JP5826322B2 - Surface-treated copper foil, copper-clad laminate, printed wiring board, electronic device, circuit forming substrate for semiconductor package, semiconductor package, and printed wiring board manufacturing method - Google Patents

Description

  The present invention relates to a surface-treated copper foil, a copper clad laminate, a printed wiring board, an electronic device, a circuit forming substrate for a semiconductor package, a semiconductor package, and a method for manufacturing the printed wiring board.

  Subtractive method is the main method of circuit formation method for printed wiring board and semiconductor package substrate, but M-SAP (Modified Semi-Additive Process) and copper foil surface profile are used due to further miniaturization in recent years. 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 copper foil. That is, first, the entire surface of the copper foil laminated on the resin base material is etched, the etching base material surface to which the copper 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. Finally, a fine circuit is formed by etching (flash etching, quick etching) the electroless copper plating layer with an etching solution containing sulfuric acid and hydrogen peroxide solution. In this process example, the catalyst treatment for electroless copper plating, the pickling treatment for cleaning the copper surface, etc. are the same for each company, and the description thereof is omitted. (Patent Document 1, Patent Document 2)

JP 2006-196863 A JP 2007-242975 A

  In the semi-additive method using the profile of the copper foil surface, the copper foil laminated on the resin is generally etched. However, etching requires costs for chemicals to be used, wastewater treatment, and the like, and also has a large environmental load. Further, when removing the copper foil by etching, the profile on the surface of the copper foil may be impaired depending on the type of substrate and the etching conditions. For this reason, removal of the copper foil by etching is not preferable.

  As a result of intensive studies, the present inventors have provided a release layer on the copper foil in a copper foil having surface irregularities or roughened particles, and the physical properties of the resin substrate when the copper foil is bonded to the resin substrate. In the process of removing the copper foil from the resin base material, it is not necessary to perform etching, and the profile of the copper foil surface transferred to the surface of the resin base material is not impaired, and at a good cost. It has been found that the copper foil can be removed.

The present invention completed on the basis of the above knowledge has, in one aspect, surface irregularities having no roughened particles and Rz of 0.1 to 5.0 μm measured according to JIS B0601 (1994). And a release layer provided on the surface of the copper foil having surface irregularities, and the resin base when a resin base material is bonded to the copper foil from the release layer side. A surface-treated copper foil having a release layer that allows the material to be peeled , wherein the surface-treated copper foil is bonded with a resin base material from the release layer side, and the resin base material, By peeling off the surface-treated copper foil without etching, a step of obtaining a resin base material in which the surface profile of the copper foil is transferred to the release surface, and the side of the release surface of the resin base material in which the surface profile is transferred Printed circuit having a circuit forming process It is a surface treated copper foil used in the method of manufacturing.

In another aspect of the present invention, the copper foil having roughened particles is provided on the roughened particle surface of the copper foil, and the resin base material is bonded to the copper foil from the release layer side. A surface-treated copper foil provided with a release layer that allows the resin base material to be peeled , wherein the resin base material is bonded to the surface-treated copper foil from the release layer side; and A step of obtaining a resin base material in which the surface profile of the copper foil is transferred to a release surface by peeling the surface-treated copper foil from the material without etching, and a resin base material in which the surface profile is transferred It is a surface-treated copper foil used for the manufacturing method of a printed wiring board provided with the process of forming a circuit in the said peeling surface side .

  In one embodiment, the surface-treated copper foil according to the present invention 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 copper foil from the release layer side. is there.

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

In another embodiment of the surface-treated copper foil according to 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 R1 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 still another embodiment, the surface-treated copper foil according to the present invention is a group comprising a heat-resistant layer, a rust-proof layer, a chromate treatment layer, and a silane coupling treatment layer between the copper foil and the release layer. One or more selected layers are provided.

  In another embodiment of the surface-treated copper foil according to the present invention, a resin layer is provided on the surface of the surface-treated copper foil.

  In still another embodiment, the surface-treated copper foil according to the present invention is a resin on the surface of one or more layers selected from the group consisting of the heat-resistant layer, the rust-proof layer, the chromate-treated layer, and the silane coupling-treated layer. A layer is provided.

  In still another embodiment of the surface-treated copper foil according to the present invention, the resin layer is an adhesive resin, a primer, or a semi-cured resin.

  In still another embodiment of the surface-treated copper foil according to the present invention, the surface-treated copper foil has a thickness of 9 to 70 μm.

  Another aspect of the present invention is a copper-clad laminate including the surface-treated copper foil of the present invention and a resin base material provided on the release layer side of the surface-treated copper foil.

  In the copper-clad laminate according to 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 using the surface-treated copper foil of the present invention.

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

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

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

  After bonding the resin base material to the copper foil, when removing the copper foil from the resin base material, there is no need to etch, and the profile of the copper foil surface transferred to the surface of the resin base material is not impaired, and good A surface-treated copper foil capable of removing a copper foil at a cost is provided.

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

The surface-treated copper foil according to the present invention does not have roughened particles, and the copper foil has surface irregularities having an Rz of 0.1 to 5.0 μm measured according to JIS B0601 (1994); A release layer provided on the surface of the copper foil having surface irregularities, and a release layer that allows the resin substrate to be peeled when the resin substrate is bonded to the copper foil from the release layer side; Is provided. Note that the release layer may be provided on both sides of the copper foil. Further, the bonding may be performed by pressure bonding.
The surface-treated copper foil according to the present invention is provided on the roughened surface side of the copper foil having a roughened surface on another side surface, and a resin base material is pasted from the release layer side to the copper foil. And a release layer that enables the resin base material when peeled together to be peeled off. Note that the release layer may be provided on both sides of the copper foil.
The copper foil (also referred to as raw foil) may be formed of either an electrolytic copper foil or a rolled copper foil. The thickness of copper foil is not specifically limited, For example, it can be 5-105 micrometers. Moreover, since it becomes easy to peel off from the resin base material, the thickness of the surface-treated copper foil is preferably 9 to 70 μm, more preferably 12 to 35 μm, and more preferably 18 to 35 μm. Is more preferable.

Although it does not specifically limit as a manufacturing method of copper foil (raw foil), For example, when producing general electrolytic raw foil, electrolysis conditions can be made into the following.
Electrolytic conditions for general electrolytic green foil:
Cu: 80 to 120 g / L
H ₂ SO _4: 80~120g / L
Chloride ion (Cl ⁻ ): 30 to 100 ppm
Leveling agent (Nika): 0.1-10ppm
Electrolyte temperature: 50-65 ° 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
Moreover, when producing double-sided flat electrolytic raw foil, electrolysis conditions can be made into the following.
Electrolytic conditions for double-sided flat electrolytic green foil Copper: 80-120 g / L
Sulfuric acid: 80-120 g / L
Chlorine: 30-100ppm
Leveling agent 1 (bis (3sulfopropyl) disulfide): 10 to 30 ppm
Leveling agent 2 (amine compound): 10 to 30 ppm
Electrolyte temperature: 50-65 ° C
Electrolysis time: 0.5 to 10 minutes (adjusted according to the thickness of copper to be deposited and current density)
Current density: 70 to 100 A / dm ²
Electrolyte linear velocity: 1.5-5 m / sec
As the amine compound, an amine compound having the following chemical formula can be used.

(In the above chemical formula, R ₁ and R ₂ are selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group.)

  In the present invention, “peeling” the resin base material from the copper foil means that the resin base material is physically removed from the copper foil by peeling or the like instead of removing the copper foil from the resin base material by chemical treatment such as etching. It means to peel off. When the resin substrate is peeled off after being bonded to the surface-treated copper foil of the present invention as described above, the resin substrate and the surface-treated copper foil are separated by a release layer. A part of the release layer, roughened particles of the copper foil described later, a heat-resistant layer, a rust-preventing layer, a chromate treatment layer, a silane coupling treatment layer, etc. may remain, but it is preferable that no residue exists. .

  The surface-treated copper 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 copper foil from the release layer side. If controlled in this way, physical peeling of the resin base material becomes easy, and the profile of the copper foil surface 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.

  In one aspect, the surface-treated copper foil according to the present invention has unevenness in which the copper foil does not have roughened particles and the Rz measured in accordance with JIS B0601 (1994) is 0.1 to 5.0 μm. Or a surface having roughened particles. According to such a configuration, when the copper foil is peeled off after the surface-treated copper foil is bonded to the resin base material, the profile of the copper foil surface is transferred to the surface of the resin base material. Can be easily removed. Moreover, the profile of the copper foil surface is firmly transferred to the resin base material surface, and furthermore, sufficient adhesion of electroless / electro copper plating in the semi-additive process can be secured.

  The roughened particle layer formed on the surface of the copper foil can be formed by using an electrolytic bath made of sulfuric acid / copper sulfate containing at least one kind selected from alkyl sulfate salts, tungsten ions, and arsenic ions. , Consisting of spherical particles or fine particles. The surface roughness of the roughened particle layer can be controlled by appropriately adjusting the electrolytic treatment conditions. Moreover, if the copper foil is composed of an electrolytic copper foil, the matte surface of the electrolytic copper foil may be a roughened surface of the copper foil. The surface roughness of the matte surface of the electrolytic copper foil can be controlled by appropriately adjusting the electrolytic treatment conditions.

The roughened particle layer can be produced using an electrolytic bath made of sulfuric acid / copper sulfate containing at least one kind of a substance selected from alkyl sulfate salts, tungsten ions, and arsenic ions. Examples of specific processing conditions are as follows.
(Liquid composition 1)
CuSO ₄ .5H ₂ O 39.3 to 118 g / L
Cu 10-30g / L
H ₂ SO ₄ 10-150 g / L
Na ₂ WO ₄ · 2H ₂ O 0-90 mg / L
W 0-50mg / L
Sodium dodecyl sulfate addition amount 0-50pp
H ₃ AsO ₃ (60% aqueous solution) 0-6315 mg / L
As 0-2000mg / L
(Electroplating condition 1)
Temperature 30 ~ 70 ℃
(Current condition 1)
Current density 25-110 A / dm ²
Plating time 0.5-20 seconds

(Liquid composition 2)
CuSO ₄ .5H ₂ O 78-314 g / L
Cu 20-80g / L
H ₂ SO ₄ 50-200 g / L

(Electroplating condition 2)
Temperature 30 ~ 70 ℃
(Current condition 2)
Current density 5-50A / dm ²
Plating time 1-60 seconds

Moreover, you may form a roughening particle layer as follows. First, a Cu—Co—Ni ternary alloy layer is formed. Co and Ni content are 1-4 mass% Co and 0.5-1.5 mass% Ni. The processing conditions for the ternary alloy plating are shown below.
(Liquid composition)
Cu 10-20g / L
Co 1-10g / L
Ni 1-10g / L
pH 1-4
(Electroplating conditions)
Temperature 40-50 degrees Celsius
Current density 20-30A / dm ²
Processing time 1-5 seconds

After the roughening treatment, a cobalt plating layer or a plating layer made of cobalt and nickel is formed as a two-step plating thereon. The conditions for cobalt plating or cobalt and nickel plating are as follows: Cobalt plating (liquid composition)
Cobalt plating Co 1-30g / L
pH 1.0-3.5
(Electroplating conditions)
Temperature 30-80 ° C
Current density 1-10A / dm ²
Processing time 0.5-4 seconds

・ Cobalt-nickel plating (liquid composition)
Co 1-30g / L, Ni 1-30g / L
pH 1.0-3.5
(Electroplating conditions)
Temperature 30-80 ° C
Current density 1-10A / dm ²
Processing time 0.5-4 seconds

The roughened particle layer may be formed by spherical roughening. Examples of the processing conditions are shown below.
(Liquid composition)
Cu 20-30 g / L (added with copper sulfate pentahydrate, and so on)
H ₂ SO ₄ 80-120 g / L
Arsenic 1.0-2.0g / L
(Electroplating conditions)
Temperature 35-40 ° C
Current density 70A / dm ² (above limit current density of bath)
Processing time 0.5-20 seconds

  The surface plated with roughening under the above conditions is covered with a copper electrolytic bath made of sulfuric acid and copper sulfate to prevent the roughening particles from falling off. Examples of the covering plating conditions are shown below.

(Liquid composition)
Cu 40-50g / L
H ₂ SO ₄ 80-120 g / L
(Electroplating conditions)
Temperature 43-47 ° C
Current density 29A / dm ² [below the limit current density of the bath]
Processing time 0.5-20 seconds

  The surface which does not have the roughening particle | grains of copper foil, and has the unevenness | corrugation whose Rz measured based on JISB0601 (1994) is 0.1-5.0 micrometers, or the surface which has roughening particle | grains is The surface roughness Rz is preferably 0.1 to 5.0 μm. If the surface roughness Rz is less than 0.1 μm, sufficient adhesion of the electroless copper plating in the semi-additive process cannot be secured, and there is a possibility that the wiring may be peeled off after the formation of the fine wiring, which exceeds 5.0 μm. As a result, there is a possibility that the fine wiring forming ability in the semi-additive process is lowered. The surface roughness Rz is more preferably 0.2 to 4.0 μm, still more preferably 0.3 to 3.5 μm, and still more preferably 0.4 to 3.0 μm.

  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. Thus, by forming the release layer, when the surface-treated copper foil and the resin base material are bonded together, the adhesiveness is moderately lowered, and the peel strength can be adjusted to the above range.

formula:

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

  The silane compound 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 copper 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 copper 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 base material and the copper foil to the above-mentioned range, the silane compound has three alkoxy groups and the 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 copper foil tends to decrease when a silane compound that has undergone hydrolysis and condensation after a sufficient stirring time is 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 composed of a compound having two or more mercapto groups in the molecule, and the resin base material and copper are interposed 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 copper 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 copper 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 copper 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 copper 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 copper 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 substrate and the copper 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 base material and the copper foil to 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 substrate and the copper 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. .

  In the surface-treated copper foil according to the present invention, at least one layer selected from the group consisting of a heat-resistant layer, a rust preventive layer, a chromate treatment layer, and a silane coupling treatment layer is provided between the copper foil and the release layer. It 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. .

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 of a resin base material and copper foil can be improved more.

  Further, on the surface of the copper layer, the roughened particle layer, the heat-resistant layer, the rust-preventing layer, the silane coupling treatment layer or the chromate treatment layer, International Publication No. WO2008 / 053878, JP2008-1111169, Patent No.5024930, International The surface treatment described in publication number WO2006 / 028207, patent 4828427, international publication number WO2006 / 134868, patent 5046927, international publication number WO2007 / 105635, patent 5180815, JP2013-19056A may be performed. it can.

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

  The resin layer may be an adhesive resin, that is, an adhesive, a primer, or a semi-cured insulating resin layer (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 may contain a thermosetting resin or may be a thermoplastic resin. The resin layer may include a thermoplastic resin. The resin layer 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 may be, 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. 2002-179772, Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003-302068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003 No. 249739, Japanese Patent No. 4136509, Japanese Patent Application Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Application Laid-Open No. 2004-349654, Japanese Patent No. 4286060, Japanese Patent Application Laid-Open No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent Application Laid-Open No. No. 5-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004 / 005588, Japanese Patent Application Laid-Open No. 2006-257153, Japanese Patent Application Laid-Open No. 2007-326923, Japanese Patent Application Laid-Open No. 2008-11169, and Japanese Patent No. 5024930. No. WO 2006/028207, Japanese Patent No. 4828427, JP 2009-67029, International Publication No. WO 2006/134868, Japanese Patent No. 5046927, JP 2009-173017, International Publication No. WO 2007/105635, Patent No. 5180815, 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 / 145179, International Publication Number Nos. WO2011 / 068157, JP-A-2013-19056 (resins, resin curing agents, compounds, curing accelerators, dielectrics, reaction catalysts, crosslinking agents, polymers, prepregs, skeletal materials, etc.) and / or You may form using the formation method and formation apparatus of a resin layer.

  A copper-clad laminate can be produced by providing a resin substrate on the release layer side of the surface-treated copper foil according to the present invention. The copper-clad laminate has 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 nonwoven composite base epoxy. You may form with resin and glass cloth base-material epoxy resin. The resin substrate may be a prepreg or may contain a thermosetting resin. Moreover, a printed wiring board can be produced by forming a circuit on the surface-treated copper foil of the copper-clad 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.

A fine circuit can be formed by the semi-additive method using the copper foil of the present invention. FIG. 1 shows a schematic example of a semi-additive method using a copper foil profile. In the semi-additive method, a surface profile of copper foil is used. Specifically, first, the surface-treated copper foil of the present invention is laminated on the resin base material from the release layer side to produce a copper clad laminate. Next, the copper foil (surface-treated copper foil) of the copper clad laminate is peeled off without being etched. Next, after the surface of the resin base material to which the copper 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 peeled surface of the resin base material to which the copper 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 copper 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 a semi-additive method, a step of preparing the surface-treated copper foil and the resin base material according to the present invention,
Laminating a resin base material from the release layer side on the surface-treated copper foil,
A step of peeling off the surface-treated copper foil after laminating the surface-treated copper foil and the resin base material;
Providing a through hole or / and a blind via on the release surface of the resin base material produced by peeling off the surface-treated copper foil,
Performing a desmear process on the region including the through hole or / and the blind via,
Cleaning the resin substrate surface with dilute sulfuric acid for the resin substrate and the region including the through hole or / and the blind via, and providing an electroless plating layer (for example, an electroless copper plating layer);
Providing a plating resist on the electroless plating layer;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer (for example, an electrolytic copper plating layer) in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

In another embodiment of the method for producing a printed wiring board according to the present invention using a semi-additive method, a step of preparing the surface-treated copper foil and the resin base material according to the present invention,
Laminating a resin base material from the release layer side on the surface-treated copper foil,
A step of peeling off the surface-treated copper foil after laminating the surface-treated copper foil and the resin base material;
For the peeled surface of the resin base material generated by peeling off the surface-treated copper foil, the step of washing the resin base material 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 manner, a circuit can be formed on the release surface of the resin base material after the surface-treated copper foil is peeled off, and a printed circuit formation substrate and a circuit formation substrate for a semiconductor package can be manufactured. Furthermore, a printed wiring board and a semiconductor package can be manufactured using the circuit formation substrate. Furthermore, an electronic device can be manufactured using the printed wiring board and the semiconductor package.

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

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

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

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

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

  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 general electrolytic raw foil and double-sided flat electrolytic raw foil of the thickness of Table 1 were produced on the following electrolysis conditions.
(1) General electrolytic raw foil Cu 120 g / L
H ₂ SO ₄ 100 g / L
Chloride ion ^(Cl -) 70 ppm
Leveling agent (Nika) 3ppm
Electrolyte temperature 60 ℃
Current density 70A / dm ²
Electrolyte linear velocity 2m / sec
(2) Double-sided flat electrolytic raw foil Electrolytic conditions of double-sided flat electrolytic raw foil Cu 120 g / L
H ₂ SO ₄ 100 g / L
Chloride ion ^(Cl -) 70 ppm
Leveling agent 1 (bis (3sulfopropyl) disulfide) 20ppm
Leveling agent 2 (amine compound) 20ppm
Electrolyte temperature 60 ℃
Current density 70A / dm ²
Electrolyte linear velocity 2m / sec
As the amine compound, an amine compound having the following chemical formula can be used.
(In the above chemical formula, R ₁ and R ₂ are selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group.)

・ 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.

(1) Roughening treatment [Spherical roughening (normal)]
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 98g / L
Cu 25g / L
H ₂ SO ₄ 100 g / L
Arsenic 1.5g / L
(Electroplating temperature 1) 38 ° C
(Current condition 1) Current density 70 A / dm ² (above the limiting current density of the bath)
Subsequently, plating was 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 176 g / L
Cu 45g / L
H ₂ SO ₄ 100 g / L
(Electroplating temperature 2) 45 ° C
(Current condition 2) Current density: 29 A / dm ² (less than the limit current density of the bath)

[Fine roughening (Type 1)]
First, roughening treatment was performed under the following conditions. The ratio of the limiting current density during the formation of roughened particles was 2.50.
(Liquid composition 1)
CuSO ₄ .5H ₂ O 58.9 g / L
Cu 15g / L
H ₂ SO ₄ 100 g / L
Na ₂ WO ₄ · 2H ₂ O 5.4 mg / L
Sodium dodecyl sulfate addition amount 10ppm
(Electroplating temperature 1) 40 ° C
(Current condition 1) Current density 54 A / dm ²
Subsequently, normal plating was performed under the following conditions.
(Liquid composition 2)
CuSO ₄ · 5H ₂ O 176 g / L
Cu 45g / L
H ₂ SO ₄ 100 g / L
(Electroplating temperature 2) 45 ° C
(Current condition 2) Current density 41 A / dm ²

[Fine roughening (Type 2)]
First, after forming a Cu—Co—Ni ternary alloy layer under the following liquid composition 1 and electroplating condition 1, cobalt plating is applied on the ternary alloy layer under the following liquid composition 2 and electroplating condition 2. Formed.
(Liquid composition 1)
Cu 10-20g / L
Co 1-10g / L
Ni 1-10g / L
pH 1-4
(Electroplating temperature 1) 40-50 ° C
(Current condition 1) Current density 25 A / dm ²
(Liquid composition 2)
Co 1-30g / L
Ni 1-30g / L
pH 1.0-3.5
(Electroplating temperature 2) 30-80 ° C
(Current condition 2) Current density 5A / dm ²

(2) Barrier treatment (heat-resistant treatment)
For Examples 9, 11, and 12, a barrier (heat resistant) treatment was performed under the following conditions to form a brass plating layer.
(Liquid composition)
Cu 70g / L
Zn 5g / L
NaOH 70g / L
NaCN 20g / L
(Electroplating conditions)
Temperature 70 ° C
Current density 8A / dm ² (multistage processing)

(3) Rust prevention treatment About Examples 10, 11, and 12, the rust prevention treatment (zinc chromate treatment) was performed under the following conditions to form a rust prevention treatment layer.
(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 process About Example 11 and 12, the silane coupling material application | coating process was performed on the following conditions, and the silane coupling layer was formed.
(Liquid composition)
Alkoxysilane 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 coating was 30 hours, the alcohol concentration in the aqueous solution was 0 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.

  About the release layer of Examples 19-54 and Comparative Examples 6-7, when it was based on a silane compound, the release layer formation conditions which are not described in the below-mentioned table were made the same with the release layer A. Further, in the case of using a mercapto compound, the release layer forming conditions not described in the table below were the same as those of the release layer B. For the metal alkoxide, the release layer formation conditions not described in the table below were the same as those for the release layer C.

(6) Resin Layer Formation Treatment For Example 12, a resin layer was formed under the following conditions after barrier treatment, rust prevention treatment, silane coupling material application, and release layer formation.
(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 was applied to the release layer forming surface of Example 12, and after a drying treatment at 120 ° C. for 3 minutes and at 160 ° C. for 3 minutes in the nitrogen atmosphere, a heat treatment was finally performed at 300 ° C. for 2 minutes. The copper foil provided with the resin layer was produced. The thickness of the resin layer was 2 μm.

・ Evaluation of surface roughness Rz of copper foil (raw foil) and surface-treated copper foil Surface-treated copper foil was used in accordance with JIS B0601 (1994) using a contact roughness meter SP-11 manufactured by Kosaka Laboratory Ltd. The ten-point average roughness Rz of the treated surface was measured. The measurement position was changed 10 times, and the values for 10 measurements were obtained. Similarly, the surface roughness Rz of the copper foil (raw foil) before the surface treatment was also measured.

-Manufacture of a copper clad laminated board Any one of the following resin base materials 1-3 was bonded to the process side surface of each surface treatment copper foil.
Base material 1: GHPL-830 MBT manufactured by Mitsubishi Gas Chemical Co., Ltd.
Base material 2: 679-FG manufactured by Hitachi Chemical Co., Ltd.
Base material 3: EI-6785TS-F manufactured by Sumitomo Bakelite Co., Ltd.
The recommended conditions of each substrate manufacturer were used for the temperature, pressure, and time of the lamination press.

-Evaluation of peel strength (peel strength) Based on IPC-TM-650, the normal peel strength at the time of peeling a resin base material from copper foil with the tensile tester Autograph 100 was measured with respect to the copper clad laminated board.

-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.

・ Wiring formability With a semi-additive method in accordance with Fig. 1, electroless copper plating and electrolytic copper plating are applied to the resin base material, and the plated copper is processed by etching on the plated copper laminated plate with a copper layer thickness of 12μm. Then, L (line) / S (space) = 30 μm / 30 μm circuit was formed. At this time, the wiring formed on the resin substrate was observed with an optical microscope with a magnification of 100 to 500 times, and the case where there was no missing circuit was OK (◯), and the case where it was NG (×).
Each test condition and evaluation result are shown in Tables 1-4.

As shown in Tables 1 to 4, in Examples 1 to 54, a predetermined release layer was provided, the peel strength was suppressed, and the failure mode of the resin was only the interface. For this reason, it can be said that it can be physically peeled off after being bonded to the resin base material.
On the other hand, Comparative Examples 1 to 7 did not have a release layer, or the compound used to form the release layer was inappropriate, so the release layer could not be formed, the peel strength was high, and the resin The failure mode was either aggregation or a mixture of aggregation and interface. For this reason, it can be said that it cannot be physically peeled off after being bonded to the resin base material.

Claims (17)

A copper foil having no roughening particles and having surface irregularities with Rz of 0.1 to 5.0 μm measured according to JIS B0601 (1994);
A release layer provided on the surface of the copper foil having surface irregularities, and the resin substrate can be peeled when the resin substrate is bonded to the copper foil from the release layer side. A release layer,
A surface-treated copper foil comprising:
Bonding the resin base material from the release layer side to the surface-treated copper foil;
From the resin base material, by removing the surface-treated copper foil without etching, obtaining a resin base material in which the surface profile of the copper foil is transferred to the release surface;
Forming a circuit on the release surface side of the resin substrate to which the surface profile is transferred;
The surface-treated copper foil used for the manufacturing method of the printed wiring board provided with. Copper foil having roughened particles;
A release layer provided on the roughened particle surface of the copper foil, and a release layer that allows the resin substrate to be peeled when the resin substrate is bonded to the copper foil from the release layer side. Mold layer,
A surface-treated copper foil comprising:
Bonding the resin base material from the release layer side to the surface-treated copper foil;
From the resin base material, by removing the surface-treated copper foil without etching, obtaining a resin base material in which the surface profile of the copper foil is transferred to the release surface;
Forming a circuit on the release surface side of the resin substrate to which the surface profile is transferred;
The surface-treated copper foil used for the manufacturing method of the printed wiring board provided with. The surface-treated copper foil according to claim 1 or 2 , wherein when the resin base material is bonded to the copper foil from the release layer side, the peel strength when the resin base material is peeled is 200 gf / cm or less. 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.)
Silane compounds shown, the surface-treated copper foil according to the hydrolysis products, any one of claims 1 to 3 in which the condensate of the hydrolysis products obtained by using singly or in combination. The release layer, a surface-treated copper foil according to any one of claims 1 to 3 comprising using a compound having two or less mercapto group in the molecule. 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, titanate compound, zirconate compound, hydrolyzate products thereof, and condensates of the hydrolyzate products shown in any one of claims 1 to 3 are used. Surface treated copper foil. Between the release layer and the copper foil, any heat-resistant layer, the anticorrosive layer, according to claim 1 to 6 provided with one or more layers selected from the group consisting of chromate treatment layer and a silane coupling treatment layer The surface-treated copper foil as described in one. Surface treated copper foil according to any one of claims 1 to 7, the resin layer provided on the surface of the surface treated copper foil. The surface-treated copper foil of Claim 7 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 heat-resistant layer, an antirust layer, a chromate treatment layer, and a silane coupling treatment layer. The surface-treated copper foil according to claim 8 or 9 , wherein the resin layer is an adhesive resin, a primer, or a semi-cured resin. Surface treated copper foil according to any one of claims 1-10 the thickness of the surface treated copper foil is a 9～70Myuemu. Copper-clad laminate comprising a surface treated copper foil according to any one, a resin substrate provided on the release layer side of the surface treated copper foil according to claim 1 to 11. The copper-clad laminate according to claim 12 , wherein the resin base material is a prepreg or contains a thermosetting resin. Printed circuit board using the surface treated copper foil according to any one of claims 1 to 11. A semiconductor package comprising the printed wiring board according to claim 14 . An electronic device using the printed wiring board according to claim 14 or the semiconductor package according to claim 15 . A step of bonding a resin base material to the surface-treated copper foil according to any one of claims 1 to 11 , from the release layer side;
From the resin base material, by removing the surface-treated copper foil without etching, obtaining a resin base material in which the surface profile of the copper foil is transferred to the release surface;
Forming a circuit on the release surface side of the resin substrate to which the surface profile is transferred;
A method of manufacturing a printed wiring board comprising: