KR20180111660A - Copper foil with release layer, laminate, method of manufacturing printed wiring board and method of manufacturing electronic device - Google Patents

Abstract

Provided is a copper foil with a release layer which can be used for manufacturing a fine circuit on a circuit-embedded substrate or the like with a simple process. The copper foil with a release layer is sequentially provided with the release layer, a barrier layer, and a copper foil.

Description

TECHNICAL FIELD [0001] The present invention relates to a copper foil with a release layer, a laminate, a method of manufacturing a printed wiring board, and a manufacturing method of an electronic device. BACKGROUND OF THE INVENTION 1. Field of the Invention [0002]

The present invention relates to a copper foil with a release layer, a laminate, a method of producing a printed wiring board, and a method of manufacturing electronic equipment.

Printed circuit boards have made great strides over the past half century and have been used in almost all electronic devices today. In recent years, miniaturization and high performance of electronic apparatuses have been demanded, and high-density mounting of mounting parts and signal frequency have been developed. As for printed wiring boards, there has been a demand for miniaturization (fine pitching) When an IC chip is placed on a printed wiring board, fine pitching of L (line) / S (space) = 20 mu m / 20 mu m or less is required.

First, the printed wiring board is manufactured from a copper-clad laminate in which an insulating substrate mainly including a copper foil and a glass epoxy substrate, a BT resin, and a polyimide film is bonded. The interlacing is performed by a method (lamination method) in which an insulating substrate and a copper foil are laminated and heated and pressed, or a method of applying varnish, which is a precursor of an insulating substrate material, to a surface having a coating layer of a copper foil and heating and curing do.

Japanese Patent Application Laid-Open No. 2005-101137

In recent years, various kinds of methods for manufacturing printed wiring boards have been developed and used according to purposes. For example, a circuit plating is formed on the surface of a copper foil, a buried resin is provided on the ultra-thin copper layer so as to cover the formed circuit plating (so that the circuit plating is buried), the resin layer is laminated, (Embedded Trace Substrate) such as a printed wiring board is manufactured in accordance with a so-called embedding method in which blind vias are formed by exposing the circuit plating by hole processing at a position where a circuit and wiring are electrically connected between a plurality of layers of the laminate.

As an example of a method of manufacturing the circuit-embedded substrate, first, a circuit is formed on the surface of the copper foil, and resin is laminated so as to cover the circuit to form a buried circuit. Then, the copper foil is removed by etching to expose a circuit embedded in the resin, and a printed wiring board is manufactured using the above-mentioned embedding circuit.

However, as described above, if the embedded circuit is formed by laminating the resin to cover the circuit, and then the copper foil is removed by etching to expose the embedded circuit, the buried circuit is eroded by the etching of the copper foil.

Further, in the case of manufacturing the above-mentioned circuit-embedded substrate and the like, there is a problem that the manufacturing process of the printed wiring board becomes complicated because it is necessary to form a circuit by providing a plating resist on the surface of the copper foil.

The inventors of the present invention have conducted intensive studies and found that a fine circuit on a circuit-embedded substrate or the like can be fabricated by a simple process by providing a barrier layer having a predetermined solubility to a copper etchant between the copper foil and the release layer Respectively.

The present invention completed on the basis of the above findings is, in one aspect, a copper foil with a release layer provided with a release layer, a barrier layer, and a copper foil in this order.

In one embodiment of the copper foil with a release layer of the present invention, the barrier layer has a solubility in copper etchant of 0.1 or less.

In a further embodiment of the copper foil with a release layer according to the present invention, the copper etchant is any one of the following (3-1) to (3-4).

(3-1) Copper chloride etchant

(Furtherance)

Cupric chloride: 25 wt%

Hydrochloric acid: 4.6 wt%

REST: Water

(3-2) Iron chloride etchant

(Furtherance)

Ferric chloride: 37wt% (Bordeaux 40 ° B'e)

REST: Water

(3-3) Alkali etchant

(Furtherance)

CuCl ₂ : 295 g / L

NH ₃ : 9.4 mol / L

REST: Water

(3-4) Sulfuric acid-aqueous solution of hydrogen peroxide

(Furtherance)

35 wt% hydrogen peroxide: 80 mL / L

Concentrated sulfuric acid: 120 mL / L

REST: Water

The copper foil with a release layer according to another embodiment of the present invention is further characterized in that the barrier layer is a Ni layer, a Ti layer, a Cr layer, a V layer, a Zr layer, a Ta layer, an Au layer, a Pt layer, A Ru layer, an Rh layer, an Ir layer, a W layer, a Mo layer, or a group consisting of Ni, Ti, V, Zr, Ta, Au, Pt, Os, Pd, Ru, Rh, Ir, W, Mo, A layer containing an alloy including at least one selected from the group consisting of Ni, Ti, V, Zr, Ta, Au, Pt, Os, Pd, Ru, Rh, Ir, W, Mo, Si and Cr Oxide, or nitride containing at least one selected from the group consisting of a carbide, an oxide, and a nitride.

The copper foil with a release layer according to the present invention is further characterized in that the barrier layer is made of a Mo single crystal, a Cr single crystal, a Ni single crystal, a Ni-Mo-Cr alloy containing 20 mass% or more of Cr, -W alloy, or a Ni-Mo alloy.

In another embodiment of the copper foil with a release layer of the present invention, the number of pinholes of the barrier layer is 100 / dm 2 or less.

In another embodiment of the copper foil with a release layer of the present invention, the thickness precision (accuracy) of the barrier layer is 20% or less.

The copper foil with a release layer according to another embodiment of the present invention is further characterized in that the thickness of the barrier layer is 0.03 탆 or more.

The release-coated copper foil of the present invention is also, in another embodiment, 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 the 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 the hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom.

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

In another embodiment, the release layer-coated copper foil of the present invention has a compound in which the release layer has two or less mercapto groups in the molecule.

The release-coated copper foil of the present invention is also, in another embodiment, 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 the hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom, M is Al, Ti or Zr, n is 0, 1 or 2, m is an integer of 1 or more and equal to or less than ¹ , and at least one of R ¹ is an alkoxy group. , And 4 for Ti and Zr)

A hydrolysis product of the aluminate salt compound, a hydrolysis product of the titanate salt compound, a hydrolysis product of the zirconate compound, a hydrolysis product of the aluminate salt compound, A condensate of a decomposition product of the decomposition product, a condensate of a hydrolysis product of the titanate compound, or a condensate of a hydrolysis product of the zirconate compound, either singly or in combination.

The copper foil with a release layer according to another embodiment of the present invention is further characterized in that the release layer has a resin coating film composed of one or a plurality of resins selected from silicon, an epoxy resin, a melamine resin and a fluorine resin .

The copper foil with a release layer according to the present invention may further comprise a heat resistant layer, a rust preventive layer, a passivating layer, and / or a passivation layer between the copper foil and the barrier layer or between the barrier layer and the release layer, And at least one layer selected from the group consisting of a treatment layer and a silane coupling treatment layer.

The copper foil with a release layer according to the present invention is also a copper foil with a release layer formed on the surface of the copper foil opposite to the release layer in a group consisting of a roughening treatment layer, a heat resistant layer, a rust preventive layer, a chromate treatment layer and a silane coupling treatment layer And at least one layer selected from the above.

The copper foil with a release layer according to another embodiment of the present invention is a copper foil with a release layer in which the roughening treatment layer is made of at least one selected from the group consisting of Cu, Ni, P, W, As, Mo, Cr, Ti, Fe, V, Or a layer made of an alloy containing at least one of them.

The copper foil with a release layer of the present invention is also a copper foil having a resin layer on at least one layer selected from the group consisting of the roughened layer, the heat resistant layer, the anticorrosive layer, the chromate treatment layer and the silane coupling treatment layer Respectively.

In another aspect, the present invention is a laminate having the copper foil with a release layer of the present invention.

In another aspect, the present invention is a laminate comprising a copper foil with a release layer of the present invention and a resin, wherein a part or all of the cross section of the release layer-covered copper foil is covered with the resin.

In another aspect of the present invention, there is provided a copper foil having two release-coated copper foils of the present invention and a resin, wherein one of the two copper foils with a release- And the other side of the release layer side surface of the copper foil with the other release side layer and the other side of the resin are laminated.

In another aspect, the present invention is a method for producing a printed wiring board using the copper foil with a release layer of the present invention.

According to another aspect of the present invention, there is provided a method for manufacturing a copper foil, comprising the steps of: laminating an insulating substrate 1 on a surface of the release layer side of a copper foil with a release layer of the present invention; A step of covering the circuit with the insulating substrate 2 to embed the circuit; a step of removing the insulating substrate 1 from the laminated body of the circuit embedded in the insulating substrate 2 and the barrier layer, Exposing the barrier layer, and exposing a circuit buried in the insulating substrate 2 by removing the exposed barrier layer.

According to another aspect of the present invention, there is provided a method for manufacturing a copper foil, comprising the steps of: laminating an insulating substrate and a surface of a release layer side of a copper foil with a release layer of the present invention; A step of forming a circuit and a resin layer on the resin at least once, and a step of forming a resin layer and a circuit on the resin, And a step of removing the release layer and the barrier layer from the peeled copper foil with a release layer adhered thereto.

According to another aspect of the present invention, there is provided a method of manufacturing an electronic device using the printed wiring board manufactured by the method of the present invention.

According to the present invention, it is possible to provide a copper foil with a release layer capable of manufacturing a microcircuit in a circuit-embedded substrate or the like in a simple and easy process.

1 is a schematic view showing a method of forming an embedding circuit using a copper foil with a release layer according to an embodiment of the present invention.

<Copper foil with a release layer>

The copper foil with a release layer according to the present invention comprises a release layer, a barrier layer, and a copper foil in this order. With this configuration, it becomes possible to form a circuit by a subtractive method on the copper foil and then to form a buried circuit. Therefore, there is an advantage that the manufacturing process of the printed wiring board is simplified. The barrier layer preferably has a solubility in copper etchant of 0.1 or less. Here, the solubility in the copper etchant is defined by the following equation. The etching rate (탆 / s) when the barrier layer is etched with copper etchant and the etching rate (탆 / s) when copper is etched with copper etchant are measured using a copper etchant having the same composition.

Solubility of the barrier layer in copper etchant (-) = etching rate (탆 / s) / etching rate (탆 / s) when copper is etched with copper etchant when the barrier layer is etched with copper etchant

That is, the smaller value of the solubility of the barrier layer in the copper etchant means that the barrier layer is less likely to dissolve in the copper etchant.

Here, the etching rate can be obtained by the following method.

The etching rate refers to the thickness of a copper etchant (copper etchant) eroded per unit time. For example, the etching rate can be calculated as follows.

The mass W1 (g) of the sample before etching is measured. The mass W2 (g) of the sample after etching for a predetermined time t (s) is measured. The etching rate is calculated by the following equation.

(G / m &lt; 3 &gt;) x sample etching area (mu m / s) = {mass W1 (g) of sample before etching - mass W2 M &lt; 2 &gt;) x etching time t (s)

When measuring the above-described etching speed, for example, an etching solution of sulfuric acid-hydrogen peroxide, a copper etchant (ferric chloride aqueous solution), a ferric chloride etchant (cupric chloride aqueous solution), or an alkali etchant ) Can be used. Examples and conditions of the specific composition of the etching solution are as follows.

· Copper Chloride

(Furtherance)

Copper Chloride: 25 wt%

Hydrochloric acid: 4.6 wt%

REST: Water

(Condition)

Solution temperature: 50 ° C

Spray pressure: 0.15 MPa

· Chloride iron oxide

Ferric chloride: 37wt% (Bordeaux 40 ° B'e)

REST: Water

(Condition)

Solution temperature: 50 ° C

Spray pressure: 0.15 MPa

· Alkaline etchant

CuCl ₂ : 295 g / L

NH ₃ : 9.4 mol / L

REST: Water

(Condition)

Solution temperature: 50 ° C

Spray pressure: 0.15 MPa

· Sulfuric acid-aqueous solution of hydrogen peroxide

(Furtherance)

35 wt% hydrogen peroxide: 80 mL / L

Concentrated sulfuric acid: 120 mL / L

REST: Water

(Condition)

Solution temperature: 50 ° C

Spray pressure: 0.15 MPa

The copper foil is typically provided in the form of a rolled copper foil or a copper foil produced by a dry plating method such as electrolytic copper foil or sputtering. Generally, the electrolytic copper foil is produced by electrolytically depositing copper from a copper sulfate plating bath onto a drum of titanium or stainless steel. The rolled copper foil is produced by repeatedly performing the plastic working and the heat treatment using a rolling roll. Examples of the material of the copper foil include high purity copper such as tough pitch copper (JIS H3100 alloy number C1100) and oxygen free copper (JIS H3100 alloy number C1020 or JIS H3510 alloy number C1011) A copper alloy to which Zr or Mg is added, and a copper alloy such as a Colson type copper alloy to which Ni and Si are added can be used. The upper limit of the thickness of the copper foil is not particularly limited, but is typically 3000 탆 or less, for example, 2000 탆 or less, such as 1000 탆 or less, for example, 500 탆 or less, For example, 200 mu m or less, for example, 150 mu m or less, for example, 100 mu m or less. The lower limit of the thickness of the copper foil is not particularly limited, but is typically at least 1 탆, for example, at least 2 탆, such as at least 3 탆, such as at least 4 탆, For example, 6 mu m or more, for example, 7 mu m or more, for example, 8 mu m or more, for example, 9 mu m or more, for example, 10 mu m or more.

The barrier layer preferably has a solubility in copper etchant of 0.1 or less. If the solubility of copper in the etchant is not more than 0.1, the barrier layer is less soluble or less etched than copper in the copper etchant (copper etching solution). A Ni layer, a Ti layer, a Cr layer, a V layer, a Zr layer, a Ta layer, an Au layer, a Pt layer, an Os layer, a Pd layer, a Ru layer, a Rh layer, An Ir layer, a W layer, a Mo layer or an alloy containing at least one of Ni, Ti, V, Zr, Ta, Au, Pt, Os, Pd, Ru, Rh, Ir, W, Mo, Or a carbide or an oxide or nitride containing at least one of Ni, Ti, V, Zr, Ta, Au, Pt, Os, Pd, Ru, Rh, Ir, W, Mo, Or the like is preferably used. As the barrier layer having a solubility in copper etchant of 0.1 or less, it is preferable that the barrier layer is composed of a Mo base, a Cr base, a Ni base, a Ni-Mo-Cr alloy containing 20 mass% or more of Cr, a Ni-Mo alloy, As shown in Fig. Here, the Mo layer means that the barrier layer is made of a Mo layer. The term "Cr group" means that the barrier layer is made of a Cr layer. The Ni layer means that the barrier layer is made of a Ni layer.

From the viewpoint that the barrier layer is not eroded well from the copper etchant, the solubility of the barrier layer in the copper etchant is preferably 0.09 or less, more preferably 0.08 or less, preferably 0.07 or less, more preferably 0.06 or less, Preferably 0.04 or less, more preferably 0.03 or less, more preferably 0.02 or less, and still more preferably 0.01 or less. If the barrier layer is not well eroded from the copper etchant, the barrier layer may be eroded by the copper etchant to reduce the likelihood of pitting. As a result, there is a possibility that the resin substrate (core) and the resin for embedding the circuit are likely to come into contact and bond, and there is a case that the core dismounting described later is likely to occur. The lower limit of the solubility in the copper etchant of the barrier layer is not particularly limited, but may be, for example, 0, for example, greater than 0, for example, 0.000000 or more, for example, 0.000001 or more, For example, at least 0.00001, such as at least 0.0000, such as at least 0.0001, such as at least 0.0002, such as at least 0.0003, such as at least 0.0004, such as at least 0.0005, such as at least 0.0006, For example, 0.0007 or more, for example, 0.0008 or more, for example, 0.0009 or more, for example, 0.0010 or more.

When the thickness of the barrier layer is 0.01 탆 or more, the resin substrate (core) may be easily peeled off from the printed wiring board. The thickness of the barrier layer is preferably at least 0.02 탆, more preferably at least 0.03 탆, more preferably at least 0.04 탆, more preferably at least 0.05 탆, preferably at least 0.06 탆, more preferably at least 0.07 탆, Preferably 0.1 m or more, more preferably 0.11 m or more, more preferably 0.12 m or more, further preferably 0.13 m or more, more preferably 0.14 m or more, and more preferably 0.15 m or more Preferably at least 0.20 mu m, more preferably at least 0.25 mu m, more preferably at least 0.30 mu m, at least 0.35 mu m, preferably at least 0.40 mu m, more preferably at least 0.45 mu m, Preferably 0.55 占 퐉 or larger, more preferably 0.60 占 퐉 or larger, and 0.65 占 퐉 Or more, more preferably 0.70 占 퐉 or more.

The upper limit of the thickness of the barrier layer is not particularly limited but may be, for example, 100 占 퐉 or less, for example, 80 占 퐉 or less, for example, 60 占 퐉 or less, for example, 40 占 퐉 or less, For example, 5 mu m or less, for example, 3 mu m or less, for example, 2 mu m or less.

· When the barrier layer is Cr group

(Plating solution)

Chromic anhydride: 100 to 300 g / L

Sulfuric acid: 0.5 to 10.0 g / L

Solution temperature: 40 to 60 ° C

Current density: 0.2 to 60 A / dm 2

· When the barrier layer is Ni group

(Plating solution)

Nickel sulfate · 7H ₂ O: 100 to 300 g / L

Sodium citrate: 5-100 g / L

Temperature: 30 ~ 60 ℃

pH: 2.0 to 7.0

Current density: 0.2 to 40 A / dm 2

In the case of a Ni-Mo-Cr alloy in which the barrier layer contains Cr at 20 mass% or more

(Plating solution)

Nickel sulfate · 7H ₂ O: 20 to 100 g / L

Sodium molybdate · 2H ₂ O: 10 to 80 g / L

Chromic anhydride: 50-200 g / L

Sodium citrate: 10 to 100 g / L

Temperature: 30 ~ 60 ℃

pH: 2.0 to 7.0

Current density: 0.2 to 20 A / dm 2

· When the barrier layer is a Ni-Mo alloy

(Plating solution)

Nickel sulfate · 7H ₂ O: 50 to 300 g / L

Sodium molybdate · 2H ₂ O: 30 to 150 g / L

Sodium citrate: 40-200 g / L

Temperature: 30 ~ 60 ℃

pH: 2.0 to 7.0

Current density: 0.2 to 20 A / dm 2

· When the barrier layer is a Ni-W alloy

(Plating solution)

Nickel sulfate · 7H ₂ O: 50 to 300 g / L

Sodium tungstate: 30 to 150 g / L

Sodium citrate: 40-200 g / L

Temperature: 30 ~ 60 ℃

pH: 2.0 to 7.0

Current density: 0.2 to 20 A / dm 2

The conventional copper foil with a release layer has no barrier layer having a resistance to dissolution in the copper etchant and no copper foil with a release layer is used for the embedding method. This is considered to be due to the possibility of erosion to the release layer by etching. On the contrary, since the copper foil with a release layer of the present invention has a barrier layer having resistance to copper etchant between the copper foil and the release layer, there is no fear that the release layer is eroded by etching. Therefore, the release layer can exert its function in the circuit formation according to the subtractive method in the embedding method. Under these circumstances, when a circuit is formed on the copper foil by the subtractive method in the formation of the embedding circuit using the copper foil with a release layer, a barrier layer having resistance to copper etchant on the side opposite to the etching side of the copper foil So that the circuit is not easily attracted. That is, a fine circuit on a circuit-embedded substrate or the like can be manufactured by a simple and easy process.

It is preferable that the number of pinholes of the barrier layer is 100 / dm 2 or less. As the number of pinholes in the barrier layer becomes 100 / dm 2 or less, erosion of the liquid from the pinholes can be suppressed well during etching. In addition, by making the resin base (core) and the resin for embedding the circuit come in contact with and through the pinholes of the barrier layer, the phenomenon that the resin base (core) is not easily peeled off from the copper foil with the release layer can be prevented . The number of pinholes in the barrier layer is more preferably 20 pieces / dm 2 or less, more preferably 5 pieces / dm 2 or less, further preferably 4 pieces / dm 2 or less, still more preferably 3 pieces / dm 2 or less More preferably not more than 0.7 number / dm 2, even more preferably not more than 0.4 number / dm 2, more preferably not more than 0.2 number / dm 2, Or less, more preferably 0 number / dm 2. The lower limit of the number of pinholes of the barrier layer is not particularly limited. For example, the lower limit of the number of pinholes of the barrier layer may be 0 / dm 2 or more, for example 0.01 or more dm 2 or more, Dpi / m2 or more, for example, 0.6 dpi / dm2 or more, for example, 1 / dm2 or more.

In addition, the number of pinholes can be reduced by setting the barrier layer by dry plating such as sputtering, or by setting the current density slightly higher when the barrier layer is provided by wet plating.

It is preferable that the thickness precision of the barrier layer is 20% or less. When the thickness precision of the barrier layer is 20% or less, it is possible to reduce an extremely thin portion of the barrier layer when etching. Thereby, it is possible to reduce the exposure of the resin base material (core) by reducing the thickness of the barrier layer due to the etching of the pinhole or barrier layer. Accordingly, when the resin base material (core) is brought into contact with and bonded to the resin for embedding the circuit in the exposed portion of the resin base material (core), the resin base material (core) It may be possible to prevent it from happening. The thickness precision of the barrier layer is more preferably 15% or less, more preferably 13% or less, further preferably 10% or less, further preferably 7% or less, further preferably 5% or less, , More preferably not more than 3%, further preferably not more than 2%. The lower limit of the thickness precision of the barrier layer is not particularly limited, but may be, for example, at least 0%, such as at least 0.0001%, such as at least 0.001%, such as at least 0.01%, such as at least 0.10% For example, 0.15% or more, for example, 0.20% or more, for example, 0.25% or more.

Further, the thickness precision of the barrier layer can be reduced by providing the barrier layer by dry plating such as sputtering, or by setting the current density slightly higher when the barrier layer is provided by wet plating.

Next, the release layer will be described. The releasing layer of the copper foil with a release layer is such that the resin base material can be peeled off when the resin base material is pressed from the release layer side by pressing or the like. At this time, the resin substrate and the copper foil fall into the release layer.

(1) Silane compound

The release layer may be formed of 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) singly or in combination.

expression:

(3)

(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 any one of these hydrocarbon groups in which at least one hydrogen atom is substituted with a halogen atom , R ³ and R ⁴ each independently represent 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 to be.)

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 has been substituted with a halogen atom, in the absence of an alkoxy group, Tend to deteriorate too much. The silane compound is required to have at least one hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, and 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 with the barrier layer tends to increase. In addition, the alkoxy group according to the present invention includes an alkoxy group in which at least one hydrogen atom is substituted with a halogen atom.

The silane compound preferably has three alkoxy groups, and the hydrocarbon group (one or more hydrogen atoms include a hydrocarbon group substituted with a halogen atom). In the above formula, R ³ and R ⁴ are both an alkoxy group.

Examples of the alkoxy group include, but are not limited to, a methoxy group, an ethoxy group, an n- or iso-propoxy group, an n-, iso- or tert-butoxy group, n-, iso- or neo- Branched or cyclic alkoxy groups of 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, .

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 iso-propyl, n-, iso- or tert-butyl, n-, , n-decyl, and the like, and alkyl groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms, which are linear or branched.

The cycloalkyl group includes, but is 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 thryl group, a xylyl group), a 1- or 2-naphthyl 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 silane compounds are methyltrimethoxysilane, ethyltrimethoxysilane, n- or iso-propyltrimethoxysilane, n-, iso- or tert-butyltrimethoxysilane, n-, iso- or neo Phenyltrimethoxysilane, alkyl-substituted phenyltrimethoxysilane (for example, p- (methyl) phenyltriethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane, Methoxysilane), methyltriethoxysilane, ethyltriethoxysilane, n- or iso-propyltriethoxysilane, n-, iso- or tert-butyltriethoxysilane, pentyltriethoxysilane, hexyltri Phenyl triethoxysilane, alkyl substituted phenyltriethoxysilane (e.g., p- (methyl) phenyltriethoxysilane), (3,3 (meth) acryloxypropyltriethoxysilane, , 3-trifluoropropyl) trimethoxysilane, and tridecafluorooctyltriethoxy And the hydrolysis products of these, and the hydrolysis products thereof, and the hydrolysis products of these hydrolysis products, such as methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, trimethylfluorosilane, dimethyldibromosilane, diphenyldibromosilane, And the like. Of these, propyltrimethoxysilane, methyltriethoxysilane, hexyltrimethoxysilane, phenyltriethoxysilane and decyltrimethoxysilane are preferable from the viewpoint of availability.

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

The release layer may be composed of a compound having two or less mercapto groups in the molecule.

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 And at least one selected from these can be used.

Thiol has one mercapto group in the molecule and is represented, for example, as 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 different carbon or nitrogen, respectively.

The thiocarboxylic acid is, for example, R-CO-SH in which the hydroxyl group of the organic carboxylic acid is 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. Thiocarboxylic acid can also be used in the form of a salt. Further, compounds having two thiocarboxylic acid groups can be used.

The dithiocarboxylic acid is, for example, R- (CS) -SH in which two oxygen atoms in the carboxy group of the organic carboxylic acid are replaced with sulfur atoms. R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may contain a hydroxyl group or an amino group. In addition, dithiocarboxylic acid can be used in the form of a salt. Also, compounds having two dithiocarboxylic acid groups can be used.

The thiosulfonic acid is a compound in which the hydroxyl group of the organic sulfonic acid is substituted 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, for example, 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 different carbons, respectively. It is also possible to use dithiosulfonic acid 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.

The alkyl group includes, but is not limited to, methyl, ethyl, n- or iso-propyl, n-, iso- or tert- An octyl group, an n-decyl group, and other straight or branched alkyl groups of 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.

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

Examples of the aromatic hydrocarbon group suitable for R include a phenyl group, a phenyl group substituted with an alkyl group (e.g., a thryl group, a xylyl group), a 1- or 2-naphthyl group, and an anthryl group, 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, benzimidazole, benzotriazole, thiazole, and benzothiazole. The heterocyclic group includes either or both of a hydroxyl group and an amino group There may be.

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- 1-dodecanethiol, 10-amino-1-dodecanethiol, 1-dodecanethiol sulfonic acid, Sodium thiophenol, thiobenzoic acid, 4-amino-thiophenol, p-toluenethiol, 2,4-dimethylbenzenethiol, 3-mercapto-1,2,4 triazole, 2- mercaptobenzothiazole, . Of these, 3-mercapto-1,2-propanediol is preferred from the viewpoint of water solubility and waste disposal.

(3) Metal alkoxide

The release layer may be formed of an aluminate compound, a titanate compound, a zirconate compound, a hydrolysis product thereof, or a condensate of the hydrolysis product (hereinafter, simply referred to as a metal alkoxide) May be used alone or in combination.

[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 any hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom, M is any one of 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 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, Tend to deteriorate too much. The metal alkoxide is required to have 0 to 2 hydrocarbon groups selected from the group consisting of alkyl groups, cycloalkyl groups and aryl groups, and any one of these hydrocarbon groups in which at least one hydrogen atom has been substituted with a halogen atom. When the hydrocarbon group has three or more hydrocarbon groups, the adhesion with the barrier layer tends to be too low. In addition, the alkoxy group according to the present invention includes an alkoxy group in which at least one hydrogen atom is substituted with a halogen atom. In adjusting the peel strength with the barrier layer to the above range, the metal alkoxide preferably has two or more alkoxy groups and one or two hydrocarbon groups (one or more hydrogen atoms include a hydrocarbon group substituted with a halogen atom) .

Examples of the alkyl group include, but are not limited to, methyl, ethyl, n- or iso-propyl, 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 methyl, ethyl, n-propyl, isopropyl, n-butyl,

The cycloalkyl group includes, but is not limited to, a cycloalkyl group having 3 to 10 carbon atoms, preferably 5 to 7 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl 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 thryl group, a xylyl group), a 1- or 2-naphthyl group, and an anthryl group, An aryl group having 6 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 - or neopentyl dimethoxy aluminum, hexyl dimethoxy aluminum, octyl dimethoxy aluminum, decyl dimethoxy aluminum, phenyl dimethoxy aluminum; Alkyl substituted phenyl dimethoxy aluminum (e.g., p- (methyl) phenyl dimethoxy aluminum), dimethyl methoxy aluminum, triethoxy aluminum, methyl diethoxy aluminum, ethyl diethoxy aluminum, n- or iso-propyl diethoxy For example, aluminum, n-, iso- or tert-butyldiethoxyaluminum, pentyldiethoxyaluminum, hexyldiethoxyaluminum, octyldiethoxyaluminum, decyldiethoxyaluminum, phenyldiethoxyaluminum, alkyl substituted phenyldiethoxyaluminum , p- (methyl) phenyldiethoxy aluminum), dimethyl ethoxy aluminum, triisopropoxy aluminum, methyl diisopropoxy aluminum, ethyl diisopropoxy aluminum, n- or iso-propyl diethoxy aluminum, diisopropoxy aluminum, iso- or tert-butyl diisopropoxy aluminum, pentyl diisopropoxy aluminum, hexyl diisopropoxy aluminum, octyl diisopropoxy (Phenyl) diisopropoxy aluminum, dimethyl isopropoxyaluminum, (3) phenyldiisopropoxyaluminum, alkyl substituted phenyldiisopropoxyaluminum such as p- (methyl) phenyldiisopropoxyaluminum, , 3,3-trifluoropropyl) dimethoxyaluminum, and tridecafluorooctyldiethoxyaluminum, methyldichloroaluminum, dimethylchloroaluminum, dimethylchloroaluminum, phenyldichloroaluminum, dimethylfluoroaluminum, dimethylbromoaluminum, Diphenyl bromo aluminum, hydrolysis products of these, and condensates of hydrolysis products thereof. Of these, trimethoxyaluminum, triethoxyaluminum and triisopropoxyaluminum are preferable from the viewpoint of availability.

Examples of preferable titanate compounds include tetramethoxytitanium, methyltrimethoxytitanium, ethyltrimethoxytitanium, n- or isopropyltrimethoxytitanium, n-, iso- or tert-butyltrimethoxytitanium, n -, iso- or neopentyltrimethoxytitanium, hexyltrimethoxytitanium, octyltrimethoxytitanium, decyltrimethoxytitanium, phenyltrimethoxytitanium; Alkyl substituted phenyltrimethoxytitanium (for example, p- (methyl) phenyltrimethoxytitanium), dimethyldimethoxytitanium, tetraethoxytitanium, methyltriethoxytitanium, ethyltriethoxytitanium, n- or iso -Propyltriethoxytitanium, n-, iso- or tert-butyltriethoxytitanium, pentyltriethoxytitanium, hexyltriethoxytitanium, octyltriethoxytitanium, decyltriethoxytitanium, phenyltriethoxytitanium , Alkyl-substituted phenyltriethoxytitanium (for example, p- (methyl) phenyltriethoxytitanium), dimethyldiethoxytitanium, tetraisopropoxytitanium, methyltriisopropoxytitanium, ethyltriisopropoxytitanium, n- or iso-propyltriethoxytitanium, n-, iso- or tert-butyltriisopropoxytitanium, pentyltriisopropoxytitanium, hexyltriisopropoxytitanium, octyltriisopropoxytitanium, decyl Triisopropoxy titanium, Phenyl triisopropoxytitanium, alkyl-substituted phenyl triisopropoxytitanium (for example, p- (methyl) phenyltriisopropoxytitanium), dimethyl diisopropoxytitanium, (3,3,3-trifluoro Propyl) trimethoxytitanium, and tridifluorooctyltriethoxytitanium, methyltrichlorotitanium, dimethyldichlorotitanium, trimethylchlorotitanium, phenyltrichlorotitanium, dimethyldifluorotitanium, dimethyldibromotitanium, diphenyl Dibromotitan, hydrolysis products thereof, and condensates of the hydrolysis products thereof. Of these, tetramethoxytitanium, tetraethoxytitanium and tetraisopropoxytitanium are preferable from the viewpoint of availability.

Examples of preferable 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-substituted phenyltriethoxyzirconium (for example, p- (methyl) phenyltriethoxyzirconium), dimethyldiethoxyzirconium, tetraisopropoxyzirconium, methyltriisopropoxyzirconium, ethyltriisopropoxyzirconium, n- or iso-propyltriethoxyzirconium, n-, iso- or tert-butyltriisopropoxyzirconium, pentyltrisisob There may be mentioned, for example, bis (trimethylsilyl) amines such as bis (trimethylsilyl) amide, tetramethylammonium fluoride, tetraisopropoxy zirconium, hexyltriisopropoxyzirconium, octyltriisopropoxyzirconium, decyltriisopropoxyzirconium, phenyltriisopropoxyzirconium, ) Phenyl triisopropoxytitanium), dimethyl diisopropoxy zirconium, (3,3,3-trifluoropropyl) trimethoxy zirconium, and tridifluorooctyl triethoxy zirconium, methyl trichloro zirconium, dimethyl Condensates of hydrolyzed products of these, and condensates of these hydrolyzed products, and the like can be given as examples of the hydrolyzed products of these hydrolyzates, such as dichlorosilane, trimethylchlorosiliconium, phenyltrichlorosilonium, dimethyldifluorozirconium, dimethyldibromozirconium, diphenyldibromo zirconium, have. Of these, tetramethoxy zirconium, tetraethoxy zirconium and tetraisopropoxy zirconium are preferable from the viewpoint of availability.

(4) a release layer made of a resin coating film

A resin coating film composed of one or a plurality of resins selected from silicone, an epoxy resin, a melamine resin and a fluorine resin is used to adhere the resin layer as a support to the barrier layer, It is possible to adjust the peel strength range as described below.

The adjustment of the peel strength for realizing such adhesion is carried out by using a resin coating film composed of one or a plurality of resins selected from silicon, an epoxy resin, a melamine resin and a fluorine resin as described later. Such a resin coating film is subjected to a printing treatment under a predetermined condition as described later, and the adhesion between the resin layer and the resin substrate as a support is adjusted by a hot press. As a result, And the like.

Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, brominated epoxy resin, amine type epoxy resin, flexible epoxy resin, hydrogenated bisphenol A type epoxy resin, Phenoxy resins, and the like.

Examples of the melamine resin include a methyl etherified melamine resin, a butylated urea melamine resin, a butylated melamine resin, a methylated melamine resin, and a butyl alcohol-modified melamine resin. The melamine resin may be a resin mixed with the above-mentioned resin, a butylated urea resin, a butylated benzoguanamine resin or the like.

The number average molecular weight of the epoxy resin is preferably 2000 to 3000, and the number average molecular weight of the melamine resin is preferably 500 to 1000. By having such a number average molecular weight, the resin can be made into a coating material, and the adhesion strength of the resin coating film can be easily adjusted to a predetermined range.

Examples of the fluororesin include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, and polyvinyl fluoride.

Examples of silicones include methylphenylpolysiloxane, methylhydrogenpolysiloxane, dimethylpolysiloxane, modified dimethylpolysiloxane, and mixtures thereof. Examples of the denaturation include denaturing such as epoxy modification, alkyl modification, amino modification, carboxyl modification, alcohol modification, fluorine modification, alkylaralkyl polyether modification, epoxy polyether modification, polyether modification, alkyl high alcohol ester modification, Polyester modification, acyloxyalkyl modification, halogenated alkyl acyloxyalkyl modification, halogenated alkyl modification, aminoglycol modification, mercapto modification, hydroxyl group-containing polyester modification and the like.

If the film thickness of the resin coating film is too thin, the resin coating film is too thin, which makes it difficult to form and the productivity tends to deteriorate. Further, even if the film thickness exceeds a certain size, a new improvement in the peelability of the resin coating film can not be seen, and the manufacturing cost of the resin coating film tends to increase. From this viewpoint, the resin coating film preferably has a film thickness of 0.1 to 10 mu m, more preferably 0.5 to 5 mu m. The film thickness of the resin coating film is achieved by applying a resin coating material in a predetermined coating amount in the procedure described below.

In the resin coating film, silicon functions as a releasing agent for the resin coating film. Here, if the total amount of the epoxy resin and the melamine resin is too large as compared with the silicon, the peel strength imparted by the resin coating film between the barrier layer and the resin substrate as the support becomes large, It may not be easily peeled off by force. On the other hand, if the total amount of the epoxy resin and the melamine resin is too small, the peeling strength described above becomes small, so that the copper foil may peel off during transportation or processing. From this point of view, the total amount of the epoxy resin and the melamine resin is preferably contained in an amount of 10 to 1500 parts by mass, more preferably 20 to 800 parts by mass, relative to 100 parts by mass of silicon .

Further, the fluororesin functions as a releasing agent as well as silicon, and has an effect of improving the heat resistance of the resin coating film. If the amount of the fluororesin is too large as compared with that of silicon, the above-mentioned peeling strength becomes small). Therefore, there is a case where the laminate is peeled off during transportation or processing, and the temperature required for the printing process described later increases. From this viewpoint, the fluororesin is preferably 0 to 50 parts by mass, more preferably 0 to 40 parts by mass with respect to 100 parts by mass of silicon.

Resin coating film, in addition to the fluoropolymer in accordance with the silicone and epoxy resin and / or melamine resin and, if necessary, SiO _2, MgO, Al ₂ O _3, BaSO _4, and Mg (OH) a surface roughening particles at least one compound selected from ₂ And may further contain. As the resin coating film contains surface roughening particles, the surface of the resin coating film becomes irregular. By the unevenness, the surface of the copper foil provided on the barrier layer coated with the resin coating film becomes convex and becomes a surface with no gloss. The content of the surface roughening particles is not particularly limited as long as the resin coating film is uneven, but is preferably 1 to 10 parts by mass with respect to 100 parts by mass of silicon.

The particle size of the surface roughening particles is preferably 15 nm to 4 탆. Here, the particle diameter means the average particle diameter (average value of the maximum particle diameter and the minimum particle diameter) measured from a scanning electron microscope (SEM) photograph and the like. As the particle diameter of the surface roughening particles is in the above range, the amount of irregularities on the surface of the resin coating film can be easily adjusted, and as a result, the amount of irregularities on the surface of the resin layer as the support layer and the support layer can be easily adjusted. Specifically, the amount of irregularities of the surface of the barrier layer and the resin substrate as the support is about 4.0 占 퐉 at the maximum height roughness Ry in accordance with JIS.

- Resin laminated on the release layer side of the copper foil with a release layer (insulating substrate 1 described later)

As the resin that can be laminated on the release layer side of the copper foil with a release layer, a known resin can be used. In addition, a known resin used as a plate-like carrier can be used. Further, a resin layer described later can be used for the above-mentioned resin. The resin that can be laminated on the release layer side of the copper foil with a release layer is not particularly limited, but a phenol resin, a polyimide resin, an epoxy resin, a natural rubber, a pine resin and the like can be used. Do. A prepreg may also be used. It is recommended that the prepress before the copper foil is in the B-stage state. Prepreg (C stage) linear expansion coefficient is ^{12 ~ 18 (× 10 -6 /} ℃) and a constituent material of the copper foil of the substrate of 16.5 (× 10 ^-6 / ℃), or 17.3 (× 10 ^-6 of the SUS plate in a press / ° C), it is advantageous in that the position of the circuit due to a phenomenon (scaling change) different from that of the substrate size before and after the pressing is difficult to occur. In addition, with the synergistic effect of these advantages, it becomes possible to produce ultra-thin multilayer coreless substrates. The prepreg used here may be the same as or different from the prepreg constituting the circuit board.

This prepreg has a high glass transition temperature (Tg) in view of keeping the peel strength after heating in the optimum range, and is preferably in the range of 120 to 320 占 폚, preferably 170 to 240 占 폚, (Tg). The glass transition temperature (Tg) is a value measured by DSC (differential scanning calorimetry).

It is also preferable that the coefficient of thermal expansion of the resin is within + 10% and -30% of the thermal expansion rate of the copper foil. Accordingly, it is possible to effectively prevent the positional difference of the circuit due to the difference in thermal expansion between the copper foil and the resin, to reduce the generation of defective products, and to improve the yield.

The thickness of the resin is not particularly limited. The resin may be a resin for a rigid printed wiring board or a resin for a flexible printed wiring board. In addition, when the resin is thin, thermal distribution in the resin during hot press may be good. Further, since the resin does not bend well when the resin is thick, the manufacturing process of the printed wiring board may easily proceed. From the viewpoint of facilitating the production process of the printed wiring board, the thickness of the resin is preferably 5 占 퐉 or more, more preferably 5 占 퐉 or more, more preferably 10 占 퐉 or more, preferably 20 占 퐉 or more, , Preferably 40 m or more, more preferably 50 m or more, and more preferably 100 m or more. The thickness of the resin is preferably 5000 占 퐉 or less, more preferably 4000 占 퐉 or less, more preferably 3000 占 퐉 or less, more preferably 2000 占 퐉 or less, and 1500 占 퐉 or less Preferably not more than 1300 占 퐉, more preferably not more than 1000 占 퐉, more preferably not more than 900 占 퐉, more preferably not more than 400 占 퐉.

<Laminate>

The laminate (copper-clad laminate or the like) can be produced using the copper foil with a release layer of the present invention.

The laminate using the copper foil with a release layer of the present invention may be laminated in the order of &quot; release layer / barrier layer / copper foil / resin or prepreg &quot;.

&Lt; Hardening treatment and other surface treatment &gt;

On the surface of the copper foil of the copper foil with a release layer (for example, the surface of the copper foil on the side opposite to the side having the release layer), for example, to improve the adhesion with the insulating substrate or to adjust the adhesion with resin It is also possible to provide a harmonized treatment layer. The roughening treatment can be carried out, for example, by forming roughened particles of copper or a copper alloy. The harmony treatment may be fine. The roughening treatment layer may be a layer made of any one or a combination of any one selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, titanium, iron, vanadium, cobalt, good. It is also possible to carry out a coarsening treatment in which secondary particles or tertiary particles are further provided by a single body of nickel, cobalt, copper, zinc or an alloy after the coarse particles are formed of copper or a copper alloy. Thereafter, a single body and / or alloy and / or oxide of nickel, cobalt, copper, zinc, tin, molybdenum, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, A heat-resistant layer or a rust-preventive layer may be formed of a nitride and / or a silicide, and further the surface thereof may be subjected to a treatment such as a chromate treatment or a silane coupling treatment. Or the alloy and / or alloy of nickel, cobalt, copper, zinc, tin, molybdenum, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group element, iron, tantalum And / or an oxide and / or a nitride and / or a silicide may be formed on the surface of the heat-resistant layer or the rust-preventive layer, and further the surface thereof may be subjected to a treatment such as a chromate treatment or a silane coupling treatment. That is, 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 on the surface of the roughened treatment layer, At least one layer selected from the group consisting of a rust-preventive layer, a chromate treatment layer and a silane coupling treatment layer may be formed. The heat-resistant layer, rust-preventive layer, chromate treatment layer and silane coupling treatment layer may be formed of a plurality of layers (for example, two or more layers, three layers or more).

For example, the copper-cobalt-nickel alloy plating as the roughening treatment is a copper-cobalt-nickel alloy plating having an adhesion amount of 15 to 40 mg / dm 2 of copper-100 to 3000 μg / dm 2 of cobalt-100 to 1500 μg / So that the same ternary alloy layer can be formed. When the Co deposition amount is less than 100 占 퐂 / dm2, the heat resistance is deteriorated and the etching property is sometimes deteriorated. When the Co deposition amount is more than 3000 占 퐂 / dm2, it is not preferable when the effect of magnetism must be taken into consideration, etching unevenness occurs, and acid resistance and chemical resistance may be deteriorated. When the Ni deposition amount is less than 100 占 퐂 / dm2, the heat resistance may be deteriorated. On the other hand, if the amount of Ni adhered exceeds 1500 占 퐂 / dm2, the etching residue sometimes becomes large. The preferred Co deposition amount is 1000 to 2500 g / dm 2, and the preferable nickel deposition amount is 500 to 1200 g / dm 2. Here, the term "etching unevenness" means that when Co is etched with copper chloride, Co remains unmelted, and the etching residue means that Ni remains unmelted when subjected to alkali etching with ammonium chloride.

An example of a general bath and plating condition for forming such a ternary copper-cobalt-nickel alloy plating is as follows:

Plating bath composition: 10 to 20 g / L of Cu, 1 to 10 g / L of Co, 1 to 10 g / L of Ni

pH: 1-4

Temperature: 30 ~ 50 ℃

Current density (D _k ): 20 to 30 A / dm 2

Plating time: 1 to 5 seconds

The chromate treatment layer refers to a layer treated with a liquid containing chromic anhydride, chromic acid, bichromic acid, chromic acid salt or bichromate. The chromate treatment layer contains elements (metals, alloys, oxides, nitrides, sulfides and the like) such as Co, Fe, Ni, Mo, Zn, Ta, Cu, Al, P, W, Sn, As and Ti Maybe. Specific examples of the chromate treatment layer include a chromate treatment layer treated with an aqueous solution of chromic anhydride or potassium dichromate, a chromate treatment layer treated with a treatment liquid containing chromic anhydride or potassium dichromate and zinc, and the like.

The silane coupling treatment layer may be formed using a known silane coupling agent, and may be an epoxy silane, an amino silane, a methacryloxy silane, a mercapto silane, a vinyl silane, an imidazole silane, a triazine A silane coupling agent such as silane, or the like. 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.

Further, the surface of the copper foil of the copper foil with a release layer, or the surface of the roughening treatment layer, the heat resistant layer, the anticorrosive layer, the silane coupling treatment layer or the chromate treatment layer is disclosed in International Publication Nos. WO2008 / 053878, Japanese Patent Publication No. 5024930, 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, The surface treatment described in JP-A-2013-19056 can be carried out.

It is also possible to provide a roughened layer on the surface of the copper foil of the copper foil with a release layer, or it may be provided with one or more layers selected from the group consisting of a heat resistant layer, a rustproof layer, a chromate treatment layer and a silane coupling treatment layer Maybe.

It is also possible to provide a roughened layer on the surface of the copper foil of the copper foil with a release layer and a heat resistant layer and a rust preventive layer on the roughened layer and a chromate treatment layer on the heat resistant layer and the rust preventive layer, A silane coupling treatment layer may be provided on the chromate treatment layer.

The resin layer may be provided on the surface of the copper foil of the copper foil with a release layer or on the roughened layer or on the heat resistant layer or the rustproof layer, the chromate treatment layer or the silane coupling treatment layer. The resin layer may be an insulating resin layer.

The resin layer may be an adhesive or may be an insulating resin layer in a semi-cured state for bonding (B stage). The semi-cured state (B-stage state) includes a state in which the insulating resin layer can be stacked and stored without touching even when the surface thereof is touched with a finger, and a curing reaction occurs when further heat-treated.

The resin layer may include a thermosetting resin or a thermoplastic resin. The resin layer may include a thermoplastic resin. The kind thereof is not particularly limited, and examples thereof include epoxy resin, polyimide resin, polyfunctional cyanate ester compound, maleimide compound, polyvinyl acetal resin, urethane resin, polyethersulfone, polyether sulfone resin, aromatic poly Amide resins, aromatic polyamide resin polymers, rubber resins, polyamines, aromatic polyamines, polyamideimide resins, rubber modified epoxy resins, phenoxy resins, carboxyl group modified acrylonitrile-butadiene resins, polyphenylene oxides, bismaleimide tri A polyphenylene ether resin, a 2,2-bis (4-cyanuric acid) resin, a polyphenylene ether resin having a crosslinkable functional group, Propane, phosphorus-containing phenol compounds, manganese naphthenate, 2,2-bis (4-glycidylphenyl) propane, polyphenylene ether cyanate resin, siloxane modified polyamideimide resin, cyanoester resin, phosphazene resin, rubber modified polyamideimide resin, isoprene, hydrogenated polybutadiene, A resin containing at least one member selected from the group consisting of polyvinyl butyral, polymer epoxy, aromatic polyamide, fluorine resin, bisphenol, block copolymerized polyimide resin and cyanoester resin is preferable.

The epoxy resin has two or more epoxy groups in the molecule and can be used without particular problems as long as it can be used for electric and electronic materials. The epoxy resin is preferably an epoxy resin epoxidized using a compound having two or more glycidyl groups in the molecule. The epoxy resin may be at least one selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, novolak type epoxy resin, cresol novolak type epoxy resin, alicyclic epoxy resin, Epoxy resin, phenol novolak type epoxy resin, naphthalene type epoxy resin, brominated bisphenol A type epoxy resin, orthocresol novolak type epoxy resin, rubber modified bisphenol A type epoxy resin, glycidyl amine type epoxy resin, triglyceride type epoxy resin, Glycidyl amine compounds such as N, N-diglycidyl aniline, glycidyl ester compounds such as tetrahydrophthalic acid diglycidyl ester, phosphorus-containing epoxy resins, biphenyl-type epoxy resins , Biphenyl novolak type epoxy resin, trishydroxyphenyl methane type epoxy resin, tetraphenyl ethane type epoxy resin group Either alone or in combination of two or more selected from can be used as a mixture, or chena hydrogenation of the epoxy resin can be used a halogenated material.

An epoxy resin containing phosphorus known as phosphorus-containing epoxy resin can be used. The phosphorus-containing epoxy resin is, for example, an epoxy resin obtained as a derivative from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide having two or more epoxy groups in the molecule desirable.

The resin layer may be formed using a known resin, a resin curing agent, a compound, a curing accelerator, a dielectric (a dielectric including an inorganic compound and / or an organic compound, a dielectric including a metal oxide, A polymer, a prepreg, and a skeleton material. The resin layer may be formed, for example, in International Publication Nos. WO2008 / 004399, WO2008 / 053878, 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, JP-A-2002-359444, JP-A-2003-304068, JP-A-3992225, JP-A-2003-249739, JP-A-4136509, JP-A- 2004-82687, 4025177, 2004-349654, 4286060, 2005-262506, 4570070, 2005-53218, and 3949676, Japanese Patent Application Laid- , Japanese Patent Publication 4178415, International Publication Nos. WO2004 / 005588, JP-A-2006-257153, JP-A-2007-326923, JP-A-2008-111169, JP-A-5024930, WO2006 / 028207 , Japanese Patent Publication No. 4828427, Japanese Patent Application Laid-Open No. 2009-67029, International Publication Nos. WO2006 / 134868, Japanese Patent Publication No. 5046927, Japanese Patent Application Laid-Open No. 2009-173017, International Publication No. WO2007 / 105635, Japanese Laid-Open Patent Publication No. 5180815, International Publication No. WO2008 / 114858, International Publication No. WO2009 / 008471, Japanese Laid-Open Patent Publication No. 2011-14727, International Publication No. WO2009 / 001850, International Publication No. WO2009 / 145179, International Publication No. WO2011 / 068157, A method of forming a resin layer, a resin curing agent, a compound, a curing accelerator, a dielectric substance, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and / or a resin layer described in Patent Publication No. 2013-19056 It may be formed by using.

These resins are dissolved in, for example, a solvent such as MEK (methyl ethyl ketone) or toluene to form a resin solution, which is then spread on the copper foil or on the copper foil with a release layer or on the heat resistant layer, Coating layer or the silane coupling agent layer by, for example, a roll coater method, and then, if necessary, drying by heating to remove the solvent to obtain a B-stage state. For drying, for example, a hot-air drying furnace may be used, and the drying temperature may be 100 to 250 占 폚, preferably 130 to 200 占 폚.

The copper foil with a release layer (the copper foil with a release layer with a resin attached thereto) having the resin layer has a structure in which the resin layer is superimposed on a substrate and then the whole is thermally pressed to thermally cure the resin layer, After a prescribed wiring pattern is formed on the copper foil of the attached copper foil, the copper foil is peeled off from the resin layer.

By using the copper foil with a release layer with a resin, the number of sheets of prepreg material used at the time of manufacturing the multilayer printed wiring board can be reduced. Further, the copper clad laminate can be produced without using any prepreg material as a base material. At this time, an insulating resin may be undercoated on the surface of the substrate to further improve the smoothness of the surface.

In addition, when the prepreg material is not used, the material cost of the prepreg material is saved, and the lamination step is simplified, which is economically advantageous.

The thickness of the resin layer is preferably 0.1 to 80 mu m. If the thickness of the resin layer is larger than 0.1 占 퐉, the resin substrate and the copper foil with a release layer may be prevented from being inadvertently peeled off from the manufacturing process of the printed wiring board.

On the other hand, if the thickness of the resin layer is made thinner than 80 탆, it is easier to form a resin layer having a desired thickness in one coating step, and extra material cost and process steps are not required, . Further, since the formed resin layer may have good flexibility, there is a case where cracks or the like are hardly generated at the time of handling. Further, excessive resin flow may not occur at the time of thermocompression bonding with the inner layer material, so that the release layer-coated copper foil and the resin substrate may be laminated smoothly.

In addition, a printed circuit board is completed by mounting electronic parts on a printed wiring board. In the present invention, the &quot; printed wiring board &quot; 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 parts are mounted, or an electronic device may be manufactured using the printed board on which the electronic parts are mounted . Hereinafter, some examples of the steps of manufacturing a printed wiring board using the copper foil with a release layer according to the present invention.

In an embodiment of the method for manufacturing a printed wiring board according to the present invention, a buried circuit may be formed using a subtractive method. In the present invention, the subtractive method refers to a method of forming a conductor pattern by selectively removing unnecessary portions of a copper foil on a copper clad laminate by etching or the like. Hereinafter, an example of a printed wiring board manufacturing method including a step of forming a buried circuit by the subtractive method using the copper foil with a release layer of the present invention will be described. In the present specification, the term &quot; circuit &quot; refers to a concept including wiring.

Fig. 1 is a schematic view for explaining a method of forming an embedding circuit using a copper foil with a release layer according to an embodiment of the present invention. A method of forming an embedding circuit using a copper foil with a release layer according to an embodiment of the present invention is characterized in that a resin (insulating substrate 1) is first laminated on the release layer side of the copper foil with a release layer of the present invention (Fig. 1 (b)). Then, a dry film DF is laminated on the copper foil side of the copper foil with a release layer formed by laminating the resin (insulating substrate 1) (Fig. 1 (c)). Then, after the dry film is patterned by exposure / development (Fig. 1 (d)), the copper foil is etched with copper etchant to form a circuit (Fig.

At this time, since the barrier layer under the copper foil has a solubility in copper etchant of 0.1 or less, it is possible to form a circuit which is not drawn long. As a result, a fine circuit can be formed.

Then, the dry film is peeled off to expose the circuit (FIG. 1F). Then, the exposed circuit is covered with a resin (insulating substrate 2) to embed the circuit (Fig. 1 (g)). Then, the resin (insulating substrate 1) is peeled off from the laminated body of the circuit embedded in the resin (insulating substrate 2) and the barrier layer with the release layer to expose the barrier layer (FIG. Then, the exposed barrier layer is removed by etching to expose a circuit embedded in the resin (insulating substrate 2) (i in FIG. 1). Thus, a buried circuit can be obtained, and a printed wiring board using the buried circuit can be manufactured. As the etching solution for removing the barrier layer, a known etching solution can be used. Further, the barrier layer may be removed by a known method such as mechanical polishing and / or polishing using a shot blast and / or an abrasive such as colloidal silicic acid.

When a copper foil with a release layer of the present invention is laminated on one side of the resin (insulating substrate 1) from the release layer side, a laminate having the copper foil, the barrier layer, the release layer and the resin in this order can be obtained.

The embedded circuit may be provided on both sides of the above-described resin (insulating substrate 1) after the above-described copper foil with a release layer of the present invention is laminated from both sides of the above-mentioned resin (insulating substrate 1) . In the case of laminating the copper foil with a release layer of the present invention on both sides of the above-mentioned resin (insulating substrate 1) from the release layer side, the laminate having the copper foil, barrier layer, release layer, resin, release layer, barrier layer, Can be obtained. When the copper foil with a release layer of the present invention is laminated on both sides of the resin (insulating substrate 1) from the release layer side, the productivity of the printed wiring board is improved.

Further, a buried resin (resin) can be used for the insulating substrates 1 and 2. Known resins and prepregs can be used for the above-mentioned embedding resin. For example, glass poison prepreg impregnated with BT (bismaleimide triazine) resin or BT resin, ABF film made by Ajinomoto Fine Techno Co., Ltd. or ABF can be used. In addition, known resins or resin layers and / or resins and / or prepregs described in this specification can be used for the insulating substrates 1 and 2 and the buried resin (resin).

The method for manufacturing a printed wiring board according to the present invention is a method for manufacturing a printed wiring board comprising the steps of laminating a resin substrate and a surface of a release layer side of a copper foil with a release layer according to the present invention to form a circuit on a copper foil of a copper foil with a release layer laminated with the resin substrate, A step of burying the circuit with a resin, and a step of peeling off the release-layer-attached copper foil from the resin substrate (coreless method). And then removing the release layer and the barrier layer from the separated copper foil with the release layer adhered thereon (coreless method).

The method for manufacturing a printed wiring board according to the present invention is a method for manufacturing a printed wiring board comprising the steps of laminating a resin substrate and a surface of a release layer side of a copper foil with a release layer according to the present invention to form a circuit on a copper foil of a copper foil with a release layer laminated with the resin substrate, A step of forming a circuit and a resin layer on the resin at least once after the circuit is embedded in the resin after the resin layer and the circuit are formed, and a step of peeling the release-layer-attached copper foil from the resin substrate after the resin layer and the circuit are formed (Coreless method) may be used. And then removing the release layer and the barrier layer from the separated copper foil with the release layer adhered thereon (coreless method).

A method of manufacturing a printed wiring board according to the present invention is a method of manufacturing a printed wiring board comprising the steps of laminating a resin substrate and a surface of a release layer side of a copper foil with a release layer of the present invention, A step of burying the circuit with a resin, and a step of peeling off the release-layer-attached copper foil from the resin substrate (coreless method). And then removing the release layer, the barrier layer and the copper foil from the separated copper foil with the release layer adhered thereon (coreless method).

In the present specification, the terms "surface of a laminate" and "surface of a laminate" include the surface (top surface) of the other layer when the layer has another layer on the surface thereof.

In addition, in the above-described method for producing a coreless substrate, it is preferable that the copper foil with a release layer or the laminate (the laminate having the copper foil / barrier layer / release layer / resin in this order or the copper foil / barrier layer / release layer / resin A release layer, a barrier layer, and a copper foil in this order) is covered with a resin so as to form a release layer or a release layer constituting the laminate, It is possible to prevent the chemical liquid from penetrating between the attached copper foil and the one copper foil with a release layer, and to prevent the copper foil with the release layer from being corroded, have. As the &quot; resin covering part or all of the cross section of the copper foil with a release layer &quot; or &quot; resin covering part or all of the cross section of the laminate, &quot; a resin usable for the resin layer or a known resin can be used. Further, in the above-described method for producing a coreless substrate, at least a part of the outer periphery of the laminated portion of the copper foil or the laminate with the release layer (the laminated portion of the copper foil with the release layer and the resin) May be covered with a resin or a prepreg. The copper foil with a release layer is covered with a resin or prepreg over the entire surface of the outer periphery of the laminated portion (the laminate portion of the copper foil with a release layer and the resin) of the above-described laminate when viewed from the plane It is good. When viewed from a plane, it is preferable that the resin or prepreg is larger than the laminated portion of the copper foil or the laminate or the laminate with a release layer, and the resin or prepreg is laminated on both surfaces of the copper foil or laminate with a release layer, It is preferable to form a laminate having a structure in which a copper foil or a laminate with a release layer is covered with a resin or a prepreg. With such a constitution, when the copper foil with a release layer or the laminate is viewed from the plane, the laminated portion of the copper foil or the laminate with the release layer is covered with the resin or the prepreg and the other member is covered with the resin in the lateral direction It is possible to prevent the laminate resin and the copper foil with a release layer from being peeled off during handling. In addition, it is possible to prevent the penetration of the chemical liquid into the laminated partial interface in the chemical liquid treatment step as described above by covering the copper foil with a release layer or the laminated part of the laminate with the resin or the prepreg so as not to expose the outer periphery, Corrosion and erosion of layered copper foil can be prevented. Further, when separating one foil-laden copper foil with a release layer from a pair of foil-laden foil-laminated foils of the laminate, it is preferable that the copper foil with a release layer covered with a resin or prepreg or a laminate portion of the laminate Part is strongly adhered firmly by a resin or a prepreg, it may be necessary to remove the laminated portion by cutting or the like.

The step of forming the resin layer and the circuit on the laminate at least once and the step of peeling the release layer-attached copper foil from the laminate after the resin layer and the circuit are formed at least once are performed, It is possible to manufacture a printed wiring board which does not have such a structure. A resin layer and a circuit may be provided on one or both surfaces of the laminate. The resin layer and the circuit may be provided in the order of the resin layer and the circuit, or may be provided in the order of the circuit and the resin layer.

The resin substrate, the resin layer, the resin, and the prepreg used in the above-described laminate may be the resin layer described in this specification, and the resin, the resin curing agent, the compound, the curing accelerator, the dielectric, A catalyst, a cross-linking agent, a polymer, a prepreg, a skeleton or the like.

The above-described copper foil or laminate with a release layer may be smaller than the resin or prepreg, the resin substrate or the resin layer when viewed from the top.

[ Example ]

Hereinafter, the present invention will be described in more detail with reference to examples of the present invention, but the present invention is not limited to these examples.

(Example: Copper foil with a release layer)

On the copper foil, the electroconductive copper foil JTC foil (12 占 퐉 thick) made of JX Metal Co., Ltd. was used and the electroconductive copper foil had a composition as shown in Tables 1 to 4 on the S-surface (glossy surface) side of the electrolytic copper foil and had a thickness of 0.02 占 퐉, And a barrier layer of 1 mu m were formed by sputtering or electrolytic plating. The electroplating conditions (plating liquid composition, temperature, current density) are shown below. With respect to the current density, when setting the barrier layers shown in Tables 3 and 4, the current density shown in Tables 3 and 4 was set.

· Barrier layer formation by sputtering

Each of the barrier layers was formed under the following conditions using a sputtering target having the same composition as the barrier layer shown in Table 1 as a sputtering target.

Apparatus: Sputtering apparatus of ULVAC CO., LTD.

Output: DC 50W

Argon pressure: 0.2 Pa

· Metal chrome single plating (Cr plating in the table)

Chromic anhydride: 250 g / L

Sulfuric acid: 1.3-2.5 g / L

Temperature: 45-55 ℃

Current density: 40 A / dm 2

· Nickel base plating (Ni plating in the table)

Nickel sulfate · 7H ₂ O: 250 g / L

Sodium citrate · 2H ₂ O: 8 g / L

pH: 2.5

Temperature: 50 ° C

Current density: 20 A / dm 2

Nickel-tungsten alloy plating (Ni-W plating in the table)

Nickel sulfate · 7H ₂ O: 100 g / L

Sodium tungstate: 50 g / L

Sodium citrate: 50 g / L

Temperature: 50 ° C

Current density: 4 A / dm 2

Nickel-cobalt alloy plating (Ni-Co plating in the table)

Cobalt sulfate · 7H ₂ O: 25-30 g / L

Nickel sulfate · 7H ₂ O: 45-50 g / L

pH: 2.15-2.35

Temperature: 50 ° C

Current density: 10 A / dm 2

Nickel-molybdenum alloy plating (1) (Ni-Mo (1) plating in the table)

Nickel sulfate · 7H ₂ O: 100 g / L

Sodium molybdate · 2H ₂ O: 100 g / L

Sodium citrate: 50 g / L

Temperature: 50 ° C

Current density: 1 A / dm 2

Nickel-molybdenum alloy plating (2) (Ni-Mo (2) plating in the table)

Nickel sulfate · 7H ₂ O: 100 g / L

Sodium molybdate · 2H ₂ O: 5 g / L

Sodium citrate: 50 g / L

Temperature: 50 ° C

Current density: 1 A / dm 2

Nickel-molybdenum alloy plating (3) (Ni-Mo (3) plating in the table)

Nickel sulfate · 7H ₂ O: 100 g / L

Sodium molybdate · 2H ₂ O: 15 g / L

Sodium citrate: 50 g / L

Temperature: 50 ° C

Current density: 1 A / dm 2

Nickel-molybdenum alloy plating (4) (Ni-Mo (4) plating in the table)

Nickel sulfate · 7H ₂ O: 100 g / L

Sodium molybdate · 2H ₂ O: 250 g / L

Sodium citrate: 50 g / L

Temperature: 50 ° C

Current density: 1 A / dm 2

Nickel-molybdenum-chromium alloy plating (Ni-Mo-Cr plating in the table)

Nickel sulfate · 7H ₂ O: 300 g / L

Anhydrous chromic acid: 100 g / L

Sodium molybdate · 2H ₂ O: 40 g / L

Sulfuric acid: 1 g / L

Temperature: 50 ° C

Current density: 20 A / dm 2

Thereafter, the release layer was formed on the barrier layer under the following conditions.

· Silane coupling treatment

Treatment liquid:

Silane compound: n-propyltrimethoxysilane

Silane concentration: 0.4 vol%

Treatment liquid before use: Agitation time: 12 hours

Alcohol concentration: 0 vol%

pH: 4 to 7

Processing time: 30 seconds (application by spray nozzle)

(Evaluation test)

<Core disassembly>

Then, a copper foil with a release layer was laminated on the resin substrate (core) from the release layer side, and then a circuit of line / space = 20 占 퐉 / 20 占 퐉 was formed on the copper foil with the release layer- The circuit was embedded with resin to produce a printed wiring board.

The composition of the etchant and the etching conditions for forming the circuit according to the subtractive method were set as follows.

Composition and etching condition of etchant

· Copper Chloride

(Furtherance)

Copper Chloride: 25 wt%

Hydrochloric acid: 4.6 wt%

REST: Water

(Condition)

Solution temperature: 50 ° C

Spray pressure: 0.15 MPa

· Chloride iron oxide

Ferric chloride: 37wt% (Bordeaux 40 ° B'e)

REST: Water

(Condition)

Solution temperature: 50 ° C

Spray pressure: 0.15 MPa

· Alkaline etchant

CuCl ₂ : 295 g / L

NH ₃ : 9.4 mol / L

REST: Water

(Condition)

Solution temperature: 50 ° C

Spray pressure: 0.15 MPa

A full cone type spray nozzle was used for the etching solution.

After that, it was examined whether core disassembly is possible. The core disassembly was carried out under the following conditions.

Core disassembly: 10 samples of the above-mentioned printed wiring board were produced. The resin substrate (core) used as the support was peeled off from the above-mentioned printed wiring board to evaluate whether or not the resin substrate (core) could be peeled off without destroying or deforming the printed wiring board.

&Quot; Disconnection of the core due to dissolution of the barrier layer &quot; means that the resin substrate, which is the core at least three times in 10 times, can not be peeled off from the printed wiring board.

&Quot; O: &quot; means that the number of times that the resin substrate was not peeled off from the printed wiring board was less than twice in 10 times.

Table 1 shows the composition of the barrier layer formed by the above sputtering and evaluation of core dismersion by each thickness. Table 2 shows the composition of the barrier layer formed by the electrolytic plating and the evaluation of core disintegration by each thickness. The plating rate at the time of electrolytic plating is shown in the "plating rate (nm / sec)" in Table 2.

[Table 1]

[Table 2]

&Lt; Solubility in copper etchant &gt;

The etching rate (탆 / s) when copper was etched by copper etchant was measured as follows. And the mass W1 (g) of the sample before etching (JTC foil) by the copper etchant is measured. And the mass W2 (g) of the sample after the etching for 30 (s) for a predetermined time is measured. Then, the etching rate was calculated by the following equation. The portion other than the portion to be etched of the sample was masked with an acid-resistant tape. And the sample was exposed by etching only the size portion of 5 cm square (5 cm in length × 5 cm in width).

(G / cm 3) of copper (Cu / Cu) was calculated by the following equation (1): Etching rate (탆 / s) when copper was etched by copper etchant = {W1 Etched area 25 (c㎡) 占 Etching time 30 (s)} 占 10 ⁴ (占 퐉 / cm)

The etching rate (占 퐉 / s) when the barrier layer was etched with copper etchant was measured as follows. Parts other than the portion to be etched of the sample were masked with an acid-resistant tape. The sample was exposed only for 5 cm x 5 cm on the side having the barrier layer of the sample, and etching was performed for 30 seconds using the above-described copper etchant. Then, the concentration of the element constituting the barrier layer in the copper etchant after etching was measured by ICP-MS (inductively coupled plasma mass spectrometer). The etching rate (占 퐉 / s) when the barrier layer was etched with copper etchant was calculated according to the following formula.

(M / s) = {total concentration (g / L) of elements constituting the barrier layer in the copper etchant solution x amount (L) of the copper etchant solution} / {barrier the density of the elements constituting the layer (g / c㎥) × sample etched area 25 (c㎡) × etching time of 30 ^{(s)} × 10 4 (} ㎛ / cm)

The total concentration (g / L) of the elements constituting the barrier layer in the copper etchant was the sum of the concentration of each element constituting the barrier layer. For example, when the element constituting the barrier layer is A, B and C, the concentration of element A in the copper etchant after etching is a (g / L), the concentration of element B is b (g / L) (G / L), the total concentration (g / L) of the elements constituting the barrier layer in the copper etchant is represented by a + b + c.

When the barrier layer is composed of a plurality of elements, the density of the elements constituting the barrier layer is calculated as follows. Even though the barrier layer is an alloy composed of a plurality of elements, the density of the elements constituting the barrier layer is calculated assuming that the density of each element is the same as that of a single element (when it is not an alloy).

For example, when the elements constituting the barrier layer are A, B and C and the concentrations of the elements A, B and C in the barrier layer are Ca (mass%), Cb (mass%) and Cc (mass% And the density of the elements A, B, and C is ρa (g / cm3), ρb (g / cm3), and ρc (g / cm3), respectively.

(G / cm3) of the elements constituting the barrier layer = 100 / {Ca /? A + Cb /? B + Cc /? C}

Then, using the value of the etching rate (占 퐉 / s) when the barrier layer measured by the above method was etched with copper etchant and the etching rate (占 퐉 / s) when copper was etched with copper etchant, The solubility of copper in the barrier layer to the etchant was calculated.

Solubility of the barrier layer in copper etchant (-) = etching rate (탆 / s) / etching rate (탆 / s) when copper is etched with copper etchant when the barrier layer is etched with copper etchant

The solubility (-) of the obtained barrier layer to the copper etchant is shown in Tables 1 to 4. Means that the solubility (-) of the barrier layer to the copper etchant is 0.01 or less. &Quot; x &quot; means that the solubility (-) of the barrier layer to the copper etchant is greater than 0.01.

&Lt; Evaluation of pinhole of barrier layer &gt;

The sample was pickled with a 10 wt% sulfuric acid aqueous solution and then immersed in a 0.2 mass% ammonium persulfate aqueous solution at a temperature of 30 캜 for 3 minutes. When the sample was observed from the side of the barrier layer, A discoloration spot including a circle having a diameter of 0.1 mm was determined to be a pin hole. The number of pin holes per unit area (number / dm 2) was measured. When the number of pin holes was less than 1 / dm 2, " The above-mentioned measurement was carried out on three samples (size of a sample: 10 cm square (10 cm in length × 10 cm in width)), and the average value of three samples was defined as the number of pinholes per unit area (pieces / dm 2). Table 3 shows the relationship between the current density of the plating liquid when forming the barrier layer and the number of "pinholes (number / d m2) / core disassembly" of each thickness of the barrier layer with respect to the barrier layer of each composition . The above-mentioned core disassembly is evaluated by &quot;? &Quot;, &quot; x (the barrier layer is dissolved and the core disassembly is impossible) &quot; The core disassembly in Table 3 is the result when the above-described alkali etchant is used as the copper etchant.

[Table 3]

<Evaluation of Thickness and Thickness Accuracy of Barrier Layer>

The thickness of the barrier layer was measured as follows with respect to the experimental examples described in Tables 1 to 3 above. The measurement results are shown in Tables 1 to 3. The current density of the plating liquid at the time of forming the barrier layer and the precision of the thickness of the barrier layer at each thickness of the barrier layer were evaluated for each barrier layer formed by Ni simple plating or Ni-Mo alloy plating, I conducted together.

The thickness of the barrier layer was measured as follows. A sample of 5 cm in size (5 cm in length × 5 cm in width) was dissolved in an aqueous nitric acid solution (nitric acid volume: water volume = 1: 2). Thereafter, in the nitric acid aqueous solution after dissolving the sample, the concentration of the element constituting the barrier layer was measured by ICP-MS (inductively coupled plasma mass spectrometer). The thickness of the barrier layer was calculated according to the following equation.

(G / L) of the barrier layer in the nitric acid aqueous solution / (amount of the nitric acid aqueous solution) / {the density of the elements constituting the barrier layer (g / cm &lt; ) X area of the sample 25 (c m2)} x104 (占 퐉 / cm)

The total concentration (g / L) of the elements constituting the barrier layer in the aqueous acetic acid solution was the sum of the concentrations of the elements constituting the barrier layer. For example, assuming that the elements constituting the barrier layer are A, B and C, the concentration of the element A in the aqueous nitric acid solution is a (g / L), the concentration of the element B is b (g / L) c (g / L), the total concentration (g / L) of the elements constituting the barrier layer in the nitric acid aqueous solution is represented by a + b + c.

When the barrier layer is composed of a plurality of elements, the density of the elements constituting the barrier layer is calculated by the same method as in the case of measuring the etching rate (占 퐉 / s) when the barrier layer is etched with copper etchant did.

When the sample is not dissolved in the above-mentioned nitric acid aqueous solution, the above-described measurement may be performed using a solution for dissolving the sample in place of the nitric acid aqueous solution.

The above-described measurement of the thickness of the barrier layer was performed at five points (N = 1 to N) in the width direction (TD, direction perpendicular to the traveling direction (MD) of the electrolytic copper foil in the electrolytic copper foil production apparatus) 5) was sampled and carried out. Then, an average value and a standard deviation (?) Of thickness measurement values of the barrier layer were obtained. The calculation formula of the thickness accuracy was as follows.

Thickness precision (%) = 3? 占 100 / average value

The evaluation results are shown in Table 4. The "core disassembly" in Table 4 indicates the evaluation by the above-mentioned <core disassembly>: "◯" and "× (the barrier layer is dissolved and the core disassembly is impossible)". The core disassembly in Table 4 is the result when the above-described alkali etchant is used as the copper etchant.

[Table 4]

Claims (28)

A release layer, a barrier layer, and a copper foil in this order. The method according to claim 1,
Wherein the barrier layer has a solubility in copper etchant of 0.1 or less. 3. The method of claim 2,
Wherein the copper etchant is any one of the following (3-1) to (3-4).
(3-1) Copper chloride etchant
(Furtherance)
Copper Chloride: 25 wt%
Hydrochloric acid: 4.6 wt%
REST: Water
(3-2) Iron chloride etchant
(Furtherance)
Ferric chloride: 37wt% (Bordeaux 40 ° B'e)
REST: Water
(3-3) Alkali etchant
(Furtherance)
CuCl ₂ : 295 g / L
NH ₃ : 9.4 mol / L
REST: Water
(3-4) Sulfuric acid-aqueous solution of hydrogen peroxide
(Furtherance)
35 wt% hydrogen peroxide: 80 mL / L
Concentrated sulfuric acid: 120 mL / L
REST: Water The method according to claim 1,
Wherein the barrier layer is at least one of Ni layer, Ti layer, Cr layer, V layer, Zr layer, Ta layer, Au layer, Pt layer, Os layer, Pd layer, Ru layer, Rh layer, Ir layer, W layer, ,
A layer containing an alloy containing at least one selected from the group consisting of Ni, Ti, V, Zr, Ta, Au, Pt, Os, Pd, Ru, Rh, Ir, W, Mo, or,
An oxide or a nitride containing at least one selected from the group consisting of Ni, Ti, V, Zr, Ta, Au, Pt, Os, Pd, Ru, Rh, Ir, W, Mo, Which is a layer containing a release layer. 3. The method of claim 2,
Wherein the barrier layer comprises at least one of Ni layer, Ti layer, Cr layer, V layer, Zr layer, Ta layer, Au layer, Pt layer, Os layer, Pd layer, Ru layer, Rh layer, Ir layer, W layer, or,
A layer containing an alloy containing at least one selected from the group consisting of Ni, Ti, V, Zr, Ta, Au, Pt, Os, Pd, Ru, Rh, Ir, W, Mo, or,
An oxide or a nitride containing at least one selected from the group consisting of Ni, Ti, V, Zr, Ta, Au, Pt, Os, Pd, Ru, Rh, Ir, W, Mo, Which is a layer containing a release layer. The method of claim 3,
Wherein the barrier layer comprises at least one of Ni layer, Ti layer, Cr layer, V layer, Zr layer, Ta layer, Au layer, Pt layer, Os layer, Pd layer, Ru layer, Rh layer, Ir layer, W layer, or,
A layer containing an alloy containing at least one selected from the group consisting of Ni, Ti, V, Zr, Ta, Au, Pt, Os, Pd, Ru, Rh, Ir, W, Mo, or,
An oxide or a nitride containing at least one selected from the group consisting of Ni, Ti, V, Zr, Ta, Au, Pt, Os, Pd, Ru, Rh, Ir, W, Mo, Which is a layer containing a release layer. The method according to claim 1,
Wherein the barrier layer is made of a Mo-based alloy, a Cr-based alloy, a Ni-based alloy, a Ni-Mo-Cr alloy containing 20% by mass or more of Cr, a Ni-W alloy or a Ni-Mo alloy. 3. The method of claim 2,
Wherein the barrier layer is made of a Mo-based alloy, a Cr-based alloy, a Ni-based alloy, a Ni-Mo-Cr alloy containing 20% by mass or more of Cr, a Ni-W alloy or a Ni-Mo alloy. The method of claim 3,
Wherein the barrier layer is made of a Mo-based alloy, a Cr-based alloy, a Ni-based alloy, a Ni-Mo-Cr alloy containing 20% by mass or more of Cr, a Ni-W alloy or a Ni-Mo alloy. 10. The method according to any one of claims 1 to 9,
And the number of pinholes of the barrier layer is not more than 100 pieces / dm2. 10. The method according to any one of claims 1 to 9,
And the thickness precision of the barrier layer is 20% or less. 10. The method according to any one of claims 1 to 9,
Wherein the barrier layer has a thickness of 0.03 占 퐉 or more. 10. The method according to any one of claims 1 to 9,
A copper foil with a release layer satisfying any one or two, or three or four of the following (13-1) to (13-4).
(13-1) any one or two of the following (13-1-1) and (13-1-2) are satisfied,
(13-1-1) The barrier layer satisfies any one of the following solubility in copper etchant:
0.09 or less,
0.08 or less,
0.07 or less,
0.06 or less,
· 0.05 or less,
0.04 or less,
0.03 or less,
0.02 or less,
· 0.01 or less,
(13-1-2) The barrier layer satisfies any one of the following solubility in copper etchant:
· Greater than zero
· More than 0.000000,
· 0.000001 or more,
· More than 0.00000,
· More than 0.00001,
· 0.0000 or more,
0.0001 or more,
0.0002 or more,
0.0003 or more,
0.0004 or more,
0.0005 or more,
0.0006 or more,
0.0007 or more,
0.0008 or more,
0.0009 or more,
· More than 0.0010,
(13-2) Any one or two of the following (13-2-1) and (13-2-2) are satisfied,
(13-2-1) the number of pinholes of the barrier layer satisfies any one of the following:
· 20 pieces / dm2 or less,
· 5 / dm2 or less,
- 4 / dm2 or less,
3 pieces / dm2 or less,
2 pieces / dm2 or less,
揃 1 / dm 2 or less,
- 0.7 pieces / dm2 or less,
· 0.4 pieces / dm2 or less,
0.2 pieces / dm2 or less,
(13-2-2) The number of pinholes of the barrier layer satisfies any one of the following:
0 &gt; / d &lt; 2 &gt;
· 0.01 pieces / dm2 or more,
· 0.1 pieces / dm2 or more,
(13-3) Any one or two of the following (13-3-1) and (13-3-2) are satisfied,
(13-3-1) The thickness precision of the barrier layer satisfies any one of the following:
· Less than 15%
· 13% or less,
· Less than 10%
· Less than 7%
· Less than 5%
· 4% or less,
· Less than 3%
· Less than 2%
(13-3-2) The thickness precision of the barrier layer satisfies any one of the following:
· 0% or more,
· 0.0001% or more,
· 0.001% or more,
· 0.01% or more,
· 0.10% or more,
· 0.15% or more,
· 0.20% or more,
· 0.25% or more,
(13-4) Any one or two of the following (13-4-1) and (13-4-2) are satisfied,
(13-4-1) the thickness of the barrier layer satisfies any one of the following:
0.04 占 퐉 or more,
? 0.05 占 퐉 or more,
0.06 占 퐉 or more,
0.07 占 퐉 or more,
0.08 占 퐉 or more,
0.09 占 퐉 or more,
? 0.10 占 퐉 or more,
? 0.11 占 퐉 or more,
? 0.12 占 퐉 or more,
? 0.13 占 퐉 or more,
? 0.14 占 퐉 or more,
? 0.15 占 퐉 or more,
? 0.20 占 퐉 or more,
? 0.25 占 퐉 or more,
? 0.30 占 퐉 or more,
- 0.35 탆 or more,
- 0.40 탆 or more,
? 0.45 占 퐉 or more,
? 0.50 占 퐉 or more,
? 0.55 占 퐉 or more,
? 0.60 占 퐉 or more,
- 0.65 탆 or more,
? 0.70 占 퐉 or more,
(13-4-2) The thickness of the barrier layer satisfies any one of the following:
? 100 占 퐉 or less,
? 80 占 퐉 or less,
占 60 占 퐉 or less,
· 40 μm or less,
· 20 μm or less,
· 10 μm or less,
? 5 占 퐉 or less,
· 3 μm or less,
· It is 2 μm or less. 10. The method according to any one of claims 1 to 9,
Wherein 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 the 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 the hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom.
, The hydrolysis product of the silane compound, and the hydrolysis product of the silane compound, either singly or in combination. 10. The method according to any one of claims 1 to 9,
Wherein the release layer has a compound having two or less mercapto groups in the molecule. 10. The method according to any one of claims 1 to 9,
Wherein 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 the hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom, and M is Al, Ti or Zr, n is 0, 1 or 2, m is an integer of 1 or more and equal to or less than ¹ , and at least one of R ¹ is an alkoxy group. , And 4 for Ti and Zr)
A hydrolysis product of the aluminate salt compound, a hydrolysis product of the titanate salt compound, a hydrolysis product of the zirconate compound, a hydrolysis product of the aluminate salt compound, A copper foil with a release layer, which comprises a condensate of a decomposition product, a condensate of a hydrolysis product of the titanate compound, or a condensate of a hydrolysis product of the zirconate compound, singly or in combination. 10. The method according to any one of claims 1 to 9,
Wherein the release layer has a resin coating film composed of one or a plurality of resins selected from silicone, an epoxy resin, a melamine resin and a fluorine resin. 10. The method according to any one of claims 1 to 9,
At least one selected from the group consisting of a heat resistant layer, an anticorrosive layer, a chromate treatment layer and a silane coupling treatment layer is provided on either or both of the barrier layer and the release layer or between the copper foil and the barrier layer, Or more, with a release layer. 10. The method according to any one of claims 1 to 9,
Wherein the copper foil has at least one layer selected from the group consisting of a roughening treatment layer, a heat resistant layer, a rust preventive layer, a chromate treatment layer and a silane coupling treatment layer on a surface of the copper foil opposite to the release layer. 20. The method of claim 19,
Wherein the roughening treatment layer is a layer made of any one or a combination of any one selected from the group consisting of Cu, Ni, P, W, As, Mo, Cr, Ti, Fe, V, , Copper foil with release layer. 20. The method of claim 19,
Wherein the resin layer is provided on at least one layer selected from the group consisting of the roughened treatment layer, the heat resistant layer, the rust preventive layer, the chromate treatment layer and the silane coupling treatment layer. A laminate having the copper foil with a release layer according to any one of claims 1 to 9. A laminate comprising the copper foil with a release layer according to any one of claims 1 to 9 and a resin, wherein a part or the whole of a section of the copper foil with a release layer is covered with the resin. A copper foil with a releasable layer according to any one of claims 1 to 9 and a resin, wherein one of the two releasing layer-attached copper foils, And the other side of the release layer side surface of the other copper foil with a release layer and the other side of the resin are laminated. A printed wiring board manufacturing method for producing a printed wiring board using the copper foil with a release layer according to any one of claims 1 to 9. A process for producing a copper foil with a release layer according to any one of claims 1 to 9, which comprises laminating an insulating substrate (1) on a surface of the release layer side,
A step of forming a circuit on the copper foil of the copper foil with a release layer laminated with the insulating substrate 1 according to the subtractive method,
A step of covering the circuit with the insulating substrate 2 to embed the circuit,
A step of peeling the insulating substrate 1 from the laminated body of the circuit embedded in the insulating substrate 2 and the barrier layer with the release layer to expose the barrier layer;
A step of exposing a circuit buried in the insulating substrate 2 by removing the exposed barrier layer
And a step of forming the printed circuit board. A process for producing a copper foil with a release layer according to any one of claims 1 to 9,
A step of forming a circuit in a copper foil portion of a copper foil with a release layer laminated on the insulating substrate and then burying the circuit with a resin and then providing two layers of a circuit and a resin layer on the resin at least once,
A step of peeling the release layer-adhering copper foil from the resin substrate after the two layers of the resin layer and the circuit are formed, and
Removing the release layer and the barrier layer from the peeled copper foil with a release layer adhered thereto
And a step of forming the printed circuit board. A method of manufacturing an electronic device using the printed wiring board manufactured by any one of the following methods (28-1) to (28-3).
(28-1) A method for producing a printed wiring board using the copper foil with a release layer according to any one of claims 1 to 9,
(28-2) A step of laminating the insulating substrate 1 on the side of the release layer side of the copper foil with a release layer according to any one of claims 1 to 9,
A step of forming a circuit on the copper foil of the copper foil with a release layer laminated with the insulating substrate 1 according to the subtractive method,
A step of covering the circuit with the insulating substrate 2 to embed the circuit,
A step of peeling the insulating substrate 1 from the laminated body of the circuit embedded in the insulating substrate 2 and the barrier layer with the release layer to expose the barrier layer;
And exposing the circuit buried in the insulating substrate 2 by removing the exposed barrier layer,
(28-3) A process for producing a copper foil with a release layer as set forth in any one of claims 1 to 9,
A step of forming a circuit on a copper foil portion of the copper foil with a release layer adhered to the insulating substrate and then embedding the circuit with a resin and then providing a circuit and a resin layer on the resin at least once,
A step of peeling the release layer-adhering copper foil from the resin substrate after the two layers of the resin layer and the circuit are formed, and
And removing the release layer and the barrier layer from the peeled copper foil with a release layer adhering thereto.

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