JP2003027034A - Adherent cover film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare an adherent cover film which has an excellent fine- processability and comprises a polyimide film and a polyimide-based adhesive that develop sufficient heat resistance and adhesive properties. SOLUTION: This adherent cover film has a constitution of laminating a 0.5-5 μm bonding layer on a high-modulus very thin polyimide film which has a thickness of 10 μm or less, preferably 3-7.5 μm and contains no inorganic filler, and realizes a fine-processability that has never been experienced by making the total thickness 10 μm or less. Further, by constituting the bonding layer being with a soluble thermoplastic polyimide resin, an epoxy resin and a curing agent thereof, the cover film develops excellent electric reliability, adhesive properties and heat resistance.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thin adhesive film that requires fine processing. More specifically, flexible printed circuit boards, TAB (Tape Autom)
The present invention relates to an adhesive cover film that is useful in fields requiring fine workability, heat resistance, and adhesiveness of tapes for bonded bonding, composite lead frames, laminated materials, electronic parts, and the like.

[0002]

2. Description of the Related Art In recent years, electronic devices have become more sophisticated, have higher performance,
The miniaturization is progressing, and the miniaturization and the weight reduction of the electronic components used in association with them are demanded. Therefore, semiconductor device packaging methods and wiring materials or wiring components for mounting them have been required to have higher density, higher functionality and higher performance. In particular, semiconductor packages, COL and LOC packages, MCM (M
There is a demand for a cover film material that can be finely processed and has good adhesiveness, which can be suitably used for a high-density mounting material such as a multi-chip module) and a printed wiring board material such as a multi-layer FPC. However, conventionally, a cover film material used in these fields has a thickness of 50 μm or more from the viewpoint of adhesion reliability and electrical reliability. Since a thick aspect ratio makes it difficult to process, a thick adhesive cover film having a thickness of 10 μm or more is not suitable for applications requiring fine processing of 5 μm or less. Further, in this field, an adhesive film in which a phenolic or epoxy adhesive or an acrylic adhesive is laminated on one or both sides of a polyimide film has been used so far. Also for the adhesive layer, a polyimide adhesive is gradually used from the viewpoint of reliability such as heat resistance and electric characteristics.

Since polyimide has excellent heat resistance among various organic polymers, it is widely used in the fields of space and aviation, and is also used as an adhesive material. But,
It is necessary to use a polyimide adhesive with high heat resistance for bonding.
It requires high temperature around 0 ° C and high pressure, and the adhesive strength is not so high.

[0004]

Therefore, the present inventors have found that
The present invention has been completed as a result of intensive studies aimed at solving the above problems and providing an adhesive cover film that is easy to be microfabricated while maintaining heat resistance and adhesiveness.

[0005]

The present invention provides a novel adhesive cover film having the following constitution, which achieves the above object. 1) A solvent-soluble thermoplastic polyimide, on at least one surface of a thin polyimide film having a particle size of 10 μm or less and an average particle size of 1 μm or more and 100 particles / mm ² or less,
The adhesive containing the epoxy resin and the curing agent is 0.5 to
It has a structure of stacking with a thickness of 5 μm, and the total thickness is 10 μm.
An adhesive cover film that is: 2) An adhesive composed of a solvent-soluble thermoplastic polyimide, an epoxy resin, and a curing agent on at least one surface of a thin polyimide film having a particle size of 3 to 7.5 μm and an average particle size of 1 μm or more of 100 particles / mm ² or less. 0.5
It has a structure of stacking with a thickness of ~ 5 μm, and the total thickness is 10 μm
An adhesive cover film having a thickness of m or less. 3) The glass transition temperature of the solvent-soluble thermoplastic polyimide is 200 ° C. or lower, and 50 mol% or more of the acid dianhydride residues contained in the solvent-soluble thermoplastic polyimide is represented by the general formula (1).

[0006]

[Chemical 3] The adhesive cover film according to 1) or 2), which is an ester dianhydride residue represented by: 4) In the solvent-soluble thermoplastic polyimide, 50 mol% or more of diamine residues contained in the polyimide are represented by the following general formula (2).

[0007]

[Chemical 4] The adhesive cover film according to any one of 1) to 3), which is a residue of a diamine compound represented by.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The adhesive cover film of the present invention is obtained by laminating an adhesive comprising a solvent-soluble thermoplastic polyimide, an epoxy resin and a curing agent on at least one side of a polyimide film. It is necessary that the polyimide film used has a thickness of 10 μm or less. Further, it is preferable that the fine workability is thin, and the handleability is thick, so that it is preferably 3 to 7.5 μm. Further, the polyimide film has an elastic modulus of 600 kg / mm ² or more and an elongation rate of 5%.
The above films are desirable. If the elastic modulus is low, the handleability is difficult, and if the elongation is low, the material may break during processing. Polyimide usually contains powder such as an inorganic filler, but when used in the adhesive cover film of the present invention, if a large amount of powder having an average particle size or more is present, it tends to be difficult to perform fine processing. It is preferable to use a polyimide film containing 100 or less powders / mm ² . The number of powders present in the film can be confirmed with a transmission microscope. Further, the adhesive layer has a thickness of 0.
The thickness is preferably 5 to 5 μm, and more preferably 1 to 5 μm from the viewpoint of adhesiveness. In the present invention, it is important that the total thickness after the adhesive is laminated on the thin polyimide film is 10 μm or less. If it is more than that, the fine workability is deteriorated. The adhesive used for the adhesive cover film of the present invention contains a solvent-soluble thermoplastic polyimide, an epoxy resin and a curing agent. The adhesive is prepared by dissolving each adhesive constituent component in an organic solvent to obtain an adhesive solution, casting it into a mold-releasing film, removing the organic solvent by heating and peeling it from the mold-releasing film, and pasting it on a polyimide film. Alternatively, the adhesive solution may be directly applied to the polyimide film and the solvent may be removed to obtain the desired adhesive cover film. The adhesive solution is obtained by dissolving a solvent-soluble thermoplastic polyimide, an epoxy resin and a curing agent in an organic solvent, but since the solvent can be removed by drying at a relatively low temperature, an organic solvent containing a cyclic ether solvent is used. Is preferred. Tetrahydrofuran (THF), 1,4-dioxane and dioxolane can be preferably used as the cyclic ether solvent. When a mixed organic solvent obtained by mixing a plurality of solvents is used, it is preferable to combine it with a polar organic solvent.
The effect of the present invention is more easily exhibited when the content is 0% by weight or more, preferably 50% by weight or more. The organic polar solvent to be combined with the cyclic ether solvent includes sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, N, N-dimethylacetamide, An acetamide-based solvent such as N, N-diethylacetamide may be used.

The solvent-soluble polyimide of the present invention refers to a solvent that dissolves in the solvent dioxolane at 25 ° C. by 10% or more.

Most of the thermoplastic polyimides are insoluble or sparingly soluble in these solvents, but the soluble thermoplastic polyimide of the present invention contains 50 or more acid dianhydride residues contained in the molecule.
More than mol% is general formula (1)

[0011]

[Chemical 5] Since it is characterized by being an ester dianhydride residue represented by, it can be dissolved in these organic solvents. Preferred examples of the acid dianhydride represented by the general formula (1) include 2,2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride. , P-phenylene bis (trimellitic acid monoester anhydride), 4,4'-biphenylene bis (trimellitic acid monoester anhydride), 1,4-naphthalene bis (trimellitic acid monoester anhydride), 1, 2-
Ethylene bis (trimellitic acid monoester anhydride),
1,3-trimethylene bis (trimellitic acid monoester anhydride), 1,4-tetramethylene bis (trimellitic acid monoester anhydride), 1,5-pentamethylene bis (trimellitic acid monoester anhydride) , 1,6-hexamethylene bis (trimellitic acid monoester anhydride) and the like are represented by the formula (3)

[0012]

[Chemical 6] 2,2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride represented by is particularly preferable.

The diamine component to be reacted with the acid dianhydride is represented by the following general formula (2)

[0014]

[Chemical 7] A diamine compound represented by, and particularly bis (aminophenoxyphenyl) sulfone is preferable. In the general formula (2), a plurality of Y's may be the same or different in each repeating unit, and the hydrogen of each benzene ring is appropriately substituted with various substituents within the range conceivable to those skilled in the art. Can be replaced. For example, a hydrocarbon group such as a methyl group or an ethyl group, or B
Examples thereof include halogen groups such as r and Cl, but are not limited to these substituents. Further, in the diamine compound represented by the general formula (2), the diamine compound having an amino group at the meta position has excellent solubility in the organic solvent of the thermoplastic polyimide using the same, and thus has excellent processability. A drug solution is obtained, which is preferable. The diamine compound represented by the general formula (2) may be used as a mixture of two or more kinds.

The thermoplastic polyimide which is soluble in the polyimide adhesive solution of the present invention is obtained by dehydrating and ring-closing a polyamic acid polymer which is a precursor thereof. This polyamic acid solution is obtained by using the above-mentioned acid dianhydride and the above-mentioned diamine compound in substantially equimolar amounts and polymerizing them in an organic polar solvent.

This polyamic acid or polyimide is obtained from a polyamic acid polymer obtained by dissolving or diffusing a diamine compound and an acid dianhydride in an organic polar solvent in an inert atmosphere such as argon or nitrogen. .

The order of adding each component is not particularly limited, and the acid dianhydride may be added to the organic polar solvent first, and the diamine compound may be added to form a solution of the polyamic acid polymer. It is also possible to first add a suitable amount to an organic polar solvent first, then add the acid dianhydride, and finally add the remaining diamine compound to form a solution of the polyamic acid polymer. There are various other polymerization methods known to those skilled in the art.

Examples of the organic polar solvent used in the reaction for producing the polyamic acid solution include sulfoxide-based solvents such as dimethyl sulfoxide and diethyl sulfoxide,
Formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, acetamide solvents such as N, N-dimethylacetamide and N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone , Phenol, o-, m- or p-cresol, xynol, halogenated phenols, phenolic solvents such as catechol, hexamethylphosphoramide, γ-butyrolactone and the like.
Furthermore, if necessary, these organic polar solvents may be used in combination with an aromatic hydrocarbon such as xylene or toluene.

The polyamic acid polymer obtained above is dehydrated and ring-closed by a thermal or chemical method to obtain a thermoplastic polyimide. As the imidization method, both a thermal method of heat-treating a polyamic acid solution for dehydration and a chemical method of dehydrating with a dehydrating agent are used. Examples of the dehydrating agent by a chemical method include aliphatic acid anhydrides such as acetic anhydride, and aromatic acid anhydrides. Examples of the catalyst include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, and heterocyclic tertiary amines such as pyridine and isoquinoline. The thermoplastic polyimide obtained as described above can be used as it is as a solution containing an epoxy resin and a curing agent and used as an adhesive layer of the adhesive cover film of the present invention. Or used in the polymerization of polyamic acid, which dissolves the solvent well, but in a poor solvent in which the polyimide is difficult to dissolve, the polyimide solution is added, the polyimide resin is precipitated to remove unreacted monomers, and purified, and dried to obtain a solid. It is also possible to dissolve it in an organic solvent again, mix it with an epoxy resin and a curing agent, and use it as an adhesive layer of the adhesive cover film of the present invention. As the poor solvent used, acetone, methanol, ethanol, isopropanol, benzene, methyl cellosolve,
Methyl ethyl ketone and the like can be mentioned.

As a thermal method, for example, a method of polymerizing a polyamic acid, then placing it in a vacuum oven, heating it under reduced pressure to imidize, and taking out as a solid polyimide resin can be mentioned.

The epoxy resin used in the adhesive of the present invention is not particularly limited, and bisphenol A type resin such as Epicoat 828 (manufactured by Yuka Shell Co.), orthocresol novolak resin such as 180S65 (manufactured by Yuka Shell Co., Ltd.), 157S.
70 (manufactured by Yuka Shell Co., Ltd.) and other bisphenol A novolac resins, 1032H60 (manufactured by Yuka Shell Co., Ltd.) and other trishydroxyphenylmethane novolac resins, ESN37
5, naphthalene aralkyl novolac resin, tetraphenylolethane 1031S (made by Yuka Shell Co., Ltd.), YG
D414S (Tohto Kasei), Trishydroxyphenylmethane EPPN502H (Nippon Kayaku), special bisphenol VG3101L (Mitsui Chemicals), special naphthol NC7
000 (Nippon Kayaku), biphenyl type epoxy NC300
0 (Nippon Kayaku), TETRAD-X, TETRAD-C
Typical examples are glycidyl amine type resins such as those manufactured by Mitsubishi Gas Chemical Co., Inc.

The mixing ratio of the epoxy resin is 1 to 50 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight of the thermoplastic polyimide. If it is too small, the adhesive strength will be low, and if it is too large, the flexibility and heat resistance will be poor.

The curing agent may be any one generally used as a curing agent for epoxy resins. The curing agent is added to the adhesive to improve water absorption, heat resistance, adhesiveness, etc., and is typically a general curing agent for epoxy such as acid dianhydride type, amine type, and imidazole type, Examples include accelerators and various coupling agents.

The composition of the adhesive used in the adhesive cover film of the present invention has been described above. The concentration of the adhesive solution when forming the adhesive layer is determined by the solid content (thermoplasticity) with the solution weight as the denominator. (Polyimide + epoxy resin + curing agent)
The amount is 5 to 50% by weight, preferably 10 to 40% by weight, particularly preferably 15 to 30% by weight. Further, the dissolution procedure and the like may be appropriately determined in consideration of workability and the like.

The adhesive cover film according to the present invention obtained as described above has characteristics that it can be suitably used for TAB tapes, composite lead frames, laminated materials and the like. Specifically, since it has a thin structure, it has excellent fine workability, heat resistance and adhesiveness, and can be bonded at a low temperature of 200 ° C. or less. An example of the bonding conditions in this case is a heating temperature of 150 ° C.
200 ° C., pressure 0.1 to 10 MPa, heating time 5 to 20
The condition is about a minute.

[0026]

Example Preparation of Base Polyimide Film (1) Dimethylformamide (hereinafter referred to as DMF) was placed in a polyimide film reactor containing no inorganic filler, and ODA was 4.5 equivalents and p-PDA was 5.5 equivalents.
The mixture was stirred until DA and p-PDA were completely dissolved. Next, 4.5 equivalents of TMHQ was added and then stirred for 30 minutes.
Then, 5 equivalents of PMDA was added and stirred for 120 minutes. Then, a solution prepared by dissolving 0.5 equivalent of PMDA in DMF was gradually added, and the mixture was cooled and stirred for 60 minutes to obtain a DMF solution of polyamic acid. The amount of DMF used was adjusted so that the total weight of the diamine component and the acid dianhydride component was 15% by weight of the weight of the polyamic acid organic solvent solution. Next, the polyamic acid organic solvent solution was mixed with DMF, acetic anhydride and isoquinoline, extruded from a die and cast on an endless belt. After baking, the volatile components are heated and dried on the endless belt until the weight of the film becomes 50%, the green sheet with self-supporting property is peeled off from the endless belt, and then both ends of the sheet are continuously conveyed. It was fixed to a pin sheet to be heated and conveyed to a heating furnace of 200, 400, 510 ° C. and heated. Further, it was gradually cooled to room temperature in an annealing furnace. The film was peeled off from the pin when it was taken out from the Xu furnace. The thickness of the film was 7.5 μm. (2) A DMF solution of polyamic acid was obtained in the same manner as the polyimide film (1) containing an inorganic filler. Incidentally, D
The amount of MF used was adjusted such that the total weight of the diamine component and the acid dianhydride component combined was 15% by weight of the weight of the polyamic acid organic solvent solution. Next, the polyamic acid organic solvent solution was mixed with DMF, AA, IQ and calcium phosphate (inorganic filler), extruded from a die and cast on an endless belt. After baking, the volatile components on the endless belt are heated and dried to 50% of the weight of the film, the self-supporting green sheet is peeled off from the endless belt, and then both ends of the sheet are continuously conveyed. 200, 400, 51
It was transferred to a heating furnace at 0 ° C. and heated. Further, it was gradually cooled to room temperature in an annealing furnace. The film was peeled off from the pin when it was taken out from the Xu furnace. The thickness of the film was 7.5 μm. When the obtained film was evaluated by a transmission microscope, 300 or more powders having a size of 1 to 10 μ were present.

Example 1 In a glass flask having a capacity of 1000 ml, 263 g of dimethylformamide (hereinafter referred to as DMF) and 0.13 of 3,3′-bis (aminophenoxyphenyl) sulfone (hereinafter referred to as BAPS-M) were added.
Add 12 mol and stir in a nitrogen atmosphere while stirring 2.
0.112 mol of 2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ', 4,4'-tetracarboxylic dianhydride (hereinafter referred to as ESDA) was gradually added. Stir in an ice bath for 30 minutes and the viscosity becomes 1500p
When reaching the oise, the stirring was stopped to obtain a polyamic acid solution.

113 g of DMF was added to this polyamic acid solution,
After adding 26 g of β-picoline and 45 g of acetic anhydride and stirring for 30 minutes, the mixture was further stirred at 100 ° C. for 1 hour for imidization. Then, this solution was dripped little by little in the methanol stirred at high speed. The filamentous polyimide precipitated in methanol was crushed with a mixer, washed with Soxhlet in methanol, and dried at 110 ° C. for 2 hours to obtain a polyimide powder. 20 g of the polyimide powder obtained above, 5 g of Epicoat 1032H60 (produced by Yuka Shell Co., Ltd.),
4,4'-diaminodiphenyl sulfone (curing agent)
1.5 g was added to 102 g of THF, and the mixture was stirred and dissolved to obtain a polyimide-based adhesive solution (solid content concentration:
SC = 20%).

The resulting polyimide adhesive solution was added to 7.5
It was cast on a polyimide film (without inorganic filler) having a thickness of μm, dried at 100 ° C. for 10 minutes, and then dried at 150 ° C. for 10 minutes to obtain a film-like laminated member having a thickness of 10 μm.

Example 2 A soluble thermoplastic polyimide was obtained in the same manner as in Example 1 except that TMEG was used as the acid component. 20 g of the polyimide powder obtained above, Epicoat 1
5 g of 032H60 (produced by Yuka Shell Co., Ltd.) and 10 g of 1.5 g of 4,4′-diaminodiphenyl sulfone (curing agent)
It was added to 2 g of THF and dissolved by stirring to obtain a polyimide-based adhesive solution (solid content concentration: SC = 20.
%).

The obtained polyimide adhesive solution was added to 7.5
It was cast on a polyimide film (without inorganic filler) having a thickness of μm, dried at 100 ° C. for 10 minutes, and then dried at 150 ° C. for 10 minutes to obtain a film-like laminated member having a thickness of 10 μm.

(Example 3) A soluble thermoplastic polyimide was obtained in the same manner as in Example 1 except that APB was used as the amine component. 20 g of the polyimide powder obtained above, Epicoat 1
5 g of 032H60 (produced by Yuka Shell Co., Ltd.) and 10 g of 1.5 g of 4,4′-diaminodiphenyl sulfone (curing agent)
It was added to 2 g of THF and dissolved by stirring to obtain a polyimide-based adhesive solution (solid content concentration: SC = 20.
%). The resulting polyimide-based adhesive solution was cast on a polyimide film (without inorganic filler) having a thickness of 7.5 μm, dried at 100 ° C. for 10 minutes, and then dried at 150 ° C. for 10 minutes to obtain a film-like laminated member having a thickness of 10 μm. Got (Example 4) A soluble thermoplastic polyimide was obtained in the same manner as in Example 1 except that TMEG was used as the acid component and APB was used as the amine component. 20 g of the polyimide powder obtained above, 5 g of Epicoat 1032H60 (produced by Yuka Shell Co., Ltd.), 4,4 ′
-1.5 g of diaminodiphenyl sulfone (curing agent) was added to 102 g of THF and dissolved by stirring to obtain a polyimide adhesive solution (solid content concentration: SC = 20.
%).

The obtained polyimide adhesive solution was added to 7.5
It was cast on a polyimide film (without inorganic filler) having a thickness of μm, dried at 100 ° C. for 10 minutes, and then dried at 150 ° C. for 10 minutes to obtain a film-like laminated member having a thickness of 10 μm. (Example 5) The polyimide powder obtained in Example 1 was used as 20
g, TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Inc.) 5 g,
4,4'-diaminodiphenyl sulfone (curing agent)
1.5 g was added to 102 g of THF, and the mixture was stirred and dissolved to obtain a polyimide-based adhesive solution (solid content concentration:
SC = 20%).

The obtained polyimide adhesive solution was added to 7.5
It was cast on a polyimide film (without inorganic filler) having a thickness of μm, dried at 100 ° C. for 10 minutes, and then dried at 150 ° C. for 10 minutes to obtain a film-like laminated member having a thickness of 10 μm.

Comparative Example 1 The polyimide-based adhesive solution obtained in Example 1 was dried on a 25 μm-thick polyimide film (Apical 25AH, manufactured by Kanegafuchi Chemical Industry Co., Ltd.) and then dried.
It was cast to have a thickness of 5 μm, dried at 100 ° C. for 10 minutes and then dried at 150 ° C. for 10 minutes to obtain a film-like laminated member having a thickness of 0 μm.

Comparative Example 2 3,3′-bis (aminophenoxyphenyl) sulfone (hereinafter, referred to as BAPS-M) was added to 263 g of dimethylformamide (hereinafter, referred to as DMF) in a glass flask having a capacity of 1,000 ml.
12 mol was added, and 0.112 mol of biphenyltetracarboxylic dianhydride (hereinafter referred to as BPDA) was gradually added with stirring under a nitrogen atmosphere. 30 in an ice bath
After stirring for 1 minute, the stirring was stopped when the viscosity reached 1500 poise to obtain a polyamic acid solution.

In this polyamic acid solution, 113 g of DMF,
After adding 26 g of β-picoline and 45 g of acetic anhydride and stirring for 30 minutes, the mixture was further stirred at 100 ° C. for 1 hour for imidization. Then, this solution was dripped little by little in the methanol stirred at high speed. The filamentous polyimide precipitated in methanol was crushed with a mixer, washed with Soxhlet in methanol, and dried at 110 ° C. for 2 hours to obtain a polyimide powder. The polyimide powder obtained above could not be dissolved in THF. (Solid content concentration: SC = 2
0%).

Comparative Example 3 In a glass flask having a capacity of 1000 ml, 263 g of dimethylformamide (hereinafter, referred to as DMF) was added with 0.112 mol of oxydianiline (hereinafter, referred to as ODA), and the mixture was stirred under a nitrogen atmosphere while 2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ', 4,4'-tetracarboxylic dianhydride (hereinafter referred to as ESDA) 0.112mo
1 was added slowly. The mixture was stirred in an ice bath for 30 minutes, and when the viscosity reached 1500 poise, the stirring was stopped to obtain a polyamic acid solution.

To this polyamic acid solution, 113 g of DMF,
After adding 26 g of β-picoline and 45 g of acetic anhydride and stirring for 30 minutes, the mixture was further stirred at 100 ° C. for 1 hour for imidization. Then, this solution was dripped little by little in the methanol stirred at high speed. The filamentous polyimide precipitated in methanol was crushed with a mixer, washed with Soxhlet in methanol, and dried at 110 ° C. for 2 hours to obtain a polyimide powder. The polyimide powder obtained above could not be dissolved in THF (solid content concentration: SC = 20).
%).

(Comparative Example 4) 20 g of the soluble thermoplastic polyimide obtained in Example 1 was dissolved in THF to obtain a soluble thermoplastic polyimide solution. The resulting solution is 7.5 μm
Cast on a thick polyimide film (Apical 7.5 HP, manufactured by Kanegafuchi Chemical Industry Co., Ltd.) and dry at 100 ° C. for 10 minutes.
It was dried at 150 ° C. for 10 minutes to obtain a film-like laminated member having a thickness of 10 μm.

(Comparative Example 5) Platabond M1276
(Copolymer nylon, manufactured by Nippon Rilsan Co., Ltd.), 10 g of Epicoat 1032H60 (manufactured by Yuka Shell Co., Ltd.) and 1 g of diaminodiphenyl sulfone were dissolved in 83 g of THF to obtain an adhesive solution. The obtained solution was cast on a 7.5 μm-thick polyimide film (Apical 7.5 HP, manufactured by Kaneka Corporation), dried at 100 ° C. for 10 minutes, and then 1
It was dried at 50 ° C. for 10 minutes to obtain a film-like laminated member having a thickness of 10 μm.

(Comparative Example 6) A polyimide adhesive solution obtained in the same manner as in Example 1 was cast on a polyimide film (with an inorganic filler) having a thickness of 7.5 μm and the temperature was maintained at 100 ° C. for 10 minutes.
After drying for 10 minutes, dry at 150 ℃ for 10 minutes, thickness 10μm
The film-like laminated member of was obtained.

(Characteristic evaluation of film-like laminated member) 1. Fine machinability Laser processing was performed under the following conditions, and the shape was observed by SEM. The degree of taper and the degree of perforation were evaluated in three levels. Equipment used: UV solid laser (YAG third harmonic), λ
= 355 nm Hole diameter: 40 μm Speed: 100 holes / sec Laser oscillation: 20 kHz ○ ・ ・ Taper and hole are both good △ ・ ・ Burr remains but burr remains × ・ ・ There is a part without hole 2 ． Peeling strength The peeling strength when the laminated member and the copper foil were bonded was measured by the following procedure. The film-shaped laminated member and the electrolytic copper foil of 18 μm were heated and pressed at a temperature of 200 ° C. and a pressure of 3 MPa for 20 minutes to obtain a copper-clad flexible laminated plate.
The peel strength of the obtained copper-clad flexible laminate,
It was measured according to JIS C6481. However, the conductor width is 3
It was measured in mm. 3. The peel strength after 150 ° C. × 1000 hours was measured according to JIS C6481 using the copper clad laminate obtained in Heat resistance 2. However, the conductor width was measured at 3 mm.

Table 1 shows the characteristic evaluation results of the film-like laminated members of Examples and Comparative Examples.

[0045]

[Table 1]

[0046]

The adhesive cover film of the present invention has a thickness of 10 μm.
m or less, preferably 0.5 to 0.5 mm for a highly elastic ultrathin polyimide film containing no inorganic filler and having a thickness of 3 to 7.5 μm.
The total thickness is 10
By setting the thickness to be equal to or less than μm, it is possible to realize unprecedented fine workability. Further, by forming the adhesive layer with a soluble thermoplastic polyimide resin, an epoxy resin and a curing agent thereof, it is possible to have excellent electrical reliability, adhesiveness and heat resistance.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 4F100 AK49A AK49B AK53B AT00A                       BA02 CA02B CA02H CB01B                       DE01A DE01H JB16B JJ03                       JL01 JL11 JL11B YY00A                 4J004 AA02 AA13 AA16 AA17 AB05                       CA06 FA04 FA05 FA08                 4J040 EC001 EC061 EC071 EC121                       EH031 JA09 KA16 LA02                       LA06 LA08 NA20 PA23

Claims (4)

[Claims] 1. An average particle size of 10 μm or less and an average particle size of 1 μm
A composition in which an adhesive containing a solvent-soluble thermoplastic polyimide, an epoxy resin and a curing agent is laminated to a thickness of 0.5 to 5 μm on at least one surface of a thin polyimide film having 100 or less powders / mm ² or less. An adhesive cover film having a total thickness of 10 μm or less. 2. The average particle diameter is 3 μm and the particle size is 3 μm to 7.5 μm.
An adhesive composed of a solvent-soluble thermoplastic polyimide, an epoxy resin, and a curing agent is laminated to a thickness of 0.5 to 5 μm on at least one surface of a thin polyimide film having 100 or more m or more powders / mm ² or less. An adhesive cover film having a total thickness of 10 μm or less. 3. The glass transition temperature of the solvent-soluble thermoplastic polyimide is 200 ° C. or lower, and 50 mol% or more of the acid dianhydride residues contained in the solvent-soluble thermoplastic polyimide is represented by the general formula (1) 1] The adhesive cover film according to claim 1 or 2, which is an ester dianhydride residue represented by: 4. In the solvent-soluble thermoplastic polyimide, 50 mol% or more of diamine residues contained in the polyimide are represented by the following general formula (2): It is the residue of the diamine compound represented by these, The adhesive cover film as described in any one of Claims 1-3.