JP2003251741A - Polyimide metal laminated sheet and manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyimide metal laminated sheet wherein the adhesion between a metal leaf and a polyimide layer is excellent and which can be used suitably as a material of a high-density circuit board, and a manufacturing method thereof. <P>SOLUTION: In the polyimide metal laminated sheet, a metal layer is formed at least on one side of the polyimide layer. The relative surface roughness of the side of the metal layer being in contact with the polyimide layer is less than 0.30 μm in arithmetic mean roughness (RA), while the amount of deposition of silicon on the side of the metal layer in contact with the polyimide layer is 0.001-0.01 mg/dm<SP>2</SP>, that of chromium 0.01-0.05 mg/dm<SP>2</SP>, that of zinc 0.07 mg/dm<SP>2</SP>or less and that of nickel 0.07-0.5 mg/dm<SP>2</SP>. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide metal laminated board widely used for flexible wiring boards and the like, and a method for manufacturing the same, and more particularly to a high density circuit board material having excellent adhesion between a metal layer and a polyimide layer. The present invention relates to a polyimide metal laminated plate having excellent light transmittance, which can be preferably used as the above, and a manufacturing method thereof.

[0002]

2. Description of the Related Art In recent years, with the miniaturization of electronic equipment, the use of a polyimide metal laminated plate, which enables high density mounting of components and elements as a circuit board material, has been increasing. The wiring width is 10 to 50 μm in order to cope with higher density.
There is a demand for a polyimide-metal laminated plate suitable for processing of a fine pattern, and it is required that the peel strength, which is an index of the adhesion between the metal and the polyimide, is high from the viewpoint of the reliability of wiring.

By the way, a metal foil used for a polyimide metal laminate is made of nickel, zinc, which is called roughening treatment or surface treatment, in order to develop a peel strength with polyimide.
A metal component such as chromium is subjected to a plating treatment or a dipping treatment, and further various silane coupling agents are applied to the outermost layer and dried. Roughening treatment of the metal foil surface is a suitable method to obtain high peel strength, but the problem of short-circuiting between wirings is apt to occur due to metal etching residue called root residue, which has recently been solved. Therefore, attempts have been made to reduce the roughening process. However,
When a metal foil having a small roughening treatment, that is, a metal foil having an Ra as an index of surface roughness of less than 0.30 μm is used, the root strength is improved but the peel strength is from about 0.1 to 1.
Due to the large variation up to about 0 kN / m, the yield was remarkably low and the production was practically difficult.

In a metal foil having a low surface roughness which is hardly subjected to roughening treatment, physical adhesion called anchoring effect (anchor effect) does not work between the polyimide layer and the metal layer,
In order to develop peel strength, chemical interaction between the surface treatment of polyimide and metal foil is required. For this purpose, it is necessary to optimize the combination of surface treatment type and concentration of the metal foil, but there has been no successful example so far. on the other hand,
A flexible metal laminate using a polyimide resin as an insulating layer has excellent characteristics such as heat resistance, chemical resistance, dimensional stability, and electrical characteristics, and therefore various flexible printed wiring boards (FPC), ICs and LSIs. Are widely used for tape automated bonding (TAB), chip-on-film (COF), etc. Also, in recent years, circuit design has become finer, and it is necessary to accurately detect the position of the circuit by image processing when aligning the circuit or mounting an IC chip on the circuit.

For example, in a process of joining an IC or LSI chip called a circuit called inner lead bonding (ILB) to a circuit in a TAB or COF manufacturing line, alignment marks and wirings themselves on the circuit side and marks and bumps on the chip side are formed. It is necessary to recognize the so-called junction point by image processing and to finely adjust the misalignment between the chip and the circuit before joining, but in general TAB, holes called device holes are formed in the insulating layer, so the chip side It is easy to recognize the marks and bumps and there are few problems of misalignment. However, in TAB and COF called an area tab method without such a device hole, it is necessary to recognize marks and bumps on the chip side through the insulating layer, so if the light transmittance of the insulating layer is low, the image becomes unclear. The alignment accuracy is poor and the yield is reduced.

In order to overcome such a problem, a metal film is formed on a polyimide resin film, for example, a Kapton film manufactured by Toray DuPont Co., Ltd. by sputter deposition, and then a metal such as copper is formed by electrolytic plating. A flexible metal laminate obtained by depositing is used. In this method, the surface of the film used for the insulating layer is smooth, and since it is flat with almost no change even after sputter deposition, the light transmittance is high, and image recognition during ILB can be performed, but the manufacturing cost is high, and The adhesion between the metal and the insulating layer is weak, and there is a process of heating especially when bonding IC chips, but in the case of sputtered products, the adhesion after such heating is significantly reduced, and wiring during circuit processing and subsequent processes It has a fatal problem of peeling off, and various measures have been taken to improve it, but it has not been solved yet.

There is also a flexible metal laminate called casting, which is obtained by directly coating and drying a polyimide resin dissolved in a solvent on a metal foil. In this method, in order to secure the adhesion with the metal foil. In addition, conventionally, it was necessary to use a metal foil with a high surface roughness, and the surface of the insulating layer that was in contact with the metal foil became uneven, resulting in poor light transmission due to diffused reflection of light, and image recognition through the insulating layer. Could not be used for applications that require.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, which is excellent in peel strength between a metal layer and a polyimide layer, has less variation, and is capable of forming a fine wiring pattern. To provide a polyimide metal laminate having reliability and suitable for a high-density circuit board material, and a method for manufacturing the same. Another object of the present invention is to provide a flexible metal laminate which is capable of recognizing an image through the insulating layer and has excellent light transmittance of the insulating layer, and also has high adhesion, and a method for producing the same.

[0009]

A polyimide metal laminate according to the present invention is a laminate in which a metal layer is formed on at least one side of a polyimide layer, and a zinc layer on the surface of the metal layer in contact with the polyimide layer is used. It is characterized in that the adhered amount is 0.07 mg / dm ² or less.

The polyimide metal laminate of the present invention is
The surface roughness of the surface of the metal layer in contact with the polyimide layer is less than 0.30 μm in terms of arithmetic average roughness (Ra), and the amount of silicon deposited on the surface of the metal layer in contact with the polyimide layer is 0.001 to 0.001.
0.01 mg / dm ² , and the amount of deposited chromium is 0.0
1 to 0.05 mg / dm ² , and a preferable amount of nickel is 0.07 to 0.5 mg / dm ² . Further, in the polyimide metal laminate of the present invention, it is a preferred embodiment that the polyimide layer after the metal layer is removed by etching has a light transmittance of 10% or more. In the present invention, the metal layer is (1) nickel and / or nickel-zinc alloy, (2) zinc and / or zinc-
Obtained from a metal foil in which a treatment layer is formed by surface-treating a chromium alloy, (3) chromium and / or a zinc-chromium alloy in this order, and a silane coupling agent treatment is performed on the treatment layer. Is preferred.

The treatment layer is made of vanadium, molybdenum,
It is preferable to contain at least one component selected from cobalt, tin, iron, phosphorus, indium, tungsten, aluminum and manganese. In the present invention, the polyimide layer may be a multilayer in which adjacent layers are composed of two or more polyimide layers having different components.

The polyimide in contact with the metal layer is
1,3-bis (3-aminophenoxy) benzene, 4,4
-Bis (3-aminophenoxy) biphenyl and 3,
At least one diamine selected from the group consisting of 3'-diaminobenzophenone and 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3', 4,
A thermoplastic polyimide synthesized from at least one tetracarboxylic dianhydride selected from the group consisting of 4'-benzophenone tetracarboxylic dianhydride and pyromellitic dianhydride, or a composition containing the thermoplastic polyimide. Preferably there is.

The method for producing a polyimide metal laminate according to the present invention is characterized in that a single-layer or multi-layer polyimide film and a metal foil are thermocompression bonded to produce the above-mentioned polyimide metal laminate. Further, in the method for producing a polyimide metal laminate according to the present invention, it is preferable that the polyimide precursor varnish is applied to a metal foil and then dried to produce the above-mentioned polyimide metal laminate.

Furthermore, the method for producing a polyimide metal laminated plate according to the present invention includes the following laminated body (i) or laminated body (ii)
And a laminate (i) or a laminate (ii) below are laminated so that the metal layer is the outermost layer to produce a polyimide metal laminate: laminate (i): single-layer or multi-layer A laminate obtained by heat-pressing a polyimide film and a metal foil and having a metal layer only on one surface (ii): One obtained by applying a precursor varnish of polyimide to the metal foil and then drying. A laminate having a metal layer only on the surface.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The polyimide metal laminate and the method for producing the same according to the present invention will be specifically described below. The polyimide metal laminate according to the present invention has a metal layer formed on at least one surface of the polyimide layer.

Metal Layer The metal layer forming the polyimide metal laminate according to the present invention is selected from copper and copper alloys, stainless steel and its alloys, nickel and nickel alloys (including 42 alloys), aluminum and aluminum alloys, and the like. It is formed of a metal, preferably copper or a copper alloy.

In the metal layer, the surface roughness of the surface in contact with the polyimide layer is less than 0.30 μm in terms of arithmetic average roughness (Ra), preferably 0.28 μm or less, more preferably 0.
It is 25 μm or less, particularly preferably 0.20 μm or less. When the surface roughness of the metal layer on the side in contact with the polyimide layer is within the above range, the metal residue tends to be reduced.
The method of measuring the arithmetic mean roughness will be described later.

The surface of the metal layer that contacts the polyimide layer
Is a 10-point average roughness (R
z) is desired to be 2.5 μm or less, preferably 1.5
It is less than or equal to μm, and more preferably less than or equal to 1.0 μm.
The 10-point average roughness (Rz) is the arithmetic average roughness (R
It is measured in the same manner as a). With the polyimide layer of the metal layer
On the contact surface, the amount of zinc attached is 0 to 0.07 mg / dm ²
And preferably the amount of silicon deposited is 0.001
0.01 mg / dm²And the amount of chromium deposited is 0.0
1-0.05 mg / dm²And the amount of zinc attached is 0
0.07mg / dm²And the amount of nickel deposited was 0.
07-0.5 mg / dm²And more preferably
Has a silicon deposition amount of 0.002 to 0.006 mg / d.
m², Chromium adhesion amount is 0.02-0.03mg / d
m², Zinc adhesion amount is 0-0.05mg / dm², Nicke
Adhesion amount of 0.1-0.35mg / dm²In the range of
It Higher deposition of silicon, chromium, zinc and nickel
Within the above range, stable polyimide layer and high peel strength
Tend to develop. Silicon, chromium, zinc and
The method for measuring the amount of nickel deposited will be described later.

The silicon in the metal layer is preferably derived from treatment with a silane coupling agent. Furthermore, (1)
A treatment layer is formed by surface-treating nickel and / or nickel-zinc alloy, (2) zinc and / or zinc-chromium alloy, and (3) chromium and / or zinc-chromium alloy in this order, and the treatment layer is formed. It is preferably obtained from a metal foil on which the silane coupling agent is treated.

When the surface treatment is performed in this order, the metal layer is excellent in peel strength, heat resistance and etching property. The treatment layer preferably contains at least one component selected from vanadium, molybdenum, cobalt, tin, iron, phosphorus, indium, tungsten, aluminum and manganese. The content of these components is preferably in the range of 0 to 0.5 mg / dm ² . When a metal selected from these metals is contained, the metal layer tends to have improved etching properties and heat resistance, and the peel strength after heating tends to be stable. The peel strength at room temperature and after heating is preferably 0.2 kN / m or more, more preferably 0.3 kN / m or more, and particularly preferably 0.5 kN / m or more.

Polyimide Layer The polyimide layer forming the polyimide metal laminate of the present invention is a single layer or a multi-layer, and in the case of a multi-layer, it is preferable that adjacent layers are made of polyimide having different components from each other. The difference in the component of the polyimide means that the kind and / or the content of the monomer unit are different. Further, at least one of the layers forming the single-layer polyimide layer or the multi-layer polyimide layer may be formed of a composition (mixture) composed of two or more different polyimides.

When the polyimide layer is a single layer, it is preferably composed of thermoplastic polyimide or a polyimide composition containing thermoplastic polyimide. When it is a multi-layer, it is preferably composed of a non-thermoplastic polyimide layer and a polyimide composition layer containing a thermoplastic polyimide layer or a thermoplastic polyimide, and the surface contacting the metal layer for excellent adhesion with the metal layer. Is preferably a thermoplastic polyimide or a composition containing a thermoplastic polyimide.

The thermoplastic polyimide used for the polyimide layer is 1,3-bis (3-aminophenoxy).
At least one diamine selected from the group consisting of benzene, 4,4-bis (3-aminophenoxy) biphenyl and 3,3′-diaminobenzophenone, and 3,3 ′,
At least one tetracarboxylic acid selected from the group consisting of 4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride and pyromellitic dianhydride A polyimide synthesized from a dianhydride is preferable. Further, when the polyimide used for the polyimide layer is a polyimide composition containing a thermoplastic polyimide, it is desirable to contain 10% by weight or more of the thermoplastic polyimide.

As the non-thermoplastic polyimide film used for the polyimide layer, a commercially available non-thermoplastic polyimide film can be used in addition to the one obtained by coating and drying a precursor varnish of non-thermoplastic polyimide. For example, Upilex S, Upilex SGA, Upilex SN
(Ube Industries, Ltd., trade name), Kapton H, Kapton V, Kapton EN (Toray DuPont Co., Ltd., trade name), Apical AH, Apical NPI, Apical HP
(Kanefuchi Chemical Industry Co., Ltd., trade name) and the like.

When a commercially available non-thermoplastic polyimide film is used, the thickness is usually 3 μm or more and 75 μm or less, preferably 7.5 μm or more and 40 μm or less. When the precursor varnish of non-thermoplastic polyimide is applied and dried, the thickness is 0.1 μm or more and 40 μm or less, preferably 0.5 μm or more and 25 μm or less, and most preferably 0.5 μm or more and 16 μm or less. The thickness of the thermoplastic polyimide layer is 0.1 μm or more and 20 μm or less, preferably 0.1 μm or more and 10 μm or less, and most preferably 0.1 μm.
It is not less than m and not more than 5 μm. Furthermore, if the total thickness of the polyimide layer becomes too thick, it becomes impossible to use it for necessary applications such as bending because the rigidity becomes strong, and if it is too thin, there is a constraint that it cannot be used in terms of insulation and handling, The total thickness is preferably 3 μm or more and 75 μm or less, and more preferably the thickness of the thermoplastic polyimide layer and the non-thermoplastic polyimide layer is adjusted within the above range so that the total thickness is 10 μm or more and 45 μm or less.
When the thickness of the polyimide layer is within the above range, the polyimide metal laminate tends to have excellent insulating properties, flexibility, workability, and low cost. The polyimide resin layer that is not in direct contact with the metal foil may not include the thermoplastic polyimide resin, and existing polyimide and / or polyamideimide resin can be selected, but 10% or more as an insulating layer. Since it is preferable to have a light-transmitting property, a resin having an amorphous structure that easily transmits light is desirable. Also, when various blend materials are used in the insulating layer resin, the light transmittance is It is preferable to determine the mixing ratio so as not to reduce the ratio to 10% or less.

The light transmittance of the polyimide after the metal foil is removed by etching is the alignment of the chip through the polyimide film when recognizing the pattern of the wiring through the polyimide film and mounting a chip such as an IC on the wiring. It is necessary for image processing such as mark recognition. In particular,
When the surface roughness of the metal foil used is high, the unevenness on the surface of the metal foil is transferred to the polyimide layer even after the metal foil is removed by etching, so that light is diffusely reflected and the image cannot be recognized. Therefore, depending on the thickness of the polyimide, if the thickness is 35 μm, the wavelength of light is 600 nm.
It is desired that the light transmittance at that time is 10% or more, preferably 40% or more, more preferably 55% or more. Method for Producing Polyimide Metal Laminate The polyimide metal laminate according to the present invention can be produced, for example, by the following method. (1) A method of thermocompression bonding a single-layer or multi-layer polyimide film and a metal foil. (2) A method in which a polyimide precursor varnish is applied to a metal foil and then dried. (3) A method of laminating the following laminate (i) or laminate (ii) and the following laminate (i) or laminate (ii) such that the metal layer is the outermost layer.

Laminate (i): Laminated laminate having a metal layer on only one surface obtained by heat-pressing a single-layer or multilayer polyimide film and a metal foil (ii): Precursor varnish of polyimide A laminate having a metal layer only on one surface, which is obtained by applying the above to a metal foil and then drying.

More specifically, there are the following methods. (1) A method of heat-pressing a metal foil onto one or both surfaces of a single layer film of thermoplastic polyimide. The thermoplastic polyimide film is obtained, for example, by applying a thermoplastic polyimide varnish and drying it. (2) A non-thermoplastic polyimide film is coated with one or more thermoplastic polyimide precursor varnishes on one or both surfaces of the non-thermoplastic polyimide film and dried to heat at least one surface of the non-thermoplastic polyimide film. A method of producing a laminate having a plastic polyimide layer, and then thermocompression-bonding a metal foil to one or both sides of the laminate. In this case, the metal foil is preferably laminated so as to be in contact with the thermoplastic polyimide layer of the multilayer polyimide film. Examples of the non-thermoplastic polyimide film include those mentioned above. (3) One or more layers of non-thermoplastic polyimide precursor varnish having the same or different components are applied to one surface of the non-thermoplastic polyimide film and dried, while the other surface of the non-thermoplastic polyimide film is thermoplastic polyimide. One or more layers of the precursor varnish of are applied and dried to produce a laminate,
Then, a method of heating and pressing a metal foil on the surface of the thermoplastic polyimide of the laminate. (4) A method of coating one or more layers of one or more polyimide precursor varnish on a metal foil and drying. (5) One or more layers of one or more polyimide precursor varnishes are applied to a metal foil and dried to produce a laminate, and then a polyimide metal laminate produced by any one of the methods (1) to (4) above. A method of laminating by thermocompression bonding. In this method, the laminate is laminated so that the metal layer is the outermost layer.

The metal foil used for producing the polyimide metal laminate is copper and copper alloys, stainless steel and its alloys, nickel and nickel alloys (including 42 alloy),
It is formed of a metal selected from aluminum and aluminum alloys, and is preferably copper or copper alloy.
The surface roughness of the metal foil in contact with the polyimide is less than 0.30 μm in terms of arithmetic average roughness (Ra), preferably 0.28 μm or less, more preferably 0.25 μm or less, and most preferably 0.20 μm. It is the following.

Further, the surface of the metal foil which is in contact with the polyimide is
10-point average roughness (Rz), which is another indicator of surface roughness
Is preferably 2.5 μm or less, preferably 1.5 μm
Hereafter, it is more preferably 1.0 μm or less. The amount of zinc attached is 0 to 0.0 on the surface of the metal foil in contact with the polyimide.
7 mg / dm ² , preferably the amount of silicon deposited is 0.001 mg / dm ² or more and 0.01 mg / dm ² or less, and the amount of chromium deposited is 0.01 mg / dm ² or more 0.1.
05mg / dm ² or less, zinc adhesion amount is 0.07
mg / dm ² or less and the amount of nickel deposited is 0.07
Within the range of mg / dm ² or more and 0.5 mg / dm ² or less,
Preferably, the amount of silicon deposited is 0.002 mg / dm ^2.
Above 0.006 mg / dm ² or less, the adhesion amount of chromium 0.02 mg / dm ² or more 0.03 mg / dm ² or less, the adhesion amount of the zinc is 0.05 mg / dm ² or less, the adhesion amount of nickel 0.1mg / Dm ² or more and 0.35 mg / dm ² or less.

The silicon in the metal layer is preferably derived from the treatment with a silane coupling agent. Furthermore, (1)
A treatment layer is formed by surface-treating nickel and / or nickel-zinc alloy, (2) zinc and / or zinc-chromium alloy, and (3) chromium and / or zinc-chromium alloy in this order, and the treatment layer is formed. It is preferably obtained from a metal foil having a silane coupling agent treated thereon.

When the surface treatment is performed in this order, the metal layer is excellent in peel strength, heat resistance and etching property. The treatment layer preferably contains vanadium, molybdenum, cobalt, tin, iron, phosphorus, indium, tungsten, aluminum and manganese. The content of these is preferably in the range of 0 to 0.5 mg / dm ² .

A metal foil having such a deposition amount of silicon, chromium, zinc and nickel in a specific range can be obtained, for example, by surface-treating the metal foil by the following method. The dipping method is generally used for the treatment with the silane coupling agent. Examples of treatment methods other than the silane coupling agent treatment include an immersion method, an electroplating method, a chemical plating method, a vapor deposition method, a sputtering method, and a methacholine method. Considering productivity, the immersion method and the electroplating method are preferable. .

The thickness of this metal foil is not particularly limited as long as it can be used in the form of a tape, but is usually 0.1 μm or more and 150 μm or less, preferably 2 μm or more and 150 μm or less, and further 3 μm or more and 50 μm or less. The range is more preferably 3 μm or more and 35 μm or less, and most preferably 3 μm or more and 12 μm or less. When producing the polyimide metal laminate, the surface of the non-thermoplastic polyimide may be subjected to plasma treatment, corona discharge treatment, or the like.

As the method of thermocompression bonding, a method of laminating between a metal roll heated by heating using oil or the like as a heat medium or a metal roller heated by dielectric heating, or a roll whose surface is lined with rubber, or a hot press is used. There is a method etc., the former is suitable for manufacturing continuous roll products,
The latter is suitable for the production of cut sheet-shaped single-wafer products, and can be appropriately used depending on the application.

Further, the heating and pressure bonding conditions can be appropriately selected from atmospheric air such as air, nitrogen and argon, and the heating temperature must be a temperature mainly according to the glass transition temperature of the thermoplastic polyimide, and usually 100 to 100. It may be performed at 400 ° C, preferably 150 to 300 ° C. The heating time is 0.01 second or more and 15 hours or less, and the heating pressure may be in the range of 0.1 to 30 MPa, usually 0.5 to 10 M.
Pa.

For the purpose of further improving the adhesion,
Post-treatment may be carried out using an autoclave or the like. Post-processing is performed under the following conditions. Aftertreatment temperature is usually 1
50 to 400 ° C, preferably 200 to 350 ° C,
The treatment time is 1 minute to 50 hours, the pressure is in the range of atmospheric pressure to 3 MPa, and it is preferable to replace the inside of the autoclave with vacuum or an inert gas such as nitrogen or argon in order to prevent oxidation of the metal foil.

When applying the polyimide precursor varnish to the metal foil or the polyimide film, a solvent can be used. Such a solvent is not particularly limited as long as it can dissolve the precursor varnish of the polyimide to be used, and for example, N-methyl-2-pyrrolidone,
N, N-dimethylacetamide or the like is used. As a polyimide precursor varnish coating apparatus, a general coating apparatus such as a roll coater, a die coater, a gravure coater, a dip coater, a spray coater, a comma coater, a curtain coater, or a bar coater can be used. It can be appropriately selected according to the viscosity and the coating thickness.

As a drying apparatus for the polyimide precursor varnish, a roll support using a heat source such as hot air or infrared rays heated by electricity or oil, a drying furnace of an air float system can be appropriately used, and deterioration of the resin or metal foil For the purpose of preventing discoloration due to oxidation, and if necessary, the dry atmosphere may be replaced with a gas other than air, such as nitrogen, argon or hydrogen.

The drying temperature of the polyimide precursor varnish is
The temperature may be in the range of 60 to 600 ° C., and it is preferable to raise the temperature stepwise so that the film formation of the insulating layer does not cause a problem such as foaming or a wrinkled surface, the film thickness is uniform, and This is preferable because a resin having excellent stability can be obtained, and the drying time may be appropriately selected from about 0.05 to 500 minutes.

[0041]

The polyimide metal laminate according to the present invention is
The peel strength between the metal layer and the polyimide layer is high, and the peel strength is stable. The polyimide metal laminate according to the present invention can form a fine wiring pattern, and is suitable as a highly reliable and high-density circuit board material. Further, according to the present invention, image recognition is possible through the insulating layer,
It is possible to inexpensively provide a flexible metal laminate having an insulating layer having excellent light transmittance and also having high adhesion.

[0042]

EXAMPLES The present invention will now be described in more detail with reference to examples. The surface treatment adhesion amount of the metal foil, the maximum roughness of the surface of the metal foil, and the peel strength between the metal foil and the thermoplastic polyimide layer shown in the examples were measured by the following methods. (1) Using a fluorescent X-ray measuring device for surface treatment adhesion analysis, a sample cut into a disc with a diameter of 40 mm is measured. It was calculated by converting to the amount of adhesion per area. The unit is mg / dm ² . (2) Arithmetic mean roughness: Ra (μm) Surface roughness meter (manufactured by Kosaka Laboratory, model: Surfcoder SE
-30D) according to JIS B-0601,
The cutoff value is 0.25 mm and the measurement length is 2.5 mm.
On the surface of the metal foil in contact with the insulating layer, three arbitrary points were measured so that they were at right angles and parallel to each other along the flow direction at the time of manufacturing the metal foil, and the average of the obtained three large values was calculated as the arithmetic mean rough. Satoshi (3) Peel strength after normal temperature and heat resistance test (kN /
m) A sample having a length of 50 mm and a width of 1 mm which is parallel to the flow direction of the metal foil is subjected to heat treatment in an environment of room temperature of 23 ° C. and 50% RH and heat treatment in an oven of 150 ° C. for 168 hours. According to C-6471, the peeling speed of the metal foil from the insulating layer is 50 mm / min so that the angle is 90 degrees.
Peel and measure the stress.

The measurement pieces are sampled at equal intervals from the width direction of the metal foil at 10 points, and the peel strength is an average value of 10 points. (4) Light transmittance (%) As a sample, a metal foil obtained by etching away a ferric oxide / hydrochloric acid solution was used.
Vis-NIR) is used to determine the light transmittance at 600 nm. Further, the solvent used in the examples, acid dianhydride,
Abbreviations of diamine are as follows. DMAc: N, N-dimethylacetamide NMP: N-methyl-2-pyrrolidone PPD: p-phenylenediamine ODA: 4,4′-diaminodiphenyl ether m-BP: 4,4′-bis (3-aminophenoxy) biphenyl APB 1,3-bis (3-aminophenoxy) benzene BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride PMDA: pyromellitic dianhydride BTDA: 3,3', 4,4 '-Benzophenone tetracarboxylic dianhydride

[0044]

[Synthesis Example 1] In a container equipped with a stirrer and a nitrogen introducing tube,
1636 g of DMAc was added as a solvent, and APB was added to this.
146.2 g was added, and the mixture was stirred at room temperature until dissolved. Then, 142.5 g of BPDA was added and stirred at 60 ° C. to obtain a polyamic acid solution. The resulting polyamic acid solution has a polyamic acid content of 15
% By weight and E-type viscosity at 25 ° C. was 550 cps.

[0045]

[Synthesis example 2] In a container equipped with a stirrer and a nitrogen introducing tube,
DMAc 1718.6 g was added as a solvent, to which A
146.2 g of PB was added, and the mixture was stirred at room temperature until dissolved. Then add BTDA 157.1g and add 6
Stirring was performed at 0 ° C. to obtain a polyamic acid solution.
The obtained polyamic acid solution had a polyamic acid content of 15% by weight and had an E-type viscosity at 25 ° C. of 500 cp.
It was s.

[0046]

[Synthesis Example 3] In a container equipped with a stirrer and a nitrogen introducing tube,
DMAc 644g and NMP 161g were added as a solvent, and PPD 40.5g (75 mol%) and ODA 17.5 g (17.5 mol%) were added to this, and it heated and stirred at 50-60 degreeC and melt | dissolved. After that, cool with ice to about 30 ° C, and then use BPDA 7
8.0 g was added and the mixture was heated to 60 ° C. and stirred for about 2 hours.
Further, 13.8 g (7.5 mol%) of m-BP was added and stirring was performed while maintaining the temperature at 60 ° C. Finally PM
51.3 g of DA was added and the mixture was stirred at 60 ° C. for 2 hours to obtain a polyamic acid solution. The obtained polyamic acid solution had a polyamic acid content of 20% by weight and had a temperature of 25 ° C.
E-type viscosity at 19000 cps.

[0047]

[Synthesis Example 4] In a container equipped with a stirrer and a nitrogen introducing tube,
As the solvent, DMAc 846.9 g and NMP 362.9
g, and PPD 16.2 g (30 mol
%) And 49.1 g (49 mol%) of ODA, and the mixture was heated to 50 to 60 ° C. with stirring to be dissolved. After that, cool with ice to about 30 ° C, then BP
25.1 g of DA was added and the mixture was heated to 60 ° C. and stirred for about 2 hours. Furthermore, m-BP 38.7 g (21 mol%)
Was added and the mixture was stirred while maintaining the temperature at 60 ° C. Finally, 84.4 g of PMDA was added and stirred at 60 ° C. for 2 hours to obtain a polyamic acid solution. The resulting polyamic acid solution has a polyamic acid content of 15% by weight,
The E-type viscosity at 25 ° C. was 400 cps.

[0048]

Example 1 A polyamic acid solution (hereinafter referred to as “varnish”) prepared in Synthesis Example 1 was formed on one surface of a commercially available polyimide resin film (trade name: Kapton 100EN manufactured by Toray DuPont Co., Ltd.). It was applied by a roll coater so that the thickness after drying was 4 μm, dried at 150 ° C. for 2 minutes, and then the varnish prepared in Synthesis Example 4 was applied on the other surface by a roll coater so that the thickness after drying was 5 μm. Apply
After drying at 70 ℃ for 5 minutes and 110 ℃ for 5 minutes, 140 ℃ for 2 minutes, 18
Drying at 0 ° C. for 5 minutes, 265 ° C. for 2 minutes in an air-float drying oven to obtain a polyimide in which a thermoplastic polyimide resin layer, a polyimide resin film layer, and a non-thermoplastic polyimide resin layer are laminated in this order. An insulating film was obtained.

Next, the insulating film and a commercially available copper foil (manufactured by Furukawa Circuit Foil Co., Ltd., trade name: F0-W)
S, thickness 9 μm, Ra: 0.17 μm, surface treatment is shown in Table 1.
In a condition of a pressure of 1.4 MPa at 240 ° C. with a roll laminator covered with silicon rubber, a copper foil and an insulating film are laminated so that the copper foil is in contact with the thermoplastic polyimide layer, and then the batch type is used. In an autoclave at a temperature of 280 ° C. for 4 hours in a nitrogen atmosphere to obtain a polyimide metal laminate.

As a result of evaluating the obtained polyimide metal laminate, the peel strengths in the normal state and after the heat resistance test were 0.97 and 0.45 kN / m, respectively, and the light transmittance was 55%.
Met.

[0051]

Example 2 A polyimide metal laminate was obtained in the same manner as in Example 1 except that the surface treatment of the metal foil was different as shown in Table 1. As a result of evaluating the obtained polyimide metal laminate, the peel strengths in the normal state and after the heat resistance test were 0.88 and 0.40 kN / m, respectively, and the light transmittance was 55%.

[0052]

Example 3 A polyimide metal laminate was obtained in the same manner as in Example 1 except that the surface treatment of the metal foil was different as shown in Table 1. As a result of evaluating the obtained polyimide metal laminate, the peel strengths in the normal state and after the heat resistance test were 0.86 and 0.45 kN / m, respectively, and the light transmittance was 55%.

[0053]

Example 4 A polyimide metal laminate was obtained in the same manner as in Example 1 except that the surface treatment of the metal foil was different as shown in Table 1. As a result of evaluating the obtained polyimide metal laminate, the peel strengths in the normal state and after the heat resistance test were 1.1 and 0.45 kN / m, respectively, and the light transmittance was 55%.

[0054]

Example 5 A polyimide metal was prepared in the same manner as in Example 1 except that the varnish prepared in Synthesis Example 2 was used instead of the varnish prepared in Synthesis Example 1 and the metal foil used in Example 4 was used. A laminated body was obtained. As a result of evaluating the obtained polyimide metal laminate, the peel strengths in the normal state and after the heat resistance test were 0.78 and 0.40 kN / m, respectively, and the light transmittance was 55%.

[0055]

Example 6 Commercially available copper foil (manufactured by Furukawa Circuit Foil Co., Ltd., trade name: F1-WS, thickness 12 μm, Ra:
0.28 μm, the surface treatment is shown in Table 1), the varnish prepared in Synthesis Example 3 was applied on a metal foil with a roll coater so that the thickness after drying was 0.7 μm, and dried at 80 ° C. for 1 minute. Subsequently, the varnish prepared in Synthesis Example 3 was applied by a die coater so that the thickness after drying was 10 μm, and 1
After drying at 15 ° C. for 3 minutes, the varnish of Synthesis Example 1 was subsequently applied by a roll coater so that the thickness after drying was 2 μm, and at 80 ° C. for 1 minute, 140 ° C., 150 ° C., 160 ° C., 1
Dry at 70 ° C, 180 ° C and 190 ° C for 2 minutes each in an air float type drying furnace, and further dry at 280 ° C and 37 ° C.
A polyimide metal laminate of a single-sided metal foil was obtained by drying in a furnace under a nitrogen atmosphere at 0 ° C. for 3 minutes each.

Using the obtained polyimide metal laminate,
The polyimide metal laminates of the single-sided metal foil were laminated together under the same conditions as in Example 1 so that the outermost layer was the metal foil layer, to obtain a polyimide metal laminate of the double-sided metal foil. Polyimide metal laminate of the obtained double-sided metal foil, normal and,
The peel strength after the heat resistance test is 0.88 and 0.7, respectively.
The light transmittance was 13% at 5 kN / m.

[0057]

Comparative Example 1 A polyimide metal laminate was obtained in the same manner as in Example 1 except that the surface treatment of the metal foil was different as shown in Table 1. As a result of evaluating the obtained polyimide metal laminate, the peel strengths in the normal state and the heat resistance test were 0.18 and 0.10 kN / m, respectively, and the light transmittance was 55%.

[0058]

Comparative Example 2 A polyimide metal laminate was obtained in the same manner as in Example 1 except that the surface treatment of the metal foil was different as shown in Table 1. As a result of evaluating the obtained polyimide metal laminate, the peel strengths in the normal state and after the heat resistance test were 0.54 and 0.20 kN / m, respectively, and the light transmittance was 55%.

Example 7 A polyimide metal laminate was obtained in the same manner as in Example 1 except that the surface roughness of the metal foil was different as shown in Table 1. As a result of evaluating the obtained polyimide metal laminate, the peel strengths in the normal state and after the heat resistance test were 0.85 and 0.76 kN / m, respectively, and the light transmittance was 2%.

[0059]

[Table 1]

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view of a flexible metal laminate according to one aspect of the present invention.

FIG. 2 is a schematic cross-sectional view of a flexible metal laminate according to another aspect of the present invention.

[Explanation of symbols] 1 ... Polyimide layer 1a ... Non-thermoplastic polyimide layer 1a '... Non-thermoplastic polyimide layer 1b ... Thermoplastic polyimide layer 2 ... Metal layer

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Masataka Kobayashi             580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc.             Inside the company (72) Inventor Koji Hirota             580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc.             Inside the company (72) Inventor Yoichi Kodama             580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc.             Inside the company F-term (reference) 4F100 AB01B AB13B AB16B AB18B                       AB20B AB31B AB33B AK49A                       BA02 DD07 EJ172 EJ422                       EJ67B EJ68B GB43 JL00                       JL11 JN08A

Claims (6)

[Claims] 1. A laminate having a metal layer formed on at least one surface of a polyimide layer, wherein the amount of zinc deposited on the surface of the metal layer in contact with the polyimide layer is 0.07 mg / dm ² or less. Characteristic polyimide metal laminated board. 2. The surface roughness of the surface of the metal layer in contact with the polyimide layer is less than 0.30 μm in terms of arithmetic average roughness (Ra), and the amount of silicon deposited on the surface of the metal layer in contact with the polyimide layer is 0. a 001~0.01mg / dm ^2, the amount of deposition of chromium is 0.01-0.05 mg / dm ^2, and wherein the amount of adhesion of the nickel is 0.07~0.5mg / dm ² The polyimide metal laminate according to claim 1. 3. The metal layer comprises (1) nickel and / or
Or nickel-zinc alloy, (2) zinc and / or zinc-chromium alloy, (3) chromium and / or zinc-
3. A treatment layer is formed by surface-treating a chromium alloy in this order, and the treatment layer is obtained from a metal foil treated with a silane coupling agent. The polyimide metal laminate described in. 4. The treatment layer according to claim 3, wherein the treatment layer contains at least one component selected from vanadium, molybdenum, cobalt, tin, iron, phosphorus, indium, tungsten, aluminum and manganese. Polyimide metal laminate. 5. The polyimide metal laminate according to claim 1, wherein the polyimide layer has a light transmittance of 10% or more after the metal layer is removed by etching. 6. A single-layer or multi-layer polyimide film and a metal foil are thermocompression-bonded to each other.
5. The method for producing a polyimide metal laminate according to any one of 5 above.