JP2898674B2 - Process for producing siloxane-modified polyimide and its precursor - Google Patents

Description

The present invention relates to a siloxane-modified polyimide excellent in heat resistance and adhesiveness and a precursor thereof.

[Conventional technology]

Polyimide is used in various fields because of its excellent heat resistance. However, since it is generally used in the state of a polyamic acid as a precursor because it does not dissolve in a solvent, a high temperature of 300 ° C. or more is required for ring closure. For this reason, when used for a semiconductor, there is a problem that the reliability of the element is reduced.

Further, since the modulus of elasticity is usually as high as 300 kgf / mm ² or more, when the film is used as an interlayer insulating film or a protective film of a semiconductor, if the film thickness is large, the film peels off from the substrate due to stress.

Furthermore, polyimide resins generally have low adhesive strength to glass or silicon wafers, and are disclosed in JP-A-58-27721, JP-A-59-43026 and JP-A-63-205322 to increase the adhesive strength. As described above, a method of using diaminosiloxane for a part of the diamine component is known.

[A semester the invention seeks to solve]

However, in the method described in the above publication, although the adhesive strength of polyimide is improved, the glass transition temperature or softening point is increased as the content of diaminosiloxane is increased as shown in JP-A-63-205322. There was a problem that it dropped sharply.

The present invention solves such a problem, and provides a polyimide excellent in heat resistance as well as adhesiveness.

[Means for solving the problem]

The siloxane-modified polyimide in the invention has a general formula (I) (Wherein, R ¹ is an optionally substituted tetravalent organic group and R ² is an optionally substituted divalent organic group having no siloxane bond in the main chain) Structural unit and general formula (II) (Where R ³ is an optionally substituted tetravalent organic group, R ⁴ and R ⁷ are optionally substituted divalent organic groups, and R ⁵ and R ⁶ are optionally substituted R ⁴ and R ⁷ may be the same or different, a plurality of R ⁵ and a plurality of R ⁶ may be the same or different, and n is 1 A polyimide having the structural unit represented by the general formula (I) and not having the structural unit represented by the general formula (II) (hereinafter referred to as “comparison”). Polyimide)).

In the above general formulas (I) and (II), R ¹ , R ² , R ³ , R ⁴ ,
Examples of the substituent which may be bonded to R ⁵ , R ⁶ and R ⁷ include halogen such as fluorine and chlorine, alkyl such as methyl and ethyl, and alkoxy such as methoxy and ethoxy. , R ⁴ and R ⁷ are preferably divalent hydrocarbon groups, but may have an oxygen, nitrogen or heterocyclic ring in the main chain, and R ¹ , R ² and R 7
³ preferably contains an aromatic ring.

The siloxane-modified polyimide can be obtained, for example, by reacting a tetracarboxylic dianhydride or a derivative thereof, an aromatic diamine or an aromatic diisocyanate, and a diaminosiloxane or a diisocyanate siloxane. It can be obtained by reacting an anhydride or a derivative thereof with an aromatic diamine or an aromatic diisocyanate.

As the tetracarboxylic dianhydride, a compound represented by the general formula (A) (Wherein, in the formula, R represents a methyl group or a trifluoromethyl group, and a structure for forming a tetracarboxylic dianhydride is further bonded to each benzene ring). And more specifically, those represented by the general formula (B) (Wherein, R is the same as general formula (A), (wherein, R is the same as general formula (A), and X is
Is And p represents an integer of 1 or more. Each benzene ring may be substituted with a halogen such as fluorine or chlorine, an alkyl group such as a methyl group or an ethyl group, or an alkoxy group such as a methoxy group or an ethoxy group. Acid dianhydride represented by the general formula (C) (However, R is the same as in the general formula (A), and each benzene ring is substituted with halogen such as fluorine and chlorine, alkyl group such as methyl group and ethyl group, and alkoxy group such as methoxy group and ethoxy group. The acid dianhydride represented by the formula:

Illustrating the preferred tetracarboxylic dianhydride, Among them, 2,2-
Bis (tolylritoxyphenyl) propane anhydride is particularly preferred.

Other examples of tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride and 1,2,5,6-naphthalenetetracarboxylic dianhydride. Anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,2 ', 3,3'-diphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxy Phenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) sulphonic anhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether Anhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5 , 8-Tetracarboxylic dianhydride, 2,7-dichloronaphthalene-
1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9, 10-tetracarboxylic dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethaneni anhydride, 1,1tobis (3,4-dicarboxyphenyl) ethaneni anhydride, bis (2, 3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfoni dianhydride, benzene-1,2,3,4 -Tetracarboxylic dianhydride, 3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride, 2,3,2', 3'-benzophenonetetracarboxylic dianhydride, 2, 3,3 ', 4'-benzophenonetetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic Dianhydride, ethylene tetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexa Hydronaphthalene-1,2,5,6-tetracarboxylic dianhydride,
Cyclopentane-1,2,3,4-tetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride Compound, 1,2,3,4-butanetetracarboxylic dianhydride, dicyclo- (2,2,2) -oct (7) -ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,3 ', 4'-biphenylcarboxylic dianhydride, 3,4,3', 4'-biphenyltetracarboxylic dianhydride, 2,3,2 ', 3'-biphenyltetra Carboxylic anhydride, 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-tetramethyldisilosane dianhydride, p-phenylene-bis (trimellitic acid monoester acid anhydride), ethylene glycol Bis (trimellitic anhydride), 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, bis [4-
(3,4-Dicarboxyphenoxy) phenyl] sulfone dianhydride, 4,4 ′-(1,4-phenylene) bis (3,5,6-
Triphenylphenylphthalic anhydride), 4,4 '-(oxydi-
1,4-phenylene) bis (3,5,6-triphenylphthalic anhydride).

The tetracarboxylic dianhydride may be used in the form of its free acid (tetracarboxylic acid). The derivatives include diesters of the acid dianhydride (dimethyl ester, diethyl ester, etc.), acid chlorides and the like.

As the aromatic diamine, the aforementioned general formula (A)
The one having a structure represented by the following formula is preferable. (Wherein, R is the same as general formula (A), and q
Is an integer of 1 or more, and each benzene ring may be substituted with a halogen such as fluorine or chlorine, an alkyl group such as a methyl group or an ethyl group, or an alkoxy group such as a methoxy group or an ethoxy group. Diamine, general formula (E) (Wherein, R is the same as general formula (A), and Z
And Z 'each independently -O -, - S -, - SO 2 -,
--CH ₂ -or And r is 1 or 2, and each benzene ring may be substituted with a halogen such as fluorine or chlorine, an alkyl group such as a methyl group or an ethyl group, or an alkoxy group such as a methoxy group or an ethoxy group. A) a diamine represented by general formula (F): (Wherein, R is the same as general formula (A),
R 'represents a methyl group or a hexafluoromethyl group;
Is -SO _2- , -S-, -O-, -CH ₂ -or And Z and Z ′ are each independently —SO ₂ —, —S—, —O—, or —CH ₂ —, and each benzene ring is a halogen such as fluorine or chlorine, an alkyl group such as a methyl group or an ethyl group, a methoxy group, an ethoxy group or the like. Which may be substituted with an alkoxy group or the like).

As the diamine represented by the general formula (D), 2,2-
Bis (p-aminophenyl) propane, 2,2-bis (m
-Aminophenyl) propane, 2- (p-aminophenyl) -2- (m-aminophenyl) propane, 4,4'-
[1,4-phenylenebis (1-methylethylidene)] bisaniline, 4,4 '-[1,3-phenylenebis (1-methylethylidene)] bisaniline, 2,2-bis (4-amino-3,5-dimethylphenyl) Enyl) propane, 2,2-bis (4
-Amino-3,5-diethylphenyl) propane, 4,4'-
[1,4-phenylenebis (1-methylethylidene)] bis (2,6-dimethylaniline), 4,4 '-[1,3-phenylenebis (1-methylethylidene)] bis (2,6-dimethylaniline) , 3,3'-dimethyl-4,4'-diaminodiphenylpropane, 3,3'-diethoxy-4,4'-diaminodiphenylpropane, 3,3'-dichloro-4,4'-diaminodiphenylpropane, etc. is there.

As the aromatic diamine represented by the general formula (E),
2,2-bis [4- (4-aminophenoxy) phenyl)
Propane, 2,2-bis [4- (3-aminophenoxy)
Phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-
Bis [4- (4-aminophenylthio) phenyl) propane, 2,2-bis [4- (4-aminobenzoyl) phenyl] propane, 2,2-bis [4- (4-aminophenylsulfonyl) Phenyl) propane, 2,2-bis [4-
(4-aminophenylmethyl) phenyl] propane.

As the aromatic diamine represented by the general formula (F),
4'-bis [3- (4-amino-α, α'-dimethylbenzyl) phenoxy] diphenylsulfone, 4,4'-bis [3 (4-amino-α, α'-dimethylbenzyl) phenoxy] benzophenone , 4,4'-bis [4- (4-
Amino-α, α'-dimethylbenzyl) phenoxy] diphenylsulfone, 4,4'-bis [4 (4-amino-
α, α′-dimethylbenzyl) phenoxy] benzophenone, 4- [3- (4-amino-α, α′-dimethylbenzyl) phenoxy] -4 ′-[4- (4-amino-
α, α′-dimethylbenzyl) phenoxy] diphenylsulfone, 4- [3- (4-amino-α, α′-dimethylbenzyl) phenoxy] -4 ′-[4-amino-α,
α′-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [3- (3-amino-α, α′-dimethylbenzyl) phenoxy] diphenylsulfone,
4'-bis [3- (3-amino-αα'-dimethylbenzyl) phenoxy] benzophenone, 4,4'-bis [2
-(4-amino-α, α'-dimethylbenzyl) phenoxy] diphenylsulfone, 4,4'-bis [2- (4-
Amino-α, α′-dimethylbenzyl) phenoxy] benzophenone, 3,3′-bis [3- (4-amino-α,
α′-dimethylbenzyl) phenoxy] diphenylsulfone, 3,3′-bis [3- (4-amino-α, α′-dimethylbenzyl) phenoxy] benzophenone, 4,4 ′
-Bis [4- (4-amino-α, α'-dimethylbenzyl) phenylthio] diphenyl ether, 4,4'-bis [4- (4-amino-α, α'-dimethylbenzyl) benzoyl] diphenyl Propane, 4,4'-bis [4-
(4-amino-α, α′-dimethylbenzyl) phenylsulfone] benzophenone, 4,4′-bis [4- (4-
Amino-α, α'-di (trifluoromethyl) benzyl) phenoxy] diphenylsulfone.

Other examples of aromatic diamines include 2,2-bis (4-
Amino-phenyl) propane, 2,6-diamino-pyridine, bis- (4-amino-phenyl) diethylsilane,
Bis- (4-amino-phenyl) diphenylsilane, benzidine, 3,3'-dichloro-benzidine, 3,3'-dimethoxybenzidine, bis- (4-amino-phenyl) ethylphosphoxide, bis- (4-amino -Phenyl) -N-butylamine, bis- (4-amino-phenyl) -N-methylamine, 3,3'-dimethyl-4,4'-
Diaminodiphenyl, N- (3-aminophenyl) -4
-Aminobenzamide, 4-aminophenyl-3-aminobenzoic acid, 3,3'-dimethyl-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 3,3'-dibromo-4,4'-diaminodiphenylmethane, 3, -3'-dihydroxy-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenyl ether , 3,3'-dimethoxy-4,4 '
-Diaminodiphenyl ether, 3,3'-diethoxy-
4,4'-diaminodiphenyl ether, 3,3'-dichloro-4,4'-diaminodiphenyl ether, 3,3'-dihydroxy-4,4'-diaminodiphenyl ether, 3,3'-
Dimethyl-4,4'-diaminodiphenylsulfone, 3,3 '
-Dimethoxy-4,4'-diaminodiphenylsulfone,
3,3'-diethoxy-4,4'-diaminodiphenylsulfone, 3,3'-dichloro-4,4'-diaminodiphenylsulfone, 3,3'-dihydroxy-4,4'-diaminodiphenylsulfone 3,3'-dimethyl-4,4'-diaminodiphenyl sulfide, 3,3'-dimethoxy-4,4'-diaminodiphenyl sulfide, 3,3'-diethoxy-4,4 '
-Diaminodiphenyl sulfide, 3,3'-dichloro-4,4'-diaminodiphenyl sulfide, 3,3'-dihydroxy-4,4'-diaminodiphenyl sulfide, 3,3 ' -Diaminodiphenylmethane, 3,3'-diaminodiphenylether, 3,3'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfide, 3,
3'-diaminobenzophenone, 2,4-diaminotoluene, 2,6-diaminotoluene, paraphenylenediamine, meta-phenylenediamine, 4,4'-diamino-diphenylmethane, 4,4'-diamino-di Phenyl sulfide, 4,4'-diamino-diphenyl sulfone, 4,4'-diamino-diphenyl ether, 3,4'-diamino-diphenyl ether, 1,5-diamino-naphthalene, 3,3 '
-Dimethoxyvezidine, 2,4-bis (beta-amino-
t-butyl) toluene, bis- (para-beta-amino-t-butyl-phenyl) ether, bis- (para-beta-methyl-delta-amino-pentyl) benzene,
Bis-parlor- (1,1-dimethyl-5-amino-pentyl) benzene, 1-isopropyl-2,4-metaphenylenediamine, m-xylenediamine and the like. As the diamine, an aliphatic diamine may be used. As the aliphatic diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, diamino-propyltetramethylene diamine, 3-amino diamine Methylheptamethylenediamine, 4,4'-dimethylheptamethylenediamine, 2,11-diamino-dodecane, 1,2-bis- (3-amino-propoxy) ethane, 2,2-dimethyl-propylenediamine, 8-methoxy -Hexamethylenediamine,
3,3′-dimethylbenzidine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylbutamethylenediamine,
5-methyl-nonamethylenediamine, 2,17-diamino-
Eicosadecane, 1,4-diamino-cyclohexane, 1,1
There are 0-diamino-1,10-dimethyldecane, 1,12-diamino-octadecane and the like.

The diaminosiloxane has a general formula (G) (Wherein, R ⁴ , R ⁵ , R ⁶ , R ⁷ and n represent the general formula (II)
Are the same as described above). In particular, Etc. However, in the above formulas (a) to (f), m is a number in the range of 1 to 100, and is preferably 1 or more and 40 or less on average from the viewpoint of improving the adhesiveness. Among the diaminosiloxanes, in the above formula (a), m is 1, about 10 on average, about 20 on average, about 30 on average, about 50 on average, and about 100 on average, respectively. LP-7100, X-22-161AS, X-22-1-61A, X-22-161B, X-22-
It is commercially available as 161C and X-22-161E (both are brand names of Shin-Etsu Chemical Co., Ltd.). One or more of these diaminosiloxanes can be used.

As the diamine and the diaminosiloxane, a corresponding diisocyanate in which an amino group is replaced with an isocyanate group may be used instead. The diisocyanate corresponding to diaminosiloxane is called diisocyanate siloxane.

Diaminosiloxane or diisocyanate siloxane is not particularly limited as long as the softening point of the siloxane-modified polyimide is used in a range that is higher than the softening point of the comparative polyimide, but is preferably a diamine component or a diisocyanate. It is used in an amount of 30% by weight or less based on the whole components.

In the present invention, polyimide can be produced as follows. When diamines are used as a partner for the reaction of the acid dianhydride, they are used in an organic solvent, if necessary, in the presence of a catalyst such as tributylamine, triethylamine, or triphenyl phosphite, at 100 ° C or higher, preferably 180 ° C or higher. To imidization to directly obtain a polyimide (catalyst is 0 to 10
It is preferably used in an amount of 15% by weight, particularly preferably 0.01 to 15% by weight), and a polyamic acid (partially ring-closed) as a polyimide precursor by reacting an acid dianhydride and a diamine in an organic solvent at less than 100 ° C. Varnish which may be imidized), and then the varnish is heated for imidization, or acid anhydrides such as acetic anhydride, propionic anhydride and benzoic anhydride, dicyclohexylcarbodiimide and the like. A method of adding a ring-closing agent such as carbodiimide and, if necessary, a ring-closing catalyst such as pyridine, isoquinoline, trimethylamine, aminopyridine, imidazole and the like to chemically ring-close (imidize) (the ring-closing agent and the ring-closing catalyst are acid anhydride 1 It is preferably used within a range of 1 to 8 moles based on the moles).

As the organic solvent, N-methyl-pyrrolidone, N,
Aprotic polar solvents such as N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, sulfolane, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidone, tetrahydrofuran, diglyme, triglyme, monoglyme, dioxane, etc. Ether solvents and the like.

These solvents include phenol, cresol, xylenol, p-chlorophenol, benzene, toluene, xylene, methyl ethyl ketone, acetone, methyl cellosolve, cellosolve acetate, methanol, ethanol,
Solvents such as isopropanol, methylene chloride, chloroform, trichlene, tetrachloroethane and the like can be mixed and used.

In the production of the above-mentioned polyimide and polyamic acid which is a precursor thereof, a solid-phase reaction, a melting reaction at 300 ° C. or lower, and the like can be optionally used.

When diisocyanate is used as a reaction partner of the acid dianhydride, the reaction can be carried out according to the above-described method for directly obtaining a polyimide. However, it is sufficient that the reaction temperature is at least room temperature, especially at least 60 ° C.

In the present invention, the acid dianhydride and its reaction partner are preferably used in approximately equimolar amounts, but an excess amount of any one is allowed to be 10 mol%, particularly preferably up to 5 mol%.

Above, the same can be carried out using a derivative of tetracarboxylic dianhydride. In this case, a corresponding polyimide precursor can be produced.

The siloxane-modified polyimide in the present invention has a higher softening point than the comparative polyimide.In this case, the comparative polyimide to be compared is obtained by removing diaminosiloxane or diisocyanate siloxane from the diamine component or diisocyanate compound component of the siloxane-modified polyimide. Except for this, it is obtained by reacting under the same conditions as the siloxane-displaced polyimide. However,
In the production of the comparative polyimide, the ratio of the diamine component containing no diaminosiloxane or diisocyanate siloxane or the ratio of the total amount of the diisocyanate compound component to the total amount of the acid anhydride component (mol%) is as follows. The same proportion (mol%) of the entire component or diisocyanate compound component to the entire acid anhydride component is used.

The siloxane-modified polyimide according to the present invention comprises, as a main acid component, an acid dianhydride having a structure represented by the general formula (A) therein and / or a diamine siloxane other than diaminosiloxane or diisocyanate siloxane as a main diamine component. When a diamine having a structure represented by the following formula or a diisocyanate corresponding to the diamine is contained as a constituent component, the diamine is preferably soluble in the organic solvent as described above. The siloxane-modified polyimide soluble in the organic solvent is not limited to such, but such siloxane-modified polyimide has a reduced viscosity (resin concentration, 0.1%).
1g / dl, solvent dimethylformamide, measurement temperature 30 ℃)
It is preferably at least 0.1 dl / g, particularly preferably at least 0.3 dl / g. If this is too small, the film-forming properties tend to decrease.

The siloxane-modified polyimide in the present invention tends to have a higher embedding rate than the comparative polyimide.

[Wherein, R ⁸ and R ⁹ each independently represent hydrogen or an alkyl group, and R ¹ and R ² are the same as in the general formula (I)] and the general formula (IV) [Wherein, R ₁₀ and R ₁₁ each independently represent hydrogen or an alkyl group, and R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and n are the same as in the general formula (II)]. Has units.

The precursor of the siloxane-modified polyimide in the present invention refers to the above-mentioned polyimide precursor and its partially ring-closed imidized product. Polyimide precursors obtained without the use of diaminosiloxanes and diisocyanatesiloxanes are similarly defined.

The precursor of the siloxane-modified polyimide is soluble in the organic solvent as described above, and has a reduced viscosity (resin concentration of 0.1 g / d).
l, solvent dimethylformamide, measurement temperature 30 ℃) 0.1dl
/ g or more, particularly preferably 0.3 dl / g or more. If the reduced particle size is too small, the film-forming property tends to decrease.

The siloxane-modified polyimide in the present invention is useful for molding materials for extrusion molding, injection molding, transfer molding, etc., adhesives, protective films for semiconductors, and the like. Available in condition. The siloxane-modified polyimide can be produced from the above-mentioned precursor as appropriate and used for testing, and the precursor can be used in a varnish-like or film-like state. In the above, when the varnish is formed, it is dissolved in the organic solvent as described above.

〔Example〕

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these ranges.

Example 1 In a four-necked flask equipped with a stirrer, a thermometer, a calcium chloride tube, and a nitrogen gas inlet tube, 4,4 '-[1,4-phenylenebis (1-methylethylidene)] bisaniline (BAP) was placed.
3.10 g, 1.72 g of X-22-161A (where m in the formula (a) is 19 on average), 30 g of tetrahydrofuran (THF), and 5 g of dimethylformamide (DMF) as a diaminosiloxane were added and uniformly dissolved. After adding 5.76 g of 2,2'-bis (trimellitoxyphenyl) propane dianhydride (BPA-TMA) little by little at room temperature, the mixture was reacted at room temperature for 2 hours to obtain a polyamic acid varnish. Substantially no unreacted monomer was present.
This polyamic acid had a reduced viscosity (resin concentration of 0.1 g / dl, solvent DMF, measurement temperature of 30 ° C., the same applies hereinafter) of 0.52 dl / g. 2.6 g of acetic anhydride and 2.0 g of pyridine were added to the polyamic acid varnish and reacted at room temperature for 3 hours to obtain a polyimide varnish. This polyimide varnish is reprecipitated from ethanol,
It was pulverized and dried to obtain a polyimide powder. This polyimide had a reduced viscosity of 0.45 dl / g and was soluble in THF and dioxane. The softening point (load 25kgf / cm ² , heating rate 1
0 ° C / min, measured by the penetration method;
℃, 5% weight loss temperature [Td, measured at a heating rate of 10 ° C / min (in air). same as below. ] At 395 ° C. The elastic modulus of a 25-μm-thick film produced from a varnish obtained by dissolving the polyimide powder in dioxane was 150 kgf / mm ² .
No adhesion was observed when the adhesion of the coating film applied on a glass slope and dried at 200 ° C. for 1 hour was measured by a burdock test. The evaluation of the lumping test was performed based on the number of peeled squares with respect to 25 squares in total.

Examples 2 to 3 and Comparative Examples 1 to 4 Polyimides were obtained in the same manner as in Example 1 except that the amounts of BAP and X-22-161A were changed as shown in Table 1. The characteristics are shown in Table 1 together with the results of Example 1.

The siloxane-modified polyimides obtained in Examples 1 to 3 and the polyimide acid as a precursor thereof are represented by the general formulas (I) to (IV) in which R ¹ and R ³ have the formulas And R ² is In it R ⁴ and R ⁷ are CH _{2 3,} R ⁵ and R ⁶ is a methyl group, n is an average 19, the general formula (III) and (IV)
Wherein R ⁸ , R ⁹ , R ₁₀ and R ₁₁ are hydrogen.

Working breed 4, Comparative Examples 5-7 Instead of X-22-161A as diaminosiloxane, X-22-
161E (m in the above formula (a) is 94 on average), X-22-161AS
(Where m in the formula (a) is an average of 8), X-22-161B (where m in the formula (a) is an average of 38), and X-22-161C (where m in the formula (a) is an average) 45), and a polyimide was obtained in the same manner as in Example 1 except that the amounts of these polysiloxane and BAP were changed as shown in Table 2. Table 2 shows the characteristics.

The siloxane-modified polyimide and its precursor obtained in Example 4 have similar structural units, but differ in the ratio and n in the general formulas (II) and (IV).

The infrared absorption spectra of the siloxane-modified polyimide and the polyimide (comparative polyimide) obtained in Examples 1 to 4 and Comparative Example 1 are shown in FIGS. First to first
In FIG. 4, the absorption at 800 cm ⁻¹ is absorption based on dimethylsiloxane, and the sharp absorption at about 1800 cm ⁻¹ is absorption based on imide ring.

〔The invention's effect〕

The siloxane-modified polyimide according to claims 1, 3 and 4, and the polyimide obtained by imidizing the siloxane-displaced polyimide precursor according to claims 2, 5 and 6 have excellent heat resistance and adhesiveness.

[Brief description of the drawings]

1 is an infrared absorption spectrum of the siloxane-modified polyimide obtained in Example 1, FIG. 2 is an infrared absorption spectrum of the siloxane-modified polyimide obtained in Example 2, FIG.
FIG. 4 shows the infrared absorption spectrum of the siloxane-modified polyimide obtained in Example 3; FIG. 4 shows the infrared absorption spectrum of the siloxane-modified polyimide obtained in Example 4;
The figure shows the infrared absorption spectrum of the polyimide obtained in Comparative Example 1.

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Yasuo Miyadera No.48, Wadai, Tsukuba, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Tsukuba Development Laboratory Co., Ltd. (56) References 57-29030 (JP, A) JP-A-58-72924 (JP, A) JP-A-59-219330 (JP, A) JP-A-58-188053 (JP, A) JP-A-60-177660 (JP, A A) JP-A-61-42573 (JP, A) JP-A-61-118424 (JP, A) JP-A-63-260924 (JP, A) JP-A-63-317554 (JP, A) JP-A-64 JP-A-31124 (JP, A) JP-A-64-56731 (JP, A) JP-A-1-121325 (JP, A) JP-A-2-91124 (JP, A) JP-A-2-91125 (JP, A) JP-A-2-140232 (JP, A) JP-A-2-208321 (JP, A) JP-B-43-27439 (JP B1)

Claims (1)

(57) [Claims] (A) General formula (1) (Wherein, R represents a methyl group or a trifluoromethyl group, X represents —C (） O) —O— or —O—,
p represents an integer of 1 or more, and each benzene ring is halogen,
Which may be substituted with an alkyl group or an alkoxy group) or a general formula (2) (Wherein, R represents a methyl group or a trifluoromethyl group, and each benzene ring may be substituted with a halogen, an alkyl group, or an alkoxy group). Dianhydride, (B) general formula (3) (Wherein, R represents a methyl group or a trifluoromethyl group, q represents an integer of 1 or more, and each benzene ring is
Which may be substituted with a halogen, an alkyl group or an alkoxy group) or a general formula (4) (Wherein, R and R ′ each independently represent a methyl group or a trifluoromethyl group, and Y represents —C (＝ O)
_{-, - SO 2 -, -} S -, - O -, - CH 2 - or -C (CH _{2) 2}
And Z and Z ′ each independently represent —C (＝ O) —, —SO ₂ —, —S—, —O— or —CH ₂ , and each benzene ring is a halogen, an alkyl group, an alkoxy group. Diamine (including the corresponding diisocyanate) selected from diamines represented by the following general formulas (5): (Wherein, R ⁴ and R ⁷ represent a divalent organic group which may have a substituent, and R ⁵ and R ⁶ represent a monovalent hydrocarbon group which may have a substituent. , R ⁴ and R ⁷ may be the same or different, and a plurality of R ⁵ and a plurality
R ⁶ may be the same as or different from each other, and n is an integer of 1 or more), and reacts a diaminosiloxane (including a corresponding diisocyanate) represented by the following general formula (A): From a polyimide (comparative polyimide) obtained by reacting an acid dianhydride selected from the acid dianhydrides of (2) and (B) a diamine selected from diamines of the general formula (3) or (4) A method for producing a siloxane-modified polyimide having a high softening point.