JP2016049651A - Methods for manufacturing copper foil with carrier, copper-clad laminate, printed wiring board, and electronic device, and copper foil with carrier, copper-clad laminate, printed wiring board, and electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing copper foil with carrier in which the occurrence of blisters during thermo-compression bonding when bonding from an ultra-thin copper layer side to a resin is well 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 240°C for 0.5 to 4 hours. In the heat treatment step, the heat treatment is carried out in an inert gas atmosphere. The copper foil with carrier before the heat treatment has a roughened treatment layer on either or both of ultra-thin copper layer surface or a carrier surface.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, a method for producing an electronic device, a copper foil with a carrier, a copper clad laminate, a printed wiring board, and 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 a copper foil with a carrier, the emphasis has so far been on ensuring the peel strength between the ultrathin copper layer and the resin substrate. Therefore, sufficient investigation has not yet been made on the circuit formability of the ultrathin copper layer, and there is still room for improvement.

  When the copper foil with a carrier is bonded to the resin from the ultrathin copper layer side, it is heat-pressed and heat treated in a normal pressure atmosphere to stabilize the resin layer. At that time, bubbles (bubbles) may be generated between the carrier and the ultrathin copper layer by a gas such as water vapor. When such blisters occur, the ultrathin copper layer used for circuit formation sinks, causing a problem of adversely affecting circuit formability. This invention provides the manufacturing method of copper foil with a carrier by which generation | occurrence | production of a swelling is suppressed favorably in the case of thermocompression bonding when bonding to resin from the ultra-thin copper layer side.

  The present invention completed on the basis of the above knowledge is, in one aspect, heated at 120 to 240 ° C. for 0.5 to 4 hours with respect to the carrier-attached copper foil provided with the carrier, the intermediate layer, and the ultrathin copper layer in this order. It is a manufacturing method of the copper foil with a carrier including the heat processing process which processes.

  The manufacturing method of the copper foil with a carrier of this invention performs heat processing for 1-4 hours at 160-200 degreeC in the said heat processing process in one Embodiment.

  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 heat treatment is performed at 180 to 200 ° C. for 2 to 4 hours.

  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 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 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 has 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, a process of forming a circuit on the ultrathin copper layer 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 of the carrier-attached copper foil so that the circuit is buried;
Forming a circuit on the resin layer;
Forming the circuit on the resin layer, and then peeling the carrier; and
After the carrier is peeled off, the printed wiring board includes a step of exposing the circuit embedded in the resin layer formed on the surface of the ultrathin copper layer by removing the ultrathin copper layer Is the method.

  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.

In yet another aspect of the present invention, a carrier-attached copper foil comprising a carrier, an intermediate layer, and an ultrathin copper layer in this order, wherein the carrier-attached copper foil is thermocompression-bonded from the ultrathin copper foil side (press conditions: 220 ° C. × 2 hours) to produce a copper-clad laminate by bonding to a prepreg having surface irregularities satisfying the following conditions (1) and (2), and the copper-clad laminate is 220 ° C. under a nitrogen atmosphere. After heat treatment under the condition of × 10 hours, the carrier is peeled off, and then the number of blisters is 0 when the number of blisters measured on the carrier-side peeled surface is φ10 μm or more. It is a copper foil with a carrier that is / 625 cm ² or more and 20 or less / 625 cm ² .
(1) In the cross-sectional shape of the surface obtained by non-contact type roughness measurement, the average value of the height from the adjacent concave portion to the convex portion is 20 to 60 μm.
(2) In the cross-sectional shape of the surface obtained by non-contact type roughness measurement, the average value of the distance between the adjacent recesses is 400 to 700 μm.

In one embodiment of the copper foil with a carrier of the present invention, the number of blisters is 0/625 cm ² or more and 10 or less / 625 cm ² .

In another embodiment of the copper foil with a carrier of the present invention, the number of blisters is 0/625 cm ² or more and 5 or less / 625 cm ² .

In still another embodiment of the copper foil with a carrier according to the present invention, the number of blisters is 0/625 cm ² or more and 3 or less / 625 cm ² .

In another embodiment of the copper foil with a carrier according to the present invention, the copper foil with carrier is bonded to the bismaleimide triazine resin prepreg by thermocompression bonding at 220 ° C. for 2 hours. After producing a laminated board, the said copper clad laminated board was cut | disconnected to width 5cm, and the carrier side of the said copper foil with a carrier peeled according to JISC6471 with the peeling speed of 50 mm / min, and the peeling angle of 90 degrees. When the peel strength of the carrier is 5 to 30 N / m, a recess having a diameter of 10 μm or more present on the carrier-side peel surface is defined as a blister, and the number of blisters when the number of blisters is measured is 0/625 cm ² or more 20 / 625 cm ² or less.

  In yet another aspect, the present invention is a copper clad laminate produced using the carrier-attached copper foil of the present invention.

  In still another aspect, the present invention is a printed wiring board manufactured using the carrier-attached copper foil of the present invention.

  In yet another aspect, the present invention is an electronic device manufactured using the printed wiring board of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the production method of copper foil with a carrier by which generation | occurrence | production of a swelling can be suppressed favorably in the case of thermocompression bonding when bonding to resin from the ultra-thin copper layer side 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. It is a graph which shows the non-contact-type roughness measurement result of the uneven | corrugated surface of the bismaleimide triazine resin prepreg used in the Example. It is a schematic diagram which shows the measurement location of the sample sheet which concerns on an Example.

<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. Subsequently, a printed wiring board or the like having a predetermined circuit is produced by, for example, copper plating and / or etching on the intended conductor pattern of the ultrathin copper layer bonded to the insulating substrate. Here, when the surface of the ultra-thin copper layer is bonded to the insulating substrate and thermocompression bonded as described above, bubbles (float) are generated by a gas such as water vapor generated in the carrier / ultra-thin copper layer or the roughened layer. ) May occur. When such blisters occur, the ultrathin copper layer used for circuit formation sinks, causing a problem of adversely affecting circuit formability. On the other hand, in the manufacturing method of the 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 120-240 with respect to the said copper foil with a carrier. Heat treatment is carried out at a temperature of 0.5 to 4 hours. In this way, by performing heat treatment at 120 to 240 ° C. for 0.5 to 4 hours in advance, gas such as water vapor generated in the carrier / ultra thin copper layer or the roughened layer is removed. Therefore, when the copper foil with a carrier is bonded to an insulating substrate and thermocompression bonded, the occurrence of swelling can be suppressed satisfactorily. In the preliminary heat treatment, when the temperature is less than 120 ° C. or the heating time is less than 0.5 hour, it is difficult to sufficiently remove gas such as water vapor. Further, in the preliminary heat treatment, when the temperature is over 240 ° C. or the heating time is over 4 hours, the discoloration of the copper foil due to oxidation, the deterioration of the adhesion characteristics between the carrier and the ultrathin copper layer, etc. Problem arises. In the heat treatment step, the heat treatment is preferably performed at 160 to 200 ° C. for 1 to 4 hours, and more preferably at 180 to 200 ° C. for 2 to 4 hours. Further, in the heat treatment step, it is preferable to perform the heat treatment in an atmosphere that does not include a gas such as water vapor that causes blistering, for example, heating in an inert gas atmosphere such as helium, neon, argon, nitrogen, or the like. It is preferable to carry out the treatment.

<Copper foil with carrier>
Hereinafter, unless otherwise specified, the embodiment of the copper foil with carrier will be described before the pre-heating treatment according to the present invention, but the embodiment is the one after the pre-heating treatment (copper foil with carrier according to the present invention) The same applies to the carrier-added copper foil produced by the production 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 copper foil with a carrier of the present invention has surface irregularities that satisfy the following conditions (1) and (2) by thermocompression bonding (press condition: 220 ° C. × 2 hours) of the copper foil with a carrier from the ultrathin copper foil side. A copper-clad laminate is prepared by laminating the prepreg, and the carrier is peeled after heat-treating the copper-clad laminate under a nitrogen atmosphere at 220 ° C. for 10 hours, followed by peeling on the carrier side. The number of blisters is 0/625 cm ² or more and 20 or less / 625 cm ² when the number of bulges is measured.
(1) In the cross-sectional shape of the surface obtained by non-contact type roughness measurement, the average value of the height from the adjacent concave portion to the convex portion is 20 to 60 μm.
(2) In the cross-sectional shape of the surface obtained by non-contact type roughness measurement, the average value of the distance between the adjacent recesses is 400 to 700 μm.

Thus, in the copper foil with a carrier of the present invention, the occurrence of blistering is satisfactorily suppressed during thermocompression bonding when bonding the resin from the ultrathin copper layer side. The blister number is preferably from 0/625 cm ² or more 10 or less / 625 cm ^2, more preferably from 0/625 cm ² or more 5 or less / 625 cm ^2, 3 or 0/625 cm ² or more Even more preferably below / 625 cm ² .

After the copper foil with a carrier of the present invention was prepared by bonding the ultrathin copper foil side of the copper foil with a carrier to the bismaleimide triazine resin prepreg by thermocompression bonding at 220 ° C. for 2 hours, The copper clad laminate was cut into a width of 5 cm, and the carrier side of the copper foil with carrier was peeled off at a peeling speed of 50 mm / min and a peeling angle of 90 ° according to JIS C6471, and the peel strength of the carrier was 5 when ~30N / m, preferably blistering number when measuring the number of the carrier side φ10μm more recesses present in the release surface of is 0/625 cm ² or more 20/625 cm ² or less. According to such a configuration, since the peel strength of the carrier is an appropriate value of 5 to 30 N / m, when the printed wiring board is manufactured, the carrier is less likely to fall off by itself, and when the carrier is peeled off Since it can be removed relatively easily, productivity is improved when a printed wiring board is manufactured. Furthermore, since the swelling number is small and zero / 625 cm ² or more 20/625 cm ² or less, and decrease the defect rate of the printed wiring board, there is an advantage that the yield is improved. Also, when the peel strength of the carrier is 5 to 30 N / m, the number of blisters when the number of irregularities of φ10 μm or more present on the peel surface on the carrier side and the surface of the ultrathin copper layer on the copper clad laminate is measured Is more preferably 0 piece / 625 cm ² or more and 10 pieces / 625 cm ² or less, and even more preferably 0 piece / 625 cm ² or more and 5 pieces / 625 cm ² or less, 0 piece / 625 cm ² or more and 3 pieces / 625 cm. ^Even more preferred is ² or less.

<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, LCD 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.
Note that in the case that contains the nickel intermediate layer is preferably nickel coating weight is 100~40000μg / dm ^2, preferably a 500~30000μg / dm ^2, a 800~20000μg / dm ² Is more preferable, and 900 to 15000 μg / dm ² is more preferable.
Further, it if contains a chromium intermediate layer, the chromium coating weight is preferably from 1-1000 / dm ^2, is preferably 2~800μg / dm ^2, a 3~150μg / dm ² Is preferably 4 to 100 μg / dm ² , and more preferably 5 to 50 μg / dm ² .
Incidentally, if included in the intermediate layer of molybdenum (Mo) is preferably contained 50 [mu] g / dm ² or more 1000 [mu] g / dm ² or less Mo, and more preferably contains 70 [mu] g / dm ² or more 650μg / dm ² or less.
Incidentally, if included zinc in the intermediate layer (Zn) it is is preferably contains Zn 1 [mu] g / dm ² or more 120 [mu] g / dm ² or less, more preferably containing 2 [mu] g / dm ² or more 70 [mu] g / dm ² or less, It is more preferable to contain 5 μg / dm ² or more and 50 μg / dm ² or less.

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. One or more 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 one surface or both surfaces of the ultrathin copper layer A layer may be provided or a surface treatment layer may be provided. The surface treatment layer may be one or more layers 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.

The carrier-attached copper foil may include one or more layers selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a silane coupling-treated layer on the roughening-treated layer.
Further, a heat-resistant layer and a rust-proof layer may be provided on the roughening-treated layer, a chromate-treated layer may be provided on the heat-resistant layer and the rust-proof layer, and a silane coupling treatment is provided on the chromate-treated layer. A layer may be provided.
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. In a state in which the samples are stacked (laminated body), the values are calculated based on Equation 1 from the result of measuring the resin outflow weight at the time of pressing at 171 ° C., pressing pressure of 14 kgf / cm 2 and pressing time of 10 minutes. is there.

  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 made based on Examples and Comparative Examples. In addition, a present Example is an example to the last, and is not restrict | limited only to this example.

1. Manufacture of copper foil with a carrier The copper foil with a carrier which concerns on Examples 1-9 was produced in the following procedures.
First, a long electrolytic copper foil having the thickness shown in Table 1 was prepared as a carrier. As the electrolytic copper foil, JTC foil manufactured by JX Nippon Mining & Metals was used. An intermediate layer was formed by electroplating the glossy surface (shiny surface) of this copper foil with a roll-to-roll-type continuous plating line under the following conditions.

“A + B” in the “Layer Configuration” column in the “Intermediate Layer” column of Table 1 indicates that the B process was performed after the A process. For example, “Ni + chromate” means that chromate treatment was performed after nickel plating.
"Ni": Nickel plating (Liquid composition) Nickel sulfate: 270-280 g / L, Nickel chloride: 35-45 g / L, Nickel acetate: 10-20 g / L, Trisodium citrate: 15-25 g / L, luster Agents: Saccharin, butynediol, etc. Sodium dodecyl sulfate: 55-75 ppm
(PH) 4-6
(Liquid temperature) 55-65 degreeC
(Current density) 1 to 11 A / dm ²
(Energization time) 1 to 20 seconds

"Chromate": electrolytic chromate treatment (Liquid composition) potassium dichromate: 1-10 g / L, zinc: 0-5 g / L, molybdenum: 0-5 g / L
(PH) 7-10
(Liquid temperature) 40-60 ° C
(Current density) 0.1-2.6 A / dm ²
(Coulomb amount) 0.5 to 90 As / dm ²
(Energization time) 1 to 30 seconds

“Organic”: Organic substance layer forming treatment An aqueous solution containing carboxybenzotriazole (CBTA) at a concentration of 1 to 30 g / L and having a liquid temperature of 40 ° C. and a pH of 5 was showered and sprayed for 20 to 120 seconds.

Subsequently, on the roll-to-roll type continuous plating line, an ultrathin copper layer having the thickness shown in Table 1 is formed on the intermediate layer by electroplating under the following conditions, and a copper foil with a carrier is formed. Manufactured.
-Ultrathin copper layer Copper concentration: 30-120 g / L
H ₂ SO ₄ concentration: 20 to 120 g / L
Bis (3sulfopropyl) disulfide concentration: 10-100 ppm
Tertiary amine compound: 10 to 100 ppm
Chlorine: 10-100ppm
Electrolyte temperature: 20-80 ° C
Current density: 10 to 100 A / dm ²
In addition, the following compounds were used as the above-mentioned tertiary amine compound.
(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. Here, R ₁ And R ₂ were both methyl groups.)
The above compound can be obtained, for example, by mixing a predetermined amount of Deconal Ex-314 manufactured by Nagase ChemteX Corporation and dimethylamine and reacting at 60 ° C. for 3 hours.

Surface treatment was performed on the surface of the ultrathin copper layer described above under the following surface treatment conditions.
-Surface treatment conditions of Examples 1-3-Roughening treatment 1
(Liquid composition 1)
Cu: 10-30 g / L
H ₂ SO _4: 10~150g / L
W: 0 to 50 mg / L
Sodium dodecyl sulfate: 0 to 50 mg / L
As: 0 to 200 mg / L
(Electroplating condition 1)
Temperature: 30-70 ° C
Current density: 25 to 110 A / dm ²
Roughening coulomb amount: 50 to 500 As / dm ²
Plating time: 0.5 to 20 seconds, roughening treatment 2
(Liquid composition 2)
Cu: 20-80 g / L
H ₂ SO ₄ : 50 to 200 g / L
(Electroplating condition 2)
Temperature: 30-70 ° C
Current density: 5 to 50 A / dm ²
Roughening coulomb amount: 50 to 300 As / dm ²
Plating time: 1 to 60 seconds, rust prevention treatment (liquid composition)
NaOH: 40-200 g / L
NaCN: 70 to 250 g / L
CuCN: 50-200 g / L
Zn (CN) ₂ : _{2 to} 100 g / L
As ₂ O ₃ : 0.01 to 1 g / L
(Liquid temperature)
40-90 ° C
(Current condition)
Current density: 1 to 50 A / dm ²
Plating time: 1 to 20 seconds, chromate treatment K ₂ Cr ₂ O ₇ (Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2 to 10 g / L
NaOH or KOH: 10-50 g / L
ZnOH or ZnSO ₄ .7H ₂ O: 0.05 to 10 g / L
pH: 7-13
Bath temperature: 20-80 ° C
Current density: 0.05 to 5 A / dm ²
Time: 5 to 30 seconds. Silane coupling treatment After applying 0.1 vol% to 0.3 vol% of 3-glycidoxypropyltrimethoxysilane aqueous solution, 0.1 to 10 in air at 100 to 200 ° C. Dry and heat for seconds.

-Surface treatment conditions of Examples 4-6-Roughening treatment 1
Liquid composition: Copper 10-20 g / L, sulfuric acid 50-100 g / L
Liquid temperature: 25-50 degreeC
Current density: 1 to 58 A / dm ²
Coulomb amount: 4 to 81 As / dm ²
・ Roughening 2
Liquid composition: Copper 10-20 g / L, nickel 5-15 g / L, cobalt 5-15 g / L
pH: 2-3
Liquid temperature: 30-50 degreeC
Current density: 24 to 50 A / dm ²
Coulomb amount: 34 to 48 As / dm ²
・ Rust prevention treatment Liquid composition: Nickel 5-20g / L, Cobalt 1-8g / L
pH: 2-3
Liquid temperature: 40-60 degreeC
Current density: 5 to 20 A / dm ²
Coulomb amount: 10-20 As / dm ²
-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 to ^{2 A} / dm ² (Can also be electroless because of immersion chromate treatment)
Coulomb amount: 0 to ^{2 As} / dm ² (can also be electroless because of immersion chromate treatment)
Silane coupling treatment Application of diaminosilane aqueous solution (diaminosilane concentration: 0.1 to 0.5 wt%)

-Surface treatment conditions of Examples 7-9-Roughening treatment Cu: 10-20 g / L
Co: 1-10 g / L
Ni: 1 to 10 g / L
pH: 1-4
Liquid temperature: 40-50 degreeC
Current density Dk: 20 to 30 A / dm ²
Time: 1-5 seconds Cu adhesion amount: 15-40 mg / dm ²
Co adhesion amount: 100 to 3000 μg / dm ²
Ni adhesion amount: 100 to 1000 μg / dm ²
・ Rust prevention treatment Zn: over 0 to 20 g / L
Ni: more than 0 to 5 g / L
pH: 2.5-4.5
Liquid temperature: 30-50 degreeC
Current density Dk: more than 0 to 1.7 A / dm ²
Time: 1 second Zn deposition amount: 5-250 μg / dm ²
Ni adhesion amount: 5 to 300 μg / dm ²
・ Chromate treatment K ₂ Cr ₂ O ₇
(Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2 to 10 g / L
NaOH or KOH: 10-50 g / L
ZnO or ZnSO ₄ .7H ₂ O: 0.05 to 10 g / L
pH: 7-13
Bath temperature: 20-80 ° C
Current density 0.05-5A / dm ²
Time: 5 to 30 seconds Cr adhesion amount: 10 to 150 μg / dm ²
・ Silane coupling treatment Vinyltriethoxysilane aqueous solution (vinyltriethoxysilane concentration: 0.1 to 1.4 wt%)
pH: 4-5
Bath temperature: 25-60 ° C
Immersion time: 5 to 30 seconds

Moreover, about the copper foil with a carrier of Examples 1, 4, and 7, the following heat treatment, chromate treatment, and silane coupling treatment were performed on the surface treatment layer.
Moreover, about the copper foil with a carrier of Examples 2 and 5, only the heat-resistant process was performed. For the copper foil with carrier of Example 3, only the chromate treatment was performed. For the carrier-attached copper foil of Example 6, only the silane coupling treatment was performed. About the copper foil with a carrier of Example 9, the chromate process and the silane coupling process were performed in this order.

・ Heat-resistant treatment (forms a heat-resistant layer)
Liquid composition: Nickel 5-20 g / L, cobalt 1-8 g / L
pH: 2-3
Liquid temperature: 40-60 degreeC
Current density: 5 to 20 A / dm ²
Coulomb amount: 10-20 As / dm ²

・ Chromate treatment (form chromate treatment layer)
Liquid composition: potassium dichromate 1-10 g / L, zinc 0-5 g / L
pH: 3-4
Liquid temperature: 50-60 degreeC
Current density: 0 to ^{2 A} / dm ² (for immersion chromate treatment)
Coulomb amount: 0 to ^{2 As} / dm ² (for immersion chromate treatment)

・ Silane coupling treatment (forms a silane coupling treatment layer)
The silane coupling agent coating treatment was performed by spraying an aqueous solution having a pH of 7 to 8 and 60 ° C. containing 0.2 to 2% by mass of alkoxysilane.

-Pre-heating treatment (pre-baking)-
Next, each copper foil with a carrier was subjected to the following heat treatment under a nitrogen gas atmosphere as “pre-heating treatment (pre-baking)”.
-250 ° C x 0.5 or 4 hours pre-bake-240 ° C x 0.3, 0.5, 3, 4 or 5 hours pre-bake-220 ° C x 4 hours pre-bake-200 ° C x 0.3 0.5, 1, 2, 4 or 5 hours pre-bake 195 ° C x 4, 6 or 10 hours pre-bake 190 ° C x 4 hours pre-bake 180 ° C x 0.3, 0.5 Pre-baked for 1, 2, 4 or 6 hours · 170 ° C x 4 hours pre-baked · 160 ° C x 0.3, 0.5, 1, 2, 4 or 5 hours pre-baked · 150 ° C x 1, 2 4 hours pre-bake 120 ° C x 0.3, 0.5, 1, 2, 3, 4 or 6 hours pre-bake 110 ° C x 0.5 or 4 hours pre-bake

2. Evaluation of Copper Foil with Carrier The following evaluation tests were performed on the copper foil with carrier produced as described above. In addition, the copper foil with a carrier of an evaluation object shall be the thing after the above-mentioned various prebaking, and the thing without prebaking. Evaluation conditions and evaluation results are shown in Tables 2-9.

-Evaluation of peel strength-
After bonding the ultrathin copper foil side of the copper foil with a carrier to the bismaleimide triazine resin prepreg by thermocompression bonding (press condition: 220 ° C. × 2 hours), a copper clad laminate (CCL) was produced, and then the CCL was 5 cm wide. Then, the carrier side of the copper foil with carrier was peeled at a peeling speed of 50 mm / min, the peeling angle was 90 °, and the strength was peeled according to JIS C6471.

-Evaluation of balloon-
There may be a case where a prepreg having a certain degree of surface irregularities is produced due to a difference in the production process. And when this inventor investigated, when the said prepreg with the unevenness | corrugation of the surface to some extent was used, it turned out that a blister is easy to generate | occur | produce. Therefore, in the present invention, a prepreg having surface irregularities satisfying the following conditions (1) and (2) was used for evaluation by simulating a prepreg having surface irregularities to some extent. The surface of the bismaleimide triazine resin prepreg can be adjusted by chemical polishing or mechanical polishing. Moreover, as long as it has the surface shape which satisfy | fills the said (1) and (2), you may use a commercially available prepreg in the evaluation of the swelling of this invention.

(1) In the cross-sectional shape of the surface obtained by the non-contact type roughness measurement, the average height from the adjacent concave portion to the convex portion is 20 to 60 μm (41.7 μm in this example):
The average value of the height from the adjacent concave part to the convex part of the prepreg was measured under the following conditions using a non-contact type roughness measuring machine (OLYMPUS Laser Microscope LEXT OLS 4000). In FIG. 5, the non-contact-type roughness measurement result of the uneven | corrugated surface of the said bismaleimide triazine resin prepreg is shown. The vertical axis in FIG. 5 indicates the height of the unevenness (μm), and the horizontal axis indicates the measurement position (μm) when measured along the planar direction of the measurement surface.
<Measurement conditions>
Cut-off: None Reference length: 1600 μm to 1850 μm (1680-1750 μm in this example)
Measurement ambient temperature: 23-25 ° C
First, a convex part is specified, the height of the highest part of the convex part is H1, the lowest part on both sides of the convex part is a concave part, and the heights are L1 and L2. And the height K1 from an adjacent recessed part to a convex part is calculated as follows.
K1 = ((H1-L1) + (H1-L2)) / 2
And the arithmetic average value of the height K1 from an adjacent recessed part to a convex part was made into the average value of the height from an adjacent recessed part to a convex part. In this example, the following measurement results were obtained.
K1 = (H1-L1) + (H1-L2)) / 2
K2 = (H2-L2) + (H2-L3)) / 2
H1 = 67.4 μm, H2 = 72.0 μm, L1 = 24.2 μm, L2 = 30.0 μm, L3 = 28.0 μm, K1 = 40.3 μm, K2 = 43.0 μm
Average value of height from adjacent concave part to convex part = (K1 + K2) /2=41.7 μm

(2) In the cross-sectional shape of the surface obtained by the non-contact type roughness measurement, the average value of the distance between the adjacent recesses is 400 to 700 μm (535 to 558 μm in this example):
The distance between the recesses adjacent to each other in the prepreg was measured as follows.
In the graph shown in FIG. 5 measured using the non-contact type roughness measuring device (Olympus Laser Microscope LEXT OLS 4000), the value representing the position of the recess 1 is X1 (μm), and the value representing the position of the recess 2. Is X2 (μm), and the value representing the position of the recess 3 is X3 (μm). And the distance W1 of the adjacent recessed part 1 and the recessed part 2 and the distance W2 of the adjacent recessed part 2 and the recessed part 3 were calculated | required with the following formula | equation.
Distance W1 = X2-X1 = 629.2 μm between the adjacent recess 1 and recess 2
Distance W2 between adjacent concave portion 2 and concave portion 3 = X3-X2 = 502.6 μm
X1 = 285.1 μm, X2 = 914.3 μm, X3 = 1416.9 μm
Average value of distance between adjacent recesses (μm) = (W1 + W2) /2=565.9 μm
In addition, the average value of the height from the adjacent concave portion to the convex portion and the average value of the distance between the adjacent concave portion and the concave portion are on the line where the height of the convex portion is the highest and the height of the concave portion is the lowest. In, it calculates | requires by measuring linearly using a non-contact-type roughness measuring machine.

  Since the bismaleimide triazine resin prepreg used in the examples has a network structure of glass fibers, it is affected by the glass fibers and has periodic irregularities.

A copper foil with a carrier is bonded to a bismaleimide triazine resin prepreg having surface irregularities satisfying the above conditions (1) and (2) by thermocompression bonding (press condition: 220 ° C. × 2 hours) from the ultrathin copper foil side. After the copper-clad laminate (CCL) was produced, the CCL was heat-treated under a nitrogen atmosphere at 220 ° C. for 10 hours, and then the carrier was peeled off. Subsequently, the number of recesses having a diameter of 10 μm or more present on the carrier-side peeling surface was measured visually and with a microscope for a sample having a size of 25 cm × 25 cm (area 625 cm ² ). Here, a recess having a diameter of 10 μm or more refers to a recess having a minimum circle diameter of 10 μm or more surrounding the recess. Then, the number of recesses of φ10 μm or more present on the peeling surface on the carrier side was calculated as the number of blisters per 625 cm ² (pieces / 625 cm ² ).
In addition, after lamination | stacking by press with copper foil with a carrier and a prepreg, the unevenness | corrugation on the surface of a prepreg may become large compared with immediately after a press when it heats by 220 degreeC x 10 hours in the above-mentioned nitrogen atmosphere. In that case, if the temperature of the press conditions is increased slightly, for example, set to 230 to 270 ° C., and the time is set slightly shorter to 1.5 to 2 hours, when heated at 220 ° C. for 10 hours, unevenness on the surface of the prepreg is observed. It is preferable because it is less likely to be larger than immediately after pressing.

-Degree of oxidation-
Each copper foil with a carrier is subjected to a pre-heat treatment (pre-bake) or without a pre-heat treatment, and after heat treatment under a nitrogen atmosphere at 220 ° C. for 10 hours, one winding The sample of length 1m of the 2nd volume was loosened and observed visually. 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 ×.

<Metal adhesion amount of intermediate layer>
The amount of nickel adhered was measured by ICP emission analysis using an ICP emission spectrophotometer (model: SPS3100) manufactured by SII after dissolving the sample with nitric acid having a concentration of 20% by mass. Dissolved in hydrochloric acid with a concentration of 7% by mass at 100 ° C. and measured by quantitative analysis by atomic absorption spectrometry using a VARIAN atomic absorption spectrophotometer (model: AA240FS). The sample was dissolved in a mixed solution of nitric acid and hydrochloric acid (nitric acid concentration: 20% by mass, hydrochloric acid concentration: 12% by mass), and was subjected to atomic absorption spectrometry using an atomic absorption spectrophotometer (model: AA240FS) manufactured by VARIAN. Measurement was performed by quantitative analysis. In addition, the measurement of the said nickel, zinc, chromium, and molybdenum adhesion amount was performed as follows. First, after peeling the ultra-thin copper layer from the copper foil with carrier, only the vicinity of the surface on the intermediate layer side of the ultra-thin copper layer is dissolved (only the thickness of 0.5 μm is dissolved from the surface). The amount of adhesion on the surface on the intermediate layer side is measured. Further, after peeling off the ultrathin copper layer, only the vicinity of the surface on the intermediate layer side of the carrier is dissolved (only the thickness of 0.5 μm from the surface is dissolved), and the amount of adhesion on the surface of the carrier on the intermediate layer side is measured. And the value which totaled the adhesion amount of the surface by the side of the intermediate | middle layer of an ultra-thin copper layer and the adhesion amount of the surface by the side of the intermediate | middle layer of a carrier was made into the metal adhesion amount of an intermediate | middle layer. In addition, when the unevenness of the ultrathin copper layer is large and the thickness of the ultrathin copper layer is 1.5 μm or less, the thickness of 0.5 μm was dissolved from the surface on the intermediate layer side of the ultrathin copper layer. In some cases, the roughening component on the surface of the ultrathin copper layer may also dissolve. Therefore, in such a case, 30% of the thickness of the ultrathin copper layer on the intermediate layer side is dissolved.
When the sample is difficult to dissolve in nitric acid having a concentration of 20% by mass or hydrochloric acid having a concentration of 7% by mass, a mixed solution of nitric acid and hydrochloric acid (nitric acid concentration: 20% by mass, hydrochloric acid concentration: 12% by mass) After dissolving the sample, the amount of nickel, zinc and chromium deposited can be measured by the above-described method.
The “metal adhesion amount” means the metal adhesion amount (mass) per sample unit area (1 dm ² ).

<Thickness of organic material in the intermediate layer>
After peeling the ultrathin copper layer of the carrier-attached copper foil from the carrier, XPS measurement was performed on the surface of the exposed ultrathin copper layer on the intermediate layer side and the surface of the exposed carrier on the intermediate layer side 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 was defined as B (nm), and the sum of A and B was defined as the thickness (nm) of the organic substance in the intermediate layer. Note that the measurement interval of the atomic concentration of the metal in the depth direction (x: unit nm) is preferably 0.18 to 0.30 nm (in terms of SiO ₂ ). In this example, the atomic concentration of the metal in the depth direction was measured at 0.28 nm (SiO ₂ equivalent) intervals (measured every 0.1 minutes by sputtering time).
In addition, the depth profile of the carbon concentration by the XPS measurement is as follows. A total of three locations, one in each region within 50 mm and one in a 50 mm × 50 mm region at the center, that is, the surface on the intermediate layer side of the exposed ultrathin copper layer and the intermediate layer side of the exposed carrier A total of six locations were created on the surface. FIG. 6 shows three measurement points on the surface of the exposed ultrathin copper layer on the intermediate layer side and three points on the surface of the exposed carrier on the intermediate layer side. Subsequently, from the depth profile created for each of the three regions on the exposed intermediate layer side surface of the exposed ultrathin copper layer and the exposed intermediate layer side of the carrier, on the intermediate layer side of the above described ultrathin copper layer, respectively. The depth A (nm) at which the carbon concentration first became 3 at% or less from the surface, and the depth B (nm) at which the carbon concentration first became 3 at% or less from the surface on the intermediate layer side of the carrier were calculated. The sum of the arithmetic average value of A (nm) and the arithmetic average value of B (nm) was defined as the thickness (nm) of the organic substance in the intermediate layer.
When the sample size is small, the above-mentioned region within 50 mm from both ends and the 50 mm × 50 mm region at the center may overlap.
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 )
XPS means X-ray photoelectron spectroscopy. In the present invention, it is assumed that an XPS measuring device (model 5600MC or an equivalent measuring device manufactured and sold by ULVAC-PHI) is used by ULVAC-PHI. If such a measuring device cannot be obtained, Other XPS measurements can be performed by setting the measurement interval of each element concentration in the depth direction to 0.10 to 0.30 nm (converted to SiO ₂ ) and the sputtering rate to 1.0 to 3.0 nm / min (converted to SiO ₂ ). An apparatus may be used.

Claims (25)

  The manufacturing method of copper foil with a carrier including the heat processing process which heat-processes at 120-240 degreeC for 0.5 to 4 hours with respect to copper foil with a carrier provided with the carrier, the intermediate | middle layer, and the ultra-thin copper layer in this order.   The manufacturing method of the copper foil with a carrier of Claim 1 which performs the heat processing for 1-4 hours at 160-200 degreeC in the said heat processing process.   The manufacturing method of the copper foil with a carrier of Claim 2 which performs the heat processing for 2 to 4 hours at 180-200 degreeC in the said heat processing process.   The manufacturing method of the copper foil with a carrier as described in any one of Claims 1-3 which heat-processes in inert gas atmosphere in the said heat processing process.   The carrier-attached copper foil according to any one of claims 1 to 4, wherein the copper foil with a carrier before the heat treatment has a roughening treatment 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 5.   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 1-4.   The manufacturing method of the copper foil with a carrier as described in any one of Claims 1-4 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 5 or 6 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 includes 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 the copper foil with a carrier of 7.   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 1-10 in which the said roughening process layer is provided in the surface on the opposite side.   The manufacturing method of the copper foil with a carrier as described in any one of Claims 1-10 in which the copper foil with a carrier before the said heat processing has an intermediate | middle layer and an ultra-thin copper layer in this order on both surfaces of the said carrier.   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 1-12.   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 1-12. Preparing a copper foil with a carrier and an insulating substrate produced by the method according to any one of claims 1 to 12,
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. Forming a circuit on the ultrathin copper layer side surface of the carrier-attached copper foil produced by the method according to any one of claims 1 to 12,
Forming a resin layer on the ultrathin copper layer side surface of the carrier-attached copper foil so that the circuit is buried;
Forming a circuit on the resin layer;
Forming the circuit on the resin layer, and then peeling the carrier; and
After the carrier is peeled off, the printed wiring board includes a step of exposing the circuit embedded in the resin layer formed on the surface of the ultrathin copper layer by removing the ultrathin copper layer Method.   The manufacturing method of the electronic device using the printed wiring board produced by the method as described in any one of Claims 14-16. A carrier-attached copper foil provided with a carrier, an intermediate layer, and an ultrathin copper layer in this order,
The copper foil with carrier is bonded to a prepreg having surface irregularities satisfying the following conditions (1) and (2) by thermocompression bonding (press condition: 220 ° C. × 2 hours) from the ultrathin copper foil side. A laminate was prepared, and the copper-clad laminate was heat-treated under a nitrogen atmosphere at 220 ° C. for 10 hours, and then the carrier was peeled off, and subsequently a recess of φ10 μm or more present on the peeled surface on the carrier A copper foil with a carrier, wherein the number of swelling when the number of swelling is measured is 0/625 cm ² or more and 20 or less / 625 cm ² .
(1) In the cross-sectional shape of the surface obtained by non-contact type roughness measurement, the average value of the height from the adjacent concave portion to the convex portion is 20 to 60 μm.
(2) In the cross-sectional shape of the surface obtained by non-contact type roughness measurement, the average value of the distance between the adjacent recesses is 400 to 700 μm. The copper foil with a carrier according to claim 18, wherein the number of swellings is 0/625 cm ² or more and 10 or less / 625 cm ² . The copper foil with a carrier according to claim 19, wherein the number of swellings is 0/625 cm ² or more and 5 or less / 625 cm ² . 21. The copper foil with a carrier according to claim 20, wherein the number of swellings is 0/625 cm ² or more and 3 or less / 625 cm ² . The copper-clad laminate was prepared by bonding the ultrathin copper foil side of the copper foil with carrier to the bismaleimide triazine resin prepreg by thermocompression bonding at 220 ° C. for 2 hours, and then making the copper-clad laminate 5 cm wide When the carrier peeled off according to JIS C6471 at a peeling speed of 50 mm / min and a peeling angle of 90 ° on the carrier side of the copper foil with carrier is 5-30 N / m, the carrier the φ10μm more recesses present on the release surface of the side and blistering, any one of claims 18 to 21 blisters number when measuring the number of blisters is 0/625 cm ² or more 20/625 cm ² or less The copper foil with a carrier as described in 2.   The copper clad laminated board manufactured using the copper foil with a carrier as described in any one of Claims 18-22.   The printed wiring board manufactured using the copper foil with a carrier as described in any one of Claims 18-22.   The electronic device manufactured using the printed wiring board of Claim 24.