JPH10316931A - Polyimide coating composition and polyimide coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyimide coating compsn. of which the problem with degradation in adhesive properties due to a heating and moistening treatment has been remarkably improved. SOLUTION: This compsn. essentially contains a polyimide precursor mainly comprising structural units represented by the formula and has a fluorine content (a content of fluorine contained in R1 and R2) of 1.0-7.0%. In the formula, R1 is a 2C or higher tetravalent org. group; R2 is a 2C or higher divalent org. group; and R3 and R4 are each independently H, an alkali metal ion, an ammonium ion, or a 1-30C org. group. The polyimide coating film is formed from a compsn. essentially contg. a polyimide precursor mainly comprising strutural units represented by the formula and has a fluorine contetn of 1.0-7.0%. A semiconductor having the polyimide coating film as the protective film is also provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide coating composition useful for producing electric and electronic materials such as semiconductor devices and multilayer wiring boards.
More specifically, the present invention relates to a polyimide coating composition which has remarkably improved the problem of reduced adhesion due to heat and humidity treatment.

[0002]

2. Description of the Related Art Polyimides have attracted attention in the field of electronic materials such as semiconductor protective films and interlayer insulating films because of their excellent heat resistance, electrical properties and mechanical properties. When polyimide is used as a semiconductor protective film, the adhesion to the lower inorganic film and the upper sealing resin greatly affects the reliability of the semiconductor. It is known that even if the adhesiveness of polyimide is good at the beginning, it tends to decrease by heating and humidifying treatment. This is not preferable because it may lead to a decrease in the reliability of the semiconductor.

In recent years, high integration of semiconductor devices and LOC (L
With the adoption of the “ad On Chip” package,
Even higher performance has been required for polyimide coating agents. For example, it has been required to maintain good initial adhesion to an inorganic film or a sealing resin even after a long-term heating and humidifying treatment. Similar demands have been increasing when a photosensitive polyimide coating agent is used for a protective film of a semiconductor device.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned drawbacks of the prior art, and an object of the present invention is to maintain a good initial adhesive force for a long period of time even after heating and humidifying treatment. An object of the present invention is to provide a characteristic polyimide coating agent.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted various studies on the adhesion of a polyimide coating agent. As a result, if the polyimide skeleton is allowed to contain fluorine in a specific range which has been considered to be inferior in adhesion, Surprisingly, they have found that the initial adhesion is good and that the decrease in adhesion after heating and humidification can be suppressed to a low level, and based on this finding, the present invention has been completed.

That is, the object of the present invention is achieved by adopting the following constitution.

The general formula (1)

Embedded image A polyimide coating composition comprising a structural unit represented by the following formula as a main component, and a polyimide precursor having a fluorine content of 1.0 to 7.0% in R1 and R2 as an essential component; R1 is a tetravalent organic group having at least two or more carbon atoms; R2 is a divalent organic group having at least two or more carbon atoms; R3 and R4 are hydrogen, an alkali metal ion, an ammonium ion, or a carbon atom; R3 and R4 may be the same or different), and a composition containing a polyimide precursor having a structural unit represented by the above general formula as a main component as an essential component. A polyimide coating film having a fluorine content of 1.0 to 7.0%, and a semiconductor having the polyimide coating film as a protective film.

The polyimide precursor having a structural unit represented by the general formula (1) in the present invention includes a polymer having an imide ring or other cyclic structure by heating or an appropriate catalyst (hereinafter referred to as “polyimide polymer”). Call) can be given.

In the above general formula (1), R1 is at least 2
It is a tetravalent organic group having at least two carbon atoms. In view of the heat resistance of the polyimide polymer, R1 is preferably a trivalent or tetravalent group containing an aromatic ring or an aromatic heterocyclic ring and having 6 to 30 carbon atoms. Preferred specific examples of R1 include 3,3 ', 4,4'-biphenyltetracarboxylic acid, 3,3', 4,4'-diphenylethertetracarboxylic acid, 3,3 ', 4,4'- Diphenylhexafluoropropanetetracarboxylic acid, 3,3 ', 4,4'-
Benzophenonetetracarboxylic acid, 3,3 ', 4,4'
-Residues such as, but not limited to, diphenylsulfonetetracarboxylic acid, pyromellitic acid, butanetetracarboxylic acid, and cyclopentanetetracarboxylic acid. From the viewpoint of the heat resistance of the polyimide polymer, particularly preferred specific examples include 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-diphenylethertetracarboxylic acid, and 3,3 ', 4,4'-diphenylhexafluoropropanetetracarboxylic acid, 3,
3 ′, 4,4′-benzophenonetetracarboxylic acid,
Residues such as 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid and pyromellitic acid are exemplified.

In the present invention, the polyimide precursor is R
1 may be composed of one of these, or 2
Copolymers composed of more than one kind may be used.

In the above general formula (1), R2 is at least 2
It is a divalent organic group having at least two carbon atoms. In view of the heat resistance of the polyimide polymer, R2 is preferably a divalent group containing an aromatic ring or an aromatic heterocyclic ring and having 6 to 30 carbon atoms. Preferred specific examples of R2 include, but are not limited to, the residues of the compounds shown below and the hydrogenated compounds thereof.

Paraphenylene diamine, metaphenylene diamine, methyl paraphenylene diamine, methyl metaphenylene diamine, dimethyl paraphenylene diamine, dimethyl metaphenylene diamine, trimethyl paraphenylene diamine, trimethyl metaphenylene diamine, tetramethyl paraphenylene diamine, tetramethyl meta Phenylenediamine, trifluoromethylparaphenylenediamine, trifluoromethylmetaphenylenediamine, bis (trifluoro) methylparaphenylenediamine, bis (trifluoro) methylmetaphenylenediamine, methoxyparaphenylenediamine, methoxymetaphenylenediamine, trifluoromethoxy Paraphenylenediamine, trifluoromethoxymetaphenylenediamine, fluoro Paraphenylenediamine, fluorometaphenylenediamine, chloroparaphenylenediamine, chlorometaphenylenediamine, bromoparaphenylenediamine, bromometaphenylenediamine, carboxyparaphenylenediamine, carboxymetaphenylenediamine, methoxycarbonylparaphenylenediamine, methoxycarbonylmetaphenylenediamine , Diaminodiphenylmethane, bis (aminomethylphenyl) methane, bis (aminotrifluoromethylphenyl) methane, bis (aminoethylphenyl) methane, bis (aminochlorophenyl) methane, bis (aminodimethylphenyl) methane, bis (aminodiethylphenyl) ) Methane, diaminodiphenylpropane, bis (aminomethylphenyl) propane, bis (amino (Trifluoromethylphenyl) propane, bis (aminoethylphenyl) propane, bis (aminochlorophenyl) propane, bis (aminodimethylphenyl) propane, bis (aminodiethylphenyl) propane, diaminodiphenylhexafluoropropane, bis (aminomethylphenyl) Hexafluoropropane, bis (aminotrifluoromethylphenyl) hexafluoropropane, bis (aminoethylphenyl) hexafluoropropane, bis (aminochlorophenyl) hexafluoropropane,
Bis (aminodimethylphenyl) hexafluoropropane, bis (aminodiethylphenyl) hexafluoropropane, diaminodiphenylsulfone, bis (aminomethylphenyl) sulfone, bis (aminoethylphenyl) sulfone, bis (aminotrifluoromethylphenyl) sulfone, Bis (aminodimethylphenyl) sulfone, bis (aminodiethylphenyl) sulfone, diaminodiphenylether, bis (aminomethylphenyl)
Ether, bis (aminotrifluoromethylphenyl)
Ether, bis (aminoethylphenyl) ether, bis (aminodimethylphenyl) ether, bis (aminodiethylphenyl) ether, dimethylbenzidine, bis (trifluoromethyl) benzidine, dichlorobenzidine, bis (aminophenoxy) benzene, bis (amino) Phenoxyphenyl) propane, bis (aminophenoxyphenyl) hexafluoropropane, bis (aminophenoxyphenyl) ether, bis (aminophenoxyphenyl) methane, bis (aminophenoxyphenyl) sulfone.

The polyimide precursor in the present invention is represented by R
2 may be composed of one of these, or 2
Copolymers composed of more than one kind may be used.

Further, in order to improve the adhesiveness of the polyimide polymer, it is possible to copolymerize an aliphatic group having a siloxane bond as R2 as long as the heat resistance is not reduced. A preferred specific example is bis (3
-Aminopropyl) tetramethyldisiloxane and the like, but are not limited thereto.

In the structural unit represented by the above general formula (1), the fluorine content in R 1 and R 2 is 1.0 to 7.0.
It is important to be in the% range. The fluorine content here is a value obtained by multiplying the total number of fluorine atoms present in R1 and R2 by the atomic weight 19 of fluorine and dividing by the sum of the molecular weights of R1 and R2, wherein R1 and R2 are composed of several types. In the case of, multiply the average number of fluorine atoms calculated from the number of fluorine atoms contained in each R1 and R2 and the mole fraction of R1 and R2 components containing fluorine by the atomic weight of fluorine 19, This is a value obtained by dividing by the sum of the average molecular weights of R1 and R2 calculated from the molecular weights and molar fractions of the respective R1 and R2 components. When the fluorine content is less than 1.0%,
No effect of the introduction of fluorine is recognized, and the adhesiveness after heating and humidification is greatly reduced as in the case of ordinary polyimide. On the other hand, when the fluorine content is more than 7.0%, the water and oil repellency of the polyimide film becomes remarkable, and the initial adhesion decreases.

A more preferable range of the fluorine content determined by the above definition is 2.0 to 6.0%.

In the polyimide coating composition of the present invention, the content of fluorine in R1 and R2 represented by the general formula (1) is defined. However, the content of fluorine in the resulting polyimide coating film is further reduced. It is even more important. Typically, it can also be specified by the fluorine content in the residue (that is, the thermosetting product) obtained after heating the polyimide coating composition at 350 ° C. for 1 hour in a nitrogen atmosphere. The heat treatment can be preferably used as long as it is generally used for curing polyimide, such as an inert oven or a vertical diffusion furnace. The fluorine content in the residue after the heat treatment can be determined by an ion electrode method, an absorptiometric method, an ion chromatographic method or the like.

The preferred range of the fluorine content in the residue is 0.8 to 6.0%, more preferably 1.5 to 6.0%.
~ 5.0%.

R1 and R2 represented by the above general formula (1)
The fluorine content therein can be adjusted by using a component containing fluorine in R1 and / or R2 alone or by copolymerizing with a component not containing fluorine.

Preferred specific examples of the fluorine-containing R1 component include residues such as 4,4'-diphenylhexafluoropropanetetracarboxylic acid, trifluoromethylpyromellitic acid, and bis (trifluoromethyl) pyromellitic acid. But not limited thereto. The fluorine-containing R1 component may be a single component or a copolymer of a plurality of components.

Preferred examples of the fluorine-containing R2 component include trifluoromethyl paraphenylenediamine, trifluoromethyl metaphenylenediamine, bis (trifluoro) methylparaphenylenediamine, bis (trifluoro) methyl metaphenylenediamine, Trifluoromethoxy paraphenylenediamine, trifluoromethoxymetaphenylenediamine, fluoroparaphenylenediamine, fluorometaphenylenediamine, diaminodiphenylhexafluoropropane, bis (aminomethylphenyl) hexafluoropropane, bis (aminotrifluoromethylphenyl) hexafluoro Propane, bis (aminoethylphenyl) hexafluoropropane, bis (aminochlorophenyl) hexafluoropropane, bis (a (Minodimethylphenyl) hexafluoropropane, bis (aminodiethylphenyl) hexafluoropropane, bis (aminotrifluoromethylphenyl) sulfone, bis (aminotrifluoromethylphenyl) ether, bis (trifluoromethyl) benzidine, bis (aminophenoxy) (Phenyl) hexafluoropropane, and the like. The fluorine-containing R2 component may be a single component or a copolymer composed of a plurality of components.

In the general formula (1), R 3 and R 4 represent hydrogen, an alkali metal ion, an ammonium ion, or an organic group having 1 to 30 carbon atoms. As the organic group having 1 to 30 carbon atoms, an aliphatic organic group is preferable, and examples of the contained organic group include a hydrocarbon group, a hydroxyl group, a carbonyl group, a carboxyl group, a urethane group, a urea group, and an amide group. It is not limited to these. Preferred specific examples include methyl, ethyl, isopropyl, butyl, t-butyl, ethyl methacrylate, ethyl acrylate, propyl methacrylate, propyl acrylate, ethyl methacrylamide, propyl methacryl Examples include, but are not limited to, an amide group, an ethylacrylamide group, and a propylacrylamide group. Further, R3 and R4 are more preferably hydrogen, an alkali metal ion, or an ammonium ion, and most preferably hydrogen, from the viewpoint of easy desorption and rapid conversion to polyimide.

The above R3 and R4 may each be a single species or a mixture of two or more species. R3 and R4 may be the same or different.

The polyimide precursor in the present invention may be composed of only the structural unit represented by the general formula (1), or may be a copolymer or a blend with another structural unit. . At that time, it is preferable that the content of the structural unit represented by the general formula (1) is 80% or more. The type and amount of the structural unit used for copolymerization or blending are preferably selected within a range that does not significantly impair the heat resistance of the polyimide-based polymer obtained by the final heat treatment.

These polyimide precursors are synthesized by a known method. That is, when R3 and R4 are hydrogen, a tetracarboxylic dianhydride and a diamine are selectively combined, and these are combined with N-methyl-2-pyrrolidone,
A known method such as a reaction in a polar solvent containing N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, hexamethylphosphorotriamide or the like as a main component, or a solvent containing γ-butyrolactone as a main component. Synthesized by

When R 3 and R 4 are alkyl groups, after reacting a tetracarboxylic dianhydride with an alcohol compound, an acid chloride is synthesized using thionyl chloride or the like, and then an appropriate diamine is selectively obtained. Or selectively combined with a diamine using a suitable dehydrating agent such as dicyclohexylcarbodiimide, and these are combined with N-methyl-2-pyrrolidone, N, N-dimethylacetamide,
It is synthesized by a known method such as a reaction in a polar solvent containing N, N-dimethylformamide, dimethylsulfoxide, hexamethylphosphorotriamide or the like as a main component or a solvent containing γ-butyrolactone as a main component.

In order to impart photosensitivity to the polyimide coating composition of the present invention, the R3 and R4 components are added to ethyl methacrylate, ethyl acrylate, propyl methacrylate, propyl acrylate, ethyl methacrylamide, Use of a methacrylamide group, an ethylacrylamide group, a propylacrylamide group, and / or a compound represented by the general formula (2) containing an ethylenically unsaturated double bond and an amino group (R4, R5,
R6 is an organic group having 1 to 30 carbon atoms, at least one of which contains an ethylenically unsaturated double bond).

In the compound represented by the above general formula (2), R
5, R6 and R7 represent an organic group having 1 to 30 carbon atoms. The organic group is preferably an aliphatic organic group. Examples of the organic group include, but are not limited to, a hydrocarbon group, a hydroxyl group, a carbonyl group, a carboxyl group, a urethane group, a urea group, and an amide group. Further, in order to improve the photosensitive performance, it is preferable that at least one of R5, R6 and R7 contains an ethylenically unsaturated double bond.

Preferred specific examples of the general formula (2) include dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylamide, dimethylaminopropyl methacrylate, diethylaminopropyl methacrylate, dimethylaminopropyl Acrylate, diethylaminopropyl acrylate, diethylaminopropyl methacrylamide, dimethylaminopropyl acrylamide, diethylaminopropyl acrylamide, dimethylaminoethyl methacrylamide, diethylaminoethyl methacrylamide, dimethylaminoethyl acrylamide, diethylaminoethyl acrylamide, and the like. Not.

The compound represented by the general formula (2) may be a single compound or a mixture of two or more compounds.

Further, the polyimide coating agent of the present invention can contain a photoinitiator and / or a photosensitizer.

The photoinitiator suitable for the present invention includes N-
Phenyldiethanolamine, N-phenylglycine,
Aromatic amines such as Michler's ketone, 3-phenyl-
A cyclic oxime compound represented by 5-isoxazolone, a chain oxime compound represented by 1-phenylpropanedione-2- (O-ethoxycarbonyl) oxime, benzophenone, methyl o-benzoylbenzoate,
Dibenzyl ketone, benzophenone derivatives such as fluorenone, thioxanthone, 2-methylthioxanthone,
Examples thereof include thioxanthone derivatives such as 2-isopropylthioxanthone, but are not limited thereto.

Examples of sensitizers suitable for the present invention include aromatic monoazides such as azidoanthraquinone and azidobenzalacetophenone, coumarin compounds such as 3,3'-carbonylbis (diethylaminocoumarin), benzanthrone and phenanthrenequinone. In some cases, aromatic ketones such as those generally used for photocurable resins and those used as charge transfer agents for electrophotography can be preferably used.

The photoinitiator and the sensitizer are added to the polymer in an amount of 0.1%.
It is preferably added in an amount of from 01 to 30% by weight, more preferably from 0.1 to 20% by weight. If the ratio is outside this range, the photosensitivity is lowered and the mechanical properties of the polymer are lowered. These photoinitiators and sensitizers alone,
Alternatively, two or more kinds can be used in combination.

In order to enhance the photosensitivity of the composition of the present invention, a photoreactive monomer may be used as appropriate.

The photoreactive monomer includes 2-hydroxyethyl methacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, propylene. Glycol dimethacrylate,
Examples include, but are not limited to, methylenebismethacrylamide, methylenebisacrylamide, and the like.

The photoreactive monomer is used in an amount of 1 to 1 with respect to the polymer.
It is preferable to add in the range of 30% by weight. If the ratio is outside this range, care must be taken because the photosensitivity is reduced and the mechanical properties of the polyimide polymer are reduced. These photoreactive monomers can be used alone or in combination of two or more.

In order to improve the adhesion between the coating film of the composition of the present invention or the polyimide film after the heat treatment and the support, an adhesion aid may be appropriately used.

Examples of the adhesion promoter include oxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-
Organic silicon compounds such as methacryloxypropyltrimethoxysilane, or aluminum chelate compounds such as aluminum monoethylacetoacetate diisopropylate and aluminum tris (acetylacetonate) or titanium chelate compounds such as titanium bis (acetylacetonate) are preferable. Used.

Further, other additives may be contained in such a range that the adhesion to the substrate, the sensitivity and the heat resistance are not significantly reduced.

Next, the method of using the composition of the present invention will be described. The composition of the present invention can be patterned by a known fine processing technique using actinic radiation.

First, the composition of the present invention is applied on a suitable support. As the material of the support, for example, metal,
Examples include, but are not limited to, glass, semiconductors, metal oxide insulating films, silicon nitride, and the like.

As a coating method, means such as spin coating using a spinner, spray coating using a spray coater, dipping, printing, and roll coating can be used. The thickness of the applied film can be adjusted depending on the application means, the solid content concentration and the viscosity of the composition, but is usually applied in the range of 0.1 to 150 μm.

Next, the substrate coated with the polyimide precursor is dried to obtain a polyimide precursor composition film. Drying is
Use an oven, hot plate, infrared ray, etc.
To 180 ° C., preferably 60 to 150 ° C.
It is more preferable to carry out within the range. The drying time is preferably from one minute to several hours.

Next, exposure is performed using a mask having a desired pattern. The exposure amount is 50 to 1000 mJ /
A range of cm 2 is preferred. A particularly preferred range is 100 to
It is 600 mJ / cm2. By using an appropriate sensitizer, exposure can be performed using an exposure machine such as an i-line stepper, a g-line stepper, a mask aligner, and a mirror projection.

The resolution of the pattern at the time of development is improved,
When the allowable range of the developing conditions is increased, a step of performing a baking process before the development may be adopted. The temperature is preferably in the range of 50 to 180 ° C., particularly preferably 60 to 180 ° C.
A range of 150 ° C. is more preferred. The time is preferably from 10 seconds to several hours. If the ratio is out of this range, the reaction may not proceed or all the regions may not be dissolved.

Next, a relief pattern is obtained by dissolving and removing the unirradiated portion with a developing solution. A suitable developer can be selected according to the structure of the polyimide precursor, but an aqueous alkali solution such as ammonia, tetramethylammonium hydroxide, diethanolamine or the like can be preferably used. Further, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphortriamide, etc. which are the solvents of the present composition are used alone. Or methanol, ethanol, isopropyl alcohol, water, methyl carbitol, ethyl carbitol, toluene, xylene, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate, ethyl-3-ethoxypro A mixture of the composition with a poor solvent such as pionate, 2-heptanone, and ethyl acetate can also be preferably used.

In the development, the above-mentioned developer is applied to the coating film surface as it is.
Alternatively, emit in the form of a mist, immerse in a developer,
Alternatively, it can be performed by a method such as applying ultrasonic waves while dipping.

Next, it is preferable to wash the relief pattern formed by development with a rinsing liquid. When rinsing with an organic solvent as a rinsing liquid, methanol, ethanol, isopropyl alcohol, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl-
3-methoxypropionate, ethyl-3-ethoxypropionate, 2-heptanone, ethyl acetate and the like are preferably used.

The polymer of the relief pattern obtained by the above treatment is a precursor of a polyimide-based polymer having heat resistance, and becomes a heat-resistant polymer having an imide ring or other cyclic structure by heat treatment. The heat treatment is preferably performed at 135 to 500 ° C.,
More preferably, it is performed at 450 ° C. The heat treatment is usually performed stepwise or continuously while increasing the temperature.

[0051]

The present invention will be specifically described below with reference to examples. The scope of the present invention is not limited by these examples. The characteristics in each example were determined in the following manner.

(1) Fluorine content in R1 and R2 The fluorine content in R1 and R2 is a value obtained by dividing the fluorine content in R1 and R2 represented by the general formula (1) by the molecular weight of R1 and R2. Which is obtained according to the following equation.

[F] = (Nfc + Nfa) * 19 / (Mc + Ma) In the above formula, Nfc represents the number of fluorine atoms contained in R 1 in the structural unit represented by the general formula (1). When two or more kinds are used, the average number of fluorine atoms calculated from the number of fluorine atoms contained in R1 of each component and the molar ratio used is used. Nfa represents the number of fluorine atoms contained in R2;
When two or more are used, the average number of fluorine atoms calculated from the number of fluorine atoms contained in R2 of each component and the molar ratio used is used. Mc represents the molecular weight of R1 and is determined by subtracting the sum of the atomic weights of 4 carbons and 6 oxygens from the molecular weight of the tetracarboxylic anhydride used as a raw material. When there are two or more types of R1, the average molecular weight calculated from the molecular weight of R1 of each component and the molar ratio used is used. Ma represents the molecular weight of R2, and is obtained by subtracting the sum of the atomic weights of two nitrogens and four hydrogens from the molecular weight of the diamine used as a raw material. R2
When two or more are used, the average molecular weight calculated from the molecular weight of R2 of each component and the molar ratio used is used.

(2) Fluorine content in the coating film After the polyimide coating composition is spin-coated and pre-baked on a silicon wafer under predetermined conditions,
Heat treatment was performed at 350 ° C. for 1 hour in a nitrogen atmosphere in an oven to obtain a cured polyimide film having a thickness of about 10 μm. After the polyimide cured film was isolated from the silicon wafer, it was subjected to combustion and alkali treatment, and the fluorine content in the polyimide cured film was determined by an ion electrode method.

(3) Adhesion to Inorganic Film A polyimide film was formed on a silicon wafer having a nitride film having a thickness of about 3000 Å on the surface by the procedure described in each embodiment. Using a razor, 1m on polyimide film
Cuts were made in a grid pattern at m intervals, and peeling tests were performed with cellophane tape. This sample was placed in a pressure cooker (1.5 atm, 120 ° C., 100% RH, P
(Abbreviated as CT) for 100 hours and subjected to the same peeling test as above.

(4) Adhesion to sealing resin A polyimide film was formed on a bare silicon wafer by the procedure described in each embodiment. On a polyimide film, a sealing resin TM20-100 manufactured by Toray Industries, Inc. was formed into a column having a height of 5 mm and a diameter of 5 mm by transfer molding. Using Tensilon (Toyo Baldwin Co., Ltd.), the strength when the sealing resin was peeled off from the polyimide film was determined. PCT (1.5 atm, 1
(20 ° C., 100% RH) for 100 hours, and then subjected to the same peeling test as above, followed by PCT
The strength was compared with the strength without treatment.

In Synthesis Examples and Table 1, abbreviations of polyimide raw materials are used in the following manner.

BAPS bis [4- (4-aminophenoxy) phenyl] sulfone SiDA bis (3-aminopropyl) tetramethyldisiloxane 6FDA 3,3 ′, 4,4′-diphenylhexafluoropropanetetracarboxylic dianhydride PMDA Pyromellitic anhydride HHFAPP bis [4- (4-aminophenoxy) phenyl] hexafluoropropane 3,4'-DAE 3,4'-diaminodiphenyl ether BTDA 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride Compound TFMB 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl DAE 4,4'-diaminodiphenyl ether Synthesis Example 1 BAPS in a 1-liter four-necked flask under a nitrogen stream
41.1 g and 1.2 g of SiDA were dissolved in 274.4 g of N-methyl-2-pyrrolidone at 20 ° C. Then 6
8.9 g of FDA and 17.4 g of PMDA were added and reacted at 55 ° C. for 4 hours. The resulting polyimide precursor composition was used as varnish A. Varnish A, R1 and R
Table 1 and Table 2 show the fluorine content in No. 2 and the fluorine content in the polyimide coating film.

Synthesis Example 2 HFBA was placed in a 1-liter four-necked flask under a nitrogen stream.
PP 10.4 g, 3,4'-DAE 15.0 g, SiD
A3.5 g of N-methyl-2-pyrrolidone
At 20 ° C. Then, 3,3 ', 4,4'-
30.6 g of benzophenonetetracarboxylic dianhydride was added and reacted at 55 ° C. for 4 hours. Then, the mixture was cooled to 20 ° C., and 2.9 g of N-phenylglycine, 5.7 g of ethylene glycol dimethacrylate, 36.3 g of diethylaminoethyl methacrylate, and N-methyl-2-pyrrolidone 5
A photosensitive polyimide precursor composition was prepared by adding 0.4 g, and was used as Varnish B. Tables 1 and 2 show the charged composition of varnish B, the fluorine content in R1 and R2, and the fluorine content in the polyimide coating film.

Synthesis Example 3 BTDA in a 1-liter four-necked flask under a nitrogen stream
32.2 g, 2-hydroxyethyl methacrylate 2
7.0 g was dissolved in 100 ml of γ-butyrolactone, and 17.0 g of pyridine was added dropwise in an ice bath. Then at room temperature 12
Stirring was continued for hours. Dicyclohexylcarbodiimide 4
A mixture of 1.2 g and 60 ml of γ-butyrolactone was added in an ice bath, and 4.8 g of TFMB, 16.0 g of DAE, and γ-butyrolactone were added.
A mixture of 100 ml of butyrolactone was added. After stirring for 6 hours in an ice bath, 10 ml of methanol was added, and after stirring for another 1 hour, the reaction solution was filtered, and the filtrate was added to ethanol 1
Added in Ol. After collecting the precipitate by filtration,
Vacuum dried. The polyimide precursor 20.0 g thus obtained, 1-phenyl-3-ethoxypropanetrione-2- (O-benzoyl) oxime 0.8 g,
0.12 g of (p-dimethylaminostyryl) benzoxazole, 1-phenyl-5-mercapto-1,2,2
0.2 g of 3,4-tetrazole, 0.01 g of 2-nitrosonaphthol, 1.2 g of trimethylolpropane triacrylate, benzophenone-3,3'-bis (N-
(3-triethoxysilyl) propylamide) -4,4
-Dicarboxylic acid (0.4 g) was dissolved in N-methyl-2-pyrrolidone (27.3 g) to prepare a photosensitive polyimide precursor composition, which was designated as Varnish C. Varnish C charge composition, R
Tables 1 and 2 show the fluorine content in R1 and R2 and the fluorine content in the polyimide coating film.

Synthesis Example 4 Synthesis Example 1 except that 1.3 g of 6FDA, 20.1 g of PMDA, and 254.8 g of N-methyl-2-pyrrolidone were used.
In the same manner as in the above, a polyimide precursor composition was prepared, and Varnish D was obtained. Tables 1 and 2 show the charged composition of Varnish D, the fluorine content in R1 and R2, and the fluorine content in the polyimide coating film.

Synthesis Example 5 HFBA was placed in a 1-liter four-necked flask under a nitrogen stream.
PP 20.7 g, 3,4'-DAE 11.0 g, SiD
A1.2 g of N-methyl-2-pyrrolidone 148.3 g
At 20 ° C. After that, 30.6 g of BTDA was added and reacted at 55 ° C. for 4 hours. Thereafter, the mixture was cooled to 20 ° C., and 3.2 g of N-phenylglycine, 6.4 g of ethylene glycol dimethacrylate, 36.1 g of diethylaminoethyl methacrylate, 6 g of N-methyl-2-pyrrolidone 6
A photosensitive polyimide precursor composition was prepared by adding 0.3 g, and was used as Varnish E. Tables 1 and 2 show the charged composition of the varnish E, the fluorine content in R1 and R2, and the fluorine content in the polyimide coating film.

Synthesis Example 6 BTDA in a 1-liter four-necked flask under a nitrogen stream
32.2 g, 2-hydroxyethyl methacrylate 2
7.0 g was dissolved in 100 ml of γ-butyrolactone, and 17.0 g of pyridine was added dropwise in an ice bath. Then at room temperature 12
Stirring was continued for hours. Dicyclohexylcarbodiimide 4
A mixture of 1.2 g and γ-butyrolactone 60 ml was added in an ice bath, and TFMB 30.4 g and γ-butyrolactone 1 were added.
00 ml of the mixture was added. After stirring for 6 hours in an ice bath, 10 ml of methanol was added. After stirring for 1 hour, the reaction solution was filtered, and the filtrate was added to 10 l of ethanol. The precipitate was collected by filtration and dried under vacuum. The thus obtained polyimide precursor 20.0
g, 1-phenyl-3-ethoxypropanetrione-2
-(O-benzoyl) oxime 0.8 g, 2- (p-dimethylaminostyryl) benzoxazole 0.12
g, 1-phenyl-5-mercapto-1,2,3,4-
0.2 g of tetrazole, 0.0 of 2-nitrosonaphthol
1 g, trimethylolpropane triacrylate 1.2
g, benzophenone-3,3'-bis (N- (3-triethoxysilyl) propylamide) -4,4-dicarboxylic acid, 0.4 g, and 27.3 g of N-methyl-2-pyrrolidone.
Dissolved in to produce a photosensitive polyimide precursor composition,
Varnish F was used. Varnish F, R1 and R
Table 1 and Table 2 show the fluorine content in No. 2 and the fluorine content in the polyimide coating film.

Example 1 Varnish A was spin-coated on a silicon wafer with a spinner, and then heated at 80 ° C. for 2 minutes using a vacuum adsorption type hot plate (SCW636, manufactured by Dainippon Screen Co., Ltd.).
Drying was performed at 100 ° C. for 2 minutes to form a prebaked film. The thickness of this prebaked film was 10 μm. Thereafter, heat treatment was performed at 140 ° C. for 30 minutes and at 350 ° C. for 60 minutes in a nitrogen atmosphere. The adhesion of the obtained polyimide film to the inorganic film was good as shown in Table 2, the adhesion strength to the sealing resin was high, and the decrease in strength after the PCT treatment was small.

Example 2 Varnish B was spin-coated and dried in the same manner as in Example 1 to form a prebaked film. The thickness of this prebaked film is 10
μm. Then, at 140 ° C. in a nitrogen atmosphere for 30 minutes.
Heat treatment at 350 ° C. for 60 minutes. The adhesion of the obtained polyimide film to the inorganic film was good as shown in Table 2, the adhesion strength to the sealing resin was high, and the decrease in strength after the PCT treatment was small.

The pre-baked film obtained in the same manner as above was applied to an i-line stepper (NSR-1755 manufactured by Nikon Corporation).
Exposure was performed according to I7A) with an exposure amount of 400 mJ / cm 2. After baking at 80 ° C. for 1 minute on a hot plate, N-methylpyrrolidone (70 parts) and xylene (3 parts) were added.
(0 parts), and spray paddle development was carried out. Then, it was rinsed with isopropyl alcohol for 20 seconds, and spin-dried with a spinner. Then, at 140 ° C, 3
Heat treatment was performed at 350 ° C. for 60 minutes for 0 minute, and the pattern was observed using an optical microscope.

Example 3 Varnish C was spin-coated and dried in the same manner as in Example 1 to form a prebaked film. The thickness of this prebaked film is 10
μm. Then, at 140 ° C. in a nitrogen atmosphere for 30 minutes.
Heat treatment at 350 ° C. for 60 minutes. The adhesion of the obtained polyimide film to the inorganic film was good as shown in Table 2, the adhesion strength to the sealing resin was high, and the decrease in strength after the PCT treatment was small.

The prebaked film obtained in the same manner as above was exposed at an exposure of 500 mJ / cm 2 by an i-line stepper. After baking at 80 ° C. for 1 minute on a hot plate, spray development was performed using cyclopentanone. Then, it was rinsed with propylene glycol monomethyl ether acetate for 20 seconds and spin-dried with a spinner. After that, it is 30 minutes at 140.degree.
When heat treatment was performed for 0 minutes and the pattern was observed using an optical microscope, a good pattern having a resolution of 10 μm was shown.

Comparative Example 1 Varnish D was spin-coated and dried in the same manner as in Example 1 to form a prebaked film. The thickness of this prebaked film is 10
μm. Then, at 140 ° C. in a nitrogen atmosphere for 30 minutes.
Heat treatment at 350 ° C. for 60 minutes. The adhesion of the obtained polyimide film to the inorganic film was good as shown in Table 2, and the initial adhesion strength to the sealing resin was high.
The magnitude of the decrease in strength after the PCT treatment was large.

Comparative Example 2 Varnish E was spin-coated and dried in the same manner as in Example 2 to form a prebaked film. The thickness of this prebaked film is 10
μm. Then, at 140 ° C. in a nitrogen atmosphere for 30 minutes.
Heat treatment at 350 ° C. for 60 minutes. The adhesion of the obtained polyimide film to the inorganic film was good as shown in Table 2, but the adhesion strength to the sealing resin was low regardless of the presence or absence of the PCT treatment.

Comparative Example 3 Varnish F was spin-coated and dried in the same manner as in Example 3 to form a prebaked film. The thickness of this prebaked film is 10
μm. Then, at 140 ° C. in a nitrogen atmosphere for 30 minutes.
Heat treatment at 350 ° C. for 60 minutes. The adhesion of the obtained polyimide film to the inorganic film was poor as shown in Table 2, and the adhesion strength to the sealing resin was low regardless of the presence or absence of the PCT treatment.

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[Table 1]

[Table 2]

[0073]

According to the present invention, it is possible to obtain a polyimide coating composition which has remarkably improved the problem of the decrease in adhesion due to the heating and humidifying treatment.

Claims (8)

[Claims] 1. A compound of the general formula (1) A polyimide coating composition comprising a structural unit represented by the following formula as a main component and a polyimide precursor having a fluorine content of 1.0 to 7.0% in R1 and R2 as an essential component. (R1 is a tetravalent organic group having at least 2 or more carbon atoms, R2 is a divalent organic group having at least 2 or more carbon atoms, R3 and R4 are hydrogen, an alkali metal ion, an ammonium ion, or Represents an organic group having 1 to 30 carbon atoms. R3 and R4 may be the same or different. 2. The polyimide coating composition according to claim 1, wherein said fluorine content is 2.0 to 6.0%. 3. The polyimide coating composition according to claim 1, wherein R3 and R4 in the formula (1) are hydrogen. 4. A composition of the general formula (2) containing an ethylenically unsaturated double bond and an amino group in the composition. A compound represented by the formula:
The polyimide coating composition according to the above. (R5, R6,
R7 is an organic group having 1 to 30 carbon atoms, at least one of which contains an ethylenically unsaturated double bond) 5. The polyimide coating composition according to claim 1, wherein said composition contains a photoinitiator and / or a photosensitizer. 6. A compound of the general formula (1) A polyimide coating film obtained from a composition containing, as an essential component, a polyimide precursor containing a structural unit represented by the following formula as a main component, and having a fluorine content of 0.8 to 6.0%. (R1 is a tetravalent organic group having at least 2 or more carbon atoms, R2 is a divalent organic group having at least 2 or more carbon atoms, R3 and R4 are hydrogen, an alkali metal ion, an ammonium ion, or Represents an organic group having 1 to 30 carbon atoms. R3 and R4 may be the same or different. 7. The polyimide coating film according to claim 6, wherein said fluorine content is 1.5 to 5.0%. 8. A semiconductor having the polyimide coating film according to claim 6 as a protective film.