JP2016050325A - Methods for manufacturing copper foil with carrier, copper-clad laminate, printed wiring board, and electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide copper foil with carrier in which the occurrence of warpage during bonding with insulation substrate is sufficiently suppressed.SOLUTION: Provided is a method for manufacturing copper foil with carrier, including a heat treatment step for carrying out a heat treatment to copper foil with carrier having a carrier, an intermediate layer, and an ultra-thin copper layer in this order, at 120 to 220°C for 1 to 8 hours. In the heat treatment step, the heat treatment is carried out in a state of applying a tensile stress of 5.0 to 30.0 MPa to the copper foil with carrier.SELECTED DRAWING: Figure 4

Description

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

  Generally, a printed wiring board is manufactured through a process in which an insulating substrate is bonded to a copper foil to form a copper-clad laminate, and then a conductor pattern is formed on the copper foil surface by etching. In recent years, with the increasing needs for miniaturization and higher performance of electronic devices, higher density mounting of components and higher frequency of signals have progressed, and conductor patterns have become finer (fine pitch) and higher frequency than printed circuit boards. Response is required.

  Recently, copper foils with a thickness of 9 μm or less and further with a thickness of 5 μm or less have been required in response to the fine pitch, but such ultra-thin copper foils have low mechanical strength and are used in the manufacture of printed wiring boards. Copper foil with a carrier has appeared, in which a thick metal foil is used as a carrier, and an ultrathin copper layer is electrodeposited through a release layer, since it is easily broken or wrinkled. After bonding the surface of the ultrathin copper layer to an insulating substrate and thermocompression bonding, the carrier is peeled and removed through the peeling layer. After forming a circuit pattern with resist on the exposed ultra-thin copper layer, the micro-thin copper layer is etched with a sulfuric acid-hydrogen peroxide etchant (MSAP: Modified-Semi-Additive-Process). Is formed.

  Here, for the surface of the ultrathin copper layer of the copper foil with a carrier that becomes the adhesive surface with the resin, the peel strength between the ultrathin copper layer and the resin base material is mainly sufficient, and the peel strength Is required to be sufficiently retained after high-temperature heating, wet processing, soldering, chemical processing, and the like. As a method of increasing the peel strength between the ultrathin copper layer and the resin base material, generally, a large amount of roughened particles are adhered on the ultrathin copper layer having a large surface profile (unevenness, roughness). The method is representative.

  However, if a very thin copper layer with such a large profile (irregularity, roughness) is used on a semiconductor package substrate that needs to form a particularly fine circuit pattern among printed wiring boards, unnecessary copper particles during circuit etching Will remain, causing problems such as poor insulation between circuit patterns.

  For this reason, in WO2004 / 005588 (Patent Document 1), a copper foil with a carrier that is not subjected to a roughening treatment on the surface of an ultrathin copper layer is used as a copper foil with a carrier for use in a fine circuit including a semiconductor package substrate. It has been tried. The adhesion (peeling strength) between the ultrathin copper layer not subjected to such roughening treatment and the resin is affected by the low profile (unevenness, roughness, roughness) of the general copper foil for printed wiring boards. There is a tendency to decrease when compared. Therefore, the further improvement is calculated | required about copper foil with a carrier.

  Therefore, in Japanese Patent Application Laid-Open No. 2007-007937 (Patent Document 2) and Japanese Patent Application Laid-Open No. 2010-006071 (Patent Document 3), the surface of the ultrathin copper foil with carrier that contacts (adheres) the polyimide resin substrate is Ni. It is described that a layer or / and a Ni alloy layer are provided, a chromate layer is provided, a Cr layer or / and a Cr alloy layer are provided, a Ni layer and a chromate layer are provided, and a Ni layer and a Cr layer are provided. Has been. By providing these surface treatment layers, the adhesion strength between the polyimide resin substrate and the ultra-thin copper foil with carrier is not roughened, or the desired adhesive strength is achieved while reducing the degree of the roughening treatment (miniaturization). It has gained. Further, it is described that the surface treatment is performed with a silane coupling agent or the rust prevention treatment is performed.

WO2004 / 005588 JP 2007-007937 A JP 2010-006071 A

  In the development of copper foil with a carrier, the emphasis has so far been on ensuring the peel strength between the ultrathin copper layer and the insulating substrate. For this reason, the problem of warping of the copper foil with a carrier when bonded to an insulating substrate has not yet been sufficiently studied, and there is still room for improvement. Specifically, when bonding the copper foil and the insulating substrate, if the copper foil warp is extremely large, the copper foil transport device will fail and stop, or the copper foil will be caught and bend / wrinkle There may be a handling problem, that is, a production technical problem. In addition, warping may remain in the completed copper clad laminate due to warpage of the copper foil, and a problem may occur in the next process using the copper clad laminate. Furthermore, since the copper foil with a carrier is a composite composed of a carrier foil, a release layer, and an ultrathin copper layer, the warpage tends to increase due to differences in mechanical properties or crystal structures of these components. Then, this invention makes it a subject to provide the copper foil with a carrier in which generation | occurrence | production of the curvature at the time of bonding with an insulated substrate was suppressed favorably.

  In one aspect, the present invention completed on the basis of the above knowledge is subjected to heat treatment at 120 to 220 ° C. for 1 to 8 hours on a carrier-attached copper foil provided with a carrier, an intermediate layer, and an ultrathin copper layer in this order. It is a manufacturing method of the copper foil with a carrier which heat-processes in the said heat treatment process in the state which made the copper foil with a carrier act the 5.0-30.0MPa tensile stress in the said heat treatment process.

  In one embodiment of the method for producing a copper foil with a carrier according to the present invention, in the heat treatment step, the copper foil with a carrier is subjected to a heat treatment in a state where a tensile stress of 10.0 to 30.0 MPa is applied.

  In another embodiment of the method for producing a copper foil with a carrier of the present invention, heat treatment is performed in a state where a tensile stress of 15.0 to 30.0 MPa is applied to the copper foil with a carrier.

  The manufacturing method of the copper foil with a carrier of this invention is another one Embodiment. WHEREIN: The heat processing for 2 to 6 hours are performed at 140-180 degreeC in the said heat processing process.

  In still another embodiment of the method for producing a copper foil with a carrier according to the present invention, the heat treatment is performed in an inert gas atmosphere in the heat treatment step.

  In still another embodiment of the method for producing a copper foil with a carrier of the present invention, the tensile strength of the carrier is 300 MPa or more after the heat treatment step.

  In another embodiment of the method for producing a copper foil with a carrier of the present invention, the residual stress on the surface of the ultrathin copper foil after the heat treatment step is 10 MPa or less.

  In yet another embodiment of the method for producing a copper foil with a carrier according to the present invention, in the heat treatment step, the copper foil with a carrier is wound around a metal hollow tube.

  In still another embodiment of the method for producing a copper foil with a carrier according to the present invention, in the heat treatment step, the copper foil with a carrier is heated at a tension of 20 to 100 kgf / m when wound around a metal hollow tube. Process.

  In another embodiment of the method for producing a copper foil with a carrier according to the present invention, in the heat treatment step, the hollow tube is 1 to 600 in a state in which the copper foil with a carrier is wound around a metal hollow tube. Heat treatment is performed while rotating at a speed of rotation / hour.

  In another embodiment of the method for producing a copper foil with a carrier according to the present invention, the tensile strength of the carrier measured at room temperature after the heat treatment step is 300 MPa or more.

  In still another embodiment of the method for producing a copper foil with a carrier according to the present invention, the copper foil with a carrier before the heat treatment is roughened on one or both of the ultrathin copper layer surface and the carrier surface. It has a treatment layer.

  In still another embodiment of the method for producing a copper foil with a carrier according to the present invention, the copper foil with a carrier before the heat treatment is formed on the surface of the roughening treatment layer, a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and It has 1 or more types of layers selected from the group which consists of a silane coupling process layer.

  In still another embodiment of the method for producing a copper foil with a carrier according to the present invention, the copper foil with a carrier before the heat treatment is formed on the surface of the ultrathin copper layer with a heat resistant layer, a rust preventive layer, a chromate treated layer, and It has 1 or more types of layers selected from the group which consists of a silane coupling process layer.

  In still another embodiment of the method for producing a copper foil with a carrier according to the present invention, the copper foil with a carrier before the heat treatment includes a resin layer on the ultrathin copper layer.

  The manufacturing method of the copper foil with a carrier of this invention is another one Embodiment. WHEREIN: The copper foil with a carrier before the said heat processing equips the said roughening process layer with a resin layer.

  In still another embodiment of the method for producing a copper foil with a carrier according to the present invention, the copper foil with a carrier before the heat treatment is composed of the heat-resistant layer, the rust prevention layer, the chromate treatment layer, and the silane coupling treatment layer. A resin layer is provided on one or more layers selected from the above.

  In still another embodiment of the method for producing a copper foil with a carrier according to the present invention, the carrier-added copper foil before the heat treatment has an intermediate layer and an ultrathin copper layer in this order on one surface of the carrier. The roughening layer is provided on the surface of the carrier opposite to the surface on the ultrathin copper layer side of the carrier.

  In still another embodiment of the method for producing a copper foil with a carrier according to the present invention, the carrier-added copper foil before the heat treatment has an intermediate layer and an ultrathin copper layer in this order on one surface of the carrier. A copper foil with an intermediate layer and an ultrathin copper layer in this order on both sides of the carrier.

  In another aspect, the present invention is a method for producing a copper-clad laminate using the carrier-added copper foil produced by the method for producing a copper foil with carrier of the present invention.

  In still another aspect, the present invention is a method for manufacturing a printed wiring board using the carrier-attached copper foil produced by the method for producing a copper foil with carrier of the present invention.

In yet another aspect of the present invention, a step of preparing a copper foil with a carrier and an insulating substrate prepared by the method for producing a copper foil with a carrier of the present invention,
A step of laminating the copper foil with carrier and an insulating substrate; and
After laminating the carrier-attached copper foil and the insulating substrate, forming a copper-clad laminate through a step of peeling the carrier of the carrier-attached copper foil,
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 yet another aspect of the present invention, the step of forming a circuit on the ultrathin copper layer side surface or the carrier side surface of the carrier-attached copper foil produced by the method for producing a carrier-attached copper foil of the present invention,
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. It is a manufacturing method of a printed wiring board including the process of exposing the circuit which has been carried out.

  In still another aspect, the present invention is a method for manufacturing an electronic device using a printed wiring board manufactured by the method for manufacturing a copper foil with a carrier according to the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the copper foil with a carrier by which generation | occurrence | production of the curvature at the time of bonding with an insulating substrate was suppressed favorably can be provided.

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.

<Method for producing copper foil with carrier>
As a usage form of the carrier-attached copper foil provided with the carrier, the intermediate layer, and the ultrathin copper layer in this order, first, the surface of the ultrathin copper layer is bonded to an insulating substrate, and the carrier is peeled off after thermocompression bonding. Next, a resist having a predetermined pattern is provided on the ultrathin copper layer bonded to the insulating substrate. Subsequently, an etching process is performed with a predetermined etching solution, and an ultrathin copper layer not covered with the resist is removed to form a target conductor pattern. For example, a printed wiring board having a predetermined circuit Etc. are produced. Here, when the carrier-attached copper foil and the insulating substrate are bonded together, if the warpage of the copper foil with the carrier is extremely large, the copper foil conveying device may stop due to a malfunction, or the copper foil may be caught and folded or wrinkled. Handling problems may occur. In addition, warping may remain in the completed copper clad laminate due to warpage of the copper foil, and a problem may occur in the next process using the copper clad laminate. On the other hand, in the manufacturing method of copper foil with a carrier of this invention, after preparing the copper foil with a carrier provided with the carrier, the intermediate | middle layer, and the ultra-thin copper layer in this order, it is 120-220 with respect to the said copper foil with a carrier. Heat treatment is performed at 1 ° C. for 1 to 8 hours. Thus, since the residual stress in the ultra-thin copper layer formed by electroplating is relieved by performing heat treatment at 120 to 220 ° C. for 1 to 8 hours in advance, Generation | occurrence | production of the curvature of the copper foil with a carrier at the time of bonding with an insulating substrate can be suppressed favorably. In the preliminary heat treatment, when the temperature is less than 120 ° C. or the heating time is less than 1 hour, the residual stress is not sufficiently relaxed, and it becomes difficult to suppress warpage. In addition, in the prior heat treatment, when the temperature is over 220 ° C. or the heating time is over 8 hours, the mechanical strength of the carrier is lowered and the rigidity required as a support for the ultrathin copper layer cannot be maintained. The handling property is extremely deteriorated. In the heat treatment step, heat treatment is preferably performed at 140 to 180 ° C. for 2 to 6 hours.

Moreover, in the said heat processing process, in order to accelerate | stimulate the curvature correction effect by tension annealing, it heat-processes in the state which made 5.0-30.0 MPa tensile stress act on copper foil with a carrier. In order to apply the tensile stress, for example, there is a method of winding a copper foil with a carrier while applying a predetermined tension to a cylindrical or rod-shaped winding core. The tensile stress is obtained by dividing the tension applied at this time by the cross-sectional area of the copper foil with a carrier. In the heat treatment step, the heat treatment is preferably performed in a state in which a tensile stress of 10.0 to 30.0 MPa is applied to the copper foil with a carrier in order to promote the warp correction effect by tension annealing. It is more preferable to perform the heat treatment in a state where a tensile stress of 30.0 MPa is applied. In order to perform the above-described tension annealing, it is preferable to set the transport tension higher than that in the prior art when winding around the hollow tube.
In the heat treatment step, it is preferable to perform the heat treatment in an atmosphere that does not contain gas such as oxygen and water vapor that cause oxidation and deterioration of the carrier surface and the ultrathin copper layer surface. Preferably, the heat treatment is performed in an inert gas atmosphere such as neon, argon, or nitrogen.

  In the manufacturing method of the copper foil with a carrier of this invention, it is preferable to heat-process in the said heat processing process in the state which wound the copper foil with a carrier around metal hollow tubes. By heat-treating the copper foil with carrier wrapped around a metal hollow tube, it can be heated from the inside with respect to the copper foil with carrier by venting into a metal tube with good heat conduction, An efficient heat treatment becomes possible. The metal hollow tube is not particularly limited, but is preferably made of, for example, carbon steel or stainless steel, and the size is 7 cm to 20 cm in outer diameter and 0.5 cm to 3.0 cm in thickness. Can do.

In the method for producing a copper foil with a carrier according to the present invention, in the heat treatment step, it is preferable to perform the heat treatment with a tension of 20 to 100 kgf / m when the copper foil with a carrier is wound around a metal hollow tube. . The tension is a tension per unit width (width 1 m) of the carrier-attached copper foil. By setting the tension to 20 kgf / m or more, oxygen entrainment can be suppressed and oxidation of the copper foil with carrier can be prevented. Moreover, the wrinkle which generate | occur | produces at the time of winding can be prevented because the said tension | tensile_strength shall be 100 kgf / m or less.
The tension is more preferably 20 to 50 kgf / m, and even more preferably 20 to 30 kgf / m.

  In the method for producing a copper foil with a carrier of the present invention, in the heat treatment step, the hollow tube is wound at a speed of 1 to 600 revolutions / hour in a state where the copper foil with a carrier is wound around a metal hollow tube. Heat treatment is preferably performed while rotating. By performing the heat treatment while rotating the hollow tube at a relatively low speed of not less than 1 rotation / hour and not more than 600 rotation / hour, oxygen entrained between the wound copper foil is released and heated. Oxidation of the copper foil with carrier during processing can be prevented. The rotation speed of the hollow tube is more preferably 1 to 180 rotations / hour.

In the manufacturing method of the copper foil with a carrier of this invention, it is preferable that the tensile strength of the carrier measured at normal temperature after the said heat processing process is 300 Mpa or more. Thus, the rigidity when functioning as a carrier of ultra-thin copper foil is fully maintained because the tensile strength of the carrier measured at room temperature after the heat treatment step is 300 MPa or more.
The tensile strength of the carrier is more preferably 350 MPa or more, still more preferably 380 MPa or more, more typically 350 to 500 MPa, and still more typically 380 to 450 MPa.

<Copper foil with carrier>
Hereinafter, unless otherwise specified, the embodiment of the copper foil with carrier will be described before the heat treatment according to the present invention, but the embodiment is the one after the heat treatment (production of the copper foil with carrier according to the present invention). The same applies to the copper foil with carrier produced by the method.
The copper foil with a carrier of this invention has a carrier, an intermediate | middle layer, and an ultra-thin copper layer in this order. The method of using the copper foil with carrier itself is well known to those skilled in the art. For example, the surface of the ultra-thin copper layer is made of paper base phenol resin, paper base epoxy resin, synthetic fiber cloth base epoxy resin, glass cloth / paper composite. Substrate epoxy resin, glass cloth / glass nonwoven fabric composite substrate epoxy resin and glass cloth substrate epoxy resin, polyester film, polyimide film, liquid crystal polymer film, fluororesin film, etc. Then, an ultrathin copper layer bonded to an insulating substrate is etched into a target conductor pattern, and finally a printed wiring board can be manufactured.

The carrier-attached copper foil produced by the method for producing a carrier-attached copper foil of the present invention, that is, the carrier-attached copper foil after the heat treatment step, preferably has a carrier tensile strength of 300 MPa or more. According to such a configuration, it is possible to effectively suppress the warp caused by the ultrathin copper layer by the rigidity of the carrier, and to impart sufficient rigidity, that is, handleability as a support for the ultrathin copper layer. it can.
The tensile strength is more preferably 350 MPa or more, typically 300 to 600 MPa, and more typically 350 to 450 MPa.

The copper foil with a carrier produced by the method for producing a copper foil with a carrier of the present invention, that is, the copper foil with a carrier after the heat treatment step, preferably has an ultrathin copper foil surface having a residual stress of 10 MPa or less. . According to such a configuration, the residual stress of the ultrathin copper foil is sufficiently relaxed, and the warpage as the carrier-attached copper foil can be suppressed.
When the surface treatment layer is formed by roughening treatment, heat treatment, rust prevention treatment, chromate treatment, silane coupling treatment, etc. on the surface of the ultrathin copper layer of the carrier-attached copper foil of the present invention, the residual stress is as follows. It is a residual stress measured from above the surface treatment layer. The residual stress is preferably 10 MPa or less, more preferably 5 MPa or less, typically 0 to 10 MPa, and more typically 0 to 5 MPa.

<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, polyimide film, and LCP film.
Carriers that can be used in the present invention are 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 titanium or stainless steel drum, and the rolled copper foil is produced by repeating plastic working and heat treatment with a rolling roll. Examples of copper foil materials include high-purity copper such as tough pitch copper (JIS H3100 alloy number C1100) and oxygen-free copper (JIS H3100 alloy number C1020 or JIS H3510 alloy number C1011), for example, Sn-containing copper, Ag-containing copper, Cr A copper alloy such as a copper alloy added with Zr or Mg, or a Corson copper alloy added with Ni, Si or the like can also be used.
Moreover, as electrolytic copper foil, it can produce with the following electrolyte solution composition and manufacturing conditions.
In addition, the remainder of the process liquid used for manufacture of the copper foil described in this specification, surface treatment of copper foil, plating of copper foil, etc. is water unless otherwise specified.
<Electrolytic solution composition>
Copper: 90-110 g / L
Sulfuric acid: 90-110 g / L
Chlorine: 50-100ppm
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.)

<Production conditions>
Current density: 70 to 100 A / dm ²
Electrolyte temperature: 50-60 ° C
Electrolyte linear velocity: 3-5 m / sec
Electrolysis time: 0.5 to 10 minutes In addition, when the term “copper foil” is used alone in this specification, a copper alloy foil is also included.

  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 8 to 70 μm, more typically 12 to 70 μm, and more typically 18 to 35 μm. Moreover, it is preferable that the thickness of a carrier is small from a viewpoint of reducing raw material cost. Therefore, the thickness of the carrier is typically 5 μm or more and 35 μm or less, preferably 5 μm or more and 18 μm or less, preferably 5 μm or more and 12 μm or less, preferably 5 μm or more and 11 μm or less, preferably 5 μm or more and 10 μm or less. It is as follows. In addition, when the thickness of a carrier is small, it is easy to generate | occur | produce a wrinkle in the case of a carrier foil. In order to prevent the generation of folding wrinkles, for example, it is effective to smooth the transport roll of the copper foil manufacturing apparatus with a carrier and to shorten the distance between the transport roll and the next transport roll. In addition, when the copper foil with a carrier is used for the embedding method (embedded process) which is one of the manufacturing methods of a printed wiring board, the rigidity of a carrier needs to be high. Therefore, when used in the embedding method, the thickness of the carrier is preferably 18 μm or more and 300 μm or less, preferably 25 μm or more and 150 μm or less, preferably 35 μm or more and 100 μm or less, and 35 μm or more and 70 μm or less. Even more preferred.

<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. The intermediate layer may be provided on both sides of the carrier.

  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 layer made of 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. It can comprise by forming.

  An intermediate layer containing Ni can be provided on one or both sides of the carrier. The intermediate layer is formed by laminating any one layer of nickel or an alloy containing nickel on the carrier and a layer containing any one or more of chromium, a chromium alloy, and an oxide of chromium in this order. It is preferable. In addition, it is preferable that zinc is contained in any one layer of nickel or an alloy containing nickel and / or a layer containing any one or more of chromium, a chromium alloy, and an oxide of chromium. Here, the alloy containing nickel is composed of nickel and one or more elements selected from the group consisting of cobalt, iron, chromium, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. An alloy. The alloy containing nickel may be an alloy composed of three or more elements. The chromium alloy is an alloy composed of chromium and one or more elements selected from the group consisting of cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. Say. The chromium alloy may be an alloy composed of three or more elements. Further, the layer containing any one or more of chromium, a chromium alloy, and a chromium oxide may be a chromate treatment layer. Here, the chromate-treated layer refers to a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. Chromate treatment layer is any element such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium (metal, alloy, oxide, nitride, sulfide, etc.) May be included). Specific examples of the chromate treatment layer include a pure chromate treatment layer and a zinc chromate treatment layer. In the present invention, a chromate treatment layer treated with an anhydrous chromic acid or potassium dichromate aqueous solution is referred to as a pure chromate treatment layer. In the present invention, a chromate treatment layer treated with a treatment liquid containing chromic anhydride or potassium dichromate and zinc is referred to as a zinc chromate treatment layer.

The intermediate layer is any one of nickel, nickel-zinc alloy, nickel-phosphorus alloy and nickel-cobalt alloy on the carrier, and any of zinc chromate treatment layer, pure chromate treatment layer and chromium plating layer. It is preferable that one kind of layer is laminated in this order, and the intermediate layer is constituted by laminating a nickel layer or a nickel-zinc alloy layer and a zinc chromate treatment layer in this order on the carrier. More preferably, the nickel-zinc alloy layer and the pure chromate treatment layer or the zinc chromate treatment layer are laminated in this order. Since the adhesive force between nickel and copper is higher than the adhesive force between chromium and copper, when the ultrathin copper layer is peeled off, it peels at the interface between the ultrathin copper layer and the chromate treatment 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. Further, it is preferable to form a chromate treatment layer on the intermediate layer instead of chrome plating. Since chromium plating forms a dense chromium oxide layer on the surface, when an ultrathin copper foil is formed by electroplating, the electrical resistance increases and pinholes are likely to occur. The surface on which the chromate treatment layer is formed has a chromium oxide layer that is less dense than chrome plating, so resistance to formation of ultrathin copper foil by electroplating is less likely to reduce pinholes. it can. Here, by forming a zinc chromate treatment layer as a chromate treatment layer, the resistance when forming an ultrathin copper foil by electroplating is lower than that of a normal chromate treatment layer, and the generation of pinholes is further suppressed. be able to.
When using electrolytic copper foil as a carrier, it is preferable to provide an intermediate layer on the shiny surface from the viewpoint of reducing pinholes.

  Among the intermediate layers, the chromate treatment layer is thinly present at the interface of the ultrathin copper layer, while the ultrathin copper layer does not peel off from the carrier before the laminating process on the insulating substrate, while after the laminating process on the insulating substrate It is preferable for obtaining the property that the ultrathin copper layer can be peeled from the carrier. When the chromate treatment layer is present at the boundary between the carrier and the ultrathin copper layer without providing a nickel layer or an alloy layer containing nickel (for example, a nickel-zinc alloy layer), the peelability is hardly improved, and the chromate treatment layer If the nickel layer or the alloy layer containing nickel (for example, nickel-zinc alloy layer) and the ultrathin copper layer are directly laminated, the nickel amount in the nickel layer or the alloy layer containing nickel (for example, nickel-zinc alloy layer) Accordingly, the peel strength is too strong or too weak to obtain an appropriate peel strength.

  Further, if the chromate treatment layer is present at the boundary between the carrier and the nickel layer or nickel-containing alloy layer (for example, nickel-zinc alloy layer), the intermediate layer is also peeled along with the peeling of the ultrathin copper layer, that is, the carrier. And the intermediate layer is undesirably peeled off. Such a situation may occur not only when the chromate treatment layer is provided at the interface with the carrier, but also when the amount of chromium is excessive even if the chromate treatment layer is provided at the interface with the ultrathin copper layer. This is because copper and nickel are likely to be in solid solution, so if they are in contact with each other, the adhesive force increases due to mutual diffusion and is difficult to peel off, while chromium and copper are less likely to dissolve and cause mutual diffusion. It is considered that the adhesion between the chromium and copper interface is weak and easy to peel off. Further, when the nickel amount in the intermediate layer is insufficient, there is only a very small amount of chromium between the carrier and the ultrathin copper layer, so that they are in close contact with each other and are difficult to peel off.

The intermediate nickel layer or nickel-containing alloy layer (for example, nickel-zinc alloy layer) is formed by wet plating such as electroplating, electroless plating and immersion plating, or dry plating such as sputtering, CVD and PDV. can do. Electroplating is preferable from the viewpoint of cost. When the carrier is a resin film, the intermediate layer can be formed by dry plating such as CVD and PDV or wet plating such as electroless plating and immersion plating.
In addition, the chromate treatment layer can be formed with, for example, electrolytic chromate or immersion chromate, but the chromium concentration can be increased, and the peel strength of the ultra-thin copper layer from the carrier is improved. Preferably formed.

  Even if the intermediate | middle layer of the copper foil with a carrier of this invention is laminated | stacked in order of the organic layer containing either a nickel layer and a nitrogen containing organic compound, a sulfur containing organic compound, and carboxylic acid on a carrier. Good. Moreover, the intermediate layer of the copper foil with a carrier of the present invention is formed by laminating an organic material layer containing any of a nitrogen-containing organic compound, a sulfur-containing organic compound and a carboxylic acid, and a nickel layer on the carrier. May be. Moreover, BTA (benzotriazole), MBT (mercaptobenzothiazole), etc. are mentioned as an organic substance containing either the said nitrogen containing organic compound, sulfur containing organic compound, and carboxylic acid.

Moreover, as an organic substance which an intermediate | middle layer contains, it is preferable to use what consists of 1 type (s) or 2 or more types selected from a nitrogen containing organic compound, a sulfur containing organic compound, and carboxylic acid. Among the nitrogen-containing organic compound, the sulfur-containing organic compound, and the carboxylic acid, the nitrogen-containing organic compound includes a nitrogen-containing organic compound having a substituent. Specific nitrogen-containing organic compounds include 1,2,3-benzotriazole, carboxybenzotriazole, N ′, N′-bis (benzotriazolylmethyl) urea, 1H-1 which are triazole compounds having a substituent. 2,4-triazole, 3-amino-1H-1,2,4-triazole and the like are preferably used.
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.
The organic material is preferably contained in a thickness of 25 nm to 80 nm, more preferably 30 nm to 70 nm. The intermediate layer may contain a plurality of types (one or more) of the aforementioned organic substances.
In addition, the thickness of organic substance can be measured as follows.

<Thickness of organic material in the intermediate layer>
After peeling off the ultrathin copper layer of the carrier-attached copper foil from the carrier, the surface of the exposed ultrathin copper layer on the intermediate layer side and the exposed surface of the intermediate layer side of the carrier are subjected to XPS measurement to create a depth profile. The depth at which the carbon concentration first becomes 3 at% or less from the surface on the intermediate layer side of the ultrathin copper layer is defined as A (nm), and the carbon concentration is initially 3 at% or less from the surface on the intermediate layer side of the carrier. The resulting depth can be defined as B (nm), and the sum of A and B can be defined as the thickness (nm) of the organic substance in the intermediate layer.
XPS operating conditions are shown below.
・ Device: XPS measuring device (ULVAC-PHI, Model 5600MC)
・ Achieving vacuum: 3.8 × 10 ⁻⁷ Pa
X-ray: Monochromatic AlKα or non-monochromatic MgKα, X-ray output 300 W, detection area 800 μmφ, angle between sample and detector 45 °
Ion beam: ion species Ar ⁺ , acceleration voltage 3 kV, sweep area 3 mm × 3 mm, sputtering rate 2.8 nm / min (in terms of SiO ₂ )

  The method for using the organic substance contained in the intermediate layer will be described below with reference to the method for forming the intermediate layer on the carrier foil. The intermediate layer is formed on the carrier by dissolving the above-mentioned organic substance in a solvent and immersing the carrier in the solvent, or showering, spraying method, dropping method and electrodeposition method on the surface on which the intermediate layer is to be formed. Etc., and there is no need to adopt a particularly limited method. At this time, the concentration of the organic agent in the solvent is preferably in the range of a concentration of 0.01 g / L to 30 g / L and a liquid temperature of 20 to 60 ° C. in all the organic substances described above. The concentration of the organic substance is not particularly limited, and there is no problem even if the concentration is originally high or low. In addition, the organic substance thickness of an intermediate | middle layer tends to become large, so that the density | concentration of organic substance is high, and the contact time of the carrier to the solvent which dissolved the organic substance mentioned above is long. And when the organic substance thickness of an intermediate | middle layer is thick, it exists in the tendency for the effect of organic substance to suppress the spreading | diffusion to the ultra-thin copper layer side of Ni to become large.

<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 can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfamate, copper cyanide, etc., and the copper layer can be formed at a high current density. A copper sulfate bath is preferred. The thickness of the ultrathin copper layer is not particularly limited, but is generally thinner than the carrier, for example, 12 μm or less. It is typically 0.5-12 μm, more typically 1-5 μm, even more typically 1.5-5 μm, and even more typically 2-5 μm. The ultra thin copper layer may be provided on both sides of the carrier.

<Roughening treatment and other surface treatment>
A roughening treatment layer may be provided on the surface of the ultrathin copper layer by performing a roughening treatment, for example, in order to improve the adhesion to 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 is a layer made of any single substance selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium, and zinc, or an alloy containing one or more of them. Also good. Moreover, after forming the roughened particles with copper or a copper alloy, a roughening treatment can be performed in which secondary particles or tertiary particles are further formed of nickel, cobalt, copper, zinc alone or an alloy. Thereafter, a heat-resistant layer or a rust-preventing layer may be formed of nickel, cobalt, copper, zinc alone or an alloy, and the surface thereof may be further subjected to a treatment such as a chromate treatment or a silane coupling treatment. Alternatively, a heat-resistant layer or a rust-preventing layer may be formed from nickel, cobalt, copper, zinc alone or an alloy without roughening, and the surface may be subjected to a treatment such as chromate treatment or silane coupling treatment. Good. That is, one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate treatment layer, and a silane coupling treatment layer may be formed on the surface of the roughening treatment layer. One or more layers selected from the group consisting of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer may be formed on the surface. In addition, the above-mentioned heat-resistant layer, rust prevention layer, chromate treatment layer, and silane coupling treatment layer may each be formed of a plurality of layers (for example, 2 layers or more, 3 layers or more, etc.).
Here, the chromate-treated layer may be the above-mentioned chromate-treated layer or other chromate-treated layer.

As the heat-resistant layer and the rust-proof layer, known heat-resistant layers and rust-proof layers can be used. For example, the heat-resistant layer and / or the anticorrosive layer is a group of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, tantalum A layer containing one or more elements selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements Further, it may be a metal layer or an alloy layer made of one or more elements selected from the group consisting of iron, tantalum and the like. The heat-resistant layer and / or rust preventive layer is a group of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, and tantalum. An oxide, nitride, or silicide containing one or more elements selected from the above may be included. Further, the heat-resistant layer and / or the rust preventive layer may be a layer containing a nickel-zinc alloy. Further, the heat-resistant layer and / or the rust preventive layer may be a nickel-zinc alloy layer. The nickel-zinc alloy layer may contain 50 wt% to 99 wt% nickel and 50 wt% to 1 wt% zinc, excluding inevitable impurities. The total adhesion amount of zinc and nickel in the nickel-zinc alloy layer may be 5 to 1000 mg / m ² , preferably 10 to 500 mg / m ² , preferably 20 to 100 mg / m ² . Further, the ratio of the nickel adhesion amount and the zinc adhesion amount of the layer containing the nickel-zinc alloy or the nickel-zinc alloy layer (= nickel adhesion amount / zinc adhesion amount) is 1.5 to 10. It is preferable. Further, the nickel - in adhesion amount of nickel in the zinc alloy layer is preferably from ^{0.5mg / m 2 ~500mg / m 2} , 1mg / m 2 ~50mg / m 2 - zinc alloy layer or the nickel containing More preferably. When the heat-resistant layer and / or rust prevention layer is a layer containing a nickel-zinc alloy, the interface between the copper foil and the resin substrate is eroded by the desmear liquid when the inner wall such as a through hole or via hole comes into contact with the desmear liquid. It is difficult to improve the adhesion between the copper foil and the resin substrate.

For example heat-resistant layer and / or anticorrosive layer has coating weight of 1 mg / m ² -100 mg / m ^2, preferably from 5 mg / m ² and to 50 mg / m ² of nickel or nickel alloy layer, the adhesion amount is 1 mg / m ² to 80 mg / m ^2, preferably it may be obtained by sequentially laminating a tin layer of ^{5mg / m 2 ~40mg / m 2} , wherein the nickel alloy layer of nickel - molybdenum, nickel - zinc, nickel - molybdenum - cobalt You may be comprised by any one of these. The heat-resistant layer and / or anticorrosive layer, it is ^{preferably, 10mg / m 2 ~70mg / m} 2 total deposition amount of nickel or nickel alloy and tin is 2mg / m ² ~150mg / m 2 It is more preferable. Further, the heat-resistant layer and / or the rust preventive layer is preferably [nickel or nickel adhesion amount in nickel or nickel alloy] / [tin adhesion amount] = 0.25 to 10, preferably 0.33 to 3. More preferred. When the heat-resistant layer and / or rust-preventing layer is used, the carrier-clad copper foil is processed into a printed wiring board, and the subsequent circuit peeling strength, the chemical resistance deterioration rate of the peeling strength, and the like are improved.

  In addition, you may use a well-known silane coupling agent for the silane coupling agent used for a silane coupling process, for example, using an amino-type silane coupling agent or an epoxy-type silane coupling agent, a mercapto-type silane coupling agent. Good. 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 silane coupling treatment layer may be formed using a silane coupling agent such as an epoxy silane, an amino silane, a methacryloxy silane, or a mercapto silane. In addition, you may use 2 or more types of such silane coupling agents in mixture. Especially, it is preferable to form using an amino-type silane coupling agent or an epoxy-type silane coupling agent.

  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 Good.

The silane coupling treatment 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 in terms of silicon atoms. / M ² is desirable. In the case of the above-mentioned range, the adhesiveness between the base resin and the surface-treated copper foil can be further improved.

  In addition, on the surface of an ultrathin copper layer, a roughening treatment layer, a heat-resistant layer, a rust prevention layer, a silane coupling treatment layer or a chromate treatment layer, International Publication No. WO2008 / 053878, JP2008-1111169, Patent No. 5024930 , International Publication No. WO2006 / 028207, Patent No. 4828427, International Publication No. WO2006 / 134868, Patent No. 5046927, International Publication No. WO2007 / 105635, Patent No. 5180815, JP2013-19056A. be able to.

The carrier-attached copper foil includes a resin layer on the ultrathin copper layer, the roughened layer, the heat-resistant layer, the rust-proof layer, the chromate-treated layer, or the silane coupling-treated layer. May be. The resin layer may be an insulating resin layer.
Moreover, the copper foil with a carrier may be provided with a roughening treatment layer on the carrier, and is selected from the group consisting of a roughening treatment layer, a heat-resistant layer, a rust prevention layer, a chromate treatment layer and a silane coupling treatment layer on the carrier. One or more layers may be provided. The roughening treatment layer, the heat-resistant layer, the rust prevention layer, the chromate treatment layer and the silane coupling treatment layer may be provided by using known methods, and according to the methods described in the present specification, claims and drawings. It may be provided. Providing one or more layers selected from the roughening treatment layer, heat-resistant layer, rust prevention layer, chromate treatment layer, and silane coupling treatment layer on the carrier is possible from the surface side having the roughening treatment layer, etc. When the substrate is laminated on a support such as a resin substrate, the carrier and the support are less likely to be peeled off.

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

  The resin layer may contain a thermosetting resin or may be a thermoplastic resin. The resin layer may include a thermoplastic resin. The 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. 2002-179722, Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003-302068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003 No. 249739, Japanese Patent No. 4136509, Japanese Patent Application Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Application Laid-Open No. 2004-349654, Japanese Patent No. 4286060, Japanese Patent Application Laid-Open No. 2005-262506, Japanese Patent No. 4570070, 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 tree 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, Select from the group of 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 as suitable to be.

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 -Glycidyl amine compounds such as diglycidyl aniline, glycidyl ester compounds such as diglycidyl tetrahydrophthalate, phosphorus-containing epoxy resins, biphenyl type epoxy resins, One or two or more types selected from the group of phenyl novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetraphenylethane type epoxy resin can be used, or a hydrogenated product of the epoxy resin or Halogenated substances 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 of the copper foil with a carrier is coated on the surface of the ultrathin copper layer 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 are sampled from a resin-treated surface-treated copper foil with a resin thickness of 55 μm. A value calculated based on Equation 1 from the result of measuring the resin outflow weight at the time when the sample was laminated (laminate) 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. It is.

  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 having a thickness of one layer of 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 the 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 thicker than 120 μm, it is difficult to form a resin layer having a desired 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.

Furthermore, a printed circuit board is completed by mounting electronic components on the printed wiring board. In the present invention, the “printed wiring board” includes a printed wiring board, a printed circuit board, and a printed board on which electronic parts are mounted as described above.
In addition, an electronic device may be manufactured using the printed wiring board, an electronic device may be manufactured using a printed circuit board on which the electronic components are mounted, and a print on which the electronic components are mounted. An electronic device may be manufactured using a substrate. Below, some examples of the manufacturing process of the printed wiring board using the copper foil with a 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 a 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,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Removing all of the ultrathin copper layer exposed by peeling the carrier by a method such as etching or plasma using a corrosive solution such as acid,
Providing a through hole or / and a blind via in the resin exposed by removing the ultrathin copper layer by etching;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the resin and the through hole or / and the blind via;
Providing a plating resist on the electroless plating layer;
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 from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

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 the carrier-attached copper foil and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via in the ultrathin copper layer exposed by peeling the carrier and the insulating resin substrate;
Performing a desmear process on the region including the through hole or / and the blind via,
Removing all of the ultrathin copper layer exposed by peeling the carrier by a method such as etching or plasma using a corrosive solution such as acid,
Providing an electroless plating layer for the resin and the region including the through hole or / and the blind via exposed by removing the ultrathin copper layer by etching or the like;
Providing a plating resist on the electroless plating layer;
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 from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

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 the carrier-attached copper foil and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via in the ultrathin copper layer exposed by peeling the carrier and the insulating resin substrate;
Removing all of the ultrathin copper layer exposed by peeling the carrier by a method such as etching or plasma using a corrosive solution such as acid,
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the resin and the region including the through hole or / and the blind via exposed by removing the ultrathin copper layer by etching or the like;
Providing a plating resist on the electroless plating layer;
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 from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

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 the carrier-attached copper foil and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Removing all of the ultrathin copper layer exposed by peeling the carrier by a method such as etching or plasma using a corrosive solution such as acid,
Providing an electroless plating layer on the surface of the resin exposed by removing the ultrathin copper layer by etching;
Providing a plating resist on the electroless plating layer;
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 from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer and the ultrathin copper layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

  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,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the through hole or / and the blind via;
Providing a plating resist on the surface of the ultrathin copper layer exposed by peeling the carrier,
Forming a circuit by electrolytic plating after providing the plating resist;
Removing the plating resist;
Removing the ultra-thin copper layer exposed by removing the plating resist by flash etching;
including.

In another 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 carrier-attached copper foil and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
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 from which the plating resist has been removed is formed;
Removing the plating resist;
Removing an ultrathin copper layer in a region other than the region where the circuit is formed by flash etching or the like;
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, on the conductor circuit, by performing a thickness by electroless plating treatment (further electrolytic plating treatment if necessary) on a through hole or via hole, It refers to a method of manufacturing a printed wiring board.

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using a partly additive method, a step of preparing the copper foil with carrier and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Applying catalyst nuclei to the region containing the through-holes and / or blind vias;
Providing an etching resist on the surface of the ultrathin copper layer exposed by peeling the carrier,
Exposing the etching resist to form a circuit pattern;
Removing the ultrathin copper layer and the catalyst nucleus by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit;
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 core by a method such as etching or plasma using a corrosive solution such as an acid;
Providing an electroless plating layer in a region where the solder resist or plating resist is not provided,
including.

  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 method for producing a printed wiring board according to the present invention using a subtractive method, a step of preparing the carrier-attached copper foil and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the through hole or / and the blind via;
Providing an electroplating layer on the surface of the electroless plating layer;
A step of providing an etching resist on the surface of the electrolytic plating layer or / and the ultrathin copper layer;
Exposing the etching resist to form a circuit pattern;
Removing the ultrathin copper layer and the electroless plating layer and the electrolytic plating layer by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit;
Removing the etching resist;
including.

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 the carrier-attached copper foil and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the through hole or / and the blind via;
Forming a mask on the surface of the electroless plating layer;
Providing an electroplating layer on the surface of the electroless plating layer on which no mask is formed;
A step of providing an etching resist on the surface of the electrolytic plating layer or / and the ultrathin copper layer;
Exposing the etching resist to form a circuit pattern;
Removing the ultra-thin copper layer and the electroless plating layer by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit;
Removing the etching resist;
including.

  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. However, the present invention is not limited thereto, and the carrier has an ultrathin copper layer on which a roughened layer is not formed. 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.
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.
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.
Next, as shown to FIG. 2-E, a carrier is peeled from the copper foil with a carrier of the 2nd layer.
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.
Next, as shown in FIG. 4J, the ultrathin copper layers on both surfaces are removed by flash etching, and the surface of the circuit plating in the resin layer is exposed.
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.

  Moreover, the copper foil with a carrier used for the said 1st layer may have a board | substrate on the carrier side surface of the said copper foil with a carrier. By having the said board | substrate, since the copper foil with a carrier used for the 1st layer is supported and it becomes difficult to wrinkle, there exists an advantage that productivity improves. As the substrate, any substrate can be used as long as it has an effect of supporting the carrier-attached copper foil used in the first layer. For example, the carrier, prepreg, resin layer or known carrier, prepreg, resin layer, metal plate, metal foil, inorganic compound plate, inorganic compound foil, organic compound plate, organic compound A foil can be used.

  Although there is no restriction | limiting in particular about the timing which forms a board | substrate in the carrier side surface, It is necessary to form before peeling a carrier. In particular, it is preferably formed before the step of forming a resin layer on the ultrathin copper layer side surface of the copper foil with carrier, and the step of forming a circuit on the ultrathin copper layer side surface of the copper foil with carrier More preferably, it is formed before.

  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. The embedding resin may include a thermosetting resin or a thermoplastic resin. The embedding resin may include a thermoplastic resin. The type of the embedded resin is not particularly limited. For example, epoxy resin, polyimide resin, polyfunctional cyanate compound, maleimide compound, polyvinyl acetal resin, urethane resin, block copolymer polyimide resin, block copolymer Resin including polyimide resin, paper base phenolic resin, paper base epoxy resin, synthetic fiber cloth base epoxy resin, glass cloth / paper composite base epoxy resin, glass cloth / glass non-woven composite base epoxy resin and glass A cloth base epoxy resin, a polyester film, a polyimide film, a liquid crystal polymer film, a fluororesin film, etc. can be mentioned as a suitable thing.

  Hereinafter, description will be given based on experimental examples. In addition, this experiment example is an example to the last, and is not restrict | limited only to this example.

1. Production of Copper Foil with Carrier A copper foil with a carrier was produced by the following procedure.
First, a long electrolytic copper foil or rolled copper foil having a thickness shown in Table 1 was prepared as a carrier.
The electrolytic copper foil was manufactured under the following conditions.
(Electrolytic bath composition)
Cu: 80 to 120 g / L
H ₂ SO _4: 80~120g / L
Cl: 20-80 mg / L
Nika: 0.1-6.0 mg / L
(Electrolytic conditions)
Liquid temperature: 55-65 degreeC
Current density: 100 A / dm ²
Electrolyte flow rate: 1.5 m / sec

  As the rolled copper foil, Examples 9 and 12 used tough pitch copper (tough pitch copper specified in JIS H3100 C1100), and Examples 10 and 11 used oxygen-free copper (oxygen-free copper specified in JIS H3100 C1020). “Rolled copper foil (Ag 180 ppm)” in the carrier type column of Table 1 means that 180 mass ppm of Ag was added to tough pitch copper.

<Intermediate layer of experimental example>
An intermediate layer was formed on the glossy surface (shiny surface) of the copper foil by electroplating using a roll-to-roll-type continuous plating line under the following conditions.
-Ni layer Nickel sulfate: 250-300 g / L
Nickel chloride: 35 to 45 g / L
Nickel acetate: 10-20g / L
Trisodium citrate: 15-30 g / L
Brightener: Saccharin, butynediol, etc. Sodium dodecyl sulfate: 30-100 ppm
pH: 4-6
Bath temperature: 50-70 ° C
Current density: 3-15 A / dm ²
Adhesion amount: 4000 μg / dm ²

After washing with water and pickling, on the roll-to-roll-type continuous plating line, a Cr layer with an adhesion amount of 10 μg / dm ² was deposited on the Ni layer by electrolytic chromate treatment under the following conditions. .
Electrolytic chromate treatment Liquid composition: potassium dichromate 1-10 g / L, zinc 0-5 g / L
pH: 3-4
Liquid temperature: 50-60 degreeC
Current density: 0.1-2.6 A / dm ²
Coulomb amount: 0.5-30 As / dm ²

<Ultrathin copper layer in the experimental example>
Subsequently, on a roll-to-roll type continuous plating line, an ultrathin copper layer having a thickness of 3 μm was formed on the intermediate layer by electroplating under the following conditions to produce a copper foil with a carrier.
-Ultrathin copper layer Copper concentration: 30-120 g / L
H ₂ SO ₄ concentration: 20 to 120 g / L
Electrolyte temperature: 20-80 ° C
Current density: 10 to 100 A / dm ²

<Surface treatment layer of experimental example>
Surface treatment was performed on the surface of the ultrathin copper layer described above under the following surface treatment conditions. Table 1 shows the layer structure of the surface treatment layer formed by the surface treatment.
In some experimental examples, the surface of the ultrathin copper layer is selected from Cu—W alloy plating, Cu—P alloy plating, and Cu—Co—Ni alloy plating under the following conditions as a roughening treatment. Went.

Cu-W alloy plating (Examples 1, 2, 15, 16)
Liquid composition: Cu 15 g / liter, sulfuric acid 100 g / liter, W 5 mg / liter Temperature: 25 ° C.
(First stage)
Current density (D _k ): 90 A / dm ²
Time: 1.5 seconds (second stage)
Current density (D _k ): 20 A / dm ²
Time: 3 seconds

Cu-P alloy plating (Examples 3 and 4)
Liquid composition: Cu 30 g / liter, sulfuric acid 100 g / liter, P 500 mg / liter Temperature: 30 ° C.
(First stage)
Current density (D _k ): 140 A / dm ²
Time: 0.6 seconds (second stage)
Current density (D _k ): 20 A / dm ²
Time: 2.0 seconds

Cu-Co-Ni alloy plating (Examples 5, 6, 14)
Liquid composition: Cu 15 g / liter, Co 8 g / liter, Ni 8 g / liter pH: 1-3
Temperature: 40 ° C
(First stage)
Current density (D _k ): 45 A / dm ²
Time: 0.6 seconds (second stage)
Current density (D _k ): 30 A / dm ²
Time: 0.8 seconds

  Next, at least one treatment selected from the following heat treatment, rust prevention treatment, chromate treatment, and silane coupling treatment was performed in this order. The surface was washed with water before each treatment.

・ Heat-resistant treatment (forms a heat-resistant layer)
Liquid composition: Co 1-8 g / liter, Ni 10-20 g / liter pH: 2-3
Temperature: 40 ° C
Current density (D _k ): 5 A / dm ²
Time: 1.0 seconds

・ Rust prevention treatment (forms a rust prevention layer)
Liquid composition: Ni 15-30 g / liter, Zn 1-10 g / liter pH: 2-4
Temperature: 40 ° C
Current density (D _k ): 5 A / dm ²
Time: 1.0 seconds

・ Electrolytic chromate treatment (form chromate treatment layer)
Solution _{composition: K 2 Cr 2 O 7:} 1~10g / l, Zn: 0 to 5 g / l pH: 2 to 4
Temperature: 40 ° C
Current density (D _k ): 1 A / dm ²
Time: 1.0 seconds

・ Silane coupling treatment (forms a silane coupling treatment layer)
A silane coupling agent coating treatment is performed by spraying a 1.0% by volume aqueous solution of 3-glycidoxypropyltrimethoxysilane on the surface to be treated, and then dried for 2 seconds or more in an atmosphere of 70 ° C. or more and 200 ° C. or less The surface moisture was removed.

・ Resin layer (Example 13, 14, 15)
The resin layer is applied to the surface of the ultrathin copper layer by applying a pre-curing resin using a gravure coating method, and then adjusting the thickness of the resin coating to 10 μm using a doctor blade in a dry atmosphere at 200 ° C. The resin component was cured while volatilizing the solvent. The resin used was an epoxy resin (bisphenol A type epoxy resin manufactured by DIC Corporation).

  In Example 16, the surface of the roughening treatment (Cu—W alloy plating), heat-resistant layer, rust prevention layer, chromate treatment layer, silane coupling treatment layer is also applied to the carrier surface opposite to the ultrathin copper layer side. Processed.

-Heat treatment-
Next, each copper foil with a carrier was subjected to heat treatment under the conditions shown in Table 2 under a nitrogen gas atmosphere having a purity of 99.9% or more as heat treatment. The rate of temperature increase until reaching the heat treatment temperature was 100 ° C./hour, and the cooling time to room temperature after the heat treatment was 1 to 6 hours.
Moreover, about Examples 1-16, it heat-processed in the state which wound the copper foil with a carrier around the hollow tube (outer diameter 11cm, thickness 0.5cm) made from stainless steel.
Moreover, the heat treatment was performed with the tension at the time of winding around the hollow tube set as shown in Table 2, respectively.
Moreover, the heat processing was performed by setting the rotational speed of the said hollow tube as the setting of Table 2, respectively.

2. Evaluation of Copper Foil with Carrier For the copper foil with carrier of Examples 1 to 16 produced as described above, the following evaluation tests were performed before and after the heat treatment, respectively. The evaluation results are shown in Table 2. In addition, about the description of the number of the experiment example after a heating of Table 2, for example, "Example 1-1"-"Example 1-15" are samples after heating "Example 1" which is a sample before a heating, respectively. Indicates.

-Evaluation of residual stress-
The residual stress was measured by the X-ray diffraction method for the copper foil with a carrier after being heat-treated under the conditions shown in Table 2. In this method, from the measured values of the lattice spacing of a large number of crystals constituting the copper layer to be measured, the copper lattice spacing measured in a known stress-free state, and the copper elastic constant and Poisson's ratio, Determine the residual stress on the surface. The residual stress was measured using an R-ray diffraction apparatus RINT2100 manufactured by Rigaku Corporation. Calibration of the diffraction angle was performed using a standard Si crystal. The residual stress was calculated using the measurement value of the diffraction peak top using the calculation software attached to the Rigaku Corporation X-ray diffractometer RINT2100. Since the penetration depth of X-rays is usually about several μm to 10 μm, the average lattice spacing and residual stress taking into account the influence of X-ray attenuation in the penetration depth range are determined from the measurement surface surface layer. In the copper foil with carrier, the thickness of the copper foil carrier and the ultrathin copper layer is almost equal to or greater than the X-ray penetration depth, so the measured residual stress is the residual stress on the surface of the copper foil carrier and the ultrathin copper layer. You can think of it as a representation. In addition, when surface treatment such as roughening treatment, heat treatment, rust prevention treatment, chromate treatment, and silane coupling treatment is performed on the outer surface of the ultrathin copper layer, after the surface treatment (of the surface treatment layer) Residual stress was measured from above. In addition, when surface treatment such as roughening treatment, heat treatment, rust prevention treatment, chromate treatment, silane coupling treatment is performed on the outer surface of the copper foil carrier, after the surface treatment (from above the surface treatment layer) ) It is preferable to measure the residual stress. Moreover, the residual stress was measured similarly about the sample before heat processing.

-Measurement of warpage-
The amount of warpage was determined by cutting the copper foil with a carrier after heat treatment under the conditions shown in Table 2 into 10 cm square and 100 cm square sheets and statically placing it on the horizontal plane with the ultrathin copper layer side up. After placing, the maximum value of the height of lifting from the horizontal surface of the four corners of the sheet was measured. When the sheet corner was not lifted and warped downward, the maximum value of the sheet height at the corner of the sheet was measured with the ultrathin copper layer side down. Further, the amount of warpage was similarly measured for the sample before the heat treatment.

−Measurement of carrier tensile strength−
After stripping and removing the ultrathin copper layer from the carrier-attached copper foil after the heat treatment under the conditions shown in Table 2, the carrier is strip-shaped with a width of 12.7 mm and a length of 150 mm using a precision cutter. A test piece for measuring tensile strength was prepared. The test piece was subjected to a tensile test using an autograph AGS-100G manufactured by Shimadzu Corporation, and the tensile strength of the carrier was measured. The distance between grips (initial length) during measurement was set to 50 mm, and the tensile speed was set to 50 mm / min. Tensile strength values were calculated as nominal stresses. Similarly, the tensile strength of the carrier was measured for the sample before the heat treatment.

-Observation of wrinkles-
The presence or absence of wrinkles in the range of a length of 5 m on the surface of the ultrathin copper layer after the heat treatment of each experimental example was visually observed. When the number of places where wrinkles having a length of 10 cm or more were confirmed was 0, the case of 1 was ◯, the case of 2 was △, and the case of 3 or more was x.

-Degree of oxidation-
For each experimental example, after the heat treatment, the first volume was unwound and a sample having a length of 1 m of the second volume was visually observed. At this time, the color change area due to oxidation is 5% or less, ◎, the color change area due to oxidation is over 5% and 10% or less, and the color change area due to oxidation is over 10% and 15% or less. ◯, the case where the discoloration area due to oxidation is more than 15% and 20% or less is Δ, and the case where the discoloration area due to oxidation is more than 20% is ×.

(Evaluation results)
Examples 1-5 to 1-22, Example 2-1 to Example 2-6, Example 3-1 to Example 3-11, Example 4-1 to Example 16-1 are all measured in 10 cm square and 100 cm square. , The occurrence of warping after heat treatment was well suppressed. In Examples 1-1 to 1-4, in the measurement of 10 cm square, the occurrence of warpage after heat treatment was all well suppressed.
In Example 1-23, the temperature of the heat treatment was low, and the amount of warpage after the heat treatment was poor.
In Example 1-24, the heat treatment time was short, and the amount of warpage after the heat treatment was poor.

Claims (24)

  Including a heat treatment step of performing heat treatment at 120 to 220 ° C. for 1 to 8 hours on the carrier-attached copper foil provided with the carrier, the intermediate layer, and the ultrathin copper layer in this order. The manufacturing method of copper foil with a carrier which heat-processes in the state which made 5.0-30.0 MPa tensile stress act on foil.   The manufacturing method of the copper foil with a carrier of Claim 1 which heat-processes in the said heat processing process in the state which made 10.0-30.0 MPa tensile stress act on the copper foil with a carrier.   The manufacturing method of the copper foil with a carrier of Claim 1 or 2 which heat-processes in the said heat processing process in the state which made the tensile stress of 15.0-30.0 MPa act on the copper foil with a carrier.   The manufacturing method of the copper foil with a carrier as described in any one of Claims 1-3 which performs the heat processing for 2 to 6 hours at 140-180 degreeC in the said heat processing process.   The manufacturing method of the copper foil with a carrier as described in any one of Claims 1-4 which heat-processes in inert gas atmosphere in the said heat processing process.   The manufacturing method of the copper foil with a carrier as described in any one of Claims 1-5 whose tensile strength after the said heat processing process is 300 Mpa or more.   The manufacturing method of the copper foil with a carrier as described in any one of Claims 1-6 whose residual stress of the ultra-thin copper foil surface after the said heat processing process is 10 Mpa or less.   The manufacturing method of the copper foil with a carrier as described in any one of Claims 1-7 which heat-processes in the said heat processing process in the state which wound copper foil with a carrier around metal hollow tubes.   The manufacturing method of the copper foil with a carrier of Claim 8 which heat-processes by making the tension | tensile_strength at the time of winding the copper foil with a carrier around a metal hollow tube into 20-100 kgf / m in the said heat processing process.   In the said heat processing process, it heat-processes, rotating the said hollow tube at the speed of 1-600 rotation / hour in the state which wound the copper foil with a carrier around the metal hollow tube. The manufacturing method of copper foil with a description.   The method for producing a copper foil with a carrier according to any one of claims 1 to 10, wherein the tensile strength of the carrier measured at room temperature after the heat treatment step is 300 MPa or more.   The carrier-attached copper foil according to any one of claims 1 to 11, wherein the copper foil with a carrier before the heat treatment has a roughened layer on one or both of the surface of the ultrathin copper layer and the surface of the carrier. A method for producing copper foil.   The copper foil with a carrier before the heat treatment has at least one layer selected from the group consisting of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer on the surface of the roughening treatment layer. The manufacturing method of the copper foil with a carrier of Claim 12.   The copper foil with a carrier before the heat treatment has at least one layer selected from the group consisting of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer on the surface of the ultrathin copper layer. The manufacturing method of the copper foil with a carrier as described in any one of Claims 1-11.   The manufacturing method of the copper foil with a carrier as described in any one of Claims 1-11 with which the copper foil with a carrier before the said heat processing equips the said ultra-thin copper layer with a resin layer.   The manufacturing method of the copper foil with a carrier of Claim 12 or 13 with which the copper foil with a carrier before the said heat processing equips the said roughening process layer with a resin layer.   The copper foil with a carrier before the heat treatment is provided with a resin layer on one or more layers selected from the group consisting of the heat-resistant layer, the rust prevention layer, the chromate treatment layer, and the silane coupling treatment layer. Or the manufacturing method of copper foil with a carrier of 14.   The copper foil with carrier before the heat treatment is a copper foil with carrier having an intermediate layer and an ultrathin copper layer in this order on one surface of the carrier, and the surface of the carrier on the ultrathin copper layer side and The manufacturing method of the copper foil with a carrier as described in any one of Claims 1-17 by which the said roughening process layer is provided in the surface on the opposite side.   The copper foil with carrier before the heat treatment is a copper foil with carrier having an intermediate layer and an ultrathin copper layer in this order on one side of the carrier, and the intermediate layer and the ultrathin copper layer on both sides of the carrier. The manufacturing method of the copper foil with a carrier as described in any one of Claims 1-17 which have these in this order.   The manufacturing method of the copper clad laminated board using the copper foil with a carrier produced by the method as described in any one of Claims 1-19.   The manufacturing method of the printed wiring board using the copper foil with a carrier produced by the method as described in any one of Claims 1-19. Preparing a carrier-attached copper foil and an insulating substrate produced by the method according to any one of claims 1 to 19,
A step of laminating the copper foil with carrier and an insulating substrate; and
After laminating the carrier-attached copper foil and the insulating substrate, forming a copper-clad laminate through a step of peeling the carrier of the carrier-attached copper foil,
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. A step of forming a circuit on the ultrathin copper layer side surface or the carrier side surface of the carrier-attached copper foil produced by the method according to any one of claims 1 to 19,
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 manufacturing method of the electronic device using the printed wiring board produced by the method as described in any one of Claims 21-23.