WO2017022807A1

WO2017022807A1 - Printed wiring board production method, surface-treated copper foil, laminate, printed wiring board, semiconductor package, and electronic device

Info

Publication number: WO2017022807A1
Application number: PCT/JP2016/072848
Authority: WO
Inventors: 雅之高森; 雅史石井
Original assignee: Ｊｘ金属株式会社
Priority date: 2015-08-03
Filing date: 2016-08-03
Publication date: 2017-02-09

Abstract

Provided are a printed wiring board production method and a surface-treated copper foil allowing for the removal of copper foil at a good cost without losing the profile of the copper foil surface transferred onto the surface of a resin substrate, in a step for removing the copper foil from the resin substrate by providing a release layer to the copper foil and making the physical peeling of the resin substrate possible when the copper foil has been bonded to the resin substrate. The printed wiring board production method comprises: a step for bonding the resin substrate to the surface-treated copper foil provided with the release layer on the surface thereof, such bonding performed from the release layer side; a step for removing the surface-treated copper foil from the resin substrate to obtain the resin substrate to which the surface profile of the copper foil has been transferred to a peeling surface of the resin substrate; and a step for forming a plating pattern on the peeling surface side of the resin substrate to which the surface profile has been transferred.

Description

Printed wiring board manufacturing method, surface-treated copper foil, laminate, printed wiring board, semiconductor package, and electronic device

The present invention relates to a method for producing a printed wiring board, a surface-treated copper foil, a laminate, a printed wiring board, a semiconductor package, and an electronic device.

Subtractive methods are the mainstream for circuit formation methods for printed wiring boards and semiconductor package substrates. However, with the recent finer wiring, M-SAP (Modified Semi-Additive Process) and copper foil surface profiles were used. New methods such as the semi-additive method are emerging.

Among these new circuit formation methods, the following can be cited as an example of the semi-additive method using the surface profile of the latter copper foil. That is, first, the entire surface of the copper foil laminated on the resin base material is etched, the etching base material surface to which the copper foil surface profile is transferred is drilled with a laser or the like, and an electroless copper plating layer for conducting the drilled portion is formed. The electroless copper plating surface is coated with a dry film, the dry film of the circuit forming part is removed by UV exposure and development, and the electroless copper plating surface not coated with the dry film is electroplated with copper. Then, the electroless copper plating layer is etched (flash etching, quick etching) with an etching solution containing sulfuric acid and hydrogen peroxide solution, and a fine circuit is formed (Patent Document 1 and Patent Document 2). ).

JP 2006-196863 A JP 2007-242975 A

However, in the conventional semi-additive method using the copper foil surface profile, the copper foil surface profile can be transferred to the surface of the resin substrate without damaging the copper foil surface, and the copper foil can be removed at a good cost. There is still room for consideration.

As a result of intensive studies, the inventor has provided a release layer on the copper foil, and enables physical peeling of the resin base material when the copper foil is bonded to the resin base material. In the process of removing from the resin base material, it was found that the copper foil can be removed at a good cost without impairing the profile of the copper foil surface transferred to the surface of the resin base material.

The present invention completed on the basis of the above knowledge, in one aspect, a step of bonding a resin base material from the release layer side to a surface-treated copper foil provided with a release layer on the surface, and the resin base material And removing the surface-treated copper foil to obtain a resin base material having the surface profile of the copper foil transferred to the release surface, and to the release surface side of the resin base material to which the surface profile has been transferred. And a process for forming a plating pattern.

In another aspect of the present invention, a step of bonding a resin base material from the release layer side to a surface-treated copper foil provided with a release layer on the surface, and from the resin base material, the surface-treated copper foil Removing the substrate, obtaining a resin base material on which the surface profile of the copper foil is transferred to the release surface, and forming a print pattern on the release surface side of the resin base material on which the surface profile is transferred. It is a manufacturing method of the printed wiring board provided with.

According to another aspect of the present invention, a step of bonding a resin base material from the release layer side to a surface-treated copper foil provided with a release layer on the surface; A step of obtaining a resin base material in which the surface profile of the copper foil is transferred to the release surface by removing the foil, and a step of providing a build-up layer on the release surface side of the resin base material to which the surface profile is transferred Is a method for manufacturing a printed wiring board comprising:

In one embodiment, the method for producing a printed wiring board of the present invention has a strength of 500 g / cm when the untreated surfaces of the resin constituting the buildup layer and the resin base material are bonded together and pulled apart. ² or less.

In another embodiment of the method for producing a printed wiring board of the present invention, the resin constituting the build-up layer contains a liquid crystal polymer or polytetrafluoroethylene.

In another embodiment of the method for producing a printed wiring board of the present invention, the release layer has the following formula:
Wherein R ¹ is an alkoxy group or a halogen atom, and R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by: M is any one of Al, Ti, Zr, n is 0 or 1 or 2, m is an integer from 1 to M valence, (At least one of R ¹ is an alkoxy group, where m + n is a valence of M, that is, 3 for Al and 4 for Ti and Zr.)
The aluminate compound, the titanate compound, the zirconate compound, the hydrolysis products thereof, and the condensates of the hydrolysis products are used singly or in combination.

In another embodiment of the method for producing a printed wiring board of the present invention, the release layer has the following formula:

Wherein R ¹ is an alkoxy group or a halogen atom, and R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by R ³ and R ⁴ are each independently a halogen atom, an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group Or any one of these hydrocarbon groups in which one or more hydrogen atoms are replaced by halogen atoms.)
Or a hydrolyzate thereof, or a condensate of the hydrolyzate, alone or in combination.

In yet another embodiment of the method for producing a printed wiring board of the present invention, the release layer uses a compound having two or less mercapto groups in the molecule.

In yet another embodiment of the method for producing a printed wiring board of the present invention, the copper foil has a convex portion on the surface of the release layer, and the convex portion is formed by using an electron microscope. The surface of the copper foil is photographed on the release layer side surface with the stage placed 45 ° tilted from the horizontal plane, and the height from the constricted portion of the convex portion to the tip of the convex portion measured based on the obtained photograph is taken. When the thickness is a, the maximum width at the widest portion of the convex portion is b, and the minimum width of the constricted portion of the convex portion is c, both of the following expressions are satisfied.
When a / b ≦ 1, (bc) /b≦0.2 and b ≧ 10 nm
When a / b> 1, (bc) /b≦0.03 and b ≧ 10 nm

In still another embodiment of the method for producing a printed wiring board of the present invention, a group consisting of a heat-resistant layer, a rust-proof layer, a chromate treatment layer, and a silane coupling treatment layer between the copper foil and the release layer. One or more layers selected from are provided.

In yet another embodiment of the method for producing a printed wiring board of the present invention, the surface of one or more layers selected from the group consisting of the heat-resistant layer, the rust prevention layer, the chromate treatment layer, and the silane coupling treatment layer, A resin layer is provided.

In another embodiment of the method for producing a printed wiring board of the present invention, a resin layer is provided on the surface of the surface-treated copper foil on the release layer side.

In another embodiment of the method for producing a printed wiring board of the present invention, the resin layer is an adhesive resin, a primer, or a semi-cured resin.

In still another embodiment of the method for producing a printed wiring board of the present invention, the surface-treated copper foil has a thickness of 9 to 70 μm.

Still another aspect of the present invention is a surface-treated copper foil having a copper foil and a release layer provided on the surface of the copper foil, wherein the copper foil is convex on the release layer side surface. The projecting part has a portion, and the electron microscope is used to photograph the release layer side surface of the copper foil in a state where the stage on which the copper foil is placed is inclined 45 ° from the horizontal plane. When the height from the constricted part of the convex part to the tip of the convex part measured based on the above is a, the maximum width at the widest part of the convex part is b, and the minimum width of the constricted part of the convex part is c, This is a surface-treated copper foil that satisfies all the equations.
When a / b ≦ 1, (bc) /b≦0.2 and b ≧ 10 nm
When a / b> 1, (bc) /b≦0.03 and b ≧ 10 nm

In one embodiment of the surface-treated copper foil of the present invention, the copper foil does not have roughened particles on the release layer side surface.

In another embodiment of the surface-treated copper foil of the present invention, the release layer has the following formula:

Wherein R ¹ is an alkoxy group or a halogen atom, and R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by: M is any one of Al, Ti, Zr, n is 0 or 1 or 2, m is an integer from 1 to M valence, (At least one of R ¹ is an alkoxy group, where m + n is a valence of M, that is, 3 for Al and 4 for Ti and Zr.)
The aluminate compound, the titanate compound, the zirconate compound, the hydrolysis products thereof, and the condensates of the hydrolysis products are used singly or in combination.

In yet another embodiment of the surface-treated copper foil of the present invention, the release layer uses a compound having two or less mercapto groups in the molecule.

In another embodiment, the surface-treated copper foil of the present invention is selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate treatment layer, and a silane coupling treatment layer between the copper foil and the release layer. Provide one or more layers.

In yet another embodiment, the surface-treated copper foil of the present invention has a resin layer on the surface of one or more layers selected from the group consisting of the heat-resistant layer, the rust-proof layer, the chromate-treated layer, and the silane coupling-treated layer. Is provided.

In another embodiment of the surface-treated copper foil of the present invention, a resin layer is provided on the surface of the release layer side.

In yet another embodiment of the surface-treated copper foil of the present invention, the resin layer is an adhesive resin, a primer, or a semi-cured resin.

In yet another embodiment, the surface-treated copper foil of the present invention has a thickness of 9 to 70 μm.

Further another aspect of the present invention is a laminate including the surface-treated copper foil of the present invention and a resin base material provided on the release layer side of the surface-treated copper foil.

In one embodiment of the laminate of the present invention, the resin base material is a prepreg or contains a thermosetting resin.

In still another aspect, the present invention is a printed wiring board provided with the surface-treated copper foil of the present invention.

In yet another aspect, the present invention is a printed wiring board manufactured using the surface-treated copper foil of the present invention.

In still another aspect, the present invention is a semiconductor package provided with the printed wiring board of the present invention.

In yet another aspect, the present invention is an electronic device including the printed wiring board of the present invention or the semiconductor package of the present invention.

In the step of removing the copper foil from the resin base material by providing a release layer on the copper foil and enabling physical peeling of the resin base material when the copper foil is bonded to the resin base material, Provided are a printed wiring board manufacturing method and a surface-treated copper foil capable of removing a copper foil at a good cost without impairing the profile of the surface of the copper foil transferred to the surface of a resin substrate.

It is a cross-sectional schematic diagram of the copper foil which has a convex part (the case where there is a case where there is no constriction part). It is a cross-sectional schematic diagram of the copper foil which has a roughening particle | grain (nodule). It is a cross-sectional schematic diagram of the state which bonded the copper foil of FIG. 2 to the resin base material from the roughening particle side surface. It is a cross-sectional schematic diagram of the state which formed the plating pattern in the resin base material surface after removing copper foil in FIG. It is a cross-sectional schematic diagram of the state which formed the plating pattern on the resin base material formed by this invention. A schematic example of a semi-additive construction method using a copper foil profile is shown. Sample No. 58 is a microscopic observation photograph of the surface of the release layer side of the surface-treated copper foil according to 58. Sample No. 5 is a microscopic observation photograph of the release layer side surface of the surface-treated copper foil according to 55. It is a schematic diagram of the sample (copper foil) and stage for showing the evaluation method of the convex part of the mold release layer side surface of surface treatment copper foil.

(Printed wiring board manufacturing method)
In one aspect of the method for producing a printed wiring board of the present invention, on the surface-treated copper foil provided with a release layer on the surface, a step of bonding a resin base material from the release layer side, and from the resin base material, Removing the surface-treated copper foil to obtain a resin base material in which the surface profile of the copper foil is transferred to the release surface; and a plating pattern on the release surface side of the resin base material to which the surface profile is transferred Forming a step. With such a configuration, a release layer is provided on the copper foil, and the physical peeling of the resin base material when the copper foil is bonded to the resin base material becomes possible, and the copper foil is removed from the resin base material. In the process, the copper foil can be removed at a good cost without impairing the profile of the surface of the copper foil transferred to the surface of the resin base material. In the manufacturing method, after forming a plating pattern, a desired circuit can be formed using the plating pattern to produce a printed wiring board.

In another aspect of the method for producing a printed wiring board of the present invention, a step of bonding a resin base material from the release layer side to a surface-treated copper foil having a release layer provided on the surface; and the resin Removing the surface-treated copper foil from the base material to obtain a resin base material in which the surface profile of the copper foil is transferred to the release surface; and the release surface of the resin base material to which the surface profile is transferred Forming a printed pattern on the side. With such a configuration, a release layer is provided on the copper foil, and the physical peeling of the resin base material when the copper foil is bonded to the resin base material becomes possible, and the copper foil is removed from the resin base material. In the process, the copper foil can be removed at a good cost without impairing the profile of the surface of the copper foil transferred to the surface of the resin base material. In the manufacturing method, for example, after forming a print pattern using an ink jet containing conductive paste or the like in ink, a desired printed circuit is formed using the print pattern to produce a printed wiring board. it can.

Furthermore, the manufacturing method of the printed wiring board of the present invention is, in still another aspect, a step of bonding a resin base material from the release layer side to the surface-treated copper foil provided with a release layer on the surface; Removing the surface-treated copper foil from the resin base material to obtain a resin base material having the copper foil surface profile transferred to the release surface; and removing the resin base material to which the surface profile has been transferred Providing a buildup layer on the surface side. With such a configuration, a release layer is provided on the copper foil, and the physical peeling of the resin base material when the copper foil is bonded to the resin base material becomes possible, and the copper foil is removed from the resin base material. In the process, the copper foil can be removed at a good cost without impairing the profile of the surface of the copper foil transferred to the surface of the resin base material. Here, the resin constituting the build-up layer provided on the surface of the resin base material is bonded to each other without any treatment of the resin and the resin base material (the resin constituting the build-up layer and the resin base material). The strength (pull strength) when pulled and peeled off may be 500 g / cm ² or less. The resin constituting the build-up layer provided on the surface of the resin base material has a strength (pull strength) of 500 g / pull when the resin and the resin base material are bonded to each other without any treatment and then pulled and peeled off. Even if the value is as low as cm ² or less, when the profile of the copper foil surface is transferred to the resin substrate, the adhesion between the resin constituting the build-up layer and the resin substrate is improved, and the pull strength is increased. For example, 800 g / cm ² or more, more preferably 1000 g / cm ² or more.

Here, the “build-up layer” refers to a layer having a conductive layer, a wiring pattern or a circuit, and an insulator such as a resin. The shape of the insulator such as the resin may be a layer. Further, the above-described conductive layer, wiring pattern, or circuit and an insulator such as resin may be provided in any order or position.
The build-up layer can be produced by providing a conductive layer, a wiring pattern or a circuit, and an insulator such as a resin on the release surface side of the resin base material on which the surface profile of the copper foil is transferred to the release surface. As a method for forming the conductive layer, the wiring pattern, or the circuit, a known method such as a semi-additive method, a full additive method, a subtractive method, or a partial additive method can be used.
The build-up layer may have a plurality of layers, or may have a plurality of conductive layers, wiring patterns or circuits, and an insulator (layer) such as a resin.
The plurality of conductive layers, wiring patterns, or circuits may be electrically insulated by an insulator such as resin. After through holes and / or blind vias are formed in an insulating material such as a resin through a plurality of electrically conductive layers, wiring patterns, or circuits by laser and / or drilling, the through holes and / or blind vias are formed. Alternatively, electrical connection may be made by forming conductive plating such as copper plating.
In addition, the surface-treated copper foil having a release layer provided on the surface is bonded to both surfaces of the resin base material from the release layer side, and then the surface-treated copper foil is removed to form both surfaces of the resin base material. A printed wiring board may be manufactured by transferring the surface profile of the surface-treated copper foil and providing a circuit, a wiring pattern, or a build-up layer on both surfaces of the resin substrate.

As an insulator such as a resin constituting such a build-up layer, the resins, resin layers, and resin base materials described in the present specification can be used. Known resins, resin layers, resin base materials, insulators, A prepreg, a base material in which a glass cloth is impregnated with a resin, or the like can be used. The insulator such as a resin may include an inorganic substance and / or an organic substance. Moreover, insulators, such as resin which comprises a buildup layer, may be formed with the material which has low dielectric constants, such as LCP (liquid crystal polymer) or polytetrafluoroethylene. In recent years, with the expansion of high-frequency products, a movement to incorporate a material having a low dielectric constant such as LCP (liquid crystal polymer) or polytetrafluoroethylene (Teflon: registered trademark) into the structure of a printed circuit board has been activated. At that time, since these materials are thermoplastic, shape change is unavoidable during hot press processing, and the basic mass production that the production yield is not improved by the substrate configuration with LCP (liquid crystal polymer) or polytetrafluoroethylene alone. I have the above challenges. In the manufacturing method of the present application described above, even for such a problem, a thermosetting resin such as an epoxy resin is used as a resin substrate, and it is bonded to the resin substrate so that it has excellent high-frequency characteristics and heat. The printed wiring board which can prevent the shape deformation at the time of adding can be provided.

(Surface treated copper foil)
As the surface-treated copper foil used in the method for producing a printed wiring board of the present application described above, the following surface-treated copper foil is preferably used. That is, the surface-treated copper foil is a surface-treated copper foil having a copper foil and a release layer provided on the surface of the copper foil, and the copper foil is convex on the release layer side surface. Have Here, the cross-sectional schematic diagram of the copper foil which has the convex part which specified "a", "b", and "c" in FIG. 1 is shown. As shown in FIG. 9, the convex portion is obtained by taking a picture of the surface of the release layer side of the copper foil in a state where the stage on which the copper foil is placed is inclined 45 ° from the horizontal plane, as shown in FIG. The height from the constricted portion of the convex portion to the tip of the convex portion measured based on the photograph (hereinafter, for example, FIG. 8 described later) is a, the maximum width at the widest portion of the convex portion is b, When the minimum width of the constricted portion is c, it is preferable that both the following expressions are satisfied.
When a / b ≦ 1, (bc) /b≦0.2 and b ≧ 10 nm
When a / b> 1, (bc) /b≦0.03 and b ≧ 10 nm

In addition, when the roughening process particle | grains are formed in the surface of copper foil, "a", "b", and "c" of a convex part select and measure a measurable convex part. Here, the above-mentioned measurable convex portion means a convex portion where the constricted portion can be observed. The convex part where the constricted part is observable is a convex part capable of observing the ridge line (illustrated in FIG. 8) of the convex part.
Further, the “necked portion” is a portion where the width of the convex portion on the surface of the copper foil becomes narrow after the width is once increased from the tip of the convex portion when observed in the direction approaching the copper foil.
“Width of convex part” is the width of the photo divided by the contour or ridge line of the convex part when a line crossing the convex part is drawn parallel to the horizontal frame of the photograph on the photograph obtained with a scanning electron microscope. This is the length of a straight line that crosses the convex part drawn parallel to the frame. Here, when there are three or more ridge lines on the convex portion, the two closest ridge lines are selected.
The “minimum width c of the constricted portion” is a minimum value of the width of the convex portion in the constricted portion. For example, in FIG. 8, the flat part (line segment) of the ridgeline of a convex part is shown. If there is no constriction, c = b.
"Height a from the constricted part of the convex part to the leading end of the convex part" refers to the line crossing the convex part parallel to the horizontal frame of the photograph drawn when measuring the minimum width c of the constricted part from the leading end of the convex part When a perpendicular line is drawn, the distance (a ′) to the intersection of a line crossing the convex part parallel to the horizontal frame of the photograph drawn when measuring the minimum width c of the constricted part and the perpendicular line drawn from the tip of the convex part ) And the square root of 2.
The “tip of the convex portion” means a portion that is estimated to be the highest of the convex portion determined based on the shadow of the photographed unevenness when the photograph is observed (see FIG. 7).
The “maximum width b in the widest part” is a convex part of a straight line that intersects the convex part parallel to the horizontal frame of the photograph between the tip of the convex part and the constricted part when the convex part has a constricted part. The longest length delimited by the outline.

The convex portion of the copper foil may be a convex portion in the surface irregularities generated during the electrolytic treatment during the formation of the copper foil, or a convex portion due to the roughened particles generated by the roughening treatment. Also good.

In the conventional method using the surface profile of copper foil, for example, a copper foil (FIG. 2) having rough particles (nodules) is bonded to the resin substrate from the surface of the rough particles (FIG. 3), and then copper By removing the foil, the profile of the copper foil surface is transferred to the surface of the resin substrate, and a plating pattern or the like is formed on the transfer surface (FIG. 4).

Here, when there are nodules on the surface of the copper foil, depending on the shape, a gap is generated in the transfer profile to the resin base material surface after removing the copper foil, and depending on the size of the gap, the plating solution used when forming the plating pattern may be It may not be possible to enter. At this time, as shown in FIG. 4, a gap remains between the resin base material surface and the plating pattern to be formed. If such voids remain, a reliability test (for example, a heat test at 250 ° C. ± 10 ° C. × 1 hour when a printed wiring board or the like is formed by forming a circuit using a plating pattern is used. ) Due to expansion in the vicinity of the gap, causing problems such as circuit peeling or substrate swelling.

For such a problem, according to the above-described surface-treated copper foil of the present invention, the copper foil has a convex portion on the surface of the release layer, and the convex portion is cut in a direction perpendicular to the height direction. In the cross section, it has a constricted part while proceeding from the copper foil surface to the widest part of the cross section, the height of the convex part is a, and the widest in the cross section when cut in the direction perpendicular to the height direction. Where b is the maximum width of the portion and c is the minimum width of the constricted portion, if a / b ≦ 1, then (bc) /b≦0.2 and b ≧ 10 nm are satisfied, and a In the case of / b> 1, in order to satisfy (bc) /b≦0.03 and b ≧ 10 nm, the resin substrate surface and the formed plating pattern (or print pattern or build-up layer) There is no gap between them, or even if they occur, the plating solution (print pattern shape) If when the ink containing a conductive paste or the like, the resin material as long as the formation of the build-up layer) satisfies the void. For this reason, after that, when a printed wiring board or the like is produced using a plating pattern (or a printing pattern or a build-up layer), a reliability test (for example, a heating test at 250 ° C. ± 10 ° C. × 1 hour) Generation | occurrence | production of a circuit peeling or a board | substrate swelling can be suppressed favorably (FIG. 5).

In the above formula, when a / b ≦ 1, it is more preferable that (bc) /b≦0.15, and even more preferable that (bc) /b≦0.10. Further, when a / b> 1, it is more preferable that (bc) /b≦0.25, and even more preferable that (bc) /b≦0.20. Moreover, it is preferable that copper foil does not have a roughening particle | grain on the mold release layer side surface.

The release layer has a function of making the resin substrate peelable when the resin substrate is bonded to the copper foil from the release layer side. Note that the release layer may be provided on both sides of the copper foil. Further, the bonding may be performed by pressure bonding.
The copper foil (also referred to as raw foil) is formed of an electrolytic copper foil, and the thickness of the copper foil is not particularly limited, and can be, for example, 5 to 105 μm. Further, since the peeling from the resin base material is easy, the thickness of the surface-treated copper foil is preferably 9 to 70 μm, more preferably 12 to 35 μm, and further preferably 18 to 35 μm. Is more preferable.

Although it does not specifically limit as a manufacturing method of copper foil (raw foil), For example, an electrolytic copper foil can be produced on the following electrolysis conditions.
Electrolytic conditions for electrolytic green foil:
Cu: 30 to 190 g / L
H ₂ SO ₄ : 100 to 400 g / L
Chloride ion (Cl ⁻ ): 10 to 200 ppm by mass
Electrolyte temperature: 25-80 ° C
Electrolysis time: 10 to 300 seconds (adjusted according to the thickness of copper to be deposited and current density)
Current density: 50 to 150 A / dm ²
Electrolyte linear velocity: 1.5-5m / sec
In addition, the value of above-mentioned a and b can be enlarged by making copper concentration of electrolyte solution high. Moreover, the value of a and b mentioned above can be made small by making the copper concentration of electrolyte solution low. Further, by increasing the temperature of the electrolytic solution, the values of a and b described above can be increased. Moreover, the value of a, b, c mentioned above can be made small by making the temperature of electrolyte solution low. Further, by increasing the chloride ion concentration, the values of a and b described above can be increased. Note that, by increasing the chloride ion concentration, there is a tendency that the value of a is larger than the value of b. Further, by reducing the chloride ion concentration, the values of a and b described above can be reduced. In addition, by decreasing the chloride ion concentration, there is a tendency that the value of a is smaller than the value of b is smaller. By increasing the plating time, the values of a, b, and c described above can be increased. By shortening the plating time, the values of a, b, and c described above can be reduced.

In the present invention, removing the copper foil from the resin base material means removing the copper foil from the resin base material by chemical treatment such as etching, or physically peeling the resin base material from the copper foil by peeling or the like. It means to do. When the resin substrate is removed after being bonded to the surface-treated copper foil of the present invention as described above, the resin substrate and the surface-treated copper foil are separated by a release layer. At this time, a part of the release layer, roughened particles of copper foil described later, a heat-resistant layer, a rust preventive layer, a chromate treatment layer, a silane coupling treatment layer, etc. may remain on the release surface of the resin substrate. Preferably, no residue is present.

The surface-treated copper foil according to the present invention preferably has a peel strength of 200 gf / cm or less when the resin substrate is peeled off when the resin substrate is bonded to the copper foil from the release layer side. If controlled in this way, physical peeling of the resin base material becomes easy, and the profile of the copper foil surface is transferred to the resin base material better. The peel strength is more preferably 150 gf / cm or less, even more preferably 100 gf / cm or less, even more preferably 50 gf / cm or less, typically 1 to 200 gf / cm, and more Typically 1 to 150 gf / cm.

Next, the release layer that can be used in the present invention will be described.
(1) Silane compound A silane compound having a structure represented by the following formula, a hydrolysis product thereof, or a condensate of the hydrolysis product (hereinafter simply referred to as a silane compound) is used alone or in combination. Thus, by forming the release layer, when the surface-treated copper foil and the resin base material are bonded together, the adhesiveness is moderately lowered, and the peel strength can be adjusted to the above range.

formula:

Wherein R ¹ is an alkoxy group or a halogen atom, and R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by R ³ and R ⁴ are each independently a halogen atom, an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group Or any one of these hydrocarbon groups in which one or more hydrogen atoms are replaced by halogen atoms.)

The silane compound must have at least one alkoxy group. A hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group in the absence of an alkoxy group, or any one of these hydrocarbons in which one or more hydrogen atoms are substituted with a halogen atom When a substituent is comprised only by group, there exists a tendency for the adhesiveness of a resin base material and copper foil to fall too much. The silane compound is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or any one of these hydrocarbon groups in which one or more hydrogen atoms are substituted with a halogen atom. It is necessary to have at least one. This is because when the hydrocarbon group does not exist, the adhesion between the resin base material and the copper foil tends to increase. The alkoxy group includes an alkoxy group in which one or more hydrogen atoms are substituted with a halogen atom.

In adjusting the peel strength between the resin base material and the copper foil to the above-mentioned range, the silane compound has three alkoxy groups and the hydrocarbon group (a hydrocarbon group in which one or more hydrogen atoms are substituted with a halogen atom). It is preferable to have one). In terms of the above formula, both R ³ and R ⁴ are alkoxy groups.

Alkoxy groups include, but are not limited to, methoxy, ethoxy, n- or iso-propoxy, n-, iso- or tert-butoxy, n-, iso- or neo-pentoxy, n-hexoxy Group, cyclohexyloxy group, n-heptoxy group, n-octoxy group and the like, straight chain, branched or cyclic carbon number of 1-20, preferably carbon number of 1-10, more preferably carbon number of 1- 5 alkoxy groups.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkyl group include, but are not limited to, methyl group, ethyl group, n- or iso-propyl group, n-, iso- or tert-butyl group, n-, iso- or neo-pentyl group, and n-hexyl. A linear or branched alkyl group having 1 to 20, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, such as a group, n-octyl group and n-decyl group.

Examples of the cycloalkyl group include, but are not limited to, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like, which have 3 to 10 carbon atoms, preferably 5 to 7 carbon atoms. An alkyl group is mentioned.

The aryl group includes a phenyl group, a phenyl group substituted with an alkyl group (eg, tolyl group, xylyl group), 1- or 2-naphthyl group, anthryl group, etc., having 6 to 20, preferably 6 to 14 carbon atoms. An aryl group is mentioned.

In these hydrocarbon groups, one or more hydrogen atoms may be substituted with a halogen atom, and may be substituted with, for example, a fluorine atom, a chlorine atom, or a bromine atom.

Examples of preferred silane compounds include methyltrimethoxysilane, ethyltrimethoxysilane, n- or iso-propyltrimethoxysilane, n-, iso- or tert-butyltrimethoxysilane, n-, iso- or neo-pentyl. Trimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane; alkyl-substituted phenyltrimethoxysilane (eg, p- (methyl) phenyltrimethoxysilane), methyltriethoxysilane, ethyl Triethoxysilane, n- or iso-propyltriethoxysilane, n-, iso- or tert-butyltriethoxysilane, pentyltriethoxysilane, hexyltriethoxysilane, octyltriethoxy Silane, decyltriethoxysilane, phenyltriethoxysilane, alkyl-substituted phenyltriethoxysilane (eg, p- (methyl) phenyltriethoxysilane), (3,3,3-trifluoropropyl) trimethoxysilane, and trideca Fluorooctyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, trimethylfluorosilane, dimethyldibromosilane, diphenyldibromosilane, their hydrolysis products, and condensates of these hydrolysis products Etc. Among these, propyltrimethoxysilane, methyltriethoxysilane, hexyltrimethoxysilane, phenyltriethoxysilane, and decyltrimethoxysilane are preferable from the viewpoint of availability.

In the step of forming the release layer, the silane compound can be used in the form of an aqueous solution. Alcohols such as methanol and ethanol can be added in order to increase the solubility in water. The addition of alcohol is particularly effective when a highly hydrophobic silane compound is used. By stirring the aqueous solution of the silane compound, hydrolysis of the alkoxy group is promoted, and when the stirring time is long, condensation of the hydrolysis product is promoted. In general, the peel strength between the resin substrate and the copper foil tends to decrease when a silane compound that has undergone hydrolysis and condensation after a sufficient stirring time is used. Therefore, the peel strength can be adjusted by adjusting the stirring time. Although not limited, the stirring time after the silane compound is dissolved in water can be, for example, 1 to 100 hours, and typically 1 to 30 hours. Of course, there is a method of using without stirring.

The higher the concentration of the silane compound in the aqueous solution of the silane compound, the lower the peel strength between the metal foil and the plate carrier, and the peel strength can be adjusted by adjusting the concentration of the silane compound. Although not limited, the concentration of the silane compound in the aqueous solution can be 0.01 to 10.0% by volume, and typically 0.1 to 5.0% by volume.

The pH of the aqueous solution of the silane compound is not particularly limited and can be used on either the acidic side or the alkaline side. For example, it can be used at a pH in the range of 3.0 to 10.0. From the standpoint that no special pH adjustment is required, the pH is preferably in the range of 5.0 to 9.0, which is near neutral, and more preferably in the range of 7.0 to 9.0. .

(2) Compound having two or less mercapto groups in the molecule The release layer is composed of a compound having two or more mercapto groups in the molecule, and the resin base material and copper are interposed via the release layer. Adhesion with the foil can also be appropriately reduced to adjust the peel strength.
However, when a compound having three or more mercapto groups in the molecule or a salt thereof is bonded between the resin substrate and the copper foil, it is not suitable for the purpose of reducing the peel strength. This is because when there is an excessive amount of mercapto groups in the molecule, an excessive amount of sulfide bonds, disulfide bonds or polysulfide bonds are generated by the chemical reaction between the mercapto groups, or between the mercapto group and the plate carrier, or the mercapto group and the metal foil, This is because it is considered that the peel strength may be increased by forming a strong three-dimensional crosslinked structure between the resin base material and the copper foil. Such a case is disclosed in Japanese Patent Laid-Open No. 2000-196207.

Examples of the compound having two or less mercapto groups in the molecule include thiol, dithiol, thiocarboxylic acid or a salt thereof, dithiocarboxylic acid or a salt thereof, thiosulfonic acid or a salt thereof, and dithiosulfonic acid or a salt thereof. At least one selected from these can be used.

Thiol has one mercapto group in the molecule and is represented by, for example, R-SH. Here, R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may contain a hydroxyl group or an amino group.

Dithiol has two mercapto groups in the molecule and is represented by, for example, R (SH) ₂ . R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may contain a hydroxyl group or an amino group. Two mercapto groups may be bonded to the same carbon, or may be bonded to different carbons or nitrogens.

The thiocarboxylic acid is one in which a hydroxyl group of an organic carboxylic acid is substituted with a mercapto group, and is represented by, for example, R—CO—SH. R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may contain a hydroxyl group or an amino group. The thiocarboxylic acid can also be used in the form of a salt. A compound having two thiocarboxylic acid groups can also be used.

Dithiocarboxylic acid is one in which two oxygen atoms in the carboxy group of an organic carboxylic acid are substituted with sulfur atoms, and is represented by, for example, R- (CS) -SH. R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may contain a hydroxyl group or an amino group. Dithiocarboxylic acid can also be used in the form of a salt. A compound having two dithiocarboxylic acid groups can also be used.

The thiosulfonic acid is obtained by replacing the hydroxyl group of an organic sulfonic acid with a mercapto group, and is represented by, for example, R (SO ₂ ) -SH. R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may contain a hydroxyl group or an amino group. Further, thiosulfonic acid can be used in the form of a salt.

Dithiosulfonic acid is one in which two hydroxyl groups of organic disulfonic acid are substituted with mercapto groups, and is represented by, for example, R-((SO ₂ ) -SH) ₂ . R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may contain a hydroxyl group or an amino group. Two thiosulfonic acid groups may be bonded to the same carbon, or may be bonded to different carbons. Dithiosulfonic acid can also be used in the form of a salt.

Here, examples of the aliphatic hydrocarbon group suitable as R include an alkyl group and a cycloalkyl group, and these hydrocarbon groups may contain either or both of a hydroxyl group and an amino group.

Examples of the alkyl group include, but are not limited to, methyl group, ethyl group, n- or iso-propyl group, n-, iso- or tert-butyl group, n-, iso- or neo-pentyl group, n And straight-chain or branched alkyl groups having 1 to 20, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, such as -hexyl group, n-octyl group, and n-decyl group. .

Further, the cycloalkyl group is not limited, but it has 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, etc., preferably 5 to 7 carbon atoms. Of the cycloalkyl group.

In addition, examples of suitable aromatic hydrocarbon groups as R include phenyl groups, phenyl groups substituted with alkyl groups (eg, tolyl groups, xylyl groups), 1- or 2-naphthyl groups, anthryl groups, and the like. -20, preferably 6-14 aryl groups, and these hydrocarbon groups may contain either or both of a hydroxyl group and an amino group.

Also, examples of the heterocyclic group suitable as R include imidazole, triazole, tetrazole, benzimidazole, benzotriazole, thiazole, and benzothiazole, which may contain either or both of a hydroxyl group and an amino group.

Preferred examples of the compound having two or less mercapto groups in the molecule include 3-mercapto-1,2, propanediol, 2-mercaptoethanol, 1,2-ethanedithiol, 6-mercapto-1-hexanol, 1- Octanethiol, 1-dodecanethiol, 10-hydroxy-1-dodecanethiol, 10-carboxy-1-dodecanethiol, 10-amino-1-dodecanethiol, sodium 1-dodecanethiolsulfonate, thiophenol, thiobenzoic acid, Examples include 4-amino-thiophenol, p-toluenethiol, 2,4-dimethylbenzenethiol, 3-mercapto-1,2,4 triazole, and 2-mercapto-benzothiazole. Of these, 3-mercapto-1,2-propanediol is preferred from the viewpoint of water solubility and waste disposal.

In the release layer forming step, a compound having two or less mercapto groups in the molecule can be used in the form of an aqueous solution. Alcohols such as methanol and ethanol can be added in order to increase the solubility in water. The addition of alcohol is particularly effective when a compound having two or less mercapto groups in a highly hydrophobic molecule is used.

The higher the concentration of the compound having two or less mercapto groups in the molecule in the aqueous solution, the lower the peel strength between the resin substrate and the copper foil, and the compound having two or less mercapto groups in the molecule. The peel strength can be adjusted by adjusting the concentration. Although not limited, the concentration of the compound having 2 or less mercapto groups in the molecule in the aqueous solution can be 0.01 to 10.0% by weight, typically 0.1 to 5.0%. % By weight.

The pH of the aqueous solution of the compound having two or less mercapto groups in the molecule is not particularly limited and can be used on either the acidic side or the alkaline side. For example, it can be used at a pH in the range of 3.0 to 10.0. From the standpoint that no special pH adjustment is required, the pH is preferably in the range of 5.0 to 9.0, which is near neutral, and more preferably in the range of 7.0 to 9.0. .

(3) Metal alkoxide The release layer is formed from an aluminate compound, titanate compound, zirconate compound, or a hydrolysis product thereof having a structure represented by the following formula, or a condensation product of the hydrolysis product (hereinafter simply referred to as metal alkoxide and May be used alone or in combination. By adhering the resin base material and the copper foil through the release layer, the adhesion is moderately lowered and the peel strength can be adjusted.

In the formula, R ¹ is an alkoxy group or a halogen atom, and R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms. Any one of these substituted hydrocarbon groups, M is any one of Al, Ti, and Zr, n is 0 or 1 or 2, m is an integer from 1 to M, and R ^At least one of ¹ is an alkoxy group. M + n is the valence of M, that is, 3 for Al and 4 for Ti and Zr.

The metal alkoxide must have at least one alkoxy group. A hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group in the absence of an alkoxy group, or any one of these hydrocarbons in which one or more hydrogen atoms are substituted with a halogen atom When a substituent is comprised only by group, there exists a tendency for the adhesiveness of a resin base material and copper foil to fall too much. The metal alkoxide is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or any one of these hydrocarbon groups in which one or more hydrogen atoms are substituted with a halogen atom. It is necessary to have 0-2. This is because when there are three or more hydrocarbon groups, the adhesion between the resin substrate and the copper foil tends to be too low. The alkoxy group includes an alkoxy group in which one or more hydrogen atoms are substituted with a halogen atom. In adjusting the peel strength between the resin base material and the copper foil to the above-mentioned range, the metal alkoxide has two or more alkoxy groups and the hydrocarbon group (a hydrocarbon in which one or more hydrogen atoms are substituted with a halogen atom). It preferably has one or two groups).

Further, examples of the aromatic hydrocarbon group suitable as R ² include a phenyl group, a phenyl group substituted with an alkyl group (eg, tolyl group, xylyl group), 1- or 2-naphthyl group, anthryl group, and the like. Examples thereof include 6 to 20, preferably 6 to 14, aryl groups, and these hydrocarbon groups may contain one or both of a hydroxyl group and an amino group. In these hydrocarbon groups, one or more hydrogen atoms may be substituted with a halogen atom, and may be substituted with, for example, a fluorine atom, a chlorine atom, or a bromine atom.

Examples of preferred aluminate compounds include trimethoxyaluminum, methyldimethoxyaluminum, ethyldimethoxyaluminum, n- or iso-propyldimethoxyaluminum, n-, iso- or tert-butyldimethoxyaluminum, n-, iso- or neo- Pentyl dimethoxy aluminum, hexyl dimethoxy aluminum, octyl dimethoxy aluminum, decyl dimethoxy aluminum, phenyl dimethoxy aluminum; alkyl-substituted phenyl dimethoxy aluminum (for example, p- (methyl) phenyl dimethoxy aluminum), dimethylmethoxy aluminum, triethoxy aluminum, methyl diethoxy aluminum Ethyldiethoxyaluminum, n- or iso-propyldiethyl Aluminum, n-, iso- or tert-butyldiethoxyaluminum, pentyldiethoxyaluminum, hexyldiethoxyaluminum, octyldiethoxyaluminum, decyldiethoxyaluminum, phenyldiethoxyaluminum, alkyl-substituted phenyldiethoxyaluminum (eg p -(Methyl) phenyldiethoxyaluminum), dimethylethoxyaluminum, triisopropoxyaluminum, methyldiisopropoxyaluminum, ethyldiisopropoxyaluminum, n- or iso-propyldiethoxyaluminum, n-, iso- or tert-butyl Diisopropoxy aluminum, pentyl diisopropoxy aluminum, hexyl diisopropoxy aluminum, octyl dii Propoxyaluminum, decyldiisopropoxyaluminum, phenyldiisopropoxyaluminum, alkyl-substituted phenyldiisopropoxyaluminum (eg, p- (methyl) phenyldiisopropoxyaluminum), dimethylisopropoxyaluminum, (3,3,3-tri Fluoropropyl) dimethoxyaluminum and tridecafluorooctyldiethoxyaluminum, methyldichloroaluminum, dimethylchloroaluminum, dimethylchloroaluminum, phenyldichloroaluminum, dimethylfluoroaluminum, dimethylbromoaluminum, diphenylbromoaluminum, their hydrolysis products, And condensates of these hydrolysis products. Among these, from the viewpoint of availability, trimethoxyaluminum, triethoxyaluminum, and triisopropoxyaluminum are preferable.

Examples of preferred titanate compounds include tetramethoxy titanium, methyl trimethoxy titanium, ethyl trimethoxy titanium, n- or iso-propyl trimethoxy titanium, n-, iso- or tert-butyl trimethoxy titanium, n-, iso- Or neo-pentyltrimethoxytitanium, hexyltrimethoxytitanium, octyltrimethoxytitanium, decyltrimethoxytitanium, phenyltrimethoxytitanium; alkyl-substituted phenyltrimethoxytitanium (eg p- (methyl) phenyltrimethoxytitanium), dimethyldimethoxy Titanium, tetraethoxy titanium, methyl triethoxy titanium, ethyl triethoxy titanium, n- or iso-propyl triethoxy titanium, n-, iso- or tert-butyl triethoxy titanium, Nitrotriethoxytitanium, hexyltriethoxytitanium, octyltriethoxytitanium, decyltriethoxytitanium, phenyltriethoxytitanium, alkyl-substituted phenyltriethoxytitanium (eg p- (methyl) phenyltriethoxytitanium), dimethyldiethoxytitanium , Tetraisopropoxytitanium, methyltriisopropoxytitanium, ethyltriisopropoxytitanium, n- or iso-propyltriethoxytitanium, n-, iso- or tert-butyltriisopropoxytitanium, pentyltriisopropoxytitanium, hexyltri Isopropoxytitanium, octyltriisopropoxytitanium, decyltriisopropoxytitanium, phenyltriisopropoxytitanium, alkyl-substituted phenyltriisopropoxytitanium ( For example, p- (methyl) phenyltriisopropoxytitanium), dimethyldiisopropoxytitanium, (3,3,3-trifluoropropyl) trimethoxytitanium, and tridecafluorooctyltriethoxytitanium, methyltrichlorotitanium, dimethyldichloro Examples include titanium, trimethylchlorotitanium, phenyltrichlorotitanium, dimethyldifluorotitanium, dimethyldibromotitanium, diphenyldibromotitanium, hydrolysis products thereof, and condensates of these hydrolysis products. Among these, tetramethoxy titanium, tetraethoxy titanium, and tetraisopropoxy titanium are preferable from the viewpoint of availability.

Examples of preferred zirconate compounds include tetramethoxyzirconium, methyltrimethoxyzirconium, ethyltrimethoxyzirconium, n- or iso-propyltrimethoxyzirconium, n-, iso- or tert-butyltrimethoxyzirconium, n-, iso- Or neo-pentyltrimethoxyzirconium, hexyltrimethoxyzirconium, octyltrimethoxyzirconium, decyltrimethoxyzirconium, phenyltrimethoxyzirconium; alkyl-substituted phenyltrimethoxyzirconium (eg, p- (methyl) phenyltrimethoxyzirconium), dimethyldimethoxy Zirconium, tetraethoxyzirconium, methyltriethoxyzirconium, ethyltriethoxyzirconium, -Or iso-propyltriethoxyzirconium, n-, iso- or tert-butyltriethoxyzirconium, pentyltriethoxyzirconium, hexyltriethoxyzirconium, octyltriethoxyzirconium, decyltriethoxyzirconium, phenyltriethoxyzirconium, alkyl-substituted phenyl Triethoxyzirconium (eg, p- (methyl) phenyltriethoxyzirconium), dimethyldiethoxyzirconium, tetraisopropoxyzirconium, methyltriisopropoxyzirconium, ethyltriisopropoxyzirconium, n- or iso-propyltriethoxyzirconium, n -, Iso- or tert-butyltriisopropoxyzirconium, pentyltriisopropoxy Luconium, hexyltriisopropoxyzirconium, octyltriisopropoxyzirconium, decyltriisopropoxyzirconium, phenyltriisopropoxyzirconium, alkyl-substituted phenyltriisopropoxyzirconium (eg, p- (methyl) phenyltriisopropoxytitanium), dimethyldi Isopropoxyzirconium, (3,3,3-trifluoropropyl) trimethoxyzirconium, and tridecafluorooctyltriethoxyzirconium, methyltrichlorozirconium, dimethyldichlorozirconium, trimethylchlorozirconium, phenyltrichlorozirconium, dimethyldifluorozirconium, dimethyldibromo Zirconium, diphenyldibromozirconium and their hydrolysis Products, and condensates of these hydrolysis products. Among these, tetramethoxyzirconium, tetraethoxyzirconium, and tetraisopropoxyzirconium are preferable from the viewpoint of availability.

In the step of forming the release layer, the metal alkoxide can be used in the form of an aqueous solution. Alcohols such as methanol and ethanol can be added in order to increase the solubility in water. The addition of alcohol is particularly effective when a highly hydrophobic metal alkoxide is used.

The higher the concentration of the metal alkoxide in the aqueous solution, the lower the peel strength between the resin substrate and the copper foil, and the peel strength can be adjusted by adjusting the metal alkoxide concentration. Although not limited, the concentration of the metal alkoxide in the aqueous solution can be 0.001 to 1.0 mol / L, and typically 0.005 to 0.2 mol / L.

The pH of the aqueous solution of the metal alkoxide is not particularly limited and can be used on either the acidic side or the alkaline side. For example, it can be used at a pH in the range of 3.0 to 10.0. From the standpoint that no special pH adjustment is required, the pH is preferably in the range of 5.0 to 9.0, which is near neutral, and more preferably in the range of 7.0 to 9.0. .
(4) Others A known release material, such as a silicon-based release agent or a resin coating having a release property, can be used for the release layer.

The surface-treated copper foil according to the present invention is selected from the group consisting of a roughened layer, a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a silane coupling-treated layer between the copper foil and the release layer. More than one seed layer may be provided. Here, the chromate-treated layer refers to a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. Chromate treatment layer is any element such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium (metal, alloy, oxide, nitride, sulfide, etc.) May be included). Specific examples of the chromate treatment layer include a chromate treatment layer treated with chromic anhydride or a potassium dichromate aqueous solution, a chromate treatment layer treated with a treatment solution containing anhydrous chromic acid or potassium dichromate and zinc, and the like. .

A roughening process layer can be formed by the following processes, for example. Note that the values of a and b described above can be increased by increasing the copper concentration in the plating solution used for the roughening treatment. Further, by reducing the copper concentration in the plating solution used for the roughening treatment, the values of a and b described above can be reduced. Further, by increasing the concentration of a metal other than copper in the plating solution used for the roughening treatment, the values of a and b described above can be reduced. Further, by increasing the temperature of the plating solution, the values of a and b described above can be increased. Moreover, the value of a, b, c mentioned above can be made small by lowering the temperature of the plating solution. By increasing the plating time, the values of a, b, and c described above can be increased. By shortening the plating time, the values of a, b, and c described above can be reduced.
(Spherical roughening)
Spherical rough particles are formed using a copper roughening plating bath described below, which is made of Cu, H ₂ SO ₄ and As.
・ Liquid composition 1
CuSO ₄ · 5H ₂ O 78 ~ 196g / L
Cu 20-50g / L
H ₂ SO ₄ 50-200 g / L
Arsenic 0.7-3.0g / L
(Electroplating temperature 1) 30 ~ 76 ℃
(Current condition 1) Current density 35 to 105 A / dm ² (above the limiting current density of the bath)
(Plating time 1) 1 to 240 seconds Subsequently, plating is performed in a copper electrolytic bath made of sulfuric acid and copper sulfate in order to prevent the rough particles from falling off and to improve the peel strength. The covering plating conditions are described below.
・ Liquid composition 2
CuSO ₄ · 5H ₂ O 88-352g / L
Cu 22-90g / L
H ₂ SO ₄ 50-200 g / L
(Electroplating temperature 2) 25-80 ° C
(Current condition 2) Current density: 15 to 32 A / dm ² (below the limit current density of the bath)
(Plating time 1) 1 to 240 seconds

[Fine roughening (Type 1)]
First, roughening is performed under the following conditions. The ratio of the current density at the time of roughening (processing) particle formation to the limiting current density to the limiting current density ratio (= current density at the time of roughening (processing) particle formation / limit current density) is 2.10-2. 90.
・ Liquid composition 1
CuSO ₄ .5H ₂ O 29.5 to 118 g / L
Cu 7.5-30g / L
H ₂ SO ₄ 50-200 g / L
Na ₂ WO ₄ · 2H ₂ O 2.7 to 10.8 mg / L
Sodium dodecyl sulfate addition amount 5-20ppm
(Electroplating temperature 1) 20 ~ 70 ℃
(Current condition 1) Current density 34 to 74 A / dm ²
(Plating time 1) 1 to 180 seconds Subsequently, normal plating is performed under the following conditions.
・ Liquid composition 2
CuSO ₄ · 5H ₂ O 88-352g / L
Cu 40-90g / L
H ₂ SO ₄ 50-200 g / L
(Electroplating temperature 2) 30 ~ 65 ℃
(Current condition 2) Current density 21 to 45 A / dm ²
(Plating time 2) 1 to 180 seconds

[Fine roughening (Type 2)]
First, a Cu—Co—Ni ternary alloy layer is formed under the following liquid composition 1 and electroplating condition 1, and then a cobalt-nickel alloy plating is applied onto the ternary alloy layer with the following liquid composition 2 and electric plating. It is formed under plating condition 2.
・ Liquid composition 1
Cu 10-20g / L
Co 1-10g / L
Ni 1 ~ 10g / L
pH 1-4
(Electroplating temperature 1) 30-50 ° C
(Current condition 1) Current density 25 to 45 A / dm ²
(Plating time 1) 1-60 seconds ・ Liquid composition 2
Co 1-30g / L
Ni 1-30g / L
pH 1.0-3.5
(Electroplating temperature 2) 30 ~ 80 ℃
(Current condition 2) Current density 3-10A / dm ²
(Plating time 2) 1-60 seconds

Moreover, a well-known heat resistant layer and a rust preventive layer can be used as a heat resistant layer and a rust preventive layer. For example, the heat-resistant layer and / or the anticorrosive layer is a group of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, tantalum A layer containing one or more elements selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements Further, it may be a metal layer or an alloy layer made of one or more elements selected from the group consisting of iron, tantalum and the like. The heat-resistant layer and / or rust preventive layer is a group of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, and tantalum. An oxide, nitride, or silicide containing one or more elements selected from the above may be included. Further, the heat-resistant layer and / or the rust preventive layer may be a layer containing a nickel-zinc alloy. Further, the heat-resistant layer and / or the rust preventive layer may be a nickel-zinc alloy layer. The nickel-zinc alloy layer may contain 50 wt% to 99 wt% nickel and 50 wt% to 1 wt% zinc, excluding inevitable impurities. The total adhesion amount of zinc and nickel in the nickel-zinc alloy layer may be 5 to 1000 mg / m ² , preferably 10 to 500 mg / m ² , preferably 20 to 100 mg / m ² . The ratio of the nickel adhesion amount and the zinc adhesion amount of the layer containing the nickel-zinc alloy or the nickel-zinc alloy layer (= nickel adhesion amount / zinc adhesion amount) is 1.5 to 10. It is preferable. Further, the amount of nickel deposited on the layer containing the nickel-zinc alloy or the nickel-zinc alloy layer is preferably 0.5 mg / m ² to 500 mg / m ² , and 1 mg / m ² to 50 mg / m ² . More preferably.

For example, the heat-resistant layer and / or the rust preventive layer has a nickel or nickel alloy layer with an adhesion amount of 1 mg / m ² to 100 mg / m ² , preferably 5 mg / m ² to 50 mg / m ² , and an adhesion amount of 1 mg / m ^2. A tin layer of ˜80 mg / m ² , preferably 5 mg / m ² ˜40 mg / m ² may be sequentially laminated. The nickel alloy layer may be nickel-molybdenum, nickel-zinc, nickel-molybdenum-cobalt. You may be comprised by any one of these. The heat-resistant layer and / or rust-preventing layer preferably has a total adhesion amount of nickel or nickel alloy and tin of 2 mg / m ² to 150 mg / m ² and 10 mg / m ² to 70 mg / m ² . It is more preferable. In addition, the heat-resistant layer and / or the rust-preventing layer preferably has [amount of nickel deposited in nickel or nickel alloy] / [amount of tin deposited] = 0.25 to 10, preferably 0.33 to 3. More preferred.

In addition, you may use a well-known silane coupling agent for the silane coupling agent used for a silane coupling process, for example, using an amino-type silane coupling agent or an epoxy-type silane coupling agent, a mercapto-type silane coupling agent. Good. Silane coupling agents include vinyltrimethoxysilane, vinylphenyltrimethoxylane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 4-glycidylbutyltrimethoxysilane, and γ-aminopropyl. Triethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxysilane, imidazolesilane, triazinesilane, γ-mercaptopropyltrimethoxysilane or the like may be used.

The silane coupling treatment layer may be formed using a silane coupling agent such as epoxy silane, amino silane, methacryloxy silane, mercapto silane, or the like. In addition, you may use 2 or more types of such silane coupling agents in mixture. Especially, it is preferable to form using an amino-type silane coupling agent or an epoxy-type silane coupling agent.

The amino silane coupling agent referred to here is N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, 3- Aminopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, N- (3 -Acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- (2-aminoethyl-3-aminopropyl) Trimethoxysilane, -(2-aminoethyl-3-aminopropyl) tris (2-ethylhexoxy) silane, 6- (aminohexylaminopropyl) trimethoxysilane, aminophenyltrimethoxysilane, 3- (1-aminopropoxy) -3,3 -Dimethyl-1-propenyltrimethoxysilane, 3-aminopropyltris (methoxyethoxyethoxy) silane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, ω-aminoundecyltrimethoxysilane, 3- ( 2-N-benzylaminoethylaminopropyl) trimethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, (N, N-diethyl-3-aminopropyl) trimethoxysilane, (N, N -Dimethyl-3-aminopropyl) Trimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, γ-aminopropyltriethoxysilane, N -Β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxysilane may be selected from the group consisting of Good.

The silane coupling treatment layer is 0.05 mg / m ² to 200 mg / m ² , preferably 0.15 mg / m ² to 20 mg / m ² , preferably 0.3 mg / m ² to 2.0 mg in terms of silicon atoms. / M ² is desirable. In the case of the above-mentioned range, the adhesiveness of a resin base material and copper foil can be improved more.

Further, on the surface of the copper foil, the roughened particle layer, the heat-resistant layer, the rust-preventing layer, the silane coupling treatment layer, the chromate treatment layer or the release layer, an international publication number WO2008 / 053878, JP2008-1111169, Patent No. Surface treatment described in No. 5024930, International Publication No. WO2006 / 028207, Patent No. 4828427, International Publication No. WO2006 / 134868, Patent No. 5046927, International Publication No. WO2007 / 105635, Patent No. 5180815, JP2013-19056A It can be performed.

A resin layer may be provided on the surface of the surface-treated copper foil according to the present invention. The resin layer is usually provided on the release layer.

The resin layer on the surface of the surface-treated copper foil may be an adhesive resin, that is, an adhesive, a primer, or an insulating resin layer in a semi-cured state (B stage state) for adhesion. Good. The semi-cured state (B stage state) is a state in which there is no sticky feeling even if the surface is touched with a finger, the insulating resin layer can be stacked and stored, and a curing reaction occurs when subjected to heat treatment. Including that. The resin layer on the surface of the surface-treated copper foil is preferably a resin layer that exhibits an appropriate peel strength (for example, 2 gf / cm to 200 gf / cm) when in contact with the release layer. Further, it is preferable to use a resin that follows the unevenness of the surface of the copper foil and hardly causes voids or bubbles that may cause swelling. For example, when the resin layer is provided on the copper foil surface, a resin having a low viscosity such as a resin viscosity of 10,000 mPa · s (25 ° C.) or less, more preferably a resin viscosity of 5000 mPa · s (25 ° C.) or less is used. It is preferable to provide a resin layer. Even if an insulating substrate that does not easily follow the unevenness of the surface of the copper foil is used by providing the aforementioned resin layer between the insulating substrate laminated on the surface-treated copper foil and the surface-treated copper foil, the resin layer is a copper foil. Since it follows the surface, it is effective because it is possible to make it difficult for voids and bubbles to occur between the surface-treated copper foil and the insulating substrate.

The resin layer on the surface of the surface-treated copper foil may contain a thermosetting resin or may be a thermoplastic resin. The resin layer on the surface of the surface-treated copper foil may contain a thermoplastic resin. The resin layer on the surface of the surface-treated copper foil may contain a known resin, resin curing agent, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton material and the like. The resin layer on the surface of the surface-treated copper foil is, for example, International Publication No. WO2008 / 004399, International Publication No. WO2008 / 053878, International Publication No. WO2009 / 088453, JP-A-11-5828, JP-A-11-140281, Patent No. 3184485, International Publication No. WO 97/02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179444, Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003-304068, Patent No. 3992225, JP 2003-249739, JP 4136509, JP 2004-82687, JP 4025177, JP 2004-349654, JP 4286060, JP 2005-262506, JP 457. No. 070, JP-A-2005-53218, Patent No. 3949676, Patent No. 4178415, International Publication Numbers WO2004 / 005588, JP-A-2006-257153, JP-A-2007-326923, JP-A-2008-111169, Patent No. No. 5024930, International Publication No. WO2006 / 028207, Japanese Patent No. 4828427, Japanese Unexamined Patent Publication No. 2009-67029, International Publication No. WO2006 / 134868, Japanese Patent No. 5046927, Japanese Unexamined Patent Publication No. 2009-173017, International Publication No. WO2007 / 105635, Patent No. No. 5180815, International Publication Number WO2008 / 114858, International Publication Number WO2009 / 008471, JP2011-14727, International Publication Number WO2009 / 001850, International Publication Number WO2009 / 45179, substances described in International Publication No. WO2011 / 068157, JP-A-2013-19056 (resins, resin curing agents, compounds, curing accelerators, dielectrics, reaction catalysts, crosslinking agents, polymers, prepregs, skeletal materials, etc. ) And / or a resin layer forming method and a forming apparatus.

(Laminated body, semiconductor package, electronic equipment)
A laminate can be produced by providing a resin substrate on the release layer side of the surface-treated copper foil according to the present invention. In the laminate, the resin base material is a paper base phenol resin, a paper base epoxy resin, a synthetic fiber cloth base epoxy resin, a glass cloth / paper composite base epoxy resin, a glass cloth / glass non-woven composite base epoxy resin, and You may form with glass cloth base-material epoxy resin. The resin substrate may be a prepreg or may contain a thermosetting resin. Moreover, a printed wiring board can be produced by forming a circuit on the surface-treated copper foil of the laminate. Furthermore, a printed circuit board can be produced by mounting electronic components on a printed wiring board. In the present invention, the “printed wiring board” includes a printed wiring board, a printed circuit board, and a printed board on which electronic parts are mounted in this manner. In addition, an electronic device may be manufactured using the printed wiring board, an electronic device may be manufactured using a printed circuit board on which the electronic components are mounted, and a print on which the electronic components are mounted. An electronic device may be manufactured using a substrate. The “printed circuit board” includes a circuit forming substrate for a semiconductor package. Furthermore, a semiconductor package can be manufactured by mounting electronic components on a circuit forming substrate for a semiconductor package. Further, an electronic device may be manufactured using the semiconductor package.

A fine circuit can be formed by the semi-additive method using the copper foil of the present invention. FIG. 6 shows a schematic example of the semi-additive method using a copper foil profile. In the semi-additive method, a surface profile of copper foil is used. Specifically, first, the surface-treated copper foil of the present invention is laminated on the resin base material from the release layer side to produce a laminate. Next, the copper foil (surface-treated copper foil) of the laminate is removed by etching or peeled off. Next, after the surface of the resin base material to which the copper foil surface profile has been transferred is washed with dilute sulfuric acid or the like, electroless copper plating is performed. Then, a portion of the resin base material that does not form a circuit is covered with a dry film or the like, and electroless (electrolytic) copper plating is applied to the surface of the electroless copper plating layer that is not covered with the dry film. Then, after removing the dry film, a fine circuit is formed by removing the electroless copper plating layer formed in the portion where the circuit is not formed. Since the fine circuit formed in the present invention is in close contact with the peeled surface of the resin base material to which the copper foil surface profile of the present invention has been transferred, its adhesion (peel strength) is good.
Another embodiment of the semi-additive method is as follows.

The semi-additive method refers to a method in which a thin electroless plating is performed on a resin substrate or copper foil, a pattern is formed, and then a conductor pattern is formed using electroplating and etching. Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using a semi-additive method, a step of preparing the surface-treated copper foil and the resin base material according to the present invention,
Laminating a resin base material from the release layer side on the surface-treated copper foil,
After laminating the surface-treated copper foil and the resin base material, the step of removing the surface-treated copper foil by etching or peeling off,
Providing a through hole or / and a blind via on the release surface of the resin base material produced by peeling off the surface-treated copper foil,
Performing a desmear process on the region including the through hole or / and the blind via,
Cleaning the resin substrate surface with dilute sulfuric acid for the resin substrate and the region including the through hole or / and the blind via, and providing an electroless plating layer (for example, an electroless copper plating layer);
Providing a plating resist on the electroless plating layer;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer (for example, an electrolytic copper plating layer) in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

In another embodiment of the method for producing a printed wiring board according to the present invention using a semi-additive method, a step of preparing the surface-treated copper foil and the resin base material according to the present invention,
Laminating a resin base material from the release layer side on the surface-treated copper foil,
After laminating the surface-treated copper foil and the resin base material, the step of removing the surface-treated copper foil by etching or peeling off,
For the peeled surface of the resin base material generated by peeling off the surface-treated copper foil, the step of washing the resin base material surface with dilute sulfuric acid or the like and providing an electroless plating layer (for example, electroless copper plating layer)
Providing a plating resist on the electroless plating layer;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer (for example, an electrolytic copper plating layer) in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

In this manner, a circuit is formed on the release surface of the resin base material after the surface-treated copper foil is peeled off, and a printed circuit formation substrate and a circuit formation substrate for a semiconductor package can be manufactured. Furthermore, a printed wiring board and a semiconductor package can be manufactured using the circuit formation substrate. Furthermore, an electronic device can be manufactured using the printed wiring board and the semiconductor package.

On the other hand, in another embodiment of the method for producing a printed wiring board according to the present invention using the full additive method, a step of preparing the surface-treated copper foil and the resin base material according to the present invention,
Laminating a resin base material from the release layer side on the surface-treated copper foil,
After laminating the surface-treated copper foil and the resin base material, the step of removing the surface-treated copper foil by etching or peeling off,
The step of washing the resin substrate surface with dilute sulfuric acid or the like for the peel surface of the resin substrate produced by peeling off the surface-treated copper foil,
Providing a plating resist on the cleaned resin substrate surface;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electroless plating layer (for example, an electroless copper plating layer or a thick electroless plating layer) in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
including.
In the semi-additive method and the full additive method, there may be an effect that the electroless plating layer can be easily provided by cleaning the surface of the resin base material. In particular, when the release layer remains on the surface of the resin base material, a part or all of the release layer is removed from the surface of the resin base material by the cleaning. There may be an effect that it becomes easier to provide an electroless plating layer. For the cleaning, cleaning by a known cleaning method (type of liquid to be used, temperature, liquid application method, etc.) can be used. Further, it is preferable to use a cleaning method capable of removing a part or all of the release layer of the present invention.

Thus, by a full additive method, a circuit is formed on the release surface of the resin base material after the surface-treated copper foil is peeled off, and a printed circuit forming substrate and a circuit forming substrate for a semiconductor package can be manufactured. Furthermore, a printed wiring board and a semiconductor package can be manufactured using the circuit formation substrate. Furthermore, an electronic device can be manufactured using the printed wiring board and the semiconductor package.

The surface of the copper foil or the surface-treated copper foil is measured with an apparatus such as a scanning electron microscope equipped with XPS (X-ray photoelectron spectrometer), EPMA (electron beam microanalyzer), EDX (energy dispersive X-ray analysis). If Si is detected, it can be inferred that a silane compound is present on the surface of the copper foil or the surface-treated copper foil. When the peel strength (peel strength) between the surface-treated copper foil and the resin substrate is 200 gf / cm or less, the silane compound that can be used for the release layer according to the present invention is used. Can be estimated.

Moreover, the surface of the copper foil or the surface-treated copper foil is measured with an apparatus such as a scanning electron microscope equipped with XPS (X-ray photoelectron spectrometer), EPMA (electron beam microanalyzer), EDX (energy dispersive X-ray analysis). , S is detected, and when the peel strength (peel strength) between the surface-treated copper foil and the resin substrate is 200 gf / cm or less, the surface of the copper foil or surface-treated copper foil is subjected to the invention according to the present invention. It can be inferred that there are compounds having two or less mercapto groups in the molecule that can be used for the release layer.

Moreover, the surface of the copper foil or the surface-treated copper foil is measured with an apparatus such as a scanning electron microscope equipped with XPS (X-ray photoelectron spectrometer), EPMA (electron beam microanalyzer), EDX (energy dispersive X-ray analysis). , Al, Ti, Zr are detected, and when the peel strength (peel strength) between the surface-treated copper foil and the resin substrate is 200 gf / cm or less, the surface of the copper foil or surface-treated copper foil It can be inferred that the metal alkoxide that can be used in the release layer of the invention according to the present invention exists.

Experimental examples are shown below as examples and comparative examples of the present invention, but these examples are provided for better understanding of the present invention and its advantages, and are intended to limit the invention. is not.

-Manufacture of raw foil (copper foil before surface treatment) The electrolytic raw foil of the thickness of Table 1 was produced on the following electrolysis conditions.
(Electrolytic solution composition)
Cu 120g / L
H ₂ SO ₄ 100 g / L
Chloride ion ^(Cl -) 70 ppm
Electrolyte temperature 60 ℃
Current density 70A / dm ²
Electrolyte linear velocity 2m / sec

・ Surface treatment Next, as a surface treatment, roughening treatment, barrier treatment (heat-resistant treatment), rust prevention treatment, silane coupling treatment, resin on the M surface (matte surface) of the raw foil under the following conditions Any one of the layer forming processes or a combination of the processes was performed. Subsequently, a release layer was formed on the treated side surface of the copper foil under the following conditions. In addition, when there was no mention in particular, each process was performed in this description order. In Table 1, “None” in each processing column indicates that these processing were not performed.

(1) Roughening [Spherical roughening]
Spherical roughened particles were formed using a copper roughening plating bath described below consisting of Cu, H ₂ SO ₄ and As.
・ Liquid composition 1
CuSO ₄ · 5H ₂ O 78 ~ 118g / L
Cu 20-30g / L
H ₂ SO ₄ 12g / L
Arsenic 1.0-3.0g / L
(Electroplating temperature 1) 25-33 ° C
(Current condition 1) Current density 78 A / dm ² (above the limiting current density of the bath)
(Plating time 1) 1 to 45 seconds Subsequently, plating was performed in a copper electrolytic bath made of sulfuric acid and copper sulfate in order to prevent falling off of the roughened particles and to improve the peel strength. The covering plating conditions are described below.
・ Liquid composition 2
CuSO ₄ · 5H ₂ O 156g / L
Cu 40g / L
H ₂ SO ₄ 120 g / L
(Electroplating temperature 2) 40 ° C
(Current condition 2) Current density: 20 A / dm ² (less than the limit current density of the bath)
(Plating time 2) 1-60 seconds

[Fine roughening (Type 1)]
First, roughening treatment was performed under the following conditions. The ratio of the limiting current density during the formation of roughened particles was 2.70.
・ Liquid composition 1
CuSO ₄ .5H ₂ O 19.6-58.9 g / L
Cu 5-15g / L
H ₂ SO ₄ 120 g / L
Na ₂ WO ₄ · 2H ₂ O 6.0 to 10.4 mg / L
Sodium dodecyl sulfate addition amount 10ppm
(Electroplating temperature 1) 20 ~ 35 ℃
(Current condition 1) Current density 57A / dm ²
(Plating time 1) 1 to 25 seconds Subsequently, normal plating was performed under the following conditions.
・ Liquid composition 2
CuSO ₄ · 5H ₂ O 156g / L
Cu 40g / L
H ₂ SO ₄ 120 g / L
(Electroplating temperature 2) 30-40 ° C
(Current condition 2) Current density 38 A / dm ²
(Plating time 2) 1 to 45 seconds

[Fine roughening (Type 2)]
First, after forming a Cu—Co—Ni ternary alloy layer with the following liquid composition 1 and electroplating condition 1, cobalt plating is applied on the ternary alloy layer with the following liquid composition 2 and electroplating condition 2. Formed.
・ Liquid composition 1
Cu 8-18g / L
Co 1-10g / L
Ni 1 ~ 10g / L
pH 1-4
(Electroplating temperature 1) 30-40 ° C
(Current condition 1) Current density 30 A / dm ²
(Plating time 1) 1-30 seconds ・ Liquid composition 2
Co 1-30g / L
Ni 1-30g / L
pH 1.0-3.5
(Electroplating temperature 2) 20 ~ 70 ℃
(Current condition 2) Current density 1 to 4 A / dm ²
(Plating time 2) 1 to 25 seconds

(2) Barrier treatment (heat-resistant treatment)
Sample No. For 9, 11, 12, 27, 29, 30, 45, 47, and 48, a barrier (heat resistant) treatment was performed under the following conditions to form a brass plating layer.
(Liquid composition)
Cu 70g / L
Zn 5g / L
NaOH 70g / L
NaCN 20g / L
(Electroplating conditions)
Temperature 70 ° C
Current density 8A / dm ² (multistage processing)

(3) Rust prevention treatment Sample No. For 10 to 12, 28 to 30, and 46 to 48, a rust prevention treatment (zinc chromate treatment) was performed under the following conditions to form a rust prevention treatment layer.
(Liquid composition)
CrO ₃ 2.5g / L
Zn 0.7g / L
Na ₂ SO ₄ 10 g / L
pH 4.8
(Zinc chromate condition)
Temperature 54 ° C
Current density 0.7 As / dm ²

(4) Silane coupling treatment Sample No. For Nos. 11 to 12, a silane coupling material coating treatment was performed under the following conditions to form a silane coupling layer.
(Liquid composition)
Tetraethoxysilane content 0.4%
pH 7.5
Application method Spraying solution

(5) Formation of release layer Sample No. As shown in Table 1, any of the following release layers A to E was formed for 1 to 16, 19 to 34, 37 to 52, and 55 to 60.
[Release layer A]
An aqueous solution of a silane compound (n-propyltrimethoxysilane: 4 wt%) is applied to the treated surface of the copper foil using a spray coater, and then the copper foil surface is dried in air at 100 ° C. for 5 minutes to separate it. A mold layer A was formed. The stirring time from when the silane compound was dissolved in water to before coating was 30 hours, the alcohol concentration in the aqueous solution was 0 vol%, and the pH of the aqueous solution was 3.8 to 4.2.

[Release layer B]
Sodium 1-dodecanethiolsulfonate is used as a compound having two or less mercapto groups in the molecule, and an aqueous solution of sodium 1-dodecanethiolsulfonate (sodium 1-dodecanethiolsulfonate: 3 wt%) is applied to a spray coater. Using it, it apply | coated to the processing surface of copper foil, Then, it was made to dry in 100 degreeC air for 5 minutes, and the release layer B was produced. The pH of the aqueous solution was 5-9.

[Release layer C]
Using triisopropoxyaluminum, which is an aluminate compound, as the metal alkoxide, an aqueous solution of triisopropoxyaluminum (triisopropoxyaluminum concentration: 0.04 mol / L) was applied to the treated surface of the copper foil using a spray coater. Then, the release layer C was produced by drying in air at 100 ° C. for 5 minutes. The stirring time from when the aluminate compound was dissolved in water to before coating was 2 hours, the alcohol concentration in the aqueous solution was 0 vol%, and the pH of the aqueous solution was 5-9.

[Release layer D]
Using titanate compound n-decyl-triisopropoxytitanium as metal alkoxide, an aqueous solution of n-decyl-triisopropoxytitanium (n-decyl-triisopropoxytitanium concentration: 0.01 mol / L) After using it and apply | coating to the process surface of copper foil, it was made to dry for 5 minutes in 100 degreeC air, and the release layer D was produced. The stirring time from dissolving the titanate compound in water to before coating was 24 hours, the alcohol concentration in the aqueous solution was 20 vol% methanol, and the pH of the aqueous solution was 5-9.

[Release layer E]
Using a zirconate compound n-propyl-tri-n-butoxyzirconium as a metal alkoxide, an aqueous solution of n-propyl-tri-n-butoxyzirconium (concentration of n-propyl-tri-n-butoxyzirconium: 0.04 mol / L) After apply | coating to the processing surface of copper foil using a spray coater, it was made to dry in 100 degreeC air for 5 minutes, and the release layer E was produced. The stirring time from dissolving the titanate compound in water to before coating was 12 hours, the alcohol concentration in the aqueous solution was 0 vol%, and the pH of the aqueous solution was 5-9.

(6) Resin layer forming treatment Sample No. For 12, 30, and 48, after barrier treatment, rust prevention treatment, silane coupling material application, and release layer formation, a resin layer was further formed under the following conditions.
(Resin synthesis example)
To a 2-liter three-necked flask equipped with a stainless steel vertical stirring bar, a trap with a nitrogen inlet tube and a stopcock, and a reflux condenser with a ball condenser, 117.68 g (400 mmol) of 4′-biphenyltetracarboxylic dianhydride, 87.7 g (300 mmol) of 1,3-bis (3-aminophenoxy) benzene, 4.0 g (40 mmol) of γ-valerolactone, 4. 8 g (60 mmol), N-methyl-2-pyrrolidone (hereinafter referred to as NMP) 300 g, and toluene 20 g were added, heated at 180 ° C. for 1 hour, cooled to near room temperature, and then 3, 4, 3 ′, 4′- 29.42 g (100 mmol) of biphenyltetracarboxylic dianhydride, 82.12 g of 2,2-bis {4- (4-aminophenoxy) phenyl} propane (200 mmol), 200 g of NMP, and 40 g of toluene were added, mixed at room temperature for 1 hour, and then heated at 180 ° C. for 3 hours to obtain a block copolymerized polyimide having a solid content of 38%. The block copolymerized polyimide had the following general formula (1): general formula (2) = 3: 2, number average molecular weight: 70000, and weight average molecular weight: 150,000.

The block copolymerized polyimide solution obtained in the synthesis example was further diluted with NMP to obtain a block copolymerized polyimide solution having a solid content of 10%. In this block copolymerized polyimide solution, bis (4-maleimidophenyl) methane (BMI-H, Kay-Isei) is contained in a solid content weight ratio of 35 and a solid content weight ratio of block copolymer polyimide of 65 (that is, included in the resin solution). Bis (4-maleimidophenyl) methane solid content weight: block copolymerized polyimide solid content weight contained in resin solution = 35: 65) A resin solution was prepared by dissolving and mixing at 60 ° C. for 20 minutes. Thereafter, the resin solution was applied to the release layer forming surface of Example 12, and after a drying treatment at 120 ° C. for 3 minutes and at 160 ° C. for 3 minutes in the nitrogen atmosphere, a heat treatment was finally performed at 300 ° C. for 2 minutes. The copper foil provided with the resin layer was produced. The thickness of the resin layer was 2 μm.

(7) Various evaluations ・ Evaluation of convex part on surface of release layer of surface-treated copper foil Using a scanning electron microscope manufactured by JEOL Ltd., as shown in FIG. The surface of the surface-treated copper foil was photographed on the surface of the release layer side of the surface-treated copper foil inclined at 45 ° from the horizontal plane, and the surface-treated copper foil was released on the side of the release layer based on the obtained photograph (for example, FIG. 8 described later). With respect to the convex portions on the surface, “height a from the constricted portion of the convex portion to the tip of the convex portion”, “maximum width b at the widest portion”, and “minimum width c of the constricted portion” shown in FIG. The observation magnification of the scanning electron microscope was 30,000 to 1,000,000 times. The stage on which the sample was placed was tilted in a direction perpendicular to the direction of the vertical frame of the photograph and along a rotation axis parallel to the direction of the horizontal frame of the photograph.
In the evaluation, as shown in FIG. 1, the values of “a”, “b”, and “c” are measured for each convex portion, and “a”, “b”, and “c” of 100 or more convex portions are measured. The values of the arithmetic average values were “a”, “b”, and “c”, respectively. In addition, when the roughening process particle | grains were formed on the surface of copper foil, "a", "b", and "c" of the convex part selected and measured the convex part which can be measured. Here, the above-mentioned measurable convex portion means a convex portion where the constricted portion can be observed. The convex part where the constricted part is observable is a convex part capable of observing the ridge line (illustrated in FIG. 8) of the convex part.
Here, the “necked portion” is a portion where the width of the convex portion on the surface of the copper foil becomes narrow after the width once widens from the tip of the convex portion when observed in the direction approaching the copper foil.
“Width of convex part” is the width of the photo divided by the contour or ridge line of the convex part when a line crossing the convex part is drawn parallel to the horizontal frame of the photograph on the photograph obtained with a scanning electron microscope. This is the length of a straight line that crosses the convex part drawn parallel to the frame. Here, when there are three or more ridge lines on the convex portion, the two closest ridge lines are selected.
The “minimum width c of the constricted portion” is a minimum value of the width of the convex portion in the constricted portion. When there is no constricted part, c = b.
"Height a from the constricted part of the convex part to the leading end of the convex part" refers to the line crossing the convex part parallel to the horizontal frame of the photograph drawn when measuring the minimum width c of the constricted part from the leading end of the convex part When a perpendicular line is drawn, the distance (a ′) to the intersection of a line crossing the convex part parallel to the horizontal frame of the photograph drawn when measuring the minimum width c of the constricted part and the perpendicular line drawn from the tip of the convex part ) And the square root of 2.
The “tip of the convex portion” means a portion that is estimated to be the highest of the convex portion determined based on the shadow of the photographed unevenness when the photograph is observed (see FIG. 7).
The “maximum width b in the widest part” is a convex part of a straight line that intersects the convex part parallel to the horizontal frame of the photograph between the tip of the convex part and the constricted part when the convex part has a constricted part. The longest length delimited by the outline.

-Manufacture of Laminate Any of the following resin base materials 1 to 3 was bonded to the treated side surface of each surface-treated copper foil.
Base material 1: GHPL-830 MBT manufactured by Mitsubishi Gas Chemical Co., Ltd.
Base material 2: 679-FG manufactured by Hitachi Chemical Co., Ltd.
Base material 3: EI-6785TS-F manufactured by Sumitomo Bakelite Co., Ltd.
The recommended conditions of each substrate manufacturer were used for the temperature, pressure, and time of the lamination press.

・ Evaluation of peelability of surface-treated copper foil Measure the normal peel strength when peeling the resin base material from the copper foil with the tensile tester Autograph 100 according to IPC-TM-650 for the laminate. The peelability of the surface-treated copper foil was evaluated based on the above criteria.
○: The range was 2 to 200 gf / cm.
X: Less than 2 gf / cm or more than 200 gf / cm.

-Evaluation of resin fracture mode The peeled surface of the resin base material after the peeling was observed with an electron microscope, and the resin fracture mode (aggregation, interface, coexistence of aggregation and interface) was observed. Regarding the resin failure mode, “interface” indicates that the resin was peeled at the interface between the copper foil and the resin, and “aggregation” indicates that the peel strength was too strong and the resin was broken. Indicates that the “interface” and “aggregation” are mixed.

・ Evaluation of circuit peeling and substrate swelling Using plating solution [liquid composition, Cu: 50 g / L, H ₂ SO ₄ : 50 g / L, Cl: 60 ppm] on the peeling surface of the resin base materials 1 to 3 after the above peeling. A copper plating pattern (line / space = 50 μm / 50 μm) was formed (Example 1). Further, a printing pattern (line / space = 50 μm / 50 μm) was formed on the release surface of the resin base material after peeling by ink jet using ink containing a conductive paste (Example 2). In addition, a resin layer composed of a liquid crystal polymer (assuming a resin constituting the build-up layer) was laminated on the release surface of the resin substrate after peeling (Example 3).
Next, whether or not circuit peeling or substrate swelling occurred was confirmed by a reliability test (heating test at 250 ° C. ± 10 ° C. × 1 hour). The size of the evaluation sample was 250 mm × 250 mm, and three samples were measured for each sample number.
The case where circuit peeling and substrate swelling did not occur was evaluated as “◎”. Slight circuit peeling or substrate swelling occurred (3 or less in one sample), but those that could be used as a product when the locations to be used were selected were evaluated as “◯”. In addition, a large number of circuit peeling or substrate swelling occurred (more than 3 in one sample), and those that could not be used as a product were evaluated as “x”.
Tables 1 to 4 show the test conditions and evaluation results.

・ Strength when the resin constituting the buildup layer and the untreated surfaces of the resin base material are bonded to each other, and then the resin and the resin base material are pulled and peeled. On the untreated surfaces of the resin base materials 1 to 3 On the other hand, a liquid crystal polymer (Vecstar manufactured by Kuraray Co., Ltd .: CT-F thickness: 50 μm) assumed as a resin constituting the build-up layer has a size of 1 cm square, a lamination temperature of 295 ± 5 ° C., a lamination pressure of 1 MPa, Lamination time: Laminated in 30 minutes. And the 1 cm square metal plate with a wire was joined to the laminated | stacked liquid crystal polymer using the adhesive agent. The wire is made of metal and is joined to the central portion of the 1 cm square metal plate by welding or soldering. Then, using a tensile tester Autograph 100, the maximum load when the resin (liquid crystal polymer) constituting the buildup layer was pulled and peeled from the resin base materials 1 to 3 was measured by pulling the wire. The measurement was performed at arbitrary three locations, and the arithmetic average value at the three locations was defined as the maximum load A (g). The wire pulling speed was 50 mm / min. The direction in which the wire is pulled was a direction perpendicular to the surface of the metal plate. Then, A (g / cm ² ) was defined as the strength when the resin constituting the build-up layer and the untreated surfaces of the resin base materials 1 to 3 were bonded together and pulled and peeled off. As a result of the measurement, the strength when the resin (liquid crystal polymer) constituting the build-up layer and the untreated surfaces of the resin substrates 1 to 3 are bonded to each other and pulled apart in any of the resin substrates 1 to 3 Was 500 g / cm ² or less. Moreover, after laminating each copper foil sample shown in Table 1 on the resin base materials 1 to 3 shown in Table 1, the copper foil sample was peeled off from the resin base material, and the uneven profile on the copper foil surface was transferred. A resin substrate was obtained. And the resin (liquid crystal polymer) which comprises a buildup layer is laminated | stacked on the surface of the resin base material which the uneven | corrugated profile of the said copper foil surface transcribe | transferred similarly to the above, Then, a resin base material and a buildup layer are attached. The strength at the time of peeling off the constituent resin was measured. As a result, in the above-mentioned ". Evaluation of circuit peeling and substrate swelling", the experimental example with an evaluation of "◎" has a strength of 1000 g when the resin base material and the resin constituting the buildup layer are pulled and peeled. / Cm ² or more, and in the experimental example with an evaluation of “◯”, the strength when the resin base material and the resin constituting the buildup layer are pulled and peeled is 800 g / cm ² or more, and the evaluation is “×”. In the experimental example, the strength when the resin substrate and the resin constituting the buildup layer were pulled and peeled was 600 g / cm ² or less.

As shown in Tables 1 to 4, Example No. 1 provided with a predetermined release layer was provided. 1-16, no. 19-34, no. In 37 to 52 and 55 to 60, the peel strength was suppressed, and the fracture mode of the resin was only the interface. As described above, when the copper foil was removed after being bonded to the resin base material, the copper foil was successfully removed without impairing the profile of the copper foil surface transferred to the surface of the resin base material.
On the other hand, no release layer was provided or the compound used to form the release layer was inappropriate. 17-18, no. 35-36, no. In Nos. 53 to 54, a release layer could not be formed, the peel strength was high, and the resin fracture mode was either aggregation or a mixture of aggregation and an interface. Thus, after bonding with the resin base material, when removing copper foil, the profile of the copper foil surface transcribe | transferred to the surface of the resin base material was impaired, and copper foil was not able to be removed favorably.
In FIG. The microscope observation photograph of the mold release layer side surface of the surface treatment copper foil which concerns on 58 is shown.
In FIG. The microscope observation photograph of the mold release layer side surface of the surface treatment copper foil which concerns on No.55 is shown.

Claims

A step of attaching a resin base material from the release layer side to a surface-treated copper foil provided with a release layer on the surface;
Removing the surface-treated copper foil from the resin base material to obtain a resin base material in which the surface profile of the copper foil is transferred to the release surface;
Forming a plating pattern on the release surface side of the resin substrate to which the surface profile is transferred;
A method of manufacturing a printed wiring board comprising:
A step of attaching a resin base material from the release layer side to a surface-treated copper foil provided with a release layer on the surface;
Removing the surface-treated copper foil from the resin base material to obtain a resin base material in which the surface profile of the copper foil is transferred to the release surface;
Forming a print pattern on the release surface side of the resin substrate to which the surface profile is transferred;
A method of manufacturing a printed wiring board comprising:
A step of attaching a resin base material from the release layer side to a surface-treated copper foil provided with a release layer on the surface;
Removing the surface-treated copper foil from the resin base material to obtain a resin base material in which the surface profile of the copper foil is transferred to the release surface;
Providing a build-up layer on the release surface side of the resin substrate to which the surface profile has been transferred;
A method of manufacturing a printed wiring board comprising:
The printed wiring board manufacturing method according to claim 3, wherein the strength of the resin constituting the buildup layer and the untreated surfaces of the resin base material is bonded to each other and pulled and peeled off is 500 g / cm 2 or less. Method.
The method for producing a printed wiring board according to claim 3 or 4, wherein the resin constituting the build-up layer contains a liquid crystal polymer or polytetrafluoroethylene.
The release layer has the following formula:

Wherein R 1 is an alkoxy group or a halogen atom, and R 2 is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by: M is any one of Al, Ti, Zr, n is 0 or 1 or 2, m is an integer from 1 to M valence, (At least one of R 1 is an alkoxy group, where m + n is a valence of M, that is, 3 for Al and 4 for Ti and Zr.)
An aluminate compound, a titanate compound, a zirconate compound, a hydrolysis product thereof, or a condensate of the hydrolysis product shown in any one of 1 to 5 above is used. Manufacturing method of printed wiring board.
The release layer has the following formula:

Wherein R 1 is an alkoxy group or a halogen atom, and R 2 is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by R 3 and R 4 are each independently a halogen atom, an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group Or any one of these hydrocarbon groups in which one or more hydrogen atoms are replaced by halogen atoms.)
The method for producing a printed wiring board according to any one of Claims 1 to 5, wherein the silane compound, the hydrolysis product thereof, and the condensate of the hydrolysis product are used singly or in combination.
The method for producing a printed wiring board according to any one of claims 1 to 5, wherein the release layer comprises a compound having two or less mercapto groups in the molecule.
The copper foil has a convex portion on the surface of the release layer, and the convex portion is released from the copper foil in a state where a stage on which the copper foil is placed is inclined 45 ° from a horizontal plane using an electron microscope. The height from the constricted part of the convex part to the tip of the convex part measured based on the obtained photograph is taken as a, the maximum width at the widest part of the convex part is b, the convex part The method for producing a printed wiring board according to any one of claims 1 to 8, wherein all of the following formulas are satisfied, where c is a minimum width of the constricted portion.
When a / b ≦ 1, (bc) /b≦0.2 and b ≧ 10 nm
When a / b> 1, (bc) /b≦0.03 and b ≧ 10 nm
10. One or more layers selected from the group consisting of a heat resistant layer, a rust preventive layer, a chromate treatment layer, and a silane coupling treatment layer are provided between the copper foil and the release layer. A method for producing a printed wiring board according to claim 1.
The method for producing a printed wiring board according to claim 10, wherein a resin layer is provided on a surface of one or more layers selected from the group consisting of the heat-resistant layer, the rust-proof layer, the chromate-treated layer, and the silane coupling-treated layer.
The method for producing a printed wiring board according to any one of claims 1 to 11, wherein a resin layer is provided on a surface of the release layer side of the surface-treated copper foil.
The method for producing a printed wiring board according to claim 11 or 12, wherein the resin layer is an adhesive resin, a primer, or a semi-cured resin.
The method for producing a printed wiring board according to any one of claims 1 to 13, wherein the thickness of the surface-treated copper foil is 9 to 70 µm.
A surface-treated copper foil having a copper foil and a release layer provided on the surface of the copper foil,
The copper foil has a convex portion on the surface of the release layer, and the convex portion is released from the copper foil in a state where a stage on which the copper foil is placed is inclined 45 ° from a horizontal plane using an electron microscope. The height from the constricted part of the convex part to the tip of the convex part measured based on the obtained photograph is taken as a, the maximum width at the widest part of the convex part is b, the convex part The surface-treated copper foil which satisfy | fills all the following formula when the minimum width | variety of a constriction part is set to c.
When a / b ≦ 1, (bc) /b≦0.2 and b ≧ 10 nm
When a / b> 1, (bc) /b≦0.03 and b ≧ 10 nm
The surface-treated copper foil according to claim 15, wherein the copper foil does not have roughened particles on the surface of the release layer.
The release layer has the following formula:

Wherein R 1 is an alkoxy group or a halogen atom, and R 2 is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by: M is any one of Al, Ti, Zr, n is 0 or 1 or 2, m is an integer from 1 to M valence, (At least one of R 1 is an alkoxy group, where m + n is a valence of M, that is, 3 for Al and 4 for Ti and Zr.)
The surface-treated copper foil according to claim 15 or 16, wherein the aluminate compound, titanate compound, zirconate compound, hydrolysis products thereof, and condensates of the hydrolysis products are used singly or in combination.
The release layer has the following formula:

Wherein R 1 is an alkoxy group or a halogen atom, and R 2 is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by R 3 and R 4 are each independently a halogen atom, an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group Or any one of these hydrocarbon groups in which one or more hydrogen atoms are replaced by halogen atoms.)
The surface-treated copper foil according to claim 15 or 16, wherein the silane compound, the hydrolysis product thereof, and the condensate of the hydrolysis product are used singly or in combination.
The surface-treated copper foil according to claim 15 or 16, wherein the release layer comprises a compound having 2 or less mercapto groups in the molecule.
Any one or more layers selected from the group consisting of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer are provided between the copper foil and the release layer. The surface-treated copper foil as described in one.
21. The surface-treated copper foil according to claim 20, wherein a resin layer is provided on the surface of one or more layers selected from the group consisting of the heat-resistant layer, the rust-proof layer, the chromate-treated layer, and the silane coupling-treated layer.
The surface-treated copper foil according to any one of claims 15 to 21, wherein a resin layer is provided on the surface of the release layer side.
The surface-treated copper foil according to claim 21 or 22, wherein the resin layer is an adhesive resin, a primer, or a semi-cured resin.
The surface-treated copper foil according to any one of claims 15 to 23, having a thickness of 9 to 70 µm.
A laminate comprising the surface-treated copper foil according to any one of claims 15 to 24 and a resin base material provided on the release layer side of the surface-treated copper foil.
The laminate according to claim 25, wherein the resin base material is a prepreg or contains a thermosetting resin.
A printed wiring board comprising the surface-treated copper foil according to any one of claims 15 to 24.
A printed wiring board manufactured using the surface-treated copper foil according to any one of claims 15 to 24.
A semiconductor package comprising the printed wiring board according to claim 27 or 28.
An electronic device comprising the printed wiring board according to claim 27 or 28 or the semiconductor package according to claim 29.