TWI684522B - Manufacturing method of copper foil with release layer, laminate, printed wiring board, and manufacturing method of electronic equipment - Google Patents

Abstract

The present invention provides a copper foil with a release layer, which can make a buried circuit, and can well suppress corrosion of the buried circuit when the buried circuit is exposed by etching. The copper foil with a mold release layer of the present invention includes a mold release layer, a copper foil, and a barrier layer in this order.

Description

Method for manufacturing copper foil with release layer, laminate, printed wiring board, and method for manufacturing electronic equipment

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

Printed wiring boards have made great progress in the past half century, and are now used in almost all electronic machines. With the increasing demand for miniaturization and high performance of electronic devices in recent years, the high-density mounting of mounted components and the increase in the frequency of signals continue to progress, and the printed wiring boards are required to be finer (micro-pitch) or higher in conductor patterns Respond frequently.

The printed wiring board is first manufactured as a copper-clad laminate, which is formed by bonding copper foil to an insulating substrate mainly composed of a glass epoxy substrate, BT resin, polyimide film, or the like. For the lamination, the following method is used: a method in which an insulating substrate and a copper foil are overlapped and heated and pressed (lamination method); or a varnish that is a precursor of an insulating substrate material is applied to the surface of the copper foil with the coating layer and The method of heating and hardening (casting method).

In recent years, printed wiring boards manufactured by various manufacturing methods according to purposes have been developed and utilized. For example, a circuit embedding substrate (ETS, Embedded Trace Substrate) such as a printed wiring board manufactured by a so-called embedding method is known. The embedding method is to form a circuit plating layer on the surface of an extremely thin copper foil to cover the formed In the method of circuit plating (in which the circuit plating is buried), a resin layer is embedded on an extremely thin copper foil and a resin layer is laminated, and a printed wiring board or the like is formed using the embedded circuit plating layer (Patent Document 1).

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2005-101137

As an example of the method for manufacturing the embedded circuit board, first, an electric circuit is formed on the surface of an extremely thin copper foil, and a resin is laminated so as to cover the electric circuit to form an embedded circuit. Next, after the carrier copper foil laminated on the ultra-thin copper foil is peeled off, the ultra-thin copper foil is removed by etching, thereby exposing the circuit embedded in the resin, thereby producing a printed wiring board using the embedded circuit.

However, if the embedded circuit is formed by covering the circuit as described above to form a buried circuit, then the ultrathin copper foil is removed by etching to expose the buried circuit, there may be buried by the etching of the ultrathin copper foil The problem of erosion into the circuit.

In addition, in order to easily perform various processing on the copper foil, the processing may be performed in a state where the copper foil is supported by being bonded to a support such as resin. In this case, by providing a release layer on the surface of the copper foil that is attached to the support such as resin, the support such as resin can be easily peeled off after processing. Regarding such a copper foil with a release layer, there has not been an example of the embedding method as described above.

The present inventors have conducted intensive research and found that by providing a barrier layer on the surface of the copper foil with a release layer opposite to the surface of the release layer side, the copper foil with a release layer can be used to make the embedding Circuit, and can well suppress corrosion of the buried circuit when the buried circuit is exposed by etching.

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

Regarding the copper foil with a release layer of the present invention, in one embodiment, the barrier layer is a C layer, a Ni layer, a Ti layer, a Cr layer, a V layer, a Zr layer, a Ta layer, an Au layer, a Pt layer, Os layer, Pd layer, Ru layer, Rh layer, Ir layer, W layer, or contains a material selected from Ni, Ti, V, Zr, Ta, Au, Pt, Os, Pd, Ru, Rh, Ir, W, Si A layer of any one or more alloys in the group consisting of Cr and Cr, or containing a layer containing Ni, Ti, V, Zr, Ta, Au, Pt, Os, Pd, Ru, Rh, Ir, W, Si, and Cr Any one or more layers of carbide, oxide, or nitride in the group.

With respect to the copper foil with a mold release layer of the present invention, in another embodiment, the barrier layer is composed of at least one selected from the group consisting of Ni, Ti, Cr, titanium oxide, chromium oxide, and carbon .

With respect to the copper foil with a mold release layer of the present invention, in yet another embodiment, the barrier layer has one or more layers selected from the group consisting of a Ni layer, a Ti layer, and a Cr layer.

With respect to the copper foil with a mold release layer of the present invention, in yet another embodiment, the barrier layer is any one or more layers selected from the group consisting of a Ni layer, a Ti layer, and a Cr layer.

The barrier layer is any layer selected from the group consisting of a Ni layer, a Ti layer, and a Cr layer.

With respect to the copper foil with a mold release layer of the present invention, in yet another embodiment, the thickness of the barrier layer is 0.001 μm or more and 10 μm or less.

With respect to the copper foil with a release layer of the present invention, in yet another embodiment, the thickness of the copper foil is 0.1 μm or more and 100 μm or less.

With respect to the copper foil with a mold release layer of the present invention, in another embodiment, the mold release layer has a silane compound represented by the following formula, a hydrolysate of the silane compound, and the silane compound individually or in combination. The condensation product of the hydrolysate.

(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 the hydrocarbon group in which one or more hydrogen atoms are replaced by a halogen atom, R ³ and R ⁴ are each independently a halogen atom, or an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or a hydrocarbon group in which one or more hydrogen atoms are substituted with a halogen atom )

With respect to the copper foil with a mold release layer of the present invention, in another embodiment, the mold release layer has a compound having two or less thiol groups in the molecule.

With respect to the copper foil with a mold release layer of the present invention, in yet another embodiment, the mold release layer has an aluminate compound, a titanate compound, a zirconate compound represented by the following formula alone or in combination. The hydrolysis product of the aluminate compound, the hydrolysis product of the titanate compound, the hydrolysis product of the zirconate compound, the condensate of the hydrolysis product of the aluminate compound, the The condensate of the hydrolysate or the hydrolysate of the zirconate compound.

(R ¹ ) _m -M-(R ² ) _n

(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 the hydrocarbon group in which one or more hydrogen atoms are replaced by a halogen atom, M is Al, Ti, or Zr, n is 0, 1, or 2, m is an integer of 1 or more and the valence of M or less, and at least one of R ¹ is an alkoxy group. m+n is the valence of M, that is, 3 for Al, 4 for Ti and Zr)

With respect to the copper foil with a mold release layer of the present invention, in yet another embodiment, the mold release layer has a resin coating film made of silicone and selected from epoxy-based resins, melamine-based resins and The fluororesin is composed of any one or more resins.

In another embodiment, the copper foil with a mold release layer of the present invention has a roughening treatment layer, a heat-resistant layer, a rust prevention layer, and a chromate treatment layer selected between the copper foil and the barrier layer One or more layers in the group consisting of silane coupling treatment layers.

In yet another embodiment, the copper foil with a mold release layer of the present invention has a surface selected from a roughening treatment layer, a heat-resistant layer, and a rust prevention layer on the surface of the barrier layer opposite to the copper foil side. One or more layers in the group consisting of a chromate treatment layer and a silane coupling treatment layer.

Regarding the copper foil with a mold release layer of the present invention, in yet another embodiment, the roughening treatment layer is selected from the group consisting of Cu, Ni, P, W, As, Mo, Cr, Ti, Fe, V, Co A layer composed of any single element or an alloy containing any one or more of the elements in the group consisting of Zn and Zn.

In yet another embodiment, the copper foil with a mold release layer of the present invention has a coupling treatment selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a silane between the copper foil and the mold-release layer More than one layer in a group of layers.

In another embodiment, the copper foil with a mold release layer of the present invention includes a resin layer on the surface of the mold release layer side.

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

The present invention in still another aspect is a laminate including a copper foil with a mold release layer of the present invention and a resin, and a part or all of the end surface of the copper foil is covered with the resin.

The present invention in another form is a laminate having two copper foils with a mold release layer and a resin of the present invention, and one of the two copper foils with a mold release layer attached The surface area of the release layer side of the copper foil of the layer and one area of the resin are formed by layering the surface area of the release layer side of the copper foil with the release layer and another area of the resin.

In still another aspect, the present invention is a method of manufacturing a printed wiring board, which uses the copper foil with a release layer of the present invention to manufacture a printed wiring board.

The present invention in another embodiment is a method for manufacturing a printed wiring board, which includes the steps of: laminating a support or an insulating substrate 1 on the release layer side of the copper foil with a release layer of the present invention; A step of providing a patterned anti-plating layer on the barrier layer side of the copper foil on which the support or the insulating substrate 1 is attached with a release layer; when the patterned anti-plating layer is provided After the copper plating layer is provided on the barrier layer of the layer, the anti-plating layer is removed to form a copper-plated circuit; the copper-plated circuit is covered with an insulating substrate 2 to thereby form the copper-plated circuit Step of embedding; after embedding the copper-plated circuit, remove the support or the insulating substrate 1 on the side surface of the release layer, thereby removing the copper foil with the release layer The step of exposing the side surface of the mold layer; the step of removing the copper foil from the exposed side surface of the release layer by etching to expose the surface of the barrier layer; and removing the exposed barrier layer by etching, by This step exposes the circuit buried in the insulating substrate 2.

The present invention in another embodiment is a method of manufacturing a printed wiring board, which uses the laminate of the present invention to manufacture a printed wiring board.

In still another aspect, the present invention is a method of manufacturing an electronic device, which uses a printed wiring board manufactured by the method of the present invention to manufacture an electronic device.

According to the copper foil with a mold release layer of the present invention, a buried circuit can be produced, and corrosion of the buried circuit when the buried circuit is exposed by etching can be suppressed well.

1, 2‧‧‧ Insulated substrate

10, 11‧‧‧ barrier layer

20, 21, 60 ‧‧‧ copper foil

30, 31‧‧‧ Release layer

40‧‧‧Anti-plating layer

50‧‧‧copper plating

51, 61‧‧‧ Copper-plated circuit

1 is a schematic diagram showing a part of a method for forming a buried circuit using a copper foil with a mold release layer according to an embodiment of the present invention.

2 is a schematic diagram showing a part of a method for forming a buried circuit using a copper foil with a release layer according to an embodiment of the present invention.

3 is a schematic diagram showing a part of a method for forming a buried circuit using a copper foil with a release layer according to an embodiment of the present invention.

4 is a schematic diagram showing a part of a method for forming a buried circuit using a copper foil with a mold release layer according to an embodiment of the present invention.

5 is a schematic view of a laminate in which copper foils with release layers are provided on both surfaces of an insulating substrate according to another embodiment of the present invention.

<Copper foil with release layer>

Sequentially equipped with release layer, copper foil and barrier layer. The copper foil is typically provided in the form of a rolled copper foil, an electrolytic copper foil, or a copper foil manufactured by a dry plating method such as sputtering. In general, electrolytic copper foil is produced by electrolysis of copper from a copper sulfate plating bath onto a drum of titanium or stainless steel, and rolled copper foil is produced by repeating plastic processing and heat treatment using a calender roll. As the material of the copper foil, in addition to high-purity copper such as refined copper (JIS H3100 alloy number C1100) or oxygen-free copper (JIS H3100 alloy number C1020 or JIS H3510 alloy number C1011), for example, copper added with Sn, added Copper alloys such as copper with Ag, copper alloys with addition of Cr, Zr, or Mg, and Carson-based copper alloys with addition of Ni, Si, etc.

The thickness of the copper foil is not particularly limited, and is, for example, 0.1 μm or more and 100 μm or less, 1 μm or more and 1000 μm or less, or 1 μm or more and 500 μm or less, or 1 μm or more and 300 μ m or less, or 3 μm or more and 100 μm or less, or 5 μm or more and 70 μm or less, or 6 μm or more and 35 μm or less, or 9 μm or more and 18 μm or less.

The barrier layer has resistance to dissolution of copper etchant, that is, it has the following properties: for copper etchant (copper etchant), it is less soluble than copper or is etched at a slower rate than copper. The etching speed refers to the thickness eroded by the etching liquid per unit time. For example, the etching speed can be calculated as follows.

The mass W1(g) of the sample before etching was measured. Measure the mass W2(g) of the etched sample at a specific time t(s). Furthermore, the etching rate is calculated by the following formula.

Etched rate (μ m / s) = {quality W1 sample before etching (g) - mass of the specimen W2 (g)} / {a barrier layer having a density (g / μ m ³⁾ × samples were etched area ( μ m ² )×etching time t (s))

In addition, when measuring the etching speed, for example, a sulfuric acid-hydrogen peroxide aqueous solution can be used as a copper etching solution.

As the barrier layer having resistance to dissolution of the copper etchant, it is preferable to use a C 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, or any one containing Ni, Ti, V, Zr, Ta, Au, Pt, Os, Pd, Ru, Rh, Ir, W, Si, and Cr Alloy layer, or contains carbide, oxide, or nitride containing any one or more of Ni, Ti, V, Zr, Ta, Au, Pt, Os, Pd, Ru, Rh, Ir, W, Si, and Cr The layers etc. As the barrier layer having resistance to dissolution with respect to the copper etchant, a barrier layer composed of any one kind or two or more kinds selected from the group consisting of Ni, Ti, Cr, titanium oxide, chromium oxide, and carbon is more preferable. In addition, since it is more effective as a barrier layer, the barrier layer preferably has one or more layers selected from the group consisting of a Ni layer, a Ti layer, and a Cr layer. In addition, since it is more effective as a barrier layer, the barrier layer is preferably one or more layers selected from the group consisting of a Ni layer, a Ti layer, and a Cr layer. In addition, since it is more effective as a barrier layer, the barrier layer is preferably a layer selected from the group consisting of a Ni layer, a Ti layer, and a Cr layer. In addition, the barrier layer is preferably a Ni layer. In addition, the barrier layer is preferably a Ti layer. In addition, the barrier layer is preferably a Cr layer.

In addition, the Ni layer or the alloy layer containing Ni is preferably formed as follows. The reason is that the surface of the Ni layer or the alloy layer containing Ni becomes smooth, and the very thin copper layer and/or the barrier layer side of the copper layer formed on the Ni layer or the alloy layer containing Ni are opposite to the barrier layer The surface on the side also becomes smooth, so the ultra-thin copper layer and/or the fine circuit formability of the copper layer are improved.

‧Formation of Ni layer or alloy layer containing Ni

The Ni layer or the alloy layer containing Ni can be formed by performing nickel plating or alloy plating containing nickel. At this time, it is important that the final processing is a dense and uniform plating without defects. Nickel plating or alloy plating containing nickel is performed under the following conditions.

‧Plating solution

Nickel: 20~200g/L

Other elements: 0.1~200g/L (only in the case of alloy plating containing nickel)

Boric acid: 5~60g/L

Liquid temperature: 40~65℃

pH value: 1.5~5.0, preferably 2.0~3.0. By lowering the pH and performing the plating treatment in stages, hydrogen gas is generated and the cathode surface becomes a reducing environment. Therefore, it is possible to suppress generation of moisture, causative factors such as oxides, hydroxides, and hydrates.

Current density: 0.5~20A/dm ² , preferably 2~8A/dm ² . The treatment at a low current density is preferred because rough plating is not likely to occur, resulting in fewer defects and dense plating.

‧Stirring (liquid circulation)

100~1000L/minute. A large amount of liquid circulation will make the generated hydrogen gas detach better, and fewer defects such as pinholes. In addition, it has the effect of reducing the thickness of the diffusion layer, and can suppress the generation of hydroxides and other factors causing moisture generation.

‧Conveying speed of plated objects

2~30m/min, preferably 5~10m/min. A slow transport speed will form a smooth and dense Ni layer or an alloy layer containing nickel.

‧Additives

As the additive, the following primary gloss agent and secondary gloss agent are preferably used. By this, the crystal becomes smooth and dense. Therefore, defects due to plating are reduced, and moisture absorption is reduced.

(Primary gloss agent)

1-5 Naphthalene-disulfonic acid sodium: 2~10g/L, 1-3-6 Naphthalene-trisulfonic acid sodium: 10~30g/L, p-toluene-amide: 0.5~4g/L, saccharin sodium: Any one of 0.5~5g/L.

(Secondary gloss agent)

Formalin: 0.5~5g/L, gelatin: 0.005~0.5g/L, thiourea: 0.05~1.0g/L, propargyl alcohol: 0.01~0.3g/L, 1-4 butyne diol: 0.05~0.5 g/L, ethylene cyanohydrin: Any one of 0.05~0.5g/L.

The lower limit of the thickness of the barrier layer is not particularly limited. For example, it may be 0.001 μm or more, preferably 0.01 μm or more, and more preferably 0.05 μm or more. In addition, the upper limit of the thickness of the barrier layer is not particularly limited, and for example, it may be 10 μm or less, preferably 5 μm or less, and more preferably 1 μm or less.

Regarding the copper foil with a mold release layer of the present invention, a circuit is formed on the surface of the copper foil, a resin is laminated to cover the circuit to form a buried circuit, and then the copper foil is removed by etching to expose the buried circuit At this time, since a barrier layer having a resistance to dissolution with a copper etchant is provided, there is no fear that the copper foil will be eroded to the buried circuit due to the etching of the copper foil.

In the release layer of the copper foil with a release layer of the present invention, a support such as a resin substrate when the support such as a resin substrate is bonded by pressure bonding or the like can be peeled from the release layer side. At this time, the support such as the resin base material and the copper foil are separated by the release layer.

(1) Silane compound

The release layer may be composed of a silane compound having the structure represented by the following formula, or a hydrolyzed product of the silane compound, or a condensate of the hydrolyzed product (hereinafter, abbreviated as silane compound) alone or in combination. form.

(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 the hydrocarbon group in which one or more hydrogen atoms are replaced by a halogen atom, R ³ and R ⁴ are each independently a halogen atom, or an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or a hydrocarbon group in which one or more hydrogen atoms are substituted with a halogen atom ).

The silane compound must have at least one alkoxy group. When there is no alkoxy group but only a hydrocarbon group selected from the group consisting of alkyl groups, cycloalkyl groups, and aryl groups, or any one of these hydrocarbon groups in which one or more hydrogen atoms are substituted with halogen atoms constitutes a substituent, The adhesion between the resin substrate and the copper foil tends to decrease excessively. In addition, the silane compound must have at least one hydrocarbon group selected from the group consisting of alkyl groups, cycloalkyl groups, and aryl groups, or any one of these hydrocarbon groups in which one or more hydrogen atoms are replaced with halogen atoms. The reason is that in the absence of the hydrocarbon group, the adhesion between the resin substrate and the copper foil tends to increase. In addition, the alkoxy group of the present invention also includes alkoxy groups in which one or more hydrogen atoms are replaced by halogen atoms.

The silane compound preferably has three alkoxy groups and one hydrocarbon group (including a hydrocarbon group in which more than one hydrogen atom is replaced by a halogen atom). In the above formula, both R ³ and R ⁴ are alkoxy groups.

The alkoxy group is not limited, and examples thereof include methoxy, ethoxy, n- or isopropoxy, n-, i-or tertiary butoxy, n-, i-or neopentyloxy, n-hexyloxy, and cyclohexyl. Linear, branched, or cyclic carbon numbers of 1 to 20, preferably 1 to 10, more preferably 1 to 5 carbon atoms, such as oxy, n-heptyloxy, and n-octyloxy Alkoxy.

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

The alkyl group is not limited, and examples thereof include straight groups such as methyl, ethyl, n- or isopropyl, n-, i-or tertiary butyl, n-, i-or neopentyl, n-hexyl, n-octyl, and n-decyl groups. The chain or branched chain has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.

The cycloalkyl group is not limited, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like having 3 to 10 carbon atoms, preferably 5 to 7 carbon atoms. base.

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

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

Examples of preferred silane compounds include methyltrimethoxysilane, ethyltrimethoxysilane, n- or isopropyltrimethoxysilane, n-, iso- or tertiary-butyltrimethoxysilane, n-, XOR neopentyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane; alkyl substituted phenyltrimethoxysilane (for example, (Methyl) phenyl trimethoxy silane), methyl triethoxy silane, ethyl triethoxy silane, n- or isopropyl triethoxy silane, n-, iso- or tertiary butyl triethoxy Silane, pentyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, phenyltriethoxysilane, alkyl-substituted phenyltriethoxysilane Silanes (for example, p-(methyl)phenyltriethoxysilane), (3,3,3-trifluoropropyl)trimethoxysilane, and tridecylfluorooctyltriethoxysilane, methyl Trichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, trimethylfluorosilane, dimethyldibromosilane, diphenyldibromosilane, hydrolysis products of these, and these Condensate of the hydrolysate and so on. Among these, from the viewpoint of availability, propyltrimethoxysilane, methyltriethoxysilane, hexyltrimethoxysilane, phenyltriethoxysilane, and decyltrimethoxy are preferable Silane.

(2) Compounds with 2 or less thiol groups in the molecule

The release layer can also be composed of a compound having two or less thiol groups in the molecule.

Examples of the compound having two or less mercapto groups in the molecule include thiol, dithiol, thiocarboxylic acid or its salt, dithiocarboxylic acid or its salt, sulfuric acid or its salt, and disulfonic acid or its As the salt, at least one selected from these can be used.

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

Dithiol has two mercapto groups in the molecule, for example, represented by R(SH) ₂ . R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may also contain a hydroxyl group or an amine group. In addition, the two mercapto groups may be bonded to the same carbon, or may be bonded to different carbon or nitrogen.

Thiocarboxylic acid is formed by replacing the hydroxyl group of an organic carboxylic acid with a mercapto group, for example, represented by R-CO-SH. R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may also contain a hydroxyl group or an amine group. In addition, thiocarboxylic acid can also be used in the form of a salt. In addition, compounds having two thiocarboxylic acid groups can also be used.

Dithiocarboxylic acid is formed by replacing two oxygen atoms in the carboxyl group of an organic carboxylic acid with sulfur atoms, for example, represented by R-(CS)-SH. R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may also contain a hydroxyl group or an amine group. In addition, dithiocarboxylic acid can also be used in the form of a salt. In addition, compounds having two dithiocarboxylic acid groups can also be used.

Sulfuric acid is formed by replacing the hydroxyl group of an organic sulfonic acid with a mercapto group, for example, represented by R(SO ₂ )-SH. R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may also contain a hydroxyl group or an amine group. In addition, sulfuric acid can also be used in the form of a salt.

Disulfonic acid is formed by replacing two hydroxyl groups of an organic disulfonic acid with sulfhydryl groups, for example, represented by R-((SO ₂ )-SH) ₂ . R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may also contain a hydroxyl group or an amine group. In addition, the two sulfonic acid groups may be bonded to the same carbon or different carbons. In addition, disulfonic acid can also be used in the form of a salt.

Here, examples of the aliphatic hydrocarbon group suitable as R include alkyl groups and cycloalkyl groups, and these hydrocarbon groups may include any one or two of hydroxyl groups and amine groups.

In addition, the alkyl group is not limited, and examples thereof include methyl, ethyl, n- or isopropyl, n-, iso- or tertiary butyl, n-, iso-or neopentyl, n-hexyl, n-octyl, and n-decyl groups. The straight-chain or branched-chain carbons have 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.

In addition, the cycloalkyl group is not limited, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, and the like having 3 to 10 carbon atoms, preferably 5 to 7 carbon atoms. Cycloalkyl.

In addition, suitable aromatic hydrocarbon groups as R include phenyl, phenyl substituted with an alkyl group (e.g., tolyl, xylyl), 1- or 2-naphthyl, anthracenyl, etc., having 6 to 20 carbon atoms Preferably, it is an aryl group of 6 to 14, and these hydrocarbon groups may also contain any one or two of a hydroxyl group and an amine group.

In addition, examples of the heterocyclic group suitable as R include imidazole, triazole, tetrazole, benzimidazole, benzotriazole, thiazole, and benzothiazole, and may include any one or both of a hydroxyl group and an amine group. .

Preferred examples of compounds having two or less mercapto groups in the molecule include 3-mercapto-1,2 propanediol, 2-mercaptoethanol, 1,2-ethanedithiol, and 6-mercapto-1-hexyl. Alcohol, 1-octane mercaptan, 1-dodecane mercaptan, 10-hydroxy-1-dodecane mercaptan, 10-carboxy-1-dodecane mercaptan, 10-amino-1-dodecane Alkyl mercaptan, sodium 1-dodecyl mercaptan sulfonate, thiophenol, thiobenzoic acid, 4-amino-thiophenol, p-toluene mercaptan, 2,4-dimethylbenzene mercaptan, 3 -Mercapto-1,2,4 triazole, 2-mercapto-benzothiazole. Among these, from the viewpoint of water solubility and waste disposal, 3-mercapto-1,2 propylene glycol is preferred.

(3) Metal alkoxide

In the release layer, an aluminate compound, a titanate compound, a zirconate compound having the structure represented by the following formula, or a hydrolysis product of these compounds, or a condensation product of the hydrolysis product (hereinafter, abbreviated) As a metal alkoxide) alone or in combination.

(R ¹ ) _m -M-(R ² ) _n

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 the hydrocarbon group in which one or more hydrogen atoms are replaced by a halogen atom, M Is Al, Ti, or Zr, n is 0, 1, or 2, m is an integer of 1 or more and the valence of M or less, and at least one of R ¹ is an alkoxy group. m+n is the valence of M, that is, 3 for Al, 4 for Ti and Zr.

The metal alkoxide must have at least one alkoxy group. When there is no alkoxy group but only a hydrocarbon group selected from the group consisting of alkyl groups, cycloalkyl groups, and aryl groups, or any one of these hydrocarbon groups in which one or more hydrogen atoms are substituted with halogen atoms constitutes a substituent, The adhesion between the resin substrate and the copper foil tends to decrease excessively. In addition, the metal alkoxide must have 0 to 2 hydrocarbon groups selected from the group consisting of alkyl groups, cycloalkyl groups, and aryl groups, or any one of these hydrocarbon groups in which one or more hydrogen atoms are replaced with halogen atoms. The reason is that when there are three or more hydrocarbon groups, the adhesion between the resin substrate and the copper foil tends to decrease excessively. In addition, the alkoxy group of the present invention also includes alkoxy groups in which one or more hydrogen atoms are replaced by halogen atoms. In terms of adjusting the peel strength of the resin substrate and the copper foil to the above range, the metal alkoxide preferably has two or more alkoxy groups and one or two of the hydrocarbon groups (including one or more hydrocarbon groups) Hydrocarbon group in which the hydrogen atom is replaced by a halogen atom).

In addition, the alkyl group is not limited, and examples thereof include methyl, ethyl, n- or isopropyl, n-, iso- or tertiary butyl, n-, iso-or neopentyl, n-hexyl, n-octyl, and n-decyl groups. The straight-chain or branched-chain carbons have 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.

In addition, the cycloalkyl group is not limited, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, and the like having 3 to 10 carbon atoms, preferably 5 to 7 carbon atoms. Cycloalkyl.

In addition, examples of the aromatic hydrocarbon group suitable as R ² include a phenyl group, a phenyl group substituted with an alkyl group (for example: tolyl group, xylyl group), 1- or 2-naphthyl group, and anthracenyl group. 20. Aryl groups of preferably 6 to 14, these hydrocarbon groups may also contain any one or two of hydroxyl and amine groups.

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

Examples of preferred aluminate compounds include trimethoxyaluminum, methyldimethoxyaluminum, ethyldimethoxyaluminum, n- or isopropyldimethoxyaluminum, n-, iso-or tri-aluminum Grade butyldimethoxyaluminum, n-, iso-or neopentyldimethoxyaluminum, hexyldimethoxyaluminum, octyldimethoxyaluminum, decyldimethoxyaluminum, phenyldimethoxyaluminum Aluminum; alkyl-substituted phenyldimethoxyaluminum (for example, p-(methyl)phenyldimethoxyaluminum), dimethylaluminum methoxide, triethoxyaluminum, methyldiethoxy Aluminum, ethyl diethoxy aluminum, n- or isopropyl diethoxy aluminum, n-, iso- or tertiary butyl diethoxy aluminum, pentyl diethoxy aluminum, hexyl diethoxy aluminum, Octyl diethoxy aluminum, decyl diethoxy aluminum, phenyl diethoxy aluminum, alkyl substituted phenyl diethoxy aluminum (for example, p-(methyl) phenyl diethoxy aluminum) , Aluminum dimethylethoxylate, aluminum triisopropoxide, aluminum aluminum diisopropoxide, aluminum aluminum diisopropoxide, aluminum n- or isopropyl diethoxylate, aluminum n-, aluminum iso-propoxide Grade butyl diisopropoxide aluminum, amyl diisopropoxide aluminum, hexyl diisopropoxide aluminum, octyl diisopropoxide aluminum, decyl diisopropoxide aluminum, phenyl diisopropoxide Aluminum alkoxide, alkyl substituted phenyl diisopropoxide aluminum (for example, p-(methyl)phenyl diisopropoxide aluminum), dimethyl isopropoxide aluminum, (3,3,3-tris (Fluoropropyl) aluminum dimethoxy, and aluminum tridecyl octyl diethoxide, aluminum aluminum dichloride, aluminum aluminum dimethyl chloride, aluminum aluminum dimethyl chloride, aluminum aluminum phenyl chloride, dimethyl fluoride Aluminum, dimethylaluminum bromide, diphenylaluminum bromide, hydrolysis products of these, and condensates of these hydrolysis products, and the like. Among these, from the viewpoint of availability, trimethoxyaluminum, triethoxyaluminum, and triisopropoxyaluminum are preferred.

Examples of preferred titanate compounds include tetramethoxytitanium, methyltrimethoxytitanium, ethyltrimethoxytitanium, n- or isopropyltrimethoxytitanium, n-, iso- or tertiary butyl Trimethoxytitanium, n-, iso-or neopentyltrimethoxytitanium, hexyltrimethoxytitanium, octyltrimethoxytitanium, decyltrimethoxytitanium, phenyltrimethoxytitanium; alkyl substituted phenyl Trimethoxytitanium (for example, p-(methyl)phenyltrimethoxytitanium), dimethyldimethoxytitanium, tetraethoxytitanium, methyltriethoxytitanium, ethyltriethoxytitanium , N- or isopropyltriethoxytitanium, n-, iso-or tertiary butyltriethoxytitanium, pentyltriethoxytitanium, hexyltriethoxytitanium, octyltriethoxytitanium, decyl Triethoxytitanium, phenyltriethoxytitanium, alkyl-substituted phenyltriethoxytitanium (for example, p-(methyl)phenyltriethoxytitanium), dimethyl diethoxytitanium , Tetraisopropoxy titanium, methyl triisopropoxy titanium, ethyl triisopropoxy titanium, n- or isopropyl triethoxy titanium, n-, iso-or tertiary butyl triisopropoxy Titanium, pentyltriisopropoxy titanium, hexyl triisopropoxy titanium, octyl triisopropoxy titanium, decyl triisopropoxy titanium, phenyl triisopropoxy titanium, alkyl substituted benzene Triisopropoxy titanium (for example, p-(methyl)phenyl triisopropoxy titanium), dimethyl diisopropoxy titanium, (3,3,3-trifluoropropyl) trimethoxy Titanium, and tritylfluorooctyltriethoxytitanium, methyltrichlorotitanium, dimethyldichlorotitanium, trimethyltitanium chloride, phenyltrichlorotitanium, dimethyldifluorotitanium, dimethyldichlorotitanium Titanium bromide, diphenyl titanium dibromide, hydrolysates of these, and condensates of these hydrolysates. Among these, from the viewpoint of ease of acquisition, tetramethoxytitanium, tetraethoxytitanium, and tetraisopropoxytitanium are preferred.

Examples of preferred zirconate compounds include tetramethoxyzirconium, methyltrimethoxyzirconium, ethyltrimethoxyzirconium, n- or isopropyltrimethoxyzirconium, n-, iso- or tertiary butyl Zirconium trimethoxyzirconium, n-, iso-or neopentyltrimethoxyzirconium, hexyltrimethoxyzirconium, octyltrimethoxyzirconium, decyltrimethoxyzirconium, phenyltrimethoxyzirconium; alkyl substituted phenyl Zirconium trimethoxy (e.g., p-(methyl)phenyl zirconium trimethoxy), zirconium dimethyl dimethoxy, zirconium tetraethoxy, zirconium methyl triethoxy, zirconium ethyl triethoxy , Zirconium or isopropyl triethoxy zirconium, n, iso or tertiary butyl triethoxy zirconium, pentyl triethoxy zirconium, hexyl triethoxy zirconium, octyl triethoxy zirconium, decyl Triethoxyzirconium, phenyltriethoxyzirconium, alkyl-substituted phenyltriethoxyzirconium (for example, p-(methyl)phenyltriethoxyzirconium), dimethyl diethoxyzirconium , Zirconium tetraisopropoxide, zirconium triisopropoxide, zirconium triisopropoxide, zirconium triisopropoxide, zirconium or isopropyl triethoxy, triisopropoxy n-, iso- or tertiary butyl Zirconium, pentyl triisopropoxy zirconium, hexyl triisopropoxy zirconium, octyl triisopropoxy zirconium, decyl triisopropoxy zirconium, phenyl triisopropoxy zirconium, alkyl substituted benzene Triisopropoxy zirconium (for example, p-(methyl)phenyl triisopropoxy titanium), dimethyl diisopropoxy zirconium, (3,3,3-trifluoropropyl) trimethoxy Zirconium, and trifluorofluorooctyltriethoxyzirconium, methyltrichlorozirconium, dimethyldichlorozirconium, trimethylchlorozirconium, phenyltrichlorozirconium, dimethyldifluorozirconium, dimethyldichloro Zirconium bromide, diphenylzirconium dibromide, hydrolysates of these, and condensation products of these hydrolysates. Among these, from the viewpoint of ease of acquisition, tetramethoxyzirconium, tetraethoxyzirconium, and tetraisopropoxyzirconium are preferred.

(4) Release layer composed of resin coating

Using a resin coating film composed of polysiloxane and any one or more resins selected from epoxy-based resins, melamine-based resins, and fluororesins, the resin substrate and the copper foil are bonded together, thereby allowing proper adhesion The property is reduced, and the peel strength is adjusted to the range as described below.

This adjustment of the peel strength for achieving adhesion is achieved by using a resin coating composed of polysiloxane, and any one or more resins selected from epoxy-based resins, melamine-based resins, and fluororesins as described below. Film. The reason is that this resin coating film is subjected to baking treatment under specific conditions as described below, and is used between the resin substrate and the copper foil, and is pressed by hot pressing to perform bonding, whereby the adhesiveness can be appropriately reduced, and The peel strength is adjusted to the above range.

Examples of epoxy resins include bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, brominated epoxy resin, amine epoxy resin, flexible epoxy resin, Hydrogenated bisphenol A epoxy resin, phenoxy resin, brominated phenoxy resin, etc.

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. In addition, the melamine-based resin may be a mixed resin of the above resin and butylated urea resin, butylated benzomelamine resin, or the like.

In addition, 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 coating of the resin can be realized, and the adhesive strength of the resin coating film can be easily adjusted to a specific range.

In addition, examples of the fluororesin include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, and polyvinyl fluoride.

Examples of polysiloxanes include methylphenylpolysiloxane, methylhydrogenpolysiloxane, dimethylpolysiloxane, modified dimethylpolysiloxane, and mixtures of these. Here, examples of the modification include epoxy modification, alkyl modification, amine modification, carboxyl modification, alcohol modification, fluorine modification, alkyl aralkyl polyether modification, epoxy poly modification Ether modification, polyether modification, alkyl higher alcohol ester modification, polyester modification, oxyalkyl modification, halogenated alkyl oxyalkyl modification, halogenated alkyl modification, amino ethyl Modification of glycol, modification of mercapto group, modification of polyester containing hydroxyl group, etc.

Regarding the resin coating film, if the film thickness is too small, the resin coating film is too thin and it is difficult to form, so the productivity is likely to decrease. In addition, even if the film thickness exceeds a fixed size, no further improvement in the peelability of the resin coating film is seen, and the manufacturing cost of the resin coating film tends to increase. From this viewpoint, the film thickness of the resin coating film is preferably 0.1 to 10 μm , and more preferably 0.5 to 5 μm . In addition, the film thickness of the resin coating film is achieved by applying a resin coating material at a specific coating amount in a program described later.

In the resin coating film, polysiloxane functions as a peeling agent for the resin coating film. Therefore, if the total amount of the epoxy-based resin and the melamine-based resin is too large compared to polysiloxane, the peeling strength imparted by the resin coating film between the resin substrate and the copper foil becomes large, so the peelability of the resin coating film Lower, sometimes not easy to peel off by hand. On the other hand, if the total amount of the epoxy-based resin and the melamine-based resin is too small, the peel strength becomes small, and therefore, the copper foil with a release layer may be peeled off during transportation or processing. From this point of view, it is preferable to contain the component in an amount of 10 to 1500 parts by mass relative to 100 parts by mass of polysiloxane, the total of epoxy resin and melamine resin, and more preferably 20 to 800 parts. Contains the amount of parts by mass.

In addition, the fluororesin functions as a release agent like polysiloxane, and has the effect of improving the heat resistance of the resin coating film. If the fluororesin is too large compared to polysiloxane, the peeling strength becomes smaller, so it may peel off during the conveyance or processing of the laminate, and the temperature required for the baking step described later increases, so it becomes not economic. From this viewpoint, the fluororesin is preferably 0-50 parts by mass, and more preferably 0-40 parts by mass with respect to 100 parts by mass of polysiloxane.

The resin coating film, in addition to polysiloxane, epoxy resin and/or melamine resin, and optionally fluorine resin, may further contain SiO ₂ , MgO, Al ₂ O ₃ , BaSO ₄ and Mg(OH ) ₂ of one or more surface roughening particles. The resin coating film contains surface roughened particles, and the surface of the resin coating film becomes uneven. Due to the unevenness, the surface of the resin substrate or copper foil coated with the resin coating film becomes uneven, and becomes a matte surface. The content of the surface roughened particles is not particularly limited as long as the resin coating film is uneven, and is preferably 1 to 10 parts by mass relative to 100 parts by mass of polysiloxane.

The particle diameter of the surface roughened particles is preferably 15 nm to 4 μm . Here, the particle diameter refers to the average particle diameter (the average value of the largest particle diameter and the smallest 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, it is easy to adjust the amount of irregularities on the surface of the resin coating film. As a result, it is easy to adjust the amount of irregularities on the surface of the resin substrate or copper foil. Specifically, the amount of irregularities on the surface of the resin substrate or copper foil is about 4.0 μm in terms of the maximum height roughness Ry prescribed by JIS.

Here, a method of manufacturing the laminate will be described.

The copper foil with a release layer is obtained through a procedure having the following steps: a step of coating the resin coating film on at least one surface of a resin substrate or a copper foil; and a baking that hardens the coated resin coating film step. Hereinafter, each step will be described.

(Coating step)

The coating step is a step of forming a resin coating film by coating a resin coating on one side or both sides of a resin substrate. The resin coating consists of polysiloxane as a main agent, epoxy-based resin as a curing agent, melamine-based resin, and It is composed of a fluororesin required as a release agent. Resin coating is made by dissolving epoxy resin, melamine resin, fluorine resin and polysiloxane in organic solvents such as alcohol. In addition, the blending amount (addition amount) in the resin coating is preferably 10 to 1500 parts by mass based on 100 parts by mass of the polysiloxane, and the total of the epoxy resin and the melamine resin. In addition, the fluororesin is preferably 0 to 50 parts by mass relative to 100 parts by mass of polysiloxane.

The coating method in the coating step is not particularly limited as long as a resin coating film can be formed, and a gravure coating method, a bar coating method, a roll coating method, a curtain flat coating method, a method using an electrostatic coating machine, etc. are used From the viewpoint of the uniformity of the resin coating film and the convenience of work, the gravure coating method is preferred. In addition, the amount of coating is preferably 1.0 to 2.0 g/m ² as the amount of resin, so that the resin coating film 3 has a preferable film thickness: 0.5 to 5 μm.

The gravure coating method is a method of forming a resin coating film on the surface of the resin substrate by transferring the resin coating material filled in the concave portion (groove) provided on the surface of the roller to the resin substrate. Specifically, the lower part of the lower roller provided with the groove on the surface is immersed in the resin paint, and the resin paint is sucked into the groove by the rotation of the lower roller. Then, the resin substrate is arranged between the lower roller and the upper roller disposed above the lower roller, and while the resin substrate is pressed against the lower roller by the upper roller, the lower roller and the upper roller are rotated to convey the resin substrate And, the resin paint sucked up into the tank is transferred (applied) to one side of the resin substrate.

In addition, by arranging the blade on the loading side of the resin substrate so as to be in contact with the surface of the lower roller, the excess resin coating that is sucked up to the surface of the roller other than the groove is removed to apply a specific coating on the surface of the resin substrate The amount of resin coating. In addition, when the number (size and depth) of the groove is large or when the viscosity of the resin coating is high, the resin coating film formed on one side of the resin substrate is less likely to be smooth. Therefore, a smoothing roller may be arranged on the carrying out side of the resin substrate to maintain the smoothness of the resin coating film.

In addition, when a resin coating film is formed on both surfaces of the resin substrate, after the resin coating film is formed on one surface of the resin substrate, the resin substrate is turned over and placed again between the lower roller and the upper roller. Then, in the same manner as described above, the resin paint in the groove of the lower roller is transferred (applied) to the back of the resin substrate.

(Baking step)

The baking step is a step of performing a baking treatment on the resin coating film formed in the coating step at 125 to 320°C (baking temperature) and 0.5 to 60 seconds (baking time). As described above, by subjecting the resin coating film formed of the resin coating with a specific blending amount to a specific condition of baking treatment, the peel strength between the resin substrate and the copper foil imparted by the resin coating film is controlled within a specific range. In the present invention, the baking temperature is the limit temperature of the resin substrate. In addition, as a heating means for the baking process, a conventionally known device is used.

Under conditions where baking becomes insufficient, for example, when the baking temperature does not reach 125°C or the baking time does not reach 0.5 seconds, the resin coating film becomes insufficiently hardened, the peel strength exceeds 200 gf/cm, and the peelability reduce. In addition, under conditions where the baking is excessive, for example, when the baking temperature exceeds 320°C, the resin coating film deteriorates, the peel strength exceeds 200 gf/cm, and the workability at the time of peeling deteriorates. Or, the resin substrate may be deteriorated due to high temperature. In addition, when the baking time exceeds 60 seconds, productivity deteriorates.

In the manufacturing method of the laminate, the resin coating in the coating step may be made of polysiloxane as the main agent, epoxy resin as the hardener, melamine-based resin, fluororesin as the release agent, and selected from SiO _2. A resin coating composed of one or more surface roughened particles of MgO, Al ₂ O ₃ , BaSO ₄ and Mg(OH) ₂ .

Specifically, the resin coating is obtained by adding surface roughened particles to the polysiloxane added resin solution. By further adding such roughened particles to the resin coating, the surface of the resin coating film becomes uneven, and the uneven surface makes the resin substrate or copper foil uneven, and becomes a matte surface. Furthermore, in order to obtain such a resin substrate or copper foil having a matte surface, it is preferable that the blending amount (adding amount) of the surface roughened particles in the resin coating is 1 to 10 parts by mass with respect to 100 parts by mass of polysiloxane. In addition, it is further preferred that the particle diameter of the surface roughened particles is 15 nm to 4 μm .

The manufacturing method of the present invention is as described above, but when the present invention is carried out, other steps may be included between or before the steps as long as they do not adversely affect the steps. For example, a cleaning step of cleaning the surface of the resin substrate may be performed before the coating step.

In addition, the release layer of the present invention may have one or more layers selected from the group consisting of alloys, metals, organic substances, and inorganic substances. As the alloy, metal, organic substance, or inorganic substance, the alloy, metal, organic substance, or inorganic substance described in the specification of the present application may also be used.

‧Support or resin that can be laminated on the release layer side of the copper foil with release layer (insulated substrate 1 described later)

As the resin that can be laminated on the release layer side of the copper foil with the release layer, a known resin can be used. In addition, as the resin, a resin layer described later can be used. In addition, the resin that can be laminated on the release layer side of the copper foil with a release layer is not particularly limited, and all resins can be used. In addition, as the resin that can be laminated on the release layer side of the copper foil with a release layer, for example, phenol resin, polyimide resin, epoxy resin, fluorine resin, liquid crystal polymer resin, cycloolefin polymer resin can be used , Polyethylene resin, polyethylene terephthalate resin, vinyl chloride resin, natural rubber, rosin, etc. In addition, the resin that can be laminated on the release layer side of the copper foil with a release layer is preferably a thermosetting resin. In addition, as a resin that can be laminated on the release layer side of the copper foil with a release layer, a prepreg can also be used. The prepreg before being bonded to the copper foil is preferably a prepreg in a state of B stage. If the linear expansion coefficient of the prepreg (stage C) is 12 to 18 (×10 ^-6 /℃), it is equivalent to 16.5 (×10 ^-6 /℃) of copper foil as the constituent material of the substrate, or SUS pressed plate 17.3 (×10 ^-6 /°C) is almost equal, which is advantageous in that the positional deviation of the circuit due to the phenomenon (scale change) of the substrate size before and after pressing differs from the substrate size at the time of design is unlikely to occur. Furthermore, as a synergistic effect of these advantages, a multi-layer ultra-thin coreless substrate can also be produced. The prepreg used here may be the same as or different from the prepreg constituting the circuit board.

Regarding the prepreg, from the viewpoint of maintaining the peel strength after heating in an optimal range, it is preferably a glass having a high glass transition temperature Tg, for example, 120 to 320°C, preferably 170 to 240°C Transfer temperature Tg. In addition, the glass transition temperature Tg is set to a value measured by DSC (differential scanning calorimetry).

In addition, it is desirable that the thermal expansion rate of the resin, prepreg, or support is +10% and within -30% of the thermal expansion rate of the copper foil. As a result, the position of the circuit due to the difference in thermal expansion between the copper foil and the resin can be effectively prevented, and defective products can be reduced to improve the yield. As the support, a metal plate or metal foil can also be used.

The thickness of the resin or the support is not particularly limited. In addition, the resin or the support may be rigid or flexible. In addition, if the thickness of the resin or the support is too thick, it will adversely affect the heat distribution during hot pressing. On the other hand, if it is too thin, it may be bent and the manufacturing process of the printed wiring board may not be performed, so The thickness of the resin or the support is usually preferably 5 μm or more and 1000 μm or less. In addition, the thickness of the resin or the support is more preferably 50 μm or more and 900 μm or less, and still more preferably 100 μm or more and 400 μm or less.

<Laminate>

The copper foil with a mold release layer of the present invention can be used to produce a laminate (copper-clad laminate, etc.).

As a laminate of the copper foil with a mold release layer of the present invention, for example, a structure in which a "support or resin or prepreg/release layer/copper foil/barrier layer" is sequentially laminated may be used.

The support, resin, or prepreg may be a resin layer described later, or may contain a resin, resin hardener, compound, hardening accelerator, dielectric, reaction catalyst, crosslinking agent, polymer for the resin layer described later. , Prepreg, skeleton material, etc. In addition, the copper foil with the release layer may be smaller than the support, resin, or prepreg in plan view.

<roughening treatment and other surface treatments>

The surface of the barrier layer of the copper foil with the release layer on the opposite side to the copper foil or between the copper foil of the copper foil with the release layer and the barrier layer may be roughened by performing a roughening treatment, for example Treat the layer to improve the adhesion to the insulating substrate or resin. The roughening treatment can be performed by forming roughened particles using copper or a copper alloy, for example. The roughening treatment may be fine roughening treatment. The roughening layer can also be selected from Cu (copper), Ni (nickel), P (phosphorus), W (tungsten), As (arsenic), Mo (molybdenum), Cr (chromium), Ti (titanium), A single element of a group composed of any one of Fe (iron), V (vanadium), Co (cobalt), and Zn (zinc) or an alloy containing any one or more of the above elements, etc. In addition, after forming the roughened particles using copper or a copper alloy, a roughening treatment may be performed in which secondary particles or tertiary particles are provided using a simple substance or alloy of nickel, cobalt, copper, zinc, or the like. Thereafter, the elemental and/or alloys of nickel, cobalt, copper, zinc, tin, molybdenum, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, tantalum and/or An oxide and/or nitride and/or silicide, etc. may be used to form a heat-resistant layer or a rust-proof layer, and the surface of the heat-resistant layer or rust-proof layer may be further subjected to chromate treatment, silane coupling treatment, or the like. Alternatively, instead of roughening, nickel, cobalt, copper, zinc, tin, molybdenum, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, and tantalum can be used. And/or alloys and/or oxides and/or nitrides and/or silicides to form a heat-resistant layer or rust-proof layer, and then the surface of the heat-resistant layer or rust-proof layer is subjected to chromate treatment and silane coupling treatment, etc. deal with. 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. The surface of the barrier layer of the copper foil opposite to the copper foil or the copper foil with the release layer of the copper foil and the barrier layer is formed from a heat-resistant layer, a rust-proof layer, a chromate treatment layer and a silane coupling treatment More than one layer in a group of layers. Alternatively, a surface layer selected from the group consisting of the roughening treatment layer and the heat-resistant layer may be formed between the surface of the barrier layer of the copper foil with the release layer and the copper foil on the side opposite to the copper foil or the copper foil with the copper foil of the release layer One or more layers in the group consisting of a layer, an anti-rust layer, a chromate treatment layer, and a silane coupling treatment layer. In addition, one or more types 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 between the copper foil of the copper foil with a release layer and the release layer Layer. The heat-resistant layer may also be a copper layer. The anti-rust layer may also be a copper layer. In addition, the heat-resistant layer, the rust-proof layer, the chromate-treated layer, and the silane coupling-treated layer may each be formed of a plurality of layers (for example, 2 or more layers, 3 or more layers, etc.).

For example, copper-cobalt-nickel alloy plating as a roughening treatment can be formed by electrolytic plating to form copper with an adhesion amount of 15-40 mg/dm ² -100-3000 μ g/dm ² cobalt -100-1500 μ It is implemented as a ternary alloy layer such as g/dm ² nickel. If the deposited mass of Co less than 100 μ g / dm ^2, there is poor heat resistance and etching properties deteriorated. If the case of poor adhesion Co amount exceeds 3000 μ g / dm ^2, then the magnetic properties must be considered, it is etched to produce spots and where acid resistance and chemical resistance deteriorates. If the deposited mass of Ni less than 100 μ g / dm ^2, there is a case where heat resistance is deteriorated. On the other hand, if the Ni deposition amount exceeds 1500 μ g / dm ^2, the etching becomes more remaining cases. The preferred adhesion amount of Co is ^{1000 ~ 2500 μ g / dm 2} , Ni deposition amount is preferably ^{500 ~ 1200 μ g / dm 2} . Here, the etching spot means that when copper chloride is used for etching, Co does not dissolve and remains, and the etching residue means that when ammonium chloride is used for alkaline etching, Ni does not dissolve but Residue.

An example of general baths and plating conditions used to form this ternary copper-cobalt-nickel alloy plating is as follows: Plating bath composition: Cu 10~20g/L, Co 1~10g/L, Ni 1~10g/L

pH value: 1~4

Temperature: 30~50℃

Current density D _k : 20~30A/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. The chromate treatment layer may also contain elements such as Co, Fe, Ni, Mo, Zn, Ta, Cu, Al, P, W, Sn, As, and Ti (also may be metals, alloys, oxides, nitrides, sulfides Things, etc.). Specific examples of the chromate treatment layer include a chromate treatment layer treated with an aqueous solution of chromic anhydride or potassium dichromate, or a chromate treated with a treatment liquid containing chromic anhydride or potassium dichromate and zinc. Processing layer, etc.

系矽烷等矽烷偶合劑等而形成。此外，這種矽烷偶合劑也可將兩種以上混合而使用。其中，較佳為使用胺基系矽烷偶合劑或環氧系矽烷偶合劑而形成的矽烷偶合處理層。 The silane coupling treatment layer may be formed using a well-known silane coupling agent, or epoxy silane, amine silane, methacryl oxysilane, mercapto silane, vinyl silane, imidazole silane, three

It is formed by silane coupling agent such as silane. In addition, this silane coupling agent can also be used by mixing two or more kinds. Among them, a silane coupling treatment layer formed using an amine-based silane coupling agent or an epoxy-based silane coupling agent is preferred.

In addition, the surface of the barrier layer side of the copper foil with the release layer 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 can be given International Publication No. WO2008/053878, Japanese Patent Laid-Open No. 2008-111169, Japanese Patent No. 5024930, International Publication No. WO2006/028207, Japanese Patent No. 4828427, International Publication No. WO2006/134868, Japanese Patent No. 5046927, International Publication No. WO2007/105635, Japanese Patent No. Surface treatment described in No. 5180815 and Japanese Patent Laid-Open No. 2013-19056.

In addition, a roughening treatment layer may be provided on the surface of the copper foil with a release layer on the barrier layer side or between the copper foil of the copper foil with a release layer and the barrier layer, or may be provided on the roughening treatment layer One or more layers selected from the group consisting of a heat-resistant layer, an anti-rust layer, a chromate treatment layer, and a silane coupling treatment layer.

In addition, a roughening treatment layer may be provided on the surface of the barrier layer side of the copper foil with release layer or between the copper foil of the copper foil with release layer and the barrier layer, and heat resistance may be provided on the roughening treatment layer The layer and the rust prevention layer may be provided with a chromate treatment layer on the heat-resistant layer or the rust prevention layer, or may be provided with a silane coupling treatment layer on the chromate treatment layer.

In addition, the surface of the copper foil with a mold release layer on the barrier layer side, or between the copper foil of the copper foil with a mold release layer and the barrier layer, or on the roughening treatment layer, or the heat-resistant layer, or A resin layer is provided on the rust prevention layer, the chromate treatment layer, or the silane coupling treatment layer. The resin layer may also be an insulating resin layer.

The resin layer may be an adhesive or an insulating resin layer in a semi-cured state (stage B) for subsequent use. The so-called semi-cured state (B-stage state) means that even if the surface of the resin layer is touched with a finger, there is no sticky feeling, and the insulating resin layer can be superimposed and stored, and further includes a curing reaction that occurs if subjected to heat treatment. status.

樹脂、熱硬化性聚苯醚樹脂、氰酸酯系樹脂、羧酸的酸酐、多元羧酸的酸酐、具有可交聯的官能基的線性聚合物、聚苯醚樹脂、2,2-雙(4-氰酸酯基苯基)丙烷、含磷的酚化合物、環烷酸錳、2,2-雙(4-縮水甘油基苯基)丙烷、聚苯醚-氰酸酯系樹脂、矽氧烷改質聚醯胺醯亞胺樹脂、氰基酯樹脂、磷腈系樹脂、橡膠改質聚醯胺醯亞胺樹脂、異戊二烯、氫化型聚丁二烯、聚乙烯丁醛、苯氧樹脂、高分子環氧樹脂、芳香族聚醯胺、氟樹脂、雙酚、嵌段共聚聚醯亞胺樹脂及氰基酯樹脂。 In addition, the resin layer may include a thermosetting resin or a thermoplastic resin. In addition, the resin layer may contain a thermoplastic resin. The type of thermoplastic resin is not particularly limited. For example, preferred thermoplastic resins include one or more resins selected from the group of resins: epoxy resins, polyimide resins, and polyfunctional cyanates. Compounds, maleimide compounds, polyvinyl acetal resins, urethane resins, polyether socks, polyether sack resins, aromatic polyamide resins, aromatic polyamide resin polymers, rubbery resins , Polyamines, aromatic polyamines, polyamidoamide resins, rubber-modified epoxy resins, phenoxy resins, carboxy-modified acrylonitrile-butadiene resins, polyphenylene oxide, bis-cis-butadiene diacrylic acid Amine tri

Resins, thermosetting polyphenylene ether resins, cyanate ester resins, carboxylic acid anhydrides, polycarboxylic acid anhydrides, linear polymers with crosslinkable functional groups, polyphenylene ether resins, 2,2-bis( 4-cyanoylphenyl)propane, phosphorus-containing phenol compound, manganese naphthenate, 2,2-bis(4-glycidylphenyl)propane, polyphenylene ether-cyanate resin, silicone Alkane-modified polyamidoamide resin, cyanoester resin, phosphazene resin, rubber-modified polyamidoamide resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, benzene Oxygen resin, high molecular epoxy resin, aromatic polyamide, fluororesin, bisphenol, block copolymerized polyimide resin and cyanoester resin.

In addition, the epoxy resin can be used without particular problems as long as it has two or more epoxy groups in the molecule and can be used for electrical and electronic materials. In addition, the epoxy resin is preferably an epoxy resin obtained by epoxidation using a compound having two or more glycidyl groups in the molecule. In addition, the epoxy resin can be used by mixing one or more types selected from the group of the following resins: bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin , Bisphenol AD epoxy resin, novolac epoxy resin, cresol novolac epoxy resin, alicyclic epoxy resin, brominated epoxy resin, phenol novolac epoxy resin, naphthalene Epoxy resin, brominated bisphenol A epoxy resin, o-cresol novolac epoxy resin, rubber modified bisphenol A epoxy resin, glycidyl amine epoxy resin, triglycidyl isocyanurate Glycidylamine compounds such as esters, N,N-diglycidylaniline, glycidyl ester compounds such as tetrahydrophthalic acid diglycidyl ester, phosphorus-containing epoxy resin, biphenyl type epoxy resin, biphenol novolac Varnish-type epoxy resin, trihydroxyphenylmethane-type epoxy resin, tetraphenylethane-type epoxy resin, or a hydrogenated or halogenated body of the epoxy resin can be used.

As the phosphorus-containing epoxy resin, a known phosphorus-containing epoxy resin can be used. In addition, the phosphorus-containing epoxy resin is preferably, for example, a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derived from a molecule having two or more epoxy groups in the molecule. Derivative epoxy resin.

The resin layer may contain any known resins, resin hardeners, compounds, hardening accelerators, and dielectrics (dielectrics containing inorganic compounds and/or organic compounds, dielectrics containing metal oxides, etc. may be used. Dielectrics), reaction catalysts, crosslinking agents, polymers, prepregs, framework materials, etc. In addition, the resin layer may use substances described in the following documents (resin, resin curing agent, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton material) Etc.) and/or a resin layer forming method and forming device: for example, International Publication No. WO2008/004399, International Publication No. WO2008/053878, International Publication No. WO2009/084533, Japanese Patent Laid-Open No. 11-5828, Japanese Patent Laid-Open 11-140281, Japanese Patent No. 3184485, International Publication No. WO97/02728, Japanese Patent No. 3676375, Japanese Patent Publication No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Publication No. 2002-179772, Japanese Patent Publication No. 2002 -359444, JP 2003-304068, JP 3992225, JP 2003-249739, JP 4136509, JP 2004-82687, JP 4025177, JP 2004- 349654, Japanese Patent No. 4286060, Japanese Patent Laid-Open No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent Laid-Open No. 2005-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004/005588, Japanese Patent Laid-Open No. 2006-257153, Japanese Patent Laid-Open No. 2007-326923, Japanese Patent Laid-Open No. 2008-111169, Japanese Patent No. 5024930, International Publication No. WO2006/028207, Japanese Patent No. 4828427, Japanese Patent Laid-Open No. 2009-67029 , International Publication No. WO2006/134868, Japanese Patent No. 5046927, Japanese Patent Laid-Open No. 2009-173017, International Publication No. WO2007/105635, Japanese Patent No. 5180815, International Publication No. WO2008/114858, International Publication No. WO2009/008471, Japan Japanese Patent Laid-Open No. 2011-14727, International Publication No. WO2009/001850, International Publication No. WO2009/145179, International Publication No. WO2011/068157, Japanese Patent Laid-Open No. 2013-19056.

These resins are dissolved in a solvent such as methyl ethyl ketone (MEK), toluene, etc. to prepare a resin solution, and the resin solution is applied to the barrier of the copper foil with a release layer by, for example, a roll coater method or the like On the surface of the layer side, or the roughened layer, the heat-resistant layer, the rust-preventive layer, or the chromate film layer, or the silane coupling agent layer, the solvent is then removed by heating and drying if necessary, It becomes the B stage state. For drying, for example, a hot air drying furnace can be used, and the drying temperature can be 100 to 250°C, preferably 130 to 200°C.

The copper foil with a mold release layer provided with the resin layer (copper foil with a resin with a mold release layer) is used as follows: after the resin layer is overlaid on the base material, the whole is hot pressed Then, the resin layer is thermally cured to form a specific wiring pattern on the surface of the copper foil on the barrier layer side.

If the resin-attached copper foil with a mold release layer is used, the number of prepreg materials used when manufacturing a multilayer printed wiring board can be reduced. Furthermore, the thickness of the resin layer can be made as thick as the interlayer insulation can be ensured, or a copper-clad laminate can be manufactured even without using a prepreg material at all. In addition, in this case, the insulating resin may be primed on the surface of the base material to further improve the smoothness of the surface.

In addition, when the prepreg material is not used, it has the following advantages: the material cost of the prepreg material is saved, and the lamination step is also simplified, so it becomes economically advantageous, and, with the prepreg material Accordingly, the thickness of the multilayer printed wiring board to be manufactured becomes thinner, and an extremely thin multilayer printed wiring board with a thickness of 100 μm or less per layer can be manufactured.

The thickness of the resin layer is preferably 0.1 to 80 μm . If the thickness of the resin layer is thinner than 0.1 μm , the adhesive force decreases, and when the copper foil with the resin-attached release layer is laminated on the base material provided with the inner layer material without interposing the prepreg material, There are cases where it is difficult to ensure the interlayer insulation from the circuit of the inner layer material.

On the other hand, if the thickness of the resin layer is thicker than 80 μm , it is difficult to form the resin layer of the target thickness in one coating step, and it takes extra material costs and man-hours, so it becomes economically disadvantageous. Furthermore, the flexibility of the formed resin layer deteriorates, so cracks and the like are likely to occur during handling, and excessive resin flow is caused during thermal compression bonding with the inner layer material, making smooth lamination difficult.

As another product form of the copper foil with a resin-attached release layer, the surface of the copper foil with a release layer on the barrier layer side, or the roughened layer, the heat-resistant layer, and rust prevention The layer, or the chromate-treated layer or the silane coupling-treated layer is coated with a resin layer to be in a semi-cured state, and then manufactured in the form of resin-coated copper foil.

Furthermore, by mounting electronic components on the printed wiring board, the printed circuit board is completed. In the present invention, the "printed wiring board" also includes a printed wiring board, a printed circuit board, and a printed board on which electronic components are mounted as described above.

In addition, the printed wiring board may be used to manufacture an electronic device, the printed circuit board mounted with electronic components may be used to manufacture an electronic device, or the printed circuit board mounted with electronic components may be used to manufacture an electronic device. Hereinafter, some examples of the manufacturing process of the printed wiring board using the copper foil with a mold release layer of this invention are shown.

Hereinafter, an example of a method of manufacturing a printed wiring board including the step of forming a buried circuit using the copper foil with a mold release layer of the present invention will be described. In addition, in this specification, the concept of "circuit" includes wiring.

1 to 4 are schematic diagrams for explaining a method of forming a buried circuit using a copper foil with a release layer according to an embodiment of the present invention. A method of forming a buried circuit using a copper foil with a release layer according to an embodiment of the present invention is to first build up an insulating substrate on the release layer 30 side of the copper foil with a release layer of the present invention (FIG. 1a) 1 (Figure 1b). Next, a patterned plating resist layer 40 is provided on the barrier layer 10 side of the copper foil on which the release layer of the insulating substrate 1 is laminated (FIG. 1c). Next, a copper plating layer 50 is provided on the barrier layer 10 provided with the patterned plating resist 40 (FIG. 2d). Next, the copper plating circuit 51 is formed by removing the plating resist layer 40 (FIG. 2e). Next, the copper plated circuit 51 is buried by covering the copper plated circuit 51 with the insulating substrate 2 (FIG. 2f). In addition, at this time, a copper foil 60 (FIG. 3g) may be further provided on the insulating substrate 2, or the copper foil 60 may be subsequently etched to form a copper-plated circuit 61 (FIG. 3h). Next, by removing the insulating substrate 1 on the surface on the release layer 30 side, the surface on the release layer 30 side of the copper foil with the release layer exposed (FIG. 3i ). Next, the copper foil 20 is removed from the exposed surface of the release layer 30 side by etching to expose the surface of the barrier layer 10 (FIG. 4j). Next, the exposed barrier layer 10 is removed by etching, thereby exposing the circuit buried in the insulating substrate 2 (FIG. 4k). The embedded circuit is obtained in this manner, so that a printed wiring board using the embedded circuit can be manufactured.

In addition, after the step of FIG. 1b, the surface of the insulating substrate 1 on which the copper foil with the release layer is not laminated may be laminated with another copper foil with the release layer, as shown in FIG. The layered body is formed by sequentially stacking a barrier layer 10/copper foil 20/release layer 30/insulating substrate 1/release layer 31/copper foil 21/barrier layer 11. In this case, a buried circuit may be formed on the copper foil with a release layer on one surface of the insulating substrate 1 as shown in FIGS. 1c to 4k. On the other hand, on the other surface of the insulating substrate 1 The copper foil with the mold release layer is formed into a buried circuit in the same procedure. In addition, in the method of manufacturing the printed wiring board, the insulating substrate 1 may also be referred to as the support.

)樹脂或作為含浸有BT樹脂的玻璃布的預浸體、Ajinomoto Fine-Techno股份有限公司製造的ABF膜或ABF。另外，所述絕緣基板1及2及所述埋入樹脂(RESIN)可使用公知的樹脂或本說明書中記載的樹脂層及/或樹脂及/或預浸體。 In addition, embedded resins (RESIN) can be used for the insulating substrates 1 and 2. As the embedding resin, a known resin or prepreg can be used. For example, BT (bis-cis-butadiene diimide tri) can be used

) A prepreg of resin or glass cloth impregnated with BT resin, ABF film or ABF manufactured by Ajinomoto Fine-Techno Co., Ltd. In addition, the insulating substrates 1 and 2 and the embedded resin (RESIN) may use a known resin or the resin layer and/or resin and/or prepreg described in this specification.

The method of manufacturing a printed wiring board of the present invention may be a method of manufacturing a printed wiring board (coreless method) including the step of: applying the release layer-side copper foil of the present invention to the barrier layer side surface Or the step of laminating the release layer side surface with the resin substrate; the surface of the copper foil with the release layer on the opposite side of the barrier layer side surface or the release layer side surface laminated with the resin substrate , At least one step of providing two layers of the resin layer and the circuit; and after forming the two layers of the resin layer and the circuit, peeling the two layers of the resin layer and the circuit from the copper foil with the release layer step. In addition, the resin layer and the circuit may be provided with a resin layer and a circuit in sequence, or may be provided with a circuit and a resin layer in sequence. Regarding the coreless method, as a specific example, first, the barrier layer side surface or the release layer side surface of the copper foil with a mold release layer of the present invention is laminated with a resin substrate to produce a laminate (also referred to as copper clad) Laminates, copper clad laminates). After that, a resin layer is formed on the surface of the copper foil with a release layer on the side opposite to the side surface of the barrier layer laminated with the resin substrate or the side surface of the release layer. It is also possible to deposit another copper foil with a release layer on the resin layer formed on the surface of the release layer side or the copper foil side, and from the release layer side or the barrier layer side. Alternatively, a laminate having the following structure may be used in the method of manufacturing the printed wiring board (coreless method): a resin substrate or a resin or prepreg as the center, and a resin substrate or a resin or prepreg as the center The two surface sides of the two layers are formed by stacking copper foil with a release layer in the order of release layer/copper foil/barrier layer or in the order of barrier layer/copper foil/release layer; or layering “release layer/ Composition of copper foil/barrier layer/resin substrate or resin or prepreg/release layer/copper foil/barrier layer; or sequentially laminating "release layer/copper foil/barrier layer/resin substrate or resin or prepreg" "Block/Barrier layer/Copper foil/Release layer"; or "Layer barrier/Copper foil/Release layer/Resin substrate or resin or prepreg/Release layer/Copper foil/Barrier layer" in order constitute. Moreover, another resin layer may be provided on the exposed surface of the barrier layer or the release layer at both ends of the laminate, and then after the copper layer or metal layer is provided, the copper layer or metal layer may be processed to borrow This forms a circuit or wiring. Furthermore, a method of embedding the circuit or wiring (a method of embedding the circuit or wiring) may be provided with another resin layer on the circuit or wiring. In addition, a copper or metal wiring or circuit may be provided on the exposed surface of the barrier layer or the release layer at both ends of the laminate, and another resin layer may be provided on the wiring or circuit to utilize the other resin Embed the wiring or circuit (bury the wiring or circuit). After that, a circuit or a wiring and a resin layer may be formed on another resin layer. In addition, the formation of such a circuit or wiring and a resin layer may be performed once or more (layer build-up method). Furthermore, regarding the laminate formed in the above manner (hereinafter, also referred to as laminate B), the copper foil with each release layer attached can be peeled from the laminate to produce a coreless substrate. In addition, in the production of the coreless substrate, two copper foils with a release layer may be used to produce a laminate having a configuration of a barrier layer/copper foil/release layer/release layer/copper foil/barrier layer described later. Or a laminate with a release layer/copper foil/barrier layer/barrier layer/copper foil/release layer or a laminate with a release layer/copper foil/barrier layer/release layer/copper foil/barrier layer The laminated body uses the laminated body as the center. The two layers of the resin layer and the circuit can be provided more than once on the surface of the barrier layer or the release layer on both sides of these laminates (hereinafter also referred to as laminate A), and the two layers of the resin layer and the circuit can be provided After one or more times, the two layers of the resin layer and the circuit provided at least once are peeled from the copper foil with each release layer to produce a coreless substrate. In addition, the resin layer and the circuit may be provided with a resin layer and a circuit in sequence, or may be provided with a circuit and a resin layer in sequence. The laminate may have other layers on the surface of the barrier layer, the surface of the release layer, between the release layer and the release layer, between the barrier layer and the barrier layer, and between the barrier layer and the release layer. The other layer may be a resin substrate or a resin layer. In addition, in this specification, "surface of copper foil", "surface of copper foil side", "surface of copper foil", "surface of release layer", "surface of release layer side", "surface of release layer", The concepts of "surface of laminate", "surface of laminate", "surface of barrier layer", "side surface of barrier layer", and "surface of barrier layer" include copper foil, release layer, laminate, and barrier layer in copper. When the foil surface, the release layer surface, the laminate surface, and the barrier layer surface have other layers, the surface (the outermost surface) of the other layer is included. In addition, the laminate preferably has a structure of barrier layer/copper foil/release layer/one or more supports/release layer/copper foil/barrier layer. The reason is that when the coreless substrate is manufactured using the laminate, because the barrier layer is disposed on the coreless substrate side, when a circuit is formed on the barrier layer and the circuit is buried, the circuit can be reduced when the barrier layer is removed Erosion.

In addition, in this specification, a "laminated body" not specifically described as "laminated body A" or "laminated body B" means a laminated body including at least the laminated body A and the laminated body B.

In addition, in the method of manufacturing the coreless substrate, a part or all of the end surface of the copper foil with a mold release layer or the laminate (including the laminate A) is covered with a resin, which is manufactured by a build-up method When printing a wiring board, it can prevent the chemical solution from penetrating into the peeling layer or one of the copper foils attached to the release layer and the other copper foil attached to the release layer, which can prevent the adhesion of the release layer caused by the penetration of the chemical solution The corrosion of the copper foil can improve the yield. As "resin that covers part or all of the end surface of the copper foil with a release layer" or "resin that covers part or all of the end surface of the laminate" used herein, resins that can be used for the resin layer or known ones can be used Of resin. In addition, in the method of manufacturing the coreless substrate, in the copper foil with the release layer or the laminate, the stacked portion of the copper foil with the release layer or the laminate as viewed from above (the stacked portion of the release layer and the copper foil or At least a part of the outer periphery of the laminated portion of the barrier layer and the copper foil or the laminated portion of the copper foil with a release layer and the other copper foil with a release layer may also be covered with resin or a prepreg. In addition, the layered product (layered product A) formed by the method for manufacturing the coreless substrate may be configured such that a pair of copper foils with a release layer can be separated from each other and contacted. In addition, the copper foil with a mold release layer or the laminate portion of the laminate with the mold release layer (the laminate portion of the release layer and the copper foil or the laminate portion of the barrier layer and the copper foil or The entire outer periphery of the laminated portion of one copper foil with a release layer and the other copper foil with a release layer) or the entire surface of the laminated portion is covered with resin or a prepreg. In addition, it is preferable that the resin or prepreg is larger than the laminated portion of the copper foil or the laminate or the laminate with the release layer in a plan view, and it is preferable to make a laminate having the following structure: the resin or the prepreg It is laminated on both sides of the copper foil or the laminate with the release layer, and the copper foil or the laminate with the release layer is wrapped (wrapped) with resin or a prepreg. By making such a configuration, when the copper foil with a release layer or a laminate is viewed from above, the laminated part of the copper foil with a release layer or a laminate is covered with a resin or a prepreg to prevent other parts from the part The side direction, that is, the direction from the lateral side with respect to the stacking direction, as a result, the peeling of the release layer and the copper foil or the copper foil with the release layer in operation can be reduced. In addition, by covering with a resin or a prepreg so as not to expose the outer periphery of the laminated portion of the copper foil with the release layer or the laminate, the chemical solution in the chemical solution treatment step as described above can be prevented The penetration of the interface of the build-up part can prevent the corrosion or erosion of the copper foil attached with the release layer. In addition, when a pair of copper foils with a release layer are separated from a pair of copper foils with a release layer from the laminate, in the laminated portion of the copper foils with a release layer or a laminate covered with resin or prepreg (Laminated part of release layer and copper foil or laminated part of barrier layer and copper foil or laminated part of one copper foil with release layer and another copper foil with release layer) By resin or prepreg, etc. In the case of firmly adhering, it may be necessary to remove the layered portion and the like by cutting or the like.

The copper foil with a release layer of the present invention may be laminated from the release layer side or the barrier layer side to the release layer side or the barrier layer side of another copper foil with a release layer of the present invention to form a laminate. In addition, the release layer side surface or the copper foil side surface of the one copper foil with a release layer may be the release layer side of the other copper foil with a release layer The surface or the side surface of the barrier layer may be a laminate obtained by directly laminating via an adhesive if necessary. In addition, the release layer or barrier layer of the one copper foil with a release layer may be joined to the release layer or barrier layer of the other copper foil with a release layer. Here, the “bonding” also includes a state where the surface treatment layer is bonded to each other when the release layer or the barrier layer has a surface treatment layer. In addition, a part or all of the end surface of the laminate may be covered with resin.

The lamination of the release layers, the barrier layers, the release layer and the barrier layer, and the copper foil with the release layer can be laminated by simply overlapping, for example, by the following method.

(a) Metallurgical joining methods: welding (arc welding, TIG (tungsten inert gas) welding, MIG (melting inert gas) welding, resistance welding, seam welding, spot welding), pressure welding (ultrasonic welding, friction stir welding ), brazing; (b) mechanical joining methods: riveting, joining using rivets (joining using self-piercing riveting, joining using rivets), stitchers; (c) physical joining methods: adhesives, (both sides) tape

By joining a part or all of the copper foil with a release layer to a part or all of the copper foil with a release layer using the bonding method, the following laminate can be manufactured, which is a The copper foil with a mold release layer and the copper foil with another mold release layer are laminated so that the copper foil with a mold release layer may be separably contacted with each other. In the case where the copper foil of one release layer and the copper foil of another release layer are weakly joined, and the copper foil of one release layer and the copper foil of another release layer are laminated, even if the The joint of the copper foil with one release layer and the copper foil with another release layer is removed, and the copper foil with one release layer and the copper foil with another release layer can also be separated. In addition, in the case where the copper foil of one release layer is strongly joined to the copper foil of another release layer, a release layer can be attached by cutting, chemical polishing (etching, etc.), mechanical polishing, etc. The part where the copper foil and the copper foil with another release layer are joined is removed, and the copper foil with one release layer is separated from the copper foil with another release layer.

In addition, at least one primary resin layer and two circuits should be provided in a layered structure such as "barrier layer/copper foil/release layer/resin substrate or resin or prepreg/release layer/copper foil/barrier layer" After the step of forming a layer and forming the two layers of the resin layer and the circuit at least once, the step of peeling off the resin substrate or the resin or the prepreg from the copper foil with a release layer of the laminate, The release layer and copper foil are removed by etching. After that, the barrier layer is removed using an etching solution that can remove the barrier layer by etching, whereby a printed wiring board having two layers of the resin layer and the circuit formed at least once and having no core can be produced. In addition, two layers of a resin layer and a circuit may be provided on one or both surfaces of the laminate. In addition, the resin layer and the circuit may be provided with a resin layer and a circuit in sequence, or may be provided with a circuit and a resin layer in sequence.

The resin substrate, resin layer, resin, and prepreg used in the laminate may be the resin layer described in this specification, or may include the resin, resin curing agent, compound, and curing used in the resin layer described in this specification. Promoters, dielectrics, reaction catalysts, cross-linking agents, polymers, prepregs, framework materials, etc.

In addition, the copper foil or laminate with the release layer may be smaller than the resin or prepreg, resin substrate, or resin layer in a plan view.

[Example]

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

(Example 1: Copper foil with release layer)

As the copper foil, electrolytic copper foil JTC foil (thickness 35 μm ) manufactured by JX Metal Co., Ltd. was used. On the S surface (glossy surface) side of the electrolytic copper foil, a thickness of 1 μ was formed by electroplating under the following conditions The Ni layer of m serves as a barrier layer.

[Nickel (Ni) plating]

‧Plating solution

Nickel: 20~200g/L

Boric acid: 5~60g/L

Liquid temperature: 40~65℃

pH value: 1.5~5.0

‧Current density: 0.5~20A/dm ²

‧Power-on time: 1~20 seconds

‧Stirring (liquid circulation volume): 100~1000L/min

‧Transport speed: 2~30m/min

‧Additives: primary gloss agent (saccharin sodium: 0.5~5g/L), secondary gloss agent (thiourea: 0.05~1g/L)

Thereafter, a release layer was formed on the surface of the electrolytic copper foil opposite to the barrier layer under the following conditions.

‧Silane coupling treatment

Treatment liquid: Silane compound: n-propyltrimethoxysilane

Silane concentration: 0.4vol%

Stirring time of the treatment solution before use: 12 hours

Alcohol concentration: 0vol%

pH value: 4~7

Processing time: 30 seconds (application by spray nozzle)

(test results)

The copper foil with a mold release layer of Example 1 was used, prepreg FR-4 was used as the resin (insulating substrate 1) laminated on the surface of the copper foil on the mold release layer side, and epoxy resin was used as the embedded resin (insulating substrate 2) As shown in Figures 1 to 4, it can be made into a buried circuit board (printed wiring board).

1‧‧‧Insulated substrate

10‧‧‧ barrier layer

20‧‧‧Copper foil

30‧‧‧Release layer

40‧‧‧Anti-plating layer

Claims (26)

A copper foil with a release layer is provided with a release layer, a copper foil and a barrier layer in this order. The copper foil with a release layer as claimed in item 1 of the patent scope, wherein the barrier layer is C 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, or contains a material selected from Ni, Ti, V, Zr, Ta, Au, Pt, Os, Pd, Ru, Rh, Ir, W, Si A layer of any one or more alloys in the group consisting of Cr and Cr, or containing a layer containing Ni, Ti, V, Zr, Ta, Au, Pt, Os, Pd, Ru, Rh, Ir, W, Si, and Cr Any one or more layers of carbide, oxide, or nitride in the group. The copper foil with a release layer as claimed in item 1 of the patent scope, wherein the barrier layer is composed of any one or two selected from the group consisting of Ni, Ti, Cr, titanium oxide, chromium oxide and carbon or Composed of three or four or five or six. The copper foil with a release layer as claimed in item 2 of the patent scope, wherein the barrier layer is selected from any one or two or two or more selected from the group consisting of Ni, Ti, Cr, titanium oxide, chromium oxide and carbon or Composed of three or four or five or six. The copper foil with a mold release layer according to any one of claims 1 to 4, wherein the barrier layer has one or more layers selected from the group consisting of a Ni layer, a Ti layer, and a Cr layer. The copper foil with a release layer according to any one of the items 1 to 4 of the patent application range, wherein the barrier layer is any one or more layers selected from the group consisting of a Ni layer, a Ti layer, and a Cr layer . The copper foil with a mold release layer according to any one of claims 1 to 4, wherein the barrier layer is any layer selected from the group consisting of a Ni layer, a Ti layer, and a Cr layer. The copper foil with a release layer according to any one of claims 1 to 4 of the patent application, wherein the thickness of the barrier layer is 0.001 μm or more and 10 μm or less. The copper foil with a release layer according to any one of the items 1 to 4 of the patent application, wherein the thickness of the copper foil is 0.1 μm or more and 100 μm or less. The copper foil with a mold release layer according to any one of items 1 to 4 of the patent application range, wherein the mold release layer has a silane compound represented by the following formula or a hydrolysate of the silane compound, alone or in combination. , The condensation product of the hydrolysate of the silane compound,

(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 the hydrocarbon group in which one or more hydrogen atoms are replaced by a halogen atom, R ³ and R ⁴ are each independently a halogen atom, or an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or a hydrocarbon group in which one or more hydrogen atoms are substituted with a halogen atom ). The copper foil with a mold release layer according to any one of items 1 to 4 of the patent application, wherein the mold release layer has a compound having 2 or less thiol groups in the molecule. The copper foil with a mold release layer according to any one of the items 1 to 4 of the patent application, wherein the mold release layer has an aluminate compound, a titanate compound represented by the following formula alone or in combination Zirconate compound, hydrolysis product of the aluminate compound, hydrolysis product of the titanate compound, hydrolysis product of the zirconate compound, condensation product of the hydrolysis product of the aluminate compound, the The condensate of the hydrolysis product of the titanate compound or the condensate of the hydrolysis product of the zirconate compound, (R ¹ ) _m -M-(R ² ) _n (where R ¹ is an alkoxy group or a halogen atom , R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group or the hydrocarbon group in which one or more hydrogen atoms are replaced by a halogen atom, M is Al, Ti, or Zr, and n is 0, 1 Or 2, m is an integer of 1 or more and the valence of M or less, at least one of R ¹ is an alkoxy group; m+n is the valence of M, that is, when it is Al, it is 3, when it is Ti, Zr Time is 4). The copper foil with a mold release layer according to any one of items 1 to 4 of the patent application range, wherein the mold release layer has a resin coating film, the resin coating film is made of polysiloxane, and is selected from epoxy The resin, melamine resin and fluororesin are composed of any one or more resins. The copper foil with a release layer according to any one of items 1 to 4 of the patent application range, wherein between the copper foil and the barrier layer, there is a roughening treatment layer, a heat-resistant layer, a rust prevention layer, One or more layers in the group consisting of a chromate treatment layer and a silane coupling treatment layer. The copper foil with a release layer as claimed in item 14 of the patent scope, wherein the roughening layer is selected from the group consisting of Cu, Ni, P, W, As, Mo, Cr, Ti, Fe, V, Co and A layer composed of any single element in the group composed of Zn or an alloy containing any one or more of the above elements. The copper foil with a release layer according to any one of the items 1 to 4 of the patent application range, wherein the surface of the barrier layer opposite to the copper foil side has a layer selected from the roughening treatment layer and the heat-resistant layer , Anti-rust layer, chromate treatment layer and silane coupling treatment layer composed of more than one layer. The copper foil with a release layer as claimed in item 16 of the patent scope, wherein the roughening layer is selected from the group consisting of Cu, Ni, P, W, As, Mo, Cr, Ti, Fe, V, Co and A layer composed of any single element in the group composed of Zn or an alloy containing any one or more of the above elements. The copper foil with a mold release layer according to any one of the items 1 to 4 of the patent application range, wherein between the copper foil and the mold release layer, there is a treatment selected from the group consisting of a heat-resistant layer, a rust-proof layer, and chromate One or more layers in the group consisting of layers and silane coupling treatment layers. The copper foil with a mold release layer according to any one of claims 1 to 4, wherein a resin layer is provided on the surface of the mold release layer side. A laminate having a copper foil with a release layer according to any one of patent application items 1 to 19. A laminate comprising a copper foil and a resin with a release layer according to any one of claims 1 to 19, and a part or all of the end surface of the copper foil is covered with the resin. A laminate having two copper foils with a release layer according to any one of patent application items 1 to 19, and a resin, and one of the two copper foils with a release layer A surface layer of the release layer side of the copper foil with a release layer and an area layer of the resin, and another surface of the release layer side of the copper foil with a release layer and the other side of the resin Layered. A method for manufacturing a printed wiring board, which uses a copper foil with a release layer according to any one of the patent application items 1 to 19 to manufacture a printed wiring board. A method for manufacturing a printed wiring board, comprising the steps of: laminating a support or an insulating substrate 1 on the release layer side of the copper foil with a release layer according to any one of claims 1 to 19 The step of providing a patterned anti-plating layer on the barrier layer side of the copper foil laminated with the support or the insulating substrate 1 with a release layer; After the copper plating layer is provided on the barrier layer of the plating layer, the anti-plating layer is removed to form a copper-plated circuit; the copper-plated circuit is covered with an insulating substrate 2 to thereby plate the copper The step of embedding the copper circuit; after embedding the copper-plated circuit, removing the support or the insulating substrate 1 on the side surface of the release layer, thereby making the copper foil with the release layer The step of exposing the release layer side surface; the step of removing the copper foil from the exposed release layer side surface by etching to expose the barrier layer surface; and removing the exposed barrier layer by etching A step of exposing the circuit buried in the insulating substrate 2 by this. A method of manufacturing a printed wiring board is to manufacture a printed wiring board using the laminate according to any one of patent application items 20 to 22. An electronic device manufacturing method is to manufacture an electronic device using a printed wiring board manufactured by the method for manufacturing a printed wiring board according to any one of claims 23 to 25.

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