JP2001323174A - Resin composition and semiconductor device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition that can give a resin coating film having high strength and having excellent flexibility and excellent heat resistance in a single step of drying a solvent, not accompanied with an imidization step and provide a good semiconductor device using the resin composition. SOLUTION: The resin composition comprises a resin (A) and a resin (B) as given below and an organic solvent: (A) an aromatic thermoplastic resin that is soluble in a polar solvent at room temperature and (B) an aromatic thermoplastic resin that is insoluble in a polar solvent at room temperature but is soluble therein by heating.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition having excellent adhesion, heat resistance and flexibility, and a semiconductor device using the same.

[0002]

2. Description of the Related Art In recent years, polyimide, polyamide imide or polyamide resins having excellent heat resistance and mechanical properties have been developed.
In the field of electronics, it is widely used as a surface protective film and an interlayer insulating film of a semiconductor device. Recently, screen printing and dispensing have attracted attention as a method for producing these surface protective films and interlayer insulating films. Examples of a material that enables screen printing include a paste obtained by dispersing a filler in a varnish such as a heat-resistant polyimide resin as a binder. The filler of this material has the effect of imparting thixotropic properties to the paste. As the filler, there is a method using silica fine particles or heat-resistant insoluble polyimide fine particles. However, these have problems that many voids and air bubbles remain at the filler interface at the time of heating and drying, and the film strength is low. In order to solve these problems, a heat-resistant resin paste described in JP-A-2-289646 has been developed. This is a paste in which a filler of polyamic acid is dispersed in a binder of polyamic acid, and the filler is first dissolved during heating and drying, then compatible with the binder, and becomes a uniform coating film during film formation. .
However, since an imidization step is required, 30
Curing conditions of 0 ° C. or higher are required. In addition, there is a problem that the elastic modulus is high and the flexibility is inferior. Further, other polyimide pastes have the same problem.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a coating film having the same resin properties as polyimide, without the imidation step, and only by a step under drying conditions of 250 ° C. or less. And a resin composition capable of obtaining a coating film having excellent flexibility, and a semiconductor device using the same.

[0004]

The present invention relates to a resin composition containing the following resin (A), resin (B) and an organic solvent, and a semiconductor device using the same. (A) Aromatic thermoplastic resin soluble in polar solvent at room temperature (B) Aromatic thermoplastic resin insoluble in polar solvent at room temperature but soluble by heating

In the present invention, the resin (A) and the resin (B) are preferably the following resins. (A) Polyetheramideimide or polyetheramide soluble in polar solvents at room temperature (B) Polyetheramideimide, polyetheramide or polyether insoluble in polar solvents at room temperature but soluble by heating Imide

In the present invention, the resin (A) is preferably obtained by reacting the following components (1), (2) and (3), or (1) and (3). (1) An aromatic diamine compound represented by the following general formula (I)

Embedded image Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkoxyl group having 1 to 9 carbon atoms or a halogen atom. X is a single bond,
-O -, - S -, - C (= O) -, - SO 2 -, - S (= O) - or of 13 represents a group represented by may be different for each repeating unit. ]

Embedded image Wherein R ₅ and R ₆ each independently represent a hydrogen atom,
It represents an alkyl group, a trifluoromethyl group, a trichloromethyl group, a halogen atom or a phenyl group. (2) Diamine compound comprising the following components (a) and / or (b) (a) Aromatic diamine compound other than general formula (I) (b) Aliphatic or alicyclic diamine compound (3) (C) Dicarboxylic acid or its reactive acid derivative (d) Tricarboxylic acid or its reactive acid derivative

In the present invention, when the resin (B) is polyetheramideimide or polyetheramide, the following components (1), (2) and (3), or (1) and (3) ) Is preferred. (1) An aromatic diamine compound represented by the following general formula (I)

Embedded image Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkoxyl group having 1 to 9 carbon atoms or a halogen atom. X is a single bond,
-O -, - S -, - C (= O) -, - SO 2 -, - S (= O) - or of a group represented by 15, it may be different for each repeating unit. ]

Embedded image Wherein R ₅ and R ₆ each independently represent a hydrogen atom,
It represents an alkyl group, a trifluoromethyl group, a trichloromethyl group, a halogen atom or a phenyl group. (2) Diamine compound comprising the following components (a) and / or (b) (a) Aromatic diamine compound other than general formula (I) (b) Aliphatic or alicyclic diamine compound (3) And (c) a dicarboxylic acid or a reaction thereof, comprising an acid compound comprising the components (c) and / or (d) of the formula (1) and a tetracarboxylic dianhydride represented by the following general formula (II) or a reactive acid derivative thereof: (D) Tricarboxylic acid or its reactive acid derivative

Embedded image Wherein Y is a single bond, -O-, -S-, -C (= O)-, -SO
_2- , -S (= O)-, a group represented by Chemical formula 17, or a divalent aromatic hydrocarbon group, an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, which differs for each repeating unit. You may. ]

Embedded image Wherein R ₅ and R ₆ each independently represent a hydrogen atom,
It represents an alkyl group, a trifluoromethyl group, a trichloromethyl group, a halogen atom or a phenyl group. In the present invention, when the resin (B) is a polyetherimide, the following components (1), (2) and (3):
Alternatively, a resin obtained by reacting (1) and (3) is preferable. (1) An aromatic diamine compound represented by the following general formula (I)

Embedded image Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkoxyl group having 1 to 9 carbon atoms or a halogen atom. X is a single bond,
-O -, - S -, - C (= O) -, - SO 2 -, - S (= O) - or a group represented by Formula 19, may be different for each repeating unit. ]

Embedded image Wherein R ₅ and R ₆ each independently represent a hydrogen atom,
It represents an alkyl group, a trifluoromethyl group, a trichloromethyl group, a halogen atom or a phenyl group. (2) Diamine compound comprising the following components (a) and / or (b) (a) Aromatic diamine compound other than general formula (I) (b) Aliphatic or alicyclic diamine compound (3) Compound comprising tetracarboxylic dianhydride represented by the general formula (II) or a reactive acid derivative thereof

Embedded image Wherein Y is a single bond, -O-, -S-, -C (= O)-, -SO
_2- , -S (= O)-, a group represented by Chemical formula 21, or a divalent aromatic hydrocarbon group, an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, which differs for each repeating unit. You may. ]

Embedded image Wherein R ₅ and R ₆ each independently represent a hydrogen atom,
It represents an alkyl group, a trifluoromethyl group, a trichloromethyl group, a halogen atom or a phenyl group. ]

In the present invention, the aliphatic or alicyclic diamine compound (b) preferably contains a diaminosiloxane represented by the following general formula (III).

Embedded image Wherein R ₇ and R ₈ are a divalent hydrocarbon group, R ₉ to R ₁₂ are an alkyl group having 1 to 9 carbon atoms, a phenylene group or a phenylene group substituted with an alkyl group, and n is an integer of 1 to 30. Represents ]

In the present invention, it is preferable to contain a low elasticity filler having rubber elasticity or a liquid rubber.

In the present invention, it is preferable that a low elasticity filler having rubber elasticity whose surface is chemically modified is contained.

In the present invention, it is preferable that the surface of the low elasticity filler is chemically modified with an epoxy group.

In the present invention, the average particle diameter of the low elasticity filler is preferably 0.1 to 50 μm.

In the present invention, the elastic modulus at 25 ° C. can be arbitrarily controlled within the range of 0.2 to 30 GPa GPa, and the elastic modulus at 150 ° C. is 10 to 100% of the elastic modulus at −65 ° C. Is preferably within the range.

In the present invention, the glass transition temperature (T
g) is preferably 180 ° C. or higher, and the thermal decomposition temperature is preferably 300 ° C. or higher.

In the present invention, the viscosity is 1 to 1000 P
It is preferable that it is within the range of a · S, has a thixotropy coefficient of 1.2 or more, and can form a precise pattern.

[0016]

Next, the resin composition of the present invention and a semiconductor device using the same will be described in detail.

An object of the present invention is to provide a high strength and low elastic modulus,
An object of the present invention is to provide a resin composition which can obtain a film having excellent flexibility without performing an imidization step and only by a solvent drying step at 250 ° C. or lower.

Another object of the present invention is to provide an aromatic thermoplastic resin which is insoluble in a polar solvent at ordinary temperature but which is soluble by heating to impart a thixotropy of the resin composition to screen printing, dispense coating, etc. Accordingly, an object of the present invention is to provide a resin composition capable of forming a precise pattern.

The polar solvent in the present invention is not particularly limited as long as it is a solvent composed of polar molecules. For example, it dissociates and easily releases protons (H +) such as alcohols and carboxylic acids. Examples thereof include a protic solvent and an aprotic solvent that does not generate a proton (H +) upon dissociation. Preferably, acetonitrile, dimethoxyethane, dimethylformamide (DMF), dimethylsulfoxide (DMSO), hexamethylphosphoric triamide (HM
Aprotic solvents such as PA), N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc) and γ-butyrolactone, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether , Triethylene glycol diethyl ether, triethylene glycol dipropyl ether, triethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dipropyl ether, tetraethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ate And ethers such as diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, and tetraethylene glycol monoethyl ether.

The room temperature in the present invention refers to a temperature condition in the case of processing without specifying or adjusting the temperature or in the case where a sample or a substance is left in a room, and is not particularly limited. , A temperature in the range of 10 to 40 ° C is preferred. Heating refers to raising the temperature to room temperature or higher, and is not particularly limited to temperature, but it is preferable to raise the temperature to 50 ° C or higher.

The polyether amide imide or polyether amide in the present invention is preferably a resin containing, as a repeating unit, an ether group of the following formula (23) and an amide or imide group of the formula (24), (25) or (26).

Embedded image

Embedded image [Here, Z ₁ represents a trivalent aromatic hydrocarbon group, an aliphatic hydrocarbon group, or an alicyclic hydrocarbon group. ]

Embedded image [Here, Z ₂ represents a divalent aromatic hydrocarbon group, an aliphatic hydrocarbon group, or an alicyclic hydrocarbon group. ]

Embedded image [Here, Z ₃ represents a tetravalent aromatic hydrocarbon group, an aliphatic hydrocarbon group, or an alicyclic hydrocarbon group. As the polyetherimide in the present invention, a resin containing an ether group represented by the following chemical formula 27 and an imide group represented by the following chemical formula 28 as a repeating unit is preferable.

Embedded image

Embedded image [Here, Z ₃ represents a tetravalent aromatic hydrocarbon group, an aliphatic hydrocarbon group, or an alicyclic hydrocarbon group. ]

The aromatic diamine compound having an ether bond represented by the general formula (I) in the present invention includes, for example, 2,2-bis [4- (4-aminophenoxy)
Phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane, 2,2- Bis [4- (4-aminophenoxy) phenyl] butane, 2,2-bis [3-methyl-4- (4
-Aminophenoxy) phenyl] butane, 2,2-bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] butane, 2,2-bis [3,5-dibromo-4- (4-amino Phenoxy) phenyl] butane, 1,1,1,3,3,3-hexafluoro-2,2-bis [4- (4-aminophenoxy)
Phenyl) propane, 1,1,1,3,3,3-hexafluoro-
2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane, 1,1-bis [4- (4-aminophenoxy) phenyl] cyclohexane, 1,1-bis [4- (4
-Aminophenoxy) phenyl] cyclopentane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] ether,
4,4′-carbonylbis (p-phenyleneoxy) dianiline, 4,4′-bis (4-aminophenoxy) biphenyl, and the like, among which 2,2-bis [4- (4
-Aminophenoxy) phenyl] propane is preferred.
If necessary, two or more aromatic diamine compounds can be used in combination.

In the present invention, the aromatic diamine compound represented by the general formula (I) is used based on the total amount of the diamine component.
It is preferably from 0.1 to 99.9 mol%, more preferably from 15 to 99.9 mol%, even more preferably from 30 to 99.9 mol%.

In the present invention, examples of the aromatic diamine compound represented by other than the general formula (I) include m-phenylenediamine, p-phenylenediamine, diamino-m-xylylene, diamino-p-xylylene, 4−
Naphthalenediamine, 2,6-naphthalenediamine, 2,7-
Naphthalenediamine, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylether, 3,3'-diaminodiphenylether, 3,4 ' -Diaminodiphenyl ether, 3,4'-diaminobiphenyl,
4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, o-tolidine, 2,4-tolylenediamine, 1,3
-Bis- (3-aminophenoxy) benzene, 1,4-bis- (3-aminophenoxy) benzene, 1,3-bis- (4
-Aminophenoxy) benzene, 1,4-bis- (4-aminophenoxy) benzene, bis- [4- (3-aminophenoxy) phenyl] sulfone, 4,4'-bis- (4-aminophenoxy) biphenyl, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 3,4 '
-Diaminodiphenyl sulfide, 2,2-bis (4-aminophenyl) -propane, 2,2-bis (4-aminophenyl) -hexafluoropropane, 2,2-bis (3-amino-
4-methylphenyl) propane, 2,2-bis (3-amino-4
-Methylphenyl) hexafluoropropane, 2,2'-dimethyl-benzidine, 2,2'-bis (trifluoromethyl)
-Benzidine, 4,4'-diamino-3,3 ', 5,5'-tetramethyldiphenylmethane, 4,4'-diamino-3,3', 5,5'-tetraethyldiphenylmethane, 4,4'-diamino -3,3 ', 5,5'-tetra-n-propyldiphenylmethane, 4,4'-diamino-3,
3 ', 5,5'-tetraisopropyldiphenylmethane, 4,4'-
Diamino-3,3 ', 5,5'-tetrabutyldiphenylmethane,
4,4'-diamino-3,3'-dimethyl-5,5'-diethyldiphenylmethane, 4,4'-diamino-3,3'-dimethyl-5,5'-diisopropyldiphenylmethane, 4,4'-diamino -3,3'-diethyl-5,5'-diisopropyldiphenylmethane, 4,4'-diamino-3,5-dimethyl-3 ', 5'-diethyldiphenylmethane, 4,4'-diamino-3,5-dimethyl -3 ', 5'-diisopropyldiphenylmethane, 4,4'-diamino-3,5-diethyl-3',
5'-diisopropyldiphenylmethane, 4,4'-diamino-
3,5-diethyl-3 ', 5'-dibutyldiphenylmethane, 4,4'-
Diamino-3,5-diisopropyl-3 ', 5'-dibutyldiphenylmethane, 4,4'-diamino-3,3'-diisopropyl-5,5'-
Dibutyldiphenylmethane, 4,4'-diamino-3,3'-dimethyl-5,5'-dibutyldiphenylmethane, 4,4'-diamino-
3,3'-diethyl-5,5'-dibutyldiphenylmethane, 4,4'-
Diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diamino-
3,3'-di-n-propyldiphenylmethane, 4,4'-diamino-
3,3'-diisopropyldiphenylmethane, 4,4'-diamino
-3,3'-dibutyldiphenylmethane, 4,4'-diamino-3,
3 ', 5-trimethyldiphenylmethane, 4,4'-diamino-3,
3 ', 5-triethyldiphenylmethane, 4,4'-diamino-3,
3 ', 5-tri-n-propyldiphenylmethane, 4,4'-diamino
-3,3 ', 5-triisopropyldiphenylmethane, 4,4'-diamino-3,3', 5-tributyldiphenylmethane, 4,4'-diamino-3-methyl-3'-ethyldiphenylmethane, 4,4 '-Diamino-3-methyl-3'-isopropyldiphenylmethane,
4,4'-diamino-3-ethyl-3'-isopropyldiphenylmethane, 4,4'-diamino-3-ethyl-3'-butyldiphenylmethane, 4,4'-diamino-3-isopropyl-3'-butyldiphenylmethane 4,4'-diamino-2,2'-bis (3,3 ', 5,5'-tetramethyldiphenyl) isopropane, 4,4'-diamino-2,
2'-bis (3,3 ', 5,5'-tetraethyldiphenyl) isopropane, 4,4'-diamino-2,2'-bis (3,3', 5,5'-tetran-propyldiphenyl ) Isopropane, 4,4'-diamino-2,2'-
Bis (3,3 ′, 5,5′-tetraisopropyldiphenyl) isopropane, 4,4′-diamino-2,2′-bis (3,3 ′, 5,5′-tetrabutyldiphenyl) isopropane, 4,4'-diamino-3,3 ', 5,
5'-tetramethyldiphenyl ether, 4,4'-diamino-
3,3 ', 5,5'-tetraethyl diphenyl ether, 4,4'-diamino-3,3', 5,5'-tetra-n-propyldiphenyl ether, 4,4'-diamino-3,3 ', 5, 5'-tetraisopropyldiphenylether, 4,4'-diamino-3,3 ', 5,5'-tetrabutyldiphenylether, 4,4'-diamino-3,3', 5,5'-tetramethyldiphenylsulfone, 4,4'-diamino-3,3 ', 5,
5'-tetraethyldiphenylsulfone, 4,4'-diamino-
3,3 ', 5,5'-tetra n-propyldiphenyl sulfone, 4,4'
-Diamino-3,3 ', 5,5'-tetraisopropyldiphenylsulfone, 4,4'-diamino-3,3', 5,5'-tetrabutyldiphenylsulfone, 4,4'-diamino-3,3 ', 5,5'-tetramethyldiphenylketone, 4,4'-diamino-3,3', 5,5'-tetraethyldiphenylketone, 4,4'-diamino-3,3 ', 5,5'- Tetra n-propyldiphenyl ketone, 4,4'-diamino-3,3 ',
5,5'-tetraisopropyldiphenylketone, 4,4'-diamino-3,3 ', 5,5'-tetrabutyldiphenylketone, 4,4'-
Diamino-3,3 ', 5,5'-tetramethylbenzanilide, 4,
4'-diamino-3,3 ', 5,5'-tetraethylbenzanilide,
4,4'-diamino-3,3 ', 5,5'-tetra-n-propyldibenzanilide, 4,4'-diamino-3,3', 5,5'-tetraisopropylbenzanilide, 4,4 '-Diamino-3,3', 5,5'-tetrabutylbenzanilide, metatoluylenediamine, 4,4'-diaminodiphenylethane, 1,4-bis (4-aminocumyl) benzene (BAP), 1, 3-bis (4-aminocumyl) benzene, 1,3
-Bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2-bis [4- (3-aminophenoxy) Phenyl] propane, bis [4- (3-aminophenoxy) phenyl] sulfone (m-APPS), bis [4- (4-aminophenoxy)
Phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane and the like. If necessary, two or more aromatic diamine compounds can be used in combination.

In the present invention, the aromatic diamine compound other than the aromatic diamine compound represented by the general formula (I) is
0.1-99.9 mol% is preferable with respect to the total amount of a diamine component, 15-99.9 mol% is more preferable, 30-99.9 mol% is further more preferable.

The dicarboxylic acid or its reactive acid derivative in the present invention includes, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, bimelic acid,
Suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, tridecandioic acid, cyclohexanedicarboxylic acid, aliphatic dicarboxylic acids such as dimer acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, oxydibenzoic acid , 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenyl sulfone dicarboxylic acid, aromatic dicarboxylic acids such as 4,4'-diphenyl dicarboxylic acid, and reactive acid derivatives thereof. Acids, isophthalic acid and their reactive acid derivatives are readily available and preferred. If necessary, two or more of the above dicarboxylic acids or reactive acid derivatives thereof can be used in combination.

In the present invention, the dicarboxylic acid or its reactive acid derivative is preferably used in an amount of 80 to 150 mol%, more preferably 90 to 150 mol%, based on the total amount of the diamine component.

Examples of the tricarboxylic acid or its reactive acid derivative include trimellitic acid, 3,3,4′-benzophenone tricarboxylic acid, 2,3,4′-diphenyltricarboxylic acid,
2,3,6-pyridine tricarboxylic acid, 3,4,4'-benzanilide tricarboxylic acid, 1,4,5-naphthalene tricarboxylic acid,
Examples include 2'-methoxy-3,4,4'-diphenylether tricarboxylic acid, 2'-chlorobenzanilide-3,4,4'tricarboxylic acid and the like. Examples of the reactive derivative of the tricarboxylic acid include acid anhydrides, halides, esters, amides, and ammonium salts of the aromatic tricarboxylic acids, and examples thereof include trimellitic anhydride,
Trimellitic anhydride monochloride, 1,4-dicarboxy-3-N, N-dimethylcarbamoylbenzene, 1,4-dicarbomethoxy-3-carboxybenzene, 1,4-dicarboxy-
Examples include 3-carbophenoxybenzene, 2,6-dicarboxy-3-carbomethoxypyridine, 1,6-carboxy-5-carbamoylnaphthalene, and ammonium salts of the aromatic tricarboxylic acid and ammonia, dimethylamine, triethylamine, and the like. Among them, trimellitic anhydride and trimellitic anhydride monochloride are preferred. If necessary, two or more of the above tricarboxylic acids or reactive acid derivatives thereof can be used in combination.

In the present invention, the tricarboxylic acid or its reactive acid derivative is used in an amount of 80 to 150 with respect to the total amount of the diamine component.
Preferably, it is used in an amount of 90 to 150 mol%, more preferably 90 to 150 mol%.

The tetracarboxylic dianhydride represented by the general formula (II) or a reactive acid derivative thereof includes 3,3
3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2',
3,3'-biphenyltetracarboxylic dianhydride, 2,3,3'4 '
-Biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane 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, bis (3,4-dicarboxyphenyl) ether dianhydride, 3,4,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 2,3,2 ′, 3′-benzophenonetetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) methylphenylsilane dianhydride , Bis (3,4-dicarboxyphenyl) diphenylsilane Product, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldicyclohexane Dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis [4-
(3,4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 4,
Examples thereof include tetracarboxylic dianhydrides such as 4-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride and reactive acid derivatives thereof. Here 3,4,
3 ', 4'-benzophenonetetracarboxylic dianhydride or bis (3,4-dicarboxyphenyl) ether dianhydride is preferred. If necessary, two or more of the above tetracarboxylic acids or their reactive acid derivatives can be used in combination.

In the present invention, when polyetheramideimide or polyetheramide is obtained, it is preferable to use 0.1 to 90 mol% of tetracarboxylic acid or its reactive acid derivative based on the total amount of the diamine component. 80 mol% is more preferred. In the present invention, when a polyetherimide is obtained, the tetracarboxylic acid or its reactive acid derivative is preferably used in an amount of 80 to 200 mol%, more preferably 90 to 180 mol%, based on the total amount of the diamine component.

The aliphatic or alicyclic diamine compound in the present invention is not particularly limited as long as it is a compound in which an amino group is bonded to an aliphatic or alicyclic hydrocarbon. -Diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane,
1,6-diaminohexane, 1,7-diaminoheptane, 1,8
-Diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 3,9-bis (3-aminopropyl) -2,4,
8,10-tetraoxaspiro [5,5] undecane (ATU),
Aliphatic diamine compounds such as methylpentamethylenediamine (MPMD) and trimethylhexamethylenediamine (TMD), 1,2-diaminocyclohexane, methylenediaminocyclohexamine (PACM), norbornanediamine (NB
DA) and other alicyclic diamine compounds, diaminosiloxanes,
Diamine compounds having a main chain of ethylene oxide, propylene oxide, a copolymer of ethylene oxide and propylene oxide, and diamine compounds having a main chain of rubber. If necessary, two or more of the above aliphatic or alicyclic diamine compounds may be used in combination.

In the present invention, the aliphatic or alicyclic diamine compound is preferably 0.1 to 95 mol%, more preferably 0.1 to 90 mol%, and more preferably 0.1 to 85 mol% based on the total amount of the diamine component.
Mole% is more preferred.

The diaminosiloxane represented by the above general formula (III) includes, for example, X-22 manufactured by Shin-Etsu Chemical Co., Ltd.
-161AS, X-22-161A, X-22-161B, Toray Dow Corning Silicone, BY16-853U, BY16-853, BY16-853B, Toshiba Silicone, TSL9386, TSL9346, TSL9306, Nippon Unicar, F2- 053-01 and the like. If necessary, two or more diaminosiloxanes can be used in combination.

In the present invention, the amount of diaminosiloxane is preferably from 0.1 to 99.9 mol%, more preferably from 0.1 to 95 mol%, even more preferably from 0.1 to 90 mol%, based on the total amount of the diamine component.

In the present invention, the acid compound of the above-mentioned dicarboxylic acid or its reactive acid derivative and the tricarboxylic acid or its reactive acid derivative alone or in combination is used in an amount of 80 to 140 mol% based on the total amount of the diamine compound. Is more preferable, and 90 to 120 mol% is more preferable. When these are used in an equimolar amount with respect to the total amount of the diamine compound, a compound having the highest molecular weight tends to be obtained.

In the present invention, the dicarboxylic acid or its reactive acid derivative and the tricarboxylic acid or its reactive acid derivative alone or in combination with the tetracarboxylic dianhydride represented by the general formula (II) or its reaction The acid compound in combination with the acidic acid derivative is preferably used in an amount of 80 to 140 mol%, more preferably 90 to 120 mol%, based on the total amount of the diamine compound. When these are used in an equimolar amount with respect to the total amount of the diamine compound, a compound having the highest molecular weight tends to be obtained.

In the synthesis in the present invention, a known method used for a reaction between a diamine component and an acid component can be used as it is, and there is no particular limitation on various conditions, and a known method can be used. This reaction is carried out in an organic solvent, for example, N-methylpyrrolidone, dimethylacedamide, dimethylformamide, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H)
-Pyrimidinone, nitrogen-containing compounds such as 1,3-dimethyl-2-imidazolidinone, sulfolane, sulfur-containing compounds such as dimethylsulfoxide, γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-heptalactone, α
-Acetyl-γ-butyrolactone, lactones such as ε-caprolactone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ketones such as acetophenone, ethylene glycol, glycerin, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, Triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dipropyl ether, triethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dipropyl ether, tetraethylene glycol dibutyl ether Ethers such as ter, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, and phenols such as phenol, cresol, xylenol , Ethyl acetate, butyl acetate, ethyl cellosolve acetate, esters such as butyl cellosolve acetate, toluene,
Examples include hydrocarbons such as xylene, diethylbenzene, and cyclohexane, and halogenated hydrocarbons such as trichloroethane, tetrachloroethane, methylene chloride, chloroform, and monochlorobenzene. These can be used alone or in combination.

In these reactions, the diamine compound and the acid compound are reacted at -78 to 100 ° C., preferably -50 to 60 ° C. in the above organic solvent.
Perform at ° C. In this reaction, the inorganic acid acceptor may be added in an amount of 90 to 400 mol% based on the total amount of the diamine compound.
Examples of the inorganic acid acceptor include tertiary amines such as triethylamine, tripropylamine, tributylamine, triamylamine and pyridine; and propylene oxide, styrene oxide and cyclohexene oxide.
2-epoxide and the like. The reaction solution gradually thickens as the reaction proceeds. In this case, a polyamic acid which is a precursor of polyether amide imide is generated.
This polyamic acid is imidized by dehydration ring closure to obtain a polyetheramideimide. 80 to 40 for this dehydration ring closure
There are a thermal ring closure method in which heat treatment is performed at 0 ° C. to perform a dehydration reaction, and a chemical ring closure method in which dehydration is performed using a dehydrating agent.

In the case of the thermal ring closure method, it is preferable to carry out the method while removing water generated by the dehydration reaction out of the system. At this time 80-40
The reaction is carried out by heating the reaction solution to 0 ° C, preferably 100 to 250 ° C. At this time, a water-azeotropic solvent such as benzene, toluene, or xylene may be used in combination to remove water azeotropically.

In the case of the chemical ring closure method, the reaction is carried out at 0 to 120 ° C., preferably 10 to 80 ° C. in the presence of a chemical dehydrating agent. As the chemical dehydrating agent, it is preferable to use, for example, acid anhydrides such as acetic anhydride, propionic anhydride, butyric anhydride, and benzoic anhydride, and carbodiimide compounds such as dicyclohexylcarbodiimide. At this time, it is preferable to use a substance that promotes the cyclization reaction, such as pyridine, isoquinoline, trimethylamine, triethylamine, aminopyridine, and imidazole. The chemical dehydrating agent is used in an amount of 90 to 600 mol% based on the total amount of the diamine compound, and the substance promoting the cyclization reaction is used in an amount of 40 to 300 mol% based on the total amount of the diamine compound. Further, a dehydration catalyst such as a phosphorus compound such as triphenyl phosphite, tricyclohexyl phosphite, triphenyl phosphate, phosphoric acid or phosphorus pentoxide, or a boron compound such as boric acid or boric anhydride may be used.

The reaction solution which has been imidized by the dehydration reaction is mixed with a large excess of a solvent which is compatible with the above organic solvent such as a lower alcohol such as methanol, water or a mixture thereof and which is a poor solvent for the resin. The mixture is poured into a solvent to obtain a resin precipitate, which is separated by filtration and the solvent is dried to obtain the polyetheramideimide of the present invention. The polyether imide in the present invention can be obtained by the same synthesis method as for the polyether amide imide.

The polyetheramideimide or polyetheramide soluble in the polar solvent at room temperature obtained by the above method is insoluble in the polar solvent at room temperature, but is soluble in the polar solvent by heating. The blending of the ether amide or polyetherimide is not particularly limited, and any blending amount may be used. Preferably, the polyetheramideimide or polyetheramideimide soluble in a polar solvent at room temperature is insoluble at room temperature with respect to a total amount of 100 parts by weight of a polyetheramideimide or polyetheramide resin, but is soluble by heating. Etheramide or polyetherimide is 10 to 300 parts by weight, more preferably 10 to 2 parts.
00 parts by weight.

In the resin composition of the present invention, the total amount of the resin is 10
The organic solvent is preferably used in an amount of 100 to 3500 parts by weight, more preferably 150 to 1000 parts by weight, based on 0 parts by weight. The organic solvent is not particularly limited, for example, N
-Methylpyrrolidone, dimethylacedamide, nitrogen-containing compounds such as dimethylformamide, sulfolane, sulfur-containing compounds such as dimethylsulfoxide, γ-butyrolactone,
lactones such as γ-valerolactone, γ-caprolactone, γ-heptalactone, α-acetyl-γ-butyrolactone, ε-caprolactone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ketones such as acetophenone, ethylene glycol, glycerin,
Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dipropyl ether, triethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether ,
Tetraethylene glycol dipropyl ether, tetraethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether,
Ethers such as tetraethylene glycol monomethyl ether and tetraethylene glycol monoethyl ether are exemplified.

The resin composition of the present invention, that is, a polyetheramideimide or a polyetheramide which is soluble at room temperature in the polar solvent obtained by the above method, is insoluble at room temperature, but becomes soluble when heated. Etheramide imide, polyether amide or a resin composition comprising two kinds of resin of polyether imide and an organic solvent is not particularly limited, for example, a polyether amide imide or polyether amide soluble in a polar solvent at room temperature. To a varnish dissolved in an organic solvent, add a polyetheramideimide, polyetheramide or polyetherimide that is insoluble in a polar solvent at room temperature but is soluble by heating, and heated to 50 to 200 ° C. And then allowed to cool to obtain a paste of a resin composition containing two types of resins.

The low elasticity filler or liquid rubber having rubber elasticity used in the present invention is not particularly limited, but elastic fillers such as acrylic rubber, fluorine rubber, silicone rubber, butadiene rubber, and liquid rubbers of these fillers. And the like. Here, silicone rubber is preferable in consideration of the heat resistance of the resin composition. Further, the surface of the filler is preferably chemically modified with an epoxy group. Amino group, acrylic group, vinyl group,
Those modified with a functional group such as a phenyl group can be used. By adding these low elasticity fillers to a thermoplastic resin having heat resistance, it is possible to reduce elasticity and control the elastic modulus without impairing heat resistance and adhesion.

The average particle diameter of the low elasticity filler having rubber elasticity whose surface is chemically modified for use in the present invention is 0.1.
It is preferable that the fine particles have a diameter of 1 to 50 μm and are spherical or amorphous. When the average particle size is less than 0.1 μm, aggregation between the particles occurs, and it tends to be difficult to sufficiently disperse the particles. Also, 50μ
If it exceeds m, the surface of the coating film tends to be rough, and it tends to be difficult to obtain a uniform coating film.

In the resin composition of the present invention, the compounding amount of the low elastic filler having rubber elasticity whose surface is chemically modified is as follows:
5 to 90 with respect to 100 parts by weight of the total amount of the aromatic thermoplastic resin.
It is preferable to use 0 parts by weight, more preferably 5 to 800 parts by weight.

In the present invention, a silicone rubber is used as a low elasticity filler having a rubber elasticity whose surface is chemically modified, and the elastic modulus can be controlled in the range of 0.2 to 3.0 GPa by changing the compounding amount. Elastic modulus of -65
It can be a value within 10 to 100% of the value of ° C. This is a reliability evaluation of -5 when a semiconductor device is manufactured.
This is an effective property during a temperature cycle test from 5 ° C to 150 ° C. In addition, the glass composition has a glass transition temperature Tg of 180 ° C. or higher and a thermal decomposition temperature of 300 ° C. or higher, and retains heat resistance to provide a low-elastic resin composition.

The resin composition of the present invention, a polyetheramideimide soluble in a polar solvent obtained by the above method at room temperature or a polyetheramide insoluble at room temperature but soluble by heating. A resin composition comprising two kinds of resins of imide, polyetheramide or polyetherimide, a low elasticity filler and an organic solvent is obtained by adding a low elasticity filler to a varnish of an aromatic thermoplastic resin, and using a triturator, three rolls. The resin composition can be obtained by kneading and stirring with a dispersing machine such as a ball mill, a planetary mixer, a disper, a homogenizer and the like.

In the present invention, additives such as a coloring agent and a coupling agent, and a resin modifier may be added. Examples of the coloring agent include carbon black, dyes, and pigments, and examples of the coupling agent include aluminate-based coupling agents, silane-based coupling agents, titanate-based coupling agents, and thiol-based coupling agents. . It is preferable that the amount of the above additives is not more than 50 parts by weight based on 100 parts by weight of the total amount of the aromatic thermoplastic resin.

In the present invention, an aromatic thermoplastic resin which is insoluble in a polar solvent at room temperature but is soluble by heating imparts thixotropy to the resin composition, and forms a precise pattern by screen printing and dispensing. It is possible to do. At this time, the viscosity of the resin composition is
1 to 1000 Pa · s is preferred. If it is less than 1 Pa · s, it becomes difficult to maintain the shape of the resin composition during printing, and stringiness of the resin composition becomes severe, making printing difficult.
If it exceeds s, the resin composition becomes hard, and handling during printing becomes very difficult, and there is a problem that it becomes difficult to form a precise pattern. The thixotropic coefficient is 1.2 to 20.
Is preferable, and the range of 1.5 to 15 is more preferable. When the thixotropy coefficient is less than 1.2, even if a precise pattern is formed, the shape is lost, and it tends to be difficult to form the precise pattern.

The method for obtaining a precise pattern with the resin composition of the present invention is not particularly limited. Examples thereof include a screen printing method, a dispensing method, a potting method, a curtain coating method, a letterpress printing method, an intaglio printing method, and a lithographic printing plate. Printing method and the like can be mentioned.

A semiconductor device using the resin composition of the present invention is obtained by applying or attaching the resin composition of the present invention to a substrate or a lead frame, and then bonding the chip. For example, the resin composition of the present invention can be applied to the surface of a semiconductor component and dried to form a protective film, thereby producing the semiconductor component. After applying or attaching this resin composition to the chip surface, it may be adhered to a substrate or a lead frame. The coating and drying can be performed by a known method. At this time, a coating film can be obtained by a solvent drying step at 250 ° C. or lower without imidization. The glass transition temperature Tg of the formed coating film is 180 ° C
As described above, the thermal decomposition temperature is 300 ° C. or higher, and the composition has sufficient heat resistance. Further, since the elastic modulus of the coating film can be controlled in the range of 0.2 to 3.0 GPa, it can be applied to any semiconductor device.

A semiconductor device using the resin composition of the present invention comprises a step of applying a resin composition of the present invention to a semiconductor substrate on which a plurality of wirings having the same structure are formed and drying to form a resin layer; Forming a rewiring electrically connected to an electrode on the semiconductor substrate on the layer, forming a protective layer on the rewiring, forming external electrode terminals on the protective layer, According to the dicing process, it is manufactured. The semiconductor substrate is not particularly limited, and examples thereof include a silicon wafer. The method for applying the resin layer is not particularly limited, and screen printing or dispensing is preferable.

In the present invention, the method for drying the resin layer can be performed by a known method. At this time, a resin layer can be obtained in a solvent drying step at 250 ° C. or lower without imidization. Thus, the resin layer can be formed without damaging the substrate on which the wiring is formed. The formed resin layer preferably has a glass transition temperature Tg of 180 ° C. or higher and a thermal decomposition temperature of 300 ° C. or higher. In addition, it also has spatter resistance, plating resistance, alkali resistance, and the like required in the process of forming a rewiring. Since the elastic modulus of the resin layer can be controlled in the range of 0.2 to 3.0 GPa, it can be applied to any semiconductor device. Thereby, the amount of warpage of the silicon wafer can be considered. The yield of semiconductor devices manufactured by this method can be expected to be improved, and productivity can be improved.

[0057]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the scope of the present invention is not limited to these examples. [Example 1]

Under a nitrogen stream, 2,2-bis [4- (4-aminophenoxy) phenyl] was placed in a 1-liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube with an oil / water separator. 98.4 g (240 mmol) of propane (BAPP)
Was added and dissolved by adding 700 g of N-methyl-2-pyrrolidone (NMP). Next, 51.2 g (244 mmol) of trimellitic anhydride chloride (TAC) was added while cooling so as not to exceed 20 ° C. After stirring at room temperature for 1 hour, 30.3 g (300 mmol) of triethylamine was added while cooling so as not to exceed 20 ° C., and the mixture was reacted at room temperature for 3 hours to produce a polyamic acid varnish. The obtained polyamic acid varnish was further subjected to a dehydration reaction at 190 ° C. for 6 hours to produce a varnish of polyetheramide imide. A precipitate obtained by pouring this varnish of polyetheramideimide into water was separated, crushed and dried to obtain a polyetheramideimide powder soluble in a polar solvent at room temperature.

Under a nitrogen stream, 2,2-bis [4- (4-aminophenoxy) phenyl] was placed in a 1-liter four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube with an oil / water separator. 98.4 g (240 mmol) of propane (BAPP)
Was added and dissolved by adding 700 g of N-methyl-2-pyrrolidone (NMP). Next, 24.8 g (122 mmol) of isophthalic acid dichloride (IPC) was added while cooling not to exceed 20 ° C.
An acid compound of 39.4 g (122 mmol) of 3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride (BTDA) was added. After stirring at room temperature for 1 hour, 30.3 g (300 mmol) of triethylamine was added while cooling not to exceed 20 ° C.
The mixture was reacted at room temperature for 3 hours to produce a polyamic acid varnish. The obtained polyamic acid varnish was further subjected to a dehydration reaction at 190 ° C. for 6 hours to produce a varnish of polyetheramide imide. A precipitate obtained by pouring this varnish of polyetheramideimide into water was separated, crushed and dried to obtain a polyetheramideimide powder which was insoluble in a polar solvent at room temperature but was soluble by heating.

In a 300 ml four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a cooling tube equipped with an oil / water separator, under nitrogen flow, the above-obtained soluble solvent at room temperature was obtained. 15 g of ether amide imide powder, 15 g of polyether amide amide powder which is insoluble in the polar solvent obtained at room temperature but is soluble by heating, γ-
70 g of butyrolactone was added and stirred. Then add this to 15
Heated at 0 ° C. for 1 hour. At this time, the varnish that was not uniform at room temperature became uniform after heating. After the heating was stopped, the mixture was allowed to cool to room temperature with stirring to obtain a tan paste containing two kinds of resins. The viscosity and thixotropic coefficient (TI value) of the obtained paste were measured using a CVO rheometer manufactured by Jusco International.

The obtained paste is applied on a silicon wafer by a screen printing machine (manufactured by Neuron Seimitsu Co., Ltd., LS-34GX with an alignment device), a nickelless additive-plated meshless metal plate (manufactured by Mesh Kogyo Co., Ltd., thickness
The printability was evaluated using a 50 μm, pattern size of 8 mm × 8 mm) and a Permalex metal squeegee (imported from Tomoe Industries). After printing, the pattern was observed with an optical microscope for blurring and drooling.

The obtained paste was mixed with Teflon (registered trademark).
The composition was applied on a substrate, heated at 250 ° C., and the organic solvent was dried to form a coating film having a thickness of 25 μm. Using a dynamic viscoelastic spectrometer (manufactured by Iwamoto Seisakusho), the tensile modulus (25 ° C, 10Hz), the elastic modulus at -65 ° C and 150 ° C (frequency 10Hz, heating rate 2 ° C / min) and The glass transition temperature (frequency 10 Hz, heating rate 2 ° C./min) was measured. Also,
The pyrolysis onset temperature was measured with a thermobalance.

A step of applying the obtained paste to the semiconductor substrate on which the wiring is formed by applying a plurality of resin layers by screen printing and drying the resin layer. A step of forming a wiring, a step of forming a protective layer on the rewiring, and a step of forming an external electrode terminal on the protective layer were performed, and a semiconductor device was manufactured by dicing. Heat cycle test (-55 ℃ / 30
min ← → 125 ° C./30 min, 1000 cycles) to determine whether cracks occur in the resin layer. The semiconductor device was evaluated as ○ when no crack was generated and as X when the crack was generated. Table 1 shows the evaluation results of the resin composition and the semiconductor device.

Example 2 In the synthesis of the polyetheramideimide soluble in the polar solvent at room temperature in Example 1, 93.3 g of bis [4- (4-aminophenoxy) phenyl] sulfone (BAPS) was used as the diamine compound. 216 mmol) and 6.0 g (24 mmol) of 1,3-bis (aminopropyl) tetramethyldisiloxane were prepared and evaluated in the same manner as in Example 1 except that the resin composition and the semiconductor device were changed. . Table 1 shows the results.

Example 3 In the synthesis of a polyetheramideimide soluble in a polar solvent at room temperature in Example 1, the diamine compound was replaced with 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP 78.7 g (192 mmol), 6.0 g of 1,3-bis (aminopropyl) tetramethyldisiloxane
(24 mmol), 4,4'-diaminodiphenyl ether 4.8
g (24 mmol), the resin composition and semiconductor were the same as in Example 1 except that the acid compound was changed to 24.8 g (122 mmol) of isophthalic dichloride and 25.6 g (122 mmol) of trimellitic anhydride chloride. The device was manufactured and evaluated. Table 1 shows the results.

Example 4 In the synthesis of a polyetheramideimide which was insoluble in the polar solvent of Example 1 at room temperature but was soluble by heating, the diamine compound was converted to bis [4-
(4-Aminophenoxy) phenyl] sulfone (BAPS) 9
Preparation and evaluation of resin composition and semiconductor device in the same manner as in Example 1 except that the amount was changed to 3.3 g (216 mmol) and 6.0 g (24 mmol) of 1,3-bis (aminopropyl) tetramethyldisiloxane. Was done. Table 1 shows the results.

Example 5 In the synthesis of a polyetheramideimide which is insoluble in the polar solvent of Example 1 at room temperature but is soluble by heating, the diamine compound was converted into 2,2-bis [4- (4 -Aminophenoxy) phenyl] propane (BA
PP) 78.7 g (192 mmol), 1,3-bis (aminopropyl) tetramethyldisiloxane 6.0 g (24 mmol), 4,
4.8 g (24 mmol) of 4'-diaminodiphenyl ether
The acid component is isophthalic dichloride 12.4 g (61 mmol), trimellitic anhydride chloride 12.8 g (61 mmol), 3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride (BTDA) 39.4 g ( The production and evaluation of the resin composition / semiconductor device were performed in the same manner as in Example 1 except that the amount was changed to 122 mmol). Table 1 shows the results.

Example 6 The polyetheramideimide soluble in the polar solvent at room temperature obtained in Example 1 and the polyetheramideimide insoluble in the polar solvent at room temperature but soluble in the polar solvent were heated. Silicone rubber filler E-601 having an average particle size of 2 μm and surface-modified with an epoxy group was added to 100 g of a yellow-brown paste (30 g of non-volatile content) containing two types of resins.
10g (Toray Dow Corning Silicone Co., Ltd.)
In addition, the mixture was kneaded and dispersed with three rolls to obtain a tan paste. As the evaluation of the dispersibility of this paste, the presence or absence of sedimentation after standing for one week and the presence or absence of agglomerates (uniform / non-uniform) during the production of the coating film were confirmed. Table 1 shows the results. Using this paste, the evaluation of the resin composition and the manufacture and evaluation of the semiconductor device were performed in the same manner as in Example 1. Table 1 shows the results.

Example 7 A resin composition / semiconductor device was manufactured in the same manner as in Example 6, except that the average particle size was 2 μm and the amount of the silicone rubber filler surface-modified with an epoxy group was changed to 15 g. Fabrication and evaluation were performed. Table 1 shows the results.

Example 8 A resin composition and a semiconductor device were manufactured in the same manner as in Example 6, except that the average particle diameter was 2 μm and the amount of the silicone rubber filler surface-modified with an epoxy group was changed to 20 g. Fabrication and evaluation were performed. Table 1 shows the results.

Example 9 A resin composition and a semiconductor device were manufactured in the same manner as in Example 6, except that the average particle diameter was 2 μm and the silicone rubber filler surface-modified with an epoxy group was changed to 25 g. Fabrication and evaluation were performed. Table 1 shows the results.

Example 10 A resin composition / semiconductor device was manufactured in the same manner as in Example 6, except that the average particle size was 2 μm and the amount of the silicone rubber filler surface-modified with an epoxy group was changed to 30 g. Fabrication and evaluation were performed. Table 1 shows the results.

Example 11 One liter of 4 equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a cooling tube with an oil / water separator was installed.
Under a nitrogen stream, 2,2-bis [4- (4-
Aminophenoxy) phenyl] propane (BAPP) 98.4g
(240 mmol) of diamine compound was added, and 700 g of N-methyl-2-pyrrolidone (NMP) was added and dissolved. next
While cooling so as not to exceed 20 ° C., 80.6 g (260 mmol) of an acid compound of bis (3,4-dicarboxyphenyl) ether dianhydride was added. After stirring at room temperature for 1 hour, a dehydration reaction was further performed at 190 ° C. for 6 hours to produce a polyetherimide varnish. The polyetherimide varnish was poured into water, and the resulting precipitate was separated, pulverized and dried to obtain a polyetherimide powder which was insoluble in a polar solvent at room temperature but was soluble by heating. The resin composition was the same as in Example 1 except that the polyether amide imide powder which was insoluble at room temperature in the polar solvent of Example 1 but was soluble by heating was changed to the polyether imide powder obtained above.・ Semiconductor devices were manufactured and evaluated. Table 2 shows the results.

Example 12 In the synthesis of the polyetheramideimide soluble in the polar solvent at room temperature in Example 1, 93.3 g of bis [4- (4-aminophenoxy) phenyl] sulfone (BAPS) was used as the diamine compound. 216 mmol) and 1,3-
Bis (aminopropyl) tetramethyldisiloxane 6.0
g (24 mmol) and insoluble in a polar solvent at room temperature, but the polyetherimide powder soluble in the solvent was changed to the polyetherimide powder obtained in Example 11 by heating. Production and evaluation of a resin composition / semiconductor device were performed in the same manner as in the above.

Example 13 In the synthesis of a polyetheramideimide soluble in a polar solvent at room temperature in Example 1, the diamine compound was replaced with 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP ) 78.7 g (192 mmol), 1,3
-Bis (aminopropyl) tetramethyldisiloxane 6.
0 g (24 mmol), 4.8 g (24 mmol) of 4,4'-diaminodiphenyl ether, the acid compound in 24.8 g (122 mmol) of isophthalic dichloride, 25.6 g (122 mmol) of trimellitic anhydride chloride, and the polar solvent In the same manner as in Example 1, except that the polyether amide imide powder insoluble at room temperature but soluble by heating was changed to the polyether imide powder obtained in Example 11, Fabrication and evaluation were performed. Table 2 shows the results.

Example 14 In the synthesis of a polyetherimide which was insoluble in the polar solvent of Example 11 at room temperature but was soluble by heating, the diamine compound was converted to bis [4-
(4-Aminophenoxy) phenyl] sulfone (BAPS)
Preparation and evaluation of resin composition and semiconductor device in the same manner as in Example 1 except that 93.3 g (216 mmol) and 1,3-bis (aminopropyl) tetramethyldisiloxane were changed to 6.0 g (24 mmol). Was done. Table 2 shows the results.

Example 15 The diamine compound was insoluble in the polar solvent of Example 11 at room temperature, but was soluble by heating. The diamine compound was converted to 2,2-bis [4- (4- [Aminophenoxy) phenyl] propane (BAPP) 78.7 g (192 mmol), 1,3-bis (aminopropyl) tetramethyldisiloxane 6.0 g (24 mmol) and 4,4'-diaminodiphenyl ether 4.8 g (24 mmol)
Preparation and evaluation of a resin composition and a semiconductor device were performed in the same manner as in Example 1 except that the amount was changed to (mmol). Table 2 shows the results.

Example 16 The polyether amide insoluble in the polar solvent of Example 6 at room temperature but soluble by heating was changed to the polyether imide obtained in Example 11 except for heating. In the same manner as in Example 6, production and evaluation of a resin composition and a semiconductor device were performed. Table 2 shows the results.

Example 17 The polyether amide imide which was insoluble in the polar solvent of Example 6 at room temperature but was soluble by heating was converted into the polyether imide obtained in Example 11 and the average particle size. Preparation and evaluation of a resin composition and a semiconductor device were performed in the same manner as in Example 6, except that the silicone rubber filler having a diameter of 2 μm and surface-modified with an epoxy group was changed to 15 g. Table 2 shows the results.

Example 18 The polyether amide imide which was insoluble in the polar solvent of Example 6 at room temperature but was soluble by heating was converted into the polyether imide obtained in Example 11, Preparation and evaluation of a resin composition and a semiconductor device were performed in the same manner as in Example 6, except that the silicone rubber filler having a diameter of 2 μm and surface-modified with an epoxy group was changed to 20 g. Table 2 shows the results.

Example 19 The polyether amide imide which was insoluble in the polar solvent of Example 6 at room temperature but was soluble by heating was converted into the polyether imide obtained in Example 11, Production and evaluation of a resin composition and a semiconductor device were performed in the same manner as in Example 6, except that the silicone rubber filler having a diameter of 2 μm and surface-modified with an epoxy group was changed to 25 g. Table 2 shows the results.

Example 20 The polyether amide imide which was insoluble in the polar solvent of Example 6 at room temperature but was soluble by heating was converted into the polyether imide obtained in Example 11 and the average particle size. Production and evaluation of a resin composition and a semiconductor device were performed in the same manner as in Example 6, except that the silicone rubber filler having a diameter of 2 μm and surface-modified with an epoxy group was changed to 30 g. Table 2 shows the results.

[Comparative Example 1] In Example 1, a polyetheramide imide which is insoluble in a polar solvent at room temperature but is insoluble in a polar solvent at room temperature, but is soluble in a polar solvent at room temperature instead of being soluble by heating. Production and evaluation of a resin composition and a semiconductor device were performed in the same manner as in Example 1 except that the resin composition was changed to only the resin composition. As a result, the resin composition
The TI value was 1.0, and in the printability evaluation, bleeding / shading was large. Further, a semiconductor device could not be manufactured from this. Table 2 shows the results.

[0084]

According to the resin composition of the present invention, a coating film having the same resin characteristics as polyimide, that is, a high strength and excellent flexibility can be obtained without an imidization step. Furthermore, a precise pattern can be formed by screen printing, dispense coating, or the like, and a semiconductor device using the resin composition of the present invention provides good characteristics.

[0085]

[Table 1]

[0086]

[Table 2]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 21/00 C08L 21/00 77/00 77/00 79/08 79/08 CBF term (Reference) 4J001 DA02 DB01 DC05 DC08 DC10 DC14 DC15 EB04 EB05 EB06 EB07 EB08 EB09 EB14 EB23 EB26 EB35 EB36 EB37 EB46 EC23 EC24 EC33 EC38 EC74 EE26F EE53F CL EE56F EE72F FB03 FB05 FC04 J03 HA10 CP033 FD013 GQ05 4J043 PA02 PA04 PA08 PC016 PC116 PC136 QB15 QB26 QB32 QB33 RA05 RA34 RA35 SA06 SA81 SA85 TA12 TA13 TA21 UA122 UA151 UA262 UB121 UB151 UB281 UB291 UB301 VAA1 VA23 ZA33 ZA33A04A33A04A

Claims (14)

[Claims] 1. A resin composition containing the following resin (A), resin (B) and an organic solvent. (A) Aromatic thermoplastic resin soluble in polar solvent at room temperature (B) Aromatic thermoplastic resin insoluble in polar solvent at room temperature but soluble by heating 2. The resin composition according to claim 1, wherein the resin (A) and the resin (B) are the following resins. (A) Polyetheramideimide or polyetheramide soluble in polar solvents at room temperature (B) Polyetheramideimide, polyetheramide or polyether insoluble in polar solvents at room temperature but soluble by heating Imide 3. The resin (A) comprises the following component (1):
3. The resin composition according to claim 1, which is obtained by reacting (2) and (3), or (1) and (3). (1) An aromatic diamine compound represented by the following general formula (I) Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkoxyl group having 1 to 9 carbon atoms or a halogen atom. X is a single bond,
-O -, - S -, - C (= O) -, - SO 2 -, - S (= O) - or of 2 represents a group represented by may be different for each repeating unit. [Chemical formula 2] Wherein R ₅ and R ₆ each independently represent a hydrogen atom,
It represents an alkyl group, a trifluoromethyl group, a trichloromethyl group, a halogen atom or a phenyl group. (2) Diamine compound comprising the following components (a) and / or (b) (a) Aromatic diamine compound other than general formula (I) (b) Aliphatic or alicyclic diamine compound (3) (C) Dicarboxylic acid or its reactive acid derivative (d) Tricarboxylic acid or its reactive acid derivative 4. The resin (B) comprises the following component (1):
The resin composition according to any one of claims 1 to 3, which is obtained by reacting (2) and (3), or (1) and (3). (1) Aromatic diamine compound represented by the following general formula (I) Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkoxyl group having 1 to 9 carbon atoms or a halogen atom. X is a single bond,
-O -, - S -, - C (= O) -, - SO 2 -, - S (= O) - or of a group represented by 4, it may differ for each repeating unit. [Formula 4] Wherein R ₅ and R ₆ each independently represent a hydrogen atom,
It represents an alkyl group, a trifluoromethyl group, a trichloromethyl group, a halogen atom or a phenyl group. (2) Diamine compound comprising the following components (a) and / or (b) (a) Aromatic diamine compound other than general formula (I) (b) Aliphatic or alicyclic diamine compound (3) And (c) a dicarboxylic acid or a reaction thereof, comprising an acid compound comprising the components (c) and / or (d) of formula (I) and a tetracarboxylic dianhydride or a reactive acid derivative thereof represented by the following general formula (II): (D) Tricarboxylic acid or its reactive acid derivative Wherein Y is a single bond, -O-, -S-, -C (= O)-, -SO
_2- , -S (= O)-, a group represented by Chemical formula 6, or a divalent aromatic hydrocarbon group, an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, which differs for each repeating unit. You may. [Formula 6] Wherein R ₅ and R ₆ each independently represent a hydrogen atom,
It represents an alkyl group, a trifluoromethyl group, a trichloromethyl group, a halogen atom or a phenyl group. ] 5. The resin (B) comprises the following component (1):
The resin composition according to any one of claims 1 to 4, which is obtained by reacting (2) and (3) or (1) and (3). (1) Aromatic diamine compound represented by the following general formula (I) Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkoxyl group having 1 to 9 carbon atoms or a halogen atom. X is a single bond,
-O -, - S -, - C (= O) -, - SO 2 -, - S (= O) - or of a group represented by 8, it may differ for each repeating unit. Embedded image Wherein R ₅ and R ₆ each independently represent a hydrogen atom,
It represents an alkyl group, a trifluoromethyl group, a trichloromethyl group, a halogen atom or a phenyl group. (2) Diamine compound comprising the following components (a) and / or (b) (a) Aromatic diamine compound other than general formula (I) (b) Aliphatic or alicyclic diamine compound (3) A compound comprising a tetracarboxylic dianhydride represented by the general formula (II) or a reactive acid derivative thereof: Wherein Y is a single bond, -O-, -S-, -C (= O)-, -SO
_2- , -S (= O)-, a group represented by Chemical formula 10, or a divalent aromatic hydrocarbon group, an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, which differs for each repeating unit. You may. ] Wherein R ₅ and R ₆ each independently represent a hydrogen atom,
It represents an alkyl group, a trifluoromethyl group, a trichloromethyl group, a halogen atom or a phenyl group. ] 6. An aliphatic or alicyclic diamine compound (b)
Contains the diaminosiloxane represented by the following general formula (III): The resin composition according to any one of claims 3 to 5. Embedded image [Wherein R ₇ and R ₈ are divalent hydrocarbon groups, R ₉ to R ₁₂ are alkyl groups having 1 to 9 carbon atoms, phenylene groups or phenylene groups substituted with alkyl groups, and n is an integer of 1 to 30] Represents ] 7. The resin composition according to claim 1, further comprising a low elastic filler having rubber elasticity or a liquid rubber. 8. The resin composition according to claim 7, comprising a low elasticity filler having a rubber elasticity whose surface is chemically modified. 9. The resin composition according to claim 7, wherein the surface of the low elasticity filler is chemically modified with an epoxy group. 10. The low elasticity filler has an average particle size of 0.1 to 5.
The resin composition according to any one of claims 7 to 9, which has a thickness of 0 µm. 11. An elastic modulus at 25 ° C. of 0.2 to 30.
GPa can be arbitrarily controlled within the range of GPaGPa.
The resin composition according to any one of claims 1 to 10, which is in a range of from 100% to 100%. 12. The glass transition temperature (Tg) is 180 ° C. or higher, and the thermal decomposition temperature is 300 ° C. or higher.
12. The resin composition according to any one of items 11 to 11. 13. The resin composition according to claim 1, having a viscosity in the range of 1 to 1000 Pa · S, a thixotropy coefficient of 1.2 or more, and capable of forming a precise pattern. 14. A semiconductor device using the resin composition according to claim 1.