KR20170118001A - Surface-treated copper foil, copper clad laminate, printed wiring board, electronic device, circuit formation substrate for semiconductor package, semicondeuctor package and process of producing printed wiring board - Google Patents

Abstract

There is no need to perform etching when the copper foil is removed from the resin substrate after the resin substrate is bonded to the copper foil and there is no possibility that the profile of the surface of the copper foil transferred to the surface of the resin substrate is damaged, Thereby providing a surface-treated copper foil. A copper foil having no surface roughening and having surface roughness of 0.1 to 5.0 탆 measured in accordance with JIS B0601 (1994), or a copper foil having roughened particles and a copper foil having surface irregularities of copper foil Or a release layer formed on the surface of the copper foil having roughened particles and capable of releasing the resin base material when the resin base material is bonded to the copper foil from the release layer side.

Description

TECHNICAL FIELD [0001] The present invention relates to a surface-treated copper foil, a copper-clad laminate, a printed circuit board, an electronic device, a circuit-forming substrate for a semiconductor package, a semiconductor package and a method for manufacturing a printed- FOR SEMICONDUCTOR PACKAGE, SEMICONDEUCTOR PACKAGE AND PROCESS OF PRODUCING PRINTED WIRING BOARD}

The present invention relates to a surface-treated copper foil, a copper clad laminate, a printed wiring board, an electronic apparatus, a circuit formation substrate for a semiconductor package, a semiconductor package, and a method for producing a printed wiring board.

Although the subtractive method is mainly used for the circuit formation method of the printed wiring board and the semiconductor package substrate, the M-SAP (Modified Semi-Additive Process) or the semi-additive method using the surface profile of the copper foil And new methods such as

Among these new circuit forming methods, the following is one 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 surface of the etched base substrate onto which the copper surface profile is transferred is punched with a laser or the like, and electroless copper plating is performed to conduct the hole forming portion. The surface of the copper plated surface was covered with a dry film, the dry film in the circuit formation portion was removed by UV exposure and development, the electroless copper plated surface not covered with the dry film was electroplated, the dry film was peeled off , And finally an electroless copper plating layer is etched (flash-etched, quick-etched) by an etching solution containing sulfuric acid and hydrogen peroxide water to form a fine circuit. In this example of the process, the catalyst treatment for electroless copper plating, the pickling treatment for cleaning the copper surface, and the like are each various, and the description thereof is omitted. (Patent Document 1, Patent Document 2)

Japanese Laid-Open Patent Publication No. 2006-196863 Japanese Patent Application Laid-Open No. 2007-242975

In the semi-additive method using the profile of the surface of the copper foil, the copper foil laminated on the resin is generally etched. However, the etching has a cost such as chemical solution to be used, wastewater treatment, etc., and also has a large load on the environment. Further, when the copper foil is removed by etching, the profile of the surface of the copper foil may be damaged, depending on the kind of the base material and the etching conditions. For this reason, it is not preferable to remove the copper foil by etching.

As a result of intensive studies, the inventors of the present invention have found that, in a copper foil having surface irregularities or roughened particles, a release layer is formed on the copper foil and the physical properties of the resin base material when the copper foil is bonded It is not necessary to etch the copper foil in the step of removing the copper foil from the resin substrate to remove the copper foil with a good cost without damaging the profile of the surface of the copper foil transferred to the surface of the resin base material I found out that it is possible.

The present invention completed on the basis of the above findings, in one aspect, provides a copper foil having no surface roughening particles and having surface roughness of 0.1 to 5.0 탆 measured in accordance with JIS B0601 (1994) A release layer formed on a surface of a copper foil having surface irregularities and a release layer for releasing the resin base material when the resin base material is bonded to the copper foil from the release layer side.

According to another aspect of the present invention, there is provided a copper foil comprising a copper foil having roughened particles and a copper foil formed on the roughened particle surface of the copper foil and capable of peeling the resin base material when the resin base material is bonded to the copper foil from the release layer side Treated copper foil.

In the surface-treated copper foil according to one embodiment of the present invention, when the resin base material is bonded to the copper foil from the release layer side, the peel strength when peeling the resin base material is 200 gf / cm or less.

The surface-treated copper foil according to still another embodiment of the present invention is characterized in that the release layer has the following formula:

[Chemical Formula 1]

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

, A hydrolysis product thereof, and a condensate of the hydrolysis product thereof, either singly or in combination.

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

The surface-treated copper foil according to still another embodiment of the present invention is characterized in that the release layer has the following formula:

(2)

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

, A titanate compound, a zirconate compound, a hydrolysis product thereof, and a condensate of the hydrolysis product thereof, either singly or in combination.

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

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

In a surface-treated copper foil according to another embodiment of the present invention, the resin layer is a resin for bonding, a primer, or a resin in a semi-cured state.

In the surface-treated copper foil according to another embodiment of the present invention, the thickness of the surface-treated copper foil is 9 to 70 탆.

Further, in the surface-treated copper foil according to another embodiment of the present invention, the surface-treated copper foil may further include a step of bonding a resin base material to the surface-treated copper foil from the release layer side, Wherein the surface profile of the copper foil is transferred to the release surface of the resin base material by peeling off the surface profile of the copper foil on the release surface of the resin base material, It is a surface treated copper foil used.

The surface-treated copper foil according to the present invention is a copper foil having no surface roughening particles and having surface roughness of 0.1 to 5.0 占 퐉 as measured according to JIS B0601 (1994) And a release layer formed on a surface of the copper foil having surface irregularities for releasing the resin base material when the resin base material is bonded to the copper foil from the release layer side, or,

And a release layer formed on the surface of the roughened particle of the copper foil and having a release layer for releasing the resin base material when the resin base material is bonded to the copper foil from the release layer side, Treated copper foil,

Is a surface-treated copper foil satisfying any one of the following (A) to (I).

(A) a peeling strength when the resin base material is peeled off when the resin base material is stuck to the copper foil from the release layer side is 200 gf / cm or less,

(B) the release layer has the following formula:

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

, The hydrolysis product thereof, and the condensation product of the hydrolysis product thereof, either singly or in combination.

(C) The release layer is formed by using a compound having two or less mercapto groups in the molecule.

(D) the release layer has the following formula:

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

, A titanate compound, a zirconate compound, a hydrolysis product thereof, and a condensate of the hydrolysis product thereof are used singly or in combination,

(E) at least one layer selected from the group consisting of a heat resistant layer, a rust prevention layer, a chromate treatment layer and a silane coupling treatment layer is formed between the copper foil and the release layer,

(F) A resin layer is formed on the surface of the surface-treated copper foil.

(G) In the above (F), the resin layer is a resin for bonding, a primer, or a resin in a semi-cured state.

(H) the thickness of the surface-treated copper foil is 9 to 70 탆,

(I) a step of bonding a resin base material to the surface-treated copper foil from the side of the release layer, and peeling the surface-treated copper foil from the resin base material without etching the surface profile to transfer the surface profile of the copper foil to the release surface A step of obtaining a resin substrate and a step of forming a circuit on the release face side of the resin substrate onto which the surface profile is transferred.

In another aspect, the present invention is a copper clad laminate comprising a surface-treated copper foil of the present invention and a resin substrate formed on the side of the release layer of the surface-treated copper foil.

In the copper-clad laminate according to the present invention, the resin base material is a prepreg or a thermosetting resin.

In another aspect, the present invention is a printed wiring board using the surface-treated copper foil of the present invention.

In another aspect, the present invention is a printed wiring board produced by using the surface-treated copper foil of the present invention.

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

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

According to another aspect of the present invention, there is provided a method for manufacturing a surface-treated copper foil, comprising the steps of: applying a resinous base material to a surface-treated copper foil of the present invention from the side of the release layer; And a step of forming a circuit on the release surface side of the resin substrate onto which the surface profile has been transferred. The present invention also provides a method for producing a printed wiring board.

In another aspect of the present invention, in the surface-treated copper foil of the present invention, after peeling the resin base material from the side of the release layer and then peeling the surface-treated copper foil from the resin base material without etching, And the surface profile of the copper foil is transferred to the reverse side.

There is no need to perform etching when the copper foil is removed from the resin substrate after the resin substrate is bonded to the copper foil and there is no possibility that the profile of the surface of the copper foil transferred to the surface of the resin substrate is damaged, Thereby providing a surface-treated copper foil.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram showing a schematic example of a semi-additive method using a profile of a copper foil. Fig.

The surface-treated copper foil according to the present invention is a surface-treated copper foil having no surface roughening particles and having a surface irregularity of Rz of 0.1 to 5.0 m measured according to JIS B0601 (1994) And a release layer for releasing the resin base material when the resin base material is bonded to the copper foil from the release layer side. The release layer may be formed on both sides of the copper foil. In addition, the bonding may be performed by pressing and bonding.

The surface-treated copper foil according to the present invention is a copper foil having a roughened surface on the other side and a resin base material formed when the resin base material is bonded to the copper foil from the release layer side on the roughened screen side of the copper foil A release layer is formed. The release layer may be formed on both sides of the copper foil.

The copper foil (also referred to as green foil) may be formed of an electrolytic copper foil or a rolled copper foil. The thickness of the copper foil is not particularly limited and may be, for example, 5 to 105 탆. In addition, the thickness of the surface-treated copper foil is preferably 9 to 70 탆, more preferably 12 to 35 탆, and even more preferably 18 to 35 탆 in terms of facilitating peeling from the resin substrate.

The production method of the copper foil (green foil) is not particularly limited, and for example, electrolytic conditions may be employed in the case of producing a general electrolytic copper foil.

Electrolysis conditions of general electrolytic growth:

Cu: 80 to 120 g / l

H ₂ SO ₄ : 80 to 120 g / ℓ

Chloride ion ^{(Cl -): 30 ~ 100} ppm

Leveling agent (glue): 0.1 to 10 ppm

Electrolyte temperature: 50 ~ 65 ℃

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

Current density: 50 to 150 A / dm 2

Electrolyte flux: 1.5 to 5 m / sec

In the case of producing double-sided flat electrolytic growth, electrolytic conditions may be employed.

Electrolytic condition of two-sided flat electrolytic growth

Copper: 80 to 120 g / l

Sulfuric acid: 80 to 120 g / l

Chlorine: 30 to 100 ppm

Leveling agent 1 (bis (3-sulfopropyl) disulfide): 10 to 30 ppm

Leveling second (amine compound): 10 to 30 ppm

Electrolyte temperature: 50 ~ 65 ℃

Electrolysis time: 0.5 to 10 minutes (Copper thickness to be deposited, adjusted by current density)

Current density: 70 to 100 A / dm 2

Electrolyte flux: 1.5 to 5 m / sec

The amine compound may be an amine compound of the following formula.

(3)

Wherein 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 substrate from the copper foil means not physically removing the copper foil from the resin substrate by chemical treatment by etching or the like but physically peeling the resin substrate from the copper foil by peeling or the like. When the resin base material is peeled off after the surface-treated copper foil of the present invention is peeled off as described above, the resin base material and the surface-treated copper foil separate from the release layer. At this time, on the release face of the resin base material, Some of the coarse particles, heat-resistant layer, rust-preventive layer, chromate treatment layer, silane coupling treatment layer and the like may remain, but it is preferable that no residue is present.

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. When controlled in this manner, the physical separation of the resin base material is facilitated, and the profile of the surface of the copper foil is more favorably transferred to the resin base material. The peel strength is more preferably 150 gf / cm or less, still more preferably 100 gf / cm or less, still more preferably 50 gf / cm or less, and typically 1 to 200 gf / cm , More typically from 1 to 150 gf / cm.

The surface-treated copper foil according to the present invention is characterized in that the copper foil does not have roughened particles on one side and has a surface with irregularities having an Rz of 0.1 to 5.0 m measured according to JIS B0601 (1994) And is formed on the surface having particles. According to such a configuration, when the surface-treated copper foil is peeled off after peeling the copper foil from the resin base material, peeling can be easily performed with a low peel even though the profile of the surface of the copper foil is transferred to the resin base material surface. In addition, the profile of the surface of the copper foil is properly transferred onto the surface of the resin substrate, and thus the adhesiveness of electroless plating and electroplating in the semiadditive process can be sufficiently secured.

The roughening particle layer formed on the surface of the copper foil can be formed using an electrolytic bath composed of a sulfuric acid / copper sulfate containing at least one of substances selected from alkyl sulfate salts, tungsten ions, and arsenic ions, Particles or fine particles. The surface roughness of the roughening particle layer can be controlled by suitably adjusting the electrolytic treatment conditions. Further, in the case where the copper foil is composed of an electrolytic copper foil, the mat surface of the electrolytic copper foil may be used as the coarsened surface of the copper foil. The surface roughness of the matte surface of the electrolytic copper foil can be controlled by suitably adjusting the electrolytic treatment conditions.

The coarsely grained particle layer can be produced by using an electrolytic bath composed of a sulfuric acid / copper sulfate containing at least one or more materials selected from alkyl sulfate salts, tungsten ions, and arsenic ions. Examples of specific treatment conditions are as follows.

(Liquid composition 1)

CuSO ₄ .5H ₂ O 39.3 to 118 g / l

Cu 10-30 g / l

H ₂ SO ₄ 10 to 150 g / ℓ

Na ₂ WO ₄ .2H ₂ O 0 to 90 mg / l

W 0 to 50 mg / l

Sodium dodecyl sulfate added 0 to 50 ppm

H ₃ AsO ₃ (60% aqueous solution) 0 to 6315 mg / l

As 0 to 2000 mg / l

(Electroplating condition 1)

Temperature 30 ~ 70 ℃

(Current condition 1)

Current density 25 ~ 110 A / dm2

Plating time 0.5 ~ 20 seconds

(Liquid composition 2)

CuSO ₄揃 5H ₂ O 78 to 314 g / ℓ

Cu 20 to 80 g / l

H ₂ SO ₄ 50-200 g / l

(Electroplating condition 2)

Temperature 30 ~ 70 ℃

(Current condition 2)

Current density 5 ~ 50 A / dm2

Plating time 1 ~ 60 seconds

The roughening particle layer may be formed as follows. First, a Cu-Co-Ni ternary alloy layer is formed. The Co and Ni contents are 1 to 4 mass% Co and 0.5 to 1.5 mass% Ni. The treatment conditions of the ternary alloy plating are shown below.

(Liquid composition)

Cu 10-20 g / l

Co 1 to 10 g / l

Ni 1 to 10 g / l

pH 1-4

(Electroplating conditions)

Temperature 40 ~ 50 ℃

Current density 20 ~ 30 A / dm2

Processing time 1 to 5 seconds

After the roughening treatment, a cobalt-plated layer or a plated layer of cobalt and nickel is formed as a two-step plating thereon. The conditions of cobalt plating or cobalt and nickel plating are as follows

· Cobalt plating

(Liquid composition)

Co 1 to 30 g / l

pH 1.0 to 3.5

(Electroplating conditions)

Temperature 30 ~ 80 ℃

Current density 1 to 10 A / dm 2

Processing time 0.5 to 4 seconds

· Cobalt-nickel plating

(Liquid composition)

Co 1 to 30 g / l, Ni 1 to 30 g / l

pH 1.0 to 3.5

(Electroplating conditions)

Temperature 30 ~ 80 ℃

Current density 1 to 10 A / dm 2

Processing time 0.5 to 4 seconds

The roughening particle layer may be formed by spherical harmonization. Examples of the treatment conditions are shown below.

(Liquid composition)

Cu 20 to 30 g / l (added as copper sulfate pentahydrate, the same applies hereinafter)

H ₂ SO ₄ 80 to 120 g / l

Arsenic 1.0 ~ 2.0 g / l

(Electroplating conditions)

Temperature 35 ~ 40 ℃

Current density of 70 A / dm 2 (above the limit current density of the bath)

Processing time 0.5 ~ 20 seconds

On the surface subjected to harmonious plating under the above conditions, plating is performed with a copper electrolytic bath composed of sulfuric acid and copper sulfate to prevent falling off of the coarse particles. Examples of the plating conditions are shown below.

(Liquid composition)

Cu 40 to 50 g / l

H ₂ SO ₄ 80 to 120 g / l

(Electroplating conditions)

Temperature 43 ~ 47 ℃

Current density 29 A / dm 2 [less than the limiting current density of the bath]

Processing time 0.5 ~ 20 seconds

The surface having unevenness of Rz of 0.1 to 5.0 占 퐉 or the surface having harmonic grains, which have no coarse grains of copper foil and have an Rz of 0.1 to 5.0 占 퐉 measured in accordance with JIS B0601 (1994), has a surface roughness Rz of 0.1 to 5.0 占 퐉 . If the surface roughness Rz is less than 0.1 mu m, the adhesion of the electroless copper plating in the semiadditive process can not be sufficiently secured, and there is a possibility that the wiring may be peeled off after the fine wiring is formed. If the surface roughness Rz is more than 5.0 mu m, There is a possibility that a problem that a fine wiring forming ability in a semiadditive process is lowered may occur. The surface roughness Rz is more preferably 0.2 to 4.0 占 퐉, still more preferably 0.3 to 3.5 占 퐉, still more preferably 0.4 to 3.0 占 퐉.

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

(1) Silane compound

A silane compound having a structure represented by the following formula, or a condensate of the hydrolysis product thereof or a hydrolysis product thereof (hereinafter, simply referred to as a silane compound) may be used singly or in combination to form a release layer, When the treated copper foil and the resin base material are bonded to each other, the adhesiveness is moderately reduced, and the peel strength can be adjusted to the above-mentioned range.

expression:

[Chemical Formula 4]

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

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

In adjusting the peel strength of the resin substrate and the copper foil to the above-mentioned range, the silane compound has three alkoxy groups and one hydrocarbon group (one or more hydrogen atoms include a hydrocarbon group substituted with a halogen atom) . When this is expressed in the above formula, both R ³ and R ⁴ are referred to as alkoxy groups.

Alkoxy groups include, but are not limited to, methoxy, ethoxy, n- or isopropoxy, n-, iso- or tert-butoxy, n-, iso- or neo- Branched or cyclic C1-20, preferably C1-10, more preferably C1-10, alicyclic or cyclic groups such as a cycloalkyl group, a cycloalkenyl group, a cyclohexyl group, an n-heptyl group, and an n- An alkoxy group having 1 to 5 carbon atoms.

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

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

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

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

These hydrocarbon groups may be substituted with at least one hydrogen atom by a halogen atom, for example, a fluorine atom, a chlorine atom, or a bromine atom.

Examples of preferred silane compounds include methyltrimethoxysilane, ethyltrimethoxysilane, n- or iso-propyltrimethoxysilane, n-, iso- or tert-butyltrimethoxysilane, n-, iso- or phenyltrimethoxysilane, alkyl-substituted phenyltrimethoxysilane (for example, p- (methyl) phenyl (meth) acrylate, phenyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane, Trimethoxysilane), methyltriethoxysilane, ethyltriethoxysilane, n- or iso-propyltriethoxysilane, n-, iso- or tert-butyltriethoxysilane, pentyltriethoxysilane, hexyl Phenyl triethoxysilane, alkyl substituted phenyltriethoxysilane (for example, p- (methyl) phenyltriethoxysilane), (3, 4-dimethylphenyltriethoxysilane), triethylsilane, triethoxysilane, octyltriethoxysilane, decyltriethoxysilane, phenyltriethoxysilane, 3,3-trifluoropropyl) trimethoxysilane, and tridecafluorooctyltriethoxysilane, methyltrichlorosilane , And the like dimethyl dichlorosilane, trimethyl chlorosilane, silane, a silane, trimethyl fluorophenyl trichloro dimethyldiallylammonium bromide mosilran, diphenyl bromo mosilran, their hydrolysis products and condensates of these hydrolysis products. Of these, propyltrimethoxysilane, methyltriethoxysilane, hexyltrimethoxysilane, phenyltriethoxysilane and decyltrimethoxysilane are preferable from the viewpoint of availability.

In the step of forming the release layer, the silane compound can be used in the form of an aqueous solution. To increase the solubility in water, an alcohol such as methanol or ethanol may be added. The addition of alcohol is particularly effective when a silane compound having high hydrophobicity is used. The aqueous solution of the silane compound accelerates the hydrolysis of the alkoxy group by stirring, and the condensation of the hydrolysis product is promoted if the stirring time is long. In general, the use of a silane compound which has undergone hydrolysis and condensation through a sufficient stirring time tends to lower the peeling strength of the resin substrate and the copper foil. Therefore, the peeling strength can be adjusted by adjusting the stirring time. The stirring time after dissolving the silane compound in water can be, for example, from 1 to 100 hours, though not limited thereto, and typically from 1 to 30 hours. Naturally, there is a method of using without stirring.

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

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

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

The releasing layer is constituted by using a compound having two or more mercapto groups in the molecule, and even when the resin base and the copper foil are laminated via the releasing layer, the adhesiveness is moderately reduced and the peel strength can be controlled.

However, when the compound or its salt having three or more mercapto groups in the molecule is interposed between the resin substrate and the copper foil, the resultant mixture is not suitable for the purpose of reducing the peel strength. This is because when a mercapto group is excessively present in a molecule, a sulfide bond, a disulfide bond, or a polysulfide bond is formed by a chemical reaction between a mercapto group or between a mercapto group and a plate-like carrier or between a mercapto group and a metal foil It is thought that the excessive peeling strength is generated by forming a strong three-dimensional cross-linked structure between the resin base material and the copper foil. Such an example is disclosed in Japanese Patent Laid-Open Publication No. 2000-196207.

Examples of the compound having two or less mercapto groups in the molecule include a thiol, a dithiol, a thiocarboxylic acid or a salt thereof, a dithiocarboxylic acid or a salt thereof, a thiosulfonic acid or a salt thereof, And salts thereof, and at least one selected from them may be used.

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

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

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

The dithiocarboxylic acid is one in which two oxygen atoms in the carboxyl group of the organic carboxylic acid are substituted with a sulfur atom 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. The 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 the 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. The thiosulfonic acid can also be used in the form of a salt.

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

Examples of suitable aliphatic hydrocarbon groups for R include an alkyl group and a cycloalkyl group, and these hydrocarbon groups may contain either or both of a hydroxyl group and an amino group.

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

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

Examples of the aromatic hydrocarbon group suitable as R include a phenyl group, a phenyl group substituted with an alkyl group (e.g., a tolyl group, a xylyl group), a 1- or 2-naphthyl group, An aryl group having 1 to 14 carbon atoms, and these hydrocarbon groups may contain either or both of a hydroxyl group and an amino group.

Examples of the heterocyclic group suitable as R include imidazole, triazole, tetrazole, benzoimidazole, benzotriazole, thiazole, and benzothiazole. It is preferable that any of the hydroxyl group and the amino group or both do.

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

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

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 of the resin base material and the copper foil tends to be lowered. In the case of adjusting the concentration of the compound having two or less mercapto groups in the molecule It is possible to adjust the peel strength. The concentration of the compound having not more than two mercapto groups in the molecule in the aqueous solution may be 0.01 to 10.0% by weight, and typically 0.1 to 5.0% by weight, although not limited thereto.

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

(3) Metal alkoxide

The releasing layer may be a single layer of an aluminate compound, a titanate compound, a zirconate compound, or a hydrolysis product thereof, or a condensation product of the hydrolysis product thereof (hereinafter, simply referred to as a metal alkoxide) Or a plurality of them may be mixed. By adhering the resin base material and the copper foil to each other through the release layer, the adhesion can be appropriately reduced and the peel strength can be controlled.

[Chemical Formula 5]

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

It is necessary that the metal alkoxide has at least one alkoxy group. In the case where a substituent is constituted only by a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom in the absence of an alkoxy group, There is a tendency to be excessively deteriorated. It is necessary that the metal alkoxide is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom, 0 to 2 hydrocarbon groups. In the case of having three or more hydrocarbon groups, the adhesion between the resin substrate and the copper foil tends to be excessively lowered. Further, the alkoxy group includes an alkoxy group in which at least one hydrogen atom is substituted with a halogen atom. In adjusting the peel strength of the resin base material and the copper foil to the above-mentioned range, the metal alkoxide preferably has two or more alkoxy groups, and the hydrocarbon group (one or more hydrogen atoms include a hydrocarbon group substituted with a halogen atom) It is preferable to have two.

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

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

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

Examples of preferred aluminate compounds are trimethoxy aluminum, methyl dimethoxy aluminum, ethyl dimethoxy aluminum, n- or iso-propyl dimethoxy aluminum, n-, iso- or tert-butyl dimethoxy aluminum, n-, iso (For example, p- (methyl) phenyldimethoxyaluminum) or an alkyl substituted phenyldimethoxyaluminum (for example, p- (methyl) phenyldimethoxyaluminum) or neopentyldimethoxyaluminum, hexyldimethoxyaluminum, octyldimethoxyaluminum, decyldimethoxyaluminum, , Dimethyl methoxy aluminum, triethoxy aluminum, methyl diethoxy aluminum, ethyl diethoxy aluminum, n- or iso-propyl diethoxy aluminum, n-, iso- or tert-butyl diethoxy aluminum, pentyl diethoxy aluminum, Diethoxy aluminum, octyl diethoxy aluminum, decyl diethoxy aluminum, phenyl diethoxy aluminum, alkyl substituted phenyl diethoxy aluminum (for example, p- (methyl) phenyl Diethoxy aluminum), dimethyl ethoxy aluminum, triisopropoxy aluminum, methyl diisopropoxy aluminum, ethyl diisopropoxy aluminum, n- or iso-propyl diethoxy aluminum, n-, iso- or tert- (E.g., isopropylaluminum, isopropylaluminum, isopropylaluminum, isopropylaluminum, isopropoxyaluminum, pentyldiisopropoxyaluminum, hexyldiisopropoxyaluminum, octyldiisopropoxyaluminum, decyldiisopropoxyaluminum, phenyldiisopropoxyaluminum, For example, p- (methyl) phenyldiisopropoxyaluminum), dimethylisopropoxyaluminum, (3,3,3-trifluoropropyl) dimethoxyaluminum, and tridecafluorooctyldiethoxyaluminum, methyldichloro Aluminum, dimethylchloroaluminum, dimethylchloroaluminum, phenyldichloroaluminum, dimethylfluoroaluminum, dimethylbromoaluminum, diphenylbromoaluminum Titanium, and the like can be mentioned those of the hydrolysis products and condensates of these hydrolysis products. Of these, trimethoxyaluminum, triethoxyaluminum and triisopropoxyaluminum are preferable from the viewpoint of availability.

Examples of preferred titanate compounds include tetramethoxytitanium, methyltrimethoxytitanium, ethyltrimethoxytitanium, n- or isopropyltrimethoxytitanium, n-, iso- or tert-butyltrimethoxytitanium, hexyltrimethoxytitanium, octyltrimethoxytitanium, decyltrimethoxytitanium, phenyltrimethoxytitanium, alkyl-substituted phenyltrimethoxytitanium (for example, phenyltrimethoxytitanium, naphthyltrimethoxytitanium, isopropyltriethoxytitanium, n-isopropyltriethoxytitanium, n-isopropyltriethoxytitanium, p-methylphenyltrimethoxytitanium, dimethyldimethoxytitanium, tetraethoxytitanium, methyltriethoxytitanium, Or tert-butyltriethoxytitanium, pentyltriethoxytitanium, hexyltriethoxytitanium, octyltriethoxytitanium, decyltriethoxytitanium, phenyltriethoxytitanium, alkyl-substituted phenyltriethoxytitanium (for example, , p- (methyl) phenyltriethoxytitanium), dimethyldiethoxytitanium, tetraisopropoxy But are not limited to, cadmium, cadmium, cadmium, manganese, titanium, titanium, titanium, titanium, titanium, , Hexyltriisopropoxytitanium, octyltriisopropoxytitanium, decyltriisopropoxytitanium, phenyltriisopropoxytitanium, alkyl-substituted phenyltriisopropoxytitanium (for example, p- (methyl) phenyl tri (3,3,3-trifluoropropyl) trimethoxytitanium, and tridecafluorooctyltriethoxytitanium, methyl trichlorotitanium, dimethyldichlorotitanium, dimethyldichlorotitanium, Trimethylchlorotitanium, phenyltrichlorotitanium, dimethyldifluorotitanium, dimethyldibromotitanium, diphenyldibromotitan, hydrolysis products of these, and condensates of these hydrolysis products. Of these, tetramethoxytitanium, tetraethoxytitanium and tetraisopropoxytitanium are preferable from the viewpoint of availability.

Examples of preferred zirconate compounds include tetramethoxyzirconium, methyltrimethoxyzirconium, ethyltrimethoxyzirconium, n- or iso-propyltrimethoxyzirconium, n-, iso- or tert-butyltrimethoxyzirconium , n-, iso- or neopentyltrimethoxyzirconium, hexyltrimethoxyzirconium, octyltrimethoxyzirconium, decyltrimethoxyzirconium, phenyltrimethoxyzirconium, alkyl-substituted phenyltrimethoxyzirconium (for example, , p- (methyl) phenyltrimethoxyzirconium), dimethyldimethoxyzirconium, tetraethoxyzirconium, methyltriethoxyzirconium, ethyltriethoxyzirconium, n- or iso-propyltriethoxyzirconium, n-, iso - or tert-butyltriethoxyzirconium, pentyltriethoxyzirconium, hexyltriethoxyzirconium, octyltriethoxyzirconium, decyltriethoxyzirconium, phenyltriethoxyzirconium, alkyl (E.g., p- (methyl) phenyltriethoxyzirconium), dimethyldiethoxyzirconium, tetraisopropoxyzirconium, methyltriisopropoxyzirconium, ethyltriisopropoxyzirconium, n- Or isopropyl triethoxy zirconium, n-, iso- or tert-butyl triisopropoxy zirconium, pentyl triisopropoxy zirconium, hexyl triisopropoxy zirconium, octyl triisopropoxy zirconium, Phenyl triisopropoxy zirconium, alkyl substituted phenyl triisopropoxy zirconium (for example, p- (methyl) phenyl triisopropoxy titanate), dimethyl diisopropoxy zirconium, (3,3,3 -Trifluoropropyl) trimethoxy zirconium, and tridecafluorooctyltriethoxy zirconium, methyl trichloro zirconium, dimethyldichlorozirconium, trimethyl chlorozirconium, Phenyl trichloro zirconium, dimethyl difluorozirconium, dimethyl dibromo zirconium, diphenyl dibromo zirconium, hydrolysis products of these, condensates of these hydrolysis products, and the like. Of these, tetramethoxy zirconium, tetraethoxy zirconium and tetraisopropoxy zirconium are preferable from the viewpoint of availability.

In the step of forming the release layer, the metal alkoxide can be used in the form of an aqueous solution. To increase the solubility in water, an alcohol such as methanol or ethanol may be added. Addition of an alcohol is particularly effective when a metal alkoxide having high hydrophobicity is used.

When the concentration of the metal alkoxide in the aqueous solution is higher, the peeling strength between the resin substrate and the copper foil tends to be lowered, and the peel strength can be adjusted by adjusting the metal alkoxide concentration. Although not limited, the concentration of the metal alkoxide in the aqueous solution may be 0.001 to 1.0 mol / l, and may be typically 0.005 to 0.2 mol / l.

The pH of the aqueous solution of the metal alkoxide is not particularly limited and can be used on the acidic side or on the alkaline side. For example, at a pH in the range of 3.0 to 10.0. From the viewpoint that no specific pH adjustment is required, the pH is preferably in the range of about 5.0 to 9.0, which is near neutral, and more preferably in the range of 7.0 to 9.0.

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 may be formed between the copper foil and the release layer. Here, the chromate treatment layer refers to a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromic acid or dichromate. The chromate treatment layer contains elements (metal, alloy, oxide, nitride, sulfide, and the like) such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium You can. Specific examples of the chromate treatment layer include a chromate treatment layer treated with an aqueous solution of chromic anhydride or potassium dichromate or a chromate treatment layer treated with a treatment liquid containing chromic anhydride or potassium dichromate and zinc.

As the heat-resistant layer and the rust-preventive layer, well-known heat-resistant layer and rust-preventive layer can be used. For example, the heat-resistant layer and / or the rust-preventive layer may be formed of a material selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, Or a layer containing at least one element selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, May be a metal layer or an alloy layer composed of at least one kind of element selected from the group consisting of The heat resistant layer and / or the rust preventive layer may be selected from the group of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, Nitride, or silicide containing at least one element selected from the group consisting of oxides, nitrides, and silicides. The heat-resistant layer and / or rust-preventive layer may be a layer containing a nickel-zinc alloy. The heat-resistant layer and / or rust-preventive layer may be a nickel-zinc alloy layer. The nickel-zinc alloy layer may contain 50 wt% to 99 wt% of nickel and 50 wt% to 1 wt% of zinc, other than inevitable impurities. The total adhesion amount of zinc and nickel in the nickel-zinc alloy layer may be 5 to 1000 mg / m 2, preferably 10 to 500 mg / m 2, and preferably 20 to 100 mg / m 2. It is also preferable that the ratio of the adhesion amount of nickel to the adhesion amount of nickel (= adhesion amount of nickel / adhesion amount of zinc) of the nickel-zinc alloy layer or the nickel-zinc alloy layer is 1.5 to 10. The adhesion amount of nickel in the nickel-zinc alloy layer or the nickel-zinc alloy layer is preferably 0.5 mg / m 2 to 500 mg / m 2, more preferably 1 mg / m 2 to 50 mg / m 2 Do.

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

The silane coupling agent used in the silane coupling treatment may be a known silane coupling agent, for example, an amino silane coupling agent or an epoxy silane coupling agent or a mercapto silane coupling agent. Examples of the silane coupling agent include vinyltrimethoxysilane, vinylphenyltrimethoxysilane,? -Methacryloxypropyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane, 4-glycidylbutyltrimethoxy Aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) butoxy) propyl-3-aminopropyl Trimethoxysilane, imidazole silane, triazinilane, gamma-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. These silane coupling agents may be used in combination of two or more. Among them, it is preferable to use an amino-based silane coupling agent or an epoxy-based silane coupling agent.

Examples of the amino-based silane coupling agent include N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, 3- Aminopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxy Silane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- Aminopropyl) trimethoxysilane, N- (2-aminoethyl-3-aminopropyl) tris (2-ethylhexoxy) silane, 6- (aminohexylaminopropyl) , Aminophenyltrimethoxysilane, 3- (1-aminopropoxy) -3,3-dimethyl-1-propenyltrimethoxysilane, 3- 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, omega -aminoundecyltrimethoxysilane, 3- (2-N-benzylaminoethylamino Propyl) trimethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, (N, N-diethyl- Aminopropyl) trimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) butoxy) propyl-3-aminopropyltriethoxysilane, N- Methoxysilane, and methoxysilane.

The silane coupling treatment layer is preferably used in a range of 0.05 mg / m 2 to 200 mg / m 2, preferably 0.15 mg / m 2 to 20 mg / m 2, preferably 0.3 mg / m 2 to 2.0 mg / . In the above-mentioned range, the adhesion between the resin substrate and the copper foil can be further improved.

In addition, the surface of the copper layer, the roughening particle layer, the heat resistant layer, the rust preventive layer, the silane coupling treatment layer or the chromate treatment layer can be coated with an antireflective layer, International Publication No. WO2006 / 028207, Japanese Patent Publication No. 4828427, International Publication Nos. WO2006 / 134868, Japanese Patent Publication No. 5046927, International Publication Nos. WO2007 / 105635, Japanese Patent Publication No. 5180815, Japanese Laid-Open Patent Publication No. 2013-19056 Can be carried out.

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

The resin layer may be an adhesive resin, that is, an adhesive, a primer, or an insulating resin layer in a semi-cured state (B-stage state) for bonding. The semi-cured state (B-stage state) includes a state in which the insulating resin layer can be stacked and stored without being tacky even when the surface is touched with a finger, and a curing reaction occurs when subjected to heat treatment.

The resin layer may include a thermosetting resin or a thermoplastic resin. The resin layer may contain a thermoplastic resin. The resin layer may contain a known resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton or the like. In addition, the resin layer may be formed, for example, in International Publication Nos. WO2008 / 004399, WO2008 / 053878, International Publication Nos. WO2009 / 084533, JP-A 11-5828, Japanese Patent Publication No. 3184485, International Publication No. WO97 / 02728, Japanese Patent Publication No. 3676375, Japanese Patent Application Laid-Open No. 2000-43188, Japanese Patent Publication No. 3612594, Japanese Patent Application Laid-Open No. 2002-179772, Japanese Patent Application Laid- 2002-359444, JP-A-2003-304068, JP-A-3992225, JP-A-2003-249739, JP-A-4136509, JP-A-2004-82687, JP- 4025177, 2004-349654, 4286060, 2005-262506, 4570070, 2005-53218, and 3949676, Japanese Patent Application Laid- , Japanese Patent Publication No. 4178415, International Publication Japanese Patent Application Laid-Open Nos. WO2004 / 005588, JP-A-2006-257153, JP-A-2007-326923, JP-A-2008-111169, JP-A-5024930, WO2006 / 028207, Japanese Patent Application Laid-Open No. 2009-71817, International Publication No. WO2007 / 105635, Japanese Patent Publication No. 5180815, International Patent Publication No. International Publication Nos. WO2008 / 114858, WO2009 / 008471, JP-A-2011-14727, WO009 / 001850, WO2009 / 145179, WO2011 / 068157, JP-A-2013-19056 (Resin, curing accelerator, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton, etc.) and / or a method of forming a resin layer and a forming apparatus .

A copper-clad laminate can be produced by forming a resin base material on the release layer side of the surface-treated copper foil of the present invention. The copper-clad laminate is obtained by forming a resin base material on a base material such as paper base phenol resin, paper base epoxy resin, synthetic fiber base epoxy resin, glass / paper composite base epoxy resin, glass / glass nonwoven composite base epoxy resin, . The resin substrate may be a prepreg, or may include a thermosetting resin. In addition, a printed wiring board can be produced by forming a circuit in the surface-treated copper foil of the copper clad laminate. In addition, a printed circuit board can be manufactured by mounting electronic parts 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 the electronic parts are mounted. The electronic device may be manufactured using the printed wiring board, the electronic device may be manufactured using the printed circuit board on which the electronic device is mounted, or an electronic device may be manufactured using the printed board on which the electronic device is mounted . The "printed circuit board" includes a circuit-forming substrate for a semiconductor package. In addition, a semiconductor package can be manufactured by mounting electronic parts on a circuit formation substrate for a semiconductor package. Further, an electronic device may be manufactured using the semiconductor package.

The microcircuit can be formed by the semi-additive method using the copper foil of the present invention. Fig. 1 shows a schematic example of the semi-additive method using the profile of the copper foil. In the semi-additive method, the surface profile of the copper foil is used. Specifically, first, the surface-treated copper foil of the present invention is laminated on the resin substrate from the release layer side to prepare a copper clad laminate. Next, the copper foil (surface-treated copper foil) of the copper clad laminate is peeled without etching. Next, the surface of the resin base material onto which the copper surface profile is transferred is cleaned with dilute sulfuric acid or the like, and electroless copper plating is performed. Then, a portion of the resin substrate where no circuit is formed is covered with a dry film or the like, and the surface of the electroless copper plating layer which is not covered with the dry film is subjected to electric (electrolytic) copper plating. Thereafter, after the dry film is removed, a fine circuit is formed by removing the electroless copper plating layer formed on the portion where no circuit is formed. The microcircuit formed in the present invention is in close contact with the peeling surface of the resin substrate on which the copper surface profile of the present invention is transferred, so that the adhesion (fill 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 base or a copper foil to form a pattern, and then a conductive pattern is formed by electroplating and etching. Therefore, in one embodiment of the method for producing the printed wiring board according to the present invention using the semi-additive method, the step of preparing the surface-treated copper foil and the resin substrate according to the present invention,

A step of laminating a resin base material on the surface treated copper foil from the release layer side,

A step of peeling the surface-treated copper foil after the surface-treated copper foil and the resin base material are laminated,

A step of forming a through hole and / or a blind via on the peeling surface of the resin substrate produced by peeling the surface-treated copper foil,

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

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

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

A step of exposing the plating resist, thereafter removing the plating resist in a region where a circuit is formed,

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

A step of removing the plating resist,

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

In another embodiment of the method for producing a printed wiring board according to the present invention using the semi-additive method, a step of preparing a surface-treated copper foil and a resin substrate according to the present invention,

A step of laminating a resin base material on the surface treated copper foil from the release layer side,

A step of peeling the surface-treated copper foil after the surface-treated copper foil and the resin base material are laminated,

A step of cleaning the surface of the resin base material with dilute sulfuric acid or the like to form an electroless plating layer (for example, electroless copper plating layer) on the release surface of the resin base material produced by peeling the surface-

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

A step of exposing the plating resist, thereafter removing the plating resist in a region where a circuit is formed,

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

A step of removing the plating resist,

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

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

On the other hand, in another embodiment of the method for producing a printed wiring board according to the present invention using the pull additive method, a step of preparing a surface-treated copper foil and a resin substrate according to the present invention,

A step of laminating a resin base material on the surface treated copper foil from the release layer side,

A step of peeling the surface-treated copper foil after the surface-treated copper foil and the resin base material are laminated,

A step of washing the surface of the resin base material with dilute sulfuric acid or the like on the release face of the resin base material produced by peeling the surface-

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

A step of exposing the plating resist, thereafter removing the plating resist in a region where a circuit is formed,

A step of forming an electroless plating layer (for example, an electroless copper plating layer or an electroless plating layer formed to have a thickness) in a region where the circuit where the plating resist is removed is formed,

And removing the plating resist.

Further, in the semi-additive method and the full additive method, there is an effect that the electroless plating layer can be easily formed by washing the surface of the resin base material. Particularly, when the release layer remains on the surface of the resin substrate, since the release layer is partially or entirely removed from the resin substrate surface by the cleaning, the surface of the resin substrate is cleaned to form a more electroless plating layer There is an effect that it becomes easy. The cleaning may be performed by a known cleaning method (kind of liquid to be used, temperature, method of applying liquid, etc.). It is also 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 substrate after the surface-treated copper foil is peeled off by the full additive method, whereby a printed circuit formation substrate and a circuit formation substrate for a semiconductor package can be manufactured. Further, a printed wiring board and a semiconductor package can be manufactured by using the circuit-forming substrate. Further, 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 was measured by a device such as a scanning electron microscope equipped with XPS (X-ray photoelectron spectroscopy), EPMA (electron beam microanalyzer) and EDX (energy dispersive X-ray analysis) It can be presumed that the silane compound exists on the surface of the copper foil or the surface-treated copper foil. When the peel strength (peel strength) of the surface-treated copper foil and the resin substrate is 200 gf / cm or less, it can be assumed that the silane compound usable for the release layer of the invention related to the present invention is used.

The surface of the copper foil or the surface-treated copper foil is measured by a device such as a scanning electron microscope equipped with XPS (X-ray photoelectron spectroscopy), EPMA (electron beam microanalyzer), EDX (energy dispersive X-ray analysis) And when the peel strength (peel strength) of the surface-treated copper foil and the resin substrate is 200 gf / cm or less, the surface of the copper foil or the surface-treated copper foil, It can be presumed that a compound having two or less mercapto groups is present.

The surface of the copper foil or the surface-treated copper foil is measured by a device such as a scanning electron microscope equipped with XPS (X-ray photoelectron spectroscopy), EPMA (electron beam microanalyzer) and EDX (energy dispersive X-ray analysis) , Ti and Zr are detected and when the peel strength (peel strength) of the surface-treated copper foil and the resin substrate is 200 gf / cm or less, the surface of the copper foil or the surface treated copper foil can be used for the release layer of the invention It is presumed that the above-mentioned metal alkoxide exists.

Example

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

· Fabrication of bright green (copper before surface treatment)

General electrolytic growth and double-sided flat electrolytic growth with the thicknesses shown in Table 1 were produced under the following respective electrolytic conditions.

(1) General electrolytic decay

Cu 120 g / l

H ₂ SO ₄ 100 g / l

Chloride ion (Cl ^-) 70 ppm

Leveling agent (glue) 3 ppm

Electrolyte temperature 60 ℃

Current density 70 A / dm 2

Electrolyte flux 2 m / sec

(2) Two-sided flat electric discharge

Electrolytic condition of two-sided flat electrolytic growth

Cu 120 g / l

H ₂ SO ₄ 100 g / l

Chloride ion (Cl ^-) 70 ppm

Leveling 1st (bis (3-sulfopropyl) disulfide) 20 ppm

Leveling Second (amine compound) 20 ppm

Electrolyte temperature 60 ℃

Current density 70 A / dm 2

Electrolyte flux 2 m / sec

The amine compound may be an amine compound of the following formula.

[Chemical Formula 6]

Wherein 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 the surface treatment, any of the roughening treatment, the barrier treatment (heat-resistant treatment), the rust-preventive treatment, the silane coupling treatment, and the resin layer formation treatment is carried out on the M- Alternatively, each process was combined. Subsequently, a release layer was formed on the treated side of the copper foil under the following conditions. Unless otherwise noted, each treatment was carried out in this order.

(1) Harmonization processing

[Spherical harmony (normal)]

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

(Liquid composition 1)

CuSO ₄ .5H ₂ O 98 g / l

Cu 25 g / l

H ₂ SO ₄ 100 g / l

Arsenic 1.5 g / ℓ

(Electroplating temperature 1) 38 캜

(Current condition 1) Current density 70 A / dm 2 (above the limit current density of the bath)

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

(Liquid composition 2)

_{CuSO 4 · 5H 2 O 176 g} / ℓ

Cu 45 g / l

H ₂ SO ₄ 100 g / l

(Electroplating temperature 2) 45 캜

(Current condition 2) Current density: 29 A / dm 2 (less than the limit current density of the bath)

[Fine-tuning (Type 1)]

First, coarsening treatment was carried out under the following conditions. The ratio of the critical current density at the formation of the harmonic particles was 2.50.

(Liquid composition 1)

_{CuSO 4 · 5H 2 O 58.9 g} / ℓ

Cu 15 g / l

H ₂ SO ₄ 100 g / l

Na ₂ WO ₄ .2H ₂ O 5.4 mg / l

Sodium dodecyl sulfate added 10 ppm

(Electroplating temperature 1) 40 DEG C

(Current condition 1) Current density 54 A / dm < 2 >

Subsequently, normal plating was carried out under the following conditions.

(Liquid composition 2)

_{CuSO 4 · 5H 2 O 176 g} / ℓ

Cu 45 g / l

H ₂ SO ₄ 100 g / l

(Electroplating temperature 2) 45 캜

(Current condition 2) Current density 41 A / d < 2 >

[Fine tuning (Type 2)]

First, a Cu-Co-Ni ternary alloy layer was formed in the following liquid composition 1 and electroplating condition 1, and cobalt plating was formed on the ternary alloy layer in the following liquid composition 2 and electroplating condition 2 .

(Liquid composition 1)

Cu 10-20 g / l

Co 1 to 10 g / l

Ni 1 to 10 g / l

pH 1-4

(Electroplating temperature 1) 40 to 50 DEG C

(Current condition 1) Current density 25 A / d < 2 >

(Liquid composition 2)

Co 1 to 30 g / l

Ni 1 to 30 g / l

pH 1.0 to 3.5

(Electroplating temperature 2) 30 to 80 DEG C

(Current condition 2) Current density 5 A / dm 2

(2) Barrier treatment (heat-resistant treatment)

For Examples 9, 11 and 12, the barrier (heat-resistant) treatment was carried out under the following conditions to form a brass plating layer.

(Liquid composition)

Cu 70 g / l

Zn 5 g / l

NaOH 70 g / l

NaCN 20 g / l

(Electroplating conditions)

Temperature 70 ° C

Current density 8 A / dm2 (multi-stage treatment)

(3) Rust treatment

For Examples 10, 11 and 12, rust-preventive treatment (zinc chromate treatment) was carried out under the following conditions to form a rust-preventive treatment layer.

(Liquid composition)

CrO ₃ 2.5 g / ℓ

Zn 0.7 g / l

Na ₂ SO ₄ 10 g / l

pH 4.8

(Zinc chromate conditions)

Temperature 54 ° C

Current density 0.7 As / dm 2

(4) Silane coupling treatment

For Examples 11 and 12, the silane coupling material coating treatment was carried out under the following conditions to form a silane coupling layer.

(Liquid composition)

Alkoxysilane content 0.4%

pH 7.5

Spray method Spray solution

(5) Formation of release layer

[Release Layer A]

An aqueous solution of a silane compound (n-propyltrimethoxysilane: 4 wt%) was applied to the treated surface of the copper foil using a spray coater, and then the surface of the copper foil was dried in air at 100 ° C for 5 minutes, . The silane compound was dissolved in water (in water), and the stirring time until the application was 30 hours, the alcohol concentration in the aqueous solution was 0 vol%, and the pH of the aqueous solution was 3.8-4.2.

[Release Layer B]

An aqueous solution of sodium 1-dodecanethiosulfonate (concentration of sodium 1-dodecanethiosulfonate) was used as a compound having two or less mercapto groups in the molecule by using 1-dodecanethiosulfonate sodium, Coated on the treated surface of the copper foil using a coater and then dried in air at 100 ° C for 5 minutes to prepare a release layer B. The pH of the aqueous solution was adjusted to 5 to 9.

[Release Layer C]

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

[Release Layer D]

(N-decyl-triisopropoxytitanium concentration: 0.01 mol / l) of n-decyl-triisopropoxytitanium was used as the metal alkoxide, and n-dodecyltriisopropoxytitanium as the titanate compound was used as the metal alkoxide , And was applied to the treated surface of the copper foil using a spray coater, followed by drying in air at 100 ° C for 5 minutes to prepare a release layer D. The titanate compound was dissolved in water, and the stirring time until application was 24 hours. The alcohol concentration in the aqueous solution was adjusted to 20 vol% methanol and the pH of the aqueous solution was adjusted to 5 to 9.

[Release Layer E]

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

In the case of the release layers of Examples 19 to 54 and Comparative Examples 6 to 7, in the case of using the silane compounds, the release layer formation conditions not described in the later-described tables were the same as those of the release layer A. The release layer formation conditions not described in the following table were the same as those for the release layer B because of the mercapto compound. The conditions for forming the release layer, which are not described in the following tables, were the same as those for the release layer C because of the metal alkoxide.

(6) Resin layer formation treatment

In Example 12, after the barrier treatment, the anti-rust treatment, the silane coupling agent application, and the release layer formation, the resin layer was further formed under the following conditions.

(Resin synthesis example)

A 3-neck flask equipped with a reflux condenser equipped with a stainless steel anchor stirrer, a nitrogen inlet tube and a stopcock equipped with a bead-equipped cooling tube was charged with 3,4,3 ', 4' -Biphenyltetracarboxylic acid dianhydride, 87.7 g (300 mmol) of 1,3-bis (3-aminophenoxy) benzene and 4.0 g (40 mmol) of gamma -valerolactone, , 300 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and 20 g of toluene were added. The mixture was heated at 180 占 폚 for 1 hour and then cooled to room temperature Thereafter, 29.42 g (100 mmol) of 3,4,3 ', 4'-biphenyltetracarboxylic dianhydride, 82.12 g (200 mmol) of 2,2-bis {4- (4-aminophenoxy) 200 g of NMP and 40 g of toluene were added and mixed at room temperature for 1 hour and then heated at 180 占 폚 for 3 hours to obtain a block copolymerized polyimide having a solid content of 38%. The block copolymer polyimide had the following general formula (1): general formula (2) = 3: 2, number average molecular weight: 70000, and weight average molecular weight:

(7)

The block copolymer polyimide solution obtained in Synthesis Example was further diluted with NMP to obtain a block copolymer polyimide solution having a solid content of 10%. (4-maleimide phenyl) methane (BMI-H, K-ion) was added to this block copolymer polyimide solution in a solid weight ratio of 35 and a block copolymer polyimide weight ratio of 65 (4-maleimidophenyl) methane solids weight: weight of solid content of block copolymer polyimide contained in the resin solution = 35:65) and dissolved and mixed at 60 占 폚 for 20 minutes to prepare a resin solution. Thereafter, the resin solution was coated on the release layer-formed surface of Example 12, dried at 120 DEG C for 3 minutes and then at 160 DEG C for 3 minutes under a nitrogen atmosphere, and finally heated at 300 DEG C for 2 minutes To prepare a copper foil having a resin layer. The thickness of the resin layer was set to 2 탆.

· Evaluation of surface roughness Rz of copper foil (fresh foil) and surface treated copper foil

Ten-point average roughness Rz of the treated surface of the surface-treated copper foil was measured in accordance with JIS B0601 (1994) using a contact-contact roughness meter SP-11 manufactured by Kosaka Laboratory Co., The measurement position was changed 10 times, and the value at 10 measurements was obtained. In the same manner, the surface roughness Rz of the copper foil (fresh foil) before the surface treatment was also measured.

· Fabrication of copper clad laminate

Each of the following resin substrates 1 to 3 was bonded to the treated surface of each surface-treated copper foil.

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

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

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

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

· Evaluation of peel strength (peel strength)

For the copper clad laminate, the state peel strength at the time of peeling the resin base material from the copper foil with the tensile tester Autograph 100 was measured in accordance with IPC-TM-650.

· Evaluation of failure mode of resin

The peeling surface of the resin substrate after peeling was observed with an electron microscope, and the failure mode of the resin (cohesion, interface, aggregation and confluence of the interface) was observed. "Cohesion" indicates that the peeling strength is too strong and the resin is broken. "Mixed" indicates that the resin is broken, and "Cohesion" indicates that the resin is broken. And " cohesion " coexist.

Wiring Formability

1, electroless copper plating and electrolytic copper plating were performed on the resin base material, and the plated copper-clad laminate with the copper layer thickness of 12 탆 was plated copper by etching, L (line) / S (space) = 30 mu m / 30 mu m circuit was formed. At this time, the wirings formed on the resin substrate were observed with an optical microscope of 100 to 500 times, and it was determined as NG (x) that the circuit was free from any missing (OK).

The test conditions and evaluation results are shown in Tables 1 to 4.

As shown in Tables 1 to 4, in Examples 1 to 54, a predetermined release layer was formed, the peel strength was suppressed, and the resin was in the failure mode only at the interface. For this reason, it can be said that it is possible to physically peel off the resin substrate after the resin is bonded to the resin substrate.

On the other hand, in Comparative Examples 1 to 7, the releasing layer could not be formed because the releasing layer was not formed, or the compound used for forming the releasing layer was inadequate, so that the peel strength was large, It was either cohesion or a mixture of interfaces. Therefore, it can be said that it is impossible to physically peel off the resin after it has been bonded to the resin base.

Claims (29)

A copper foil having a surface unevenness of Rz of 0.1 to 5.0 m measured according to JIS B0601 (1994)
A surface-treated copper foil having a release layer formed on a surface of the copper foil having surface irregularities,
Wherein the release layer has the following formula:

(Wherein R ¹ is an alkoxy group or a halogen atom, R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom, and M M is at least one of Al, Ti and Zr, n is 0, 1 or 2, m is an integer equal to or greater than ¹ , and at least one of R ¹ is an alkoxy group. 3 for Al, and 4 for Ti and Zr.)
, A titanate compound, a zirconate compound, a hydrolysis product thereof, or a condensate of the hydrolysis product. The method according to claim 1,
Wherein at least one layer selected from the group consisting of a heat resistant layer, a rust prevention layer, a chromate treatment layer and a silane coupling treatment layer is formed between the copper foil and the release layer. 3. The method according to claim 1 or 2,
Wherein a resin layer is formed on the surface of the surface-treated copper foil. The method of claim 3,
Wherein the surface-treated copper foil has a thickness of 9 to 70 占 퐉. 3. The method according to claim 1 or 2,
A step of bonding a resin substrate to the surface-treated copper foil from the release layer side,
A step of peeling the surface-treated copper foil from the resin base material without etching, thereby obtaining a resin base material onto which the surface profile of the copper foil is transferred to the release surface;
And a step of forming a circuit on the release face side of the resin substrate onto which the surface profile has been transferred. A copper foil having no roughened particles and having surface roughness of 0.1 to 5.0 mu m measured in accordance with JIS B0601 (1994)
And a release layer formed on a surface of the copper foil having surface irregularities for releasably separating the resin base material when the resin base material is bonded to the copper foil from the release layer side, Of the surface-treated copper foil.
(A) the release layer has the following formula:

(Wherein R ¹ is an alkoxy group or a halogen atom, R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom, and R ³ and R ⁴ are each independently a halogen atom or an alkoxy group or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom.
, The hydrolysis product thereof, and the condensation product of the hydrolysis product thereof, either singly or in combination.
(B) the release layer is formed by using a compound having two or less mercapto groups in the molecule,
(C) the release layer has the following formula:

(Wherein R ¹ is an alkoxy group or a halogen atom, R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom, and M M is at least one of Al, Ti and Zr, n is 0, 1 or 2, m is an integer equal to or greater than ¹ , and at least one of R ¹ is an alkoxy group. 3 for Al, and 4 for Ti and Zr.)
, A titanate compound, a zirconate compound, a hydrolysis product thereof, or a condensate of the hydrolysis product,
(D) at least one layer selected from the group consisting of a heat resistant layer, a rust prevention layer, a chromate treatment layer and a silane coupling treatment layer is formed between the copper foil and the release layer,
(E) A resin layer is formed on the surface of the surface-treated copper foil.
(F) In the above (E), the resin layer is a resin for bonding, a primer, or a resin in a semi-cured state.
(G) The thickness of the surface-treated copper foil is 9 to 70 mu m.
(H) A method of manufacturing a copper foil, comprising the steps of: (a) bonding a resin base material to the surface-treated copper foil from the side of the release layer; and peeling the surface-treated copper foil from the resin base material without etching the surface profile, A step of obtaining a resin substrate and a step of forming a circuit on the release face side of the resin substrate onto which the surface profile is transferred.
(I) a step of bonding the resin base material to the surface-treated copper foil from the side of the release layer, and peeling the surface-treated copper foil from the resin base material without etching the surface profile, Or a method of transferring the surface profile of the copper foil to the resin base material is used. The method according to claim 6,
When the resin base material is peeled off from the copper foil after the resin base material is bonded to the copper foil from the release layer side and the peeling surface of the peeled resin base material is observed with an electron microscope, Is an interface,
Wherein the peeling strength when the resin base material is peeled off is 190 gf / cm or less when the resin base material is bonded to the copper foil from the release layer side. A copper clad laminate comprising the surface-treated copper foil according to claim 1 or 2 and a resin substrate formed on the release layer side of the surface-treated copper foil. 9. The method of claim 8,
Wherein the resin substrate is a prepreg, or comprises a thermosetting resin. A printed wiring board using the surface-treated copper foil according to claim 1 or 2. A printed wiring board produced by using the surface-treated copper foil according to claim 1 or 2. A semiconductor package comprising the printed wiring board according to claim 11. An electronic device using the printed wiring board according to claim 11. A method for manufacturing a semiconductor device, comprising the steps of: applying a resin base material to the surface-treated copper foil according to claim 1 or 2 from the release layer side;
A step of peeling the surface-treated copper foil from the resin base material without etching, thereby obtaining a resin base material onto which the surface profile of the copper foil is transferred to the release surface;
And forming a circuit on the release surface side of the resin base material onto which the surface profile is transferred. A printed wiring board produced by the method for manufacturing a printed wiring board according to claim 14. A surface-treated copper foil according to any one of claims 1 to 3, wherein the surface-treated copper foil is peeled off from the resin base material after the resin base material is bonded to the surface of the release- The transferred resin substrate. 17. The method of claim 16,
Wherein the resin substrate is a prepreg or a resin substrate comprising a thermosetting resin, onto which the surface profile of the copper foil is transferred. A printed wiring board produced by using the resin substrate onto which the surface profile of the copper foil according to claim 17 is transferred. A semiconductor package comprising the printed wiring board according to claim 18. An electronic device using the printed wiring board according to claim 18. An electronic device using the semiconductor package according to claim 19. A method for manufacturing a semiconductor device, comprising the steps of: applying a resin base material to the surface-treated copper foil according to claim 1 or 2 from the release layer side;
And peeling the surface-treated copper foil from the resin base material without etching the resin base material to obtain a resin base material having the surface profile of the copper foil transferred to the release surface. A process for producing a surface-treated copper foil and a resin substrate according to claim 1 or 2,
A step of bonding the resin base material to the surface-treated copper foil from the release layer side,
And peeling the surface-treated copper foil from the resin base material without etching to obtain a resin base material having a surface profile of the copper foil transferred to the release surface. 24. The method of claim 23,
Wherein the resin substrate is a prepreg or a method of transferring a surface profile of a copper foil, which comprises a thermosetting resin, to a resin substrate. A method for producing a printed wiring board, wherein a printed wiring board is manufactured using the resin base material onto which the surface profile of the copper foil is transferred by the method according to claim 23. A printed wiring board using the resin substrate onto which the surface profile of the copper foil is transferred by the method according to claim 23. A semiconductor package comprising the printed wiring board according to claim 26. An electronic device using the printed wiring board according to claim 26. 23. A resin substrate, wherein the surface profile of the copper foil is transferred by a method of transferring the surface profile of the copper foil according to claim 23 to the resin substrate.

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