JP6588290B2 - Metal foil with release layer, laminate, printed wiring board, semiconductor package, electronic device, laminate manufacturing method, and printed wiring board manufacturing method - Google Patents

Description

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

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

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

JP 2006-196863 A JP 2007-242975 A

  However, in the conventional semi-additive method using the 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.

  As a result of intensive studies, the present inventors have provided a release layer on a metal foil having a predetermined water-repellent surface, and can physically peel the resin substrate when the metal foil is bonded to the resin substrate. In the process of removing the metal foil from the resin base material, 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. I found. Furthermore, by attaching the metal foil once peeled and removed to the resin base material again, it becomes possible to obtain a transfer shape of the metal foil surface on the resin surface a plurality of times or continuously, and a good printed wiring board can be obtained. It was found that it can be produced at a manufacturing cost.

  In one aspect, the present invention completed on the basis of the above knowledge is a metal foil that can be repeatedly subjected to a process of physical peeling after being bonded to a resin substrate.

  In one embodiment, the metal foil of the present invention can be repeatedly carried out 2 to 4 times after being physically bonded to the resin base material.

  In another embodiment, the metal foil of the present invention has a surface with a three-dimensional arithmetic average roughness Sa of 0.10 to 1.50 μm.

  In one embodiment, the metal foil of the present invention has a thickness of 5 to 105 μm.

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

  In yet another embodiment, the metal foil of the present invention is a kind 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 on the surface of the metal foil. The above layers are provided.

  In yet another embodiment, the metal foil of the present invention has a 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. A resin layer is provided.

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

  In another aspect of the present invention, the metal foil of the present invention and a release layer provided on the surface side of the metal foil having surface irregularities, and the resin from the release layer side to the metal foil It is a metal foil with a release layer provided with the release layer which makes the said resin base material peelable when a base material is bonded together.

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

In another embodiment of the metal foil with a release layer of the present invention, the release layer has the following formula:
Wherein R ¹ is an alkoxy group or a halogen atom, and R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms 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 metal foil with a release layer of the present invention, the release layer uses a compound having two or less mercapto groups in the molecule.

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

  In still another aspect, the present invention is a laminate including the metal foil of the present invention and a resin base material.

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

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

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

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

  In yet another aspect of the present invention, a step of bonding a resin base material to the metal foil of the present invention or the metal foil with a release layer of the present invention, and the metal foil or the release layer from the resin base material. A step of obtaining a resin base material in which a surface profile of the metal foil or the metal foil with a release layer is transferred to a release surface by peeling off the metal foil with etching, and a resin to which the surface profile is transferred And a step of forming a circuit on the peeling surface side of the substrate.

  In one embodiment of the method for producing a printed wiring board of the present invention, by using a metal foil peeled off from the resin base material, a surface profile is transferred to another resin base material. One or more steps of forming a circuit on the peeling surface side are further provided.

  In another 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, a step of bonding a resin base material to the metal foil of the present invention or the metal foil with a release layer of the present invention, and the metal foil or the release layer from the resin base material. A step of obtaining a resin base material in which a surface profile of the metal foil or the metal foil with a release layer is transferred to a release surface by peeling off the metal foil with etching, and a resin to which the surface profile is transferred And a step of providing a build-up layer on the release surface side of the substrate.

  In yet another embodiment of the method for producing a printed wiring board according to the present invention, a surface profile is transferred to another resin base material using a metal foil peeled off from the resin base material. One or more steps of providing a build-up layer on the release surface side of the substrate are further provided.

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

  In still another embodiment of the method for producing a printed wiring board of the present invention, the metal foil is used in a process of physically peeling the metal foil from the resin substrate after the metal foil and the resin substrate are bonded together. Metal foil used more than once.

  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. Furthermore, by attaching the metal foil once peeled and removed to the resin base material again, it becomes possible to obtain a transfer shape of the metal foil surface on the resin surface a plurality of times or continuously, and a good printed wiring board can be obtained. It can be manufactured at a manufacturing cost.

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

(Metal foil, metal foil with release layer)
The metal foil of this invention is a metal foil which can be performed by repeating the process of physically peeling after bonding with a resin base material a plurality of times. Further, the metal foil with a release layer of the present invention is a release layer provided on the metal foil of the present invention and a surface side having surface irregularities of the metal foil, and from the release layer side, It is a metal foil with a release layer provided with the release layer which makes the said resin base material peelable when a resin base material is bonded together to metal foil. Metal foil surface transferred to the surface of the resin base material in the process of removing the metal foil from the resin base material by enabling physical peeling of the resin base material when the metal foil is bonded to the resin base material The metal foil can be removed at a good cost without impairing the profile. Furthermore, by attaching the metal foil once peeled and removed to the resin base material again, it becomes possible to obtain a transfer shape of the metal foil surface on the resin surface a plurality of times or continuously, and a good printed wiring board can be obtained. It can be manufactured at a manufacturing cost. Moreover, the metal foil of this invention may be able to be performed by repeating the process which peels physically after bonding with a resin base material 2-4 times.
In this way, by providing a release layer that firmly bonds to the metal foil surface on the metal foil, and enabling the physical peeling of the resin substrate when the metal foil is bonded to the resin substrate, In the step of removing the metal foil from the resin substrate, the bonding and peeling steps are repeated a plurality of times while maintaining good peelability when physically peeling after bonding the metal foil and the resin substrate. It becomes possible.

  The metal foil of the present invention preferably has a surface with a three-dimensional arithmetic average roughness Sa of 0.10 to 1.50 μm. If the surface three-dimensional arithmetic average roughness Sa is 1.50 μm or more, there is a possibility that a problem that the peel strength when the metal foil is bonded to the resin becomes too high may occur. Sa is preferably 1.00 μm or less, and more preferably 0.70 μm or less. Sa is preferably 0.10 μm or more in that the metal foil does not peel naturally and the peelability is in an appropriate range.

  In addition, you may provide a release layer on both surfaces of metal foil. Further, the lamination or lamination of the metal foil and the resin base material, and the lamination of a laminated member such as a circuit or a resin or a build-up layer on the resin base material may be performed by pressure bonding.

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. Moreover, since peeling from a resin base material becomes easy, it is preferable that the thickness of metal foil is 9-70 micrometers, it is more preferable that it is 12-35 micrometers, and it is still more preferable that it is 18-35 micrometers. .

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 ⁻ ): 10 to 200 ppm by mass
Electrolyte temperature: 25-80 ° C
Electrolysis time: 10 to 300 seconds (adjusted according to the thickness of copper to be deposited and current density)
Current density: 50 to 150 A / dm ²
Electrolyte linear velocity: 1.5-5 m / 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 base material is removed after being bonded to the metal foil of the present invention as described above, the resin base material and the 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 metal foil according to the present invention preferably has a peel strength of 200 gf / cm or less when the resin base material is peeled off when the resin base material is bonded to the metal foil. 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 metal foil and the resin base material are bonded together, the adhesiveness is appropriately reduced, and the peel strength can be adjusted to the above range.

formula:

Wherein R ¹ is an alkoxy group or a halogen atom, and R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms 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 needs to have at least one alkoxy group. A hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group in the absence of an alkoxy group, or any one of these hydrocarbons in which one or more hydrogen atoms are substituted with a halogen atom When a substituent is comprised only by group, there exists a tendency for the adhesiveness of a resin base material and metal foil to fall too much. The silane compound is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or any one of these hydrocarbon groups in which one or more hydrogen atoms are substituted with a halogen atom. It is necessary to have at least one. This is because when the hydrocarbon group does not exist, the adhesion between the resin base material and the metal foil tends to increase. The alkoxy group includes an alkoxy group in which one or more hydrogen atoms are substituted with a halogen atom.

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

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

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

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

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

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

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

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

The higher the concentration of the silane compound in the aqueous solution of the silane compound, the lower the peel strength between the metal foil and the plate carrier, and the peel strength can be adjusted by adjusting the concentration of the silane compound.
In addition, by increasing the concentration of the silane compound in the aqueous solution of the silane compound, even if the metal foil is used a plurality of times, the peel strength is less likely to increase than before. The density | concentration of the silane compound in the aqueous solution of a silane compound can be 8-15 volume%. If the concentration is less than 8% by volume, the peel strength may be easily increased when the metal foil is used a plurality of times. If it exceeds 15% by volume, the silane compound may be poorly dissolved, and the metal foil may be used as a resin. When laminated with a substrate, if the metal foil is used a plurality of times due to the unreacted silane compound, the peel strength tends to increase.
Moreover, after apply | coating a silane compound to the process surface of metal foil (copper foil), it is preferable to implement a drying process twice. The first drying is performed only for the purpose of drying the solution of the silane compound. In the second drying, for the hydroxyl groups in the silane compound that have not undergone the condensation reaction, the condensation reaction is completely terminated and the remaining OH groups (hydroxyl groups) are eliminated, so that the release layer formed by the silane compound is removed. There is an effect that the peel strength is hardly increased when the metal foil is used a plurality of times. 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.
Moreover, when using the water-alcohol mixed solution of a silane compound, 20-80 volume% is preferable for the alcohol concentration in the said solution in order to dissolve the silane compound which is hard to dissolve in water uniformly. 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. It remains, the release layer becomes fragile, and if the metal foil is used a plurality of times, the peel strength may be easily increased.

  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 necessary, it is preferable to set the pH in the range of 5.0 to 9.0, which is near neutral, and more preferable to set the pH in the range of 7.0 to 9.0. .

(2) Compound having two or less mercapto groups in the molecule The release layer is constituted by using a compound having two or more mercapto groups in the molecule, and the resin base material and the metal via the release layer. Adhesion with the foil can also be appropriately reduced to adjust the peel strength.
However, when a compound having three or more mercapto groups in the molecule or a salt thereof is 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 the mercapto group and the plate carrier, or the mercapto group and the metal foil, This is because it is considered that the peel strength may be increased by forming a strong three-dimensional crosslinked structure between the resin base material and the metal foil. Such a case is disclosed in Japanese Patent Laid-Open No. 2000-196207.

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

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

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

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

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

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

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

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

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

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

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

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

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

  In the step of forming the release layer, the compound having 2 or less mercapto groups in the molecule can be used in the form of an aqueous solution. Alcohols such as methanol and ethanol can be added in order to increase the solubility in water. The addition of alcohol is particularly effective when a compound having two or less mercapto groups in a highly hydrophobic molecule is used.

The higher the concentration of the compound having two or less mercapto groups in the molecule in the aqueous solution, the lower the peel strength between the resin substrate and the metal foil, and the compound having two or less mercapto groups in the molecule. The peel strength can be adjusted by adjusting the concentration. Also, by increasing the concentration in the aqueous solution of the compound having 2 or less mercapto groups in the molecule, even if the metal foil is used multiple times, the peel strength is higher than before. Becomes difficult to rise. 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, the peel strength may be easily increased when the metal foil is used a plurality of times. When the concentration exceeds 15% by volume, the compound having two or less mercapto groups in the molecule may be used. When poor melting occurs and the metal foil is laminated with a resin substrate, the peel strength may increase easily if the metal foil is used more than once due to a compound having two or less mercapto groups in the undissolved molecule. There is.
Moreover, 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 (copper foil). The first drying is performed only for the purpose of drying a solution of a compound having two or less mercapto groups in the molecule. In the second drying, the second drying has not more than two mercapto groups in the molecule by adjusting the arrangement of compounds having not more than two mercapto groups in the molecule coordinated on the surface of the metal foil. The release layer formed of the compound becomes stronger, and there is an effect that the peel strength is hardly increased when the metal foil is used a plurality of times. 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 two or less mercapto groups in the molecule is used, the alcohol concentration in the solution is a compound having two or less mercapto groups in the molecule that is hardly soluble in water. Is preferably dissolved in an amount of 20 to 80% by volume. 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 the release layer may become brittle. The arrangement of compounds having two or less mercapto groups in molecules closely coordinated on the surface of the foil is disturbed, the release layer becomes brittle, and when a metal foil is used a plurality of times, the peel strength may be easily increased.

  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 necessary, it is preferable to set the pH in the range of 5.0 to 9.0, which is near neutral, and more preferable to set the pH in the range of 7.0 to 9.0. .

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

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

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

In addition, examples of the aromatic hydrocarbon group suitable as R ² include a phenyl group, a phenyl group substituted with an alkyl group (eg, tolyl group, xylyl group), 1- or 2-naphthyl group, anthryl group, and the like. Examples 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), dimethyl methoxy aluminum, triethoxy aluminum, methyl diethoxy aluminum Ethyldiethoxyaluminum, n- or iso-propyldiethoxy Luminium, n-, iso- or tert-butyldiethoxyaluminum, pentyldiethoxyaluminum, hexyldiethoxyaluminum, octyldiethoxyaluminum, decyldiethoxyaluminum, phenyldiethoxyaluminum, alkyl-substituted phenyldiethoxyaluminum (eg p -(Methyl) phenyldiethoxyaluminum), dimethylethoxyaluminum, triisopropoxyaluminum, methyldiisopropoxyaluminum, ethyldiisopropoxyaluminum, n- or iso-propyldiethoxyaluminum, n-, iso- or tert-butyl Diisopropoxy aluminum, pentyl diisopropoxy aluminum, hexyl diisopropoxy aluminum, octyl diiso Ropoxyaluminum, decyldiisopropoxyaluminum, phenyldiisopropoxyaluminum, alkyl-substituted phenyldiisopropoxyaluminum (eg, p- (methyl) phenyldiisopropoxyaluminum), dimethylisopropoxyaluminum, (3,3,3- Trifluoropropyl) dimethoxyaluminum, and tridecafluorooctyldiethoxyaluminum, methyldichloroaluminum, dimethylchloroaluminum, dimethylchloroaluminum, phenyldichloroaluminum, dimethylfluoroaluminum, dimethylbromoaluminum, diphenylbromoaluminum, and their hydrolysis products And condensates of these hydrolysis products. Among these, from the viewpoint of availability, trimethoxyaluminum, triethoxyaluminum, and triisopropoxyaluminum are preferable.

  Examples of preferred titanate compounds include tetramethoxy titanium, methyl trimethoxy titanium, ethyl trimethoxy titanium, n- or iso-propyl trimethoxy titanium, n-, iso- or tert-butyl trimethoxy titanium, n-, iso- Or neo-pentyltrimethoxytitanium, hexyltrimethoxytitanium, octyltrimethoxytitanium, decyltrimethoxytitanium, phenyltrimethoxytitanium; alkyl-substituted phenyltrimethoxytitanium (eg, p- (methyl) phenyltrimethoxytitanium), dimethyldimethoxy Titanium, tetraethoxy titanium, methyl triethoxy titanium, ethyl triethoxy titanium, n- or iso-propyl triethoxy titanium, n-, iso- or tert-butyl triethoxy titanium, Tiltlyethoxytitanium, Hexyltriethoxytitanium, Octyltriethoxytitanium, Decyltriethoxytitanium, Phenyltriethoxytitanium, Alkyl-substituted phenyltriethoxytitanium (eg, p- (methyl) phenyltriethoxytitanium), Dimethyldiethoxytitanium, Tetraisopropoxytitanium, methyltriisopropoxytitanium, ethyltriisopropoxytitanium, n- or iso-propyltriethoxytitanium, n-, iso- or tert-butyltriisopropoxytitanium, pentyltriisopropoxytitanium, hexyltriiso Propoxy titanium, octyltriisopropoxy titanium, decyl triisopropoxy titanium, phenyl triisopropoxy titanium, alkyl substituted phenyl triisopropoxy titanium (example P- (methyl) phenyltriisopropoxytitanium), dimethyldiisopropoxytitanium, (3,3,3-trifluoropropyl) trimethoxytitanium, and tridecafluorooctyltriethoxytitanium, methyltrichlorotitanium, dimethyldichloro Examples include titanium, trimethylchlorotitanium, phenyltrichlorotitanium, dimethyldifluorotitanium, dimethyldibromotitanium, diphenyldibromotitanium, hydrolysis products thereof, and condensates of these hydrolysis products. Among these, tetramethoxy titanium, tetraethoxy titanium, and tetraisopropoxy titanium are preferable from the viewpoint of availability.

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

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

The higher the concentration of the metal alkoxide in the aqueous solution, the lower the peel strength between the resin base material and the metal foil, and the peel strength can be adjusted by adjusting the metal alkoxide concentration.
In addition, by increasing the concentration of the metal alkoxide in the aqueous solution, even if the metal foil is used a plurality of times, the peel strength is less likely to increase 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, the peel strength may be easily increased when the metal foil is used a plurality of times. If it exceeds 15% by volume, the metal alkoxide is poorly dissolved, and the metal foil is resin. When laminated with a substrate, if the metal foil is used a plurality of times due to unreacted compounds, the peel strength tends to increase.
Moreover, after apply | coating a metal alkoxide to the process surface of metal foil (copper foil), it is preferable to implement two drying processes. The first drying is performed only for the purpose of drying the metal alkoxide solution. In the second drying, the hydroxyl group in the metal alkoxide that has not undergone the condensation reaction is completely terminated and the remaining OH group (hydroxyl group) is eliminated, so that the release layer formed of the metal alkoxide is removed. There is an effect that the peel strength is hardly increased when the metal foil is used a plurality of times. 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.
Moreover, when using the water-alcohol mixed solution of metal alkoxide, the alcohol concentration in the solution is preferably 20 to 80% by volume in order to uniformly dissolve the metal alkoxide which 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. It remains, the release layer becomes fragile, and if the metal foil is used a plurality of times, the peel strength may be easily increased.

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

  The metal foil according to the present invention may be provided with 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. Here, the chromate-treated layer refers to a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. Chromate treatment layer is any element such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium (metal, alloy, oxide, nitride, sulfide, etc.) May be included). Specific examples of the chromate treatment layer include a chromate treatment layer treated with chromic anhydride or a potassium dichromate aqueous solution, a chromate treatment layer treated with a treatment solution containing anhydrous chromic acid or potassium dichromate and zinc, and the like. .

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

Moreover, a well-known heat resistant layer and a rust preventive layer can be used as a heat resistant layer and a rust preventive layer. For example, the heat-resistant layer and / or the 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 . Further, the ratio of the nickel adhesion amount and the zinc adhesion amount of the layer containing the nickel-zinc alloy or the nickel-zinc alloy layer (= nickel adhesion amount / zinc adhesion amount) is 1.5 to 10. It is preferable. Further, the nickel - in adhesion amount of nickel in the zinc alloy layer is preferably from ^{0.5mg / m 2 ~500mg / m 2} , 1mg / m 2 ~50mg / m 2 - zinc alloy layer or the nickel containing More preferably.

For example heat-resistant layer and / or anticorrosive layer has coating weight of 1 mg / m ² -100 mg / m ^2, preferably from 5 mg / m ² and to 50 mg / m ² of nickel or nickel alloy layer, the adhesion amount is 1 mg / m ² to 80 mg / m ^2, preferably it may be obtained by sequentially laminating a tin layer of ^{5mg / m 2 ~40mg / m 2} , wherein the nickel alloy layer of nickel - molybdenum, nickel - zinc, nickel - molybdenum - cobalt You may be comprised by any one of these. The heat-resistant layer and / or anticorrosive layer, it is ^{preferably, 10mg / m 2 ~70mg / m} 2 total deposition amount of nickel or nickel alloy and tin is 2mg / m ² ~150mg / m 2 It is more preferable. Further, the heat-resistant layer and / or the rust preventive layer is preferably [nickel or nickel adhesion amount in nickel or nickel alloy] / [tin adhesion amount] = 0.25 to 10, preferably 0.33 to 3. More preferred.

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

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

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

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

  In addition, 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, an international publication number WO2008 / 053878, JP2008-1111169A, Patent No. Surface treatments described in Japanese Patent No. 5024930, International Publication No. WO2006 / 028207, Patent No. 4828427, International Publication No. WO2006 / 134868, Patent No. 5046927, International Publication No. WO2007 / 105635, Patent No. 5180815, JP2013-19056A It can be performed. Thus, the metal foil of the present invention includes a surface-treated metal foil.

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

  The resin layer on the surface of the metal foil may contain a thermosetting resin or may be a thermoplastic resin. The resin layer on the surface of the metal foil may contain a thermoplastic resin. The resin layer on the surface of the metal foil may contain a known resin, resin curing agent, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton material, and the like. The resin layer on the surface of the metal foil is, for example, International Publication No. WO2008 / 004399, International Publication No. WO2008 / 053878, International Publication No. WO2009 / 084533, JP-A-11-5828, JP-A-11-140281, Patent 3184485. International Publication No. WO 97/02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179744, Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003-304068, Japanese Patent No. 3992225 No., JP 2003-249739, JP 4136509, JP 2004-82687, JP 4025177, JP 2004-349654, JP 4228660, JP 2005-262506, JP 457007. No., JP-A-2005-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication Nos. No., International Publication No. WO2006 / 028207, Japanese Patent No. 4828427, Japanese Unexamined Patent Publication No. 2009-67029, International Publication No. WO2006 / 134868, Japanese Patent No. 5046927, Japanese Unexamined Patent Publication No. 2009-173017, International Publication No. WO2007 / 105635, Japanese Patent No. 5180815. No., International Publication Number WO2008 / 114858, International Publication Number WO2009 / 008471, Japanese Patent Application Laid-Open No. 2011-14727, International Publication Number WO2009 / 001850, International Publication Number WO2009 / 145 79, substances described in International Publication Nos. WO2011 / 068157 and JP2013-19056 (resins, resin curing agents, compounds, curing accelerators, dielectrics, reaction catalysts, crosslinking agents, polymers, prepregs, skeleton materials, etc. ) And / or a resin layer forming method and a forming apparatus.

(Laminated body, semiconductor package, electronic equipment)
A laminate can be produced by providing a resin base material on the 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 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 according to the present invention includes a step of bonding a resin base material to the metal foil of the present invention or the metal foil with a release layer according to the present invention, and from the resin base material, A step of obtaining a resin base material in which a surface profile of the metal foil or the metal foil with a release layer is transferred to a release surface by peeling the metal foil or the metal foil with a release layer without etching, and Forming a circuit on the release surface side of the resin base material to which the surface profile has been transferred. With such a configuration, it is possible to physically peel the resin base material when the metal foil is bonded to the resin base material with or without the release layer provided on the metal foil. In the step of removing from the material, the metal foil can be removed at a favorable cost without impairing the surface profile transferred from the surface of the metal foil 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.
In the present specification, the “surface profile” refers to an uneven surface shape. Moreover, the manufacturing method of the printed wiring board of this invention uses the metal foil peeled off from the said resin base material, and transfers the surface profile to another resin base material, The said peeling of said another resin base material One or more steps of forming a circuit on the surface side may be further provided.
In addition, the metal foil may be a metal foil that is used once or more in a step of physically peeling the metal foil from the resin base material after the metal foil and the resin base material are bonded together.

Furthermore, the manufacturing method of the printed wiring board of this invention is another one side. WHEREIN: The process of bonding a resin base material to the metal foil of this invention, The said metal foil or the said release layer is attached from the said resin base material. By peeling off the metal foil without etching, a step of obtaining a resin base material on which the surface profile of the metal foil is transferred to the release surface, and build on the release surface side of the resin base material on which the surface profile is transferred Providing an up layer. With such a configuration, it is possible to physically peel the resin base material when the metal foil is bonded to the resin base material with or without the release layer provided on the metal foil. In the step of removing from the material, 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. Moreover, even if the resin component of the resin base material and the resin component of the buildup layer are different or the same due to the predetermined uneven surface transferred to the resin base material, both have good adhesion. It becomes possible to paste them together. Moreover, the manufacturing method of the printed wiring board of this invention uses the metal foil peeled off from the said resin base material, and transfers the surface profile to another resin base material, The said peeling of said another resin base material One or more steps of providing a build-up layer on the surface side may be further provided.
In addition, the metal foil may be a metal foil that is used once or more in a step of physically peeling the metal foil from the resin base material after the metal foil and the resin base material are bonded together.

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

  As an insulator such as a resin constituting such a build-up layer, the resins, resin layers, and resin base materials described in the present specification can be used. Known resins, resin layers, resin base materials, insulators, A prepreg, a base material in which a glass cloth is impregnated with a resin, or the like can be used. The 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 surface 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 metal foil with a release layer of the present invention is laminated on the resin base material from the release layer side to produce a laminate. Next, the metal foil of the laminate is removed by etching or peeled off. Next, after the surface of the resin base material to which the metal foil surface profile has been transferred is washed with dilute sulfuric acid or the like, electroless copper plating is performed. Then, a portion of the resin 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 the method for producing a printed wiring board according to the present invention using the semi-additive method, the metal foil according to the present invention or the metal foil with a release layer according to the present invention and a resin base material are prepared. Process,
A step of laminating a resin base material on the metal foil or the metal foil with a release layer,
After laminating the metal foil and the resin base material, the step of removing the metal foil by etching or peeling off,
A step of providing a through hole or / and a blind via on an exposed surface or a peeled surface of a resin substrate generated by removing or peeling the metal foil;
Performing a desmear process on the region including the through hole or / and the blind via,
Cleaning the resin substrate surface with dilute sulfuric acid for the resin substrate and the region including the through hole or / and the blind via, and providing an electroless plating layer (for example, an electroless copper plating layer);
Providing a plating resist on the electroless plating layer;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer (for example, an electrolytic copper plating layer) in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

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

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

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

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

  The surface of the metal foil was measured with a scanning electron microscope equipped with XPS (X-ray photoelectron spectrometer), EPMA (electron beam microanalyzer), EDX (energy dispersive X-ray analysis), and Si was detected. Then, it can be inferred that a silane compound is present on the surface of the metal foil. In addition, when the peel strength (peel strength) between the 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 according to the present invention is used. .

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

  In addition, the surface of the metal foil was measured with a scanning electron microscope equipped with XPS (X-ray photoelectron spectrometer), EPMA (electron beam microanalyzer), EDX (energy dispersive X-ray analysis), Al, Ti, When Zr is detected and the peel strength (peel strength) between the metal foil and the resin substrate is 200 gf / cm or less, the metal that can be used for the release layer of the present invention on the surface of the metal foil It can be inferred that alkoxide is present.

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

-Manufacture of raw foil (copper foil before surface treatment) The electrolytic raw foil of the thickness of Table 1 was produced on the following electrolysis conditions.
(Electrolytic solution composition)
Cu 120g / L
H ₂ SO ₄ 100 g / L
Chloride ion ^(Cl -) 70 ppm
Fish glue 6ppm
Electrolyte temperature 60 ℃
Current density 70A / dm ²
Electrolyte linear velocity 2m / sec
In Example 11, 80 ppm of the additive bis (3-sulfopropyl) disulfide (SPS) was added to the above electrolyte.

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

(2) 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 metal 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 when the silane compound was dissolved 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]
After applying a water-methanol mixed solution containing 8 vol% of a silane compound (n-hexyltrimethoxysilane) by volume on the treated surface of a metal foil (copper foil) using a spray coater, 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 when the silane compound was dissolved 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 when the silane compound was dissolved 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 D. The stirring time from when the silane compound was dissolved 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. 15 minutes after the surface of the metal foil (copper foil) was dried in
A release layer E was formed by heat treatment in air at 0 ° C. for 1 minute. The stirring time from dissolving the silane compound in water to before coating is 30 hours, and the methanol concentration in the solution is 4 by volume.
0 vol%, 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 1-dodecanethiolsulfonate sodium (sodium 1-dodecanethiolsulfonate: 8 vol%) is used. After applying to the treated surface of the metal foil (copper foil) using a spray coater, the metal foil (copper foil) surface was dried in air at 100 ° C. for 1 minute and then heated in air at 150 ° C. for 1 minute. The release layer F was formed by processing. 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 a metal alkoxide, a water-methanol mixed solution of triisopropoxyaluminum (triisopropoxyaluminum concentration: 8 vol%), and treatment of metal foil (copper foil) using a spray coater. After the coating on the surface, the surface of the metal foil (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 application 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. After applying to the treated surface of the metal foil (copper foil) using, dry the surface of the metal foil (copper foil) for 1 minute in air at 100 ° C and then heat-treat in air at 150 ° C for 1 minute Thus, a 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 metal foil (copper foil) surface was dried in air at 100 ° C. for 1 minute and then heated in air at 150 ° C. for 1 minute. The release layer I was formed by processing. 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, pyridine 4. 8 g (60 mmol), N-methyl-2-pyrrolidone (hereinafter referred to as NMP) 300 g, and toluene 20 g were added, heated at 180 ° C. for 1 hour, cooled to near room temperature, and then 3, 4, 3 ′, 4′−. 29.42 g (100 mmol) of biphenyltetracarboxylic dianhydride, 82.12 g of 2,2-bis {4- (4-aminophenoxy) phenyl} propane (200 mmol), 200 g of NMP, and 40 g of toluene were added, mixed at room temperature for 1 hour, and then heated at 180 ° C. for 3 hours to obtain a block copolymerized polyimide having a solid content of 38%. The block copolymerized polyimide had the following general formula (1): general formula (2) = 3: 2, number average molecular weight: 70000, and weight average molecular weight: 150,000.

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

(7) Various evaluations-Measurement of three-dimensional arithmetic average height (Sa) The three-dimensional arithmetic average roughness Sa of the metal foil surface was measured by the ISO25178 compliant mode using a laser microscope LEXT OLS4100 manufactured by Olympus Corporation. Sa is the average value of the Sa values measured at 10 arbitrary locations, and is the Sa value. The measurement area of Sa was 258 μm long × 258 μm wide. In addition, the temperature at the time of measurement was 23-25 degreeC.

-Manufacture of a laminated body Any one of the following resin base materials 1-3 was bonded to the release layer side surface of each 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 metal foil Based on IPC-TM-650, the normal peel strength when peeling a resin base material from a copper foil with a tensile tester Autograph 100 was measured for the laminate, and the following criteria The peelability of the metal foil was evaluated.
B: The range was from 2 to 200 gf / cm.
C: It was over 200 gf / cm.

-Evaluation of resin peeling mode The peeling surface of the resin base material after peeling was observed with an electron microscope, and the resin peeling mode (aggregation, interface, coexistence of aggregation and interface) was observed. Regarding the resin peeling mode, "Interface" indicates that the resin was peeled at the interface between the copper foil and the resin, and "Agglomeration" indicates that the peel strength was too strong and the resin was destroyed. Indicates that the “interface” and “aggregation” are mixed.
Production of the above laminate, evaluation of peelability, and evaluation of the resin peeling mode are repeated 2 to 4 times by laminating the once peeled copper foil again with the resin base material, and each time from the first to the fourth time. I went there.

(Evaluation results)
In each of Examples 1 to 13, the process of physically peeling after bonding to the resin substrate could be repeated a plurality of times. Moreover, the peelability at the time of physically peeling a metal foil from a resin base material was favorable.
In Comparative Example 1, the process of physically peeling after bonding to the resin base material could not be repeated a plurality of times. Moreover, the peelability when physically peeling the metal foil from the resin substrate was poor.

Claims (28)

And a metal foil and the release layer, physically separated to process metal foil release layer can be a carried out by repeating a plurality of times after the bonding to the resin substrate from the release layer side. 2. The metal foil with a release layer according to claim 1, wherein the step of physically peeling after bonding to the resin substrate from the release layer side can be repeated 2 to 4 times. The metal foil with a release layer according to claim 1 or 2, wherein the metal foil has a surface having a three-dimensional arithmetic average roughness Sa of 0.10 to 1.50 µm. The metal foil with a release layer according to any one of claims 1 to 3, wherein the metal foil has a thickness of 5 to 105 µm. The metal foil with a release layer according to any one of claims 1 to 4, wherein the metal foil is a copper foil. The surface of the said metal foil has provided the 1 or more types of layer selected from the group which consists of a roughening process layer, a heat-resistant layer, a rust prevention layer, a chromate process layer, and a silane coupling process layer. The metal foil with a release layer according to one item. Having 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 on the side opposite to the release layer of the metal foil,
The mold release of Claim 6 which provided the resin layer on the surface of the 1 or more types of layer selected from the group which consists of the said roughening process layer, a heat-resistant layer, a rust prevention layer, a chromate process layer, and a silane coupling process layer. Metal foil with layers . The metal foil with a release layer according to any one of claims 1 to 7, wherein a resin layer is provided on a surface of the release layer. Having 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 on the release layer side of the metal foil;
The release layer has the release layer 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. The metal foil with a release layer according to claim 6, wherein a resin layer is provided on the surface. The metal foil with a release layer according to any one of claims 7 to 9 , wherein the resin layer is an adhesive resin, a primer, or a semi-cured resin. The release layer is provided on the surface side of the metal foil having the surface irregularities, and the resin base material can be peeled when the resin base material is bonded to the metal foil from the release layer side. The metal foil with a release layer according to any one of claims 1 to 10, which is a release layer. The release layer has the following formula:
Wherein R ¹ is an alkoxy group or a halogen atom, and R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by: M is any one of Al, Ti, Zr, n is 0 or 1 or 2, m is an integer from 1 to M valence, (At least one of R ¹ is an alkoxy group, where m + n is a valence of M, that is, 3 for Al and 4 for Ti and Zr.)
An aluminate compound, a titanate compound, a zirconate compound, a hydrolysis product thereof, or a condensate of the hydrolysis product shown in any one of claims 1 to 11 is used. Metal foil with release layer. The release layer has the following formula:
Wherein R ¹ is an alkoxy group or a halogen atom, and R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms 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 metal foil with a release layer according to any one of claims 1 to 11, wherein the silane compound, the hydrolysis product thereof, and the condensate of the hydrolysis product are used singly or in combination. The metal foil with a release layer according to any one of claims 1 to 11, wherein the release layer is formed using a compound having two or less mercapto groups in the molecule. Laminate comprising a metal foil release layer, and a resin base material provided before KiHanare type layer coated metal foil according to any one of claims 1-14.   The laminate according to claim 15, wherein the resin base material is a prepreg or contains a thermosetting resin. A printed circuit board surface profile of the release layer with a metal foil with a resin substrate which has been transferred as claimed in any one of claims 1-14.   A semiconductor package comprising the printed wiring board according to claim 17. An electronic device comprising the printed wiring board according to claim 17 or the semiconductor package according to claim 18 . Method for producing a laminate for producing a laminate by using a release layer coated metal foil according to any one of claims 1-14. Claim 1-14 or a method for manufacturing a printed wiring board for producing a printed wiring board using the release layer with a metal foil according to one of. A step of bonding a resin base material to the metal foil with a release layer according to any one of claims 1 to 14 ,
From the resin base material, before the peeled off it without etching the KiHanare type layer with a metal foil, to obtain a resin substrate surface profile before KiHanare type layer with a metal foil is transferred onto 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: A step of forming a circuit on the release surface side of the another resin substrate by transferring the surface profile to another resin substrate using the metal foil with a release layer peeled off from the resin substrate. The method for producing a printed wiring board according to claim 22, further comprising one or more of the above.   The method for manufacturing a printed wiring board according to claim 22 or 23, wherein the circuit formed on the release surface side of the resin substrate to which the surface profile is transferred is a plating pattern or a printing pattern. A step of bonding a resin base material to the metal foil with a release layer according to any one of claims 1 to 14 ,
From the resin base material, before the peeled off it without etching the KiHanare type layer with a metal foil, to obtain a resin substrate surface profile before KiHanare type layer with a metal foil is transferred onto 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:   One step of providing a build-up layer on the release surface side of the another resin base material by transferring the surface profile to another resin base material using the metal foil peeled off from the resin base material. Or the manufacturing method of the printed wiring board of Claim 25 provided with two or more.   27. The method for producing a printed wiring board according to claim 25 or 26, wherein the resin constituting the build-up layer contains a liquid crystal polymer or polytetrafluoroethylene. The metal foil with a release layer is used at least once in the step of physically peeling the metal foil with a release layer from a resin base material after the metal foil with a release layer and a resin base material are bonded together. It is the said metal foil with a mold release layer , The manufacturing method of the printed wiring board as described in any one of Claims 22-27.