Instead, there is a risk that undissolved residue will occur during alkaline development.

In Patent Document 2, as a photosensitive resin composition having excellent storage stability and capable of water-based development, a soluble polyimide containing a polymerizable functional group and containing a carboxyl group and / or a hydroxyl group is acrylic-modified. Although it is described, there is no description of an aliphatic diamine compound as a raw material for a diamine compound of polyimide.

Patent Document 3 describes aromatic diamines and diaminos having reactive functional groups with epoxy groups as polyimides used in imide-based photosensitive resin compositions having heat resistance, chemical resistance (alkali resistance), and high insulating properties. A diamine using polysiloxane as a raw material for a diamine compound is described, and a diamine having a hydroxyl group or a carboxyl group is mentioned as a diamine having a functional group reactive with the epoxy group thereof, and an aliphatic diamine compound is mentioned as a raw material for the diamine compound of polyimide. There is no description of.

Patent Document 4 describes tetracarboxylic acid dianhydride containing an alicyclic tetracarboxylic acid dianhydride such as 3,3', 4,4'-bicyclohexanetetracarboxylic acid dianhydride (H-BPDA) as an essential component. A photosensitive polyimide that can be developed with an alkaline aqueous solution using a substance component and a diamine component containing an aromatic diamine having two carboxyl groups in the molecule as an essential component as a raw material is described, but can be used in combination. There is no description of an aliphatic diamine compound as a raw material for the diamine compound.

Japanese Patent No. 5530363 Japanese Unexamined Patent Publication No. 2004-325980 Japanese Unexamined Patent Publication No. 2002-351573 Japanese Patent No. 5501672

The higher the alkali solubility of the resist used in the manufacture of semiconductor integrated circuits, printed wiring boards, liquid crystal panels, etc., is not the better, 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, although polyimides to which alkali solubility has been imparted have been conventionally 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, as diamine residues, residues derived from a diamine compound having a hydroxyl group and / or residues derived from a diamine compound having a carboxyl group. The present invention has been completed by finding that a polyimide containing a residue derived from an aliphatic diamine compound can solve the above-mentioned problems.

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

[1] A tetracarboxylic acid residue derived from tetracarboxylic acid dianhydride, a diamine residue derived from a diamine compound having a hydroxyl group (hereinafter referred to as "hydroxyl-containing diamine residue"), and / or carboxyl. A diamine residue derived from a diamine compound having a group (hereinafter referred to as "carboxyl group-containing diamine residue") and a diamine residue derived from an aliphatic diamine compound (hereinafter referred to as "aliphatic diamine residue"). A polyimide containing (referred to as).

[2] The ratio of the total of the hydroxyl group-containing diamine residues and / or the carboxyl group-containing diamine residues to the total diamine residues contained in the polyimide is 5 to 70 mol%, and the ratio of the aliphatic diamine residues is 30 to 95 mol. %. The polyimide according to [1].

[3] The hydroxyl group-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 diamine compound having a carboxyl group. The diamine residue derived from, wherein the aliphatic diamine residue is a diamine residue derived from an alicyclic diamine compound having no hydroxyl group or carboxyl group according to [1] or [2]. Diamine.

[4] The polyimide according to any one of [1] to [3], which has a tetracarboxylic acid residue derived from an alicyclic tetracarboxylic dianhydride.

[5] The OH equivalent based on the hydroxyl group-containing diamine residue is 100 to 30,000 g / eq. And / or the polyimide according to any one of [1] to [4], wherein the acid value based on the carboxyl group-containing diamine residue is 5 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 embodiments 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 will be done.

The polyimide of the present invention has a tetracarboxylic acid residue derived from tetracarboxylic acid dianhydride, a diamine residue derived from a diamine compound having a hydroxyl group (hereinafter, referred to as "hydroxyl-containing diamine residue"), and a diamine residue. / Or a diamine residue derived from a diamine compound having a carboxyl group (hereinafter referred to as "carboxyl group-containing diamine residue") and a diamine residue derived from an aliphatic diamine compound (hereinafter referred to as "aliphatic diamine"). It is characterized by containing at least (referred to as "residue").
That is, the polyimide of the present invention is not a polyamic acid but a polyimide, so that it is excellent in storage stability and heat resistance, and because it has an aliphatic structure derived from an aliphatic diamine residue, it is excellent in solvent solubility and a hydroxyl group. By including the contained diamine residue and / or the 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. However, there are a method of forming a polyimide by a dehydration ring closure 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 "hydroxyl-containing diamine residue" is not limited to "diamine residue derived from a diamine compound having a hydroxyl group" but "diamine residue derived from a diamine compound having a hydroxyl group". You may. Similarly, the "carboxyl group-containing diamine residue" is not limited to "a diamine residue derived from a diamine compound having a carboxyl group", but is "a diamine residue derived from a diamine compound having a carboxyl group". The “diamine residue” may be not limited to the “diamine residue derived from the aliphatic diamine compound” but may be the “diamine residue derived from the aliphatic diamine compound”.
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 the diamine compounds exemplified below.

[Tetracarboxylic acid residue]
The tetracarboxylic acid residue contained in the polyimide of the present invention is not particularly limited, and the tetracarboxylic acid dianhydride of the tetracarboxylic acid residue contained in the polyimide of the present invention includes various aromatic tetracarboxylic acid dianhydrides. Examples thereof include aliphatic tetracarboxylic acid dianhydrides.

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

Among these, since the viscosity at the time of production is easy to control, tetracarboxylic acid dianhydride having one aromatic ring in one molecule or tetracarboxylic acid dianhydride having two or more independent aromatic rings in one molecule. A substance is preferable, and a tetracarboxylic acid dianhydride having two or more independent aromatic rings in one molecule is particularly preferable.

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

Examples of the tetracarboxylic acid dianhydride having two or more independent aromatic rings in one molecule include 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride and bis (2,3-di). Carboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid 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'-benzophenone tetracarboxylic acid dianhydride, 2,2', 3,3'-benzophenone tetracarboxylic acid dianhydride, 4,4'- Oxydiphthalic acid dianhydride, 4,4- (p-phenylenedioxy) diphthalic acid dianhydride, 4,4- (m-phenylenedioxy) diphthalic acid dianhydride, 2,2', 6,6'- Biphenyltetracarboxylic acid dianhydride and the like can be mentioned.

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-Phenantrentetracarboxylic acid dianhydride and the like.

Examples of the aliphatic tetracarboxylic dianhydride include an alicyclic tetracarboxylic dianhydride and a chain aliphatic tetracarboxylic dianhydride.

Examples of the alicyclic tetracarboxylic acid dianhydride include 3,3', 4,4'-bicyclohexanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1 , 2,3,4-Cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4 -Cyclobutanetetracarboxylic acid dianhydride, 5- (2,5-dioxotetrahydrofuryl) -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-en-2,3,5,6-tetracarboxylic acid dianhydride, 4- (2,5-dioxotetratetra-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 dianhydride include ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride and the like. Can be mentioned.

In addition, examples of the tetracarboxylic acid dianhydride include silicone-based tetracarboxylic acid dianhydride and, for example, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-. Hexafluoropropane dianhydride (also known as 4,4'-(hexafluoroisopropylidene) -diphthalic acid dianhydride), 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3 , 3,3-Hexafluoropropane dianhydride, 2,2'-bis (trifluoromethyl) -4,4', 5,5'-biphenyltetracarboxylic acid dianhydride, 4,4'-(hexafluoro) Trimethylene) diphthalic acid dianhydride, 4,4'-(octafluorotetramethylene) diphthalic acid dianhydride, 2,2'-bis (trifluoromethyl) -4,4', 5,5'-biphenyltetra Carboxydic dianhydride, 4,4'-(hexafluorotrimethylene) diphthalic acid dianhydride, 4,4'-(octafluorotetramethylene) diphthalate dianhydride, 2,2-bis (3,4-) Dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3 -Hexafluoropropane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2, 3-Dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride or the like, tetracarboxylic acid dianhydride containing a fluorine atom can also be used.

Among the above-mentioned tetracarboxylic dianhydrides, the alicyclic tetracarboxylic dianhydride is preferable from the viewpoint of introducing an alicyclic structure to increase the solvent solubility of polyimide and making it excellent in storage stability. In particular, it is preferable to use 3,3', 4,4'-bicyclohexanetetracarboxylic dianhydride. From the viewpoint of production stability and heat resistance, a tetracarboxylic dianhydride having two or more independent aromatic rings in one molecule, such as 3,3', 4,4'-biphenyltetracarboxylic dianhydride, is used. Is preferable.

The polyimide of the present invention may contain only one type of tetracarboxylic acid residue, or may contain two or more types.

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

Alkali solubility is imparted by the polyimide of the present invention containing a hydroxyl group-containing diamine residue and / or a carboxyl group-containing diamine residue as a diamine residue. In addition, the inclusion of an aliphatic diamine residue tends to increase the solubility in a solvent, 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. Although the hydroxyl group-containing diamine residue is lower than the carboxyl group-containing diamine residue, it is more effective in contributing to the addition of alkali solubility than the diamine residue derived from the diamine compound containing no hydroxyl group or carboxyl group. In addition, the aliphatic diamine residue tends to have a structure that inhibits the intramolecular interaction, and thus functions to improve the solvent solubility. Since this aliphatic diamine residue does not contribute to imparting alkali solubility, if the polyimide contains both a hydroxyl group-containing diamine residue and / or a carboxyl group-containing diamine residue and an aliphatic diamine residue, the content ratio thereof. By adjusting the above, it becomes possible to easily control the degree of alkali solubility according to the application.

<Hydroxy group-containing diamine residue>
The hydroxyl group-containing diamine residue is a residue derived from a diamine compound having a hydroxyl group, and the diamine compound having a hydroxyl group is a diamine compound having at least two amino groups and at least one hydroxyl group in one molecule. If there is, there is no particular limitation, but from the viewpoint of enhancing alkali solubility, an aromatic diamine compound having two amino groups and two phenolic hydroxyl groups in one molecule is preferable, and a compound having a fluorine atom is further mentioned. May be. Specifically, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 3,3'-diamino-4,4'-dihydroxydiphenylether, 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) Phenyl) fluorene and the like 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.

When the polyimide of the present invention contains a hydroxyl group-containing diamine residue, a diamine having two or more types of hydroxyl groups even if the polyimide contains a residue derived from a diamine compound having one type of hydroxyl group as the hydroxyl group-containing diamine residue. It may contain residues derived from the compound.

<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 diaminobenzoic acid such as 3,5-diaminobenzoic acid, 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, and carboxydiphenyl ether such as 4,4'-diamino-2,2', 5,5'-tetracarboxydiphenyl ether. Compounds, diphenyl sulfone compounds such as 3,3'-diamino-4,4'-dicarboxydiphenyl sulfone, bis (hydroxy) such as 2,2-bis [4- (4-amino-3-carboxyphenyl) phenyl] propane. Examples thereof include bis [(-carboxyphenoxy) phenyl] sulfone compounds such as phenoxy) biphenyl compound and 2,2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] sulfone, and control and production of solubility thereof. From the viewpoint of improving stability and heat resistance, preferably diaminobenzoic acid (3,5-diaminobenzoic acid), 3,4-diaminobenzoic acid, 1,3-diamino-4,6-dicarboxybenzene, 1, It is a monocyclic compound (monocyclic aromatic diamine compound having a carboxyl group) such as 2-diamino-4,6-dicarboxybenzene and 1,3-diamino-4,5-dicarboxybenzene, and more preferably diamino. It is benzoic acid.

When the polyimide of the present invention contains a carboxyl group-containing diamine residue, it may contain a residue derived from a diamine compound having one type of carboxyl group as the carboxyl group-containing diamine residue. It may contain a residue derived from a diamine compound having a carboxyl group.

<Alphatic diamine residue>
The aliphatic diamine residue is a diamine residue derived from the aliphatic diamine compound, and the aliphatic diamine compound thereof includes an alicyclic diamine compound and a chain aliphatic diamine compound having no carboxyl group and a hydroxyl group. And so on.

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

Examples of the chain aliphatic diamine compound include (1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-hexamethylenediamine, 1,5). -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, solvent solubility, and production stability, and an alicyclic diamine compound having a cyclohexane ring is preferable, and a compound having two or more cyclohexane rings is particularly preferable. ..

The polyimide of the present invention may contain residues derived from one type of aliphatic diamine compound as aliphatic diamine residues, and may contain residues derived from two or more types of aliphatic diamine compounds. It may be a thing.

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

Examples of other diamine compounds of other diamine residues include aromatic diamine compounds having no hydroxyl group and carboxyl group.

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 at the time of 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 diamine 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. Will be. 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.

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 hydroxyl group-containing diamine residue and / or carboxyl group-containing diamine residue and aliphatic diamine residue>
The polyimide of the present invention reliably contains the hydroxyl group-containing diamine residue and / or the carboxyl group-containing diamine residue and the aliphatic diamine residue as the diamine residue, and in order to surely obtain the above effect, the total diamine residue contained in the polyimide is used. The total ratio of the hydroxyl group-containing diamine residue and / or the carboxyl group-containing diamine residue in the group is preferably 5 mol% or more, particularly preferably 10 mol% or more, and particularly preferably 15 mol% or more. Further, 70 mol% or less is preferable, 60 mol% or less is more preferable, and 55 mol% or less is further preferable.
The ratio of the aliphatic diamine residue to the total diamine residue is not particularly limited, but is usually 30 mol% or more, preferably 40 mol% or more, more preferably 45 mol% or more, and usually 95 mol% or less, preferably 90 mol. % Or less, more preferably 85 mol% or less.

The polyimide of the present invention reliably contains the hydroxyl group-containing diamine residue and / or the carboxyl group-containing diamine residue and the aliphatic diamine residue as the diamine residue, and in order to surely obtain the above effect, the total diamine residue contained in the polyimide remains. The total ratio of the hydroxyl group-containing diamine residue and / or the carboxyl group-containing diamine residue and the aliphatic diamine residue in the group is preferably 50 mol% or more, particularly 60 mol% or more, particularly 70 to 100 mol%. Is preferable.

[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 obtained 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 within 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 100 to 30,000 g / eq based on a hydroxyl group-containing diamine residue. And / or the acid value based on the carboxyl group-containing diamine residue is preferably in the range of 5 to 150 mg-KOH / g.

When the OH equivalent and / or the acid value is within the above range, excellent alkali solubility and its controllability can be obtained in the coexistence with the aliphatic diamine residue.

The OH equivalent of the polyimide can be obtained by calculation from the molecular weight and the molar ratio of the constituent residues, and the OH equivalent is also obtained in this way in the examples described later. Further, the acid value of the polyimide can be obtained by calculation from the molecular weight and the 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 1 M potassium hydroxide aqueous solution. This dissolution concentration can be appropriately adjusted in the range of 0.1 to 30% by mass.

The polyimide of the present invention also has excellent solvent solubility, and for example, exhibits a solubility of 5% by mass or more at room temperature (23 ° C.) in a solvent or the like used for producing a polyimide precursor described later. ..

[Manufacturing method of polyimide]
The polyimide of the present invention is produced according to a conventional method except that a tetracarboxylic acid dianhydride raw material and a diamine compound having at least a hydroxyl group and / or a diamine compound having a carboxyl group and an aliphatic diamine compound are used as a diamine compound raw material. be able to. 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 acid dianhydride and a diamine compound and imidizing the polyimide precursor to obtain a polyimide, and a method of directly producing a polyimide from the tetracarboxylic acid 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 is preferably higher, and is usually 80% or more, particularly 90 to 100%.

<Method of manufacturing polyimide via polyimide precursor>
(Manufacturing of polyimide precursor)
The polyimide precursor of the present invention is obtained by reacting a tetracarboxylic acid dianhydride with a diamine compound having a hydroxyl group and / or a diamine compound having a carboxyl group and an aliphatic diamine compound as essential in a solvent. Be done. The method for reacting the tetracarboxylic dianhydride and the diamine compound in the solvent is not particularly limited. Further, the order and method of adding 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 the mixture 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. be. 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. Since 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 stirred.

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 performing 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 under air or under 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, mesitylen, 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 solvent such as glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate; amide-based solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone; Solvents; heterocyclic solvents such as pyridine, picolin, lutidine, quinoline, isoquinoline; phenolic solvents such as phenol and cresol; lactone-based 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 is 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.

(Imidization of polyimide precursor)
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 any conventionally known method, and examples thereof include thermal imidization in which thermal cyclization is carried out, chemical imidization in which chemical imidization is carried out, 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 solvents as those 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 at the time of 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, it tends to be possible to produce with a solution viscosity that is easy to produce with high production efficiency.

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, usually 300 ° C. or lower, preferably 280 ° C. or lower, and more preferably 250 ° C. or lower. It is preferable to carry out the imidization reaction 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 under air or under an inert atmosphere.

Further, as an imidization promoter that promotes imidization, a compound having a function of enhancing nucleophilicity and electrophilicity 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. Carboxylic acid 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 Ppyridine, 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.

Among these, at least one selected from the group consisting of a tertiary amine compound, a carboxylic acid compound and a heterocyclic compound 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, and more preferably 1 mol% or more with respect to 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 in the presence of a solvent with a dehydration condensing agent.

Examples of the solvent used for chemical imidization include the same solvents as those used for 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 anhydrous acetic acid and anhydrous trifluoroacetic acid; 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, anhydrous chloroacetic acid, phenylphosphonic dichloride, thionyl chloride, thionyl bromide, thionyliodide, thionylfluo Halogen compounds such as rides; phosphorus compounds such as phosphorus trichloride, triphenyl phosphite, cyanide diethyl phosphate; 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 to be used in this range, imidization can be performed efficiently.

The concentration of the polyimide precursor at the time of 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 under air or under 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>
Polyimide can be directly obtained from a tetracarboxylic dianhydride and a diamine compound by using a conventionally known method. This method involves the synthesis and imidization of the poimide precursor, and the imidization without stopping the reaction or isolating the precursor.

The order and method of adding the tetracarboxylic acid dianhydride and the diamine compound are not particularly limited, but for example, the temperature at which the tetracarboxylic acid 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 easily extended and the 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 added to a poor solvent to precipitate the polyimide in a solid state, and then redissolved in another solvent for use.

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 or diisopropyl ether; a ketone solvent such as acetone, methyl ethyl ketone, isobutyl ketone or 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, 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.

As the solvent for redissolving the polyimide, for example, a hydrocarbon solvent such as hexane, cyclohexane, heptane, benzene, toluene, xylene, mesitylene, anisole; N, N-dimethylformamide, N, N-dimethylacetamide, 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 solubility, solvent solubility, storage stability, and heat resistance, and in particular, due to its excellent alkali solubility, 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. be. 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, etc. 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 a 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, the 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.

The alkali of the alkaline developer used here includes sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, ammonium hydrogencarbonate, and tetramethylammonium hydroxide. Tetraethylammonium Hydroxide, Tetrapropylammonium Hydroxide, Tetraisopropylammonium Hydroxide, N-Methyldietanolamine, N-Ethyldietanolamine, N, N-dimethylethanolamine, Trietanolamine, 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.
MCHM: 4,4'-methylenebis (2-methylcyclohexylamine) isomer mixture CHDA: 1,4-cyclohexyldiamine ABA: 3,5-diaminobenzoic acid BAPA: 2,2-bis (3-amino-4-hydroxy) Phenyl) Propane m-TB: 2,2'-dimethylbenzidine BPDA: 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride H-BPDA: 3,3', 4,4'-bicyclohexanetetra Carboxylic acid dianhydride ODPA: 4,4'-oxydiphthalic acid anhydride DMAc: N, N-dimethylacetamide

The evaluation method of the obtained polyimide is as follows.
[Alkaline soluble]
At room temperature (23 ° C.), a polyimide solution was added to 5 g of a 1 M potassium hydroxide aqueous solution so that the resin solid content was 5 mg, the mixture was stirred for 2 hours, and then visually observed and evaluated according to the following criteria.
Although DMAc is contained in the polyimide solution, the amount of DMAc is very small with respect to the amount of the potassium hydroxide aqueous solution, so that it does not significantly affect the evaluation of alkali solubility.
◯: Completely dissolved without remaining undissolved, and good alkali solubility.
Δ: Partially dissolved and slightly inferior in alkali solubility.
×: 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 calorimetric 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]
Add MCHM: 15.26 g (0.064 mol), DMAc: 45 g, acetic acid: 0.11 g to a four-necked flask equipped with a reflux nitrogen gas introduction tube, a cooler, a Dean-Stark aggregator filled with toluene, and a stirrer. After stirring, ABA: 2.43 g (0.016 mol), BPDA: 23.07 g (0.078 mol), and DMAc: 45 g were added, and the mixture was stirred in an oil bath at 80 ° C. for 8 hours. Then, 24.5 g of toluene was added, and the mixture was heated under reflux in an oil bath at 190 ° C. for 12 hours. Toluene was distilled off under normal pressure to obtain a polyimide solution 1.
The obtained polyimide solution 1 was evaluated for alkali solubility and heat resistance, and the results are shown in Table 1.
Further, when Td _5% was measured for this polyimide solution 1, it was confirmed to have high heat resistance of 402 ° C.

[Example 2]
The MCHM of Example 1 was 8.35 g (0.035 mol), acetic acid was 0.07 g, ABA was 9.04 g (0.035 mol), and BPDA was H-BPDA: 21.01 g (0.069 mol). , DMAc was changed to 115 g in total, and toluene was changed to 23.0 g, and the polyimide solution 2 was obtained by the same method as in Example 1.
The obtained polyimide solution 2 was evaluated for alkali solubility, and the results are shown in Table 1.

[Comparative Example 1]
The MCHM of Example 1 was CHDA: 5.14 g (0.045 mol), ABA was m-TB: 9.55 g (0.045 mol), BPDA was ODPA: 27.36 g (0.088 mol), and N, The reaction was carried out in the same manner as in Example 1 except that N-dimethylacetamide was changed to 126 g in total and toluene was changed to 25.2 g, but the product was precipitated and a polyimide solution was not obtained.
In Comparative Example 1, the slurry obtained by the reaction was used to evaluate the alkali solubility as described above, and the results are shown in Table 1.

In Table 1, the acid value and OH equivalent of each polyimide are also shown.

From Table 1, it can be seen that the polyimides of Examples 1 and 2 containing a hydroxyl group-containing diamine residue and / or a carboxyl group-containing diamine residue and an aliphatic 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 a BPDA residue is also excellent in heat resistance.
On the other hand, Comparative Example 1 used only an aliphatic diamine compound and an aromatic diamine compound as the diamine compound, and since the carboxyl group also did not have a hydroxyl group, it was inferior in alkali solubility.

Claims (4)

From a tetracarboxylic acid residue derived from tetracarboxylic acid dianhydride, a diamine residue derived from a diamine compound having a hydroxyl group (hereinafter referred to as "hydroxyl-containing diamine residue" ), and an aliphatic diamine compound. A polyimide containing an induced diamine residue (hereinafter referred to as "aliphatic diamine residue").
The tetracarboxylic acid residue is a tetracarboxylic acid residue derived from the aliphatic tetracarboxylic dianhydride.
Polyimide in which the aliphatic diamine residue is a diamine residue derived from 4,4'-methylenebis (2-methylcyclohexylamine). The polyimide according to claim 1, wherein the ratio of the hydroxyl group-containing diamine residue to the total diamine residue contained in the polyimide is 5 to 70 mol%, and the ratio of the aliphatic diamine residue is 30 to 95 mol%. The polyimide according to claim 1 or 2, wherein the hydroxyl group-containing diamine residue is a diamine residue derived from an aromatic diamine compound having two phenolic hydroxyl groups . The OH equivalent based on the hydroxyl group-containing diamine residue is 100 to 30,000 g / eq . The polyimide according to any one of claims 1 to 3.