JPH0691778A - Manufacture of long both-side flexible metal laminated plate - Google Patents

Abstract

PURPOSE:To improve a peel strength and to prevent generation of a blister at the time of dipping it in a solder bath by laminating resin of a long one-side flexible metal laminated plate on a resin layer side of a metal laminated plate using refractory resin by heating-pressurizing, and then heating it at a glass transition temperature or higher. CONSTITUTION:The method for manufacturing a long both-side flexible metal laminated plate comprises the steps of laminating a metal foil of copper, nickel, etc., or a resin layer of a long one-side flexible metal laminated plate 1 using another refractory resin at the resin layer side of the plate 1 using the resin made of polyimide resin by continuously heating-pressurizing to form a laminated plate 8, and then post-heating it at glass transition temperature or higher of the resin. As the method for continuously pressurizing and laminating, a roll press 5 is used. The roll of one or both sides is formed of rubber. Or, the post-heating is conducted under pressure after it is wound in a rolled state by a winder 6.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a double-sided flexible metal laminate, which is becoming widespread in the field of electronic industry. The present invention relates to a method for manufacturing a flexible metal laminated plate.

[0002]

2. Description of the Related Art A flexible metal laminated plate is mainly used as a base material for a flexible printed wiring board, but is also used as a surface heating element, an electromagnetic wave shielding material, a flat cable, a packaging material and the like. . Further, in recent years, with the miniaturization and high density of electronic devices using a printed wiring board, efficient high density can be achieved, so that the use of double-sided flexible metal laminated plates is increasing.
Furthermore, TAB (Tape a
There is an increasing demand for a long double-sided flexible metal laminate as a film carrier for utomated bonding).

However, since the conventional double-sided flexible metal laminate is manufactured by sticking metal foils on both sides of a polyimide film using an adhesive such as an epoxy resin, heat resistance, chemical resistance, and The properties such as flame retardancy and electrical properties are controlled by the properties of the adhesive used, and the excellent properties of polyimide are not fully utilized, and particularly the heat resistance is not sufficient.

In order to overcome the drawbacks of the conventional double-sided flexible metal laminate having this adhesive, a metal foil or a polyimide layer of the all-polyimide single-sided flexible metal laminate is directly attached to the polyimide layer of the all-polyimide one-side flexible metal laminate. Attempts have been made to obtain an all-polyimide double-sided flexible metal laminate plate that has no adhesive by heating and pressing. According to our study, problems such as low peel strength and blistering during immersion in a solder bath have occurred. In addition, according to our study, especially for a long-sized all-polyimide double-sided flexible metal laminated plate which cannot be manufactured by a batch press machine and has a length of 2 m or more, it is possible to uniformly heat and pressurize it when laminating it. At present, satisfactory results have not been obtained because it is difficult to pressurize and it is difficult to take a long pressurizing time.

[0005]

DISCLOSURE OF THE INVENTION According to the present invention, there is no adhesive layer in order to fully utilize the characteristics of a super heat resistant resin film having excellent heat resistance, chemical resistance, flame retardancy and electrical characteristics. The purpose is to provide a long-shaped all-heat-resistant resin double-sided flexible metal laminate plate, which has a particularly high peel strength, does not cause blisters when immersed in a solder bath, has no adhesive layer, and has a length of 2 m. It is intended to provide a long-sized excellent all-super heat-resistant resin double-sided flexible metal laminate plate as described above. Such a long double-sided flexible metal laminate is extremely useful industrially, especially in the electronics industry.

[0006]

Means for Solving the Problems The inventors of the present invention do not have an adhesive agent that causes deterioration of various characteristics, have a high peel strength, and have no blisters when soaking in a solder bath As a result of diligent examination of the method for producing a heat-resistant resin double-sided flexible metal laminate, the peel strength of the laminate using the all-super heat-resistant resin polyimide single-sided flexible metal laminate is improved according to the heating temperature and the heating time, The present invention was completed by discovering that blisters at the time of dipping in a solder bath can be eliminated by applying uniform pressure so as to eliminate voids between the layers of the laminate.

That is, according to the present invention, a long-sided single-sided flexible metal laminated plate using a super heat-resistant resin is provided with a metal foil or another super-heat-resistant resin on the resin layer side. Continuously heats the resin layer of the flexible metal laminate
A method for producing a long-sized all-ultra-heat-resistant resin double-sided flexible metal laminate, which comprises press-laminating and then post-heating at a temperature not lower than the glass transition temperature of the resin, preferably super-heat-resistant The resin is a polyimide resin and is a method of using a roll press as a method of continuously pressing and laminating, and the surface of one or both rolls is made of rubber as a method of continuously pressing and laminating. A method using a press, or a method in which post-heating is rolled up and then performed under pressure.

The present invention also has a peel strength of 0.8 kgf.
/ Cm or more and 5 kgf / cm or less, and also provides a new long-shaped all-ultra-heat-resistant resin double-sided flexible metal laminated plate that does not show swelling or peeling even if immersed in a solder bath at 260 ° C for 5 seconds or more To do.

According to our study, when laminating by continuously heating and pressurizing, it is necessary to pressurize uniformly so as not to leave voids between the layers between the laminated bodies in order to prevent swelling during immersion in the solder bath. is important. As a method of continuously pressurizing and laminating, there is also an inching press or the like, but the method by roll pressing can easily achieve uniform heating / pressurization without leaving voids between the above-mentioned laminated bodies, and in terms of production efficiency. ,preferable. Even more preferably, the rotation unevenness of the roll, the unevenness of the roll diameter,
Even if there is unevenness in the thickness of a single-sided flexible metal laminate or copper foil, it can be absorbed by large elastic deformation, and pressure lamination with extremely high uniformity can be realized.The surface of the roll on one or both sides is made of rubber. One is to use a roll press. The type of rubber used for the roll at this time is not particularly limited as long as it is an elastomer, and natural rubber, butadiene rubber, isoprene rubber, styrene-butadiene rubber,
Examples thereof include nitrile rubber, acrylic rubber, urethane rubber, chloroprene rubber, butyl rubber, and the like. These may be used alone or in combination of two or more, or may be vulcanized. When the roll is used directly as a heating source,
Silicone rubber, fluororubber and the like having high heat resistance are preferable.
Although not generally called rubber, a plastic material having an elastic modulus of 100 kgf / mm ² or less accompanied by large elastic deformation may be used.

The temperature for continuously heating and pressurizing and laminating is preferably the glass transition temperature of the resin or higher, more preferably the glass transition temperature + 20 ° C. or higher. At this time, the press source, the roll itself, or another heater may be used as the heating source. Further, the linear pressure at the time of pressurizing is preferably about 0.5 to 10 kgf / cm.

In the present invention, it is important to post-heat above the glass transition temperature of the resin after laminating the all-super heat-resistant resin single-sided flexible metal laminate. In the case of continuous lamination, it is difficult to take sufficient heating / pressurizing time to develop adhesive strength. Therefore, when the post-heating is not performed at all, the adhesive strength is such that thin papers are attached to each other by static electricity, and it cannot be used at all. However, post-heating above the glass transition temperature of the resin probably causes a physical bond due to mutual diffusion or a chemical bond due to a cross-linking reaction to develop an adhesive force, and generally required peel strength of 1.0 kgf. We have found that it will be possible to secure a sufficient value of / cm or more.

The temperature of post-heating after the lamination is higher than the glass transition temperature of the resin, and the resin must be in a rubber state.
Even if post-heating is performed at a temperature lower than this, the peel strength is low, and swelling occurs when the solder bath is dipped, so that it cannot be used practically. Further, industrially, the glass transition temperature of the resin is preferably + 50 ° C. or higher because the post-heating time can be shortened.

The time for post-heating depends on the heat-resistant resin used in the laminate, but is generally preferably 5 minutes or longer,
It is more preferably 30 minutes to 50 hours. Further, the post-heating operation may be carried out continuously, or if the post-heating time is long, it may be carried out batchwise by winding it into a roll and then using a heating dryer.

Further, when the post-heating operation is carried out under pressure using an autoclave or the like, it is possible to suppress the minute peeling due to the minute adhesion failure and further improve the peel strength, so that the long run is stably produced. Is more preferable. The pressure at this time is 0.5 kgf / cm
Higher than ^{2 is} more preferable, but due to the problem of pressure vessel, 1
It is preferably 00 kgf / cm ² or less.

The post-heating operation may be performed in an atmosphere of an inert gas such as nitrogen, argon or carbon dioxide in order to prevent the metal foil as the support from being oxidized. Examples of the super heat resistant resin include thermosetting resins such as Zyloc resin, imide resin, and imideamide resin, and thermoplastic resins include polyether sulfone, polysulfone, polyether ether ketone, polyimide, and Zydac. Resin etc. are mentioned.

As the thermosetting resin, it is preferable to use a long-sided single-sided flexible metal laminated plate in which the resin layer is B-staged. Hereinafter, the present invention will be described by taking a thermoplastic polyimide as an example for easy understanding. First, a polyimide solution dissolved in a solvent is cast on a metal foil and then heated to remove the solvent, or a polyamic acid solution, which is a polyimide precursor, is cast on the metal foil and then heated to remove the solvent and the imidization reaction. To obtain an all-polyimide single-sided flexible metal laminate plate, and then continuously heat a metal foil on the polyimide layer side of the all-polyimide one-sided flexible metal laminate plate.
Laminate by pressurizing or by heating and pressing continuously with the polyimide layers of the all-polyimide single-sided flexible metal laminate obtained by the previous method inside, and then laminating at a temperature above the glass transition temperature of the resin. The long all-polyimide double-sided flexible metal laminate is manufactured by heating.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. FIG. 1 is a schematic diagram for explaining the present invention. A long metal foil having a long-shaped all-polyimide single-sided flexible metal laminated plate 1 unwound from an unwinding machine 2 and unwound from another unwinding machine 3, or a long-sized all-polyimide single-sided flexible metal laminated board 4; Preferably, the roll press 5 is used to continuously heat and pressurize the layers so that the layers are wound up by a winder 6 into a roll, and then the autoclave 7 is used, preferably in an inert gas atmosphere, to give a glass transition temperature of the resin. After heating for 5 minutes or more,
Long all-polyimide double-sided flexible metal laminate 8
To manufacture.

The polyimide in the present invention has the general formula (I)

[0019]

[Chemical 1] (In the formula, R ₁ is an aliphatic group, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-fused cyclic aromatic group in which an aromatic group is linked directly or by a crosslinking member. A diamine compound represented by a divalent group selected from the group consisting of groups) and a compound represented by the general formula (II)

[0020]

[Chemical 2] (In the formula, R ₂ is an aliphatic group, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-fused cyclic aromatic group in which aromatic groups are linked directly or by a crosslinking member. A tetracarboxylic acid dianhydride represented by a tetravalent group selected from the group consisting of groups)

[0021]

[Chemical 3] (Wherein R ₁ and R ₂ are each as defined above).

Examples of the diamine compound represented by the general formula (I) include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 2-chloro-1, 2-phenylenediamine, 4-chloro-1,2-
Phenylenediamine, 2,3-diaminotoluene, 2,
4-diaminotoluene, 2,5-diaminotoluene,
2,6-diaminotoluene, 3,4-diaminotoluene, 2-methoxy-1,4-phenylenediamine, 4-
Methoxy-1,2-phenylenediamine, 4-methoxy-1,3-phenylenediamine, benzidine, 3,3 '
-Dichlorobenzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether,
3,3'-diaminodiphenyl sulfide, 3,4'-
Diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl sulfoxide, 3,4′-diaminodiphenyl sulfoxide, 4,4′-diaminodiphenyl sulfoxide, 3,
3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 3,
4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane,
3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [ 4- (3-
Aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane,
1,2-bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4- (4-aminophenoxy) phenyl] ethane, 2,2-bis [4- (3-aminophenoxy) Phenyl] propane, 2,2-bis [4
-(4-aminophenoxy) phenyl] propane, 2,
2-bis [4- (3-aminophenoxy) phenyl] butane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy)
Benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (3- Aminophenoxy) phenyl]
Ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3 -Aminophenoxy) phenyl] sulfoxide, bis [4- (4-
Aminophenoxy) phenyl] sulfoxide, bis [4
-(3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone,
Bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis [4- (3-aminophenoxy)
Benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 4,4′-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [3- (3-Aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4
-Amino-α, α-dimethylbenzyl) phenoxy] diphenyl sulfone, bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] ketone, bis [4-
{4- (4-aminophenoxy) phenoxy} phenyl] sulfone, 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3
Examples include -bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene and the like, and these may be used alone or in combination of two or more.

Examples of the tetracarboxylic acid dianhydride represented by the general formula (II) are those represented by the general formula (II):
R ₂ is an aliphatic group; ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, etc., R ₂ is a cyclic aliphatic group; cyclopentane tetracarboxylic dianhydride, cyclohexane tetracarboxylic acid Dianhydride, R
₂ is a monocyclic aromatic group; 1,2,3,4-benzenetetracarboxylic dianhydride, pyromellitic dianhydride,
R ₂ is a condensed polycyclic aromatic group; 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-
Naphthalenetetracarboxylic dianhydride, 1,2,5,6
-Naphthalenetetracarboxylic dianhydride, 3,4,9,
10-perylene tetracarboxylic dianhydride, 2,3
6,7-anthracene tetracarboxylic dianhydride, 1,
2,7,8-phenanthrene tetracarboxylic dianhydride, R ₂ is a non-fused cyclic aromatic group linked directly to an aromatic group; 3,3 ', 4,4'-biphenyl tetracarboxylic acid anhydride, 2,2 ', 3,3'-biphenyl tetracarboxylic dianhydride, R ₂ is a non-fused cyclic aromatic groups linked by a bridge member to an aromatic group; 3,3', 4, 4 '
-Benzophenone tetracarboxylic dianhydride, 2,
2 ', 3,3'-benzophenone tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl)
Propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) ether Dianhydride, bis (3,4
-Dicarboxyphenyl) sulfone dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride,
1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 4 , 4 '-(p-phenylenedioxy)
Examples thereof include diphthalic acid dianhydride and 4,4 ′-(m-phenylenedioxy) diphthalic acid dianhydride, and these may be used alone or in admixture of two or more.

To the polyimide of the present invention, a coupling agent is added to increase the adhesive strength with the metal foil, a surfactant is added to improve the surface smoothness, and other characteristics of the polyimide are changed. You may add the additive and filler for making it.

The method for producing the polyimide of the present invention is not particularly limited, and conventionally known methods can be applied. There is no particular limitation on the method of casting the polyimide solution or polyamic acid solution of the present invention on a metal foil and heating and drying to obtain an all-polyimide single-sided flexible metal laminate plate. Conventionally known comma coater, T-die, roll coater It may be applied using a coating device such as a knife coater or a reverse coater, and heated and dried for a sufficient time and temperature to cure.

The polyimide layer of the present invention can be a single layer,
It may be composed of multiple polyimide layers having different glass transition points, but it is preferable that the polyimide layer of the surface to be laminated is at least a thermoplastic polyimide in order to increase the peel strength, and further, the polyimide to be laminated The glass transition point of the layer is preferably equal to or lower than the glass transition points of other polyimide layers, because the heat resistance as a double-sided flexible metal laminate plate can be increased and the temperature at the time of pressing by a press can be lowered.

The type of the metal foil used in the present invention is not particularly limited, and usually copper, nickel, aluminum or the like is used. Copper foil is often used as the metal foil for forming the printed circuit, but either rolled copper foil or electrolytic copper foil can be used. The thickness of the metal foil is usually 7 to 100 μm, preferably 10 to 50 μm. In addition, in order to enhance the adhesive force between the metal foil and the polyimide that is in direct contact with the metal foil, a simple substance of metal or its oxide or alloy on the metal foil, for example, when the metal foil is a copper foil, a simple substance of copper or copper oxide is used. Inorganic substances such as nickel-copper alloy and zinc-copper alloy may be formed, and
Coupling agents such as aminosilane, epoxysilane, and mercaptosilane other than inorganic substances may be formed on the metal foil. The present invention also has a peel strength of 0.8 kgf / c.
m or more and 5 kgf / cm or less, and no blistering or peeling is observed even when immersed in a solder bath at 260 ° C. for 5 seconds or more,
This is a new long-shaped all-super heat resistant resin double-sided flexible metal laminate.

[0028]

【Example】

Synthesis Example 1 Equimolar amounts of 4,4′-bis (3-aminophenoxy) biphenyl and bis (3,4-dicarboxyphenyl) ether dianhydride were mixed at room temperature under a nitrogen atmosphere under N, N-dimethylacetamide solvent. Polymerization was carried out for about 20 hours to obtain a polyamic acid solution. The logarithmic viscosity (N,
N-dimethylacetamide, concentration 0.5g / 100ml
Solvent, measured at 35 ° C) was 2.0 dl / g and glass transition temperature was 230 ° C. 19w of this polyamic acid solution
It was diluted to t% and the rotational viscosity was adjusted to 10,000 cps.

Synthesis Example 2 Equimolar amounts of 1,3-bis (3-aminophenoxy) benzene and 3,3 ', 4,4'-benzophenonetetracarboxylic acid were mixed at room temperature under a nitrogen atmosphere with N, N-dimethyl. Polymerization was performed for about 20 hours in an acetamide solvent to obtain a polyamic acid solution. Logarithmic viscosity of this polyamic acid solution (N, N-dimethylacetamide, concentration 0.5 g / 100 ml solvent,
Measured at 35 ° C.) is 1.3 dl / g, glass transition temperature is 2
It was 00 ° C. This polyamic acid solution was diluted to 18 wt% to adjust the rotational viscosity to 10,000 cps.

Example 1 Using a coating machine, 3 parts of the polyamic acid obtained in Synthesis Example 1 was used.
Directly and uniformly apply to a rolled copper foil with a thickness of 5 μm, dry in a drier, and heat at 300 ° C. for 10 minutes to complete the imidization reaction to obtain a long all-polyimide single-sided flexible metal laminate plate. It was The residual solvent amount of this polyimide was 0.1 wt% or less, and the thickness was 15 μm. All-polyimide single-sided flexible metal laminate plate so that the polyimide layers are aligned inside, temperature 260 ° C, line pressure 2k
Under the condition of gf / cm, continuous roll pressing was performed using a roll press machine whose both roll surfaces were made of rubber, and wound into a roll shape. Then, this was post-heated in an inert gas atmosphere at a temperature of 280 ° C. or higher for a glass transition temperature for 30 minutes using a heat dryer to obtain a long all-polyimide double-sided flexible metal laminate plate. The peel strength of this double-sided flexible metal laminate is 2.0 kgf / cm,
It has sufficient strength compared to the commonly required peel strength of 1.0 kgf / cm, and no blistering or peeling is observed even after immersion in a solder bath at 260 ° C for 60 seconds, and heat resistance is also satisfactory. It was possible.

Comparative Example 1 The peel strength of a long-sided double-sided flexible metal laminate plate which was subjected to continuous roll pressing and no post-heating was carried out in exactly the same manner as in Example 1 had a large variation, and the peel strength was 0. It was 1 kgf / cm or less, and after dipping in a solder bath at 260 ° C. for 10 seconds, a lot of blistering and peeling occurred, and neither peel strength nor heat resistance was satisfactory.

Example 2 Using a coating machine, the polyamic acid obtained in Synthesis Example 1 was mixed with 3 parts.
Directly and uniformly apply it directly to a 5 μm thick electro-deposited copper foil, dry in a dryer and heat at 300 ° C. for 10 minutes to complete the imidization reaction to obtain a long all-polyimide single-sided flexible metal laminate plate. It was This polyimide had a residual solvent amount of 0.1 wt% or less and a thickness of 25 μm. This long all-polyimide single-sided flexible metal laminate plate and an electrolytic copper foil having a thickness of 35 μm are arranged using the device having the configuration shown in FIG. Temperature 2
Continuous roll pressing was performed by a roll pressing machine under the conditions of 60 ° C. and a linear pressure of 2 kgf / cm, and wound into a roll shape.
Next, this was post-heated in an inert gas atmosphere at a temperature of 280 ° C. for 10 minutes using a heat dryer to obtain a long all-polyimide double-sided flexible metal laminate plate. The peel strength of this double-sided flexible metal laminate is 1.5 kgf / c
Even after immersion in a solder bath at 260 ° C. for 60 seconds, no blistering or peeling was observed, and the peel strength and heat resistance were sufficiently satisfactory.

COMPARATIVE EXAMPLE 2 The same procedure as in Example 2 was carried out until continuous roll pressing, and post-heating was carried out for 10 hours at 150 ° C., which is lower than the glass transition temperature of the resin, in an inert gas atmosphere. The peel strength of the double-sided flexible metal laminated plate has a large variation and is 0.1 kgf / cm on average, and the peel strength is 260 ° C.
-A large number of rice grain-sized blisters and peeling occurred even after immersion in a solder bath for 10 seconds, and neither peel strength nor heat resistance was satisfactory.

Example 3 Example 2 was repeated except that the polyamic acid obtained in Synthesis Example 2 was used.
A long-shaped all-polyimide double-sided flexible metal laminate was obtained in the same manner as in. The peel strength of this double-sided flexible metal laminate is 1.7 kgf / cm, and is 260 ° C.
No blistering or peeling was observed even after immersion in the solder bath for 60 seconds, and the peel strength and heat resistance were sufficiently satisfactory.

Example 4 The same process as in Example 1 was carried out until the roll press, and the length was 200 m.
The double-sided metal laminate of the present invention is obtained by using an autoclave in an inert gas atmosphere at a temperature of 280 ° C. and a gauge pressure of 9 kgf / cm ² for 10 minutes, followed by heating and pressurization to form a long, all-polyimide double-sided flexible metal laminate Was manufactured. 20m of manufactured 200m double-sided flexible metal laminate
When I sampled at intervals of 1m and inspected,
There was almost no variation in any part, the peel strength was 2.2 kgf / cm, and no blistering or peeling was observed even after immersion in a solder bath at 260 ° C for 60 seconds.
It was possible to stably manufacture even a very long product over m.

[0036]

As described above, according to the present invention,
A long-sided double-sided flexible metal laminate having excellent heat resistance, no adhesive layer and high reliability can be easily manufactured. The present invention also has a peel strength of 0.8 kgf / cm or more and 5 kgf / cm or less, and the peel strength of a solder bath at 260 ° C.
It is intended to provide a novel long-shaped all-super heat-resistant resin double-sided flexible metal laminate plate in which no swelling or peeling is observed even after soaking for more than a second.

[Brief description of drawings]

FIG. 1 is a schematic diagram of an embodiment of the present invention.

[Explanation of symbols]

1 Long all-polyimide single-sided flexible metal laminate 2 Unwinder 3 Unwinder 4 Long metal foil or long all-polyimide single-sided flexible metal laminate 5 Roll press 6 Winder 7 Autoclave 8 Long double-sided Flexible metal laminate

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Keisuke Tsushima 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Shigeki Kijima 1190 Kasama-cho, Sakae-ku, Yokohama, Kanagawa Mitsui Toatsu Chemicals (72) Inventor Shigeyuki Takagi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemicals, Inc.

Claims (6)

[Claims] 1. A long-sided single-sided flexible metal laminated plate using a metal foil or another super-heat-resistant resin on the resin layer side of a long-sided single-sided flexible metallic laminated plate using a super-heat resistant resin. The method for producing a long-sized all-ultra-heat-resistant resin double-sided flexible metal laminate plate, characterized in that the resin layer is continuously heated and pressed to be laminated, and then post-heated at a temperature not lower than the glass transition temperature of the resin. . 2. The method according to claim 1, wherein the super heat resistant resin is a polyimide resin. 3. The manufacturing method according to claim 1, wherein a roll press is used as a method for continuously applying pressure and laminating. 4. The production method according to claim 3, wherein a roll press in which the surface of the roll on one side or both sides is made of rubber is used as a method for continuously pressing and laminating. 5. The manufacturing method according to claim 1, wherein the post-heating is carried out under pressure after being wound into a roll. 6. A peel strength of 0.8 kgf / cm or more 5
Elongated, all-super heat resistant resin double-sided flexible metal laminate with a kgf / cm or less and no blistering or peeling even when immersed in a solder bath at 260 ° C for 5 seconds or more.