JP6522974B2 - Copper foil with carrier, laminate, method of producing laminate, and method of producing printed wiring board - Google Patents

Description

  The present invention relates to a copper foil with carrier, a laminate, a printed wiring board, and a method of manufacturing the printed wiring board.

  Printed wiring boards have made great strides over the past half century, and are now used in almost all electronic devices. In recent years, with the miniaturization of electronic devices and the increase in needs for high performance, high density mounting of mounted components and high frequency of signals have progressed, and the conductor pattern has been miniaturized (fine pitched) or high frequency for printed wiring boards. Correspondence etc. are calculated | required, and when mounting an IC chip especially on a printed wiring board, fine pitch formation of L (line) / S (space) = 20 micrometers / 20 micrometers or less is calculated | required.

  First, the printed wiring board is manufactured as a copper-clad laminate in which a copper foil and an insulating substrate mainly made of a glass epoxy substrate, a BT resin, a polyimide film or the like are bonded. Bonding may be performed by laminating an insulating substrate and a copper foil and forming them by heating and pressing (lamination method), or applying a varnish, which is a precursor of an insulating substrate material, to a surface having a copper foil covering layer, A heating and curing method (casting method) is used.

  The thickness of the copper foil used in the copper-clad laminate is becoming 9 μm or even 5 μm or less as the fine pitch is being made, and the foil thickness is becoming thinner. However, when the foil thickness is 9 μm or less, the handling property when forming a copper-clad laminate by the above-mentioned laminating method or casting method is extremely deteriorated. Then, the copper foil with a carrier which used the thick metal foil as a carrier, and formed the ultra-thin copper layer in this via the peeling layer has appeared. As a general usage method of the copper foil with a carrier, as disclosed by patent document 1 grade | etc., After bonding the surface of an ultra-thin copper layer to a resin substrate and thermocompression-bonding, a carrier is via a peeling layer. Peel off.

  In the production of a printed wiring board using a copper foil with a carrier, a typical usage of the copper foil with a carrier is to first laminate a copper foil with a carrier from an ultrathin copper layer side to a resin substrate and then from an ultrathin copper layer Peel the carrier. Next, a plating resist formed of a photocurable resin is provided on the exposed ultrathin copper layer by peeling off the carrier. Next, the predetermined area of the plating resist is exposed to light to harden the area. Then, after removing the unhardened plating resist of a non-exposure area | region, an electrolytic-plating layer is provided in the said resist removal area | region. Next, the cured plating resist is removed to obtain a resin substrate on which a circuit is formed, and a printed wiring board is manufactured using this.

JP, 2006-022406, A

  In the manufacturing method of the printed wiring board using the copper foil with a carrier as described above, in general, the foreign material on the surface of the copper foil with a carrier or the surface of the printed wiring board is made using a synthetic rubber cleaning roller having adhesiveness. May be removed. At this time, the roughening treatment layer provided on the very thin copper layer side surface of the copper foil with carrier in order to improve the adhesion to the insulating resin corresponds to the miniaturization of wiring and high frequency signal transmission as described above. Because it is smooth and fine. For this reason, when the cleaning roller is applied, the fine roughening particles constituting the roughening treatment layer fall off from the surface of the copper foil and are transferred and adhered as conductive foreign matter on the cleaning roller. The conductive foreign matter adhering to the surface of the cleaning roller in this way may move again to the original copper foil or printed wiring board surface if the cleaning is further continued, and in such a case, the circuit to be formed on the copper foil It causes the short circuit to occur.

  Therefore, it is an object of the present invention to provide a copper foil with carrier in which the falling off of the roughened particles in the roughened particle layer provided on the very thin copper layer side surface is well suppressed and the peel strength is good. I assume.

  In order to achieve the above object, the inventors of the present invention conducted intensive studies to find that the diameter of the roughened particles constituting the roughened layer to be treated on the surface of the copper foil with a carrier is very thin. It has been found that the problem can be solved by suppressing the generation density of roughened particles exceeding 1 μm and controlling the density of roughened particles having a diameter of 0.1 μm or more and 1.0 μm or less.

The present invention has been completed on the basis of the above findings, and in one aspect, it is a copper foil with a carrier having a surface treatment layer including a carrier, an intermediate layer, an extremely thin copper layer, and a roughening treatment layer in this order Among the roughening particles constituting the roughening treatment layer, those having a diameter of more than 1 μm are suppressed to 5 or less in a range of 10 μm square, and 10 μm of roughening particles having a diameter of 0.1 μm or more and 1 μm or less The carrier-attached copper foil which has a density of 500 or more and 3000 or less in a square range, and has a 10-point average roughness Rz of 0.3 to 1.5 μm on the surface of the copper foil with a carrier on the very thin copper layer side. is there.

  In one embodiment of the copper foil with carrier according to the present invention, among the roughening particles constituting the roughening treatment layer, those having a diameter exceeding 1 μm are suppressed to 2 or less in a 10 μm square range, and 0.1 μm Roughened particles having a diameter of 1 μm or more are present in a 10 μm square at a density of 500 or more and 3,000 or less.

  In another embodiment of the copper foil with carrier according to the present invention, among the roughening particles constituting the roughening treatment layer, those having a diameter exceeding 1 μm are suppressed to 2 or less in a 10 μm square range, and 0 Roughened particles having a diameter of 1 μm or more and 1 μm or less are present at a density of 2000 or more and 3000 or less in a 10 μm square range.

  In still another embodiment, the copper foil with a carrier according to the present invention has a thickness of 0.1 μm to 6 μm both inclusive.

In still another embodiment of the copper foil with carrier according to the present invention, the adhesion amount per unit area of the surface treatment layer is 0.1 g / m ² or more and 5 g / m ² or less.

In still another embodiment of the copper foil with carrier according to the present invention, the adhesion amount per unit area of the surface treatment layer is 0.8 g / m ² or more and 1.5 g / m ² or less.

  In still another embodiment of the copper foil with carrier according to the present invention, a roughened layer is formed on the surface of the carrier opposite to the very thin copper layer.

  In still another embodiment of the copper foil with carrier according to the present invention, the roughened layer formed on the surface of the ultrathin copper layer is made of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium and zinc. A layer consisting of an alloy containing any one or more selected from the group consisting of

  In still another embodiment, the copper foil with carrier according to the present invention includes a resin layer on the surface of the roughened layer formed on the surface of the ultrathin copper layer.

  In still another embodiment, the copper foil with carrier according to the present invention has a heat-resistant layer, an anticorrosive layer, a chromate treatment layer and a silane coupling treatment layer on the surface of the roughening treatment layer formed on the surface of the ultrathin copper layer. And one or more layers selected from the group consisting of

  In still another embodiment, the copper foil with a carrier according to the present invention is the heat resistant layer, the rustproof layer, the chromate treated layer, and the silane provided on the surface of the roughened layer formed on the surface of the ultrathin copper layer. A resin layer is provided on one or more layers selected from the group consisting of a coupling treatment layer.

  In still another embodiment, the copper foil with carrier according to the present invention comprises a resin layer on the surface treatment layer surface.

  In still another embodiment of the copper foil with carrier according to the present invention, the resin layer is a bonding resin.

  In still another embodiment of the copper foil with carrier according to the present invention, the resin layer is a resin in a semi-cured state.

The present invention in another aspect, a method for producing a laminate for producing a product Sotai using copper foil with carrier of the present invention.

  According to still another aspect of the present invention, there is provided a laminate comprising the copper foil with carrier of the present invention and a resin, wherein a part or all of the end face of the copper foil with carrier is covered with the resin. It is.

In the present invention yet another aspect, a method for manufacturing a printed wiring board for producing a print wiring board using the copper foil with carrier of the present invention.

  In still another aspect of the present invention, the process of preparing the copper foil with carrier and the insulating substrate of the present invention, the process of laminating the copper foil with carrier and the insulating substrate, the copper foil with carrier and the insulating substrate After laminating, a copper-clad laminate is formed through the step of peeling off the carrier of the copper foil with a carrier, and then the circuit is formed by a semi-additive method, a subtractive method, a partly additive method or a modified semi-additive method. It is a manufacturing method of a printed wiring board including the process of forming these.

  In still another aspect of the present invention, a process of forming a circuit on the surface of the copper foil with a carrier according to the present invention, the ultra thin copper layer of the copper foil with a carrier such that the circuit is embedded. A step of forming a resin layer on the side surface, a step of forming a circuit on the resin layer, a step of peeling the carrier after forming the circuit on the resin layer, and the step of peeling the carrier It is a manufacturing method of a printed wiring board including the process of exposing the circuit buried in the resin layer which was formed in the ultra-thin copper layer side surface by removing the ultra-thin copper layer.

In still another aspect of the present invention, the step of laminating the copper foil with carrier according to the present invention on the resin substrate from the carrier side, the step of forming a circuit on the ultrathin copper layer side surface of the copper foil with carrier,
Forming a resin layer on the surface of the copper foil with carrier so as to bury the circuit, forming a circuit on the resin layer, and forming the circuit on the resin layer, The step of peeling the carrier, and after peeling the carrier, the ultra-thin copper layer is removed to expose the circuit embedded in the resin layer formed on the very-thin copper layer side surface. It is a manufacturing method of a printed wiring board including a process of

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

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

  ADVANTAGE OF THE INVENTION According to this invention, drop-off | omission of roughening particle | grains in the roughening particle layer provided in the ultra-thin copper layer side surface can be suppressed favorably, and the copper foil with a carrier with favorable peeling strength can be provided. .

A to C are schematic views of the cross section of the wiring board in the steps up to circuit plating and resist removal, according to a specific example of the method for producing a printed wiring board using the copper foil with carrier of the present invention. D to F are schematic views of a cross section of a wiring board in a process from resin and second layer copper foil lamination with carrier to laser drilling according to a specific example of the method for producing a printed wiring board using the copper foil with carrier of the present invention It is. G to I are schematic views of a cross section of a wiring board in steps from via fill formation to first layer carrier peeling 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. J to K are schematic views of a cross section of a wiring board in steps from flash etching to formation of bumps and copper pillars according to a specific example of the method for producing a printed wiring board using the copper foil with a carrier of the present invention. The surface SEM observation photograph after the roughening process of the copper foil of Example 2 is shown. The surface SEM observation photograph after the roughening process of the copper foil of the comparative example 1 is shown. The SEM observation photograph of the drop-off roughening particle | grains on the adhesive sheet of the comparative example 1 is shown.

<Carrier>
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 an alloy foil, an insulating resin film, a polyimide film, and an LCD film.
The carrier that can be used in the present invention is typically provided in the form of rolled copper foil or electrolytic copper foil. Generally, an electrolytic copper foil is manufactured by electrolytically depositing copper on a drum of titanium or stainless steel from a copper sulfate plating bath, and a rolled copper foil is manufactured by repeating plastic working and heat treatment by rolling rolls. In addition to copper of high purity such as tough pitch copper (JIS H3100 alloy No. C1100) and oxygen free copper (JIS H3100 alloy No. C1020 or JIS H3510 alloy No. C1011) as copper foil materials, for example, Sn containing copper, Ag containing copper, Cr It is also possible to use a copper alloy such as a copper alloy to which Zr, Mg or the like is added, or a Corson-based copper alloy to which Ni, Si or the like is added. The carrier is preferably an electrodeposited copper foil or a rolled copper foil because of its high electrical conductivity, and it is further preferred that the electrodeposited copper foil is low in manufacturing cost and easier to control the surface roughness of the carrier side. preferable. In addition, when the term "copper foil" is used independently in this specification, copper alloy foil shall also be included.

  The thickness of the carrier that can be used in the present invention is not particularly limited, but may be suitably adjusted to a thickness suitable for serving as a carrier, for example, 12 μm or more. However, if it is too thick, the production cost will increase, so in general, the thickness is preferably 35 μm or less. Thus, the thickness of the carrier is typically 12 to 300 μm, more typically 12 to 150 μm, more typically 12 to 70 μm, and more typically 18 to 35 μm.

<Middle class>
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 difficult to peel from the carrier prior to the lamination step on the insulating substrate with the copper foil with carrier, while the ultrathin copper layer from the carrier is after the lamination step on the insulating substrate The configuration is not particularly limited as long as it is a configuration that allows peeling. For example, the intermediate layer of the copper foil with a carrier according to the present invention may be made of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, their alloys, their hydrates, their oxides, One or more selected from the group consisting of organic substances may be included. Also, the intermediate layer may be a plurality of layers.
Also, for example, the intermediate layer is a single metal layer consisting of a kind of element selected from the group of elements consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn from the carrier side Or form an alloy layer composed of one or more elements selected from the group of elements composed of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, Hydrates or oxides or organic substances of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn It can be constituted by forming the following layer.
Also, for example, the intermediate layer may be a single metal layer made of any one element in the group of elements of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn from the carrier side, or Cr An alloy layer composed of one or more elements selected from the group of elements of Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, and then Cr, Ni, Co, Fe, Mo, Ti , W, P, Cu, Al, Zn, or a single metal layer of any one element group, or Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn It can be constituted by an alloy layer composed of one or more elements selected from the element group. In addition, a layer configuration that can be used as an intermediate layer may be used for other layers.

Also, for example, the intermediate layer can be configured by laminating a nickel layer, a nickel-phosphorus alloy layer or a nickel-cobalt alloy layer, and a chromium-containing layer in this order on the carrier. Since the adhesion between nickel and copper is higher than the adhesion between chromium and copper, when peeling off the very thin copper layer, it peels off at the interface between the very thin copper layer and the chromium. In addition, a barrier effect is expected in the nickel of the intermediate layer to prevent the diffusion of the copper component from the carrier into the ultrathin copper layer. Adhesion amount of nickel in the intermediate layer is preferably 100 [mu] g / dm ² or more 40000μg / dm ² or less, more preferably 100 [mu] g / dm ² or more 4000μg / dm ² or less, more preferably 100 [mu] g / dm ² or more 2500 g / dm ² or less, more Preferably, it is 100 μg / dm ² or more and less than 1000 μg / dm ² , and the adhesion amount of chromium in the intermediate layer is 5 μg / dm ² or more and 500 μg / dm ² or less, and 5 μg / dm ² or more and 100 μg / dm ² or less It is more preferable that

  The chromium-containing layer may be a chromium plating layer, a chromium alloy plating layer, or a chromate-treated layer. Here, the chromate-treated layer means a layer treated with a solution containing chromic acid anhydride, chromic acid, dichromic acid, chromate or dichromate. Chromate treatment layer is cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, titanium and other elements (metals, alloys, oxides, nitrides, sulfides, etc.) May be included. Specific examples of the chromate treatment layer include a chromate treatment layer treated with a chromic acid anhydride or potassium dichromate aqueous solution, a chromate treatment layer treated with a treatment solution containing chromic acid anhydride or potassium dichromate and zinc, etc. .

The intermediate layer of the copper foil with carrier according to the present invention is formed by laminating the nickel layer or the alloy layer containing nickel on the carrier, and the organic layer containing any of the nitrogen-containing organic compound, the sulfur-containing organic compound and the carboxylic acid. The adhesion amount of nickel in the intermediate layer may be 100 to 40000 μg / dm ² .

Also, for example, as the organic substance contained in the intermediate layer, it is preferable to use one or two or more selected from nitrogen-containing organic compounds, sulfur-containing organic compounds, and carboxylic acids. Among nitrogen-containing organic compounds, sulfur-containing organic compounds and carboxylic acids, nitrogen-containing organic compounds include nitrogen-containing organic compounds having a substituent. As specific nitrogen-containing organic compounds, 1,2,3-benzotriazole which is a triazole compound having a substituent, carboxybenzotriazole, N ′, N′-bis (benzotriazolylmethyl) urea, 1H-1 It is preferable to use 2,4-triazole, 3-amino-1H-1,2,4-triazole and the like.
As the sulfur-containing organic compound, mercaptobenzothiazole, thiocyanuric acid, 2-benzimidazole thiol and the like are preferably used.
As the carboxylic acid, it is particularly preferable to use a monocarboxylic acid, and among them, it is preferable to use oleic acid, linoleic acid, linolenic acid and the like.
It is preferable to contain 8 nm-80 nm by thickness of the above-mentioned organic substance, and it is more preferable to contain 30 nm-70 nm. The intermediate layer may contain a plurality of types (one or more) of the aforementioned organic substances.
The thickness of the organic substance can be measured as follows.

<Organic thickness of the middle layer>
After peeling the ultrathin copper layer of the copper foil with carrier from the carrier, 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 are measured by XPS to create a depth profile. Then, let A (nm) be the depth at which the carbon concentration first falls to 3 at% or less from the surface on the intermediate layer side of the ultrathin copper layer, and the carbon concentration to 3 at% or less from the surface on the intermediate layer side of the carrier first. The obtained depth can be B (nm), and the sum of A and B can be the thickness (nm) of the organic substance in the intermediate layer.
The operating conditions of XPS are shown below.
-Device: XPS measuring device (ULVAC-PHI, model 5600 MC)
-Ultimate vacuum: 3.8 × ^10-7 Pa
X-ray: monochromatic AlKα or non-monochromatic MgKα, X-ray output 300 W, detection area 800 μmφ, angle 45 ° between sample and detector
・ Ion line: ion species Ar ⁺ , acceleration voltage 3 kV, sweep area 3 mm × 3 mm, sputtering rate 2.8 nm / min (SiO ₂ equivalent)

  The method of using the organic substance contained in the intermediate layer will be described below while also describing the method of forming the intermediate layer on the carrier foil. The formation of the intermediate layer on the carrier is carried out by dissolving the above-mentioned organic substance in a solvent and immersing the carrier in the solvent, or showering the surface on which the intermediate layer is to be formed, a spraying method, a dropping method and an electrodeposition method There is no need to adopt a particularly limited method. The concentration of the organic agent in the solvent at this time is preferably in the range of 0.01 g / L to 30 g / L and the liquid temperature of 20 to 60 ° C. in all of the aforementioned organic substances. The concentration of the organic substance is not particularly limited, and the high or low concentration of the organic substance is not a problem. In addition, the organic substance thickness of an intermediate | middle layer tends to become large, so that the contact time of the carrier to the solvent which dissolved the organic substance mentioned above is so long that the density | concentration of organic substance is high.

Also, for example, the intermediate layer can be configured by laminating nickel and molybdenum or cobalt or a molybdenum-cobalt alloy in this order on the carrier. The adhesion between nickel and copper is higher than the adhesion between molybdenum or cobalt and copper, so when peeling off the ultrathin copper layer, the interface between the ultrathin copper layer and the molybdenum or cobalt or molybdenum-cobalt alloy It comes to peel off. In addition, a barrier effect is expected in the nickel of the intermediate layer to prevent the diffusion of the copper component from the carrier into the ultrathin copper layer.
In the intermediate layer, the adhesion amount of nickel is 100 to 40000 μg / dm ² , the adhesion amount of molybdenum is 10 to 1000 μg / dm ² , and the adhesion amount of cobalt is 10 to 1000 μg / dm ² . As described above, in the copper foil with carrier of the present invention, the amount of Ni on the surface of the ultrathin copper layer after peeling off the ultrathin copper layer from the copper foil with carrier is controlled. In order to control the amount of Ni on the surface of the ultrathin copper layer, the amount of Ni attached to the intermediate layer is reduced, and metal species (Co, Mo) to suppress the diffusion of Ni to the ultrathin copper layer are added to the intermediate layer Is preferably contained. From this viewpoint, the amount of nickel deposited is preferably to 100~40000μg / dm ^2, preferably to 200~20000μg / dm ^2, more preferably to 300~15000μg / dm ^2, 300~10000μg It is more preferable to set / dm ² . If included molybdenum in the intermediate layer, a molybdenum deposition amount is preferably set to 10~1000μg / dm ^2, the molybdenum deposition amount is preferably set to 20~600μg / dm ^2, and 30~400μg / dm ² It is more preferable to do. If included cobalt in the intermediate layer, the cobalt coating weight is preferably set to 10~1000μg / dm ^2, cobalt deposition amount is preferably set to 20~600μg / dm ^2, and 30~400μg / dm ² It is more preferable to do.
As described above, when the intermediate layer is formed by stacking nickel and molybdenum or cobalt or a molybdenum-cobalt alloy in this order on the carrier, plating for providing a molybdenum or cobalt or a molybdenum-cobalt alloy layer is performed. If the current density in the process is lowered and the carrier transport rate is decreased, the density of the molybdenum or cobalt or molybdenum-cobalt alloy layer tends to be increased. As the density of the layer containing molybdenum and / or cobalt increases, the nickel in the nickel layer is less likely to diffuse, and the amount of Ni on the surface of the ultrathin copper layer after peeling can be controlled.

<Strike plating>
An ultra-thin copper layer is provided on the middle layer. This may be preceded by strike plating with a copper-phosphorus alloy to reduce pinholes in the ultra-thin copper layer. The strike plating includes copper pyrophosphate plating solution and the like.

<Ultra-thin copper layer>
An ultra-thin copper layer is provided on the middle layer. In addition, another layer may be provided between the intermediate layer and the ultrathin copper layer. The extremely thin copper layer can be formed by electroplating using an electrolytic bath of copper sulfate, copper pyrophosphate, copper sulfamate, copper cyanide, etc., and is used for general electrolytic copper foils, with high current density A copper sulfate bath is preferred because copper foil formation is possible. The thickness of the ultrathin copper layer is preferably 0.1 μm to 6 μm. According to such a configuration, the fine wiring formability is improved. The thickness of the ultrathin copper layer is more preferably 0.1 μm or more and 3 μm or less, still more preferably 0.2 μm or more and 1.5 μm or less, and still more preferably 0.3 μm or more and 1.2 μm or less preferable. Moreover, you may use the layer of the structure which can be used as an intermediate | middle layer in another layer.

  A laminate (such as a copper-clad laminate) can be produced using the copper foil with a carrier of the present invention. The laminate may be, for example, a configuration in which "ultrathin copper layer / intermediate layer / carrier / resin or prepreg" is laminated in order, "carrier / intermediate layer / ultrathin copper layer / resin or prepreg" The structure may be laminated in the order of “very thin copper layer / intermediate layer / carrier / resin or prepreg / carrier / intermediate layer / very thin copper layer”, or The structure may be laminated in the order of carrier / intermediate layer / very thin copper layer / resin or prepreg / very thin copper layer / intermediate layer / carrier. The resin or the prepreg may be a resin layer to be described later, and a resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, etc. May be included. The copper foil with carrier may be smaller than the resin or the prepreg in plan view.

<Copper foil with carrier>
The copper foil with carrier of the present invention has a surface treatment layer including a carrier, an intermediate layer, a very thin copper layer, and a roughening treatment 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 a very thin copper layer is a paper base phenolic resin, paper base epoxy resin, synthetic fiber cloth base epoxy resin, glass cloth / paper composite Ultra-thin film bonded to insulating substrate such as base epoxy resin, glass cloth / glass nonwoven fabric composite base epoxy resin and glass cloth base epoxy resin, polyester film, polyimide film etc A copper layer can be etched to a target conductor pattern, and finally a laminate (copper-clad laminate etc.), a printed wiring board or the like can be manufactured.

  The roughening treatment layer in the surface treatment layer has roughening particles, and among roughening particles constituting the roughening treatment layer, those having a diameter exceeding 1 μm are suppressed to 5 or less in a 10 μm square range, and 0 . Roughened particles having a diameter of 1 μm or more and 1 μm or less are controlled to be present at a density of 500 or more and 3,000 or less in a 10 μm square range. Here, the diameter of the roughened particles indicates the minimum diameter of the circle surrounding the roughened particles. With such a configuration, the generation of powder on the surface of the copper foil with a carrier on the very thin copper layer side is favorably suppressed. Among the roughening particles constituting the roughening treatment layer, those having a diameter of more than 1 μm are preferably 2 or less in a 10 μm square, more preferably 1 or less, further preferably 0. More preferable. In addition, roughened particles having a diameter of 0.1 μm to 1 μm are preferably present at a density of 2000 to 3000 in a 10 μm square, and more preferably at a density of 2000 to 2800. Preferably, it is even more preferably present at a density of 2000 or more and 2500 or less.

Also, preferably the amount deposited per unit area of the surface treated layer is 0.1 g / m ² or more 5 g / m ² or less. With such a configuration, the generation of powder on the surface of the copper foil with a carrier on the very thin copper layer side is better suppressed. The adhesion amount per unit area of the surface treatment layer is more preferably 0.8 g / m ² or more and 1.5 g / m ² or less, and preferably 0.9 g / m ² or more and 1.4 g / m ² or less It is further more preferable, and it is still more preferable that it is 1 g / m ² or more and 1.2 g / m ² or less.

  The roughening treatment can be performed, for example, by forming roughened particles with copper or a copper alloy. The roughening process may be fine. The roughening treatment layer is a layer made of an alloy containing any one or more selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium and zinc, and the like. It is also good. In addition, after roughening particles are formed of copper or copper alloy, roughening treatment may be performed in which secondary particles or tertiary particles are further formed of nickel, cobalt, copper, zinc, an alloy or the like. The roughening treatment layer may be formed using a sulfuric acid / copper sulfate electrolytic bath containing one or more selected from the group consisting of a sulfuric acid alkyl ester salt, tungsten and arsenic. Thereafter, the heat-resistant layer or the rust-preventing layer may be formed of nickel, cobalt, copper, zinc singly or as an alloy or the like, and the surface may be further subjected to a treatment such as chromate treatment or silane coupling treatment. Alternatively, a heat-resistant layer or rustproof layer may be formed of nickel, cobalt, copper, zinc singly or as an alloy without roughening, and the surface may be further treated by chromate treatment, silane coupling treatment, etc. Good. That is, one or more layers selected from the group consisting of a heat-resistant layer, an antirust layer, a chromate treatment layer and a silane coupling treatment layer may be formed on the surface of the roughening treatment layer, a carrier or ultrathin copper At least one layer selected from the group consisting of a heat-resistant layer, an antirust layer, a chromate treatment layer, and a silane coupling treatment layer may be formed on the surface of the layer. The above-mentioned heat-resistant layer, rust-preventive layer, chromate-treated layer, and silane coupling-treated layer may each be formed of a plurality of layers (for example, two or more layers, three or more layers, etc.). Note that these surface treatments hardly affect the surface roughness of the carrier and the ultrathin copper layer.

  The roughening treatment can be performed, for example, by forming roughened particles with copper or a copper alloy. The roughened layer is preferably composed of fine particles from the viewpoint of fine pitch formation. With regard to electroplating conditions for forming roughened particles, the particles tend to be finer if the current density is high, the copper concentration in the plating solution is low, or the coulomb amount is large.

A roughening treatment layer may be provided on the surface of the carrier opposite to the very thin copper layer side, for example, by performing a roughening treatment to improve the adhesion to the resin substrate. According to such a configuration, when the copper foil with a carrier according to the present invention is laminated on a resin substrate from the carrier side, the adhesion between the carrier and the resin substrate is improved, and the carrier is produced in the process of producing a printed wiring board. It becomes difficult to peel off the resin substrate.
Moreover, it is not necessary to form a roughening process layer in the surface on the opposite side to the very thin copper layer side of a carrier. When the roughened layer is not formed on the surface of the carrier opposite to the very thin copper layer side, there is an advantage that the peel strength between the carrier and the very thin copper layer can be easily controlled.
In addition, a roughening treatment layer may be provided on the surface of the ultrathin copper layer by performing a roughening treatment, for example, to improve the adhesion to the insulating substrate.

  In the present invention, a surface treatment layer such as a roughening treatment layer, a heat-resistant layer, an anticorrosion layer, a chromate treatment layer, or a silane coupling treatment layer is formed, or no roughening treatment layer is formed. The surface opposite to the ultrathin copper layer is not particularly limited as long as it is the surface opposite to the ultrathin copper layer with respect to the carrier, and may be, for example, the surface of the carrier itself When the surface treatment layer is formed on the side opposite to the ultrathin copper layer of the carrier, it may be the surface (including the surface of the outermost layer) of any layer in the surface treatment layer.

  The copper foil with a carrier according to the present invention preferably has a ten-point average roughness Rz of 0.3 to 1.5 μm on the surface on the very thin copper layer side. Moreover, it is more preferable that 10-point average roughness Rz of the ultra-thin copper layer side surface of the said copper foil with a carrier is 0.5-1.4 micrometers.

<Printed wiring board and laminate>
A laminated body (copper-clad laminate etc.) can be produced by, for example, sticking a copper foil with a carrier from the ultra-thin copper layer side to an insulating resin board, thermocompression-bonding, and peeling off a carrier. Thereafter, the copper circuit of the printed wiring board can be formed by etching the ultrathin copper layer portion. The insulating resin board used here is not particularly limited as long as it has properties applicable to a printed wiring board, but for example, paper base phenol resin, paper base epoxy resin, synthetic fiber cloth base for rigid PWB Materials such as epoxy resin, glass cloth / paper composite base epoxy resin, glass cloth / glass non-woven composite base epoxy resin, glass cloth base epoxy resin, etc., and using polyester film or polyimide film for FPC it can. The printed wiring board and the laminate produced in this manner can be mounted on various electronic components that require high-density mounting of the mounted components.
In the present invention, a "printed wiring board" includes a printed wiring board on which components are mounted, a printed circuit board and a printed circuit board. In addition, two or more printed wiring boards of the present invention can be connected to produce a printed wiring board in which two or more printed wiring boards are connected, and at least one printed wiring board of the present invention and another Two printed wiring boards according to the present invention or printed wiring boards not corresponding to the printed wiring board according to the present invention can be connected, and electronic devices can be manufactured using such printed wiring boards. In the present invention, "copper circuit" includes copper wiring.

In addition, the copper foil with carrier may be provided with a roughening treatment layer on an extremely thin copper layer, and on the roughening treatment layer, a heat-resistant layer, an anticorrosion layer, a chromate treatment layer, and a silane coupling treatment layer And one or more layers selected from the group consisting of
In addition, a roughening treatment layer may be provided on the ultrathin copper layer, a heat-resistant layer and an anticorrosion layer may be provided on the roughening treatment layer, and a chromate treatment layer is provided on the heat-resistant layer and the anticorrosion layer. A silane coupling treatment layer may be provided on the chromate treatment layer.
Further, the copper foil with carrier is provided with a resin layer on the ultra-thin copper layer, on the roughening treatment layer, or on the heat-resistant layer, anticorrosive layer, chromate treatment layer, or silane coupling treatment layer. It is good.

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

  The resin layer may contain a thermosetting resin or may be a thermoplastic resin. In addition, the resin layer may contain a thermoplastic resin. The resin layer may contain a known resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton and the like. In addition, the resin layer may be formed of, for example, International Publication Number WO2008 / 004399, International Publication Number WO2008 / 053878, International Publication Number WO2009 / 084533, Japanese Patent Application Laid-Open No. 11-5828, Japanese Patent Application No. 11-140281, Patent No. 3184485, International Publication Nos. WO 97/02728, Patent No. 3676375, JP-A 2000-43188, Patent No. 3612594, JP-A 2002-179772, JP-A 2002-359444, JP-A 2003-304068, JP 3992225, JP-A 2003 No. 249739, Patent No. 4136509, Japanese Patent No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent No. 2004-349654, Japanese Patent No. 4286060, Japanese Patent No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent No. 20 Patent No. 5-53218, Patent No. 3949676, Patent No. 4178415, International Publication No. WO 2004/005588, Japanese Patent Publication No. 2006-257153, Japanese Patent Publication 2007-326923, Japanese Patent Publication 2008-111169, Patent No. 5024930, International Publication No. WO2006 / 028207, Patent No. 4828427, Japanese Patent Application Publication No. 2009-67029, International Publication No. WO2006 / 134868, Patent No. 5046927, Japanese Patent Application Publication No. 2009-1730017, International Publication No. WO2007 / 105635, Patent No. 5180815, International Publication No. WO2008 / 114858, International Publication No. WO2009 / 008471, Japanese Patent Application Publication No. 2011-14727, International Publication No. WO2009 / 001850, International Publication No. WO2009 / 145179, International Publication No. WO2011 / 068157, JP-A-2013-19056 (a resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeletal material, 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, polyether sulfone (also referred to as polyether sulfone or polyether sulfone), polyether sulfone (also referred to as polyether sulfone or polyether sulfone) resin, aromatic polyamide resin, aromatic Polyamide resin polymer, rubber resin, polyamine, aromatic polyamine, polyamide imide resin, rubber modified epoxy resin, phenoxy resin, carboxyl group modified acrylonitrile-butadiene resin, polyphenylene oxide, bismaleimide triazine resin Fat, thermosetting polyphenylene oxide resin, cyanate ester resin, anhydride of carboxylic acid, anhydride of polyvalent carboxylic acid, 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, cyano ester resin, phosphazene resin, Select from the group of rubber modified polyamideimide resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, phenoxy, high molecular weight epoxy, aromatic polyamide, fluorocarbon resin, bisphenol, block copolymer polyimide resin and cyano ester resin It can be mentioned resins containing one or more kinds as suitable to be.

The epoxy resin may be used without particular problems as long as it has two or more epoxy groups in the molecule and can be used for electrical and electronic materials. The epoxy resin is preferably an epoxy resin which is epoxidized using a compound having two or more glycidyl groups in the molecule. In addition, 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 epoxy resin, naphthalene epoxy resin, brominated bisphenol A epoxy resin, ortho cresol novolac epoxy resin, rubber modified bisphenol A epoxy resin, glycidyl amine epoxy resin, triglycidyl isocyanurate, N, N Glycidyl amine compounds such as -diglycidyl aniline, glycidyl ester compounds such as tetrahydrophthalic acid diglycidyl ester, phosphorus-containing epoxy resin, biphenyl type epoxy resin, biphenyl It may be used by mixing one or two or more selected from the group consisting of phenyl novolac epoxy resin, trishydroxyphenylmethane epoxy resin, tetraphenylethane epoxy resin, or a hydrogenated product of the above epoxy resin or Halogenated products can be used.
A phosphorus-containing epoxy resin known as the phosphorus-containing epoxy resin can be used. Also, 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 contain a dielectric (dielectric filler).
When a dielectric (dielectric filler) is included in any of the above resin layers or resin compositions, it can be used for forming a capacitor layer to increase the electric capacity of the capacitor circuit. As the dielectric (dielectric filler), 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), etc. The dielectric powder of complex oxide having a pebroskite structure is used.

  The dielectric (dielectric filler) may be powdery. When the dielectric (dielectric filler) is powdery, the powder properties of the dielectric (dielectric filler) have a particle diameter in the range of 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 straight line across the dielectric particle is the longest. The length of a dielectric particle is taken as the diameter of the dielectric particle. And let the average value of the diameter of the particle | grains of the dielectric in a measurement visual field be the particle size of a dielectric.

The resin and / or resin composition and / or compound contained in the aforementioned resin layer may be, for example, methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene, methanol, ethanol, propylene glycol monomethyl ether The resin solution (resin varnish) is dissolved in a solvent such as dimethylformamide, dimethylacetamide, cyclohexanone, ethyl cellosolve, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, etc. The carrier-coated copper foil is coated, for example, by a roll coater method on the surface on the very thin copper layer side, and then dried by heating if necessary to remove the solvent and make it into a B-stage state. For drying, for example, a hot air drying furnace may be used, 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 may be a resin liquid. In addition, it is most preferable at the present stage from the environmental point of view 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 degreeC-200 degreeC for a solvent.
Moreover, it is preferable that the said resin layer is a semi-hardened resin film which has a resin flow in the range of 5%-35% when it measures based on MIL-P-13949G in MIL specification.
In the present specification, resin flow refers to four 10 cm square samples from a resin-coated surface-treated copper foil having a resin thickness of 55 μm in accordance with MIL-P-13949G in the MIL standard. In a state where samples are stacked (laminate), they are bonded under the conditions of press temperature 171 ° C, press pressure 14kgf / cm2 and press time 10 minutes, and the resin outflow weight at that time is measured by the value calculated based on equation 1 from the result of measurement. is there.

  The surface-treated copper foil provided with the resin layer (surface-treated copper foil with resin) is made by laminating the resin layer on a substrate and then thermocompression bonding the whole to thermally cure the resin layer, and then the surface-treated copper foil When the carrier is an ultrathin copper layer of copper foil with carrier, the carrier is peeled off to expose the ultrathin copper layer (naturally, it is the surface on the middle layer side of the ultrathin copper layer) It is used in the aspect of forming a predetermined | prescribed wiring pattern from the surface on the opposite side to the side by which the roughening process of the surface treatment copper foil is carried out.

  By using this surface-treated copper foil with resin, it is possible to reduce the number of used prepreg materials at the time of manufacturing a multilayer printed wiring board. In addition, the thickness of the resin layer can be made such that interlayer insulation can be secured, or a copper-clad laminate can be produced even when no prepreg material is used at all. At this time, the surface of the substrate may be undercoated with an insulating resin to further improve the surface smoothness.

In the case where a prepreg material is not used, the material cost of the prepreg material is saved, and the lamination process is simplified, which is economically advantageous. Furthermore, the multilayer printed wiring board manufactured by the thickness of the prepreg material The thickness is reduced, and there is an advantage that an extremely thin multilayer printed wiring board in which the thickness of one layer is 100 μm or less can be manufactured.
The thickness of the resin layer is preferably 0.1 to 500 μm, more preferably 0.1 to 300 μm, still more preferably 0.1 to 200 μm, and 0.1 to 120 μm. More preferable.

When the thickness of the resin layer is smaller than 0.1 μm, the adhesive force is reduced, and the circuit of the inner layer material when the copper foil with a carrier with a resin is laminated on the base material provided with the inner layer material without interposing the prepreg material. It may be difficult to secure interlayer insulation between them. On the other hand, if the thickness of the resin layer is greater than 120 μm, it may be difficult to form the resin layer of the desired thickness in one application step, which may be economically disadvantageous because extra material costs and man-hours are required.
In addition, when the copper foil with a carrier which has a resin layer is used for manufacturing an ultra-thin multilayer printed wiring board, the thickness of the said resin layer is 0.1 micrometer-5 micrometers, More preferably, 0.5 micrometer-5 micrometers, More preferably, the thickness is 1 μm to 5 μm to reduce the thickness of the multilayer printed wiring board.
When the resin layer contains a dielectric, the thickness of the resin layer is preferably 0.1 to 50 μm, more preferably 0.5 μm to 25 μm, and more preferably 1.0 μm to 15 μm. preferable.
The total resin layer thickness of the cured resin layer and the semi-cured resin layer is preferably 0.1 μm to 120 μm, preferably 5 μm to 120 μm, and preferably 10 μm to 120 μm, and 10 μm to 60 μm. Is more preferable. The thickness of the cured resin layer is preferably 2 μm to 30 μm, preferably 3 μm to 30 μm, and more preferably 5 to 20 μm. The thickness of the semi-cured resin layer is preferably 3 μm to 55 μm, preferably 7 μm to 55 μm, and more preferably 15 to 115 μm. If the total resin layer thickness exceeds 120 μm, it may be difficult to produce a thin multilayer printed wiring board, and if it is less than 5 μm, it becomes easy to form a thin multilayer printed wiring board, but the insulating layer between the inner layer circuits This is because the resin layer may be too thin, which may make the insulation between the circuits in the inner layer unstable. When the thickness of the cured resin layer is less than 2 μm, it may be necessary to consider the surface roughness of the copper foil roughened surface. On the other hand, when the thickness of the cured resin layer exceeds 20 μm, the effect of the cured resin layer may not be particularly improved, and the total insulating layer thickness becomes large.

In addition, when the thickness of the said resin layer shall be 0.1 micrometer-5 micrometers, in order to improve the adhesiveness of a resin layer and copper foil with a carrier, a heat-resistant layer and / or an anticorrosion layer on an ultra-thin copper layer After providing the chromate treatment layer and / or the silane coupling treatment layer, it is preferable to form a resin layer on the heat-resistant layer, the rustproof layer, or the chromate treatment layer or the silane coupling treatment layer.
In addition, the thickness of the above-mentioned resin layer says the average value of the thickness measured by cross-sectional observation in ten arbitrary points.

  Furthermore, as another product form of the carrier-coated copper foil with resin, it is possible to form the above-mentioned ultra-thin copper layer, or the above-mentioned heat-resistant layer, anticorrosive layer, or the above chromate treated layer, or the above silane coupling treated layer After coating with a resin layer and bringing it into a semi-cured state, it is also possible to peel off the carrier and produce it in the form of a resin-coated copper foil without a carrier.

  Furthermore, as another product form of the carrier-coated copper foil with resin, it is possible to form the above-mentioned ultra-thin copper layer, or the above-mentioned heat-resistant layer, anticorrosive layer, or the above chromate treated layer, or the above silane coupling treated layer After coating with a resin layer and bringing it into a semi-cured state, it is also possible to peel off the carrier and produce it in the form of a resin-coated copper foil without a carrier.

<Method of manufacturing printed wiring board>
In one embodiment of the 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 the insulating substrate, the carrier After laminating the attached copper foil and the insulating substrate so that the very thin copper layer side faces the insulating substrate, the carrier of the copper foil with carrier is peeled off to form a copper-clad laminate, and then a semi-additive method, Forming a circuit by any one of a modified semi-additive method, a partly additive method and a subtractive method. The insulating substrate may be one including an inner layer circuit.

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

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using a semi-additive method, a step of preparing a copper foil with a carrier according to the present invention and an insulating substrate,
Laminating the copper foil with carrier and the insulating substrate;
Removing the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Removing the carrier and removing the exposed very thin copper layer by etching using a corrosive solution such as acid or plasma, etc .;
Providing a through hole or / and a blind via in the resin exposed by removing the very thin copper layer by etching;
Performing a desmearing process on an area including the through holes and / or blind vias;
Providing an electroless plating layer on a 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 to be formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist is removed is to be 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 a copper foil with a carrier according to the present invention and an insulating substrate;
Laminating the copper foil with carrier and the insulating substrate;
Removing the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Removing the carrier and removing the exposed very thin copper layer by etching using a corrosive solution such as acid or plasma, etc .;
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 to be formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist is removed is to be 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, in the modified semi-additive method, a metal foil is laminated on an insulating layer, a non-circuit forming portion is protected by a plating resist, copper plating of the circuit forming portion is performed by electrolytic plating, and then the resist is removed. And a method of forming a circuit on the insulating layer by removing the metal foil other than the circuit formation portion by (flash) etching.

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using the modified semi-additive method, a step of preparing a copper foil with carrier according to the present invention and an insulating substrate;
Laminating the copper foil with carrier and the insulating substrate;
Removing the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing the through hole or / and the blind via in the exposed ultrathin copper layer and the insulating substrate by peeling off the carrier;
Performing a desmearing process on an area including the through holes and / or blind vias;
Providing an electroless plating layer on the area including the through holes and / or blind vias;
Providing a plating resist on the surface of the ultrathin copper layer exposed by peeling off the carrier;
Forming a circuit by electrolytic plating after providing the plating resist;
Removing the plating resist;
Removing the ultrathin 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, a step of preparing a copper foil with a carrier according to the present invention and an insulating substrate;
Laminating the copper foil with carrier and the insulating substrate;
Removing 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 to be formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist is removed is to be 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, in the partly additive method, a catalyst core is provided on a substrate provided with a conductor layer, and a substrate provided with holes for through holes and via holes as necessary, and a conductor circuit is formed by etching. And a method of manufacturing a printed wiring board by providing a solder resist or a plating resist as necessary, and thickening the through holes, via holes, etc. on the conductor circuit by electroless plating.

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using the partory additive method, a step of preparing a copper foil with a carrier according to the present invention and an insulating substrate,
Laminating the copper foil with carrier and the insulating substrate;
Removing the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing the through hole or / and the blind via in the exposed ultrathin copper layer and the insulating substrate by peeling off the carrier;
Performing a desmearing process on an area including the through holes and / or blind vias;
Applying catalytic nuclei to the area including the through holes and / or blind vias;
Providing an etching resist on the surface of the ultrathin copper layer exposed by peeling off the carrier;
Exposing the etching resist to form a circuit pattern;
Forming a circuit by removing the ultra-thin copper layer and the catalyst core by a method such as etching using a corrosive solution such as acid or plasma,
Removing the etching resist;
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 using a corrosive solution such as acid or plasma;
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 selectively removing an unnecessary portion of the copper foil on the copper clad laminate by etching or the like to form a conductor pattern.

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 a copper foil with a carrier according to the present invention and an insulating substrate,
Laminating the copper foil with carrier and the insulating substrate;
Removing the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing the through hole or / and the blind via in the exposed ultrathin copper layer and the insulating substrate by peeling off the carrier;
Performing a desmearing process on an area including the through holes and / or blind vias;
Providing an electroless plating layer on the area including the through holes and / or blind vias;
Providing an electrolytic plating layer on the surface of the electroless plating layer;
Providing an etching resist on the surface of the electrolytic plating layer or / and the very thin copper layer;
Exposing the etching resist to form a circuit pattern;
Removing the ultra-thin copper layer, the electroless plating layer and the electrolytic plating layer by a method such as etching using a corrosive solution such as acid or plasma 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 the subtractive method, a step of preparing a copper foil with a carrier according to the present invention and an insulating substrate;
Laminating the copper foil with carrier and the insulating substrate;
Removing the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing the through hole or / and the blind via in the exposed ultrathin copper layer and the insulating substrate by peeling off the carrier;
Performing a desmearing process on an area including the through holes and / or blind vias;
Providing an electroless plating layer on the area including the through holes and / or blind vias;
Forming a mask on the surface of the electroless plating layer;
Providing an electrolytic plating layer on the surface of the electroless plating layer where the mask is not formed;
Providing an etching resist on the surface of the electrolytic plating layer or / and the very thin copper layer;
Exposing the etching resist to form a circuit pattern;
Forming a circuit by 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 acid;
Removing the etching resist;
including.

  The step of providing through holes or / and blind vias and the subsequent desmear step may not be performed.

Here, a specific example of the method for producing a printed wiring board using the copper foil with a carrier of the present invention will be described in detail with reference to the drawings.
First, as shown to FIG. 1-A, the copper foil with a carrier (1st layer) which has the ultra-thin copper layer by which the roughening process layer was formed in the surface is prepared.
Next, as shown to FIG. 1-B, a resist is apply | coated on the roughening process layer of an ultra-thin copper layer, exposure and image development are performed, and a resist is etched in a defined shape.
Next, as shown in FIG. 1C, plating for a circuit is formed, and then the resist is removed to form a circuit plating of a predetermined shape.
Next, as shown in Fig. 2-D, the embedded resin is provided on the ultrathin copper layer to cover the circuit plating (so that the circuit plating is buried), and the resin layer is laminated, and then another carrier is attached. Bond the copper foil (second layer) from the very thin copper layer side.
Next, as shown in FIG. 2E, the carrier is peeled off from the second layer of copper foil with carrier.
Next, as shown in FIG. 2F, laser drilling is performed at a predetermined position of the resin layer to expose the circuit plating to form a blind via.
Next, as shown in FIG. 3G, copper is buried in the blind vias to form a via fill.
Next, as shown in FIG. 3-H, circuit plating is formed on the via fill as shown in FIG. 1-B and FIG. 1-C.
Next, as shown in FIG. 3I, the carrier is peeled off from the first layer of copper foil with carrier.
Next, as shown in FIG. 4J, the ultrathin copper layer on both surfaces is removed by flash etching to expose the surface of the circuit plating in the resin layer.
Next, as shown in FIG. 4K, bumps are formed on the circuit plating in the resin layer, and copper pillars are formed on the solder. Thus, a printed wiring board using the copper foil with carrier of the present invention is produced.

  The other copper foil with carrier (second layer) may use the copper foil with carrier of the present invention, may use a conventional copper foil with carrier, and may further use a normal copper foil. Further, one or more layers of circuits may be further formed on the circuit of the second layer shown in FIG. 3H, and the circuit formation thereof may be carried out by the semi-additive method, the subtractive method, the partory additive method or the modified semi It may be carried out by any of the additive methods.

  Further, the copper foil with carrier used in the first layer may have a substrate on the carrier side surface of the copper foil with carrier. By having the said board | substrate or a resin layer, since the copper foil with a carrier used for 1st layer is supported and it becomes difficult to get wrinkled, there exists an advantage that productivity improves. As the substrate, any substrate can be used as long as it supports the copper foil with carrier used in the first layer. For example, the carrier described in the present specification as the substrate, a prepreg, a resin layer or a known carrier, a prepreg, a resin layer, a metal plate, a metal foil, a plate of an inorganic compound, a foil of an inorganic compound, a plate of an organic compound, an organic compound 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 preferable to form it before the step of forming a resin layer on the surface of the copper foil with a carrier on the ultra thin copper layer side, and in the step of forming a circuit on the surface of the copper foil with a carrier on the ultra thin copper layer side. It is more preferable to form before.

It is preferable that the copper foil with a carrier which concerns on this invention is controlled so that the color difference of the ultra-thin copper layer surface may satisfy following (1). In the present invention, the "color difference on the surface of the very thin copper layer" refers to the color difference on the surface of the very thin copper layer, or the color difference on the surface of the surface treatment layer when various surface treatments such as roughening treatment are applied. . That is, in the copper foil with carrier according to the present invention, the color difference of the surface of the ultrathin copper layer or roughened layer, heat resistant layer, rustproof layer, chromate treated layer or silane coupling layer satisfies the following (1) It is preferable that it is controlled.
(1) The color difference ΔE * ab based on JIS Z8730 on the surface of the ultrathin copper layer or roughened layer, heat resistant layer, rustproof layer, chromate layer or silane coupling layer is 45 or more.

  Here, the color differences ΔL, Δa, Δb are each measured with a color difference meter, are added black / white / red / green / yellow / blue, and are shown using the L * a * b color system based on JIS Z8730. It is a comprehensive index, and is expressed as ΔL: black and white, Δa: red-green, Δb: yellow-blue. Further, ΔE * ab is expressed by the following equation using these color differences.

The above color difference can be adjusted by increasing the current density when forming the ultrathin copper layer, decreasing the copper concentration in the plating solution, and increasing the linear flow velocity of the plating solution.
The color difference described above can also be adjusted by roughening the surface of the very thin copper layer and providing a roughened layer. In the case of providing the roughened layer, the current density is made higher (for example, 40 to 60 A) by using an electrolytic solution containing one or more elements selected from the group consisting of copper and nickel, cobalt, tungsten, and molybdenum. / Dm < ² > and it can adjust by shortening processing time (for example, 0.1-1.3 second). When a roughening treatment layer is not provided on the surface of the ultrathin copper layer, a plating bath in which the concentration of Ni is twice or more that of other elements is used to form an ultrathin copper layer or heat resistant layer or a rustproof layer or chromate Ni alloy plating (for example, Ni-W alloy plating, Ni-Co-P alloy plating, Ni-Zn alloy plating) on the surface of the treated layer or silane coupling treated layer has a lower current density (0.1 to 1. This can be achieved by setting the processing time to be longer (20 seconds to 40 seconds) at 3 A / dm ² ).

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

  When the color difference on the surface of the ultrathin copper layer or roughened layer, heat resistant layer, rustproof layer, chromate layer or silane coupling layer is controlled as described above, the contrast with the circuit plating becomes sharp. , The visibility becomes good. Therefore, in the manufacturing process of the printed wiring board as described above, for example, as shown in FIG. 2C, it is possible to form the circuit plating at a predetermined position with high accuracy. Further, according to the method for manufacturing a printed wiring board as described above, since the circuit plating is embedded in the resin layer, removal of the ultrathin copper layer by flash etching as shown in FIG. 4-J, for example In this case, the circuit plating is protected by the resin layer and its shape is maintained, thereby facilitating the formation of the fine circuit. In addition, since the circuit plating is protected by the resin layer, the migration resistance is improved and the conduction of the wiring of the circuit is well suppressed. For this reason, formation of a fine circuit becomes easy. In addition, as shown in Fig. 4-J and Fig. 4-K, when the ultra-thin copper layer is removed by flash etching, the exposed surface of the circuit plating has a concaved shape from the resin layer, so bumps are formed on the circuit plating. Further, copper pillars can be easily formed thereon, and the manufacturing efficiency is improved.

  In addition, well-known resin and a prepreg can be used for embedding resin (resin). For example, a prepreg which is a glass cloth impregnated with BT (bismaleimide triazine) resin or BT resin, ABF film or ABF manufactured by Ajinomoto Fine Techno Co., Ltd. can be used. In addition, the resin layer and / or the resin and / or the prepreg described in the present specification can be used as the embedding resin (resin).

  Further, in the method for producing a printed wiring board of the present invention, a step of laminating the resin substrate and the surface on the very thin copper layer side or the carrier side of the copper foil with carrier of the present invention, ultrathin laminated with the resin substrate The process of providing two layers of a resin layer and a circuit at least once on the surface of copper foil with a carrier on the opposite side to the copper layer side surface or the said carrier side surface, and forming two layers of the said resin layer and a circuit It may be the manufacturing method (coreless construction method) of a printed wired board including the process of making the above-mentioned career or the ultra-thin copper layer exfoliate from the above-mentioned copper foil with a carrier after carrying out. About the said coreless construction method, first, the ultra-thin copper layer side surface or the carrier side surface of the copper foil with a carrier of the present invention is laminated on a resin substrate. Thereafter, a resin layer is formed on the surface of the very thin copper layer side laminated on the resin substrate or the surface of the copper foil with carrier opposite to the surface on the carrier side. Another copper foil with a carrier may be laminated from the carrier side to the resin layer formed on the carrier side surface. In this case, a carrier / intermediate layer / ultrathin copper layer or a copper foil with carrier is laminated in the order of carrier / intermediate layer / ultrathin copper layer or in the order of ultrathin copper layer / intermediate layer / carrier on both surface sides of the resin substrate centering on the resin substrate It has become. Another resin layer may be provided on the exposed surfaces of the ultrathin copper layers or carriers at both ends, and a copper layer may be provided, and then the copper layer may be processed to form a circuit. Furthermore, another resin layer may be provided on the circuit so as to embed the circuit. Moreover, you may provide formation of such a circuit and a resin layer once or more (build-up method). And about the laminated body formed in this way, the ultra-thin copper layer or carrier of each copper foil with a carrier can be peeled from a carrier or an ultra-thin copper layer, and a coreless board | substrate can be produced.

  In the method of manufacturing a coreless substrate described above, when a printed wiring board is manufactured by a build-up method, soaking of the chemical solution into the intermediate layer is performed by covering a part or all of the end face of the copper foil with carrier with resin. It is possible to prevent the separation of the very thin copper layer and the carrier due to the infiltration of the chemical solution, and the yield can be improved. As "resin which covers a part or all of the end face of copper foil with a carrier" used here, resin which can be used for a resin layer can be used. In order to separate the carrier and the ultrathin copper layer, it is necessary to cut off the portion of the end face of the copper foil with carrier covered with the resin. Further, in the method of manufacturing a coreless substrate described above, at least a part of the outer periphery of the laminated portion of the copper foil with carrier may be covered with a resin or a prepreg when viewed in plan in the copper foil with carrier. Moreover, the laminated body formed with the manufacturing method of the above-mentioned coreless board | substrate may make a pair of copper foil with a carrier contact mutually separably. Moreover, when it planarly views in the said copper foil with a carrier, it may be covered with resin or a prepreg over the whole outer periphery of the lamination | stacking part of copper foil with a carrier. With such a configuration, when the copper foil with carrier is viewed in plan, the laminated portion of the copper foil with carrier is covered with the resin or the prepreg, and the other members are in the lateral direction of this portion, that is, with respect to the laminating direction. As a result, it is possible to prevent contact from the direction from the side, and as a result, it is possible to reduce peeling of the copper foils with carrier during handling. In addition, by covering the outer periphery of the laminated portion of the carrier-attached copper foil with the resin or the prepreg so as not to expose, it is possible to prevent the chemical solution from entering the interface in the chemical treatment process as described above. It can prevent corrosion and erosion. When one copper foil with carrier is separated from a pair of copper foil with carrier, or when the copper foil of carrier with copper foil and the copper foil (very thin copper layer) are separated, they are covered with resin or prepreg. It is necessary to remove the laminated portion of the copper foil with carrier by cutting or the like.

  EXAMPLES The present invention will be described in more detail by the following examples of the present invention, but the present invention is not limited by these examples.

1. Production of Carrier Attached Copper Foil As Examples 1 to 7 and Comparative Examples 1 to 4, an electrolytic copper foil having a thickness of 18 μm (JTC foil manufactured by JX Nippon Mining & Metals Co., Ltd. Examples other than Example 5, Comparative Examples) or rolled A copper foil (tough pitch copper foil JIS H3100 alloy number: C1100, only in Example 5) is used as a carrier, and an intermediate layer and an intermediate layer are formed on the carrier (in the case of using an electrodeposited copper foil, a glossy surface is formed). An ultrathin copper layer was formed in this order to obtain a copper foil with a carrier having a thickness of 0.6 to 5 μm.

-Intermediate layer formation The intermediate layer was formed in the carrier as described in the "intermediate layer" column of the table. The processing conditions are shown below. For example, “Ni / organic matter” means that the organic matter treatment is performed after the nickel plating treatment.
(1) "Ni": Ni treatment The shiny side (shiny side) of the above-mentioned electrodeposited copper foil or rolled copper foil is electroplated in a roll-to-roll type continuous plating line under the following conditions: 8000 μg / A deposited amount of dm ² Ni layer was formed.
Liquid composition: Nickel sulfate concentration 200 to 300 g / L, trisodium citrate concentration 2 to 10 g / L
pH: 2 to 4
Liquid temperature: 40 to 70 ° C
Current density: 1 to 15 A / dm ²
The remainder of the treatment liquid used for electrolysis, surface treatment, plating or the like used in the present invention is water unless otherwise specified.

(2) "Chromate": Electrolytic chromate treatment A Cr layer with a loading amount of 10 μg / dm ² was deposited by electrolytic chromate treatment under the following conditions.
Liquid composition: potassium dichromate concentration 1 to 10 g / L, zinc concentration 0 to 5 g / L
pH: 3 to 4
Liquid temperature: 50 to 60 ° C
Current density: 0.1 to 3.0 A / dm ²

-"Organic substance": Organic layer formation process It carried out by showering and spraying aqueous solution of 40 degreeC of liquid temperature and pH 5 containing a density | concentration of 1-30 g / L for 20 to 120 seconds.
The thickness of the organic layer was 13 nm as a result of measuring the thickness of the organic layer by the method described above.

・ "Ni-Mo": Nickel-molybdenum alloy plating (Liquid composition) Nitric sulfate hexahydrate: 50 g / dm ³ , sodium molybdate dihydrate: 60 g / dm ³ , sodium citrate: 90 g / dm ³
(Liquid temperature) 30 ° C
(Current density) 1 to 4 A / dm ²
(Energization time) 3 to 25 seconds Ni adhesion amount: 3250 μg / dm ²
Mo adhesion amount: 420 μg / dm ²

・ "Cr": Chromium plating (Liquid composition) CrO ₃ : 200 to 400 g / L, H ₂ SO ₄ : 1.5 to ₄ g / L
(PH) 1 to 4
(Liquid temperature) 45-60 ° C
(Current density) 10 to 40 A / dm ²
(Energization time) 1 to 20 seconds Cr adhesion amount: 350 μg / dm ²

・ "Co-Mo": Cobalt-Molybdenum alloy plating (Liquid composition) Sulfuric acid Co: 50 g / dm ³ , Sodium molybdate dihydrate: 60 g / dm ³ , Sodium citrate: 90 g / dm ³
(Liquid temperature) 30-80 ° C
(Current density) 1 to 4 A / dm ²
(Energization time) 3 to 25 seconds Co adhesion amount: 420 μg / dm ²
Mo adhesion amount: 560 μg / dm ²

Ultra-thin copper layer formation Subsequently, on a roll-to-roll continuous plating line, an ultra-thin copper layer with a thickness of 0.6 to 5 μm is formed on the intermediate layer by electroplating under the conditions shown below. To produce a copper foil with a carrier.
Liquid composition: Copper concentration 30 to 120 g / L, sulfuric acid concentration 20 to 120 g / L, Cl ⁻ : 20 to 50 mass ppm, polyethylene glycol: 10 to 100 mass ppm, bis (3 sulfopropyl) disulfide: 10 to 30 mass ppm , Thiourea: 10 to 50 mass ppm
Liquid temperature: 20 to 80 ° C
Current density: 10 to 100 A / dm ²

  Next, any one of the roughening treatments (1) to (3) described in the table, or (1) and (3), (2) and (3), on the surface of the copper foil with carrier on the ultrathin copper layer side ) Were successively performed in this order, and further, each surface treatment of heat resistance treatment, rust prevention treatment, and silane coupling agent application was applied. In Comparative Example 3, no roughening treatment was performed. Each processing condition is shown below.

[Roughening treatment]
Roughening treatment (1) (Examples 1 and 7 and Comparative Example 1):
Electrolyte composition: Cu 25-40 g / L (added with copper sulfate pentahydrate, the same applies hereinafter), sulfuric acid 80-120 g / L
Liquid temperature: 20 to 40 ° C
Current density: 80 to 120 A / dm ²
Energization time: 0.5 to 1.5 seconds For the carrier side surface of the copper foil with a carrier subjected to the above roughening treatment (1) or the very thin copper layer side surface, for prevention of falling off of roughened particles and improvement of peel strength The plating was performed in a copper electrolytic bath consisting of sulfuric acid and copper sulfate. Cover plating conditions are described below.
Liquid composition: Copper concentration 20 to 40 g / L, sulfuric acid concentration 80 to 120 g / L
Liquid temperature: 20 to 40 ° C
Current density: 1 to 15 A / dm ²
Energization time: 1 to 3 seconds

Roughening treatment (2) (Examples 5 and 6, Comparative Example 2):
Liquid composition: Copper concentration 10 to 30 g / L (added with copper sulfate pentahydrate, the same shall apply hereinafter), sulfuric acid concentration 80 to 120 g / L
Liquid temperature: 15 to 30 ° C
Current density: 60 to 100 A / dm ²
Energization time: 1.0 to 1.5 seconds

A copper electrolytic bath consisting of sulfuric acid and copper sulfate on the carrier side surface of the copper foil with a carrier that has been subjected to the above roughening treatment (2) or on the very thin copper layer side surface in order to prevent the falling off of roughened particles and improve the peel strength. Cover plating was done. Cover plating conditions are described below.
Liquid composition: Copper concentration 20 to 40 g / L, sulfuric acid concentration 80 to 120 g / L
Liquid temperature: 40 to 50 ° C
Current density: 5 to 20 A / dm ²
Energization time: 1 to 6 seconds

Roughening treatment (3) (Examples 1 to 5, Comparative Examples 1 and 4):
Liquid composition: Copper concentration 10 to 20 g / L, cobalt concentration 1 to 10 g / L, nickel concentration 1 to 10 g / L
pH: 1 to 4
Liquid temperature: 30 to 50 ° C
Current density: 30 to 70 A / dm ²
Energization time: 0.1 to 1.0 seconds

In addition, when the current density of roughening treatment (1), (2) and (3) is high, the frequency of abnormal deposition is improved, and the number of particles of 1 μm or more increases. This can also be understood by comparing Example 1 with Comparative Example 1 and Example 6 with Comparative Example 2 described later.
Also in the roughening treatment (3), it is preferable to divide the energization into a plurality of times to set the current density lower. When the current density exceeds 70 A / dm ² , local current concentration occurs, and the coarsened particle density exceeding 1 μm in diameter starts to increase rapidly, and the other large number of coarsened particles smaller than 1 μm in diameter become too small. The adhesion with the ultrathin copper layer is impaired, and it becomes easy to drop off. In that case, the adhesion (peel strength) with the insulating resin also decreases. This can also be understood by comparing Examples 2 to 4 and Comparative Example 4.
In addition, the amount of current flow (the product of current density and current flow time) of plating in roughening treatment (1) and (2) is 50 to 90% of the current amount of roughening treatment. To prevent the

Co-Ni alloy plating and Zn-Ni alloy plating were performed on the ultrathin copper layer side surface of the copper foil with carrier roughened under the above conditions to form a heat-resistant layer. The plating conditions are described below.
Liquid composition: Cobalt concentration 1 to 30 g / L, Nickel concentration 1 to 30 g / L
pH: 1.0 to 3.5
Liquid temperature: 30 to 80 ° C
Current density 1 to 10 A / dm ²
Energization time: 1 to 10 seconds

[Heat resistant treatment]
Heat-resistant layer (zinc, nickel plating) formation processing:
Liquid composition: Nickel concentration 10 to 30 g / L, zinc concentration 1 to 15 g / L
Liquid temperature: 30 to 50 ° C
Current density 1 to 10 A / dm ²
Energization time: 1 to 10 seconds

[Antirust treatment]
・ Chromate treatment:
Liquid composition: Potassium dichromate concentration 3 to 5 g / L, zinc concentration 0.1 to 1 g / L
Liquid temperature: 30 to 50 ° C
Current density 0.1 to 3.0 A / dm ²
Energization time: 1 to 10 seconds

[Silane coupling treatment]
The silane coupling agent was applied and treated by spraying a solution of pH 7 to 8 containing 0.2 to 2% by weight of alkoxysilane.

2. Evaluation of Copper Foil with Carrier The copper foil with carrier obtained as described above was evaluated by the following method.
<Number of roughened particles>
Among coarsening particles constituting the roughening treatment layer, those having a diameter exceeding 1 μm in the range of 10 μm square and the number in the range of 10 μm square of the roughening particles having a diameter of 0.1 μm or more and 1 μm or less It measured by the method of. The size and number of particles were counted using a SEM photograph taken at 10000 ×. The measurement method of the particle size is separately sent by e-mail. An SEM photograph of 12.7 μm in width and 10.2 μm in height was measured in one field. The diameter of the roughened particles was the smallest diameter of the circle surrounding the roughened particles. The stacked roughened particles were determined as one roughened particle, and the diameter of the smallest circle surrounding the entire stacked roughened particles was taken as the diameter of the stacked roughened particles.

<Attachment amount per unit area of surface treatment layer>
The adhesion amount per unit area of the surface treatment layer was measured by the following method.
The weight (1) of the copper foil with carrier before roughening treatment of 10 cm square and the weight (2) of the copper foil with carrier after roughening treatment of 10 cm square are respectively measured, weight (1)-weight (2) The said adhesion amount was computed by the formula of.

The adhesion amount per unit area of the surface treatment layer can also be measured as follows.
<Thickness of ultra-thin copper layer>
The thickness of the ultra-thin copper layer of the produced copper foil with a carrier is observed using FIB-SIM (magnification: 10000-30000 times). Five sections are measured at intervals of 30 μm by observing the cross section of the ultrathin copper layer, and the average value is determined.
<Calculation of Weight B of Ultrathin Copper Layer>
The weight B of the ultrathin copper layer is calculated by the following equation.
Weight of ultra-thin copper layer B (g / cm ² ) = Thickness of ultra-thin copper layer (μm) × unit area (100 cm ² / cm ² ) × density of copper (8.94 g / cm ³ ) × 10 ⁻⁴ cm / μm)
<Calculation of adhesion amount of surface treatment layer>
Adhesion amount of surface treatment layer (g / m ² ) = ((weight of “very thin copper layer + surface treatment layer” A (measured with a sample of 10 cm square) (g / cm ² )) — weight of very thin copper layer B (g / cm ² )) × 10 ⁴ cm ² / m ²
<Measurement of Weight A of "Ultrathin Copper Layer + Roughened Layer"
The weight A of the "ultrathin copper layer + roughened layer" of the produced copper foil with carrier is measured by the following method.
First, after measuring the weight of the copper foil with carrier, the ultrathin copper layer with the roughening treatment layer is peeled off, the weight of the obtained carrier is measured, and the difference between the former and the latter is It was defined as the weight of the roughened layer. The ultrathin copper layer piece to be measured is a 10 cm square sheet punched out with a press.
The weight scale uses HF-400 manufactured by A & D Co., Ltd., and the press uses HAP-12 manufactured by Noguchi Press Co., Ltd.

<10-point average roughness after surface treatment>
About the ultrathin copper layer side surface of copper foil with a carrier after surface treatment, using Kosaka Research Institute Ltd. contact-type roughness meter Surfcorder SE-3C according to JIS B0601-1994, ten point average roughness Rz Was measured in the TD direction (lateral direction). Under the conditions of measurement reference length 0.8 mm, evaluation length 4 mm, cutoff value 0.25 mm, feed speed 0.1 mm / sec, the direction (TD, ie width) perpendicular to the traveling direction of the carrier in the carrier manufacturing device The measurement position was changed in the direction, and the measurement was performed ten times, and the average value of ten measurement values was taken as the value of the ten-point average roughness (Rz).

<Peel strength>
30 kgf / cm ^{2 in} air with respect to the resin base material (Mitsubishi Gas Chemical Co., Ltd. product: GHPL-832NX-A) from the copper foil with a carrier after the surface treatment of an Example and a comparative example from the ultra-thin copper layer side After laminating and laminating was performed by heating at 220 ° C. for 2 hours, the carrier was peeled off from the copper foil with carrier. Thereafter, the intermediate layer side surface of the exposed ultrathin copper layer was plated with copper, and the total thickness of the ultrathin copper layer and the copper plating layer was 18 μm. After that, JIS C 6471 (1995, the method of peeling the copper foil from the resin base material by the method of peeling the copper foil from the resin base material in the extremely thin copper layer and the copper plating layer is 8.1. (1) Peeling off was performed according to method A (a method of peeling the copper foil in the direction of 90 ° with respect to the copper foil-removed surface), and the peel strength at that time was measured.

<Transfer sheet dirt>
On the very thin copper layer side surface of copper foil with a carrier, transfer sheet dirt was evaluated by the following method.
・ Collecting area: Area 250000 mm ² (width 250 mm × length 1000 mm)
Cleaning roller used for collection: Nanocleen roller manufactured by Teknek (Techneck Japan Ltd.) After cleaning the very thin copper layer side surface with the above collection roller, a transfer sheet (transfer sheet model number: ARBS-1400) from the roller The powder was transferred to Subsequently, the transfer sheet was observed at 500 times using an optical microscope, and the roughened particles that had fallen off were observed to evaluate the stain of the transfer sheet.
The contamination of the transfer sheet was evaluated according to the following criteria.
◎: Drop-off roughened particles are not observed :: Drop-off roughened particles are hardly observed. (Less than 1 μm in diameter)
X: The roughening particle | grains (diameter 1 micrometer or more) which fell off were observed.
Test conditions and results are shown in Table 1 and Table 2.

(Evaluation results)
In Examples 1 to 7, in all cases, the falling off of the roughening particles in the roughening particle layer provided on the very thin copper layer side surface is favorably suppressed, and the copper foil with carrier having good peel strength is obtained. ing.
On the other hand, in all of Comparative Examples 1 to 4, the falling off of the roughening particles in the roughening particle layer provided on the very thin copper layer side surface was poor, or the peel strength was poor.
The surface SEM observation photograph after the roughening process of the copper foil of Example 2 is shown in FIG.
The surface SEM observation photograph after the roughening process of the copper foil of the comparative example 1 is shown in FIG.
The SEM observation photograph of the drop-off roughening particle | grains on the adhesive sheet of the comparative example 1 is shown in FIG.

Claims (22)

It is a copper foil with a carrier having a surface treatment layer including a carrier, an intermediate layer, an ultrathin copper layer, and a roughening treatment layer in this order, wherein the diameter of the roughening particles constituting the roughening treatment layer is 1 μm. Roughened particles having a diameter of not less than 5 in a range of 10 μm to 10 μm and having a diameter of 0.1 μm to 1 μm are present at a density of 500 to 3000 in a range of 10 μm .
The carrier attached copper foil in which the 10-point average roughness Rz of the ultrathin copper layer side surface of the carrier attached copper foil is 0.3 to 1.5 μm.   Among the roughening particles constituting the roughening treatment layer, those having a diameter of more than 1 μm are suppressed to 2 or less in a 10 μm square range, and 10 μm square of roughening particles having a diameter of 0.1 μm or more and 1 μm or less The copper foil with a carrier according to claim 1, wherein the density is in the range of 500 to 3,000.   Among the roughening particles constituting the roughening treatment layer, those having a diameter of more than 1 μm are suppressed to 2 or less in a 10 μm square range, and 10 μm square of roughening particles having a diameter of 0.1 μm or more and 1 μm or less The copper foil with a carrier according to claim 2, wherein the density is in the range of 2,000 to 3,000.   The copper foil with a carrier according to any one of claims 1 to 3, wherein the thickness of the ultrathin copper layer is 0.1 μm or more and 6 μm or less. The copper foil with a carrier according to any one of claims 1 to 4, wherein the adhesion amount per unit area of the surface treatment layer is 0.1 g / m ² or more and 5 g / m ² or less. The copper foil with a carrier according to claim 5, wherein the adhesion amount per unit area of the surface treatment layer is 0.8 g / m ² or more and 1.5 g / m ² or less. The copper foil with a carrier as described in any one of Claims 1-6 in which the roughening process layer is formed in the surface on the opposite side to the said ultra-thin copper layer of the said carrier. Any one or more selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium and zinc, and the roughened layer formed on the surface of the ultra-thin copper layer The copper foil with a carrier according to any one of claims 1 to 7 , which is a layer comprising an alloy containing The copper foil with a carrier according to any one of claims 1 to 8 , wherein a resin layer is provided on the surface of the roughened layer formed on the surface of the ultrathin copper layer. The surface of the roughening treatment layer formed on the surface of the ultrathin copper layer has one or more layers selected from the group consisting of a heat-resistant layer, an anticorrosion layer, a chromate treatment layer, and a silane coupling treatment layer. The copper foil with a carrier as described in any one of 1-8 . One or more layers selected from the group consisting of the heat-resistant layer, the rustproof layer, the chromate treatment layer, and the silane coupling treatment layer provided on the surface of the roughening treatment layer formed on the surface of the ultrathin copper layer The copper foil with a carrier according to claim 10 , wherein a resin layer is provided on the top. The copper foil with a carrier according to any one of claims 1 to 11 , wherein a resin layer is provided on the surface treatment layer surface. The copper foil with carrier according to any one of claims 9 , 11 and 12 , wherein the resin layer is a bonding resin. Copper foil with carrier according to any one of the claims 9 resin layer is a semi-cured resin, 11-13. Method for producing a laminate for producing a product Sotai using copper foil with carrier according to any one of claims 1-14. A laminate comprising a copper foil and resin coated carrier according to any one of claims 1-14, laminate part or all of the end face of the copper foil the carrier is covered with the resin . Method for manufacturing a printed wiring board using the copper foil with carrier to produce a print wiring board according to any one of claims 1-14. A process of preparing the copper foil with carrier according to any one of claims 1 to 14 and an insulating substrate,
Laminating the copper foil with carrier and the insulating substrate;
After laminating the copper foil with carrier and the insulating substrate, a copper-clad laminate is formed through a step of peeling the carrier of the copper foil with carrier.
And then forming a circuit by any of a semi-additive method, a subtractive method, a partial additive method or a modified semi-additive method. Forming a circuit on the ultra-thin copper layer-side surface of the copper foil with carrier according to any one of claims 1-14,
Forming a resin layer on the very thin copper layer side surface of the copper foil with carrier so that the circuit is buried;
Forming a circuit on the resin layer;
Separating the carrier after forming a circuit on the resin layer;
A process for producing a printed wiring board including the step of exposing a circuit embedded in the resin layer formed on the surface of the ultrathin copper layer by removing the ultrathin copper layer after peeling off the carrier. Method. A step of laminating the copper foil with carrier according to any one of claims 1 to 14 onto the resin substrate from the carrier side,
Forming a circuit on the very thin copper layer side surface of the copper foil with carrier;
Forming a resin layer on the very thin copper layer side surface of the copper foil with carrier so that the circuit is buried;
Forming a circuit on the resin layer;
Separating the carrier after forming a circuit on the resin layer;
A process for producing a printed wiring board including the step of exposing a circuit embedded in the resin layer formed on the surface of the ultrathin copper layer by removing the ultrathin copper layer after peeling off the carrier. Method. A step of laminating the resin substrate with the ultrathin copper layer side surface or the carrier side surface of the copper foil with carrier according to any one of claims 1 to 14 ,
Providing at least once two layers of a resin layer and a circuit on the very thin copper layer side surface opposite to the side laminated with the resin substrate of the copper foil with carrier or the carrier side surface;
The manufacturing method of the printed wiring board including the process of making the said carrier or the ultra-thin copper layer peel from the said copper foil with a carrier, after forming two layers of the said resin layer and a circuit. A process of laminating the carrier side surface of the copper foil with carrier according to any one of claims 1 to 14 and a resin substrate,
Providing at least once two layers of a resin layer and a circuit on the very thin copper layer side surface opposite to the side laminated with the resin substrate of the copper foil with carrier;
The manufacturing method of the printed wiring board including the process of making the said carrier peel from the said copper foil with a carrier, after forming two layers of the said resin layer and a circuit.