JP2018122590A - Metallic foil with release layer, metallic foil, laminate, printed wiring board, semiconductor package, electronic apparatus and method for manufacturing printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metallic foil which controls a state of unevenness of a surface of a metallic foil, and enables physical peeling of a resin base material when a release layer is provided on the metallic foil and the metallic foil is stuck to a resin base material, and to provide a printed wiring board having a fine circuit at excellent cost.SOLUTION: There are provided a metallic foil having a first surface and a second surface, where a root mean square height Sq of the first surface is 0.01 μm or more and 1 μm or less; and a metallic foil with release layer having a release layer provided on the second surface of the metallic foil.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a metal foil with a release layer, a metal foil, a laminate, a printed wiring board, a semiconductor package, an electronic device, and a method for manufacturing a printed wiring board.

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

  Among these new circuit forming methods, the following can be cited as an example of the semi-additive method using the surface profile of the latter metal foil. That is, first, the entire surface of the metal foil laminated on the resin base material is etched, the etching base material surface on which the metal 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 surface profile of the metal foil, there is still room for studying the production of a printed wiring board having a fine circuit at a good cost.

  As a result of intensive studies, the present inventors have controlled the unevenness of the surface of the metal foil. In addition, a release layer is provided on the surface of the metal foil opposite to the surface on which the unevenness is controlled, and physical peeling of the resin base material is performed when the metal foil is bonded to the resin base material. Made possible. And it discovered that it became possible to manufacture the printed wiring board which has a fine circuit with favorable cost by using the above-mentioned metal foil as follows. That is, after the surface side having the release layer of the metal foil was bonded to the resin base material, a circuit was formed on the surface of the metal foil in which the uneven state was controlled. Next, a resin was laminated on the surface of the metal foil on which the circuit was formed so that the circuit was embedded. After that, the metal foil was peeled off from the resin base material, and the metal foil was removed to expose the above-mentioned circuit, thereby finding that a printed wiring board having a fine circuit could be manufactured at a good cost. .

  The present invention completed on the basis of the above knowledge has, in one aspect, a metal foil having a first surface and a second surface, wherein the root mean square height Sq of the first surface is 0.01 μm or more and 1 μm or less. And the metal foil with a release layer provided with the release layer provided in the 2nd surface of the said metal foil.

  In one embodiment of the metal foil with a release layer of the present invention, the metal foil has a root mean square height Sq of the second surface of 0.25 μm to 1.6 μm.

  In another embodiment of the metal foil with a release layer of the present invention, the ratio (Sq / Rsm) of the root mean square height Sq of the second surface of the metal foil to the average interval Rsm of the irregularities is 0.03 or more. It has surface irregularities of 0.40 or less.

  In still another embodiment of the metal foil with a release layer of the present invention, the thickness of the metal foil is 1 μm or more and 105 μm or less.

  In another embodiment of the metal foil with a release layer of the present invention, the metal foil is a copper foil.

  In yet another embodiment, the metal foil with a release layer according to the present invention has a roughened layer, a heat-resistant layer on the first surface of the metal foil and / or between the metal foil and the release layer. One or more layers selected from the group consisting of a layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer are provided.

  In yet another embodiment, the metal foil with a release layer of the present invention is the roughening treatment layer, the heat-resistant layer, the rust prevention layer, the chromate treatment layer and the silane coupling treatment provided on the first surface of the metal foil. The resin layer is provided in one or more layers selected from the group consisting of layers.

  In still another embodiment of the metal foil with a release layer of the present invention, the resin layer is an adhesive resin, a primer, or a semi-cured resin.

In another embodiment of the metal foil with a release layer 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 of the hydrocarbon group A hydrocarbon group in which an atom is substituted with a halogen atom, M is any one of Al, Ti, and Zr, n is 0, 1 or 2, and m is 1 or more and a valence of M or less. And at least one of R ¹ is an alkoxy group, m + n is the valence of M. The valence of M is 3 for Al and 4 for Ti and Zr.)
Aluminate compound, titanate compound, zirconate compound, hydrolysis product of aluminate compound, hydrolysis product of titanate compound, hydrolysis product of zirconate compound, condensate of hydrolysis product of aluminate compound, titanate It contains at least one or two or more selected from the group consisting of a condensation product of a hydrolysis product of a compound and a condensation product of a hydrolysis product of a zirconate compound.

In another embodiment of the metal foil with a release layer 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 of the hydrocarbon group A hydrocarbon group substituted with a halogen atom, and R ³ and R ⁴ are each independently selected from the group consisting of a halogen atom, an alkoxy group, an alkyl group, a cycloalkyl group and an aryl group; Alternatively, it is a hydrocarbon group in which one or more hydrogen atoms of the hydrocarbon group are substituted with a halogen atom.)
Or at least one selected from the group consisting of a hydrolysis product of the silane compound and a condensate of the hydrolysis product.

  In another embodiment of the metal foil with a release layer of the present invention, the release layer uses a compound having two or less mercapto groups in the molecule.

  In still another embodiment of the metal foil with a release layer of the present invention, a resin layer is provided on the surface of the release layer.

  In still another embodiment of the metal foil with a release layer of the present invention, the resin layer is an adhesive resin, a primer, or a semi-cured resin.

  In another aspect, the present invention is a metal foil having a first surface and a second surface, wherein the root mean square height Sq of the first surface is 0.01 μm or more and 1 μm or less.

  In one embodiment of the metal foil of the present invention, the root mean square height Sq of the second surface is 0.25 μm or more and 1.6 μm or less.

  In another embodiment of the metal foil of the present invention, the ratio (Sq / Rsm) between the root mean square height Sq of the second surface of the metal foil and the average interval Rsm of the irregularities (Sq / Rsm) is 0.03 or more and 0.40 or less. Surface irregularities.

  In another embodiment of the metal foil of the present invention, the thickness of the metal foil is 1 μm or more and 105 μm or less.

  In still another embodiment of the metal foil of the present invention, the metal foil is a copper foil.

  In yet another embodiment of the metal foil of the present invention, a roughening treatment layer, a heat-resistant layer, a rust prevention layer, a chromate treatment is applied to the first surface of the metal foil and / or the second surface of the metal foil. One or more layers selected from the group consisting of a layer and a silane coupling treatment layer are provided.

  In yet another embodiment, the metal foil of the present invention is a group consisting of the roughening treatment layer, the heat resistant layer, the rust prevention layer, the chromate treatment layer, and the silane coupling treatment layer provided on the first surface of the metal foil. A resin layer is provided on one or more layers selected from the above.

  In yet another aspect of the present invention, the metal foil with a release layer of the present invention or the metal foil of the present invention, and a laminate comprising the metal foil with a release layer or a resin substrate provided on the metal foil Is the body.

  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 metal foil with a release layer of the present invention or the metal 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 still 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 yet another aspect of the present invention, the step of bonding an insulating substrate to the metal foil with a release layer of the present invention or the metal foil of the present invention, the metal foil with a release layer or the metal foil from the insulating substrate. The step of obtaining the insulating substrate having the release layer or the surface profile of the metal foil transferred to the release surface, and the insulating substrate to which the surface profile has been transferred It is a manufacturing method of a printed wiring board including the process of forming a circuit in the exfoliation side.

  In one embodiment of the method for producing a printed wiring board of the present invention, the circuit formed on the peeling surface side of the insulating substrate to which the surface profile is transferred is a plating pattern or a printing pattern.

  In yet another aspect of the present invention, the step of bonding an insulating substrate to the metal foil with a release layer of the present invention or the metal foil of the present invention, the metal foil with a release layer or the metal foil from the insulating substrate. The step of obtaining the insulating substrate having the release layer or the surface profile of the metal foil transferred to the release surface, and the insulating substrate to which the surface profile has been transferred It is a manufacturing method of the printed wiring board including the process of providing a buildup layer in the peeling surface side.

  In one 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, a fluororesin, a low dielectric constant polyimide, a polyphenylene ether, a cycloolefin polymer, or polytetrafluoroethylene.

  In yet another aspect of the present invention, the step of bonding the insulating substrate 1 to the metal foil with a release layer of the present invention or the metal foil of the present invention from the release layer side or the second surface side of the metal foil, A step of forming a circuit on the first surface side of the metal foil with a release layer laminated on the insulating substrate 1 or the metal foil, a step of embedding the circuit in the insulating substrate 2 by covering the circuit with the insulating substrate 2 A step of peeling the insulating substrate 1 from the metal foil with a release layer or the metal foil to expose the metal foil with a release layer or the metal foil, and the exposed metal foil with a release layer or the metal foil It is a manufacturing method of a printed wiring board including the process of removing metal foil.

In yet another aspect of the present invention, the step of bonding the insulating substrate 1 to the metal foil with a release layer of the present invention or the metal foil of the present invention from the release layer side or the second surface side of the metal foil, A step of laminating a dry film on the metal foil with a release layer laminated on the insulating substrate 1 or a first surface side of the metal foil of the metal foil, a step of forming a circuit after patterning the dry film,
Peeling the dry film to expose the circuit, covering the exposed circuit with an insulating substrate 2 to embed the circuit in the insulating substrate 2, the metal foil with a release layer or the metal foil from the metal foil A method of manufacturing a printed wiring board, comprising: a step of peeling the insulating substrate 1 to expose the metal foil with a release layer or the metal foil; and a step of removing the exposed metal foil with a release layer or the metal foil. It is.

  It is possible to control the state of unevenness on the surface of the metal foil, and to provide a release layer on the metal foil so that the resin substrate can be physically peeled when the metal foil is bonded to the resin substrate. By providing the metal foil, a printed wiring board having a fine circuit can be manufactured at a favorable cost.

AC is a schematic diagram of the wiring board cross section in the process to circuit plating and the resist removal based on the specific example of the manufacturing method of the printed wiring board using the copper foil with a mold release layer of this invention. D to F are wiring boards in steps from resin and copper foil lamination with a second release layer to laser drilling according to a specific example of a method for producing a printed wiring board using a copper foil with a release layer of the present invention. It is a schematic diagram of a cross section. GI is a schematic diagram of a cross section of a wiring board in a process from via fill formation to first release layer peeling, according to a specific example of a method for manufacturing a printed wiring board using a copper foil with a release layer of the present invention. It is. J to K are schematic views of a cross section of a wiring board in steps from flash etching to bump / copper pillar formation according to a specific example of a method of manufacturing a printed wiring board using a copper foil with a release layer of the present invention. It is a schematic diagram which shows the semi-additive construction method using the profile of copper foil.

(Metal foil)
The metal foil of the present invention is a metal foil having a first surface and a second surface, and having a root mean square height Sq of 0.01 μm or more and 1 μm or less on the surface on the first surface side. Thus, the uneven | corrugated state of the surface of metal foil was controlled by controlling the root mean square height Sq of a 1st surface. And it becomes possible to manufacture the printed wiring board which has a fine circuit with favorable cost by using the above-mentioned metal foil as follows. That is, a release layer is provided on the surface of the metal foil opposite to the surface on which the unevenness is controlled, and physical peeling of the resin substrate when the metal foil is bonded to the resin substrate is performed. to enable. And after bonding the surface side which has the mold release layer of the above-mentioned metal foil to a resin base material, a circuit is formed in the surface of the metal foil which controlled the state of the unevenness | corrugation of the above-mentioned surface. Next, a resin is laminated on the surface of the metal foil on which the circuit is formed so that the circuit is embedded. Thereafter, the metal foil is peeled off from the resin base material, and the printed circuit board can be manufactured by removing the metal foil and exposing the above-described circuit. When a printed wiring board is manufactured by the above-described method, a circuit can be formed without providing an electroless plating layer on a resin substrate by electroless plating. Therefore, the manufacturing cost of the printed wiring board can be reduced. Further, the circuit is protected by being embedded in the resin. Therefore, when the metal foil is removed by etching or the like, the circuit is not easily eroded by etching or the like. Therefore, a fine circuit can be formed.
In this specification, “the first surface of the metal foil” and “the second surface of the metal foil” are a roughening treatment layer, a heat-resistant layer, a rust prevention layer, a chromate treatment layer, a silane coupling treatment on the surface of the metal foil. When a surface treatment layer such as a layer or a release layer is provided, it means the surface after the surface treatment layer is provided (the surface of the outermost layer). In the present specification, the “first surface” is also referred to as “one surface”, and the “second surface” is also referred to as “the other surface”.

  Since the root mean square height Sq of the first surface of the metal foil of the present invention is 0.01 μm or more, the adhesiveness with the above-described circuit or the resin in which the circuit is embedded is improved. As a result, peeling or dropping of the circuit or the resin in which the circuit is embedded from the metal foil is reduced. In addition, since the metal foil of the present invention has a root mean square height Sq of 1 μm or less on the first surface, the circuit formability is good.

  When the root mean square height Sq is less than 0.01 μm on the first surface of the metal foil, the unevenness of the unevenness on the surface of the metal foil may be too small. Therefore, the adhesion between the metal foil and the above-described circuit or the resin in which the circuit is embedded may deteriorate. As a result, the circuit or the resin in which the circuit is embedded may be peeled off or dropped from the metal foil. On the first surface of the metal foil, if the root mean square height Sq exceeds 1 μm, the unevenness of the surface of the metal foil may become too large. As a result, it may be necessary to perform etching or the like for a longer time when the metal foil is removed at a portion where the convex portion of the surface of the metal foil is large. As a result, circuit erosion due to etching or the like becomes large, and the wiring formability may deteriorate. The root mean square height Sq of the first surface of the metal foil is preferably 0.95 μm or less, preferably 0.93 μm or less, preferably 0.90 μm or less, and 0.85 μm or less. Is preferably 0.80 μm or less, preferably 0.75 μm or less, preferably 0.70 μm or less, preferably 0.68 μm or less, and 0.67 μm or less. It is preferably 0.65 μm or less, preferably 0.60 μm or less, preferably 0.55 μm or less, preferably 0.50 μm or less, and 0.45 μm or less. Preferably, it is 0.40 μm or less, preferably 0.35 μm or less, preferably 0.32 μm or less, and 0.30 μm or less. Preferably, it is 0.25 μm or less, preferably 0.24 μm or less, preferably 0.22 μm or less, preferably 0.20 μm or less, and 0.19 μm or less. Preferably, it is 0.18 μm or less, preferably 0.17 μm or less, and more preferably 0.15 μm or less. The root mean square height Sq of the first surface of the metal foil is preferably 0.015 μm or more, preferably 0.02 μm or more, preferably 0.025 μm or more, 0.03 μm or more. It is preferably 0.035 μm or more, preferably 0.04 μm or more, preferably 0.045 μm or more, and more preferably 0.05 μm or more.

  The second surface of the metal foil preferably has a root mean square height Sq of 0.25 μm to 1.6 μm. Since the root mean square height Sq of the second surface of the metal foil is 0.25 to 1.6 μm, the metal foil is peeled off while maintaining good peelability after bonding the metal foil and the resin base material. Laminated members such as circuits, resins, and build-up layers follow the surface of the resin substrate without voids (or very little voids) due to the uneven shape transferred to the surface of the resin substrate. It is possible to provide a laminated member such as a resin substrate surface with good adhesion.

  When the root mean square height Sq of the second surface of the metal foil is less than 0.25 μm, the unevenness on the surface of the resin substrate obtained by peeling the metal foil after bonding the metal foil and the resin substrate is small. There is a possibility that the problem of insufficient adhesion with different resins may occur. When the thickness exceeds 1.6 μm, the peelability when peeling the metal foil after bonding the metal foil and the resin base material deteriorates. In addition, the uneven shape on the surface of the resin base material after the metal foil is peeled off may be so deep that a laminated member such as a circuit, a resin, or a build-up layer may not follow the uneven shape. The root mean square height Sq is preferably 0.30 to 1.4 [mu] m, more preferably 0.4 to 1.0 [mu] m, and even more preferably 0.4 to 0.96 [mu] m.

  It is preferable that the ratio (Sq / Rsm) of the root mean square height Sq of the second surface of the metal foil to the average interval Rsm of the unevenness is 0.03 or more and 0.40 or less. Since the ratio (Sq / Rsm) between the root mean square height Sq of the second surface of the metal foil and the average interval Rsm of the unevenness is 0.03 or more and 0.40 or less, the metal foil and the resin base material were bonded together. While maintaining good exfoliation, the laminated parts such as circuits, resins, and build-up layers follow without any gaps (or very little gaps) due to the irregular shape transferred to the surface of the resin substrate after peeling the metal foil. It becomes possible to provide laminated members such as circuits, resins and build-up layers on the surface of the resin base material with good adhesion.

  When the ratio (Sq / Rsm) of the root mean square height Sq of the second surface of the metal foil to the average interval Rsm of the unevenness is less than 0.03, the metal foil is bonded to the resin foil after the metal foil and the resin substrate are bonded together. The unevenness of the surface of the resin base material obtained by peeling is small, causing a problem that the adhesiveness between the resin base material and a laminated member such as a circuit, resin, build-up layer, etc. is insufficient. The peelability when peeling the metal foil after bonding the metal foil and the resin base material deteriorates, and the uneven shape on the surface of the resin base material after the metal foil is peeled is too deep, resulting in a circuit, resin or build-up layer. There arises a problem that the laminated member does not follow the uneven shape. The ratio (Sq / Rsm) between the root mean square height Sq of the second surface of the metal foil and the average interval Rsm of the unevenness (Sq / Rsm) is preferably 0.05 or more, and more preferably 0.10 or more. The ratio (Sq / Rsm) between the root mean square height Sq of the second surface of the metal foil and the average interval Rsm of the irregularities (Sq / Rsm) is preferably 0.25 or less, preferably 0.24 or less, More preferably, it is 20 or less.

(Metal foil with release layer)
The metal foil with a release layer of the present invention has a first surface and a second surface, and has a root mean square height Sq of 0.01 μm or more and 1 μm or less of the first surface, A release layer provided on the second surface side of the metal foil, and releasing the resin substrate when the resin substrate is bonded to the metal foil from the release layer side And a release layer-attached metal foil. Thus, the uneven | corrugated state of the surface of metal foil was controlled by controlling the root mean square height Sq of a 1st surface. In addition, a release layer is provided on the surface of the metal foil opposite to the surface on which the unevenness is controlled, and physical peeling of the resin base material is performed when the metal foil is bonded to the resin base material. Made possible. And it becomes possible to manufacture the printed wiring board which has a fine circuit with favorable cost by using the above-mentioned metal foil as follows. That is, after the surface side having the release layer of the metal foil is bonded to the resin base material, a circuit is formed on the surface of the metal foil in which the surface irregularities are controlled. Next, a resin is laminated on the surface of the metal foil on which the circuit is formed so that the circuit is embedded. Thereafter, the metal foil is peeled off from the resin base material, and the printed circuit board can be manufactured by removing the metal foil and exposing the above-described circuit. When a printed wiring board is manufactured by the above-described method, a circuit can be formed without providing an electroless plating layer on a resin substrate by electroless plating. Therefore, the manufacturing cost of the printed wiring board can be reduced. Further, the circuit is protected by being embedded in the resin. Therefore, when the metal foil is removed by etching or the like, the circuit is not easily eroded by etching or the like. Therefore, a fine circuit can be formed.

  Since the metal foil of the metal foil with a release layer has a root mean square height Sq of 0.01 μm or more on the first surface, which is the surface on which the release layer is not formed, the above circuit or circuit is Adhesion with the embedded resin is improved. As a result, peeling or dropping of the circuit or the resin in which the circuit is embedded from the metal foil is reduced. In addition, since the metal foil has a root mean square height Sq of 1 μm or less on the first surface, which is the surface on which the release layer is not formed, the circuit formability is improved.

  When the root mean square height Sq is less than 0.01 μm on the first surface, which is the surface on which the release layer of the metal foil is not formed, the unevenness of the surface of the metal foil is too small. There is. If the unevenness of the surface of the metal foil becomes too small, high convexity or deep concaveity that contributes to the adhesion between the metal foil and the circuit and the adhesion between the metal foil and the resin in which the circuit or circuit is embedded. In some cases, the adhesion between the metal foil and the above-described circuit or the resin in which the circuit is embedded may deteriorate. As a result, the circuit or the resin in which the circuit is embedded may be peeled off or dropped from the metal foil. Further, when the root mean square height Sq exceeds 1 μm on the first surface, which is the surface where the release layer of the metal foil is not formed, the unevenness of the surface of the metal foil may become too large. is there. As a result, it may be necessary to perform etching or the like for a longer time when the metal foil is removed at a portion where the convex portion of the surface of the metal foil is large. As a result, circuit erosion due to etching or the like becomes large, and the wiring formability may deteriorate. The root mean square height Sq of the first surface, which is the surface on which the release layer is not formed, is preferably 0.95 μm or less, preferably 0.93 μm or less, and 0.90 μm or less. Preferably, it is 0.85 μm or less, preferably 0.80 μm or less, preferably 0.75 μm or less, preferably 0.70 μm or less, and 0.68 μm or less. Preferably, it is 0.67 μm or less, preferably 0.65 μm or less, preferably 0.60 μm or less, preferably 0.55 μm or less, and 0.50 μm or less. Preferably, it is 0.45 μm or less, preferably 0.40 μm or less, preferably 0.35 μm or less, and preferably 0.32 μm or less. It is preferably 0.30 μm or less, preferably 0.25 μm or less, preferably 0.24 μm or less, preferably 0.22 μm or less, and 0.20 μm or less. Preferably, it is 0.19 μm or less, preferably 0.18 μm or less, preferably 0.17 μm or less, and more preferably 0.15 μm or less. The root mean square height Sq of the first surface, which is the surface on which the release layer is not formed, is preferably 0.015 μm or more, preferably 0.02 μm or more, and 0.025 μm or more. Preferably, it is 0.03 μm or more, preferably 0.035 μm or more, preferably 0.04 μm or more, preferably 0.045 μm or more, 0.05 μm or more. It is more preferable that

  The second surface, which is the surface on which the release layer of the metal foil is formed, preferably has a root mean square height Sq of 0.25 μm or more and 1.6 μm or less. Since the root mean square height Sq of the second surface, which is the surface on which the release layer of the metal foil is formed, is 0.25 to 1.6 μm, the metal foil and the resin base material are bonded together While maintaining good releasability, laminated members such as circuits, resins, and build-up layers have no voids (or voids) on the resin substrate surface due to the uneven shape transferred to the resin substrate surface after peeling the metal foil. It is possible to provide a laminated member such as a circuit, a resin or a build-up layer on the surface of the resin base material with good adhesion.

  When the root mean square height Sq of the second surface, which is the surface on the side where the release layer of the metal foil is formed, is less than 0.25 μm, the metal foil and the resin base material are bonded together after bonding The unevenness of the surface of the resin substrate obtained by peeling is small, and there is a possibility that the problem of insufficient adhesion with different resins may occur. When the thickness exceeds 1.6 μm, the metal foil and the resin substrate are bonded together. In addition to worsening the peelability when peeling back the metal foil, the uneven shape on the surface of the resin substrate after peeling the metal foil is too deep, and laminated members such as circuits, resins and build-up layers follow the uneven shape. There is a risk of not doing so. The root mean square height Sq is preferably 0.30 to 1.4 [mu] m, more preferably 0.4 to 1.0 [mu] m, and even more preferably 0.4 to 0.96 [mu] m.

  The ratio (Sq / Rsm) of the root mean square height Sq of the second surface, which is the surface on the side where the release layer of the metal foil is formed, to the average interval Rsm of the irregularities is 0.03 or more and 0.40 or less. Preferably there is. The ratio (Sq / Rsm) of the root mean square height Sq of the second surface, which is the surface on the side where the release layer of the metal foil is formed, to the average interval Rsm of the irregularities is 0.03 or more and 0.40 or less. Therefore, while maintaining good peelability after bonding the metal foil and the resin base material, lamination of circuits, resins, build-up layers, etc. by the uneven shape transferred to the surface of the resin base material after peeling the metal foil The member follows without a void (or with very few voids), and a laminated member such as a circuit, a resin, or a buildup layer can be provided on the surface of the resin substrate with good adhesion.

  When the ratio (Sq / Rsm) of the root mean square height Sq of the second surface, which is the surface on the side where the release layer of the metal foil is formed, to the average interval Rsm of the unevenness is less than 0.03, the metal Unevenness on the surface of the resin base material obtained by peeling the metal foil after pasting the foil and resin base material is small, and the adhesion between the resin base material and laminated members such as circuits, resins and build-up layers is insufficient When the value exceeds 0.40, the peelability when the metal foil is peeled off after the metal foil and the resin base material are bonded is deteriorated, and the surface of the resin base material after the metal foil is peeled off is deteriorated. There is a problem that the uneven shape is too deep, and laminated members such as a circuit, a resin, and a build-up layer do not follow the uneven shape. The ratio (Sq / Rsm) of the root mean square height Sq of the second surface, which is the surface on the side where the release layer of the metal foil is formed, to the average interval Rsm of the irregularities is 0.05 or more. Preferably, it is 0.10 or more. The ratio (Sq / Rsm) of the root mean square height Sq of the second surface, which is the surface on the side where the release layer of the metal foil is formed, to the average interval Rsm of the irregularities (Sq / Rsm) is 0.25 or less. Preferably, it is 0.24 or less, and more preferably 0.20 or less.

Metal foil (also referred to as raw foil) is not particularly limited, but copper foil, aluminum foil, nickel foil, copper alloy foil, nickel alloy foil, aluminum alloy foil, stainless steel foil, iron foil, iron alloy foil, zinc foil, zinc An alloy foil, a cobalt foil, a cobalt alloy foil, or the like can be used. Moreover, a well-known metal foil can be used as a metal foil.
The thickness of metal foil (raw foil) is not specifically limited, For example, it can be set to 1-105 micrometers, 3-105 micrometers, or 5-105 micrometers. Moreover, since peeling from a resin base material becomes easy, it is preferable that the thickness of metal foil is 9-70 micrometers, it is more preferable that it is 12-35 micrometers, and it is still more preferable that it is 18-35 micrometers. . Further, from the viewpoint of ease of removal of metal foil (raw foil) by etching or the like, it is preferable that the thickness of the metal foil is thin. For example, the thickness of the metal foil is preferably 105 μm or less, preferably 70 μm or less, preferably 35 μm or less, preferably 18 μm or less, and more preferably 12 μm or less. Further, from the viewpoint of easy handling of the metal foil (raw foil), it is preferable that the metal foil is thicker. For example, the thickness of the metal foil is preferably 1 μm or more, and more preferably 3 μm or more.

Hereinafter, a copper foil will be described as an example of a metal foil (raw foil). Although it does not specifically limit as a manufacturing method of metal foil (raw foil), For example, an electrolytic copper foil can be produced on the following electrolysis conditions. In addition, the following method is applicable also to metal foils (electrolytic metal foil, rolled metal foil) other than copper foil.
<Method for producing electrolytic copper foil>
The electrolytic copper foil of the present invention is produced by electrolytically depositing copper from a copper sulfate plating bath onto a titanium or stainless steel drum. Although the electrolysis conditions are not particularly limited, for example, an electrolytic copper foil can be produced under the following conditions.
Electrolyte composition:
Cu: 30 to 190 g / L
H ₂ SO ₄ : 100 to 400 g / L
Chloride ion (Cl ⁻ ): 60 to 200 ppm by mass
Nika: 1-10ppm
(Bis (3-sulfopropyl) disulfide (SPS): 10-100 ppm as required)
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: 1.5-5 m / sec
In this specification, the rest of the electrolytic solution, the plating solution, the silane coupling treatment solution, the solution used for the treatment for forming the release layer and the treatment solution for the surface treatment is water unless otherwise specified.

The electrolytic drum used at this time has a root mean square height Sq of the drum surface of 1.0 μm or less, preferably 0.70 μm or less. In the electrolytic drum having the root mean square height Sq on its surface, first, the surface of a titanium or stainless steel drum is polished with a polishing belt having a count of P150 to P2500. At this time, the polishing belt is wound by a predetermined width in the drum width direction, and polishing is performed by rotating the drum while moving the polishing belt in the drum width direction at a predetermined speed. The rotational speed of the drum surface during the polishing is 120 to 195 m / min. The rotational speed of the drum surface is expressed by the following formula.
Rotational speed of drum surface (m / min) = number of revolutions per minute of electrolysis drum (times / min) × perimeter length of electrolysis drum per revolution (m / times)
Perimeter length of electrolysis drum per rotation (m / time) = diameter of electrolysis drum (m) × circumference π / 1 (time)
The polishing time is the product of the time required to pass one point (position in the width direction) on the drum surface and the number of passes in one pass of the polishing belt. The time for passing one point on the drum surface in one pass described above was a value obtained by dividing the width of the polishing belt by the moving speed of the polishing belt in the width direction of the drum. The single pass of the polishing belt means that the surface of the drum in the circumferential direction is polished once from one end in the drum axis (width) direction (width direction of the electrolytic copper foil) to the other end. It means polishing with a belt. That is, the polishing time is expressed by the following formula.
Polishing time (minutes) = width of polishing belt per pass (cm / time) / moving speed of polishing belt (cm / minute) × number of passes (times)

  The polishing time is 3 to 25 minutes in the present invention, and 6 to 25 minutes when the drum surface is wetted with water during polishing in the present invention. As an example of calculation of the polishing time, for example, when a moving speed is set to 20 cm / min with a polishing belt having a width of 10 cm, the polishing time for one pass at one point on the drum surface is 0.5 minutes. This is calculated by multiplying the total number of passes (for example, 0.5 minutes × 10 passes = 5 minutes). By increasing the number of the polishing belt and / or increasing the rotational speed of the drum surface and / or increasing the polishing time and / or wetting the drum surface with water during polishing The root mean square height Sq of the surface can be reduced. Also, by reducing the count of the polishing belt and / or reducing the rotational speed of the drum surface and / or shortening the polishing time and / or drying the drum surface during polishing The root mean square height Sq of the drum surface can be increased. Note that the root mean square height Sq can be reduced by increasing the polishing time. Further, the root mean square height Sq can be increased by shortening the polishing time. The count of the above-described abrasive belt means the particle size of the abrasive used in the abrasive belt. And the particle size of the said abrasives is based on FEPA (Federation of European Producers of Abbreviations) -standard 43-1: 2006, 43-2: 2006.

  Also, the root mean square height Sq can be reduced by wetting the drum surface with water during polishing. Also, the root mean square height Sq can be increased by drying the drum surface during polishing.

The root mean square height Sq of the electrolytic drum surface can be measured as follows.
-A resin film (polyvinyl chloride) is swollen by immersing it in a solvent (acetone).
-The swollen resin film is brought into contact with the surface of the electrolytic drum. After the acetone is volatilized from the resin film, the resin film is peeled off, and a replica of the electrolytic drum surface is collected.
-The replica is measured with a laser microscope, and the value of the root mean square height Sq is measured.
The value of the root mean square height Sq of the obtained replica is taken as the root mean square height Sq of the electrolytic drum surface.

Further, the ratio (Sq / Rsm) of the root mean square height Sq, Sq and the average interval Rsm of the irregularities (Sq / Rsm) can be adjusted by the above electrolysis conditions. If the electrolysis time (copper thickness) and / or current density is increased within the above range, Sq and Sq / Rsm increase. On the other hand, if the chloride ion concentration, the glue concentration, the SPS concentration and / or the electrolyte solution linear velocity are increased within the above range, Sq and Sq / Rsm tend to decrease. These electrolysis conditions may be adjusted according to the required degree of peelability and the required adhesion to the laminated member.
Further, the above-described Sq may be adjusted by performing mechanical polishing such as buffing or chemical polishing such as etching on the first surface and / or the second surface of the metal foil. (The term “polishing” here includes those that increase the degree of surface irregularities.)

<Method for producing rolled copper foil>
The metal foil (raw foil) may be a rolled copper foil (rolled metal foil). The rolled copper foil (rolled metal foil) controls the oil film equivalent at the time of the final cold rolling, controls the Sq of the rolling roll of the final cold rolling, and the workability of the final cold rolling. By controlling, 2 of the 1st surface which is a surface where the release layer of a metal foil is not formed, and / or the 2nd surface which is the surface where the release layer is scheduled to be formed The root mean square height Sq can be 1.6 μm or less, 1.0 μm or less, 0.70 μm or less, and / or 0.01 μm or more, or 0.25 μm or more. By increasing the oil film equivalent at the time of final cold rolling, and / or by increasing the value of Sq of the rolling roll of final cold rolling, and / or by reducing the workability of final cold rolling, The root mean square height of the first surface, which is the surface on which the release layer of the metal foil is not to be formed, and / or the second surface, which is the surface on which the release layer is to be formed. The value of Sq can be increased. By reducing the oil film equivalent at the time of final cold rolling, and / or by reducing the value of Sq of the rolling roll of final cold rolling, and / or by increasing the workability of final cold rolling, The root mean square height of the first surface, which is the surface on which the release layer of the metal foil is not to be formed, and / or the second surface, which is the surface on which the release layer is to be formed. The value of Sq can be reduced.
Also, after the final cold rolling, the first surface that is the surface on which the release layer of the metal foil is not to be formed and / or the second surface that is the surface on which the release layer is to be formed Alternatively, the above-described Sq may be adjusted by performing mechanical polishing such as buffing or chemical polishing such as etching. (The term “polishing” here includes those that increase the degree of surface irregularities.)

Next, the release layer that can be used in the present invention will be described.
(1) Silane compound At least one selected from the group consisting of a silane compound represented by the following formula, a hydrolysis product of the silane compound and a condensation product of the hydrolysis product (hereinafter simply referred to as a silane compound) or By forming the release layer including two or more, when the metal foil and the resin base material are bonded together, the adhesiveness is appropriately reduced, 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 of a hydrocarbon group Is a hydrocarbon group substituted with a halogen atom, and R ³ and R ⁴ are each independently a hydrocarbon group selected from the group consisting of a halogen atom, an alkoxy group, an alkyl group, a cycloalkyl group and an aryl group, or (A hydrocarbon group in which one or more hydrogen atoms of a hydrocarbon group are substituted with a halogen atom.)

  The silane compound needs to 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 metal 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 metal 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 substrate and the metal foil to the above-mentioned range, the silane compound has three alkoxy groups and the above 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.

Examples of the alkoxy group include, but are not limited to, methoxy group, ethoxy group, n- or iso-propoxy group, n-, iso- or tert-butoxy group, n-, iso- or neo-pentoxy group, n-hexoxy. Group, cyclohexyloxy group, n-heptoxy group, n-octoxy group, etc., linear, branched, or cyclic carbon number of 1 to 20, preferably 1 to 10, more preferably 1 to 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, an n-octyl group, and an n-decyl group.

  Examples of the cycloalkyl group include, but are not limited to, cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, cyclooctyl groups, and the like. An alkyl group is mentioned.

  As the aryl 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 Lan, 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 metal foil tends to decrease when a silane compound that has undergone hydrolysis and condensation after a sufficient stirring time has been used. Therefore, the peel strength can be adjusted by adjusting the stirring time. Although it is 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 it is not limited, the density | concentration in the aqueous solution of a silane compound can be 0.01-10.0 volume%, and can be 0.1-5.0 volume% typically.

  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 in a pH range of 3.0 to 10.0. From the standpoint that no special pH adjustment is necessary, it is preferable to set the pH in the range of 5.0 to 9.0, which is near neutral, and more preferable to set the pH in the range of 7.0 to 9.0. .

(2) Compound having two or less mercapto groups in the molecule The release layer is constituted by using a compound having two or more mercapto groups in the molecule, and the resin base material and the metal 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 interposed between the resin substrate and the metal foil and bonded, 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 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 metal 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.

  The thiol has one mercapto group in the molecule and is represented by R-SH, for example. 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.

  A thiocarboxylic acid is one in which a hydroxyl group of an organic carboxylic acid is substituted with a mercapto group, and is represented by R-CO-SH, for example. 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.

  The dithiocarboxylic acid is one in which two oxygen atoms in the carboxy group of the 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 an organic disulfonic acid are each substituted with a mercapto group, 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 -A linear or branched alkyl group having 1 to 20, preferably 1 to 10, more preferably 1 to 5 carbon atoms, such as a hexyl group, an n-octyl group, and an n-decyl group. .

  Moreover, as a cycloalkyl group, although it is not limited, C3-C10, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, Preferably it is C5-C7 Of the cycloalkyl group.

  Further, examples of the aromatic hydrocarbon group suitable as R 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. -20, preferably 6-14 aryl groups are mentioned, and these hydrocarbon groups may contain either or both of a hydroxyl group and an amino group.

  Moreover, 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 2 or less mercapto groups in the molecule include 3-mercapto-1,2propanediol, 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. Among these, 3-mercapto-1,2 propanediol is preferable from the viewpoint of water solubility and waste disposal.

  In the step of forming the release layer, the compound having 2 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 metal foil, and the compound having two or less mercapto groups in the molecule. The peel strength can be adjusted by adjusting the concentration. Although it is 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 in a pH range of 3.0 to 10.0. From the standpoint that no special pH adjustment is necessary, it is preferable to set the pH in the range of 5.0 to 9.0, which is near neutral, and more preferable to set the pH in the range of 7.0 to 9.0. .

(3) Metal alkoxide Release layer, aluminate compound, titanate compound, zirconate compound, hydrolysis product of aluminate compound, hydrolysis product of titanate compound, hydrolysis product of zirconate compound having the structure shown in the following formula At least one or two selected from the group consisting of a product, a condensate of a hydrolysis product of an aluminate compound, a condensate of a hydrolysis product of a titanate compound and a condensate of a hydrolysis product of a zirconate compound It is good also as a structure included above, or the structure which was individual or mixed. Hereinafter, the condensate of the hydrolysis product is also simply referred to as a metal alkoxide. By adhering the resin base material and the metal 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 of the hydrocarbon group Is a hydrocarbon group substituted with a halogen atom, M is any one of Al, Ti, and Zr, n is 0, 1 or 2, and m is an integer of 1 or more and a valence of M or less. And at least one of R ¹ is an alkoxy group. m + n is the valence of M. The valence of M is 3 for Al and 4 for Ti and Zr.

  The metal alkoxide needs to 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 metal 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 to 2 pieces. This is because when there are three or more hydrocarbon groups, the adhesion between the resin base material and the metal 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 substrate and the metal foil within 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).

  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 -A linear or branched alkyl group having 1 to 20, preferably 1 to 10, more preferably 1 to 5 carbon atoms, such as a hexyl group, an n-octyl group, and an n-decyl group. .

  Moreover, as a cycloalkyl group, although it is not limited, C3-C10, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, Preferably it is C5-C7 Of the cycloalkyl group.

In addition, 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 of the aryl group include 6 to 20, preferably 6 to 14, 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), dimethyl methoxy aluminum, triethoxy aluminum, methyl diethoxy aluminum Ethyldiethoxyaluminum, n- or iso-propyldiethoxy Luminium, 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 diiso Ropoxyaluminum, decyldiisopropoxyaluminum, phenyldiisopropoxyaluminum, alkyl-substituted phenyldiisopropoxyaluminum (eg, p- (methyl) phenyldiisopropoxyaluminum), dimethylisopropoxyaluminum, (3,3,3- Trifluoropropyl) dimethoxyaluminum, and tridecafluorooctyldiethoxyaluminum, methyldichloroaluminum, dimethylchloroaluminum, dimethylchloroaluminum, phenyldichloroaluminum, dimethylfluoroaluminum, dimethylbromoaluminum, diphenylbromoaluminum, and 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, Tiltlyethoxytitanium, 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, hexyltriiso Propoxy titanium, octyltriisopropoxy titanium, decyl triisopropoxy titanium, phenyl triisopropoxy titanium, alkyl substituted phenyl triisopropoxy titanium (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, n Or iso-propyltriethoxyzirconium, n-, iso- or tert-butyltriethoxyzirconium, pentyltriethoxyzirconium, hexyltriethoxyzirconium, octyltriethoxyzirconium, decyltriethoxyzirconium, phenyltriethoxyzirconium, alkyl-substituted phenyltri Ethoxyzirconium (eg, p- (methyl) phenyltriethoxyzirconium), dimethyldiethoxyzirconium, tetraisopropoxyzirconium, methyltriisopropoxyzirconium, ethyltriisopropoxyzirconium, n- or iso-propyltriethoxyzirconium, n- , Iso- or tert-butyltriisopropoxyzirconium, pentyltriisopropoxydi Konium, 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 hydrolyzed products Examples thereof include condensates of these products and hydrolysis products thereof. 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 base material and the metal 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 necessary, it is preferable to set the pH in the range of 5.0 to 9.0, which is near neutral, and more preferable to set the pH 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 metal foil has a roughened layer, a heat-resistant layer, a rust preventive layer on the first surface of the metal foil and / or on the second surface of the metal foil and / or between the metal foil and the release layer. One or more layers selected from the group consisting of a layer, a chromate treatment layer, and a silane coupling treatment 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.
(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 78-196 g / L
Cu 20-50g / L
H ₂ SO ₄ 50-200 g / L
Arsenic 0.7-3.0g / L
(Electroplating temperature 1) 30-76 ° C
(Current condition 1) Current density 35 to 105 A / dm ² (above the limit 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 roughened particles from falling off and improve the peel strength. The covering plating conditions are described below.
・ Liquid composition 2
CuSO ₄ .5H ₂ O 88-352 g / 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 (less than the limit current density of the bath)
(Plating time 1) 1 to 240 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 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. 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 . Further, 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 nickel - in adhesion amount of nickel in the zinc alloy layer is preferably from ^{0.5mg / m 2 ~500mg / m 2} , 1mg / m 2 ~50mg / m 2 - zinc alloy layer or the nickel containing More preferably.

For example heat-resistant layer and / or anticorrosive layer has coating weight of 1 mg / m ² -100 mg / m ^2, preferably from 5 mg / m ² and to 50 mg / m ² of nickel or nickel alloy layer, the adhesion amount is 1 mg / m ² to 80 mg / m ^2, preferably it may be obtained by sequentially laminating a tin layer of ^{5mg / m 2 ~40mg / m 2} , wherein the nickel alloy layer of nickel - molybdenum, nickel - zinc, nickel - molybdenum - cobalt You may be comprised by any one of these. The heat-resistant layer and / or anticorrosive layer, it is ^{preferably, 10mg / m 2 ~70mg / m} 2 total deposition amount of nickel or nickel alloy and tin is 2mg / m ² ~150mg / m 2 It is more preferable. Further, the heat-resistant layer and / or the rust-preventing layer is preferably [nickel or nickel adhesion amount in nickel or nickel alloy] / [tin adhesion amount] = 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 an epoxy silane, an amino silane, a methacryloxy silane, or a mercapto silane. 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, N (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) Limethoxysilane, 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 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 between the resin base material and the metal foil can be further improved.

  Further, the surface of a metal foil, a roughened particle layer, a heat-resistant layer, a rust-preventing layer, a silane coupling treatment layer, a chromate treatment layer or a release layer is provided with International Publication Nos. WO2008 / 053878, JP2008-111169A, Patent No. Surface treatments described in Japanese Patent 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. Thus, the metal foil of the present invention includes a surface-treated metal foil.

  A resin layer is provided on the surface of one or more layers selected from the group consisting of a roughening treatment layer, a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer provided on the first surface of the metal foil. It may be done.

  The resin layer provided on the first surface of the metal 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. There may be. 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 metal 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 metal foil and hardly causes voids or bubbles that may cause blistering. For example, when the resin layer is provided on the surface of the metal foil, 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. By providing the aforementioned resin layer between the insulating substrate laminated on the metal foil and the metal foil, the resin layer follows the surface of the metal foil even when an insulating substrate that does not easily follow the surface roughness of the metal foil is used. Therefore, it is effective because it is possible to make it difficult for voids and bubbles to be generated between the metal foil and the insulating substrate.

  Further, the resin layer provided on the first surface of the metal foil may contain a thermosetting resin or a thermoplastic resin. The resin layer on the surface of the metal foil may contain a thermoplastic resin. The resin layer on the surface of the metal 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 metal foil is, for example, International Publication No. WO2008 / 004399, International Publication No. WO2008 / 053878, International Publication No. WO2009 / 084533, JP-A-11-5828, JP-A-11-140281, Patent 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. 2002-179744, Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003-304068, Japanese Patent No. 3992225 No., JP 2003-249739, JP 4136509, JP 2004-82687, JP 4025177, JP 2004-349654, JP 4228660, JP 2005-262506, JP 457007. No. 2005-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication Nos. WO 2004/005588, JP 2006-257153 A, JP 2007-326923 A, JP 2008-1111169 A, Patent No. 5024930. No., 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, Japanese Patent No. 5180815. No., International Publication Number WO2008 / 114858, International Publication Number WO2009 / 008471, Japanese Patent Application Laid-Open No. 2011-14727, International Publication Number WO2009 / 001850, International Publication Number WO2009 / 145 79, substances described in International Publication Nos. WO2011 / 068157 and JP2013-19056 (resins, resin curing agents, compounds, curing accelerators, dielectrics, reaction catalysts, crosslinking agents, polymers, prepregs, skeleton 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 laminating a metal foil with a release layer and a resin substrate provided on the metal foil with a release layer. 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 metal 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.

(Printed wiring board manufacturing method)
In one aspect, the method for producing a printed wiring board of the present invention includes a step of bonding an insulating substrate to the metal foil with a release layer of the present invention, and peeling the metal foil with a release layer from the insulating substrate without etching. Thus, the method includes a step of obtaining an insulating substrate in which the surface profile of the metal foil with a release layer is transferred to the peeling surface, and a step of forming a circuit on the peeling surface side of the insulating substrate to which the surface profile is transferred. With such a configuration, physical peeling of the resin base material when the metal foil is bonded to the resin base material is possible, and in the step of removing the metal foil from the resin base material, the metal foil is applied to the surface of the resin base material. The metal foil can be removed at a good cost without impairing the surface profile transferred from the surface. In the manufacturing method, the circuit may be formed by a plating pattern. In this case, after forming a plating pattern, a desired circuit can be formed using the plating pattern to produce a printed wiring board. Further, the circuit may be formed with a printed pattern. In this case, for example, after a print pattern is formed using an ink jet containing conductive paste or the like in the ink, a desired printed circuit is formed using the print pattern, and a printed wiring board can be manufactured.
In the present specification, the “surface profile” refers to an uneven surface shape.

  In yet another aspect of the method for producing a printed wiring board of the present invention, a step of bonding an insulating substrate to the metal foil with a release layer of the present invention, and etching the metal foil with a release layer from the insulating substrate Without peeling off the surface, and obtaining the insulating substrate in which the surface profile of the metal foil with a release layer is transferred to the peeling surface, and providing the build-up layer on the peeling surface side of the insulating substrate to which the surface profile is transferred. Prepare. With such a configuration, the resin base material can be physically peeled when the metal foil is bonded to the resin base material, and transferred to the surface of the resin base material in the step of removing the metal foil from the resin base material. It is possible to remove the metal foil at a favorable cost without impairing the profile of the metal foil surface. Moreover, even if the resin component of the resin base material and the resin component of the buildup layer are different or the same due to the predetermined uneven surface transferred to the resin base material, both have good adhesion. It becomes possible to paste them together.

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. In addition, the conductive layer, the wiring pattern, or the circuit described above and an insulator such as a resin may be provided in any manner.
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 metal 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 a resin (layer).
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 by using a laser and / or a drill for a plurality of electrically conductive layers, wiring patterns, or circuits, the through holes and / or blind vias are formed. Alternatively, electrical connection may be made by forming conductive plating such as copper plating.

  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 resin may contain an inorganic substance and / or an organic substance. The resin constituting the build-up layer is formed of a material having a low relative dielectric constant such as LCP (liquid crystal polymer), fluororesin, low dielectric constant polyimide, polyphenylene ether, cycloolefin polymer, or polytetrafluoroethylene. Also good. In recent years, with the expansion of high-frequency products, materials with low dielectric constants such as LCP (liquid crystal polymer), fluororesin, low dielectric constant polyimide, polyphenylene ether, cycloolefin polymer, or polytetrafluoroethylene (Teflon: registered trademark) are printed. The movement to take in the structure of the substrate is becoming active. At that time, since these materials are thermoplastic, shape change is unavoidable during hot press processing, and LCP (liquid crystal polymer), fluororesin, low dielectric constant polyimide, polyphenylene ether, cycloolefin polymer or polytetrafluoroethylene alone However, there is a basic mass production problem that the production yield is not improved by the substrate configuration in the above. In the manufacturing method of the present invention described above, for such a problem, a thermosetting resin such as an epoxy resin is used as a resin substrate, and it is bonded to this to provide excellent high frequency characteristics. Therefore, it is possible to provide a printed wiring board that can prevent deformation of the shape at the time of adding.

According to still another aspect of the method for producing a printed wiring board of the present invention, the metal foil with a release layer of the present invention or the metal foil of the present invention is insulated from the release layer side or the second surface side of the metal foil. A step of bonding the substrate 1, a step of forming a circuit on the first surface side of the metal foil with the release layer or the metal foil laminated with the insulating substrate 1, and the circuit by covering the circuit with the insulating substrate 2. A step of embedding in the insulating substrate 2, a step of peeling the insulating substrate 1 from the metal foil with a release layer or the metal foil to expose the metal foil with a release layer or the metal foil, and the exposed release A step of removing the metal foil with a mold layer or the metal foil.
Moreover, the manufacturing method of the printed wiring board of this invention is another one side. WHEREIN: On the metal foil with a release layer of this invention, or the metal foil of this invention, the said release layer side or the 2nd surface side of the said metal foil The step of laminating the insulating substrate 1 from the step, the step of laminating the dry film on the first surface side of the metal foil of the metal foil with the release layer or the metal foil laminated the insulating substrate 1, and after patterning the dry film A step of forming a circuit, a step of peeling the dry film to expose the circuit, a step of embedding the circuit in the insulating substrate 2 by covering the exposed circuit with the insulating substrate 2, and a metal with a release layer Peeling the insulating substrate 1 from the foil or the metal foil to expose the metal foil with the release layer or the metal foil, and removing the exposed metal foil with the release layer or the metal foil. Including.
In this way, a metal foil that provides a release layer on the metal foil whose surface unevenness is controlled and enables physical peeling of the resin substrate when the metal foil is bonded to the resin substrate is used. Thus, it is possible to manufacture a printed wiring board having a fine circuit at a favorable cost. Moreover, the physical peeling of the resin base material when the metal foil is bonded to the resin base material becomes possible, and the metal foil surface transferred to the surface of the resin base material in the step of removing the metal foil from the resin base material It is possible to remove the metal foil at a favorable cost without impairing the profile.

Here, the specific example of the manufacturing method of the printed wiring board using the metal foil with a release layer of this invention is demonstrated in detail using drawing.
First, as shown to FIG. 1-A, the metal foil (1st layer) with a release layer laminated | stacked on the resin substrate from the release layer side is prepared.
Next, as shown in FIG. 1-B, a resist is applied onto the metal foil, exposed and developed, and the resist is etched into a predetermined shape.
Next, as shown in FIG. 1-C, after the plating for the circuit is formed, the resist is removed to form a circuit plating having a predetermined shape.
Next, as shown in FIG. 2-D, an embedded resin is provided on the metal foil so as to cover the circuit plating (so that the circuit plating is buried), and then a resin layer is laminated, followed by another release layer. A metal foil (second layer) is bonded from the first metal foil side.
Next, as shown to FIG. 2-E, a resin substrate is peeled from the metal foil with a 2nd release layer.
Next, as shown in FIG. 2-F, laser drilling is performed at a predetermined position of the resin layer to expose the circuit plating and form a blind via.
Next, as shown in FIG. 3G, copper is embedded in the blind via to form a via fill.
Next, as shown in FIG. 3H, circuit plating is formed on the via fill as shown in FIGS. 1-B and 1-C.
Next, as shown to FIG. 3-I, a resin substrate is peeled from the metal foil with a 1st release layer.
Next, as shown in FIG. 4-J, the metal foils on both surfaces are removed by flash etching to expose the surface of the circuit plating in the resin layer.
Next, as shown in FIG. 4K, bumps are formed on the circuit plating in the resin layer, and copper pillars are formed on the solder. Thus, the printed wiring board using the metal foil with a release layer of this invention is produced.
In the above printed wiring board manufacturing method, “metal foil” is replaced with resin substrate, “resin substrate” is replaced with metal foil, and a circuit is formed on the surface of the metal foil with a release layer on the resin substrate side. It is also possible to manufacture a printed wiring board by embedding a circuit with a resin.

  As another metal foil with a release layer (second layer), the metal foil with a release layer of the present invention may be used, a conventional metal foil with a release layer may be used, and a normal copper foil. May be used. Further, one or more circuits may be formed on the second layer circuit shown in FIG. 3H, and these circuits may be formed by a semi-additive method, a subtractive method, a partial additive method, or a modified semi-conductor method. You may carry out by any method of an additive method.

  According to the method for manufacturing a printed wiring board as described above, since the circuit plating is embedded in the resin layer, for example, when removing the metal foil by flash etching as shown in FIG. Circuit plating is protected by the resin layer and its shape is maintained, which facilitates formation of a fine circuit. Further, since the circuit plating is protected by the resin layer, the migration resistance is improved, and the continuity of the circuit wiring is satisfactorily suppressed. For this reason, formation of a fine circuit becomes easy. When the metal foil is removed by flash etching as shown in FIGS. 4-J and 4-K, the exposed surface of the circuit plating has a shape recessed from the resin layer. Further, copper pillars can be easily formed thereon, and the production efficiency is improved.

  A known resin or prepreg can be used as the embedding resin (resin). For example, a prepreg that is a glass cloth impregnated with BT (bismaleimide triazine) resin or BT resin, an ABF film or ABF manufactured by Ajinomoto Fine Techno Co., Ltd. can be used. Moreover, the resin layer and / or resin and / or prepreg as described in this specification can be used for the embedding resin (resin).

  Moreover, the metal foil with a release layer used for the first layer may have a substrate or a resin layer on the surface of the metal foil with a release layer. By having the said board | substrate or resin layer, since the metal foil with a mold release layer used for the first layer is supported and it becomes difficult to wrinkle, there exists an advantage that productivity improves. As the substrate or resin layer, any substrate or resin layer can be used as long as it has an effect of supporting the metal foil with a release layer used in the first layer. For example, the carrier, prepreg, resin layer or known carrier, prepreg, resin layer, metal plate, metal foil, inorganic compound plate, inorganic compound foil, organic compound plate described in the present specification as the substrate or resin layer, Organic compound foils can be used.

Moreover, the schematic diagram of the semi-additive method using the surface profile of metal foil is shown in FIG. In the semi-additive method, a surface profile of a metal foil is used. Specifically, first, the metal foil with a release layer of the present invention is laminated on the resin base material from the release layer side to produce a laminate. Next, the metal foil of the laminate is removed by etching or peeled off. Next, after the surface of the resin base material to which the metal 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 substrate 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 release surface of the resin base material to which the metal 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 metal 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 the semi-additive method, the metal foil according to the present invention or the metal foil with a release layer according to the present invention and a resin base material are prepared. Process,
Laminating a resin base material from the metal foil or the metal foil with a release layer from the side where the surface profile is controlled or the release layer side;
After laminating the metal foil and the resin base material, the step of removing the metal foil by etching or peeling off,
Providing a through hole or / and a blind via on the exposed or peeled surface of the resin substrate generated by removing or peeling the metal 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 or the like 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, the metal foil according to the present invention or the metal foil with a release layer according to the present invention and a resin base material are prepared. Process,
Laminating a resin base material from the metal foil or the metal foil with a release layer from the side where the surface profile is controlled or the release layer side;
After laminating the metal foil and the resin base material, the step of removing the metal foil by etching or peeling off,
For the exposed or peeled surface of the resin substrate produced by removing or peeling the metal foil, the step of washing the resin substrate surface with dilute sulfuric acid or the like 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 this way, a circuit is formed on the release surface of the resin base material after the metal foil is peeled off, and a printed circuit forming substrate and a semiconductor package circuit forming substrate 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, the metal foil or the metal foil with a release layer is provided on the side or the surface where the surface profile is controlled. A step of laminating a resin base material from the mold layer side,
Laminating a resin base material from the metal foil or the metal foil with a release layer from the side where the surface profile is controlled or the release layer side;
After laminating the metal foil and the resin base material, the step of removing the metal foil by etching or peeling off,
For the exposed or peeled surface of the resin base material produced by removing or peeling the metal foil, the step of washing the resin base material surface with dilute sulfuric acid, etc.
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, the release layer is partially or entirely 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. Moreover, it is preferable to use the washing | cleaning method which can remove a part or all of the mold release layer of this invention.

  In this way, a circuit is formed on the exposed or peeled surface of the resin base material after the metal foil is removed or peeled off by a semi-additive method or a full additive method, and a printed circuit forming substrate and a circuit forming substrate for a semiconductor package are formed. Can be produced. 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.

  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.

-Production of raw foil (copper foil before surface treatment) (Examples 1-16, 19, Comparative Examples 1-3)
A rotating drum (electrolytic drum) made of titanium was prepared. Next, polishing was performed under the electrolytic drum surface control conditions shown in Table 1 to obtain an electrolytic drum having a predetermined root mean square height Sq on the surface. Specifically, the surface of the electrolytic drum was polished by a count polishing belt described in Table 1. At this time, the polishing belt was wound by a predetermined width in the drum width direction, and was polished by rotating the drum while moving the polishing belt in the drum width direction. Table 1 shows the rotational speed of the drum surface during the polishing. The polishing time was the product of the time required to pass one point on the drum surface in one pass and the number of passes based on the width of the polishing belt and the moving speed of the polishing belt. Here, a single pass of the polishing belt means that the circumferential surface of the rotating drum is polished by one polishing belt from one end in the axial direction (width direction of the electrolytic copper foil) to the other end. It means to do.
That is, the polishing time is expressed by the following formula.
Polishing time (minutes) = width of polishing belt per pass (cm / time) / moving speed of polishing belt (cm / minute) × number of passes (times)

  In Examples 2, 5, 8, 14 to 16, and Comparative Example 3, the surface of the drum was wetted with water when the surface of the electrolytic drum was polished.

Next, an electrode was placed in the electrolytic cell with the electrolytic drum and a predetermined inter-electrode distance around the drum. Next, in Examples 1 to 10, 12, 14 to 16, and Comparative Examples 2 and 3, electrolysis was performed in the electrolytic cell under the following conditions, and copper was deposited on the surface of the electrolytic drum while rotating the electrolytic drum. The current density and electrolyte linear velocity at this time are shown in Table 1.
(Electrolytic solution composition)
Cu 120g / L
H ₂ SO ₄ 100 g / L
Chloride ion ^(Cl -) 70 ppm
Fish glue 6ppm
Electrolyte temperature 60 ℃
In Examples 11 and 19 and Comparative Example 1, 80 ppm of the additive bis (3-sulfopropyl) disulfide (SPS) was added in addition to the electrolytic solution.
In Example 13, the same electrolyte solution composition as in Examples 1 to 10, 12, 14 to 16, and Comparative Examples 2 and 3 was used except that the chloride ion concentration was 2 ppm or less and 2 ppm of fish was added instead of fish. Using.

  Next, the copper deposited on the surface of the rotating electrolytic drum was peeled off to continuously produce an electrolytic copper foil having a thickness shown in Table 1.

(Example 17)
The tough pitch copper ingot was repeatedly rolled and annealed to a thickness of 0.2 mm. Then, the final cold rolling was performed, and the thickness of the copper foil was 80 μm. The workability of the final cold rolling was 60%. Further, the degree of rolling process = (plate thickness before rolling−plate thickness after rolling) / plate thickness before rolling × 100% oil film equivalent 20000.
The oil film equivalent is represented by the following formula.
Oil film equivalent = {(rolling oil viscosity [cSt]) × (sheet feeding speed [mpm] + roll peripheral speed [mpm])} / {(roll biting angle [rad]) × (yield stress of material [kg / mm ² ])}
The rolling oil viscosity [cSt] is a kinematic viscosity at 40 ° C.
The roll used in the final cold rolling was a roll having a surface of Sq = 0.20 μm. Adjustment of the surface of a rolling roll can make the value of Sq small by making grinding time longer than usual when grinding a rolling roll. Further, the value of Sq can be increased by shortening the grinding time.

(Example 18)
The ingot of the copper alloy (brass) of Zn 25 mass%, the remainder Cu and inevitable impurities was repeatedly rolled and annealed to a thickness of 0.2 mm. Then, the final cold rolling was performed under the following conditions, and the thickness of the copper foil was 80 μm. The workability of the final cold rolling was 60%. Rolling degree = (sheet thickness before rolling−sheet thickness after rolling) / sheet thickness before rolling × 100%
The oil film equivalent was 20000.
The oil film equivalent is represented by the following formula.
Oil film equivalent = {(rolling oil viscosity [cSt]) × (sheet feeding speed [mpm] + roll peripheral speed [mpm])} / {(roll biting angle [rad]) × (yield stress of material [kg / mm ² ])}
The rolling oil viscosity [cSt] is a kinematic viscosity at 40 ° C.
The roll used in the final cold rolling was a roll having a surface of Sq = 0.20 μm. Adjustment of the surface of a rolling roll can make the value of Sq small by making grinding time longer than usual when grinding a rolling roll. Further, the value of Sq can be increased by shortening the grinding time.

-Surface treatment Next, as the surface treatment, each of the followings is applied to any one surface of the raw foil if it is an electrolytic copper foil on the M surface (deposition surface, mat surface) of the raw foil, and if it is a rolled copper foil. Under the conditions, any of roughening treatment, heat resistance treatment, rust prevention treatment, silane coupling treatment, resin layer formation treatment, or a combination of each treatment 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. In Examples 5, 7, 8, and 10, the S surface (drum side surface, shiny surface, and glossy surface) was also subjected to the same process as described above for the M surface. In the examples and comparative examples in which the release layer was formed, the surface opposite to the side on which the release layer of copper foil was formed was the first surface, and the surface on which the release layer of copper foil was formed was The second side. Moreover, in the Example and comparative example in which the release layer was not formed, the surface on the S surface side of the electrolytic copper foil was the first surface, and the surface on the M surface side of the electrolytic copper foil was the second surface.

(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 78-118 g / L
Cu 20-30g / L
H ₂ SO ₄ 12g / L
Arsenic 1.0-3.0 g / 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, in order to prevent the roughened particles from falling off and improve the peel strength, the plating was performed in a copper electrolytic bath made of sulfuric acid and copper sulfate. 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 to 60 seconds

(2) Heat resistance treatment (barrier treatment)
(Liquid composition)
Ni 13g / L
Zn 5g / L
pH 2
(Electroplating conditions)
Temperature 40 ℃
Current density 8A / dm ²

(3) Rust prevention treatment (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 (liquid composition)
Tetraethoxysilane content 0.4%
pH 7.5
Application method Spraying solution

(5) Formation of release layer [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. A mold layer A was formed. The stirring time from when the silane compound was dissolved in water to before application was 30 hours, the alcohol concentration in the aqueous solution was 10 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, an aqueous solution of sodium 1-dodecanethiolsulfonate (sodium 1-dodecanethiolsulfonate: 3 wt%), and 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 dissolving the aluminate compound 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 a titanate compound n-decyl-triisopropoxy titanium as a metal alkoxide, an aqueous solution of n-decyl-triisopropoxy titanium (n-decyl-triisopropoxy titanium 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 application 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 (n-propyl-tri-n-butoxyzirconium concentration: 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 formation treatment In Example 1, after the release layer was formed, 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, pyridine 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, Silica Chemical) is contained in a solid content weight ratio of 35 and a solid content weight ratio of block copolymerized 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 is coated on the release layer forming surface, dried in a nitrogen atmosphere at 120 ° C. for 3 minutes, and at 160 ° C. for 3 minutes, and finally heat-treated at 300 ° C. for 2 minutes to obtain a resin layer. The copper foil provided with was produced. The thickness of the resin layer was 2 μm.

(7) Various evaluations ・ Evaluation of the root mean square height Sq of both surfaces of the metal foil and the ratio (Sq / Rsm) of the root mean square height Sq to the average interval Rsm of the irregularities (Sq / Rsm) When surface treatment such as roughening treatment is performed, the surface on the side subjected to surface treatment after the surface treatment, and when a release layer is formed, the release layer after providing the release layer is The root mean square height Sq and the ratio (Sq / Rsm) of the mean square root height Sq to the average spacing Rsm (Sq / Rsm) of the surface provided side) are a laser microscope LEXT OLS4100 manufactured by Olympus Corporation. It measured using. Rsm was measured by the JIS B 0601 2001 compliant mode, and Sq was measured by the ISO25178 compliant mode. In addition, the average value of the values of Rsm and Sq measured at arbitrary 10 locations for both Rsm and Sq was taken as the value of Rsm and Sq. The measurement length of Rsm was 258 μm, and the measurement area of Sq was 258 μm long × 258 μm wide. And based on the obtained value, the ratio (Sq / Rsm) of the root mean square height Sq and the average interval Rsm of unevenness was calculated. In addition, the temperature at the time of measurement was 23-25 degreeC.

-Circuit forming property on metal foil The laminated body 1 was manufactured by laminating a resin base material on the surface (second surface) of the metal foil with a release layer or the second surface of the metal foil. Then, the surface opposite to the side laminated with the resin base of the metal foil with release layer (first side), or the side opposite to the side laminated with the resin base of metal foil (first side) ), A resist was applied, exposed and developed, and the resist was etched in a line shape. Next, after forming a Cu plating for a circuit having a thickness of 12 μm, the resist is removed, whereby 20 lines each having a line-and-space (L / S) of 12 μm / 12 μm and a length of 1 mm are obtained. The book was formed. Thereafter, a bismaleimide triazine resin prepreg was laminated by thermocompression bonding so that the circuit was embedded on the surface of the metal foil with release layer formed side or the surface of the metal foil formed circuit side. Then, after peeling the resin base material laminated | stacked on the surface (2nd surface) of the above-mentioned metal foil with a mold release layer, or the 2nd surface of metal foil, the metal foil with a mold release layer exposed Alternatively, the metal foil was removed by etching with ferric chloride. The etching described above was performed until the circuit and the bismaleimide triazine resin prepreg around the circuit were completely exposed. Subsequently, the difference (μm) between the maximum value and the minimum value of the circuit width as viewed from the circuit upper surface was measured, and the average value was measured at five locations. If the difference between the maximum value and the minimum value was 2 μm or less, it was determined that the circuit had good circuit linearity, and “◎” was given. In addition, when the difference between the maximum value and the minimum value exceeds 2 μm and is 3 μm or less, “◎” is given. In addition, when the difference between the maximum value and the minimum value is more than 3 μm and not more than 4 μm, it is defined as “◯◯”. In addition, when the difference between the maximum value and the minimum value exceeds 4 μm and is 5 μm or less, “◯” is given. In addition, when the difference between the maximum value and the minimum value exceeds 5 μm, the mark is “x”.

-Circuit peeling on metal foil;
A laminate 1 was manufactured by laminating a resin base material on the surface (second surface) on the release layer side of the metal foil with a release layer or on the second surface of the metal foil. Then, the surface opposite to the side laminated with the resin base of the metal foil with release layer (first side), or the side opposite to the side laminated with the resin base of metal foil (first side) ), A resist was applied, exposed and developed, and the resist was etched in a line shape. Next, after forming a Cu plating for a circuit having a thickness of 12 μm, the resist is removed, whereby 20 lines each having a line-and-space (L / S) of 12 μm / 12 μm and a length of 1 mm are obtained. The book was formed. At this time, when the resist was removed, the number of times the circuit was peeled from the surface of the metal foil with a release layer and the surface of the metal foil was measured. If the surface of the metal foil with release layer and the number of times the circuit is peeled from the surface of the metal foil is 0 out of 10 times, “◎◎”, and if it is 1 out of 10 times, “◎”, In case of 2 to 3 times out of 10 times, “◯” was given, and in case of 4 times out of 10 times, “x” was given.

-Manufacture of the laminated body 2 Each of the following resin base materials 1-3 was bonded together to the surface (2nd surface) of the release layer side of each metal foil, or the 2nd surface of metal 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 peel strength In accordance with IPC-TM-650, the normal peel strength when peeling the resin base material from the copper foil with the tensile tester Autograph 100 was measured for the laminate 2, and the metal was measured according to the following criteria. The peelability of the foil was evaluated. The results are shown in the column of “Peel strength” in Table 1. The peel strength is preferably 2 to 200 gf / cm.
A: The range was from 2 to 200 gf / cm.
X: It was 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. The fracture mode of the resin is preferably “interface”.

- circuit peeling, the peeled surface of the resin base material 1-3 after evaluation the separation of the substrate blistering, the plating solution [solution composition, Cu: 50g / L, H 2 SO 4: 50g / L, Cl: 60ppm) using A copper plating pattern (line / space = 40 μm / 40 μm) was formed (Example 1). In Example 1, as in the semi-additive method described above, before the formation of the copper plating pattern, cleaning and electroless copper plating are performed on the peeling surfaces of the resin substrates 1 to 3 after peeling. gave. Thereafter, the dry film was laminated on the electroless copper plating layer. Then, exposure and development were performed to etch the dry film in a line shape, and the dry film at a place where a copper plating pattern was to be formed was removed. Next, the aforementioned copper plating pattern was formed by electroplating on the electroless copper plating layer not covered with the dry film. And after formation of a copper plating pattern, the electroless copper plating layer of the part which did not form a dry film and a copper plating pattern was removed. In addition, a printing pattern (line / space = 40 μm / 40 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 “◎”. Although circuit peeling or substrate swelling occurred slightly (3 or less in one sample), what could be used as a product by selecting the location to be used was 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 products were evaluated as “x”.
Table 1 shows the test conditions and evaluation results.

(Evaluation results)
Examples 1-19 are the examples of metal foil whose root mean square height Sq of the 1st surface is 0.01-1 micrometer, the circuit formation property on metal foil is favorable, and the circuit on metal foil is Peeling was successfully suppressed. Examples 1 to 18 are examples in which a release layer is provided on the second surface side, or examples where Sq and / or Sq / Rsm of the second surface of the metal foil are controlled within a predetermined range. The peelability when physically peeling the metal foil from the resin base material was good, and circuit peeling and generation of substrate swelling could be suppressed satisfactorily. Example 19 is an example in which a release layer is provided on the second surface side, and the peelability when physically peeling the metal foil from the resin substrate was good.
In Comparative Examples 1 and 2, the root mean square height Sq of the first surface exceeded 1 μm, and the circuit formability on the metal foil was poor. In Comparative Example 3, the root mean square height Sq of the first surface was less than 0.01 μm, and circuit peeling on the metal foil could not be sufficiently suppressed.

Claims (31)

Having a first side and a second side;
A metal foil having a root mean square height Sq of 0.01 μm or more and 1 μm or less of the first surface; and
A release layer provided on the second surface of the metal foil,
A metal foil with a release layer.   2. The metal foil with a release layer according to claim 1, wherein the second foil has a root mean square height Sq of 0.25 μm to 1.6 μm.   The ratio of the root mean square height Sq of the 2nd surface of the said metal foil and the average space | interval Rsm of an unevenness | corrugation (Sq / Rsm) has 0.03 or more and 0.40 or less surface unevenness | corrugation. Metal foil with release layer.   The metal foil with a release layer according to any one of claims 1 to 3, wherein the thickness of the metal foil is 1 µm or more and 105 µm or less.   The metal foil with a release layer according to any one of claims 1 to 4, wherein the metal foil is a copper foil.   A group consisting of a roughening treatment layer, a heat-resistant layer, a rust prevention layer, a chromate treatment layer and a silane coupling treatment layer on the first surface of the metal foil and / or between the metal foil and the release layer. Metal foil with a release layer as described in any one of Claims 1-5 which provided the 1 or more types of layer selected from.   A resin layer is provided on one or more layers selected from the group consisting of the roughening treatment layer, the heat-resistant layer, the rust prevention layer, the chromate treatment layer, and the silane coupling treatment layer provided on the first surface of the metal foil. The metal foil with a release layer according to claim 6.   The metal foil with a release layer according to claim 7, wherein the resin layer is an adhesive resin, a primer, or a semi-cured resin. 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 of the hydrocarbon group A hydrocarbon group in which an atom is substituted with a halogen atom, M is any one of Al, Ti, and Zr, n is 0, 1 or 2, and m is 1 or more and a valence of M or less. And at least one of R ¹ is an alkoxy group, m + n is the valence of M. The valence of M is 3 for Al and 4 for Ti and Zr.)
Aluminate compound, titanate compound, zirconate compound, hydrolysis product of aluminate compound, hydrolysis product of titanate compound, hydrolysis product of zirconate compound, condensate of hydrolysis product of aluminate compound, titanate The compound according to any one of claims 1 to 8, comprising at least one or two or more selected from the group consisting of a condensate of a hydrolysis product of a compound and a condensate of a hydrolysis product of a zirconate compound. Metal foil with 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 of the hydrocarbon group A hydrocarbon group substituted with a halogen atom, and R ³ and R ⁴ are each independently selected from the group consisting of a halogen atom, an alkoxy group, an alkyl group, a cycloalkyl group and an aryl group; Alternatively, it is a hydrocarbon group in which one or more hydrogen atoms of the hydrocarbon group are substituted with a halogen atom.)
It contains at least one or two or more selected from the group consisting of a silane compound, a hydrolysis product of the silane compound and a condensate of the hydrolysis product shown in any one of claims 1 to 9. The metal foil with a release layer as described.   The metal foil with a release layer according to any one of claims 1 to 10, wherein the release layer is formed using a compound having two or less mercapto groups in the molecule.   The metal foil with a release layer according to any one of claims 1 to 11, wherein a resin layer is provided on a surface of the release layer.   The metal foil with a release layer according to claim 12, wherein the resin layer is an adhesive resin, a primer, or a semi-cured resin.   A metal foil having a first surface and a second surface, wherein the root mean square height Sq of the first surface is 0.01 μm or more and 1 μm or less.   The metal foil according to claim 14, wherein the root mean square height Sq of the second surface is 0.25 µm or more and 1.6 µm or less.   The ratio of the root mean square height Sq of the second surface of the metal foil to the average interval Rsm (Sq / Rsm) of the unevenness has a surface unevenness of 0.03 or more and 0.40 or less. Metal foil.   The thickness of the said metal foil is 1 micrometer or more and 105 micrometers or less, The metal foil as described in any one of Claims 14-16.   The metal foil according to any one of claims 14 to 17, wherein the metal foil is a copper foil.   The first surface of the metal foil and / or the second surface of the metal foil was selected from the group consisting of a roughening treatment layer, a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer. The metal foil according to any one of claims 14 to 18, wherein one or more layers are provided.   A resin layer is provided on one or more layers selected from the group consisting of the roughening treatment layer, the heat-resistant layer, the rust prevention layer, the chromate treatment layer, and the silane coupling treatment layer provided on the first surface of the metal foil. The metal foil according to claim 19.   The metal foil with a release layer according to any one of claims 1 to 13, or the metal foil according to any one of claims 14 to 20, and the metal foil with a release layer or the metal foil. And a laminated body provided with the resin base material.   The laminate according to claim 21, wherein the resin base material is a prepreg or contains a thermosetting resin.   The printed wiring board provided with the metal foil with a release layer as described in any one of Claims 1-13, or the metal foil as described in any one of Claims 14-20.   A semiconductor package comprising the printed wiring board according to claim 23.   An electronic device comprising the printed wiring board according to claim 23 or the semiconductor package according to claim 24. A step of bonding an insulating substrate to the metal foil with a release layer according to any one of claims 1 to 13 or the metal foil according to any one of claims 14 to 20,
An insulating substrate in which the metal foil with a release layer or the surface profile of the metal foil is transferred to a release surface by peeling the metal foil with the release layer or the metal foil from the insulating substrate without etching. Obtaining and
A method for manufacturing a printed wiring board, comprising a step of forming a circuit on the peeling surface side of an insulating substrate onto which the surface profile has been transferred.   27. The method for manufacturing a printed wiring board according to claim 26, wherein the circuit formed on the peeling surface side of the insulating substrate to which the surface profile is transferred is a plating pattern or a printing pattern. A step of bonding an insulating substrate to the metal foil with a release layer according to any one of claims 1 to 13 or the metal foil according to any one of claims 14 to 20,
An insulating substrate in which the metal foil with a release layer or the surface profile of the metal foil is transferred to a release surface by peeling the metal foil with the release layer or the metal foil from the insulating substrate without etching. Obtaining and
A method for manufacturing a printed wiring board, comprising a step of providing a build-up layer on the release surface side of the insulating substrate onto which the surface profile has been transferred.   29. The method for manufacturing a printed wiring board according to claim 28, wherein the resin constituting the build-up layer includes a liquid crystal polymer, a fluororesin, a low dielectric constant polyimide, a polyphenylene ether, a cycloolefin polymer, or polytetrafluoroethylene. The metal foil with a release layer according to any one of claims 1 to 13 or the metal foil according to any one of claims 14 to 20, the release layer side or the second surface of the metal foil. Bonding the insulating substrate 1 from the side,
Forming the circuit on the first surface side of the metal foil with the release layer or the metal foil laminated with the insulating substrate 1;
Embedding the circuit in the insulating substrate 2 by covering the circuit with the insulating substrate 2;
Peeling the insulating substrate 1 from the metal foil with the release layer or the metal foil to expose the metal foil with the release layer or the metal foil, and
The manufacturing method of the printed wiring board including the process of removing the said exposed metal foil with a release layer or the said metal foil. The metal foil with a release layer according to any one of claims 1 to 13 or the metal foil according to any one of claims 14 to 20, the release layer side or the second surface of the metal foil. Bonding the insulating substrate 1 from the side,
A step of laminating a dry film on the metal foil with a release layer on which the insulating substrate 1 is laminated or on the first surface side of the metal foil of the metal foil;
Forming a circuit after patterning the dry film;
Peeling the dry film to expose the circuit;
A step of embedding the circuit in the insulating substrate 2 by covering the exposed circuit with the insulating substrate 2;
Peeling the insulating substrate 1 from the metal foil with the release layer or the metal foil to expose the metal foil with the release layer or the metal foil, and
The manufacturing method of the printed wiring board including the process of removing the said exposed metal foil with a release layer or the said metal foil.