JP5171690B2 - Copper-clad laminate and manufacturing method thereof - Google Patents

Description

  The present invention relates to a copper clad laminate and a method for producing the same, and more specifically, a copper clad laminate provided with a chromium-free surface treatment layer in which the copper foil used in the copper clad laminate does not contain chromium or chromate, and the copper clad laminate It relates to a manufacturing method.

  In copper foil used for copper clad laminates, from the viewpoint of satisfying various characteristics such as electrical characteristics, etching characteristics, heat resistance, and chemical resistance as copper clad laminates, rust prevention on the surface of copper foil, copper Adhesive strength between the foil and an insulating resin layer such as polyimide resin is required. Therefore, on the surface of the copper foil after the foil formation, the surface is subjected to the roughening treatment, the surface subjected to the roughening treatment is subjected to galvanization or nickel plating, and the surface is further subjected to galvanization or nickel plating. A method of applying chromate treatment as a rust-proofing layer for chemical resistance and rust-proofing has been adopted. However, the chromate film applied as such a rust-proofing layer is generally formed by electrolytic chromate, and the treatment liquid contains hexavalent chromium, which is a pollution control substance. Has come to be.

  Thus, surface treatment methods other than chromate treatment have been studied. For example, JP 2005-353918 A (Patent Document 1) discloses a copper layer having a roughened surface, a nickel layer as a barrier layer, A surface-treated copper foil for a printed wiring board is disclosed in which a zinc layer as a heat-resistant layer, a molybdenum compound layer as an antirust treatment layer, and a silane coupling treatment layer are sequentially applied. Japanese Unexamined Patent Application Publication No. 2007-009261 (Patent Document 2) discloses a surface-treated copper foil for a printed wiring board on which a rust-proofing layer made of a cerium compound film is formed. Furthermore, Japanese Unexamined Patent Application Publication No. 2008-111169 (Patent Document 3) discloses a surface-treated copper foil including a nickel alloy layer, a tin layer, and a silane coupling treatment layer as a rust prevention treatment layer. However, in the surface-treated copper foil as described in Patent Documents 1 to 3, it is necessary to provide a special metal layer such as molybdenum, cerium, or tin, and a plurality of layers having various functions are formed. Since it is necessary, there is a problem that the process of forming the surface treatment layer becomes complicated.

JP 2005-353918 A JP 2007-009261 A JP 2008-1111169 A

  The present invention has been made in view of the above-described problems of the prior art, and is a copper-clad laminate including a polyimide resin layer and a surface-treated copper foil laminated on at least one surface of the polyimide resin layer. A copper-clad laminate having a surface treatment layer having sufficient anti-rust properties yet having a sufficiently high adhesive strength between the polyimide resin layer and the surface-treated copper foil, and a method for producing the same With the goal.

  As a result of intensive studies to achieve the above object, the inventors of the present invention have provided a copper-clad laminate including a polyimide resin layer and a surface-treated copper foil laminated on at least one surface of the polyimide resin layer. By using a surface treatment layer containing a specific nickel-zinc alloy and a specific amount or more of silicon as the treated copper foil, a surface treatment layer having sufficient rust prevention properties while being chromium-free is provided. In addition, the present inventors have found that a copper-clad laminate having a sufficiently high adhesive strength between the polyimide resin layer and the surface-treated copper foil can be obtained, and the present invention has been completed.

That is, the copper clad laminate of the present invention is a copper clad laminate comprising a polyimide resin layer and a surface-treated copper foil laminated on at least one side of the polyimide resin layer,
The surface-treated copper foil is a base material copper foil and a surface-treated layer containing silicon derived from a nickel-zinc alloy and a silane coupling agent, which is formed on the surface of the polyimide resin layer on the base material copper foil. Nickel content in the surface treatment layer is 0.1 mg / dm ² or more, zinc content is 0.05 mg / dm ² or more, and nickel relative to the total of nickel and zinc contents The content ratio is in the range of 50 to 90% by mass, and the silicon content is such that the silicon peak intensity by glow discharge emission spectrometry is 50% or more with respect to the nickel peak intensity. It is characterized by.

The method for producing a copper clad laminate of the present invention is a method for producing a copper clad laminate in which a polyimide resin layer is formed by applying a polyamic acid resin solution to the surface of a surface-treated copper foil, followed by heat treatment. ,
The surface-treated copper foil is a base material copper foil and a surface-treated layer containing silicon derived from a nickel-zinc alloy and a silane coupling agent, which is formed on the surface of the polyimide resin layer on the base material copper foil. Nickel content in the surface treatment layer is 0.1 mg / dm ² or more, zinc content is 0.05 mg / dm ² or more, and nickel relative to the total of nickel and zinc contents The content ratio is in the range of 50 to 90% by mass, and the silicon content is such that the silicon peak intensity by glow discharge emission spectrometry is 50% or more with respect to the nickel peak intensity. It is the method characterized by this.

  Moreover, in the copper clad laminated board of this invention, and its manufacturing method, it is preferable that the silicon in a surface treatment layer originates in an amine-type silane coupling agent.

  According to the present invention, in a copper clad laminate comprising a polyimide resin layer and a surface-treated copper foil laminated on at least one surface of the polyimide resin layer, the surface-treated layer having sufficient rust prevention properties while being chromium-free In addition, it is possible to provide a copper clad laminate having a sufficiently high adhesive strength between the polyimide resin layer and the surface-treated copper foil, and a method for producing the same.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

First, the copper clad laminate of the present invention will be described. That is, the copper clad laminate of the present invention is a copper clad laminate comprising a polyimide resin layer and a surface-treated copper foil laminated on at least one side of the polyimide resin layer,
The surface-treated copper foil comprises a base material copper foil, and a surface treatment layer formed on the formation surface side of the polyimide resin layer in the base material copper foil, and containing a nickel-zinc alloy and silicon, The nickel content in the surface treatment layer is 0.1 mg / dm ² or more, the zinc content is 0.05 mg / dm ² or more, and the ratio of the nickel content to the total content of nickel and zinc is 50 to 50 It is in the range of 90% by mass, and the silicon content is such that the silicon peak intensity by glow discharge emission spectrometry is 50% or more with respect to the nickel peak intensity. .

  The copper clad laminate of the present invention comprises a surface-treated copper foil and a polyimide resin layer. Such a copper-clad laminate may be a single-sided copper-clad laminate provided with the surface-treated copper foil only on one side of the polyimide resin layer, and both sides provided with the surface-treated copper foil on both sides of the polyimide resin layer. A copper-clad laminate may also be used.

  The surface-treated copper foil according to the present invention comprises a base material copper foil before the surface-treated layer is formed and the surface-treated layer. Such a base material copper foil may be either an electrolytic copper foil or a rolled copper foil. The thickness of such a base material copper foil is not particularly limited as long as it is a thickness range of a copper foil used for a general copper-clad laminate, but is 70 μm or less from the viewpoint of flexibility of the copper-clad laminate. It is preferable. If the thickness exceeds 70 μm, the use of the obtained copper-clad laminate is limited, which is not preferable. Moreover, when using a copper clad laminated board as a flexible copper clad laminated board, it is preferable that the thickness of the said base material copper foil is the range of 5-35 micrometers. If the thickness of the base material copper foil is less than 5 μm, wrinkles and the like are likely to enter during production, and the production of thin copper foil tends to be costly. On the other hand, if the thickness exceeds 35 μm, the obtained copper-clad laminate When used, there is a tendency that an IC mounting substrate or the like for driving a liquid crystal display which is a display unit of a personal computer, a mobile phone or a personal digital assistant (PDA) is not sufficiently thin and small.

  From the viewpoint of improving the adhesive strength (peel strength) and chemical resistance between the copper foil and the polyimide resin layer, it is preferable to use a base material copper foil whose surface has been roughened. The ten-point average roughness (Rz) of the base material copper foil is preferably 1.5 μm or less from the above viewpoint and the flexibility of the obtained copper-clad laminate, and is preferably 0.1 to 1.m. A range of 0 μm is more preferable. The arithmetic average roughness (Ra) of the base material copper foil is preferably 0.15 μm or less. In addition, 10-point average roughness and arithmetic average roughness can be measured by a method according to the method described in JIS B 0601.

  The surface treatment layer concerning this invention is a layer formed in the formation surface side of the said polyimide resin layer in the said base material copper foil, and is a layer containing a nickel-zinc alloy and silicon. In the present invention, by forming such a surface treatment layer on the base material copper foil, the base material copper foil is provided with sufficient rust prevention property, and between the polyimide resin layer and the surface treatment copper foil. It becomes possible to improve adhesive strength. The thickness of such a surface treatment layer is preferably in the range of 10 to 50 nm. If the thickness is less than the lower limit, the surface of the base copper foil is not uniformly covered, and it is difficult to obtain a sufficient rust prevention effect. On the other hand, if the upper limit is exceeded, the solubility of the surface treatment layer in the copper etching solution is increased. (Etching property) tends to be insufficient.

In the present invention, the nickel content in the surface treatment layer needs to be 0.1 mg / dm ² or more. When the nickel content is less than 0.1 mg / dm ² , the rust preventive effect on the surface of the copper foil is not sufficient, and discoloration of the copper foil surface is likely to occur after heating or in a high temperature or high humidity environment. Moreover, it is more preferable that nickel content is the range of 0.1-3 mg / dm < ² > from a viewpoint of fully preventing that the copper from a base material copper foil diffuses into a surface treatment layer or a polyimide resin layer. .

Further, the zinc content in the surface treatment layer needs to be 0.05 mg / dm ² or more. When the zinc content is less than 0.05 mg / dm ² , the solubility (etching property) of the surface treatment layer in the copper etching solution becomes insufficient, and the polyimide is caused by thermal deterioration during the production of the copper clad laminate of the surface treatment layer. Adhesive strength between the resin layer and the surface-treated copper foil becomes insufficient. Moreover, zinc content is the range of 0.05-1.5 mg / dm < ² > from a viewpoint of further improving the etching property of a surface treatment layer, and the adhesive strength between a polyimide resin layer and a surface treatment copper foil. It is more preferable.

  Furthermore, the ratio of the nickel content to the total content of nickel and zinc in the surface treatment layer needs to be in the range of 50 to 90% by mass. If the ratio of the nickel content is less than 50% by mass, the resistance to the etching solution at the time of circuit processing is reduced, which hinders circuit processing. On the other hand, if it exceeds 90% by mass, the solubility in the etching solution is deteriorated. Therefore, the circuit processing is hindered, and the adhesive strength between the polyimide resin layer and the surface-treated copper foil becomes insufficient.

  Further, it is necessary that the silicon content in the surface treatment layer is such that the peak intensity of silicon by glow discharge emission spectrometry is 50% or more with respect to the peak intensity of nickel. When the peak strength of silicon is less than 50% of the peak strength of nickel, the adhesive strength between the polyimide resin layer and the surface-treated copper foil becomes insufficient. Further, from the viewpoint of further improving the adhesive strength between the polyimide resin layer and the surface-treated copper foil, the silicon peak strength is more preferably 60% or more with respect to the nickel peak strength. Note that the peak intensities of silicon and nickel determined by glow discharge emission spectrometry are determined by detecting the light intensity at each wavelength using a glow discharge emission spectrophotometer and creating an emission spectrum, and corresponding to silicon and nickel from the spectrum. The peak intensity (peak area) of the peak can be measured.

The surface treatment layer according to the present invention can be formed by performing a plating treatment on the surface of the base material copper foil using a plating solution containing a nickel compound, a zinc compound and a silicon compound. The plating solution is preferably a pyrophosphate plating solution, for example, more preferably a plating solution satisfying any (particularly preferably all) of the following conditions (i) to (v). .
(I) It contains nickel sulfate and the nickel concentration is 1 to 4 g / L.
(Ii) It contains zinc pyrophosphate, and the zinc concentration is 0.05 to 1 g / L.
(Iii) The concentration of potassium pyrophosphate is 10 to 500 g / L.
(Iv) The concentration of the silicon compound is 10 g / L or more (more preferably 15 to 50 g / L).
(V) The amount of ammonia water added is 25 g / L or more.

  Examples of the silicon compound used in the present invention include silane coupling agents such as amino silane, epoxy silane, methacryloxy silane, and mercapto silane. These silane coupling agents can be used alone or in combination of two or more. Among these silane coupling agents, an amino silane coupling agent is particularly preferable from the viewpoint of the stability of the pyrophosphate plating solution.

  Examples of the amino-based silane coupling agent include N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and N- (2 -Aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3 -(N-phenyl) aminopropyltrimethoxysilane, N- (vinylbenzine) -2-aminoethyl-3-aminopropyltrimethoxysilane.

As the plating conditions for forming the surface treatment layer according to the present invention, the liquid temperature is usually 15 to 50 ° C., the pH is 8 to 11, and the current density is 0.1 to 5 A / dm ^2. .

  The polyimide resin layer according to the present invention is a layer made of a polyimide resin. And such a polyimide resin is a resin generally represented by the following general formula (1), for example, in an organic polar solvent using substantially equimolar amounts of a diamine component and an acid dianhydride component. It can be produced by a known method of polymerization.

In the general formula (1), Ar ₁ represents a tetravalent organic group having one or more aromatic rings, and Ar ₂ represents a divalent organic group having one or more aromatic rings. That is, Ar ₁ is an acid dianhydride residue and Ar ₂ is an aromatic diamine residue.

As the acid dianhydride, an aromatic tetracarboxylic dianhydride represented by a general formula: O (CO) ₂ —Ar ₁ — (CO) ₂ O can be used. Moreover, as Ar < ₁ > in the said general formula, the organic group represented by the following structural formula is mentioned, for example.

  These acid dianhydrides can be used individually by 1 type or in combination of 2 or more types. Among these acid dianhydrides, pyromellitic dianhydride (PMDA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA), 3,3 ′, 4,4 '-Benzophenone tetracarboxylic dianhydride (BTDA), 3,3', 4,4'-diphenylsulfone tetracarboxylic dianhydride (DSDA), and 4,4'-oxydiphthalic dianhydride (ODPA). It is preferable to use it.

As the diamine, an aromatic diamine represented by the general formula: H ₂ N—Ar ₂ —NH ₂ can be used. Moreover, as Ar < ₂ > in the said general formula, the organic group represented by the following structural formula is mentioned, for example.

  These aromatic diamines can be used alone or in combination of two or more. Among these aromatic diamines, diaminodiphenyl ether (DAPE), 2′-methoxy-4,4′-diaminobenzanilide (MABA), 2,2′-dimethyl-4, 4′-diaminobiphenyl (m- TB), paraphenylenediamine (p-PDA), 1,3-bis (4-aminophenoxy) benzene (TPE-R), 1,3-bis (3-aminophenoxy) benzene (APB), 1,4- Bis (4-aminophenoxy) benzene (TPE-Q) and 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) are preferably used.

  Examples of the solvent used for polymerizing the diamine and the acid dianhydride include dimethylacetamide, n-methylpyrrolidinone, 2-butanone, diglyme, and xylene. These solvents can be used alone or in combination of two or more. The resin viscosity of the polyamic acid (polyimide precursor) obtained by polymerization is preferably in the range of 500 cps to 35000 cps.

  In the copper clad laminate of the present invention, the polyimide resin layer may be a single layer or a plurality of layers, but the copper clad laminate is a flexible copper clad laminate. From the viewpoint of controlling warpage and dimensional stability in some cases, and from the viewpoint of excellent adhesion strength between the copper foil and the polyimide resin layer, it is preferable to have a plurality of layers. In addition, the thickness of the polyimide resin layer is not particularly limited, but in the case of a flexible copper-clad laminate, it is preferably in the range of 6 to 60 μm, and more preferably in the range of 9 to 40 μm. If the thickness of the polyimide resin layer is less than the lower limit, defects such as wrinkles in the polyimide resin layer tend to occur during the production of the copper clad laminate, whereas if the upper limit is exceeded, the copper clad laminate is produced. There is a tendency that problems are likely to occur in dimensional stability and flexibility at the time. In addition, what is necessary is just to make it the total thickness of a several layer be in the said range, when the said polyimide resin layer consists of a plurality of layers.

In the case where the polyimide resin layer is composed of a plurality of layers, the linear expansion coefficient (CTE) is 30 × 10 ⁻⁶ (1 / K) or less, preferably 1 × 10 ⁻⁶ to 30 × 10 ⁻⁶ (1 / K) is preferably provided with a low linear expansion polyimide resin layer and a low Tg polyimide resin layer having a glass transition temperature (Tg) of 330 ° C. or lower on one side or both sides thereof. When the linear expansion coefficient of the low linear expansion polyimide resin layer exceeds 30 × 10 ⁻⁶ (1 / K), curling tends to become severe when a copper clad laminate is formed, and dimensional stability is increased. It tends to decrease.

Further, when the polyimide resin layer is composed of a plurality of layers, the low Tg polyimide resin layer has a linear expansion coefficient (CTE) exceeding 30 × 10 ⁻⁶ (1 / K) and glass. It is preferable to use one having a transition temperature of 330 ° C. or lower, a linear expansion coefficient in the range of 30 × 10 ^{−6 to} 60 × 10 ⁻⁶ (1 / K), and a glass transition temperature in the range of 200 to 330 ° C. It is more preferable to use a certain one.

  Furthermore, when the polyimide resin layer is composed of a plurality of layers as described above, it is preferable that the low linear expansion polyimide resin layer is a main resin layer. Further, the thickness of the low linear expansion polyimide resin layer is preferably 50% or more, more preferably in the range of 70 to 95% with respect to the total thickness of the plurality of layers.

Next, the manufacturing method of the copper clad laminated board of this invention is demonstrated. That is, the method for producing a copper clad laminate of the present invention is a method for producing a copper clad laminate in which a polyimide resin layer is formed by applying a polyamic acid resin solution to the surface of a surface-treated copper foil and heat-treating it. There,
The surface-treated copper foil comprises a base material copper foil, and a surface treatment layer formed on the formation surface side of the polyimide resin layer in the base material copper foil, and containing a nickel-zinc alloy and silicon, The nickel content in the surface treatment layer is 0.1 mg / dm ² or more, the zinc content is 0.05 mg / dm ² or more, and the ratio of the nickel content to the total content of nickel and zinc is 50 to 50 The silicon content is in the range of 90% by mass, and the silicon content is such that the silicon peak intensity by glow discharge emission spectrometry is 50% or more of the nickel peak intensity. .

  As the surface-treated copper foil used in the method for producing a copper-clad laminate of the present invention, it is necessary to use the same surface-treated copper foil as that used for the copper-clad laminate of the present invention. That is, it is necessary to use a surface-treated copper foil in which the nickel content, the zinc content and the silicon content in the surface treatment layer, and the ratio of the nickel content to the sum of the nickel and zinc contents satisfy the above conditions. is there.

  In the method for producing a copper clad laminate of the present invention, a polyamic acid resin solution is applied to the surface of the surface-treated copper foil and heat treated to form a polyimide resin layer to obtain a copper clad laminate.

  The method for forming the polyimide resin layer is not particularly limited. For example, a polyamic acid resin solution, which is a polyimide precursor, is directly applied to the surface of the surface-treated copper foil, and the solvent contained in the resin solution is 150 ° C. After removing to some extent at the following temperature, a method of drying and imidizing the solvent is further adopted by performing heat treatment for about 5 to 40 minutes at a temperature range of 100 to 450 ° C., preferably 300 to 450 ° C. be able to. If the temperature of the heat treatment is less than 100 ° C., the dehydration ring-closure reaction of the polyimide tends not to proceed. On the other hand, if it exceeds 450 ° C., the polyimide resin layer and the copper foil tend to deteriorate due to oxidation or the like. Moreover, as a polyamic acid and a solvent, the thing similar to the polyamic acid and solvent used for the copper clad laminated board of the said this invention can be used. When the polyimide resin layer is composed of, for example, three layers, the first polyamic acid resin solution is applied and dried, and then the second polyamic acid resin solution is applied and dried. After applying and drying the three polyamic acid resin solutions, a method of imidization can be adopted by collectively performing a heat treatment for about 5 to 40 minutes in a temperature range of 300 to 450 ° C.

  In this way, a single-sided copper-clad laminate having a surface-treated copper foil on one side of the polyimide resin layer is obtained. Moreover, as a method of producing a double-sided copper-clad laminate having surface-treated copper foil on both sides of a polyimide resin layer, (i) after producing a single-sided copper-clad laminate, facing each other with a polyimide resin layer and hot pressing (Ii) A method in which a surface-treated copper foil is thermocompression-bonded to a polyimide resin layer of a single-sided copper-clad laminate can be employed.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example. Measurement of nickel content, zinc content and silicon content in surface treatment layer of surface treated copper foil, discoloration of copper foil under high temperature and high temperature and high humidity conditions, peel strength between copper foil and polyimide resin layer Were measured or evaluated by the following methods.

(I) Measurement of nickel content and zinc content in the surface treatment layer About the surface treatment layer of the surface treated copper foil, an atomic absorption spectrophotometer (product name “NovaAA300” manufactured by Analytikjena) is used, and nickel is standard. With respect to zinc, the content of zinc was measured by an absolute calibration method.

(Ii) Measurement of silicon content in surface-treated layer About the surface-treated layer of the surface-treated copper foil, a glow discharge emission spectroscopic analyzer (manufactured by HORIBA, Ltd. (manufactured by JOBIN YVON), product name “GD-PROFILER2”) is used. Then, the light intensity for each wavelength was detected to create an emission spectrum, and the peak intensity (peak area) of the peak corresponding to silicon and nickel was measured from the spectrum. The silicon peak intensity relative to the nickel peak intensity was calculated from the measured value.

(Iii) Evaluation of discoloration of copper foil under high temperature and high temperature and high humidity conditions The surface-treated copper foil was exposed to a temperature of 150 ° C. and a temperature of 85 ° C. and a humidity of 85% for 72 hours. The copper foil surface discoloration was confirmed. When no discoloration was confirmed, it was determined as “◯”, and when discoloration was confirmed, it was determined as “x”.

(Iv) Measurement of peel strength between copper foil and polyimide resin layer Using a copper-clad laminate with a width of 1 mm as a sample and using a Tensilon tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.), the resin side of the sample is made into a stainless steel plate with double-sided tape. The peel strength when the copper foil was peeled off at a rate of 50 mm / min in the 180 ° direction was measured.

(Synthesis Example 1)
After charging 132 parts by mass of N, N-dimethylacetamide (DMAc) into a reaction vessel equipped with a thermocouple and a stirrer and capable of introducing nitrogen, 2,2-bis [4- (4-aminophenoxy) phenyl] propane 11.7 parts by mass of (BAPP) was dissolved in the container with stirring. Next, 6.3 parts by mass of diamine component and pyromellitic dianhydride (PMDA) equimolar to the diamine component are added to this solution, and then the stirring is continued at room temperature for 3 hours to proceed the polymerization reaction. Was 12% by mass, and a polyamic acid a resin solution having a solution viscosity of 3000 cps was obtained. A polyimide film was prepared using the obtained polyamic acid a, and the glass transition temperature and the linear expansion coefficient of the polyimide film were measured. The glass transition temperature was 280 ° C., and the linear expansion coefficient was 55 × 10 ⁻⁶ (1 / K).

(Synthesis Example 2)
A reaction vessel equipped with a thermocouple and a stirrer and capable of introducing nitrogen was charged with 127.5 parts by mass of N, N-dimethylacetamide (DMAc), and then 2′-methoxy-4,4′-diaminobenzanilide (MABA). ) 6.5 parts by mass and 5.1 parts by mass of 4,4′-diaminodiphenyl ether (DAPE) were dissolved in a container with stirring. Next, 10.9 parts by mass of pyromellitic dianhydride (PMDA) equimolar to the diamine component is added to this solution, and then the stirring is continued at room temperature for 3 hours to proceed the polymerization reaction. Was 15% by mass and a resin solution of polyamic acid b having a solution viscosity of 20000 cps was obtained. A polyimide film was prepared using the obtained polyamic acid b, and the linear expansion coefficient of the polyimide film was measured. The linear expansion coefficient was 13 × 10 ⁻⁶ (1 / K).

Example 1
Nickel sulfate, zinc pyrophosphate, potassium pyrophosphate, 3-aminopropyltrimethoxysilane and aqueous ammonia on the surface of the base material copper foil (untreated electrolytic copper foil, thickness: 12 μm, size: 10 cm × 10 cm) A plating solution that satisfies the following conditions, the plating solution temperature is 20 ° C., the current density is 1.5 A / dm ² , and the treatment time is 5 minutes. A treatment layer was formed to obtain a surface-treated copper foil.

Nickel concentration 2.5g / L
Zinc concentration 0.1g / L
Concentration of potassium pyrophosphate 50g / L
Concentration of 3-aminopropyltrimethoxysilane 15.2 g / L
Amount of ammonia water added 25.3 g / L.

The obtained surface-treated copper foil was measured for the silicon content in the surface-treated layer by glow discharge emission spectrometry. The silicon peak intensity was 63% of the nickel peak intensity. Further, the nickel content of the surface treatment layer is 0.14 mg / dm ^2, the zinc content was 0.08 mg / dm ^2. Furthermore, when the discoloration test of the obtained surface-treated copper foil was conducted, discoloration after 72 hours exposure could not be confirmed. The obtained results are shown in Table 1.

  On the surface of the surface-treated layer of the obtained surface-treated copper foil, the polyamic acid a obtained in Synthesis Example 1 was applied and dried at 130 ° C. for 1 minute to form a polyamic acid a film. Thereafter, the polyamic acid b obtained in Synthesis Example 2 was coated on the surface of the polyamic acid a film and dried at 130 ° C. for 4 minutes to form a polyamic acid b film. The obtained polyamic acid a was applied and dried at 130 ° C. for 1 minute to form a polyamic acid a film. Then, the temperature is raised to 350 ° C. over 15 minutes to advance imidization, and a polyimide resin layer (2 μm low Tg polyimide resin layer / 36 μm low linear expansion polyimide resin layer / 2 μm low Tg polyimide resin layer) To obtain a flexible single-sided copper-clad laminate. When the peel strength of the obtained flexible single-sided copper clad laminate was measured, the peel strength was 1.2 kN / m. The obtained results are shown in Table 1.

(Example 2)
Using the following conditions are satisfied plating solution, except that the current density was 0.5A / dm ² was obtained with a manner the surface treated copper foil and flexible single-sided copper-clad laminate as in Example 1.

Nickel concentration 2.5g / L
Zinc concentration 0.1g / L
Concentration of potassium pyrophosphate 50g / L
Concentration of 3-aminopropyltrimethoxysilane 30.5 g / L
Amount of ammonia water added 25.3 g / L.

When the content of silicon in the surface treatment layer was measured for the obtained surface-treated copper foil by glow discharge emission spectrometry, the peak intensity of silicon was 115% with respect to the peak intensity of nickel. Moreover, nickel content in a surface treatment layer was 0.13 mg / dm < ² >, and zinc content was 0.09 mg / dm < ² >. Furthermore, when the discoloration test of the obtained surface-treated copper foil was conducted, discoloration after 72 hours exposure could not be confirmed. Moreover, when the peel strength of the obtained flexible single-sided copper clad laminate was measured, the peel strength was 1.3 kN / m. The obtained results are shown in Table 1.

(Example 3)
Except that the current density 0.7 A / dm ² was obtained with a manner the surface treated copper foil and flexible single-sided copper-clad laminate as in Example 2.

The obtained surface-treated copper foil was measured for the silicon content in the surface-treated layer by glow discharge emission spectrometry. The silicon peak intensity was 111% relative to the nickel peak intensity. Further, the nickel content of the surface treatment layer is 0.21 mg / dm ^2, the zinc content was 0.11 mg / dm ^2. Furthermore, when the discoloration test of the obtained surface-treated copper foil was conducted, discoloration after 72 hours exposure could not be confirmed. Moreover, when the peel strength of the obtained flexible single-sided copper clad laminate was measured, the peel strength was 1.3 kN / m. The obtained results are shown in Table 1.

Example 4
A surface-treated copper foil and a flexible single-sided copper-clad laminate were obtained in the same manner as in Example 2 except that the treatment time was 20 minutes.

When the content of silicon in the surface treatment layer was measured for the obtained surface-treated copper foil by glow discharge emission spectrometry, the peak intensity of silicon was 115% with respect to the peak intensity of nickel. Further, the nickel content of the surface treatment layer is 0.68 mg / dm ^2, the zinc content was 0.24 mg / dm ^2. Furthermore, when the discoloration test of the obtained surface-treated copper foil was conducted, discoloration after 72 hours exposure could not be confirmed. Moreover, when the peel strength of the obtained flexible single-sided copper clad laminate was measured, the peel strength was 1.3 kN / m. The obtained results are shown in Table 1.

(Comparative Example 1)
A surface-treated copper foil and a flexible single-sided copper-clad laminate for comparison were obtained in the same manner as in Example 1 except that a plating solution satisfying the following conditions was used and the current density was 0.5 A / dm ² .

Nickel concentration 2.5g / L
Zinc concentration 0.1g / L
Concentration of potassium pyrophosphate 50g / L
Concentration of 3-aminopropyltrimethoxysilane 1.9 g / L
Amount of ammonia water added 25.3 g / L.

When the content of silicon in the surface treatment layer was measured for the obtained surface-treated copper foil by glow discharge emission spectrometry, the peak intensity of silicon was 14% with respect to the peak intensity of nickel. Moreover, nickel content in a surface treatment layer was 0.22 mg / dm < ² >, and zinc content was 0.10 mg / dm < ² >. Furthermore, when the discoloration test of the obtained surface-treated copper foil was conducted, discoloration after 72 hours exposure could not be confirmed. Moreover, when the peel strength of the obtained flexible single-sided copper clad laminate was measured, the peel strength was 0.3 kN / m. The obtained results are shown in Table 1.

(Comparative Example 2)
A surface-treated copper foil and a flexible single-sided copper-clad laminate for comparison were obtained in the same manner as in Example 1 except that a plating solution satisfying the following conditions was used and the current density was 1.0 A / dm ² .

Nickel concentration 2.5g / L
Zinc concentration 0.1g / L
Concentration of potassium pyrophosphate 50g / L
Concentration of 3-aminopropyltrimethoxysilane 3.8 g / L
Amount of ammonia water added 25.3 g / L.

When the content of silicon in the surface treatment layer was measured for the obtained surface-treated copper foil by glow discharge emission spectrometry, the peak intensity of silicon was 26% with respect to the peak intensity of nickel. Further, the nickel content of the surface treatment layer is 0.21 mg / dm ^2, the zinc content was 0.08 mg / dm ^2. Furthermore, when the discoloration test of the obtained surface-treated copper foil was conducted, discoloration after 72 hours exposure could not be confirmed. Moreover, when the peel strength of the obtained flexible single-sided copper clad laminate was measured, the peel strength was 0.6 kN / m. The obtained results are shown in Table 1.

(Comparative Example 3)
A surface-treated copper foil and a flexible single-sided copper clad laminate for comparison were obtained in the same manner as in Example 2 except that the treatment time was 2 minutes.

Nickel content of the surface treatment layer in the obtained surface-treated copper foil is 0.07 mg / dm ^2, the zinc content was 0.04 mg / dm ^2. Furthermore, when the discoloration test of the obtained surface-treated copper foil was conducted, discoloration was confirmed after exposure for 48 hours in any of the conditions of a temperature of 150 ° C., the temperature of 85 ° C., and the humidity of 85%. The obtained results are shown in Table 1.

(Comparative Example 4)
A surface-treated copper foil and a flexible single-sided copper clad laminate for comparison were obtained in the same manner as in Example 2 except that the treatment time was 3 minutes.

The nickel content in the surface treatment layer in the obtained surface-treated copper foil was 0.09 mg / dm ² , and the zinc content was 0.05 mg / dm ² . Furthermore, when the discoloration test of the obtained surface-treated copper foil was conducted, discoloration was confirmed after exposure for 48 hours in any of the conditions of a temperature of 150 ° C., the temperature of 85 ° C., and the humidity of 85%. The obtained results are shown in Table 1.

  As is clear from the results shown in Table 1, in the copper clad laminates (Examples 1 to 4) of the present invention, a surface treatment layer having sufficient antirust properties is formed, and the polyimide resin layer and It was confirmed that the adhesive strength between the surface-treated copper foil was sufficiently high. On the other hand, in the copper clad laminated board obtained by the comparative examples 1 and 2, it was confirmed that the adhesive strength between a polyimide resin layer and a surface treatment copper foil is inadequate. Furthermore, in the copper clad laminated board obtained by the comparative examples 3 and 4, it was confirmed that the rust prevention property of the surface treatment layer in surface treatment copper foil is inadequate.

  As described above, according to the present invention, in a copper-clad laminate comprising a polyimide resin layer and a surface-treated copper foil laminated on at least one side of the polyimide resin layer, it is sufficiently rust-proof while being chromium-free. In addition, it is possible to provide a copper clad laminate having a surface treatment layer having a property and a sufficiently high adhesive strength between the polyimide resin layer and the surface treatment copper foil, and a method for producing the same.

Claims (4)

A copper clad laminate comprising a polyimide resin layer and a surface-treated copper foil laminated on at least one surface of the polyimide resin layer,
The surface-treated copper foil is a base material copper foil and a surface-treated layer containing silicon derived from a nickel-zinc alloy and a silane coupling agent, which is formed on the surface of the polyimide resin layer on the base material copper foil. Nickel content in the surface treatment layer is 0.1 mg / dm ² or more, zinc content is 0.05 mg / dm ² or more, and nickel relative to the total of nickel and zinc contents The content ratio is in the range of 50 to 90% by mass, and the silicon content is such that the silicon peak intensity by glow discharge emission spectrometry is 50% or more with respect to the nickel peak intensity. A copper-clad laminate.   The copper clad laminate according to claim 1, wherein silicon in the surface treatment layer is derived from an amine-based silane coupling agent. A method for producing a copper clad laminate in which a polyamide acid resin solution is applied to the surface of a surface-treated copper foil and heat-treated to form a polyimide resin layer,
The surface-treated copper foil is a base material copper foil and a surface-treated layer containing silicon derived from a nickel-zinc alloy and a silane coupling agent, which is formed on the surface of the polyimide resin layer on the base material copper foil. Nickel content in the surface treatment layer is 0.1 mg / dm ² or more, zinc content is 0.05 mg / dm ² or more, and nickel relative to the total of nickel and zinc contents The content ratio is in the range of 50 to 90% by mass, and the silicon content is such that the silicon peak intensity by glow discharge emission spectrometry is 50% or more with respect to the nickel peak intensity. The manufacturing method of the copper clad laminated board characterized by these.   4. The method for producing a copper-clad laminate according to claim 3, wherein silicon in the surface treatment layer is derived from an amine-based silane coupling agent.