JP2010260328A - Method of manufacturing two-layer copper clad laminated sheet, and two-layer copper clad laminated sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a two-layer copper clad laminated sheet which can further inhibit oxidation discoloration after a heat treatment which raises folding resistance in the two-layer copper clad laminated sheet (two-layer CCL material) wherein a copper layer is formed on a polyimide film by sputtering and plating, and to provide the two-layer copper clad laminated sheet. <P>SOLUTION: The two-layer copper clad laminated sheet is obtained by forming a metal layer of one selected from Ni, Co, and Cr or an alloy layer consisting of two or more of them on a polyimide film by sputtering; forming a copper layer on the metal layer or the alloy layer by sputtering or plating; and further forming a layer consisting of Cr and/or Cr oxide on the copper layer. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a two-layer copper-clad laminate in which a copper layer is formed on a polyimide film by sputtering and plating, and a method for producing a two-layer copper-clad laminate with improved folding resistance of the laminate and the same It is related with the two-layer copper clad laminated board obtained by this.
In addition, in the said 2 layer copper clad laminated board, although forming a thin intermediate | middle layer in order to increase joint strength and also forming a rust prevention layer in the uppermost layer, including this, a polyimide film and a copper layer are included. It will be referred to as a “two-layer copper-clad laminate”.

2. Description of the Related Art In recent years, a two-layer copper clad laminate (CCL) material in which a copper layer is formed on a polyimide film has been used as a circuit material for mounting driver ICs such as liquid crystal displays that require fine pitch circuits. . Among the two-layer CCL materials used as a laminate material for COF (Chip On Film), attention is particularly paid to a two-layer CCL material produced by sputtering and plating.
The two-layer CCL material is obtained by forming a submicron copper layer on a polyimide film (PI) by sputtering and then forming a copper layer by copper sulfate plating. The basic invention is described in Patent Document 1 below.

COF (Chip On Film) is used for thin televisions such as liquid crystal televisions and organic EL televisions. However, since the outer lead portion of the circuit is used by being bent, the folding resistance (folding resistance) must be high. Don't be.
However, since the fine pitch of the circuit has progressed, there has been a problem that the circuit width is narrowed and the strength is lowered. As a result, there arises a problem that the outer lead portion is disconnected.

  For this reason, as shown in the following Patent Document 2, the present inventors, when manufacturing a two-layer CCL material in which a copper layer is formed by sputtering and plating on a polyimide film, by heat treatment under specific conditions, Obtained knowledge that refraction resistance can be greatly improved, and formed a copper layer having a surface roughness (Rz) of 0.1 μm or more and 0.9 μm or less on a polyimide film by sputtering and plating 2 A two-layer copper-clad laminate that can be heat-treated at a temperature of 100 ° C. or higher and 175 ° C. or lower to retain a folding resistance of 150 times or more as measured by a refractive resistance test based on JIS C6471. The manufacturing method of the board was proposed (refer patent document 2).

This method was confirmed to be a very effective method for improving the refraction resistance, but as a result of heat treatment at a temperature of 100 ° C. or higher and 175 ° C. or lower as described above, the surface was oxidized. The problem of discoloration occurred. This surface oxidation decreases the conductivity, and is not preferable.
For this reason, the benzotriazole layer was further formed on the said copper layer as a rust prevention layer. However, in this case, when the two-layer CCL material is heat-treated as described above, the benzotriazole layer of the anticorrosive layer deteriorates, and similarly the problem of oxidative discoloration arises, which is not a fundamental solution.

US Pat. No. 5,685,970 Japanese Patent Application No. 2007-337026

  In view of the above points, in the present invention, in a two-layer copper-clad laminate (two-layer CCL material) in which a copper layer is formed on a polyimide film by sputtering and plating treatment, after heat treatment to improve folding resistance, further oxidation discoloration It is an object to obtain a method for producing a two-layer copper-clad laminate and a two-layer copper-clad laminate that can prevent the above.

As a result of diligent research to solve the above-mentioned problems, the present inventors have made Cr and / or Cr as a rust preventive layer when producing a two-layer CCL material in which a copper layer is formed on a polyimide film by sputtering and plating. It was found that oxidation discoloration can be prevented by forming an oxide layer.
Further, as an alternative layer of Cr and / or Cr oxide, a layer added with Zn and / or Zn oxide, and further a composite layer or mixed layer with the layer made of Cr and / or Cr oxide, The knowledge that the same rust prevention effect is acquired was acquired.

Based on these findings, the present application provides the following inventions.
(1) One kind of metal layer selected from Ni, Co, Cr or an alloy layer made of two or more kinds of these metals is formed on a polyimide film by sputtering, and sputtering or plating is further performed on this metal layer or alloy layer. A two-layer copper-clad laminate having a copper layer formed thereon by further comprising a layer made of Cr and / or Cr oxide on the copper layer.

  (2) One kind of metal layer selected from Ni, Co, Cr or an alloy layer made of these two or more metals is formed on the polyimide film by sputtering, and further, sputtering or plating is performed on this metal layer or alloy layer. A two-layer copper-clad laminate having a copper layer formed thereon by further comprising a layer made of Zn and / or Zn oxide on the copper layer.

  (3) One kind of metal layer selected from Ni, Co, Cr or an alloy layer made of two or more of these metals is formed on the polyimide film by sputtering, and sputtering or plating is further performed on this metal layer or alloy layer. A two-layer copper-clad laminate having a copper layer formed thereon, and further comprising a composite layer or mixed layer of Cr and / or Cr oxide and Zn and / or Zn oxide on the copper layer A two-layer copper-clad laminate characterized by the above.

The present application also provides the following inventions.
(4) The two-layer copper clad laminate according to any one of (1) to (3), wherein the copper layer has a surface roughness (Rz) of 0.1 μm or more and 0.9 μm or less.
(5) Cr deposition amount is, 11.5μg / dm ² or more of Cr content in terms above, wherein the at 40.0μg / dm ² or less (1) to according to any one of (4) 2-layer copper-clad laminate.
(6) The two-layer copper-clad laminate as described in any one of (2) to (5) above, wherein the Zn adhesion amount is 1000 μg / dm ² or less in terms of Zn amount.

  (7) One kind of metal layer selected from Ni, Co, Cr or an alloy layer made of two or more kinds of these metals is formed on the polyimide film by sputtering, and sputtering or plating is further performed on this metal layer or alloy layer. A method for producing a two-layer copper-clad laminate in which a copper layer is formed by sputtering, wherein a Cr and / or Cr oxide layer is formed on the copper layer by sputtering or plating. A method for producing a tension laminate.

  (8) One kind of metal layer selected from Ni, Co, Cr or an alloy layer made of two or more kinds of these metals is formed on the polyimide film by sputtering, and sputtering or plating is further performed on this metal layer or alloy layer. A method for producing a two-layer copper-clad laminate in which a copper layer is formed by sputtering, wherein a layer made of Zn and / or Zn oxide is further formed on the copper layer by sputtering or plating. A method for producing a laminated copper-clad laminate.

  (9) One kind of metal layer selected from Ni, Co, Cr or an alloy layer made of two or more of these metals is formed on the polyimide film by sputtering, and further, sputtering or plating is performed on this metal layer or alloy layer. 2 layer copper clad laminate for forming a copper layer by sputtering, and further a composite layer or mixed layer of Cr and / or Cr oxide and Zn and / or Zn oxide by sputtering or plating on the copper layer A process for producing a two-layer copper-clad laminate, characterized in that

  The two-layered copper-clad laminate obtained by the present invention has an excellent effect of improving folding resistance, effectively preventing breakage of the outer lead portion of the circuit, and further preventing oxidation and discoloration due to oxidation. Obtainable.

It is explanatory drawing of a test piece.

The polyimide film used for the two-layer copper-clad laminate of the present invention is not particularly limited as long as the present invention can be achieved, but a BPDA-PPD based polyimide film is preferably used.
First, after the polyimide film surface is activated by plasma treatment in a vacuum chamber, a single metal layer of Ni, Co, Cr or an alloy layer made of two or more of these metals, such as a NiCr layer (20% Cr), is formed by sputtering. To 10-30 nm.
This layer is generally called a tie coat layer. Plasma treatment and a tie coat layer on the surface of the polyimide film are effective means for improving adhesion.

Next, a submicron copper layer is formed on the tie coat by sputtering. The copper layer thus formed is referred to as a copper seed layer because it serves as a seed for the subsequent formation of an electrolytic copper layer.
Next, a plating process is performed using a copper seed layer. The plating process can be performed, for example, by electroplating using copper sulfate. The thickness of the plating can be arbitrarily adjusted by adjusting the current density, the plating time, and the electrolyte temperature during plating. Thereby, the two-layer copper clad laminated board of a polyimide film and a copper layer can be obtained. As described above, since the copper seed layer is formed, electroplating is possible.

  For the electroplating treatment, a plating solution proposed by the present applicant (see WO 2006/080148) can be used. Incidentally, in the plating solution described in the publication, a compound having a specific skeleton described by the following general formula (1) obtained by adding water to a compound having one or more epoxy groups in one molecule is added. The copper electrolyte contained as an agent is used.

Moreover, it can also plate using the electrolyte solution described in the plating solution (Japanese Unexamined Patent Application Publication No. 2004-107786) previously proposed by the present applicant.
That is, an additive comprising an amine compound having a specific skeleton and an organic sulfur compound described by the following general formula (2) obtained by addition reaction of a compound having one or more epoxy groups in one molecule with an amine compound A copper electrolyte solution can be used.
(In the following general formula (2), R ₁ and R ₂ are selected from the group consisting of a hydroxyalkyl group, an ether group, an aromatic group, an aromatic substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group. Yes, A represents an epoxy compound residue, and n represents an integer of 1 or more.)

  Moreover, in the above, the electrolyte solution in which the epoxy compound residue A of the amine compound having the specific skeleton has a linear ether bond can be used.

Furthermore, in the above, it is possible to use an electrolytic solution in which the amine compound having the specific skeleton contains any one of the following general formulas (3) to (10).
(The following general formula (3) to (10), selected R ₁ and R ₂ are hydroxyalkyl group, an ether group, an aromatic group, an aromatic-substituted alkyl group, unsaturated hydrocarbon group, from the group consisting of alkyl groups It is what

Furthermore, in the above, an electrolytic solution in which the organic compound is a compound represented by the following general formula (11) or (12) can be used.
_{^{X-R 1 - (S)}} n -R 2 -YO 3 Z 1 (11)
R ⁴ —S—R ³ —SO ₃ Z ² (12)
(In the general formula (11) and ^(12), R 1, ^{R 2} and ^{R 3} is an alkylene group having 1 to 8 carbon atoms, ^{R 4} is comprised of hydrogen and the following general formula (13) [formula 11] X in the general formula (13) is selected from the group consisting of hydrogen, sulfonic acid group, phosphonic acid group, sulfonic acid or alkali metal base of phosphonic acid or ammonium base, and Y is (It is either sulfur or phosphorus, Z ¹ and Z ² are either hydrogen, sodium, or potassium, and n is 2 or 3.)

  However, it goes without saying that the copper layer thus formed can be formed by sputtering or other wet plating, and can be arbitrarily selected according to the product shape or purpose.

  The surface roughness of the plating formed under the above electroplating conditions was measured with a non-contact type surface roughness meter (manufactured by Veeco). As a result, Ra 0.01-0.04, Rt 0.14-1.0, Rz0 0.1-0.90 could be obtained. This surface roughness satisfied the conditions for the preferred surface roughness of the present invention, that is, Rz: 0.1 μm or more and 0.9 μm or less.

Next, a two-layer copper clad laminate in which a copper layer is formed on a polyimide film by sputtering and plating treatment is heat-treated at a temperature of 100 ° C. or higher and 175 ° C. or lower, thereby resisting refraction according to JIS C6471. The folding resistance of 150 times or more measured by the property test can be retained.
The test conditions of the refraction resistance test based on JIS C6471 are as follows.
R = 0.38, load 500 gf, bending angle: 135 ° ± 5 °, 175 cpm (bending at a rate of 175 times per minute), L / S is 1 mm.
The number of times until breakage is regarded as folding resistance.

When producing the test piece, a dry film is pressure-bonded on the heat-treated two-layer copper-clad laminate, exposed to form a pattern, and etched to remove unnecessary portions of copper. Finally, the dry film is removed to form a circuit on the polyimide film. The test piece thus prepared is used.
This circuit forming method is a commonly used method, and other methods may be used.

As the copper layer etching solution, an etching solution having the following liquid composition is usually used.
(Liquid composition)
Cupric chloride solution (CuCl ₂ ), copper oxide (CuO)
Hydrochloric acid (HCl): 3.50 mol / L (adjusted in the range of 0 to 6 mol / L)
Hydrogen peroxide (H ₂ O ₂ ): 30.0 Cap (adjusted in the range of 0 to 99.9 Cap)

As shown in Patent Document 1, it is possible to obtain excellent characteristics that can greatly improve the refraction resistance. However, one problem occurred. That is, a copper oxide film is formed by the heat treatment, causing discoloration on the copper surface.
This oxide film varies depending on temperature, humidity, and time.If an oxide film is formed on the surface of copper, the oxide surface affects the conductivity when the copper surface becomes a contact point. In the case of plating on the surface, there is a problem that the adhesion of the plating is lowered.

  For this reason, a benzotriazole layer was further formed as a rust preventive layer on the copper plating layer. However, in this case, when the two-layer CCL material is heat-treated as described above, the benzotriazole layer of the rust preventive layer deteriorates and similarly causes a problem of oxidative discoloration, which cannot be said to be a fundamental problem solving method.

  For this reason, as a result of intensive studies, the inventors of the present application made an attempt to form a Cr and / or Cr oxide layer on a copper layer by sputtering or plating. As a result, in the above heat treatment, a copper oxide film was not formed, or no discoloration occurred on the copper surface. In addition, this does not affect the refraction resistance of the two-layer copper clad laminate of the present invention, and therefore the refraction resistance can be greatly improved by a series of steps, and the oxidation resistance of the copper surface is also improved. It was possible to obtain a two-layer copper-clad laminate capable of improving the properties and preventing discoloration.

In this case, a Cr and / or Cr oxide layer is formed on the copper layer, but the same effect can be obtained by forming a layer made of Zn and / or Zn oxide by sputtering or plating instead. I was able to get it.
In addition, from the above, it is naturally possible to form a composite layer or mixed layer of Cr and / or Cr oxide and Zn and / or Zn oxide on the copper layer by sputtering or plating. Should be easily understood, and the present invention includes these.

  The surface roughness of the copper layer is preferably a layered copper clad laminate having a surface roughness (Rz) of 0.1 μm or more and 0.9 μm or less. This is a favorable condition that it is advantageous for forming a subsequent antirust layer and does not impair the function as a two-layer copper-clad laminate.

As anticorrosive layer, in the case of Cr and / or Cr oxide, 11.5μg / dm ² or more of Cr content in terms, it is desirable that 40.0μg / dm ² or less.
Even if it is less than 11.5 μg / dm ² , there is a certain effect, but the effect may be reduced depending on the heat treatment conditions of the two-layer copper clad laminate, that is, temperature, humidity, and time. Considering the effect as a rust film, it can be said to be 11.5 μg / dm ² or more.
On the other hand, if it exceeds 40.0 μg / dm ² , the effect is saturated, and a thickness greater than that is wasted, so the upper limit was set. However, it does not prevent the thickness from being increased if necessary.

Further, in the case of Zn and / or Zn oxide as the anticorrosive layer, it is desirable to set it to 1000 μg / dm ² or less in terms of Zn amount.
In the case of a thickness exceeding this, the effect is saturated and the oxidation resistance is improved, but a brass color (brass color) is produced, and the refraction resistance is lowered, so that it is 1000 μg / dm ² or less. Is good.

The reason for this decrease in resistance to refraction is that Zn is diffused into Cu by heat treatment to become an alloy, and a part of the uniform copper layer is lost (a two-layer structure of Cu and CuZn alloy layer). This may be the cause. However, even if this is taken into consideration, it does not prevent the thickness from being increased as necessary.
On the other hand, the lower limit is not particularly limited. This is because even a slight amount affects the oxidation resistance and discoloration resistance (prevention effect).

  As apparent from the above, there is no problem in forming a composite layer or mixed layer of Cr and / or Cr oxide and Zn and / or Zn oxide on the copper layer. In this case, it will be easily understood that the two-layer copper-clad laminate can be arbitrarily designed in consideration of the oxidation resistance and discoloration resistance (prevention effect).

Hereinafter, the features of the present invention will be specifically described based on examples and comparative examples. In addition, the following description is for making an understanding of this invention easy, and is not restrict | limited to this. That is, modifications, embodiments, and other examples based on the technical idea of the present invention are included in the present invention.
The following examples and comparative examples are for confirming the antirust effect and the refraction resistance when the antirust treatment conditions are changed.

Example 1
Using a 34 μm thick polyimide film (Upilex SGA, manufactured by Ube Industries, Ltd.), coating the NiCr layer (20% Cr) with a thickness of 25 nm by sputtering, and then a copper layer having a thickness of 8 μm by sputtering and plating. Formed. Furthermore, the antirust process was implemented on the conditions shown in Table 1.

That is, using an electrolytic solution containing chromium, CrO ₃ concentration: 3 g / L, pH: 4.7, liquid temperature: 50 ° C., current density: 4.0 A / dm ² , electric quantity: 6.0 C / dm Electroplating was performed under the condition of ² to deposit Cr and / or CrO ₃ . The amount of Cr and / or CrO ₃ deposited was 13.2 μg / dm ² in terms of Cr. In this case, since it is extremely difficult to determine the abundance ratio of Cr and CrO ₃ , all of them are Cr equivalent amounts.

  This two-layer copper-clad laminate was heat-treated at 170 ° C. for 2 hours using a heat treatment furnace. After the heat treatment, a range of 1 m was visually observed in the length direction to observe whether or not oxidation (discoloration) occurred. Furthermore, on the two-layer copper clad laminate after this heat treatment, a dry film is laminated, and this is further exposed to form a pattern, and unnecessary portions of copper are removed by etching with the above etching solution, A circuit with L / S = 1 mm was formed.

  Finally, the dry film was removed to prepare a test piece having a size of 15 mm × 130 mm. The circuit on the polyimide film is composed of one continuous line, but the circuit is folded in the longitudinal direction of the polyimide film so that six circuits are arranged in parallel. An explanatory view of the test piece is shown in FIG.

  Using this test piece, a refraction resistance test based on JIS C6471 was performed. A tester manufactured by Tester Sangyo was used. The test was performed under the conditions of R = 0.38, load: 500 gf, bending angle: 135 degrees, 175 cpm (bending at a rate of 175 times per minute). As a result, the folding resistance after the heat treatment was 180 times or more, and excellent folding resistance was obtained. At this time, as shown in Table 1, no discoloration due to oxidation was observed on the copper layer surface.

(Example 2)
Copper plating was performed in the same manner as in Example 1 above, and the rust prevention treatment conditions shown in Table 1 were CrO ₃ concentration: 3 g / L, Zn concentration: 0.5 g / L, pH: 4.7, liquid temperature: 50 ° C, current density: 4.0A / dm ^2, the amount of electricity: with the proviso that 6.0c / dm ^2, carried out electroplating, was deposited Cr and / or CrO ₃ and Zn and / or ZnO. The amount of Cr and / or CrO ₃ deposited was 22.8 μg / dm ² in terms of Cr, and the amount of Zn and / or ZnO deposited was 124.0 μg / dm ² in terms of Zn. Other conditions were the same as those in Example 1.

In this case, since it is extremely difficult to determine the abundance ratio of Cr and CrO ₃ and the abundance ratio of Zn and ZnO, both are converted into Cr equivalent and Zn equivalent.
Furthermore, after heat-treating this two-layer copper clad laminate under the same conditions as in Example 1, the folding resistance after the heat treatment and the presence or absence of oxidation were observed.
As a result, the folding endurance after the heat treatment was 180 times or more. As shown in Table 1, no discoloration due to oxidation was observed.

(Example 3)
Copper plating was performed in the same manner as in Example 1 above, and the rust prevention treatment conditions shown in Table 1 were CrO ₃ concentration: 3 g / L, Zn concentration: 4 g / L, pH: 4.7, liquid temperature: 50 ° C. Then, electroplating was performed under the conditions of current density: 4.0 A / dm ² and electric quantity: 20 C / dm ² to deposit Cr and / or CrO ₃ and Zn and / or ZnO. The amount of Cr and / or CrO ₃ deposited was 25.4 μg / dm ² in terms of Cr, and the amount of Zn and / or ZnO deposited was 986.2 μg / dm ² in terms of Zn. Other conditions were the same as those in Example 1.

In this case, since it is extremely difficult to determine the abundance ratio of Cr and CrO ₃ and the abundance ratio of Zn and ZnO, both are converted into Cr equivalent and Zn equivalent.
Furthermore, after heat-treating this two-layer copper clad laminate under the same conditions as in Example 1, the folding resistance after the heat treatment and the presence or absence of oxidation were observed.
As a result, the folding endurance after the heat treatment was 180 times or more. As shown in Table 1, no discoloration due to oxidation was observed.

Example 4
Copper plating was performed in the same manner as in Example 1 above, and the rust prevention treatment conditions shown in Table 1 were CrO ₃ concentration: 1.5 g / L, Zn concentration: 1 g / L, pH: 4.7, liquid temperature: 50 ° C, current density: 4.0A / dm ^2, the amount of electricity: with the proviso that 6.0c / dm ^2, carried out electroplating, was deposited Cr and / or CrO ₃ and Zn and / or ZnO. The amount of Cr and / or CrO ₃ deposited was 11.6 μg / dm ² in terms of Cr, and the amount of Zn and / or ZnO deposited was 117.3 μg / dm ² in terms of Zn. Other conditions were the same as those in Example 1.

In this case, since it is extremely difficult to determine the abundance ratio of Cr and CrO ₃ and the abundance ratio of Zn and ZnO, both are converted into Cr equivalent and Zn equivalent.
Furthermore, after heat-treating this two-layer copper clad laminate under the same conditions as in Example 1, the folding resistance after the heat treatment and the presence or absence of oxidation were observed.
As a result, the folding endurance after the heat treatment was 180 times or more. As shown in Table 1, no discoloration due to oxidation was observed.

(Example 5)
Copper plating was performed in the same manner as in Example 1 above, and the rust prevention treatment conditions shown in Table 1 were CrO ₃ concentration: 6 g / L, Zn concentration: 1 g / L, pH: 4.7, liquid temperature: 50 ° C. Then, electroplating was performed under the conditions of current density: 4.0 A / dm ² and electric quantity: 6.0 C / dm ² , and Cr and / or CrO ₃ and Zn and / or ZnO were adhered. The amount of Cr and / or CrO ₃ deposited was 49.3 μg / dm ² in terms of Cr, and the amount of Zn and / or ZnO deposited was 131.5 μg / dm ² in terms of Zn. Other conditions were the same as those in Example 1.

In this case, since it is extremely difficult to determine the presence ratio and Zn and abundance of ZnO and Cr and CrO _3, both Cr equivalent amount, it was Zn equivalent amount.
Furthermore, after heat-treating this two-layer copper clad laminate under the same conditions as in Example 1, the folding resistance after the heat treatment and the presence or absence of oxidation were observed.
As a result, the folding endurance after the heat treatment was 180 times or more. As shown in Table 1, no discoloration due to oxidation was observed.

(Comparative Example 1)
In the same manner as in Example 1, copper plating was performed and the rust prevention treatment conditions shown in Table 1 were CrO ₃ concentration: 3 g / L, Zn concentration: 5 g / L, pH: 4.7, liquid temperature: 50 ° C., current Electroplating was carried out under the conditions of density: 4.0 A / dm ² and electric quantity: 20 C / dm ² to deposit Cr and / or CrO ₃ and Zn and / or ZnO. The amount of Cr and / or CrO ₃ deposited was 21.8 μg / dm ² in terms of Cr, and the amount of Zn and / or ZnO deposited was 1362.4 μg / dm ² in terms of Zn. Other conditions were the same as those in Example 1.

In this case, since it is extremely difficult to determine the abundance ratio of Cr and CrO ₃ and the abundance ratio of Zn and ZnO, both are converted into Cr equivalent and Zn equivalent.
The two-layer copper-clad laminate was heat-treated under the same conditions as in Example 1, and the presence or absence of oxidation was observed. As a result, in Comparative Example 1, the appearance was changed to a brass color, and the folding resistance was lower than that in the example. This is considered to be because the amount of Zn adhering as a rust-preventing layer was large, so that it diffused into an alloy by heat treatment.

(Comparative Example 2)
The same as in Example 1 above, except that copper plating was performed, and the rust prevention treatment conditions were the same as those of benzotriazole, which is a general organic rust prevention treatment.
When this two-layer copper-clad laminate was heat-treated under the same conditions as in Example 1, folding resistance of about 150 times was obtained, but discoloration due to oxidation was observed.

  The two-layer copper-clad laminate obtained by the present invention has an excellent effect of improving folding resistance, effectively preventing breakage of the outer lead portion of the circuit, and preventing oxidation due to heat or the like. Therefore, it is optimal as a circuit material for mounting a driver IC such as a liquid crystal display that requires a fine pitch circuit.

Claims (9)

  A single metal layer selected from Ni, Co and Cr or an alloy layer made of two or more of these metals is formed on a polyimide film by sputtering, and a copper layer is formed on the metal layer or alloy layer by sputtering or plating. A two-layer copper-clad laminate comprising: a layer made of Cr and / or Cr oxide on the copper layer.   A single metal layer selected from Ni, Co and Cr or an alloy layer made of two or more of these metals is formed on a polyimide film by sputtering, and a copper layer is formed on the metal layer or alloy layer by sputtering or plating. A two-layer copper-clad laminate comprising: a layer made of Zn and / or a Zn oxide on the copper layer.   A single metal layer selected from Ni, Co and Cr or an alloy layer made of two or more of these metals is formed on a polyimide film by sputtering, and a copper layer is formed on the metal layer or alloy layer by sputtering or plating. A two-layer copper-clad laminate formed with a composite layer or mixed layer of Cr and / or Cr oxide and Zn and / or Zn oxide on the copper layer. A two-layer copper-clad laminate.   The surface roughness (Rz) of a copper layer is 0.1 micrometer or more and 0.9 micrometer or less, The two-layer copper clad laminated board as described in any one of Claims 1-3. The ^two- layer copper-clad laminate according to any one of claims 1 to 4, wherein the Cr adhesion amount is 11.5 µg / dm ² or more and 40.0 µg / dm ² or less in terms of Cr amount. . The two-layer copper-clad laminate according to any one of claims 2 to 5, wherein the Zn adhesion amount is 1000 µg / dm ² or less in terms of Zn amount.   A single metal layer selected from Ni, Co and Cr or an alloy layer made of two or more of these metals is formed on a polyimide film by sputtering, and a copper layer is formed on the metal layer or alloy layer by sputtering or plating. A two-layer copper-clad laminate, wherein a Cr and / or Cr oxide layer is formed on the copper layer by sputtering or plating. Manufacturing method.   A single metal layer selected from Ni, Co and Cr or an alloy layer made of two or more of these metals is formed on a polyimide film by sputtering, and a copper layer is formed on the metal layer or alloy layer by sputtering or plating. A method for producing a two-layer copper-clad laminate, wherein a layer made of Zn and / or Zn oxide is further formed on the copper layer by sputtering or plating. A manufacturing method of a laminated board.   A single metal layer selected from Ni, Co and Cr or an alloy layer made of two or more of these metals is formed on a polyimide film by sputtering, and a copper layer is formed on the metal layer or alloy layer by sputtering or plating. And a composite layer or mixed layer of Cr and / or Cr oxide and Zn and / or Zn oxide is formed on the copper layer by sputtering or plating. A method for producing a two-layer copper-clad laminate, wherein