WO2017051905A1

WO2017051905A1 - Surface-treated metal foil, laminated body, printed wiring board, semiconductor package, electronic device, and method for producing printed wiring board

Info

Publication number: WO2017051905A1
Application number: PCT/JP2016/078117
Authority: WO
Inventors: 晃正森山; 雅史石井
Original assignee: Ｊｘ金属株式会社
Priority date: 2015-09-25
Filing date: 2016-09-23
Publication date: 2017-03-30
Also published as: TW201718937A; TWI618814B; JP6498091B2; CN107921749A; KR20180051600A; JP2017061080A

Abstract

To provide a metal foil such that a release layer is provided to the metal foil to allow the metal foil to be physically peeled from a resin substrate once the metal foil has been affixed to the resin substrate, thereby making it possible to: remove the metal foil in a cost-efficient manner in a step for removing the metal foil from the resin substrate, without any damage to the profile of the surface of the metal foil transferred to the surface of the resin substrate; and cause resins having different resin components to be affixed together with high adhesiveness. A surface-treated metal foil having a surface-treated layer on at least one surface, wherein the water contact angle of the surface-treated-layer-side surface is 90° or greater.

Description

Surface-treated metal foil, laminate, printed wiring board, semiconductor package, electronic device, and printed wiring board manufacturing method

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

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

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

JP 2006-196863 A JP 2007-242975 A

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

In recent years, techniques for manufacturing a laminate by laminating a build-up layer such as a circuit or resin on a resin have been researched and developed. In this case, sufficient adhesion may not be obtained between the build-up layer such as a circuit or resin and the resin, and it is necessary to provide unevenness on the resin on one side to improve the adhesion due to the anchoring effect. Although there are physical processing, chemical processing, and the like as a method for forming irregularities on the cured resin surface, these may not be suitable depending on the physical properties and chemical properties of the resin. Then, further development is desired also about the technique which provides buildup layers, such as a circuit and resin, with favorable adhesiveness in resin.

As a result of intensive studies, the present inventors have provided a surface treatment layer such as a release layer on the surface of the metal foil so that the metal foil has a predetermined water-repellent surface. When pasted together, physical peeling of the metal foil from the resin substrate was made possible. And, as described above, by enabling physical peeling of the metal foil from the resin base material, the profile of the surface of the metal foil transferred to the surface of the resin base material in the step of removing the metal foil from the resin base material It has been found that the metal foil can be removed at a favorable cost without impairing the thickness. Furthermore, a metal foil having a predetermined water-repellent surface is bonded to the resin base material and cured, and then the metal foil is removed to transfer the profile to the resin base material surface. It has been found that the layers can be laminated with good adhesion.

The present invention completed on the basis of the above knowledge is, in one aspect, a surface-treated metal foil having a surface-treated layer on at least one surface, and a water contact angle on the surface of the surface-treated layer is 90 degrees or more. It is a surface-treated metal foil.

In one embodiment of the metal foil of the present invention, the kurtosis Rku defined by JIS B 0601 on the surface of the surface treatment layer is 2.0 to 4.0.

In another embodiment of the metal foil of the present invention, the surface treatment layer includes the release layer, and the release layer is formed by attaching the resin base material to the metal foil from the release layer side. The resin base material is made peelable.

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

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

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

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

In still another embodiment of the surface-treated metal foil of the present invention, a roughened layer, a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a silane coupling-treated layer are provided between the metal foil and the release layer. One or more layers selected from the group consisting of are provided.

In still another embodiment, the surface-treated metal foil of the present invention 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. A resin layer is provided on the surface.

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

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

In still another embodiment, the surface-treated metal foil of the present invention has a thickness of 5 to 210 μm.

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

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

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

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

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

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

In yet another aspect of the present invention, the surface-treated metal foil of the present invention is bonded to a resin base material from the surface-treated layer side, and the surface-treated metal foil is etched from the resin base material. A step of obtaining a resin base material having the surface profile of the metal foil transferred to the release surface by peeling, and a step of forming a circuit on the side of the release surface of the resin base material to which the surface profile has been transferred. A method for manufacturing a printed wiring board.

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

In yet another aspect of the present invention, the surface-treated metal foil of the present invention is bonded to a resin base material from the surface-treated layer side, and the surface-treated metal foil is etched from the resin base material. A step of obtaining a resin base material having a surface profile of the metal foil transferred to a release surface by peeling, and a step of providing a build-up layer on the side of the release surface of the resin base material to which the surface profile has been transferred. It is a manufacturing method of the provided printed wiring board.

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

In the step of removing the metal foil from the resin substrate by providing a release layer on the metal foil and enabling physical peeling of the resin substrate when the metal foil is bonded to the resin substrate, The metal foil can be removed at a good cost without impairing the profile of the surface of the metal foil transferred to the surface of the resin substrate. Moreover, a buildup layer can be provided in the resin base material with favorable adhesiveness.

A schematic example of a semi-additive construction method using a copper foil profile is shown.

(Surface-treated metal foil)
The surface-treated metal foil of the present invention is a surface-treated metal foil having a surface-treated layer on at least one surface, that is, one surface or both surfaces, and a water contact angle on the surface of the surface-treated layer is 90 degrees. That's it. Further, in one embodiment, the surface-treated metal foil of the present invention includes a release layer, and the release layer has a resin base material bonded to the metal foil from the release layer side. The resin substrate is made peelable. Thus, by providing a surface treatment layer such as a release layer on the surface of the metal foil, the metal foil has a water-repellent surface with a water contact angle of 90 degrees or more. As a result, the metal foil is attached to the resin substrate. When combined, physical peeling of the metal foil from the resin substrate becomes possible. And by enabling physical peeling of the metal foil from the resin base material, in the step of removing the metal foil from the resin base material, the profile of the metal foil surface transferred to the surface of the resin base material is not impaired. It becomes possible to remove the metal foil at a good cost. Further, a metal foil having a water repellent surface with a water contact angle of 90 degrees or more is bonded to the resin base material and cured, and then the metal foil is removed to transfer the profile to the resin base material surface. It becomes possible to laminate a build-up layer such as a circuit or a resin with good adhesion on the resin base material.

Since the surface-treated metal foil has a water-repellent surface with a water contact angle of 90 degrees or more, the metal after peeling the metal foil while maintaining good peelability after bonding the metal foil and the resin base material It becomes possible to provide the resin base material surface to which the uneven profile on the foil surface is transferred and a buildup layer such as a circuit or a resin with good adhesion.

When the water contact angle of the water repellent surface of the surface-treated metal foil is less than 90 degrees, there arises a problem that the peel strength when the metal foil is bonded to the resin becomes too high. The water contact angle of the water repellent surface of the metal foil is preferably 90 degrees or more, and more preferably 110 degrees or more. In addition, the water contact angle of the water repellent surface of the surface-treated metal foil is preferably 120 degrees or less from the viewpoint that the metal foil does not peel naturally and the peelability falls within an appropriate range.

The uneven shape on the surface-treated metal foil surface is also important as a factor that affects the peel strength. When the kurtosis Rku on the surface of the metal foil on which the release layer is provided is in the range of 2.0 to 4.0, good release properties of the metal foil and build-up of circuits and resins provided after the metal foil is peeled off It is possible to achieve both good adhesion of the layers.
In this specification, “surface”, “surface of metal foil” and “surface of metal foil” are a roughened layer, a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a silane coupling-treated layer on the surface of the metal foil. When a surface treatment layer such as a release layer is provided, it means the surface after the surface treatment layer is provided (the surface of the outermost layer).

The release layer may be provided on both sides of the metal foil. Further, the bonding may be performed by pressure bonding. Moreover, you may provide a release layer on both surfaces of metal foil.

The metal foil (also referred to as raw foil) is not particularly limited, but copper foil, aluminum foil, nickel foil, copper alloy foil, nickel alloy foil, aluminum alloy foil, stainless steel foil, iron foil, iron alloy foil, etc. may be used. it can.
The thickness of the metal foil (raw foil) is not particularly limited, and can be, for example, 5 to 105 μm. In addition, the thickness of the metal foil is preferably 9 to 70 μm, more preferably 12 to 35 μm, and even more preferably 18 to 35 μm, since it can be easily peeled off from the resin base material. .

Hereinafter, a copper foil will be described as an example of a metal foil (raw foil). Although it does not specifically limit as a manufacturing method of copper foil (raw foil), For example, an electrolytic copper foil can be produced on the following electrolysis conditions.
Electrolytic conditions for electrolytic green foil:
Cu: 30 to 190 g / L
H ₂ SO ₄ : 100 to 400 g / L
Chloride ion (Cl ⁻ ): 60 to 200 ppm by mass
Nika: 1-10ppm
Electrolyte temperature: 25-80 ° C
Electrolysis time: 10 to 300 seconds (adjusted according to the thickness of copper to be deposited and current density)
Current density: 50 to 150 A / dm ²
Electrolyte linear velocity: 1.5-5m / sec

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

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

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

formula:

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

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

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

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

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

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

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

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

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

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

The higher the concentration of the silane compound in the aqueous solution of the silane compound, the lower the peel strength between the metal foil and the plate carrier, and the peel strength can be adjusted by adjusting the concentration of the silane compound.
Moreover, water repellency can be improved more conventionally than by making the density | concentration of the silane compound in the aqueous solution of a silane compound high. The concentration of the silane compound in the aqueous solution of the silane compound can be 8 to 15% by volume. When the concentration is less than 8% by volume, water repellency is insufficient (specifically, the water contact angle may be less than 90 degrees), and when it exceeds 15% by volume, poor dissolution of the silane compound occurs. When the metal foil is laminated with the resin substrate, there is a risk that swelling due to the unreacted silane compound occurs.
Moreover, it is preferable to implement the drying process twice after applying the silane compound to the treated surface of the metal foil. The first drying is performed only for the purpose of drying the aqueous solution of the silane compound. The second drying has the effect of improving water repellency by terminating all condensation reactions for hydroxyl groups in the silane compound that have not undergone the condensation reaction and eliminating the remaining OH groups (hydroxyl groups). The first drying can be performed at 80 to 120 ° C. × 10 seconds to 2 minutes, and the second drying can be performed at 120 to 200 ° C. × 30 seconds to 5 minutes.
When a water-alcohol mixed solution of silane compound is used, the alcohol concentration in the solution is preferably 20 to 80% by volume in order to uniformly dissolve the silane compound that is hardly soluble in water. If the alcohol concentration in the solution is less than 20% by volume, the silane compound may not dissolve, and if it exceeds 80% by volume, the hydrolysis reaction will be incomplete. Residual, water repellency is lowered, and the contact angle of water may be reduced.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The higher the concentration of the compound having two or less mercapto groups in the molecule in the aqueous solution, the lower the peel strength between the resin substrate and the metal foil, and the compound having two or less mercapto groups in the molecule. The peel strength can be adjusted by adjusting the concentration.
Moreover, water repellency can be improved more conventionally than by making the density | concentration in the aqueous solution of the compound which has two or less mercapto groups in a molecule | numerator high. The concentration of the compound having two or less mercapto groups in the molecule in the aqueous solution can be 8 to 15% by volume. When the concentration is less than 8% by volume, water repellency is insufficient (specifically, the water contact angle may be less than 90 degrees). When the concentration is more than 15% by volume, two or less in the molecule. When a compound having a mercapto group is poorly dissolved and the metal foil is laminated with a resin substrate, there is a possibility that swelling due to an unreacted compound may occur.
In addition, it is preferable to perform the drying process twice after applying a compound having two or less mercapto groups in the molecule to the treated surface of the metal foil. The first drying is performed only for the purpose of drying an aqueous solution of a compound having two or less mercapto groups in the molecule. The second drying has the effect of improving water repellency by adjusting the arrangement of compounds having two or less mercapto groups in the molecule coordinated on the surface of the metal foil. The first drying can be performed at 80 to 120 ° C. × 10 seconds to 2 minutes, and the second drying can be performed at 120 to 200 ° C. × 30 seconds to 5 minutes.
Further, when a water-alcohol mixed solution of a compound having 2 or less mercapto groups in the molecule is used, the alcohol concentration in the solution is a compound having 2 or less mercapto groups in the molecule which is hardly soluble in water. Is preferably 20 to 80% by volume in order to dissolve uniformly. When the alcohol concentration in the solution is less than 20% by volume, a compound having two or less mercapto groups in the molecule may not dissolve, and when it exceeds 80% by volume, it is densely coordinated on the surface of the metal foil. There is a possibility that the arrangement of compounds having two or less mercapto groups in the molecule is disturbed, the water repellency is lowered, and the contact angle of water is reduced.

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

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

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

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

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

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

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

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

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

The higher the concentration of the metal alkoxide in the aqueous solution, the lower the peel strength between the resin base material and the metal foil, and the peel strength can be adjusted by adjusting the metal alkoxide concentration.
Further, by increasing the concentration of the metal alkoxide in the aqueous solution, the water repellency can be improved more than before. The concentration of the metal alkoxide in the aqueous solution can be 8 to 15% by volume. If the concentration is less than 8% by volume, water repellency is insufficient (specifically, the water contact angle may be less than 90 degrees), and if it exceeds 15% by volume, poor dissolution of the metal alkoxide occurs. When the metal foil is laminated with the resin substrate, there is a possibility that swelling due to the unreacted compound occurs.
Moreover, it is preferable to carry out the drying process twice after applying the metal alkoxide to the treated surface of the metal foil. The first drying is performed only for the purpose of drying the aqueous solution of the metal alkoxide. The second drying has the effect of improving the water repellency by terminating all condensation reactions for the hydroxyl groups in the metal alkoxide that have not undergone the condensation reaction and eliminating the remaining OH groups (hydroxyl groups). The first drying can be performed at 80 to 120 ° C. × 10 seconds to 2 minutes, and the second drying can be performed at 120 to 200 ° C. × 30 seconds to 5 minutes.
When a water-alcohol mixed solution of metal alkoxide is used, the alcohol concentration in the solution is preferably 20 to 80% by volume in order to uniformly dissolve the metal alkoxide that is hardly soluble in water. If the alcohol concentration in the solution is less than 20% by volume, the metal alkoxide may not dissolve, and if it exceeds 80% by volume, the hydrolysis reaction will be incomplete, so that the metal alkoxide is not hydrolyzed as it is. Residual, water repellency is lowered, and the contact angle of water may be reduced.

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

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

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

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

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

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

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

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

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

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

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

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

Also, the resin layer on the surface of the surface-treated metal foil may contain a thermosetting resin or a thermoplastic resin. Further, the resin layer on the surface of the surface-treated metal foil may contain a thermoplastic resin. The resin layer on the surface of the surface-treated metal foil may contain a known resin, resin curing agent, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton material, and the like. The resin layer on the surface of the surface-treated metal foil is, for example, International Publication No. WO2008 / 004399, International Publication No. WO2008 / 053878, International Publication No. WO2009 / 088453, JP-A-11-5828, JP-A-11-140281, Patent No. 3184485, International Publication No. WO 97/02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179444, Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003-304068, Patent No. 3992225, JP 2003-249739, JP 4136509, JP 2004-82687, JP 4025177, JP 2004-349654, JP 4286060, JP 2005-262506, JP 45. 0070, JP 2005-53218, JP 3949676, JP 4178415, International Publication Nos. WO 2004/005588, JP 2006-257153, JP 2007-326923, JP 2008-111169, Patent No. No. 5024930, International Publication No. WO2006 / 028207, Japanese Patent No. 4828427, Japanese Unexamined Patent Publication No. 2009-67029, International Publication No. WO2006 / 134868, Japanese Patent No. 5046927, Japanese Unexamined Patent Publication No. 2009-173017, International Publication No. WO2007 / 105635, Patent No. No. 5180815, International Publication Number WO2008 / 114858, International Publication Number WO2009 / 008471, JP2011-14727, International Publication Number WO2009 / 001850, International Publication Number WO2009 145179, International Publication No. WO2011 / 068157, JP2013-19056A (resins, resin curing agents, compounds, curing accelerators, dielectrics, reaction catalysts, crosslinking agents, polymers, prepregs, skeleton materials, etc. ) And / or a resin layer forming method and a forming apparatus.

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

(Printed wiring board manufacturing method)
In one aspect, the method for producing a printed wiring board of the present invention includes a step of bonding a resin base material from the release layer side to the surface-treated metal foil of the present invention, and the surface-treated metal foil from the resin base material. The step of obtaining a resin base material having the surface profile of the metal foil transferred to the release surface by peeling without etching, and forming a circuit on the side of the release surface of the resin base material to which the surface profile has been transferred A process. With such a configuration, a release layer is provided on the metal foil, and the resin substrate can be physically peeled when the metal foil is bonded to the resin substrate, and the metal foil is removed from the resin substrate. In the process, the metal foil can be removed at a good cost without impairing the profile of the surface of the metal foil transferred to the surface of the resin base material. In the manufacturing method, the circuit may be formed by a plating pattern. In this case, after forming a plating pattern, a desired circuit can be formed using the plating pattern to produce a printed wiring board. Further, the circuit may be formed with a printed pattern. In this case, for example, after a print pattern is formed using an ink jet containing conductive paste or the like in the ink, a desired printed circuit is formed using the print pattern, and a printed wiring board can be manufactured.

Furthermore, in another aspect of the method for producing a printed wiring board of the present invention, a step of bonding a resin base material from the release layer side to the surface-treated metal foil of the present invention, and from the resin base material, By peeling off the surface-treated metal foil without etching, a step of obtaining a resin base material in which the surface profile of the metal foil is transferred to the release surface, and the side of the release surface of the resin base material in which the surface profile is transferred Providing a build-up layer. With such a configuration, a release layer is provided on the metal foil, and the resin substrate can be physically peeled when the metal foil is bonded to the resin substrate, and the metal foil is removed from the resin substrate. In the process, the metal foil can be removed at a good cost without impairing the profile of the surface of the metal foil transferred to the surface of the resin base material. Further, even if the resin component of the resin base material and the resin component of the buildup layer are different depending on the predetermined surface shape transferred to the resin base material, it is possible to bond them with good adhesion. .

Here, the resin constituting the build-up layer provided on the surface of the resin base material is bonded to each other without any treatment of the resin and the resin base material (the resin constituting the build-up layer and the resin base material). The strength (pull strength) when pulled and peeled off may be 500 g / cm ² or less.

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

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

A fine circuit can be formed by a semi-additive method using the metal foil of the present invention. FIG. 1 shows a schematic example of a semi-additive method using a profile of a metal foil (for example, a copper foil). In the semi-additive method, a surface profile of a metal foil is used. Specifically, first, the surface-treated metal foil of the present invention is laminated on the resin base material from the release layer side to produce a laminate. Next, the metal foil of the laminate is removed by etching or peeled off. Next, after the surface of the resin base material to which the metal foil surface profile has been transferred is washed with dilute sulfuric acid or the like, electroless copper plating is performed. Then, a portion of the resin base material that does not form a circuit is covered with a dry film or the like, and electroless (electrolytic) copper plating is applied to the surface of the electroless copper plating layer that is not covered with the dry film. Then, after removing the dry film, a fine circuit is formed by removing the electroless copper plating layer formed in the portion where the circuit is not formed. Since the fine circuit formed in the present invention is in close contact with the release surface of the resin base material to which the metal foil surface profile of the present invention has been transferred, its adhesion (peel strength) is good.
Another embodiment of the semi-additive method is as follows.

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

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

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

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

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

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

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

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

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

-Production of raw foil (metal foil (copper foil) before surface treatment) An electrolytic raw foil having the thickness shown in Table 1 was produced under the following electrolysis conditions.
(Electrolytic solution composition)
Cu 120g / L
H ₂ SO ₄ 100 g / L
Chloride ion ^(Cl -) 70 ppm
Fish glue 6ppm
Electrolyte temperature 60 ℃
Current density 70A / dm ²
Electrolyte linear velocity 2m / sec

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

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

(2) Barrier treatment (heat-resistant treatment)
(Liquid composition)
Ni 13g / L
Zn 5g / L
pH 2
(Electroplating conditions)
Temperature 40 ℃
Current density 8A / dm ²

(3) Rust prevention treatment (liquid composition)
CrO ₃ 2.5g / L
Zn 0.7g / L
Na ₂ SO ₄ 10 g / L
pH 4.8
(Zinc chromate condition)
Temperature 54 ° C
Current density 0.7 As / dm ²

(4) Silane coupling treatment (liquid composition)
Tetraethoxysilane content 0.4%
pH 7.5
Application method Spraying solution

(5) Formation of release layer [Release layer A]
A water-methanol mixed solution containing a silane compound (n-propyltrimethoxysilane) in a volume ratio of 8 vol% is applied to the treated surface of the metal foil (copper foil) using a spray coater, and then air at 100 ° C. Then, the surface of the copper foil was dried for 1 minute, followed by heat treatment in air at 150 ° C. for 1 minute to form a release layer A. The stirring time from dissolving the silane compound in water to before coating was 30 hours, the methanol concentration in the solution was 40 vol% by volume, and the pH of the aqueous solution was 3.8 to 4.2.

[Release layer B]
A water-methanol mixed solution containing a silane compound (n-hexyltrimethoxysilane) in a volume ratio of 8 vol% is applied to the treated surface of the metal foil (copper foil) using a spray coater, and then air at 100 ° C. Then, the surface of the copper foil was dried for 1 minute, followed by heat treatment in air at 150 ° C. for 1 minute to form a release layer B. The stirring time from dissolving the silane compound in water to before coating was 30 hours, the methanol concentration in the solution was 40 vol% by volume, and the pH of the aqueous solution was 3.8 to 4.2.

[Release layer C]
A water-methanol mixed solution containing a silane compound (n-decyltrimethoxysilane) in a volume ratio of 8 vol% is applied to the treated surface of the metal foil (copper foil) using a spray coater, and then air at 100 ° C. Then, the surface of the copper foil was dried for 1 minute, followed by heat treatment in air at 150 ° C. for 1 minute to form a release layer C. The stirring time from dissolving the silane compound in water to before coating was 30 hours, the methanol concentration in the solution was 40 vol% by volume, and the pH of the aqueous solution was 3.8 to 4.2.

[Release layer D]
A water-methanol mixed solution containing a silane compound (dimethyldimethoxysilane) in a volume ratio of 8 vol% is applied to the treated surface of the metal foil (copper foil) using a spray coater, and then 1 in 100 ° C. air. After the copper foil surface was dried for 1 minute, a heat treatment was performed in air at 150 ° C. for 1 minute to form a release layer B. The stirring time from dissolving the silane compound in water to before coating was 30 hours, the methanol concentration in the solution was 40 vol% by volume, and the pH of the aqueous solution was 3.8 to 4.2.

[Release layer E]
A water-methanol mixed solution containing a silane compound (trifluoropropyltrimethoxysilane) in a volume ratio of 8 vol% is applied to the treated surface of the metal foil (copper foil) using a spray coater, and then air at 100 ° C. Then, the surface of the copper foil was dried for 1 minute, followed by heat treatment in air at 150 ° C. for 1 minute to form a release layer B. The stirring time from dissolving the silane compound in water to before coating was 30 hours, the methanol concentration in the solution was 40 vol% by volume, and the pH of the aqueous solution was 3.8 to 4.2.

[Release layer F]
Sodium 1-dodecanethiolsulfonate is used as a compound having two or less mercapto groups in the molecule, and a water-methanol mixed solution of sodium 1-dodecanethiolsulfonate (sodium 1-dodecanethiolsulfonate: 8 vol%) is used. After applying to the treated surface of the metal foil (copper foil) using a spray coater, the copper foil surface was dried in air at 100 ° C. for 1 minute and then heat-treated in air at 150 ° C. for 1 minute. A release layer F was formed. The methanol concentration in the solution was 40 vol% by volume, and the pH of the solution was 5-9.

[Release layer G]
Triisopropoxyaluminum, which is an aluminate compound, is used as the metal alkoxide, and a water-methanol mixed solution of triisopropoxyaluminum (triisopropoxyaluminum concentration: 8 vol%) is treated with a spray coater on the metal foil (copper foil). After coating on the surface, the surface of the copper foil was dried in air at 100 ° C. for 1 minute, and then heat-treated in air at 150 ° C. for 1 minute to form a release layer G. The stirring time from when the aluminate compound was dissolved in water to before coating was 2 hours, the alcohol concentration in the solution was 40 vol% by volume, and the pH of the solution was 5-9.

[Release layer H]
Using a titanate compound n-decyl-triisopropoxytitanium as a metal alkoxide, a water-methanol mixed solution of n-decyl-triisopropoxytitanium (n-decyl-triisopropoxytitanium concentration: 8 vol%) is spray coated. Is applied to the treated surface of the metal foil (copper foil) using, and then the copper foil surface is dried in air at 100 ° C. for 1 minute, and then heat-treated in air at 150 ° C. for 1 minute to release the release layer. H was formed. The stirring time from dissolving the titanate compound in water to before coating was 24 hours, the alcohol concentration in the solution was 40 vol% by volume, and the pH of the aqueous solution was 5-9.

[Release layer I]
Using a zirconate compound n-propyl-tri-n-butoxyzirconium as a metal alkoxide, a water-methanol mixed solution of n-propyl-tri-n-butoxyzirconium (n-propyl-tri-n-butoxyzirconium concentration: 8 vol%) After applying to the treated surface of the metal foil (copper foil) using a spray coater, the copper foil surface was dried in air at 100 ° C. for 1 minute and then heat-treated in air at 150 ° C. for 1 minute. A release layer I was formed. The stirring time from dissolving the titanate compound in water to before coating was 12 hours, the alcohol concentration in the solution was 40 vol% by volume, and the pH of the aqueous solution was 5-9.

(6) Resin layer formation treatment In Example 1, after the release layer was formed, a resin layer was further formed under the following conditions.
(Resin synthesis example)
To a 2-liter three-necked flask equipped with a stainless steel vertical stirring bar, a trap with a nitrogen inlet tube and a stopcock, and a reflux condenser with a ball condenser, 117.68 g (400 mmol) of 4′-biphenyltetracarboxylic dianhydride, 87.7 g (300 mmol) of 1,3-bis (3-aminophenoxy) benzene, 4.0 g (40 mmol) of γ-valerolactone, 4. 8 g (60 mmol), N-methyl-2-pyrrolidone (hereinafter referred to as NMP) 300 g, and toluene 20 g were added, heated at 180 ° C. for 1 hour, cooled to near room temperature, and then 3, 4, 3 ′, 4′- 29.42 g (100 mmol) of biphenyltetracarboxylic dianhydride, 82.12 g of 2,2-bis {4- (4-aminophenoxy) phenyl} propane (200 mmol), 200 g of NMP, and 40 g of toluene were added, mixed at room temperature for 1 hour, and then heated at 180 ° C. for 3 hours to obtain a block copolymerized polyimide having a solid content of 38%. The block copolymerized polyimide had the following general formula (1): general formula (2) = 3: 2, number average molecular weight: 70000, and weight average molecular weight: 150,000.

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

(7) Various evaluations-Evaluation of water contact angle The water contact angle of the metal foil surface was measured by FACE CA-D manufactured by Kyowa Interface Science Co., Ltd. The water used for the measurement is ion-exchanged water having a pH of 6 to 8 and a temperature of 25 ° C. The measurement of each contact was performed within 1 minute after the droplet was dropped on the surface of the metal foil.

-Measurement of Kurtosis (Rku) Kurtosis (Rku) on the surface of the metal foil was measured in a JIS B 0601 2001 compliant mode using a laser microscope OLS4100 manufactured by Olympus Corporation. The measurement length was 258 μm. The temperature during measurement was 23 to 25 ° C.

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

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

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

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

In each of Examples 1 to 13, the water contact angle on the surface of the surface treatment layer is 90 degrees or more, and the peelability when physically peeling the metal foil from the resin base material is good. The occurrence of swelling was successfully suppressed.
In Comparative Example 1, the water contact angle on the surface of the surface treatment layer side is less than 90 degrees, the peelability when physically peeling the metal foil from the resin base material is poor, and circuit peeling and generation of substrate swelling are caused. It was not possible to suppress well.

Claims

A surface-treated metal foil having a surface treatment layer on at least one surface,
The surface treatment metal foil whose water contact angle of the said surface treatment layer side surface is 90 degree | times or more.
The surface-treated metal foil according to claim 1, wherein the kurtosis Rku defined by JIS B 0601 on the surface of the surface treatment layer side is 2.0 to 4.0.
The surface treatment layer includes a release layer, and the release layer enables the resin base material to be peeled when the resin base material is bonded to the metal foil from the release layer side. The surface-treated metal foil described.
The release layer has the following formula:

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

Wherein R 1 is an alkoxy group or a halogen atom, and R 2 is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by R 3 and R 4 are each independently a halogen atom, an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group Or any one of these hydrocarbon groups in which one or more hydrogen atoms are replaced by halogen atoms.)
The surface-treated metal foil according to claim 3, wherein the silane compound, the hydrolysis product thereof, and the condensate of the hydrolysis product are used singly or in combination.
The surface-treated metal foil according to claim 3, wherein the release layer comprises a compound having two or less mercapto groups in the molecule.
One or more layers selected from the group consisting of a roughening treatment layer, a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer are provided between the metal foil and the release layer. 3. The surface-treated metal foil according to 3.
The surface treatment according to claim 7, wherein a resin layer is provided on the surface of one or more layers selected from the group consisting of the roughening treatment layer, the heat-resistant layer, the rust prevention layer, the chromate treatment layer, and the silane coupling treatment layer. Metal foil.
The surface-treated metal foil according to any one of claims 3 to 8, wherein a resin layer is provided on the surface of the release layer side.
The surface-treated metal foil according to claim 8 or 9, wherein the resin layer is an adhesive resin, a primer, or a semi-cured resin.
The surface-treated metal foil according to any one of claims 1 to 10, wherein the thickness is 5 to 210 µm.
The surface-treated metal foil according to any one of claims 1 to 11, wherein the metal foil is a copper foil.
A laminate comprising the surface-treated metal foil according to any one of claims 1 to 12 and a resin base material provided on a release layer side of the surface-treated metal foil.
The laminate according to claim 13, wherein the resin base material is a prepreg or contains a thermosetting resin.
A printed wiring board comprising the surface-treated metal foil according to any one of claims 1 to 12.
A semiconductor package comprising the printed wiring board according to claim 15.
An electronic device comprising the printed wiring board according to claim 15 or the semiconductor package according to claim 16.
Bonding the resin base material from the surface-treated layer side to the surface-treated metal foil according to any one of claims 1 to 12,
From the resin base material, by removing the surface-treated metal foil without etching, obtaining a resin base material in which the surface profile of the metal foil is transferred to the release surface;
Forming a circuit on the release surface side of the resin substrate to which the surface profile is transferred;
A method of manufacturing a printed wiring board comprising:
The method for manufacturing a printed wiring board according to claim 18, wherein the circuit formed on the release surface side of the resin base material to which the surface profile is transferred is a plating pattern or a printing pattern.
Bonding the resin base material from the surface-treated layer side to the surface-treated metal foil according to any one of claims 1 to 12,
From the resin base material, by removing the surface-treated metal foil without etching, obtaining a resin base material in which the surface profile of the metal foil is transferred to the release surface;
Providing a build-up layer on the release surface side of the resin substrate to which the surface profile has been transferred;
A method of manufacturing a printed wiring board comprising:
The method for producing a printed wiring board according to claim 20, wherein the resin constituting the build-up layer contains a liquid crystal polymer or polytetrafluoroethylene.