KR20180090210A - Metal foil with release layer, metal foil, laminate, printed wiring board, semiconductor package, method of manufacturing printed wiring board and electronic device - Google Patents

Abstract

The present invention provides a metal foil capable of physical separation of a resin substrate when the metal foil is bonded to the resin substrate by controlling an unevenness state of the surface of the metal foil and providing a release layer on the metal foil. Therefore, the present invention produces a printed wiring board having a fine circuit at good cost. The metal foil comprises: the first surface and the second surface, wherein a square root mean square root height (Sq) of the first surface is equal to or more than 0.01 μm and equal to or less than 1 μm; and the release layer provided on the second surface of the metal foil.

Description

TECHNICAL FIELD OF THE INVENTION [0001] 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 apparatus and a manufacturing method of a printed wiring board. ELECTRONIC DEVICE}

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 manufacturing method of a printed wiring board.

In the circuit formation method of the printed wiring board and the semiconductor package substrate, the subtractive method is the mainstream. However, in recent years, as a result of further fine wiring, a modified semi-additive process (M-SAP) And new methods such as

Among these new circuit forming methods, the following are examples of the semi-additive method using the surface profile of the metal foil, which is the latter. That is, first, the metal foil laminated on the resin substrate is etched all over, and an electroless copper plating layer for continuing the perforation is provided by drilling a surface of the etched base material onto which the metal foil surface profile has been transferred with a laser or the like, Coated with a dry film, and the dry film in the circuit formation portion was removed by UV exposure and development. Electroless copper plating was provided on the electroless copper plated surface not covered with the dry film, the dry film was peeled off, (Flash etching, quick etching) of the electroless copper plating layer by an etchant containing hydrogen peroxide and the like to form a fine circuit (Patent Document 1, Patent Document 2).

Patent Document 1: JP-A-2006-196863 Patent Document 2: JP-A-2007-242975

However, in the conventional semi-additive method using the profile of the surface of the metal foil, there is still room for investigation for manufacturing a printed circuit board having a fine circuit at a good cost.

As a result of intensive studies, the inventors of the present invention have controlled the unevenness state of the metal foil surface. In addition, a release layer is provided on the surface of the metal foil opposite to the surface where the unevenness is controlled, so that the resin substrate can be physically peeled off when the metal foil is bonded to the resin base. It has been found that it is possible to produce a printed circuit board having a fine circuit at a good cost by using the above-described metal foil as follows. That is, after bonding the surface side having the release layer of the metal foil to the resin substrate, a circuit was formed on the surface of the metal foil where the above-mentioned unevenness state was controlled. Then, the resin was laminated so that the circuit was embedded on the surface of the metal foil on which the circuit was formed. Thereafter, the metal foil was peeled off from the resin substrate and the metal foil was removed to expose the above-described circuit, thereby making it possible to manufacture a printed wiring board having a fine circuit at a good cost.

 The present invention completed on the basis of the above findings is a metal foil having a first surface and a second surface in one aspect and having a square root mean square height (Sq) of the first surface of not less than 0.01 탆 and not more than 1 탆, And a release layer provided on the second surface.

In one embodiment of the metal foil with a release layer according to the present invention, the square root mean square height (Sq) of the second surface of the metal foil is 0.25 탆 or more and 1.6 탆 or less.

The metal foil with a release layer according to another embodiment of the present invention is characterized in that the surface roughness (Sq / Rsm) of the square root mean square root height (Sq) of the second surface of the metal foil to the mean spacing (Rsm) .

In the metal foil with a release layer according to another embodiment of the present invention, the thickness of the metal foil is 1 占 퐉 or more and 105 占 퐉 or less.

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

The metal foil with a release layer according to another embodiment of the present invention is the metal foil with a release layer according to still another embodiment of the present invention, wherein 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 with a release layer according to another embodiment of the present invention is a metal foil with a release layer provided on the first surface of the metal foil, wherein the one kind selected from the group consisting of the roughening treatment layer, heat resistant layer, rust preventive layer, chromate treatment layer and silane coupling treatment layer A resin layer is provided on the above layer.

In another embodiment of the metal foil with a release layer of the present invention, the resin layer is a resin for bonding, a primer, or a resin in a semi-cured state.

In a further embodiment of the metal foil with a release layer according to the present invention, the release layer has the following formula:

[Chemical Formula 1]

(Wherein R ¹ is an alkoxy group or a halogen atom, R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or a hydrocarbon group in which at least one hydrogen atom of the hydrocarbon group is substituted with a halogen atom, M is any one of Al, Ti and Zr, n is 0, 1 or 2, m is an integer of not less than 1 and not more than M, at least one of R ¹ is an alkoxy group, m + The mantissa of M is 3 for Al, and 4 for Ti and Zr.)

A hydrolysis product of a titanate compound, a hydrolysis product of a zirconate compound, a hydrolysis product of a hydrolysis product of an aluminate compound, an aluminate compound, A condensate of a hydrolysis product of a titanate compound, and a condensate of a hydrolysis product of a zirconate salt compound.

In a further embodiment of the metal foil with a release layer according to the present invention, the release layer has the following formula:

(2)

(Wherein R ¹ is an alkoxy group or a halogen atom, R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or a hydrocarbon group in which at least one hydrogen atom of the hydrocarbon group is substituted with a halogen atom, R ³ and R ⁴ each independently represent 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 at least one hydrogen atom of the hydrocarbon group is substituted with a halogen atom. )

, A hydrolysis product of the silane compound, and a condensate of the hydrolysis product.

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

In 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 another embodiment of the metal foil with a release layer of the present invention, the resin layer is a resin for bonding, a primer, or a resin in a semi-cured state.

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

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

In another embodiment of the metal foil of the present invention, the surface roughness of the second surface of the metal foil is not less than 0.03 and not more than 0.40, wherein a ratio (Sq / Rsm) of a root mean square height (Sq) .

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

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

In the metal foil of the present invention, it is preferable that the metal foil is formed 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 on the first surface of the metal foil and / At least one selected layer is provided.

In the metal foil of the present invention, it is preferable that the metal foil further comprises at least one layer 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 A resin layer is provided.

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

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

In another aspect, the present invention is a printed wiring board comprising the metal foil with a release layer of the present invention or the metal foil of the present invention.

According to another aspect of the present invention, there is provided a semiconductor package including the printed wiring board of the present invention.

According to another aspect of the present invention, there is provided an electronic device including the printed wiring board of the present invention or the semiconductor package of the present invention.

According to another aspect of the present invention, there is provided a method of manufacturing a metal foil, comprising the steps of: bonding an insulating substrate to a metal foil with a release layer of the present invention or a metal foil of the present invention; A step of obtaining an insulating substrate on which the surface profile of the metal foil or the metal foil is transferred to the rear surface and a step of forming a circuit on the front surface of the insulating substrate to which the surface profile has been transferred to be.

In a method of manufacturing a printed wiring board of the present invention, the circuit formed on the release face side of the insulating substrate onto which the surface profile is transferred is a plating pattern or a printed pattern.

According to another aspect of the present invention, there is provided a method of manufacturing a metal foil, comprising the steps of: bonding an insulating substrate to a metal foil with a release layer of the present invention or a metal foil of the present invention; A step of obtaining an insulating substrate on which a surface profile of the metal foil with the release layer or the metal foil is transferred on a rear surface thereof and a step of providing a buildup layer on the release surface side of the insulating substrate onto which the surface profile is transferred, Method.

The method for producing a printed wiring board according to the present invention is characterized in that the resin constituting the buildup layer contains a liquid crystal polymer, a fluorine resin, a low dielectric constant polyimide, a polyphenylene ether, a cycloolefin polymer or polytetrafluoroethylene do.

According to another aspect of the present invention, there is provided a method for manufacturing a metal foil, comprising the steps of: bonding an insulating substrate (1) to a metal foil with a release layer or a metal foil of the present invention from the side of the release layer or the second surface of the metal foil; A step of forming a circuit on the first metal foil or the metal foil on which the first metal foil is laminated, the step of covering the circuit with the insulating substrate (2) and embedding the circuit in the insulating substrate (2) A step of peeling the insulating substrate (1) from the metal foil 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.

According to another aspect of the present invention, there is provided a method for manufacturing a metal foil, comprising the steps of: bonding an insulating substrate (1) to a metal foil with a release layer or a metal foil of the present invention from the side of the release layer or the second surface of the metal foil; Laminating a metal foil with a release layer or a dry film on the first surface side of the metal foil, a step of forming a circuit after patterning the dry film,

Exposing the circuit by peeling the dry film; covering the exposed circuit with an insulating substrate (2) to embed the circuit in the insulating substrate (2); removing the metal foil or the metal foil A step of peeling the 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 possible to provide a metal foil that can physically peel the resin base material when the metal foil is bonded to the resin base material by controlling the unevenness state of the surface of the metal foil and by providing a release layer on the metal foil, A printed wiring board can be manufactured.

Figs. 1A to 1C are schematic views of a wiring board section in a process up to the removal of a circuit plating resist, which is related to a concrete example of a printed wiring board manufacturing method using the copper foil with a release layer of the present invention.
Fig. 2D is a schematic view of a section of a wiring board in a process from a resin related to a concrete example of the method for producing a printed wiring board using the copper foil with a release layer of the present invention to a laser perforation from a laminate of a copper foil with a release layer of a second layer .
3G to 3I are schematic views of a wiring board section in a process from the via fill formation to the release layer peeling of the first layer, which is related to a specific example of the printed wiring board production method using the copper foil with a release layer of the present invention.
4A to 4K are schematic views of a wiring board section in a process from flash etching to bump copper filler formation, which is related to a specific example of a printed wiring board manufacturing method using the copper foil with a release layer of the present invention.
5 is a schematic view showing a semi-additive method using a copper foil profile.

(Metal foil)

The metal foil of the present invention is a metal foil having a first surface and a second surface, and the square root mean square height (Sq) of the first surface side surface is not less than 0.01 탆 and not more than 1 탆. Thus, the surface roughness of the surface of the metal foil was controlled by controlling the square root mean square height (Sq) of the first surface. The above-described metal foil can be used as follows to make a printed circuit board having a fine circuit at a good cost. That is, a release layer is provided on the surface of the metal foil opposite to the surface on which the unevenness state is controlled, so that the resin substrate can be physically peeled off when the metal foil is bonded to the resin substrate. After bonding the surface side having the release layer of the metal foil to the resin substrate, a circuit is formed on the surface of the metal foil on which the unevenness state of the surface is controlled. Then, the resin is laminated so that the circuit is embedded on the surface of the metal foil on which the circuit is formed. Thereafter, the metal foil is peeled off from the resin substrate and the metal foil is removed to expose the above-described circuit, whereby a printed wiring board can be manufactured. When a printed wiring board is manufactured by the above-described method, it is possible to form a circuit without providing the electroless plating layer on the resin substrate by electroless plating. Therefore, the manufacturing cost of the printed wiring board can be reduced. In addition, the circuit described above is buried in resin to protect the circuit. Therefore, when the metal foil is removed by etching or the like, the circuit is not eroded well by etching or the like. Therefore, a fine circuit can be formed.

Herein, the terms "first surface of metal foil" and "second surface of metal foil" refer to a surface treatment layer such as a roughening treatment layer, a heat resistant layer, a rust prevention layer, a chromate treatment layer, a silane coupling treatment layer, (Surface of the outermost layer) after the surface treatment layer is provided. 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 square root mean square height Sq of the first surface of the metal foil of the present invention is not less than 0.01 mu m, the adhesion to the resin in which the above-mentioned circuit or circuit is embedded is improved. As a result, the case where the resin in which the circuit or the circuit is embedded from the metal foil peels off or falls off is reduced. In the metal foil of the present invention, since the square root mean square height (Sq) of the first surface is 1 占 퐉 or less, circuit formability is improved.

On the first surface of the metal foil, if the square root mean square root height (Sq) is less than 0.01 탆, the deviation of the irregularities of the metal foil surface may be too small. Therefore, the adhesion between the metal foil and the resin in which the above-mentioned circuit or circuit is embedded may deteriorate. As a result, the resin in which the circuit or the circuit is embedded from the metal foil may peel off or fall off. On the first surface of the metal foil, if the square root mean square root height (Sq) exceeds 1 占 퐉, the irregularities of the metal foil surface may become too rugged. As a result, in a portion where the convex portion of the metal foil surface is large, it may be necessary to etch the metal foil for a longer period of time. As a result, erosion of the circuit due to etching or the like is increased, resulting in deterioration in wiring formability. The square root mean square root height (Sq) of the first surface of the metal foil is preferably 0.95 탆 or less, more preferably 0.93 탆 or less, preferably 0.90 탆 or less, preferably 0.85 탆 or less, Preferably not more than 0.70 mu m, more preferably not more than 0.70 mu m, more preferably not more than 0.70 mu m, more preferably not more than 0.70 mu m, more preferably not more than 0.70 mu m, More preferably 0.45 mu m or less, more preferably 0.35 mu m or less, more preferably 0.32 mu m or less, more preferably 0.30 mu m or less, more preferably 0.25 mu m or less, and most preferably 0.24 mu m or less Preferably 0.22 占 퐉 or smaller, more preferably 0.20 占 퐉 or smaller, and 0.19 占 퐉 or smaller Preferably 0.18 mu m or less, more preferably 0.17 mu m or less, and more preferably 0.15 mu m or less. The square root mean square root height (Sq) of the first surface of the metal foil is preferably 0.015 탆 or more, more preferably 0.02 탆 or more, and is preferably 0.025 탆 or more, more preferably 0.03 탆 or more, Mu m or more, more preferably 0.045 mu m or more, and more preferably 0.05 mu m or more.

The second surface of the metal foil preferably has a square root mean square height (Sq) of 0.25 탆 or more and 1.6 탆 or less. Since the square root mean square root height Sq of the second surface of the metal foil is 0.25 to 1.6 占 퐉, the metal foil and the resin base material can be easily peeled from the surface of the resin substrate after peeling off the metal foil, A lamination member such as a circuit, a resin, and a buildup layer follows the resin substrate surface with no gaps (or a very small gap), and a lamination member such as a circuit, a resin, and a buildup layer can be provided on the resin substrate surface with good adhesion .

If the square root mean square root height (Sq) of the second surface of the metal foil is less than 0.25 占 퐉, there is a problem that the irregularities on the surface of the resin substrate obtained by peeling the metal foil after bonding the metal foil and the resin substrate are small and the adhesion with other resins becomes insufficient If the thickness exceeds 1.6 mu m, the peelability of the metal foil after the metal foil is peeled off after the metal foil is bonded to the resin base material is deteriorated. In addition to the deterioration of the surface of the resin base material after peeling off the metal foil, There is a possibility that a problem that a lamination member such as an up layer does not conform to the concavo-convex shape may occur. The square root mean square root height (Sq) is preferably 0.30 to 1.4 占 퐉, more preferably 0.4 to 1.0 占 퐉, and still more preferably 0.4 to 0.96 占 퐉.

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 mean spacing (Rsm) of the recesses and protrusions is 0.03 or more and 0.40 or less. Since the ratio (Sq / Rsm) of the root mean square height (Sq) of the second surface of the metal foil to the average spacing (Rsm) of the recesses and protrusions is 0.03 or more and 0.40 or less, the peelability , A laminated member such as a circuit, a resin, or a buildup layer, which is transferred to the surface of the resin substrate after the metal foil is peeled off, is followed without gaps (or with a very small gap) and a laminated member such as a circuit, So that it can be provided on the surface of the resin substrate by adhesion.

When the ratio (Sq / Rsm) of the square root mean square root height (Sq) of the second surface of the metal foil to the average interval (Rsm) of the recesses and protrusions is less than 0.03, the metal foil and the resin base material are bonded, The adhesion between the resin substrate and a lamination member such as a circuit or a resin or a buildup layer becomes insufficient. When the ratio exceeds 0.40, the peeling property when the metal foil is peeled after bonding the metal foil and the resin substrate is deteriorated There is a problem that the concavo-convex shape of the surface of the resin substrate after the metal foil is peeled off is too deep, so that the lamination member such as circuit, resin, build-up layer does not conform to the concavo-convex shape. The ratio (Sq / Rsm) of the root mean square height (Sq) of the second surface of the metal foil to the average spacing (Rsm) of the recesses and protrusions is preferably 0.05 or more, more preferably 0.10 or more. The ratio (Sq / Rsm) of the root mean square root height (Sq) of the second surface of the metal foil to the mean spacing (Rsm) of the recesses and protrusions is preferably 0.25 or less, more preferably 0.24 or less, and still more preferably 0.20 or less.

(Metal foil with a release layer)

The metal foil with a release layer according to the present invention comprises a metal foil having a first surface and a second surface and a square root mean square root height (Sq) of the first surface of not less than 0.01 탆 and not more than 1 탆, And a release layer for releasing the resin base material when the resin base material is bonded to the metal foil from the release layer side. Thus, the surface roughness of the surface of the metal foil was controlled by controlling the square root mean square height (Sq) of the first surface. In addition, a release layer is provided on the metal foil surface opposite to the surface where the unevenness is controlled, and physical separation of the resin base material when the metal foil is bonded to the resin base material is made possible. The above-described metal foil can be used as follows to make a printed circuit board having a fine circuit at a good cost. That is, after bonding the surface side having the release layer of the metal foil to the resin substrate, a circuit is formed on the surface of the metal foil on which the surface irregularities are controlled. Then, the resin is laminated so that the circuit is embedded on the surface of the metal foil on which the circuit is formed. Thereafter, the metal foil is peeled from the resin substrate and the metal foil is removed to expose the above-described circuit, thereby making it possible to produce a printed wiring board. When the printed wiring board is manufactured by the above-described method, it is possible to form a circuit without providing the electroless plating layer on the resin substrate by electroless plating. Therefore, the manufacturing cost of the printed wiring board can be reduced. In addition, the above-mentioned circuit is embedded in the resin and the circuit is protected. Therefore, when the metal foil is removed by etching or the like, the circuit is not eroded well by etching or the like. Therefore, a fine circuit can be formed.

The metal foil of the metal foil with a release layer has a square root mean square height (Sq) of the first surface, which is the side on which the release layer is not formed, of not less than 0.01 mu m, so that the adhesion to the resin in which the above- . As a result, peeling or peeling off of the resin in which the circuit or circuit is embedded from the metal foil is reduced. In addition, since the square root mean square height (Sq) of the first surface which is the side of the metal foil on which the release layer is not formed is 1 占 퐉 or less, circuit formability is improved.

If the square root mean square root height (Sq) is less than 0.01 mu m on the first side of the metal foil on which the release layer is not formed, the deviation of the concave and convex on the metal foil surface may be too small. When the deviation of the irregularities on the surface of the metal foil becomes too small, there may be a case where a high convex portion or a deep concave portion contributing 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 is decreased. The adhesion between the metal foil and the resin in which the above-mentioned circuit or circuit is embedded may deteriorate. As a result, the resin in which the circuit or the circuit is embedded from the metal foil may peel off or fall off. If the square root mean square root height (Sq) of the metal foil on the first surface, which is the side on which the release layer is not formed, exceeds 1 占 퐉, the deviation of the irregularities of the metal foil surface may become too large. As a result, when the metal foil is removed, it may be necessary to etch the metal foil surface for a longer time in a portion where the convex portion of the metal foil surface is large. As a result, erosion of the circuit due to etching or the like is increased, and the wiring formability is sometimes deteriorated. The square root mean square root height (Sq) of the first surface, which is the side on which the release layer is not formed, is preferably 0.95 占 퐉 or less, more preferably 0.93 占 퐉 or less and preferably 0.90 占 퐉 or less, Preferably not more than 0.75 mu m, more preferably not more than 0.70 mu m, more preferably not more than 0.68 mu m, more preferably not more than 0.67 mu m, preferably not more than 0.65 mu m, more preferably not more than 0.60 mu m, Preferably not more than 0.45 mu m, more preferably not more than 0.40 mu m, more preferably not more than 0.35 mu m, preferably not more than 0.32 mu m, more preferably not more than 0.30 mu m, and preferably not more than 0.25 mu m Preferably 0.24 占 퐉 or less, more preferably 0.22 占 퐉 or less, and most preferably 0.20 占 퐉 or less Is preferred, it 0.19㎛ or less is preferable, and preferably not more than 0.18㎛, it is more preferable that not more than 0.17㎛ or less, and 0.15㎛. The square root mean square root height (Sq) of the first surface, which is the side on which the release layer is not formed, is preferably at least 0.015 탆, more preferably at least 0.02 탆, more preferably at least 0.025 탆, It is preferably 0.035 mu m or more, more preferably 0.04 mu m or more, more preferably 0.045 mu m or more, and still more preferably 0.05 mu m or more.

It is preferable that the square root mean square root height (Sq) of the second face, which is the face on which the release layer of the metal foil is formed, is 0.25 탆 or more and 1.6 탆 or less. Since the square root mean square root height (Sq) of the second surface of the metal foil on which the release layer is formed is 0.25 to 1.6 m, A lamination member such as a circuit, a resin, and a buildup layer follows the surface of the resin substrate without gaps (or with a very small gap) by the convexo-concave shape transferred to the resin substrate surface, So that it can be provided on the surface of the resin substrate by adhesion.

If the square root mean square root height (Sq) of the second surface, which is the side on which the release layer of the metal foil is formed, is less than 0.25 占 퐉, the surface roughness of the resin substrate obtained by peeling the metal foil after bonding the metal foil and the resin base is small, There is a possibility that the adhesion between the metal foil and the resin substrate becomes insufficient. On the other hand, if the thickness exceeds 1.6 占 퐉, the peelability at the time of peeling the metal foil after bonding the metal foil to the resin substrate is deteriorated, The shape is too deep, and there is a possibility that a problem arises that a laminated member such as a circuit, a resin, and a buildup layer does not conform to the concavo-convex shape. The square root mean square root height (Sq) is preferably 0.30 to 1.4 탆, more preferably 0.4 to 1.0 탆, and even more preferably 0.4 to 0.96 탆.

It is preferable that the ratio (Sq / Rsm) of the square root mean square root height (Sq) of the second surface, which is the side on which the release layer of the metal foil is formed, and the mean spacing (Rsm) of the recesses and protrusions is 0.03 or more and 0.40 or less. Since the ratio (Sq / Rsm) of the square root mean square root height (Sq) of the second surface, which is the side on which the release layer of the metal foil is formed, to the average interval Rsm of the ruggedness is 0.03 or more and 0.40 or less, The laminate member such as circuit, resin, buildup layer, or the like is closely followed (or the gap is very small) by the convexo-concave shape transferred onto the resin substrate surface after peeling off the metal foil, A lamination member such as a build-up layer can be provided on the resin substrate surface with good adhesion.

If the ratio (Sq / Rsm) of the square root mean square root height (Sq) of the second surface, which is the side on which the release layer of the metal foil is formed, to the average spacing Rsm of the recesses and protrusions is less than 0.03, The surface irregularities of the resin substrate obtained by peeling the resin substrate are small and the adhesion between the resin substrate and a lamination member such as a circuit, a resin and a buildup layer becomes insufficient. On the other hand, when the thickness exceeds 0.40, The peelability at the time of peeling is deteriorated, and the concavity and convexity of the surface of the resin substrate after peeling the metal foil is too deep, so that there arises a problem that the laminated members such as circuit, resin and buildup layer do not conform to the concavo-convex shape. The ratio (Sq / Rsm) of the square root mean square root height (Sq) of the second surface, which is the side on which the release layer of the metal foil is formed, to the average spacing Rsm of the recesses and protrusions is preferably 0.05 or more and more preferably 0.10 or more. The ratio (Sq / Rsm) of the square root mean square root height (Sq) of the second surface and the average interval (Rsm) of the recesses and protrusions to the surface of the metal foil on which the release layer is formed is preferably 0.25 or less, More preferably 0.20 or less.

The metal foil (also called foil) is not particularly limited, but may be 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, Foil, cobalt alloy foil and the like can be used. In addition, a metal foil known as a metal foil can be used.

The thickness of the metal foil (fresh foil) is not particularly limited and may be, for example, 1 to 105 탆, 3 to 105 탆, or 5 to 105 탆. The thickness of the metal foil is preferably 9 to 70 mu m, more preferably 12 to 35 mu m, and even more preferably 18 to 35 mu m since it can be easily removed from the resin substrate. In addition, from the viewpoint of easy removal by etching or the like of the metal foil (fresh foil), the metal foil is preferably thin. For example, the thickness of the metal foil is preferably 105 占 퐉 or less, more preferably 70 占 퐉 or less, preferably 35 占 퐉 or less, more preferably 18 占 퐉 or less, and most preferably 12 占 퐉 or less. From the viewpoint that the metal foil (fresh foil) can be easily handled, the thickness of the metal foil is preferably thick. For example, the thickness of the metal foil is preferably 1 占 퐉 or more, more preferably 3 占 퐉 or more.

Hereinafter, the copper foil will be described as an example of the metal foil (fresh foil). The method for producing the metal foil (fresh foil) is not particularly limited, and for example, an electrolytic copper foil can be produced according to the following electrolysis conditions. The following methods are also applicable to metal foils other than copper foils (electrolytic metal foil, rolled metal foil).

≪ Electrolytic copper foil manufacturing method >

The electrolytic copper foil of the present invention is produced by electrolytically depositing copper from a copper sulfate plating bath onto a drum of titanium or stainless steel. The electrolytic condition is not particularly limited, but an electrolytic copper foil can be produced by the following conditions, for example.

Electrolyte composition:

Cu: 30 to 190 g / L

H ₂ SO ₄ : 100 to 400 g / L

Chloride ion (Cl ^-): 60 ~ 200 ppm by weight

Glue: 1 ~ 10ppm

(Optionally, bis (3-sulfopropyl) disulfide (SPS): 10 to 100 ppm)

Electrolyte temperature: 25 ~ 80 ℃

Electrolysis time: 10 to 300 seconds (Copper thickness to be deposited, adjusted by current density)

Current density: 50 to 150 A / dm 2

Electrolyte flux: 1.5 to 5 m / sec

In the present specification, the remaining amount of the electrolyte solution, the plating solution, the silane coupling treatment solution, the solution used for forming the release layer, and the treatment solution for surface treatment is water unless otherwise specified.

The square root mean square root height (Sq) of the surface of the drum used in this electrolytic drum is 1.0 占 퐉 or less, preferably 0.70 占 퐉 or less. The electrolytic drum having the square root mean square height (Sq) on its surface is first polished with an abrasive belt having the number of times P150 to P2500 on the surfaces of titanium and stainless steel drums. At this time, the abrasive belt is wound by a predetermined width in the width direction of the drum, and the abrasive belt is rotated at a predetermined speed in the width direction of the drum while rotating the drum. The rotation speed of the drum surface at the time of polishing is set at 120 to 195 m / min. The rotational speed of the drum surface is expressed by the following equation.

(Revolutions per minute) of the electrolytic drum (revolutions per minute) x circumferential length per revolution of the electrolytic drum (m / revolutions)

(M / rev) per one rotation of the electrolytic drum = diameter (m) of the electrolytic drum x circumference? / 1

The polishing time is the product of the passage time of one point (in the width direction) of the surface of the drum and the number of passes in one pass of the abrasive belt. The time for passing one point of the surface of the drum by the above-described one pass is a value obtained by dividing the width of the abrasive belt by the moving speed in the width direction of the abrasive belt drum. The one-time passage of the abrasive belt means that the circumferential surface of the drum is polished with a polishing belt from one end to the other end in the axis (width) direction of the drum (the width direction of the electrolytic copper foil) it means. That is, the polishing time is expressed by the following equation.

Polishing time (minute) = width of abrasive belt per pass (cm / rev) / moving speed of abrasive belt (cm / min) x number of passes (times)

The polishing time is 3 to 25 minutes in the present invention, and 6 to 25 minutes in the case of wetting the surface of the drum at the time of polishing in the present invention. As an example of the polishing time calculation, when the moving speed is 20 cm / min with a 10 cm wide polishing belt, the polishing time of one pass on one surface of the drum is 0.5 minutes. This is multiplied by the total number of passes (for example, 0.5 minutes x 10 passes = 5 minutes). It is possible to increase the number of abrasive belts and / or to increase the rotation speed of the drum surface, and / or to increase the polishing time, and / or by squashing the drum surface with water at the time of polishing, The mean square root height Sq can be reduced. It is also possible to reduce the number of grinding belts and / or lower the rotation speed of the drum surface, and / or to shorten the polishing time and / or to dry the drum surface during polishing, The square root mean square root height Sq can be increased. In addition, by making the polishing time longer, the square root mean square root height Sq can be reduced. In addition, the root-mean-square root height Sq can be increased by shortening the polishing time. The number of the above-mentioned abrasive belt means the particle size of the abrasive used in the abrasive belt. The particle size of the abrasive is in accordance with the Federation of European Producers of Abrasives (FEPA) standard 43-1: 2006, 43-2: 2006.

In polishing, the surface of the drum may be wetted with water to reduce the square root mean square root height (Sq). In addition, the surface of the drum can be dried at the time of polishing to increase the square root mean square root height (Sq).

The square root mean square height (Sq) of the electrolytic drum surface can be measured as follows.

· The resin film (polyvinyl chloride) is swelled by immersion in a solvent (acetone).

The swollen resin film is brought into contact with the surface of the electrolytic drum to peel off the resin film after the acetone has volatilized from the resin film, and the replica on the electrolytic drum surface is collected.

Measure the replicas with a laser microscope to determine the value of the root mean square height (Sq).

Then, the value of the square root mean square root height Sq of the obtained replica is taken as the square root mean square root height Sq of the electrolytic drum surface.

In addition, the ratio (Sq / Rsm) of the root-mean-square root height (Sq), Sq and the average spacing (Rsm) of the irregularities can be adjusted in accordance with the electrolysis conditions. If the electrolytic time (copper thickness) and / or current density is increased within the above range, Sq and Sq / Rsm become large. On the other hand, if the chloride ion concentration, the glue concentration, the SPS concentration, and / or the electrolyte flux are increased within the above range, Sq and Sq / Rsm tend to decrease. These electrolytic conditions may be adjusted according to the degree of the required releasability and the adhesion with the required lamination member.

Further, the first and / or second surface of the metal foil may be subjected to chemical polishing such as mechanical polishing such as buff polishing or chemical polishing such as etching to adjust the above-described Sq (here, the polishing is performed by adding the degree of surface irregularities .

≪ Process for producing rolled copper foil &

The metallic foil (fresh foil) may be rolled copper foil (rolled metal foil). The rolled copper foil (rolled metal foil) controls the equivalence of the film in the final cold rolling and controls the Sq of the rolling roll of the final cold rolling and the final cold rolling so that the releasing layer of the metal foil The square root mean square root height (Sq) of the second surface, which is the side on which the release layer is to be formed, is 1.6 占 퐉 or less, 1.0 占 퐉 or less, 0.70 占 퐉 or less and / or 0.01 Mu m or more and 0.25 mu m or more. It is possible to increase the equivalence of the oil film at the final cold rolling and / or to increase the Sq value of the rolling roll of the final cold rolling and / or to decrease the degree of final cold rolling, It is possible to increase the value of the square root mean square root height Sq of the first face, which is a face to be a predetermined face, and / or the second face, which is a face to be formed with a release layer. By decreasing the film equivalent weight at the time of final cold rolling and / or by decreasing the value of the rolling roll Sq of the final cold rolling and / or by increasing the degree of processing of the final cold rolling, the releasing layer of the metal foil is not formed The value of the square root mean square root height (Sq) of the first face which is a face to be a predetermined face and / or the second face which is a face to which a release layer is to be formed can be made small.

After the final cold rolling, the first surface, which is the surface on which the release layer of the metal foil is to be formed, and / or the second surface, which is the surface to be formed with the release layer, is subjected to mechanical polishing such as buff polishing, Chemical polishing may be performed to adjust the above-described Sq (the polishing referred to here also includes adding the surface roughness).

Next, the release layer usable in the present invention will be described.

(1) Silane compound

A release layer comprising at least one or more selected from the group consisting of a silane compound represented by the following formula, a condensate of a hydrolysis product of a silane compound and a hydrolysis product (hereinafter simply referred to as a silane compound) Thus, when the metal foil and the resin base material are bonded to each other, the adhesiveness is moderately reduced and the peel strength can be controlled within the above range.

expression:

(3)

(Wherein R ¹ is an alkoxy group or a halogen atom, R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or a hydrocarbon group in which at least one hydrogen atom of the hydrocarbon group is substituted with a halogen atom, R ³ and R ⁴ each independently represent a hydrocarbon group in which at least one hydrogen atom in the hydrocarbon group or hydrocarbon group selected from the group consisting of a halogen atom, an alkoxy group, an alkyl group, a cycloalkyl group and an aryl group is substituted with a halogen atom.

The silane compound needs to have at least one alkoxy group. In the case where a substituent is constituted by a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom, The adhesion tends to be too low. It is necessary that the silane compound is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or at least one hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom. If the hydrocarbon group is not present, the adhesion between the resin substrate and the metal foil tends to increase. Further, the alkoxy group includes an alkoxy group in which at least one hydrogen atom is substituted with a halogen atom.

It is preferable that the silane compound has three alkoxy groups and one hydrocarbon group (one or more hydrogen atoms include a hydrocarbon group substituted with a halogen atom) Do. In terms of the above formula, both R ³ and R ⁴ are referred to as alkoxy groups.

The alkoxy group includes, but is not limited to, a methoxy group, an ethoxy group, an n- or iso-propoxy group, n-, iso- or tert-butoxy group, n-, iso- or neo- Branched or cyclic alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, .

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The alkyl group includes, but is not limited to, methyl, ethyl, n- or isopropyl, n-, iso- or tert-butyl, n-, iso- or neopentyl, n- An alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl and n-decyl groups.

Examples of the cycloalkyl group include, but are not limited to, cycloalkyl groups having 3 to 10 carbon atoms, preferably 5 to 7 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group .

Examples of the aryl group include an aryl group having 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms such as a phenyl group, a phenyl group substituted with an alkyl group (e.g., a trityl group, a xylyl group), a 1- or 2-naphthyl group, .

These hydrocarbon groups may be substituted with at least one hydrogen atom by a halogen atom, 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 phenyltrimethoxysilane, alkyl-substituted phenyltrimethoxysilane (for example, p- (methyl) phenyl (meth) acrylate, phenyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, Trimethoxysilane), methyltriethoxysilane, ethyltriethoxysilane, n- or iso-propyltriethoxysilane, n-, iso- or tert-butyltriethoxysilane, pentyltriethoxysilane, hexyl Phenyltriethoxysilane, alkyl-substituted phenyltriethoxysilane (e.g., p- (methyl) phenyltriethoxysilane), (3, 3,3-trifluoropropyl) trimethoxysilane, and tridecafluorooctyltriethoxysilane , Condensates of hydrolysis products of these, and condensation products thereof, such as methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, trimethylfluorosilane, dimethyldibromosilane, diphenyldibromosilane, And the like. Of 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. To increase the solubility in water, an alcohol such as methanol or ethanol may be added. The addition of alcohol is particularly effective when a silane compound having high hydrophobicity is used. The aqueous solution of the silane compound accelerates the hydrolysis of the alkoxy group by stirring, and the condensation of the hydrolysis product is promoted if the stirring time is long. In general, the use of a silane compound which has undergone hydrolysis and condensation through a sufficient stirring time tends to lower the peeling strength between the resin substrate and the metal foil. Therefore, the peeling strength can be adjusted by adjusting the stirring time. The stirring time after dissolving the silane compound in water can be, for example, from 1 to 100 hours, although not limited thereto, and typically from 1 to 30 hours. Naturally, there is a method of using without stirring.

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

The pH of the aqueous solution of the silane compound is not particularly limited and can be used on the acidic side or on the alkaline side. For example, at a pH in the range of 3.0 to 10.0. From the viewpoint that the pH adjustment is unnecessary in particular, the pH is preferably in the range of about 5.0 to 9.0, which is near neutral, and more preferably in the range of 7.0 to 9.0.

(2) a compound having two or less mercapto groups in the molecule

The releasing layer is constituted by using a compound having two or more mercapto groups in the molecule, and the resin substrate and the metal foil are bonded to each other through the releasing layer, whereby the adhesiveness is suitably decreased and the peeling strength can be controlled.

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 together, it is not suitable for the purpose of reducing the peel strength. This is because when a mercapto group is excessively present in a molecule, a sulfide bond, a disulfide bond or a polysulfide bond is formed by a chemical reaction between a mercapto group or between a mercapto group and a plate-like carrier or between a mercapto group and a metal foil It is considered that there is a case where the excessive peeling strength is increased due to the excessive formation of a three-dimensional crosslinked structure between the resin base material and the metal foil. Such an example is disclosed in Japanese Patent Laid-Open Publication 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 And at least one selected from these can be used.

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

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

Thiocarboxylic acid has a hydroxyl group of an organic carboxylic acid substituted by a mercapto group, for example, R-CO-SH. R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may contain a hydroxyl group or an amino group. Thiocarboxylic acid can also be used in the form of a salt. Further, compounds having two thiocarboxylic acid groups can be used.

The dithiocarboxylic acid is represented by R- (CS) -SH in which two oxygen atoms in the carboxyl group of the organic carboxylic acid are substituted with sulfur atoms. R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may contain a hydroxyl group or an amino group. In addition, dithiocarboxylic acid can be used in the form of a salt. Also, compounds having two dithiocarboxylic acid groups can be used.

The thiosulfonic acid is a compound in which the hydroxyl group of the organic sulfonic acid is substituted with a mercapto group, 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. The thiosulfonic acid can also be used in the form of a salt.

The dithiosulfonic acid is represented by R - ((SO ₂ ) -SH) _{2 in} which two hydroxyl groups of the organic disulfonic acid are each substituted with a mercapto group. R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may contain a hydroxyl group or an amino group. The two thiosulfuric acid groups may be bonded to the same carbon or may be bonded to different carbons, respectively. The dithiosulfonic acid can also be used in the form of a salt.

Examples of the preferable aliphatic hydrocarbon group 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, ethyl, n- or iso-propyl, n-, iso- or tert- an n-octyl group, and an n-decyl group. The alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms may be used.

The cycloalkyl group includes, but is not limited to, a cycloalkyl group having a carbon number of 3 to 10, preferably 5 to 7 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group And a cycloalkyl group.

Preferred examples of the aromatic hydrocarbon group for R include a phenyl group, a phenyl group substituted with an alkyl group (e.g., a thryl group, a xylyl group), a 1- or 2-naphthyl group, and an anthryl group, To 14 carbon atoms, and these hydrocarbon groups may contain either or both of a hydroxyl group and an amino group.

Examples of the heterocyclic group which is preferable as R include imidazole, triazole, tetrazole, benzimidazole, benzotriazole, thiazole and benzothiazole. The heterocyclic group includes either or both of a hydroxyl group and an amino group There may be.

Preferable examples of the compound having two or less mercapto groups in the molecule include 3-mercapto-1,2-propanediol, 2-mercaptoethanol, 1,2-ethanedithiol, 6-mercapto- 1-dodecanethiol, 10-amino-1-dodecanethiol, 1-dodecanethiol sulfonic acid, Sodium, thiophenol, thiobenzoic acid, 4-amino-thiophenol, p-toluenethiol, 2,4-dimethylbenzenethiol, 3-mercapto-1,2,4 triazole, 2-mercaptobenzothiazole . Of these, 3-mercapto-1,2-propanediol is preferred from the standpoint of water solubility and waste disposal.

In the step of forming the release layer, the compound having two or less mercapto groups in the molecule can be used in the form of an aqueous solution. To increase the solubility in water, an alcohol such as methanol or ethanol may be added. The addition of alcohol is particularly effective when using a compound having two or less mercapto groups in a molecule having high hydrophobicity.

The concentration of the compound having two or less mercapto groups in the molecule in the aqueous solution is high and the peeling strength between the resin substrate and the metal foil tends to be lowered. By adjusting the concentration of the compound having two or less mercapto groups in the molecule The peel strength can be adjusted. The concentration of the compound having not more than two mercapto groups in the molecule in the aqueous solution may be 0.01 to 10.0% by weight, and typically 0.1 to 5.0% by weight, although not limited thereto.

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 the acidic side or on the alkaline side. For example, it can be used at a pH in the range of 3.0 to 10.0. From the viewpoint that a special pH adjustment is unnecessary, the pH is preferably in the range of about 5.0 to 9.0, which is near neutral, and more preferably in the range of 7.0 to 9.0.

(3) Metal alkoxide

The release layer may be formed by using an aluminate compound, a titanate compound, a zirconate compound, a hydrolysis product of an aluminate compound, a hydrolysis product of a titanate compound, a hydrolysis product of a zirconate compound, A condensate of a hydrolysis product of a titanate compound, a condensate of a hydrolysis product of a titanate compound, and a condensate of a hydrolysis product of a zirconate compound, Or a plurality of them may be mixed. The condensate of the hydrolysis product is hereinafter simply referred to as a metal alkoxide. The resin substrate and the metal foil are bonded to each other through the release layer, whereby the adhesiveness is appropriately lowered and the peel strength can be controlled.

[Chemical Formula 4]

Wherein R ¹ is an alkoxy group or a halogen atom, R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or a hydrocarbon group in which at least one hydrogen atom of the hydrocarbon group is substituted with a halogen atom and M Is one of Al, Ti and Zr, n is 0, 1 or 2, m is an integer of 1 or more and less than or equal to M, and at least one of R ¹ is an alkoxy group. m + n is the mantissa of M. The mantissa of M is 3 for Al and 4 for Ti and Zr.

The metal alkoxide must have at least one alkoxy group. In the case where a substituent is constituted by a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom, The adhesion tends to be too low. The metal alkoxide is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, and it is necessary that the metal alkoxide has 0 to 2 of any one hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom. If the number of the hydrocarbon groups is 3 or more, the adhesion between the resin substrate and the metal foil tends to be too low. Further, the alkoxy group includes an alkoxy group in which at least one hydrogen atom is substituted with a halogen atom. To adjust the peel strength between the resin substrate and the metal foil to the above-mentioned range, the metal alkoxide preferably has two or more alkoxy groups and one or two hydrocarbon groups (one or more hydrogen atoms include a hydrocarbon group substituted with a halogen atom) .

Examples of the alkyl group include, but are not limited to, methyl, ethyl, n- or iso-propyl, n-, iso- or tert- an n-octyl group, and an n-decyl group. The alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms may be used.

The cycloalkyl group includes, but is not limited to, a cycloalkyl group having a carbon number of 3 to 10, preferably 5 to 7 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group And a cycloalkyl group.

Preferred examples of the aromatic hydrocarbon group as R ² include a phenyl group, a phenyl group substituted with an alkyl group (e.g., a thryl group, a xylyl group), a 1- or 2-naphthyl group, and an anthryl group, An aryl group having 6 to 14 carbon atoms, and these hydrocarbon groups may contain either or both of a hydroxyl group and an amino group. These hydrocarbon groups may be substituted with at least one hydrogen atom by a halogen atom, for example, a fluorine atom, a chlorine atom, or a bromine atom.

Examples of preferred aluminate compounds include trimethoxy aluminum, methyl dimethoxy aluminum, ethyl dimethoxy aluminum, n- or iso-propyl dimethoxy aluminum, n-, iso- or tert-butyl dimethoxy aluminum, n-, phenyldimethoxy aluminum (for example, p- (methyl) phenyldimethoxyaluminum, phenyldimethoxyaluminum, phenyldimethoxyaluminum, alkyl substituted phenyldimethoxyaluminum ), Dimethylmethoxyaluminum, triethoxyaluminum, methyldiethoxyaluminum, ethyldiethoxyaluminum, n- or iso-propyldiethoxyaluminum, n-, iso- or tert-butyldiethoxyaluminum, pentyldiethoxyaluminum, Hexyldiethoxy aluminum, octyl diethoxy aluminum, decyl diethoxy aluminum, phenyl diethoxy aluminum, alkyl substituted phenyl di Propoxy aluminum, diisopropoxy aluminum, ethyl diisopropoxy aluminum, n- or iso-propyl di-n-propoxy aluminum (for example, p- (methyl) phenyldiethoxy aluminum), dimethyl ethoxy aluminum, Propoxy aluminum, octyl aluminum, n-, iso- or tert-butyl diisopropoxy aluminum, pentyl diisopropoxy aluminum, hexyl diisopropoxy aluminum, octyl diisopropoxy aluminum, decyl diisopropoxy aluminum, (E.g., p- (methyl) phenyl diisopropoxy aluminum), dimethyl isopropoxy aluminum, (3,3,3-trifluoropropyl) dimethoxy aluminum , And tridecafluorooctyldiethoxyaluminum, methyldichloroaluminum, dimethylchloroaluminum, dimethylchloroaluminum, phenyldichloroaluminum, dimethyl fl ual Oro include aluminum, dimethyl aluminum-bromo-diphenyl-bromo-aluminum, and their hydrolysis products, and their degradation products of hydrolysis condensate and the like. Of these, trimethoxyaluminum, triethoxyaluminum and triisopropoxyaluminum are preferable from the viewpoint of availability.

Examples of preferable titanate compounds include tetramethoxytitanium, methyltrimethoxytitanium, ethyltrimethoxytitanium, n- or isopropyltrimethoxytitanium, n-, iso- or tert-butyltrimethoxytitanium, n -, iso-or neopentyltrimethoxytitanium, hexyltrimethoxytitanium, octyltrimethoxytitanium, decyltrimethoxytitanium, phenyltrimethoxytitanium, alkyl-substituted phenyltrimethoxytitanium (for example, p - (methyl) phenyltrimethoxytitanium), dimethyldimethoxytitanium, tetraethoxytitanium, methyltriethoxytitanium, ethyltriethoxytitanium, n- or isopropyltriethoxytitanium, n-, iso- or butyltriethoxytitanium, pentyltriethoxytitanium, hexyltriethoxytitanium, octyltriethoxytitanium, decyltriethoxytitanium, phenyltriethoxytitanium, alkyl-substituted phenyltriethoxytitanium (for example, , p- (methyl) phenyltriethoxytitanium), dimethyldiethoxytitanium, tetraisopropoxytitanium, methyltriisopropoxytitanium, ethyltriisopropoxytitanium, n- or iso-propyltriethoxytitanium, n -, iso-or tert-butyltriisopropoxytitanium, pentyltriisopropoxytitanium, hexyltriisopropoxytitanium, octyltriisopropoxytitanium, decyltriisopropoxytitanium, phenyltriisopropoxytitanium , Alkyl-substituted phenyltriisopropoxytitanium (for example, p- (methyl) phenyltriisopropoxytitanium), dimethyl diisopropoxytitanium, (3,3,3-trifluoropropyl) trimethoxytitanium , And tridecafluorooctyltriethoxytitanium, methyltrichlorotitanium, dimethyldichlorotitanium, trimethylchlorotitanium, phenyltrichlorotitanium, dimethyldifluorotitanium, dimethyldibromotitanium, diphenyldibromotitanium,Of hydrolysis products, and the like can be mentioned those of the singer of the degradation product condensate. Of these, tetramethoxytitanium, tetraethoxytitanium and tetraisopropoxytitanium 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, hexyltrimethoxyzirconium, octyltrimethoxyzirconium, decyltrimethoxyzirconium, phenyltrimethoxyzirconium, alkyl-substituted phenyltrimethoxyzirconium (for example, phenyltrimethoxyzirconium, isopropyltriethoxyzirconium, n-, iso- propyltriethoxyzirconium, n-, iso-, di- or p-toluenesulfonate), dimethyldimethoxyzirconium, tetraethoxyzirconium, methyltriethoxyzirconium, Or tert-butyltriethoxyzirconium, pentyltriethoxyzirconium, hexyltriethoxyzirconium, octyltriethoxyzirconium (E.g., p- (methyl) phenyltriethoxyzirconium), dimethyldiethoxyzirconium, tetraisopropoxyzirconium, tetraisopropoxyzirconium, methyltriethoxyzirconium, and alkyl substituted phenyltriethoxyzirconium Triisopropoxy zirconium, ethyl triisopropoxy zirconium, n- or iso-propyl triethoxy zirconium, n-, iso- or tert-butyl triisopropoxy zirconium, pentyl triisopropoxy zirconium, (Phenyl) triisopropoxyzirconium, alkyl substituted phenyltriisopropoxyzirconium (for example, p- (methyl) phenyltriisopropoxytitanium), alkyltriisopropoxyzirconium Dimethyl diisopropoxy zirconium, (3,3,3-trifluoropropyl) trimethoxy zirconium, and tride Tetrafluoroethylenediamine, tetrafluoroethylenediamine, tetrafluoroethylenediamine, tetrafluoroethylenediamine, tetrafluoroethylenediamine, tetrafluoroethylenediamine, tetrafluoroethylenediamine, tetrafluoroethylenediamine, fluoroheptyltriethoxy zirconium, Decomposition products and condensates of the hydrolysis products thereof, and the like. Of these, tetramethoxy zirconium, tetraethoxy zirconium and tetraisopropoxy zirconium 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. To increase the solubility in water, an alcohol such as methanol or ethanol may be added. Addition of an alcohol is particularly effective when a metal alkoxide having high hydrophobicity is used.

When the concentration of the metal alkoxide in the aqueous solution is high, the peeling strength between the resin base material and the metal foil tends to be lowered, 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 may be 0.001 to 1.0 mol / L, and may be typically 0.005 to 0.2 mol / L.

The pH of the metal alkoxide aqueous solution is not particularly limited, and can be used on the acidic side or on the alkaline side. For example, it can be used at a pH in the range of 3.0 to 10.0. From the viewpoint that a special pH adjustment is unnecessary, the pH is preferably in the range of about 5.0 to 9.0, which is near neutral, and more preferably in the range of 7.0 to 9.0.

(4) Others

A known releasing material such as a silicone releasing agent and a releasing resin film can be used for the releasing layer.

The metal foil is formed 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, 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 May be provided. Here, the chromate treatment layer refers to a layer treated with a liquid containing chromic anhydride, chromic acid, bichromic acid, chromic acid salt or dichromate. The chromate treatment layer contains elements (metals, alloys, oxides, nitrides, sulfides and the like) such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium Maybe. Specific examples of the chromate treatment layer include a chromate treatment layer treated with an aqueous solution of chromic anhydride or potassium dichromate, a chromate treatment layer treated with a treatment liquid containing chromic anhydride or potassium dichromate and zinc, and the like.

The roughening treatment layer can be formed by, for example, the following treatment.

[Old harmony]

Spherical roughening particles are formed by using the copper plating bath described below, which is made of Cu, H ₂ SO ₄ , and As.

Solution composition 1

_{CuSO 4 · 5H 2 O 78 ~} 196 g / L

Cu 20 to 50 g / L

H ₂ SO ₄ 50-200 g / L

Arsenic 0.7 ~ 3.0 g / L

(Electroplating temperature 1) 30 to 76 ° C

(Current condition 1) Current density 35 to 105 A / dm 2 (over limit current density of bath)

(Plating time 1) 1 to 240 seconds

Subsequently, coating plating is performed with a copper electrolytic bath composed of sulfuric acid and copper sulfate to prevent the coarse particles from falling off and to improve the peeling strength. The plating plating conditions are described below.

· Liquid composition 2

CuSO ₄ .5H ₂ O 88 to 352 g / L

Cu 22 to 90 g / L

H ₂ SO ₄ 50-200 g / L

(Electroplating temperature 2) 25 to 80 DEG C

(Current condition 2) Current density: 15 to 32 A / dm 2 (less than the limit current density of bath)

(Plating time 1) 1 to 240 seconds

As the heat-resistant layer and the rust-preventive layer, known heat-resistant layers and rust-preventive layers can be used. For example, the heat-resistant layer and / or the rust-preventive layer may be formed of a material selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, Or a layer containing at least one element selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, May be a metal layer or an alloy layer composed of at least one element selected from the group of The heat resistant layer and / or the rust preventive layer may be selected from the group of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, Nitride, or silicide including at least one element selected from the group consisting of oxides, nitrides, and silicides. The heat-resistant layer and / or rust-preventive layer may be a layer containing a nickel-zinc alloy. The heat-resistant layer and / or rust-preventive layer may be a nickel-zinc alloy layer. The nickel-zinc alloy layer may contain 50 wt% to 99 wt% of nickel and 50 wt% to 1 wt% of 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, and preferably 20 to 100 mg / m 2. It is also preferable that the ratio of the adhesion amount of nickel to the adhesion amount of nickel (= adhesion amount of nickel / adhesion amount of zinc) of the nickel-zinc alloy layer or the nickel-zinc alloy layer is 1.5 to 10. The adhesion amount of nickel in the nickel-zinc alloy layer or the nickel-zinc alloy layer is preferably 0.5 mg / m 2 to 500 mg / m 2, more preferably 1 mg / m 2 to 50 mg / m 2 Do.

For example, the heat-resistant layer and / or the rust-preventive layer may be formed of a nickel or nickel alloy layer having an adhesion amount of 1 mg / m2 to 100 mg / m2, preferably 5 mg / m2 to 50 mg / m2, M 2 to 40 mg / m 2, and the nickel alloy layer may be formed of any one of nickel-molybdenum, nickel-zinc, and nickel-molybdenum-cobalt It may be composed of one kind. The total thickness of the heat-resistant layer and / or the rust-preventive layer is preferably 2 mg / m 2 to 150 mg / m 2, more preferably 10 mg / m 2 to 70 mg / m 2. Further, the heat resistant layer and / or the rust preventive layer preferably has a nickel adhesion amount of [nickel or nickel alloy] / [tin adhesion amount] = 0.25 to 10, more preferably 0.33 to 3. [

As the silane coupling agent used for the silane coupling treatment, a known silane coupling agent may be used, and for example, an amino silane coupling agent or an epoxy silane coupling agent or a mercapto silane coupling agent may be used . Examples of the silane coupling agent include vinyltrimethoxysilane, vinylphenyltrimethoxysilane,? -Methacryloxypropyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane, 4-glycidylbutyltrimethoxysilane Aminopropyltrimethoxysilane, N-3- (aminoethyl) gamma -aminopropyltrimethoxysilane, N-3- (4- (3- aminopropoxy) Propyl trimethoxy silane, imidazole silane, triazin silane, gamma-mercaptopropyl trimethoxy silane, 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 methacryloylic clock silane, or a mercapto silane. These silane coupling agents may be used in combination of two or more. Among them, those formed using an amino-based silane coupling agent or an epoxy-based silane coupling agent are preferable.

Examples of the amino-based silane coupling agent include N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, 3- Aminopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxy Silane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- Aminopropyl) trimethoxysilane, N- (2-aminoethyl-3-aminopropyl) tris (2-ethylhexoxy) silane, 6- (aminohexylaminopropyl) , Aminophenyltrimethoxysilane, 3- (1-aminopropoxy) -3,3-dimethyl-1-propenyltrimethoxysilane, 3-aminopropyltris 3-aminopropyltriethoxysilane, 3-aminodecyltrimethoxysilane, 3- (2-N-benzylaminoethylaminopropyl) silane, (N, N-dimethyl-3-aminopropyl) trimethoxysilane, bis (2-hydroxyethyl) Aminopropyl) trimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) Aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) propoxy) propyl-3-aminopropyltrimethoxysilane, N- And silane.

The silane coupling treatment layer is provided in a range of 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 / m 2 in terms of silicon atoms . In the above-mentioned range, the adhesion between the resin base material and the metal foil can be further improved.

The surface of the metal foil, the roughening particle layer, the heat resistant layer, the rust preventive layer, the silane coupling treatment layer, the chromate treatment layer or the release layer may be coated with an antireflective coating composition described in International Publication Nos. WO2008 / 053878, JP-A-2008-111169, , International Publication No. WO2006 / 028207, Japanese Patent No. 4828427, International Publication Nos. WO2006 / 134868, Japanese Patent No. 5046927, International Publication Nos. WO2007 / 105635, Japanese Patent No. 5180815, Japanese Patent Laid-Open Publication No. 2013-19056 Surface treatment can be carried out. As described above, the metal foil of the present invention also includes a surface-treated metal foil.

A resin layer may be provided on the surface of at least one layer selected from the group consisting of a roughening treatment layer, a heat-resistant layer, a rust-preventive layer, a chromate treatment layer and a silane coupling treatment layer provided on the first surface of the metal foil.

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 bonding. The semi-cured state (B-stage state) includes a state in which the insulating resin layer can be stacked and stored without being tacky even when the surface thereof is touched with a finger, and a curing reaction occurs when further heat-treated. The resin layer on the surface of the metal foil is preferably a resin layer which develops a suitable peel strength (for example, 2 gf / cm 2 to 200 gf / cm 2) upon contact with the release layer. In addition, it is preferable to use a resin which follows the irregularities on the surface of the metal foil and which does not allow mixing of voids or bubbles which may cause expansion. For example, when the resin layer is provided on the surface of the metal foil, the viscosity of the resin is 10,000 mPa · s (25 ° C.) or less, more preferably the viscosity of the resin is 5000 mPa · s (25 ° C.) It is preferable to provide a resin layer using a resin having a low refractive index. Since the resin layer follows the surface of the metal foil even when an insulating substrate which does not follow the irregularities of the surface of the metal foil is used by providing the resin layer between the insulating substrate and the metal foil laminated on the metal foil, It is possible to prevent air gaps and air bubbles from being generated between the electrodes.

The resin layer provided on the first surface of the metal foil may include a thermosetting resin or a thermoplastic resin. The resin layer on the surface of the metal foil may include a thermoplastic resin. The resin layer on the surface of the metal foil may contain a known resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg and a skeleton. The resin layer on the surface of the metal foil is disclosed in, for example, International Publication Nos. WO2008 / 004399, WO2008 / 053878, WO2009 / 084533, JP-A-11-5828, JP- Japanese Patent No. 3184485, International Publication No. WO97 / 02728, Japanese Patent No. 3676375, Japanese Patent Application Laid-Open Nos. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Application Laid-Open No. 2002-179772, Japanese Patent Laid-Open Nos. 2002-359444, 2003-304068, 3992225, 2003-249739, 4136509, 2004-82687, 4025177 Japanese Patent Laid-Open Publication No. 2004-349654, Japanese Patent No. 4286060, Japanese Patent Laid-Open Publication No. 2005-262506, Japanese Patent No. 4570070, Japanese Laid-Open Patent Publication No. 2005-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415 International Publication No. WO2004 / Japanese Laid-Open Patent Publication No. 2006-257153, Japanese Laid-Open Patent Publication No. 2007-326923, Japanese Laid-Open Patent Publication No. 2008-111169, Japanese Patent No. 5024930, International Publication Nos. WO2006 / 028207, Japanese Patent No. 4828427, Patent Publication No. 2009-67029, International Publication Nos. WO2006 / 134868, Japanese Patent No. 5046927, Japanese Patent Laid-Open Publication No. 2009-173017, International Publication Nos. WO2007 / 105635, Japanese Patent No. 5180815, International Publication No. WO2008 / 114858, The materials disclosed in the publications WO2009 / 008471, JP-A-2011-14727, WO2009 / 001850, WO2009 / 145179, WO2011 / 068157 and JP-A-2013-19056 A resin, a curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton, etc.) and / or a method of forming a resin layer and a forming apparatus.

(Laminate, semiconductor package, electronic device)

A laminate can be produced by laminating a metal foil with a release layer and a resin base material provided on a release foil-laminated metal foil. The laminate may be formed by forming a resin substrate with a paper base phenol resin, a paper base epoxy resin, a synthetic fiber base epoxy resin, a glass fiber / paper composite epoxy resin, a glass fiber / glass nonwoven composite base epoxy resin, It is also good. The resin substrate may be a prepreg or may include a thermosetting resin. In addition, a printed wiring board can be manufactured by forming a circuit on the metal foil of the laminate. In addition, a printed circuit board can be manufactured by mounting electronic parts on a printed wiring board. The " printed wiring board " in the present invention includes a printed wiring board, a printed circuit board, and a printed board on which the electronic parts are mounted. The electronic device may be manufactured using the printed wiring board, the electronic device may be manufactured using the printed circuit board on which the electronic parts are mounted, or an electronic device may be manufactured using the printed board on which the electronic parts are mounted . The "printed circuit board" includes a circuit-forming substrate for a semiconductor package. In addition, a semiconductor package can be manufactured by mounting electronic parts on a circuit-forming substrate for a semiconductor package. In addition, an electronic device can be manufactured using the semiconductor package.

(Manufacturing method of printed wiring board)

The method for manufacturing a printed wiring board according to the present invention comprises the steps of bonding an insulating substrate to a metal foil with a release layer of the present invention and removing the metal foil with a release layer from the insulating substrate without etching, And a step of forming a circuit on the release surface side of the insulating substrate to which the surface profile has been transferred. With this configuration, the resin substrate can be physically peeled off when the metal foil is bonded to the resin substrate, and in the step of removing the metal foil from the resin substrate, the surface profile transferred from the surface of the metal foil is not damaged on the surface of the resin substrate, The metal foil can be removed at a cost. In the above manufacturing method, the circuit may be formed of a plating pattern. In this case, after a plating pattern is formed, a desired circuit can be formed using the plating pattern to produce a printed wiring board. The circuit may be formed in a printed pattern. In this case, for example, a printed pattern can be formed using an inkjet containing a conductive paste or the like in the ink, and then a desired printed circuit can be formed using the printed pattern to produce a printed wiring board.

In the present specification, the term " surface profile "

According to another aspect of the present invention, there is provided a method of manufacturing a printed wiring board, comprising the steps of bonding an insulating substrate to a metal foil with a release layer of the present invention and removing the metal foil with a release layer from the insulating substrate without etching, A step of obtaining an insulating substrate on which the surface profile of the bonded metal foil is transferred and a step of providing a buildup layer on the separated surface side of the insulating substrate to which the surface profile is transferred. With this configuration, it is possible to physically peel the resin base material when the metal foil is bonded to the resin base material. In the step of removing the metal foil from the resin base material, it is possible to prevent the profile of the surface of the metal foil transferred onto the resin base material from being damaged So that the metal foil can be removed. In addition, even if the resin component of the resin substrate and the resin component of the buildup layer are different or the same from each other by the predetermined uneven surface transferred to the resin substrate, both can be bonded with good adhesion.

Here, the " buildup 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. The conductive layer, the wiring pattern, or the insulator such as the circuit and the resin may be arbitrarily provided.

The build-up layer can be produced by providing a conductive layer, a wiring pattern, or an insulator such as a circuit and a resin on the release side of the resin substrate 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, known methods such as a semiadditive method, a pull additive method, a subtractive method, and a palladium 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 resin (layers).

The plurality of conductive layers, wiring patterns, or circuits may be electrically insulated by an insulator such as a resin. A plurality of electrically insulated conductive layers, wiring patterns, or circuits are formed on the insulator such as resin by laser and / or drill through holes and / or blind vias, and then copper plating or the like is applied to the through holes and / Or may be electrically connected by forming a conductive plating of the insulating layer.

The insulator such as a resin constituting the buildup layer may be a resin, a resin layer or a resin substrate described in the present specification, and may be a resin, a resin layer, a resin substrate, an insulator, a prepreg, And the like can be used. The resin may include an inorganic material and / or an organic material. The resin constituting the buildup layer is formed of a material having a low dielectric constant such as LCP (liquid crystal polymer), fluorine resin, low dielectric constant polyimide, polyphenylene ether, cycloolefin polymer, or polytetrafluoroethylene . In recent years, with the expansion of high frequency products, a material having a low dielectric constant such as LCP (liquid crystal polymer), fluorine resin, low dielectric constant polyimide, polyphenylene ether, cycloolefin polymer or polytetrafluoroethylene (Teflon) The movement into the structure of the printed board is becoming more active. In view of the fact that these materials are thermoplastic, it is difficult to avoid a change in shape during hot press processing, and LCP (liquid crystal polymer), fluorine resin, low dielectric constant polyimide, polyphenylene ether, cycloolefin polymer or polytetrafluoroethylene And the basic production problem that the production yield does not improve with the substrate composition in the organization is held. With the above-described manufacturing method of the present invention, a thermosetting resin such as an epoxy resin is used as the resin substrate and the resin substrate is bonded with the thermosetting resin, so that the high frequency property is excellent and the shape deformation when heat is applied can be prevented A printed wiring board can be provided.

According to another aspect of the present invention, there is provided a method for manufacturing a printed wiring board, comprising the steps of bonding an insulating substrate (1) to a metal foil with a release layer or a metal foil of the present invention on the release layer side or the second surface side of the metal foil, A step of forming a circuit on the first face side of the metal foil or the metal foil with the release layer laminated thereon, the step of covering the circuit with the insulating substrate (2) and embedding the circuit in the insulating substrate (2) , The 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 step of removing the exposed metal foil with a release layer or the metal foil To the printed wiring board.

According to another aspect of the present invention, there is provided a method for manufacturing a printed wiring board, comprising the steps of: bonding an insulating substrate (1) to a metal foil with a release layer of the present invention or a metal foil of the present invention from the side of the release layer or the second surface of the metal foil A step of laminating a metal foil with a release layer laminated with the insulating substrate 1 or a dry film on the first surface side of the metal foil of the metal foil; a step of forming a circuit after patterning the dry film; A step of covering the exposed circuit with an insulating substrate (2) to embed the circuit in the insulating substrate (2), a step of removing the insulating substrate (1) from the metal foil with a release layer or the metal foil A step of exposing 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 a step.

By using the metal foil which is provided with the releasing layer on the metal foil whose surface irregularities are controlled and which enables the physical separation of the resin base material when the metal foil is bonded to the resin base material, printing with a fine circuit at a good cost A wiring board can be manufactured. In addition, it is possible to physically peel the resin substrate when the metal foil is bonded to the resin substrate, so that the metal foil can be peeled from the resin substrate without harming the profile of the surface of the metal foil transferred to the surface of the resin substrate, Can be removed.

Hereinafter, a specific example of a method for producing a printed wiring board using the metal foil with a release layer of the present invention will be described in detail with reference to the drawings.

First, as shown in Fig. 1-A, a release layer-adhered metal foil (first layer) laminated on the resin substrate from the release layer side is prepared.

Next, as shown in Fig. 1-B, a resist is coated on the metal foil, and exposure and development are performed to etch the resist into a predetermined shape.

Then, as shown in Fig. 1-C, after circuit plating is formed, the resist is removed to form circuit plating of a predetermined shape.

Next, as shown in FIG. 2-D, a resin layer is laminated on the metal foil so as to cover the circuit plating (so that the circuit plating is buried), and subsequently the other metal foil with a release layer (second layer) Layer metal sheet.

Next, as shown in Fig. 2-E, the resin substrate is peeled off from the release layer-adhered metal foil of the second layer.

Next, as shown in Fig. 2-F, laser perforations are made at predetermined positions of the resin layer to expose the circuit plating to form blind vias.

Then, as shown in FIG. 3-G, copper is buried in the blind via to form a via fill.

Then, as shown in FIG. 3-H, circuit plating is formed on the via fill as shown in FIG. 1-B and FIG. 1-C.

Then, as shown in Fig. 3-I, the resin substrate is peeled off from the release layer-adhered metal foil of the first layer.

Then, as shown in FIG. 4-J, the metal foil on both surfaces is removed by flash etching to expose the circuit-plating surface in the resin layer.

Next, as shown in Fig. 4-K, bumps are formed on the circuit plating in the resin layer, and a copper filler is formed on the solder. Thus, a printed wiring board using the metal foil with a release layer of the present invention is produced.

In addition, in the above-described method for producing a printed wiring board, the "metal foil" is replaced with a resin substrate, the "resin substrate" is replaced with a metal foil, a circuit is formed on the resin substrate side surface of the metal foil with a release layer, It is also possible to manufacture a wiring board.

The other metal foil with a release layer (second layer) may be a metal foil with a release layer according to the present invention, a metal foil with a release layer according to the present invention, or a conventional copper foil. In addition, one or more layers may be formed on the second layer circuit shown in FIG. 3-H, and the formation of these circuits may be performed by a semi-additive method, a subtractive method, a pattern additive method, Or a semi-additive method.

According to the above-described method of manufacturing a printed wiring board, since the circuit plating is embedded in the resin layer, when the metal foil is removed by flash etching as shown in FIG. 4-J, And the shape thereof is retained, thereby facilitating the formation of a fine circuit. Further, since the circuit plating is protected by the resin layer, migration resistance is improved, and conduction of the circuit wiring is suppressed well. Therefore, formation of a fine circuit is facilitated. When the metal foil is removed by flash etching as shown in Figs. 4-J and 4-K, since the exposed surface of the circuit plating becomes depressed from the resin layer, the bumps are formed on the circuit plating, The filler is easily formed and the production efficiency is improved.

Known resins and prepregs can be used for the embedding resin (resin). For example, a prepreg which is glass fiber impregnated with BT (bismaleimide triazine) resin or BT resin, ABF film manufactured by Ajinomoto Fine Techno Co., Ltd. or ABF can be used. The resin layer and / or the resin and / or the prepreg described in this specification can be used for the above-mentioned embedding resin (resin).

The metal foil with a releasing layer used in the first layer may have a substrate or a resin layer on the surface of the releasing-layer-attached metal foil. The metal foil with a release layer used in the first layer having the substrate or the resin layer is supported and the wrinkle does not enter easily, thereby improving the productivity. Further, any substrate or resin layer can be used for the substrate or resin layer as long as it has the effect of supporting the metal foil with a release layer used in the first layer. Examples of the substrate or resin layer include a carrier, a prepreg, a resin layer or a known carrier, a prepreg, a resin layer, a metal plate, a metal foil, a plate of an inorganic compound, a foil of an inorganic compound, , A foil of an organic compound can be used.

5 is a schematic view of the semi-additive method using the surface profile of the metal foil. In the semi-additive method, the surface profile of the metal foil is used. Specifically, first, a metal foil with a release layer of the present invention is laminated on the resin substrate from the release layer side, and a laminate is produced. Then, the metal foil of the laminate is removed by etching or removed. Subsequently, the surface of the resin substrate onto which the metal foil surface profile is transferred is cleaned with dilute sulfuric acid or the like, and electroless copper plating is performed. Then, a portion of the resin substrate where no circuit is formed is covered with a dry film or the like, and electroplating copper plating is performed on the surface of the electroless copper plating layer not covered with the dry film. Thereafter, after the dry film is removed, the electroless copper plating layer formed on the portion where no circuit is formed is removed to form a fine circuit. The fine circuit formed in the present invention is in close contact with the release surface of the resin substrate to which the metal foil surface profile of the present invention is transferred, so that the adhesion strength (peel strength) is improved.

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 applied to a resin substrate or a metal foil to form a pattern, and then a conductive pattern is formed by electroplating and etching. Therefore, in one embodiment of the method for manufacturing a printed wiring board according to the present invention using the semi-additive method, a step of preparing a metal foil relating to the present invention or a metal foil with a release-

A step of laminating a resin base material on the metal foil or the metal foil with a release-type layer from the side whose surface profile is controlled or the release-

A step of removing or peeling the metal foil after the metal foil and the resin substrate are laminated,

A step of providing a through hole and / or a blind via on the exposed or peeled surface of the resin substrate formed by removing or peeling the metal foil,

A step of performing a desmear treatment on a region including the through hole and / or the blind via,

A step of cleaning the surface of the resin base material with dilute sulfuric acid or the like to provide an electroless plating layer (for example, an electroless copper plating layer) on the region including the resin base material and the through hole and / or the blind via,

A step of providing a plating resist on the electroless plating layer,

A step of exposing the plating resist to light and then removing a plating resist in a region where a circuit is formed,

A step of providing an electrolytic plating layer (for example, an electrolytic copper plating layer) in a region where the circuit where the plating resist is removed is formed,

A step of removing the plating resist,

And removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like.

In another embodiment of the method for manufacturing a printed wiring board according to the present invention using the semi-additive method, a metal foil according to the present invention or a metal foil with a release layer and a resin substrate,

A step of laminating a resin base material on the metal foil or the metal foil with a release-type layer from the side whose surface profile is controlled or the release-

A step of removing or peeling the metal foil after the metal foil and the resin substrate are laminated,

A step of cleaning the surface of the resin substrate with dilute sulfuric acid or the like to prepare an electroless plating layer (for example, electroless copper plating layer) on the exposed or peeled surface of the resin substrate formed by removing or peeling the metal foil,

A step of providing a plating resist on the electroless plating layer,

A step of exposing the plating resist to light and then removing a plating resist in a region where a circuit is formed,

A step of providing an electroplating layer (for example, an electrolytic copper plating layer) in a region where the circuit is removed from which the plating resist has been removed,

A step of removing the plating resist,

And removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like.

In this manner, a circuit is formed on the release surface of the resin substrate after the metal foil is peeled off, whereby a printed circuit formation substrate and a circuit formation substrate for a semiconductor package can be manufactured. In addition, a printed wiring board and a semiconductor package can be manufactured by using the circuit formation substrate. In addition, 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 pull additive method, a step of laminating a resin base material on the metal foil or the metal foil with a release- ,

A step of laminating a resin base material on the metal foil or the metal foil with a release-type layer from the side whose surface profile is controlled or the release-

A step of removing or peeling the metal foil after the metal foil and the resin substrate are laminated,

A step of washing the surface of the resin substrate with dilute sulfuric acid or the like on the exposed surface or the cleaved surface of the resin substrate formed by removing or peeling the metal foil,

A step of providing a plating resist on the cleaned resin substrate surface,

A step of exposing the plating resist to light and then removing a plating resist in a region where a circuit is formed,

A step of providing an electroless plating layer (for example, an electroless copper plating layer or a thick electroless plating layer) in a region in which the circuit from which the plating resist is removed is formed,

And removing the plating resist.

Further, in the semi-additive method and the full additive method, there is a case where the surface of the resin base material is washed to provide an effect of easily providing an electroless plating layer. Particularly, when the release layer remains on the surface of the resin substrate, since the release layer is partially or entirely removed from the resin substrate surface by the cleaning, cleaning of the surface of the resin substrate further facilitates the formation of the electroless plating layer There is a case that it is effective to lose. The cleaning may be performed by a known cleaning method (kind of liquid to be used, temperature, coating method of liquid, etc.). It is preferable to use a cleaning method capable of removing part or all of the release layer of the present invention.

In this manner, a circuit is formed on the exposed or peeled surface of the resin substrate after the metal foil is removed or peeled by the semi-add method or the full additive method to produce a circuit-forming substrate and a circuit-forming substrate for a semiconductor package . In addition, a printed wiring board and a semiconductor package can be manufactured by using the circuit formation substrate. In addition, an electronic device can be manufactured using the printed wiring board and the semiconductor package.

[Example]

EXAMPLES Hereinafter, examples and comparative examples of the present invention will be described, but these examples are provided for better understanding of the present invention and its advantages, and are not intended to limit the invention.

· Fabrication of bright green (copper before surface treatment)

(Examples 1 to 16 and 19, Comparative Examples 1 to 3)

A titanium-made rotary drum (electrolytic drum) was prepared. Then, the surface was polished under the electrolytic drum surface control conditions shown in Table 1 to obtain an electrolytic drum having a predetermined square root mean square height (Sq) on the surface. Specifically, the surface of the electrolytic drum was polished with the number of polishing belts shown in Table 1. At this time, the polishing belt was wound by a predetermined width only in the width direction of the drum and the polishing belt was rotated in the width direction of the drum while rotating the drum. Table 1 shows the rotation speed of the drum surface at the time of polishing. The polishing time was obtained by multiplying the number of passes by the passage time of one point on the surface of the drum in one pass from the width of the polishing belt and the moving speed of the polishing belt. Here, the single pass of the abrasive belt means that the circumferential surface of the rotary drum is polished once with an abrasive belt from one end of the axial direction (the width direction of the electrolytic copper foil) to the other end thereof.

That is, the polishing time is expressed by the following equation.

Polishing time (minute) = width of abrasive belt per pass (cm / rev) / moving speed of abrasive belt (cm / min) x number of passes (times)

For Examples 2, 5, 8, 14 to 16, and Comparative Example 3, the surface of the drum was wetted with water at the time of polishing the surface of the electrolytic drum.

Then, electrodes were arranged in the electrolytic bath at a predetermined gap between the electrolytic drum and the drum. Next, in Examples 1 to 10, 12, 14 to 16, and Comparative Examples 2 and 3, electrolysis was conducted in an electrolytic bath under the following conditions, and copper was precipitated on the surface of the electrolytic drum while rotating the electrolytic drum. The current density and electrolyte flux at this time are shown in Table 1.

(Electrolyte composition)

Cu 120 g / L

H ₂ SO ₄ 100 g / L

Chloride ion (Cl ^-) 70ppm

Fish Glue 6ppm

Electrolyte temperature 60 ℃

In Examples 11 and 19 and Comparative Example 1, 80 ppm of bis (3-sulfopropyl) disulfide (SPS) as an additive was added in addition to the electrolytic solution.

In Example 13, the same electrolytic solution compositions as in Examples 1 to 10, 12, 14 to 16, and Comparative Examples 2 and 3 were used except that the chloride ion concentration was 2 ppm or less and 2 ppm of animal glue was added instead of fish glue.

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

(Example 17)

Tough pitch copper ingots were rolled and annealed to a thickness of 0.2 mm. Thereafter, final cold rolling was carried out to make the thickness of the copper foil 80 mu m. The final degree of cold rolling was 60%. Rolling processing degree = (plate thickness before rolling-plate thickness after rolling) / plate thickness before rolling × 100% oil film equivalent 20000.

The film equivalent is given by the following equation.

The yield stress of the material [kg / m < 2 >] is calculated by the following equation: < EMI ID = )}

The viscosity of the rolling oil [cSt] is the dynamic viscosity at 40 ° C.

The roll used in the final cold rolling was a roll whose surface was Sq = 0.20 mu m. The surface of the rolled roll can be adjusted by grinding the rolling roll longer than usual, thereby reducing the value of Sq. In addition, it is possible to shorten the grinding time and increase the value of Sq.

(Example 18)

The ingot of the copper alloy (brass) of 25% by mass of Zn, the remainder of Cu and inevitable impurities was rolled and annealed repeatedly to a thickness of 0.2 mm. Thereafter, final cold rolling was carried out under the following conditions to make the thickness of the copper foil 80 mu m. The final degree of cold rolling was 60%. Rolling processing degree = (plate thickness before rolling-plate thickness after rolling) / plate thickness before rolling x 100%

The film equivalent was 20,000.

The film equivalent is given by the following equation.

The yield stress of the material [kg / m < 2 >] is calculated by the following equation: < EMI ID = )}

The viscosity of the rolling oil [cSt] is the kinematic viscosity at 40 ° C.

The roll used in the final cold rolling was a roll whose surface was Sq = 0.20 mu m. Adjustment of the surface of the rolled roll can be performed by grinding the rolling roll longer than usual and reducing the value of Sq. In addition, it is possible to shorten the grinding time and increase the value of Sq.

·Surface treatment

Then, as the surface treatment, an electrolytic copper foil is subjected to a roughening treatment, a heat treatment, a rust-preventive treatment, a silane couple A ring treatment, and a resin layer forming treatment, or a combination of the treatments. Subsequently, a release layer was formed on the treated surface of the copper foil under the following conditions. In addition, unless otherwise noted, each treatment was carried out in this order. In Table 1, "No" in each processing column indicates that this processing has not been performed. In Examples 5, 7, 8, and 10, the S surface (drum surface, shiny surface, glossy surface) was treated in the same manner as the M surface described above. In the examples and comparative examples in which the release layer was formed, the side opposite to the side where the release layer of the copper foil was formed was defined as the first side, and the side on which the release layer of the copper foil was formed was defined as the second side. In Examples and Comparative Examples in which no release layer was formed, the S surface side of the electrolytic copper foil was regarded as the first surface, and the M surface side of the electrolytic copper foil was regarded as the second surface.

(1) Harmonization processing

[Old harmony]

Spherical coarsely grained particles were formed by using the copper plating bath described below, which was made of Cu, H ₂ SO ₄ , and As.

Solution composition 1

_{CuSO 4 · 5H 2 O 78 ~} 118 g / L

Cu 20 to 30 g / L

H ₂ SO ₄ 12 g / L

Arsenic 1.0 ~ 3.0 g / L

(Electroplating temperature 1) 25 to 33 ° C

(Current condition 1) Current density 78 A / dm 2 (above the limit current density of the bath)

(Plating time 1) 1 to 45 seconds

Subsequently, coating plating was carried out with a copper electrolytic bath composed of sulfuric acid and copper sulfate to prevent falling off of the coarse particles and to improve peel strength. The plating plating conditions are described below.

· Liquid composition 2

_{CuSO 4 · 5H 2 O 156g /} L

Cu 40 g / L

H ₂ SO ₄ 120 g / L

(Electroplating temperature 2) 40 캜

(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 treatment (barrier treatment)

(Liquid composition)

Ni 13 g / L

Zn 5 g / L

pH 2

(Electroplating conditions)

Temperature 40 ° C

Current density 8 A / dm 2

(3) Rust treatment

(Liquid composition)

CrO ₃ 2.5 g / L

Zn 0.7 g / L

Na ₂ SO ₄ 10 g / L

pH 4.8

(Zinc chromate conditions)

Temperature 54 ° C

Current density 0.7 As / dm 2

(4) Silane coupling treatment

(Liquid composition)

Tetraethoxysilane content 0.4%

pH 7.5

Spray method Spray solution

(5) Formation of release layer

[Release Layer A]

An aqueous solution of a silane compound (n-propyltrimethoxysilane: 4 wt%) was applied to the treated surface of the copper foil using a spray coater, and then the surface of the copper foil was dried in air at 100 ° C for 5 minutes to form a release layer A . The silane compound was dissolved in water, and the stirring time until the application was 30 hours, the alcohol concentration in the aqueous solution was 10 vol%, and the pH of the aqueous solution was 3.8-4.2.

[Release Layer B]

An aqueous solution of sodium 1-dodecanethiosulfonate (sodium dodecanethiosulfonate concentration: 3 wt%) was prepared by using a 1-dodecanethiosulfonate sodium as a compound having two or less mercapto groups in a molecule by a spray coater , And then dried in air at 100 ° C for 5 minutes to prepare a release layer B. The pH of the aqueous solution was adjusted to 5 to 9.

[Release Layer C]

An aqueous triisopropoxy aluminum solution (triisopropoxy aluminum concentration: 0.04 mol / L) was sprayed onto the treated surface of the copper foil using triisopropoxy aluminum, which is an aluminate compound, as a metal alkoxide, using a spray coater And then dried in air at 100 ° C for 5 minutes to prepare a release layer C. After the aluminate compound was dissolved in water, the stirring time until the application was 2 hours, the alcohol concentration in the aqueous solution was 0 vol%, and the pH of the aqueous solution was 5 to 9.

[Release Layer D]

An aqueous solution of n-decyltriisopropoxytitanium (n-decyltriisopropoxytitanium concentration: 0.01 mol / L) was dissolved in a spray coater using n-decyltriisopropoxytitanium as a titanium alkoxide compound as a metal alkoxide And then dried in air at 100 ° C. for 5 minutes to prepare a release layer D. The thiocarbonate compound was dissolved in water, and the stirring time until application was 24 hours. The alcohol concentration in the aqueous solution was adjusted to 20 vol% of methanol and the pH of the aqueous solution was adjusted to 5 to 9.

[Release Layer E]

(N-propyl-tri-n-butoxyzirconium concentration: 0.04 mol / mol) in the presence of n-propyl-tri-n-butoxyzirconium zirconate as a metal alkoxide, L) was applied to the treated surface of the copper foil using a spray coater and then dried in air at 100 ° C for 5 minutes to prepare a release layer E. The dissolution time of the titanate compound in water was 12 hours, the alcohol concentration in the aqueous solution was 0 vol%, and the pH of the aqueous solution was 5 to 9 before the application.

(6) Resin layer formation treatment

In Example 1, after formation of the release layer, a resin layer was further formed under the following conditions.

(Resin synthesis example)

Into a 2-liter three-necked flask equipped with an anchor-shaped stirrer bar made of stainless steel, a nitrogen inlet tube and a trap equipped with a stopcock and equipped with a reflux condenser equipped with a bead- (400 mmol) of biphenyltetracarboxylic acid dianhydride, 87.7 g (300 mmol) of 1,3-bis (3-aminophenoxy) benzene, 4.0 g (40 mmol) of γ- valerolactone, 4.8 g 300 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 20 g of toluene were added and the mixture was heated at 180 占 폚 for 1 hour and cooled to near room temperature. Then, 3,4,3 ' (200 mmol) of 2,2-bis {4- (4-aminophenoxy) phenyl} propane, 200 g of NMP and 40 g of toluene were added and mixed at room temperature for 1 hour. Then, 180 Lt; 0 > C for 3 hours to obtain a block copolymerized polyimide having a solid content of 38%. The block copolymer polyimide had the following general formula (1): general formula (2) = 3: 2, number average molecular weight: 70000, and weight average molecular weight:

[Chemical Formula 5]

The block copolymer polyimide solution obtained in Synthesis Example was further diluted with NMP to obtain a block copolymer polyimide solution having a solid content of 10%. (4-maleimidephenyl) methane (BMI-H, Keigasease) was added to the block copolymer polyimide solution at a solids weight ratio of 35 and a block copolymer polyimide solids weight ratio of 65 (that is, Bis (4-maleimidophenyl) methane solid content weight: solid content of block copolymer polyimide contained in the resin solution = 35: 65) was dissolved and mixed at 60 占 폚 for 20 minutes to prepare a resin solution. Thereafter, the above-mentioned resin solution was coated on the release layer formation surface, and the resin solution was applied in a nitrogen atmosphere at 120 캜 for 3 minutes and at 160 캜 for 3 minutes, and finally at 300 캜 for 2 minutes to form a resin layer A copper foil was produced. The thickness of the resin layer was set to 2 탆.

(7) Various evaluations

Evaluation of the ratio (Sq / Rsm) of the square root mean square height (Sq) and the square root mean square height (Sq) and the mean spacing (Rsm)

The surface of each metal foil (the surface of the surface to be surface-treated after surface treatment in the case of surface treatment such as roughening treatment and the surface on which the release layer after the release layer is provided when the release layer is formed) The ratio (Sq / Rsm) of the square root height (Sq), the root mean square height (Sq) and the average spacing (Rsm) of the irregularities was measured using a laser microscope LEXT OLS 4100 manufactured by Olympus Corporation. Rsm was measured according to JIS B 0601 2001 conforming mode and Sq was measured according to ISO 25178 compliant mode. In addition, the average values of Rsm and Sq values measured at arbitrary 10 places in both of Rsm and Sq were taken as the values of Rsm and Sq. The measurement length of Rsm was 258 mu m and the measurement area of Sq was 258 mu m in length and 258 mu m in width. Then, the ratio (Sq / Rsm) of the square root mean square height (Sq) to the irregularity mean interval (Rsm) was calculated based on the obtained values. The temperature at the time of measurement was set at 23 to 25 占 폚.

· Circuit formability on metal foil

(Second face) of the release layer side of the metal foil with a release layer, or a resin base material was laminated on the second face of the metal foil to produce a laminate (1). Thereafter, a resist is applied to a surface (first surface) opposite to the side of the metal foil with a release layer adhered to the resin base material (first surface) or the surface opposite to the side where the metal foil is laminated with the resin base material The development was carried out, and the resist was etched in a line shape. Then, a 12 μm-thick circuit Cu plating for circuit was formed, and the resist was removed to form a line-shaped circuit (wiring) having a line and space (L / S) of 12 μm / 12 μm and a length of 1 mm Formed. Thereafter, a bismaleimide triazine resin prepreg was laminated by thermocompression so that a circuit was embedded on the side where the metal foil circuit with a release layer was formed, or the side where a metal foil circuit was formed. Thereafter, the resin substrate laminated on the face (second face) on the release layer side or on the second face of the metal foil of the above-mentioned release-type layer-adhered metal foil is peeled off and then the exposed metal foil or metal foil with the release- . In addition, the etching described above was carried out until the bismaleimide triazine resin prepreg around the circuit and the circuit described above was completely exposed. Subsequently, the difference (mu m) between the maximum value and the minimum value of the circuit width seen from the top surface of the circuit was measured, and the average value was obtained by measuring five points. When the difference between the maximum value and the minimum value is 2 mu m or less, it is judged to have good circuit linearity and is determined as " & cir & ". When the difference between the maximum value and the minimum value is more than 2 mu m but not more than 3 mu m, "? &Quot; When the difference between the maximum value and the minimum value is more than 3 占 퐉 but not more than 4 占 퐉, it is determined as "占". When the difference between the maximum value and the minimum value is more than 4 占 퐉 but not more than 5 占 퐉, it is determined to be?. When the difference between the maximum value and the minimum value is more than 5 mu m, it is determined as " x ".

Circuit stripping on metal foil;

The resin substrate was laminated on the face (second face) on the release layer side of the metal foil with a release layer or on the second face of the metal foil to produce a laminate (1). Thereafter, a resist is applied to a surface (first surface) opposite to the surface of the metal foil with a release layer adhered to the resin base material (first surface) or a surface opposite to the surface of the metal foil laminated with the resin base material The development was carried out, and the resist was etched in a line shape. Subsequently, after forming Cu plating for a circuit having a thickness of 12 탆, the resist was removed to form 20 lines / lines (wirings) each having a line and space (L / S) of 12 탆 / . At this time, when the resist was removed, the number of times the circuit was peeled off from the surface of the metal foil with a release layer and the surface of the metal foil was measured. Quot ;, "? &Quot;, "? &Quot;, "? &Quot;, "? &Quot;, "? &Quot;, " &Quot;, and " x " in the case of four or more times among 10 times.

Preparation of laminate (2)

The following resin substrates 1 to 3 were bonded to the surface (second surface) of the metal foil on the release layer side or the second surface of the metal foil.

Material 1: GHPL-830 MBT manufactured by Mitsubishi Gas Chemical Co., Ltd.

Material 2: 679-FG manufactured by Hitachi Kasei Kogyo Co., Ltd.

Material 3: EI-6785TS-F manufactured by Sumitomo Bakelite Co., Ltd.

The temperature, pressure, and time of the laminated press were based on the recommended conditions of the manufacturer of each substrate.

· Evaluation of Peel Strength

With respect to the layered product 2, the state peel strength at the time of peeling the resin base material from the copper foil with the tensile tester Autograph 100 according to IPC-TM-650 was measured, and the peelability of the metal foil was evaluated according to the following criteria . The results are shown in the " peel strength " The peel strength is preferably 2 to 200 gf / cm.

?: Was in the range of 2 to 200 gf / cm.

X: less than 2 gf / cm or greater than 200 gf / cm.

· Evaluation of resin failure mode

The peeling surface of the resin substrate after peeling was observed with an electron microscope, and the failure modes of the resin (aggregation, interface, aggregation and interfacial adhesion) were observed. "Cohesion" indicates that the peeling strength is so strong that the resin is broken, and "coexistence" refers to the case where the "interface" and the "cohesion" &Quot; The failure mode of the resin is preferably " interface ".

· Circuit stripping, evaluation of board expansion

Plating the peeling surface of the resin substrate after the peeling 1-3 [solution composition, Cu: 50g / L, H 2 SO 4: 50g / L, Cl: 60ppm) the utilization by copper plating pattern (line / space = 40㎛ / 40 占 퐉) (Example 1). Before the above-described copper plating pattern was formed in the same manner as in the semi-additive method described in Example 1, cleaning and electroless copper plating were performed on the peeling surfaces of the resin substrates 1 to 3 after peeling described above. Thereafter, the dry film was laminated on the electroless copper plating layer. Then, the dry film was etched in a line shape by performing exposure to remove the dry film at the place where the copper plating pattern was to be formed. Then, the above-mentioned copper plating pattern was formed on the electroless copper plating layer not covered with the dry film by electroplating. After the copper plating pattern was formed, the dry film and the portion of the electroless copper plating layer where the copper plating pattern was not formed were removed. A print pattern (line / space = 40 占 퐉 / 40 占 퐉) was formed by ink jet printing using the ink containing a conductive paste on the release surface of the resin substrate after peeling (Example 2). A resin layer (a resin constituting the buildup layer was assumed) made of a liquid crystal polymer was laminated on the release surface of the resin substrate after peeling (Example 3).

Then, it was confirmed whether or not circuit peeling or substrate expansion occurred according to the reliability test (heating test at 250 占 10 占 폚 for 1 hour). The size of the evaluation sample was 250 mm x 250 mm, and three samples were measured for each sample number.

&Quot; & cir & & Circuit peeling or substrate expansion occurred a little (3 or less out of one sample), and when a used portion was selected, a product which can be used as a product was evaluated as "? &Quot;. In addition, a large number of circuit peeling or substrate expansion occurred (more than 3 out of one sample), and the product which could not be used as a product was evaluated as " x ".

Table 1 shows the test conditions and evaluation results.

[Table 1]

(Evaluation results)

Examples 1 to 19 are examples of the metal foil having the square root mean square height (Sq) of the first face of 0.01 to 1 占 퐉, and the circuit formability on the metal foil is good and the circuit peeling on the metal foil can be satisfactorily suppressed. Examples 1 to 18 are examples in which the release layer is provided on the second surface side, Sq and / or Sq / Rsm of the second surface of the metal foil are controlled to a predetermined range, and the metal foil is physically peeled off from the resin substrate It was possible to satisfactorily suppress the occurrence of circuit peeling and substrate expansion. Example 19 is an example in which a release layer is provided on the second surface side, and the peeling property when the metal foil is physically peeled from the resin base material is good.

In Comparative Examples 1 and 2, the square root mean square height (Sq) of the first surface exceeded 1 占 퐉 and the circuit formability on the metal foil was poor. In Comparative Example 3, the square root mean square height (Sq) of the first side was less than 0.01 mu m, and the peeling of the circuit on the metal foil was not sufficiently suppressed.

Claims (37)

Having a first side and a second side,
A metal foil having a square root mean square height (Sq) of the first face of not less than 0.01 탆 and not more than 1 탆,
A release layer provided on the second surface of the metal foil,
The metal foil having a release layer. The method according to claim 1,
Wherein the metal foil has a square root mean square height (Sq) of the second face of not less than 0.25 m and not more than 1.6 m. The method according to claim 1,
And a ratio (Sq / Rsm) of a square root mean square height (Sq) of the second surface of the metal foil to an average spacing (Rsm) of the irregularities is 0.03 or more and 0.40 or less. 3. The method of claim 2,
And a ratio (Sq / Rsm) of a square root mean square height (Sq) of the second surface of the metal foil to an average spacing (Rsm) of the irregularities is 0.03 or more and 0.40 or less. A metal foil having a first side and a second side,
And a release layer provided on the second surface of the metal foil.
And,
Wherein the root mean square height (Sq) of the first surface satisfies the following (5-1) and (5-2).
(5-1) The square root mean square height (Sq) of the first surface satisfies any one of the following:
? 0.01 占 퐉 or more,
0.020 占 퐉 or more,
0.025 占 퐉 or more,
(5-2) The square root mean square height (Sq) of the first surface satisfies any one of the following:
占 퐉 or less,
? 0.90 占 퐉 or less,
- 0.32 탆 or less,
? 0.25 占 퐉 or less. A metal foil having a first side and a second side,
And a release layer provided on the second surface of the metal foil.
And,
The metal foil with a release layer satisfying the following (6-1) and satisfying any one or two of (6-2) and (6-3).
(6-1) The square root mean square height (Sq) of the first surface satisfies the following (6-1-1) and (6-1-2)
(6-1-1) The square root mean square height (Sq) of the first surface satisfies any one of the following:
? 0.01 占 퐉 or more,
0.020 占 퐉 or more,
0.025 占 퐉 or more,
(6-1-2) The square root mean square height (Sq) of the first surface satisfies any one of the following:
占 퐉 or less,
? 0.90 占 퐉 or less,
- 0.32 탆 or less,
? 0.25 占 퐉 or less,
(6-2) the ratio (Sq / Rsm) of the root mean square height (Sq) of the second surface of the metal foil to the mean spacing (Rsm) of the recesses and protrusions satisfies any one or two of the following:
· 0.05 or more,
? 0.24 or less,
(6-3) The square root mean square height (Sq) of the second surface of the metal foil satisfies any one or two of the following:
? 0.25 占 퐉 or more,
占 퐉 or less. 7. The method according to any one of claims 1 to 6,
Wherein the metal foil has a thickness of 1 占 퐉 or more and 105 占 퐉 or less. 7. The method according to any one of claims 1 to 6,
Wherein the metal foil is a copper foil. 7. The method according to any one of claims 1 to 6,
At least one layer 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 is provided between the first surface of the metal foil and / or the second surface of the metal foil and the release layer Metal foil with a release layer. 10. The method of claim 9,
And a resin layer provided on at least one layer 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. 11. The method of claim 10,
Wherein the resin layer is a resin for bonding, a primer, or a semi-cured resin. 7. The method according to any one of claims 1 to 6,
Wherein the release layer has the following formula:
[Chemical Formula 1]

(Wherein R ¹ is an alkoxy group or a halogen atom, R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or a hydrocarbon group in which at least one hydrogen atom of the hydrocarbon group is substituted with a halogen atom, M is any one of Al, Ti and Zr, n is 0, 1 or 2, m is an integer of not less than 1 but not more than M, at least one of R ¹ is an alkoxy group, m + The mantissa of M is 3 for Al, and 4 for Ti and Zr.)
A hydrolysis product of a titanate compound, a hydrolysis product of a zirconate compound, a hydrolysis product of a hydrolysis product of an aluminate compound, an aluminate compound, A condensation product of a hydrolysis product of a zirconium salt compound, and a condensate of a hydrolysis product of a zirconium salt compound. 7. The method according to any one of claims 1 to 6,
Wherein the release layer has the following formula:
(2)

(Wherein R ¹ is an alkoxy group or a halogen atom, R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or a hydrocarbon group in which at least one hydrogen atom of the hydrocarbon group is substituted with a halogen atom, R ³ and R ⁴ each independently represent 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 at least one hydrogen atom of the hydrocarbon group is substituted with a halogen atom. )
, A hydrolysis product of the silane compound, and a condensate of the hydrolysis product. The metal foil with a release layer according to any one of claims 1 to 5, wherein the metal foil is at least one selected from the group consisting of a silane compound represented by formula 7. The method according to any one of claims 1 to 6,
Wherein the release layer comprises a compound having two or less mercapto groups in a molecule. 7. The method according to any one of claims 1 to 6,
And a resin layer provided on a surface of the release layer. 16. The method of claim 15,
Wherein the resin layer is a resin for bonding, a primer, or a semi-cured resin. A metal foil having a first surface and a second surface, wherein the square root mean square height (Sq) of the first surface is not less than 0.01 탆 and not more than 1 탆. 18. The method of claim 17,
Wherein the root mean square height (Sq) of the second surface is 0.25 탆 or more and 1.6 탆 or less. 18. The method of claim 17,
(Sq / Rsm) of the square root mean square height (Sq) of the second surface of the metal foil to the mean spacing (Rsm) of the irregularities is 0.03 or more and 0.40 or less. 19. The method of claim 18,
(Sq / Rsm) of the square root mean square height (Sq) of the second surface of the metal foil to the mean spacing (Rsm) of the irregularities is 0.03 or more and 0.40 or less. Having a first side and a second side,
Wherein the root mean square height Sq of the first surface satisfies the following (21-1) and (21-2).
(21-1) the square root mean square height (Sq) of the first surface satisfies any one of the following:
? 0.01 占 퐉 or more,
0.020 占 퐉 or more,
0.025 占 퐉 or more,
(21-2) The square root mean square height (Sq) of the first surface satisfies any one of the following:
占 퐉 or less,
? 0.90 占 퐉 or less,
- 0.32 탆 or less,
? 0.25 占 퐉 or less. Having a first side and a second side,
The metal foil satisfies the following (22-1) and satisfies any one or two of (22-2) and (22-3).
(22-1) The square root mean square height Sq of the first surface satisfies the following (22-1-1) and (22-1-2)
(22-1-1) The square root mean square height (Sq) of the first surface satisfies any one of the following:
? 0.01 占 퐉 or more,
0.020 占 퐉 or more,
0.025 占 퐉 or more,
(22-1-2) The square root mean square height (Sq) of the first surface satisfies any one of the following:
占 퐉 or less,
? 0.90 占 퐉 or less,
- 0.32 탆 or less,
? 0.25 占 퐉 or less,
(22-2) The ratio (Sq / Rsm) of the root mean square height (Sq) of the second surface of the metal foil to the mean spacing (Rsm) of the recesses and protrusions satisfies any one or two of the following:
· 0.05 or more,
? 0.24 or less,
(22-3) The square root mean square height (Sq) of the second surface of the metal foil satisfies any one or two of the following:
? 0.25 占 퐉 or more,
占 퐉 or less. 23. The method according to any one of claims 17 to 22,
Wherein the metal foil has a thickness of 1 占 퐉 or more and 105 占 퐉 or less. 23. The method according to any one of claims 17 to 22,
Wherein the metal foil is a copper foil. 23. The method according to any one of claims 17 to 22,
Wherein at least one layer selected from the group consisting of a roughening treatment layer, a heat resistant layer, a rust preventing layer, a chromate treatment layer and a silane coupling treatment layer is provided on the first surface of the metal foil and / or the second surface of the metal foil. 26. The method of claim 25,
And a resin layer provided on at least one layer 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. A metal foil with a release layer according to any one of claims 1 to 6 or a metal foil according to any one of claims 17 to 22 and a metal foil with a release layer or a resin substrate provided on the metal foil sieve. 28. The method of claim 27,
Wherein the resin substrate is a prepreg or a laminate comprising a thermosetting resin. A printed wiring board comprising the metal foil with a release layer according to any one of claims 1 to 6 or the metal foil according to any one of claims 17 to 22. 29. A semiconductor package comprising the printed wiring board according to claim 29. An electronic device comprising the printed wiring board according to claim 29 or the semiconductor package according to claim 30. A process for producing a metal foil with a release layer according to any one of claims 1 to 6 or a process for bonding an insulating substrate to the metal foil according to any one of claims 17 to 22,
Removing the metal foil with a release layer or the metal foil from the insulating substrate without etching so as to obtain an insulating substrate on which the surface profile of the metal foil with a release layer or the metal foil is transferred to the release face;
A step of forming a circuit on the release surface side of the insulating substrate onto which the surface profile is transferred
Wherein the step of forming the printed wiring board comprises the steps of: 33. The method of claim 32,
Wherein the circuit formed on the release face side of the insulating substrate onto which the surface profile is transferred is a plating pattern or a print pattern. A process for producing a metal foil with a release layer according to any one of claims 1 to 6 or a process for bonding an insulating substrate to the metal foil according to any one of claims 17 to 22,
Removing the metal foil with a release layer or the metal foil from the insulating substrate without etching so as to obtain an insulating substrate on which the surface profile of the metal foil with a release layer or the metal foil is transferred to the release face;
A step of providing a build-up layer on the release face side of the insulating substrate onto which the surface profile is transferred
Wherein the step of forming the printed wiring board comprises the steps of: 35. The method of claim 34,
Wherein the resin constituting the buildup layer comprises a liquid crystal polymer, a fluorine resin, a low dielectric constant polyimide, a polyphenylene ether, a cycloolefin polymer or polytetrafluoroethylene. A metal foil with a release layer according to any one of claims 1 to 6 or a metal foil according to any one of claims 17 to 22, wherein the insulating substrate (1) is bonded to the mold release layer side or the metal foil second surface side ,
A step of forming a circuit on the metal foil with a release layer laminated with the insulating substrate (1) or the first surface of the metal foil,
A step of covering the circuit with an insulating substrate (2) and embedding the circuit 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
Removing the exposed metal foil with a release layer or the metal foil
Wherein the step of forming the printed wiring board comprises the steps of: A metal foil with a release layer according to any one of claims 1 to 6 or a metal foil according to any one of claims 17 to 22, wherein the insulating substrate (1) is bonded to the mold release layer side or the metal foil second surface side ,
A step of laminating a metal foil with a release layer laminated with the insulating substrate (1) or a dry film on the first surface side of the metal foil of the metal foil;
A step of forming a circuit after patterning the dry film,
A step of peeling the dry film to expose the circuit,
A step of covering the exposed circuit with an insulating substrate (2) and embedding the circuit 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
Removing the exposed metal foil with a release layer or the metal foil
Wherein the step of forming the printed wiring board comprises the steps of:

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