JP2785357B2 - Process for producing polyimide isoindoloquinazolinedione and its precursor - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing polyimide isoindoloquinazolinedione and a precursor thereof.

[Conventional technology]

Hitherto, polyimide isoindoloquinazolinedione and polyimide have been used as heat-resistant electric insulating materials as constituent materials of electronic components such as interlayer insulating films for semiconductors, surface protective films, and α-ray shielding films. In general, these polymers are prepared by applying a precursor to a substrate such as a silicon wafer, a glass plate, or a metal plate, forming a partially imidized film by heat treatment, and forming a resist on the film in a desired pattern. The resist was then immersed in an etching solution to dissolve and remove the insoluble portion, and then the resist was peeled off, heat-treated again, and completely cured to prepare various films.

Examples of the polyimide isoindoloquinazolinedione include acid dianhydrides such as 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether-3-carbonamide. A diaminoamide compound of 1,
Those obtained by reacting a diaminosiloxane such as 3-bis (aminopropyl) tetramethyldisiloxane and a diamine are known (for example, Japanese Patent Publication No. 60-43370).
No.).

On the other hand, polyimide-based polymers are disclosed in JP-A-60-124625.
As shown in the official gazette, a radical reaction type crosslinking agent,
It is known that crosslinking by using a vulcanization accelerator improves solvent resistance. Other methods include heating a polyimide-based polymer to 300 ° C or higher, and a polyimide-based polymer having an end group such as an acetylene group. There is a method of obtaining a polyimide-based crosslinked polymer by, for example, heating the above polymer to 250 ° C. or higher.

[Problems to be solved by the invention]

Conventional polyimide isoindoloquinazolinedione as described in JP-B-60-43370 requires a temperature exceeding 250 ° C. in order to completely cure, and thus has a heat resistance exceeding 250 ° C. The disadvantage is that it cannot be applied to devices that do not. Further, the conventional polyimide isoindoloquinazolinedione has a high elastic modulus, and there is a fear of cracking and peeling off from the substrate.

On the other hand, many of the conventional polyimides still require a temperature exceeding 250 ° C. for complete curing. Two
Although some polyimides can be cured at temperatures below 50 ° C., polyimides generally have the disadvantage of low tensile strength. Further, as a material that can be treated at a temperature of 250 ° C. or less, there is a polyimide resin which has already been completely imidized as described in JP-A-61-4700, but a polyimide which has been completely imidized. It is known that the rate of dissolving and removing unnecessary portions by immersing in the above-mentioned etching solution is much slower than that of a resin in which only a part of imidization has progressed ( (Functional materials, May and June 1984) The above-mentioned processing (etching processing) cannot be used for applications that need to be performed.

On the other hand, according to the method disclosed in Japanese Patent Application Laid-Open No. 60-124625 or the like, the addition of the crosslinking agent causes a problem that the physical properties of the polymer are greatly changed as the curing temperature is increased, and the processability and workability are reduced.

The present invention is intended to solve such a problem, and can be completely cured at 250 ° C. or less, can be etched, and has excellent adhesion to substrates such as silicon wafers and metal plates. It is intended to provide a method for producing dione and its precursor. Further, the present invention provides a method for producing a polyimide isoindoloquinazolinedione which has improved solvent resistance by introducing a crosslinked structure by a method different from the above method, and which is more excellent in processability.

[Means for solving the problem]

The present invention relates to a composition comprising a) 1-35 mol% of hexacarboxylic trianhydride and b) a compound of the general formula (I) Wherein n represents an integer of 2 to 16; a carboxylic anhydride containing 99 to 65 mol% of a tetracarboxylic dianhydride containing an alkylenebistrimellitate dianhydride; and c) a general formula Formula (II) (Wherein, Ar is an aromatic group, Y is Group and diaminoamide compound in which at least one is represented by are bonded to adjacent carbon atoms of Ar) of the two -NH ₂ group, d) a diamine having a reactive unsaturated group and an aromatic ring in the molecule (Diamine I) and e) an aromatic diamine having at least one substituent ortho to the at least one amino group [d] above
And a process for producing a polyimide isoindoloquinazolinedione precursor, characterized by reacting a diamine II].

The acid trianhydride may be a compound having three amino groups (for example, 3,3 ', 5-triaminobenzophenone, etc.) or a compound having three hydroxyl groups and trimellitic anhydride chloride having an amide bond or an ester bond. The amino group or the hydroxyl group can be obtained by reacting
Compound and two methyl groups in ortho-position with each other, such as 3,4-dimethylbenzoic acid chloride. It can be obtained by reacting benzene (dimethylbenzoic acid chloride) having one substituent as a substituent to form an amide bond or an ester bond, oxidizing a methyl group to form a carboxyl group, and then dehydrating. 1,3,5-
After a coupling reaction between trichlorobenzene and dimethylbenzoic acid chloride, the compound can be produced by oxidizing a methyl group and further dehydrating. Furthermore, after reacting a compound having three hydroxyl groups with dimethylchlorobenzene such as 1,2-dimethyl-4-chlorobenzene to form an ether bond, the methyl group is oxidized to a carboxyl group, and then dehydrated to produce a product. can do.

The acid trianhydride thus obtained is, for example, of the general formula (III) (Wherein, R represents a trivalent organic group).

Since the above-mentioned acid trianhydride is easy to produce, it can be obtained by reacting a compound having three hydroxyl groups in a molecule with trimellitic anhydride chloride in an organic solvent in the presence of a tertiary amine. preferable. Compounds having three hydroxyl groups in the molecule include glycerin, trimethylolethane, trimethylolpropane, 1,2,6-hexanetriol,
2,4-dihydroxy-3-hydroxymethylpentane,
2,6-bis (hydroxymethyl) butan-3-ol,
3-methylpentane-1,3,5-triol, 1,3,5-trihydroxybenzene, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene, 2,4,5-triol Hydroxybutylphenone, 2,3,4-trihydroxybenzaldehyde, α, α ′, α ″-(4-hydroxyphenyl) -1,3,5-triisopropylbenzene, 2,6-bis [(2- (Hydroxy-5-methylphenyl) methyl]-
4-methylphenol, 2,3,4-trihydroxyacetophenone and the like. Organic solvents that are preferably used in such a ratio that trimellitic anhydride chloride is 3 moles per mole of the compound having three hydroxyl groups in the molecule include benzene, toluene, xylene, tetrahydrofuran, 1,4-dioxane, There are diethyl ether, 1,2-dichloroethane, chlorobenzene, dichloromethane and the like, and two or more kinds may be used in combination. It is better to use the organic solvent dried with a molecular sieve or the like. Examples of the tertiary amine include pyridine, triethylamine, and tributylamine, and two or more of them may be used in combination. The tertiary amine is preferably used in an amount of 1 to 2 equivalents based on trimellitic anhydride chloride. The reaction temperature and reaction time are not particularly limited, but are preferably 50 ° C. or lower and within 3 hours. Within this range, an oligomer-like substance may be formed, and the yield may decrease.

The acid trianhydride thus obtained has the general formula (IV) (Where R ₁ is a trivalent organic group).

The acid trianhydride is from 1 to 35 based on the total amount of the acid anhydride.
Mol%, particularly preferably 2 to 30 mol%. If it is less than 1 mol%, the effect of crosslinking is small, and if it is more than 35 mol%, gelation occurs during the synthesis of the precursor, and a uniform varnish cannot be obtained. Further, within the above range, two or more kinds may be used in combination.

Acid dianhydrides that can be used in the present invention include:
Since the precursor can be subjected to a ring-closing reaction at a relatively low temperature, the general formula (I) (Wherein, n represents an integer of 2 to 16), and an alkylenebistrimellitate dianhydride represented by the following formula is preferable.
Examples of such acid dianhydrides include ethylene glycol bis (trimellitic anhydride), propanediol bis (trimellitic anhydride), butanediol bis (trimellitic anhydride), pentanediol bis (trimellitic anhydride), There are hexane diol bis (trimellitic anhydride), octane diol bis (trimellitic anhydride), decane diol bis (trimellitic anhydride), hexadecane diol bis (trimellitic anhydride), and the like. More than one kind can be used in combination, and 50 to 99 mol% based on the total amount of the acid anhydride.
(Especially 50 to 98 mol%) are preferably used. When these acid dianhydrides are small, the curing temperature increases, and the curing temperature increases.
It is difficult to reach 250 ° C or less.

Other acid dianhydrides that can be used in addition to the above acid dianhydride include pyromellitic anhydride, 2,2 bis (2,3-dicarboxyphenyl) hexafluoropropane dianhydride, 3,3 ′, 4,4'-diphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,2 '2,3,3'-Diphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride 3,4,9,10-perylenetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, Naphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic Acid dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic acid Acid dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis ( 3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4 , 3 ', 4'-benzophenonetetracarboxylic dianhydride, 2,3,2', 3'-benzophenonetetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenone Tet Lacarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, decahydro Naphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic acid Dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic acid Acid dianhydride, bicyclo- (2,2,2) -oct (7) -ene-2,3,5,6-
Tetracarboxylic dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 3,4,3', 4'-biphenyltetracarboxylic dianhydride, 2,3,2 ', 3'-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) methylphenylsilane dianhydride, Bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, bis (2,3-dicarboxyphenyl) dimethylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) Benzene dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-
Tetramethyldicyclohexane dianhydride, p-phenylbis (trimellitic acid monoester anhydride), 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis [4 -(3,4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride and the like. , One or more of these are used.

These other acid dianhydrides are used as needed so that the total amount of the acid anhydride is 100 mol%.

As the diaminoamide compound represented by the general formula (II), for example, The compound shown by is used.

In the above, Y represents SO ₂ or CO. X is O, CH ₂ , S
It represents O ₂ , S, CO, etc., and one amino group and Y—NH ₂ are located at ortho positions to each other. To give a concrete example, 4,4'-
Diaminodiphenyl ether-3-sulfonamide, 3,
4'-diaminodiphenyl ether-4-sulfonamide, 3,4'-diaminodiphenyl ether-3'-sulfonamide, 3,3'-diaminodiphenyl ether-4
-Sulfonamide, 4,4'-diaminodiphenylmethane-3-sulfonamide, 3,4'-diaminodiphenylmethane-4-sulfonamide, 3,4'-diaminodiphenylmethane-3'-sulfonamide, 3,3'-diaminodiphenylmethane-4-sulfonamide, 4,4'-diaminodiphenylsulfone-3-sulfonamide, 3,4'-
Diaminodiphenylsulfone-4-sulfonamide, 3,
4'-diaminodiphenylsulfone-3'-sulfonamide, 3,3'-diaminodiphenylsulfone-4-sulfonamide, 4,4'-diaminodiphenylsulfide-3-sulfonamide, 3,4'- Diaminodiphenyl sulfide-4-sulfonamide, 3,3'-diaminodiphenyl sulfide-4-sulfonamide, 3,4'-
Diaminodiphenyl sulfide-3'-sulfonamide, 1,4-diaminobenzene-2-sulfonamide, 4,
4'-diaminodiphenyl ether-3-carbonamide, 3,4'-diaminodiphenyl ether-4-carbonamide, 3,4'-diaminodiphenyl ether-3 '
-Carbonamide, 3,3'-diaminodiphenylether-4-carbonamide, 4,4'-diaminodiphenylmethane-3-carbonamide, 3,4'-diaminodiphenylmethane-4-carbonamide, 3 4,4'-diaminodiphenylmethane-3'-carbonamide, 3,3'-diaminodiphenylmethane-4-carbonamide, 4,4'-
Diaminodiphenylsulfone-3-carbonamide, 3,
4'-diaminodiphenylsulfone-4-carbonamide, 3,4'-diaminodiphenylsulfone-3'-carbonamide, 3,3'-diaminodiphenylsulfone-4
-Carbonamide, 4,4'-diaminodiphenyl sulfide-3-carbonamide, 3,4'-diaminodiphenyl sulphide-4-carbonamide, 3,3'-diaminodiphenyl sulphide-4-carboxylic Amide, 3,
4'-diaminodiphenyl sulfide-3'-sulfonamide, 1,4-diaminobenzene-2-carbonamide and the like.

These diaminoamide compounds may be used in combination of two or more.

The amount of the diaminoamide compound used is preferably 10 to 50 mol% based on the total amount of the diaminoamide compound and the diamine. If the amount of the diaminoamide compound is too small, the effect of improving the heat resistance tends to decrease, and if it is too large, the curing temperature of the precursor obtained in the present invention tends to increase.

Examples of the diamine I include 2- (2-methacryloyloxy) ethyloxycarbonyl-4,4'-diaminodiphenyl ether and 2,2'-di- (2-methacryloyloxy) ethyloxycarbonyl-4,4'- Diaminodiphenyl ether and the like; (Where X is Or -CH ₂ -O- are shown, R ₂ is a diamine represented by an organic group containing an ethylenically unsaturated group). As the ethylenically unsaturated group represented by R ₂ in the diamine represented by the general formula (V), for example, and so on.

As the diamine represented by the general formula (V), 3,5-
Ethyl diaminobenzoate acrylic acid ester, 3,5-diaminobenzoic acid ethyl methacrylate, 3,5-diaminobenzoic acid glycidyl acrylate ester, 3,5
Glycidyl methacrylate diaminobenzoate, cinnamate 3,5-diaminobenzoate, ethyl acrylate 2,4-diaminobenzoate, ethyl methacrylate 2,4-diaminobenzoate, 2,4-diaminobenzoate Glycidyl acrylate ester, 2,4-
Glycidyl methacrylate diaminobenzoate,
Examples include 2,4-diaminobenzoic acid cinnamate, 3,5-diaminobenzyl acrylate, and 3,5-diaminobenzyl methacrylate.

The diamine I may be used in combination of two or more. The amount of the diamine I used is preferably 5 to 80 mol% based on the total amount of the diaminoamide compound and the diamine. If the amount is too small, the effect of crosslinking tends to be small.

The diami II has the general formula (VI) [However, R ₃ , R ₄ , R ₅ and R ₆ are each independently hydrogen, an alkyl group such as a methyl group, an ethyl group, an isopropyl group, a butyl group, a fluorine-substituted alkyl group, a methoxy group, an ethoxy group, a butoxy group. And other alkoxy groups or halogens (chlorine,
Bromine, fluorine or iodine), R ₃ , R ₄ , R ₅ and R ₆
At least one of them is a group other than hydrogen, and X ′ is —SO ₂ — or —S— or a bond]. In the general formula (VI), R ₃ and
Those in which at least one of the at least one and R ₅ and R ₆ of R ₄ is a group other than hydrogen are particularly preferred.

Examples of the diamine represented by the above general formula (VI) include 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3 '-Dimethoxy-4,4'-diaminodiphenylmethane, 3,3'-diethoxy-4,4'-diaminodiphenylmethane, 3,3'-difluoro-4,4'-diaminodiphenylmethane, 3, 3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dibromo-4,4'-diaminodiphenylmethane, 3,3'-di (trifluoromethyl) -4,4'-diamino Diphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenyl ether, 3,3'-diisopropyl-4,4'-diaminodiphenyl ether, 3,3'-dimethoxy-4,4'- Diaminodiphenyl ether, 3,3'-diethoxy-4,4'-diaminodiphenyl ether 3,3'-difluoro-4,4'-diaminodiphenyl ether, 3,3'-dichloro-4,4'-diaminodiphenyl ether, 3,3'-dibromo-4,4'-diaminodiphenyl ether 3,3'-di (trifluoromethyl) -4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminodiphenyl sulfone, 3,3'-dimethoxy-4,4 '-Diaminodiphenylsulfone, 3,3'-diethoxy-4,4'-diaminodiphenylsulfone, 3,3'-difluoro-4,4'-diaminodiphenylsulfone, 3,3'-dichloro-4, 4'-diaminodiphenylsulfone, 3,3'-dibromo-4,4'-diaminodiphenylsulfone, 3,3'-di (trifluoromethyl) -4,4'-diaminodiphenylsulfone, 3,3 '-Dimethyl-4,4'-diaminodiphenylpropane, 3,3'-dimethoxy 4,4'-diaminodiphenylpropane, 3,3'-diethoxy-4,4'-diaminodiphenylpropane, 3,3'-difluoro-4,4'-diaminodiphenylpropane, 3,3'-dichloro -4,4'-diaminodiphenylpropane, 3,3'-dibromo-4,4'-diaminodiphenylpropane, 3,3'-di (trifluoromethyl) -4,4'-diaminodiphenylpropane, 3,3'-dimethyl-4,4'-diaminodiphenyl sulfide, 3,3'-dimethoxy-4,4'-diaminodiphenyl sulfide, 3,3'-diethoxy-4,4'- Diaminodiphenyl sulfide, 3,3'-difluoro-4,4'-diaminodiphenyl sulfide, 3,3'-dichloro-4,4'-diaminodiphenyl sulfide, 3,3'- Dibromo-4,4'-diaminodiphenyl sulfide, 3,3'-di (trifluoromethyl) -4,4 ' -Diaminodiphenyl sulfide, 3,3'-dimethyl-4,4'-diaminodiphenylhexafluoropropane, 3,3'-dimethoxy-4,4'-diaminodiphenylhexafluoropropane, 3,3 '-Diethoxy-4,4'-diaminodiphenylhexafluoropropane,3,3'-difluoro-4,4'-diaminodiphenylhexafluoropropane,3,3'-dichloro-4,4'-diaminodiphenylhexa Fluoropropane, 3,3'-dibromo-4,4'-diaminodiphenylhexafluoropropane, 3,3'-di (trifluoromethyl) -4,4'-diaminodiphenylhexafluoropropane, 3,3 '-Dimethyl-4,4'-diaminobenzophenone,3,3'-dimethoxy-4,4'-diaminobenzophenone,3,3'-diethoxy-4,4'-diaminobenzophenone, 3,3 '-Difluo -4,4'-diaminobenzophenone, 3,3'-dichloro-4,4'-diaminobenzophenone, 3,3'-dibromo-4,4'-diaminobenzophenone, 3,3'- Di (trifluoromethyl) -4,4'-diaminobenzophenone, 3,3'-dimethylbenzidine, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3, 3 ', 5,5'-tetraisopropyl-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetramethoxy-4,4'-diaminodiphenylmethane, 3,3 ', 5 , 5'-tetraethoxy-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetrafluoro-4,4'-diaminodiphenylmethane, 3,3', 5,5'- Tetrachloro-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetrabromo-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetra (trifluoromethyl 4,4'
Diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenyl ether, 3,3', 5,5'-tetraethyl-4,4'-diaminodiphenyl ether, 3,3-5,5'-tetramethoxy-4,4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetraethoxy-4,4'-diaminodiphenyl ether, 3,3', 5,5'-tetrafluoro-4,4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetrachloro-4,4'-diaminodiphenyl ether, 3,3', 5,5 '-Tetrabromo-4,4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetra (trifluoromethyl) -4,4'-
Diaminodiphenyl ether, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylsulfone, 3,3', 5,5'-tetramethoxy-4,4'-diaminodiphenylsulfone 3,3 ', 5,5'-tetraethoxy-4,4'-diaminodiphenylsulfone, 3,3', 5,5'-tetrafluoro-4,4'-diaminodiphenylsulfone, 3,3 ', 5,5'-tetrachloro-4,4'-diaminodiphenylsulfone, 3,3', 5,5'-tetrabromo-4,4'-diaminodiphenylsulfone, 3,3 ', 5,5 '-Tetra (trifluoromethyl) -4,4'-
Diaminodiphenylsulfone, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylpropane, 3,3', 5,5'-tetramethoxy-4,4'-diaminodiphenylpropane 3,3 ', 5,5'-tetraethoxy-4,4'-diaminodiphenylpropane, 3,3', 5,5'-tetrafluoro-4,4'-diaminodiphenylpropane, 3,3 ', 5,5'-tetrachloro-4,4'-diaminodiphenylpropane, 3,3', 5,5'-tetrabromo-4,4'-diaminodiphenylpropane, 3,3 ', 5,5 '-Tetra (trifluoromethyl) -4,4'-
Diaminodiphenylpropane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylsulfide, 3,3', 5,5'-tetramethoxy-4,4'-diaminodi Phenyl sulfide, 3,3 ', 5,5'-tetraethoxy-4,4'-diaminodiphenyl sulfide, 3,3', 5,5'-tetrafluoro-4,4'-diaminodi Phenyl sulfide, 3,3 ', 5,5'-tetrachloro-4,4'-diaminodiphenyl sulfide, 3,3', 5,5'-tetrabromo-4,4'-diaminodiphen Nylsulfide, 3,3 ', 5,5'-tetra (trifluoromethyl) -4,4'-
Diaminodiphenyl sulfide, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylhexafluoropropane, 3,3', 5,5'-tetramethoxy-4,4'- Diaminodiphenylhexafluoropropane, 3,3 ', 5,5'-tetraethoxy-4,4'-diaminodiphenylhexafluoropropane, 3,3', 5,5'-tetrafluoro-4,4'- Diaminodiphenylhexafluoropropane, 3,3 ', 5,5'-tetrachloro-4,4'-diaminodiphenylhexafluoropropane, 3,3', 5,5'-tetrabromo-4,4'-diamino Diphenylhexafluoropropane, 3,3 ', 5,5'-tetra (trifluoromethyl) -4,4'-
Diaminodiphenylhexafluoropropane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminobenzophenone, 3,3', 5,5'-tetramethoxy-4,4'-diaminobenzo Phenone, 3,3 ', 5,5'-tetraethoxy-4,4'-diaminobenzophenone, 3,3', 5,5'-tetrafluoro-4,4'-diaminobenzophenone, 3 , 3 ', 5,5'-Tetrachloro-4,4'-diaminobenzophenone, 3,3', 5,5'-Tetrabromo-4,4'-diaminobenzophenone, 3,3 ', 5 , 5'-Tetra (trifluoromethyl) -4,4'-
Diaminobenzophenone, 3,3 ', 5,5'-tetraisopropyl-4,4'-diaminodiphenylmethane, 3,3'-diisopropyl-5,5'-dimethyl-4,4'-diaminodiphenyl Methane, 3,3'-diisopropyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-diisopropyl-5,5'-dimethyl-4,4'-diaminodiphenylether, 3,3'-diisopropyl-5,5'-diethyl-4,4'-diaminodiphenyl ether, 3,3'-diisopropyl-5,5'-dimethyl-4,4'-diaminodiphenylpropane, 3, 3'-diisopropyl-5,5'-dimethyl-4,4'-diaminodiphenylpropane, 3,3'-diisopropyl-5,5'-dimethyl-4,4'-diaminodiphenylsulfone, 3,3 '-Diisopropyl-5,5'-diethyl-4,4'-diaminodiphenylsulfone, Etc. There are, may be used in combination of two or more.

Diamines other than the diamine represented by the general formula (VI) II
Examples thereof include m-xylylenediamine, 2,4-diaminotoluene, and 2,6-diaminotoluene.

The diamine II is preferably used in an amount of 0.5 to 85 mol% based on the total amount of the diamine and diaminoamide compound. If it is less than 0.5 mol%, gelation may occur during the synthesis of the polyimide, and a uniform varnish may not be obtained.

Examples of the diamine that may be used in combination with the diamine I and the diamine II include 4-aminophenyl-3-aminobenzoic acid, 2,2-bis (4-aminophenyl) propane, 2,6-diaminopyridine, and bis- (4-aminophenyl) diethylsilane, bis- (4-aminophenyl) diphenylsilane, bis- (4-aminophenyl) ethylphosphoxide, bis- (4-aminophenyl) -N-butylamine, bis- (4-aminophenyl) -N -Methylamine, N- (3-aminophenyl) -4-aminobenzamide, 4-aminophenyl-3-aminobenzoic acid, 3,3'-diaminodiphenylmethane, 3,3'-diaminodiphenyl ether, 3,3 '-Diaminodiphenylsulfone, 3,3'-diaminodiphenylpropane, 3,3'-diaminodi Enylsulfide, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, 3,3'-diaminobenzophenone, 4,4'-diamino Diphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 2,4-bis (β -Amino-t-butyl) toluene, bis (p-β-amino-t-butyl-phenyl) ether, bis (p-β-methyl-γ-amino-pentyl) benzene, bis-p- (1,1- Dimethyl-5-aminopentyl) benzene, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, tetra Tylenediamine, propylenediamine, 3-methylheptamethylenediamine, 4,4'-dimethylheptamethylenediamine, 2,11-diaminododecane, 1,2-bis (3-aminopropoxy) ethane, 2,2-dimethylpropylenediamine 3-methoxy-hexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 5-methylnonamethylenediamine, 2,17-diaminoicosadecane, 1,4-diaminocyclohexane, There are 1,10-diamino-1,10-dimethyldecane, 1,12-diaminooctadecane and the like, and two or more kinds may be used in combination. Among these diamines, aromatic diamines are preferred in terms of heat resistance.

Diaminosiloxane may be appropriately used as a part of the diamine in order to enhance the adhesion of the polyimide isoindoloquinazolinedione to a silicon wafer, glass, or the like.

The diaminosiloxane is, for example, represented by the general formula (VII) (Where R 'is a divalent hydrocarbon group, R "is a monovalent hydrocarbon group, m is an integer of 1 or more, and two R'
And a plurality of R ″ s may be the same or different).

As the diaminosiloxane, specifically, And the like.

Diaminosiloxanes are described, for example, in U.S. Pat.
It is synthesized by the method described in the specification.

Two or more diaminosiloxanes can be used in combination.

The proportion of diaminosiloxane copolymerized is preferably from 0.2 to 10 mol%, particularly preferably from 0.2 to 5 mol%, based on the total amount of the above diaminoamide compound and diamine, from the viewpoint of adhesion and etching processability. %.

The diamine and diaminoamide compounds are adjusted so that their total amount is 100 mol%.

In the present invention, the polyimide isoindoloquinazolinedione precursor is obtained by using the acid anhydride and the total amount of the diaminoamide compound and the diamine in equimolar or substantially equivalent amounts, and reacting them.

This reaction is preferably performed in an organic solvent,
As the organic solvent, N-methyl-2-pyrrolidone, N,
Organic polar solvents such as N-dimethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, dimethylsulfoxide, hexamethylphosphoramide,
Preferably, the precursor is easily dissolved, and an aromatic solvent such as toluene, cresol, or phenol may be used in combination with the organic polar solvent to such an extent that the dissolution of the precursor is not hindered. 30% by weight based on the total amount of
The following is preferred.

The reaction is preferably carried out by first dissolving a diaminoamide compound and a diamine in an organic solvent, and then adding an acid dianhydride and an acid trianhydride at 80 ° C. or lower, preferably 0 to 50 ° C. As a result, the reaction proceeds quickly, and the viscosity of the reaction solution increases for removal.

Further, when the diamine II is 0.5 to 50 mol% based on the total amount of the diaminoamide compound and the diamine, particularly 0.5 to 50 mol% is preferable.
In the case of 4040 mol%, the production of the polyimide isoindoloquinazolinedione precursor is carried out by reacting an acid dianhydride with a diamine other than diamine II and a diaminoamide compound, and then reacting by adding diamine II, Further, it is preferable to react the acid trianhydride thereafter. When a diamine other than diamine II and a diaminoamide compound are used in an amount of 99.5 to 50 mol% based on the total amount of the diamine and diaminoamide compound, great care must be taken to prevent gelation during the reaction. According to this, the reaction can be easily performed without concern about gelation.

The precursor is dissolved in an organic solvent (varnish)
It is preferable to use them.

Polyimide isoindoloquinazolinedione can be obtained by subjecting the precursor to dehydration ring closure (curing). The dehydration ring closure can be performed by heat treatment at a temperature of 150 to 250 ° C, preferably 170 to 220 ° C. During this heat treatment, polymerization by the ethylenically unsaturated groups occurs, and the polyimide isoindoloquinazolinedione is further crosslinked. In this dehydration ring closure, a dehydrating agent such as acetic anhydride or phosphoric acid may be used.

The production of polyimide isoindoloquinazolinedione is
After the reaction solution containing the polyimide isoindoloquinazolinedione precursor is directly or after being concentrated or diluted (that is, after forming the body varnish), the reaction solution is applied to a silicon wafer, glass, a metal plate, or the like, and then formed. You may.

Etching of the thus obtained polyimide isoindoloquinazolinedione film can be performed by a conventional method using a well-known etching solution such as hydrazine, an ethylenediamine mixture, and tetramethylammonium hydroxide.

〔Example〕

Hereinafter, the present invention will be described with reference to examples, but the scope of the present invention is not limited by these examples.

Synthesis of acid trianhydride A In a four-necked flask equipped with a thermometer, a stirrer, and a drying tube, 84.2 g (0.4 mol) of trimellitic anhydride chloride was placed.
l) Add 600 ml of xylene and stir. When the trimellitic anhydride chloride is dissolved, 12.28 g of glycerin (0.
13mol), pyridine 31.64g (0.4mol), xylene 100ml
Is added dropwise at room temperature. After completion of the dropwise addition, stirring is continued for about 1 hour. After completion of the reaction, the obtained crystals were separated, washed with methanol and hexane, and then recrystallized with acetic anhydride to obtain trimellitate triglyceride (hereinafter, referred to as acid anhydride A).

Synthesis of acid trianhydride B In a four-necked flask equipped with a thermometer, a stirrer, and a drying tube, add 84.2 g (0.4 mol) of trimellitic anhydride chloride.
l) Add 600 ml of toluene and stir. When the trimellitic anhydride chloride was dissolved, 17.89 g (0.13 mol) of trimethylolpropane and 60.7 g (0.6 mol of triethylamine) were added.
l) was dissolved in 100 ml of tetrahydrofuran and added dropwise while cooling in an ice bath. After completion of the dropwise addition, acid trianhydride A
By performing the same operation as in the above case, 1,1,1-tris (methyl trimellitate) propane (hereinafter referred to as acid trianhydride B) was obtained.

Synthesis of acid trianhydride B In a four-necked flask equipped with a thermometer, a stirrer, and a drying tube, add 84.2 g (0.4 mol) of trimellitic anhydride chloride.
l), stir in 600ml of benzene. Once the trimellitic anhydride chloride is dissolved, trimethylolethane
A solution of 16.02 g (0.13 mol) and 63.2 g (0.8 mol) of pyridine in 200 ml of 1,4-dioxane was added dropwise at 50 ° C. After completion of the dropwise addition, the same operation as in the case of the acid trianhydride A is performed to perform 1,1,1
-Tris (methyl trimellitate) ethane (hereinafter referred to as acid trianhydride C) was obtained.

The acid anhydrides A, B and C were each confirmed to be a single component by high performance liquid chromatography. The measurement conditions are as follows.

Measurement conditions: Equipment Toyo Soda's HLC-801 type solvent tetrahydrofuran column Toyo Soda's G2000H x 1 + G3000H x 3 Flow rate 1 ml / min Example 1 Thermometer, stirring device, four-necked flask equipped with a drying tube In addition, 4,4'-diaminodiphenyl ether-3-carbonamide 47.1 g (0.20 mol), 3,5-diaminobenzoic acid ethyl methacrylate 71.3 g (0.27 mol), 3,3 ',
127.0 g (0.50 mol) of 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 7.5 g of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane (0.03m
ol), and 2500 g of N, N'-dimethylacetamide,
Stir until a homogeneous solution is obtained. The contents were cooled on ice and, at a temperature of about 5 ° C., 369.3 g (0.90 mol) of ethylene glycol bis (trimellitic anhydride) and 54.2 g (0.10 mol) of acid anhydride A
The mixture of l) was added slowly. The reaction was carried out at 5 ° C. for 5 hours to obtain a polyimide isoindoloquinazolinedione precursor.

Example 2 In a four-necked flask equipped with a thermometer, a stirrer, and a drying tube, 47.1 g (0.20 mol) of 4,4'-diaminodiphenylether-3-carbonamide, ethyl methacryl 3,5-diaminobenzoate were added. 79.2 g (0.30 mol) of acid ester, 3,3 ',
127.0 g (0.50 mol) of 5,5'-tetramethyl-4,4'-diaminodiphenylmethane and N, N-dimethylacetamide
2500 g was added and stirred until a homogeneous solution was obtained. The contents were ice-cooled, and a mixture of 369.3 g (0.90 mol) of ethylene glycol bis (trimellitic anhydride) and 54.2 g (0.10 mol) of acid anhydride A was gradually added at a temperature of about 5 ° C. 5 ℃
For 5 hours to obtain a polyimide isoindoloquinazolinedione precursor.

Comparative Example 1 In a four-necked flask equipped with a thermometer, a stirring device, and a drying tube, 71.3 g (0.27 mol) of 3,5'-diaminobenzoic acid ethyl methacrylate, 3,3 ', 5,5'-tetra 177.8 g of methyl-4,4'-diaminodiphenylmethane (0.70mo
l), 7.5 g (0.03 mol) of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane and 2500 g of N, N-dimethylacetamide are added until a homogeneous solution is obtained. Stirred. The contents were cooled on ice and, at a temperature of about 5 ° C., 369.3 g of ethylene glycol bis (trimellitic anhydride) (0.
A mixture of 90 mol) and 54.2 g (0.10 mol) of acid anhydride A was slowly added. The reaction was performed at 5 ° C. for 5 hours to obtain a polyimide resin precursor.

Example 3 In a four-necked flask equipped with a thermometer, a stirrer, and a drying tube, 35.3 g (0.15 mol) of 4,4'-diaminodiphenylether-3-carbonamide, ethyl methacryl 2,4-diaminobenzoate were placed. Acid ester 39.6g (0.15mol), 3,3 ',
5,5'-tetraisopropyl-4,4'-diaminodiphenylmethane 155.0 g (0.50 mol), 4,4'-diaminodiphenyl ether 54.0 g (0.27 mol), 1,3-bis (3-aminopropyl ) -1,1,3,3-tetramethyldisiloxane 7.5 g
(0.03 mol) and 3000 g of N, N-dimethylformamide were added and stirred until a homogeneous solution was obtained. The contents were cooled on ice and, at a temperature of about 5 ° C., 226.0 g (0.50 mol) of pentanediol bis (trimellitic anhydride), 58.9 g of 3,3 ′, 4,4′-bisphenyltetracarboxylic dianhydride (0.20 mol) and a mixture of 196.8 g (0.30 mol) of acid anhydride B were slowly added. The reaction was carried out at 5 ° C. for 5 hours to obtain a polyimide isoindoloquinazolinedione precursor.

Comparative Example 2 In a four-necked flask equipped with a thermometer, a stirring device, and a drying tube, 35.3 g (0.15 mol) of 4,4'-diaminodiphenyl ether-3-carbonamide, ethyl methacryl 2,4-diaminobenzoate were added. Acid ester 39.6g (0.15mol), 3,3 ',
5,5'-tetraisopropyl-4,4'-diaminodiphenylmethane 155.0 g (0.50 mol), 4,4'-diaminodiphenyl ether 54.0 g (0.27 mol), 1,3-bis (3-aminopropyl ) -1,1,3,3-tetramethyldisiloxane 7.5 g
(0.03 mol) and 3000 g of N, N-dimethylformamide were added and stirred until a homogeneous solution was obtained. The contents were cooled on ice, and at a temperature of about 5 ° C., 205.0 g (0.70 mol) of 3,3 ′, 4,4′-bisphenyltetracarboxylic dianhydride and acid anhydride B19
6.8 g (0.30 mol) of the mixture was also added slowly. afterwards,
The reaction was carried out at 5 ° C. for 5 hours to obtain a polyimide isoindoloquinazolinedione precursor.

Example 4 In a four-necked flask equipped with a thermometer, a stirrer, and a drying tube, 47.1 g (0.20 mol) of 4,4'-diaminodiphenylether-3-carbonamide, ethyl acryl 3,5-diaminobenzoate were added. Acid ester 125.0 g (0.5 mol), 4,4'-
33.7 g (0.17 mol) of diaminodiphenylmethane, 7.5 g (0.03 mol) of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane and 2500 g of N-methyl-2-pyrrolidone And stirred until a homogeneous solution was obtained. The content was cooled on ice, and 424.9 g (0.97 mol) of butanediol bis (trimellitic anhydride) was gradually added at a temperature of about 5 ° C. After reacting at 5 ℃ for about 2 hours, at room temperature 3,3 '
-Dimethyl-4,4'-diaminodiphenylmethane 22.6 g
(0.10mol), stir for 30 minutes, and then
12.8 g (0.02 mol) of acid anhydride C was added. The mixture was reacted at room temperature for 3 hours to obtain a polyimide isoindoloquinazolinedione precursor.

Comparative Example 3 In a four-necked flask equipped with a thermometer, a stirring device, and a drying tube, 47.1 g (0.20 mol) of 4,4'-diaminodiphenylether-3-carbonamide, 4,4'-diaminodiphenylmethane were added. 132.7 g (0.67 mol), 7.5 g of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane
(0.03 mol) and 2500 g of N-methyl-2-pyrrolidone were added and stirred until a homogeneous solution was obtained. The content was cooled on ice, and 429.9 g (0.97 mol) of butanediol bis (trimellitic anhydride) was gradually added at a temperature of about 5 ° C. 5 ℃
And then react at room temperature for 3,2'-dimethyl-4,4 '.
-Add 22.6 g (0.10 mol) of diaminodiphenylmethane and add 30
After stirring for 1 minute, acid anhydride C12.8 g (0.02
mol) was added. The mixture was reacted at room temperature for 3 hours to obtain a polyimide isoindoloquinazolinedione precursor.

Example 5 In a four-necked flask equipped with a thermometer, a stirrer, and a drying tube, 23.5 g (0.10 mol) of 4,4'-diaminodiphenylether-3-carbonamide, ethyl acryl 3,5-diaminobenzoate were placed. 200.0 g (0.80 mol) of acid ester, 7.5 g (0.03 mol) of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane and 3000 g of N, N-dimethylformamide were added. Stir until a homogeneous solution is obtained.
Next, at room temperature, a mixture of 246.0 g (0.60 mol) of ethylene glycol bis (trimellitic anhydride) and 88.4 g (0.30 mol) of 3,3 ', 4,4'-bisphenyltetracarboxylic dianhydride was gradually added. Was added. After stirring at room temperature for 3 hours,
2,5 g (0.07 mol) of 5,5'-tetraethyl-4,4'-diaminodiphenylmethane was added, stirred for 30 minutes, and then 64.6 g (0.10 mol) of acid anhydride B was added. The reaction was further performed at room temperature for 2 hours to obtain a polyimide isoindoloquinazolinedione precursor.

Example 6 In a four-necked flask equipped with a thermometer, a stirring device, and a drying tube, 23.5 g (0.10 mol) of 4,4'-diaminodiphenyl ether-3-carbonamide, ethyl acryl 3,5-diaminobenzoate were placed. Acid ester 75.0 g (0.30 mol), 3,4'-
94.0 g (0.47 mol) of diaminodiphenyl ether, 1,3-
7.5 g (0.03 mol) of bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane and 2500 g of N-methyl-2-pyrrolidone were added and stirred until a homogeneous solution was obtained. The content was cooled on ice, and at a temperature of about 5 ° C., 469.8 g (0.90 mol) of decanediol bis (trimellitic anhydride) was added and reacted for 3 hours. Thereafter, at room temperature, 3,3'-dimethyl-4,4'-diaminodiphenylmethane 22.6 g (0.10 mol)
Was added and the mixture was stirred for about 30 minutes, and then 64.2 g (0.10 mol) of acid anhydride C was added. The reaction was carried out at room temperature for 2 hours to obtain a polyimide isoindoloquinazolinedione precursor.

Comparative Example 4 In a four-necked flask equipped with a thermometer, a stirring device, and a drying tube, 23.5 g (0.10 mol) of 4,4'-diaminodiphenylether-3-carbonamide, ethyl acryl 3,5-diaminobenzoate were placed. Acid ester 75.0 g (0.30 mol), 3,3'-
Dimethyl-4,4'-diaminodiphenylmethane 22.6 g (0.
10mol), 94.0 g of 3,4'-diaminodiphenyl ether
(0.47 mol), 1,3-bis (3-aminopropyl) -1,1,1
7.5 g (0.03 mol) of 3,3-tetramethyldisiloxane and N
2500 g of -methyl-2-pyrrolidone was added and stirred until a homogeneous solution was obtained. The contents are cooled on ice and, at a temperature of about 5 ° C., 522.0 g of decanediol bis (trimellitic anhydride)
(1.00 mol) was added. The mixture was reacted at about 5 ° C. for 5 hours to obtain a polyimide isoindoloquinazolinedione precursor.

Example 7 In a four-necked flask equipped with a thermometer, a stirrer, and a drying tube, 70.6 g (0.30 mol) of 4,4'-diaminodiphenylether-3-carbonamide, ethyl methacryl 3,5-diaminobenzoate were added. 150.5 g (0.57 mol) of acid ester, 1,3-
7.5 g (0.03 mol) of bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane and 2500 g of N, N-dimethylacetamide were added and stirred until uniform. The content was ice-cooled, and at a temperature of about 5 ° C., 395.2 g (0.80 mol) of octanediol bis (trimellitic anhydride) was added and reacted for 3 hours. Thereafter, at room temperature, 3,5.4 g of 3,3'5,5'-tetramethyl-4,4'-diaminodiphenylmethane (0.10 mol
l), stir for about 30 minutes, and then
108.4 g (0.20 mol) of acid anhydride A were added. The reaction was carried out at room temperature for 2 hours to obtain a polyimide isoindoloquinazolinedione precursor.

Comparative Example 5 In a four-necked flask equipped with a thermometer, a stirrer, and a drying tube, 70.6 g (0.30 mol) of 4,4'-diaminodiphenyl ether-3-carbonamide, ethyl methacryl 3,5-diaminobenzoate were added. 176.9 g (0.67 mol) of acid ester, 1,3-
7.5 g (0.03 mol) of bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane and 2500 g of N, N-dimethylacetamide were added and stirred until uniform. The content was cooled on ice and, at a temperature of about 5 ° C., 395.2 g (0.80 mol) of octanediol (bistrimelitic anhydride) and acid anhydride A
108.4 g (0.20 mol) of the mixture was slowly added. It gelled in about 10 minutes after the addition was completed.

The polyimide isoindoloquinazolinedione precursor and the polyimide resin precursor obtained in the above Examples 1 to 7 and Comparative Examples 1 to 4 were applied to a silicon wafer by spin coating, and then 100 ° C, 150 ° C, 230 ° C (Comparative Example 100 ℃ for 2、2
(00.degree. C., 300.degree. C.) for 30 minutes each to produce a silicon wafer with a polyimide isoindoloquinazolinedione and a polyimide resin film, which was subjected to an adhesion test.

The precursor varnish was cast on a glass plate and heated under the above conditions to obtain a polyimide isoindoloquinazolinedione and polyimide resin film of about 3 μm. The obtained film was subjected to solvent resistance, thermal decomposition temperature, and mechanical property tests.

Further, the precursor varnish was subjected to measurement of a curing temperature.

 The measurement conditions are as shown below.

1) Curing temperature A polyimide isoindoloquinazolinedione precursor varnish is applied on a glass plate, immersed in distilled water to deposit a polyimide isoindoloquinazolinedione precursor film, and then cured at 80 ° C and 0.5 mmHg or less. A sample obtained by vacuum drying for a time is used as a sample, and the dehydration amount is measured at various temperatures using a high-speed differential thermal balance, and a temperature at which the dehydration amount becomes constant is determined.

2) Thermal decomposition temperature Using a thermobalance, the temperature was measured at a temperature increase of 10 ° C./min and the sample amount was about 8 mg, and the 5% weight loss temperature was defined as the thermal decomposition temperature.

3) Tensile strength and modulus of elasticity A test piece was cut to a width of 10 mm and a length of 50 mm, and the distance between fulcrums was 30 mm, the tensile speed was 5 mm / min, and the measurement temperature was room temperature using Tensilon.

4) Adhesion The test piece was tested at 121 ° C and 2 atm (in saturated steam) for 1 hour.
The samples were treated for 00 hours, and evaluated by a go-batch test according to JIS K-5400.

5) Solvent resistance The test pieces were immersed in various solvents at room temperature for 10 minutes, and the appearance was visually evaluated.

As is clear from Table 1, Example 1 is superior in adhesion to Example 2 (without using diaminosiloxane), and Examples 1 and 2 are significantly superior to Comparative Example 1 in tensile strength.
Examples 1 to 7 are significantly lower in curing temperature and elastic modulus than Comparative Example 2. Further, Examples 1 to 7 are Comparative Examples 3 (no diamine having an ethylenically unsaturated group was used) and Comparative Example 4
Excellent solvent resistance compared to (no acid trianhydride used).

〔The invention's effect〕

When the polyimide isoindoloquinazolinedione precursor obtained according to claims 1 to 8 is subjected to a ring closure reaction according to the method according to claims 9 to 10, the curing temperature can be lowered, and the obtained polyimide isoindoloquinazoline dione is obtained. Shows excellent solvent resistance, and particularly the precursor obtained by the method of claim 8 has excellent adhesion. The precursor obtained in claim 4 can further lower the curing temperature.

The polyimide isoindoloquinazolinedione obtained by the method according to claims 9 to 10 is excellent in these properties in a well-balanced manner.

────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Yasuo Miyadera 48 Tsukuba, Tsukuba, Ibaraki Pref. Hitachi Chemical Co., Ltd. Tsukuba Development Laboratory (58) Field surveyed (Int.Cl. ⁶ , DB name) C08G 73 / 10 C08G 73/14 C08G 73/06 CAS (STN) REGISTRY (STN)

Claims (6)

(57) [Claims] 1. a) General formula (IV) (Wherein, R ₁ represents a trivalent residue obtained by removing three hydroxyl groups from a compound having three hydroxyl groups in the molecule): 1 to 35 mol% of hexacarboxylic trianhydride represented by the following formula: b) general formula (I) (Wherein, n represents an integer of 2 to 16) tetracarboxylic dianhydride containing an alkylenebistrimellitate dianhydride represented by the following formula: a carboxylic anhydride containing 99 to 65 mol%; c) Any of the following diaminoamide compounds (Wherein, Y represents SO ₂ or CO, and X ″ represents O, C
H ₂ , SO ₂ , S or CO, wherein one amino group and Y—NH ₂ are located ortho to each other), and d) a general formula (V) (Where X is Or -CH ₂ -O- are shown, R ₂ is a carbon - diamine represented by a group having a carbon double bond) and e) the general formula (VI) (Wherein, R ₃ , R ₄ , R ₅ and R ₆ each independently represent hydrogen, an alkyl group, a fluorine-substituted alkyl group, an alkoxy group or a halogen, and R ₃ , R ₄ , R ₅ and R ₆ At least one of them is a group other than hydrogen, X ′ is —CH ₂ —, Or a bond containing a diamine represented by the following formula: 2. The polyimide isoindoloquinazolinedione precursor according to claim 1, wherein the alkylenebistrimellitate dianhydride represented by the general formula (I) is used in an amount of 50 to 99 mol% based on the total amount of the carboxylic anhydride. Manufacturing method. 3. An aromatic diamine (e) in an amount of 0.5 to 50 mol% based on the total amount of the diaminoamide compound (c) and the diamine, and a diamine other than the aromatic diamine (e) and the diaminoamide compound (c). After reacting the tetracarboxylic dianhydride (b) with a diamine other than the aromatic diamine (e) and the diaminoamide compound (c), the aromatic diamine (e) is The method for producing a polyimide isoindoloquinazolinedione precursor according to claim 1, wherein the precursor is added and reacted, and thereafter, hexacarboxylic trianhydride (a) is added and reacted. 4. The process for producing a polyimide isoindoloquinazolinedione precursor according to claim 1, wherein 0.2 to 10 mol% of diaminosiloxane is used based on the total amount of diaminoamide compound (c) and diamine. . 5. A polyimide isoindoloquinazolinedione prepared by the method according to claim 1, wherein the precursor is dehydrated and ring-closed. Manufacturing method. 6. The method for producing a polyimide isoindoloquinazolinedione according to claim 5, wherein the polyimide isoindoloquinazolinedione precursor is formed into a film, followed by dehydration ring closure.