JP2018171902A - Copper foil with release layer, laminate, method for producing printed wiring board and method for producing electronic apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a copper foil with a release layer capable of preparing a fine circuit in a circuit buried substrate or the like by a simple step.SOLUTION: There is provided a copper foil with a release layer which comprises a release layer, a barrier layer and a copper foil in this order.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a copper foil with a release layer, a laminate, a method for producing a printed wiring board, and a method for producing an electronic device.

  Printed wiring boards have made great progress over the last half century and are now used in almost all electronic devices. In recent years, with the increasing needs for miniaturization and higher performance of electronic devices, higher density mounting of components and higher frequency of signals have progressed, and conductor patterns have become finer (fine pitch) and higher frequency than printed circuit boards. In particular, when an IC chip is mounted on a printed wiring board, a fine pitch of L (line) / S (space) = 20 μm / 20 μm or less is required.

  A printed wiring board is first manufactured as a copper clad laminate in which an insulating substrate mainly composed of a copper foil and a glass epoxy substrate, BT resin, polyimide film or the like is bonded. Bonding is performed by laminating an insulating substrate and a copper foil and applying heat and pressure (laminating method), or by applying a varnish that is a precursor of an insulating substrate material to a surface having a coating layer of copper foil, A heating / curing method (casting method) is used.

JP 2005-101137 A

  In recent years, various methods for producing printed wiring boards have been developed and used depending on the purpose. For example, circuit plating is formed on the surface of the copper foil, and a resin layer is laminated on the copper foil so as to cover the formed circuit plating (so that the circuit plating is buried). Circuit embedded boards such as printed wiring boards (ETS, Embedded Trace Substrate) by the so-called embedding method, in which holes are drilled, circuit plating is exposed, blind vias are formed, and circuits and wiring are conducted between multiple layers of the laminate. ) Has been produced.

  As an example of a method for manufacturing the circuit-embedded substrate, first, a circuit is formed on the surface of the copper foil, a resin is laminated so as to cover the circuit, and an embedded circuit is formed. Next, by removing the copper foil by etching, the circuit embedded in the resin is exposed, and a printed wiring board is manufactured using the embedded circuit.

  However, after laminating the resin so as to cover the circuit as described above and forming the embedded circuit, if the copper foil is removed by etching to expose the embedded circuit, the embedded circuit is eroded by the etching of the copper foil. There was a problem.

  Further, when the above-described circuit-embedded substrate or the like is produced, 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.

  As a result of intensive studies, the present inventors provide a barrier layer having a predetermined solubility with respect to the copper etchant between the copper foil and the release layer, thereby producing a fine circuit in a circuit-embedded substrate or the like in a simple process. I found that I can do it.

  The present invention completed on the basis of the above knowledge is, in one aspect, a release layer-attached copper foil including 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 a copper etchant of 0.1 or less.

In another embodiment of the copper foil with a release layer of the present invention, the copper etchant is any one of the following (3-1) to (3-4).
(3-1) Copper chloride etchant (Composition)
Cupric chloride: 25 wt%
Hydrochloric acid: 4.6 wt%
The rest: water (3-2) iron chloride etchant (composition)
Ferric chloride: 37wt% (Baume degree is 40 ° B'e)
The rest: water (3-3) alkali etchant (composition)
CuCl ₂ : 295 g / L
NH ₃ : 9.4 mol / L
The rest: water (3-4) sulfuric acid-hydrogen peroxide aqueous solution (composition)
35wt% hydrogen peroxide: 80mL / L
Concentrated sulfuric acid: 120 mL / L
The rest: water

  In another embodiment of the release layer copper foil of the present invention, the barrier layer is a 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, Mo layer or Ni, Ti, V, Zr, Ta, Au, Pt, Os, Pd, Ru, Rh, Ir, W, Mo, Si and Cr 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, Si, and It is a layer containing a carbide, oxide or nitride containing at least one selected from the group consisting of Cr.

  In still another embodiment of the copper foil with a release layer of the present invention, the barrier layer contains Mo alone, Cr alone, Ni alone, Ni—Mo—Cr alloy containing 20% by mass or more of Cr, Ni—W. It is made of an alloy or Ni-Mo alloy.

In yet another embodiment of the release layer-attached copper foil of the present invention, the number of pinholes in the barrier layer is 100 / dm ² or less.

  In another embodiment of the release layer-attached copper foil of the present invention, the thickness accuracy of the barrier layer is 20% or less.

  In yet another embodiment of the copper foil with a release layer of the present invention, the barrier layer has a thickness of 0.03 μm or more.

In another embodiment of the copper foil with a release layer of the present invention, the release layer has the following formula:
Wherein R ¹ is an alkoxy group or a halogen atom, R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen The hydrocarbon group substituted with an atom, and R ³ and R ⁴ are each independently a halogen atom, an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group Or the above hydrocarbon group in which one or more hydrogen atoms are replaced by halogen atoms.)
The silane compound, the hydrolysis product of the silane compound, and the condensate of the hydrolysis product of the silane compound are used alone or in combination.

  In still another embodiment of the copper foil with a release layer of the present invention, the release layer has a compound having two or less mercapto groups in the molecule.

In another embodiment of the copper foil with a release layer of the present invention, the release layer has the following formula:
Wherein R ¹ is an alkoxy group or a halogen atom, R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen The hydrocarbon group substituted with an atom, M is Al, Ti or Zr, n is 0, 1 or 2, m is an integer of 1 or more and a valence of M or less, and at least one of R ¹ Is an alkoxy group, where m + n is the valence of M, ie 3 for Al and 4 for Ti and Zr)
Of the aluminate compound, titanate compound, zirconate compound, hydrolysis product of the aluminate compound, hydrolysis product of the titanate compound, hydrolysis product of the zirconate compound, hydrolysis product of the aluminate compound It has a condensate, a condensate of the hydrolysis product of the titanate compound, or a condensate of the hydrolysis product of the zirconate compound, alone or in combination.

  In yet another embodiment of the copper foil with a release layer of the present invention, the release layer is made of silicone, and any one or more resins selected from epoxy resins, melamine resins, and fluororesins. It has a resin coating composed of

  In yet another embodiment, the release layer-attached copper foil of the present invention is either between the copper foil and the barrier layer, or between the barrier layer and the release layer, or both. And one or more layers selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a silane coupling-treated layer.

  In yet another embodiment, the copper foil with a release layer according to the present invention has a roughened layer, a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a surface opposite to the release layer of the copper foil. It has 1 or more types of layers selected from the group which consists of a silane coupling process layer.

  In another embodiment of the copper foil with a release layer of the present invention, the roughening layer is made of Cu, Ni, P, W, As, Mo, Cr, Ti, Fe, V, Co, and Zn. It is a layer made of any single element selected from the group or an alloy containing one or more of them.

  In yet another embodiment, the release layer-attached copper foil of the present invention is one type selected from the group consisting of the roughening treatment layer, the heat-resistant layer, the rust prevention layer, the chromate treatment layer, and the silane coupling treatment layer. A resin layer is provided on the above layers.

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

  According to still another aspect of the present invention, there is provided a laminate including the release layer-attached copper foil of the present invention and a resin, wherein a part or all of the end surface of the release layer-attached copper foil is covered with the resin. It is a laminated body.

  In yet another aspect of the present invention, the copper foil with a release layer according to the present invention includes two release layer copper foils and a resin. The release layer side surface and one surface of the resin are laminated, and the release layer side surface of the other release layer-attached copper foil and the other surface of the resin are laminated.

  In yet another aspect, the present invention is a printed wiring board manufacturing method for manufacturing a printed wiring board using the release layer-attached copper foil of the present invention.

  In another aspect of the present invention, the step of laminating the insulating substrate 1 on the surface of the release layer side of the copper foil with a release layer of the present invention, the copper foil with a release layer laminated with the insulating substrate 1 Forming a circuit on the copper foil by a subtractive method, embedding the circuit by covering the circuit with an insulating substrate 2, and insulating the circuit from a laminated body of the circuit embedded in the insulating substrate 2 and the barrier layer. A printed wiring board comprising: a step of peeling the substrate 1 with the release layer to expose the barrier layer; and a step of exposing the circuit embedded in the insulating substrate 2 by removing the exposed barrier layer It is a manufacturing method.

  In yet another aspect of the present invention, a step of laminating the release layer side surface of the copper foil with a release layer of the present invention and an insulating substrate, a copper foil of a copper foil with a release layer laminated with the insulating substrate After forming a circuit in a part and then embedding the circuit with a resin, a step of providing at least once a circuit and a resin layer on the resin, after forming the resin layer and the two layers of the circuit A method for producing a printed wiring board, comprising: a step of peeling the release layer copper foil from the resin substrate; and a step of removing the release layer and the barrier layer from the peeled release layer copper foil. It is.

  In still another aspect of the present invention, there is provided an electronic device manufacturing method for manufacturing an electronic device using the printed wiring board manufactured by the method of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the copper foil with a mold release layer which can produce the fine circuit in a circuit embedding board | substrate etc. with a simple process can be provided.

It is a schematic diagram which shows the formation method of the embedded circuit using the copper foil with a release layer which concerns on one Embodiment of this invention.

<Copper foil with release layer>
The copper foil with a release layer of the present invention includes a release layer, a barrier layer, and a copper foil in this order. With such a configuration, it is possible to form an embedded circuit after circuit formation is performed on the copper foil by a subtractive method. 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 with respect to the copper etchant is defined by the following equation. The etching rate (μm / s) when the barrier layer is etched with a copper etchant and the etching rate (μm / s) when copper is etched with a copper etchant are measured using a copper etchant having the same composition.
Solubility of barrier layer in copper etchant (-) = Etching rate when etching barrier layer with copper etchant (μm / s) / Etching rate when etching copper with copper etchant (μm / s)
That is, a smaller solubility value of the barrier layer with respect to the copper etchant means that the barrier layer is less soluble in the copper etchant.

Here, the etching rate can be determined by the following method.
The etching rate means a thickness eroded by a copper etchant (copper etching solution) 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 the predetermined time t (s) etching is measured. Then, the etching rate is calculated by the following equation.
Etching rate (μm / s) = {mass of sample before etching W1 (g) −mass of sample W2 (g)} / {density of elements constituting sample (g / μm ³ ) × etched area of sample (Μm ² ) × etching time t (s)}
When measuring the etching rate, for example, a sulfuric acid-hydrogen peroxide solution, a copper chloride etchant (cupric chloride aqueous solution), an iron chloride etchant (ferric chloride aqueous solution) or an alkali etchant as a copper etchant. (Alkaline etching solution) can be used. Examples of the specific composition of the etching solution and conditions are as follows.

・ Copper chloride etchant (composition)
Cupric chloride: 25 wt%
Hydrochloric acid: 4.6 wt%
The rest: water (conditions)
Liquid temperature: 50 ° C
Spray pressure: 0.15 MPa

・ Iron chloride etchant Ferric chloride: 37wt% (Baume degree is 40 ° B'e)
The rest: water (conditions)
Liquid temperature: 50 ° C
Spray pressure: 0.15 MPa

・ Alkali etchant CuCl ₂ : 295 g / L
NH ₃ : 9.4 mol / L
The rest: water (conditions)
Liquid temperature: 50 ° C
Spray pressure: 0.15 MPa

・ Sulfuric acid-hydrogen peroxide solution (composition)
35wt% hydrogen peroxide: 80mL / L
Concentrated sulfuric acid: 120 mL / L
The rest: water (conditions)
Liquid temperature: 50 ° C
Spray pressure: 0.15 MPa

  The copper foil is typically provided in the form of a rolled copper foil, an electrolytic copper foil, or a copper foil produced by a dry plating method such as sputtering. In general, the electrolytic copper foil is produced by electrolytically depositing copper on a titanium or stainless steel drum from a copper sulfate plating bath. Moreover, a rolled copper foil is manufactured by repeating plastic working and heat treatment with a rolling roll. Examples of copper foil materials 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), for example, Sn-containing copper, Ag-containing copper, Cr A copper alloy such as a copper alloy added with Zr or Mg, or a Corson copper alloy added with Ni, Si or the like can also be used. The upper limit of the thickness of the copper foil need not be particularly limited, but is typically, for example, 3000 μm or less, such as 2000 μm or less, such as 1000 μm or less, such as 500 μm or less, such as 300 μm or less, such as 200 μm or less, such as 150 μm or less, such as 100 μm. It is as follows. The lower limit of the thickness of the copper foil is not particularly limited, but typically, for example, 1 μm or more, such as 2 μm or more, such as 3 μm or more, such as 4 μm or more, such as 5 μm or more, such as 6 μm or more, such as 7 μm or more, such as 8 μm. For example, it is 9 μm or more, for example, 10 μm or more.

  The barrier layer preferably has a solubility in copper etchant of 0.1 or less. If the solubility of the barrier layer in the copper etchant is 0.1 or less, the barrier layer is less soluble or less etched than copper in the copper etchant (copper etching solution). As a barrier layer having a solubility in copper etchant of 0.1 or less, 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, Mo layer or any one or more of Ni, Ti, V, Zr, Ta, Au, Pt, Os, Pd, Ru, Rh, Ir, W, Mo, Si and Cr A layer containing an alloy containing Ni, Ti, V, Zr, Ta, Au, Pt, Os, Pd, Ru, Rh, Ir, W, Mo, Si, and a carbide or oxide containing any one or more of Cr Alternatively, a layer containing nitride is preferably used. As a barrier layer having a solubility in copper etchant of 0.1 or less, the barrier layer is composed of Mo alone, Cr alone, Ni alone, Ni—Mo—Cr alloy containing 20% by mass or more of Cr, Ni—Mo alloy, Alternatively, it is preferably made of a Ni—W alloy. Here, the barrier layer is that Mo alone means that the barrier layer is made of a Mo layer. Moreover, the barrier layer being Cr alone means that the barrier layer is made of a Cr layer. When the barrier layer is Ni alone, it means that the barrier layer is made of a Ni layer.

  From the viewpoint that the barrier layer is not easily eroded from the copper etchant, the solubility of the barrier layer in the copper etchant is preferably 0.09 or less, preferably 0.08 or less, and 0.07 or less. Preferably, it is 0.06 or less, preferably 0.05 or less, preferably 0.04 or less, preferably 0.03 or less, and 0.02 or less. It is preferable that it is 0.01 or less. If the barrier layer is not easily eroded from the copper etchant, the barrier layer may be less likely to be eroded by the copper etchant to open a hole. As a result, there is a possibility that the resin base material (core) and the resin that embeds the circuit come into contact with and joins together, and the core disassembly described later may be easily performed. The lower limit of the solubility of the barrier layer in the copper etchant is not particularly limited, but is 0, for example, greater than 0, for example, 0.000000 or more, for example, 0.000001 or more, for example, 0.00000 or more, for example, 0.00001 or more. For example, 0.0000 or more, such as 0.0001 or more, such as 0.0002 or more, such as 0.0003 or more, such as 0.0004 or more, such as 0.0005 or more, such as 0.0006 or more, such as 0.0007 or more, for example. It is 0.0008 or more, for example, 0.0009 or more, for example, 0.0010 or more.

The thickness of the barrier layer is preferably 0.01 μm or more because the resin substrate (core) may be easily peeled off from the printed wiring board. The thickness of the barrier layer is preferably 0.02 μm or more, preferably 0.03 μm or more, preferably 0.04 μm or more, preferably 0.05 μm or more, and 0.06 μm or more. Preferably, it is 0.07 μm or more, preferably 0.08 μm or more, preferably 0.09 μm or more, preferably 0.10 μm or more, and 0.11 μm or more. It is preferably 0.12 μm or more, preferably 0.13 μm or more, preferably 0.14 μm or more, preferably 0.15 μm or more, and 0.20 μm or more. Preferably, it is 0.25 μm or more, preferably 0.30 μm or more, preferably 0.35 μm or more, and 0.40 μm or more. Preferably, it is 0.45 μm or more, preferably 0.50 μm or more, preferably 0.55 μm or more, preferably 0.60 μm or more, 0.65 μm or more It is preferable that it is 0.70 μm or more.
The upper limit of the thickness of the barrier layer is not particularly limited, but is, for example, 100 μm or less, such as 80 μm or less, such as 60 μm or less, such as 40 μm or less, such as 20 μm or less, such as 10 μm or less, such as 5 μm or less, such as 3 μm or less, such as 2 μm or less. It is.

-When the barrier layer is Cr alone (plating solution)
Chromic anhydride: 100-300 g / L
Sulfuric acid: 0.5-10.0 g / L
Liquid temperature: 40-60 degreeC
Current density: 0.2 to 60 A / dm ²

・ When the barrier layer is made of Ni alone (plating solution)
Nickel sulfate 7H ₂ O: 100 to 300 g / L
Sodium citrate: 5 to 100 g / L
Liquid temperature: 30-60 degreeC
pH: 2.0-7.0
Current density: 0.2 to 40 A / dm ²

-When the barrier layer is a Ni-Mo-Cr alloy containing 20 mass% or more of Cr (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
Liquid temperature: 30-60 degreeC
pH: 2.0-7.0
Current density: 0.2 to 20 A / dm ²

・ When the barrier layer is Ni-Mo alloy (plating solution)
Nickel sulfate 7H ₂ O: 50-300 g / L
Sodium molybdate · 2H ₂ O: 30 to 150 g / L
Sodium citrate: 40 to 200 g / L
Liquid temperature: 30-60 degreeC
pH: 2.0-7.0
Current density: 0.2 to 20 A / dm ²

・ When the barrier layer is Ni-W alloy (plating solution)
Nickel sulfate 7H ₂ O: 50-300 g / L
Sodium tungstate: 30-150 g / L
Sodium citrate: 40 to 200 g / L
Liquid temperature: 30-60 degreeC
pH: 2.0-7.0
Current density: 0.2 to 20 A / dm ²

  The conventional copper foil with a release layer does not have a barrier layer that is resistant to dissolution with such a copper etchant, and there has been no example of using the copper foil with a release layer in the embedding method. This is considered to be due to the possibility that the release layer may be eroded by etching. On the other hand, since the copper foil with a release layer of the present invention includes a barrier layer that is resistant to dissolution with a copper etchant between the copper foil and the release layer, there is no possibility that the release layer is eroded by etching. . Therefore, in the circuit formation by the subtractive method in the embedding method, the release layer can exhibit its function. Under such circumstances, when forming a circuit on the copper foil by the subtractive method in forming the embedded circuit using the release layer copper foil, it is dissolved in the copper etchant on the side opposite to the etching side of the copper foil. Since the resistant barrier layer is provided, the circuit is less likely to be skirted. That is, a fine circuit on a circuit-embedded substrate or the like can be manufactured by a simple process.

The number of pinholes in the barrier layer is preferably 100 / dm ² or less. When the number of pinholes in the barrier layer is 100 / dm ² or less, liquid erosion from the pinholes can be satisfactorily suppressed during etching. In addition, the resin base material (core) and the resin for embedding the circuit come into contact with each other through the pinholes in the barrier layer and are bonded, so that the resin base material (core) is difficult to peel off from the copper foil with a release layer. Sometimes it can be difficult to happen. The number of pinholes in the barrier layer is more preferably 20 pieces / dm ² or less, still more preferably 5 pieces / dm ² or less, still more preferably 4 pieces / dm ² or less, 3 pieces / Dm ² or less is still more preferred, 2 / dm ² or less is even more preferred, 1 / dm ² or less is even more preferred, and 0.7 / dm ² or less. Is more preferably 0.4 / dm ² or less, still more preferably 0.2 / dm ² or less, and even more preferably 0 / dm ^2. . The lower limit of the number of pinholes in the barrier layer is not particularly limited, but is, for example, 0 / dm ² or more, for example, 0.01 / dm ² or more, for example, 0.1 / dm ² or more, for example, 0.4. / Dm ² or more, for example, 0.6 / dm ² or more, for example, 1 / dm ² or more.
Note that the number of pinholes can be reduced by setting the current density higher when the barrier layer is provided by dry plating such as sputtering or when the barrier layer is provided by wet plating.

The thickness accuracy of the barrier layer is preferably 20% or less. When the thickness accuracy of the barrier layer is 20% or less, a portion where the barrier layer is extremely thin may be reduced during etching. Thereby, it may be possible to reduce exposure of the resin base material (core) due to thinning due to pinholes in the barrier layer or etching of the barrier layer. As a result, the resin base material (core) and the resin for embedding the circuit come into contact with each other at the exposed portion of the resin base material (core), and the resin base material (core) has a release layer. In some cases, it can be difficult to cause the copper foil to peel off. The thickness accuracy of the barrier layer is more preferably 15% or less, more preferably 13% or less, still more preferably 10% or less, still more preferably 7% or less, and even more preferably 5%. Is more preferably 4% or less, still more preferably 3% or less, still more preferably 2% or less. The lower limit of the thickness accuracy of the barrier layer is not particularly limited, but is, for example, 0% or more, such as 0.0001% or more, such as 0.001% or more, such as 0.01% or more, such as 0.10% or more. It is 0.15% or more, for example, 0.20% or more, for example, 0.25% or more.
The thickness accuracy of the barrier layer can be reduced by providing the barrier layer by dry plating such as sputtering or by setting the current density higher when providing the barrier layer by wet plating.

Next, the release layer will be described. The release layer of the release layer-attached copper foil enables the resin substrate to be peeled when the resin substrate is bonded to the release layer side by pressure bonding or the like. At this time, the resin base material and the copper foil are separated by the release layer.
(1) Silane Compound The release layer is 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) alone or A plurality of combinations may be formed.

formula:

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

  The silane compound needs to have at least one alkoxy group. A hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group in the absence of an alkoxy group, or any one of these hydrocarbons in which one or more hydrogen atoms are substituted with a halogen atom When a substituent is comprised only by group, there exists a tendency for adhesiveness with a barrier layer to fall too much. The silane compound is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or any one of these hydrocarbon groups in which one or more hydrogen atoms are substituted with a halogen atom. It is necessary to have at least one. This is because in the absence of the hydrocarbon group, the adhesion with the barrier layer tends to increase. The alkoxy group according to the present invention includes an alkoxy group in which one or more hydrogen atoms are substituted with halogen atoms.

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

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

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

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

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

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

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

(2) 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. At least one selected from these can be used.

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

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

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

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

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

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

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

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

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

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

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

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

(3) Metal alkoxide The release layer is composed 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 metal alkoxide and May be configured singly or in combination.

In the formula, R ¹ is an alkoxy group or a halogen atom, and R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms. Any one of these substituted hydrocarbon groups, M is any one of Al, Ti, and Zr, n is 0 or 1 or 2, m is an integer from 1 to M, and R ^At least one of ¹ is an alkoxy group. M + n is the valence of M, that is, 3 for Al and 4 for Ti and Zr.

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

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

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

In addition, examples of the aromatic hydrocarbon group suitable as R ² include a phenyl group, a phenyl group substituted with an alkyl group (eg, tolyl group, xylyl group), 1- or 2-naphthyl group, anthryl group, and the like. Examples thereof include 6 to 20, preferably 6 to 14, aryl groups, and these hydrocarbon groups may contain one or both of a hydroxyl group and an amino group.
In these hydrocarbon groups, one or more hydrogen atoms may be substituted with a halogen atom, and may be substituted with, for example, a fluorine atom, a chlorine atom, or a bromine atom.

  Examples of preferred aluminate compounds include trimethoxyaluminum, methyldimethoxyaluminum, ethyldimethoxyaluminum, n- or iso-propyldimethoxyaluminum, n-, iso- or tert-butyldimethoxyaluminum, n-, iso- or neo- Pentyl dimethoxy aluminum, hexyl dimethoxy aluminum, octyl dimethoxy aluminum, decyl dimethoxy aluminum, phenyl dimethoxy aluminum; alkyl-substituted phenyl dimethoxy aluminum (for example, p- (methyl) phenyl dimethoxy aluminum), dimethyl methoxy aluminum, triethoxy aluminum, methyl diethoxy aluminum Ethyldiethoxyaluminum, n- or iso-propyldiethoxy Luminium, n-, iso- or tert-butyldiethoxyaluminum, pentyldiethoxyaluminum, hexyldiethoxyaluminum, octyldiethoxyaluminum, decyldiethoxyaluminum, phenyldiethoxyaluminum, alkyl-substituted phenyldiethoxyaluminum (eg p -(Methyl) phenyldiethoxyaluminum), dimethylethoxyaluminum, triisopropoxyaluminum, methyldiisopropoxyaluminum, ethyldiisopropoxyaluminum, n- or iso-propyldiethoxyaluminum, n-, iso- or tert-butyl Diisopropoxy aluminum, pentyl diisopropoxy aluminum, hexyl diisopropoxy aluminum, octyl diiso Ropoxyaluminum, decyldiisopropoxyaluminum, phenyldiisopropoxyaluminum, alkyl-substituted phenyldiisopropoxyaluminum (eg, p- (methyl) phenyldiisopropoxyaluminum), dimethylisopropoxyaluminum, (3,3,3- Trifluoropropyl) dimethoxyaluminum, and tridecafluorooctyldiethoxyaluminum, methyldichloroaluminum, dimethylchloroaluminum, dimethylchloroaluminum, phenyldichloroaluminum, dimethylfluoroaluminum, dimethylbromoaluminum, diphenylbromoaluminum, and their hydrolysis products And condensates of these hydrolysis products. Among these, from the viewpoint of availability, trimethoxyaluminum, triethoxyaluminum, and triisopropoxyaluminum are preferable.

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

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

(4) Release layer comprising resin coating film Using a resin coating film composed of silicone and any one or more resins selected from epoxy resins, melamine resins and fluororesins, a barrier By laminating the layer and the resin base material as the support, the adhesion is moderately reduced, and the peel strength can be adjusted to a range as described later.

  As described later, the adjustment of the peel strength for realizing such adhesion is composed of silicone and any one or a plurality of resins selected from an epoxy resin, a melamine resin, and a fluororesin. This is done by using a resin coating. Such a resin coating film is subjected to a baking process under predetermined conditions as described later, and is hot-pressed and bonded between the barrier layer and the resin base material as a support, so that the adhesiveness is appropriately This is because the peel strength can be adjusted to the above-described range.

  Epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, brominated epoxy resin, amine type epoxy resin, flexible epoxy resin, hydrogenated bisphenol A type epoxy resin, phenoxy resin, Examples thereof include brominated phenoxy resin.

  Examples of the melamine-based resin include methyl etherified melamine resin, butylated urea melamine resin, butylated melamine resin, methylated melamine resin, and butyl alcohol-modified melamine resin. The melamine resin may be a mixed resin of the resin and 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 paint and the adhesive 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 silicone include methylphenylpolysiloxane, methylhydropolysiloxane, dimethylpolysiloxane, modified dimethylpolysiloxane, and mixtures thereof. Here, the modification is, for example, epoxy modification, alkyl modification, amino modification, carboxyl modification, alcohol modification, fluorine modification, alkylaralkyl polyether modification, epoxy polyether modification, polyether modification, alkyl higher alcohol ester modification, polyester modification. And acyloxyalkyl modification, halogenated alkylacyloxyalkyl modification, halogenated alkyl modification, aminoglycol modification, mercapto modification, hydroxyl group-containing polyester modification, and the like.

  In the resin coating film, when the film thickness is too small, the resin coating film is too thin and difficult to form, so that productivity is easily lowered. Moreover, even if a film thickness exceeds a fixed magnitude | size, the further improvement of the peelability of a resin coating film is not seen, but the manufacturing cost of a resin coating film tends to become high. From such a viewpoint, the resin coating film preferably has a thickness of 0.1 to 10 μm, and more preferably 0.5 to 5 μm. Moreover, the film thickness of a resin coating film is achieved by apply | coating a resin coating material by the predetermined application amount in the procedure mentioned later.

  In the resin coating film, silicone functions as a release agent for the resin coating film. Therefore, if the total amount of epoxy resin and melamine resin is too much compared to silicone, the peel strength imparted by the resin coating film between the barrier layer and the resin substrate as the support increases, The peelability of the film may be reduced, and it may not be easily peeled manually. On the other hand, if the total amount of the epoxy resin and the melamine resin is too small, the above-described peeling strength is reduced, and thus the copper foil may be peeled off during transport or processing. From this viewpoint, it is preferable that the total of the epoxy resin and the melamine resin is included in an amount of 10 to 1500 parts by mass, and more preferably 20 to 800 parts by mass with respect to 100 parts by mass of silicone. Is preferred.

  Further, like silicone, the fluororesin functions as a release agent and has the effect of improving the heat resistance of the resin coating film. If the amount of fluororesin is too much compared to silicone, the aforementioned peel strength will be reduced, which may cause peeling when the laminate is transported or processed, and it will be uneconomical because the temperature required for the baking process described later will increase. . 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 silicone.

The resin coating film is selected from SiO ₂ , MgO, Al ₂ O ₃ , BaSO ₄ and Mg (OH) ₂ in addition to silicone and epoxy resin and / or melamine resin and, if necessary, fluororesin 1 You may further contain the surface roughening particle | grains of a seed | species or more. When the resin coating film contains surface roughening particles, the surface of the resin coating film becomes uneven. Due to the unevenness, the surface of the copper foil provided on the barrier layer to which the resin coating film is applied becomes uneven and becomes a matte surface. Although content of the surface roughening particle | grains will not be specifically limited if a resin coating film is uneven | corrugated, 1-10 mass parts is preferable with respect to 100 mass parts of silicone.

  The particle diameter of the surface roughened particles is preferably 15 nm to 4 μm. Here, the particle diameter means an average particle diameter (average value of the maximum particle diameter and the minimum particle diameter) measured from a scanning electron microscope (SEM) photograph or the like. When the particle diameter of the surface roughened particles is within the above range, the unevenness of the surface of the resin coating film can be easily adjusted, and as a result, the unevenness of the surface of the barrier layer and the resin substrate as the support is adjusted. It becomes easy to do. Specifically, the unevenness on the surface of the barrier layer and the resin base material as the support is about 4.0 μm in terms of the maximum height roughness Ry defined by JIS.

Resin that can be 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 release layer copper foil, a known resin can be used. Moreover, the well-known resin used as a plate-shaped carrier can be used. Moreover, the below-mentioned resin layer can be used for the above-mentioned resin. The resin that can be laminated on the release layer side of the release layer copper foil is not particularly limited, but phenol resin, polyimide resin, epoxy resin, natural rubber, pine resin, and the like can be used. A thermosetting resin is preferable. A prepreg can also be used. The prepreg before being bonded to the copper foil is preferably in a B-stage state. The linear expansion coefficient of the prepreg (C stage) is 12 to 18 (× 10 ⁻⁶ / ° C.), 16.5 (× 10 ⁻⁶ / ° C.) of the copper foil as the constituent material of the substrate, or 17 of the SUS press plate .3 (× 10 ⁻⁶ / ° C.) is advantageous in that it is difficult to cause circuit misalignment due to a phenomenon (scaling change) in which the substrate size before and after pressing differs from that at the time of design. Furthermore, as a synergistic effect of these merits, it becomes possible to produce a multilayer ultra-thin coreless substrate. The prepreg used here may be the same as or different from the prepreg constituting the circuit board.

  The prepreg preferably has a high glass transition temperature Tg from the viewpoint of maintaining the peel strength after heating in an optimum range, and is, for example, a glass transition temperature Tg of 120 to 320 ° C, preferably 170 to 240 ° C. The glass transition temperature Tg is a value measured by DSC (differential scanning calorimetry).

  Moreover, it is desirable that the thermal expansion coefficient of the resin is within + 10% and −30% of the thermal expansion coefficient of the copper foil. As a result, it is possible to effectively prevent circuit misalignment due to the difference in thermal expansion between the copper foil and the resin, reduce the occurrence of defective products, and improve the yield.

  The thickness of the resin need not be particularly limited. The resin may be a resin for rigid printed wiring boards or a resin for flexible printed wiring boards. When the resin is thin, the heat distribution in the resin during hot pressing may be good. Moreover, since it becomes difficult to bend when resin is thick, it may become easy to flow through the manufacturing process of a printed wiring board. From the viewpoint of facilitating the manufacturing process of the printed wiring board, the thickness of the resin is preferably 5 μm or more, preferably 5 μm or more, preferably 10 μm or more, preferably 20 μm or more, It is preferably 30 μm or more, preferably 40 μm or more, preferably 50 μm or more, and more preferably 100 μm or more. Further, from the viewpoint of improving the heat distribution in the resin during hot pressing, the thickness of the resin is preferably 5000 μm or less, preferably 4000 μm or less, preferably 3000 μm or less, and 2000 μm or less. Preferably, it is 1500 μm or less, preferably 1300 μm or less, preferably 1000 μm or less, preferably 900 μm or less, and more preferably 400 μm or less.

<Laminate>
A laminated body (a copper clad laminated body etc.) can be produced using the copper foil with a release layer of the present invention.
As a laminated body using the copper foil with a release layer of this invention, the structure laminated | stacked in order of "release layer / barrier layer / copper foil / resin or prepreg" may be sufficient, for example.

<Roughening treatment and other surface treatment>
For example, the copper foil surface of the release layer-attached copper foil (for example, the copper foil surface opposite to the side having the release layer) has good adhesion to, for example, an insulating substrate, or adhesion to a resin. A roughening treatment layer may be provided by performing a roughening treatment for adjusting the above. The roughening treatment can be performed, for example, by forming roughened particles with copper or a copper alloy. The roughening process may be fine. The roughening treatment layer is made of any single element selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, titanium, iron, vanadium, cobalt, and zinc, or an alloy containing one or more of them. It may be a layer or the like. Moreover, after forming the roughened particles with copper or a copper alloy, a roughening treatment can be performed in which secondary particles or tertiary particles are further formed of nickel, cobalt, copper, zinc alone or an alloy. Subsequently, nickel, cobalt, copper, zinc, tin, molybdenum, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, tantalum and / or alloys and / or oxidation A heat-resistant layer or a rust-preventing layer may be formed with a material and / or a nitride and / or a silicide, and the surface may be further subjected to a treatment such as a chromate treatment or a silane coupling treatment. Or without roughening treatment, nickel, cobalt, copper, zinc, tin, molybdenum, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, tantalum, and / or Alternatively, a heat-resistant layer or a rust-preventing layer may be formed with an alloy and / or oxide and / or nitride and / or silicide, and the surface thereof may be further subjected to treatment such as chromate treatment or silane coupling treatment. That is, one or more layers selected from the group consisting of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer may be formed on the surface of the roughening treatment layer. You may form 1 or more types of layers selected from the group which consists of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer on the copper foil surface of foil. In addition, the above-mentioned heat-resistant layer, rust prevention layer, chromate treatment layer, and silane coupling treatment layer may each be formed of a plurality of layers (for example, 2 layers or more, 3 layers or more, etc.).

For example, copper as a roughening treatment - cobalt - nickel alloy plating, by electrolytic plating, deposition amount in the nickel-cobalt -100~1500μg / dm ² of copper -100~3000μg / dm ² of 15~40mg / dm ² Such a ternary alloy layer can be formed. If the amount of deposited Co is less than 100 μg / dm ² , the heat resistance may deteriorate and the etching property may deteriorate. When the amount of Co deposition exceeds 3000 μg / dm ² , it is not preferable when the influence of magnetism must be taken into account, etching spots may occur, and acid resistance and chemical resistance may deteriorate. If the Ni adhesion amount is less than 100 μg / dm ² , the heat resistance may deteriorate. On the other hand, when the Ni adhesion amount exceeds 1500 μg / dm ² , the etching residue may increase. A preferable Co adhesion amount is 1000 to 2500 μg / dm ² , and a preferable nickel adhesion amount is 500 to 1200 μg / dm ² . Here, the etching stain means that Co remains without being dissolved when etched with copper chloride, and the etching residue means that Ni remains without being dissolved when alkaline etching is performed with ammonium chloride. It means that.

An example of a general bath and plating conditions for forming such a ternary copper-cobalt-nickel alloy plating is as follows:
Plating bath composition: Cu 10-20 g / L, Co 1-10 g / L, Ni 1-10 g / L
pH: 1-4
Temperature: 30-50 ° C
Current density D _k : 20 to 30 A / dm ²
Plating time: 1-5 seconds

The chromate-treated layer refers to a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. Chromate treatment layer is any element such as Co, Fe, Ni, Mo, Zn, Ta, Cu, Al, P, W, Sn, As and Ti (metal, alloy, oxide, nitride, sulfide, etc.) May be included). Specific examples of the chromate treatment layer include a chromate treatment layer treated with chromic anhydride or a potassium dichromate aqueous solution, a chromate treatment layer treated with a treatment solution containing anhydrous chromic acid or potassium dichromate and zinc, and the like. .
The silane coupling treatment layer may be formed using a known silane coupling agent, such as epoxy silane, amino silane, methacryloxy silane, mercapto silane, vinyl silane, imidazole silane, triazine. You may form using silane coupling agents, such as silane. In addition, you may use 2 or more types of such silane coupling agents in mixture. Especially, it is preferable to form using an amino-type silane coupling agent or an epoxy-type silane coupling agent.
Further, on the surface of the copper foil of the release layer copper foil, or the surface of the roughening treatment layer, the heat-resistant layer, the rust prevention layer, the silane coupling treatment layer or the chromate treatment layer, International Publication No. WO2008 / 053878, JP2008 -11169, Patent No. 5024930, International Publication No. WO2006 / 028207, Patent No. 4828427, International Publication No. WO2006 / 134868, Patent No. 5046927, International Publication No. WO2007 / 105635, Patent No. 5180815, JP2013-19056A The surface treatment described in No. can be performed.

In addition, a roughening treatment layer may be provided on the surface of the copper foil of the release layer copper foil, and the heat treatment layer, the rust prevention layer, the chromate treatment layer, and the silane coupling treatment layer are formed on the roughening treatment layer. One or more layers selected from may be provided.
Moreover, a roughened layer may be provided on the surface of the copper foil of the release layer copper foil, and a heat-resistant layer and a rust-proof layer may be provided on the roughened layer, and the heat-resistant layer and the rust-proof layer are provided. A chromate treatment layer may be provided thereon, and a silane coupling treatment layer may be provided on the chromate treatment layer.
Also, a resin layer on the copper foil surface of the release layer copper foil, on the roughening treatment layer, on the heat resistant layer, on the rust prevention layer, on the chromate treatment layer, or on the silane coupling treatment layer May be provided. The resin layer may be an insulating resin layer.

  The resin layer may be an adhesive or may be a semi-cured (B stage) insulating resin layer for bonding. The semi-cured state (B stage state) is a state in which there is no sticky feeling even if the surface is touched with a finger, the insulating resin layer can be stacked and stored, and a curing reaction occurs when subjected to heat treatment. Including that.

  The resin layer may contain a thermosetting resin or may be a thermoplastic resin. The resin layer may include a thermoplastic resin. The type is not particularly limited. For example, epoxy resin, polyimide resin, polyfunctional cyanate ester compound, maleimide compound, polyvinyl acetal resin, urethane resin, polyethersulfone, polyethersulfone resin, aromatic polyamide Resin, aromatic polyamide resin polymer, rubber resin, polyamine, aromatic polyamine, polyamideimide resin, rubber modified epoxy resin, phenoxy resin, carboxyl group-modified acrylonitrile-butadiene resin, polyphenylene oxide, bismaleimide triazine resin, thermosetting polyphenylene Oxide resins, cyanate ester resins, carboxylic acid anhydrides, polycarboxylic acid anhydrides, linear polymers having crosslinkable functional groups, polyphenylene ether resins, 2,2-bis (4 -Cyanatophenyl) propane, phosphorus-containing phenol compound, manganese naphthenate, 2,2-bis (4-glycidylphenyl) propane, polyphenylene ether-cyanate resin, siloxane-modified polyamideimide resin, cyanoester resin, phosphazene resin, A resin containing at least one selected from the group consisting of rubber-modified polyamideimide resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, polymer epoxy, aromatic polyamide, fluororesin, bisphenol, block copolymer polyimide resin, and cyanoester resin It can be mentioned as a suitable thing.

The epoxy resin has two or more epoxy groups in the molecule and can be used without any problem as long as it can be used for electric / 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 is bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, brominated ( Brominated) epoxy resin, phenol novolac type epoxy resin, naphthalene type epoxy resin, brominated bisphenol A type epoxy resin, orthocresol novolac type epoxy resin, rubber modified bisphenol A type epoxy resin, glycidylamine type epoxy resin, triglycidyl isocyanurate Glycidylamine compounds such as N, N-diglycidylaniline, glycidyl ester compounds such as tetrahydrophthalic acid diglycidyl ester, phosphorus-containing epoxy resins, bif 1 type or 2 types or more selected from the group of nil type epoxy resin, biphenyl novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetraphenylethane type epoxy resin can be used, or said epoxy resin These hydrogenated products and halogenated products can be used.
As the phosphorus-containing epoxy resin, a known epoxy resin containing phosphorus 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. Is preferred.

  The resin layer may be made of any known dielectric such as a known resin, resin curing agent, compound, curing accelerator, dielectric (dielectric including an inorganic compound and / or organic compound, dielectric including a metal oxide). May be included), a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and the like. The resin layer may be, for example, International Publication No. WO2008 / 004399, International Publication No. WO2008 / 053878, International Publication No. WO2009 / 084533, JP-A-11-5828, JP-A-11-140281, Patent 3184485, International Publication. No. WO 97/02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179722, Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003-302068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003 No. -249739, Japanese Patent No. 4136509, Japanese Patent Application Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Application Laid-Open No. 2004-349654, Japanese Patent No. 4286060, Japanese Patent Application Laid-Open No. 2005-262506, Japanese Patent No. 4570070, No. 5-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004 / 005588, Japanese Patent Application Laid-Open No. 2006-257153, Japanese Patent Application Laid-Open No. 2007-326923, Japanese Patent Application Laid-Open No. 2008-11169, and Japanese Patent No. 5024930. No. WO 2006/028207, Japanese Patent No. 4828427, JP 2009-67029, International Publication No. WO 2006/134868, Japanese Patent No. 5046927, JP 2009-173017, International Publication No. WO 2007/105635, Patent No. 5180815, International Publication Number WO2008 / 114858, International Publication Number WO2009 / 008471, Japanese Patent Application Laid-Open No. 2011-14727, International Publication Number WO2009 / 001850, International Publication Number WO2009 / 145179, International Publication Number Nos. WO2011 / 068157, JP-A-2013-19056 (resins, resin curing agents, compounds, curing accelerators, dielectrics, reaction catalysts, crosslinking agents, polymers, prepregs, skeletal materials, etc.) and / or You may form using the formation method and formation apparatus of a resin layer.

  These resins are dissolved, for example, in a solvent such as MEK (methyl ethyl ketone) and toluene to form a resin solution, which is formed on the copper foil, the copper foil with a release layer, the heat-resistant layer, the rust-proof layer, or the On the chromate film layer or the silane coupling agent layer, for example, it is applied by a roll coater method or the like, and then heated and dried as necessary to remove the solvent to obtain a B stage state. For example, a hot air drying furnace may be used for drying, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C.

  The copper foil with a release layer provided with the resin layer (copper foil with a release layer with resin) is laminated on the base material and then thermocompression bonded to the resin layer to thermally cure the resin layer. After a predetermined wiring pattern is formed on the copper foil of the release layer-attached copper foil, the copper foil is peeled off from the resin layer.

  When this resin-attached release layer-attached copper foil is used, the number of prepreg materials used in the production of the multilayer printed wiring board can be reduced. In addition, a copper-clad laminate can be produced even if no prepreg material is used as the substrate. At this time, the surface smoothness can be further improved by undercoating the surface of the substrate with an insulating resin.

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

  The thickness of the resin layer is preferably 0.1 to 80 μm. If the thickness of the resin layer is greater than 0.1 μm, it may be possible to prevent the resin base material and the release layer-attached copper foil from unintentionally peeling in the printed wiring board manufacturing process.

  On the other hand, if the thickness of the resin layer is less than 80 μm, it may be easier to form the resin layer with the desired thickness in a single coating process, which makes it less expensive to take extra material costs and man-hours. May be advantageous. Furthermore, since the formed resin layer may have good flexibility, cracks or the like may not easily occur during handling. Moreover, an excessive resin flow may hardly occur at the time of thermocompression bonding with the inner layer material, and the copper foil with a release layer and the resin base material may be smoothly laminated.

Furthermore, a printed circuit board is completed by mounting electronic components on the printed wiring board. In the present invention, the “printed wiring board” includes a printed wiring board, a printed circuit board, and a printed board on which electronic parts are mounted as described above.
In addition, an electronic device may be manufactured using the printed wiring board, an electronic device may be manufactured using a printed circuit board on which the electronic components are mounted, and a print on which the electronic components are mounted. An electronic device may be manufactured using a substrate. Below, some examples of the manufacturing process of the printed wiring board using the copper foil with a release layer which concern on this invention are shown.

  In one embodiment of the method for manufacturing a printed wiring board according to the present invention, the embedded 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. Below, the example of the manufacturing method of a printed wiring board including the process of forming a buried circuit by a subtractive method using the copper foil with a release layer of this invention is demonstrated. In this specification, “circuit” is a concept including wiring.

FIG. 1 is a schematic diagram for explaining a method for forming an embedded circuit using a release layer-attached copper foil according to an embodiment of the present invention. In a method for forming an embedded circuit using a release layer-attached copper foil according to an embodiment of the present invention, first, a resin (insulating substrate) is provided on the release layer side of the release layer-attached copper foil of the present invention (FIG. 1a). 1) are stacked (FIG. 1b). Next, a dry film (DF) is laminated on the copper foil side of the release layer-attached copper foil on which the resin (insulating substrate 1) is laminated (FIG. 1c). Next, after patterning the dry film by exposure / development (FIG. 1d), the copper foil is etched with a copper etchant to form a circuit (FIG. 1e).
At this time, since the barrier layer under the copper foil has a solubility to the copper etchant of 0.1 or less, it is possible to form a circuit that does not skirt. As a result, a fine circuit can be formed.
Next, the dry film is peeled to expose the circuit (FIG. 1f). Next, the circuit is embedded by covering the exposed circuit with resin (insulating substrate 2) (FIG. 1g). Next, the resin (insulating substrate 1) is peeled off from the laminate of the circuit embedded in the resin (insulating substrate 2) and the barrier layer with a release layer to expose the barrier layer (FIG. 1h). Next, by removing the exposed barrier layer by etching, the circuit embedded in the resin (insulating substrate 2) is exposed (FIG. 1i). In this way, an embedded circuit can be obtained, and a printed wiring board using the embedded circuit can be manufactured. A known etching solution can be used as the etching solution for removing the barrier layer. The barrier layer may be removed by a known method such as mechanical polishing and / or shot blasting and / or polishing using an abrasive such as colloidal silica.
When the copper foil with a release layer of the present invention is laminated on one side of the above-described resin (insulating substrate 1) from the release layer side, a laminate having a copper foil, a barrier layer, a release layer and a resin in this order is obtained. can get.
In addition, after laminating the copper foil with a release layer of the present invention from both sides of the resin (insulating substrate 1) from the release layer side, the both surfaces of the resin (insulating substrate 1) as described above An embedded circuit may be provided. When the copper foil with a release layer of the present invention is laminated on both surfaces of the resin (insulating substrate 1) from the release layer side, the copper foil, the barrier layer, the release layer, the resin, the release layer, the barrier layer, and A laminate having copper foil in this order is obtained. When the copper foil with a release layer of the present invention is laminated on both surfaces of the resin (insulating substrate 1) from the release layer side, productivity of the printed wiring board is improved.

  Note that an embedded resin (resin) can be used for the insulating substrates 1 and 2. A known resin or prepreg can be used as the embedding resin. For example, a prepreg that is a glass cloth impregnated with BT (bismaleimide triazine) resin or BT resin, an ABF film or ABF manufactured by Ajinomoto Fine Techno Co., Ltd. can be used. In addition, as the insulating substrates 1 and 2 and the embedded resin (resin), a known resin or a resin layer and / or a resin and / or a prepreg described in this specification can be used.

  The method for producing a printed wiring board of the present invention includes a step of laminating the release layer side surface of the copper foil with a release layer of the present invention and a resin substrate, and copper of the copper foil with a release layer laminated with the resin substrate. A method for manufacturing a printed wiring board (coreless method), including a step of forming a circuit in a foil portion and then embedding the circuit with a resin, and a step of peeling the copper foil with a release layer from the resin substrate. Also good. Then, the manufacturing method (coreless construction method) of a printed wiring board including the process of removing a mold release layer and a barrier layer from the peeled copper foil with a mold release layer may be sufficient.

  The method for producing a printed wiring board of the present invention includes a step of laminating the release layer side surface of the copper foil with a release layer of the present invention and a resin substrate, and copper of the copper foil with a release layer laminated with the resin substrate. After forming the circuit in the foil part and then embedding the circuit with resin, providing the circuit and the resin layer on the resin at least once, and after forming the resin layer and the circuit, the resin A printed wiring board manufacturing method (coreless method) including a step of peeling the release layer-attached copper foil from the substrate may be used. Then, the manufacturing method (coreless construction method) of a printed wiring board including the process of removing a mold release layer and a barrier layer from the peeled copper foil with a mold release layer may be sufficient.

The method for producing a printed wiring board of the present invention includes a step of laminating the release layer side surface of the copper foil with a release layer of the present invention and a resin substrate, and copper of the copper foil with a release layer laminated with the resin substrate. A printed wiring board manufacturing method (coreless method) including a step of forming a circuit on a foil and then embedding the circuit with a resin, and a step of peeling the copper foil with a release layer from the resin substrate. May be. Then, the manufacturing method (coreless construction method) of a printed wiring board including the process of removing a mold release layer, a barrier layer, and copper foil from the peeled copper foil with a mold release layer may be sufficient.
In the present specification, “the surface of the laminated body” and “the surface of the laminated body” have a concept including the surface (outermost surface) of the other layer when the laminated body has another layer on the surface.

  In addition, in the manufacturing method of the above-mentioned coreless substrate, a copper foil with a release layer or the above-described laminate (a laminate having copper foil / barrier layer / release layer / resin in this order, or copper foil / barrier layer / When manufacturing a printed wiring board by the build-up method by covering part or all of the end face of the release layer / resin / release layer / barrier layer / copper foil in this order) with a resin, The copper foil with a release layer can be prevented from permeating the chemical solution between the copper foil with one release layer and the copper foil with another release layer constituting the release layer or laminate. And resin separation and corrosion of the release layer copper foil can be prevented, and the yield can be improved. As used herein, “resin that covers part or all of the end face of the release layer copper foil” or “resin that covers part or all of the end face of the laminate” may be a resin that can be used for the resin layer or a known one Resin can be used. Further, in the above-described coreless substrate manufacturing method, the copper foil with release layer or the laminated portion of the laminate (lamination of the copper foil with release layer and the resin) when viewed in plan in the copper foil or laminate with the release layer At least a part of the outer periphery of (part) may be covered with resin or prepreg. Moreover, when the copper foil with a release layer is viewed in plan, the entire outer periphery of the laminated portion (laminated portion of the release layer copper foil and the resin) or the entire laminated portion is resin or prepreg. It may be covered. Also, when viewed in plan, the resin or prepreg is preferably larger than the laminated layer of the release layer copper foil or laminate or laminate, and the resin or prepreg is disposed on both sides of the release layer copper foil or laminate. It is preferable that the laminated copper foil or the laminated body has a structure in which the release layer is laminated (wrapped) with a resin or a prepreg. With such a configuration, when the copper foil with release layer or laminate is viewed in plan, the laminated portion of the copper foil with release layer or laminate is covered with resin or prepreg, and other members are It will be possible to prevent from hitting from the side direction of the part, that is, the direction from the side with respect to the lamination direction, and as a result, the peeling of the resin of the laminate and the copper foil with the release layer during handling may be reduced. it can. Also, by preventing the outer periphery of the laminated part of the release layer copper foil or laminated body from being exposed with a resin or prepreg, the chemical solution can be prevented from entering the interface of the laminated part in the chemical treatment process as described above. Thus, corrosion and erosion of the release layer copper foil can be prevented. When separating one copper foil with a release layer from a pair of copper foils with a release layer of the laminate, the copper foil with a release layer covered with a resin or a prepreg or a laminated portion of the laminate (release) When the layered copper foil and the resin layer are firmly adhered to each other by resin or prepreg, the layered part may need to be removed by cutting or the like.

In addition, the step of providing the resin layer and the circuit at least once in the laminate, and the step of peeling the copper foil with a release layer from the laminate after forming the resin layer and the circuit at least once. By implementing it, a printed wiring board having no core can be produced. Note that 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, resin layer, resin, and prepreg used in the laminate described above may be the resin layer described in this specification, and the resin, resin curing agent, compound, and curing used in the resin layer described in this specification. An accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and the like may be included.
In addition, when the copper foil or laminated body with a above-mentioned mold release layer is planarly viewed, it may be smaller than resin, a prepreg, a resin substrate, or a resin layer.

  The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples.

(Example: Copper foil with release layer)
The copper foil used was an electrolytic copper foil JTC foil (thickness 12 μm) manufactured by JX Metals Co., Ltd., and had the composition described in Tables 1 to 4 on the S surface (glossy surface) side of the electrolytic copper foil. 02 μm, 0.1 μm, 0.5 μm and 1 μm barrier layers were formed by sputtering or electrolytic plating. The electroplating conditions (plating solution composition, temperature, current density) are shown below. Regarding the current density, when the barrier layers described in Tables 3 and 4 were provided, the current densities described in Tables 3 and 4 were set.

-Formation of barrier layer by sputtering A sputtering target having the same composition as the barrier layer described in Table 1 was used as a sputtering target, and each barrier layer was formed under the following conditions.
Equipment: Sputtering equipment manufactured by ULVAC, Inc. Output: DC50W
Argon pressure: 0.2 Pa

・ Metal chromium simple plating (Cr plating in the table)
Chromic anhydride: 250 g / L
Sulfuric acid: 1.3-2.5 g / L
Temperature: 45-55 ° C
Current density: 40 A / dm ²

・ Simple nickel 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
Chromic anhydride: 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, a 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 stirring time before use: 12 hours Alcohol concentration: 0 vol%
pH: 4-7
Processing time: 30 seconds (application by spray nozzle)

(Evaluation test)
<Core dismantling>
Next, after laminating the copper foil with a release layer on the resin substrate (core) from the release layer side, a circuit of line / space = 20 μm / 20 μm is formed on the copper foil of the copper foil with the release layer by a subtractive method. Then, the printed circuit board was fabricated by embedding the circuit with resin.
Note that the composition of the etchant and the etching conditions when forming the circuit by the subtractive method were as follows.

Etchant composition and etching conditions ・ Copper chloride etchant (Composition)
Cupric chloride: 25 wt%
Hydrochloric acid: 4.6 wt%
The rest: water (conditions)
Liquid temperature: 50 ° C
Spray pressure: 0.15 MPa
・ Iron chloride etchant Ferric chloride: 37wt% (Baume degree is 40 ° B'e)
The rest: water (conditions)
Liquid temperature: 50 ° C
Spray pressure: 0.15 MPa
・ Alkali etchant CuCl ₂ : 295 g / L
NH ₃ : 9.4 mol / L
The rest: water (conditions)
Liquid temperature: 50 ° C
Spray pressure: 0.15 MPa

A full cone type spray nozzle was used for the etching solution.
After that, we examined whether the core could be dismantled. The core dismantling was performed under the following conditions.
Core dismantling: Ten samples of the printed wiring board described above were prepared. And the resin substrate (core) which was used as the support was peeled from the above-mentioned printed wiring board, and it was evaluated whether or not the resin substrate (core) could be peeled without breaking or deforming the printed wiring board.
“The barrier layer dissolves and the core cannot be disassembled”: means that the resin substrate that is the core 3 times or more out of 10 times could not be peeled from the printed wiring board.
“◯”: The number of times that the resin substrate could not be peeled from the printed wiring board was 2 times or less out of 10 times.

  Table 1 shows the composition of the barrier layer formed by the sputtering and the evaluation of the core disassembly by each thickness. Table 2 shows the composition of the barrier layer formed by the above electrolytic plating and the evaluation of core disassembly by each thickness. In addition, the plating rate at the time of electrolytic plating is described in the “Plating rate (nm / second)” column of Table 2.

<Solubility in copper etchant>
The etching rate (μm / s) when copper was etched with a copper etchant was measured as follows. The mass W1 (g) of the sample (JTC foil) before etching with the copper etchant is measured. The mass W2 (g) of the sample after the predetermined time 30 (s) etching is measured. And the etching rate was computed with the following formula | equation. Note that portions of the sample other than the portion to be etched were masked with an acid resistant tape. Etching was performed by exposing the sample only to a portion having a size of 5 cm square (5 cm long × 5 cm wide).
Etching rate when copper is etched with a copper etchant (μm / s) = {mass of sample W1 (g) before etching−mass of sample W2 (g)} / {copper density 8.94 (g / cm ³ ) × sample etched area 25 (cm ² ) × etching time 30 (s)} × 10 ⁴ (μm / cm)

Moreover, the etching rate (μm / s) when the barrier layer was etched with a copper etchant was measured as follows. Parts of the sample other than the part to be etched were masked with acid-resistant tape. Only the 5 cm × 5 cm portion on the side having the barrier layer of the sample was etched using the above-described copper etchant for 30 seconds while exposing the sample. And the density | concentration of the element which comprises the barrier layer in the copper etchant liquid after an etching was measured using ICP-MS (inductively coupled plasma mass spectrometer). And the etching rate (micrometer / s) at the time of etching a barrier layer with a copper etchant was computed by the following formula | equation.
Etching rate (μm / s) when the barrier layer is etched with a copper etchant = {total concentration (g / L) of elements constituting the barrier layer in the copper etchant solution × amount of copper etchant solution (L)} / { Density of the elements constituting the barrier layer (g / cm ³ ) × etched area of the sample 25 (cm ² ) × etching time 30 (s)} × 10 ⁴ (μm / cm)

  The total concentration (g / L) of the elements constituting the barrier layer in the copper etchant solution was the sum of the concentrations of the respective elements constituting the barrier layer. For example, the elements constituting the barrier layer are 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), and the element When the concentration of C is c (g / L), the total concentration (g / L) of the elements constituting the barrier layer in the copper etchant liquid is represented by a + b + c.

  When the barrier layer is composed of a plurality of elements, the density of the elements composing the barrier layer was calculated as follows. Even if the barrier layer was an alloy composed of a plurality of elements, the density of each element was calculated assuming that the density of each element was the same as that of a simple substance (in the case of not being an alloy).

For example, 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%), respectively. When the densities of elements A, B, and C are ρa (g / cm ³ ), ρb (g / cm ³ ), and ρc (g / cm ³ ), respectively, the following formulas were used.
Density of elements constituting the barrier layer (g / cm ³ ) = 100 / {Ca / ρa + Cb / ρb + Cc / ρc}

Then, using the value of the etching rate (μm / s) when the barrier layer measured by the above method is etched with a copper etchant and the etching rate (μm / s) when copper is etched with a copper etchant, The solubility of the barrier layer in the copper etchant was calculated according to the following formula.
Solubility of barrier layer in copper etchant (-) = Etching rate when etching barrier layer with copper etchant (μm / s) / Etching rate when etching copper with copper etchant (μm / s)

  The solubility (-) with respect to the copper etchant of the obtained barrier layer was described in Tables 1-4. “◯” means that the solubility (−) of the barrier layer in the copper etchant was 0.01 or less. “X” means that the solubility (−) of the barrier layer in the copper etchant was larger than 0.01.

<Evaluation of pinhole in barrier layer>
After pickling the sample with a 10 wt% sulfuric acid aqueous solution, the sample was immersed in a 0.2 mass% ammonium polysulfide aqueous solution at a temperature of 30 ° C for 3 minutes, and the sample discolored when observed from the barrier layer side. The discolored portion including a circle having a diameter of 0.1 mm was determined as a pinhole. Then, the number of pinholes per unit area (pieces / dm ² ) is measured. When the number is less than 1 piece / dm ² , “◯”, when 1-100 pieces / dm ² , “Δ”, 100 pieces / dm ^2. When super, it was evaluated as “×”. The above measurement was performed on three samples (sample size: 10 cm square (vertical 10 cm × width 10 cm)), and the average value of the three samples was calculated as the number of pinholes per unit area (pieces / dm ² ). It was. Table 3 shows the relationship of “number of pinholes (pieces / dm ² ) / core dismantling” in the current density of the plating solution and the thickness of each barrier layer for the barrier layer of each composition. Show. The core disassembly property indicates the evaluation by the above-mentioned <core disassembly>: “◯”, “× (barrier layer dissolves and core disassembly is not possible)”. In Table 3, the core dismantling property is a result when the above-described alkali etchant is used as the copper etchant.

<Evaluation of barrier layer thickness and thickness accuracy>
For the experimental examples described in Tables 1 to 3, the thickness of the barrier layer was measured as follows. The measurement results are shown in Tables 1 to 3. In addition, for each barrier layer formed by Ni simple plating or Ni-Mo alloy plating, evaluation of the thickness accuracy of the barrier layer in the current density of the plating solution at the time of forming the barrier layer and each thickness of the barrier layer Was carried out as follows.
The thickness of the barrier layer was measured as follows. A sample having a size of 5 cm square (5 cm long × 5 cm wide) was dissolved in an aqueous nitric acid solution (nitric acid volume: water volume = 1: 2). Then, the density | concentration of the element which comprises a barrier layer in the nitric acid aqueous solution after dissolving a sample was measured using ICP-MS (inductively coupled plasma mass spectrometer). And the thickness of the barrier layer was computed with the following formula | equation.
Barrier layer thickness (μm) = {total concentration of elements constituting barrier layer in nitric acid aqueous solution (g / L) × amount of nitric acid aqueous solution (L)} / {density of elements constituting barrier layer (g / cm ³ ) × sample area 25 (cm ² )} × 10 ⁴ (μm / cm)

The total concentration (g / L) of the elements constituting the barrier layer in the nitric acid aqueous solution was the sum of the concentrations of the respective elements constituting the barrier layer. For example, the elements constituting the barrier layer are A, B, and C, the concentration of element A in the nitric acid aqueous solution is a (g / L), the concentration of element B is b (g / L), and the concentration of element C is In the case of 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.
Further, when the barrier layer is composed of a plurality of elements, the density of the elements composing the barrier layer is the same as that for measuring the etching rate (μm / s) when the above-mentioned barrier layer is etched with a copper etchant. Calculated with
In addition, when the sample is not dissolved by the above-mentioned nitric acid aqueous solution, the above-described measurement may be performed using a solution for dissolving the sample instead of the nitric acid aqueous solution.

The measurement of the thickness of the barrier layer described above was performed at 5 points at equal intervals in the width direction of the release layer-attached copper foil (TD, the direction perpendicular to the traveling direction (MD) of the electrolytic copper foil in the electrolytic copper foil manufacturing apparatus) ( N = 1 to 5) were taken. And the average value and standard deviation ((sigma)) of the measured thickness value of a barrier layer were calculated | required. The formula for calculating the thickness accuracy was as follows.
Thickness accuracy (%) = 3σ × 100 / average value

  The evaluation results are shown in Table 4. “Core disassembly” in Table 4 indicates the evaluation by the above-described <core disassembly>: “◯”, “× (barrier layer dissolves and core disassembly cannot be performed)”. In Table 4, the core dismantling property is the result when the above-described alkali etchant is used as the copper etchant.

Claims (23)

  A copper foil with a release layer comprising a release layer, a barrier layer, and a copper foil in this order.   The copper foil with a release layer according to claim 1, wherein the barrier layer has a solubility in a copper etchant of 0.1 or less. The copper foil with a release layer according to claim 2, wherein the copper etchant is any one of the following (3-1) to (3-4).
(3-1) Copper chloride etchant (Composition)
Cupric chloride: 25 wt%
Hydrochloric acid: 4.6 wt%
The rest: water (3-2) iron chloride etchant (composition)
Ferric chloride: 37wt% (Baume degree is 40 ° B'e)
The rest: water (3-3) alkali etchant (composition)
CuCl ₂ : 295 g / L
NH ₃ : 9.4 mol / L
The rest: water (3-4) sulfuric acid-hydrogen peroxide aqueous solution (composition)
35wt% hydrogen peroxide: 80mL / L
Concentrated sulfuric acid: 120 mL / L
The rest: water The barrier layer
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, Mo 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, Si and Cr, or ,
Carbide, oxide, or any one or more selected from the group consisting of Ni, Ti, V, Zr, Ta, Au, Pt, Os, Pd, Ru, Rh, Ir, W, Mo, Si and Cr It is a layer containing nitride, Copper foil with a release layer as described in any one of Claims 1-3.   The said barrier layer is formed with Mo single-piece | unit, Cr single-piece | unit, Ni single-piece | unit, Ni-Mo-Cr alloy containing 20 mass% or more of Cr, Ni-W alloy, or Ni-Mo alloy. The copper foil with a release layer as described in any one of these. The copper foil with a release layer according to any one of claims 1 to 5, wherein the number of pinholes in the barrier layer is 100 / dm ² or less.   The thickness accuracy of the said barrier layer is 20% or less, Copper foil with a release layer as described in any one of Claims 1-6.   The thickness of the said barrier layer is 0.03 micrometer or more, The copper foil with a mold release layer as described in any one of Claims 1-7. The release layer has the following formula:
Wherein R ¹ is an alkoxy group or a halogen atom, R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen The hydrocarbon group substituted with an atom, and R ³ and R ⁴ are each independently a halogen atom, an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group Or the above hydrocarbon group in which one or more hydrogen atoms are replaced by halogen atoms.)
A release layer according to any one of claims 1 to 8, which has a silane compound, a hydrolysis product of the silane compound, and a condensate of the hydrolysis product of the silane compound alone or in combination. Copper foil.   The copper foil with a release layer as described in any one of Claims 1-9 in which the said release layer has a compound which has a 2 or less mercapto group in a molecule | numerator. The release layer has the following formula:
Wherein R ¹ is an alkoxy group or a halogen atom, R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen The hydrocarbon group substituted with an atom, M is Al, Ti or Zr, n is 0, 1 or 2, m is an integer of 1 or more and a valence of M or less, and at least one of R ¹ Is an alkoxy group, where m + n is the valence of M, ie 3 for Al and 4 for Ti and Zr)
Of the aluminate compound, titanate compound, zirconate compound, hydrolysis product of the aluminate compound, hydrolysis product of the titanate compound, hydrolysis product of the zirconate compound, hydrolysis product of the aluminate compound The separation according to any one of claims 1 to 10, which has a condensate, a condensate of a hydrolysis product of the titanate compound, or a condensate of a hydrolysis product of the zirconate compound, alone or in combination. Copper foil with mold layer.   The said release layer has a resin coating film comprised with silicone and any one or several resin selected from an epoxy-type resin, a melamine-type resin, and a fluororesin. The copper foil with a release layer as described in the paragraph.   From one or both of the copper foil and the barrier layer or between the barrier layer and the release layer, a heat resistant layer, a rust preventive layer, a chromate treatment layer and a silane coupling treatment layer. The copper foil with a release layer according to any one of claims 1 to 12, which has one or more layers selected from the group consisting of:   One or more layers selected from the group consisting of a roughening treatment layer, a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer are formed on the surface of the copper foil opposite to the release layer. The copper foil with a release layer as described in any one of Claims 1-13 which has.   The roughening layer is an alloy containing any one or more selected from the group consisting of Cu, Ni, P, W, As, Mo, Cr, Ti, Fe, V, Co, and Zn. The copper foil with a release layer according to claim 14, which is a layer comprising:   The resin layer is provided on one or more types of layers selected from the group consisting of the roughening treatment layer, the heat-resistant layer, the rust prevention layer, the chromate treatment layer, and the silane coupling treatment layer. Copper foil with a release layer.   The laminated body which has a copper foil with a mold release layer as described in any one of Claims 1-16.   It is a laminated body containing copper foil with a mold release layer as described in any one of Claims 1-16, and resin, Comprising: Part or all of the end surface of the copper foil with mold release layer is covered with the said resin. Laminated body.   It has two copper foils with a release layer as described in any one of Claims 1-16, and resin, The said copper foil with one release layer of the said two copper foils with a release layer A laminate in which a release layer side surface and one surface of the resin are laminated, and the release layer side surface of the other release layer copper foil and the other surface of the resin are laminated.   The manufacturing method of a printed wiring board which manufactures a printed wiring board using the copper foil with a release layer as described in any one of Claims 1-16. A step of laminating the insulating substrate 1 on the surface of the release layer side of the release layer-attached copper foil according to any one of claims 1 to 16.
Forming a circuit by a subtractive method on the copper foil of the release layer-attached copper foil on which the insulating substrate 1 is laminated,
Embedding the circuit by covering the circuit with an insulating substrate 2;
Peeling the insulating substrate 1 from the laminate of the circuit embedded in the insulating substrate 2 and the barrier layer with the release layer to expose the barrier layer; and
A method of manufacturing a printed wiring board, including a step of exposing a circuit embedded in the insulating substrate 2 by removing the exposed barrier layer. A step of laminating the release layer side surface of the copper foil with a release layer according to any one of claims 1 to 16 and an insulating substrate,
After forming a circuit in the copper foil portion of the release layer-attached copper foil laminated with the insulating substrate and then embedding the circuit with a resin, two layers of the circuit and the resin layer are formed on the resin at least once. Providing step,
After forming the resin layer and the two layers of the circuit, peeling the copper foil with a release layer from the resin substrate, and
The manufacturing method of a printed wiring board including the process of removing the said mold release layer and the said barrier layer from the said peeled copper foil with a mold release layer.   The manufacturing method of the electronic device which manufactures an electronic device using the printed wiring board manufactured by the method as described in any one of Claims 20-22.