JP2018115247A - Polyimide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyimide that has excellent alkali solubility, solvent solubility, storage stability, and heat resistance, and allows the alkali solubility to be easily controlled according to the required level of alkali solubility.SOLUTION: A polyimide contains a tetracarboxylic acid residue induced from tetracarboxylic acid dianhydride, a diamine residue induced from a diamine compound having a hydroxy group and/or a diamine residue induced from a diamine compound having a carboxyl group, and a diamine residue induced from an aliphatic diamine compound.SELECTED DRAWING: None

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. It relates to a polyimide that can be used.

  Resist used for manufacturing a semiconductor integrated circuit, a printed wiring board, a liquid crystal panel, and the like includes a positive resist and a negative resist. The difference between the two is that, in the positive resist, the exposed area is removed by a development 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, the resist resin has been changed to polyimide in order to improve heat resistance and the like.
In addition, as a developing solution, there are an organic solvent-based developing solution and an alkaline aqueous solution. In recent years, an alkaline aqueous solution has been used in order to reduce environmental load.

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

  In Patent Document 1, 3,3 ′, 4,4′-bicyclohexanetetracarboxylic dianhydride or 1,2,4,5-cyclohexanetetracarboxylic acid is used as a polyimide used for an alkali developable polyimide resin composition. A phenolic hydroxyl group-containing polyimide obtained by polycondensation reaction of a tetracarboxylic dianhydride having a dianhydride as an essential component and a diamine compound having a phenolic hydroxyl group-containing diamine compound (aminophenol compound) as an essential component has been proposed. ing. However, according to the study by the present inventors, a polyimide obtained from a diamine component having a phenolic hydroxyl group and 3,3 ′, 4,4′-bicyclohexanetetracarboxylic dianhydride is sufficiently soluble in an alkaline aqueous solution. Rather, there is a risk that undissolved residue may occur during alkali development.

  Patent Document 2 discloses a photosensitive resin composition having excellent storage stability and capable of water-based development, which is obtained by acrylically modifying a soluble polyimide containing a polymerizable functional group and containing a carboxyl group and / or a hydroxyl group. Although described, there is no description of an aliphatic diamine compound as a polyimide diamine compound raw material.

  Patent Document 3 discloses an aromatic diamine having a reactive functional group with an epoxy group and diamino as a polyimide used in an imide-based photosensitive resin composition having heat resistance, chemical resistance (alkali resistance) and high insulation. Although the thing which used polysiloxane as the diamine compound raw material is described and the diamine which has a hydroxyl group or a carboxyl group is mentioned as a diamine which has a reactive functional group with the epoxy group, an aliphatic diamine compound as a diamine compound raw material of a polyimide There is no description.

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

Japanese Patent No. 5530363 JP 2004-325980 A JP 2002-351073 A Japanese Patent No. 5501672

  Resist used in the manufacture of semiconductor integrated circuits, printed wiring boards, liquid crystal panels, etc. is not so good in alkali solubility that it is suitable for the composition and temperature of the alkali developer used, the workability in the manufacturing process, and the required characteristics. It is desirable to be soluble in alkali. Conventionally, however, polyimides imparted with alkali solubility have been proposed, but there is no problem of controlling the degree of alkali solubility, and no effort has been made to control alkali solubility.

  An object of the present invention is to provide a polyimide that is excellent in alkali solubility, solvent solubility, storage stability, and heat resistance, and can easily control alkali solubility depending on the required degree of alkali solubility.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors, as a diamine residue, a residue derived from a diamine compound having a hydroxyl group and / or a residue derived from a diamine compound having a carboxyl group And the polyimide containing the residue induced | guided | derived from an aliphatic diamine compound discovered that the said subject could be solved, and completed this invention.

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

[1] A tetracarboxylic acid residue derived from tetracarboxylic dianhydride and a diamine residue derived from a diamine compound having a hydroxyl group (hereinafter referred to as “hydroxyl group-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”) And polyimide).

[2] The ratio of the total of the hydroxyl group-containing diamine residues and / or carboxyl group-containing diamine residues in 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. % Of polyimide according to [1].

[3] The monocyclic aromatic diamine compound in which 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 has a carboxyl group [1] or [2], wherein the aliphatic diamine residue is a diamine residue derived from an alicyclic diamine compound having no hydroxyl group and carboxyl group. Polyimide.

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

[5] An OH equivalent based on the hydroxyl group-containing diamine residue is 100 to 30000 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 can easily control alkali solubility depending on the required degree of alkali solubility.
Such a polyimide of the present invention can be suitably used as a resist resin used in the production of semiconductor integrated circuits, printed wiring boards, liquid crystal panels and the like.

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. However, the description of each constituent element described below is a representative example of embodiments of the present invention, and the present invention is not limited to these unless it exceeds the gist. Is not to be done.

The polyimide of the present invention includes a tetracarboxylic acid residue derived from tetracarboxylic dianhydride, a diamine residue derived from a diamine compound having a hydroxyl group (hereinafter referred to as “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”) and a diamine residue derived from an aliphatic diamine compound (hereinafter referred to as “aliphatic diamine”). And at least “residue”.
That is, the polyimide of the present invention is not a polyamic acid but a polyimide, so that it has excellent storage stability and heat resistance, and has an aliphatic structure derived from an aliphatic diamine residue, so that it has excellent solvent solubility, By including the containing diamine residue and / or the carboxyl group-containing diamine residue, it is possible to easily impart alkali solubility and control it.

  As shown in the following reaction formula (I), a polyimide precursor (polyamic acid, polyamic acid) is produced by a polycondensation reaction between a tetracarboxylic dianhydride and a diamine compound. However, there are a method for preparing polyimide by dehydration ring-closing reaction of this polyimide precursor and a method for directly producing polyimide from tetracarboxylic 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 group-containing diamine residue” is not limited to “a diamine residue derived from a hydroxyl group-containing diamine compound” but “a diamine residue derived from a hydroxyl group-containing diisocyanate compound”. May be. Similarly, the “carboxyl group-containing diamine residue” is not limited to “a diamine residue derived from a diamine compound having a carboxyl group” but “a diamine residue derived from a diisocyanate compound having a carboxyl group”. The “aliphatic diamine residue” is not limited to “a diamine residue derived from an aliphatic diamine compound” but may be a “diamine residue derived from an aliphatic diisocyanate compound”.
As a diisocyanate compound used for manufacture of the polyimide of this invention, the compound which replaced "diamine" with "diisocyanate" among the names of the diamine compound illustrated below is mentioned.

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

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

  Among these, since the viscosity at the time of production is easy to control, tetracarboxylic dianhydride having one aromatic ring in one molecule or tetracarboxylic dianhydride having two or more independent aromatic rings in one molecule In particular, tetracarboxylic dianhydrides having two or more independent aromatic rings in one molecule are preferred.

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

  Examples of the tetracarboxylic dianhydride having two or more independent aromatic rings in one molecule include 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 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′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 4,4′- Oh Shidiphthalic dianhydride, 4,4- (p-phenylenedioxy) diphthalic dianhydride, 4,4- (m-phenylenedioxy) diphthalic dianhydride, 2,2 ′, 6,6′- Biphenyltetracarboxylic dianhydride etc. are mentioned.

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

  Examples of the aliphatic tetracarboxylic dianhydride include alicyclic tetracarboxylic dianhydrides and chain aliphatic tetracarboxylic dianhydrides.

  Examples of the alicyclic tetracarboxylic dianhydride include 3,3 ′, 4,4′-bicyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1 , 2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4 -Cyclobutanetetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, tricyclo [6.4.0.0 (2 7)] dodecane-1,8: 2,7-tetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 4- (2,5-dioxotetrahydride Lofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 1,1′-bicyclohexane-3,3 ′, 4,4′-tetracarboxylic dianhydride Thing etc. are mentioned.

  Examples of the chain aliphatic tetracarboxylic dianhydride include ethylene tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride, etc. Is mentioned.

  Other examples of the tetracarboxylic dianhydride include silicone-based tetracarboxylic dianhydrides and, for example, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3- Hexafluoropropane dianhydride (also known as 4,4 ′-(hexafluoroisopropylidene) -diphthalic dianhydride), 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3 , 3,3-hexafluoropropane dianhydride, 2,2′-bis (trifluoromethyl) -4,4 ′, 5,5′-biphenyltetracarboxylic dianhydride, 4,4 ′-(hexafluoro Trimethylene) diphthalic dianhydride, 4,4 ′-(octafluorotetramethylene) diphthalic dianhydride, 2,2′-bis (trifluoromethyl) -4,4 ′, 5,5′-biphenyltetra Carvone Dianhydride, 4,4 ′-(hexafluorotrimethylene) diphthalic dianhydride, 4,4 ′-(octafluorotetramethylene) diphthalic dianhydride, 2,2-bis (3,4-dicarboxy) Phenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexa Fluoropropane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2,3- A tetracarboxylic dianhydride containing a fluorine atom such as dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride can also be used.

  Of the above tetracarboxylic dianhydrides, an alicyclic diamine compound is preferred from the viewpoint of introducing an alicyclic structure to enhance the solvent solubility of the polyimide and having excellent storage stability. It is preferable to use ', 4,4'-bicyclohexanetetracarboxylic dianhydride. From the viewpoint of production stability and heat resistance, tetracarboxylic dianhydride having two or more independent aromatic rings in one molecule such as 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is used. It is preferable.

  As for the tetracarboxylic acid residue contained in the polyimide of this invention, only 1 type may be sufficient and 2 or more types may be contained.

[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.

  When the polyimide of the present invention contains a hydroxyl group-containing diamine residue and / or a carboxyl group-containing diamine residue as a diamine residue, alkali solubility is imparted. Further, 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, remarkably good alkali solubility is imparted by the introduction of a carboxyl group-containing diamine residue. Although the hydroxyl group-containing diamine residue is also lower than the carboxyl group-containing diamine residue, the effect of contributing to imparting alkali solubility is higher than that of a diamine residue derived from a diamine compound not containing a hydroxyl group or a carboxyl group. In addition, the aliphatic diamine residue tends to have a structure that inhibits intermolecular interaction, and thus functions to improve solvent solubility. Since this aliphatic diamine residue does not contribute to imparting alkali solubility, if it is a polyimide containing both a hydroxyl group-containing diamine residue and / or a carboxyl group-containing diamine residue and an aliphatic diamine residue, its content ratio By adjusting the value, it becomes possible to easily control the degree of alkali-solubility according to the application.

<Hydroxyl-containing diamine residue>
The hydroxyl group-containing diamine residue is a residue derived from a hydroxyl group-containing diamine compound, and the hydroxyl group-containing diamine compound is a diamine compound having at least two amino groups and at least one hydroxyl group in one molecule. If there is no particular limitation, from the viewpoint of enhancing alkali solubility, preferably an aromatic diamine compound having two amino groups and two phenolic hydroxyl groups in one molecule, and further a compound having a fluorine atom It may be. Specifically, 3,3′-diamino-4,4′-dihydroxydiphenyl sulfone, 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) Phenyl) fluorene and the like, 3,3′-diamino-4,4′-dihydroxydiphenylsulfone, 3,3′-diamino-4,4′-dihydroxybenzo Phenone, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 9,9′-bis (3-amino-4) -Hydroxyphenyl) fluorene is preferred, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 3,3'-diamino-4, 4′-dihydroxybenzophenone and 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane are particularly preferred.

  When the polyimide of the present invention contains a hydroxyl group-containing diamine residue, even if it contains a residue derived from a diamine compound having one kind of hydroxyl group as the hydroxyl group-containing diamine residue, a diamine having two or more kinds of hydroxyl groups It may contain a residue derived from a 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 acids such as 3,5-diaminobenzoic acid, 3,3 Carboxyphenyl compounds such as'-diamino-4,4'-dicarboxybiphenyl,4,4'-diamino-2,2',5,5'-tetracarboxybiphenyl,4,4'-diamino-3,3' -Carboxydiphenylalkanes such as dicarboxydiphenylmethane, 3,3'-diamino-4,4'-dicarboxydiphenylmethane, Carboxydiphenyl ethers such as 4,4'-diamino-2,2 ', 5,5'-tetracarboxydiphenyl ether Compounds, 3,3′-diamino-4,4′-dicarboxydiphenylsulfone and other dipheny Sulfone compounds, bis (hydroxyphenoxy) biphenyl compounds such as 2,2-bis [4- (4-amino-3-carboxyphenyl) phenyl] propane, 2,2-bis [4- (4-amino-3-carboxy) And bis [(-carboxyphenoxy) phenyl] sulfone compounds such as phenoxy) phenyl] sulfone, and the like. From the viewpoint of controlling solubility, improving production stability and heat resistance, diaminobenzoic acid (3,5- Diaminobenzoic acid), 3,4-diaminobenzoic acid, 1,3-diamino-4,6-dicarboxybenzene, 1,2-diamino-4,6-dicarboxybenzene, 1,3-diamino-4,5 -Monocyclic compounds (monocyclic aromatic diamine compounds having a carboxyl group) such as dicarboxybenzene, more preferably diaminobenzoic acid Perfume 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 kind of carboxyl group as the carboxyl group-containing diamine residue. It may contain a residue derived from a diamine compound having a carboxyl group.

<Aliphatic diamine residue>
The aliphatic diamine residue is a diamine residue derived from an aliphatic diamine compound, and the aliphatic diamine compound does not have a carboxyl group or a hydroxyl group, and an alicyclic diamine compound and a chain aliphatic diamine compound. Etc.

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

  Examples of the chain aliphatic diamine compounds 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, from the viewpoints of heat resistance, solvent solubility, and production stability, alicyclic diamine compounds are preferable, and alicyclic diamine compounds having cyclohexane rings are particularly preferable, and those having two or more cyclohexane rings are particularly preferable. .

  The polyimide of the present invention may contain a residue derived from one kind of aliphatic diamine compound as an aliphatic diamine residue, or may contain a residue derived from two or more kinds 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 a diamine residue. // residues derived from carboxyl group-containing diamine residues, aliphatic diamine residues and other diamine compounds (hereinafter sometimes referred to as “other diamine compounds”) (hereinafter referred to as “other diamine residues”). May be referred to as “.”).

  Other diamine compounds of other diamine residues include aromatic diamine compounds that do not have a hydroxyl group or a 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, a diamine compound having a condensed aromatic ring in one molecule, and the like. 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 in terms of facilitating viscosity control during production, and two or more independent fragrances are preferable. 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, 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, '-Bis (4-aminophenoxy) biphenyl, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, N- (4-aminophenoxy) -4-amino Benzamine, bis (3-aminophenyl) sulfone, norbornanediamine and the like can be mentioned. Among them, from the viewpoint of solubility, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, (4- (4-aminophenoxy) phenyl) sulfone, 4,4′-diaminodiphenylsulfone, 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, 3,7-diamino-2,8- Examples 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) fe [Ru] hexafluoropropane, 2,2-bis [4- {4-amino-2- (trifluoromethyl) phenoxy} phenyl] hexafluoropropane, 2,2-bis (3-amino-4-methylphenyl) hexa Fluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-aminophenyl) hexafluoro Examples thereof include diamine compounds containing fluorine atoms such as propane and 2,2-bis {4- (4-aminophenoxy) -3,5-dibromophenyl} hexafluoropropane.

  When the polyimide of this invention contains the said other diamine residue, only 1 type may be sufficient as another diamine residue, and 2 or more types may be contained.

<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 has a total diamine residue contained in the polyimide in order to reliably obtain the above-mentioned effect by including a hydroxyl group-containing diamine residue and / or a carboxyl group-containing diamine residue and an aliphatic diamine residue as diamine residues. 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, particularly preferably 15 mol% or more. Moreover, 70 mol% or less is preferable, 60 mol% or less is more preferable, and 55 mol% or less is further more preferable.
The ratio of the aliphatic diamine residues to the total diamine residues 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 has a total diamine residue contained in the polyimide in order to reliably obtain the above-mentioned effect by including a hydroxyl group-containing diamine residue and / or a carboxyl group-containing diamine residue and an aliphatic diamine residue as diamine residues. 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%. It is preferable.

[Molecular weight]
The weight average molecular weight (Mw) of the polyimide of the present invention is not particularly limited, but is usually 1000 or more, preferably 3000 or more, more preferably 5000 or more in terms of polystyrene-equivalent weight average molecular weight. Moreover, it is 200000 or less normally, Preferably it is 180000 or less, More preferably, it is 150,000 or less. It is preferable for the weight average molecular weight to be in the above range since solvent solubility, composition viscosity and the like tend to be handled with ordinary production equipment. In addition, the polystyrene equivalent weight average molecular weight of a polyimide can be calculated | required by gel permeation chromatography (GPC).

  The number average molecular weight (Mn) of the polyimide of the present invention is not particularly limited, but is usually 500 or more, preferably 1000 or more, and more preferably 2500 or more in terms of polystyrene-reduced number average molecular weight. Further, it is usually 100,000 or less, preferably 90000 or less, more preferably 80000 or less. It is preferable for the number average molecular weight to be in the above range since solvent solubility, composition viscosity and the like tend to be handled with ordinary production equipment. The number average molecular weight in terms of polystyrene 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, more preferably 1.2 or more. Moreover, it is 10 or less normally, Preferably it is 9 or less, More preferably, it is 8 or less. When the molecular weight distribution is in the above range, for example, when used as a resist, a film having excellent uniformity and smoothness tends to be obtained.

[OH equivalent / acid value]
The polyimide of the present invention has an OH equivalent based on a hydroxyl group-containing diamine residue of 100 to 30000 g / eq. 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 acid value is within the above ranges, excellent alkali solubility and controllability can be obtained in the presence of an aliphatic diamine residue.

  The OH equivalent of polyimide can be obtained by calculation from the molecular weight and molar ratio of the constituent residues, and the OH equivalent was also obtained in the same manner 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 manner in the examples described later.

[Alkali soluble / solvent soluble]
The polyimide of the present invention is excellent in alkali solubility. For example, the polyimide of the present invention exhibits alkali solubility of about 0.1% by mass or more in a 1M aqueous potassium hydroxide solution at room temperature (23 ° C.). This dissolution concentration can be appropriately adjusted within the range of 0.1 to 30% by mass.

  The polyimide of the present invention is also excellent in solvent solubility. For example, the solubility at room temperature (23 ° C.) with respect to a solvent or the like used in the production of the polyimide precursor described later exhibits a solubility of 5% by mass or more. .

[Production method of polyimide]
The polyimide of the present invention is produced according to a conventional method except that a tetracarboxylic 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 polyimide production method of the present invention is a method in which a polyimide precursor is produced from a tetracarboxylic dianhydride and a diamine compound and then imidized to obtain a polyimide, and a polyimide is produced directly from a tetracarboxylic dianhydride and a diamine compound. There is a way to do it.

  In addition, when imidating a polyimide precursor and manufacturing a polyimide, the imidation rate in particular is although it does not restrict | limit, It is so preferable that it is high, and is 80% or more normally, Especially 90-100%.

<Method for producing polyimide via polyimide precursor>
(Production of polyimide precursor)
The polyimide precursor of the present invention is obtained by reacting a tetracarboxylic dianhydride, a diamine compound having a hydroxyl group and / or a diamine compound having a carboxyl group and an aliphatic diamine compound in a solvent. It is done. The method for reacting the tetracarboxylic dianhydride and the diamine compound in a solvent is not particularly limited. Moreover, the addition order and addition method of a tetracarboxylic dianhydride and a 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 making a diamine compound into such a range, it exists in the tendency for the yield of the polyimide precursor obtained to improve.

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

  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 liquid 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 increase. Moreover, when this concentration is not too high, the viscosity does not become too high, and the reaction liquid 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. The temperature is preferably 100 ° C. or lower.
The reaction time is usually 1 hour or longer, preferably 2 hours or longer, usually 100 hours or shorter, preferably 42 hours or shorter. By carrying out under such conditions, the polyimide precursor tends to be obtained at a low cost and in a high yield.
The pressure during the reaction may be normal pressure, pressurization, or reduced pressure. The atmosphere may be air or an inert atmosphere.

  The solvent used when making tetracarboxylic dianhydride and a diamine compound react is not specifically limited. For example, hydrocarbon solvents such as hexane, cyclohexane, heptane, benzene, toluene, xylene, mesitylene, anisole; halogenated carbon tetrachloride, methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, fluorobenzene, etc. Hydrocarbon solvents; ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, methoxybenzene; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Glycol solvents such as glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate; N, N Amide solvents such as dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone; sulfone solvents such as dimethyl sulfoxide; heterocyclic solvents such as pyridine, picoline, lutidine, quinoline, isoquinoline; phenol, cresol Phenol solvents such as γ-butyrolactone, γ-valerolactone, lactone solvents such as δ-valerolactone, and the like. These solvents may be used alone or in combination of two or more in any ratio and combination.

  The obtained polyimide precursor may be subjected to the next imidization as it is, or may be used by being precipitated in a solid state by adding it to a poor solvent.

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

(Imidization of polyimide precursor)
A polyimide can be obtained by dehydrating and cyclizing the polyimide precursor obtained by the above method in the presence of a solvent. Although imidation can be performed using any conventionally known method, for example, thermal imidization for thermal cyclization, chemical imidization for chemical cyclization, and the like can be given. These imidation reactions may be performed alone or in combination.

<Heat 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 at the time of manufacturing the polyimide precursor and the solvent at the time of manufacturing the polyimide may be the same or different.
In this case, water generated by imidization may be discharged out of the system in order to inhibit the ring closure reaction. The concentration of the polyimide precursor during the imidation 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 carrying out in this range, the production efficiency tends to be high and the solution viscosity tends to be easy to produce.

The imidation 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. Performing in this range is preferable 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 reduced pressure. The atmosphere may be air or an inert atmosphere.

  In addition, as an imidization accelerator for promoting 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-methylpyrrolidine, N-ethylpyrrolidine Tertiary amine compounds such as N-methylpiperidine, N-ethylpiperidine, imidazole, pyridine, quinoline, isoquinoline; acetic acid, 4-hydroxyphenylacetic acid, 3-hydroxybenzoic acid, N-acetylglycine, N-benzoylglycine, etc. Carboxylic acid compounds; polyhydric phenol compounds such as methyl 3,5-dihydroxyacetophenone, methyl 3,5-dihydroxybenzoate, pyrogallol, methyl gallate, ethyl gallate, naphthalene-1,6-diol; 2-hydride Xipyridine, 3-hydroxypyridine, 4-hydroxypyridine, 4-pyridinemethanol, N, N-dimethylaminopyridine, nicotine aldehyde, isonicotialdehyde, picolinaldehyde, picolinaldehyde oxime, nicotinaldehyde oxime, isonicotialdehyde oxime, picolinic acid Ethyl, ethyl nicotinate, ethyl isonicotinate, nicotinamide, isonicotinamide, 2-hydroxynicotinic acid, 2,2′-dipyridyl, 4,4′-dipyridyl, 3-methylpyridazine, quinoline, isoquinoline, phenanthroline, 1 , 10-phenanthroline, imidazole, benzimidazole, heterocyclic compounds such as 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 individually by 1 type, or may be used 2 or more types by arbitrary ratios and combinations.

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. Moreover, it is preferable that it is 50 mol% or less, and it is more preferable that it is 10 mol% or less. When the amount of the imidization accelerator used is in the above range, the imidization reaction tends to proceed efficiently.
Moreover, the timing which adds an imidation promoter can be adjusted suitably, may be before a heating start and may be during a heating. Moreover, you may add in multiple times.

<Chemical imidization>
A polyimide can be obtained by chemically imidizing a polyimide precursor using 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.

  Examples of the dehydrating 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 and tosyl chloride and the like. Chlorides of: acetyl chloride, acetyl bromide, propionyl iodide, acetyl fluoride, propionyl chloride, propionyl bromide, propionyl iodide, propionyl fluoride, isobutyryl chloride, isobutyryl bromide, isobutyryl iodide, isobuty Ryl fluoride, 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, thionyl iodide, thionyl fluoride Halide compounds such as rides; Phosphorus compounds such as phosphorus trichloride, triphenyl phosphite, and cyanide diethyl phosphate; and the like.

  Among 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 individually by 1 type, or may be used 2 or more types by arbitrary ratios and combinations.

  The amount of these dehydrating 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, relative to 1 mol of the polyimide precursor. By making the use amount of the dehydration condensing agent within this range, imidization can be efficiently performed.

  Although there is no restriction | limiting in particular in the density | concentration of the polyimide precursor at the time of imidation reaction, Usually, 1 mass% or more, Preferably it is 5 mass% or more, and is 70 mass% or less normally, Preferably it is 40 mass% or less. By setting it as this range, it exists in the tendency which can improve production efficiency and can manufacture with the solution viscosity which is easy to manufacture.

The imidization reaction temperature is not particularly limited, but is usually 0 ° C. or higher, preferably 10 ° C. or higher, more preferably 20 ° C. or higher. Moreover, it is 150 degrees C or less normally, Preferably it is 130 degrees C or less, More preferably, it is 100 degrees C or less. Since it exists in the tendency for an imidation reaction to advance efficiently by performing in this range, it is preferable. Furthermore, it is preferable because side reactions other than the imidization reaction are suppressed.
The pressure during the reaction may be normal pressure, increased pressure, or reduced pressure. The atmosphere may be air or 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 in the heating imidization.

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

  There are no particular limitations on the order and method of addition of tetracarboxylic dianhydride and diamine compound. For example, the temperature at which the reaction until imidization proceeds by sequentially adding tetracarboxylic dianhydride and diamine compound to the solvent. The polyimide is obtained by stirring at.

  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. By making the quantity of a diamine compound into such a range, it exists in the tendency for the yield of the polyimide obtained to improve.

The concentration 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 polymerization.
The total concentration of tetracarboxylic dianhydride and 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 within an appropriate range, elongation of molecular weight tends to occur, 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.

  Also, when polyimide is obtained from tetracarboxylic dianhydride and diamine compound, heating imidization and / or chemical imidization can be employed as in the case of obtaining polyimide from a polyimide precursor. 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 so that the polyimide is precipitated in a solid state and then re-dissolved 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, ether solvents such as diethyl ether and diisopropyl ether; ketone solvents such as acetone, methyl ethyl ketone, isobutyl ketone and methyl isobutyl ketone; And alcohol solvents such as methanol, ethanol, isopropyl alcohol, and the like. Among them, alcohol solvents such as isopropyl alcohol are preferable because precipitates can be obtained efficiently and the boiling point is low and the drying tends to be easy. These solvents may be used alone or in combination of two or more in any ratio and combination.

  Examples of the solvent for re-dissolving polyimide include hydrocarbon solvents such as hexane, cyclohexane, heptane, benzene, toluene, xylene, mesitylene, and anisole; N, N-dimethylformamide, N, N-dimethylacetamide, N Amide solvents such as methyl-2-pyrrolidone; aprotic solvents such as dimethyl sulfoxide; glycol solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate; Etc. Among 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 combination of two or more in any ratio and combination.

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

When the polyimide of the present invention is used as a resist used in the production of semiconductor integrated circuits, printed wiring boards, liquid crystal panels, etc., an anion regenerating agent, photoacid generator, alkali dissolution accelerator, photocrosslinking agent, etc., if necessary Is used as a photosensitive composition.
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.

  Solvents suitable 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, sulfolane, tetramethylurea, N, N-dimethylacetamide, Examples thereof include dimethylformamide, dimethyl sulfoxide, acetonitrile, diglyme, phenol, cresol, toluene, methylene chloride, chloroform, tetrahydrofuran, dioxane, acetone and the like.

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

  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 speed, and the like of the resist solution. For example, a layer and a relief structure having a layer thickness of 0.1 to 500 μm, preferably 1 to 100 μm are formed. In the case of a thin layer or an insulating layer in a multilayer circuit, the thickness may be about 1 to 50 μm. After apply | coating a resist to a base material, after carrying out preliminary drying normally at 50-120 degreeC, after carrying out exposure by a desired pattern, alkali image development is performed.

  Examples of the alkali developer used here include sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, tetramethylammonium hydroxide, Tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylethanolamine, triethanolamine, triisopropanolamine, triisopropyl An amine etc. are mentioned.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

In the following, the abbreviations of 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 dianhydride H-BPDA: 3,3 ′, 4,4′-bicyclohexanetetra Carboxylic dianhydride ODPA: 4,4′-oxydiphthalic anhydride DMAc: N, N-dimethylacetamide

Moreover, the evaluation method of the obtained polyimide is as follows.
[Alkali soluble]
At room temperature (23 ° C.), the polyimide solution was added to 5 g of 1M aqueous potassium hydroxide so that the resin solid content was 5 mg, stirred for 2 hours, visually observed, and evaluated according to the following criteria.
In addition, although DMAc is contained in the polyimide solution, since DMAc is very small with respect to the amount of potassium hydroxide aqueous solution, it does not have a big influence on evaluation of alkali solubility.
○: Complete dissolution without remaining undissolved, good alkali solubility.
Δ: Partially dissolved and slightly insoluble in alkali.
X: Not soluble, poor alkali solubility.

[Heat-resistant]
After the polyimide solution is applied to the glass substrate, it is baked at 350 ° C. for 30 minutes, and then the polyimide film obtained by peeling off from the glass substrate is measured by a thermogravimetric / differential calorimeter simultaneous measurement device (TG-DTA), and the weight is reduced by 5%. The temperature (Td _5% ) was evaluated as the heat resistant temperature.
A higher Td of _5% is more preferable.

[Example 1]
MCHM: 15.26 g (0.064 mol), DMAc: 45 g, acetic acid: 0.11 g were added to a four-necked flask equipped with a refluxing nitrogen gas inlet tube, a condenser, a Dean-Stark agglomerator 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. Thereafter, 24.5 g of toluene was added, and the mixture was heated to reflux in an oil bath at 190 ° C. for 12 hours. Toluene was distilled off at 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.
Moreover, when Td _5% was measured about this polyimide solution 1, it was confirmed that it is 402 degreeC and high heat resistance.

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

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

  In Table 1, the acid value and OH equivalent of each polyimide are 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.
Moreover, 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 uses only an aliphatic diamine compound and an aromatic diamine compound as the diamine compound, and the carboxyl group does not have a hydroxyl group, so that it is inferior in alkali solubility.

Claims (5)

  It has a tetracarboxylic acid residue derived from tetracarboxylic dianhydride, a diamine residue derived from a diamine compound having a hydroxyl group (hereinafter referred to as “hydroxyl group-containing diamine residue”) and / or a carboxyl group. A diamine residue derived from a diamine compound (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”). ).   The ratio of the total of the hydroxyl group-containing diamine residues and / or carboxyl group-containing diamine residues in 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 claim 1.   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 derived from a monocyclic aromatic diamine compound having a carboxyl group. The polyimide according to claim 1, wherein the aliphatic diamine residue is a diamine residue derived from an alicyclic diamine compound having no hydroxyl group and carboxyl group.   The polyimide according to any one of claims 1 to 3, which has a tetracarboxylic acid residue derived from an alicyclic tetracarboxylic dianhydride.   An OH equivalent based on the hydroxyl group-containing diamine residue is 100 to 30000 g / eq. The polyimide according to any one of claims 1 to 4, wherein an acid value based on the carboxyl group-containing diamine residue is 5 to 150 mg-KOH / g.