TW201529295A - Copper foil provided with carrier, copper-clad laminated board, printed wiring board, electronic device, and method for manufacturing printed wiring board - Google Patents

Abstract

Provided is a copper foil provided with a carrier, said foil having superior dimensional stability and favorable circuit forming properties. The copper foil provided with a carrier has an ultra-thin copper layer measuring 1 to 9 [mu]m in thickness. A copper-clad laminate incorporating the copper foil provided with a carrier demonstrates a peel strength of 2 to 50 g/cm from the ultra-thin copper layer of the carrier. The number of blisters that occur between the carrier and the ultra-thin copper layer when the copper-clad laminate is heated at 220 DEG C for 4 hours and result in deformation of the outer surface of the ultra-thin copper layer is no more than 20/dm2. The number of pinholes confirmed in the ultra-thin copper layer when the carrier is peeled off from the ultra-thin copper layer after the copper-clad laminate is heated at 220 DEG C for 4 hours is no more than 400/m2.

Description

Carrier copper foil, copper clad laminate, printed wiring board, electronic device, and printed wiring board manufacturing method

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 printed wiring board.

In recent years, with the integration of semiconductors, the miniaturization of circuits for semiconductor package substrates and printed wiring boards for semiconductors has been progressing, and it has become increasingly difficult to form fine circuits by a subtractive process. Therefore, as a result of further fine wiring, the following novel circuit formation method has been attracting attention: pattern copper plating is performed using an extremely thin copper foil as a power supply layer, and finally an extremely thin copper layer is removed by flash etching. Wiring is formed; a copper foil surface profile is used to form fine wiring. These methods are generally referred to as the SAP method (semi-additive process).

The SAP method using the contour of the surface of the copper foil is described, for example, in Patent Document 1. As an example of a typical SAP method using the surface profile of such a copper foil, it is enumerated below. That is, the entire surface of the copper foil laminated on the resin is etched, the surface of the etched substrate is etched, and the entire surface or part of the opening and the substrate are subjected to desmear treatment, and the dry film is attached thereto. Opening and etching surfaces, exposing and developing a dry film that does not form a circuit, and using chemical reagents Part of the dry film is removed, electroless copper plating, copper plating is performed on the surface of the etched substrate on which the surface profile of the copper foil which is not coated with the dry film is transferred, and finally the electroless copper plating layer is removed by flash etching to form a fine Wiring.

Patent Document 1: Japanese Laid-Open Patent Publication No. 2006-196863

It is preferable that the copper foil of the copper clad laminate used in the circuit formation method is thin. This is because when the entire surface or a part of the copper foil of the copper clad laminate is etched, the amount of etching liquid used and the amount of the drain treatment reagent can be reduced, which is very small from the viewpoint of cost and environmental burden. it is good. Moreover, although the copper foil used for the copper-clad laminate is thinner, if it is too thin, when the copper-clad laminate is operated, crushing or scratching may occur on the surface of the ultra-thin copper layer, depending on the degree. It can even damage the surface of the substrate on the underside of the very thin copper layer. Therefore, the formation of the copper layer is poor (the plating thickness is poor, etc.) in the electroless-plating copper which is the main process of the SAP method, or the circuit formation is poor (breaking, etc.) during the flash etching, and the printed wiring is damaged. Board function.

In addition, when the copper-clad laminate in which the carrier copper foil is laminated on the resin is peeled off from the ultra-thin copper layer, if the peel strength is too large, the function as a printed wiring board of the final product is impaired. The reason is that if the peel strength of the carrier is too strong, the extremely thin copper layer is broken and adheres to the carrier side, and further, the resin adheres to the extremely thin copper layer side and the resin layer is damaged, which is caused by electrolessness in the main process of the SAP method. - Poor formation of copper layer when electroplating copper (poor plating thickness, etc.), or fast The circuit is poorly formed during flash etching (open circuit, etc.). Further, when the carrier is peeled off from the ultra-thin copper layer, since a large stress is applied to the substrate itself, warpage occurs in the substrate, which is caused by poor dimensional accuracy in the subsequent steps of manufacturing the printed wiring board.

On the other hand, if the peel strength is too weak, the carrier is peeled off from the ultra-thin copper layer in the next operation process of the copper-clad laminate, and the risk of damage to the surface of the ultra-thin copper layer is high. In this case, the above-mentioned functional defects are also caused by damage to the surface of the substrate which is present on the lower side of the surface of the ultra-thin copper layer.

Further, in order to completely cure the resin, the copper-clad laminate is usually subjected to heat treatment (curing of the resin) at a temperature of 100 to 220 ° C for 10 minutes to 4 hours without pressure. If bubbles are generated due to bubbles or water vapor between the ultra-thin copper foil and the carrier due to the heat treatment, not only the surface of the extremely thin copper layer but also the surface of the substrate on the lower side thereof is pitted. It has an adverse effect on the formation of fine circuits.

Regarding these aspects, it has not been fully explored in the prior art, and there is still room for improvement. Therefore, an object of the present invention is to provide a copper foil with a carrier which is excellent in dimensional stability and has excellent circuit formation properties.

In order to achieve the above object, the inventors of the present invention have repeatedly conducted intensive studies, and as a result, have found that excellent dimensional stability can be achieved without problems, and L/S (line/pitch) = 30/30 μm or less is formed in the SAP method. In the fine wiring, the peeling strength of the carrier of the copper foil with a copper-clad laminate is controlled to an appropriate range; and the carrier-very thin copper layer after the heat treatment is applied to the copper-clad laminate under a predetermined condition is suppressed. The expansion occurs; the number of pinholes observed in the ultra-thin copper layer when the carrier is peeled off from the ultra-thin copper layer after heat treatment is applied to the copper-clad laminate under predetermined conditions.

The invention is based on the above findings, and in one aspect, is a copper foil with carrier, which is provided with a carrier, an intermediate layer and an ultra-thin copper layer in sequence, and the thickness of the ultra-thin copper layer is 1~9 μm. In the copper-clad laminate having the above-mentioned copper foil with a carrier, the peel strength of the carrier from the ultra-thin copper layer is 2 to 50 g/cm, and when the copper-clad laminate is heated at 220 ° C for 4 hours, Expanding between the carrier and the ultra-thin copper layer and deforming the surface of the ultra-thin copper layer to 20/dm ² or less, and heating the copper-clad laminate at 220 ° C for 4 hours, then removing the carrier from the above-mentioned extremely thin When the copper layer was peeled off, the pinholes confirmed on the extremely thin copper layer were 400/m ² or less.

In one embodiment, the copper foil with a carrier of the present invention, when the copper foil with the carrier is heated at 220 ° C for 4 hours, is formed between the carrier and the ultra-thin copper layer and deforms the surface of the ultra-thin copper layer. The expansion is 10/dm ² or less.

In another embodiment, the copper foil with a carrier of the present invention is formed by heating the copper foil with the carrier at 220 ° C for 4 hours, and is formed between the carrier and the ultra-thin copper layer to deform the surface of the ultra-thin copper layer. The expansion is 0 / dm ² .

In still another embodiment of the copper foil with a carrier of the present invention, after the carrier copper foil is heated at 220 ° C for 4 hours, the carrier is removed from the ultra-thin copper layer, and the ultra-thin copper layer is confirmed. The pinhole is 200 pieces/m ² or less.

In still another embodiment of the copper foil with a carrier of the present invention, after the carrier copper foil is heated at 220 ° C for 4 hours, the carrier is removed from the ultra-thin copper layer, and the ultra-thin copper layer is confirmed. The pinholes are 50/m ² or less.

In still another embodiment of the copper foil with a carrier of the present invention, the ultra-thin copper layer has a thickness of 1 to 3 μm.

In still another embodiment of the copper foil with a carrier of the present invention, the carrier has a peel strength of 5 to 20 g/cm from the ultra-thin copper layer.

In still another embodiment of the copper foil with a carrier of the present invention, the ultra-thin copper layer is provided on both sides of the carrier.

In still another embodiment, the copper foil with a carrier of the present invention has a roughened layer on either or both surfaces of the ultra-thin copper layer side surface and the carrier side surface.

In still another embodiment of the present invention, the roughened layer is any one selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium, and zinc. A simple substance or a layer composed of any one or more alloys.

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 at least one surface or both surfaces on the surface of the ultra-thin copper layer side and the surface side of the carrier side selected from the group consisting of a roughened layer, a heat-resistant layer, and a rustproof layer. One or more layers of the group consisting of a chromate treatment layer and a decane coupling treatment layer.

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

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

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

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, the copper foil with a carrier of the present invention is used in a semi-additive method.

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

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

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

According to still another aspect of the present invention, a method of manufacturing a printed wiring board includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and stacking the copper foil with the insulating substrate and the insulating substrate And after laminating the carrier-attached copper foil and the insulating substrate, the copper-clad laminate is formed by the step of peeling off the carrier of the carrier-attached copper foil. Thereafter, the step of forming the circuit is performed by any one of a semi-additive method, a subtractive method, a partial addition method, or a modified semi-additive method.

According to still another aspect of the present invention, a method of manufacturing a printed wiring board includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and forming the copper foil with the carrier and the insulating substrate to form a layer a step of forming a circuit by using a copper clad laminate; and a step of forming a circuit by any one of a semi-additive method, a subtractive method, a partial addition method, or a modified semi-additive method; In the step, the carrier is peeled off before the etching or opening treatment of the ultra-thin copper layer is being performed.

In still another aspect, the present invention provides a method of manufacturing a printed wiring board, comprising the steps of: forming a circuit on the side surface of the ultra-thin copper layer of the copper foil with carrier of the present invention or the side surface of the carrier; a step of forming a resin layer on the surface of the ultra-thin copper layer side of the copper foil with a carrier or the surface of the carrier side by burying the above-mentioned circuit; forming a circuit on the resin layer; after forming a circuit on the resin layer, a step of peeling off the carrier or the ultra-thin copper layer; and removing the ultra-thin copper layer or the carrier by peeling off the carrier or the ultra-thin copper layer, thereby forming the side surface of the ultra-thin copper layer or the carrier side The step of exposing the circuit buried in the above resin layer to the surface.

In one embodiment, the method of manufacturing a printed wiring board according to the present invention is in the above tree The step of forming a circuit on the grease layer is a step of bonding another copper foil with a carrier to the resin layer from the side of the ultra-thin copper layer, and forming the above-mentioned circuit using a copper foil with a carrier adhered to the resin layer.

In another embodiment of the method for producing a printed wiring board according to the present invention, another copper foil with a carrier bonded to the resin layer is a copper foil with a carrier of the present invention.

In still another embodiment of the method for producing a printed wiring board according to the present invention, the step of forming a circuit on the resin layer is performed by a semi-additive method, a subtractive method, a partial addition method or a modified semi-additive method. Perform any method.

In still another embodiment of the present invention, a copper foil with a carrier formed on the surface of the substrate has a substrate or a resin layer on a carrier side surface or an extremely thin copper layer side surface of the carrier copper foil. .

According to the present invention, it is possible to provide a copper foil with a carrier which is excellent in dimensional stability and has good circuit formability.

Fig. 1 shows a schematic illustration of a semi-additive method using a contour of a copper foil.

<With carrier copper foil>

The copper foil with a carrier of the present invention comprises a carrier, an intermediate layer laminated on the carrier, and an extremely thin copper layer laminated on the intermediate layer. Further, the carrier copper foil may be provided with a carrier, an intermediate layer, and an extremely thin copper layer in this order. The copper foil with a carrier may have a surface treatment layer such as a roughening treatment layer on one surface or both surfaces of the carrier side surface and the ultra-thin copper layer surface.

When a roughened layer is provided on the side of the carrier side of the carrier-coated copper foil, when the carrier copper foil is laminated on a support such as a resin substrate from the surface side of the carrier side, the support such as the carrier and the resin substrate is changed. It has the advantage of being difficult to peel off. Further, in the case where the surface is to be made smoother, the roughening layer may not be provided.

The method of using the carrier copper foil itself is well known, for example, bonding the surface of the ultra-thin copper layer 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 film, fluororesin film and other insulating substrates, After the thermocompression bonding, the carrier is peeled off, and the ultra-thin copper layer next to the insulating substrate is etched into a target conductor pattern, and finally a printed wiring board can be manufactured.

<carrier>

The carrier which can be used in the present invention is typically a metal foil or a resin film, for example, a copper foil, a copper alloy foil, a nickel foil, a nickel alloy foil, an iron foil, a ferroalloy foil, a stainless steel foil, an aluminum foil, an aluminum alloy foil, an insulating resin film. Provided in the form of a polyimide film or an LCD film.

The carrier which can be used in the present invention 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 drum of titanium or stainless steel, and the rolled copper foil is repeatedly produced by plastic working and heat treatment using a calender roll. As the material of the copper foil, in addition to high-purity copper such as refined copper (JIS H3100 alloy No. C1100) or oxygen-free copper (JIS H3100 alloy No. C1020 or JIS H3510 alloy No. C1011), for example, Sn-doped copper or Ag-doped copper may be used. A copper alloy such as Cr, Zr or Mg or a copper alloy to which a Cassson copper alloy such as Ni or Si is added is added.

Further, the electrolytic copper foil can be produced by the following electrolyte composition and production conditions.

<electrolyte composition>

Copper: 90~110g/L

Sulfuric acid: 90~110g/L

Chlorine: 50~100ppm

Leveling agent (glue): 0.1~10ppm

<Manufacturing conditions>

Current density: 70~100A/dm ²

Electrolyte temperature: 50~60°C

Electrolyte line speed: 3~5m/sec

Electrolysis time: 0.5~10 minutes (adjusted according to the thickness of the carrier copper and current density)

In addition, in the present specification, when the term "copper foil" is used alone, a copper alloy foil is also included.

In addition, the remainder of the treatment liquid (etching liquid, electrolyte solution) used for electrolysis, etching, surface treatment, plating, etc. described in the present specification is water unless otherwise specified.

The thickness of the carrier which can be used in the present invention is not particularly limited, and may be appropriately adjusted to a suitable thickness in order to realize the action as a carrier, and may be, for example, 5 μm or more. However, if the thickness is too large, the production cost is increased. Therefore, it is usually preferably 35 μm or less. Therefore, the thickness of the carrier is typically 8 to 70 μm, more typically 12 to 70 μm, and more typically 18 to 35 μm. Further, in terms of reducing the cost of raw materials, the thickness of the carrier is preferably small. Therefore, the thickness of the carrier is typically 5 μm or more and 35 μm or less, preferably 5 μm or more and 18 μm or less, preferably 5 μm or more and 12 μm or less, preferably 5 μm or more and 11 μm or less, and preferably 5 μm or more and 10 μm or less. Furthermore, in the case where the thickness of the carrier is small, it is easy to cause bending when the carrier is passed through the foil. In order to prevent the occurrence of bending, for example, it is effective to flatten the conveying roller of the carrier copper foil manufacturing apparatus. Slide or shorten the distance between the transfer roller and the next transfer roller. Further, in the case of using a copper foil with a carrier in an embedding method (Enbedded Process) which is one of the methods for producing a printed wiring board, the rigidity of the carrier must be high. Therefore, in the case of the embedding method, the thickness of the carrier is preferably 18 μm or more and 300 μm or less, preferably 25 μm or more and 150 μm or less, preferably 35 μm or more and 100 μm or less, and more preferably 35 μm or more and 70 μm or less.

<intermediate layer>

An intermediate layer is provided on one or both sides of the carrier. Other layers may also be provided between the carrier and the intermediate layer. The intermediate layer used in the present invention is configured such that the extremely thin copper layer is not easily peeled off from the carrier before the step of laminating the carrier copper foil to the insulating substrate, and on the other hand, the ultra-thin copper layer after the step of laminating the insulating substrate can be Peel off from the carrier. For example, the intermediate layer of the copper foil with a carrier of the present invention may contain, in addition to Ni, an oxide selected from the group consisting of Cr, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, and the like. One or more of a group consisting of substances and organic substances. Also, the intermediate layer may be a plurality of layers.

Further, the intermediate layer is preferably formed by sequentially laminating one layer of nickel or a nickel-containing alloy on the carrier, and one or more layers of chromium, a chromium alloy, and an oxide of chromium. Further, it is preferable that zinc is contained in any one of layers of nickel or a nickel-containing alloy and/or one or more layers containing chromium, a chromium alloy, and an oxide of chromium. Here, the alloy containing nickel means one or more elements selected from the group consisting of nickel and cobalt, iron, chromium, molybdenum, zinc, bismuth, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. The alloy that is formed. The nickel-containing alloy may be an alloy composed of three or more elements. Further, the term "chromium alloy" means an alloy composed of chromium and one or more elements selected from the group consisting of cobalt, iron, nickel, molybdenum, zinc, bismuth, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. . The chromium alloy may also be an alloy composed of three or more elements. Also, containing chromium, chromium alloy, chromium oxidation Any one or more of the layers may also be a chromate treatment layer. Here, the chromate treatment layer refers to a layer treated with a solution containing chromate or dichromate. The chromate treatment layer may also contain metals such as cobalt, iron, nickel, molybdenum, zinc, bismuth, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. In the present invention, the chromate treatment layer treated with an aqueous solution of chromic anhydride or potassium dichromate is referred to as a pure chromate treatment layer. Further, in the present invention, the chromate treatment layer treated with the treatment liquid containing chromic acid anhydride or potassium dichromate and zinc is referred to as a zinc chromate treatment layer.

Further, the intermediate layer is preferably a layer of any one of nickel, a nickel-zinc alloy, a nickel-phosphorus alloy, and a nickel-cobalt alloy, and a zinc chromate treatment layer and a pure chromate treatment layer. And one of the chrome plating layers, and the intermediate layer is further preferably formed by sequentially laminating a nickel layer or a nickel-zinc alloy layer and a zinc chromate treatment layer on the carrier, or sequentially laminating nickel- It is composed of a zinc alloy layer and a pure chromate treatment layer or a zinc chromate treatment layer. The adhesion between nickel and copper is higher than the adhesion between chromium and copper. Therefore, when the ultra-thin copper layer is peeled off, it is peeled off at the interface between the ultra-thin copper layer and the chromate-treated layer. Further, for the nickel of the intermediate layer, it is expected to prevent the barrier effect of the copper component from diffusing from the carrier to the extremely thin copper layer. Further, it is preferred that the intermediate layer is not chrome-plated but a chromate-treated layer is formed. Since chrome plating forms a dense chromium oxide layer on the surface, when an extremely thin copper foil is formed by plating, the electric resistance rises and pinholes are likely to occur. The surface on which the chromate-treated layer is formed is formed with a chromium oxide layer which is not denser than chromium plating. Therefore, it is difficult to form an electric resistance when forming an extremely thin copper foil by electroplating, and pinholes can be reduced. Here, by forming the zinc chromate treatment layer as the chromate treatment layer, the electric resistance when forming an extremely thin copper foil by electroplating is lower than that of the usual chromate treatment layer, and the occurrence of pinholes can be further suppressed.

In the case of using an electrolytic copper foil as a carrier, it is preferable to provide an intermediate layer on the shiny side from the viewpoint of reducing pinholes.

When the chromate treatment layer in the intermediate layer is present thinly at the interface of the ultra-thin copper layer, the ultra-thin copper layer is not peeled off from the carrier before the lamination step to the insulating substrate, and on the other hand, it can be obtained on the insulating substrate. It is preferred that the ultra-thin copper layer is peeled off from the carrier after the lamination step. When the nickel layer or the nickel-containing alloy layer (for example, a nickel-zinc alloy layer) is not provided and the chromate-treated layer is present at the boundary between the carrier and the ultra-thin copper layer, the peeling property is hardly improved, and the chromic acid is not removed. When the salt layer is directly treated with a nickel layer or a nickel-containing alloy layer (for example, a nickel-zinc alloy layer) and an extremely thin copper layer, a nickel layer or a nickel-containing alloy layer (for example, a nickel-zinc alloy layer) is used. The amount of nickel in the film is too strong or too weak to obtain a suitable peel strength.

Moreover, if the chromate treatment layer is present at the boundary between the support and the nickel layer or the nickel-containing alloy layer (for example, a nickel-zinc alloy layer), the intermediate layer is also peeled off when the ultra-thin copper layer is peeled off, that is, on the carrier and Peeling occurs between the intermediate layers, which is not preferable. Such a situation occurs not only when a chromate treatment layer is provided at the interface with the carrier, but also when the chromate treatment layer is provided at the interface with the ultra-thin copper layer. The reason for this is that copper and nickel are easily dissolved in a solid state. Therefore, if these contacts are made, the adhesion force is increased by mutual diffusion, and the adhesion is less likely to occur. On the other hand, since chromium and copper are not easily dissolved, it is less likely to occur. Diffusion, so the interface between chromium and copper is weaker and easy to peel off. Further, when the amount of nickel in the intermediate layer is insufficient, only a trace amount of chromium is present between the carrier and the ultra-thin copper layer, so that the two are in close contact with each other and become difficult to peel off.

The nickel layer of the intermediate layer or the alloy layer containing nickel (for example, a nickel-zinc alloy layer) may be, for example, wet plating such as electroplating, electroless plating, and immersion plating, or dry plating such as sputtering, CVD, and PDV. Formed by plating. From the viewpoint of cost, electroplating is preferred. Further, in the case where the carrier is a resin film, the intermediate layer can be formed by dry plating such as CVD and PDV or wet plating such as electroless plating and immersion plating.

Further, the chromate treatment layer may be formed, for example, by electrolytic chromate or impregnated chromate. However, since the chromium concentration is increased and the peel strength of the ultra-thin copper layer from the carrier is improved, it is preferably electrolytic chromic acid. Salt formation.

Further, it is preferable that the adhesion amount of nickel in the intermediate layer is 100 to 40000 μg/dm ² , the adhesion amount of chromium is 5 to 100 μg/dm ² , and the adhesion amount of zinc is 1 to 70 μg/dm ² . As described above, the copper foil with a carrier of the present invention controls the amount of Ni on the surface of the ultra-thin copper layer after the self-attached carrier copper foil is peeled off from the ultra-thin copper layer, and it is preferable to control the amount of Ni on the surface of the ultra-thin copper layer after such peeling. The intermediate layer contains a metal species (Cr, Zn) which reduces the amount of Ni adhesion of the intermediate layer and suppresses the diffusion of Ni toward the ultra-thin copper layer side. On such viewpoint, Ni content of the intermediate layer is preferably 100 ~ 40000μg / dm ^2, more preferably 200μg / dm ² or more 20000μg / dm ² or less, more preferably 500μg / dm ² or more 10000μg / dm ² or less, more It is preferably 700 μg/dm ² or more and 5000 μg/dm ² or less. Further, Cr is preferably contained in an amount of 5 to 100 μg/dm ² , more preferably 8 μg/dm ² or more and 50 μg/dm ² or less, still more preferably 10 μg/dm ² or more and 40 μg/dm ² or less, still more preferably 12 μg/dm ² or more. 30 μg / dm ² or less. Zn preferably contains 1 ~ 70μg / dm ^2, more preferably 3μg / dm ² or more 30μg / dm ² or less, more preferably 5μg / dm ² or more 20μg / dm ² or less.

The intermediate layer of the copper foil with carrier of the present invention is formed by sequentially laminating a nickel layer on the carrier, and an organic layer containing any one of a nitrogen-containing organic compound, a sulfur-containing organic compound and a carboxylic acid, in the intermediate layer. The adhesion amount of nickel may also be 100 to 40000 μg/dm ² . Further, the intermediate layer of the copper foil with a carrier of the present invention is formed by sequentially laminating an organic layer containing any one of a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid, and a nickel layer on the carrier. The amount of nickel attached to the layer may also be from 100 to 40000 μg/dm ² . As described above, the copper foil with a carrier of the present invention controls the amount of Ni on the surface of the ultra-thin copper layer after the self-attached carrier copper foil is peeled off from the ultra-thin copper layer, and it is preferable to control the amount of Ni on the surface of the ultra-thin copper layer after such peeling. The intermediate layer contains an organic layer containing any one of a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid, which reduces the Ni adhesion amount of the intermediate layer and suppresses diffusion of Ni to the ultra-thin copper layer side. On such viewpoint, Ni content of the intermediate layer is preferably 100 ~ 40000μg / dm ^2, more preferably 200μg / dm ² or more 20000μg / dm ² or less, more preferably 300μg / dm ² or more 10000μg / dm ² or less, more Jia is 500μg / dm ² or more 5000μg / dm ² or less. In addition, examples of the organic substance containing the nitrogen-containing organic compound, the sulfur-containing organic compound, and the carboxylic acid include BTA (benzotriazole), MBT (mercaptobenzothiazole), and the like.

In addition, as the organic substance contained in the intermediate layer, one or two or more kinds selected from the group consisting of organic compounds containing nitrogen, organic compounds containing sulfur, and carboxylic acids are preferably used. Among the nitrogen-containing organic compounds, sulfur-containing organic compounds, and carboxylic acids, the nitrogen-containing organic compound includes a nitrogen-containing organic compound having a substituent. As the specific nitrogen-containing organic compound, it is preferred to use a triazole compound having a substituent, that is, 1,2,3-benzotriazole, carboxybenzotriazole, N', N'-bis(benzotriazole). Methyl)urea, 1H-1,2,4-triazole and 3-amino-1H-1,2,4-triazole and the like.

As the sulfur-containing organic compound, mercaptobenzothiazole, sodium 2-mercaptobenzothiazole, trimeric thiocyanate, 2-benzimidazolethiol or the like is preferably used.

As the carboxylic acid, a monocarboxylic acid is particularly preferably used, and among them, oleic acid, linoleic acid, linoleic acid, and the like are preferably used.

The organic substance preferably has a thickness of 25 nm or more and 80 nm or less, more preferably 30 nm or more and 70 nm or less. The intermediate layer may also contain a plurality of (one or more) of the above organic substances.

Further, the thickness of the organic substance can be measured as follows.

<intermediate layer organic matter thickness>

After the ultra-thin copper layer with the carrier copper foil was peeled off from the carrier, the intermediate layer side surface of the exposed ultra-thin copper layer and the intermediate layer side surface of the exposed carrier were subjected to XPS measurement to prepare a depth profile. Then, the depth from the intermediate layer side surface of the ultra-thin copper layer to the carbon concentration of 3 at% or less is set to A (nm), and the depth from the intermediate layer side surface of the carrier to the carbon concentration is initially set to 3 at% or less. In the case of B (nm), the total of A and B is set as the thickness (nm) of the organic substance in the intermediate layer.

The operating conditions of XPS are shown below.

. Device: XPS measuring device (ULVAC-PHI, model 5600MC)

. Ultimate vacuum: 3.8×10 ^-7 Pa

. X-ray: monochromatic AlK α or non-monochromatic MgK α, X-ray output 300W, detection area 800μm , the angle between the sample and the detector is 45°

. Ion beam: ion type Ar ⁺ , accelerating voltage 3kV, scanning area 3mm × 3mm, sputtering rate 2.8nm / min (SiO ₂ conversion)

Regarding the method of using the organic substance contained in the intermediate layer, the method of forming the intermediate layer on the carrier foil will be described below. The intermediate layer is formed on the carrier, and the organic substance is dissolved in a solvent, and the carrier is immersed in the solvent, or the surface to be formed with the intermediate layer may be subjected to a shower method, a spray method, a dropping method, an electrodeposition method, or the like, without A specially defined method is employed. In this case, the concentration of the organic agent in the solvent is preferably in the range of 0.01 g/L to 30 g/L and the liquid temperature of 20 to 60 ° C in all of the above organic matters. The concentration of the organic substance is not particularly limited, and the original concentration is higher or lower without any problem. Further, there is a tendency that the higher the concentration of the organic substance, the longer the contact time of the carrier with the solvent for dissolving the organic substance, and the greater the thickness of the organic substance of the intermediate layer. Further, when the thickness of the organic material in the intermediate layer is thick, the effect of suppressing the diffusion of Ni to the extremely thin copper layer side tends to be large.

Further, the intermediate layer is preferably formed by sequentially laminating nickel, molybdenum or cobalt or a molybdenum-cobalt alloy on the carrier. The adhesion between nickel and copper is higher than that of molybdenum or cobalt and copper. Therefore, when the ultra-thin copper layer is peeled off, it is peeled off at the interface between the ultra-thin copper layer and the molybdenum or cobalt or molybdenum-cobalt alloy. Further, for the nickel of the intermediate layer, it is expected to prevent the barrier effect of the copper component from diffusing from the carrier to the extremely thin copper layer.

Further, the nickel may be an alloy containing nickel. Here, the alloy containing nickel means one or more elements selected from the group consisting of nickel and cobalt, iron, chromium, molybdenum, zinc, bismuth, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. The alloy that is formed. Further, the molybdenum may be an alloy containing molybdenum. Here, the alloy containing molybdenum refers to one or more elements selected from the group consisting of molybdenum and a group selected from the group consisting of cobalt, iron, chromium, nickel, zinc, lanthanum, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. The alloy that is formed. Further, the cobalt may be an alloy containing cobalt. Here, the alloy containing cobalt means one or more elements selected from the group consisting of cobalt and molybdenum, iron, chromium, nickel, zinc, bismuth, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. The alloy that is formed.

The molybdenum-cobalt alloy may also contain an element other than molybdenum or cobalt (for example, one selected from the group consisting of cobalt, iron, chromium, molybdenum, zinc, bismuth, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium). The above elements).

In the case of using an electrolytic copper foil as a carrier, it is preferable to provide an intermediate layer on the shiny side from the viewpoint of reducing pinholes.

When the molybdenum or cobalt or molybdenum-cobalt alloy layer in the intermediate layer is thinly present at the interface of the ultra-thin copper layer, the ultra-thin copper layer is not peeled off from the carrier before the lamination step to the insulating substrate, and on the other hand, It is preferable since the ultra-thin copper layer can be peeled off from the carrier after the lamination step of the insulating substrate. When the nickel layer is not provided and the molybdenum or cobalt or molybdenum-cobalt alloy layer is present at the boundary between the carrier and the ultra-thin copper layer, the peeling property is hardly improved, and no molybdenum or cobalt or molybdenum-cobalt is present. In the case where the nickel layer is directly laminated with the ultra-thin copper layer, there is a case where the peel strength of the nickel in the nickel layer is too strong or too weak, and the appropriate peel strength cannot be obtained.

Further, if a molybdenum or cobalt or molybdenum-cobalt alloy layer is present at the boundary between the support and the nickel layer, there is a case where the intermediate layer is also peeled off when the ultra-thin copper layer is peeled off, that is, peeling occurs between the carrier and the intermediate layer. Therefore, it is not good. This condition occurs not only when a molybdenum or cobalt or molybdenum-cobalt alloy layer is provided at the interface with the carrier, but also when a molybdenum or cobalt or molybdenum-cobalt alloy layer is provided at the interface with the ultra-thin copper layer. Too much will happen. This is considered to be because copper and nickel are easily dissolved in the solid state. Therefore, if these contacts are made, the adhesion force is increased by mutual diffusion, and the adhesion is less likely to occur. On the other hand, since molybdenum or cobalt and copper are not easily dissolved, it is difficult to form. Interdiffusion occurs, so that the interface between the molybdenum or cobalt or molybdenum-cobalt alloy layer and the copper is weak and easy to peel off. Further, when the amount of nickel in the intermediate layer is insufficient, there is a case where only a trace amount of molybdenum or cobalt is present between the carrier and the ultra-thin copper layer, so that the two are in close contact with each other and become difficult to peel off.

The intermediate layer of nickel and cobalt or molybdenum-cobalt alloy can be formed, for example, by wet plating such as electroplating, electroless plating, and immersion plating, or dry plating such as sputtering, CVD, and PDV. Further, molybdenum can be formed only by dry plating such as CVD and PDV. From the viewpoint of cost, electroplating is preferred.

In the intermediate layer, it is preferable that the adhesion amount of nickel is 100 to 40000 μg/dm ² , the adhesion amount of molybdenum is 10 to 1000 μg/dm ² , and the adhesion amount of cobalt is 10 to 1000 μg/dm ² . As described above, the copper foil with a carrier of the present invention controls the amount of Ni on the surface of the ultra-thin copper layer after the self-attached carrier copper foil is peeled off from the ultra-thin copper layer, and it is preferable to control the amount of Ni on the surface of the ultra-thin copper layer after such peeling. The intermediate layer contains a metal species (Co, Mo) which reduces the amount of Ni adhesion of the intermediate layer and suppresses the diffusion of Ni toward the ultra-thin copper layer side. From this point of view, the nickel adhesion amount is preferably from 100 to 40,000 μg/dm ² , preferably from 200 to 20,000 μg/dm ² , more preferably from 300 to 15,000 μg/dm ² , still more preferably from 300 to 10,000 μg/ Dm ² . When the intermediate layer contains molybdenum, the molybdenum adhesion amount is preferably 10 to 1000 μg/dm ² , and the molybdenum adhesion amount is preferably 20 to 600 μg/dm ² , more preferably 30 to 400 μg/dm ² . When the intermediate layer contains cobalt, the cobalt adhesion amount is preferably 10 to 1000 μg/dm ² , and the cobalt adhesion amount is preferably 20 to 600 μg/dm ² , more preferably 30 to 400 μg/dm ² .

Further, in the case where the intermediate layer is sequentially laminated with nickel and molybdenum or cobalt or a molybdenum-cobalt alloy as described above, if the plating treatment for setting the molybdenum or cobalt or molybdenum-cobalt alloy layer is reduced, The lower current density and the slower transport speed of the carrier tend to increase the density of the molybdenum or cobalt or molybdenum-cobalt alloy layer. When the density of the layer containing molybdenum and/or cobalt is increased, the nickel of the nickel layer is less likely to diffuse, and the amount of Ni on the surface of the extremely thin copper layer after peeling can be controlled.

In the case where the intermediate layer is provided only on one side, it is preferable to provide a rust-proof layer such as a Ni plating layer on the surface opposite to the carrier. Further, in the case where the intermediate layer is provided by the chromate treatment or the zinc chromate treatment or the plating treatment, it is considered that a part of the metal to which the chromium or zinc adheres is, in particular, a hydrate or an oxide.

In the copper foil with a carrier according to the present invention, the copper-clad laminate using the copper foil with a carrier has a peel strength of the carrier from the ultra-thin copper layer of 2 to 50 g/cm. Since the peel strength of the carrier from the ultra-thin copper layer is controlled to be 2 g/cm or more, the carrier in various processes using the carrier-attached copper foil can be favorably controlled to be unexpectedly peeled off. Moreover, since the peel strength of the carrier from the ultra-thin copper layer is controlled to be 50 g/cm or less, in the process of peeling the carrier from the ultra-thin copper layer, there is no case where the carrier has a portion of the extremely thin copper layer. Peeled well. The peel strength of the carrier from the ultra-thin copper layer is preferably from 2 to 30 g/cm, more preferably from 5 to 25 g/cm, still more preferably from 5 to 20 g/cm.

The copper foil with a carrier of the present invention is controlled by pinholes which are confirmed in an extremely thin copper layer when the copper-clad laminate using the copper foil with the carrier is heated at 220 ° C for 4 hours and the carrier is peeled off from the ultra-thin copper layer. It is 400 / m ² or less. The pinhole of the ultra-thin copper layer is produced in the case where the carrier copper foil is produced in the manufacturing step, or after the carrier copper foil is attached to the resin substrate or the like, and the carrier is peeled off from the ultra-thin copper layer. A situation occurs when the peel strength is too large. Since the copper foil with carrier of the present invention can well control the generation of pinholes in the manufacturing step, the peel strength of the carrier from the ultra-thin copper layer is further controlled to an appropriate value, so that the ultra-thin copper layer at the time of carrier peeling can be satisfactorily suppressed. The generation of pinholes. After the carrier copper foil is heated at 220 ° C for 4 hours, when the carrier is peeled off from the ultra-thin copper layer, the pinhole confirmed on the ultra-thin copper layer is preferably 200 / m ² or less, more preferably 100 / m ² More preferably, it is 50 / m ² or less.

The copper foil with a carrier of the present invention is controlled such that when the copper-clad laminate using the copper foil with a carrier of the present invention is heated at 220 ° C for 4 hours, the surface deformation of the ultra-thin copper layer is expanded to 20 / m ² the following. When the carrier copper foil is heated, bubbles (swelling) are generated due to a gas such as water vapor generated between the carrier/very thin copper layer. If such expansion occurs, the following problem occurs: the degree of expansion is extremely thin, and the copper layer is dented, which adversely affects circuit formation. On the other hand, in the copper foil with a carrier of the present invention, the occurrence of expansion of the surface deformation of the ultra-thin copper layer is favorably suppressed, and the circuit formation property of the ultra-thin copper layer is improved. When the carrier copper foil is heated at 220 ° C for 4 hours and the expansion is more than 20 / m ² , it is difficult to form a finer wiring than L / S = 30 μm / 30 μm when etching the ultra-thin copper layer, such as L / A fine wiring of S = 25 μm / 25 μm, for example, a fine wiring of L/S = 20 μm / 20 μm, for example, a fine wiring of L / S = 15 μm / 15 μm. In addition, the above-mentioned "heating at 220 ° C for 4 hours" is a typical heating condition when the carrier-attached copper foil is bonded to an insulating substrate and thermocompression bonding is performed.

In addition, the above-mentioned "copper-clad laminate using the copper foil with a carrier of the present invention" means a copper-clad laminate obtained by the following steps (1) and (2):

(1) Lamination step [Laminating copper foil with a carrier on the resin substrate from the side of the ultra-thin copper layer]

Temperature: 100~240°C

Time: 30 minutes to 4 hours

Pressure: 1~50Kg/cm ²

(2) Curing step (atmospheric pressure heat treatment) [heating the layered body obtained in the step (1)]

Temperature: 100~240°C

Time: 10 minutes to 4 hours

The copper foil with a carrier of the present invention is preferably controlled to expand the surface of the ultra-thin copper layer by 10 pieces/m ² when the copper-clad laminate using the copper foil with the carrier is heated at 220 ° C for 4 hours. In the following, it is more preferably controlled to 5 pieces/m ² or less, and even more preferably controlled to 0 pieces/m ² or less.

The copper-clad laminate using the copper foil with a carrier as described above is used in an extremely thin copper layer in which the peel strength of the carrier from the ultra-thin copper layer is controlled and the carrier is peeled off from the ultra-thin copper layer during heating. It is important to control the number of pinholes and the number of expanded copper foils which are generated during heating to deform the surface of the ultra-thin copper layer.

The expansion between the carrier/very thin copper layer of the copper clad laminate is considered to be intermediate chromatography or adhesion of a hydrate or hydroxide which decomposes by heat to become water vapor. Therefore, in order to suppress it, it is necessary to apply an intermediate layer forming condition in which a hydrate or a hydroxide is difficult to precipitate or adhere, or to decompose-remove a precipitated or attached hydrate or hydroxide.

In addition, the peel strength of the self-extremely thin copper layer of the carrier of the copper-clad laminate must be extremely thin copper The copper of the layer and the metal component of the intermediate layer are moderately dissolved. In order to reduce the peeling strength, it is necessary to suppress the solid solution of the copper component of the ultra-thin copper layer and the metal component of the intermediate layer. Therefore, as a countermeasure thereto, a metal component (chromium or an alloy thereof) for suppressing solid solution with copper may be mentioned. , molybdenum or its alloys, etc., or a metal component (zinc, etc.) that promotes solid solution with copper. In addition, in order to improve the peeling strength, it is necessary to promote the solid solution of the copper component of the ultra-thin copper layer and the metal component of the intermediate layer to some extent. Therefore, as a countermeasure against this, a metal component (chromium) which suppresses solid solution with copper can be mentioned. Or an alloy thereof, molybdenum or an alloy thereof, or an organic layer, or a metal component (zinc or the like) that promotes solid solution with copper. The peel strength can be controlled by applying or adjusting the composition which suppresses and promotes solid solution with copper.

Further, as for the pinholes, as described above, although the peel strength (macroscopic control) from the ultra-thin copper layer for the copper clad laminate control carrier is effective, the peel strength is microscopically uniform by uniformly forming the intermediate layer. (microscopic control) is also effective. In the latter case, even when the measured value of the peel strength becomes high to some extent, the generation of pinholes is suppressed.

[Plating conditions for forming the intermediate layer]

By forming the intermediate layer by the following plating conditions, it is possible to produce a peel strength which suppresses the self-polar copper layer of the carrier as described above, and confirms the peeling of the carrier from the ultra-thin copper layer in the ultra-thin copper layer. The number of pinholes to which the number of pinholes is caused, and the number of pinholes which deform the surface of the extremely thin copper layer during heating is generated. In one embodiment, the copper layer and the zinc chromate-treated layer are sequentially laminated on the carrier to form an intermediate layer, and the parameters thereof are strictly controlled to obtain a desired copper foil. Further, as another embodiment, a desired carrier copper foil can be obtained by sequentially laminating a carrier layer and forming a nickel layer and an organic layer to form an intermediate layer, and controlling the parameters thereof. In still another embodiment, the carrier is formed of a nickel-molybdenum alloy plating layer to form an intermediate layer, and the parameters thereof are controlled to obtain a desired carrier copper foil.

[Formation of nickel plating layer]

As a main means for solving the problem, it is necessary to form a nickel plating layer as an intermediate layer densely and uniformly. In order to achieve this, the nickel plating conditions must be controlled.

Nickel plating:

In the nickel plating process, there are nickel plating treatment (degreasing, pickling) and nickel plating. As a necessary means for solving the problem, it is necessary to control the composition (additive, pH, metal concentration) of the nickel plating bath, the stirring condition of the plating bath when nickel plating, and the current density of nickel plating. Further, although it is not treated before deplating (degreasing, pickling), it is preferable. The conditions of these are described below.

(1) Processing before forming the intermediate layer

In order to more effectively carry out the formation of the intermediate layer, one or both of degreasing and pickling may be carried out.

Pickling - skimming:

For the purpose of cleaning the surface of the intermediate layer and improving the surface wettability, and performing the pickling effectively in the case of pickling after the degreasing treatment, degreasing is carried out. The conditions for degreasing are as follows.

Degreasing solution: sodium hydroxide 1~100g/L

Treatment method: impregnation

Further, in order to reduce the surface tension and perform more effective degreasing, an appropriate amount of a surfactant may be added. Further, in order to perform more effective degreasing, electrolytic degreasing may be used in combination. As a degreasing method at this time, the following methods are mentioned, for example.

Cathodic degreasing only (about 10A/dm ² )

Anode degreasing only (about 5A/dm ² )

Cathode degreasing → anode degreasing

Cathode degreasing→anode degreasing→cathode degreasing

The pickling can also be carried out by removing the copper oxide on the surface of the carrier copper to expose the active copper surface for the purpose of subsequent processing. As a method of pickling, the following methods are mentioned, for example.

Pickling solution: sulfuric acid 10~100mL/L

Treatment method: impregnation

Further, in order to expose the active copper surface more effectively, an oxidizing agent such as persulfate or hydrogen peroxide may be added as appropriate.

(2) forming an intermediate layer

(2-1) Nickel plating

As a condition for obtaining a dense and uniform nickel plating film, it is necessary to control the pH value, current density, and stirring of the plating bath. The conditions for nickel plating are described below.

Nickel concentration: 20~200g/L

Boric acid concentration: 5~60g/L

Liquid temperature: 40~65°C

pH: 1.5~5.0, more preferably 2.0~3.0

Since the surface of the cathode becomes a reducing environment by lowering the pH value, hydrogen gas is generated, so that generation of hydroxide, water, and substance can be suppressed.

Current density: 0.5~20A/dm ² , more preferably 2~8A/dm ²

By reducing the current density, it is difficult to form a scorch plating layer, which can be a more dense plating layer.

Stirring (solution circulation): 100~1000L/min

If the amount of solution circulation is large, the gas released due to the generated hydrogen gas becomes good, so the needle There are fewer defects such as holes. Further, the effect of reducing the thickness of the diffusion layer is to suppress the formation of hydroxide, water, and matter.

Transfer speed (process speed in the length direction): 2~30m/min, more 5~10m/min

A slower and dense nickel film can be formed at a slower transfer speed.

additive:

By using a brightener in the additive, the crystal is dense and smooth, and the amount of formation of hydroxide, water, and substance which causes expansion is reduced. The additives used are as described below.

(primary gloss agent)

2~10g/L of 1-5 naphthalene ‧ disulfonate, or 10~30g / L of 1-3-6 naphthalene ‧ trisulphonate, or 0.5 ~ 4g / L of p-toluenesulfonic acid ‧ guanamine, Or any of 0.5~5g/L sodium saccharin.

(secondary gloss agent)

0.5~5g/L of formalin, or 0.005~0.5g/L of gelatin, or 0.05~1.0g/L of thiourea, or 0.01~0.3g/L of propargyl alcohol, or 0.05~0.5g/L Any one of 1-4 butynediol or 0.05 to 0.5 g/L of 2-cyanohydrin.

(2-2) Nickel-molybdenum alloy plating

As a condition for obtaining a dense and uniform nickel-molybdenum alloy plating film, it is necessary to control the pH value, current density, and stirring of the plating bath. The conditions for nickel-molybdenum alloy plating are described below.

Nickel sulfate: 10~200g/L

Sodium molybdate: 5~60g/L

Sodium citrate concentration: 2~120g/L

Liquid temperature: 20~60°C

pH: 4~7, more preferably 4~5

Since the surface of the cathode becomes a reducing environment by lowering the pH value, hydrogen gas is generated, so that generation of hydroxide, water, and substance can be suppressed.

Current density: 1~10A/dm ² , more preferably 2~4A/dm ²

By reducing the current density, it is difficult to form a scorch plating layer, which can be a more dense plating layer.

Stirring (solution circulation): 100~1000L/min

When the amount of solution circulation is large, since the gas release of the generated hydrogen gas is good, defects such as pinholes are reduced. Further, the effect of reducing the thickness of the diffusion layer is to suppress the formation of hydroxide, water, and matter.

Transfer speed (process speed in the length direction): 2~30m/min, more 5~10m/min

A slower and dense nickel-molybdenum alloy film can be formed at a slower transfer speed.

(3-1) Zinc chromate treatment

Regarding the zinc chromate treatment performed on the above nickel plating layer, a general zinc chromate treatment can be applied, and the conditions are as follows. However, in order to adjust the peel strength of the carrier, it is necessary to adjust the chromium concentration in the chromate bath to the zinc concentration (adjust the chromium concentration/zinc concentration ratio).

Chromium concentration: 0.5~6.0g/L

Zinc concentration: 0.1~2.0g/L

Chromium concentration / zinc concentration: 3~20

pH: 2.5~5.0

Liquid temperature: 25~60°C

Current density: 0.1~4A/dm ²

(3-2) Treatment of forming an organic layer

Regarding the treatment for forming the organic layer on the nickel plating layer described above, for example, the following treatment conditions can be applied.

Carboxybenzotriazole (CBTA): concentration 1~30g/L

Liquid temperature: 35~45°C

pH: 4.5~5.5

Shower spray time: 20~120 seconds

[Treatment after formation of the intermediate layer to the formation of an extremely thin copper layer]

Heat treatment:

By the heat treatment after the formation of the intermediate layer and before the copper plating, there is an effect of removing the water and the hydroxide and the hydroxide itself which are held or precipitated in the intermediate layer when the intermediate layer is formed. As such conditions, the following conditions are mentioned, for example.

Heating conditions: 100 to 200 ° C × 1 minute, preferably 180 ° C × 1 minute

Heating method: IR heater

An oven can also be used instead of the IR heater. Alternatively, by heating while supplying hydrogen gas, it is also possible to have a reducing effect and more effective.

Restore processing:

Since the post-treatment with a reducing agent can reduce the oxygen in the intermediate layer, for example, formic acid can also be used. As such conditions, the following conditions are mentioned, for example.

Formic acid concentration: 0.1~100g/L

Treatment method: impregnation

<very thin copper layer>

An extremely thin copper layer is provided on the intermediate layer. Other layers may be provided between the intermediate layer and the ultra-thin copper layer. The ultra-thin copper layer can be formed by electroplating using an electrolytic bath of copper sulfate, copper pyrophosphate, copper sulfonate, copper cyanide or the like, and is preferable in terms of forming a copper layer at a high current density. It is a copper sulfate bath. Regarding the thickness of the extremely thin copper layer, too thin is not preferable. The reason for this is that, in the case of using a semi-additive method in which a thin copper layer is used as a power supply layer for electroplating copper to form a fine circuit, in the process before the manufacturing process of the printed wiring board, since it is extremely thin in order to remove The intermediate layer component on the copper layer is usually subjected to a small amount of etching on the surface of the ultra-thin copper layer using a chemical reagent such as a sulfuric acid-hydrogen peroxide aqueous solution, and thus a certain thickness of copper is necessary. Further, if the ultra-thin copper layer is too thin, the risk of pinholes due to insufficient nucleation when the extremely thin copper layer is formed becomes high. On the other hand, the thickness of the ultra-thin copper layer is too thick to be too good. The reason is because when a semi-additive method using a profile of a copper foil is used, since an extremely thin copper layer is entirely or partially etched, if the ultra-thin copper layer is too thick, etching must be performed for a long time, and further, etching is performed. As a result of the increased environmental load, the cost of electricity for plating increases, and the cost of wastewater treatment increases. For this reason, the thickness of the ultra-thin copper layer is 1 to 9 μm, preferably 1 to 5 μm, more preferably 1.5 to 3 μm. An extremely thin copper layer can also be provided on both sides of the carrier.

The copper foil with carrier of the present invention may also have one or more layers selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a decane coupling treatment layer on the ultra-thin copper layer.

Further, the copper foil with a carrier of the present invention may have a roughened layer on either or both surfaces of the side surface of the ultra-thin copper layer and the side surface of the carrier, or may further have one or more layers selected from the roughened layer. a layer of a group consisting of a heat resistant layer, a rust preventive layer, a chromate treated layer, and a decane coupling treatment layer. Further, the copper foil with a carrier of the present invention is on the surface of the extremely thin copper layer side and the side surface of the carrier One or more surfaces may be provided in one or more layers selected from the group consisting of a roughened layer, a heat-resistant layer, a rustproof layer, a chromate-treated layer, and a decane coupling treatment layer. Further, in the case where the surface is to be smoothed, the surface of the ultra-thin copper layer side and the surface of the carrier side or both surfaces may be provided with no heat treatment layer, rust preventive layer, or One or more layers of the group consisting of a chromate treatment layer and a decane coupling treatment layer.

The ultra-thin copper layer can be formed by electroplating on the intermediate layer on a continuous roll line of a roll-to-roll type using the conditions shown below.

Copper concentration: 80~120g/L

Sulfuric acid concentration: 80~120g/L

Chloride ion concentration: 30~100ppm

Leveling agent 1 (bis(3-sulfopropyl) disulfide): 10~30ppm

Leveling agent 2 (amine compound): 10~30ppm

Further, the following amine compound was used as the leveling agent 2.

(In the above chemical formula, R ₁ and R ₂ are those selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group)

Electrolyte temperature: 50~80°C

Current density: 100A/dm ²

The application time is adjusted according to the thickness of the extremely thin copper layer

Regarding the copper foil with a carrier, the following roughening treatment, heat treatment, chromate treatment, and decane coupling treatment may be performed on the ultra-thin copper layer.

‧ roughening

(electrolyte composition)

Cu: 10~20g/L

Co: 1~10g/L

Ni: 1~10g/L

pH: 1~4

(electrolyte temperature)

40~50°C

(current condition)

Current density: 25A/dm ²

‧ Heat-resistant treatment (formation of heat-resistant layer)

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

pH: 2~3

Liquid temperature: 40~60°C

Current density: 5~20A/dm ²

‧ chromate treatment (formation of chromate treatment layer)

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

‧ decane coupling treatment (formation of decane coupling treatment layer)

The decane coupling agent coating treatment was carried out by spraying an aqueous solution of 60 ° C containing 0.2 to 2% by mass of alkoxysilane and having a pH of 7 to 8.

Further, the copper foil with a carrier may be provided with a resin layer on the ultra-thin copper layer or the roughened layer or the heat-resistant layer, the rust-proof layer, the chromate-treated layer or the decane coupling treatment layer. The above resin layer may also be an insulating resin layer.

The resin layer may be an adhesive or an insulating resin layer which is followed by a semi-hardened state (B-stage state). The semi-hardened state (B-stage state) includes a state in which the insulating resin layer is superimposed and stored even if the surface is touched with a finger, and the heat-treated reaction is caused by further heat treatment.

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 polyimine resin, a polyfunctional cyanate compound, a maleimide compound, and a butylene.醯imino resin, polyvinyl acetal resin, urethane resin, polyether sulfone, polyether oxime resin, aromatic polyamide resin, polyamidamine (polyamide imide) resin, rubber modified epoxy resin, phenoxy resin, carboxyl modified acrylonitrile-butadiene resin, polyphenylene oxide, bis-xenylenediamine three A resin such as a resin, a thermosetting polyphenylene ether resin, a cyanate resin, or an acid anhydride containing a polyvalent carboxylic acid. Further, the resin layer may be a resin layer containing a block copolymerized polyimide resin or a resin layer containing a block copolymerized polyimide resin and a polysynyleneimine compound. Moreover, those having two or more epoxy groups in the epoxy resin may be used without any particular problem as long as they can be used for electrical or electronic materials. Further, the epoxy resin is preferably an epoxy resin which is epoxidized by using a compound having two or more epoxy propyl groups in the molecule. Further, it may be selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, novolak type epoxy resin, cresol novolac ( Cresol novolac) epoxy resin, alicyclic epoxy resin, brominated epoxy resin, glycidylamine epoxy resin, triglycidylisocyanurate, N,N-diepoxy a glycidylamine compound such as propylaniline, a glycidyl ester compound such as diglycidyl tetrahydrophthalate, a phosphorus-containing epoxy resin, a biphenyl type epoxy resin, a biphenyl novolac type epoxy resin, or the like One or a mixture of two or more of a group of a hydroxyphenylmethane type epoxy resin and a tetraphenylethane type epoxy resin may be used in combination, or a hydrogenated body or a halogenated body of the above epoxy resin may be used.

The resin layer may contain a known resin, a resin curing agent, a compound, a curing accelerator, and a dielectric (a dielectric containing an inorganic compound and/or an organic compound, a dielectric containing a metal oxide, or the like may be used. Dielectric), reaction catalyst, crosslinking agent, polymer, prepreg, framework material, and the like. In addition, the resin layer may be, for example, International Publication No. WO 2008/004399, International Publication No. WO 2008/053878, International Publication No. WO 2009/084533, Japanese Patent Laid-Open No. Hei No. Hei No. Hei No. Hei No. Hei No. 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 Japanese Patent No. 4025177, Japanese Patent Laid-Open No. 2004-349654, Japanese Patent No. 4,286,060, Japanese Patent Laid-Open No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent Laid-Open No. 2005-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415 No., International Publication No. WO2004/005588, Japanese Laid-Open 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 No., No. 2009-67029, International Publication No. 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 And the materials described in International Publication No. WO2009/008471, Japanese Patent Laid-Open No. 2011-14727, International Publication No. WO2009/001850, International Publication No. WO2009/145179, International Publication No. WO2011/068157, Japanese Patent Laid-Open No. 2013-19056 (Resin, Method for forming resin hardener, compound, hardening accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton material, etc. and/or resin layer, forming device To form.

These resins are dissolved in, for example, methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene, methanol, ethanol, propylene glycol Methyl ether, dimethylformamide, dimethylacetamide, cyclohexanone, ethyl cellosolve, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N a solvent such as N-dimethylformamide to form a resin liquid, which is applied to the above-mentioned ultra-thin copper layer by a roll coating method or the like, or the heat-resistant layer, the rust-proof layer, or the aforementioned chromic acid treatment. The layer or the layer of the decane coupling agent is then subjected to heat drying as needed to remove the solvent to form a B-stage state. For drying, for example, a hot air drying oven may be used, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C. The composition of the resin layer may be dissolved by using a solvent to form a resin solid content of 3 wt% to 60 wt%, preferably 10 wt% to 40 wt%. %, more preferably from 25 wt% to 40 wt% of the resin liquid. Further, from the viewpoint of the environment, it is most preferable to use a mixed solvent of methyl ethyl ketone and cyclopentanone for dissolution at this stage.

A copper foil with a carrier (the copper foil with a resin attached) having the above resin layer is used in such a manner that after the resin layer and the substrate are superposed, the entire resin is thermally pressed to heat the resin layer. After hardening, the carrier is peeled off to expose an extremely thin copper layer (of course, the exposed portion is the surface on the intermediate layer side of the ultra-thin copper layer), and a predetermined wiring pattern is formed on the surface of the intermediate layer side.

When the copper foil with a carrier with a resin is used, the number of sheets of the prepreg used when manufacturing the multilayer printed wiring board can be reduced. Further, the copper clad laminate can be produced even if the thickness of the resin layer is such that the thickness of the interlayer insulation can be ensured or the prepreg material is not used at all. Further, at this time, the insulating resin may be applied to the surface of the substrate to further improve the smoothness of the surface.

In addition, when the prepreg material is not used, since the material cost of the prepreg material can be saved and the lamination step is also simplified, it is economically advantageous, and has the following advantages: since there is no thickness of the prepreg material Therefore, the thickness of the multilayer printed wiring board to be manufactured is reduced, and in particular, for the copper foil with a carrier to which the resin is attached, 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 120 μm.

When the thickness of the resin layer is thinner than 0.1 μm, the bonding strength is lowered, and it is sometimes difficult to laminate the resin-attached carrier copper foil to the substrate having the inner layer material without interposing the prepreg material. Ensure interlayer insulation between the inner layer material and the circuit. Further, the total resin layer thickness of the cured resin layer and the semi-hardened resin layer is preferably 0.1 μm to 120 μm, and practically preferably 35 μm to 120 μm. Further, in each case, the thickness of the cured resin layer is preferably 5 to 20 μm, and the thickness of the semi-hardened resin layer is preferably 15 to 115 μm. The reason is that if the total resin layer thickness exceeds 120 μm, it may be difficult to manufacture a multilayer printed wiring board having a small thickness, and if it is less than 35 μm, the capacity is small. It is easy to form a multilayer printed wiring board having a small thickness, but the resin layer which is an insulating layer between the circuits of the inner layer is too thin, and there is a tendency that the insulation between the circuits of the inner layer tends to be unstable. Further, when the thickness of the cured resin layer is less than 5 μm, the surface roughness of the roughened surface of the copper foil may be considered. On the other hand, if the thickness of the hardened resin layer exceeds 20 μm, the effect achieved by the hardened resin layer may not be particularly improved, and the total thickness of the insulating layer may become thick. Further, the thickness of the cured resin layer may be 3 μm to 30 μm. Further, the thickness of the semi-hardened resin layer may be 7 μm to 55 μm. Further, the total thickness of the cured resin layer and the semi-cured resin layer may be 10 μm to 60 μm.

Further, when the copper foil with a carrier-attached resin is used for producing an extremely thin multilayer printed wiring board, the thickness of the resin layer is 0.1 μm to 5 μm, more preferably 0.5 μm to 5 μm, and even more preferably 1 μm to 5 μm is preferable because the thickness of the multilayer printed wiring board can be reduced. Further, when the thickness of the resin layer is 0.1 μm to 5 μm, in order to improve the adhesion between the resin layer and the copper foil, it is preferred to heat the layer and/or the rustproof layer and/or the chromic acid layer and/or After the decane coupling treatment layer is disposed on the roughened layer, a resin layer is formed on the heat-resistant layer or the rust-preventive layer or the chromic acid-treated layer or the decane coupling treatment layer.

Further, when the resin layer contains a dielectric, the thickness of the resin layer is preferably from 0.1 to 50 μm, more preferably from 0.5 μm to 25 μm, still more preferably from 1.0 μm to 15 μm. In addition, the thickness of the said resin layer means the average value of the thickness measured by the observation profile at arbitrary 10 points.

On the other hand, when the thickness of the resin layer is made thicker than 120 μm, it is difficult to form a resin layer of a desired thickness in one application step, and additional material cost and work amount are required, which is economically disadvantageous. Further, since the formed resin layer is inferior in flexibility, cracks or the like are likely to occur during handling, or when it is thermally bonded to the inner layer material, excess resin is discharged, and it is difficult to smoothly laminate.

Further, in another product form with a copper foil with a carrier attached thereto, the resin layer may be coated on the ultra-thin copper layer, or the heat-resistant layer, the rust-proof layer, or the chromic acid-treated layer, or the decane coupling described above. After the semi-hardened state is formed on the treated layer, the carrier is subsequently peeled off, and is produced in the form of a resin-attached copper foil in which no carrier is present.

Hereinafter, several examples of manufacturing steps of a printed wiring board using the copper of the present invention will be disclosed.

An embodiment of the method for producing a printed wiring board according to the present invention includes 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 insulating substrate; and forming a very thin copper layer After the side of the insulating substrate is opposed to the insulating substrate, the copper foil and the insulating substrate are laminated, and then the copper-clad laminate is formed by peeling off the carrier of the copper foil with the carrier, and then the semi-additive method is modified. A method of forming a circuit by any of a semi-additive method, a partial addition method, and a subtractive method. The insulating substrate can also be set as an inner layer circuit inlet.

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

Fig. 1 shows a schematic example of a semi-additive method using a copper foil profile. In this method, the surface profile of the copper foil is used. Specifically, first, the copper foil of the present invention is laminated on a resin substrate to produce a copper clad laminate. Next, the copper foil of the copper clad laminate was subjected to the entire surface etching. Next, electroless copper plating is applied to the surface of the resin substrate (the entire surface etching substrate) to which the surface profile of the copper foil is transferred. Then, the resin substrate (the entire surface etching substrate) is coated with a dry film or the like without forming an electric circuit, and the surface of the electroless copper plating layer which is not coated with the dry film is plated (electrolyzed) with copper. Then, after the dry film is removed, the electroless copper plating layer formed in the portion where the circuit is not formed is removed, whereby A subtle circuit.

An embodiment of a method for producing a printed wiring board according to the present invention using a semi-additive method includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and laminating the copper foil with the insulating substrate; After laminating the copper foil with the carrier and the insulating substrate, the carrier of the copper foil with the carrier is peeled off; and the ultra-thin copper layer exposed by peeling off the carrier is completely removed by etching or plasma etching using an etching solution such as acid; Providing a through hole or/and a blind hole in the resin exposed by removing the ultra-thin copper layer by etching; removing a region containing the through hole or/and the blind hole; and containing the resin and the above An electroless plating layer is disposed in a region of the through hole or/and the blind hole; a plating resist is disposed on the electroless plating layer; and the plating resist is exposed, and then the plating of the region where the circuit is formed is removed a resisting agent; an electrolytic plating layer disposed on the circuit-formed region from which the plating resist is removed; removing the plating resist; and removing the circuit formed by the flash etching or the like Electroless plating cladding layer region outside the domain.

Another embodiment of the method for producing a printed wiring board according to the present invention using a semi-additive method includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and laminating the copper foil with the carrier and the insulating substrate; After laminating the copper foil with the carrier and the insulating substrate, the carrier of the copper foil with the carrier is peeled off; and the ultra-thin copper layer exposed by peeling off the carrier is completely removed by etching or plasma etching using an etching solution such as acid; An electroless plating layer is provided on the surface of the resin exposed by removing the ultra-thin copper layer by etching or the like; a plating resist is provided on the electroless plating layer; and the plating resist is exposed, and then removed a plating resist formed in a region of the circuit; an electrolytic plating layer disposed on the circuit-formed region from which the plating resist is removed; removing the plating resist; and removing by flash etching or the like Formed with a circuit An electroless plating layer and an extremely thin copper layer in areas other than the area.

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

Therefore, in one embodiment of the method for producing a printed wiring board of the present invention using the modified semi-additive method, the method comprises the steps of: preparing the copper foil and the insulating substrate with a carrier of the present invention; and the copper foil and the insulating substrate with the carrier After laminating the copper foil with the carrier and the insulating substrate, the carrier of the copper foil with the carrier is peeled off; and the through hole or/and the blind hole are provided on the ultra-thin copper layer and the insulating substrate exposed by peeling off the carrier; The area containing the through hole or/and the blind hole is subjected to desmear treatment; the electroless plating layer is disposed in the region containing the through hole or/and the blind hole; and the surface of the extremely thin copper layer exposed by peeling off the carrier is plated a resisting agent; after the plating resist is disposed, the circuit is formed by electrolytic plating; the plating resist is removed; and the ultra-thin copper layer exposed by removing the plating resist is removed by flash etching.

In another embodiment of the method for producing a printed wiring board of the present invention using the modified semi-additive method, the method comprises the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and laminating the copper foil with the carrier and the insulating substrate After laminating the copper foil with the carrier and the insulating substrate, the carrier of the copper foil with the carrier is peeled off; a plating resist is provided on the extremely thin copper layer exposed by peeling the carrier; and the plating resist is exposed. Thereafter, removing the plating resist in the region where the circuit is formed; providing an electrolytic plating layer in the circuit-formed region from which the plating resist is removed; removing the plating resist; and flash etching The electroless plating layer and the ultra-thin copper layer located in a region other than the above-described region in which the circuit is formed are removed.

In the present invention, the partial addition method refers to a substrate in which a conductor layer is provided, a catalyst core is provided on a substrate formed by passing through a via hole or an auxiliary hole, and etching is performed to form a conductor circuit. After a solder resist or a plating resist is required, a via hole, an auxiliary hole, or the like is thickened on the conductor circuit by electroless plating to form a printed wiring board.

Therefore, in one embodiment of the method for producing a printed wiring board of the present invention using a partial addition 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 with the insulating substrate After laminating the copper foil with the carrier and the insulating substrate, the carrier of the copper foil with the carrier is peeled off; and the through hole or/and the blind hole are provided on the ultra-thin copper layer and the insulating substrate exposed by peeling the carrier; The region of the through hole or/and the blind hole is subjected to desmear treatment; the catalyst core is provided in the region containing the through hole or/and the blind hole; and the etching resist is disposed on the surface of the extremely thin copper layer exposed by peeling off the carrier; Exposing the etching resist to form a circuit pattern; removing the ultra-thin copper layer and the catalyst core by etching or plasma etching using an etching solution such as acid to form a circuit; removing the etching resist; Etching or plasma etching of an etching solution such as an acid to remove the surface of the insulating substrate exposed by the ultra-thin copper layer and the catalyst core, and providing a solder resist or a plating resist; Region of the solder resist or plating resist provided the electroless plating layer.

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 one embodiment of the method for producing a printed wiring board of the present invention using the subtractive method, the method comprises the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and laminating the copper foil with the carrier; After laminating the copper foil with the carrier and the insulating substrate, the carrier of the copper foil with the carrier is peeled off; the ultra-thin copper layer and the insulation are exposed after peeling off the carrier a through hole or/and a blind hole is disposed on the substrate; a desmear treatment is performed on the region including the through hole or/and the blind hole; and an electroless plating layer is disposed in the region including the through hole or/and the blind hole; An electroless plating layer is disposed on the surface of the electroless plating layer; an etching resist is disposed on the surface of the electrolytic plating layer or/and the ultra-thin copper layer; and the etching resist is exposed to form a circuit pattern; Etching or plasma etching of the etching solution removes the ultra-thin copper layer, the electroless plating layer and the electrolytic plating layer to form a circuit, and removes the etching resist.

Another embodiment of the method for producing a printed wiring board according to the present invention using the subtractive method includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; and laminating the copper foil with the insulating substrate; After laminating the copper foil with the carrier and the insulating substrate, the carrier of the copper foil with the carrier is peeled off; and the through hole or/and the blind hole are provided on the ultra-thin copper layer and the insulating substrate exposed by peeling off the carrier; a region of the hole or/and the blind hole is subjected to desmear treatment; an electroless plating layer is disposed in the region containing the through hole or/and the blind hole; a mask is formed on the surface of the electroless plating layer; An electrolytic plating layer is disposed on a surface of the electroless plating layer of the cover; an etching resist is disposed on a surface of the electrolytic plating layer or/and the ultra-thin copper layer; and the etching resist is exposed to form a circuit pattern; The ultra-thin copper layer and the electroless plating layer are removed by etching or plasma etching of an etching solution such as acid to form a circuit; and the etching resist is removed.

The step of providing a through hole or/and a blind hole, and the subsequent desmear step may also be omitted.

Moreover, the method for producing a printed wiring board according to the present invention includes the steps of: preparing a copper foil with a carrier of the present invention and an insulating substrate; laminating the copper foil with the carrier and the insulating substrate to form a copper clad laminate; and the copper clad laminate By semi-additive method, subtractive method, partial addition method or modified half The circuit is formed by any of the methods of addition, and further, in the step of forming the circuit, the carrier is peeled off before the etching or opening process of the ultra-thin copper layer is being performed. With this configuration, the very thin ultra-thin copper layer surface is supported and protected by the carrier just before the very thin copper layer is being processed. Therefore, the operability of the extremely thin copper layer and the suppression of damage to the extremely thin copper layer become good.

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. Further, in the method for producing a printed wiring board described below, a copper which is not provided with a roughened layer may be used.

Step 1: First, a copper foil (layer 1) with a very thin copper layer or carrier is prepared, and the ultra-thin copper layer and the carrier are formed with a roughened layer on the surface.

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

Step 3: Next, after forming a plating layer for the circuit, the resist is removed, thereby forming a circuit plating of a predetermined shape.

Step 4: Next, a resin layer is laminated on the ultra-thin copper layer or on the carrier by covering the circuit plating layer (in the form of a buried circuit plating layer), and then the additional resin layer is bonded from the very thin copper layer side or the carrier side. Carrier copper foil (layer 2).

Step 5: Next, the carrier is stripped from the carrier copper foil of the second layer. Alternatively, a copper foil having no carrier may be used as the second layer.

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

Step 7: Next, the copper is buried in the blind via to form a via fill.

Step 8: Next, on the hole filling, in the case of further need, the above step 2 And the way of 3 forms a circuit coating.

Step 9: Next, the carrier or the ultra-thin copper layer is stripped from the carrier copper foil of the first layer.

Step 10: Next, the ultra-thin copper layer on both surfaces is flash-etched (when the second layer is provided with a copper foil, it is a copper foil; when the carrier is roughened, the first layer is provided) In the case of a plating layer for a circuit, the carrier is removed to expose the surface of the circuit plating layer in the resin layer.

Step 11: Next, bumps are formed on the circuit plating layer in the resin layer, and a pillar is formed on the solder. A printed wiring board using the copper foil with a carrier of the present invention was produced in this manner.

The above-mentioned additional 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 circuit of one layer or a plurality of layers may be further formed, or may be a semi-additive method, a subtractive method, a partial addition method or a modified semi-additive method. Either method performs its circuit formation.

According to the method for manufacturing a printed wiring board described above, since the circuit plating layer is embedded in the resin layer, for example, when the ultra-thin copper layer is removed by flash etching as in step 10, the circuit plating layer is protected by the resin layer. The shape is maintained, whereby the fine circuit can be easily formed. Further, since the circuit plating layer is protected by the resin layer, the migration resistance is improved, and the conduction of the wiring of the circuit is favorably suppressed. Therefore, a fine circuit can be easily formed. Moreover, as shown in steps 10 and 11, when the ultra-thin copper layer is removed by flash etching, since the exposed surface of the circuit plating layer is recessed from the resin layer, bumps can be easily formed on the circuit plating layer. And the copper pillars can be easily formed further thereon to improve the manufacturing efficiency.

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

Further, the copper foil with a carrier to be used for the first layer may have a substrate or a resin layer on the surface of the copper foil to be coated. The copper foil with a carrier used for the first layer is supported by the substrate or the resin layer, and wrinkles are less likely to occur, so that productivity is improved. Further, if the substrate or the resin layer has an effect of supporting the copper foil with a carrier to be used for the first layer, all of the substrate or the resin layer can be used. For example, 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, a foil of an inorganic compound, an organic compound plate, or an organic compound described in the present specification can be used. The foil serves as the aforementioned substrate or resin layer.

Further, the printed circuit board is completed by mounting the electronic component on the printed wiring board. In the present invention, the "printed wiring board" also includes a printed wiring board, a printed circuit board, and a printed circuit board on which electronic components are mounted in this manner.

Moreover, an electronic device can be produced using the printed wiring board, and an electronic device can be manufactured 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]

Hereinafter, description will be made based on examples and comparative examples. Furthermore, this embodiment is merely an example and is not limited to this example.

1. Manufacture of carrier copper foil

As the carrier, a long strip of electrolytic copper foil having the thickness described in the table was prepared.

The electrolytic copper foil is JTC raw foil manufactured by JX Nippon Mining & Metal Co., Ltd.

The intermediate layer was formed by electroplating the shiny side of the copper foil by a roll-to-roll type continuous plating line under the following conditions.

[Plating conditions for forming the intermediate layer]

By forming the intermediate layer by the plating conditions of the following examples, the peel strength of the self-exact thin copper layer using the carrier in the copper-clad laminate with the carrier copper foil can be prepared and heated under predetermined conditions. When the carrier is peeled off from the ultra-thin copper layer, the number of pinholes confirmed in the ultra-thin copper layer, the number of occurrences of expansion between the carrier and the ultra-thin copper layer and the deformation of the surface of the ultra-thin copper layer when heated under the predetermined conditions are suppressed. With the carrier copper foil. The respective processing conditions are shown below.

[Forming an intermediate layer]

(1) Processing before forming the intermediate layer

In Examples 1 to 12 and Comparative Examples 1 and 2, the carrier was subjected to the degreasing and pickling treatments described below. In Comparative Examples 3 to 6, no degreasing or pickling treatment was carried out.

Degreasing:

Chemical reagent: 40~50g/L aqueous sodium hydroxide solution

Treatment method: impregnation

Processing time: about 10 seconds

Pickling:

Chemical reagent: 40~60g/L aqueous solution of sulfuric acid

Treatment method: impregnation

Processing time: about 10 seconds

(2-1) Nickel plating: Examples 1 to 10, 12, and Comparative Examples 1 to 6

Chemical reagents:

Nickel concentration: 70~80g/L

Boric acid concentration: 30~40g/L

Liquid temperature: 50~55°C

pH: 2.5~3.0

Current density: 5A/dm ²

Stirring (liquid circulation amount): 500L/min

Transfer speed: 5~10m/min

(Adjusted to nickel plating adhesion of 3000μg/dm ² )

With respect to Examples 1, 2, 3, 5, 8, and 9, and Comparative Example 3, the following two kinds of brighteners were further added.

additive:

One brightener: 1-5 naphthalene sodium disulfonate 4~6g/L

Secondary gloss: thiourea 0.05~1.0g/L

(2-2) Nickel-Molybdenum Alloy Plating: Example 11

Chemical reagents:

Nickel sulfate: 35~45g/L

Sodium molybdate dihydrate concentration: 50~60g/L

Sodium citrate concentration: 85~95g/L

Liquid temperature: 28~32°C

pH: 4~5

Current density: 3A/dm ²

Stirring (liquid circulation amount): 500L/min

Transfer speed: 5~10m/min

(Adjusted to a nickel adhesion of 400 μg/dm ² and a molybdenum adhesion of 200 μg/dm ² )

(3-1) Zinc chromate treatment: Examples 1 to 10, Comparative Examples 1 to 6

The conditions for treating zinc chromate formed on the above nickel plating layer are set to the following conditions.

Chromium concentration: 0.5~6.0g/L

Zinc concentration: 0.1~2.0g/L

pH: 2.5~5.0

Liquid temperature: 25~60°C

Current density: 0.1~4A/dm ²

In order to adjust the peel strength, the weight concentration ratio (chromium concentration/zinc concentration) of the chromium concentration to the zinc concentration in the chromate bath was adjusted as follows.

Examples 9, 10, Comparative Example 1: Chromium concentration / zinc concentration = 14

Examples 1 to 5 and Comparative Examples 2 to 5: chromium concentration/zinc concentration=10

Example 6: Chromium concentration / zinc concentration = 7

Examples 7-8: Chromium concentration/zinc concentration=5

Comparative Example 6: chromium concentration / zinc concentration = 3

(3-2) Organic layer formation treatment: Example 12

The treatment for forming an organic layer on the nickel plating layer described above is carried out under the following conditions.

Carboxybenzotriazole (CBTA): concentration 5g / L

Liquid temperature: 40 ° C

pH: 5

Shower spray time: 25 seconds

[Treatment after formation of the intermediate layer until the formation of a very thin copper layer]

After forming the intermediate layer, heat treatment was performed under the following conditions using an IR heater until an extremely thin copper layer was formed.

Examples 1 to 4, 6, 7, 11, 12, and Comparative Example 4: 200 ° C × 1 minute

Example 8: 150 ° C × 1 minute

Example 9, Comparative Example 1: 50 ° C × 1 minute

Example 10: 100 ° C × 1 minute

Regarding Example 5 and Comparative Examples 2, 3, 5, and 6, heat treatment was not performed.

Then, on the roll-to-roll type continuous plating line, an ultra-thin copper layer having the thickness described in the table was formed by electroplating under the conditions shown below, and a copper foil with a carrier was produced. These conditions are applied to all of the comparative examples and examples.

Copper concentration: 100~110g/L

Sulfuric acid concentration: 80~90g/L

Chloride ion concentration: 40~60ppm

Leveling agent 1 (bis(3-sulfopropyl) disulfide): 20~30ppm

Leveling agent 2 (amine compound): 15~20ppm

Further, the following amine compound was used as the leveling agent 2.

(In the above chemical formula, R ₁ and R ₂ are those selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group)

Electrolyte temperature: 55 ° C

Current density: 100A/dm ²

The application time is adjusted according to the thickness of the extremely thin copper layer

In all of the examples and comparative examples, the following roughening treatment, heat treatment, chromate treatment, and decane coupling treatment were carried out on the ultra-thin copper layer with the carrier copper foil.

‧ roughening

(electrolyte composition)

Cu: 15~20g/L

Co: 5~10g/L

Ni: 5~10g/L

pH: 2~3

(electrolyte temperature)

55 ° C

(current condition)

Current density: 25A/dm ²

‧ Heat-resistant treatment (formation of heat-resistant layer)

Liquid composition: nickel 10~15g/L, cobalt 3~5g/L

pH: 2.5

Liquid temperature: 50 ° C

Current density: 10A/dm ²

‧ chromate treatment (formation of chromate treatment layer)

Liquid composition: potassium dichromate 5~8g/L, zinc 1~2g/L

pH: 3.5

Liquid temperature: 55~60°C

Current density: 1A/dm ²

‧ decane coupling treatment (formation of decane coupling treatment layer)

The decane coupling agent is applied by spraying an aqueous solution of 60 ° C containing 0.5 to 1% by mass of alkoxy decane and having a pH of 7 to 8.

2. Evaluation of carrier copper foil

Each of the samples of the examples and the comparative examples obtained in the above manner was subjected to various evaluations as follows.

‧ peel strength

The aluminum foil side of the carrier copper foil is thermocompression bonded to the BT resin in the atmosphere at a pressure of 20 kgf/cm ² and 220 ° C for 2 hours (using two pieces of three) A double-sandylene diimide-based resin, a prepreg having a thickness of 100 μm manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used to produce a double-sided copper-clad laminate.

Then, the carrier of the copper clad laminate was stretched from the ultra-thin copper layer by a force measuring device, and the peel strength was measured in accordance with a 90° peeling method (JIS C 6471 8.1).

‧The number of expansions (heated at 220 ° C for 4 hours)

The double-sided copper-clad laminate produced under the above conditions was heated in an atmospheric heating furnace at 220 ° C for 4 hours. After heating, the carrier was peeled off by hand, and the surface deformation of the ultra-thin copper layer was visually counted and converted into a number per 1 m ² .

‧The number of pinholes

The double-sided copper-clad laminate produced under the above conditions was heated in an atmospheric heating furnace at 220 ° C for 4 hours. Next, the carrier adhered to both sides of the copper-clad laminate is peeled off, and the entire surface of the ultra-thin copper foil on one side (the side) is coated with an adhesive film, and the chemical-resistant tape is used to shield the four sides, and copper (II) chloride is used. The commercially available etching solution as the main component etches the entire surface of the opposite side (opposite side). Further, the chemical resistant tape and the adhesive film on the four sides of the side are peeled off. Thereafter, the pinholes present on the extremely thin copper layer on the side are visually inspected by a light penetrating method, and the marks are marked. Then, the pinholes marked with the marks were observed with an optical microscope, and pinholes having a diameter of 10 μm or more were counted, and the number per unit area was set. Further, in the case where a straight line is taken up by the pinhole observed by the optical microscope, the length of the longest portion of the straight line that crosses the pinhole is the diameter of the pinhole.

‧Operability

The evaluation of the operability of the double-sided copper-clad laminate to which the ultra-thin copper foil with a carrier was attached was as follows. In other words, one side of the 50 cm square double-sided copper-clad laminate which was laminated and pressed was faced to the ground, and was naturally dropped 10 times from the height of 1 m. Next, the opposite surface of the double-sided copper-clad laminate was faced to the ground, and was naturally dropped 10 times from the height of 1 m. After the completion of the test, the carrier copper of the copper foil with the carrier coated on both sides of the double-sided copper-clad laminate was visually confirmed, and the edge of the carrier was not peeled off from the copper laminate. ), even if there are few but also peelers, it is judged as NG (×).

‧ warpage

The copper foil with a carrier was set as a square-shaped sheet sample of a longitudinal direction × width = 10 cm × 10 cm, and it was placed on a flat table, and the amount of warpage of the four corners was measured, and the average value was made into the amount of warpage.

‧Circuit formation evaluation in the semi-additive method

With respect to the double-sided copper-clad laminate produced under the above conditions, the formation of fine wiring having a line/pitch of 15/15 μm and 30/30 μm was carried out by the following procedure. Further, during the steps of the plural, a general water washing or pickling is carried out.

‧ heating of copper laminates

The double-sided copper-clad laminate was heated in an atmospheric heating furnace at 220 ° C for 4 hours in a state in which the carrier copper foil was attached.

‧ Stripping carrier with carrier copper foil

The carrier with the carrier copper foil was slowly peeled off by hand from both sides of the copper clad laminate.

‧ etch the entire surface

Both sides of the ultra-thin copper layer on both sides of the copper-clad laminate are completely etched using a commercially available etching solution containing copper (II) chloride as a main component.

The subsequent work is performed only on one side of the resin substrate.

‧ Electroless copper plating

The catalyst and electroless copper plating for depositing electroless copper were applied to the entire one side of the substrate surface on which the entire surface was etched. The thickness of the electroless copper plating was set to 1 μm.

Chemical reagent: KAP-8 bath made by Kanto Chemicals

Electroless copper plating conditions:

CuSO ₄ concentration 0.06mol/L

HCHO concentration 0.5mol/L

EDTA concentration 0.12mol/L

pH 12.5

Add 剤: 2,2'-bipyridine

Additive concentration: 10mg/L

Surfactant: REG-1000

Surfactant concentration: 500mg/L

‧Substrate pretreatment

In order to clean the surface of the electroless copper plating, the following degreasing and pickling treatments were carried out.

Degreasing treatment:

Chemical reagent: 3vol% sodium hydroxide solution

Temperature: 40 ° C

Time: 60 minutes

Pickling:

Chemical reagent: 10 vol% SAS aqueous solution (5% aqueous hydrochloric acid solution manufactured by Murata Co., Ltd.)

Temperature: 23 ° C

Time: 60 seconds

‧ dry film laminate

The dry film is laminated on the electroless copper plating surface by a roll-to-roller.

Product Name: Photec RY5325 manufactured by Hitachi Chemical Co., Ltd.

Laminated pressure: 0.4MPa

Laminated temperature: 110 ° C

Stacking speed: 1.5m/min

‧Dry film exposure-development

The exposure and development of the dry film were carried out under the following conditions.

exposure:

Exposure machine: EXM-1201 (using a parallel light exposure machine manufactured by ORC Manufacturing Co., Ltd.)

Light source: short arc lamp 5kW

Light meter: UV-350 SN type

Use mask: 41-segment trapezoidal plate (mask)

development:

Developer: 30 ° C, 1 wt% sodium carbonate aqueous solution

Spray pressure: 0.16MPa

‧Electroplating copper

Electrolytic plating was further carried out on the electroless copper plating layer using the following copper sulfate electrolyte solution. The copper thickness (total thickness of electroless plating and electrolytic plating) was set to 16 μm.

Chemical reagent: Cupracid HL bath (manufactured by Atoteck Japan Co., Ltd.)

Liquid temperature: 23 ° C

Current density: 1.2A/dm ²

‧ peel dry film

Stripping solution: 50 ° C, 10 Vol% R-100S + 4Vol% R101 aqueous solution (Mitsubishi Gas Chemical Co., Ltd.)

Spray pressure: 0.15MPa

‧Flash etchant

An etching treatment for removing an unnecessary portion of the copper layer was performed using the following spray etching conditions.

Spray etching conditions:

Etching solution: SE-07 (manufactured by Mitsubishi Gas Chemical Co., Ltd.) (The liquid obtained by diluting SE-07 three times with water is used as an etching solution. The concentration of sulfuric acid (H ₂ SO ₄ ) in the etching solution is 30 g. /L or more, the concentration of hydrogen peroxide (H ₂ O ₂ ) is 21 to 24 g/L, and the Cu concentration is 30 g/L or less.)

Liquid temperature: 35 ° C

Spray pressure: 2.0MPa

‧Is there any confirmation of circuit defects?

The entire surface of the substrate on which the fine circuit was formed by the above method was observed using a metal microscope (×100) to investigate whether or not the circuit was defective. The circuit defect is not set to ○ (OK), and the circuit defect is set to × (NG) even if there is a place.

The test conditions and evaluation results are shown in Table 1.

(Evaluation results)

In Examples 1 to 12, the peel strength of the carrier from the ultra-thin copper layer is 2 to 50 g/cm, and the expansion of the surface deformation of the ultra-thin copper layer is less than 20/dm ² , and the occurrence of pinholes is 400 pieces/m ² or less, both dimensional stability and circuit formation are good.

In Comparative Example 1, the carrier had a small peel strength from the ultra-thin copper layer, and thus the carrier was peeled off during the operation. Further, the occurrence of expansion of the surface of the ultra-thin copper layer is large, and the circuit formation property is poor.

In Comparative Examples 2 and 3, the occurrence of expansion of the surface deformation of the ultra-thin copper layer was large, and the circuit formation property was poor.

In Comparative Example 4, the occurrence of pinholes was large, and the circuit formation property was poor.

In Comparative Example 5, the occurrence of expansion of the surface of the ultra-thin copper layer was large, and the occurrence of pinholes was large, and the circuit formation property was poor.

In Comparative Example 6, the carrier had a large peeling strength from the ultra-thin copper layer and a large warpage. Further, pinholes are generated more and the circuit formation property is poor.

Claims (29)

The carrier copper foil is provided with a carrier, an intermediate layer and an ultra-thin copper layer in sequence, and the thickness of the ultra-thin copper layer is 1 to 9 μm. Regarding the copper-clad laminate body using the copper foil with the carrier, the carrier itself The ultra-thin copper layer has a peeling strength of 2 to 50 g/cm, and when the copper-clad laminate is heated at 220 ° C for 4 hours, it is generated between the carrier and the ultra-thin copper layer and deforms the surface of the ultra-thin copper layer. the expansion of 20 A / dm ^2, 4 hours after the copper clad laminate was heated at 220 deg.] C, when the carrier is peeled from the ultra-thin copper layer, it was confirmed that the pinhole 400 is in the ultra-thin copper layer /m ² or less. The copper foil with carrier of claim 1, wherein the copper foil with the carrier is heated at 220 ° C for 4 hours, and is formed between the carrier and the ultra-thin copper layer and deforms the surface of the ultra-thin copper layer. The expansion is 10/dm ² or less. The copper foil with carrier of claim 2, wherein the copper foil with the carrier is heated at 220 ° C for 4 hours, and is formed between the carrier and the ultra-thin copper layer and deforms the surface of the ultra-thin copper layer. The expansion is 0 / dm ² . The carrier-attached copper foil according to claim 1, wherein the carrier copper foil is heated at 220 ° C for 4 hours, and then the carrier is peeled off from the ultra-thin copper layer, and the ultra-thin copper layer is confirmed. The pinhole is 200 pieces/m ² or less. The copper foil with a carrier according to claim 4, wherein the carrier copper foil is heated at 220 ° C for 4 hours, and then the carrier is peeled off from the ultra-thin copper layer, and the copper foil is confirmed on the ultra-thin copper layer. The pinholes are 50/m ² or less. The copper foil with carrier of the first aspect of the patent application, wherein the thickness of the ultra-thin copper layer is 1 ~3μm. The copper foil with carrier of claim 1, wherein the carrier has a peel strength of 5 to 20 g/cm from the ultra-thin copper layer. The carrier copper foil according to claim 1, wherein the ultra-thin copper layer is provided on both sides of the carrier. The carrier-attached copper foil according to claim 1, wherein the surface of the ultra-thin copper layer side surface and the carrier side surface have a roughened layer. The carrier copper foil according to claim 9, wherein the roughening layer is any one selected from the group consisting of copper, nickel, cobalt, phosphorus, tungsten, arsenic, molybdenum, chromium and zinc. A simple substance or a layer composed of any one or more alloys. The carrier-attached copper foil according to claim 9, wherein the surface of the roughened layer has a group selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate-treated layer and a decane coupling treatment layer. More than one layer. The carrier-attached copper foil according to claim 1, wherein at least one surface or both surfaces of the surface of the ultra-thin copper layer side and the side surface of the carrier have a surface selected from a roughened layer, a heat-resistant layer, and a rust-proof layer. One or more layers of the group consisting of a chromate treatment layer and a decane coupling treatment layer. The carrier copper foil according to claim 1, wherein the ultra-thin copper layer is provided with a resin layer. The carrier-attached copper foil according to claim 9, wherein the roughened layer is provided with a resin layer. A copper foil with a carrier as claimed in claim 12, which is selected from the group consisting of a roughened layer and a heat resistant layer. A resin layer is provided on one or more layers of the group consisting of a layer, a rust preventive layer, a chromate treatment layer, and a decane coupling treatment layer. The copper foil with a carrier according to any one of claims 13 to 15, wherein the resin layer is followed by a resin. The carrier-attached copper foil according to any one of claims 13 to 15, wherein the resin layer is a block copolymerized polyimide resin layer or a block copolymerized polyimide resin and a polybutene A resin layer of a quinone imine compound. The carrier-attached copper foil according to any one of claims 13 to 15, wherein the resin layer is a resin in a semi-hardened state. For example, the carrier copper foil of the first application of the patent scope is used for a semi-additive method. A copper-clad laminate produced by using the carrier-attached copper foil according to any one of claims 1 to 19. A printed wiring board manufactured by using the carrier-attached copper foil according to any one of claims 1 to 19. An electronic machine using the printed wiring board of claim 21 of the patent application. A manufacturing method of a printed wiring board, comprising the steps of: preparing a copper foil with a carrier and an insulating substrate according to any one of claims 1 to 18; and stacking the copper foil with the insulating substrate; After laminating the copper foil with the carrier and the insulating substrate, the copper-clad laminate is formed by the step of peeling off the carrier of the carrier-attached copper foil, and then, by semi-additive method, subtractive method, partial addition The method of forming a circuit by either one of a method or a modified semi-additive method. A manufacturing method of a printed wiring board, comprising the steps of: preparing a copper foil with a carrier and an insulating substrate according to any one of claims 1 to 18; and laminating the copper foil with the insulating substrate to form a coating a step of forming a copper laminate; and a step of forming a circuit by the method of semi-additive, subtractive, partial addition or modified semi-addition; and forming the circuit In the step, the carrier is peeled off before the etching or opening process of the ultra-thin copper layer is being performed. A manufacturing method of a printed wiring board, comprising the steps of: forming a circuit on the side surface of the ultra-thin copper layer of the copper foil with a carrier of any one of claims 1 to 18 or the side surface of the carrier; a step of burying the circuit in a manner of forming a resin layer on the side surface of the ultra-thin copper layer of the carrier copper foil or the side surface of the carrier; forming a circuit on the resin layer; and forming a circuit on the resin layer, peeling off a step of the carrier or the ultra-thin copper layer; and forming the surface of the ultra-thin copper layer or the side surface of the carrier by removing the ultra-thin copper layer or the carrier after peeling off the carrier or the ultra-thin copper layer The step of burying the circuit buried in the resin layer is exposed. The method of manufacturing a printed wiring board according to claim 25, wherein the step of forming a circuit on the resin layer is to attach another copper foil with a carrier to the resin layer from the side of the ultra-thin copper layer. The step of forming the circuit is carried out by attaching a carrier copper foil to the resin layer. A method of manufacturing a printed wiring board according to claim 26, wherein the method is attached to the tree Another carrier-attached copper foil on the lipid layer is the carrier-attached copper foil of any one of claims 1 to 19. The carrier copper foil according to any one of claims 25 to 27, wherein the step of forming a circuit on the resin layer is performed by a semi-additive method, a subtractive method, a partial addition method or a modified half-addition method. Any method of proceeding is carried out. The copper foil with a carrier according to any one of claims 25 to 27, wherein the carrier-attached copper foil forming the circuit on the surface has a carrier side surface or an extremely thin copper layer side surface of the carrier copper foil Substrate or resin layer.