TW201504038A - Carrier copper foil, copper clad laminate, printed wiring board, electronic device, and copper foil with carrier - Google Patents

Abstract

An object of the present invention is to provide a copper foil with a carrier which can not deteriorate other characteristics of the copper foil to be attached and which does not increase the surface roughness of the extremely thin copper layer of the copper foil with a carrier. In the case, the adhesion strength between the ultra-thin copper layer and the resin substrate is increased, and the peel strength is increased. The copper foil with carrier of the present invention is provided with a carrier, an intermediate layer, an ultra-thin copper layer and a roughened layer in sequence, and the roughened layer is composed of roughened particles: the average diameter of the roughened particles is 0.05 ~1.3 μm, the average value of the average length is 0.3 to 3.0 μm, the difference between the maximum value and the minimum value of the above average diameter is divided by the average value of the above average diameters A{A=the maximum value of the average diameter of the roughened particles The difference (μm) from the minimum value / the average value (μm) of the average diameter of the roughened particles is 0.6 or less.

Description

Carrier copper foil, copper clad laminate, printed wiring board, electronic device, and copper foil with carrier

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

The printed wiring board is usually manufactured by forming a conductor pattern on the copper foil surface by etching after the insulating substrate is formed on the copper foil to form a copper clad laminate. With the increase in the demand for miniaturization and high performance of electronic devices in recent years, the high-density mounting of components and the high-frequency of signals have been developed, and the conductor pattern has been required to be miniaturized (fine pitch). Or high frequency response.

Corresponding to the micro-pitching, a copper foil having a thickness of 9 μm or less and a thickness of 5 μm or less has recently been required. However, since such an extremely thin copper foil has low mechanical strength, it is liable to be broken or wrinkled when manufacturing a printed wiring board, and thus the following is attached. The carrier copper foil is formed by using a metal foil having a thickness as a carrier and plating an extremely thin copper layer thereon via a release layer. The usual method of using the carrier copper foil is to bond the surface of the ultra-thin copper layer to the insulating substrate and thermocompression bonding, and then peel the carrier through the release layer.

Here, for the extremely thin copper layer of the copper foil with the carrier which is the adhesion surface of the resin The surface mainly requires sufficient peel strength of the extremely thin copper layer and the resin substrate, and the peel strength is sufficiently maintained after high-temperature heating, wet processing, welding, chemical treatment, and the like.

As a method of increasing the peel strength between the ultra-thin copper layer and the resin substrate, a typical method is to adhere a large amount of roughened particles to the extremely thin copper layer which increases the distribution (concavity and roughness) of the surface.

However, if such an extremely thin copper layer having a large distribution (concavity, roughness, and roughness) is used in a printed wiring board, in particular, a semiconductor package substrate in which a fine circuit pattern is required to be formed, unnecessary copper particles remain during circuit etching. Problems such as poor insulation between circuit patterns are generated.

Therefore, as a copper foil with a carrier which is used for a fine circuit mainly using a semiconductor package substrate, it is attempted to use a copper foil with a carrier which is not roughened on the surface of an extremely thin copper layer. The adhesion between the ultra-thin copper layer which is not subjected to the roughening treatment and the resin (peeling strength) is lower than that of the conventional carrier-attached copper foil due to its low distribution (concavity, roughness, roughness). The tendency (Patent Document 1).

[Previous Technical Literature]

[Patent Document 1] WO2004/005588

Therefore, further improvement is required regarding the copper foil with a carrier. An object of the present invention is to provide a copper foil with a carrier which can not deteriorate other characteristics of the copper foil to be attached and which does not increase the surface roughness of the extremely thin copper layer of the copper foil with a carrier. In this case, the adhesion strength between the ultra-thin copper layer and the resin substrate is increased, and the peel strength is increased.

In order to achieve the above object, the present inventors have repeatedly conducted intensive studies, and as a result, found that it is extremely effective to form an average value and an average value of the average value and the average length of the average diameter on the surface of the extremely thin copper layer of the copper foil with a carrier. The roughened layer composed of the roughened particles controlled by the difference between the maximum value and the minimum value of the diameter divided by the average value of the average diameter.

The present invention is based on the above findings, and is a copper foil with a carrier, which is provided with a carrier, an intermediate layer, an ultra-thin copper layer and a roughened layer in sequence, and the roughened layer is as follows The average particle diameter of the roughened particles is 0.05 to 1.3 μm, and the average length is 0.3 to 3.0 μm. The difference between the maximum value and the minimum value of the average diameter is divided by the average of the average diameters. The value obtained by the value A{A = the difference between the maximum value and the minimum value of the average diameter of the roughened particles (μm) / the average value (μm) of the average diameter of the roughened particles is 0.6 or less.

In one embodiment, the copper foil with a carrier of the present invention has an average value B of a ratio of an average length of the roughened particles to an average diameter of the roughened particles of 1.4 or more.

In another embodiment of the copper foil with a carrier of the present invention, the average value B of the ratio of the average length of the roughened particles to the average diameter of the roughened particles is 20 or less.

In still another embodiment of the copper foil with a carrier of the present invention, the difference between the maximum value and the minimum value of the average length of the roughened particles is divided by the average value of the average length of the roughened particles, C{C=rough The difference between the maximum value and the minimum value of the average length of the particles (μm) / the average value (μm) of the average length of the roughened particles is 0.5 or less.

In still another embodiment of the copper foil with a carrier of the present invention, the difference between the maximum value and the minimum value of the ratio of the average length of the roughened particles to the average diameter of the roughened particles is divided by a value obtained by the average value B of the ratio of the average length of the roughened particles to the average diameter of the roughened particles, D{D=the maximum ratio of the average length of the roughened particles to the average diameter of the roughened particles, and the ratio The difference / B} of the minimum value is 0.4 or less.

In still another embodiment of the copper foil with a carrier of the present invention, the resin layer is provided on the roughened layer.

In still another embodiment, the copper foil with a carrier of the present invention has a surface selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, and a decane coupling treatment layer on the surface of the roughened layer. More than one layer.

In still another embodiment, the copper foil with a carrier of the present invention has a resin layer on one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, and a decane coupling treatment layer. .

In still another embodiment of the copper foil with a carrier of the present invention, the resin layer is followed by a resin.

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

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

In still another embodiment of the copper foil with a carrier of the present invention, the resin layer is a block copolymerized polyimide resin layer or a resin containing a block copolymerized polyimide resin and a polysyntheimide compound. Floor.

In another aspect, the present invention is a copper foil with a carrier, which is provided with a carrier, an intermediate layer, an ultra-thin copper layer and a roughened layer in sequence, after laminating the resin layer on the roughened layer, The carrier and the intermediate layer are peeled off from the ultra-thin copper layer, and when the ultra-thin copper layer is removed by etching, the resin layer laminated on the roughened layer is laminated on the roughened layer. The average surface area of the surface of the resin layer having the unevenness of the surface of the roughened layer is 20% or more, and the maximum of the total area of the hole and the hole are The value E obtained by dividing the difference between the minimum values of the area totals by the average of the area occupied by the holes is 0.6 or less.

In still another embodiment of the copper foil with a carrier of the present invention, after the resin layer is laminated on the roughened layer, the carrier and the intermediate layer are peeled off from the ultra-thin copper layer, and then the etching is removed by etching. In the case of the ultra-thin copper layer, the surface of the resin layer laminated on the roughened layer on the side of the roughened layer has a surface on which the unevenness of the surface of the roughened layer is transferred. The average value of the area occupied by the pores on the surface of the resin layer is 20% or more, and the difference between the maximum value of the total area of the pores and the total area of the total area of the pores is divided by the average value of the total area of the pores. E is 0.6 or less.

In still another embodiment of the copper foil with a carrier of the present invention, the ten-point average roughness Rz of the surface of the surface of the roughened layer is 0.15 μm or more and 3.0 μm or less.

In still another embodiment of the copper foil with a carrier of the present invention, the intermediate layer, the ultra-thin copper layer, and the roughened layer are sequentially provided on both sides of the carrier.

In still another embodiment of the copper foil with a carrier of the present invention, the intermediate layer, the ultra-thin copper layer and the roughened layer are sequentially provided on one side of the carrier, and the other side of the carrier is roughened. Processing layer.

Further, the present invention is a resin layer having an area occupied by a hole of a surface of a resin layer which is formed by transferring unevenness of the surface of the roughened layer of the present invention. The average value of the sum is 20% or more, and the value E obtained by dividing the difference between the maximum value of the total area of the pores and the total area of the pores by the average of the area occupied by the pores is 0.6 or less.

The present invention, in still another aspect, is a printed wiring board produced by using the copper foil with a carrier of the present invention.

The present invention, in still another aspect, is an electronic device using the printed wiring board of the present invention.

In still another aspect, the present invention is a copper clad laminate which is produced by using the copper foil with a carrier of the present invention.

The present invention is a method for producing a copper foil with a carrier, which is a method for producing a copper foil with a carrier, an intermediate layer, an ultra-thin copper layer and a roughened layer, which is provided with tungsten ions. And/or an electrolytic bath composed of sulfuric acid and copper sulfate of an arsenic ion and an alkyl sulfate anion surfactant, and a roughened layer composed of copper roughened particles is formed on the surface of the ultra-thin copper layer.

In one embodiment of the method for producing a copper foil with a carrier according to the present invention, the electrolytic bath contains 2 to 100 mg/l of the surfactant.

In another embodiment of the method for producing a copper foil with a carrier according to the present invention, a plating treatment layer is formed on the roughened layer using an electrolytic bath composed of sulfuric acid and copper sulfate.

In still another embodiment of the method for producing a copper foil with a carrier according to the present invention, the heat-resistant and/or prevention element containing at least one element selected from the group consisting of zinc, nickel, copper and phosphorus is formed on the plating treatment layer. Rust layer.

In still another embodiment of the method for producing a copper foil with a carrier according to the present invention, a chromate treatment layer is formed on the heat resistant and/or rustproof layer.

In still another embodiment of the method for producing a copper foil with a carrier according to the present invention, a decane coupling treatment layer is formed on the chromate treatment layer.

According to still another aspect of the present invention, in a method of manufacturing a printed wiring board, the method includes the steps of: preparing a copper foil and an insulating substrate with a carrier of the present invention; laminating the copper foil and the insulating substrate with the carrier; and laminating the copper foil with the carrier Forming a copper clad laminate with the step of peeling off the carrier with the carrier copper foil after the insulating substrate, and then, by any of a semi-additive method, a subtractive method, a partial addition method or a modified semi-additive method The method forms a circuit.

According to still another aspect of the present invention, in a method of manufacturing a printed wiring board, the method includes the steps of: forming a circuit on a side surface of the ultra-thin copper layer of the copper foil with a carrier of the present invention; and attaching the circuit to the carrier a surface of the copper foil on the side of the ultra-thin copper layer forming a resin layer; forming a circuit on the resin layer; forming a circuit on the resin layer to peel off the carrier; and removing the ultra-thin copper layer after peeling off the carrier, thereby A circuit formed on the side surface of the ultra-thin copper layer and buried in the resin layer is exposed.

According to the present invention, it is possible to provide a copper foil with a carrier which can not deteriorate other characteristics of the copper foil to be supported and which does not increase the surface roughness of the extremely thin copper layer of the copper foil with a carrier. In this case, the adhesion strength between the ultra-thin copper layer and the resin substrate is increased, and the peel strength is increased. The copper foil with carrier of the present invention is used as a fine wiring and high frequency of printed wiring boards in recent years. It is extremely effective to form a copper foil with a carrier for forming a fine wiring such as a semiconductor package substrate which has been developed.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a conceptual diagram of the diameter and length of roughened particles in the present invention.

Fig. 2 is a reference view of the FIB-SIM photograph of the roughened layer profile in the evaluation of the average diameter and the average length of the roughened particles of the examples.

Fig. 3 is a view showing an example of the appearance of the surface of the resin.

Fig. 4 is a schematic view showing a cross-sectional view of a cross section in the width direction of the circuit pattern and a calculation method of an etching factor using the pattern.

<carrier>

The carrier of the copper foil with a carrier of the present invention may be a foil such as a copper foil, an aluminum foil, an aluminum alloy foil or an iron alloy, stainless steel, nickel or a nickel alloy. Further, in consideration of the ease of lamination of the intermediate layer on the carrier, the carrier is preferably a copper foil. The copper foil used for the carrier is typically provided in the form of a rolled copper foil or an electrolytic copper foil. Usually, an electrolytic copper foil is produced by electrically analyzing copper from a copper sulfate plating bath onto a titanium or stainless steel drum, and the rolled copper foil is repeatedly produced by plastic working and heat treatment by a calender roll. As the material of the copper foil, in addition to high-purity copper such as refined copper or oxygen-free copper, for example, a copper alloy containing Sn copper, Ag-containing copper, Cr, Zr or Mg, or the like may be used, and Ni and Si may be added. Corson is a copper alloy of copper alloy. Further, in the present specification, a copper alloy foil is also included in the term "copper foil" alone.

The thickness of the carrier which can be used in the present invention is not particularly limited, and may be appropriately adjusted so as to exhibit a suitable thickness as a carrier, and may be, for example, 12 μm or more. However, if it is too thick, the production cost becomes high, and therefore it is usually preferably 35 μm or less. Therefore, the thickness of the carrier is typically from 12 to 70 μm, more typically from 18 to 35 μm.

Further, a roughened layer may be provided on the surface of the carrier opposite to the surface on the side where the ultra-thin copper layer is provided. The roughening treatment layer may be provided by a known method or may be provided by a roughening treatment as described below. A roughening treatment layer is provided on a surface of the carrier opposite to the surface on the side where the ultra-thin copper layer is provided, and the carrier layer is provided on the support side of the resin substrate or the like on the surface side of the roughened layer. The advantage that the resin substrate becomes difficult to peel off. Furthermore, other layers may be provided between the carrier and the roughened layer.

<intermediate layer>

An intermediate layer is provided on the carrier. Other layers may also be provided between the carrier and the intermediate layer. The intermediate layer of the copper foil with carrier of the present invention preferably contains Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, or an alloy thereof, or a hydrate thereof, or It is formed by an oxide or a layer of any one or more of organic substances. The intermediate layer can also be a plurality of layers. For example, the intermediate layer is composed of a single metal layer composed of any one of elements such as Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, and Al from the carrier side, or is selected from the following layers. An alloy layer composed of one or more elements of an element group of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, and Al; and then selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti A layer composed of a hydrate or an oxide of one or more elements of the element group of W, P, Cu, and Al. Further, for example, the intermediate layer may be composed of two layers of Ni and Cr. The Ni layer is laminated in such a manner as to contact the interface with the carrier, and the Cr layer is laminated in such a manner as to contact the interface with the ultra-thin copper layer. The adhesion amount of Cr in the intermediate layer can be set to 10 to 100 μg/dm ² , and the adhesion amount of Ni can be set to 1000 to 40,000 μg/dm ² .

<very thin copper layer>

An extremely thin copper layer is provided on the intermediate layer. Other layers may be disposed between the intermediate layer and the ultra-thin copper layer. The extremely thin copper layer of the copper foil with carrier of the present invention can be formed by electroplating using an electrolytic bath of copper sulfate, copper pyrophosphate, copper sulfonate, copper cyanide or the like, since it is used in usual electrolytic copper foil. Copper foil can be formed at a high current density, and therefore a copper sulfate bath is preferred. The thickness of the ultra-thin copper layer is not particularly limited, and is usually thinner than the carrier, for example, 12 μm or less. Typically it is from 0.1 to 12 μm, more typically from 0.5 to 12 μm, and more typically from 2 to 5 μm. An extremely thin copper layer may also be provided on both sides of the carrier. Further, an intermediate layer, an ultra-thin copper layer, and the roughened layer may be provided in order on both sides of the carrier.

<Coarsening layer>

A roughened layer is formed on the surface of the ultra-thin copper layer. Other layers may be disposed between the ultra-thin copper layer and the roughened layer. The roughening treatment layer is composed of roughened particles having an average diameter of 0.05 to 1.3 μm and an average length of 0.3 to 3.0 μm. The "average diameter of the average diameter" of the roughened particles is shown on the surface of the roughened layer, and a plurality of portions are observed, and the average diameter of the roughened particles at each portion is measured, and the average of the plurality of average diameters is calculated. The value. The "average value of the average length" of the roughened particles is shown in the cross section of the roughened layer, and each of the portions is observed, and the average length of the roughened particles at each portion is measured, and the average is calculated based on the plurality of average lengths. The value obtained. Here, the "length" of the roughened particles is the height of the unevenness of the roughened particles observed in the cross section of the roughened layer. Further, the concept of the diameter and length of the roughened particles in the present invention is shown in Fig. 1.

The average value of the average diameter of the roughened particles constituting the roughened layer is When the thickness is 0.05 μm or more, the average value of the peel strength is improved. Further, since the average value of the average diameter of the roughened particles is 1.3 μm or less, the etching factor is improved. Further, since the average value of the average length of the roughened particles constituting the roughened layer is 0.3 μm or more, the average value of the peel strength is improved. Further, since the average value of the average length of the roughened particles is 3.0 μm or less, the etching factor is improved. The average value of the average diameter of the roughened particles constituting the roughened layer of the present invention is preferably 0.08 μm or more and 1.2 μm or less, more preferably 0.1 μm or more and 1.0 μm or less, and still more preferably 0.1 μm or more and 0.8 μm or less. More preferably, it is 0.1 μm or more and 0.7 μm or less, and more preferably 0.15 μm or more and 0.6 μm or less. Further, the average value of the average length of the roughened particles constituting the roughened layer of the present invention is preferably 0.4 μm or more and 2.8 μm or less, more preferably 0.5 μm or more and 2.6 μm or less, still more preferably 0.6 μm or more and 2.3. The thickness is preferably not more than 0.7 μm and not more than 2.0 μm, more preferably from 0.8 μm to 1.8 μm.

The value obtained by dividing the difference between the maximum value and the minimum value of the average diameter of the roughened particles of the roughened layer of the copper foil with carrier of the present invention divided by the average value of the average diameter A{A=the maximum diameter of the roughened particles The difference between the value and the minimum value (μm) / the average value (μm) of the average diameter of the roughened particles is 0.6 or less. With such a configuration, there is an effect that the unevenness of the average value of the peel strength is small. The upper limit of the value A is preferably 0.55 or less, more preferably 0.5 or less, still more preferably 0.45 or less, still more preferably 0.4 or less. The lower limit of the value A need not be particularly set, and is typically 0.001 or more, or 0.01 or more, or 0.05 or more.

The copper foil with a carrier of the present invention preferably has an average value B of a ratio of an average length of the roughened particles to an average diameter of the roughened particles of 1.4 or more. With such a configuration, the average value of the peel strength is improved. The ratio B is preferably 20 or less. With this configuration, there is an etching factor Improve the effect. The ratio B is more preferably 1.6 or more and 15 or less, still more preferably 1.6 or more and 15 or less, still more preferably 2.0 or more and 10 or less, still more preferably 2.2 or more and 7 or less, still more preferably 2.4 or more. 5 or less.

In the copper foil with carrier of the present invention, the difference between the maximum value and the minimum value of the average length of the roughened particles is divided by the average value of the average length of the roughened particles in the roughened layer C{C=rough The difference between the maximum value and the minimum value of the average length of the particles (μm) / the average value (μm) of the average length of the roughened particles is 0.5 or less. With such a configuration, there is an effect that the unevenness (standard deviation) of the etching factor becomes small. The value C is more preferably 0.48 or less, still more preferably 0.45 or less, and still more preferably 0.4 or less. The lower limit of the value C need not be particularly set, and is typically 0.001 or more, or 0.01 or more, or 0.05 or more.

In the roughened layer of the copper foil of the present invention, the difference between the maximum value of the ratio of the average length of the roughened particles to the average diameter of the roughened particles and the minimum value of the ratio is divided by the coarse particles. a value obtained by the average value B of the ratio of the average length to the average diameter of the roughened particles D{D=the maximum value of the ratio of the average length of the roughened particles to the average diameter of the roughened particles and the minimum value of the above ratio The difference /B} is 0.4 or less. With such a configuration, there is an effect that the unevenness of the etching factor becomes small. The value D is more preferably 0.38 or less, still more preferably 0.35 or less, still more preferably 0.3 or less. The lower limit of the value D need not be particularly set, and is typically 0.001 or more, or 0.01 or more, or 0.05 or more.

Preferably, the copper foil with a carrier of the present invention has a roughened layer on the surface of the ultra-thin copper layer, and after the resin layer is laminated on the roughened layer, the carrier and the intermediate layer are peeled off from the ultra-thin copper layer, and then borrowed. When the ultra-thin copper layer is removed by etching, the surface of the resin layer laminated on the roughened layer on the side of the roughened layer has the unevenness of the surface of the roughened layer. The average value of the total area of the pores on the surface of the resin layer of the unevenness is 20% or more, and the difference between the maximum value of the total area of the pores and the minimum of the total area of the pores is divided by the average of the total area of the pores. The value E is 0.6 or less. With such a configuration, there is an effect that the unevenness of the etching factor becomes small. Further, there is an effect that the peel strength of the resin and the ultra-thin copper layer is improved and the unevenness of the peel strength is small. The average value of the total area of the pores on the surface of the resin layer having the unevenness of the surface of the roughened layer is preferably 25% or more, more preferably 30% or more, and still more preferably 35%. The above is more preferably 40% or more, still more preferably 45% or more, and still more preferably 50% or more. The upper limit of the average value need not be specifically set, and is typically 99% or less, or 97% or less, or 96% or less. Further, the value E is more preferably 0.55 or less, still more preferably 0.50 or less, still more preferably 0.45 or less, still more preferably 0.40 or less. The lower limit of the value E need not be particularly set, and is typically 0.001 or more, or 0.01 or more, or 0.05 or more.

Further, the copper foil with a carrier of the present invention preferably has a surface roughness Rz (ten-point average roughness (JIS B0601 1994)) having a surface of the roughened layer of 0.15 μm or more and 3.0 μm or less. When the surface roughness Rz is less than 0.15 μm, the peel strength is extremely deteriorated. When the surface roughness Rz is more than 3.0 μm, there is a case where the etching factor becomes large. The surface roughness Rz is preferably 0.2 μm or more and 2.5 μm or less, more preferably 0.3 μm or more and 2.0 μm or less, more preferably 0.35 μm or more and 1.5 μm or less, still more preferably 0.4 μm or more and 1.3 μm or less, and more preferably It is 0.4 μm or more and 1.0 μm or less, more preferably 0.45 μm or more and 1.0 μm or less.

The copper foil with a carrier of the present invention may have an intermediate layer, an extremely thin copper layer and a roughened layer on one side of the carrier, and a roughened layer on the other side of the carrier.

<With carrier copper foil>

The carrier copper foil is provided with the above carrier, an intermediate layer formed on the carrier, and laminated on the intermediate layer An extremely thin copper layer and a roughened layer formed on the extremely thin copper layer. The method of using the carrier copper foil itself is well known. For example, the surface of the ultra-thin copper layer can be bonded to the paper substrate phenol resin, paper substrate epoxy resin, synthetic fiber cloth substrate epoxy resin, glass cloth - Paper composite substrate epoxy resin, glass cloth-glass non-woven composite substrate epoxy resin and glass cloth substrate epoxy resin, polyester film, polyimide film, liquid crystal polymer (LCP) film, fluororesin film, etc. After the thermal insulating material is bonded to the insulating substrate, the carrier is peeled off, and then a plating resist is provided on a portion of the surface of the ultra-thin copper layer of the insulating substrate where no wiring is provided, and then wiring is provided by plating, and then the plating resist is removed. Thereafter, an extremely thin copper foil in which no wiring is provided is removed by etching, thereby finally producing a printed wiring board. In the case of the copper foil with carrier of the present invention, the peeling site is mainly the interface between the carrier and the intermediate layer or the interface between the intermediate layer and the ultra-thin copper layer. Further, in the case where the intermediate layer is composed of a plurality of layers, there is a case where peeling occurs at the interface of the plurality of layers.

<Method for Producing Carrier Copper Foil>

In the method for producing a copper foil with a carrier according to the present invention, an electrolytic bath composed of sulfuric acid and copper sulfate containing an alkyl sulfate-based anionic surfactant is used to form roughened particles of copper on the surface of the ultra-thin copper layer. The roughened layer is formed. Surfactants are widely used industrially as additives for plating. However, in the electrolytic solution used for the roughening treatment of the ultra-thin copper layer with the carrier copper foil, there is no example of adding a surfactant, and there is no precedent for the technique for improving the bonding strength. It was confirmed that the alkyl sulfate-based anionic surfactant used in the invention of the present invention imparts significant peel strength to the copper foil with a carrier. The effect of the alkyl sulfate-based anionic surfactant has not yet been clearly put into theory. It can be considered that the hydrophilic group of the surfactant is disposed in some form on the Cu ion in the electrolyte, or the surfactant molecule is adsorbed on the surfactant. The specific portion of the surface to be plated changes the plated morphology of the roughened particles. As a result, it is considered that the current is convex and concave. The concentration of the convex portion of the plated surface of the extremely thin copper layer is suppressed, and the concave portion (the valley portion of the primary particles) which is difficult to be plated by the roughened particles is generally uniformly plated, and the plated surface and the plated surface of the extremely thin copper layer are otherwise The adhesion of the roughened particles of the plating is improved. As a result, the peel strength between the ultra-thin copper layer and the resin substrate such as the resin substrate for a printed wiring board is improved. Further, when the surface layer having the roughened layer of the ultra-thin copper layer is laminated on the resin substrate, and the ultra-thin copper layer is completely removed by etching, the roughening is performed by the resin substrate to be transferred. The average value of the area ratio of the pores obtained by the unevenness of the particles becomes an appropriate value. As a result, when an electroless plating layer or a plating layer is provided on the surface of the resin substrate on which the unevenness of the roughened particles is transferred, the adhesion between the resin substrate and the electroless plating layer and/or the plating layer is improved.

The concentration of the above surfactant is preferably from 2 to 100 mg/l. A concentration higher than this range also exhibits the same effect, but foaming of the electrolytic solution caused by the addition of the surfactant becomes remarkable, and practical operation becomes difficult. When the concentration is less than the range, there is a case where the unevenness of the average diameter of the roughened particles becomes large. Further, in the roughening treatment electrolytic bath, in addition to the above-mentioned surfactant, by adding tungsten ions and/or arsenic ions to the roughening electrolytic bath, the average diameter of the roughened particles can be reduced, and as a result, The adhesion (peeling strength) between the copper foil and the resin substrate can be improved. Thereby, the copper foil with a carrier which improves the adhesiveness (peeling strength) of the ultra-thin copper layer and resin is obtained. Further, by transferring the unevenness of the roughened layer of the carrier-attached copper foil to the resin, a copper foil with a carrier which can improve the adhesion between the resin and electroless plating or electroplating can be obtained.

Typical roughening treatment conditions of the present invention are as follows.

(liquid composition 1)

Cu: 5~30g/L (added in the form of copper sulfate pentahydrate, the same below)

H ₂ SO ₄ : 10~200g/L

Sodium dodecyl sulfate: 2~100mg/l

In addition, unless otherwise indicated, the balance of the treatment liquid used for surface treatment, plating, etc. of this invention is water.

(plating conditions)

Temperature: 60~70°C

Current density: 21~39A/dm ² (above the limit current density of the bath)

Roughening processing time: 1~20 seconds

Power consumption: 21~600As/dm ²

Linear flow rate of plating solution: 1.5~3.0m/s

Furthermore, in the present case, the linear flow rate of the plating solution in the roughening treatment is made higher than the previous one, the plating solution temperature is higher than the previous one, and the current density and the roughening treatment time are set to a specific range, and the manufacturing is successful. The unevenness of the particle size or length of the roughened particles is smaller than that of the prior carrier copper foil. This reason is not clear, and it is considered that one factor is that the material moving speed of Cu ions is improved by setting the above conditions.

In addition to the above liquid composition 1, one or both of the following As and W components are added.

(selective liquid composition 2)

As: 350~2000mg/l

W (added with tungstate): 1~10mg/l

Further, in order to prevent the coarse particles from falling off and to improve the peel strength, a plating treatment is performed on the roughened layer by an electrolytic bath composed of sulfuric acid-copper sulfate. Further, a heat-resistant and rust-preventive layer containing at least one element selected from the group consisting of zinc, nickel, copper, and phosphorus may be formed thereon. Moreover, a chromate treatment layer can be formed on the heat-resistant and rust-proof layer, and further formed on the chromate treatment layer The decane coupling treatment layer. As the plating treatment, heat resistance, rust prevention treatment, chromate treatment, and decane coupling agent combined with the present invention, a conventional heat-resistant and rust-preventive layer can be used.

The processing conditions of the plating treatment are as follows. Further, the plating solution is not particularly limited, and a known plating solution can be used. Specific examples will be given below.

(liquid composition)

Cu: 70~100g/l (added as copper sulfate pentahydrate)

H ₂ SO ₄ : 50~150g/l

(liquid temperature)

50~70°C

(current condition)

Current density: 12~37A/dm ² (below the limit current density of the bath)

Plating time: 2~20 seconds

Linear flow rate of plating solution: 1.5~3.0m/s

Furthermore, in the present case, by making the linear flow rate of the plating solution in the plating process higher than before, the plating solution temperature is higher than before, the Cu concentration is higher than before, and the current density and the roughening processing time are made specific. The range, and the unevenness in the particle size or length of the successfully produced roughened particles is smaller than that of the prior carrier copper foil. This reason is not clear, and it is considered that one factor is that the material moving speed of Cu ions is improved by setting the above conditions.

The heat-resistant and rust-preventing layer provided on the surface of the roughening treatment layer is not particularly limited, and a known treatment can be used.

For example, an elemental alloy of nickel, cobalt, copper, or zinc or an element containing one or more elements selected from the group consisting of nickel, cobalt, copper, and zinc may be used to form a heat-resistant layer or a rust-proof layer on the surface of the roughened layer. Further, the surface may be subjected to a treatment such as chromate treatment or decane coupling treatment.

Further, the surface may be subjected to a treatment such as chromate treatment or decane coupling treatment. In other words, one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventive layer, a chromate-treated layer, and a decane coupling treatment layer may be formed on the surface of the roughened layer.

Further, the heat-resistant layer, the rust-preventing layer, the chromate-treated layer, and the decane coupling treatment layer may be formed in a plurality of layers (for example, two or more layers, three or more layers, or the like).

For example, for the copper foil for printed wiring boards, a brass coating layer can be used as the heat-resistant layer or the rust-preventive layer previously used. Specific examples will be given below.

(liquid composition)

NaOH: 40~200g/l

NaCN: 70~250g/l

CuCN: 50~200g/l

Zn(CN) ₂ : 2~100g/l

As ₂ O ₃ : 0.01~1g/l

(liquid temperature)

40~90°C

(current condition)

Current density: 1~50A/dm ²

Plating time: 1~20 seconds

The chromate treatment layer may use an electrolytic chromate treatment layer or a dip chromate treatment layer. The chromate treatment layer preferably has a Cr content of 25 to 150 μg/dm ² . When the amount of Cr is less than 25 μg/dm ² , there is a possibility that the effect of the rust preventive layer is not generated. Further, when the amount of Cr exceeds 150 μg/dm ² , there is a possibility that the effect is saturated. Further, an element other than Cr such as Zn may be contained in the chromate-treated layer. An example of the conditions for forming a chromate treatment layer is described below. However, it is not necessary to be limited to this condition, and any known chromate treatment can be used. The rust-preventing treatment is one of the factors affecting the acid resistance, and the acid resistance is further improved by the chromate treatment.

(impregnated chromate treatment)

K ₂ Cr ₂ O ₇ : 1~5g/l, pH: 2.5~5.5, temperature: 25~60°C, time: 0.5~8 seconds

(electrolytic chromium, zinc treatment)

K ₂ Cr ₂ O ₇ (Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2-10 g/l, ZnOH or ZnSO ₄ . 7H ₂ O: 0.05~10g/l, pH: 2.5~5.5, bath temperature: 20~80°C, current density: 0.05~5A/dm ² , time: 0.1~10 seconds

As the decane coupling agent used in the copper foil with a carrier of the present invention, any decane coupling agent which is usually used for the copper foil can be used without particular limitation. For example, as a decane coupling agent treatment, a 0.2% epoxy decane aqueous solution can be sprayed onto the roughened surface of the copper foil, and then dried. The choice of the decane coupling agent is arbitrary, and it is preferable to consider the affinity with the resin substrate laminated with the ultra-thin copper layer.

The carrier-coated copper foil may have one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, and a decane coupling treatment layer on the roughened layer formed on the ultra-thin copper layer. Further, a resin layer may be provided on the roughened layer.

Further, the heat-treated layer and the rust-preventing layer may be provided on the roughened layer, and a chromate-treated layer may be provided on the heat-resistant layer or the rust-preventing layer, and a decane coupling may be provided on the chromate-treated layer. Processing layer. Further, a resin layer may be provided on one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, and a decane coupling treatment layer.

The resin layer may be an adhesive or an insulating resin layer which is used in a semi-hardened state (B-stage state). The semi-hardened state (B-stage state) includes a state in which the insulating resin layer can be stored in a superposed manner even if the surface is not in contact with the finger, and the insulating resin layer can be stored in a superposed manner.

Further, the resin layer may be an undercoat layer. In the present invention, the "undercoat layer" means a resin layer which allows the electroless copper plating layer and the resin substrate to be particularly firmly adhered. Further, the resin layer may be a block copolymerized polyimide resin layer or a resin layer containing a block copolymerized polyimide resin and a polysynyleneimine compound.

For example, the block copolymerized polyimine is represented by the following formula (1): general formula (2) = 3:2, and has a number average molecular weight: 70,000 and a weight average molecular weight: 150,000.

Further, examples of the polym-butylene iminoimide compound include bis(4-maleoximeimidephenyl)methane (BMI-H, K-I formation).

Further, the resin layer may contain a thermosetting resin or a thermoplastic resin. Further, the resin layer may contain a thermoplastic resin. The type thereof is not particularly limited, and examples thereof include an epoxy resin, a polyimide resin, a polyfunctional cyanate compound, and maleimide. A resin such as a compound, a polyvinyl acetal resin or a urethane resin is preferable.

The resin layer may contain a known resin, a resin curing agent, a compound, a curing accelerator, and a dielectric (any dielectric containing an inorganic compound and/or an organic compound, a dielectric containing a metal oxide, or the like may be used. Body), reaction catalyst, crosslinking agent, polymer, prepreg, framework material, and the like. Further, the above-mentioned resin layer can be used, for example, in International Publication No. WO2008/004399, International Publication No. WO2008/053878, International Publication No. WO2009/084533, Japanese Patent Laid-Open No. Hei No. Hei No. Hei No. Hei No. Hei. Japanese Patent No. 3,184,485, International Publication No. WO97/02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179772, Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003 -304068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003-249739, Japanese Patent No. 4136509, Japanese Patent Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Laid-Open No. 2004-349654, Japanese Patent No. 4286060 No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent Laid-Open No. 2005-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004/005588, Japanese Patent Publication No. 2006-257153 , Japanese Patent Laid-Open No. 2007-326923, Japanese Patent Laid-Open No. 2008-111169, Japanese Patent No. 5024930, International Publication No. WO2006/028207, Japanese Patent No. 4828427, Japanese Patent Laid-Open No. 2009-67029, International The opening number is WO2006/134868, Japanese Patent No. 5046927, Japanese Patent Laid-Open No. 2009-173017, International Publication No. WO2007/105635, Japanese Patent No. 5180815, International Publication No. WO2008/114858, International Publication No. WO2009/008471, Japan Special Opening Substances (resin, resin hardener, compound, hardening accelerator) described in No. 2011-14727, International Publication No. WO2009/001850, International Publication No. WO2009/145179, International Publication No. WO2011/068157, and Japanese Patent Laid-Open No. 2013-19056 Dielectric Formed by a method of forming a body, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and the like, and/or a resin layer.

The resin is dissolved in a solvent such as methyl ethyl ketone (MEK) or toluene to prepare a resin liquid, which is applied onto the ultra-thin copper layer, or the heat-resistant layer, by, for example, a roll coating method. The rust layer or the chromate-treated layer or the decane coupling treatment layer is then heated and dried as necessary to remove the solvent to form a B-stage state. Drying may be carried out, for example, using a hot air drying oven, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C.

The copper foil with a carrier (the copper foil with a resin) which has the above-mentioned resin layer is used in the following aspect: after superposing the resin layer on the base material, the whole resin layer is thermo-compressed, and the resin layer is thermally hardened. Then, the carrier is peeled off to expose an extremely thin copper layer (of course, the surface of the intermediate layer side of the extremely thin copper layer is exposed), and a specific wiring pattern is formed thereon.

When the copper foil with a carrier attached to the resin is used, the number of used prepreg materials for manufacturing the multilayer printed wiring board can be reduced. Further, the thickness of the resin layer is such that the thickness of the interlayer insulation can be ensured, and the copper clad laminate can be produced without using the prepreg material at all. Further, at this time, the surface of the substrate may be primed with an insulating resin to further improve the smoothness of the surface.

Further, when the prepreg material is not used, the material cost of the prepreg material is saved, and the lamination step is also simplified, which is economically advantageous, and has the following advantages: the multilayer printed wiring board manufactured The thickness of the prepreg is equivalent to the thickness of the prepreg, and it is possible to manufacture a very thin multilayer printed wiring board having a thickness of 100 μm or less.

The thickness of the resin layer is preferably from 0.1 to 80 μm.

When the thickness of the resin layer is thinner than 0.1 μm, the adhesion force is lowered, and when the pre-impregnated material is not interposed, the copper foil with a carrier attached to the resin is laminated on the substrate having the inner layer material. It becomes difficult to ensure the interlayer insulation between the circuits of the inner layer material.

On the other hand, when the thickness of the resin layer is thicker than 80 μm, it becomes difficult to form the resin layer of the target thickness in the coating step once, and the extra material cost and the number of steps are required, which is disadvantageous in terms of economy. Further, since the resin layer to be formed is inferior in flexibility, cracks and the like are likely to occur during handling, and excessive resin flow occurs when the inner layer material is thermocompression bonded, and smooth laminate formation becomes difficult.

Further, as another product form of the copper foil with a carrier to which the resin is attached, the resin layer may be coated on the roughened layer of the ultra-thin copper layer or the heat-resistant layer or the rust-preventing layer on the roughened layer. Alternatively, the chromate treatment layer or the decane coupling treatment layer is formed into a semi-hardened state, and then the carrier is peeled off and produced in the form of a resin-attached copper foil in the absence of a carrier.

<Printed wiring board and copper clad laminate>

The copper foil with a carrier is attached to the insulating resin plate from the side of the ultra-thin copper layer and thermocompression bonded, and the carrier is peeled off, whereby a copper clad laminate can be produced. Further, thereafter, the copper circuit of the printed wiring board can be formed by etching the extremely thin copper layer portion. The insulating resin sheet used herein is not particularly limited as long as it has characteristics suitable for a printed wiring board. For example, a rigid PWB can be used as a paper base phenol resin, a paper base epoxy resin, or a synthetic fiber base. Epoxy resin, glass cloth-paper composite substrate epoxy resin, glass cloth-glass non-woven composite substrate epoxy resin and glass cloth substrate epoxy resin, FPC can use polyester film or polyimide film Wait. The printed wiring board and the copper-clad laminate produced in the above manner can be mounted on various electronic components that are required to be mounted at high density.

<Method of Manufacturing Printed Wiring Board>

In one embodiment of the method for manufacturing a printed wiring board, the method includes the following steps: preparing the hair The carrier copper foil and the insulating substrate are provided; the copper foil and the insulating substrate are laminated; and the copper foil and the insulating substrate are laminated on the side of the ultra-thin copper layer and the insulating substrate, and then the copper foil with the carrier is peeled off. A copper clad laminate is formed by the step of the carrier, and thereafter, the circuit is formed by any one of a semi-additive method, a modified semi-additive method, a partial addition method, and a subtractive method. The insulating substrate can also be made to have an inner layer circuit.

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

Therefore, in an embodiment of the method for producing a printed wiring board of the present invention using a semi-additive method, the method includes the steps of: preparing a copper foil and an insulating substrate with a carrier of the present invention; and laminating the copper foil and the insulating substrate with the carrier; After laminating the carrier-attached copper foil and the insulating substrate, the carrier with the carrier copper foil is peeled off; and the ultra-thin copper layer exposed by peeling off the carrier is removed by etching or plasma etching using an acid or the like; Providing a through hole or/and a blind hole in the resin exposed by removing the ultra-thin copper layer by etching; performing desmear treatment on the region including the above-mentioned pair of perforations or/and blind holes; The electroless plating layer is disposed on the region of the perforated or/and blind via hole; the plating resist is disposed on the electroless plating layer; the plating resist is exposed, and then the plating resist is removed from the region where the circuit is to be formed. Providing a plating layer in the region where the above-mentioned plating resist is removed to form a circuit; removing the plating resist; removing the region outside the region where the circuit is to be formed by flash etching or the like The electroless plating.

In another embodiment of the method for producing a printed wiring board of the present invention using a semi-additive method, the method includes the steps of: preparing a copper foil and an insulating substrate with a carrier of the present invention; and laminating the copper foil and the insulating substrate with the carrier; After laminating the above-mentioned carrier copper foil and the insulating substrate, the carrier with the carrier copper foil is peeled off; the peeling is performed by etching or plasma using an etching solution such as acid The ultra-thin copper layer exposed by the carrier is completely removed; an electroless plating layer is disposed on a surface of the resin exposed by removing the ultra-thin copper layer by etching; a plating resist is disposed on the electroless plating layer; The resisting agent is exposed, and then the plating resist is removed from the region where the circuit is to be formed; the plating layer is disposed in the region where the plating resist is removed to form the circuit; the plating resist is removed; by flashing, etc. The electroless plating layer and the ultra-thin copper layer in the region other than the region where the circuit is to be formed are removed.

In the present invention, the modified semi-additive method refers to a method of laminating a metal foil on an insulating layer, protecting a non-circuit forming portion by a plating resist, and increasing a copper thickness of the circuit forming portion by electroplating. The plating resist is removed, and the metal foil other than the circuit forming portion is removed by etching (flash) to form an electric circuit on the insulating layer.

Therefore, in an embodiment of the method of manufacturing a printed wiring board of the present invention using the improved semi-additive method, the method comprises the steps of: preparing a copper foil with an insulating substrate of the present invention and an insulating substrate; laminating the copper foil with the carrier and insulating the carrier a substrate; after laminating the carrier-attached copper foil and the insulating substrate, peeling off the carrier of the carrier-attached copper foil; and providing a pair of perforations or/and blind vias on the extremely thin copper layer and the insulating substrate exposed by peeling off the carrier; The area of the perforation or/and the blind hole is subjected to desmear treatment; the electroless plating layer is disposed on the region containing the perforation or/and the blind hole; and the plating resist is disposed on the surface of the extremely thin copper layer exposed by peeling off the carrier; After the plating resist is provided, a circuit is formed by electroplating; the plating resist is removed; and the ultra-thin copper layer exposed by removing the plating resist is removed by flash etching.

Further, the step of forming a circuit on the resin layer may be performed by bonding another copper foil with a carrier to the resin layer from the side of the ultra-thin copper layer, and forming a copper foil with a carrier adhered to the resin layer. The steps of the above circuit. Further, another carrier copper to be attached to the above resin layer The foil may be a copper foil with a carrier of the present invention. Further, the step of forming a circuit on the above resin layer can be carried out by any one of a semi-additive method, a subtractive method, a partial addition method or a modified half-addition method. Further, the copper foil with a carrier on the surface forming circuit may include a substrate or a resin layer on the surface of the carrier of the copper foil with the carrier.

In another embodiment of the method for producing a printed wiring board of the present invention using the modified semi-additive method, the method includes the steps of: preparing a copper foil with an insulating substrate of the present invention and an insulating substrate; and laminating the copper foil and the insulating substrate with the carrier After laminating the carrier-attached copper foil and the insulating substrate, the carrier with the carrier copper foil is peeled off; a plating resist is disposed on the extremely thin copper layer exposed by peeling off the carrier; and the plating resist is exposed, and thereafter Removing a plating resist in a region where the circuit is to be formed; providing a plating layer in the region where the plating resist is removed to form the circuit; removing the plating resist; removing the region in the circuit to be formed by flash etching or the like Electroless plating and ultra-thin copper layers in areas other than those.

In the present invention, the partial addition method refers to a method of providing a catalyst to a substrate on which a conductor layer is provided, and a substrate formed by piercing a hole for a via hole or a via hole as needed. The core is etched to form a conductor circuit, and if a solder resist or a plating resist is provided as needed, a via hole or a via hole is thickened by electroless plating on the conductor circuit, thereby manufacturing a printed wiring board. .

Therefore, in an embodiment of the method of manufacturing a printed wiring board of the present invention using a partial addition method, the method comprises the steps of: preparing a copper foil and an insulating substrate with a carrier of the present invention; and laminating the copper foil and the insulating substrate with the carrier; After laminating the above-mentioned carrier copper foil and the insulating substrate, the carrier with the carrier copper foil is peeled off; the ultra-thin copper layer exposed on the carrier is peeled off and the insulating substrate is provided with a pair of perforations or/and blind via holes; / and the area of the blind hole for degumming a slag treatment; a catalyst core is provided to the region containing the perforation or/and the blind hole; an etching resist is disposed on the surface of the extremely thin copper layer exposed by peeling off the carrier; and the etching resist is exposed to form a circuit pattern; The ultra-thin copper layer and the catalyst core are removed by etching or plasma etching using an etching solution such as an acid to form a circuit; the etching resist is removed; and etching or plasma etching using an etching solution such as an acid is used. The step of providing a solder resist or a plating resist on the surface of the insulating substrate exposed by the ultra-thin copper layer and the catalyst core; and providing an electroless plating layer in a region where the solder resist or the plating resist is not provided.

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

Therefore, in an embodiment of the method for producing a printed wiring board of the present invention using the subtractive method, the method includes the steps of: preparing the copper foil and the insulating substrate with a carrier of the present invention; and laminating the copper foil and the insulating substrate with the carrier; After laminating the above-mentioned carrier copper foil and the insulating substrate, the carrier with the carrier copper foil is peeled off; the ultra-thin copper layer exposed on the carrier is peeled off and the insulating substrate is provided with a pair of perforations or/and blind holes; And the area of the blind hole is subjected to desmear treatment; an electroless plating layer is disposed on the surface containing the above-mentioned perforated or/and blind holes; a plating layer is disposed on the surface of the electroless plating layer; and the electroplated layer or/and the above-mentioned ultra-thin copper An etching resist is disposed on the surface of the layer; the etching resist is exposed to form a circuit pattern; and the ultra-thin copper layer, the electroless plating layer and the plating layer are removed by etching or plasma etching using an etching solution such as acid Forming a circuit; removing the above etch resist.

In another embodiment of the method of manufacturing a printed wiring board of the present invention using the subtractive method, the method includes the steps of: preparing a copper foil and an insulating substrate with a carrier of the present invention; laminating the copper foil and the insulating substrate with the carrier; After the above-mentioned carrier copper foil and the insulating substrate are peeled off, the above a carrier with a carrier copper foil; a perforated or/and blind via provided on the extremely thin copper layer and the insulating substrate exposed by peeling off the carrier; and desmear treatment on the region containing the above-mentioned perforated or/and blind via; Forming an electroless plating layer on the surface of the perforated or/and blind via; forming a mask on the surface of the electroless plating layer; providing a plating layer on the surface of the electroless plating layer on which the mask is not formed; and plating the layer or/and An etching resist is disposed on the surface of the ultra-thin copper layer; the etching resist is exposed to form a circuit pattern; and the ultra-thin copper layer and the electroless plating layer are removed by etching or plasma etching using an etching solution such as acid. Forming a circuit; removing the above etch resist.

The step of providing a perforation or/and a blind hole, and the subsequent desmear step may not be performed.

Here, a specific example of a method of manufacturing a printed wiring board using the copper foil with a carrier of the present invention will be described in detail.

Step 1: First, a copper foil (layer 1) with a very thin copper layer having a roughened layer formed on its surface was prepared.

Step 2: Next, a resist is applied onto the roughened layer of the ultra-thin copper layer, exposed, developed, and the resist is etched into a specific shape.

Step 3: Then, after the plating of the circuit is formed, the resist is removed, thereby forming a circuit plating of a specific shape.

Step 4: Then, in a manner of coating a circuit (plating circuit plating), a resin layer is laminated on the ultra-thin copper layer, and then a resin layer is laminated on the side of the ultra-thin copper layer. 2 layer).

Step 5: The carrier is then stripped from the carrier copper foil of the second layer. Further, the second layer may also use a copper foil which does not have a carrier.

Step 6: Then, a laser opening is performed at a specific position of the ultra-thin copper layer or the copper foil and the resin layer of the second layer to expose the circuit plating to form a blind hole.

Step 7: In turn, copper is embedded in the blind via to form a via fill.

Step 8: Then, circuit plating is formed on the filling holes in the manner of the above steps 2 and 3.

Step 9: Next, the carrier is peeled off from the carrier copper foil of the first layer.

Step 10: Then, the ultra-thin copper layer on both surfaces (copper foil in the case where the copper foil is provided on the second layer) is removed by flash etching to expose the surface of the circuit plating in the resin layer.

Step 11: Then, a bump is formed on the circuit plating in the resin layer, and a copper pillar is formed on the solder. Thus, a printed wiring board using the copper foil with a carrier of the present invention was produced.

The above-mentioned other carrier copper foil (second layer) may be a copper foil with a carrier of the present invention, or a conventional copper foil with a carrier may be used, and a usual copper foil may be used. Further, in the circuit of the second layer in the step 8, a layer or a plurality of circuits may be further formed, and the circuits may be formed by a semi-additive method, a subtractive method, a partial addition method or a modified semi-additive method. Either way.

According to the manufacturing method of the printed wiring board as described above, since the structure in which the circuit plating is embedded in the resin layer is employed, the circuit plating is protected by the resin layer when, for example, the ultra-thin copper layer is removed by flash etching as in the step 10, The shape is maintained, whereby the formation of a fine circuit becomes easy. Further, since the circuit plating is protected by the resin layer, the electric corrosion resistance is improved, and the conduction of the wiring of the circuit is well suppressed. Therefore, the formation of the fine circuit becomes easy. Further, when the ultra-thin copper layer is removed by flash etching as shown in steps 10 and 11, since the exposed surface of the circuit plating is recessed from the resin layer, it is easy to form bumps on the circuit plating. Further, it is easy to form a copper pillar thereon, and the manufacturing efficiency is improved.

Further, as the resin, a known resin or a prepreg can be used. For example, it can be used as an impregnation BT (bis-s-butylene diimine III A prepreg of glass cloth of resin or BT resin, ABF film manufactured by Ajinomoto Fine-Techno Co., Ltd. or ABF. Further, as the resin, the resin layer and/or the resin and/or the prepreg described in the present specification can be used.

Further, the copper foil with a carrier used in the first layer may have a substrate or a resin layer on the surface of the copper foil with the carrier. By having the substrate or the resin layer and supporting the copper foil with a carrier used for the first layer, wrinkles are less likely to occur, so that productivity is improved. Further, the substrate or the resin layer may be any substrate or resin layer as long as it exhibits the effect of supporting the carrier-attached copper foil used for the first layer. For example, as the substrate or the resin layer, a carrier, a prepreg, a resin layer, or a known carrier, a prepreg, a resin layer, a metal plate, a metal foil, a plate of an inorganic compound, or a foil of an inorganic compound described in the present specification can be used. , a plate of an organic compound, a foil of an organic compound.

Further, the printed circuit board is completed by mounting electronic components on the printed wiring board. In the present invention, the "printed wiring board" includes a printed wiring board, a printed circuit board, and a printed circuit board on which electronic components are mounted as described above.

Moreover, an electronic device can be produced using the printed wiring board, and an electronic device can be produced using a printed circuit board on which the electronic component is mounted, or an electronic device can be manufactured using the printed circuit board on which the electronic component is mounted.

[Examples]

Next, examples and comparative examples will be described. Furthermore, this embodiment shows a preferred example, and the present invention is not limited to the embodiments. Therefore, variations, other embodiments, or aspects included in the technical idea of the present invention are all included in the present invention.

1. Production of carrier copper foil

As a carrier, a strip of electrolytic copper foil (JTC manufactured by JX Nippon Mining & Metal Co., Ltd.) having a thickness of 35 μm was prepared. With respect to the shiny side of the copper foil, a continuous roll plating line of a roll-to-roll type was electroplated under the following conditions, thereby forming a Ni layer having an adhesion amount of 4000 μm/dm ² .

. Ni plating

Nickel sulfate: 250~300g/l

Salinated nickel: 35~45g/l

Nickel acetate: 10~20g/l

Boric acid: 15~30g/l

Gloss agent: saccharin, butynediol, etc.

Sodium dodecyl sulfate: 30~100ppm

pH: 4~6

Bath temperature: 50~70°C

Current density: 3~15A/dm ²

After washing with water and pickling, a Cr layer having an adhesion amount of 11 μg/dm ² was adhered to the Ni layer by an electrolytic chromate treatment under the following conditions on a roll-to-roll type continuous plating line.

. Electrolytic chromate treatment

Liquid composition: potassium dichromate 1~10g/l, zinc 0~5g/l

pH: 3~4

Liquid temperature: 50~60°C

Current density: 0.1~2.6A/dm ²

Coulomb amount: 0.5~30As/dm ²

Then, on the continuous plating line of the roll-to-roll type, a copper foil with a carrier was formed by plating on the Cr layer to form an extremely thin copper layer having a thickness of 1 to 12 μm.

. Very thin copper layer

Copper concentration: 30~120g/l

H ₂ SO ₄ concentration: 20~120g/l

Electrolyte temperature: 20~80°C

Current density: 10~100A/dm ²

The surface of the ultra-thin copper layer of the copper foil with a carrier obtained by the above method is subjected to surface treatment such as roughening treatment, and the first plating and the second plating are performed under the liquid composition and plating conditions shown in Tables 1 and 2. Plating. Further, in Examples 1 to 10 and Comparative Examples 1 to 3, the surface of the roughened layer was subjected to the following treatment in the order described.

. Anti-rust treatment

Zn: more than 0~20g/L

Ni: more than 0~5g/L

pH: 2.5~4.5

Liquid temperature: 30~50°C

Current density Dk: more than 0~1.7A/dm ²

Time: 1 second

Zn adhesion: 5~250μg/dm ²

Ni adhesion: 5~300μg/dm ²

. Chromate treatment

K ₂ Cr ₂ O ₇

(Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2~10g/L

NaOH or KOH: 10~50g/L

ZnO or ZnSO ₄ . 7H ₂ O: 0.05~10g/L

pH: 7~13

Bath temperature: 20~80°C

Current density 0.05~5A/dm ²

Time: 5~30 seconds

Cr adhesion: 10~150μg/dm ²

. Decane coupling treatment

Vinyl triethoxy decane aqueous solution

(Vinyl triethoxy decane concentration: 0.1~1.4wt%)

pH: 4~5

Bath temperature: 25~60°C

Immersion time: 5~30 seconds

Further, in Examples 11 to 16 and Comparative Examples 4 to 7, the surface of the roughened layer was subjected to the following treatment in the order described.

. Anti-rust treatment

(liquid composition)

NaOH: 40~200g/L

NaCN: 70~250g/L

CuCN: 50~200g/L

Zn(CN) ₂ : 2~100g/L

As ₂ O ₃ : 0.01~1g/L

(liquid temperature)

40~90°C

(current condition)

Current density: 1~50A/dm ²

Plating time: 1~20 seconds

. Chromate treatment

K ₂ Cr ₂ O ₇ (Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2~10g/L

NaOH or KOH: 10~50g/L

ZnOH or ZnSO ₄ . 7H ₂ O: 0.05~10g/L

pH: 7~13

Bath temperature: 20~80°C

Current density: 0.05~5A/dm ²

Time: 5~30 seconds

. Decane coupling treatment

After spraying 0.1 vol% to 0.3 vol% of 3-glycidoxypropyltrimethoxydecane aqueous solution, it is dried in air at 100 to 200 ° C for 0.1 to 10 seconds.

Further, in Examples 17 to 23 and Comparative Examples 8 to 12, the surface of the roughened layer was subjected to the following treatment in the order described.

. Anti-rust treatment

Liquid composition: nickel 5~20g/L, cobalt 1~8g/L

pH: 2~3

Liquid temperature: 40~60°C

Current density: 5~20A/dm ²

Coulomb amount: 10~20As/dm ²

. Chromate treatment

Liquid composition: potassium dichromate 1~10g/L, zinc 0~5g/L

pH: 3~4

Liquid temperature: 50~60°C

Current density: 0~2A/dm ² (due to impregnation of chromate, it can also be carried out without electrolysis)

Coulomb amount: 0~2As/dm ² (due to impregnation of chromate treatment, it can also be carried out without electrolysis)

. Decane coupling treatment

Coating of diamino decane aqueous solution (diamine decane concentration: 0.1 to 0.5 wt%)

2. Various evaluations of copper foil with carrier

With respect to the copper foil with a carrier obtained in the above manner, various evaluations were carried out by the following methods. The processing conditions and evaluation results are shown in Tables 1 to 4.

<surface roughness Rz>

Using a contact roughness meter SP-11 manufactured by Kosaka Research Institute Co., Ltd., according to JIS B0601-1994, ten points average roughness was measured for any five portions of the surface of the copper foil with a carrier having a roughened layer to be arithmetic The average value is taken as the surface roughness Rz. Furthermore, for heat resistance The copper foil with a layer, a rustproof layer, a chromate treatment layer, and a decane coupling treatment layer was measured, and the surface roughness Rz was measured on the surface of the roughened layer after the decane coupling treatment layer was provided.

<Average diameter and average length of roughened particles>

Five fields of view (length (length in the lateral direction of FIG. 2) 15 μm) were arbitrarily selected from the roughened layer profile, and a FIB-SIM photograph was taken using a high-performance focused ion beam apparatus (SMI3050) manufactured by SII Corporation. When the transverse direction of the photograph of the roughened particles (the direction parallel to the surface of the copper foil) is parallel (the reference example is shown in Fig. 2), the maximum length of each particle (roughened particle) is taken as the diameter of each particle. . Then, the average value of the diameters of the particles in each of the fields of view is obtained, and the average value is used as the average diameter of the roughened particles in each of the fields of view. Further, in the case where a straight line is formed in parallel with the longitudinal direction of the photograph (the direction parallel to the sheet thickness direction), the maximum length of each particle is used as the length of each particle. Then, the average value of the lengths of the particles in each of the fields of view is obtained, and the average value is used as the average length of the roughened particles in each of the fields of view. The average diameter and average length of the roughened particles in each field of view were measured. Then, the average value of the average diameters of the roughened particles and the average value of the average lengths were respectively calculated by dividing the total of the average diameter and the average length in each of the fields of view by 5 (the number of fields of view). Further, the average diameter of the largest roughened particles in the five fields of view is used as the maximum value of the average diameter of the roughened particles. The average diameter of the smallest roughened particles in the five fields of view is taken as the minimum of the average diameter of the roughened particles. Further, the length of the largest roughened particles in the five fields of view is used as the maximum value of the average length of the roughened particles. The average diameter of the smallest roughened particles in the five fields of view is taken as the minimum of the average diameter of the roughened particles. Further, the maximum value and the minimum value of the average diameter of the roughened particles are obtained from the measured values, and the value A obtained by dividing the average value by the average value of the average diameters is obtained. Further, the ratio of the average length of the roughened particles in each field of view to the average diameter of the roughened particles was determined. The average length of the roughened particles and the average diameter of the roughened particles in five fields of view The maximum value of the ratio is the maximum of the ratio of the average length of the roughened particles to the average diameter of the roughened particles. Further, the minimum value of the ratio of the average length of the roughened particles to the average diameter of the roughened particles in the five fields of view is the minimum value of the ratio of the average length of the roughened particles to the average diameter of the roughened particles. Then, the value obtained by dividing the ratio of the average length of the roughened particles of each field of view and the average diameter of the roughened particles by 5 is obtained (the ratio of the average length of the roughened particles to the average diameter of the roughened particles) Average) B. Further, a value C obtained by dividing the difference between the maximum value and the minimum value of the average length of the roughened particles by the average of the average lengths of the roughened particles is obtained. Further, the ratio of the maximum value of the ratio of the average length of the roughened particles to the average diameter of the roughened particles and the minimum value of the ratio is divided by the ratio of the average length of the roughened particles to the average diameter of the roughened particles. The value D obtained by the average value B.

<sum of the area of the hole>

The copper foil with a carrier of the examples and the comparative examples was used, and the resin was a surface-side resin which was subjected to roughening treatment on a copper foil using GHPL-830MBT manufactured by Mitsubishi Gas Chemical Co., Ltd. By removing the etching product for any layer (replica) of the surface of the copper layer of the resin of the resin 5 fields (the field of view of an area of 15μm × vertical to horizontal 15μm = 225μm ^2), SEM photographs. Then, the total area (%) of the area ratio of the pores of the resin surface on which the surface of the copper foil having the roughened surface of the carrier-attached copper foil was transferred was calculated from the field of view (the sum of the areas of the holes in the field of view = 1) Μm ² )/ Area of observation field of one field of view (μm ² ) × 100). Further, the maximum value of the total area ratio of the pores of the resin surface in the five fields of view is taken as the maximum value of the total area occupied by the pores. Further, the minimum value of the total area ratio of the pores of the resin surface in the five fields of view is taken as the minimum value of the total area occupied by the pores, and the arithmetic mean value of the area ratio of the pores of the resin surface of the five fields of view is taken as The average of the total area occupied by the pores on the surface of the resin. Further, the value E obtained by dividing the difference between the maximum value of the total area occupied by the holes and the total area of the areas occupied by the holes by the average value of the total area of the holes is calculated. Then, when the average value of the total area of the pores on the surface of the resin is 20% or more, it is good. Further, when the value E obtained by dividing the difference between the maximum value of the total area of the holes and the total area of the holes and the average value of the area occupied by the holes is 0.6 or less, it is judged to be good. Fig. 3 shows an example of the appearance of the surface of the resin.

<peel strength>

The extremely thin copper layer side of the copper foil with a carrier was attached to an insulating substrate (Bismaleimide-Triazine resin manufactured by Mitsubishi Gas Chemical Co., Ltd.) in the atmosphere at 20 kgf/cm ² and 220 ° C for 2 hours. After the pressure bonding, the carrier was peeled off, and the surface of the ultra-thin copper layer was plated with copper, and the total thickness of the ultra-thin copper layer and the copper plating was set to 15 μm. The peel strength was measured by stretching the BT resin side with a dynamometer, and measuring according to a 90° peeling method (JIS C 6471 8.1). Further, for each of the examples and the comparative examples, the peel strength was measured for five samples. Then, with respect to each of the examples and the comparative examples, the maximum value, the minimum value, and the average value of the peel strengths of the five samples were determined. Then, with respect to each of the examples and the comparative examples, the value obtained by dividing the difference between the maximum value and the minimum value of the peel strength by the average value of the peel strength was also calculated. Further, the circuit width at the time of measuring the peel strength was set to 10 mm. In addition, when the peeling strength is 0.5 kN/m or more, it is good. If the difference between the maximum value and the minimum value of the peel strength divided by the average value of the peel strength is 0.4 or less, it is good.

<etching property>

The copper foil with a carrier was attached to the polyimide substrate and heat-pressed at 220 ° C for 2 hours, after which the ultra-thin copper layer was peeled off from the carrier. Then, after applying a photosensitive resist on the surface of the ultra-thin copper layer on the polyimide substrate, 50 circuits of L/S=5 μm/5 μm wide are printed by the exposure step. An etching process for removing unnecessary portions of the copper layer is performed under the following spray etching conditions.

(spray etching conditions)

Etching solution: aqueous solution of ferric chloride (Pomet: 40 degrees)

Liquid temperature: 60 ° C

Spray pressure: 2.0MPa

The etching was continued, and the width of the top of the circuit was measured to be 4 μm, and the width of the bottom of the circuit (the length of the bottom side X) and the etching factor were evaluated. The etching factor is in the case of gradually diffusing etching (when a collapse occurs), and the distance from the intersection of the perpendicular line of the upper surface of the copper foil and the resin substrate when the collapse distance is assumed to be vertically etched to the circuit is set. In the case of a, the ratio of the a to the thickness b of the copper foil: b/a, the larger the value, the larger the inclination angle, the less residue of the etching residue, and the smaller the collapse. 4 is a schematic view showing a cross section of a circuit pattern in a width direction and an outline of a calculation method of an etching factor using the pattern. The width X of the bottom of the circuit was measured by SEM observation from above the circuit, and the etching factor (EF = b / a) was calculated. b (μm) is the thickness (μm) of the extremely thin copper layer. Furthermore, it is calculated by a = (X (μm) - 4 (μm)) / 2. The etch factor represents the 12 points in the measurement circuit and is averaged. Thereby, the merits of the etching property can be easily determined. Further, by calculating the standard deviation of the etching factor of 12 points, it is possible to determine the merit of the linearity of the circuit formed by the etching.

In the present invention, an etching factor of 5 or more is evaluated as etchability: ○, and it is 2.5 or more and less than 5 is evaluated as etchability: Δ, which is less than 2.5 or cannot be calculated or cannot be formed as a etchability: × , will not be peeled off as etchability: -. Further, it can be considered that the smaller the standard deviation of the etching factor, the better the linearity of the circuit. The standard deviation of the etching factor was less than 0.5 and it was judged as linearity: ○, 0.5 to less than 1.0 was judged to be linear: Δ, and 1.0 or more was judged to be linear: ×.

(Evaluation results)

In each of Examples 1 to 29, a roughened layer composed of the following roughened particles was formed on the surface of the ultra-thin copper layer, and the etching property and the peeling strength were good, and the average diameter of the roughened particles was 0.05 to 1.3. Mm, the average value of the average length is 0.3 to 3.0 μm, the difference between the maximum value and the minimum value of the average diameter is divided by the average value of the above average diameters A{A=the maximum and minimum values of the average diameter of the roughened particles The difference (μm) / the average value (μm) of the average diameter of the roughened particles is 0.6 or less.

In Comparative Examples 1 to 12, 14, and 17, the value A was more than 0.6, and the etching property was poor.

In Comparative Examples 13, 15, and 16, the average value of the average diameters exceeded 1.3 μm, and the etching property was poor.

Claims (34)

A carrier-attached copper foil is provided with a carrier, an intermediate layer, an ultra-thin copper layer and a roughened layer in sequence, and the roughened layer is composed of roughened particles: the average diameter of the roughened particles is 0.05~ 1.3 μm, the average value of the average length is 0.3 to 3.0 μm, the difference between the maximum value and the minimum value of the average diameter divided by the average value of the average diameter A{A=the maximum diameter of the average diameter of the roughened particles and The difference (μm) of the minimum value / the average value (μm) of the average diameter of the roughened particles is 0.6 or less. The carrier-attached copper foil according to claim 1, wherein an average value B of a ratio of an average length of the roughened particles to an average diameter of the roughened particles is 1.4 or more. The carrier-attached copper foil according to claim 1, wherein an average value B of a ratio of an average length of the roughened particles to an average diameter of the roughened particles is 20 or less. The copper foil with carrier of claim 1, wherein the difference between the maximum value and the minimum value of the average length of the roughened particles is divided by the average value of the average length of the roughened particles C{C=rough The difference between the maximum value and the minimum value of the average length of the particles (μm) / the average value (μm) of the average length of the roughened particles is 0.5 or less. The copper foil with carrier of claim 2, wherein the difference between the maximum value and the minimum value of the average length of the roughened particles is divided by the average value of the average length of the roughened particles C{C=rough The difference between the maximum value and the minimum value of the average length of the particles (μm) / the average value (μm) of the average length of the roughened particles is 0.5 or less. The carrier-attached copper foil according to claim 1, wherein a difference between a maximum value and a minimum value of a ratio of an average length of the roughened particles to an average diameter of the roughened particles is divided by an average length of the roughened particles and The value obtained by the average value B of the ratio of the average diameters of the roughened particles D{D= The difference between the maximum value of the ratio of the average length of the roughened particles to the average diameter of the roughened particles and the minimum value of the ratio is 0.4 or less. The carrier-attached copper foil according to claim 2, wherein a difference between a maximum value and a minimum value of a ratio of an average length of the roughened particles to an average diameter of the roughened particles is divided by an average length of the roughened particles and The value obtained by the average value B of the ratio of the average diameters of the roughened particles D{D=the difference between the maximum value of the ratio of the average length of the roughened particles to the average diameter of the roughened particles and the minimum value of the ratio/B} It is 0.4 or less. The carrier-attached copper foil according to claim 4, wherein a difference between a maximum value and a minimum value of a ratio of an average length of the roughened particles to an average diameter of the roughened particles is divided by an average length of the roughened particles and The value obtained by the average value B of the ratio of the average diameters of the roughened particles D{D=the difference between the maximum value of the ratio of the average length of the roughened particles to the average diameter of the roughened particles and the minimum value of the ratio/B} It is 0.4 or less. The carrier-attached copper foil according to claim 5, wherein a difference between a maximum value and a minimum value of a ratio of an average length of the roughened particles to an average diameter of the roughened particles is divided by an average length of the roughened particles and The value obtained by the average value B of the ratio of the average diameters of the roughened particles D{D=the difference between the maximum value of the ratio of the average length of the roughened particles to the average diameter of the roughened particles and the minimum value of the ratio/B} It is 0.4 or less. The carrier-attached copper foil according to claim 1, wherein the roughened layer has a resin layer. The carrier-attached copper foil according to claim 1, wherein the surface of the roughened layer has one or more selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, and a decane coupling treatment layer. Layer. The carrier-attached copper foil according to claim 11, wherein the resin layer is provided on one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventive layer, a chromate-treated layer, and a decane coupling treatment layer. The carrier copper foil according to claim 10, wherein the resin layer is followed by a resin. The carrier copper foil of claim 13, wherein the resin layer is a primer. The carrier copper foil according to claim 10, wherein the resin layer is a resin in a semi-hardened state. The carrier copper foil according to claim 10, wherein the resin layer is a block copolymerized polyimide resin layer or a resin containing a block copolymerized polyimide resin and a polysyntheimide compound. Floor. A copper foil with carrier, which is provided with a carrier, an intermediate layer, an ultra-thin copper layer and a roughening treatment layer in sequence, after the resin layer is laminated on the roughened layer, the carrier and the intermediate layer are self-made from the ultra-thin copper When the layer is peeled off and then the ultra-thin copper layer is removed by etching, the surface of the resin layer laminated on the roughened layer on the side of the roughened layer is transferred to the roughened layer. The average value of the total area of the pores on the surface of the resin layer which is formed by the unevenness of the surface of the treatment layer is 20% or more, and the difference between the maximum value of the total area of the pores and the minimum of the total area of the pores is divided by the pores. The value E obtained by the average of the total area is 0.6 or less. The carrier-attached copper foil according to claim 1, wherein after the resin layer is laminated on the roughened layer, the carrier and the intermediate layer are peeled off from the ultra-thin copper layer, and then the etching is removed by etching. In the case of an extremely thin copper layer, the surface of the resin layer laminated on the roughened layer on the side of the roughened layer has a surface on which the surface of the roughened layer is transferred. The average value of the total area of the holes on the surface of the resin layer formed by the unevenness is 20% or more, and the difference between the maximum value of the total area of the holes and the minimum of the total area of the holes is divided by the average of the area occupied by the holes. The value E obtained by the value is 0.6 or less. The carrier-attached copper foil according to the first aspect of the invention, wherein the surface of the surface of the roughened layer has a ten-point average roughness Rz of 0.15 μm or more and 3.0 μm or less. The carrier-attached copper foil according to claim 1, wherein the intermediate layer, the ultra-thin copper layer and the roughened layer are sequentially provided on both sides of the carrier. The copper foil with a carrier according to claim 1, wherein the intermediate layer, the ultra-thin copper layer and the roughened layer are sequentially provided on one side of the carrier, and the other side of the carrier has a roughening treatment. Floor. A resin layer in which the average value of the total area of the pores of the surface of the resin layer having the irregularities on the surface of the roughened layer of the carrier-attached copper foil of claim 17 is 20% The value E obtained by dividing the difference between the maximum value of the total area of the holes and the total area of the holes and the average of the area occupied by the holes is 0.6 or less. a resin layer which is provided with a carrier copper foil of a carrier, an intermediate layer, an ultra-thin copper layer and a roughened layer, and after the resin layer is laminated on the roughened layer, the carrier and the intermediate layer are self-contained When the ultra-thin copper layer is peeled off and the ultra-thin copper layer is removed by etching, the average of the total area of the pores of the surface of the resin layer having the unevenness of the surface of the roughened layer is transferred. The value E is 20% or more, and the value E obtained by dividing the difference between the maximum value of the total area of the pores and the total area of the pores by the average of the area occupied by the pores is 0.6 or less. A printed wiring board which is attached to any one of claims 1 to 21 A copper foil or a resin layer of the 22nd or 23rd patent application is manufactured. An electronic machine using the printed wiring board of claim 24 of the patent application. A copper-clad laminate which is produced by using the copper foil with a carrier of any one of claims 1 to 21, or the resin layer of claim 22 or 23. A method for producing a copper foil with carrier, which comprises a carrier, an intermediate layer, an ultra-thin copper layer and a roughened layer, and a method for producing a copper foil with a carrier, comprising tungsten ions and/or arsenic ions and alkyl sulfate An electrolytic bath composed of a sulfuric acid ester of a base ester-based anionic surfactant and copper sulfate forms a roughened layer composed of copper roughened particles on the surface of the ultra-thin copper layer. The method for producing a copper foil with a carrier according to claim 27, wherein the electrolytic bath contains 2 to 100 mg/l of the surfactant. A method for producing a copper foil with a carrier according to claim 27 or 28, wherein a plating treatment layer is formed on the roughened layer using an electrolytic bath composed of sulfuric acid and copper sulfate. The method for producing a copper foil with a carrier according to claim 29, wherein the heat-resistant and/or rust-proof layer containing at least one element selected from the group consisting of zinc, nickel, copper and phosphorus is formed on the plating treatment layer. . The method for producing a copper foil with a carrier according to claim 30, wherein a chromate treatment layer is formed on the heat resistant and/or rustproof layer. The method for producing a copper foil with a carrier according to claim 31, wherein a decane coupling treatment layer is formed on the chromate treatment layer. A manufacturing method of a printed wiring board, comprising the steps of: preparing a carrier copper foil and an insulating substrate according to any one of claims 1 to 21; Laminating the carrier copper foil and the insulating substrate; forming a copper clad laminate by the step of peeling off the carrier with the carrier copper foil after laminating the carrier copper foil and the insulating substrate, and then, by semi-additive method, subtracting A circuit is formed by any one of a method of forming, a partial addition, or a modified semi-additive. A manufacturing method of a printed wiring board, comprising the steps of: forming a circuit on a side surface of the ultra-thin copper layer of a copper foil with a carrier of any one of claims 1 to 21; Forming a resin layer on the side surface of the ultra-thin copper layer with the carrier copper foil; forming a circuit on the resin layer; peeling off the carrier after forming a circuit on the resin layer; and removing the ultra-thin copper layer after peeling off the carrier, This exposes the circuit buried in the resin layer formed on the side surface of the ultra-thin copper layer.