JP6293093B2 - Surface-treated copper foil, copper foil with carrier, laminate, printed wiring board, electronic device, method for producing surface-treated copper foil, and method for producing printed wiring board - Google Patents

Description

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

  In a small electronic device such as a smartphone or a tablet PC, a flexible printed wiring board (hereinafter referred to as FPC) is adopted because of easy wiring and light weight. In addition, for FPC, a desired wiring is formed by a subtractive method or an additive method using a two-layer flexible substrate in which a base layer made of metal or metal oxide is directly provided on an insulator substrate and a copper conductor layer is formed. There is a two-layer flexible printed wiring board on which a pattern is formed.

  Flat rolled copper foil is widely used for such a two-layer flexible printed wiring board. In recent years, a copper foil having a smaller thickness is preferably used in order to improve flexibility and fine etching. However, the highly flexible rolled copper foil becomes soft because the crystal size becomes large after recrystallization, and in the case of a thin foil of 10 μm or less, the apparent peel strength is lowered, and there is a problem in bonding with a resin substrate. May occur.

Therefore, for the purpose of improving the peel strength, a method of surface treatment of the adhesive surface of the copper foil resin with a silane coupling agent containing hexavalent chromium has been proposed. Silane precipitates when mixed with hexavalent chromium.
For example, Patent Documents 1 to 5 disclose these conventional techniques.

  Further, with the recent increase in needs for downsizing and higher performance of electronic devices, high density mounting of mounted components and higher frequency of signals have progressed, and excellent high frequency response is required for printed wiring boards.

  The high frequency board is required to reduce transmission loss in order to ensure the quality of the output signal. The transmission loss mainly consists of a dielectric loss due to the resin (substrate side) and a conductor loss due to the conductor (copper foil side). The dielectric loss decreases as the dielectric constant and dielectric loss tangent of the resin decrease. In a high-frequency signal, the conductor loss is mainly caused by a decrease in the cross-sectional area through which the current flows due to the skin effect that only the surface of the conductor flows as the frequency increases, and the resistance increases.

  As a technique aimed at reducing the transmission loss of the high-frequency copper foil, for example, in Patent Document 6, one or both surfaces of the metal foil surface is coated with silver or a silver alloy metal, and the silver or silver alloy coating is applied. A metal foil for a high-frequency circuit is disclosed in which a coating layer other than silver or a silver alloy is applied on the layer thinner than the thickness of the silver or silver alloy coating layer. And according to this, it is described that it is possible to provide a metal foil in which the loss due to the skin effect is reduced even in an ultra-high frequency region used in satellite communications.

  Patent Document 7 discloses that the integrated intensity (I (200)) of (200) plane obtained by X-ray diffraction on the rolled surface after recrystallization annealing of the rolled copper foil is the X-ray diffraction of fine powder copper. Roughening treatment after I (200) / I0 (200)> 40 with respect to the obtained integrated strength (I0 (200)) of (200) plane, and after performing roughening treatment by electrolytic plating on the rolled surface The arithmetic average roughness (hereinafter referred to as Ra) of the surface is 0.02 μm to 0.2 μm, the ten-point average roughness (hereinafter referred to as Rz) is 0.1 μm to 1.5 μm, and for printed circuit boards A roughened rolled copper foil for high-frequency circuits, characterized by being a material, is disclosed. And it is described that according to this, the printed circuit board which can be used under the high frequency exceeding 1 GHz can be provided.

  Furthermore, Patent Document 8 discloses an electrolytic copper foil characterized in that a part of the surface of the copper foil is an uneven surface having a surface roughness of 2 μm to 4 μm made of bump-shaped protrusions. And according to this, it describes that the electrolytic copper foil excellent in the high frequency transmission characteristic can be provided.

Japanese Patent No. 3292774 Japanese Patent No. 3306404 Japanese Patent No. 3906347 International Publication No. 2009-81889 Japanese Patent Laid-Open No. 11-158652 Japanese Patent No. 4161304 Japanese Patent No. 4770425 JP 2004-244656 A

  However, when surface treatment of the adhesive surface of the copper foil with the silane coupling agent containing hexavalent chromium is performed, it does not match the manufacturing process of the two-layer flexible printed wiring board, and the peel strength is reduced. In addition, there is a problem that the aggregation of silane in the silane coupling agent is promoted. In Patent Document 5, the electrolytic copper foil is immersed in an alkaline solution of chromic anhydride (chromic anhydride: 6 g / L; sodium hydroxide: 15 g / L; pH: 12.5; bath temperature: 25 ° C.) for 5 seconds. However, the surface-treated copper foil is produced by forming a rust preventive film on both sides of the copper foil. When a treatment liquid having a high pH is used, NaOH and KOH are taken out of the treatment liquid and dried. , Salt is formed, and good peel strength cannot be obtained.

  Moreover, regarding the transmission loss, the conductor loss caused by the conductor (copper foil side) is caused by the increase in resistance due to the skin effect as described above. This resistance is not only the resistance of the copper foil itself, but also the copper loss. There is also the influence of the resistance of the surface treatment layer formed by the roughening treatment performed to ensure adhesion to the resin substrate on the foil surface, specifically, the roughness of the copper foil surface is the main conductor loss. It is known that the transmission loss decreases as the roughness decreases.

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

  As a result of intensive research, the inventor has formed a chromium oxide surface treatment layer on the side of the copper foil that is bonded to the resin substrate, and a predetermined element and adhesion amount between the surface treatment layer and the copper foil. It was found that the peel strength of the surface-treated copper foil is improved by controlling the elution amount of copper when the surface-treated layer is immersed in a nitric acid bath under predetermined conditions. .

In one aspect, the present invention completed on the basis of the above knowledge is a copper foil, a metal layer containing at least one element selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr, and a chromium oxide. A surface-treated copper foil having a surface-treated layer formed in this order, and a total adhesion amount of elements selected from the group consisting of Ni, Co, Zn, W, Mo and Cr in the metal layer is 200 to When it was immersed in a nitric acid bath having a concentration of 20 mass% and a temperature of 25 ° C. for 30 seconds with only the surface of the surface treatment layer exposed after applying heat treatment at 250 ° C. × 10 minutes at 2000 μg / dm ² The surface-treated copper foil has an elution amount of copper into the nitric acid bath of 0.0030 g / 25 cm ² or less.

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

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

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

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

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

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

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

  In still another embodiment of the surface-treated copper foil according to 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 according to the present invention, the metal layer includes a silane coupling layer.

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

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

  In still another embodiment of the surface-treated copper foil according to the present invention, a resin layer is provided on the surface of the silane coupling layer.

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

  Another aspect of the present invention is a copper foil with a carrier having an intermediate layer and an ultrathin copper layer in this order on one or both sides of the carrier, wherein the ultrathin copper layer is the present invention. It is a copper foil with a carrier which is a surface-treated copper foil.

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

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

  In one Embodiment of the laminated body of this invention, the said surface treatment copper foil and the said resin substrate are laminated | stacked without the adhesive agent.

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

  According to still another aspect of the present invention, there is provided a laminate including the carrier-attached copper foil of the present invention and a resin, wherein the end face of the carrier-attached copper foil is partially or entirely covered with the resin. It is.

  In yet another aspect of the present invention, the carrier-attached copper foil of the present invention is separated from the carrier side or the ultrathin copper layer side of the present invention, and the carrier-side copper foil of the present invention of the other is provided. It is the laminated body laminated | stacked on the copper layer side.

  In one embodiment of the laminate of the present invention, the carrier-side surface or ultrathin copper layer side surface of the one carrier-attached copper foil and the carrier-side surface or ultrathin copper of the another carrier-attached copper foil. The layer-side surface is configured to be directly laminated through an adhesive as necessary.

  In another embodiment of the laminate of the present invention, the carrier or the ultrathin copper layer of the one carrier-attached copper foil and the carrier or the ultrathin copper layer of the other carrier-attached copper foil are joined. Has been.

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

  In yet another aspect, the present invention is a method for producing a printed wiring board using the laminate of the present invention.

  In another aspect of the present invention, the step of providing the laminate of the present invention with two layers of a resin layer and a circuit at least once, and after forming the resin layer and the two layers of the circuit at least once, It is a manufacturing method of a printed wiring board including the process of peeling the ultra-thin copper layer or the carrier from the copper foil with a carrier of the layered product.

  In yet another aspect, the present invention is a printed wiring board made from the laminate of the present invention.

  In still another aspect, the present invention is an electronic device including the printed wiring board of the present invention.

  In another aspect of the present invention, the step of providing a chromate solution over the entire surface of the copper foil to be treated, and the surface treatment of the chromium oxide by drying the chromate solution without washing with water after providing the copper foil surface. It is a manufacturing method of the surface treatment copper foil of this invention provided with the process of forming a layer.

  In one embodiment of the method for producing a surface-treated copper foil of the present invention, in the step of forming the surface treatment layer of the chromium oxide, after the chromate solution is provided on the surface of the copper foil, the liquid is drained and then not washed with water. The surface treatment layer of chromium oxide is formed by drying with.

In another one Embodiment of the manufacturing method of the surface treatment copper foil of this invention, the quantity which provided the said chromate liquid to the copper foil surface is 5-20 mg / dm < ² > after the said liquid draining.

  In another embodiment of the manufacturing method of the surface-treated copper foil of this invention, the said liquid draining is performed by spraying a roll, a braid | blade, and / or gas.

  In another embodiment of the method for producing a surface-treated copper foil of the present invention, the step of providing the chromate solution over the entire surface to be treated of the copper foil is performed by applying the chromate solution to the copper foil surface by showering. .

  In another embodiment of the method for producing a surface-treated copper foil of the present invention, the step of providing the chromate solution over the entire surface to be treated of the copper foil is performed by applying the chromate solution to the surface of the copper foil with a roller. .

  In another one Embodiment of the manufacturing method of the surface treatment copper foil of this invention, pH of the said chromate liquid is 1-10.

  In another one Embodiment of the manufacturing method of the surface treatment copper foil of this invention, pH of the said chromate liquid is 4-10.

In another aspect of the present invention, a step of preparing the carrier-attached copper foil of the present invention and an insulating substrate,
Laminating the copper foil with carrier and an insulating substrate;
After laminating the copper foil with carrier and the insulating substrate, a copper clad laminate is formed through a step of peeling the carrier of the copper foil with carrier,
Thereafter, the printed wiring board manufacturing method includes a step of forming a circuit by any one of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method.

  In one embodiment of the method for producing a printed wiring board according to the present invention, a step of forming a circuit on the ultrathin copper layer side surface or the carrier side surface of the carrier-attached copper foil of the present invention, the circuit is buried. A step of forming a resin layer on the ultrathin copper layer side surface or the carrier side surface of the carrier-attached copper foil, a step of forming a circuit on the resin layer, a circuit on the resin layer, After peeling the carrier or the ultrathin copper layer, and after peeling the carrier or the ultrathin copper layer, by removing the ultrathin copper layer or the carrier, the surface of the ultrathin copper layer or It is a manufacturing method of a printed wiring board including the process of exposing the circuit embedded in the resin layer formed in the carrier side surface.

  In yet another aspect of the present invention, the step of laminating the ultrathin copper layer side surface or the carrier side surface of the copper foil with carrier of the present invention and the resin substrate, laminating with the resin substrate of the copper foil with carrier. A step of providing two layers of a resin layer and a circuit at least once on the surface of the ultrathin copper layer opposite to the side or the carrier side surface, and after forming the two layers of the resin layer and the circuit, It is a manufacturing method of a printed wiring board including the process of exfoliating the career or the ultra-thin copper layer from copper foil with a carrier.

  In yet another aspect of the present invention, the step of laminating the carrier-side surface of the copper foil with a carrier and a resin substrate of the present invention, the ultrathin side opposite to the side of the copper foil with carrier and laminating the resin substrate The step of providing at least one layer of a resin layer and a circuit on the copper layer side surface, and after forming the two layers of the resin layer and the circuit, the ultrathin copper layer is peeled from the copper foil with carrier. It is a manufacturing method of a printed wiring board including a process.

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

AC is a schematic diagram of the wiring board cross section in the process to circuit plating and the resist removal based on the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention. DF is a schematic diagram of a cross section of a wiring board in a process from lamination of a resin and copper foil with a second layer carrier to laser drilling according to a specific example of a method for producing a printed wiring board using a copper foil with a carrier of the present invention. It is. GI is a schematic diagram of the wiring board cross section in the process from the via fill formation to the first layer carrier peeling according to a specific example of the method for manufacturing a printed wiring board using the carrier-attached copper foil of the present invention. J to K are schematic views of a cross section of a wiring board in steps from flash etching to bump / copper pillar formation according to a specific example of a method of manufacturing a printed wiring board using the carrier-attached copper foil of the present invention.

[Configuration of surface-treated copper foil]
The surface-treated copper foil of the present invention includes a copper foil, a metal layer containing at least one element selected from the group consisting of Ni, Co, Zn, W, Mo and Cr, and a surface-treated layer formed of chromium oxide. And in this order.
There is no restriction | limiting in particular in the form of the copper foil base material which can be used for this invention, Typically, the copper foil used in this invention may be either an electrolytic copper foil or a rolled copper foil. In general, the electrolytic copper foil is produced by electrolytic deposition of copper from a copper sulfate plating bath onto a drum of titanium or stainless steel, and the rolled copper foil is produced by repeating plastic working and heat treatment with a rolling roll. Rolled copper foil is often used for applications that require flexibility.
In addition to high-purity copper such as tough pitch copper and oxygen-free copper, which are usually used as conductor patterns for printed wiring boards, for example, Sn-containing copper, Ag-containing copper, Cr, Zr or Mg are added as the copper foil base material. It is also possible to use a copper alloy such as a copper alloy, a Corson copper alloy to which Ni, Si and the like are added. In addition, when the term “copper foil” is used alone in this specification, a copper alloy foil is also included.
The thickness of the copper foil substrate need not be particularly limited, but for example, 1 to 1000 μm, alternatively 1 to 500 μm, alternatively 1 to 300 μm, alternatively 3 to 100 μm, alternatively 5 to 70 μm, alternatively 6 to 35 μm, or 9 ˜18 μm.

The surface-treated copper foil of the present invention has a surface-treated layer formed of chromium oxide, and after heat treatment at 250 ° C. for 10 minutes, only the surface of the surface-treated layer is exposed. When immersed in a nitric acid bath having a concentration of 20 mass% and a temperature of 25 ° C. for 30 seconds, the elution amount of copper into the nitric acid bath is 0.0030 g / 25 cm ² or less. As the surface treatment, there is a method in which a metal chromium layer is formed on the surface of the copper foil by sputtering or the like, but the corrosion resistance against acid is inferior, and there is a possibility of being eroded by the etching solution in the circuit forming process of the flexible substrate. On the other hand, the surface treatment layer of the present invention is formed of chromium oxide, and the amount of copper eluted into the nitric acid bath is 0 when immersed in a nitric acid bath having a concentration of 20 mass% and a temperature of 25 ° C. for 30 seconds. Since it is controlled to be not more than .0030 g / 25 cm ^{2, the} corrosion resistance against the etching solution is good. In addition, the controlled amount of copper eluted into the acid in this way indicates that the surface treatment layer is densely and uniformly formed by the chromium oxide, so that the adhesion to the resin substrate is improved. And the peel strength is improved. The above “after heat treatment at 250 ° C. for 10 minutes” defines general heat treatment conditions for bonding to the polyimide substrate.

  In the surface-treated copper foil of the present invention, the amount of hexavalent chromium attached is preferably 0.1% or less of the amount of trivalent chromium attached in the surface treatment layer. According to such a configuration, the ratio of the amount of hexavalent chromium deposited is controlled, which is advantageous from the viewpoint of safety.

  In the surface-treated copper foil of the present invention, the surface-treated layer preferably has a thickness of 0.1 to 2.5 nm. Thus, when the thickness of the surface treatment layer is reduced, the etching removal property and the manufacturing cost of the surface treatment layer are improved. The thickness of the surface treatment layer is more preferably 0.3 to 1 nm.

The metal layer includes one or more elements selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr, and is selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr in the metal layer. The total adhesion amount of one or more elements is 200 to 2000 μg / dm ² . A metal layer containing one or more elements selected from the group consisting of Ni, Co, Zn, W, Mo and Cr is formed between Ni, Co, Zn, W, Mo and Cr between the copper foil and the surface treatment layer. By providing the total adhesion amount of one or more elements selected from the group consisting of 200 to 2000 μg / dm ² , the heat resistance of the copper foil can be improved, and the deterioration of the peel strength due to heating can be suppressed. Transmission loss can be suppressed satisfactorily. Here, when the transmission loss is small, signal attenuation is suppressed when signal transmission is performed at a high frequency. Therefore, stable signal transmission can be performed in a circuit that performs signal transmission at a high frequency. Therefore, a smaller transmission loss value is preferable because it is suitable for use in a circuit for transmitting a signal at a high frequency. When the total adhesion amount of the elements on the metal layer is less than 200 μg / dm ² , a sufficient heat resistance effect cannot be obtained. Moreover, when the total adhesion amount of the element on the metal layer exceeds 2000 μg / dm ² , there arises a problem that transmission loss increases. The total deposition amount of the element of the metal layer is preferably 200~1500μg / dm ^2, more preferably 200~1000μg / dm ^2, still more preferably 200~700μg / dm ^2. The metal layer may contain any element other than one or more elements selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr. For example, Cu, Al, Ti, As , Ag, Fe, Sn, Si, Zr, V, Mg, Mn, Ca, C, N, S, O, In, Au, Pt, Pd, Os, Rh, Ru, Re, Ir, Pb, Cd, Bi Or P etc. may be included. The total deposition amount of elements other than one or more elements selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr contained in the metal layer is not particularly limited, but is typically 0 to 50000 μg / dm ² , more typically 0 to 10,000 μg / dm ² , more typically 0 to 5000 μg / dm ² , and more typically 0.5 to 2000 μg / dm ² .

  The metal layer may include a roughening treatment layer, for example, in order to further improve the adhesion with the insulating substrate. The roughening treatment can be performed, for example, by forming roughened particles with copper or a copper alloy. The roughening process may be fine. The roughening treatment layer may be a single layer selected from the group consisting of copper, nickel, cobalt and zinc, or a layer made of an alloy containing one or more of them. Further, the metal layer may include a heat discoloration preventing layer and / or a rust preventing layer. The heat discoloration preventing layer and the rust preventing layer by preventing the diffusion of Cu can be formed of Zn, Cu or an alloy thereof, respectively. The rust preventive layer may include a chromate layer or a zinc chromate layer. The metal layer may include a silane coupling layer.

  In addition, you may use a well-known silane coupling agent for the silane coupling agent used in order to provide a silane coupling layer, for example, an amino-type silane coupling agent or an epoxy-type silane coupling agent, a mercapto-type silane coupling agent A methacryloxy silane coupling agent may be used. Especially, it is preferable to form using an amino-type silane coupling agent or an epoxy-type silane coupling agent. Silane coupling agents include vinyltrimethoxysilane, vinylphenyltrimethoxylane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 4-glycidylbutyltrimethoxysilane, and γ-aminopropyl. Triethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxysilane, imidazolesilane, triazinesilane, γ-mercaptopropyltrimethoxysilane or the like may be used.

  The amino silane coupling agent referred to here is N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, 3- Aminopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, N- (3 -Acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- (2-aminoethyl-3-aminopropyl) Trimethoxysilane, N (2-aminoethyl-3-aminopropyl) tris (2-ethylhexoxy) silane, 6- (aminohexylaminopropyl) trimethoxysilane, aminophenyltrimethoxysilane, 3- (1-aminopropoxy) -3,3- Dimethyl-1-propenyltrimethoxysilane, 3-aminopropyltris (methoxyethoxyethoxy) silane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, ω-aminoundecyltrimethoxysilane, 3- (2 -N-benzylaminoethylaminopropyl) trimethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, (N, N-diethyl-3-aminopropyl) trimethoxysilane, (N, N- Dimethyl-3-aminopropyl) Limethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, γ-aminopropyltriethoxysilane, N -Β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxysilane may be selected from the group consisting of Good.

The silane coupling layer is 0.05 mg / m ^{2 to} 200 mg / m ² , preferably 0.15 mg / m ^{2 to} 20 mg / m ² , preferably 0.3 mg / m ^{2 to} 2.0 mg / m in terms of silicon atoms. it is desirable to provided a range of m ^2. In the case of the above-mentioned range, the adhesiveness between the base resin and the surface-treated copper foil can be further improved.

[Production method of surface-treated copper foil]
The manufacturing method of the surface treatment copper foil of this invention is demonstrated. First, a rolled copper foil or an electrolytic copper foil is prepared. Next, the surface of the copper foil contains one or more elements selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr by a known means, and the total adhesion amount of the elements is 200 to 2000 μg / A metal layer is formed so as to be dm ² . If necessary, a roughening treatment layer, a heat discoloration prevention layer, a rust prevention layer, a silane coupling layer and the like are formed on the metal layer by known means. If necessary, a roughening treatment layer, a heat discoloration prevention layer, a rust prevention layer, a silane coupling layer, and the like are formed by a known means between the copper foil and the metal layer. Next, the chromate solution is provided on the entire surface of the copper foil to be processed. Next, the surface treatment layer of chromium oxide is formed on the copper foil surface by drying the copper foil surface without washing. In the conventional method, when the surface treatment is performed with the chromate solution, the chromate solution is provided on the surface of the copper foil, and then washed with water a plurality of times for removing impurities before the drying step. However, this washing with water forms a non-uniform chromate layer, which adversely affects the peel strength. On the other hand, in the present invention, the water washing step is not performed, and after the chromate liquid is provided on the entire surface to be treated of the copper foil, the copper foil surface is dried without washing, thereby forming a uniform chromate layer, The peel strength of the treated copper foil is improved. The step of providing the chromate solution over the entire surface to be treated of the copper foil may be performed by applying the chromate solution to the copper foil surface by a shower, or by applying the chromate solution to the copper foil surface with a roller. The chromate solution may be applied to the surface of the copper foil with a blade. The chromate solution can be applied by shower using a known spray nozzle (for example, a spray nozzle manufactured by Spraying Systems Japan Co., Ltd. or a spray nozzle manufactured by Ikeuchi Co., Ltd.). The application of the chromate solution with the roller can be performed by supplying the chromate solution to the roller surface using a known rubber roll or sponge roll and bringing the roller surface into contact with the copper foil. The application of the chromate solution with a blade can be performed using a known doctor blade or a known blade.

Further, in the method for producing a surface-treated copper foil of the present invention, in the step of forming the surface treatment layer of chromium oxide, the chromate solution is provided on the surface of the copper foil, then drained, and then dried without washing with water. Then, a chromium oxide surface treatment layer is formed. The liquid draining can be performed by blowing a roll, a blade and / or a gas. After the chromate solution is provided on the surface of the copper foil in this way, the liquid is drained and the amount of the chromate solution on the copper foil surface is controlled to suppress the attachment of hexavalent chromium to the product, and residual ions (K ⁺ ) Is less likely to be taken into the chromate film. Moreover, it is preferable that the quantity which provided the chromate liquid to the copper foil surface is 5-20 mg / dm < ² > after draining. If the amount of chromate liquid provided on the copper foil surface is less than 5 mg / dm ² , there is a possibility that a desired peel strength cannot be obtained. Further, if the amount of chromate solution provided on the surface of the copper foil is more than 20 mg / dm ² , the salt of H ₂ SO ₄ and K added for pH adjustment is precipitated because the solution is treated with a solution having the composition described later. There is a risk of problems. In addition, when performing liquid cutting with a roll, the adhesion amount of chromate liquid can be controlled by controlling the force with which a roll contacts copper foil. The force with which the roll contacts the copper foil may be set to 0.0005 to 0.015 kgf / cm per unit width (1 cm) of the copper foil. By increasing the force with which the roll comes into contact with the copper foil, the amount of chromate liquid on the copper foil surface can be reduced. Moreover, the amount of chromate liquid on the copper foil surface can be increased by reducing the force with which the roll contacts the copper foil.
Moreover, when performing liquid cutting with a blade, the adhesion amount of chromate liquid is controllable by controlling the clearance gap between a braid | blade and copper foil. The gap between the blade and the copper foil is preferably set to 0.5 to 3 μm. By increasing the gap between the blade and the copper foil, the amount of chromate liquid on the copper foil surface can be increased. By reducing the gap between the blade and the copper foil, the amount of chromate liquid on the copper foil surface can be reduced.
In addition, when removing liquid by blowing gas, the amount of chromate liquid attached is controlled by controlling the flow rate of the blowing gas and the distance between the gas blowing port of the nozzle that blows the gas and the copper foil. can do. The flow rate of the blowing gas is preferably set to 25 to 1000 L / min. Moreover, it is preferable to spray gas so that flow volume may become as equal as possible in the width direction of copper foil. The distance between the gas outlet and the copper foil is preferably set to 5 to 150 mm. By increasing the flow rate of the blowing gas and / or decreasing the distance between the gas outlet and the copper foil, the amount of chromate solution on the copper foil surface can be reduced. Moreover, the amount of chromate liquid on the copper foil surface can be increased by reducing the flow rate of the gas to be blown and / or increasing the distance between the gas blowing port and the copper foil.

The conditions of the chromate solution used for the surface treatment are as follows.
Liquid composition: CrO ₃ : 1 to 6 g / L, Na ₂ Cr ₂ O ₇ and K ₂ Cr ₂ O ₇ : 1.5 to 9 g / L in total
pH: 1-10, preferably 4-10
Temperature: 10-60 ° C, preferably 25-40 ° C
When the treatment liquid having a pH of 1 to 10 is used as described above, the elution of Ni or the like can be satisfactorily suppressed even when Ni or the like is used for the base treatment. Further, when a treatment solution having a pH of 4 to 10 is used, the elution of Zn can be satisfactorily suppressed even if Zn-chromate is used for the base treatment.
The balance of the treatment liquid used for electrolysis, surface treatment or plating used in the present invention is water unless otherwise specified.

[Copper foil with carrier]
The copper foil with a carrier which is another embodiment of the present invention has an intermediate layer and an ultrathin copper layer in this order on one side or both sides of the carrier. And the said ultra-thin copper layer is the surface treatment copper foil which is one embodiment of the above-mentioned this invention.

<Career>
Carriers that can be used in the present invention are typically metal foils or resin films, such as copper foil, copper alloy foil, nickel foil, nickel alloy foil, iron foil, iron alloy foil, stainless steel foil, aluminum foil, aluminum. It is provided in the form of alloy foil, insulating resin film (for example, polyimide film, liquid crystal polymer (LCP) film, polyethylene terephthalate (PET) film, polyamide film, polyester film, fluororesin film, etc.).
It is preferable to use a copper foil as a carrier that can be used in the present invention. This is because the copper foil has a high electrical conductivity, so that subsequent formation of an intermediate layer and an ultrathin copper layer is facilitated. The carrier is typically provided in the form of rolled copper foil or electrolytic copper foil. In general, the electrolytic copper foil is produced by electrolytic deposition of copper from a copper sulfate plating bath onto a drum of titanium or stainless steel, and the rolled copper foil is produced by repeating plastic working and heat treatment with a rolling roll. In addition to high-purity copper such as tough pitch copper and oxygen-free copper, the copper foil material is, for example, Sn-containing copper, Ag-containing copper, copper alloy added with Cr, Zr, Mg, etc., and Corson-based added with Ni, Si, etc. Copper alloys such as copper alloys can also be used.

The thickness of the carrier that can be used in the present invention is not particularly limited, but may be appropriately adjusted to a thickness suitable for serving as a carrier, and may be, for example, 5 μm or more. However, if it is too thick, the production cost becomes high, so generally it is preferably 35 μm or less. Accordingly, the thickness of the carrier is typically 12-70 μm, more typically 18-35 μm.
In addition, you may provide a roughening process layer in the surface on the opposite side to the surface in the side which provides the ultra-thin copper layer of a carrier. The said roughening process layer may be provided using a well-known method, and may be provided by the above-mentioned roughening process. Providing a roughened layer on the surface opposite to the surface on which the ultrathin copper layer of the carrier is provided, when laminating the carrier from the surface side having the roughened layer to a support such as a resin substrate, There is an advantage that the carrier and the resin substrate are hardly peeled off.

<Intermediate layer>
An intermediate layer is provided on the carrier. Another layer may be provided between the carrier and the intermediate layer. In the intermediate layer used in the present invention, the ultrathin copper layer is hardly peeled off from the carrier before the copper foil with the carrier is laminated on the insulating substrate, while the ultrathin copper layer is separated from the carrier after the lamination step on the insulating substrate. There is no particular limitation as long as it can be peeled off. For example, the intermediate layer of the copper foil with a carrier of the present invention is Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, alloys thereof, hydrates thereof, oxides thereof, One or two or more selected from the group consisting of organic substances may be included. The intermediate layer may be a plurality of layers.

  Further, for example, the intermediate layer is a single metal layer composed of one kind of element selected from the element group composed of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn from the carrier side. Or forming an alloy layer composed of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, A hydrate or oxide of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn, or an organic substance It can comprise by forming the layer which consists of.

Further, for example, the intermediate layer is a single metal layer composed of one kind of element selected from the element group composed of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn from the carrier side. Or forming an alloy layer composed of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, A single metal layer made of one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, or Cr, Ni, Co , Fe, Mo, Ti, W, P, Cu, Al, and Zn can be formed by forming an alloy layer made of one or more elements selected from the group of elements.
Moreover, a well-known organic substance can be used for the intermediate | middle layer as said organic substance, and it is preferable to use any 1 or more types of a nitrogen containing organic compound, a sulfur containing organic compound, and carboxylic acid. For example, specific nitrogen-containing organic compounds include 1,2,3-benzotriazole, carboxybenzotriazole, N ′, N′-bis (benzotriazolylmethyl) urea, 1H, which are triazole compounds having a substituent. It is preferable to use -1,2,4-triazole and 3-amino-1H-1,2,4-triazole.
For the sulfur-containing organic compound, it is preferable to use mercaptobenzothiazole, 2-mercaptobenzothiazole sodium, thiocyanuric acid, 2-benzimidazolethiol, and the like.
As the carboxylic acid, it is particularly preferable to use a monocarboxylic acid, and it is particularly preferable to use oleic acid, linoleic acid, linolenic acid, or the like.

Further, for example, the intermediate layer can be configured by laminating a nickel layer, a nickel-phosphorus alloy layer or a nickel-cobalt alloy layer, and a chromium-containing layer in this order on a carrier. Since the adhesive strength between nickel and copper is higher than the adhesive strength between chromium and copper, when the ultrathin copper layer is peeled off, it peels at the interface between the ultrathin copper layer and the chromium-containing layer. Further, the nickel of the intermediate layer is expected to have a barrier effect that prevents the copper component from diffusing from the carrier into the ultrathin copper layer. Adhesion amount of nickel in the intermediate layer is preferably 100 [mu] g / dm ² or more 40000μg / dm ² or less, more preferably 100 [mu] g / dm ² or more 4000μg / dm ² or less, more preferably 100 [mu] g / dm ² or more 2500 g / dm ² or less, more Preferably, it is 100 μg / dm ² or more and less than 1000 μg / dm ² , and the amount of chromium deposited on 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 intermediate chromium layer can be provided by chromium plating or chromate treatment.
If the thickness of the intermediate layer becomes too large, the thickness of the intermediate layer may affect the surface roughness Rz and glossiness of the surface of the ultrathin copper layer after the surface treatment. The thickness of the intermediate layer on the surface is preferably 1 to 1000 nm, preferably 1 to 500 nm, preferably 2 to 200 nm, preferably 2 to 100 nm, and 3 to 60 nm. More preferred. The intermediate layer may be provided on both sides of the carrier.

<Ultrathin copper layer>
An ultrathin copper layer is provided on the intermediate layer. Another layer may be provided between the intermediate layer and the ultrathin copper layer. The ultra-thin copper layer having the carrier is a surface-treated copper foil that is one embodiment of the present invention. The thickness of the ultrathin copper layer is not particularly limited, but is generally thinner than the carrier, for example, 12 μm or less. Typically, it is 0.5 to 12 μm, and more typically 1.5 to 5 μm. Further, strike plating with a copper-phosphorus alloy may be performed before reducing the pinholes in the ultrathin copper layer before providing the ultrathin copper layer on the intermediate layer. Examples of the strike plating include a copper pyrophosphate plating solution. The ultra thin copper layer may be provided on both sides of the carrier.
Moreover, the ultra-thin copper layer of this application can be formed on the following conditions.
-Electrolyte composition Copper: 80-120 g / L
Sulfuric acid: 80-120 g / L
Chlorine: 30-100ppm
Leveling agent 1 (bis (3sulfopropyl) disulfide): 10 to 30 ppm
Leveling agent 2 (amine compound): 10 to 30 ppm
As the amine compound, an amine compound having the following chemical formula can be used.

(In the above chemical formula, R ₁ and R ₂ are 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: 70-100 A / dm ²
Electrolyte temperature: 50-65 ° C
Electrolyte linear velocity: 1.5-5 m / sec
Electrolysis time: 0.5 to 10 minutes (adjusted according to the thickness of copper to be deposited and current density)

  A laminated body (a copper clad laminated body etc.) can be produced using the copper foil with a carrier of the present invention. For example, the laminate may have a structure in which “ultra-thin copper layer / intermediate layer / carrier / resin or prepreg” is laminated in this order, and “carrier / intermediate layer / ultra-thin copper layer / resin or prepreg”. It may be a configuration laminated in this order, or may be a configuration laminated in the order of "ultra thin copper layer / intermediate layer / carrier / resin or prepreg / carrier / intermediate layer / ultra thin copper layer" The structure may be laminated in the order of “carrier / intermediate layer / ultra thin copper layer / resin or prepreg / ultra thin copper layer / intermediate layer / carrier”, “carrier / intermediate layer / ultra thin copper layer / resin or prepreg”. The configuration may be such that “/ carrier / intermediate layer / ultra-thin copper layer” is laminated in this order. The resin or prepreg may be a resin layer which will be described later. A resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and the like used for the resin layer which will be described later. May be included. The carrier-attached copper foil may be smaller than the resin or prepreg when viewed in plan.

[Resin layer on surface treated surface]
A resin layer may be provided on the surface-treated surface of the surface-treated copper foil of the present invention. The resin layer may be an insulating resin layer. In the surface-treated copper foil of the present invention, the “surface-treated surface” means that the surface treatment is performed when a surface treatment for providing a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. is performed after the roughening treatment. It means the surface of the surface-treated copper foil after performing. In addition, when the surface-treated copper foil is an ultra-thin copper layer of a copper foil with a carrier, the “surface-treated surface” is to provide a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. after the roughening treatment When the surface treatment is performed, the surface of the ultrathin copper layer after the surface treatment is performed.

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

  The resin layer may contain a thermosetting resin or may be a thermoplastic resin. The resin layer may include a thermoplastic resin. The resin layer may contain a known resin, resin curing agent, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton material, and the like. The resin layer may be, for example, International Publication No. WO2008 / 004399, International Publication No. WO2008 / 053878, International Publication No. WO2009 / 084533, JP-A-11-5828, JP-A-11-140281, Patent 3184485, International Publication No. WO 97/02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179772, Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003-302068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003 No. 249739, Japanese Patent No. 4136509, Japanese Patent Application Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Application Laid-Open No. 2004-349654, Japanese Patent No. 4286060, Japanese Patent Application Laid-Open No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent Application Laid-Open No. No. 5-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004 / 005588, Japanese Patent Application Laid-Open No. 2006-257153, Japanese Patent Application Laid-Open No. 2007-326923, Japanese Patent Application Laid-Open No. 2008-11169, and Japanese Patent No. 5024930. No. WO 2006/028207, Japanese Patent No. 4828427, JP 2009-67029, International Publication No. WO 2006/134868, Japanese Patent No. 5046927, JP 2009-173017, International Publication No. WO 2007/105635, Patent No. 5180815, International Publication Number WO2008 / 114858, International Publication Number WO2009 / 008471, Japanese Patent Application Laid-Open No. 2011-14727, International Publication Number WO2009 / 001850, International Publication Number WO2009 / 145179, International Publication Number Nos. WO2011 / 068157, JP-A-2013-19056 (resins, resin curing agents, compounds, curing accelerators, dielectrics, reaction catalysts, crosslinking agents, polymers, prepregs, skeletal materials, etc.) and / or You may form using the formation method and formation apparatus of a resin layer.

  The type of the resin layer is not particularly limited. For example, epoxy resin, polyimide resin, polyfunctional cyanate ester compound, maleimide compound, polymaleimide compound, maleimide resin, aromatic maleimide resin , Polyvinyl acetal resin, urethane resin, polyethersulfone (also referred to as polyethersulfone or polyethersulfone), polyethersulfone (also referred to as polyethersulfone or polyethersulfone) resin, aromatic polyamide resin, aromatic Polyamide resin polymer, rubber resin, polyamine, aromatic polyamine, polyamideimide resin, rubber modified epoxy resin, phenoxy resin, carboxyl group-modified acrylonitrile-butadiene resin, polyphenylene oxide, bismaleimide triazine Fat, thermosetting polyphenylene oxide resin, cyanate ester resin, carboxylic acid anhydride, polyvalent carboxylic acid anhydride, linear polymer having crosslinkable functional group, polyphenylene ether resin, 2,2-bis (4 -Cyanatophenyl) propane, phosphorus-containing phenol compound, manganese naphthenate, 2,2-bis (4-glycidylphenyl) propane, polyphenylene ether-cyanate resin, siloxane-modified polyamideimide resin, cyanoester resin, phosphazene resin, Rubber-modified polyamide-imide resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, phenoxy, polymer epoxy, aromatic polyamide, fluororesin, bisphenol, block copolymerized polyimide resin, and cyanoester resin It can be mentioned resins containing one or more kinds that is as suitable.

The epoxy resin has two or more epoxy groups in the molecule and can be used without any problem as long as it can be used for electric / electronic materials. The epoxy resin is preferably an epoxy resin epoxidized using a compound having two or more glycidyl groups in the molecule. Also, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, brominated (brominated) epoxy Resin, phenol novolac type epoxy resin, naphthalene type epoxy resin, brominated bisphenol A type epoxy resin, orthocresol novolac type epoxy resin, rubber modified bisphenol A type epoxy resin, glycidylamine type epoxy resin, triglycidyl isocyanurate, N, N -Glycidylamine compounds such as diglycidylaniline, glycidyl ester compounds such as diglycidyl tetrahydrophthalate, phosphorus-containing epoxy resins, biphenyl type epoxy resins , Biphenyl novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, or a mixture of two or more types, or a hydrogenated product of the epoxy resin Or a halogenated compound can be used.
As the phosphorus-containing epoxy resin, a known epoxy resin containing phosphorus can be used. The phosphorus-containing epoxy resin is, for example, an epoxy resin obtained as a derivative from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide having two or more epoxy groups in the molecule. Is preferred.

(When the resin layer contains a dielectric (dielectric filler))
The resin layer may include a dielectric (dielectric filler).
In the case where a dielectric (dielectric filler) is included in any of the above resin layers or resin compositions, it can be used for the purpose of forming the capacitor layer and increase the capacitance of the capacitor circuit. Examples of the dielectric (dielectric filler) include BaTiO ₃ , SrTiO ₃ , Pb (Zr—Ti) O ₃ (common name PZT), PbLaTiO ₃ · PbLaZrO (common name PLZT), SrBi ₂ Ta ₂ O ₉ (common name SBT), and the like. A composite oxide dielectric powder having a perovskite structure is used.

  The dielectric (dielectric filler) may be powdery. When the dielectric (dielectric filler) is in powder form, the powder characteristics of the dielectric (dielectric filler) are such that the particle size ranges from 0.01 μm to 3.0 μm, preferably 0.02 μm to 2.0 μm. It is preferable that. When the dielectric is photographed with a scanning electron microscope (SEM) and a straight line is drawn on the dielectric particle on the photograph, the length of the longest straight line across the dielectric particle is The length of the dielectric particle is defined as the diameter of the dielectric particle. Then, an average value of the diameters of the dielectric particles in the measurement visual field is defined as the dielectric particle size.

Examples of the resin and / or resin composition and / or compound contained in the resin layer include methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, 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 the like to obtain a resin liquid (resin varnish). The surface-treated copper foil is coated on the roughened surface by, for example, a roll coater method, and then heated and dried as necessary to remove the solvent to obtain a B-stage state. For example, a hot air drying furnace may be used for drying, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C. The composition of the resin layer is dissolved using a solvent, and the resin solid content is 3 wt% to 70 wt%, preferably 3 wt% to 60 wt%, preferably 10 wt% to 40 wt%, more preferably 25 wt% to 40 wt%. It is good also as a resin liquid. In addition, it is most preferable at this stage from an environmental standpoint to dissolve using a mixed solvent of methyl ethyl ketone and cyclopentanone. In addition, it is preferable to use the solvent whose boiling point is the range of 50 to 200 degreeC as a solvent.
The resin layer is preferably a semi-cured resin film having a resin flow in the range of 5% to 35% when measured according to MIL-P-13949G in the MIL standard.
In this specification, the resin flow is based on MIL-P-13949G in the MIL standard. Four 10 cm square samples were sampled from a resin-treated surface-treated copper foil with a resin thickness of 55 μm. In a state where the samples were stacked (laminated body), bonding was performed under the conditions of a press temperature of 171 ° C., a press pressure of 14 kgf / cm ² , and a press time of 10 minutes, and the resin outflow weight at that time was measured. Value.

  The surface-treated copper foil (resin-treated surface-treated copper foil) provided with the resin layer is obtained by superposing the resin layer on a substrate and then thermocompressing the whole to thermally cure the resin layer, and then the surface-treated copper foil. When is an ultra-thin copper layer of a copper foil with a carrier, the carrier is peeled off to expose the ultra-thin copper layer (of course, the surface on the intermediate layer side of the ultra-thin copper layer is exposed) The surface-treated copper foil is used in a form in which a predetermined wiring pattern is formed from the surface opposite to the surface subjected to the roughening treatment.

  When this surface-treated copper foil with resin is used, the number of prepreg materials used in the production of the multilayer printed wiring board can be reduced. In addition, the copper-clad laminate can be manufactured even if the resin layer is made thick enough to ensure interlayer insulation or no prepreg material is used. At this time, the surface smoothness can be further improved by undercoating the surface of the substrate with an insulating resin.

In addition, when the prepreg material is not used, the material cost of the prepreg material is saved and the laminating process is simplified, which is economically advantageous. Moreover, the multilayer printed wiring board manufactured by the thickness of the prepreg material is used. The thickness is reduced, and there is an advantage that an extremely thin multilayer printed wiring board in which the thickness of one layer is 100 μm or less can be manufactured.
The thickness of the resin layer is preferably 0.1 to 120 μm.

When the thickness of the resin layer becomes thinner than 0.1 μm, the adhesive strength is reduced, and when this surface-treated copper foil with resin is laminated on the base material provided with the inner layer material without interposing the prepreg material, the circuit of the inner layer material It may be difficult to ensure interlayer insulation between the two. On the other hand, if the thickness of the resin layer is greater than 120 μm, it is difficult to form a resin layer having a target thickness in a single coating process, which may be economically disadvantageous because of extra material costs and man-hours.
In addition, when the surface-treated copper foil having a resin layer is used for manufacturing an extremely thin multilayer printed wiring board, the thickness of the resin layer is 0.1 μm to 5 μm, more preferably 0.5 μm to 5 μm, More preferably, the thickness is 1 μm to 5 μm in order to reduce the thickness of the multilayer printed wiring board.

  Below, some examples of the manufacturing process of the printed wiring board using the copper foil with a carrier which concerns on this invention are shown.

  In one embodiment of a method for producing a printed wiring board according to the present invention, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention, a step of laminating the copper foil with a carrier and an insulating substrate, and with the carrier After laminating the copper foil and the insulating substrate so that the ultrathin copper layer side faces the insulating substrate, a copper-clad laminate is formed through a step of peeling the carrier of the copper foil with carrier, and then a semi-additive method, a modified semi-conductor A step of forming a circuit by any one of an additive method, a partial additive method, and a subtractive method. It is also possible for the insulating substrate to contain an inner layer circuit.

  In the present invention, the semi-additive method refers to a method in which a thin electroless plating is performed on an insulating substrate or a copper foil seed layer, a pattern is formed, and then a conductive pattern is formed using electroplating and etching.

  Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using the semi-additive method, a step of preparing the copper foil with carrier and the insulating substrate according to the present invention, the copper foil with carrier and the insulating substrate Laminating the copper foil with carrier and the insulating substrate, then peeling off the carrier of the copper foil with carrier, etching the exposed ultrathin copper layer with a corrosive solution such as an acid. Removing all by a method such as plasma or plasma, providing a through hole or / and a blind via in the resin exposed by removing the ultrathin copper layer by etching, a region including the through hole or / and the blind via Including a step of desmearing the resin, the resin and the through hole or / and a blind via. A step of providing an electroless plating layer for a region, 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 a region where a circuit is formed, A step of providing an electrolytic plating layer in a region where the circuit from which the plating resist is removed is formed, a step of removing the plating resist, a flash etching of an electroless plating layer in a region other than the region where the circuit is formed, etc. The step of removing by.

  In another embodiment of the method for producing a printed wiring board according to the present invention using a semi-additive method, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention, the copper foil with a carrier and the insulating substrate Laminating the copper foil with carrier and the insulating substrate, then peeling off the carrier of the copper foil with carrier, etching the exposed ultrathin copper layer with a corrosive solution such as an acid. Removing all by a method such as plasma or plasma, providing an electroless plating layer on the surface of the resin exposed by removing the ultrathin copper layer by etching, and providing a plating resist on the electroless plating layer Exposing the plating resist to a step, and then removing the plating resist in a region where a circuit is formed; A step of providing an electrolytic plating layer in a region where the circuit is left, a step of removing the plating resist, and flushing an electroless plating layer and an ultrathin copper layer in a region other than the region where the circuit is formed Removing by etching or the like.

  In the present invention, the modified semi-additive method is 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 the copper is thickened in the circuit forming portion by electrolytic plating, and then the resist is removed. Then, a method of forming a circuit on the insulating layer by removing the metal foil other than the circuit forming portion by (flash) etching is indicated.

  Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using the modified semi-additive method, the step of preparing the copper foil with carrier and the insulating substrate according to the present invention, the copper foil with carrier and the insulation A step of laminating the substrate, a step of peeling the carrier of the copper foil with carrier and the insulating substrate after laminating the carrier-attached copper foil, a through-hole or / and in the insulating substrate and the ultrathin copper layer exposed by peeling the carrier A step of providing a blind via, a step of performing a desmear process on the region including the through hole or / and the blind via, a step of providing an electroless plating layer on the region including the through hole or / and the blind via, and exposing the substrate by peeling off the carrier A step of providing a plating resist on the surface of the ultrathin copper layer, After the, including the step of forming a circuit by electroplating, removing the plating resist, a step, is removed by flash etching ultrathin copper layer exposed by removing the plating resist.

  In addition, the step of forming a circuit on the resin layer includes bonding another copper foil with a carrier on the resin layer from the ultrathin copper layer side, and using the copper foil with a carrier bonded to the resin layer. It may be a step of forming a circuit. Moreover, the copper foil with a carrier of the present invention may be another copper foil with a carrier to be bonded onto the resin layer. Further, the step of forming a circuit on the resin layer may be performed by any one of a semi-additive method, a subtractive method, a partial additive method, or a modified 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 the said copper foil with a carrier.

  In another embodiment of the method for manufacturing a printed wiring board according to the present invention using the modified semi-additive method, the step of preparing the copper foil with carrier and the insulating substrate according to the present invention, the copper foil with carrier and the insulation A step of laminating the substrate, a step of laminating the carrier-attached copper foil and an insulating substrate, a step of peeling the carrier of the copper foil with carrier, a step of providing a plating resist on the exposed ultrathin copper layer by peeling off the carrier, Exposing the plating resist and then removing the plating resist in a region where a circuit is formed; providing an electrolytic plating layer in a region where the circuit where the plating resist is removed; The step of removing the resist, the electroless plating layer and the ultrathin copper layer in a region other than the region where the circuit is formed for flash etching, etc. The step of removing Ri including,.

  In the present invention, the partial additive method means that a catalyst circuit is formed on a substrate provided with a conductor layer, and if necessary, a substrate provided with holes for through holes or via holes, and etched to form a conductor circuit. Then, after providing a solder resist or a plating resist as necessary, it refers to a method of manufacturing a printed wiring board by thickening through holes, via holes, etc. on the conductor circuit by electroless plating.

  Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using the partly additive method, a step of preparing the copper foil with carrier and the insulating substrate according to the present invention, the copper foil with carrier and the insulating substrate Laminating the carrier-attached copper foil and the insulating substrate, then peeling the carrier of the carrier-attached copper foil, peeling the carrier and exposing the ultrathin copper layer and the insulating substrate through holes or / and blinds A step of providing a via; a step of performing a desmear process on a region including the through hole or / and a blind via; a step of applying a catalyst nucleus in a region including the through hole or / and a blind via; and an electrode exposed by peeling off the carrier Providing an etching resist on the surface of the thin copper layer, exposing the etching resist; A step of forming a circuit pattern, a step of forming a circuit by removing the ultra-thin copper layer and the catalyst nucleus by a method such as etching or plasma using a corrosive solution such as an acid, and removing the etching resist. A step of providing a solder resist or a plating resist on the surface of the insulating substrate exposed by removing the ultrathin copper layer and the catalyst nuclei by a method such as etching or plasma using a corrosive solution such as an acid, the solder resist Or a step of providing an electroless plating layer in a region where no plating resist is provided.

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

  Therefore, in one embodiment of the printed wiring board manufacturing method according to the present invention using the subtractive method, the step of preparing the copper foil with carrier and the insulating substrate according to the present invention, the copper foil with carrier and the insulating substrate, Laminating the carrier-attached copper foil and the insulating substrate, then peeling the carrier of the carrier-attached copper foil, peeling the carrier and exposing the ultrathin copper layer and the insulating substrate through holes or / and blinds A step of providing a via, a step of performing a desmear process on a region including the through hole or / and the blind via, a step of providing an electroless plating layer on the region including the through hole or / and the blind via, a surface of the electroless plating layer A step of providing an electroplating layer, and the surface of the electroplating layer and / or the ultrathin copper layer. A step of providing an etching resist, a step of exposing the etching resist to form a circuit pattern, etching or plasma using a corrosive solution such as an acid on the ultrathin copper layer, the electroless plating layer, and the electrolytic plating layer. And a step of forming a circuit by removing the etching resist, and a step of removing the etching resist.

  In another embodiment of the method for producing a printed wiring board according to the present invention using a subtractive method, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention, the copper foil with a carrier and the insulating substrate Laminating the carrier-attached copper foil and the insulating substrate, then peeling the carrier of the carrier-attached copper foil, peeling the carrier and exposing the ultrathin copper layer and the insulating substrate through holes or / and blinds A step of providing a via, a step of performing a desmear process on a region including the through hole or / and the blind via, a step of providing an electroless plating layer on the region including the through hole or / and the blind via, a surface of the electroless plating layer Forming a mask on the surface of the electroless plating layer on which the mask is not formed. A step of providing an etching resist on the surface of the electrolytic plating layer or / and the ultrathin copper layer, a step of exposing the etching resist to form a circuit pattern, the ultrathin copper layer and the electroless plating The method includes a step of forming a circuit by removing the layer by a method such as etching using a corrosive solution such as acid or plasma, and a step of removing the etching resist.

  The process of providing a through hole or / and a blind via and the subsequent desmear process 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. Here, the carrier-attached copper foil having an ultrathin copper layer on which a roughened layer is formed will be described as an example. The following method for producing a printed wiring board can be similarly performed using an attached copper foil.
First, as shown to FIG. 1-A, the copper foil with a carrier (1st layer) which has the ultra-thin copper layer in which the roughening process layer was formed on the surface is prepared. In addition, you may prepare copper foil with a carrier (1st layer) which has the carrier by which the roughening process layer was formed in the surface at the said process.
Next, as shown in FIG. 1-B, a resist is applied onto the roughened layer of the ultrathin copper layer, exposed and developed, and etched into a predetermined shape. In this step, a resist may be applied onto the roughening layer of the carrier, exposed and developed, and etched to a predetermined shape.
Next, as shown in FIG. 1-C, after the plating for the circuit is formed, the resist is removed to form a circuit plating having a predetermined shape.
Next, as shown in FIG. 2-D, an embedding resin is provided on the ultrathin copper layer so as to cover the circuit plating (so that the circuit plating is buried), and then the resin layer is laminated, followed by another carrier. A copper foil (second layer) is bonded from the ultrathin copper layer side. In addition, a resin layer is provided by laminating resin on the carrier so as to cover the circuit plating in this step (so that the circuit plating is buried), and then another carrier-attached copper foil (second layer) is placed on the carrier side. Or you may make it adhere | attach from an ultra-thin copper layer.
Next, as shown to FIG. 2-E, a carrier is peeled from the copper foil with a carrier of the 2nd layer. When the second-layer copper foil with carrier is bonded from the carrier side, the ultrathin copper layer may be peeled off from the second-layer copper foil with carrier.
Next, as shown in FIG. 2-F, laser drilling is performed at a predetermined position of the resin layer to expose the circuit plating and form a blind via.
Next, as shown in FIG. 3G, copper is embedded in the blind via to form a via fill.
Next, as shown in FIG. 3H, circuit plating is formed on the via fill as shown in FIGS. 1-B and 1-C.
Next, as shown to FIG. 3-I, a carrier is peeled from the copper foil with a carrier of the 1st layer. In addition, you may peel an ultra-thin copper layer from the copper foil with a 1st layer at the said process.
Next, as shown in FIG. 4J, ultrathin copper layers on both surfaces by flash etching (in the case where a copper foil is provided as the second layer, the copper foil, the plating for the first layer is applied to the carrier rough). When provided on the chemical treatment layer, the carrier) is removed to expose the surface of the circuit plating in the resin layer.
Next, as shown in FIG. 4K, bumps are formed on the circuit plating in the resin layer, and copper pillars are formed on the solder. Thus, the printed wiring board using the copper foil with a carrier of this invention is produced.

  As the another copper foil with a carrier (second layer), the copper foil with a carrier of the present invention may be used, a conventional copper foil with a carrier may be used, and a normal copper foil may be further used. Further, one or more circuits may be formed on the second layer circuit shown in FIG. 3H, and these circuits may be formed by a semi-additive method, a subtractive method, a partial additive method, or a modified semi-conductor method. You may carry out by any method of an additive method.

The copper foil with a carrier according to the present invention is preferably controlled so that the color difference on the surface of the ultrathin copper layer satisfies the following (1). In the present invention, the “color difference on the surface of the ultrathin copper layer” means the color difference on the surface of the ultrathin copper layer, or the color difference on the surface of the surface treatment layer when various surface treatments such as roughening treatment are applied. . That is, it is preferable that the copper foil with a carrier according to the present invention is controlled so that the color difference of the roughened surface of the ultrathin copper layer satisfies the following (1). In the surface-treated copper foil of the present invention, the term “roughened surface” means that when the surface treatment for providing a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. is performed after the roughening treatment, It means the surface of the surface-treated copper foil (ultra thin copper layer) after the treatment. In addition, when the surface-treated copper foil is an ultrathin copper layer of a copper foil with a carrier, the “roughened surface” means that after the roughening treatment, a heat-resistant layer, a rust-proof layer, a weather-resistant layer, etc. are provided. When the surface treatment is performed, the surface of the ultrathin copper layer after the surface treatment is performed.
(1) Tristimulus value of the white plate on the surface of the ultrathin copper layer (when the light source is D65 and the 10-degree field of view is X ₁₀ Y ₁₀ Z ₁₀ color system (JIS Z8701 1999) of the white plate is X ₁₀ = 80.7, Y ₁₀ = 85.6, Z ₁₀ = 91.5, and the object color of the white plate in the L ^* a ^* b ^* color system is L ^* = 94.14, a ^* = The color difference ΔE * ab based on JIS Z8730 is 45 or more when the object color is −0.90, b ^* = 0.24).

Here, color difference ΔL (L ^* a ^* b ^* defined in JIS Z8729 (2004), difference between CIE brightness L ^* of two object colors in the color system), Δa (L ^* a defined in JIS Z8729 (2004)) ^* b ^* Difference between color coordinates a ^* of two object colors in the color system, Δb (L ^* a ^* b ^* specified by JIS Z8729 (2004), color coordinates b ^* of two object colors in the color system (Difference) is a comprehensive index measured using a color difference meter, taking into account black / white / red / green / yellow / blue, and using the L ^* a ^* b ^* color system based on JIS Z8730 (2009). Yes, ΔL: black and white, Δa: red-green, Δb: yellow-blue. ΔE ^* ab is expressed by the following equation using these color differences.

The above-described color difference can be adjusted by increasing the current density when forming the ultrathin copper layer, decreasing the copper concentration in the plating solution, and increasing the linear flow rate of the plating solution.
Moreover, the above-mentioned color difference can also be adjusted by performing a roughening process on the surface of an ultra-thin copper layer and providing a roughening process layer. In the case of providing the roughening treatment layer, the current density is made higher than conventional (for example, 40 to 60 A) using an electrolytic solution containing copper and one or more elements selected from the group consisting of nickel, cobalt, tungsten, and molybdenum. / Dm ² ), and the processing time can be shortened (for example, 0.1 to 1.3 seconds). When a roughening layer is not provided on the surface of the ultrathin copper layer, use a plating bath in which the concentration of Ni is twice or more that of other elements, and use an ultrathin copper layer, heat resistant layer, rust preventive layer or chromate. Ni alloy plating (for example, Ni-W alloy plating, Ni-Co-P alloy plating, Ni-Zn alloy plating) is applied to the surface of the layer or the silane coupling layer at a lower current density (0.1 to 1.3 A / This can be achieved by setting a long processing time (20 to 40 seconds) at dm ² ).

  When the color difference ΔE * ab based on JIS Z8730 is 45 or more when the color difference on the surface of the ultrathin copper layer is 45 or more, for example, when forming a circuit on the surface of the ultrathin copper layer of the copper foil with carrier, As a result, the visibility is improved and the circuit alignment can be performed with high accuracy. The color difference ΔE * ab based on JIS Z8730 on the ultrathin copper layer surface is preferably 50 or more, more preferably 55 or more, and even more preferably 60 or more.

  When the color difference on the surface of the ultrathin copper layer is controlled as described above, the contrast with the circuit plating becomes clear and the visibility becomes good. Therefore, in the manufacturing process of the printed wiring board as described above, for example, as shown in FIG. 1-C, the circuit plating can be accurately formed at a predetermined position. In addition, according to the method for manufacturing a printed wiring board as described above, circuit plating is embedded in a resin layer, and thus, for example, removal of an ultrathin copper layer by flash etching as shown in FIG. At this time, the circuit plating is protected by the resin layer and the shape thereof is maintained, thereby facilitating the formation of a fine circuit. Further, since the circuit plating is protected by the resin layer, the migration resistance is improved, and the continuity of the circuit wiring is satisfactorily suppressed. For this reason, formation of a fine circuit becomes easy. Also, 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 has a shape recessed from the resin layer, so that bumps are formed on the circuit plating. In addition, copper pillars can be easily formed thereon, and the production efficiency is improved.

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

  Moreover, the copper foil with a carrier used for the first layer may have a substrate or a resin layer on the surface of the copper foil with a carrier. By having the said board | substrate or resin layer, the copper foil with a carrier used for the first layer is supported, and since it becomes difficult to wrinkle, there exists an advantage that productivity improves. As the substrate or resin layer, any substrate or resin layer can be used as long as it has an effect of supporting the copper foil with carrier used in the first layer. For example, as the substrate or resin layer, the carrier, prepreg, resin layer and known carrier, prepreg, resin layer, metal plate, metal foil, inorganic compound plate, inorganic compound foil, organic compound plate described in the present specification, Organic compound foils can be used.

  The surface-treated copper foil of the present invention can be bonded to a resin substrate from the surface-treated layer side to produce a laminate. The resin substrate is not particularly limited as long as it has characteristics applicable to a printed wiring board or the like. For example, a paper base phenol resin, a paper base epoxy resin, a synthetic fiber cloth base epoxy resin for rigid PWB Fluorine resin impregnated cloth, glass cloth / paper composite base epoxy resin, glass cloth / glass nonwoven fabric composite base epoxy resin and glass cloth base epoxy resin, etc., polyester film and polyimide for flexible printed circuit board (FPC) A film, a liquid crystal polymer (LCP) film, a fluororesin, and a fluororesin / polyimide composite material can be used. In addition, since a liquid crystal polymer (LCP) has a small dielectric loss, it is preferable to use a liquid crystal polymer (LCP) film for the printed wiring board for a high frequency circuit use.

  In the case of the rigid PWB, a prepreg is prepared by impregnating a base material such as a glass cloth with a resin and curing the resin to a semi-cured state. It can be performed by stacking a copper foil on a prepreg and heating and pressing. In the case of FPC, a liquid crystal polymer or a polyimide film is bonded to a copper foil under high temperature and pressure without using an adhesive, or a polyimide precursor is applied and dried via an adhesive. -A laminated board can be manufactured by performing hardening etc.

  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, the single-sided PWB, the double-sided PWB, and the multilayer PWB (3 It is applicable to rigid PWB, flexible PWB (FPC), and rigid flex PWB from the viewpoint of the type of insulating substrate material.

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” includes a printed wiring board, a printed circuit board, and a printed board on which electronic parts are mounted as described above.
In addition, an electronic device may be manufactured using the printed wiring board, an electronic device may be manufactured using a printed circuit board on which the electronic components are mounted, and a print on which the electronic components are mounted. An electronic device may be manufactured using a substrate.

Furthermore, 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” includes a printed wiring board, a printed circuit board, and a printed board on which electronic parts are mounted as described above.
In addition, an electronic device may be manufactured using the printed wiring board, an electronic device may be manufactured using a printed circuit board on which the electronic components are mounted, and a print on which the electronic components are mounted. An electronic device may be manufactured using a substrate.

Further, the method for producing a printed wiring board of the present invention includes a step of laminating the ultrathin copper layer side surface or the carrier side surface of the copper foil with a carrier of the present invention and a resin substrate, and an ultrathin layer laminated with the resin substrate. A step of providing at least once a resin layer and a circuit on the surface of the copper layer with carrier on the opposite side of the copper layer side surface or the carrier side surface, and forming two layers of the resin layer and the circuit Then, a printed wiring board manufacturing method (coreless method) including a step of peeling the carrier or the ultra-thin copper layer from the copper foil with carrier may be used. As a specific example of the coreless construction method, first, the ultrathin copper layer side surface or carrier side surface of the copper foil with carrier of the present invention and a resin substrate are laminated. Thereafter, a resin layer is formed on the surface of the ultrathin copper layer side surface laminated with the resin substrate or the surface of the carrier-attached copper foil opposite to the carrier side surface. You may laminate | stack another copper foil with a carrier from the carrier side or the ultra-thin copper layer side to the resin layer formed in the carrier side surface or the ultra-thin copper layer side surface. In this case, a copper foil with a carrier is laminated in the order of carrier / intermediate layer / ultra-thin copper layer or ultra-thin copper layer / intermediate layer / carrier in this order on both surface sides of the resin substrate with the resin substrate as the center It has become. Even if an ultrathin copper layer on both ends or the exposed surface of the carrier is provided with another resin layer, and further provided with a copper layer or metal layer, a circuit may be formed by processing the copper layer or metal layer. Good. Further, another resin layer may be provided on the circuit so as to embed the circuit. Further, such a circuit and a resin layer may be formed one or more times (build-up method). And about the laminated body formed in this way (henceforth the laminated body B), a coreless board | substrate is produced by peeling the ultra-thin copper layer or carrier of each copper foil with a carrier from a carrier or an ultra-thin copper layer. be able to. In addition, for the production of the coreless substrate described above, a laminate having a configuration of an ultrathin copper layer / intermediate layer / carrier / carrier / intermediate layer / ultra thin copper layer described later using two copper foils with a carrier, Laminate having a structure of carrier / intermediate layer / ultra thin copper layer / ultra thin copper layer / intermediate layer / carrier, or a structure of carrier / intermediate layer / ultra thin copper layer / carrier / intermediate layer / ultra thin copper layer It is also possible to produce a laminated body and use the laminated body as a center. Two layers of the resin layer and the circuit are provided at least once on the surface of the ultra-thin copper layer or carrier on both sides of these laminates (hereinafter also referred to as the laminate A), and the two layers of the resin layer and the circuit are provided at least once. Later, the coreless substrate can be manufactured by peeling off the ultrathin copper layer or carrier of each copper foil with carrier from the carrier or the ultrathin copper layer. The above-mentioned laminated body has other surfaces between the surface of the ultrathin copper layer, the surface of the carrier, between the carrier, between the ultrathin copper layer and the ultrathin copper layer, and between the ultrathin copper layer and the carrier. You may have a layer. In this specification, “surface of ultrathin copper layer”, “surface of ultrathin copper layer side”, “surface of ultrathin copper layer”, “surface of carrier”, “surface of carrier side”, “carrier surface”, “ "Surface of laminated body" and "laminated body surface" means an ultrathin copper layer, a carrier, and a laminated body, if the ultrathin copper layer surface, carrier surface, and laminated body surface have other layers, the other layer The concept includes the surface (outermost surface). Moreover, it is preferable that a laminated body has the structure of an ultra-thin copper layer / intermediate layer / carrier / carrier / intermediate layer / ultra-thin copper layer. This is because, when a coreless substrate is manufactured using the laminate, an ultrathin copper layer is disposed on the coreless substrate side, so that a circuit can be easily formed on the coreless substrate using the modified semi-additive method. In addition, since the thickness of the ultrathin copper layer is thin, it is easy to remove the ultrathin copper layer, and it becomes easier to form a circuit on the coreless substrate using the semi-additive method after the ultrathin copper layer is removed. .
In this specification, “laminate” not specifically described as “laminate A” or “laminate B” indicates a laminate including at least laminate A and laminate B.

  In the above-described coreless substrate manufacturing method, by covering part or all of the end face of the copper foil with carrier or the laminate (laminate A) with a resin, when producing a printed wiring board by the build-up method, It is possible to prevent the infiltration of the chemical solution between one copper foil with a carrier and another copper foil with a carrier constituting the intermediate layer or laminate, and separation of the ultrathin copper layer and the carrier due to the infiltration of the chemical solution Corrosion of the copper foil with carrier can be prevented, and the yield can be improved. As the “resin that covers part or all of the end face of the copper foil with carrier” or “resin that covers part or all of the end face of the laminate” used herein, a resin that can be used for the resin layer may be used. it can. Further, in the above-described coreless substrate manufacturing method, the carrier-attached copper foil or laminate when viewed in plan, the carrier-attached copper foil or laminate portion (a laminate portion of the carrier and the ultrathin copper layer, or one At least a part of the outer periphery of the laminated copper foil with carrier and another copper foil with carrier may be covered with resin or prepreg. Moreover, the laminated body (laminated body A) formed with the manufacturing method of the above-mentioned coreless board | substrate may be comprised by making a pair of copper foil with a carrier contact each other so that isolation | separation is possible. Further, when viewed in plan in the copper foil with carrier, the copper foil with carrier or the laminated portion of the laminated body (the laminated portion of the carrier and the ultrathin copper layer, or one copper foil with carrier and another copper with carrier) It may be formed by being covered with a resin or a prepreg over the entire outer periphery of the laminated portion with the foil. By adopting such a configuration, when the copper foil with a carrier or a laminate is viewed in plan, the laminated portion of the copper foil with a carrier or the laminate is covered with a resin or prepreg, and other members are in the lateral direction of this portion. That is, it becomes possible to prevent the stacking direction from being hit from the side, and as a result, peeling of the carrier during handling and the ultrathin copper layer or the copper foil with carrier can be reduced. Moreover, by covering the outer periphery of the copper foil with a carrier or the laminated part with a resin or prepreg so as not to be exposed, it is possible to prevent the chemical solution from entering the interface of the laminated part in the chemical treatment process as described above. , Corrosion and erosion of the copper foil with carrier can be prevented. When separating a single copper foil with a carrier from a pair of copper foils with a carrier, or when separating a carrier of a copper foil with a carrier and a copper foil (ultra-thin copper layer), a resin or prepreg is used. Cutting a covered copper foil with a carrier or a laminated part of a laminated body (a laminated part of a carrier and an ultrathin copper layer or a laminated part of one copper foil with a carrier and another copper foil with a carrier), etc. Need to be removed.

  The copper foil with a carrier of the present invention may be laminated from the carrier side or the ultrathin copper layer side to the carrier side or the ultrathin copper layer side of another copper foil with a carrier of the present invention. Moreover, the said carrier side surface or said ultra-thin copper layer side surface of said one copper foil with a carrier and the said carrier side surface or said ultra-thin copper layer side surface of said another copper foil with a carrier are as needed. Alternatively, a laminate obtained by directly laminating through an adhesive may be used. Further, the carrier or ultrathin copper layer of the one copper foil with carrier and the carrier or ultrathin copper layer of the other copper foil with carrier may be joined. Here, in the case where the carrier or the ultrathin copper layer has a surface treatment layer, the “joining” includes a mode in which the carriers or the ultrathin copper layer are joined to each other via the surface treatment layer. Further, part or all of the end face of the laminate may be covered with resin.

Lamination of carriers can be performed by, for example, the following method, in addition to simply overlapping.
(A) Metallurgical joining method: 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), brazing;
(B) Mechanical joining method: caulking, joining with rivets (joining with self-piercing rivets, joining with rivets), stitcher;
(C) Physical joining method: adhesive, (double-sided) adhesive tape

  By joining a part or all of one carrier and a part or all of the other carrier using the joining method described above, one carrier and the other carrier are stacked, and the carriers are brought into contact with each other in a separable manner. It is possible to manufacture a laminated body configured as described above. When one carrier and the other carrier are weakly joined and one carrier and the other carrier are laminated, one carrier is not removed even if the joint between the one carrier and the other carrier is not removed. And the other carrier can be separated. In addition, when one carrier and the other carrier are strongly bonded, the portion where one carrier and the other carrier are bonded is removed by cutting, chemical polishing (etching, etc.), mechanical polishing, or the like. Thus, one carrier and the other carrier can be separated.

  Also, a step of providing at least one layer of the resin layer and the circuit on the laminate thus configured, and after forming the two layers of the resin layer and the circuit at least once, the carrier of the laminate is provided with a carrier. A printed wiring board can be produced by carrying out a process of peeling the ultrathin copper layer or carrier from the copper foil. Note that two layers of a resin layer and a circuit may be provided on one or both surfaces of the laminate.

  As Examples 1 to 11 and Comparative Examples 1 to 10, copper foils having the thicknesses shown in Table 1 were prepared, and on one surface, a metal layer (roughening treatment layer, heat discoloration prevention layer, rust prevention layer, or As the silane coupling layer), plating treatment or sputtering treatment shown in Table 1 was performed. Here, as copper foils of Examples 1 to 4 and 7 to 11, 17, and 18 and Comparative Examples 1 to 4 and 7 to 10, rolled copper foil of tough pitch copper (JIS H3100 C1100R) manufactured by JX Nippon Mining & Metals is used. It was. Moreover, as copper foil of Examples 5-6 and Comparative Examples 5-6, JX Nippon Mining & Metals electrolytic copper foil HLP foil was used.

Moreover, the copper foil with a carrier described below as a copper foil base material of Examples 12 to 16 is prepared, and a metal layer (roughening treatment layer, heat discoloration prevention layer, rust prevention layer, or silane is provided on one surface. As the coupling layer), plating treatment or sputtering treatment shown in Table 1 was performed.
For Examples 12 to 14 and 16, an electrolytic copper foil having a thickness of 18 μm was prepared as a carrier, and for Example 15, a rolled copper foil having a thickness of 18 μm (C1100R made by JX Nippon Mining & Metals) was prepared as a carrier. Under the following conditions, an intermediate layer was formed on the surface of the carrier, and an ultrathin copper layer was formed on the surface of the intermediate layer.

Example 12
<Intermediate layer>
(1) Ni layer (Ni plating)
An Ni layer having an adhesion amount of 1000 μg / dm ² was formed on the carrier by electroplating on a roll-to-roll continuous plating line under the following conditions. Specific plating conditions are described below.
Nickel sulfate: 270-280 g / L
Nickel chloride: 35 to 45 g / L
Nickel acetate: 10-20g / L
Boric acid: 30-40 g / L
Brightener: Saccharin, butynediol, etc. Sodium dodecyl sulfate: 55-75 ppm
pH: 4-6
Bath temperature: 55-65 ° C
Current density: 10 A / dm ²

(2) Cr layer (electrolytic chromate treatment)
Next, after the surface of the Ni layer formed in (1) is washed with water and pickled, a Cr layer having an adhesion amount of 11 μg / dm ² is continuously formed on the Ni layer on a roll-to-roll-type continuous plating line. It was made to adhere by carrying out the electrolytic chromate process on the following conditions.
Potassium dichromate 1-10g / L, zinc 0g / L
pH: 7-10
Liquid temperature: 40-60 degreeC
Current density: 2 A / dm ²

<Ultrathin copper layer>
Next, after the surface of the Cr layer formed in (2) is washed with water and pickled, an ultrathin copper layer having a thickness of 1.5 μm is continuously formed on the Cr layer on a roll-to-roll-type continuous plating line. It was formed by electroplating under the following conditions to produce an ultrathin copper foil with a carrier.
Copper concentration: 90-110 g / L
Sulfuric acid concentration: 90-110 g / L
Chloride ion concentration: 50-90ppm
Leveling agent 1 (bis (3sulfopropyl) disulfide): 10 to 30 ppm
Leveling agent 2 (amine compound): 10 to 30 ppm
In addition, the following amine compound was used as the leveling agent 2.
(In the above chemical formula, R ₁ and R ₂ are selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group.)
Electrolyte temperature: 50-80 ° C
Current density: 100 A / dm ²
Electrolyte linear velocity: 1.5-5 m / sec

Example 13
<Intermediate layer>
(1) Ni-Mo layer (nickel molybdenum alloy plating)
A Ni—Mo layer having an adhesion amount of 3000 μg / dm ² was formed on the carrier by electroplating using a roll-to-roll type continuous plating line under the following conditions. 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 ° C
(Current density) 1 to 4 A / dm ²
(Energization time) 3 to 25 seconds

<Ultrathin copper layer>
An ultrathin copper layer was formed on the Ni—Mo layer formed in (1). An ultrathin copper layer was formed under the same conditions as in Example 12 except that the thickness of the ultrathin copper layer was 2 μm.

Example 14
<Intermediate layer>
(1) Ni layer (Ni plating)
A Ni layer was formed under the same conditions as in Example 12.
(2) Organic layer (Organic layer formation treatment)
Next, the surface of the Ni layer formed in (1) is washed with water and pickled, and subsequently contains carboxybenzotriazole (CBTA) at a concentration of 1 to 30 g / L with respect to the Ni layer surface under the following conditions. An organic layer was formed by spraying an aqueous solution of 40 ° C. and pH 5 after 20 to 120 seconds of showering.

<Ultrathin copper layer>
An ultrathin copper layer was formed on the organic layer formed in (2). An ultrathin copper layer was formed under the same conditions as in Example 12 except that the thickness of the ultrathin copper layer was 3 μm.

Examples 15 and 16
<Intermediate layer>
(1) Co-Mo layer (cobalt molybdenum alloy plating)
A Co—Mo layer having an adhesion amount of 4000 μg / dm ² was formed on the carrier by electroplating using a roll-to-roll type continuous plating line under the following conditions. 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 ° C
(Current density) 1 to 4 A / dm ²
(Energization time) 3 to 25 seconds

<Ultrathin copper layer>
An ultrathin copper layer was formed on the Co—Mo layer formed in (1). The ultrathin copper layer was formed under the same conditions as in Example 12 except that the thickness of the ultrathin copper layer was 5 μm in Example 15 and 3 μm in Example 16.

Next, on the surface of the rolled copper foil, the electrolytic copper foil, the copper foil with carrier, or the underlying layer (metal layer) on each copper foil, the surface treatment liquid is treated on the surface of the copper foil under the conditions shown in Table 2. The surface treatment layer was formed by applying to the whole, further washing with water and draining, and drying.
In addition, the meaning of the column of "the application method of chromate liquid" is as follows.
The “shower” was performed using a spray nozzle (standard fan nozzle manufactured by Ikeuchi Co., Ltd., jet angle category 90 °, jet quantity category 10).
The “roll” was performed using a sponge roll made of polyvinyl alcohol.
“Blade” was performed using a resin doctor blade (polyester, thickness 0.35 mm).
The “immersion chromate” was performed by immersing the copper foil in a chromate solution having the conditions described in Table 2 for 2 seconds.
The “electrolytic chromate” was treated by immersing a copper foil in a chromate solution having the conditions shown in Table 2 and passing a current through the copper foil at a current density of 2 A / dm ² for 1 second.
Further, the meanings of the columns “Liquid draining method” and “Liquid draining condition” are as follows.
“Roll” means draining with a sponge roll made of polyvinyl alcohol. Further, “liquid draining condition” when the “liquid draining method” is “roll” means the pressing force of the roll per unit width of the copper foil.
“Blade” means that the liquid was removed using a doctor blade (thickness 0.7 mm) made of silicon rubber. “Liquid draining condition” when the “liquid draining method” is “blade” means the length (distance) of the gap between the blade and the copper foil.
“Gas spraying” means that the liquid was removed by blowing air from a gas spray nozzle onto the copper foil. The distance between the gas blowing port of the gas blowing nozzle and the copper foil was 50 mm. Further, “liquid draining condition” when the “liquid draining method” is “gas spraying” means the flow rate of the gas sprayed onto the copper foil.
In Examples 17 and 18, after the above-described 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 silane coupling agent)
Silane concentration: 0.6 vol% (balance: water)
-Processing temperature: 30-40 ° C
・ Treatment time: 5 seconds ・ Drying after silane treatment: 100 ° C. × 3 seconds

Example 18
Silane used: N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (amino silane coupling agent)
Silane concentration: 5.0 vol% (balance: water)
-Processing temperature: 45-55 ° C
・ Treatment time: 5 seconds ・ Drying after silane treatment: 100 ° C. × 3 seconds

Various evaluation was performed as follows about each sample of the Example and comparative example which were produced as mentioned above.
-Metal adhesion amount of the metal layer;
(1) Ni, Co, W, Mo adhesion amount For the measurement of the adhesion amount of various metals in the metal layer, HNO ₃ (2% by weight) and HCl (5% by weight) were applied to a 50 mm × 50 mm copper foil surface film. It is dissolved in the mixed solution, and the metal concentration in the solution is quantified with an ICP emission spectroscopic analyzer (SFC-3100, manufactured by SII Nano Technology Co., Ltd.), and the amount of metal per unit area (μg / dm ² ). Calculated and led. At this time, the analysis was performed by masking as necessary so that the metal adhesion amount on the surface opposite to the surface to be measured was not mixed. When the film on the surface of the copper foil is difficult to dissolve in the above-described solution, the surface of the copper foil is used using a nitric acid aqueous solution in which a nitric acid aqueous solution having a nitric acid concentration of 60% by mass and water are mixed at a volume ratio of 1: 2. After that, the metal concentration in the obtained solution can be measured by the same method as described above.

(2) Zn and Cr adhesion amount;
The treatment layer is dissolved by boiling for 3 minutes in hydrochloric acid with a concentration of 10%, and the solution is analyzed by atomic absorption spectrometry. The amount of Zn deposited and the amount of trivalent and hexavalent chromium deposited (total of trivalent and hexavalent chromium) The amount of adhesion) was evaluated.
The amount of hexavalent chromium deposited was measured by diphenylcarbazide absorptiometry as follows.
A sample of copper foil (5 g) was cut into 50 mL of pure water, and the sample was boiled and leached for 5 minutes. Then, after adding pure water to the liquid obtained by boiling and leaching to make the volume 100 mL, the obtained liquid was used, and then “chromium (VI) [Cr (6)” described in 65.2 of JIS K0102. Among the determination methods of hexavalent chromium (chromium (VI)) described in “VI)]”, hexavalent chromium was measured according to “65.2.1 Diphenylcarbazide Absorbance Method”.
In addition, the neutralization of “65.2.1 c) Operation 1)” is not performed, and “Beaker (A) solution” in “2)” and “Beaker (B) solution” in “3)” are used. Using the liquid obtained as described above, the operations after “65.2.1 c) 2)” were performed.
In addition, Hitachi Ltd. 220A type was used for the absorptiometer. The measurement wavelength of the absorbance was 540 nm, and a glass cell having an optical path length of 10 mm was used as the sample cell.
The amount of trivalent chromium deposited was calculated from the value of the total amount of trivalent chromium and hexavalent chromium measured by atomic absorption spectrometry as described above, and the value of the amount of hexavalent chromium measured by diphenylcarbazide spectrophotometry described above. Calculated by subtracting.

A surface treatment layer formed of chromium oxide;
Elemental analysis in the surface and depth directions by ESCA was performed, and when chromium and oxygen were detected at the surface or at the same depth, it was determined that the surface treatment layer was formed of chromium oxide. In addition, since the chromium and oxygen were detected as a result of performing surface analysis by ESCA in each of the above-described examples and comparative examples, the copper foil according to each of the examples and comparative examples was a surface treatment layer formed of chromium oxide. Have

-The thickness of the surface treatment layer;
The thickness of the surface treatment layer was converted from the adhering amount of trivalent chromium as a density of 7.2 g / cm ³ . The conversion formula is as follows.
Surface treatment layer thickness (nm) = trivalent chromium adhesion (μg / dm ² ) / trivalent chromium density 7.2 g / cm ³ × 0.1 (nm × (g / cm ³ ) / (μg / Dm ² ))

・ Elution amount to nitric acid;
The sample was subjected to heat treatment at 250 ° C. for 10 minutes, and then immersed in a nitric acid bath having a concentration of 20 mass% and a temperature of 25 ° C. for 30 seconds with only the surface of the surface treatment layer exposed by 25 cm ² using a masking tape. Thereafter, the elution amount (g / 25 cm ² ) of the sample into the nitric acid bath was measured.
The elution amount was calculated by the following formula.
Elution amount (g / 25 cm ² ) = 250 ° C. × 10 minutes of heat treatment, then the sample weight before immersion in nitric acid bath (g) −250 ° C. × 10 minutes of heat treatment, then masking tape is used The weight of the sample after being immersed in a nitric acid bath having a concentration of 20 mass% and a temperature of 25 ° C. with only the surface of the surface treatment layer exposed to 25 cm ² (g)
The weight of the sample was measured with an electronic balance to 4 digits (0.1 mg) after the decimal point.

・ Peel strength;
In accordance with IPC-TM-650, the normal peel strength was measured with a tensile tester Autograph 100, and the normal peel strength of 0.7 kN / mm or more could be used for copper-clad laminate applications.

PCT (pressure cracker test);
As a pressure cracker test, it was treated at 121 ° C. under 2 atm for 48 hours, and the tensile strength was measured by the method of JIS-K7054 using the test piece after the durability test.

-Transmission loss For each sample having a thickness of 18 μm, the surface of the copper foil surface-treated side was bonded to a resin substrate (LCP: liquid crystal polymer resin (Kuraray Co., Ltd., Vecstar CTZ-50 μm (thickness)) and then etched. Then, a microstrip line was formed so that the characteristic impedance was 50Ω, and a transmission coefficient was measured using a network analyzer HP8720C manufactured by HP, and a transmission loss at a frequency of 20 GHz was obtained. In addition, the sample in which the thickness of the copper foil is less than 18 μm is applied to the surface of the copper foil after the copper foil is bonded to the resin substrate (after that, if the copper foil has a carrier, the carrier is peeled off from the copper foil). After the copper plating was performed so that the total thickness of the copper foil and the copper plating was 18 μm, the above measurement was performed.
The transmission loss was calculated by the following formula.
Transmission loss (dB / 10 cm) = 10 × log ₁₀ (output power / input power)
Table 3 shows the conditions and evaluation of each test. Table 4 shows the acceptance criteria for peel strength.

According to Table 3, each of Examples 1 to 18 was subjected to a heat treatment at 250 ° C. for 10 minutes, and then a nitric acid bath having a concentration of 20 mass% and a temperature of 25 ° C. with only the surface of the surface treatment layer exposed. When immersed for 30 seconds, the elution amount of copper into the nitric acid bath was 0.0030 g / 25 cm ² or less, and the peel strength was good.
On the other hand, each of Comparative Examples 1 to 5 and 10 was subjected to a heat treatment at 250 ° C. for 10 minutes, and then exposed to a nitric acid bath having a concentration of 20 mass% and a temperature of 25 ° C. with only the surface of the surface treatment layer exposed. When immersed for 2 seconds, the elution amount of copper into the nitric acid bath exceeded 0.0030 g / 25 cm ² and the peel strength was poor.
In Comparative Example 6, the peel strength was poor because the total adhesion amount of elements selected from the group consisting of Ni, Co, Zn, W, Mo and Cr in the metal layer was less than 200 μg / dm ² . .
In Comparative Examples 7 to 9, since the total adhesion amount of elements selected from the group consisting of Ni, Co, Zn, W, Mo and Cr in the metal layer exceeded 2000 μg / dm ² , the peel strength was poor. Transmission loss was large.

Claims (40)

A surface-treated copper having a copper foil, a metal layer containing at least one element selected from the group consisting of Ni, Co, Zn, W, Mo and Cr, and a surface treatment layer formed of chromium oxide in this order Foil,
The total adhesion amount of elements selected from the group consisting of Ni, Co, Zn, W, Mo and Cr in the metal layer is 200 to 2000 μg / dm ² ;
After heat treatment at 250 ° C. for 10 minutes, when immersed in a nitric acid bath having a concentration of 20 mass% and a temperature of 25 ° C. with only the surface of the surface treatment layer exposed, elution of copper into the nitric acid bath A surface-treated copper foil having an amount of 0.0030 g / 25 cm ² or less. ^2. The surface-treated copper foil according to claim 1, wherein the total adhesion amount of elements selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr in the metal layer is 200 to 1500 μg / dm ² . The surface-treated copper foil according to claim ² , wherein the total adhesion amount of elements selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr in the metal layer is 200 to 1000 μg / dm ² . The surface-treated copper foil according to claim 3, wherein the total adhesion amount of elements selected from the group consisting of Ni, Co, Zn, W, Mo, and Cr in the metal layer is 200 to 700 μg / dm ² .   The surface-treated copper foil according to any one of claims 1 to 4, wherein in the surface treatment layer, the amount of hexavalent chromium deposited is 0.1% or less of the amount of trivalent chromium deposited.   The surface-treated copper foil according to any one of claims 1 to 5, wherein the surface-treated layer has a thickness of 0.1 to 2.5 nm.   The surface-treated copper foil as described in any one of Claims 1-6 in which the said metal layer contains a heat discoloration prevention layer and / or a rust prevention layer.   The surface-treated copper foil according to claim 7, wherein the heat discoloration preventing layer and the rust preventing layer are Zn, Cu, or an alloy thereof.   The surface-treated copper foil of Claim 7 or 8 in which the said rust prevention layer contains a chromate layer or a zinc chromate layer.   The surface-treated copper foil as described in any one of Claims 1-9 in which the said metal layer contains a silane coupling layer.   The surface-treated copper foil as described in any one of Claims 1-10 in which the silane coupling layer was formed on the said surface treatment layer.   The surface-treated copper foil as described in any one of Claims 1-10 which equips the surface of the said surface treatment layer with a resin layer.   The surface-treated copper foil according to claim 11, wherein a resin layer is provided on a surface of the silane coupling layer.   The surface-treated copper foil of Claim 12 or 13 in which the said resin layer contains a dielectric material.   It is a copper foil with a carrier which has an intermediate | middle layer and an ultra-thin copper layer in this order on the one surface or both surfaces of a carrier, Comprising: The said ultra-thin copper layer is any one of Claims 1-14. Copper foil with carrier, which is a surface-treated copper foil.   The copper foil with a carrier according to claim 15, wherein the intermediate layer and the ultrathin copper layer are provided in this order on one surface of the carrier, and a roughening treatment layer is provided on the other surface of the carrier.   The laminated body of the surface-treated copper foil as described in any one of Claims 1-14, and a resin substrate.   The laminate according to claim 17, wherein the surface-treated copper foil and the resin substrate are laminated without using an adhesive.   The laminated body of the copper foil with a carrier of Claim 15 or 16, and a resin substrate.   It is a laminated body containing the copper foil with a carrier of Claim 15 or 16, and resin, Comprising: The laminated body with which one part or all part of the end surface of the said copper foil with a carrier is covered with the said resin.   The carrier-attached copper foil according to claim 15 or 16 from the carrier side or the ultrathin copper layer side, and the carrier-side copper foil according to claim 15 or 16 from the carrier side or the ultrathin. Laminated body laminated on the copper layer side.   The carrier side surface or the ultrathin copper layer side surface of the one copper foil with carrier and the carrier side surface or the ultrathin copper layer side surface of the other copper foil with carrier are bonded as necessary. The laminate according to claim 21, wherein the laminate is directly laminated via an agent.   The laminate according to claim 21 or 22, wherein the carrier or the ultrathin copper layer of the one copper foil with carrier and the carrier or the ultrathin copper layer of the other copper foil with carrier are joined. .   The laminate according to any one of claims 21 to 23, wherein a part or all of the end face of the laminate is covered with a resin.   The manufacturing method of the printed wiring board using the laminated body as described in any one of Claims 17-24. Providing the laminate according to any one of claims 17 to 24 with two layers of a resin layer and a circuit at least once; and
A method for producing a printed wiring board, comprising: forming the resin layer and the circuit layer at least once, and then peeling the ultrathin copper layer or the carrier from the copper foil with a carrier of the laminate.   The printed wiring board which used the laminated body as described in any one of Claims 17-24 as a material.   The electronic device provided with the printed wiring board of Claim 27.   A step of providing a chromate solution over the entire surface to be treated of the copper foil, and a step of forming a chromium oxide surface treatment layer by providing the chromate solution on the surface of the copper foil and then drying without washing with water. The manufacturing method of the surface-treated copper foil as described in any one of 1-14.   In the step of forming the chromium oxide surface treatment layer, the chromium oxide surface treatment layer is formed by providing a chromate solution on the surface of the copper foil, then draining, and then drying without washing with water. 29. A method for producing a surface-treated copper foil according to 29. The amount provided the chromate solution to the copper foil surface, after the liquid cutting, a method for producing a surface-treated copper foil according to claim 30 which is 5 to 20 mg / dm ^2.   The method for producing a surface-treated copper foil according to claim 30 or 31, wherein the liquid draining is performed by spraying a roll, a blade and / or a gas.   The process for providing the chromate solution over the entire surface of the copper foil to be treated is performed by applying the chromate solution to the copper foil surface by showering. Method. The process of providing the chromate solution on the entire surface to be treated of copper foil is performed by applying the chromate solution to the surface of the copper foil with a roller, and manufacturing the surface-treated copper foil according to any one of claims 29 to 32. Method.   The method for producing a surface-treated copper foil according to any one of claims 29 to 34, wherein the chromate solution has a pH of 1 to 10.   36. The method for producing a surface-treated copper foil according to claim 35, wherein the chromate solution has a pH of 4 to 10. Preparing a copper foil with carrier and an insulating substrate according to claim 15 or 16,
Laminating the copper foil with carrier and an insulating substrate;
After laminating the copper foil with carrier and the insulating substrate, a copper clad laminate is formed through a step of peeling the carrier of the copper foil with carrier,
Then, the manufacturing method of a printed wiring board including the process of forming a circuit by any method of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method. Forming a circuit on the ultrathin copper layer side surface or the carrier side surface of the carrier-attached copper foil according to claim 15 or 16,
Forming a resin layer on the ultrathin copper layer side surface or the carrier side surface of the copper foil with carrier so that the circuit is buried;
Forming a circuit on the resin layer;
After forming a circuit on the resin layer, peeling the carrier or the ultra-thin copper layer; and
After the carrier or the ultra-thin copper layer is peeled off, the ultra-thin copper layer or the carrier is removed to be buried in the resin layer formed on the ultra-thin copper layer-side surface or the carrier-side surface. A method of manufacturing a printed wiring board including a step of exposing a circuit that is connected. The step of laminating the ultrathin copper layer side surface or the carrier side surface of the copper foil with a carrier according to claim 15 or 16, and a resin substrate,
A step of providing at least once two layers of a resin layer and a circuit on the surface of the ultrathin copper layer opposite to the side laminated with the resin substrate of the copper foil with carrier or on the surface of the carrier; and
A method for producing a printed wiring board, comprising: a step of peeling the carrier or the ultrathin copper layer from the copper foil with a carrier after forming the resin layer and the two layers of the circuit. A step of laminating the carrier side surface of the copper foil with a carrier according to claim 15 or 16 and a resin substrate,
A step of providing two layers of a resin layer and a circuit at least once on the surface of the ultrathin copper layer side opposite to the side laminated with the resin substrate of the copper foil with carrier, and
A method of manufacturing a printed wiring board, comprising: forming the ultrathin copper layer from the copper foil with a carrier after forming the resin layer and the two layers of the circuit.