TW201547335A - Surface-processed copper foil, copper foil with carrier, laminated body, printed circuit board, electronic equipment, manufacturing method for surface-processed copper foil and manufacturing method for printed circuit board - Google Patents

Abstract

The present invention provides a surface-processed copper foil with good peeling strength, which is capable of preventing transmission loss even though it is applied to a high frequency circuit board. The surface-processed copper foil of the present invention sequentially comprises: a copper foil, a metal layer including at least one element selected from a group composed of Ni, Co, Zn, W, Mo and Cr, and a surface-processed layer formed with chrome oxide. The adhesion amount of the elements selected from the group composed of Ni, Co, Zn, W, Mo and Cr in the metal layer is 200~2000[mu]g/dm^2. After a heat process for 10 minutes under 250DEG C, if the surface-processed copper foil is soaked in a nitric acid liquid whose concentration is 20mass% and temperature is 25DEG C for 30 seconds under a state that only the surface of the surface-processed layer is exposed, the dissolution amount of copper in the nitric acid liquid is less than 0.0030g/25cm^2.

Description

Surface-treated copper foil, copper foil with carrier, laminated body, printed wiring board, electronic device, method for producing surface-treated copper foil, and method for producing printed wiring board

The present invention relates to a surface-treated copper foil, a copper foil with a carrier, a laminate, a printed wiring board, an electronic device, a method for producing a surface-treated copper foil, and a method for producing a printed wiring board.

From the standpoint of ease of wiring or lightweight, a small electronic device such as a smart phone or a tablet PC uses a flexible printed wiring board (FPC below). Further, in the FPC, there is a two-layer flexible printed wiring board in which a base layer made of a metal or a metal oxide is directly provided on an insulator substrate, and then a double-layer flexible substrate on which a copper conductor layer is formed is used. A subtractive method or an additive method forms a desired wiring pattern.

Such a two-layer flexible printed wiring board widely uses a flat rolled copper foil. In recent years, in order to further improve the bendability and the precision etching property, it is preferable to use a copper foil having a smaller thickness. However, since the crystal size of the high-bend rolled copper foil becomes large after recrystallization, it becomes soft, and when it is a thin foil of 10 μm or less, there is a problem that the apparent peel strength is lowered and the adhesion to the resin substrate occurs. Happening.

Therefore, in order to improve the peel strength, a method of surface-treating the copper foil and the resin with a decane coupling agent containing hexavalent chromium has been proposed, but this method is not a panacea if the amino decane is mixed with hexavalent chromium. Will precipitate.

These prior art techniques are disclosed, for example, in Patent Documents 1 to 5.

In addition, with the increase in the demand for miniaturization and high performance of electronic devices in recent years, high-density mounting of mounted components or high-frequency signals have progressed, and excellent high-frequency response has been demanded for printed wiring boards.

For the high-frequency substrate, in order to ensure the quality of the output signal, it is required to reduce the transmission loss. The transmission loss is mainly caused by the dielectric loss caused by the resin (substrate side) and the conductor loss caused by the conductor (copper foil side). The smaller the dielectric constant and dielectric loss tangent of the resin, the smaller the dielectric loss. In high-frequency signals, the main cause of conductor loss is that the higher the frequency, the lower the cross-sectional area of the current flow due to the skin effect of the current flowing only on the surface of the conductor, and the higher the resistance.

As a technique for reducing the transmission loss of the high-frequency copper foil, for example, Patent Document 6 discloses a metal foil for a high-frequency circuit which is coated with silver or a silver alloy on one or both sides of the surface of the metal foil, in the silver or A coating layer other than silver or a silver alloy is coated on the silver alloy coating layer so as to be thinner than the thickness of the silver or silver alloy coating layer. Further, it is described that the metal foil which can reduce the loss due to the skin effect even in the ultra-high frequency region used for satellite communication can be provided.

Further, Patent Document 7 discloses a roughened copper foil for roughening of a high-frequency circuit, characterized in that the calendering surface of the rolled copper foil after recrystallization annealing has an integral of (200) plane obtained by X-ray diffraction. The intensity (I(200)) of the (200) plane obtained by X-ray diffraction of the fine powder copper is I(200)/I0(200)>40, The arithmetic mean roughness (hereinafter referred to as Ra) of the roughened surface after the roughening treatment of the rolled surface is 0.02 μm to 0.2 μm, and the ten point average roughness (hereinafter referred to as Rz) is 0.1 μm to 1.5 μm. And it is a raw material for printed circuit boards. In addition, the record is provided to provide Printed circuit boards used at high frequencies of 1 GHz.

Further, Patent Document 8 discloses an electrolytic copper foil characterized in that a part of the surface of the copper foil is an uneven surface having a surface roughness of 2 μm to 4 μm. Further, it is described that an electrolytic copper foil excellent in high-frequency transmission characteristics can be provided.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent No. 3292774

[Patent Document 2] Japanese Patent No. 3306404

[Patent Document 3] Japanese Patent No. 3906347

[Patent Document 4] International Publication No. 2009-81889

[Patent Document 5] Japanese Patent Laid-Open No. Hei 11-158652

[Patent Document 6] Japanese Patent No. 4161304

[Patent Document 7] Japanese Patent No. 4704025

[Patent Document 8] Japanese Patent Laid-Open Publication No. 2004-244656

However, when the surface of the copper foil and the resin substrate is surface-treated with a decane coupling agent containing hexavalent chromium, there is a problem in that the peeling strength is rather lowered, which is not matched with the production steps of the double-layer flexible printed wiring board; Further, it promotes aggregation of decane in the decane coupling agent. Further, in Patent Document 5, an electrolytic copper foil is immersed in an alkaline solution of chromic anhydride (chromic anhydride: 6 g/L; sodium hydroxide: 15 g/L; pH: 12.5; bath temperature: 25 ° C) for 5 seconds. In the copper foil A surface-treated copper foil is formed on both sides of the rust-preventing film. However, if a treatment liquid having a high pH is used, NaOH and KOH are removed from the treatment liquid and dried to form a salt, and a good salt cannot be obtained. Peel strength.

Further, regarding the transmission loss, the conductor loss caused by the conductor (copper foil side) is as described above, and the resistance is increased due to the skin effect, but it is known that the resistance not only affects the resistance of the copper foil itself but also has an influence. The surface treatment layer is formed by a roughening treatment on the surface of the copper foil to ensure adhesion to the resin substrate. Specifically, the roughness of the surface of the copper foil is a main factor of conductor loss. The smaller the roughness, the less the transmission loss.

Therefore, an object of the present invention is to provide a surface-treated copper foil which is excellent in peel strength and can satisfactorily suppress transmission loss even when used for a high-frequency circuit board.

The inventors of the present invention conducted intensive studies and found that a surface treatment layer of chromium oxide was formed on the surface of the copper foil and the resin substrate, and a metal layer of a specific element and adhesion amount was provided between the surface treatment layer and the copper foil. Moreover, the amount of copper eluted when the surface-treated layer was immersed in a nitric acid bath of a specific condition was controlled, whereby the peeling strength of the surface-treated copper foil became good.

The present invention based on the above findings is a surface-treated copper foil having a copper foil in a sequence of one or more selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr. a metal layer of an element in the group and a surface treatment layer formed of chromium oxide, wherein the total amount of the elements selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr is 200~ when the nitrate bath was immersed 2000μg / dm ^2, subjected to heat treatment × 10 min 250 deg.] C, as to be exposed only the surface of the surface treatment layer in a concentration of 20mass% and a temperature of 25 ℃ for 30 seconds, the copper in the nitric acid bath elution The amount is 0.0030 g / 25 cm ² or less.

In one embodiment of the surface-treated copper foil of the present invention, the total amount of the elements selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr in the metal layer is 200 to 1500 μg/dm ² .

In another embodiment of the surface-treated copper foil of the present invention, the total amount of the elements selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr in the metal layer is 200 to 1000 μg/dm ² .

In still another embodiment of the surface-treated copper foil according to the present invention, the total amount of the elements selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr in the metal layer is 200 to 700 μg/dm. ² .

In still another embodiment of the surface-treated copper foil according to the present invention, the amount of the hexavalent chromium adhered to the surface-treated layer is 0.1% or less of the adhesion amount of the trivalent chromium.

In still another embodiment of the surface-treated copper foil of the present invention, the surface treated layer has a thickness of 0.1 to 2.5 nm.

In still another embodiment of the surface-treated copper foil of the present invention, the metal layer contains a heat-discoloring preventing layer and/or a rust-preventing layer.

In still another embodiment of the surface-treated copper foil according to the present invention, the heat-discoloring preventing layer and the rust-preventing layer are each Zn, Cu or an alloy thereof.

In still another embodiment of the surface-treated copper foil of the present invention, the rustproof layer contains a chromate layer or a zinc chromate layer.

In still another embodiment of the surface-treated copper foil of the present invention, the metal The layer contains a decane coupling layer.

In still another embodiment of the surface-treated copper foil of the present invention, a decane coupling layer is formed on the surface-treated layer.

In still another embodiment of the surface-treated copper foil of the present invention, the surface of the surface treatment layer is provided with a resin layer.

In still another embodiment of the surface-treated copper foil of the present invention, the surface of the decane coupling layer is provided with a resin layer.

In still another embodiment of the surface-treated copper foil of the present invention, the resin layer contains a dielectric.

In another aspect, the present invention is a copper foil with carrier, the copper foil with carrier has an intermediate layer and an ultra-thin copper layer on one or both sides of the carrier, and the ultra-thin copper layer is the surface treatment of the present invention. Copper foil.

In an embodiment of the copper foil with a carrier of the present invention, one side of the carrier has the intermediate layer and the ultra-thin copper layer, and the other side of the carrier has a roughened layer.

Still another aspect of the invention is a laminate of the surface-treated copper foil of the present invention and a resin substrate.

In an embodiment of the laminated body of the present invention, the surface-treated copper foil and the resin substrate are laminated without using an adhesive.

Still another aspect of the present invention is a laminate of a copper foil with a carrier and a resin substrate of the present invention.

Still another aspect of the present invention is a laminate comprising the present invention The carrier copper foil and the resin are provided, and part or all of the end faces of the copper foil with the carrier are covered with the above resin.

Still another aspect of the present invention is a laminate in which a copper foil with a carrier of the present invention is laminated from the side of the carrier or the side of the ultra-thin copper layer to the carrier side of another copper foil with a carrier of the present invention or The above-mentioned extremely thin copper layer is formed on the side.

In one embodiment, the laminate of the present invention is the carrier side surface of the one of the carrier-attached copper foils or the ultra-thin copper layer side surface and the carrier side surface of the other carrier copper foil or the ultra-thin copper layer. The side surface is formed by directly laminating via an adhesive as needed.

In another embodiment of the laminated body of the present invention, the carrier or the ultra-thin copper layer of the one of the carrier-attached copper foils is bonded to the carrier or the ultra-thin copper layer of the other carrier-attached copper foil.

In still another embodiment of the laminated body of the present invention, part or all of the end surface of the laminated body is covered with a resin.

Still another aspect of the present invention is a method of producing a printed wiring board using the laminated body of the present invention.

According to still another aspect of the present invention, in a method of manufacturing a printed wiring board, the method of manufacturing the printed wiring board includes the steps of: providing a layer of a resin layer and a circuit at least once in the layered body of the present invention; And after the two layers of the resin layer and the circuit are formed at least once, the ultra-thin copper layer or the carrier is peeled off from the copper foil with a carrier of the laminate.

In still another aspect of the invention, there is provided a printed wiring board comprising the laminate of the invention as a material.

Still another aspect of the present invention is the electric power provided with the printed wiring board of the present invention. Child machine.

According to still another aspect of the present invention, in a method of producing a surface-treated copper foil according to the present invention, the method for producing a surface-treated copper foil includes the step of providing a chromate solution on a surface of a entire processing target of the copper foil. And a step of forming a surface treatment layer of chromium oxide by setting the chromate solution on the surface of the copper foil and then drying it without washing with water.

In an embodiment of the method for producing a surface-treated copper foil according to the present invention, in the step of forming the surface treatment layer of the chromium oxide, the chromate solution is placed on the surface of the copper foil, and then deliquored, and then When washing with water, it is dried, thereby forming a surface treatment layer of chromium oxide.

In another embodiment of the method for producing a surface-treated copper foil according to the present invention, the amount of the chromate solution on the surface of the copper foil is 5 to 20 mg/dm ² after the deliquoring.

In another embodiment of the method for producing a surface-treated copper foil according to the present invention, the liquid removal is performed by blowing a roll, a blade, and/or a gas.

In another embodiment of the method for producing a surface-treated copper foil according to the present invention, the step of providing the chromate solution on the entire surface of the copper foil to be treated is performed by applying a chromate solution to the surface by using a shower. The surface of the copper foil is carried out.

In another embodiment of the method for producing a surface-treated copper foil according to the present invention, the step of providing the chromate solution on the entire surface of the copper foil to be treated is to apply the chromate solution to the copper by using a roller. The foil surface is carried out.

In another embodiment of the method for producing a surface-treated copper foil according to the present invention, the chromate solution has a pH of 1 to 10.

In another embodiment of the method for producing a surface-treated copper foil of the present invention, The pH of the chromate solution is 4-10.

According to still another aspect of the present invention, in a method of manufacturing a printed wiring board, the method of manufacturing the printed wiring board includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and using the copper foil with the carrier a step of laminating the insulating substrate; after laminating the copper foil with the carrier and the insulating substrate, the copper-clad laminate is formed by peeling off the carrier with the carrier copper foil, and then by semi-additive method (semi The step of forming a circuit by any one of a method of addition, a subtractive method, a partial additive method, or a modified semi-additive method.

In an embodiment of the method of manufacturing a printed wiring board of the present invention, the method of manufacturing the printed wiring board includes the steps of: forming the ultra-thin copper layer side surface or the carrier side surface of the copper foil with a carrier of the present invention a step of forming a resin layer on the surface of the ultra-thin copper layer side of the carrier-attached copper foil or the carrier-side surface in such a manner as to embed the above-mentioned circuit; a step of forming a circuit on the resin layer; and on the resin layer a step of separating the carrier or the ultra-thin copper layer after forming a circuit; and removing the ultra-thin copper layer or the carrier after peeling off the carrier or the ultra-thin copper layer, thereby forming the ultra-thin copper The step of exposing the layer side surface or the above-mentioned carrier side surface and burying the circuit of the above resin layer.

According to still another aspect of the present invention, in a method of manufacturing a printed wiring board, the method includes the steps of laminating the surface of the ultra-thin copper layer or the surface of the carrier side of the copper foil with a carrier of the present invention and a resin substrate. a step of providing a resin layer at least once on the side of the ultra-thin copper layer side or the side of the carrier side on the side opposite to the side on which the resin substrate is laminated with the carrier copper foil And a step of separating the two layers of the circuit; and after forming the two layers of the resin layer and the circuit, the carrier or the ultra-thin copper layer is peeled off from the copper foil with a carrier.

Still another aspect of the present invention is a method of manufacturing a printed wiring board, comprising the steps of: laminating the carrier side surface of the copper foil with a carrier of the present invention and a resin substrate; and the copper foil with the carrier a step of providing the two layers of the resin layer and the circuit at least once on the side of the ultra-thin copper layer on the side opposite to the side on which the resin substrate is laminated; and after forming the two layers of the resin layer and the circuit, the above-mentioned extremely thin The step of peeling off the copper layer from the above-mentioned carrier copper foil.

According to the present invention, it is possible to provide a surface-treated copper foil which is excellent in peel strength and can satisfactorily suppress transmission loss even when used for a high-frequency circuit substrate.

1A to 1C are schematic views showing a cross section of a wiring board in a step of a plating circuit and a resist removal in a specific example of a method of manufacturing a printed wiring board with a carrier copper foil according to the present invention.

2D to 2F are cross-sectional views of the wiring board in the step from the laminated resin and the second layer of the carrier-attached copper foil to the laser punching in the specific example of the method of manufacturing the printed wiring board with the carrier copper foil of the present invention. Pattern diagram.

3G to 3I are schematic views of a cross section of the wiring board in the step from the formation of the blind via filling layer to the peeling of the first layer carrier, in a specific example of the method of manufacturing the printed wiring board with the carrier copper foil of the present invention.

4J to 4K are schematic views showing a cross section of the wiring board in the step from the flashing to the step of forming the bump or the copper pillar in the specific example of the method of manufacturing the printed wiring board with the carrier copper foil of the present invention.

[Configuration of surface treated copper foil]

The surface-treated copper foil of the present invention has, in order, a copper foil, a metal layer containing one or more elements selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr, and a surface treatment formed of chromium oxide. Floor.

The form of the copper foil substrate which can be used in the present invention is not particularly limited. Typically, the copper foil used in the present invention may be either an electrolytic copper foil or a rolled copper foil. In general, an electrolytic copper foil is produced by electrically analyzing copper from a copper sulfate plating bath onto a drum of titanium or stainless steel, and the rolled copper foil is produced by repeatedly performing plastic working and heat treatment by a calender roll. Rolled copper foil is used in many cases in applications where bending is required.

As the material of the copper foil substrate, in addition to high-purity copper such as refined copper or oxygen-free copper which is generally used as a conductor pattern of a printed wiring board, for example, Sn-doped copper, Ag-doped copper, added with Cr, or the like may be used. A copper alloy such as Zr or Mg or a copper alloy such as a Cason copper alloy such as Ni or Si. Further, in the present specification, a copper alloy foil is also included when the term "copper foil" is used alone.

Further, the thickness of the copper foil base material is not particularly limited, and is, for example, 1 to 1000 μm, or 1 to 500 μm, or 1 to 300 μm, or 3 to 100 μm, or 5 to 70 μm, or 6 to 35 μm, or 9 to 18 μm.

The surface-treated copper foil of the present invention has a surface-treated layer formed of chromium oxide, and after applying heat treatment at 250 ° C for 10 minutes, in a state where only the surface of the surface-treated layer is exposed at a concentration of 20 mass% and a temperature of 25 ° C When the nitric acid bath was immersed for 30 seconds, the amount of copper eluted in the nitric acid bath was 0.0030 g/25 cm ² or less. As the surface treatment, a metal chromium layer is formed on the surface of the copper foil by sputtering or the like, but the corrosion resistance to the acid is inferior, and there is a possibility that the etching liquid is corroded in the circuit formation step of the flexible substrate. On the other hand, the surface treatment layer of the present invention is formed of chromium oxide, and the amount of copper eluted in the nitric acid bath is 0.0030 g/25 cm ² when immersed in a nitric acid bath at a concentration of 20 mass% and a temperature of 25 ° C for 30 seconds. Since the following methods are controlled, the corrosion resistance to the etching liquid is good. In addition, as described above, the amount of copper eluted in the acid is controlled, and the surface treatment layer is formed densely and uniformly by the chromium oxide. Therefore, the adhesion to the resin substrate is improved, and the peel strength is improved. In addition, the above-mentioned "after heat treatment at 250 ° C for 10 minutes" defines the usual heat treatment conditions for the next step with the polyimide substrate.

In the surface-treated copper foil of the present invention, it is preferable that the amount of the hexavalent chromium adhered to the surface-treated layer is 0.1% or less of the adhesion amount of the trivalent chromium. With such a configuration, the ratio of the amount of adhesion of hexavalent chromium is controlled, which is advantageous in terms of safety.

The surface-treated copper foil of the present invention preferably has a surface-treated layer having a thickness of 0.1 to 2.5 nm. If the thickness of the surface treatment layer is formed thin as described above, the etching removal property and the manufacturing cost of the surface treatment layer become good. The thickness of the surface treatment layer is more preferably from 0.3 to 1 nm.

The metal layer contains one or more elements selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr, and the metal layer is selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr. The total adhesion amount of the above elements is 200 to 2000 μg/dm ² . The content of the one or more elements selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr is 200 to 2000 μg/dm ^{2 so} that the content between the copper foil and the surface treatment layer is selected from Ni a metal layer of one or more elements in a group consisting of Co, Zn, W, Mo, and Cr, whereby the heat resistance of the copper foil is improved, deterioration of peel strength due to heating can be suppressed, and transmission loss can be satisfactorily suppressed. . Here, when the transmission loss is small, the attenuation of the signal at the time of signal transmission at a high frequency is suppressed, and therefore, in a circuit that transmits signals at a high frequency, stable signal transmission can be performed. Therefore, a copper foil having a small value of transmission loss is suitable for use in a circuit for transmitting signals at a high frequency, and thus is preferable. If the total adhesion amount of the element of the metal layer is less than 200 μg/dm ² , a sufficient heat resistance effect cannot be obtained. Further, if the total adhesion amount of the element of the metal layer exceeds 2000 μg/dm ² , there is a problem that the transmission loss increases. The total adhesion amount of the metal element layer is preferably 200 ~ 1500μg / dm ^2, more preferably 200 ~ 1000μg / dm ^2, and further more preferably 200 ~ 700μg / dm ^2. Further, the metal layer may contain any element as an element other than one or more elements selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr, and may contain, for example, Cu, Al, Ti, As, Ag, Fe. , Sn, Si, Zr, V, Mg, Mn, Ca, C, N, S, O, In, Au, Pt, Pd, Os, Rh, Ru, Re, Ir, Pb, Cd, Bi or P, and the like. The total adhesion amount of the elements other than the one or more elements selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr contained in the metal layer is not particularly limited, and is typically 0 to 50000 μg/dm ² , and more typically it is 0 ~ 10000μg / dm ^2, more typically in terms of 0 ~ 5000μg / dm ^2, more typically in terms of 0.5 ~ 2000μg / dm ^2.

For example, in order to further improve the adhesion to the insulating substrate, the metal layer may contain a roughened layer. The roughening treatment can be carried out, for example, by forming roughened particles with copper or a copper alloy. The roughening treatment can be a fine roughening treatment. The roughening treatment layer may be a layer containing any element selected from the group consisting of copper, nickel, cobalt, and zinc, or a layer composed of any one or more alloys. Further, the metal layer may contain a heat discoloration preventing layer and/or a rustproof layer. The heating discoloration preventing layer and the rust preventing layer which prevent Cu diffusion may be formed of Zn, Cu or the like, respectively. The rustproof layer may contain a chromate layer or a zinc chromate layer. Alternatively, the metal layer may also contain a decane coupling layer.

Further, as the decane coupling agent for providing the decane coupling layer, a known decane coupling agent may be used, and for example, an amino decane coupling agent or an epoxy decane coupling agent, a decyl decane coupling agent, or a methacryloxy decane may be used. Coupling agent. Among them, a decane coupling layer formed using an amino decane coupling agent or an epoxy decane coupling agent is preferred. Further, a decane coupling agent may be used: vinyl trimethoxy decane, vinyl phenyl trimethoxy decane, γ-methyl propylene methoxy propyl trimethoxy decane, γ-glycidoxy propyl trimethoxy group. Decane, 4-glycidylbutyltrimethoxydecane, γ-aminopropyltriethoxydecane, N-β(aminoethyl)γ-aminopropyltrimethoxydecane, N-3-(4- (3-aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxydecane, imidazolium, three Decane, γ-mercaptopropyltrimethoxydecane, and the like.

The amino decane coupling agent referred to herein may be a substance selected from the group consisting of N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-(N-styrene). Methyl-2-aminoethylamino)propyltrimethoxydecane, 3-aminopropyltriethoxydecane, bis(2-hydroxyethyl)-3-aminopropyltriethoxydecane, amino Propyltrimethoxydecane, N-methylaminopropyltrimethoxydecane, N-phenylaminopropyltrimethoxydecane, N-(3-propenyloxy-2-hydroxypropyl)-3- Aminopropyltriethoxydecane, 4-aminobutyltriethoxydecane, (aminoethylaminomethyl)phenethyltrimethoxydecane, N-(2-aminoethyl-3-aminopropyl) Trimethoxy decane, N-(2-aminoethyl-3-aminopropyl)tris(2-ethylhexyloxy)decane, 6-(aminohexylaminopropyl)trimethoxynonane, aminophenyl Trimethoxydecane, 3-(1-aminopropoxy)-3,3-dimethyl-1-propenyltrimethoxydecane, 3-aminopropyltris(methoxyethoxyethoxy) Decane, 3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, ω-aminoundecyl Methoxydecane, 3-(2-N-benzylaminoethylaminopropyl)trimethoxynonane, bis(2-hydroxyethyl)-3-aminopropyltriethoxydecane, (N, N -diethyl-3-aminopropyl)trimethoxydecane, (N,N-dimethyl-3-aminopropyl)trimethoxydecane, N-methylaminopropyltrimethoxydecane, N- Phenylaminopropyltrimethoxydecane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxydecane, γ-aminopropyltriethoxy Baseline, N-β(aminoethyl)γ-aminopropyltrimethoxydecane, N-3-(4-(3-aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxy Base decane.

The decane coupling layer is preferably 0.05 mg/m ² to 200 mg/m ² , preferably 0.15 mg/m ² to 20 mg/m ² , preferably 0.3 mg/m ² to 2.0 mg/in terms of ruthenium atom. Set within the range of m ² . When it is in the above range, the adhesion between the base resin and the surface-treated copper foil can be further improved.

[Method for Producing Surface-treated Copper Foil]

A method of producing the surface-treated copper foil of the present invention will be described. First, a rolled copper foil or an electrolytic copper foil is prepared. Then, by a known means, one or more elements selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr are contained, and the total adhesion amount of the elements is 200 to 2000 μg/dm ² . A metal layer is formed on the surface of the copper foil. Further, if necessary, a roughening treatment layer, a heat discoloration preventing layer, a rust preventive layer, a decane coupling layer, or the like is formed in the metal layer by a known means. Further, if necessary, a roughening treatment layer, a heat discoloration preventing layer, a rust preventive layer, a decane coupling layer, and the like are formed between the copper foil and the metal layer by a known means. Next, a chromate solution is provided on the entire surface of the copper foil to be processed. Then, the surface of the copper foil was dried without washing with water, whereby a surface treatment layer of chromium oxide was formed on the surface of the copper foil. In the conventional method, when the surface treatment is performed with a chromate solution, the chromate solution is placed on the surface of the copper foil, and before the drying step, the water is washed a plurality of times in order to remove impurities or the like. However, this water washing causes uneven formation of the chromate layer, which adversely affects the peel strength. On the other hand, in the present invention, the water washing step is not performed, and after the chromate liquid is placed on the entire surface of the copper foil to be treated, the surface of the copper foil is dried without washing, thereby forming uniform chromium. The acid layer improves the peel strength of the surface treated copper foil. The step of disposing the chromate solution on the entire surface of the copper foil can be carried out by applying a chromate solution to the surface of the copper foil by means of a shower, or by coating the chromate solution with a roller. The copper foil may be applied to the surface of the copper foil by applying a chromate solution to the surface of the copper foil. The application of the chromate solution by the shower can be carried out using a known spray nozzle (for example, a spray nozzle manufactured by Spraying Systems Japan Co., Ltd. or a spray nozzle manufactured by Ikei Co., Ltd.). The application of the chromate solution by the roll can be carried out by supplying a chromate solution to the surface of the roll using a known rubber roll or sponge roll, and bringing the surface of the roll into contact with the copper foil. The application of the chromate solution by the blade can be carried out using a known doctor blade or a known blade.

Further, in the method for producing a surface-treated copper foil according to the present invention, in the step of forming a surface treatment layer of chromium oxide, the chromate solution is placed on the surface of the copper foil, and then deliquored, and then washed without water. It is dried under this, thereby forming a surface treatment layer of chromium oxide. This deliquoring can be carried out by blowing a roll, a blade and/or a gas. The chromate solution is placed on the surface of the copper foil in the above manner, and then deliquored to control the amount of chromate liquid on the surface of the copper foil, thereby suppressing adhesion of hexavalent chromium to the product and residue ion (K ⁺ ). It is not easy to be absorbed into the chromate film. Further, the amount of the chromate solution on the surface of the copper foil is preferably 5 to 20 mg/dm ² after the liquid removal. If the amount of the chromate solution on the surface of the copper foil is less than 5 mg/dm ² , there is a problem that the desired peel strength cannot be obtained. Further, if the amount of the chromate liquid set on the surface of the copper foil exceeds 20 mg/dm ² , since it is treated by the solution of the composition described below, there is generation of H ₂ SO ₄ and K added for adjusting the pH. The problem of salt precipitation. Further, when the liquid is removed by the roll, the amount of the chromate solution adhered can be controlled by controlling the force of the contact of the roll with the copper foil. The force at which the roller is brought into contact with the copper foil can be set to be 0.0005 to 0.015 kgf/cm per unit width (1 cm) with respect to the copper foil. By increasing the force of contact between the rolls and the copper foil, the amount of chromate solution on the surface of the copper foil can be reduced. Further, by reducing the force of contact between the roll and the copper foil, the amount of chromate liquid on the surface of the copper foil can be increased.

Further, when the liquid is removed by the blade, the amount of the chromate solution adhered can be controlled by controlling the gap between the blade and the copper foil. The gap between the blade and the copper foil can be set to 0.5 to 3 μm. By increasing the gap between the blade and the copper foil, the amount of chromate solution on the surface of the copper foil can be increased. By reducing the gap between the blade and the copper foil, the amount of chromate solution on the surface of the copper foil can be reduced.

Further, when the liquid is removed by the blowing of the gas, the amount of the chromate solution adhered can be controlled by controlling the flow rate of the gas to be blown while controlling the distance between the gas discharge port of the nozzle for ejecting the gas and the copper foil. The flow rate of the gas to be blown is preferably set to 25 to 1000 L/min. Further, it is preferable to blow the gas in such a manner that the flow rate in the width direction of the copper foil is as equal as possible. In addition, the distance between the gas discharge port and the copper foil can be set to 5 to 150 mm. The amount of chromate liquid on the surface of the copper foil can be reduced by increasing the flow rate of the gas to be blown and/or reducing the distance between the gas discharge port and the copper foil. Further, by reducing the flow rate of the gas to be blown and/or increasing the distance between the gas discharge port and the copper foil, the amount of chromate liquid on the surface of the copper foil can be increased.

The conditions of the chromate solution used for the surface treatment are as follows.

Liquid composition: CrO ₃ : 1 ~ 6g / L, Na ₂ Cr ₂ O ₇ and K ₂ Cr ₂ O ₇ : a total of 1.5 ~ 9g / L

pH value: 1~10, preferably 4~10

Temperature: 10~60°C, preferably 25~40°C

When the treatment liquid having a pH of 1 to 10 is used as described above, even if Ni or the like is used for the base treatment, elution of Ni or the like can be satisfactorily suppressed. Further, when a treatment liquid having a pH of 4 to 10 is used, even if Zn-chromate is used for the substrate treatment, elution of Zn can be favorably suppressed.

Further, as long as it is not clearly described, it is used in the electrolysis, surface treatment, or plating of the present invention. The remainder of the treatment fluid used was water.

[with carrier copper foil]

The copper foil with a carrier which is another embodiment of the present invention has an intermediate layer and an extremely thin copper layer in this order on one side or both sides of the carrier. Further, the above ultra-thin copper layer is the surface-treated copper foil which is one of the embodiments of the present invention described above.

<carrier>

The carrier which can be used in the present invention is typically a metal foil or a resin film, and can be provided, for example, in the following forms: copper foil, copper alloy foil, nickel foil, nickel alloy foil, iron foil, iron alloy foil, stainless steel foil, aluminum foil, aluminum alloy foil An insulating resin film (for example, a polyimide film, a liquid crystal polymer (LCP) film, a polyethylene terephthalate (PET) film, a polyamide film, a polyester film, a fluororesin film, or the like).

As the carrier usable in the present invention, copper foil is preferably used. This is because the conductivity of the copper foil is high, so that the formation of the intermediate layer and the ultra-thin copper layer thereafter becomes easy. Typically, the support can be provided in the form of a rolled copper foil or an electrolytic copper foil. In general, an electrolytic copper foil is produced by electrically analyzing copper from a copper sulfate plating bath onto a drum of titanium or stainless steel, and the rolled copper foil is produced by repeating plastic working and heat treatment by a calender roll. As a material of the copper foil, in addition to high-purity copper such as refined copper or oxygen-free copper, for example, a copper alloy doped with Sn, Ag-doped copper, Cr, Zr or Mg, or the like may be used. A copper alloy such as Si, which is a copper alloy.

The thickness of the carrier which can be used in the present invention is not particularly limited, and may be appropriately adjusted to a thickness suitable for the action as a carrier, and may be, for example, 5 μm or more. However, if it is too thick, the production cost becomes high, so it is usually preferably 35 μm or less. Therefore, typical In other words, the thickness of the carrier is 12 to 70 μm, more typically 18 to 35 μm.

Further, a roughened layer may be provided on the surface on the opposite side of the surface on the side where the ultra-thin copper layer of the carrier is disposed. The roughening treatment layer may be provided by a known method, or may be set by the above-described roughening treatment. Providing the roughened layer on the surface on the opposite side of the surface on the side where the ultra-thin copper layer is provided on the carrier has the advantage that when the carrier is laminated on the surface of the resin substrate or the like from the surface side having the roughened layer, the carrier and the carrier The resin substrate becomes less likely to be peeled off.

<intermediate layer>

An intermediate layer is provided on the carrier. Other layers may be provided between the carrier and the intermediate layer. The intermediate layer used in the present invention is not particularly limited as long as it has a configuration in which the ultra-thin copper layer is difficult to be peeled off from the carrier before the step of laminating the carrier copper foil on the insulating substrate, and on the other hand, the insulating layer is laminated on the insulating substrate. After the step, the ultra-thin copper layer becomes peelable from the carrier. For example, the intermediate layer of the copper foil with a carrier of the present invention may contain an alloy selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, the like, and the like, One or more of a group consisting of an oxide or an organic substance. In addition, the intermediate layer may also be a plurality of layers.

Further, the intermediate layer may have, for example, a configuration in which an element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn is formed from the carrier side. a single metal layer, or an alloy layer composed of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn, a hydrate or an oxide or an organic substance formed of one or two or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn The layer that is formed.

Further, the intermediate layer may have, for example, a configuration in which an element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn is formed from the carrier side. a single metal layer, or an alloy layer composed of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn, Forming thereon a single metal layer composed of one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, or selected from Cr, Ni, An alloy layer composed of one or two or more elements selected from the group consisting of Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn.

Further, as the intermediate layer, a known organic substance can be used as the organic substance, and it is preferable to use at least one of a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid. For example, as a specific nitrogen-containing organic compound, it is preferred to use a triazole compound having a substituent, that is, 1,2,3-benzotriazole, carboxybenzotriazole, N', N'-bis (benzotriazole). Azylmethyl)urea, 1H-1,2,4-triazole and 3-amino-1H-1,2,4-triazole, and the like.

As the sulfur-containing organic compound, mercaptobenzothiazole, sodium 2-mercaptobenzothiazole, trimeric thiocyanate, 2-benzimidazolethiol or the like is preferably used.

As the carboxylic acid, a monocarboxylic acid is particularly preferably used, and among them, oleic acid, linoleic acid, linoleic acid, and the like are preferably used.

Further, the intermediate layer may be formed by, for example, sequentially depositing a nickel layer, a nickel-phosphorus alloy layer or a nickel-cobalt alloy layer and a chromium-containing layer on the carrier. Since the adhesion force of nickel and copper is higher than the adhesion force of chromium and copper, peeling is performed at the interface between the ultra-thin copper layer and the chromium-containing layer when the ultra-thin copper layer is peeled off. Further, it is expected that the nickel of the intermediate layer has a blocking effect of preventing the copper component from diffusing from the carrier to the ultra-thin copper layer. Adhesion amount of nickel in the intermediate layer is preferably from 100μg / dm ² or more and 40000μg / dm ² or less, more preferably 100μg / dm ² or more and 4000μg / dm ² or less, more preferably 100μg / dm ² or more and 2500μg / dm ² or less, more preferably 100 μg/dm ² or more and less than 1000 μg/dm ² , and the amount of chromium deposited in the intermediate layer is preferably 5 μg/dm ² or more and 100 μg/dm ² or less. When the intermediate layer is provided only on one side, it is preferable to provide a rust-proof layer such as a Ni plating layer on the opposite side of the carrier. The chromium layer of the above intermediate layer can be provided by chrome plating or chromate treatment.

If the thickness of the intermediate layer is too thick, there is a case where the thickness of the intermediate layer affects the surface roughness Rz and the glossiness of the surface of the extremely thin copper layer after the surface treatment, and thus the intermediate layer of the surface of the surface layer of the extremely thin copper layer The thickness is preferably from 1 to 1,000 nm, more preferably from 1 to 500 nm, still more preferably from 2 to 200 nm, still more preferably from 2 to 100 nm, and still more preferably from 3 to 60 nm. Furthermore, the intermediate layer can also be arranged on both sides of the carrier.

<very thin copper layer>

An extremely thin copper layer is provided on the intermediate layer. Other layers may be provided between the intermediate layer and the ultra-thin copper layer. The ultra-thin copper layer having the carrier is a surface-treated copper foil which is one of the embodiments of the present invention. The thickness of the ultra-thin copper layer is not particularly limited, and is generally thinner than the carrier, for example, 12 μm or less. Typically it is from 0.5 to 12 μm, more typically from 1.5 to 5 μm. Further, before the ultra-thin copper layer is provided on the intermediate layer, in order to reduce pinholes of the ultra-thin copper layer, it is also possible to perform strike plating using a copper-phosphorus alloy. Examples of the pre-plating include a copper pyrophosphate plating solution. In addition, an extremely thin copper layer can also be provided on both sides of the carrier.

Further, the ultra-thin copper layer of the present application can be formed under the following conditions.

. Electrolyte composition

Copper: 80~120g/L

Sulfuric acid: 80~120g/L

Chlorine: 30~100ppm

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

Leveling agent 2 (amine compound): 10~30ppm

As the above amine compound, an amine compound of the following chemical formula can be used.

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

. Manufacturing conditions

Current density: 70~100A/dm ²

Electrolyte temperature: 50~65°C

Electrolyte line speed: 1.5~5m/sec

Electrolysis time: 0.5 to 10 minutes (adjusted according to the copper thickness and current density)

A laminate (such as a copper clad laminate) can be produced by using the copper foil with a carrier of the present invention. As the laminate, for example, it is possible to sequentially laminate "very thin copper layer / intermediate layer / carrier / resin or prepreg The composition of the material may also be formed by sequentially laminating "carrier/intermediate layer/very thin copper layer/resin or prepreg", or sequentially laminating "very thin copper layer/intermediate layer/carrier/resin or The composition of the prepreg/carrier/intermediate layer/very thin copper layer can also be sequentially laminated with "carrier/intermediate layer/very thin copper layer/resin or prepreg/very thin copper layer/intermediate layer/carrier" In the configuration, a "carrier/intermediate layer/very thin copper layer/resin or prepreg/carrier/intermediate layer/very thin copper layer" may be laminated in this order. The above resin or prepreg may be the above-mentioned resin layer, or may contain a resin, a resin hardener, a compound, a hardening accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, and a pretreatment used in the resin layer described below. Dipping, skeleton materials, etc. Further, the carrier copper foil may be smaller than the resin or prepreg in plan view.

[Resin layer on the surface treated surface]

The surface treated surface of the surface-treated copper foil of the present invention may be provided with a resin layer. The above resin layer may be an insulating resin layer. In the surface-treated copper foil of the present invention, the term "surface-treated surface" refers to the surface treatment after the roughening treatment, when surface treatment for providing a heat-resistant layer, a rust-proof layer, a weather-resistant layer, or the like is performed. After the surface treatment of the surface of the copper foil. In addition, when the surface-treated copper foil is an extremely thin copper layer with a carrier copper foil, the term "surface-treated surface" means a surface for providing a heat-resistant layer, a rust-proof layer, a weather-resistant layer, or the like after the roughening treatment. At the time of the treatment, the surface of the extremely thin copper layer after the surface treatment was performed.

The resin layer may be a resin, that is, an adhesive, or an insulating resin layer in a semi-hardened state (B-stage state) for subsequent use. The semi-hardened state (B-stage state) includes a state in which the insulating resin layer can be stored in an overlapping manner even if the surface is in contact with a finger, and the insulating resin layer can be stored in a superposed manner.

Further, the above resin layer may contain a thermosetting resin or a thermoplastic tree. fat. Further, the above resin layer may contain a thermoplastic resin. The resin layer may contain a known resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and the like. Further, as the resin layer, for example, those described in the following documents (resin, resin curing agent, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton material, etc.) and/or can be used. Or a method of forming a resin layer or a forming apparatus: 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 No. 11-140281, Japan Patent No. 3,184,485, International Publication No. WO97/02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179772, Japanese Patent Laid-Open No. 2002-359444, Japanese Special Japanese Patent No. 2003-304068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003-249739, Japanese Patent No. 4136509, Japanese Patent Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Laid-Open No. 2004-349654, and Japanese Patent No. No. 4,286,060, 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, PCT Publication No. WO2004/005588, JP-A-2006-257153, JP-A-2007-326923, JP-A-2008-111169, JP-A 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, Japanese Patent Laid-Open No. 2011-14727, International Publication No. WO2009/001850, International Publication No. WO2009/145179, International Publication No. WO2011/068157, Japanese Patent Publication No. 2013-19056.

In addition, the type of the resin layer is not particularly limited, and examples thereof include one or more resins selected from the group consisting of epoxy resins, polyimine resins, and polyfunctional cyanates. a compound, a maleimide compound, a polymaleimide compound, a maleimide resin, an aromatic maleimide resin, a polyvinyl acetal resin, a urethane resin, Polyether oxime (also known as polyether sulphone, polyethersulfone), polyether oxime (also known as polyether sulphone, polyethersulfone) resin, aromatic polyamide resin, aromatic polyamide resin polymer, rubber resin, polyamine, Aromatic polyamine, polyamidoximine resin, rubber modified epoxy resin, phenoxy resin, hydroxyl modified acrylonitrile-butadiene resin, polyphenylene oxide, double malayan Amine three Resin, thermosetting polyphenylene ether resin, cyanate resin, carboxylic anhydride, polycarboxylic acid anhydride, linear polymer having crosslinkable functional groups, polyphenylene ether resin, 2,2-bis(4-cyanide) Acid ester phenyl) propane, phosphorus phenol compound, manganese naphthenate, 2,2-bis(4-glycidylphenyl)propane, polyphenylene ether-cyanate resin, oxime modified polymer Amidoxime resin, cyano ester resin, phosphazene resin, rubber modified polyamidoximine resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, phenoxy resin , polymer epoxy resin, aromatic polyamine, fluororesin, bisphenol, block copolymer polyimide resin and cyano ester resin.

Further, when the epoxy resin is a resin having two or more epoxy groups in the molecule and can be used for electrical or electronic materials, it can be used without any problem. Further, the epoxy resin is preferably an epoxy resin obtained by epoxidizing a compound having two or more glycidyl groups in its molecule. Further, one or a mixture of two or more selected from the group consisting of a hydride or a halide of the above epoxy resin: a bisphenol A type epoxy resin or a bisphenol F type epoxy resin may be used. , bisphenol S type epoxy resin, bisphenol AD type epoxy resin, phenol Aldehyde type epoxy resin, cresol novolak type epoxy resin, alicyclic epoxy resin, brominated epoxy resin, phenol novolak type epoxy resin, naphthalene type epoxy resin, brominated bisphenol A type epoxy resin, o-cresol novolac type epoxy resin, rubber modified bisphenol A type epoxy resin, glycidylamine type epoxy resin, isocyanuric acid triglycidyl ester, N, N-diminishing A glycidylamine compound such as glyceryl aniline or a glycidyl ester compound such as tetrahydrophthalic acid diglycidyl ester, a phosphorus-containing epoxy resin, a biphenyl type epoxy resin, a biphenol novolak type epoxy resin, or a trihydroxybenzene. Methane type epoxy resin, tetraphenylethane type epoxy resin.

As the phosphorus-containing epoxy resin, a known phosphorus-containing epoxy resin can be used. Further, the phosphorus-containing epoxy resin is preferably, for example, a molecule having two or more epoxy groups in the molecule derived from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9, An epoxy resin obtained in the form of a derivative of 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide).

(When the resin layer contains a dielectric (dielectric filler))

The above resin layer may contain a dielectric (dielectric filler).

When any of the above resin layers or resin compositions contains a dielectric (dielectric filler), it can be used for forming a capacitor layer to increase the capacitance of the capacitor circuit. The dielectric (dielectric filler) used was BaTiO ₃ , SrTiO ₃ , Pb(Zr-Ti)O ₃ (commonly known as PZT), and PbLaTiO ₃ . A dielectric powder of a composite oxide having a perovskite structure such as PbLaZrO (commonly known as PLZT) or SrBi ₂ Ta ₂ O ₉ (commonly known as SBT).

The dielectric (dielectric filler) can be in powder form. When the dielectric (dielectric filler) is in a powder form, the powder property of the dielectric (dielectric filler) is preferably from 0.01 μm to 3.0. A powdery dielectric (dielectric filler) in the range of μm, preferably in the range of 0.02 μm to 2.0 μm. Further, when a photo is taken on a dielectric by a scanning electron microscope (SEM) and a straight line is formed on the dielectric particles on the photo, the length of the dielectric particle having the longest straight line length across the dielectric particle is used as the dielectric particle. diameter of. Further, the average value of the diameters of the dielectric particles in the measurement field of view is used as the particle diameter of the dielectric.

The resin and/or resin composition and/or compound contained in the resin layer described above is dissolved in, for example, methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetonitrile. Amine, N-methylpyrrolidone, toluene, methanol, ethanol, propylene glycol monomethyl ether, dimethylformamide, dimethylacetamide, cyclohexanone, ethyl cellosolve, N-methyl-2- A resin liquid (resin varnish) is prepared in a solvent such as pyrrolidone, N,N-dimethylacetamide or N,N-dimethylformamide, and is applied to the surface by, for example, roll coating. The roughened surface of the copper foil is treated, and then the solvent is removed by heat drying as needed to prepare a B-stage state. Drying may be carried out, for example, using a hot air drying oven, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C. The composition of the above resin layer may be dissolved using a solvent to obtain a resin solid content of 3 wt% to 70 wt%, preferably 3 wt% to 60 wt%, preferably 10 wt% to 40 wt%, more preferably 25 wt% to 40 wt%. Resin solution. Further, from the environmental point of view, it is most preferable to use a mixed solvent of methyl ethyl ketone and cyclopentanone for dissolution at this stage. Further, the solvent is preferably a solvent having a boiling point of from 50 ° C to 200 ° C.

In addition, the resin layer is preferably a semi-cured resin film having a resin flow rate of 5% to 35% when measured in accordance with MIL-P-13949G in the MIL standard.

In the present specification, the resin fluidity is a value as follows: 4 pieces of 10 cm square samples are sampled from a resin-treated surface-treated copper foil having a resin thickness of 55 μm in accordance with MIL-P-13949G in the MIL specification. In the state in which the four samples were stacked (layered body), the bonding was carried out under the conditions of a pressing temperature of 171 ° C, a pressing pressure of 14 kgf/cm ² , and a pressing time of 10 minutes, and based on the resin outflow weight at this time. The result of the measurement was calculated based on Mathematical Formula 1.

The surface-treated copper foil (resin-treated copper foil with resin) provided with the above resin layer is used in such a manner that after the resin layer is superposed on the substrate, the entire resin layer is thermocompression bonded to the resin layer. Thermal hardening, and secondly, when the surface-treated copper foil is an extremely thin copper layer with a carrier copper foil, the carrier is peeled off to expose an extremely thin copper layer (of course, the surface of the intermediate layer side of the extremely thin copper layer is exposed), from the surface The surface on the opposite side of the roughened side of the treated copper foil forms a specific wiring pattern.

When the surface-treated copper foil with the resin is used, the number of sheets of the prepreg used when manufacturing the multilayer printed wiring board can be reduced. Further, the thickness of the resin layer can be set to ensure the thickness of the interlayer insulation, or the copper-clad laminate can be produced even if the prepreg is not used at all. Further, at this time, the surface primer of the substrate may be coated with an insulating resin to further improve the smoothness of the surface.

Further, when the prepreg material is not used, the material cost of the prepreg material is saved, and the lamination step is also simple, so that it is economically advantageous, and has the following advantages: multilayer printed wiring manufactured according to the thickness of the prepreg material When the thickness of the substrate is reduced, it is possible to manufacture an extremely thin multilayer printed wiring board having a thickness of 100 μm or less.

The thickness of the resin layer is preferably from 0.1 to 120 μm.

If the thickness of the resin layer is thinner than 0.1 μm, the adhesion force is lowered when not interposed When the prepreg is used to laminate the surface-treated copper foil with a resin to a substrate having an inner layer material, it may be difficult to ensure interlayer insulation between the inner layer material and the circuit. On the other hand, if the thickness of the resin layer is thicker than 120 μm, there is a case where it is difficult to form a resin layer having a target thickness by one coating step, which is economically disadvantageous because it takes extra material cost and man-hours.

Further, when a surface-treated copper foil having a resin layer is used for producing an extremely thin multilayer printed wiring board, it is preferable to set the thickness of the above-mentioned resin layer to 0.1 in terms of reducing the thickness of the multilayer printed wiring board. From μm to 5 μm, more preferably from 0.5 μm to 5 μm, still more preferably from 1 μm to 5 μm.

Several examples of the manufacturing steps of the printed wiring board using the copper foil with a carrier of the present invention are exemplified below.

An embodiment of the method for producing a printed wiring board according to the present invention includes the steps of: preparing the copper foil with a carrier of the present invention and an insulating substrate; and laminating the copper foil with the carrier and the insulating substrate; and forming a very thin copper layer After laminating the carrier-attached copper foil and the insulating substrate so as to face the insulating substrate, the copper-clad laminate is formed by the step of peeling off the carrier with the carrier copper foil, and then the semi-additive method and the modified half are formed. A step of forming a circuit by any one of an additive method, a partial addition method, and a subtractive method. The insulating substrate may also be a substrate to which an inner layer circuit is added.

In the present invention, the semi-additive method refers to a method of forming a pattern by plating and etching after performing a thin electroless plating on an insulating substrate or a copper foil seed layer.

Therefore, in an embodiment of the method for producing a printed wiring board of the present invention using a semi-additive method, the method includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and insulating the copper foil with the carrier a step of laminating a substrate; a step of peeling off the carrier of the carrier-attached copper foil after laminating the carrier-attached copper foil and the insulating substrate; and etching by using an acid or the like a step of removing the ultra-thin copper layer exposed by peeling off the carrier by a method such as etching or plasma, or a step of providing a via hole or/and a blind via the resin exposed by etching to remove the ultra-thin copper layer a step of desmear treatment of the region containing the through hole or/and the blind hole; a step of providing an electroless plating layer on the resin and the region including the through hole or/and the blind hole; and the electroless plating layer a step of providing a plating resist; a step of exposing the plating resist and then removing a plating resist in a region where the circuit is formed; and a step of disposing a plating layer in a region where the plating resist is formed to form the circuit The step of removing the above-mentioned plating resist; the step of removing the electroless plating layer in a region other than the region where the above-described circuit is formed by flash etching or the like.

In another embodiment of the method for producing a printed wiring board of the present invention using the semi-additive method, the method includes the steps of: preparing the copper foil with carrier of the present invention and the insulating substrate; and the copper foil and the insulating substrate with the carrier a step of laminating; a step of peeling off the carrier of the carrier-attached copper foil after laminating the carrier-attached copper foil and the insulating substrate; and exposing the carrier by etching or plasma etching using an acid or the like a step of completely removing the copper layer; a step of providing an electroless plating layer on a surface of the resin exposed by removing the ultra-thin copper layer by etching; and a step of providing a plating resist on the electroless plating layer; a step of exposing the plating resist, and then removing the plating resist in the region where the circuit is formed; a step of providing a plating layer in a region where the plating resist is removed to form the circuit; and removing the plating resist; The step of removing the electroless plating layer and the ultra-thin copper layer in a region other than the region where the above-described circuit is formed by flashing or the like.

In the present invention, the modified semi-additive method refers to a method of laminating a metal foil on an insulating layer, protecting a non-circuit forming portion by a plating resist, and thickening the copper thickness of the circuit forming portion by plating. Relief removal, removing the above-mentioned circuit forming portion by (flash) etching An outer metal foil, thereby forming an electrical circuit on the insulating layer.

Therefore, in an embodiment of the method for producing a printed wiring board of the present invention using the improved semi-additive method, the method includes the steps of: preparing the copper foil with carrier of the present invention and the insulating substrate; and the copper foil with the carrier a step of laminating the insulating substrate; and laminating the carrier with the carrier copper foil after laminating the carrier-attached copper foil and the insulating substrate; and providing a through hole or a hole in the ultra-thin copper layer and the insulating substrate exposed by peeling the carrier; a step of blinding holes; a step of desmear treatment of a region containing the above-mentioned through holes or/and blind holes; a step of providing an electroless plating layer to a region containing the above-mentioned through holes or/and blind holes; and peeling off the carrier a step of plating a resist on the surface of the exposed ultra-thin copper layer; a step of forming a circuit by electroplating after the plating resist is disposed; a step of removing the plating resist; and removing by flashing The step of removing the extremely thin copper layer exposed by the plating resist.

Further, the step of forming a circuit on the resin layer may be such that another copper foil with a carrier is bonded to the resin layer from the side of the ultra-thin copper layer, and the above-mentioned circuit is formed using a copper foil with a carrier attached to the resin layer. A step of. Further, another copper foil with a carrier attached to the above resin layer may be the copper foil with a carrier of the present invention. Further, the step of forming a circuit on the above resin layer can be carried out by any one of a semi-additive method, a subtractive method, a partial addition method, or an improved semi-additive method. Further, the copper foil with a carrier on which the circuit is formed on the surface may have a substrate or a resin layer on the surface of the carrier of the copper foil with a carrier.

In another embodiment of the method for producing a printed wiring board of the present invention using the modified semi-additive method, the method comprising the steps of: preparing the copper foil with carrier of the present invention and an insulating substrate; and the copper foil with the carrier a step of laminating an insulating substrate; a step of peeling off the carrier with the carrier copper foil after laminating the copper foil with the carrier and the insulating substrate; and peeling off the carrier a step of providing a plating resist on the exposed ultra-thin copper layer; a step of exposing the plating resist and then removing a plating resist in a region where the circuit is formed; and removing the plating resist to form the circuit a step of arranging the plating layer; a step of removing the plating resist; and a step of removing the electroless plating layer and the ultra-thin copper layer in a region other than the region where the circuit is formed by flash etching or the like.

In the present invention, the partial addition method refers to a method of applying a catalytic core to a substrate on which a conductor layer is provided, a hole through which a through hole or a hole for an auxiliary hole is formed, and etching to form a conductor. In the circuit, if a solder resist or a plating resist is provided as needed, a thickness is applied to the via hole or the auxiliary hole by the electroless plating treatment on the conductor circuit, thereby manufacturing a printed wiring board.

Therefore, in an embodiment of the method for producing a printed wiring board of the present invention using the partial addition method, the method includes the steps of: preparing the copper foil with carrier of the present invention and the insulating substrate; and insulating the copper foil with the carrier a step of laminating the substrate; a step of peeling off the carrier with the carrier copper foil after laminating the carrier-attached copper foil and the insulating substrate; and providing a through hole or/and a blind hole in the ultra-thin copper layer and the insulating substrate exposed by peeling off the carrier a step of performing desmear treatment on a region containing the above-mentioned through holes or/and blind vias; a step of imparting a catalytic core to a region containing the above-mentioned through holes or/and blind via holes; and extremely thinning exposed at the peeling of the above carrier a step of providing an etching resist on the surface of the copper layer; a step of exposing the etching resist to form a circuit pattern; and forming the extremely thin copper layer and the catalytic core by etching or plasma etching using an acid or the like a step of removing the etching resist; removing the ultra-thin copper layer by etching or plasma etching using an acid or the like, and the like The insulating substrate is exposed surface of the core is provided a solder resist or plating step plating resist; not provided in the above-described solder resist or plating resist in the region setting step no electroless plating layer.

In the present invention, the subtractive method refers to a method of selectively removing unnecessary portions of the copper foil on the copper clad laminate by etching or the like to form a conductor pattern.

Therefore, in an embodiment of the method for producing a printed wiring board of the present invention using the subtractive method, the method includes the steps of: preparing the copper foil with carrier of the present invention and the insulating substrate; and the copper foil and the insulating substrate with the carrier a step of laminating; a step of peeling off the carrier of the carrier-attached copper foil after laminating the carrier-attached copper foil and the insulating substrate; and providing a through-hole or/and a blind via in the ultra-thin copper layer and the insulating substrate exposed by peeling off the carrier a step of performing desmear treatment on a region containing the above-mentioned through holes or/and blind vias; a step of providing an electroless plating layer on a region containing the above-mentioned through holes or/and blind via holes; on the surface of the above electroless plating layer a step of providing a plating layer; a step of providing an etching resist on the surface of the plating layer or/and the ultra-thin copper layer; a step of exposing the etching resist to form a circuit pattern; and etching by etching an acid using an acid or the like Or a method of forming an electric circuit by removing the ultra-thin copper layer, the electroless plating layer, and the plating layer by a method such as plasma; and removing the etching resist.

In another embodiment of the method for producing a printed wiring board of the present invention using the subtractive method, the method includes the steps of: preparing the copper foil with a carrier of the present invention and an insulating substrate; and performing the copper foil with the carrier and the insulating substrate a step of laminating; a step of peeling off the carrier with the carrier copper foil after laminating the carrier-attached copper foil and the insulating substrate; and a step of providing a via hole or/and a blind via the ultra-thin copper layer and the insulating substrate exposed by peeling off the carrier a step of desmear treatment of the region containing the through hole or/and the blind hole; a step of providing an electroless plating layer on the region including the through hole or/and the blind hole; forming on the surface of the electroless plating layer a step of providing a plating layer on a surface of the electroless plating layer on which the mask is not formed; a step of providing an etching resist on the surface of the plating layer or/and the ultra-thin copper layer; and the etching resist Exposure to form a circuit pattern a step of forming an electric circuit by removing the ultra-thin copper layer and the electroless plating layer by etching or plasma etching using an etching solution such as an acid; and removing the etching resist.

The step of providing a through hole or/and a blind hole, and the subsequent desmear step may also be omitted.

Here, a specific example of a method of manufacturing a printed wiring board using the carrier-attached copper foil of the present invention will be described in detail using a drawing. In addition, although the copper foil with a carrier which has the ultra-thin copper layer in which the roughening process layer was formed is demonstrated here, it is not limited to this, and the attachment of the ultra-thin copper layer which does not form a roughening process layer can also be used. In the same manner as the carrier copper foil, the following method for producing a printed wiring board is carried out.

First, as shown in FIG. 1-A, a carrier-attached copper foil (first layer) having an extremely thin copper layer having a roughened layer formed on its surface is prepared. Further, in this step, a carrier-attached copper foil (first layer) having a carrier having a roughened layer formed on its surface may be prepared.

Next, as shown in Fig. 1-B, a resist is applied onto the roughened layer of the ultra-thin copper layer, exposed, developed, and the resist is etched into a specific shape. Further, in this step, a resist may be applied to the roughened layer of the carrier, exposed, developed, and the resist is etched into a specific shape.

Next, as shown in Fig. 1-C, after the plating for the circuit is formed, the resist is removed, thereby forming a circuit plating of a specific shape.

Then, as shown in FIG. 2-D, a resin layer is laminated on the ultra-thin copper layer to cover the circuit plating (buried circuit plating), and then another carrier copper foil (second layer) is attached. The bonding is carried out from the side of the extremely thin copper layer. In addition, in this step, the method of covering the circuit plating layer (the method of burying the circuit plating layer) may be performed by disposing a resin on the carrier to laminate the resin layer, and then attaching the other carrier copper foil (the second layer) from the carrier side or the pole. A thin copper layer is carried on.

Next, as shown in Fig. 2-E, the carrier is peeled off from the second layer of the carrier-attached copper foil. Further, when the second layer of the carrier copper foil is attached from the side of the carrier, the ultra-thin copper layer can also be peeled off from the second layer of the carrier-attached copper foil.

Next, as shown in Fig. 2-F, laser drilling is performed at a specific position of the resin layer to expose the circuit plating layer to form a blind hole.

Next, as shown in FIG. 3-G, copper is embedded in the blind via to form a blind via fill layer.

Next, as shown in FIG. 3-H, a circuit plating layer is formed on the blind via filling layer in the manner as shown in FIGS. 1-B and 1-C described above.

Next, as shown in Fig. 3-I, the carrier was peeled off from the first layer of the carrier-attached copper foil. Further, in this step, the ultra-thin copper layer may be peeled off from the first layer of the carrier-attached copper foil.

Next, as shown in FIG. 4-J, the ultra-thin copper layer on both surfaces is removed by flash etching (when the copper foil is provided on the second layer, it is a copper foil, and when the roughened layer of the carrier is provided with the first one) The layer circuit is a carrier when plating, and the surface of the circuit plating layer in the resin layer is exposed.

Next, as shown in Fig. 4-K, bumps are formed on the circuit plating layer in the resin layer, and copper pillars are formed on the solder. Thus, a printed wiring board using the copper foil with a carrier of the present invention was produced.

The above-mentioned other carrier-attached copper foil (second layer) may be a copper foil with a carrier of the present invention, or a conventional copper foil with a carrier may be used, and a usual copper foil may be used. In addition, one or more layers of circuits may be formed on the second layer circuit as shown in FIG. 3-H, and any one of a semi-additive method, a subtractive method, a partial addition method, or an improved semi-additive method may be utilized. The method forms these circuits.

The copper foil with a carrier of the present invention preferably controls the chromatic aberration on the surface of the ultra-thin copper layer in such a manner as to satisfy the following (1). In the present invention, the "chromatic aberration on the surface of the ultra-thin copper layer" means the chromatic aberration on the surface of the ultra-thin copper layer or the chromatic aberration on the surface of the surface-treated layer when various surface treatments such as roughening treatment are performed. That is, the copper foil with a carrier of the present invention preferably satisfies the following (1). The color difference of the roughened surface of the ultra-thin copper layer is controlled. In addition, in the surface-treated copper foil of the present invention, the "roughening treatment surface" is a surface treatment after providing a heat-resistant layer, a rust-preventing layer, a weather-resistant layer or the like after the roughening treatment, and means that the surface treatment is performed. Surface treatment of the surface of copper foil (very thin copper layer). In addition, when the surface-treated copper foil is an ultra-thin copper layer with a carrier copper foil, the "roughening treatment surface" is a surface treatment after the roughening treatment, in order to provide a heat-resistant layer, a rust-proof layer, a weather-resistant layer, or the like. In the case of the surface of the ultra-thin copper layer after the surface treatment.

(1) The surface of the ultra-thin copper layer is a white plate (the X ₁₀ Y ₁₀ Z ₁₀ color system of the white plate (JIS Z8701 1999) when the light source is set to D65 and set to a 10 degree field of view) The values are X ₁₀ =80.7, Y ₁₀ =85.6, Z ₁₀ =91.5, and the object color of the white plate in the L ^* a ^* b ^* color system is L ^* =94.14, a ^* =-0.90, b ^* =0.24 The color difference when the object color is the reference color is 45 or more based on the color difference ΔE*ab of JIS Z8730.

Here, the color difference ΔL (the difference between the CIE luminances L ^* of the two object colors in the L ^* a ^* b ^* color system defined by JIS Z8729 (2004)), Δa (specified by JIS Z8729 (2004)) The difference between the color coordinates a ^* of the two object colors in the L ^* a ^* b ^* color system, Δb (two of the L ^* a ^* b ^* color system specified by JIS Z8729 (2004) The difference of the color coordinates b ^* of the object color is measured by a color difference meter, and black/white/red/green/yellow/blue is added, using the L ^* a ^* b ^* color system based on JIS Z8730 (2009). The comprehensive index expressed is expressed in the form of ΔL: white black, Δa: red green, △ b: yellow blue. Further, ΔE ^* ab is expressed by the following formula using these chromatic aberrations.

The above color difference can be improved by increasing the current density when forming a very thin copper layer The copper concentration in the liquid is adjusted to increase the linear flow rate of the plating solution.

Further, the chromatic aberration may be adjusted by providing a roughening treatment layer by roughening the surface of the ultra-thin copper layer. When the roughening treatment layer is provided, the current density can be made higher than the conventional current density by using an electrolyte containing copper and one or more elements selected from the group consisting of nickel, cobalt, tungsten, and molybdenum (for example, 40~) 60A/dm ² ), and the processing time is adjusted to be shorter than the conventional processing time (for example, 0.1 to 1.3 seconds). When the roughened layer is not provided on the surface of the ultra-thin copper layer, a lower plating current (0.1 to 1.3 A/) can be used by using a plating bath in which the concentration of Ni is twice or more of that of other elements. Dm ² ), and set the processing time to be longer than the previous processing time (20 seconds to 40 seconds), for the surface of an extremely thin copper layer, or a heat-resistant layer, or a rust-proof layer, or a chromate layer, or a decane coupling layer This is achieved by plating a Ni alloy (for example, a Ni-W alloy plating, a Ni-Co-P alloy plating, or a Ni-Zn alloy plating).

If the color difference of the surface of the extremely thin copper layer, that is, the color difference ΔE*ab based on JIS Z8730 is 45 or more, the contrast of the extremely thin copper layer and the circuit becomes, for example, when a circuit is formed on the surface of the ultra-thin copper layer of the carrier copper foil. As a result, the visibility is improved, and the alignment of the circuit can be performed with high precision. The color difference ΔE*ab based on JIS Z8730 on the surface of the ultra-thin copper layer is preferably 50 or more, more preferably 55 or more, still more preferably 60 or more.

When the chromatic aberration on the surface of the ultra-thin copper layer is controlled as described above, the contrast with the circuit plating layer becomes clear, and the visibility becomes good. Therefore, in the manufacturing steps of the above-described printed wiring board, for example, as shown in FIG. 1-C, the circuit plating layer can be formed with high precision at a specific position. Further, according to the above-described method of manufacturing a printed wiring board, a structure in which a circuit plating layer is buried in a resin layer is employed, and therefore, when an extremely thin copper layer is removed by, for example, flash etching as shown in FIG. 4-J, a circuit plating layer is used. Protected by the resin layer, the shape is maintained, whereby the formation of the fine circuit becomes easy. In addition, Since the circuit plating layer is protected by the resin layer, the migration resistance is improved, and the conduction of the circuit wiring can be satisfactorily suppressed. Therefore, the formation of the fine circuit becomes easy. Further, when the ultra-thin copper layer is removed by flash etching as shown in FIG. 4-J and FIG. 4-K, the exposed surface of the circuit plating layer is recessed from the resin layer, and thus it becomes easy to form on the circuit plating layer. The bumps further form a copper pillar on the bumps, and the manufacturing efficiency is improved.

Further, a well-known resin or prepreg can be used as the resin. For example, BT (Bismaleimide III) can be used. A resin or a prepreg as a glass cloth impregnated with a BT resin, an ABF film manufactured by Ajinomoto Fine-Techno Co., Ltd. or ABF. Further, the resin layer and/or the resin and/or the prepreg described in the present specification can be used as the above-mentioned resin.

Further, the copper foil with a carrier used in the above first layer may have a substrate or a resin layer on the surface of the copper foil with a carrier. By having such a substrate or a resin layer, the copper foil with a carrier used for the first layer is supported and becomes less likely to wrinkle, so that productivity is improved. Further, as long as the substrate or the resin layer exhibits an effect of supporting the copper foil with a carrier used for the first layer, all of the substrate or the resin layer can be used. For example, as the substrate or the resin layer, a carrier, a prepreg, a resin layer, or a known carrier, a prepreg, a resin layer, a metal plate, a metal foil, an inorganic compound plate, an inorganic compound foil, or the like described in the specification of the present application can be used. Organic compound plate, organic compound foil.

The surface-treated copper foil of the present invention can be bonded to the resin substrate from the surface treatment layer side to produce a laminated board. The resin substrate is not particularly limited as long as it has characteristics applicable to a printed wiring board or the like. For example, a paper substrate phenol resin, a paper substrate epoxy resin, a synthetic fiber cloth substrate epoxy resin, or a fluorine can be used for the rigid PWB. Resin impregnated cloth, glass cloth-paper composite substrate epoxy resin, Glass cloth-glass non-woven composite substrate epoxy resin and glass cloth substrate epoxy resin, etc. For flexible printed circuit board (FPC), polyester film or polyimide film, liquid crystal polymer (LCP) film, fluororesin can be used. And fluororesin-polyimine composites. Further, since the dielectric loss of the liquid crystal polymer (LCP) is small, it is preferable to use a liquid crystal polymer (LCP) film for the printed wiring board for high-frequency circuit use.

In the case of rigid PWB, the bonding method is a method in which a substrate such as a glass cloth is impregnated with a resin, and a prepreg obtained by curing the resin to a semi-hardened state is prepared. This can be carried out by superposing a copper foil on a prepreg and heating and pressurizing it. In the case of FPC, a substrate such as a liquid crystal polymer or a polyimide film is laminated under a high temperature and high pressure via an adhesive or without an adhesive to a copper foil, or a polyimide precursor is coated and dried. , hardening, etc., thereby making a laminate.

The laminated board of the present invention can be used for various printed wiring boards (PWB), and is not particularly limited. For example, from the viewpoint of the number of layers of the conductor pattern, it can be applied to one-sided PWB, two-sided PWB, and multi-layered PWB (three or more layers). From the viewpoint of the type of the insulating substrate material, it can be applied to rigid PWB, flexible PWB (FPC), and soft and hard composite PWB.

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

In addition, an electronic device can be produced using the printed wiring board, and an electronic device can be produced using the printed circuit board on which the electronic component is mounted, or an electronic device can be produced using the printed circuit board on which the electronic component is mounted.

Further, the printed circuit board is completed by mounting an electronic component on the printed wiring board of the present invention. In the present invention, the "printed wiring board" also includes a printed wiring board, a printed circuit board, and a printed circuit board on which electronic components are mounted.

In addition, an electronic device can be produced using the printed wiring board, and an electronic device can be produced using the printed circuit board on which the electronic component is mounted, or an electronic device can be produced using the printed circuit board on which the electronic component is mounted.

Further, the method for producing a printed wiring board of the present invention may be a method for producing a printed wiring board (hollow method) including the above-described ultra-thin copper layer side surface or the carrier side surface of the copper foil with carrier of the present invention a step of laminating a resin substrate; and a step of providing a resin layer and a circuit layer at least once on the surface of the copper foil side of the carrier on the side of the ultra-thin copper layer or the side of the carrier side laminated on the resin substrate And a step of peeling the carrier or the ultra-thin copper layer from the carrier-attached copper foil after forming the two layers of the resin layer and the circuit. In the hollow method, as a specific example, first, the ultra-thin copper layer side surface or the carrier side surface of the copper foil with a carrier of the present invention is laminated with a resin substrate. Thereafter, a resin layer is formed on the surface of the carrier-attached copper foil on the side opposite to the ultra-thin copper layer side surface on which the resin substrate is laminated or on the side opposite to the carrier side surface. Further, a carrier copper foil may be laminated on the side of the carrier side or the side of the ultra-thin copper layer on the side surface of the side surface of the carrier or the side surface of the ultra-thin copper layer. In this case, a configuration is adopted in which the resin substrate is centered on the both surface sides of the resin substrate in the order of the carrier/intermediate layer/very thin copper layer or the order of the ultra-thin copper layer/intermediate layer/carrier. Carrier copper foil. Another resin layer may be provided on the exposed surface of the ultra-thin copper layer or the carrier at both ends, and after further providing a copper layer or a metal layer, the copper layer or the metal layer is processed to form an electric circuit. It is also possible to provide another resin layer on the circuit in such a manner as to embed the circuit. Further, the formation of such a circuit and the resin layer can be performed once or more (growth method). Then, with respect to the laminated body thus formed (hereinafter also referred to as laminated body B), the ultra-thin copper layer or the carrier of each of the carrier-attached copper foils is peeled off from the carrier or the ultra-thin copper layer to form a hollow substrate. In addition, the hollow substrate described above can also be fabricated using two copper foils with carrier. A laminate having a very thin copper layer/intermediate layer/carrier/carrier/intermediate layer/very thin copper layer as described herein, or having a carrier/intermediate layer/very thin copper layer/very thin copper layer/intermediate layer/ A laminate having a carrier structure or a laminate having a carrier/intermediate layer/very thin copper layer/carrier/intermediate layer/very thin copper layer, and the laminate is used for centering. The surface of the ultra-thin copper layer or the carrier on both sides of these laminated bodies (hereinafter also referred to as laminated body A) is provided with one or more layers of the resin layer and the circuit, and the resin layer and the circuit are provided one or more times. After the two layers, the ultra-thin copper layer or carrier of each of the carrier-attached copper foils is peeled off from the carrier or the ultra-thin copper layer to form a hollow substrate. The laminate described above may also have other layers between the surface of the ultra-thin copper layer, the surface of the carrier, the carrier and the carrier, between the ultra-thin copper layer and the ultra-thin copper layer, and between the ultra-thin copper layer and the carrier. . Further, in the present specification, when the ultra-thin copper layer, the carrier, and the laminated body have other layers on the surface of the ultra-thin copper layer, the surface of the carrier, and the surface of the laminated body, the "surface of the extremely thin copper layer" and the "very thin copper layer side" "surface", "very thin copper surface", "surface of carrier", "carrier side surface", "carrier surface", "surface of laminated body", "surface of laminated body" are surfaces including the other layer ( The most superficial) concept. Further, the laminate is preferably one having an extremely thin copper layer/intermediate layer/carrier/carrier/intermediate layer/very thin copper layer. This is because when the hollow substrate is formed using the laminated body, since an extremely thin copper layer is disposed on the hollow substrate side, it is easy to form an electric circuit on the hollow substrate by using an improved semi-additive method. Further, the reason is that since the thickness of the ultra-thin copper layer is thin, it is easy to remove the ultra-thin copper layer, and after removing the ultra-thin copper layer, it is easy to form a circuit on the hollow substrate by using a semi-additive method.

In the present specification, the "layered body" which is not particularly described as "layered body A" or "layered body B" means a layered body including at least the layered body A and the layered body B.

Further, in the method for producing a hollow substrate, a part or all of the end faces of the carrier-attached copper foil or the laminated body (layered body A) are covered with a resin, and are produced by a build-up method. When the wiring board is printed, the chemical liquid can be prevented from infiltrating between a copper foil with a carrier constituting the intermediate layer or the laminated body and the copper foil with another carrier, and the separation of the extremely thin copper layer from the carrier due to the penetration of the chemical solution can be prevented or Corrosion with the carrier copper foil, which can improve the yield. As the resin "covering a part or all of the end surface of the copper foil with a carrier" or "resin covering a part or all of the end surface of the laminated body", a resin which can be used for the resin layer can be used. Further, in the method for producing a hollow substrate, the copper foil or the laminated body may be a laminated portion of a carrier copper foil or a laminate in a plan view (a laminated portion of the carrier and the ultra-thin copper layer, or a copper foil with a carrier) At least a portion of the outer periphery of another laminated portion of the carrier copper foil is covered with a resin or a prepreg. Moreover, the laminated body (layered body A) formed by the above-described method for producing a hollow substrate can be configured such that a pair of copper foils with carriers can be brought into contact with each other. Further, the copper foil with a carrier may be a laminated portion with a carrier copper foil or a laminate in a plan view (a laminated portion of the carrier and the ultra-thin copper layer, or a laminated portion of the carrier-attached copper foil and another carrier-attached copper foil) A copper foil with a carrier which is entirely covered with a resin or a prepreg. By adopting such a configuration, when the carrier copper foil or the laminated body is viewed in a plan view, the laminated portion of the carrier copper foil or the laminated body is covered with the resin or the prepreg, and the other members can be prevented from the side direction of the portion, that is, relative. The impact is carried out in the direction in which the lamination direction is lateral, with the result that peeling of the carrier and the ultra-thin copper layer or the carrier-attached copper foil from each other during operation can be reduced. Further, by covering the resin or the prepreg so as not to expose the outer periphery of the laminated portion with the carrier copper foil or the laminate, it is possible to prevent the penetration of the interface of the chemical solution into the laminated portion in the chemical treatment step as described above. Thereby, corrosion or erosion of the copper foil with the carrier can be prevented. Further, when a pair of copper foils attached to the laminate is separated from one of the copper foils with a carrier, or when the carrier of the copper foil with the carrier is separated from the copper foil (very thin copper layer), it is necessary to remove the resin by cutting or the like. Or a laminated portion of a copper foil or laminate covered with a prepreg (a laminated portion of a carrier and an extremely thin copper layer, or a copper foil with a carrier and another copper with a carrier) The layered portion of the foil).

The copper foil with a carrier of the present invention can be laminated from the side of the carrier or the side of the ultra-thin copper layer to the side of the carrier or the ultra-thin copper layer of the copper foil with a carrier of the present invention to form a laminate. Further, the carrier side surface of the one of the carrier-attached copper foils or the ultra-thin copper layer side surface may be optionally bonded to the carrier side surface of the other carrier copper foil or the ultra-thin copper via an adhesive. A layered body in which the layer side surfaces are directly laminated. Alternatively, the carrier or the ultra-thin copper layer of the above-mentioned carrier copper foil may be bonded to the carrier or the ultra-thin copper layer of the other carrier-attached copper foil. Here, when the carrier or the ultra-thin copper layer has a surface treatment layer, the "joining" also includes a state in which the surface treatment layer is interposed to each other. Further, part or all of the end faces of the laminate may be covered with a resin.

The lamination of the carriers with each other can be carried out, for example, by the following method, in addition to simply overlapping.

(a) Metallurgical joining methods: welding (arc welding, TIG (tungsten inert gas) welding, MIG (metal inert gas) welding, electric resistance welding, seam welding, spot welding), pressure welding (ultrasonic (welding, friction stir welding), soldering; (b) mechanical joining method: caulking, joint using rivets (joining with self-piercing rivets, joining with rivets), stapler (citcher); (c) physical joint Method: adhesive, (double sided) tape

By joining a part or all of one carrier to a part or all of the other carrier by using the above bonding method, it is possible to manufacture a laminate in which one carrier is laminated with another carrier, and the carrier is contacted with each other in a separable manner. . When one carrier is weakly joined to another carrier to laminate one carrier with another carrier, one carrier can be separated from the other carrier without removing the joint of one carrier with the other carrier. In addition, When one carrier is strongly bonded to another carrier, one carrier can be separated from the other carrier by removing the portion where one carrier is bonded to the other by cutting or chemical polishing (etching, etc.), mechanical grinding, or the like. .

Further, by performing the following steps, a printed wiring board can be produced: a step of providing the resin layer and the circuit layer at least once on the layered body configured as described above; and forming the resin layer and the circuit at least once After the two layers, the step of peeling off the above-mentioned ultra-thin copper layer or carrier from the copper foil with a carrier of the above laminated body. Further, two layers of the resin layer and the circuit may be provided on one or both surfaces of the laminated body.

[Examples]

As Examples 1 to 11 and Comparative Examples 1 to 10, copper foils having the thicknesses shown in Table 1 were prepared, and one of the surfaces was subjected to a plating treatment or a sputtering treatment as shown in Table 1, to form a metal layer (thickness). The treatment layer, the heating discoloration preventing layer, the rustproof layer, or the decane coupling layer). Here, a rolled copper foil of fine copper (JIS H3100 C1100R) manufactured by JX Nippon Mining & Metal Co., Ltd. was used as the copper foils of Examples 1 to 4 and 7 to 11, 17, 18, and Comparative Examples 1 to 4 and 7 to 10. . Further, an electrolytic copper foil HLP foil manufactured by JX Nippon Mining & Metal Co., Ltd. was used as the copper foils of Examples 5 to 6 and Comparative Examples 5 to 6.

Further, the copper foil with a carrier described below was prepared as the copper foil substrate of Examples 12 to 16, and one of the surfaces was subjected to a plating treatment or a sputtering treatment as shown in Table 1 as a metal layer (roughening treatment). a layer, a heat discoloration preventing layer, a rustproof layer, or a decane coupling layer).

In Examples 12 to 14, 16, an electrolytic copper foil having a thickness of 18 μm was prepared as a carrier, and in Example 15, a rolled copper foil (C1100R manufactured by JX Nippon Mining & Metal Co., Ltd.) having a thickness of 18 μm was prepared as a carrier. Then, an intermediate layer is formed on the surface of the carrier under the following conditions, and And an extremely thin copper layer is formed on the surface of the intermediate layer.

. Example 12

<intermediate layer>

(1) Ni layer (Ni plating)

The carrier was plated by a roll-to-roll type continuous plating line under the following conditions, thereby forming an adhesion amount of Ni layer of 1000 μg/dm ² . The specific plating conditions are listed below.

Nickel sulfate: 270~280g/L

Nickel chloride: 35~45g/L

Nickel acetate: 10~20g/L

Boric acid: 30~40g/L

Gloss agent: saccharin, butynediol, etc.

Sodium lauryl sulfate: 55~75ppm

pH: 4~6

Bath temperature: 55~65°C

Current density: 10A/dm ²

(2) Cr layer (electrolytic chromate treatment)

Next, after the surface of the Ni layer formed in (1) was washed with water and pickled, it was continued on a roll-to-roll type continuous plating line, and 11 μg/dm ^{2 was} treated by electrolytic chromate treatment under the following conditions. The adhesion amount of the Cr layer adheres to the Ni layer.

Potassium dichromate 1~10g/L, zinc 0g/L

pH: 7~10

Liquid temperature: 40~60°C

Current density: 2A/dm ²

<very thin copper layer>

Next, after the surface of the Cr layer formed in (2) is washed with water and pickled, the film is continuously rolled on a roll-to-roll type continuous plating line, and a thickness of 1.5 μm is formed on the Cr layer by electroplating under the following conditions. An extremely thin copper layer is used to make an extremely thin copper foil with a carrier.

Copper concentration: 90~110g/L

Sulfuric acid concentration: 90~110g/L

Chloride ion concentration: 50~90ppm

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

Leveling agent 2 (amine compound): 10~30ppm

Further, the following amine compound was used as the leveling agent 2.

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

Electrolyte temperature: 50~80°C

Current density: 100A/dm ²

Electrolyte line speed: 1.5~5m/sec

. Example 13

<intermediate layer>

(1) Ni-Mo layer (nickel-plated molybdenum alloy)

The carrier was plated by a roll-to-roll type continuous plating line under the following conditions, thereby forming an adhesion amount of Ni-Mo layer of 3000 μg/dm ² . The specific plating conditions are listed below.

(liquid composition) sulfuric acid Ni hexahydrate: 50 g/dm ³ , sodium molybdate dihydrate: 60 g/dm ³ , sodium citrate: 90 g/dm ³

(liquid temperature) 30 ° C

(current density) 1~4A/dm ²

(Power-on time) 3~25 seconds

<very thin copper layer>

An extremely thin copper layer is formed on the Ni-Mo layer formed in (1). An extremely thin copper layer was formed under the same conditions as in Example 12 except that the thickness of the ultra-thin copper layer was changed to 2 μm.

. Example 14

<intermediate layer>

(1) Ni layer (Ni plating)

A Ni layer was formed under the same conditions as in Example 12.

(2) Organic layer (organic layer formation treatment)

Next, after the surface of the Ni layer formed in (1) is washed with water and pickled, the surface of the Ni layer is further washed and sprayed for 20 to 120 seconds at a liquid temperature of 40 ° C and a pH of 5 under the following conditions. An aqueous solution is thereby formed into an organic layer containing carboxybenzotriazole (CBTA) at a concentration of 1 to 30 g/L.

<very thin copper layer>

An extremely thin copper layer is formed on the organic layer formed in (2). An extremely thin copper layer was formed under the same conditions as in Example 12 except that the thickness of the ultra-thin copper layer was changed to 3 μm.

. Examples 15, 16

<intermediate layer>

(1) Co-Mo layer (cobalt-plated molybdenum alloy)

The carrier was plated by a roll-to-roll type continuous plating line under the following conditions, thereby forming an adhesion amount of Co-Mo layer of 4000 μg/dm ² . The specific plating conditions are listed below.

(liquid composition) sulfuric acid Co: 50 g/dm ³ , sodium molybdate dihydrate: 60 g/dm ³ , sodium citrate: 90 g/dm ³

(liquid temperature) 30 ° C

(current density) 1~4A/dm ²

(Power-on time) 3~25 seconds

<very thin copper layer>

An extremely thin copper layer is formed on the Co-Mo layer formed in (1). An extremely thin copper layer was formed under the same conditions as in Example 12 except that the thickness of the ultra-thin copper layer was set to 5 μm in Example 15 and 3 μm in Example 16.

Next, under the conditions of Table 2, the surface treatment liquid was applied to the entire copper foil on the rolled copper foil, the electrolytic copper foil or the copper foil with a carrier, or the underlying layer (metal layer) on each of the copper foils. The surface of the object to be treated is further subjected to arbitrary water washing and deliquoring, and then dried. A surface treatment layer is formed.

In addition, the meaning of the column of "coating method of chromate liquid" is as follows.

The "sprinkler" is carried out using a spray nozzle (a standard fan nozzle manufactured by Ikei Co., Ltd., with a spray angle of 90° and a spray volume of 10).

The "roller" was carried out using a sponge roll made of polyvinyl alcohol.

The "blade" was made using a resin blade (polyester, thickness 0.35 mm).

The "impregnation chromate" was carried out by immersing the copper foil in the chromate solution under the conditions described in Table 2 for 2 seconds.

The "electrolytic chromate" was treated by immersing the copper foil in the chromate solution under the conditions described in Table 2, and circulating a current of 1 second at a current density of 2 A/dm ² in the copper foil.

In addition, the meaning of the column of "de-liquidization method" and "de-liquidization conditions" is as follows.

"Roll" means deliquoring using a sponge roll made of polyvinyl alcohol. In addition, the "deliquoring condition" when the "liquid removal method" is "roller" means the pressing force of the roller per unit width of the copper foil.

The "blade" refers to a liquid removal using a squeegee blade (thickness: 0.7 mm). In addition, the "liquid removal condition" when the "liquid removal method" is "blade" means the length (distance) of the gap between the blade and the copper foil.

"Gas blowing" means deaeration by blowing air from a gas blowing nozzle to a copper foil. The distance between the gas discharge port of the gas blowing nozzle and the copper foil was set to 50 mm. In addition, the "deliquoring condition" when the "liquid removal method" is "gas blowing" is the flow rate of the gas that is directed to the copper foil.

In Examples 17 and 18, after the surface treatment layer described above was formed, a decane coupling layer was provided on the surface of the surface treatment layer by performing the following decane coupling treatment.

. Example 17

. The decane used: 3-methacryloxypropyltrimethoxydecane (methacryloxyl decane coupling agent)

. Decane concentration: 0.6 vol% (remaining part: water)

. Processing temperature: 30~40°C

. Processing time: 5 seconds

. Drying after decane treatment: 100 ° C × 3 seconds

. Example 18

. The decane used: N-2-(aminoethyl)-3-aminopropyltrimethoxydecane (amino decane coupling agent)

. Decane concentration: 5.0 vol% (remaining part: water)

. Processing temperature: 45~55°C

. Processing time: 5 seconds

. Drying after decane treatment: 100 ° C × 3 seconds

Each of the samples of the examples and the comparative examples produced as described above was subjected to various evaluations as follows.

. Metal adhesion of metal layer:

(1) Ni, Co, W, Mo adhesion

The measurement of the amount of adhesion of various metals in the metal layer was carried out by dissolving a film of a surface of a copper foil of 50 mm × 50 mm in a solution obtained by mixing HNO ₃ (2% by weight) and HCl (5% by weight), and using ICP. The luminescence spectroscopic analyzer (manufactured by SII NanoTechnology Co., Ltd., SFC-3100) quantified the metal concentration in the solution, and calculated and remitted the amount of metal per unit area (μg/dm ² ). At this time, in order to avoid mixing of the metal adhesion amount which is opposite to the surface to be measured, it is shielded and analyzed as necessary.

(2) Zn and Cr adhesion:

The solution layer was dissolved by boiling in 10% hydrochloric acid for 3 minutes, and the solution was analyzed by atomic absorption analysis, and the amount of Zn attached and the adhesion amount of trivalent and hexavalent chromium (the total adhesion amount of trivalent and hexavalent chromium) ) to conduct an evaluation.

Further, the adhesion amount of hexavalent chromium was measured by diphenyl carbazid spectrophotometry in the following manner.

The copper foil 5 g as a sample was cut into 50 mL of pure water and boiled for 5 minutes to be leached. Then, pure water is added to the liquid obtained by boiling and leaching to make the volume 100 mL, and the obtained liquid is used, followed by "chromium (VI) [Cr (VI)]" as described in 65.2 of JIS K0102. The "65.2.1 diphenylcarbazine absorbance method" in the quantitative method of hexavalent chromium (chromium (VI)) described is measured for hexavalent chromium.

In addition, the neutralization of "65.2.1c) operation 1)" is not performed, and the liquid obtained above is used as "2) "solution of beaker (A)" and "3) "solution of beaker (B)" , after the operation of "65.2.1c) 2)".

Further, the absorptiometer is a Model 220A manufactured by Hitachi. The measurement wavelength of the absorbance was set to 540 nm, and the sample cell was a groove made of glass having an optical path length of 10 mm.

The amount of trivalent chromium attached is trivalent chromium and hexavalent by using the above-mentioned atomic absorption spectrometry. The value of the total amount of adhesion of chromium was calculated by subtracting the value of the amount of adhesion of hexavalent chromium measured by the above-described diphenylcarbazine spectrophotometry.

. Surface treatment layer formed of chromium oxide:

The elements in the surface and depth directions were analyzed by ESCA, and when chromium and oxygen were detected on the surface or at the same depth, it was judged to have a surface treatment layer formed of chromium oxide. Further, the surface analysis using ESCA was performed on each of the examples and the comparative examples described above, and as a result, both chromium and oxygen were detected, and thus the copper foils of the respective examples and comparative examples had surface treatment formed of chromium oxide. Floor.

. Surface treatment layer thickness:

The thickness of the surface treatment layer was converted according to the adhesion amount of trivalent chromium, and the density was 7.2 g/cm ³ . The conversion formula is as follows.

Thickness of surface treated layer (nm) = adhesion amount of trivalent chromium (μg/dm ² ) / density of trivalent chromium 7.2 g/cm ³ × 0.1 (nm × (g/cm ³ ) / (μg / dm ² ) )

. Dissolved in nitric acid:

After heat treatment at 250 ° C for 10 minutes was applied to the sample, the surface of the surface treated layer was exposed to a state of only 25 cm ² using a masking tape, and immersed in a nitric acid bath having a concentration of 20 mass% and a temperature of 25 ° C for 30 seconds. Thereafter, the amount of elution of the sample in the nitric acid bath (g/25 cm ² ) was measured.

Further, the amount of elution was calculated by the following formula.

Dissolution amount (g/25 cm ² ) = weight (g) of a sample before being immersed in a nitric acid bath after heat treatment at 250 ° C for 10 minutes - after heat treatment at 250 ° C for 10 minutes, only a surface treatment layer was used using a masking tape The surface of the sample exposed to a state of 25 cm ² at a concentration of 20 mass% and a temperature of 25 ° C for 30 seconds after immersion in a nitric acid bath for 30 seconds (g)

The weight of the above sample was measured by an electronic balance to 4 (0.1 mg) after the decimal point.

. Peel strength:

The normal peel strength was measured by a tensile tester Autograph 100 in accordance with IPC-TM-650, and the above-described normal peel strength was 0.7 kN/mm or more as a sample which can be used for a copper clad laminate substrate.

. PCT (High Pressure Cooking Test):

The high-pressure cooking test was carried out at 121 ° C under two atmospheric pressures for 48 hours, and the tensile strength was measured by the method of JIS-K7054 using the test piece after the endurance test.

. Transmission loss

With respect to each sample having a thickness of 18 μm, the surface of the copper foil surface-treated side was bonded to a resin substrate (LCP: liquid crystal polymer resin (Vecstar CTZ-50 μm (thickness) manufactured by Kuraray Co., Ltd.)), and then etched. The microstrip line was formed so that the characteristic impedance became 50 Ω, and the transmission coefficient was measured using a network analyzer HP8720C manufactured by HP, and the transmission loss at a frequency of 20 GHz was obtained. Further, the sample having a thickness of the copper foil of less than 18 μm is a thickness of the copper foil and the copper plating after the copper foil is attached to the resin substrate (after that, when the copper foil has a carrier, the carrier is peeled off from the copper foil). The surface of the copper foil was plated with copper in a manner of 18 μm, and the above measurement was performed.

Further, the transmission loss is calculated by the following equation.

Transmission loss (dB/10cm) = 10 × log ₁₀ (output power / input power)

The conditions and evaluation of each test described above are shown in Table 3. In addition, the criteria for passing the peel strength are shown in Table 4.

According to Table 3, with respect to Examples 1 to 18, after heat treatment at 250 ° C for 10 minutes, the surface of the surface-treated layer was exposed, and the mixture was immersed in a nitric acid bath having a concentration of 20 mass% and a temperature of 25 ° C for 30 seconds. The amount of copper eluted in the nitric acid bath was 0.0030 g/25 cm ² or less, and the peel strength was good.

On the other hand, in Comparative Examples 1 to 5 and 10, after heat treatment at 250 ° C for 10 minutes was applied, the surface of the surface-treated layer was exposed, and the nitric acid bath was immersed at a concentration of 20 mass% and a temperature of 25 ° C. At the second time, the amount of copper eluted in the nitric acid bath exceeded 0.0030 g/25 cm ² , and the peel strength was poor.

Further, in Comparative Example 6, since the total amount of the elements selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr in the metal layer was less than 200 μg/dm ² , the peel strength was poor.

Further, in Comparative Examples 7 to 9, since the total adhesion amount of the elements selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr in the metal layer exceeds 2000 μg/dm ² , the peel strength is poor and the transmission loss is large. .

Claims (56)

A surface-treated copper foil having, in order, a copper foil, a metal layer containing one or more elements selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr, and a surface treatment formed of chromium oxide In the layer, the total amount of the elements selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr in the metal layer is 200 to 2000 μg/dm ² , and after heat treatment at 250 ° C for 10 minutes, only When the surface of the surface treatment layer was exposed to the surface of the nitric acid bath at a concentration of 20 mass% and a temperature of 25 ° C for 30 seconds, the amount of copper eluted in the nitric acid bath was 0.0030 g / 25 cm ² or less. The surface-treated copper foil according to the first aspect of the invention, wherein the total amount of the elements selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr in the metal layer is 200 to 1500 μg/dm ² . The surface-treated copper foil according to the second aspect of the invention, wherein the total amount of the elements selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr in the metal layer is 200 to 1000 μg/dm ² . The surface-treated copper foil according to claim 3, wherein the total amount of the elements selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr in the metal layer is 200 to 700 μg/dm ² . The surface-treated copper foil according to the first aspect of the invention, wherein the amount of the hexavalent chromium adhered to the surface treatment layer is 0.1% or less of the adhesion amount of the trivalent chromium. The surface-treated copper foil according to the second aspect of the invention, wherein the amount of the hexavalent chromium adhered to the surface-treated layer is 0.1% or less of the adhesion amount of the trivalent chromium. The surface-treated copper foil according to claim 3, wherein the amount of the hexavalent chromium adhered to the surface treatment layer is 0.1% or less of the adhesion amount of the trivalent chromium. The surface-treated copper foil according to the fourth aspect of the invention, wherein the amount of the hexavalent chromium adhered to the surface treatment layer is 0.1% or less of the adhesion amount of the trivalent chromium. The surface-treated copper foil according to claim 1, wherein the surface treatment layer has a thickness of 0.1 to 2.5 nm. The surface-treated copper foil according to claim 2, wherein the surface treatment layer has a thickness of 0.1 to 2.5 nm. The surface-treated copper foil according to claim 3, wherein the surface treatment layer has a thickness of 0.1 to 2.5 nm. The surface-treated copper foil according to claim 4, wherein the surface treatment layer has a thickness of 0.1 to 2.5 nm. The surface-treated copper foil according to claim 5, wherein the surface treatment layer has a thickness of 0.1 to 2.5 nm. The surface-treated copper foil according to claim 6, wherein the surface treatment layer has a thickness of 0.1 to 2.5 nm. The surface-treated copper foil according to claim 7, wherein the surface treatment layer has a thickness of 0.1 to 2.5 nm. The surface-treated copper foil according to claim 8, wherein the surface treatment layer has a thickness of 0.1 to 2.5 nm. The surface-treated copper foil according to any one of claims 1 to 16, wherein the metal layer contains a heat discoloration preventing layer and/or a rust preventive layer. The surface-treated copper foil according to claim 17, wherein the heat-discoloring preventing layer and the rust-preventing layer are Zn, Cu or the like. The surface-treated copper foil according to claim 17, wherein the rust-preventing layer contains a chromate layer or a zinc chromate layer. The surface-treated copper foil according to claim 18, wherein the rust-preventing layer contains a chromate layer or a zinc chromate layer. The surface-treated copper foil according to any one of claims 1 to 16, wherein the metal layer contains a decane coupling layer. The surface-treated copper foil according to any one of claims 1 to 16, wherein a decane coupling layer is formed on the surface treatment layer. The surface-treated copper foil according to any one of claims 1 to 16, which has a resin layer on the surface of the surface treatment layer. The surface-treated copper foil according to claim 22, which has a resin layer on the surface of the decane coupling layer. The surface-treated copper foil according to claim 23, wherein the resin layer contains a dielectric. The surface-treated copper foil according to claim 24, wherein the resin layer contains a dielectric. A surface-treated copper foil having, in order, a copper foil, a metal layer containing one or more elements selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr, and a surface treatment formed of chromium oxide In the layer, the total amount of the elements selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr in the metal layer is 200 to 2000 μg/dm ² , and after heat treatment at 250 ° C for 10 minutes, only When the surface of the surface treatment layer is exposed, the amount of copper eluted in the nitric acid bath is 0.0030 g/25 cm ² or less when the concentration is 20 mass% and the temperature is 25 ° C in a nitric acid bath for 30 seconds, and the surface-treated copper foil satisfies the following. At least one of (1) to (12): (1) the total adhesion amount of the element selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr in the metal layer is 200 to 1500 μg/dm ² (2) The total adhesion amount of the element selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr in the metal layer is 200 to 1000 μg/dm ² , and (3) the metal layer is selected from Ni , the total deposition amount of ^{200 ~ 700μg / dm 2, (} 4) on the surface treatment layer, hexavalent group consisting of Co, Zn, W, Mo and Cr elements The adhesion amount is 0.1% or less of the adhesion amount of the trivalent chromium, and (5) the thickness of the surface treatment layer is 0.1 to 2.5 nm, and (6) the metal layer contains the heat discoloration prevention layer and/or the rust prevention layer, (7) The heat discoloration preventing layer and the rust preventive layer are Zn, Cu or the like, respectively, (8) the rust preventive layer contains a chromate layer or a zinc chromate layer, and (9) the metal layer contains a decane coupling layer. (10) a decane coupling layer is formed on the surface treatment layer, (11) a resin layer is provided on the surface of the surface treatment layer, and (12) a decane coupling layer is formed on the surface treatment layer, and the decane coupling layer is formed on the surface treatment layer. The surface is provided with a resin layer. A copper foil with a carrier having an intermediate layer and an ultra-thin copper layer on one or both sides of the carrier, and the ultra-thin copper layer is the surface-treated copper foil according to any one of claims 1 to 27. The carrier-attached copper foil according to claim 28, wherein the intermediate layer and the ultra-thin copper layer are sequentially provided on one side of the carrier, and the roughened layer is provided on the other surface of the carrier. A laminate which is a laminate of a surface-treated copper foil and a resin substrate according to any one of claims 1 to 27. The laminate according to claim 30, wherein the surface-treated copper foil and the resin substrate are laminated without using an adhesive. A laminate which is a laminate of a carrier copper foil and a resin substrate of claim 28 or 29. A laminate comprising the carrier copper foil and resin of claim 28 or 29, and a part or all of the end faces of the copper foil with the carrier is covered with the resin. A laminated body in which a copper foil with a carrier of claim 28 or 29 is laminated from the side of the carrier or the side of the above-mentioned ultra-thin copper layer to the copper foil with a carrier of the 28th or 29th patent of another patent application. The carrier side or the ultra-thin copper layer side is formed. The laminate according to claim 34, wherein the carrier side surface of the one of the carrier-attached copper foils or the ultra-thin copper layer side surface and the carrier side surface of the other carrier copper foil or the above-mentioned extremely thin layer The side surface of the copper layer is formed by directly laminating via an adhesive as needed. The laminate according to claim 34, which is the carrier of the above-mentioned one carrier copper foil or the above-mentioned ultra-thin copper layer and the above-mentioned carrier of the other carrier copper foil or the above-mentioned ultra-thin copper Layer bonding. The laminate according to claim 35, wherein the carrier or the ultra-thin copper layer of the carrier-attached copper foil is bonded to the carrier or the ultra-thin copper layer of the other carrier-attached copper foil. As for the laminated body of claim 34, a part or all of the end faces thereof are covered with a resin. As for the laminated body of claim 36, a part or all of the end faces thereof are covered with a resin. A method of producing a printed wiring board using the laminate of any one of claims 30 to 39. A manufacturing method of a printed wiring board, comprising the steps of: providing a laminate of at least one of a resin layer and a circuit at least once in a laminate of any one of claims 30 to 39; and at least one time After the two layers of the resin layer and the circuit are formed, the ultra-thin copper layer or the carrier is peeled off from the copper foil with a carrier of the laminate. A printed wiring board using the laminate of any one of claims 30 to 39 as a material. An electronic machine comprising a printed wiring board of the 42nd patent application. A method for producing a surface-treated copper foil, which is a method for producing a surface-treated copper foil according to any one of claims 1 to 27, which comprises the step of: setting a chromate solution to a whole process of copper foil a step of forming a surface of the object; and a step of forming a chromium oxide liquid on the surface of the copper foil and then drying it without washing with water to form a surface treatment layer of chromium oxide. The method for producing a surface-treated copper foil according to claim 44, wherein in the step of forming the surface treatment layer of the chromium oxide, the chromate solution is placed on the surface of the copper foil, and then deliquored, and then When washing with water, it is dried, thereby forming a surface treatment layer of chromium oxide. The method for producing a surface-treated copper foil according to claim 45, wherein the amount of the chromate solution on the surface of the copper foil is 5 to 20 mg/dm ² after the deliquoring. The method for producing a surface-treated copper foil according to claim 45, wherein the liquid removal is performed by blowing a roll, a blade, and/or a gas. The method for producing a surface-treated copper foil according to claim 46, wherein the liquid removal is performed by blowing a roll, a blade, and/or a gas. The method for producing a surface-treated copper foil according to claim 44, wherein the step of disposing the chromate solution on the entire surface of the copper foil is to apply a chromate solution to the surface by using a shower. The surface of the copper foil is carried out. The method for producing a surface-treated copper foil according to claim 44, wherein the step of disposing the chromate solution on the entire surface of the copper foil is to apply the chromate solution to the copper by using a roller. The foil surface is carried out. The method for producing a surface-treated copper foil according to claim 44, wherein the chromate solution has a pH of 1 to 10. The method for producing a surface-treated copper foil according to claim 51, wherein the chromate solution has a pH of 4 to 10. A manufacturing method of a printed wiring board, comprising the steps of: preparing a carrier copper foil and an insulating substrate of claim 28 or 29; a step of laminating the carrier-attached copper foil and the insulating substrate; and after laminating the copper foil with the carrier and the insulating substrate, the copper-clad laminate is formed by peeling off the carrier with the carrier copper foil, and thereafter, The step of forming a circuit by any one of a semi-additive method, a subtractive method, a partial addition method, or an improved semi-additive method. A method of manufacturing a printed wiring board, comprising the steps of: forming a circuit on the side surface of the ultra-thin copper layer of the carrier-attached copper foil of claim 28 or 29 or the carrier-side surface; A method of forming a resin layer on the surface of the ultra-thin copper layer side of the carrier-attached copper foil or the carrier-side surface; forming a circuit on the resin layer; after forming a circuit on the resin layer, the carrier or a step of peeling off the ultra-thin copper layer; and after removing the carrier or the ultra-thin copper layer, removing the ultra-thin copper layer or the carrier, thereby forming the surface of the ultra-thin copper layer or the side surface of the carrier And the step of exposing the circuit buried in the above resin layer. A manufacturing method of a printed wiring board, comprising the steps of: laminating the above-mentioned ultra-thin copper layer side surface or the carrier side surface of the carrier-attached copper foil of claim 28 or 29 with a resin substrate; a step of providing the resin layer and the circuit layer at least once on the ultra-thin copper layer side surface or the carrier side surface of the carrier-attached copper foil on the side opposite to the side on which the resin substrate is laminated; and forming the resin layer and the circuit After the two layers, the above carrier or the above ultra-thin copper layer is applied from above. The step of peeling off the carrier copper foil is described. A method of manufacturing a printed wiring board, comprising the steps of: laminating the carrier side surface of a carrier copper foil of claim 28 or 29 with a resin substrate; and the resin with the carrier copper foil a step of providing the resin layer and the circuit layer at least once on the surface of the ultra-thin copper layer on the side opposite to the side of the substrate layer; and after forming the two layers of the resin layer and the circuit, the ultra-thin copper layer is formed from the above The step of peeling off the carrier copper foil.