JP2001162719A - Polyimide single-layer body having reinforcing material and method for producing the same - Google Patents

Abstract

An object of the present invention is to provide a metal foil laminate of all-polyimide which has good moldability and can be laminated with another substrate, and a method for producing the same. SOLUTION: A metal foil is laminated on one side of a multilayer polyimide film having a thermocompression-bondable polyimide layer on both sides of a heat-resistant polyimide layer with an adhesive strength of at least twice the adhesive strength between the reinforcing material and the polyimide, and Reinforcement has an adhesive strength of 0.00
A polyimide single-layer body having a reinforcing material laminated at 1 kg / cm or more and 0.5 kg / cm or less, and a method for producing the same.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide single-layer structure having a reinforcing material and a method for producing the same, and more particularly, to a single-sided multilayer polyimide film having a thermocompression-bondable polyimide layer on both sides of a heat-resistant polyimide layer. The present invention relates to a polyimide single-layer body having a reinforcing material in which a metal foil is laminated on another surface with a peelable reinforcing material, and a method for producing the same. According to the present invention, a polyimide having a reinforcing material that provides a polyimide single-sided metal foil laminate that has good moldability and hardly generates wrinkles even when the reinforcing material is peeled off for lamination with the same or different types of substrates. A single-area layer body can be obtained.

[0002]

2. Description of the Related Art Aromatic polyimide films are widely used for electronic devices such as cameras, personal computers, and liquid crystal displays. In order to use an aromatic polyimide film as a substrate material for a flexible printed board (FPC) or a tape-automated bonding (TAB), a copper foil is laminated using an adhesive such as an epoxy resin. The method has been adopted.

It has been pointed out that aromatic polyimide films are excellent in heat resistance, mechanical strength, electrical properties and the like, but deteriorate the original properties of polyimide due to poor heat resistance of an adhesive such as an epoxy resin. ing. In order to solve such problems, copper is electroplated on a polyimide film without using an adhesive, or a polyamic acid solution is applied to a copper foil, dried, imidized, or thermoplastic polyimide is thermocompressed. All-polyimide substrates have also been developed.

Further, a polyimide laminate in which a film-like polyimide adhesive is sandwiched between a polyimide film and a metal foil and a method for producing the same are known (US Pat. No. 4,543,295). However, this polyimide laminate and its manufacturing method are not easy to handle a film-like polyimide adhesive, and the peel strength (adhesion strength) of some polyimide films is not good.
There is a problem that cannot be used because it is small.

Further, a metal foil laminated polyimide film and a method for producing the same are known (Japanese Patent Laid-Open No. 4-33847).
No. JP-A-4-33848). However, these documents only describe a laminate in which a multilayer polyimide film and a metal foil are firmly bonded.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a metal foil laminate of all-polyimide which has no problem in the formability and surface characteristics of a conventionally known metal foil laminate for a substrate. To provide.

[0007]

That is, the present invention provides:
A metal foil is laminated on one side of a multilayer polyimide film having a thermocompression-bondable polyimide layer on both sides of a heat-resistant polyimide layer with an adhesive strength of at least twice the adhesive strength between the reinforcing material and the polyimide, and the reinforcing material adheres to the other surface The present invention relates to a polyimide single-layer structure having a reinforcing material laminated at a strength of 0.001 kg / cm or more and 0.5 kg / cm or less. Further, the present invention provides a metal foil on one side of a multilayer polyimide film having a thermocompression bonding polyimide layer on both sides of a heat-resistant polyimide layer,
Preferably, a metal foil having a surface roughness (Rz) of 0.5 μm or more, a reinforcing material on the other surface, preferably a surface roughness (Rz) of 3 μm
The present invention relates to a method for producing a polyimide single-layer body having a reinforcing material, characterized by stacking reinforcing materials of m or less and thermocompressing them.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be listed below. 1) A polyimide single-layered product having the above-mentioned reinforcing material, wherein the multilayer polyimide film is a multilayer extruded polyimide film in which a thermocompression-bonding polyimide layer is integrally laminated on both surfaces of a heat-resistant polyimide layer. 2) A method of producing a polyimide single-layered product having the above-mentioned reinforcing material by performing thermocompression bonding with a continuous laminating device to form a long roll-shaped laminate. 3) A method for producing a polyimide single-layer body having the above-mentioned reinforcing material, wherein thermocompression bonding is performed by a double belt press.

In the present invention, a multilayer polyimide film having a thermocompression-bondable polyimide layer on both sides of a heat-resistant polyimide layer is used. The multilayer polyimide film has a coefficient of linear expansion (50 to 200) as well as thermocompression bonding.
C.) (MD) is preferably 30 × 10 ⁻⁶ cm / cm / ° C. or less, and the tensile modulus (MD, ASTM−
D882) is preferably 300 kg / mm ² or more.

The above-mentioned multilayer polyimide film is preferably formed by laminating a heat-resistant polyimide precursor solution and a thermocompression bonding polyimide precursor solution by a co-extrusion-casting film forming method (also simply referred to as a multilayer extrusion method). Then, drying and imidizing to obtain a multilayer polyimide film, or the above-mentioned heat-resistant polyimide precursor solution is applied by casting onto a support, and the thermocompression-bondable polyimide precursor solution is applied to both sides of the dried gel film. Then, it can be obtained by a method of obtaining a multilayer polyimide film by drying and imidizing. In any of the above methods, it is preferable to dry and imidize the thermocompression-bondable polyimide precursor layer at a maximum heating temperature of 250 to 420 ° C. In particular, a self-supporting film obtained by co-extrusion-casting is preferably dried and imidized at a maximum heating temperature of 250 to 420 ° C.

The heat-resistant polyimide as the base layer of the multilayer polyimide film is preferably 3, 3 ', 4,
4'-biphenyltetracarboxylic dianhydride (hereinafter sometimes abbreviated simply as s-BPDA) and paraphenylenediamine (hereinafter sometimes abbreviated simply as PPD).
And optionally 4,4'-diaminodiphenyle-
And TELL (hereinafter may be simply abbreviated as DADE). In this case, the PPD / DADE (molar ratio) is preferably from 100/0 to 85/15. Also,
The heat-resistant polyimide as the base layer is 3, 3 ', 4,
4'-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, paraphenylenediamine and 4,4'-
It is prepared from diaminodiphenyl ether. Also,
The heat-resistant polyimide as the base layer is produced from pyromellitic dianhydride, paraphenylenediamine and 4,4'-diaminodiphenyl ether. In this case D
ADE / PPD (molar ratio) is preferably 90/10 to 10/90. Further, the heat-resistant polyimide as the base layer includes 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA) and pyromellitic dianhydride (PMDA) and paraphenylenediamine (P
PD) and 4,4'-diaminodiphenyl ether (DADE). In this case, BTDA in the acid dianhydride is 20 to 90 mol%, and PMDA is 10 to 80 mol%.
Mol%, PPD in diamine 30-90 mol%, DAD
It is preferable that E is 10 to 70 mol%.

The heat-resistant polyimide used as the base layer is preferably a polyimide film having a glass transition temperature of 350 ° C. or more which cannot be confirmed in the case of a single polyimide film, and particularly has a linear expansion coefficient (50 to 200 ° C.). ) (MD) is preferably 5 × 10 ^{−6 to} 20 × 10 ⁻⁶ cm / cm / ° C. In addition, the tensile modulus (MD, ASTM-D88
2) is preferably 300 kg / mm ² or more.
In the synthesis of the base layer polyimide, random polymerization, block polymerization, or synthesis of two kinds of polyamic acids in advance if the proportion of each component is within the above range, and mixing of both polyamic acid solutions, followed by reaction conditions To obtain a homogeneous solution.

Using each of the above components, a substantially equimolar amount of a diamine component and a tetracarboxylic dianhydride are reacted in an organic solvent to prepare a solution of a polyamic acid (partly if a uniform solution state is maintained). May be imidized).
Other aromatic tetracarboxylic dianhydride or aromatic diamine of the kind and amount that does not impair the physical properties of the substrate layer polyimide,
For example, 4,4'-diaminodiphenylmethane or the like may be used.

The thermocompression-bondable polyimide as the thermocompression-bonding layer in the present invention can be selected from various known thermoplastic polyimides, and is preferably 1,3-bis (4
-Aminophenoxybenzene) (hereinafter sometimes abbreviated as TPER) and 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride (hereinafter sometimes abbreviated as a-BPDA). Manufactured from Further, as the thermocompression-bondable polyimide as the thermocompression bonding layer, 1,3-bis (4-aminophenoxy) -2,2-dimethylpropane (DANPG) and 4,4′-oxydiphthalic dianhydride (ODPA) And a-BPDA.
Alternatively, 4,4′-oxydiphthalic dianhydride (OD
PA) and pyromellitic dianhydride and 1,3-bis (4-aminophenoxybenzene).

The above thermocompression-bondable polyimide is obtained by mixing the above-mentioned components and, if necessary, other tetracarboxylic dianhydrides and other diamines in an organic solvent at about 100 ° C. or lower.
In particular, the solution is reacted at a temperature of 20 to 60 ° C. to form a solution of polyamic acid, and the solution of polyamic acid is used as a dope solution, a thin film of the dope solution is formed, and the solvent is removed from the thin film by evaporating the solvent. And imide cyclization of the polyamic acid. Further, the solution of the polyamic acid produced as described above was used for 150 to 2 hours.
Heat to 50 ° C. or add imidizing agent to
The reaction is carried out at a temperature of 0 ° C. or less, particularly 15 to 50 ° C., and after the imide cyclization, the solvent is evaporated, or the powder is precipitated in a poor solvent to obtain a powder. An organic solvent solution of the functional polyimide can be obtained.

In the present invention, other tetracarboxylic dianhydrides, for example, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl)
Propane dianhydride or 2,3,6,7-naphthalenetetracarboxylic dianhydride such as 3,3 ′,
It may be replaced by 4,4'-biphenyltetracarboxylic dianhydride. Further, other diamines such as 4,4′-diaminodiphenyl ether, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenylmethane, and 2,2 may be used as long as the physical properties of the thermocompression-bondable polyimide are not impaired.
-Bis (4-aminophenyl) propane, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenyl) diphenyl ether, 4,4 '
-Bis (4-aminophenyl) diphenylmethane, 4,
4'-bis (4-aminophenoxy) diphenyl ether, 4,4'-bis (4-aminophenoxy) diphenylmethane, 2,2-bis [4- (aminophenoxy) phenyl] propane, 2,2-bis Flexible aromatic diamines having a plurality of benzene rings such as [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1,4
-Diaminobutane, 1,6-diaminohexane, 1,8
-Diaminooctane, 1,10-diaminodecane, 1,
It may be replaced by an aliphatic diamine such as 12-diaminododecane, or a diaminodisiloxane such as bis (3-aminopropyl) tetramethyldisiloxane. The proportion of the other aromatic diamine used is preferably 20 mol% or less, particularly preferably 10 mol% or less based on the total diamine. The proportion of the aliphatic diamine and diaminodisiloxane used is preferably 20 mol% or less based on the total diamine. Exceeding this ratio lowers the heat resistance of the thermocompression bonding polyimide. In order to block the amine end of the thermocompression-bondable polyimide, dicarboxylic acid anhydrides, for example, phthalic anhydride and a substituted product thereof, hexahydrophthalic anhydride and a substituted product thereof, succinic anhydride and a substituted product thereof, in particular, Phthalic anhydride may be used.

In order to obtain the thermocompression-bondable polyimide according to the present invention, the amount of the diamine (as the number of moles of amino group) used in the organic solvent is the total number of moles of the acid anhydride (tetraacid dianhydride and dicarboxylic acid). (Total moles of anhydrides as anhydride groups), preferably 0.92
To 1.1, particularly 0.98 to 1.1, especially 0.99 to 1.1, and the amount of the dicarboxylic anhydride used is based on the molar amount of the acid anhydride group of the tetracarboxylic dianhydride. Each component can be reacted in such a ratio that the ratio is preferably 0.05 or less.

When the use ratio of the diamine and the dicarboxylic anhydride is out of the above range, the molecular weight of the obtained polyamic acid, that is, the thermocompression-bondable polyimide is small,
The adhesive strength of the laminate with the metal foil is reduced. Also,
For the purpose of limiting the gelling of the polyamic acid, a phosphorus-based stabilizer such as triphenyl phosphite, triphenyl phosphate or the like is used in the range of 0.01 to 1% with respect to the solid content (polymer) concentration at the time of polyamic acid polymerization. Can be added.
Further, a basic organic compound can be added to the dope solution for the purpose of accelerating imidization. For example, imidazo
, 2-imidazole, 1,2-dimethylimidazo-
, 2-phenylimidazole, benzimidazole,
Isoquinoline, substituted pyridine and the like can be used in a proportion of 0.05 to 10% by weight, particularly 0.1 to 2% by weight based on the polyamic acid. Since these form a polyimide film at a relatively low temperature, they can be used to avoid insufficient imidization. In addition, for the purpose of stabilizing the adhesive strength, a thermocompression-bonding polyimide raw material dope was used.
An organic aluminum compound, an inorganic aluminum compound or an organic tin compound may be added to the mold. For example, aluminum hydroxide, aluminum triacetylacetonate or the like is used as an aluminum metal for polyamic acid.
It can be added at a ratio of at least ppm, especially 1 to 1000 ppm.

The organic solvent used for the production of the polyamic acid is N-methyl-2-pyrrolidone, N,
N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, dimethylsulfoxide, hexamethylphosphoramide, N-methylcaprolactam, cresols and the like. These organic solvents may be used alone or in combination of two or more.

In the production of the multilayer polyimide film of the present invention, for example, a polyamic acid solution of the above-mentioned heat-resistant polyimide for the base layer and a solution of the thermocompression-bondable polyimide or a precursor thereof for the thermocompression bonding layer are co-extruded, and this is extruded. Casting coating on the support surface such as stainless steel mirror surface, belt surface, etc.
It is preferable to set the semi-cured state at 100 to 200 ° C. or the dried state before that. Treating a cast film at a high temperature exceeding 200 ° C. tends to cause defects such as a decrease in adhesiveness in the production of a multilayer polyimide film. The semi-cured state or a state before that means that it is in a self-supporting state by heating and / or chemical imidization.

Co-extrusion of the above-mentioned solution of a polyamic acid for providing a polyimide for the base layer with a solution of a polyamic acid or a solution of a polyimide for providing a thermocompression-bonding polyimide is disclosed in, for example, Japanese Patent Application Laid-Open No. 3-180343 (Japanese Patent Publication No.
No. 102661), it can be supplied to a three-layer extrusion molding die by a coextrusion method and cast on a support. On both surfaces of the extruded material layer providing the base layer polyimide, a polyamic acid solution or a polyimide solution providing the thermocompression-bondable polyimide is laminated to form a multilayer film-like material, dried, and then heated to a glass transition temperature of the thermocompression-bondable polyimide. (Tg) or higher and a temperature lower than the temperature at which deterioration occurs, preferably 250 to 420 ° C. (surface temperature measured by a surface thermometer) (preferably at this temperature for 1 to 60 minutes) ) Dried and imidized,
A multilayer extruded polyimide film having a thermocompression-bondable polyimide on both sides of the substrate layer polyimide can be produced.

The thermocompression-bondable polyimide according to the present invention comprises:
By using the above-mentioned acid component and diamine component, the glass transition temperature is preferably 190 to 280 ° C., particularly 200 to 275 ° C. It does not melt at a temperature in the range of not less than the glass transition temperature and not more than 300 ° C., which is achieved by substantially not causing gelation of the polyimide, and has an elastic modulus (usually, the elastic modulus at 275 ° C. is 50 ° C.). (Approximately 0.001 to 0.5 times the modulus of elasticity).

In the present invention, the thickness of the polyimide film (layer) of the base layer is preferably 5 to 125 μm, and the thickness of the thermocompression-bondable polyimide (Y) layer is 1 to 25 μm.
m, particularly preferably 1 to 15 μm, and particularly preferably 2 to 12 μm. The thickness of the thermocompression-bondable polyimide (Y) layer is preferably not less than the surface roughness (Rz) of the metal foil used.

Examples of the metal foil (for a circuit) used in the present invention include various metal foils such as copper, aluminum, gold, and alloy foils, and preferably, rolled copper foil, electrolytic copper foil, and the like. . As the metal foil, the surface roughness Rz is equal to 0.
Those having a size of 5 μm or more are preferred. The metal foil preferably has a surface roughness Rz of 10 μm or less, particularly preferably 7 μm or less. Such a metal foil, for example, a copper foil is VLP, L
Also known as P (or HTE). The thickness of the metal foil is not particularly limited, but 5 to 60 μm, particularly 5 to 20 μm
Is preferred.

In the present invention, it is necessary to use a peelable reinforcing material. Examples of such a reinforcing material include a heat-resistant film and a metal foil having an Rz of less than 3 μm. As the heat-resistant film as the reinforcing material, a fluororesin (for example, PTFE or the like),
A polyimide film (Ubelex S or Upixex SMB, manufactured by Ube Industries) and the like. Examples of the metal foil having a surface roughness Rz of less than 3 μm include a rolled aluminum foil. In the present invention, Rz (peelable reinforcing material) <R
It is preferably z (metal foil for circuit).

In the present invention, at least one pair of pressurized sheets are prepared by laminating a metal foil on one side and the reinforcing material on the other side of a multilayer polyimide film having a thermocompression-bondable polyimide layer on both sides of the heat-resistant polyimide layer. The temperature of the pressurized part is continuously higher than the glass transition temperature of the thermocompression-bondable polyimide by 3 members.
The polyimide single-layered product of the present invention can be produced by thermocompression bonding under heating at a temperature of 0 ° C. or more and 420 ° C. or less. Such a pressing member includes a pair of pressure-bonded metal rollers.
(Compression part may be made of metal or ceramic sprayed metal) or double belt press. Particularly, it can be thermocompression-bonded and cooled under pressure. Among them, hydraulic double belt press is particularly preferable. It can be suitably mentioned. In the present invention, the above-mentioned pressure member, for example, a metal roll, preferably a double belt press is used, and the above-mentioned multilayer polyimide film, metal foil and reinforcing material are superimposed and continuously heated. By crimping, a polyimide single-layered body can be manufactured.

The method of the present invention is particularly useful when the multi-layer polyimide film and the metal foil are supplied to the pressing member in the form of a roll, respectively, and the polyimide single-layered body can be obtained in the form of a roll. It is suitable.

According to the above-described method, a metal foil is laminated on one side of the multilayer polyimide film with an adhesive strength of at least twice the adhesive strength between the reinforcing material and the polyimide, and the reinforcing material has an adhesive strength of 0.001 kg / on the other surface. It is possible to obtain a polyimide single-layered body having a reinforcing material laminated at a thickness of not less than 0.5 cm / cm and not more than 0.5 kg / cm. The polyimide single-layer layer body having the reinforcing material of the present invention has good moldability and does not cause wrinkles even when the reinforcing material is peeled off. Materials, for example, the same or different kinds of metal foils, metal plates, ceramic plates, and the like can be overlapped and laminated by pressing under heating. Alternatively, after performing a drilling process, a bending process, a drawing process, or the like, the reinforcing material is peeled off to form a one-area layer body, and another base material can be laminated on the thermocompression-bonded polyimide surface by heating under pressure.

[0029]

The present invention will be described below in more detail with reference to examples and comparative examples. In each of the following examples, parts mean parts by weight. In each of the following examples, the evaluation of physical properties and the peel strength of the copper foil laminated film were measured according to the following methods. Linear expansion coefficient: Measured (MD) at a heating rate of 20 to 200 ° C and 5 ° C / min. Peel strength of laminate: 90 ° peel strength was measured. Appearance: The reinforcing material was peeled off, and the appearance was evaluated by observing the appearance including the presence or absence of wrinkles during processing of the polyimide single-layer structure.

Reference Example Synthetic Example 1 of Dope for Producing Substrate Layer Polyimide A reaction vessel equipped with a stirrer and a nitrogen inlet tube was charged with N-methyl-
2-Pyrrolidone was added, and paraphenylenediamine (PPD) and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (s-BPDA) were further added at 1000: 9.
At a molar ratio of 98, the monomer concentration was 18% (% by weight, the same applies hereinafter). After completion of the addition, the reaction was continued for 3 hours while maintaining the temperature at 50 ° C. The obtained polyamic acid solution is a brown viscous liquid, and the solution viscosity at 25 ° C. is about 15
It was 00 poise. This solution was used as a dope.

Synthesis of Dope for Production of Thermocompression Bondable Polyimide
1 In a reaction vessel equipped with a stirrer and a nitrogen inlet tube, add N-methyl-
2-Pyrrolidone was added, and 1,3-bis (4-aminophenoxy) benzene (TPE-R) and 2,3,3
3 ', 4'-biphenyltetracarboxylic dianhydride (a
-BPDA) in a molar ratio of 1000: 1000 to give a monomer concentration of 22%, and triphenyl phosphate was added in an amount of 0.1% by weight of the monomer. After completion of the addition, the reaction was continued for 1 hour while maintaining the temperature at 25 ° C. The solution viscosity at 25 ° C. was about 2000 poise. This solution was used as a dope.

Production of Multilayer Polyimide Film A film-forming apparatus provided with a three-layer extrusion die (multi-manifold type die) of the above-mentioned base layer polyimide production dope and thermocompression bonding polyimide production dope. Used, it was cast on a metal support from a three-layer extrusion die and dried continuously with hot air at 140 ° C. to form a solidified film. After the solidified film is peeled from the support, the film is heated at 200 ° C.
Then, the temperature was gradually raised to 320 ° C. to remove the solvent and imidize, and a long three-layer extruded polyimide film was taken up on a take-up roll. The obtained three-layer extruded polyimide film has a thickness of each layer of 4 μm / 17 μm / 4 μm and a linear expansion coefficient (50-200 ° C.) of MD: 23 p.
pm / ° C, TD: 19 ppm / ° C, average: 21 ppm /
° C, the tensile modulus is 526 kg / mm ² , the glass transition temperature of the polyimide of the base layer is not confirmed at a temperature of 400 ° C or less, and the polyimide of the thermocompression bonding layer has a glass transition temperature of 25 ° C.
It was 0 ° C., the elastic modulus at 275 ° C. was 0.002 times the elastic modulus at 50 ° C., and substantially no gelation occurred.

Example 1 The above-mentioned three-layer extruded polyimide film was preheated to about 150 ° C. and continuously supplied to a double belt press, and rolled from both sides of the electrodeposited copper foil (Fukuda Metal Foil & Powder Co., Ltd.) Made by company, CF-T9, VP, Rz is 5μm, thickness 18μ
m) and a fluororesin (PTFE, Rz less than 1 μm, thickness 38 μm) are continuously supplied, and the temperature of the heating zone (maximum heating temperature) 380 ° C., the temperature of the cooling zone (minimum cooling temperature) At 117 ° C., continuously thermocompression-pressed and cooled under pressure,
The polyimide single-layer body having the reinforcing material was wound up. The evaluation results are shown below. Evaluation result of polyimide single-area layer body with reinforcing material Adhesive strength (kg / cm) Copper foil side: 1.2 kg / cm Reinforcement side: 0.001 kg / cm Workability when peeling off reinforcing material: good, no wrinkles

Example 2 A polyimide film (Ube Industries, U.S.A.) was used as a reinforcing material.
Except that Pyrex S and Rz were changed to 0.01 μm and 25 μm), the same operation as in Example 1 was performed. The results are shown below. Adhesive strength (kg / cm) Copper foil side: 1.3 kg / cm Reinforcement side: 0.002 kg / cm Workability when peeling off reinforcement: good, no wrinkles

Example 3 A polyimide film (Ube Industries, U.S.A.)
Pyrex SMB, Rz was less than 2 μm, 40 μm). The results are shown below. Adhesive strength (kg / cm) Copper foil side: 1.2 kg / cm Reinforcement side: 0.01 kg / cm Workability when peeling off reinforcement: good, no wrinkles

Example 4 Example 4 was carried out in the same manner as in Example 1 except that the reinforcing material was changed to a rolled copper foil (Rz 0.7 μm on the shiny surface laminated with polyimide, thickness 15 μm). The results are shown below. Adhesive strength (kg / cm) Copper foil side: 1.1 kg / cm Reinforcement side: 0.3 kg / cm Workability when peeling off reinforcement: good, no wrinkles

Example 5 Electrolytic copper foil (manufactured by Fukuda Metal Foil & Powder Co., Ltd.)
(CF-T9, VP, Rz is 4.5 μm, thickness 12 μm)
As a reinforcing material, a polyimide film (made by Ube Industries, UPYLEX S, Rz 0.01 μm, thickness 25 μm)
Was carried out in the same manner as in Example 1 except that was used. The results are shown below. Adhesive strength (kg / cm) Copper foil side: 1.0 kg / cm Reinforcement side: 0.002 kg / cm Workability when peeling off reinforcement: good, no wrinkles

Example 6 Electrolytic copper foil (manufactured by Fukuda Metal Foil Powder Co., Ltd.)
Except for using CF-T9, VP, and Rz of 4.5 μm and a thickness of 9 μm), the same operation as in Example 5 was performed. The results are shown below. Adhesive strength (kg / cm) Copper foil side: 0.9 kg / cm Reinforcement side: 0.002 kg / cm Workability when peeling off reinforcement: good, no wrinkles

Example 7 Rolled copper foil (manufactured by Japan Energy Co., Ltd.
BHY13HT, Rz was 0.8 μm, and thickness was 18 μm), except that the same operation as in Example 5 was performed. The results are shown below. Adhesive strength (kg / cm) Copper foil side: 1.3 kg / cm Reinforcement side: 0.002 kg / cm Workability when peeling off reinforcement: good, no wrinkles

Example 8 Rolled copper foil (manufactured by Japan Energy Co., Ltd.,
BHY22B, Rz was 0.8 μm, and thickness was 12 μm), except that Example 5 was used. The results are shown below. Adhesive strength (kg / cm) Copper foil side: 1.0 kg / cm Reinforcement side: 0.002 kg / cm Workability when peeling off reinforcement: good, no wrinkles

Example 9 The same procedure as in Example 1 was carried out except that the reinforcing material was changed to aluminum foil (Rz 1.7 μm, thickness 20 μm, manufactured by Sun Aluminum Industry Co., Ltd.). The results are shown below. Adhesive strength (kg / cm) Copper foil side: 1.0 kg / cm Reinforcement side: 0.005 kg / cm Workability when peeling off reinforcement: good, no wrinkles

Comparative Example 1 Metal foil on both sides: electrolytic copper foil (manufactured by Fukuda Metal Foil & Powder Co., Ltd., CF-T9, VP, Rz: 5 μm, thickness: 18 μm)
Was carried out in the same manner as in Example 1 except that was laminated. The results are shown below. Adhesive strength (kg / cm) Copper foil side: 1.2 kg / cm Copper foil side: 1.2 kg / cm Workability when peeling off reinforcing material: poor, wrinkles

Comparative Example 2 Metal foil on both sides: electrolytic copper foil (manufactured by Fukuda Metal Foil & Powder Co., Ltd., CF-T9, VP, Rz 4.5 μm, thickness 9 μm)
m) was carried out in the same manner as in Example 1 except that m) was laminated. The results are shown below. Adhesive strength (kg / cm) Copper foil (upper): 0.9 kg / cm Copper foil (lower): 0.8 kg / cm Workability when peeling off reinforcing material: poor, wrinkles

Example 10 The polyimide single-layered layered body reinforcing material having the reinforcing material obtained in each of Examples 1 to 9 was peeled off, and an electrolytic copper foil (18 μm thick) was used.
m) at 340 ° C. under a condition of 60 kg ² / cm × 5 minutes to obtain a substrate. During the forming process, no wrinkles were generated, the surface condition was good, and bending and drawing could be performed without any problem.

[0045]

According to the present invention, there is provided a polyimide single-sided metal foil laminate which has the above-mentioned structure, has good moldability and hardly generates wrinkles even when the reinforcing material is peeled off. Thus, a polyimide single-layer material having a material can be obtained.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kazuhiko Yoshioka 10F, 1978 Kogushi, Obe-shi, Ube-shi, Yamaguchi F-term in the Ube Chemical Plant Ube Chemical Factory 4F100 AB01D AB17 AB33D AK49A AK49B AK49C BA05 BA07 BA10D BA10E CB00 DH00E EC032 EH20 EJ192 JJ03A JL11D JL12B JL12C YY00D YY00E

Claims (5)

[Claims] 1. A multilayer polyimide film having a thermocompression-bondable polyimide layer on both sides of a heat-resistant polyimide layer, a metal foil laminated on one side with an adhesive strength of at least twice the adhesive strength between the reinforcing material and the polyimide, and Has a bonding strength of 0.00
A polyimide single-layered body having a reinforcing material laminated at 1 kg / cm or more and 0.5 kg / cm or less. 2. The polyimide single-layer laminate having a reinforcing material according to claim 1, wherein the multilayer polyimide film is a multilayer extruded polyimide film obtained by integrally laminating a thermocompression-bondable polyimide layer on both surfaces of a heat-resistant polyimide layer. 3. A reinforcing material characterized by laminating a metal foil on one surface and a reinforcing material on the other surface of a multilayer polyimide film having a thermocompression-bonding polyimide layer on both surfaces of a heat-resistant polyimide layer, and thermocompressing them. A method for producing a polyimide single-layered product having: 4. The method for producing a polyimide single-layered product having a reinforcing material according to claim 3, wherein the thermocompression bonding is performed by a continuous laminating device to form a long roll-shaped laminated product. 5. The method according to claim 3, wherein the thermocompression bonding is performed by a long roll-shaped double belt press.