TWI616122B - 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 - Google Patents

Abstract

The present invention provides a surface-treated copper foil that has a good peel strength and can suppress transmission loss well even when used in a high-frequency circuit board. The surface-treated copper foil of the present invention has a copper foil, a metal layer containing one or more elements selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr in this order, and a surface treatment made of chromium oxide. Layer, the metal layer has a total adhesion amount of an element selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr of 200 to 2000 μg / dm ² , and is subjected to heat treatment at 250 ° C. for 10 minutes to be exposed only When the state of the surface of the surface treatment layer 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 dissolved in the nitric acid bath was 0.0030 g / 25 cm ² or less.

Description

Surface-treated copper foil, copper foil with carrier, laminate, printed wiring board, electronic device, method for manufacturing surface-treated copper foil, and method for manufacturing printed wiring board

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

From the perspective of ease of wiring or lightweight, flexible printed wiring boards (hereinafter referred to as FPCs) are used in small electronic devices such as smartphones and tablet PCs. In addition, FPC includes a two-layer flexible printed wiring board in which a base layer made of metal or metal oxide is directly provided on an insulator substrate, and then a two-layer flexible substrate formed with a copper conductor layer is used. A subtractive method or an additive method forms a desired wiring pattern.

Such double-layer flexible printed wiring boards widely use flat rolled copper foil. In recent years, in order to further improve the bendability and precision etchability, it is preferable to use a thinner copper foil. However, a highly flexible rolled copper foil has a large crystal size after recrystallization, and therefore becomes soft. When the foil is thinner than 10 μm, the apparent peel strength is lowered, which causes problems in bonding with a resin substrate. Happening.

Therefore, in order to improve the peel strength, a method of surface-treating the bonding surface of copper foil and resin with a hexavalent chromium-containing silane coupling agent has been proposed. However, this method is not universal. , It will precipitate.

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

In addition, with the increasing demand for miniaturization and high performance of electronic devices in recent years, high-density mounting of mounted components or high-frequency signals have been developed, and excellent high-frequency response to printed wiring boards is required.

For high frequency substrates, in order to ensure the quality of output signals, it is required to reduce transmission loss. The transmission loss is mainly caused by a dielectric loss caused by a resin (substrate side) and a conductor loss caused by a conductor (copper foil side). The smaller the dielectric constant and the dielectric loss tangent of the resin, the smaller the dielectric loss. The main reason for conductor loss in high-frequency signals is that the higher the frequency, the smaller 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 high-frequency copper foil, for example, Patent Document 6 discloses a metal foil for a high-frequency circuit, which is covered with silver or a silver alloy on one or both sides of the surface of the metal foil. 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. In addition, it is described that a metal foil capable of reducing a loss due to a skin effect even in an ultra-high frequency region such as that used in satellite communications is described.

In addition, Patent Document 7 discloses a roughened rolled copper foil for a high-frequency circuit, which is characterized by an integral of the (200) plane obtained by X-ray diffraction of a rolled surface of the rolled copper foil after recrystallization annealing. The intensity (I (200)) is I (200) / I0 (200)> 40 relative to the integrated intensity (I0 (200)) of the (200) plane obtained by X-ray diffraction of fine powder copper. The arithmetic average roughness (hereinafter referred to as Ra) of the roughened surface after roughening the rolled surface by electroplating 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, it is documented that this can provide A printed circuit board used at a high frequency of 1 GHz.

Furthermore, Patent Document 8 discloses an electrolytic copper foil characterized in that a part of the surface of the copper foil is a concave-convex surface having a surface roughness of 2 μm to 4 μm formed by a nodular protrusion. In addition, it is described that an electrolytic copper foil excellent in high-frequency transmission characteristics can be provided by this.

[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. 11-158652

[Patent Document 6] Japanese Patent No. 4161304

[Patent Document 7] Japanese Patent No. 4704025

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

However, when a silane coupling agent containing hexavalent chromium is used to surface-treat the bonding surface of the copper foil and the resin substrate, the following problems arise: the manufacturing steps of the double-layer flexible printed wiring board are not matched, and the peel strength is reduced; Furthermore, it promotes agglomeration of silane in the silane coupling agent. In Patent Document 5, electrolytic copper foil is immersed in an alkaline solution of chromic anhydride (chromic anhydride: 6g / L; sodium hydroxide: 15g / L; pH value: 12.5; bath temperature: 25 ° C) for 5 seconds. In the copper foil On both sides, a rust-proof film is formed to produce a surface-treated copper foil. However, if a treatment solution having such a high pH value is used, after removing NaOH and KOH from the treatment solution and drying them, a salt is formed, and good results cannot be obtained. Peel strength.

As for the transmission loss, as described above, the conductor loss caused by the conductor (copper foil side) is caused by the skin effect, which increases the resistance. However, it is known that this resistance affects not only the resistance of the copper foil itself, but also the resistance. The resistance of the surface treatment layer is formed by roughening the surface of the copper foil in order to ensure the adhesion to the resin substrate. Specifically, the roughness of the surface of the copper foil is the main factor of conductor loss. The smaller the roughness, the lower the transmission loss.

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

The inventors conducted earnest research repeatedly, and as a result, found that a surface treatment layer of chromium oxide was formed on the side of the copper foil surface and the resin substrate, and a metal layer of a specific element and an adhesion amount was provided between the surface treatment layer and the copper foil. In addition, by controlling the amount of copper eluted when the surface-treated layer is immersed in a nitric acid bath under specific conditions, the peel strength of the surface-treated copper foil becomes good.

The present invention completed based on the above findings is, in one aspect, a surface-treated copper foil having, in order, a copper foil containing one or more members 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. 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 2000 μg / dm ² , after applying a heat treatment at 250 ° C. for 10 minutes, immersed in a nitric acid bath having a concentration of 20 mass% and a temperature of 25 ° C. for 30 seconds in a state in which only the surface of the surface treatment layer is exposed, the dissolution of copper in the nitric acid bath 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 adhesion amount of an 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 .

In another embodiment of the surface-treated copper foil of the present invention, a total adhesion amount of an 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 .

In still another embodiment of the surface-treated copper foil of the present invention, a total adhesion amount of an element 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 of the present invention, in the above-mentioned surface-treated layer, the amount of hexavalent chromium deposited is 0.1% or less of the amount of trivalent chromium deposited.

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

In still another embodiment of the surface-treated copper foil of the present invention, the metal layer includes a heat discoloration prevention layer and / or a rust prevention layer.

In still another embodiment of the surface-treated copper foil of the present invention, the heating discoloration preventing layer and the rust preventing layer are each made of Zn, Cu, or an alloy thereof.

In still another embodiment of the surface-treated copper foil of the present invention, the rust preventive layer includes 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 silane coupling layer.

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

In still another embodiment of the surface-treated copper foil of the present invention, the surface of the silane coupling layer includes 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 a carrier. The copper foil with a carrier has an intermediate layer and an ultra-thin copper layer in sequence on one or both sides of the carrier. The ultra-thin copper layer is the surface treatment of the present invention. Copper foil.

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

In another aspect, the present invention is a laminated body of the surface-treated copper foil and the resin substrate of the present invention.

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

The present invention is still another aspect of the present invention is a laminated body of the copper foil with a carrier and a resin substrate of the present invention.

The invention in still another aspect is a laminated body comprising the invention Copper foil with a carrier and resin, and a part or all of the end surface of the copper foil with a carrier is covered with the resin.

The present invention is still another aspect of the present invention is a laminated body, wherein one copper foil with a carrier of the present invention is laminated from the carrier side or the ultra-thin copper layer side on the carrier side of another copper foil with a carrier of the present invention or The above-mentioned extremely thin copper layer side.

In one embodiment, the laminated body of the present invention is the carrier side surface or the ultra-thin copper layer side surface of the one copper foil with a carrier and the carrier side surface or the ultra-thin copper layer of the other copper foil with a carrier. The side surface is configured by directly laminating the adhesive through an adhesive, if necessary.

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

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

This invention is another one aspect. The manufacturing method of the printed wiring board using the laminated body of this invention.

According to yet another aspect of the present invention, a method for manufacturing a printed wiring board is provided. The method for manufacturing a printed wiring board includes the following steps: performing the step of setting the two layers of the resin layer and the circuit at least once in the laminated body of the present invention; And a step of peeling the ultra-thin copper layer or the carrier from the copper foil with a carrier of the laminated body after the two layers of the resin layer and the circuit are formed at least once.

The present invention is still another aspect of a printed wiring board using the laminated body of the present invention as a material.

According to still another aspect of the present invention, there is provided a circuit board including the printed wiring board of the present invention. Child machine.

According to still another aspect of the present invention, there is provided a method for producing a surface-treated copper foil of the present invention. The method for producing a surface-treated copper foil includes the steps of: providing a chromate solution on the entire surface of a copper foil to be treated And a step of forming a surface treatment layer of chromium oxide by placing the chromate solution on the surface of the copper foil and drying it without washing with water.

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

In another embodiment of the manufacturing method of the surface-treated copper foil of this invention, the quantity of the said chromate solution provided on the copper foil surface is 5-20 mg / dm <^2> after the said liquid removal.

In another embodiment of the manufacturing method of the surface-treated copper foil of this invention, the said liquid removal is performed by blowing with 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 to apply the chromate solution to a shower by using a shower. It was performed on the surface of the said copper foil.

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. On the foil surface.

In another embodiment of the manufacturing method of the surface-treated copper foil of this invention, pH value of the said chromate solution is 1-10.

In another embodiment of the manufacturing method of the surface-treated copper foil of this invention, an upper The pH value of the chromate solution is 4-10.

In yet another aspect, the present invention is a method for manufacturing a printed wiring board. The method for manufacturing a printed wiring board includes the steps of: preparing the copper foil with a carrier and an insulating substrate of the present invention; A step of laminating an insulating substrate; after laminating the copper foil with a carrier and the insulating substrate, a step of peeling the carrier of the copper foil with a carrier is formed to form a copper-clad laminate, and thereafter, a semi-additive method step of forming a circuit by any one of an additive method, a subtractive method, a partially additive method, or a modified semi additive method.

In one embodiment of the method for manufacturing a printed wiring board according to the present invention, the method for manufacturing the printed wiring board includes the steps of forming 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. A step of forming a circuit; a step of forming a resin layer on the ultra-thin copper layer side surface of the copper foil with a carrier or the surface of the carrier side by burying the circuit; a step of forming a circuit on the resin layer; on the resin layer A step of peeling the carrier or the ultra-thin copper layer after forming the circuit; and removing the carrier or the ultra-thin copper layer after removing the carrier or the ultra-thin copper layer, thereby forming the carrier on the ultra-thin copper The step of exposing the circuit on the layer side surface or the carrier side surface and buried in the resin layer.

According to yet another aspect of the present invention, a method for manufacturing a printed wiring board includes the steps of: laminating the ultra-thin copper layer side surface of the copper foil with a carrier or the carrier side surface of the present invention with a resin substrate. Step; at least once setting the resin layer on the surface of the ultra-thin copper layer on the side of the copper foil with a carrier opposite to the side where the resin substrate is laminated or on the carrier side And a step of peeling off the carrier or the ultra-thin copper layer from the copper foil with the carrier after the two layers of the resin layer and the circuit are formed.

According to yet another aspect of the present invention, a method for manufacturing a printed wiring board includes the steps of: laminating the carrier-side surface of the copper foil with a carrier of the present invention and a resin substrate; and laminating the copper foil with a carrier. The step of setting the two layers of the resin layer and the circuit at least once on the side surface of the ultra-thin copper layer opposite to the side of the resin substrate laminated layer; and after forming the two layers of the resin layer and the circuit, The step of peeling the copper layer from the copper foil with a carrier as described above.

According to the present invention, it is possible to provide a surface-treated copper foil that has a good peel strength and that can suppress transmission loss well even when used in a high-frequency circuit board.

FIGS. 1A to 1C are schematic diagrams of a cross section of a wiring board in a specific example of a method for manufacturing a printed wiring board using a copper foil with a carrier according to the present invention, in steps from plating a circuit to removing a resist.

FIGS. 2D to 2F are cross-sectional views of a wiring board in a specific example of a method for manufacturing a printed wiring board using a copper foil with a carrier according to the present invention, in steps from laminating resin and a second layer of copper foil with a carrier to laser drilling; Pattern illustration.

FIGS. 3G to 3I are schematic diagrams of a cross section of a wiring board in a specific example of a method for manufacturing a printed wiring board using a copper foil with a carrier according to the present invention, from a step of forming a blind hole filling layer to peeling off a first-layer carrier.

FIGS. 4J to 4K are schematic diagrams of a cross section of a wiring board in a specific example of a method for manufacturing a printed wiring board using a copper foil with a carrier according to the present invention, in steps from flash etching to formation of bumps and copper pillars.

[Composition of surface-treated copper foil]

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

The form of the copper foil substrate that can be used in the present invention is not particularly limited. Typically, the copper foil used in the present invention can be any one of an electrolytic copper foil and a rolled copper foil. Generally speaking, electrolytic copper foil is produced by electrolyzing copper from a copper sulfate plating bath onto a titanium or stainless steel drum, and rolled copper foil is produced by repeatedly performing plastic processing and heat treatment using a calender roll. In applications where flexibility is required, rolled copper foil is often used.

As the material of the copper foil base material, in addition to high-purity copper such as fine 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, Cr added, Copper alloys such as Zr or Mg, and copper alloys such as Carson-based copper alloys to which Ni and Si are added. In addition, in this specification, when the term "copper foil" is used alone, a copper alloy foil is also included.

The thickness of the copper foil substrate 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 made of chromium oxide. After applying a heat treatment at 250 ° C for 10 minutes, 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 from the nitric acid bath was 0.0030 g / 25 cm ² or less. As a surface treatment, a metal chromium layer may be formed on the surface of a copper foil by sputtering or the like, but the corrosion resistance to acid is poor, and there is a possibility of being corroded by the etchant during the circuit formation step of the flexible substrate. In contrast, the surface treatment layer of the present invention is formed of chromium oxide, and the amount of copper dissolved in the nitric acid bath when immersed in a nitric acid bath having a concentration of 20 mass% and a temperature of 25 ° C. for 30 seconds is 0.0030 g / 25 cm ² Since the control is performed in the following manner, the corrosion resistance to the etchant is good. In addition, as described above, the amount of copper dissolved in the acid is controlled, which means that the surface treatment layer is densely and uniformly formed with chromium oxide, and therefore, the adhesiveness with the resin substrate becomes good, and the peel strength is improved. In addition, the above “after applying a heat treatment at 250 ° C. for 10 minutes” specifies the general heat treatment conditions when bonding to a polyimide substrate.

In the surface-treated copper foil of the present invention, in the surface-treated layer, the adhesion amount of hexavalent chromium is preferably 0.1% or less of the adhesion amount of trivalent chromium. With this configuration, the proportion of the amount of hexavalent chromium deposited is controlled, which is advantageous in terms of safety.

In the surface-treated copper foil of the present invention, the thickness of the surface-treated layer is preferably 0.1 to 2.5 nm. If the thickness of the surface-treated layer is formed thin as described above, the etching-removability and manufacturing cost of the surface-treated layer will be good. The thickness of the surface treatment layer is more preferably 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 includes one 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 . In selected from the group consisting of Ni, the total deposition amount of the group consisting of Co, Zn, W, Mo and Cr is one or more elements 200 ~ 2000μg / dm ² embodiment is provided selected from the group consisting of Ni contained in the surface treatment layer between the copper foil and the , Co, Zn, W, Mo, and Cr, a metal layer of one or more elements in the group, thereby improving the heat resistance of the copper foil, suppressing the degradation of the peeling strength due to heating, and suppressing the transmission loss well . Here, when the transmission loss is small, the attenuation of the signal when the signal is transmitted at a high frequency is suppressed, and therefore, in a circuit where the signal is transmitted at a high frequency, stable signal transmission can be performed. Therefore, a copper foil having a small transmission loss value is suitable for a circuit application in which a signal is transmitted at a high frequency, which is preferable. If the total adhesion amount of the element in the metal layer is less than 200 μg / dm ² , a sufficient heat resistance effect cannot be obtained. In addition, if the total adhesion amount of the element in the metal layer exceeds 2000 μg / dm ² , a problem arises 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. In addition, 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. For example, it may contain Cu, Al, Ti, As, Ag, and 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, etc. The total adhesion amount of an element other than one or more elements selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr contained in the metal layer need not be particularly limited, but is typically 0 to 50000 μg / dm ² , more typically 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 with the insulating substrate, the metal layer may include a roughened layer. The roughening treatment can be performed, for example, by forming roughened particles with copper or a copper alloy. The roughening process may be a fine roughening process. The roughening treatment layer may be a layer containing any one element selected from the group consisting of copper, nickel, cobalt, and zinc, or any one or more alloys. The metal layer may include a heat discoloration prevention layer and / or a rust prevention layer. The heating discoloration prevention layer and the rust prevention layer that prevent Cu from diffusing may be formed of Zn, Cu, or an alloy thereof. The rust preventive layer may include a chromate layer or a zinc chromate layer. The metal layer may include a silane coupling layer.

矽烷、γ-巰基丙基三甲氧基矽烷等。 In addition, as the silane coupling agent for providing the silane coupling layer, a known silane coupling agent can be used. For example, an amino-based silane coupling agent or an epoxy-based silane coupling agent, a mercapto-based silane coupling agent, or a methacrylic acid-based silane can be used. Coupling agent. Among them, a silane coupling layer formed using an amino-based silane coupling agent or an epoxy-based silane coupling agent is preferred. In addition, silane coupling agents can be used: vinyltrimethoxysilane, vinylphenyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidyloxypropyltrimethoxy Silane, 4-glycidylbutyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-Aminopropoxy) butoxy) propyl-3-aminopropyltrimethoxysilane, imidazolane, tris

Silane, γ-mercaptopropyltrimethoxysilane and the like.

The so-called amino-based silane coupling agent may be a substance selected from the group consisting of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and 3- (N-styrene Methyl-2-aminoethylamino) propyltrimethoxysilane, 3-aminopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, amino Propyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, N- (3-propenyloxy-2-hydroxypropyl) -3- Aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- (2-aminoethyl-3-aminopropyl ) Trimethoxysilane, N- (2-aminoethyl-3-aminopropyl) tri (2-ethylhexyloxy) silane, 6- (aminohexylaminopropyl) trimethoxysilane, aminophenyl Trimethoxysilane, 3- (1-aminopropoxy) -3,3-dimethyl-1-propenyltrimethoxysilane, 3-aminopropyltri (methoxyethoxyethoxy) Silane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, ω-aminoundecyl Methoxysilane, 3- (2-N-benzylaminoethylaminopropyl) trimethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, (N, N -Diethyl-3-aminopropyl) trimethoxysilane, (N, N-dimethyl-3-aminopropyl) trimethoxysilane, N-methylaminopropyltrimethoxysilane, N- Phenylaminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, γ-aminopropyltriethoxy Silane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) butoxy) propyl-3-aminopropyltrimethoxy Silane.

The silane coupling layer is preferably in terms of silicon atom conversion, in the range of 0.05 mg / m ² to 200 mg / m ² , preferably 0.15 mg / m ² to 20 mg / m ² , and preferably 0.3 mg / m ² to 2.0 mg / Set within m ² range. When it is the said range, the adhesiveness of a base resin and a surface-treated copper foil can be improved more.

[Manufacturing method of surface-treated copper foil]

The manufacturing method of the surface-treated copper foil of this invention is demonstrated. First, a rolled copper foil or an electrolytic copper foil is prepared. Next, by a known method, 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. Furthermore, if necessary, a roughened layer, a heat discoloration prevention layer, a rust prevention layer, a silane coupling layer, and the like are formed on the metal layer by a known method. In addition, if necessary, a roughening treatment layer, a heat discoloration prevention layer, a rust prevention layer, a silane coupling layer, and the like are formed between the copper foil and the metal layer by a known method. Next, a chromate solution is provided on the entire surface of the copper foil to be treated. Then, the surface of the copper foil is dried without being washed with water, thereby forming a surface treatment layer of chromium oxide on the surface of the copper foil. In the conventional method, when the chromate solution is used for the surface treatment, after the chromate solution is provided on the surface of the copper foil and before the drying step, water washing is performed multiple times to remove impurities and the like. However, this water washing causes uneven formation of the chromate layer, which adversely affects the peel strength. In contrast, in the present invention, the water washing step is not performed. After the chromate solution is set on the entire surface of the copper foil to be treated, the surface of the copper foil is dried without being washed, thereby forming uniform chromium. Acid salt layer to improve peel strength of surface treated copper foil. The step of providing the chromate solution on the entire surface of the copper foil to be treated may be performed by applying the chromate solution to the surface of the copper foil using a shower, or by applying the chromate solution using a roller. It may be performed on the surface of a copper foil, and it may also be performed by apply | coating a chromate solution to the surface of a copper foil by a blade. The coating of the chromate solution by a shower can be performed using a known spray nozzle (for example, a spray nozzle manufactured by Spraying Systems Japan Co., Ltd. or a spray nozzle manufactured by Ichiuchi Co., Ltd.). The coating of the chromate solution by a roller can be performed by supplying a chromate solution to a roller surface using a known rubber roller or sponge roller, and bringing the roller surface into contact with a copper foil. The chromate solution can be applied by a blade using a known doctor blade or a known blade.

In addition, in the method for producing a surface-treated copper foil of the present invention, in the step of forming a surface-treated layer of chromium oxide, a chromate solution is placed on the surface of the copper foil, the liquid is removed, and then the water is not washed. It is then dried to form a surface-treated layer of chromium oxide. This deliquoring can be performed by blowing with a roller, a blade, and / or a gas. After the chromate solution is placed on the surface of the copper foil and deliquored in the manner described above, the amount of the chromate solution on the surface of the copper foil is controlled, thereby suppressing the adhesion of hexavalent chromium to the product and the change of residual ions (K ⁺ ). The effect is that it is not easily absorbed into the chromate film. The amount of the chromate solution provided on the surface of the copper foil is preferably 5 to 20 mg / dm ² after deliquoring. If the amount of the chromate solution provided on the surface of the copper foil is less than 5 mg / dm ² , there is a risk that a desired peeling strength cannot be obtained. In addition, if the amount of the chromate solution provided on the surface of the copper foil exceeds 20 mg / dm ² , it is treated with a solution having a composition described below, so that H ₂ SO ₄ and K added to adjust the pH value may be generated. Risk of salt precipitation. In addition, when the roller is used for deliquoring, the amount of the chromate liquid adhered can be controlled by controlling the force with which the roller contacts the copper foil. The force with which the roller contacts the copper foil can be set to 0.0005 to 0.015 kgf / cm per unit width (1 cm) of the copper foil. By increasing the contact force between the roller and the copper foil, the amount of chromate solution on the surface of the copper foil can be reduced. In addition, the amount of chromate solution on the surface of the copper foil can be increased by reducing the force with which the roller contacts the copper foil.

In addition, when dehydration is performed by a blade, the amount of the chromate solution 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 ~ 3μm. 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.

In addition, when degassing is performed by gas blowing, by controlling the flow rate of the gas to be blown, and simultaneously controlling the distance between the gas outlet of the nozzle that ejects the gas and the copper foil, the amount of the chromate solution can be controlled. The flow rate of the gas to be blown is preferably set to 25 to 1000 L / min. In addition, the gas is preferably blown so that the flow rate in the width direction of the copper foil is as equal as possible. In addition, the distance between the gas outlet and the copper foil can be set to 5 to 150 mm. By increasing the flow rate of the gas to be blown and / or reducing the distance between the gas outlet and the copper foil, the amount of chromate solution on the surface of the copper foil can be reduced. In addition, the amount of chromate solution on the surface of the copper foil can be increased by reducing the flow rate of the gas to be blown and / or increasing the distance between the gas ejection port and the copper foil.

The conditions of the chromate liquid used for 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 : 1.5 ~ 9g / L in total

pH value: 1 ~ 10, preferably 4 ~ 10

Temperature: 10 ~ 60 ℃, preferably 25 ~ 40 ℃

When a 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, the elution of Ni or the like can be effectively suppressed. In addition, when a treatment solution having a pH of 4 to 10 is used, even if Zn-chromate is used for the base treatment, the elution of Zn can be well suppressed.

In addition, as long as it is not clearly described, it is used in the electrolysis, surface treatment, and plating of the present invention. The remainder of the treatment liquid used was water.

[Copper foil with carrier]

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

<Carrier>

The carrier that 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 2. Insulating resin film (such as polyimide film, liquid crystal polymer (LCP) film, polyethylene terephthalate (PET) film, polyimide film, polyester film, fluororesin film, etc.).

As a carrier usable in the present invention, copper foil is preferably used. The reason for this is that since the electrical conductivity of the copper foil is high, the formation of subsequent intermediate layers and extremely thin copper layers becomes easy. Typically, the carrier is provided in the form of a rolled copper foil or an electrolytic copper foil. Generally speaking, electrolytic copper foil is produced by electrolyzing copper from a copper sulfate plating bath onto a titanium or stainless steel drum, and rolled copper foil is produced by repeatedly performing plastic processing and heat treatment by a calender roll. As the material of the copper foil, in addition to high-purity copper such as refined copper or oxygen-free copper, for example, copper alloys such as Sn-doped copper, Ag-doped copper, Cr, Zr, or Mg may be used, and Ni and A Carson-based copper alloy such as Si is a copper alloy.

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

In addition, a roughening treatment layer may be provided on the surface of the carrier on the side where the ultra-thin copper layer is provided and the surface on the opposite side. This roughening process layer can be provided by a well-known method, and it can also be set by the said roughening process. Providing a roughened layer on the surface of the carrier on the side where the ultra-thin copper layer is provided and the surface on the opposite side of the carrier has the advantage that when the carrier is laminated to a support such as a resin substrate from the surface side having the roughened layer, the carrier and The resin substrate becomes difficult to peel.

<Middle 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 the following structure: before the step of laminating a copper foil with a carrier on an insulating substrate, it is difficult for the ultra-thin copper layer to peel off from the carrier. After the step, the extremely 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 a material selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, such alloys, such hydrates, the One or two or more of the group consisting of equal oxides and organic substances. The intermediate layer may be a plurality of layers.

In addition, the intermediate layer may be configured, for example, from the carrier side to form one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn. A single metal layer, or an alloy layer composed of one or two or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, in A hydrate or oxide, or an organic substance formed thereon 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 Composition of layers.

In addition, the intermediate layer may be configured, for example, from the carrier side to form one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn. A single metal layer, or an alloy layer composed of one or two or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, in A single metal layer composed of one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn is formed thereon, or a metal layer selected from the group consisting of Cr, Ni, An alloy layer composed of one or two or more elements in an element group consisting of Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn.

The intermediate layer may use a known organic substance as the organic substance, and it is preferable to use any one or more of a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid. For example, as the specific nitrogen-containing organic compound, it is preferable to use a triazole compound having a substituent, that is, 1,2,3-benzotriazole, carboxybenzotriazole, N ', N'-bis (benzotris Azolylmethyl) urea, 1H-1,2,4-triazole, and 3-amino-1H-1,2,4-triazole.

As the sulfur-containing organic compound, mercaptobenzothiazole, sodium 2-mercaptobenzothiazole, trimeric thiocyanate, 2-benzimidazole thiol, and the like are preferably used.

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

The intermediate layer may be formed by sequentially stacking a nickel layer, a nickel-phosphorus alloy layer, a nickel-cobalt alloy layer, and a chromium-containing layer on a carrier, for example. Since the adhesion between nickel and copper is higher than the adhesion between chromium and copper, peeling occurs at the interface between the ultra-thin copper layer and the chromium-containing layer when the ultra-thin copper layer is peeled. In addition, the nickel of the intermediate layer is expected to have a barrier effect to prevent 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 chromium adhesion amount 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 preventive layer such as a Ni plating layer on the opposite side of the carrier. The chromium layer of the intermediate layer can be provided by chromium plating or chromate treatment.

If the thickness of the intermediate layer is too thick, the thickness of the intermediate layer may affect the surface roughness Rz and gloss of the surface of the ultra-thin copper layer after the surface treatment. Therefore, the intermediate layer on the surface of the surface-treated layer of the ultra-thin copper layer The thickness is preferably 1 to 1000 nm, more preferably 1 to 500 nm, still more preferably 2 to 200 nm, still more preferably 2 to 100 nm, and even more preferably 3 to 60 nm. In addition, the intermediate layer may be provided on both sides of the carrier.

<Ultra-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 this carrier is a surface-treated copper foil as one embodiment of the present invention. The thickness of the ultra-thin copper layer is not particularly limited, and is generally thinner than the carrier, and is, for example, 12 μm or less. It is typically 0.5 to 12 μm, and more typically 1.5 to 5 μm. In addition, before the ultra-thin copper layer is provided on the intermediate layer, in order to reduce pinholes in the ultra-thin copper layer, copper-phosphorus alloy may be used for pre-plating (strike plating). Examples of the pre-plating include a copper pyrophosphate plating solution. In addition, an extremely thin copper layer may be provided on both sides of the carrier.

In addition, 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 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 ℃

Linear speed of electrolyte: 1.5 ~ 5m / sec

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

A laminated body (copper-clad laminated body, etc.) can be produced using the copper foil with a carrier of this invention. As the laminated body, for example, an “ultra-thin copper layer / intermediate layer / carrier / resin or prepreg may be sequentially laminated” Material "structure can also be used to sequentially build" carrier / intermediate layer / ultra-thin copper layer / resin or prepreg ", or can be used to sequentially build" ultra-thin copper layer / intermediate layer / carrier / resin " The composition of prepreg / carrier / intermediate layer / extremely thin copper layer "can also be sequentially laminated" carrier / intermediate layer / extremely thin copper layer / resin or prepreg / extremely thin copper layer / intermediate layer / carrier " In addition, the structure of "carrier / intermediate layer / ultra-thin copper layer / resin or prepreg / carrier / intermediate layer / ultra-thin copper layer" may be sequentially laminated. The resin or prepreg may be the resin layer described below, or may contain a resin, a resin hardener, a compound, a hardening accelerator, a dielectric, a reaction catalyst, a cross-linking agent, a polymer, a resin used in the resin layer described below. Impregnating materials, skeleton materials, etc. In addition, the copper foil with a carrier may be smaller than a resin or a prepreg in a plan view.

[Resin layer on surface treated surface]

The surface-treated surface of the surface-treated copper foil of this invention may be equipped with the resin layer. The resin layer may be an insulating resin layer. In addition, in the surface-treated copper foil of the present invention, the "surface-treated surface" refers to a surface treatment for providing a heat-resistant layer, a rust-proof layer, a weather-resistant layer, and the like after roughening treatment. After the surface treatment of the copper foil surface. In addition, when the surface-treated copper foil is an ultra-thin copper layer with a copper foil with a carrier, the "surface-treated surface" refers to a surface for providing a heat-resistant layer, a rust-proof layer, and a weather-resistant layer after roughening treatment. During the treatment, the surface of the ultra-thin copper layer after the surface treatment was performed.

The resin layer may be a resin for bonding, that is, an adhesive, or an insulating resin layer in a semi-hardened state (B-stage state) for bonding. The so-called semi-hardened state (B-stage state) includes a state in which even if the surface is touched with a finger, there is no stickiness, and the insulating resin layer can be stored in an overlapped state, and if subjected to heat treatment, a hardening reaction is caused.

The resin layer may contain a thermosetting resin or a thermoplastic tree. fat. The resin layer may contain a thermoplastic resin. The resin layer may contain a known resin, a resin hardener, a compound, a hardening accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and the like. The resin layer may be, for example, those described in the following documents (resin, resin hardener, compound, hardening accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton material, etc.) and / Or resin layer forming method and device: International Publication No. WO2008 / 004399, International Publication No. WO2008 / 053878, International Publication No. WO2009 / 084533, Japanese Patent Application Laid-Open No. 11-5828, Japanese Patent Application Laid-Open No. 11-140281, Japan Patent No. 3184485, 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 Patent No. 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, Japanese Patent No. 4286060, Japanese Patent Laid-Open No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent Laid-Open No. 2005-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004 / 005588, Japanese Patent Laid-Open No. 2006-257153, Japanese Patent Laid-Open No. 2007-326923, Japanese Patent Laid-Open No. 2008-111169, Japanese Patent No. 5024930, International Publication No. WO2006 / 028207, Japanese Patent No. 4828427, Japanese Patent Laid-Open No. 2009-67029, International Publication No. WO2006 / 134868, Japanese Patent No. 5046927, Japanese Patent Laid-Open No. 2009-173017, International Publication No. WO2007 / 105635, Japanese Patent No. 5180815, International Publication No. WO2008 / 114858, International Publication number 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 Laid-Open No. 2013-19056.

樹脂、熱硬化性聚伸苯醚樹脂、氰酸酯系樹脂、羧酸酐、多元羧酸酐、具有可交聯的官能基的線性聚合物、聚苯醚樹脂、2,2-雙(4-氰酸酯基苯基)丙烷、含磷酚化合物、環烷酸錳、2,2-雙(4-縮水甘油基苯基)丙烷、聚苯醚-氰酸酯系樹脂、矽氧烷改質聚醯胺醯亞胺樹脂、氰基酯樹脂、磷腈系樹脂、橡膠改質聚醯胺醯亞胺樹脂、異戊二烯、氫化聚丁二烯、聚乙烯醇縮丁醛、苯氧基樹脂、高分子環氧樹脂、芳香族聚醯胺、氟樹脂、雙酚、嵌段共聚聚醯亞胺樹脂及氰基酯樹脂。 The type of the resin layer is not particularly limited. For example, preferred resins include one or more resins selected from the group consisting of epoxy resins, polyimide resins, and polyfunctional cyanates. Compounds, maleimide compounds, polymaleimide compounds, maleimide resins, aromatic maleimide resins, polyvinyl acetal resins, urethane resins, Polyether fluorene (also known as polyether sulphone, polyethersulfone), polyether fluorene (also known as polyether sulphone, polyethersulfone) resin, aromatic polyamine resin, aromatic polyamine resin polymer, rubber resin, polyamine, Aromatic polyamines, polyamidoamine imine resins, rubber modified epoxy resins, phenoxy resins, hydroxyl modified acrylonitrile-butadiene resins, polyphenylene oxide, bismaleimide Amine Tri

Resin, thermosetting polyphenylene ether resin, cyanate resin, carboxylic anhydride, polycarboxylic anhydride, linear polymer with crosslinkable functional group, polyphenylene ether resin, 2,2-bis (4-cyanide Ester phenyl) propane, phosphorus-containing phenolic compounds, manganese naphthenate, 2,2-bis (4-glycidylphenyl) propane, polyphenylene ether-cyanate resin, silicone modified polymer Amidoamine imine resin, cyanoester resin, phosphazene-based resin, rubber modified polyamidoamine imine resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, phenoxy resin , Polymer epoxy resin, aromatic polyamidoamine, fluororesin, bisphenol, block copolymer polyamidoimide resin and cyanoester resin.

Moreover, if the said epoxy resin is a resin which has two or more epoxy groups in a molecule | numerator, and can be used for electrical and electronic materials, it can be used without a special problem. The epoxy resin is preferably an epoxy resin obtained by epoxidation using a compound having two or more glycidyl groups in the molecule. In addition, one or two or more selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, and hydride or halide of the above-mentioned epoxy resin may be used in combination. Bisphenol S epoxy resin, bisphenol AD epoxy resin, phenol Novolac epoxy resin, cresol novolac epoxy resin, alicyclic epoxy resin, brominated epoxy resin, phenol novolac epoxy resin, naphthalene epoxy resin, brominated bisphenol A type epoxy resin, o-cresol novolac type epoxy resin, rubber modified bisphenol A type epoxy resin, glycidyl amine type epoxy resin, isocyanuric acid triglycidyl ester, N, N-diglycidyl Glycidylamine compounds such as glyceryl aniline, glycidyl compounds such as diglycidyl tetrahydrophthalate, phosphorus-containing epoxy resins, biphenyl epoxy resins, biphenol novolac epoxy resins, trihydroxybenzene Methane type epoxy resin, tetraphenylethane type epoxy resin.

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

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

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

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

The dielectric (dielectric filler) may be powdered. When the dielectric (dielectric filler) is powdery, the powder characteristics of the dielectric (dielectric filler) are preferably 0.01 μm to 3.0 in particle size. A powdery dielectric (dielectric filler) in a range of μm, preferably 0.02 μm to 2.0 μm. In addition, when a photo is taken of a dielectric with a scanning electron microscope (SEM), and a straight line is drawn over the dielectric particles in the photo, the length of the dielectric particle that crosses the longest straight line of the dielectric particle is taken as the dielectric particle. diameter of. The average value of the diameters of the dielectric particles in the visual field was 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, dimethylacetamidine Amine, N-methylpyrrolidone, toluene, methanol, ethanol, propylene glycol monomethyl ether, dimethylformamide, dimethylacetamide, cyclohexanone, ethyl cellosolve, N-methyl-2- Pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and other solvents are used to prepare a resin solution (resin varnish), and it is coated on the surface by, for example, a roll coating method. The roughened surface of the copper foil is processed, and then the solvent is removed by heating and drying if necessary, so as to obtain a B-stage state. For example, a hot-air drying furnace may be used for drying, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C. A solvent can be used to dissolve the composition of the above resin layer to make a resin solid content of 3% to 70% by weight, preferably 3% to 60% by weight, preferably 10% to 40% by weight, and more preferably 25% to 40% by weight. Resin solution. In addition, from the environmental point of view, it is most preferable to dissolve using a mixed solvent of methyl ethyl ketone and cyclopentanone at this stage. The solvent is preferably a solvent having a boiling point in the range of 50 ° C to 200 ° C.

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

In this specification, the resin fluidity is a value as follows: According to MIL-P-13949G in the MIL specification, four 10 cm square samples were sampled from a surface-treated copper foil with a resin having a resin thickness of 55 μm. In a state where the four samples are stacked (laminated body), bonding was performed 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 the weight was measured according to the resin outflow weight at this time. The measurement result is calculated based on the mathematical formula 1.

The surface-treated copper foil (resin-coated surface-treated copper foil) including the resin layer is used in a state in which the resin layer is superimposed on a substrate, and then the whole is thermocompression bonded to the resin layer. Heat hardening. Secondly, when the surface-treated copper foil is an ultra-thin copper layer with a carrier copper foil, the carrier is peeled to expose the ultra-thin copper layer (of course, the surface on the middle layer side of the ultra-thin copper layer is exposed) from the surface. A specific wiring pattern is formed on the surface of the roughened side of the processed copper foil and on the opposite side.

The use of this resin-coated surface-treated copper foil can reduce the number of sheets of prepreg used in manufacturing a multilayer printed wiring board. In addition, the thickness of the resin layer can be set to a thickness capable of ensuring interlayer insulation, or a copper-clad laminated board can be manufactured without using a prepreg at all. In addition, at this time, the surface primer of the substrate may be coated with an insulating resin to further improve the surface smoothness.

In addition, when the prepreg material is not used, the material cost of the prepreg material is saved, and the lamination step is simplified, so it is economically advantageous and has the following advantages: multilayer printed wiring manufactured according to the thickness of the prepreg material The thickness of the substrate is reduced, and an extremely thin multilayer printed wiring board having a thickness of 100 μm or less can be manufactured.

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

If the thickness of the resin layer is thinner than 0.1 μm, then the adhesive force decreases. When the resin-coated surface-treated copper foil is laminated with a prepreg on a substrate provided with 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 greater than 120 μm, there is a case where it is difficult to form a resin layer of a target thickness in one coating step, and it is economically disadvantageous because extra material costs and man-hours are spent.

In addition, when a surface-treated copper foil having a resin layer is used to manufacture an extremely thin multilayer printed wiring board, in terms of reducing the thickness of the multilayer printed wiring board, the thickness of the resin layer is preferably set to 0.1. μm to 5 μm, more preferably 0.5 μm to 5 μm, and even more preferably 1 μm to 5 μm.

Some examples of the manufacturing steps of the printed wiring board using the copper foil with a carrier of this invention are shown below.

An embodiment of the method for manufacturing a printed wiring board of the present invention includes: a step of preparing the copper foil with a carrier and an insulating substrate of the present invention; a step of laminating the copper foil with a carrier and the insulating substrate; and using an extremely thin copper layer After the copper foil with a carrier and the insulating substrate are laminated so as to face the insulating substrate, a copper-clad laminated board is formed through a step of peeling the carrier with the copper foil with a carrier, and then a semi-additive method and a modified semi-additive method are used. Steps of forming a circuit by any of the addition method, partial addition method, and subtraction method. The insulating substrate may be a substrate incorporating an inner-layer circuit.

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

Therefore, one embodiment of the method for manufacturing a printed wiring board of the present invention using the semi-additive method includes the following steps: a step of preparing the copper foil with a carrier and an insulating substrate of the present invention; A step of laminating the substrate; a step of peeling the carrier of the copper foil with a carrier after laminating the copper foil with a carrier and an insulating substrate; and using an acid or the like to dissolve the solvent A step of removing all the ultra-thin copper layer exposed by peeling the carrier by a method such as liquid etching or plasma; a step of providing a through hole and / or a blind hole in the resin exposed by removing the ultra-thin copper layer by etching ; A step of removing dross removal processing on the area containing the above-mentioned through hole or / and blind hole; a step of providing an electroless plating layer on the above resin and the area containing the above-mentioned through hole or / and blind hole; A step of setting a plating resist; a step of exposing the above plating resist and then removing the plating resist in a region where the circuit is formed; a step of setting a plating layer in a region where the circuit is formed by removing the plating resist A step of removing the above-mentioned plating resist; a step of removing an electroless plating layer in a region other than a region where the circuit is formed by flash etching or the like.

Another embodiment of the method for manufacturing a printed wiring board of the present invention using the semi-additive method includes the steps of: preparing the copper foil with a carrier and an insulating substrate of the present invention; and combining the copper foil with a carrier and the insulating substrate. Performing a laminating step; a step of peeling the carrier with the copper foil after the carrier is laminated after the copper foil with the carrier and the insulating substrate are laminated; the carrier is peeled and exposed to a very thin thickness by etching using an etching solution such as an acid or plasma A step of removing the entire copper layer; a step of providing an electroless plating layer on the surface of the resin exposed by removing the ultra-thin copper layer by etching; 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 the region where the aforementioned plating resist is formed to form the circuit; a step of removing the aforementioned plating resist; A step of removing an electroless plating layer and an ultra-thin copper layer in a region other than a region where the circuit is formed by flash etching or the like.

In the present invention, the improved semi-additive method refers to a method in which a metal foil is laminated on an insulating layer, a non-circuit forming portion is protected by a plating resist, and a copper thickness of the circuit forming portion is thickened by plating, The resist is removed, and the circuit forming portion is removed by (flash) etching to The outer metal foil thus forms a circuit on the insulating layer.

Therefore, one embodiment of the method for manufacturing a printed wiring board of the present invention using the improved semi-additive method includes the following steps: a step of preparing the copper foil with a carrier and an insulating substrate of the present invention; A step of laminating with the insulating substrate; a step of peeling the carrier with the copper foil from the carrier after laminating the copper foil with the carrier and the insulating substrate; a through-hole or / and A step of blind holes; a step of removing dross removal processing on the area containing the above-mentioned through holes and / or blind holes; a step of providing an electroless plating layer on the areas containing the above-mentioned through holes and / or blind holes; A step of setting a plating resist on the surface of the exposed ultra-thin copper layer; a step of forming a circuit by electroplating after setting the above plating resist; a step of removing the above plating resist; and removing by flash etching The step of removing the plating resist and exposing an extremely thin copper layer.

In addition, the step of forming a circuit on the resin layer may include bonding another copper foil with a carrier to the resin layer from the ultra-thin copper layer side, and forming the circuit using the copper foil with a carrier bonded to the resin layer. A step of. In addition, another copper foil with a carrier bonded to the resin layer may be the copper foil with a carrier of the present invention. The step of forming a circuit on the resin layer can be performed by any one of a semi-additive method, a subtractive method, a partial addition method, and an improved semi-additive method. Moreover, the copper foil with a carrier which forms a circuit on the said surface may have a board | substrate or a resin layer on the surface of the carrier of this copper foil with a carrier.

Another embodiment of the method for manufacturing a printed wiring board of the present invention using the improved semi-additive method includes the steps of: preparing the copper foil with a carrier and an insulating substrate of the present invention; A step of laminating the insulating substrate; a step of peeling the carrier of the copper foil with a carrier after laminating the copper foil with a carrier and the insulating substrate; a step of peeling the carrier A step of setting a plating resist on the exposed ultra-thin copper layer; a step of exposing the above plating resist and then removing the plating resist in a region where the circuit is formed; and removing the plating resist to form the circuit A step of setting a plating layer in a region; a step of removing the above-mentioned plating resist; a step of removing an electroless plating layer and an ultra-thin copper layer in a region other than a region where the circuit is formed by flash etching or the like.

In the present invention, the partial addition method refers to a method in which a substrate provided with a conductor layer and a substrate provided with a through-hole or an auxiliary hole are provided with a catalytic nucleus as needed, and a conductor is formed by etching. After a circuit is provided with a solder resist or a plating resist as needed, a thickness of a through hole, an auxiliary hole, or the like is provided on the conductor circuit by electroless plating to manufacture a printed wiring board.

Therefore, one embodiment of the method for manufacturing a printed wiring board of the present invention using the partial addition method includes the following steps: a step of preparing the copper foil with a carrier and an insulating substrate of the present invention; A step of laminating the substrate; a step of peeling the carrier with the copper foil from the carrier after laminating the copper foil with the carrier and the insulating substrate; a through-hole or / and a blind hole provided in the ultra-thin copper layer and the insulating substrate that are exposed after the carrier is peeled off A step of performing a desmearing treatment on the area containing the above-mentioned through hole and / or blind hole; a step of providing a catalytic core to the area containing the above-mentioned through hole and / or blind hole; and exposing the carrier to be extremely thin A step of setting an etching resist on the surface of the copper layer; a step of forming a circuit pattern by exposing the etching resist; forming by removing the ultra-thin copper layer and the catalytic core by etching using an etching solution such as acid or plasma Step of circuit; step of removing the above-mentioned etching resist; removing the above-mentioned extremely thin copper layer and the above-mentioned method by etching using an etching solution such as acid or plasma The insulating substrate is exposed surface of the core is provided the step of plating solder resist or 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 a copper foil on a copper-clad laminate by etching or the like to form a conductor pattern.

Therefore, one embodiment of the method for manufacturing a printed wiring board of the present invention using the subtractive method includes the steps of: preparing the copper foil with a carrier and an insulating substrate of the present invention; and combining the copper foil with a carrier and the insulating substrate. Performing a laminating step; a step of peeling the carrier with the copper foil after the carrier is laminated after the copper foil with the carrier and the insulating substrate are laminated; providing a through-hole or / and a blind hole in the ultra-thin copper layer and the insulating substrate exposed by peeling the carrier; Step; a step of removing dross removal processing on the area containing the above-mentioned through hole and / or blind hole; a step of providing an electroless plating layer on the area containing the above-mentioned through hole and / or blind hole; A step of providing a plating layer; a step of providing an etching resist on the surface of the above-mentioned plating layer or / and the ultra-thin copper layer; a step of exposing the above-mentioned etching resist to form a circuit pattern; etching by using an etching solution such as an acid Or a method such as plasma or plasma to remove the ultra-thin copper layer, the electroless plating layer, and the electroplated layer to form a circuit; and a step of removing the etching resist.

Another embodiment of the method for manufacturing a printed wiring board of the present invention using the subtractive method includes the steps of: preparing the copper foil with a carrier and an insulating substrate of the present invention; and performing the above-mentioned copper foil with a carrier and an insulating substrate. A step of laminating; a step of peeling the carrier with the copper foil on the carrier after laminating the copper foil with the carrier and the insulating substrate; a step of setting a through-hole or / and a blind hole on the ultra-thin copper layer and the insulating substrate exposed by peeling the carrier A step of removing the drossing treatment on the area containing the above-mentioned through hole and / or blind hole; a step of providing an electroless plating layer on the area containing the above-mentioned through hole and / or blind hole; A masking step; a step of providing a plating layer on the surface of the above-mentioned electroless plated layer without a mask; a step of providing an etching resist on the surface of the above-mentioned plating layer or / and the ultra-thin copper layer; Exposure to form circuit patterns A step of forming a circuit by removing the ultra-thin copper layer and the electroless plating layer by a method such as etching using an etching solution such as acid or plasma, and a step of removing the etching resist.

The step of providing the through hole and / or the blind hole and the subsequent step of removing the dross may not be performed.

Here, the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention is demonstrated in detail using drawing. In addition, here, a copper foil with a carrier having an ultra-thin copper layer formed with a roughened layer is described as an example, but the present invention is not limited to this. Carrier copper foil was carried out similarly to the manufacturing method of the printed wiring board described below.

First, as shown in FIG. 1-A, a copper foil with a carrier (first layer) having an ultra-thin copper layer with a roughened layer formed on the surface is prepared. In this step, a copper foil with a carrier (first layer) having a carrier having a roughened layer formed on the surface may be prepared.

Next, as shown in FIG. 1-B, a resist is coated on the roughened layer of the ultra-thin copper layer, exposed and developed, and the resist is etched into a specific shape. In addition, in this step, a resist may be coated on the roughened layer of the carrier, exposed and developed, and the resist may be etched into a specific shape.

Next, as shown in FIG. 1-C, after forming a plating layer for a circuit, the resist is removed to form a circuit plating layer having a specific shape.

Then, as shown in Fig. 2-D, an embedded resin is provided on the ultra-thin copper layer to cover the circuit plating layer (the circuit plating layer is buried), and the resin layer is laminated, and then another copper foil with a carrier (second layer) Adhesion is made from the very thin copper layer side. In addition, in this step, a method of covering the circuit plating layer (a method of burying the circuit plating layer) may be provided by embedding a resin on the carrier to laminate the resin layer, and then placing another copper foil with a carrier (second layer) from the carrier side or electrode. A thin copper layer is then adhered.

Next, as shown in Figure 2-E, the carrier is peeled from the second layer of copper foil with carrier. In addition, when the second layer of copper foil with a carrier is followed from the carrier side, the ultra-thin copper layer may be peeled from the second layer of copper foil with a carrier.

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

Second, as shown in Figure 3-G, copper is embedded in the blind hole to form a blind hole filling layer.

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

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

Secondly, as shown in Figure 4-J, the ultra-thin copper layers on both surfaces are removed by flash etching (when copper foil is provided on the second layer, copper foil is provided, and when the first layer is provided on the roughening treatment layer of the carrier) The carrier for the layered circuit plating) exposes the surface of the circuit plating layer in the resin layer.

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 other copper foil with a carrier (second layer) may use the copper foil with a carrier of the present invention, or may use an existing copper foil with a carrier. Ordinary copper foil may be used. In addition, one or more layers of circuits can be formed on the second-layer circuit as shown in Figure 3-H. Any of the semi-additive method, subtractive method, partial additive method, or modified semi-additive method can be used. Method to form these circuits.

The copper foil with a carrier of the present invention preferably controls the color difference on the surface of the ultra-thin copper layer in a manner satisfying the following (1). In the present invention, the "color difference on the surface of the ultra-thin copper layer" means the color difference on the surface of the ultra-thin copper layer or the color difference 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 formula controls the color difference of the roughened surface of the ultra-thin copper layer. In addition, in the surface-treated copper foil of the present invention, the so-called "roughened surface" is a roughened surface. When a surface treatment is performed to provide a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc., it means that the surface treatment is performed. The surface treatment of copper foil (extremely thin copper layer). In addition, when the surface-treated copper foil is an ultra-thin copper layer with a copper foil with a carrier, the so-called "roughened surface" is a roughened surface, and a surface treatment is performed to provide a heat-resistant layer, a rust-proof layer, and a weather-resistant layer. In this case, it refers to the surface of the ultra-thin copper layer after the surface treatment.

(1) For the surface of the ultra-thin copper layer, three stimuli using a white plate (when the light source is set to D65 and the field of view is 10 degrees, the X ₁₀ Y ₁₀ Z ₁₀ color system (JIS Z8701 1999) of the white plate is used value _{X 10 = 80.7, Y 10 =} 85.6, Z 10 = 91.5, object colors L ^* a ^* b ^* color system of the white plate is ^{L * = 94.14, a * =} -0.90, b * = 0.24 The color difference when the object color of) is a reference color, the color difference ΔE * ab based on JIS Z8730 is 45 or more.

Here, the color difference ΔL (the difference between the CIE brightness L ^* of the two object colors in the color system L ^* a ^* b ^* specified by JIS Z8729 (2004)), Δa (specified by JIS Z8729 (2004) L ^* a ^* b ^* color coordinate a ^* difference between two object colors in the color system), △ b (L ^* a ^* b ^* two colors in the color system specified by JIS Z8729 (2004) The difference of the color coordinates b ^* of the object color) is measured with a color difference meter, and black / white / red / green / yellow / blue is added. The colorimetric system based on L ^* a ^* b ^* based on JIS Z8730 (2009) is used. The comprehensive index shown is represented by △ L: white and black, △ a: red and green, and △ b: yellow and blue. In addition, ΔE ^* ab is expressed by the following formula using these color differences.

The above-mentioned chromatic aberration can reduce the plating by increasing the current density when forming an extremely thin copper layer. The copper concentration in the liquid is adjusted to increase the linear flow velocity of the plating solution.

In addition, the above-mentioned chromatic aberration can also be adjusted by providing a roughening treatment layer to the surface of the ultra-thin copper layer and providing a roughening treatment layer. When the roughening treatment layer is provided, the current density can be made higher than the conventional current density by using an electrolytic solution containing copper and one or more elements selected from the group consisting of nickel, cobalt, tungsten, and molybdenum. 60 A / dm ² ), and adjust the processing time to be shorter than the conventional processing time (for example, 0.1 to 1.3 seconds). When a roughened layer is not provided on the surface of the ultra-thin copper layer, a plating bath with a Ni concentration more than twice that of other elements can be used at a lower current density (0.1 to 1.3 A / dm ² ), and the processing time is set to be longer than the conventional processing time (20 seconds to 40 seconds), for the surface of the ultra-thin copper layer, or heat-resistant layer, or rust-proof layer, or chromate layer, or silane coupling layer This is achieved by plating Ni alloys (for example, plating Ni-W alloys, plating Ni-Co-P alloys, and plating Ni-Zn alloys).

If the color difference on the surface of the ultra-thin copper layer, that is, the color difference ΔE * ab based on JIS Z8730 is 45 or more, for example, when a circuit is formed on the surface of the ultra-thin copper layer with a carrier copper foil, the contrast between the ultra-thin copper layer and the circuit becomes As a result, the visibility is improved, and the position of the circuit can be accurately aligned. 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, and even more preferably 60 or more.

When the chromatic aberration of the surface of the ultra-thin copper layer is controlled as described above, the contrast with the circuit plating layer becomes sharp, and the visibility becomes good. Therefore, in the manufacturing steps of the printed wiring board as described above, for example, as shown in FIG. 1-C, the circuit plating layer can be formed accurately at a specific position. In addition, according to the manufacturing method of the printed wiring board described above, the circuit plating layer is embedded in the resin layer. Therefore, when the ultra-thin copper layer is removed by flash etching as shown in Fig. 4-J, the circuit plating layer is removed. It is protected by the resin layer and its shape is maintained, thereby making it possible to form a fine circuit easily. 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 suppressed well. Therefore, formation of a fine circuit becomes easy. In addition, as shown in Figs. 4-J and 4-K, when the ultra-thin copper layer is removed by flash etching, the exposed surface of the circuit plating layer becomes a recessed shape from the resin layer, so it is easy to form on the circuit plating layer. A bump, and further a copper pillar is formed on the bump, thereby improving the manufacturing efficiency.

)樹脂或作為含浸BT樹脂而成的玻璃布的預浸料、Ajinomoto Fine-Techno股份有限公司製造的ABF膜或ABF。另外，上述嵌入樹脂(resin)可使用本說明書所記載的樹脂層及/或樹脂及/或預浸料。 As the resin, a known resin or prepreg can be used. For example, BT (bismaleimide

) Resin or prepreg as a glass cloth impregnated with BT resin, ABF film or ABF manufactured by Ajinomoto Fine-Techno Co., Ltd. As the resin, the resin layer and / or the resin and / or the prepreg described in this specification can be used.

Moreover, the copper foil with a carrier used for the said 1st layer may have a board | substrate or a resin layer on the surface of this copper foil with a carrier. By having the substrate or the resin layer, the copper foil with a carrier used in the first layer is supported, and it becomes difficult to wrinkle, and therefore has the advantage of improving productivity. In addition, as long as the substrate or the resin layer exhibits the effect of supporting the copper foil with a carrier used in 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, Organic compound board, organic compound foil.

The surface-treated copper foil of this invention can be bonded to a resin substrate from the surface-treatment layer side, and a laminated board can be manufactured. The resin substrate is not particularly limited as long as it has characteristics applicable to printed wiring boards. For example, for rigid PWB, paper substrate phenol resin, paper substrate epoxy resin, synthetic fiber cloth substrate epoxy resin, fluorine Resin impregnated cloth, glass cloth-paper composite substrate epoxy resin, Glass cloth-glass nonwoven composite epoxy resin, glass cloth 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-polyimide composite materials. In addition, since the dielectric loss of the liquid crystal polymer (LCP) is small, it is preferable to use a liquid crystal polymer (LCP) film for printed wiring boards for high-frequency circuits.

In the case of rigid PWB, a method of bonding is to impregnate a substrate such as glass cloth with a resin and prepare a prepreg formed by curing the resin to a semi-hardened state. This can be performed by superimposing a copper foil on a prepreg and applying heat and pressure. In the case of FPC, a substrate such as a liquid crystal polymer or a polyimide film is laminated on a copper foil through an adhesive or without using an adhesive at high temperature and pressure, or a polyimide precursor is coated and dried. , Hardening, etc., thereby manufacturing a laminated board.

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 single-sided PWB, double-sided PWB, and multilayer PWB (3 or more layers). From the viewpoint of the type of insulating substrate material, it can be applied to rigid PWB, flexible PWB (FPC), and soft-hard composite PWB.

A 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 may be produced using the printed wiring board, an electronic device may be produced using the printed circuit board on which the electronic component is mounted, or an electronic device may be produced using the printed circuit board on which the electronic component is mounted.

Furthermore, a printed wiring board is completed by mounting electronic components on the printed wiring board of this 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 may be produced using the printed wiring board, an electronic device may be produced using the printed circuit board on which the electronic component is mounted, or an electronic device may be produced using the printed circuit board on which the electronic component is mounted.

In addition, the method for manufacturing a printed wiring board of the present invention may be a manufacturing method (hollow method) of a printed wiring board including the steps of: interfacing the above-mentioned ultra-thin copper layer side surface of the copper foil with a carrier or the above-mentioned carrier-side surface of the present invention with A step of laminating a resin substrate; a step of providing a resin layer and a circuit at least once on the surface of the ultra-thin copper layer side laminated with the resin substrate or on the surface of the copper foil with a carrier opposite to the carrier side surface And a step of peeling the carrier or the ultra-thin copper layer from the copper foil with a carrier after forming the two layers of the resin layer and the circuit. Regarding this 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 ultra-thin copper layer side laminated with the resin substrate or the surface of the copper foil with a carrier on the opposite side of the carrier side surface. Further, from the carrier side or the ultra-thin copper layer side, another copper foil with a carrier may be laminated on the resin formed on the carrier-side surface or the ultra-thin copper layer-side surface. At this time, a structure is adopted in which a resin substrate is used as a center, and the resin substrate is laminated on the two surface sides of the resin substrate in the order of the carrier / intermediate layer / extremely thin copper layer or the order of the ultra-thin copper layer / intermediate layer / carrier. Carrier copper foil. Another layer of resin can be provided on the exposed surface of the ultra-thin copper layer or the carrier at both ends, and further, a copper layer or a metal layer is provided, and then the copper layer or the metal layer is processed to form a circuit. It is also possible to provide another resin layer on the circuit so as to bury the circuit. In addition, such a circuit and the formation of a resin layer can be performed more than once (the build-up method). Then, with respect to the multilayer body (hereinafter also referred to as multilayer body B) thus formed, the ultra-thin copper layer or carrier of each copper foil with a carrier is peeled from the carrier or the ultra-thin copper layer to produce a hollow substrate. In addition, the above-mentioned hollow substrate can also be produced by using two pieces of copper foil with a carrier. A laminated body having a composition of extremely thin copper layer / intermediate layer / carrier / carrier / intermediate layer / extremely thin copper layer as described herein, or having a carrier / intermediate layer / extremely thin copper layer / extremely thin copper layer / intermediate layer / A laminated body having a structure of a carrier or a laminated body having a structure of a carrier / intermediate layer / ultra-thin copper layer / carrier / intermediate layer / ultra-thin copper layer and using the laminated body as a center. Lay the resin layer and the circuit on the surface of the ultra-thin copper layer or the carrier on both sides of these laminates (hereinafter also referred to as laminate A) more than once, and install the resin layer and circuit more than once. After two layers, the ultra-thin copper layer or carrier of each copper foil with a carrier is peeled from the carrier or the ultra-thin copper layer, and a hollow substrate can be produced. The laminated body described above may also have other layers on the surface of the ultra-thin copper layer, the surface of the carrier, between 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. . In addition, in this specification, when the ultra-thin copper layer, the carrier, and the laminate have other layers on the surface of the ultra-thin copper layer, the surface of the carrier, or the surface of the laminate, "the surface of the ultra-thin copper layer" and "the side of the ultra-thin copper layer" "Surface", "surface of ultra-thin copper layer", "surface of carrier", "surface of carrier side", "surface of carrier", "surface of laminated body", "surface of laminated body" are surfaces set to include the other layers ( The most superficial) concept. Moreover, it is preferable that a laminated body has a structure which has an ultra-thin copper layer, an intermediate layer, a carrier, a carrier, an intermediate layer, and an ultra-thin copper layer. The reason is that when a hollow substrate is produced by using this laminated body, since an ultra-thin copper layer is arranged on the hollow substrate side, it is easy to form a circuit on the hollow substrate using the improved semi-additive method. In addition, 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. After the ultra-thin copper layer is removed, a circuit is easily formed on the hollow substrate by using a semi-additive method.

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

In addition, in the manufacturing method of the above-mentioned hollow substrate, a part or all of the end surface of the copper foil with a carrier or a laminated body (laminated body A) is covered with a resin, and is manufactured by a build-up method When printing the wiring board, it can prevent the chemical solution from penetrating between one copper foil with a carrier and the other copper foil with a carrier constituting the intermediate layer or the laminate, and can prevent the separation or separation of the ultra-thin copper layer and the carrier caused by the penetration of the chemical solution. Corrosion of copper foil with carrier can improve yield. As the "resin covering part or all of the end surface of the copper foil with a carrier" or "resin covering part or all of the end surface of the laminate" used herein, a resin that can be used for the resin layer can be used. In addition, in the above-mentioned manufacturing method of the hollow substrate, the copper foil or laminate with a carrier may be a laminated portion of the copper foil with a carrier or a laminate (a laminated portion of a carrier and an ultra-thin copper layer) or a copper foil with a carrier and At least a part of the outer periphery of another laminated layer of the copper foil with a carrier) is covered with a resin or a prepreg. In addition, the laminated body (laminated body A) formed by the above-mentioned method for manufacturing a hollow substrate can be configured by allowing a pair of copper foils with a carrier to be separated from each other. In addition, the copper foil with a carrier may be a laminated portion of a copper foil with a carrier or a laminated body (a laminated portion of a carrier and an ultra-thin copper layer, or a laminated portion of one copper foil with a carrier and another copper foil with a carrier) in a plan view. The outer periphery of the copper foil is covered with resin or prepreg and has a copper foil with a carrier. By adopting such a structure, when the copper foil with the carrier or the laminated body is viewed from the top, the laminated portion of the copper foil with the carrier or the laminated body is covered with a resin or a prepreg, which can prevent other members from facing the side of the part, that is, facing each other. The impact is performed in a direction in which the lamination direction is transverse, and as a result, the peeling of the carrier and the ultra-thin copper layer or the copper foil with the carrier during the operation can be reduced. In addition, by covering the resin or prepreg so as not to expose the outer periphery of the laminated portion of the copper foil with the carrier or the laminated body, it is possible to prevent the penetration of the medicinal solution to the interface of the laminated portion in the medicinal solution processing step described above. , Which can prevent corrosion or erosion of the copper foil with a carrier. In addition, when one of the pair of copper foils with a carrier is separated from a pair of copper foils with a carrier from the laminated body, or when the carrier with a copper foil with a carrier is separated from a copper foil (ultra-thin copper layer), it is necessary to remove the resin by cutting or the like. Or laminated part of copper foil with carrier or laminate covered by prepreg (laminated part of carrier and ultra-thin copper layer, or one copper foil with carrier and another copper with carrier Laminated layer of foil).

The copper foil with a carrier of the present invention can be laminated from the carrier side or the ultra-thin copper layer side of the carrier side or the ultra-thin copper layer side of another copper foil with a carrier of the present invention to form a laminated body. In addition, the carrier-side surface or the ultra-thin copper layer side surface of the one copper foil with a carrier and the carrier-side surface or the ultra-thin copper of the other copper foil with a carrier may be connected to the carrier-side copper foil with a carrier through an adhesive as needed. A laminated body obtained by directly laminating the layer-side surfaces. In addition, the carrier or the ultra-thin copper layer of the one copper foil with a carrier may be bonded to the carrier or the ultra-thin copper layer of the other copper foil with a carrier. Here, when the carrier or the ultra-thin copper layer has a surface treatment layer, the "bonding" also includes a state in which they are bonded to each other through the surface treatment layer. In addition, part or all of the end face of the laminated body may be covered with a resin.

Except for simply stacking the carriers, the following methods can be used, for example.

(a) Metallurgical joining methods: fusion welding (arc welding, TIG (tungsten inert gas) welding, MIG (metal inert gas) welding, resistance welding, seam welding, spot welding), pressure welding (ultrasonic Welding, friction stir welding), soft welding; (b) mechanical joining methods: caulking, joining by rivets (joining by self-piercing rivets, joining by rivets), stapler; (c) physical joining Method: Adhesive, (Double-sided) Tape

By joining a part or all of one carrier with a part or all of another carrier using the above-mentioned joining method, a laminated body constituted by laminating one carrier and another carrier and bringing the carriers into contact with each other in a separable manner can be manufactured. . When one carrier is weakly bonded to another carrier and one carrier is laminated with another carrier, the one carrier and the other carrier can be separated without removing the joint between the one carrier and 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 the one carrier is bonded to the other carrier by cutting, chemical grinding (etching, etc.), mechanical grinding, etc. .

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

[Example]

As Examples 1 to 11 and Comparative Examples 1 to 10, copper foils having the thicknesses described 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 produce metal layers (rough Chemical treatment layer, heat discoloration prevention layer, rust prevention layer, or silane coupling layer). Here, rolled copper foils of refined copper (JIS H3100 C1100R) manufactured by JX Nippon Nissei Metal Co., Ltd. were 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. . In addition, the electrolytic copper foil HLP foil manufactured by JX Nippon Nissei Metal Co., Ltd. was used as the copper foil of Examples 5 to 6 and Comparative Examples 5 to 6.

In addition, the copper foil with a carrier described below was prepared as the copper foil base material 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). Layer, heat discoloration prevention layer, rust prevention layer, or silane coupling layer).

For Examples 12 to 14 and 16, an electrolytic copper foil with a thickness of 18 μm was prepared as a carrier, and for Example 15, a rolled copper foil with a thickness of 18 μm (C1100R manufactured by JX Nippon Steel and Nippon Metal) was prepared as a carrier. Then, an intermediate layer is formed on the surface of the carrier under the following conditions, and An extremely thin copper layer is formed on the surface of the intermediate layer.

． Example 12

<Middle layer>

(1) Ni layer (Ni plating)

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

Nickel sulfate: 270 ~ 280g / L

Nickel chloride: 35 ~ 45g / L

Nickel acetate: 10 ~ 20g / L

Boric acid: 30 ~ 40g / L

Luster: Saccharin, butynediol, etc.

Sodium lauryl sulfate: 55 ~ 75ppm

pH value: 4 ~ 6

Bath temperature: 55 ~ 65 ℃

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 continuous plating line. Under the following conditions, 11 μg / dm ^{2 was} processed by electrolytic chromate treatment. The deposited Cr layer adheres to the Ni layer.

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

pH value: 7 ~ 10

Liquid temperature: 40 ~ 60 ℃

Current density: 2A / dm ²

<Ultra-thin copper layer>

Next, the surface of the Cr layer formed in (2) was washed with water and pickled, and then continued on a roll-to-roll continuous plating line. Under the following conditions, a 1.5 μm thick Cr layer was formed by electroplating. Ultra-thin copper layer to make extremely thin copper foil with 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

In addition, 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 ℃

Current density: 100A / dm ²

Linear speed of electrolyte: 1.5 ~ 5m / sec

． Example 13

<Middle layer>

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

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

(Liquid composition) Ni sulfate hexahydrate: 50 g / dm ³ , sodium molybdate dihydrate: 60 g / dm ³ , sodium citrate: 90 g / dm ³

(Liquid temperature) 30 ℃

(Current density) 1 ~ 4A / dm ²

(Power-on time) 3 ~ 25 seconds

<Ultra-thin copper layer>

An extremely thin copper layer was 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 extremely thin copper layer was set to 2 μm.

． Example 14

<Middle layer>

(1) Ni layer (Ni plating)

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

(2) Organic layer (organic layer forming treatment)

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

<Ultra-thin copper layer>

An extremely thin copper layer is formed on the organic substance 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 extremely thin copper layer was 3 μm.

． Examples 15, 16

<Middle layer>

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

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

(Liquid composition) Co sulfate: 50 g / dm ³ , sodium molybdate dihydrate: 60 g / dm ³ , sodium citrate: 90 g / dm ³

(Liquid temperature) 30 ℃

(Current density) 1 ~ 4A / dm ²

(Power-on time) 3 ~ 25 seconds

<Ultra-thin copper layer>

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

Next, under the conditions of Table 2, a surface treatment liquid was applied to the entire copper foil on the above-mentioned rolled copper foil, electrolytic copper foil, or copper foil with a carrier, or a base layer (metal layer) on each of the copper foils. The surface of the object to be treated is further washed with water and desiccated, and dried. Form a surface treatment layer.

The meaning of the "application method of chromate solution" column is as follows.

The "sprayer" is performed using a spray nozzle (a standard fan-shaped nozzle manufactured by Ichiuchi Co., Ltd. with a spray angle of 90 ° and a spray volume of 10).

The "roller" is performed using a sponge roller made of polyvinyl alcohol.

The "blade" is performed using a resin spatula (polyester, 0.35 mm in thickness).

"Immersion chromate" is performed by immersing a copper foil in the chromate solution of the conditions described in Table 2 for 2 seconds.

The "electrolytic chromate" is processed by immersing a copper foil in a chromate solution under the conditions described in Table 2 and flowing a current in the copper foil at a current density of 2 A / dm ² for 1 second.

The meanings of the "dehydration method" and "dehydration conditions" columns are as follows.

"Roller" means dehydration using a sponge roller made of polyvinyl alcohol. The "liquid removing condition" when the "liquid removing method" is "roller" refers to the pressing force of the roll per unit width of the copper foil.

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

"Gas blowing" means dehydration by blowing air to a copper foil from a gas blowing nozzle. The distance between the gas outlet of the gas blowing nozzle and the copper foil was set to 50 mm. The "liquid removal condition" when the "liquid removal method" is "gas blowing" refers to the flow rate of the gas blown by the copper foil.

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

． Example 17

． Silane used: 3-Methacryloxypropyltrimethoxysilane (methacryloxy-based silane coupling agent)

． Silane concentration: 0.6vol% (the rest: water)

． Processing temperature: 30 ~ 40 ℃

． Processing time: 5 seconds

． Drying after silane treatment: 100 ℃ × 3 seconds

． Example 18

． Silane used: N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (amino-based silane coupling agent)

． Silane concentration: 5.0vol% (remainder: water)

． Processing temperature: 45 ~ 55 ℃

． Processing time: 5 seconds

． Drying after silane treatment: 100 ℃ × 3 seconds

Various evaluations were performed on the samples of the examples and comparative examples produced as described above as follows.

． Metal adhesion of metal layer:

(1) Ni, Co, W, Mo adhesion

For the measurement of the adhesion amount of various metals in the metal layer, a film on the surface of a copper foil of 50 mm × 50 mm was dissolved in a solution prepared by mixing HNO ₃ (2% by weight) and HCl (5% by weight), and ICP was used. A luminescence spectroscopic analyzer (SII NanoTechnology Co., Ltd., SFC-3100) quantifies the metal concentration in the solution, calculates and outputs the metal amount per unit area (μg / dm ² ). At this time, in order to prevent the metal adhering amount on the opposite side from the surface to be measured from being mixed in, it is masked and analyzed as necessary.

(2) Zn and Cr adhesion:

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

The adhesion amount of hexavalent chromium was measured by the diphenyl carbazid absorbance method in the following manner.

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

In addition, "65.2.1c) Operation 1)" is not neutralized, and the liquid obtained above is used as "2)" "Beaker (A) Solution" and "3)" "Beaker (B) Solution" , Perform the operations after "65.2.1c) 2)".

The absorbance photometer is a 220A type manufactured by Hitachi. The measurement wavelength of the absorbance was 540 nm, and the sample cell was a cell having an optical path length of 10 mm made of glass.

The adhesion amount of trivalent chromium is the trivalent chromium and hexavalent value measured by the above-mentioned atomic absorption analysis. The value of the total adhesion amount of chromium was calculated by subtracting the value of the adhesion amount of hexavalent chromium measured by the above-mentioned diphenylcarbazine photometry.

． Surface treatment layer made of chromium oxide:

The elements in the surface and depth directions were analyzed by ESCA. When chromium and oxygen were detected on the surface or the same depth, it was judged to have a surface treatment layer formed of chromium oxide. In addition, the surface analysis using ESCA was performed on each of the examples and comparative examples described above, and as a result, chromium and oxygen were detected. Therefore, the copper foil of each example and comparative example has a surface treatment made of chromium oxide. Floor.

． Surface treatment layer thickness:

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

The thickness of the surface treatment layer (nm) = trivalent chromium deposition amount (μg / dm ²⁾ / trivalent chromium density of ^{7.2g / cm 3 × 0.1 (nm} × (g / cm 3) / (μg / dm 2) )

． Dissolution in nitric acid:

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

The eluted amount was calculated using the following formula.

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

The weight of the sample was measured by an electronic balance to four decimal places (0.1 mg).

． Peel strength:

According to IPC-TM-650, the normal peel strength was measured using a tensile tester Autograph 100, and the normal peel strength was 0.7 kN / mm or more as a sample that can be used for copper-clad laminated substrate applications.

． PCT (high pressure cooking test):

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

． Transmission loss

For each sample of 18 μm thickness, 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.)), followed by etching. A microstrip line was formed so that the characteristic impedance became 50Ω. The transmission coefficient was measured using a network analyzer HP8720C manufactured by HP, and the transmission loss at a frequency of 20GHz was obtained. In addition, for samples with a copper foil thickness of less than 18 μm, the total thickness of the copper foil and the copper plating was obtained after the copper foil was bonded to the resin substrate (after the copper foil is peeled from the copper foil when the carrier is removed). The above measurement was performed after copper-plating the surface of a copper foil so that it might become 18 micrometers.

The transmission loss is calculated by the following formula.

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

Table 3 shows the conditions and evaluations of the above tests. Table 4 shows the acceptance criteria of the peel strength.

According to Table 3, regarding Examples 1 to 18, when a heat treatment of 250 ° C. for 10 minutes was applied, the surface of the surface treatment layer was exposed only in a state of being immersed in a nitric acid bath having a concentration of 20 mass% and a temperature of 25 ° C. for 30 seconds The dissolution amount of copper in the nitric acid bath is 0.0030 g / 25 cm ² or less, and the peel strength is good.

On the other hand, in Comparative Examples 1 to 5, 10, after applying a heat treatment at 250 ° C. for 10 minutes, immersed in a nitric acid bath having a concentration of 20 mass% and a temperature of 25 ° C. in a state where only the surface of the surface treatment layer was exposed. In seconds, the elution amount of copper in the nitric acid bath exceeded 0.0030 g / 25 cm ² , and the peel strength was poor.

In Comparative Example 6, since the total adhesion amount of the element selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr in the metal layer was not more than 200 μg / dm ² , the peel strength was poor.

In addition, in Comparative Examples 7 to 9, since the total adhesion amount of an element 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 (55)

A surface-treated copper foil comprising, 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 made of chromium oxide Layer, the total adhesion amount of the element selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr in the above-mentioned metal layer is 200 to 2000 μg / dm ^{2. After} applying a heat treatment at 250 ° C. for 10 minutes, only when the nitric acid bath immersion exposed surface of the surface treatment layer in a state concentration of 20mass% and a temperature of 25 ℃ for 30 seconds, the amount of copper dissolution in nitric acid bath of 0.0030g / 25cm ² or less. For example, the surface-treated copper foil of the first scope of the application for a patent, wherein the total adhesion amount of an 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 . For example, the surface-treated copper foil of the second scope of the patent application, wherein 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 . The patentable scope of the application as a surface-treated copper foil Paragraph 3, wherein the total amount of the element attaching group consisting of the metal layer selected freely Ni, Co, Zn, W, Mo and Cr is 200 ~ 700μg / dm ² . For example, the surface-treated copper foil according to item 1 of the scope of patent application, wherein in the above-mentioned surface-treated layer, the adhesion amount of hexavalent chromium is 0.1% or less of the adhesion amount of trivalent chromium. For example, the surface-treated copper foil according to item 2 of the scope of patent application, wherein in the above-mentioned surface-treated layer, the adhesion amount of hexavalent chromium is 0.1% or less of the adhesion amount of trivalent chromium. For example, the surface-treated copper foil according to item 3 of the patent application scope, wherein the adhesion amount of hexavalent chromium in the surface treatment layer is 0.1% or less of the adhesion amount of trivalent chromium. For example, the surface-treated copper foil according to item 4 of the scope of patent application, wherein in the above-mentioned surface-treated layer, the adhesion amount of hexavalent chromium is 0.1% or less of the adhesion amount of trivalent chromium. For example, the surface-treated copper foil of item 1 of the patent application scope, wherein the thickness of the surface-treated layer is 0.1 to 2.5 nm. For example, the surface-treated copper foil according to item 2 of the patent application scope, wherein the thickness of the surface-treated layer is 0.1 to 2.5 nm. For example, the surface-treated copper foil of item 3 of the patent application scope, wherein the thickness of the surface-treated layer is 0.1 to 2.5 nm. For example, the surface-treated copper foil for item 4 of the scope of patent application, wherein the thickness of the surface-treated layer is 0.1 to 2.5 nm. For example, the surface-treated copper foil according to item 5 of the patent application scope, wherein the thickness of the surface-treated layer is 0.1 to 2.5 nm. For example, the surface-treated copper foil according to item 6 of the application, wherein the thickness of the surface-treated layer is 0.1 to 2.5 nm. For example, the surface-treated copper foil according to item 7 of the scope of patent application, wherein the thickness of the surface-treated layer is 0.1 to 2.5 nm. For example, the surface-treated copper foil of item 8 of the patent application scope, wherein the thickness of the surface-treated layer is 0.1 to 2.5 nm. For example, the surface-treated copper foil according to any one of claims 1 to 16, wherein the metal layer includes a heat discoloration prevention layer and / or a rust prevention layer. For example, the surface-treated copper foil according to item 17 of the scope of the patent application, wherein the heating discoloration prevention layer and the rust prevention layer are Zn, Cu, or an alloy thereof. For example, the surface-treated copper foil according to item 17 of the application, wherein the anti-rust layer includes a chromate layer or a zinc chromate layer. For example, the surface-treated copper foil according to claim 18, wherein the rust-preventive layer includes a chromate layer or a zinc chromate layer. For example, the surface-treated copper foil according to any one of claims 1 to 16, wherein the metal layer includes a silane coupling layer. For example, the surface-treated copper foil according to any of claims 1 to 16 of the patent application scope, which has a silane coupling layer formed on the surface-treated layer. For example, the surface-treated copper foil according to any one of claims 1 to 16 includes a resin layer on the surface of the surface-treated layer. For example, the surface-treated copper foil according to item 22 of the patent application scope includes a resin layer on the surface of the silane coupling layer. For example, the surface-treated copper foil according to item 23 of the application, wherein the resin layer contains a dielectric. For example, the surface-treated copper foil according to item 24 of the application, wherein the resin layer contains a dielectric. A surface-treated copper foil comprising, 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 made of chromium oxide Layer, the total adhesion amount of the element selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr in the above-mentioned metal layer is 200 to 2000 μg / dm ^{2. After} applying a heat treatment at 250 ° C. for 10 minutes, only When the surface of the surface-treated layer was exposed, when the nitric acid bath having a concentration of 20 mass% and a temperature of 25 ° C. was immersed for 30 seconds, the amount of copper dissolved in the nitric acid bath was 0.0030 g / 25 cm ² or less. The surface-treated copper foil satisfies the following (1) to (12) at least one of the conditions: (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 an 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 ; (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 trivalent chromium, (5) the thickness of the surface treatment layer is 0.1 to 2.5 nm, (6) the metal layer includes a heat discoloration prevention layer and / or a rust prevention layer, (7 ) The heat discoloration prevention layer and the rust prevention layer are Zn, Cu, or an alloy thereof, (8) the rust prevention layer contains a chromate layer or a zinc chromate layer, and (9) the metal layer contains a silane coupling layer, (10) a silane coupling layer is formed on the surface treatment layer; (11) a resin layer is provided on the surface of the surface treatment layer; (12) a silane coupling layer is formed on the surface treatment layer; The surface is provided with a resin layer. A copper foil with a carrier has an intermediate layer and an ultra-thin copper layer in sequence on one or both sides of the carrier, and the ultra-thin copper layer is a surface-treated copper foil according to any one of claims 1 to 27 of the scope of patent application. For example, the copper foil with a carrier in the scope of the patent application No. 28, wherein one side of the carrier has the intermediate layer, the ultra-thin copper layer in this order, and a roughened layer on the other side of the carrier. A laminated body is a laminated body of a surface-treated copper foil and a resin substrate according to any one of claims 1 to 27. For example, the laminated body according to item 30 of the scope of application, wherein the surface-treated copper foil and the resin substrate are laminated without an adhesive. A laminated body is a laminated body with a copper foil with a carrier and a resin substrate in the scope of patent application No. 28 or 29. A laminated body comprising the copper foil with a carrier and resin in the scope of application for patent No. 28 or 29, and a part or all of the end surface of the copper foil with a carrier is covered with the resin. A laminated body comprising a copper foil with a carrier and a copper foil with a carrier from one of the above-mentioned carrier side or the ultra-thin copper layer side of another patent application with a copper foil with a carrier from one of the patent scopes 28 or 29 The carrier side or the ultra-thin copper layer side. For example, the laminated body of the scope of application for the patent No. 34 is to combine the carrier side surface or the ultra-thin copper layer side surface of the one copper foil with a carrier and the carrier side surface or the ultra-thin surface of the other copper foil with a carrier The copper layer side surface is configured by directly laminating the adhesive layer through an adhesive if necessary. For example, the laminated body of the scope of application for the patent No. 34 is the above-mentioned carrier or the ultra-thin copper layer with the carrier copper foil and the above carrier or the ultra-thin copper with the carrier copper foil Layer bonding. For example, the laminated body of the 35th scope of the patent application is to join the above-mentioned carrier or the ultra-thin copper layer with the carrier copper foil with the above-mentioned carrier or the ultra-thin copper layer with the carrier copper foil. For example, the laminated body of the scope of application for patent No. 34, part or all of its end face is covered with resin. For example, the laminated body of item 36 of the patent application has a part or all of its end face covered with resin. A method for manufacturing a printed wiring board, comprising the steps of: performing a step of providing a resin layer and a circuit layer at least once on a multilayer body according to any one of claims 30 to 39; and at least once After forming the two layers of the resin layer and the circuit, the step of peeling the ultra-thin copper layer or the carrier from the copper foil with a carrier of the laminate. A printed wiring board using a laminate of any one of claims 30 to 39 as a material. An electronic device includes a printed wiring board having the scope of patent application No. 41. A method for manufacturing a surface-treated copper foil, which is a method for manufacturing a surface-treated copper foil according to any one of claims 1 to 27, including the following steps: a chromate solution is provided on the entire treatment of the copper foil A step of forming a surface treatment layer of chromium oxide by placing a chromate solution on the surface of a copper foil and drying it without washing with water; For example, in the method for manufacturing a surface-treated copper foil according to item 43 of the scope of patent application, in the step of forming the surface-treated layer of the chromium oxide, a chromate solution is placed on the surface of the copper foil and then The solution was deliquored and then dried without washing with water, thereby forming a surface-treated layer of chromium oxide. For example, the method for manufacturing a surface-treated copper foil according to item 44 of the application, wherein the amount of the chromate solution provided on the surface of the copper foil is 5 to 20 mg / dm ² after the liquid is removed. For example, the method for manufacturing a surface-treated copper foil according to item 44 of the application, wherein the deliquoring is performed by blowing with a roller, a blade, and / or a gas. For example, the method for manufacturing a surface-treated copper foil according to item 45 of the application, wherein the above-mentioned dehydration is performed by blowing with a roller, a blade, and / or a gas. For example, the method for manufacturing a surface-treated copper foil according to item 43 of the patent application, wherein the step of setting the chromate solution on the entire surface of the copper foil to be treated is to apply the chromate solution to the entire surface of the copper foil using a shower. It was performed on the surface of the said copper foil. For example, the method for manufacturing a surface-treated copper foil according to item 43 of the application, wherein 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. On the foil surface. For example, the method for manufacturing a surface-treated copper foil according to item 43 of the application, wherein the pH of the chromate solution is 1 to 10. For example, the method for manufacturing a surface-treated copper foil according to item 50 of the application, wherein the pH of the chromate solution is 4-10. A method for manufacturing a printed wiring board, comprising the steps of: preparing a copper foil with a carrier and an insulating substrate, and applying a laminated copper foil with a carrier, and an insulating substrate; and After laminating the copper foil with a carrier and an insulating substrate, the copper foil with a carrier is peeled off. A step of carrying a foil to form a copper-clad laminate, and thereafter, a 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 for manufacturing a printed wiring board, comprising the steps of: forming a circuit on the above-mentioned ultra-thin copper layer side surface of the copper foil with a carrier or on the above-mentioned carrier side surface of a copper foil with a carrier in the scope of patent application No. 28 or 29; A method of forming a resin layer on the ultra-thin copper layer side surface of the copper foil with a carrier or the carrier side surface; a step of forming a circuit on the resin layer; after forming a circuit on the resin layer, the carrier or The step of peeling the ultra-thin copper layer; and removing the ultra-thin copper layer or the carrier after peeling the carrier or the ultra-thin copper layer, so that the ultra-thin copper layer or the carrier is formed on the surface of the ultra-thin copper layer or the carrier And a step of exposing the circuit buried in the resin layer. A method for manufacturing a printed wiring board, comprising the steps of: laminating the ultra-thin copper layer side surface of the copper foil with a carrier or the carrier side surface of the copper foil with a carrier and a resin substrate; and Performing the step of setting the resin layer and the circuit at least once on the ultra-thin copper layer side surface of the copper foil with a carrier opposite to the resin substrate laminated side or the carrier side surface; and forming the resin layer and the circuit After the two layers, the step of peeling the carrier or the ultra-thin copper layer from the copper foil with the carrier is performed. A method for manufacturing a printed wiring board includes the following steps: The step of laminating the above-mentioned carrier-side surface of the copper foil with a carrier and a resin substrate according to item 28 or 29; performing at least one setting on the ultra-thin copper-layer-side surface of the above-mentioned copper foil with a carrier opposite to the side of the resin substrate laminated layer A step of two layers of a resin layer and a circuit; and a step of peeling the ultra-thin copper layer from the copper foil with a carrier after the two layers of the resin layer and the circuit are formed.