JP6605271B2 - Electrolytic copper foil with release layer, laminate, semiconductor package manufacturing method, electronic device 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.

  In recent years, a technique for manufacturing a laminate in which a resin and a resin are bonded to each other has been researched and developed. At this time, if the resin components are different, sufficient adhesion may not be obtained, and it is necessary to provide unevenness to the resin on one side to improve adhesion by the anchoring effect. Although there are physical processing, chemical processing, and the like as a method for forming irregularities on the cured resin surface, these may not be suitable depending on the physical properties and chemical properties of the resin. Then, further development is desired also about the technique which bonds together resin from which a resin component differs with favorable adhesiveness.

  As a result of intensive studies, the present inventors have provided a release layer on a metal foil having surface irregularities, and enables physical peeling of 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, it was found that the metal foil can be removed at a good cost without impairing the profile of the metal foil surface transferred to the surface of the resin base material. . Furthermore, a metal foil having a predetermined surface irregularity with good adhesion to the resin is bonded to the resin and cured, and then the metal foil is removed to cause the irregularity to be transferred to the resin surface. It has been found that different resins can be bonded together with good adhesion.

  The present invention completed on the basis of the above knowledge, in one aspect, has at least one surface provided with surface irregularities having a ratio (Sz / Rsm) of the maximum height Sz to the average interval Rsm of irregularities (Sz / Rsm) of 0.5 to 3.0. It is the metal foil which has.

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

  In the step of removing the metal foil from the resin substrate by providing a release layer on the metal foil and enabling physical peeling of the resin substrate when the metal foil is bonded to the resin substrate, The metal foil can be removed at a good cost without impairing the profile of the surface of the metal foil transferred to the surface of the resin substrate. Also, resins having different resin components can be bonded together with good adhesion.

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 the present invention has at least one surface, that is, a surface unevenness having a ratio of the maximum height Sz to the average interval Rsm (Sz / Rsm) of 0.5 to 3.0 on one surface or both surfaces. A metal foil having
Further, the metal foil with a release layer of the present invention is a release layer provided on the metal foil and the surface side of the metal foil having surface irregularities, and the metal foil 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.
In this way, the metal foil is removed 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. In this step, the metal foil can be removed at a good cost without impairing the profile of the surface of the metal foil transferred to the surface of the resin base material.
In this specification, “surface” and “surface of the metal foil” are a roughened layer, a heat-resistant layer, a rust-proof layer, a chromate-treated layer, a silane coupling-treated layer, a release layer, etc. on the surface of the metal foil. When the surface treatment layer is provided, it means the surface after the surface treatment layer is provided (the surface of the outermost layer).

  Since the metal foil of the present invention has surface irregularities in which the ratio (Sz / Rsm) between the maximum height Sz and the average interval Rsm between the irregularities is 0.5 to 3.0, the metal foil and the resin base material are bonded together. While maintaining good releasability, laminated members such as circuits, resins, build-up layers, etc. have no voids (or voids) on the resin substrate surface due to the uneven shape transferred to the resin substrate surface after peeling the metal foil. It is possible to provide a laminated member such as a circuit, a resin or a build-up layer on the surface of the resin base material with good adhesion.

  When the ratio (Sz / Rsm) between the maximum height Sz and the average interval Rsm between the irregularities is less than 0.5, the surface of the resin base material obtained by peeling the metal foil after bonding the metal foil and the resin base material There is a problem that the unevenness is small and the adhesion with different resins becomes insufficient, and if it exceeds 3.0, the peelability when peeling the metal foil after bonding the metal foil and the resin base material deteriorates. In addition, there is a problem that the uneven shape on the surface of the resin base material after the metal foil is peeled is too deep, and a laminated member such as a circuit, a resin, or a build-up layer does not follow the uneven shape. The ratio (Sz / Rsm) between the maximum height Sz and the average interval Rsm between the projections and depressions is preferably 0.8 to 2.5, and more preferably 1.2 to 2.0.

  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 metal foil (raw foil), For example, an electrolytic copper foil can be produced on the following electrolysis conditions.
Electrolytic conditions for electrolytic green foil:
Electrolyte composition:
Cu: 30 to 190 g / L
H ₂ SO ₄ : 100 to 400 g / L
Chloride ion (Cl ⁻ ): 60 to 200 ppm by mass
Nika: 1-10ppm
(Bis (3-sulfopropyl) disulfide (SPS): 10-100 ppm as required)
Electrolyte temperature: 25-80 ° C
Electrolysis time: 10 to 300 seconds (adjusted according to the thickness of copper to be deposited and current density)
Current density: 50 to 150 A / dm ²
Electrolyte linear velocity: 1.5-5 m / sec
In this specification, the rest of the electrolytic solution, the plating solution, the silane coupling treatment solution, the solution used for the treatment for forming the release layer and the treatment solution for the surface treatment is water unless otherwise specified.

  The ratio (Sz / Rsm) between the maximum height Sz and the average interval Rsm between the projections and depressions can be adjusted by the above electrolysis conditions. If the electrolysis time (copper thickness) and / or current density is increased within the above range, Sz / Rsm increases. On the other hand, if the chloride ion concentration, the glue concentration, the SPS concentration and / or the electrolyte solution linear velocity are increased within the above range, Sz / Rsm tends to decrease. These electrolysis conditions may be adjusted according to the required degree of peelability and the required adhesion to the laminated member.

  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, a metal foil roughening treatment layer, 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 substrate. However, it is preferred that no residue be 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. 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. Although it is not limited, the density | concentration in the aqueous solution of a silane compound can be 0.01-10.0 volume%, and can be 0.1-5.0 volume% typically.

  The pH of the aqueous solution of the silane compound is not particularly limited and can be used on either the acidic side or the alkaline side. For example, it can be used 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, the mercapto group and the plate carrier, or the mercapto group and the metal foil, This is because it is considered that the peel strength may be increased by forming a strong three-dimensional crosslinked structure between the resin base material and the metal foil. Such a case is disclosed in Japanese Patent Laid-Open No. 2000-196207.

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

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

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

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

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

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

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

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

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

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

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

  Moreover, examples of the heterocyclic group suitable as R include imidazole, triazole, tetrazole, benzimidazole, benzotriazole, thiazole, and benzothiazole, which may contain 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. Although it is not limited, the concentration of the compound having 2 or less mercapto groups in the molecule in the aqueous solution can be 0.01 to 10.0% by weight, typically 0.1 to 5.0%. % By weight.

  The pH of the aqueous solution of the compound having two or less mercapto groups in the molecule is not particularly limited and can be used on either the acidic side or the alkaline side. For example, it can be used 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), dimethylmethoxy aluminum, triethoxy aluminum, methyl diethoxy aluminum Ethyldiethoxyaluminum, n- or iso-propyldiethoxy Luminium, n-, iso- or tert-butyldiethoxyaluminum, pentyldiethoxyaluminum, hexyldiethoxyaluminum, octyldiethoxyaluminum, decyldiethoxyaluminum, phenyldiethoxyaluminum, alkyl-substituted phenyldiethoxyaluminum (eg p -(Methyl) phenyldiethoxyaluminum), dimethylethoxyaluminum, triisopropoxyaluminum, methyldiisopropoxyaluminum, ethyldiisopropoxyaluminum, n- or iso-propyldiethoxyaluminum, n-, iso- or tert-butyl Diisopropoxy aluminum, pentyl diisopropoxy aluminum, hexyl diisopropoxy aluminum, octyl diiso Ropoxyaluminum, decyldiisopropoxyaluminum, phenyldiisopropoxyaluminum, alkyl-substituted phenyldiisopropoxyaluminum (eg, p- (methyl) phenyldiisopropoxyaluminum), dimethylisopropoxyaluminum, (3,3,3- Trifluoropropyl) dimethoxyaluminum, and tridecafluorooctyldiethoxyaluminum, methyldichloroaluminum, dimethylchloroaluminum, dimethylchloroaluminum, phenyldichloroaluminum, dimethylfluoroaluminum, dimethylbromoaluminum, diphenylbromoaluminum, and their hydrolysis products And condensates of these hydrolysis products. Among these, from the viewpoint of availability, trimethoxyaluminum, triethoxyaluminum, and triisopropoxyaluminum are preferable.

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

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

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

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

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

  The metal foil which concerns on this invention is 1 or more types 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 between metal foil and a mold release layer. The layer may be provided. Here, the chromate-treated layer refers to a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. Chromate treatment layer is any element such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium (metal, alloy, oxide, nitride, sulfide, etc.) May be included). Specific examples of the chromate treatment layer include a chromate treatment layer treated with chromic anhydride or a potassium dichromate aqueous solution, a chromate treatment layer treated with a treatment solution containing anhydrous chromic acid or potassium dichromate and zinc, and the like. .

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

Moreover, a well-known heat resistant layer and a rust preventive layer can be used as a heat resistant layer and a rust preventive layer. For example, the heat-resistant layer and / or the 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.

  Further, on the surface of metal foil, roughening treatment layer, heat-resistant layer, rust prevention layer, silane coupling treatment layer, chromate treatment layer or release layer, International Publication No. WO2008 / 053878, JP2008-111169A, Patent No. Surface treatments described in Japanese Patent No. 5024930, International Publication No. WO2006 / 028207, Patent No. 4828427, International Publication No. WO2006 / 134868, Patent No. 5046927, International Publication No. WO2007 / 105635, Patent No. 5180815, JP2013-19056A It can be performed. Thus, the metal foil of the present invention includes a surface-treated metal foil.

  A resin layer 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. 2005-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication Nos. WO 2004/005588, JP 2006-257153, JP 2007-326923 A, JP 2008-111169 A, Patent No. 5024930. No., International Publication No. WO2006 / 028207, Japanese Patent No. 4828427, Japanese Unexamined Patent Publication No. 2009-67029, International Publication No. WO2006 / 134868, Japanese Patent No. 5046927, Japanese Unexamined Patent Publication No. 2009-173017, International Publication No. WO2007 / 105635, Japanese Patent No. 5180815. No., International Publication Number WO2008 / 114858, International Publication Number WO2009 / 008471, Japanese Patent Application Laid-Open No. 2011-14727, International Publication Number WO2009 / 001850, International Publication Number WO2009 / 145 79, substances described in International Publication Nos. WO2011 / 068157 and JP2013-19056 (resins, resin curing agents, compounds, curing accelerators, dielectrics, reaction catalysts, crosslinking agents, polymers, prepregs, skeleton materials, etc. ) And / or a resin layer forming method and a forming apparatus.

(Laminated body, semiconductor package, electronic equipment)
A laminate can be produced by 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 of the method for producing a printed wiring board of the present invention, the resin substrate is formed from the surface side having the surface profile of the metal foil according to the present invention or from the mold release layer side of the metal foil with a mold release layer according to the present invention. The surface profile of the metal foil or the metal foil with a release layer on the release surface is obtained by peeling the metal foil or the metal foil with a release layer from the resin substrate without etching. A step of obtaining a transferred resin substrate, and a step of forming a circuit on the release surface side of the resin substrate 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.

  Furthermore, the manufacturing method of the printed wiring board of this invention is another one side. WHEREIN: The surface side which is controlling the ratio (Sz / Rsm) of maximum space | interval Rsm and maximum height Sz to the metal foil of this invention. Alternatively, the step of laminating the resin base material from the release layer side, and peeling the metal foil or the metal foil with the release layer from the resin base material without etching, A step of obtaining a resin base material to which the surface profile has been transferred; and a step of providing a build-up layer 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 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.

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, on both surfaces of the resin base material, a metal foil in which the ratio of the maximum surface height Sz and the average interval Rsm (Rz) (Sz / Rsm) is controlled, or a metal foil provided with a release layer on the surface, Bonding from the side where the ratio (Sz / Rsm) of the maximum height Sz and the average interval Rsm between the concaves and convexes (Sz / Rsm) is controlled or the release layer side, and then removing the metal foil or the metal foil with the release layer The printed wiring board may be manufactured by transferring the surface profile of the metal foil to both surfaces of the material 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 obtained by impregnating a glass cloth 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 the semi-additive method using the surface profile of a metal 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 from the side where the ratio (Sz / Rsm) of the maximum height Sz of the surface and the average interval Rsm of the unevenness (Sz / Rsm) is controlled;
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,
A step of laminating a resin base material on the metal foil or the metal foil with a release layer from the side where the ratio (Sz / Rsm) of the maximum height Sz of the surface and the average interval Rsm of the unevenness (Sz / Rsm) is controlled;
After laminating the metal foil and the resin base material, the step of removing the metal foil by etching or peeling off,
For the exposed or peeled surface of the resin substrate produced by removing or peeling the metal foil, the step of washing the resin substrate surface with dilute sulfuric acid or the like and providing an electroless plating layer (for example, an electroless copper plating layer),
Providing a plating resist on the electroless plating layer;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer (for example, an electrolytic copper plating layer) in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

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

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

-Production of raw foil (copper foil before surface treatment) With respect to Examples 1 to 11 and Comparative Example 2, electrolytic raw foils having thicknesses described in Table 1 were prepared under the following electrolysis conditions.
(Electrolytic solution composition)
Cu 120g / L
H ₂ SO ₄ 100 g / L
Chloride ion ^(Cl -) 70 ppm
Fish glue 6ppm
Electrolyte temperature 60 ℃
The current density and the electrolyte linear velocity are shown in Table 1.
In Comparative Example 1, 80 ppm of the additive bis (3-sulfopropyl) disulfide (SPS) was added in addition to the electrolytic solution.

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

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

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

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

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

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

  The block copolymerized polyimide solution obtained in the synthesis example was further diluted with NMP to obtain a block copolymerized polyimide solution having a solid content of 10%. In this block copolymerized polyimide solution, bis (4-maleimidophenyl) methane (BMI-H, 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 ・ Evaluation of the ratio (Sz / Rsm) of the maximum height Sz of the metal foil surface and the average interval Rsm of the irregularities (Sz / Rsm) The surface of each metal foil (surface treatment when surface treatment such as roughening treatment is performed) The ratio of the maximum height Sz to the average interval Rsm between the concaves and convexes (Sz) for the surface on the side subjected to the subsequent surface treatment, or the surface on the side where the release layer is provided). / Rsm) was measured using a laser microscope LEXT OLS4100 manufactured by Olympus Corporation. Rsm was measured by the JIS B 0601 2001 compliant mode, and Sz was measured by the ISO25178 compliant mode. In addition, the average value of the Rsm and Sz values measured at arbitrary 10 locations for both Rsm and Sz was defined as the Rsm and Sz values. The measurement length of Rsm was 258 μm, and the measurement area of Sz was 258 μm long × 258 μm wide. Based on the obtained value, the ratio (Sz / Rsm) between the maximum height Sz and the average interval Rsm of the unevenness was calculated. In addition, the temperature at the time of measurement was 23-25 degreeC.

-Manufacture of a laminated body The following resin base materials 1-3 were bonded together 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.
A: The range was from 2 to 200 gf / cm.
X: Less than 2 gf / cm or more than 200 gf / cm.

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

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

(Evaluation results)
In each of Examples 1 to 11, the release layer was formed on the concavo-convex surface of the metal foil having a surface concavo-convex with a ratio (Sz / Rsm) of the maximum height Sz to the average interval Rsm between the concavo-convex portions of 0.5 to 3.0. In this example, the peelability when the metal foil was physically peeled from the resin base material was good, and the occurrence of circuit peeling and substrate swelling could be suppressed satisfactorily.
In Comparative Example 1, since the ratio (Sz / Rsm) between the maximum height Sz of the surface unevenness of the metal foil and the average interval Rsm of the unevenness was less than 0.5, circuit peeling could not be suppressed satisfactorily.
In Comparative Example 2, since the ratio (Sz / Rsm) of the maximum height Sz of the surface irregularities of the metal foil to the average interval Rsm of the irregularities was more than 3.0, when the metal foil was physically peeled from the resin base material The peelability of the film was poor, and it was not possible to satisfactorily suppress the occurrence of circuit peeling and substrate swelling.

Claims (17)

An electrolytic copper foil having surface irregularities with a ratio (Sz / Rsm) of the maximum height Sz and the average interval Rsm between the irregularities of 0.5 to 3.0 on at least one surface;
A release layer provided on the surface side having a surface roughness of the electrolytic copper foil, and a release layer which allows peeling the resin substrate when the release layer was laminated to the resin base material When,
An electrolytic copper foil with a release layer comprising The release layer with the electrodeposited copper foil according to claim 1 a thickness of the electrolytic copper foil is 5～105Myuemu. The surface of the said electrolytic copper foil provided with 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. An electrolytic copper foil with a release layer according to claim 1. 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 product thereof, and the condensate of the hydrolysis product shown in any one of claims 1 to 3 are used. Electrolytic copper 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 electrolytic copper foil with a release layer as described in any one of Claims 1-3 which uses the silane compound, its hydrolysis product, and the condensate of this hydrolysis product which are shown in any one of Claims 1-3 in combination. The electrolytic copper foil with a release layer according to any one of claims 1 to 3 , wherein the release layer comprises a compound having two or less mercapto groups in the molecule. The electrolytic copper foil with a release layer according to any one of claims 1 to 6 , wherein a resin layer is provided on the surface of the release layer. The electrolytic copper foil with a release layer according to claim 7 , wherein the resin layer is an adhesive resin, a primer, or a semi-cured resin. Laminate comprising a release layer with the electrodeposited copper foil; and a resin substrate wherein provided on the release layer with the electrodeposited copper foil to any one of claims 1-8. The laminate according to claim 9 , wherein the resin base material is a prepreg or contains a thermosetting resin. The manufacturing method of the printed wiring board using the electrolytic copper foil with a mold release layer as described in any one of Claims 1-8 . The method of manufacturing a semiconductor package using a printed wiring board manufactured by the manufacturing method of the printed wiring board according to claim 11. Printed circuit board manufactured by the manufacturing method of the printed wiring board according to claim 11, or a semiconductor package manufactured by the manufacturing method of a semiconductor package according to claim 12,
Manufacturing method of electronic equipment using A step of bonding a resin base material to the electrolytic copper foil with a release layer according to any one of claims 1 to 8 ,
From the resin base material, the electrolytic copper foil or the release layer with the electrodeposited copper foil by peeling without the etching, the surface profile of electrodeposited copper foil or the release layer with the electrodeposited copper foil is transferred onto the release surface Obtaining a finished resin substrate;
Forming a circuit on the release surface side of the resin base material to which the surface profile has been transferred. The method for manufacturing a printed wiring board according to claim 14 , wherein the circuit formed on the release surface side of the resin base material to which the surface profile is transferred is a plating pattern or a printing pattern. A step of bonding a resin base material to the electrolytic copper foil with a release layer according to any one of claims 1 to 8 ,
From the resin base material, the electrolytic copper foil or the release layer with the electrodeposited copper foil by peeling without the etching, the surface profile of electrodeposited copper foil or the release layer with the electrodeposited copper foil is transferred onto the release surface Obtaining a finished resin substrate;
Providing a build-up layer on the release surface side of the resin substrate to which the surface profile has been transferred;
A method of manufacturing a printed wiring board comprising: The method for producing a printed wiring board according to claim 16 , wherein the resin constituting the build-up layer contains a liquid crystal polymer or polytetrafluoroethylene.