CN110863221A

CN110863221A - Copper foil with carrier

Info

Publication number: CN110863221A
Application number: CN201911075883.1A
Authority: CN
Inventors: 古曳伦也; 永浦友太; 坂口和彦
Original assignee: JX Nippon Mining and Metals Corp
Current assignee: JX Nippon Mining and Metals Corp
Priority date: 2012-11-20
Filing date: 2013-11-20
Publication date: 2020-03-06
Also published as: KR20160145198A; CN104812944A; KR20150086541A; KR20190025739A; CN104812944B; WO2014080959A1; KR102051787B1; PH12015501129A1; KR101954051B1; JP2015078422A; TW201434622A; KR20190103452A; CN110117799A; KR102015838B1; TWI504504B; CN108277509A

Abstract

The invention discloses a copper foil with a carrier. Specifically, the present invention provides a copper foil with a carrier suitable for forming a fine pitch. The copper foil with a carrier of the present invention comprises a carrier, a release layer, an extra thin copper layer, and an arbitrary resin layer in this order, and the average value of Rz of the surface of the extra thin copper layer is 1.5 μm or less as measured by a contact roughness meter in accordance with JIS B0601-1982, and the standard deviation of Rz is 0.1 μm or less.

Description

Copper foil with carrier

The application is a divisional application of a Chinese patent application with the application number of 201711470157.0, the application date of 2013, 11 and 20 days, and the invention name of the divisional application is 'copper foil with carrier', and the application number of 201711470157.0 is a divisional application of a Chinese patent application with the application number of 201380060497.X, the application date of 2013, 11 and 20 days, and the invention name of the divisional application is 'copper foil with carrier'.

Technical Field

The present invention relates to a copper foil with a carrier. More specifically, the present invention relates to a copper foil with a carrier used as a material for a printed wiring board.

Background

A printed wiring board is generally manufactured by bonding a copper foil and an insulating substrate to form a copper-clad laminate, and then forming a conductor pattern on the surface of the copper foil by etching. With the recent increase in the demand for smaller and higher performance electronic devices, high-density mounting of mounted components and high-frequency signals have been advanced, and printed wiring boards are required to have finer conductor patterns (fine pitch) and to cope with high frequencies.

In recent years, copper foils with a thickness of 9 μm or less, and further 5 μm or less have been required in response to finer pitches, but such extremely thin copper foils are low in mechanical strength and are likely to be broken or wrinkled during the production of printed wiring boards, and thus carrier-attached copper foils have been developed in which an extremely thin copper layer is plated through a release layer using a thick metal foil as a carrier. After the surface of the extremely thin copper layer is bonded to an insulating substrate and thermocompression bonded, the carrier is peeled and removed via the peeling layer. A fine circuit is formed by a method (Modified-Semi-Additive-Process) in which a circuit pattern is formed on an exposed extremely thin copper layer with a resist, and then the extremely thin copper layer is etched and removed with a sulfuric acid-hydrogen peroxide etchant.

Here, the surface of the extra thin copper layer of the carrier-attached copper foil to be the surface to be bonded to the resin is mainly required to have sufficient peel strength between the extra thin copper layer and the resin base material, and to sufficiently maintain the peel strength even after high-temperature heating, wet treatment, welding, chemical treatment, or the like. As a method for improving the peel strength between an extremely thin copper layer and a resin substrate, a method of attaching a large number of roughening particles to an extremely thin copper layer having an increased surface profile (roughness, unevenness) is typically used.

However, when such an extremely thin copper layer having a large profile (unevenness, roughness) is used for a semiconductor package substrate on which a fine circuit pattern must be formed in particular in a printed wiring board, there is a problem that unnecessary copper particles remain during circuit etching, and insulation failure between circuit patterns occurs.

Therefore, WO2004/005588 (patent document 1) has attempted to use a carrier-attached copper foil without roughening the surface of the extra thin copper layer as a carrier-attached copper foil for a fine circuit application represented by a semiconductor package substrate. Adhesion (peel strength) between the resin and such an extra thin copper layer not subjected to roughening treatment tends to be lower than that of a typical copper foil for a printed wiring board due to the influence of its low profile (roughness ). Therefore, further improvement is required for the copper foil with a carrier.

Therefore, jp 2007-007937 a (patent document 2) and jp 2010-006071 a (patent document 3) describe providing a Ni layer or/and a Ni alloy layer, providing a chromate layer, providing a Cr layer or/and a Cr alloy layer, providing a Ni layer and a chromate layer, and providing a Ni layer and a Cr layer on the surface of the carrier-attached ultra-thin copper foil in contact with (or in contact with) the polyimide-based resin substrate. By providing these surface-treated layers, it is possible to obtain a desired adhesion strength without roughening treatment or with a reduced degree of roughening treatment (miniaturization) with respect to the adhesion strength between the polyimide resin substrate and the carrier-attached ultra-thin copper foil. Further, it is also described that the surface treatment or rust prevention treatment is performed with a silane coupling agent.

[ patent document 1] WO2004/005588

[ patent document 2] Japanese patent application laid-open No. 2007-007937

[ patent document 3] Japanese patent application laid-open No. 2010-006071.

Disclosure of Invention

[ problems to be solved by the invention ]

Heretofore, carrier-attached copper foils have been developed in which the center of gravity is placed so as to ensure the peel strength between an extremely thin copper layer and a resin substrate. Therefore, sufficient studies have not been made on the finer pitch, and there is still room for improvement. Accordingly, an object of the present invention is to provide a copper foil with a carrier suitable for forming a fine pitch. Specifically, the object is to provide a copper foil with carrier which can form finer wiring than the conventional limit of possible MSAP formation, i.e., L/S of 20 μm/20 μm.

[ means for solving problems ]

As a result of extensive studies to achieve the above object, the present inventors have found that a roughened surface having uniform and low roughness can be formed by reducing the roughness of the surface of an extremely thin copper layer and uniformly forming fine roughened particles in the surface of the extremely thin copper layer. The carrier-attached copper foil was found to be extremely effective in forming a fine pitch.

The present invention has been made in view of the above-mentioned findings, and in one aspect, is a carrier-attached copper foil comprising a carrier, a release layer, an extra thin copper layer, and an arbitrary resin layer in this order, wherein an average value of Rz of a surface of the extra thin copper layer is 1.5 μm or less as measured by a contact roughness meter according to JIS B0601-1982, and a standard deviation of Rz is 0.1 μm or less.

In another aspect, the present invention provides a copper foil with a carrier, which comprises a carrier, a release layer, an extra thin copper layer, and an arbitrary resin layer in this order, wherein an average value of Rt on the surface of the extra thin copper layer is 2.0 μm or less as measured by a contact roughness meter according to JIS B0601-2001, and a standard deviation of Rt is 0.1 μm or less.

In still another aspect, the present invention provides a copper foil with a carrier, which comprises a carrier, a release layer, an extra thin copper layer, and an arbitrary resin layer in this order, wherein an average value of Ra on the surface of the extra thin copper layer is 0.2 μm or less as measured by a contact roughness meter according to JIS B0601-1982, and a standard deviation of Ra is 0.03 μm or less.

In one embodiment of the copper foil with carrier of the present invention, the extra thin copper layer is roughened.

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

In yet another aspect, the present invention is a printed circuit board which is produced using the carrier-attached copper foil of the present invention.

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

[ Effect of the invention ]

The copper foil with carrier of the present invention is suitable for forming a fine pitch, and for example, a finer wiring than the limit of the formation in the MSAP step, i.e., 20 μm/20 μm, such as 15 μm/15 μm, can be formed. In particular, in the present invention, since the surface roughness of the extremely thin copper layer has high in-plane uniformity, the in-plane uniformity is improved in the flash etching when forming a circuit by the MSAP method, and therefore, the yield can be expected to be improved.

Drawings

Fig. 1 is a schematic view showing a foil transporting system using a drum.

Fig. 2 is a schematic view showing a foil transporting method using bending (zigzag folding).

Fig. 3 shows steps a to C of a specific example of a method for manufacturing a printed wiring board using the copper foil with a carrier of the present invention.

Fig. 4 shows steps D to F, which are specific examples of a method for manufacturing a printed wiring board using the copper foil with a carrier of the present invention.

Fig. 5 shows steps G to I of a specific example of a method for manufacturing a printed wiring board using the copper foil with a carrier of the present invention.

FIG. 6 shows steps J to K which are specific examples of a method for producing a printed wiring board using the copper foil with a carrier of the present invention.

Detailed Description

< 1. vector >

The carrier usable in the present invention is typically a metal foil or a resin film, and is provided in the form of, for example, a copper foil, a copper alloy foil, a nickel alloy foil, an iron alloy foil, a stainless steel foil, an aluminum alloy foil, an insulating resin film (for example, a polyimide film, a Liquid Crystal Polymer (LCP) film, a polyethylene terephthalate (PET) film, a polyamide film, a polyester film, a fluororesin film, or the like).

As the carrier usable in the present invention, a copper foil is preferably used. Typically, the carrier is provided in the form of a rolled copper foil or an electrolytic copper foil. Generally, an electrolytic copper foil is produced by electrolytically precipitating copper from a copper sulfate plating bath on a titanium or stainless steel drum, and a rolled copper foil is produced by repeating plastic working with a rolling roll and heat treatment. As a material of the copper foil, in addition to high purity copper such as fine copper or oxygen-free copper, for example, a copper alloy such as Sn-doped copper, Ag-doped copper, a copper alloy to which Cr, Zr, Mg, or the like is added, or a casson-based copper alloy to which Ni, Si, or the like is added may be used. In the present specification, the term "copper foil" used alone also includes copper alloy foils.

The thickness of the carrier usable in the present invention is not particularly limited, and may be appropriately adjusted to a suitable thickness in order to obtain the effect of the carrier, and may be, for example, 12 μm or more. However, since the production cost increases when the thickness is too large, it is generally preferable to be 70 μm or less. Therefore, the thickness of the carrier is typically 12 to 70 μm, and more typically 18 to 35 μm.

< 2 > peeling layer

A release layer is provided on the carrier. Other layers may also be provided between the copper foil carrier and the release layer. The carrier-attached copper foil may be provided with any release layer known to those skilled in the art. For example, the peeling layer is preferably formed of a layer containing at least one of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, an alloy thereof, a hydrate thereof, an oxide thereof, and an organic material. The release layer may be composed of a plurality of layers. Further, the peeling layer may have a diffusion preventing function. Here, the diffusion prevention function is a function of preventing elements from the base material from diffusing to the extremely thin copper layer side.

In one embodiment of the invention, the release layer is composed of, from the carrier side: a single metal layer composed of any one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al and Zn, or an alloy layer composed of at least one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al and Zn, which has a diffusion preventing function, and a layer composed of a hydrate, an oxide or an organic substance of at least one element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al and Zn, which is laminated thereon.

Further, for example, the release layer may be composed of the following layers from the carrier side: a single metal layer composed of any element in the element group of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, or an alloy layer composed of at least one element selected from the element group of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, and a single metal layer composed of any element in the element group of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, or an alloy layer composed of at least one element selected from the element group of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn. The total amount of each element adhered can be, for example, 1 to 6000. mu.g/dm². Further, a layer that can be used as a release layer may be used as another layer.

The release layer is preferably composed of 2 layers of Ni and Cr. In this case, the Ni layer is laminated in contact with the interface with the copper foil carrier, and the Cr layer is laminated in contact with the interface with the extra thin copper layer.

The peeling layer can be obtained by, for example, wet plating such as electroplating, electroless plating, and immersion plating, or dry plating such as sputtering, CVD, and PDV. From the viewpoint of cost, electroplating is preferable.

Further, for example, the release layer may be formed by sequentially laminating nickel, a nickel-phosphorus alloy, or a nickel-cobalt alloy and chromium on the support. Since the adhesion between nickel and copper is higher than the adhesion between chromium and copper, when an extremely thin copper layer is peeled, the peeling is performed at the interface between the extremely thin copper layer and chromium. Further, a barrier effect of preventing diffusion of a copper component from a carrier to an extremely thin copper layer is expected for nickel of the release layer. The amount of nickel attached to the release layer is preferably 100. mu.g/dm²Above and 40000. mu.g/dm²Hereinafter, more preferably 100. mu.g/dm²Above and 4000 mug/dm²Hereinafter, more preferably 100. mu.g/dm²Above 2500 [ mu ] g/dm²Hereinafter, more preferably 100. mu.g/dm²Above and less than 1000 [ mu ] g/dm²The amount of chromium adhered to the release layer is preferably 5. mu.g/dm²Above and 100. mu.g/dm²The following. When a release layer is provided only on one side, it is preferable to provide a rust preventive layer such as a Ni plating layer on the side opposite to the carrier.

Further, the peeling layer may be provided on both sides of the carrier.

< 3. ultrathin copper layer >

An extremely thin copper layer is provided on the release layer. Other layers may also be provided between the lift-off layer and the extremely thin copper layer. The extra thin copper layer can be formed by electroplating using an electrolytic bath containing copper sulfate, copper pyrophosphate, copper sulfamate, copper cyanide, or the like, and a copper sulfate bath is preferable in that a copper foil can be formed at a high current density by using a general electrolytic copper foil. The thickness of the extremely thin copper layer is not particularly limited, and is generally thinner than the carrier, for example, 12 μm or less. Typically 0.5 to 12 μm, more typically 2 to 5 μm. Furthermore, very thin copper layers may also be provided on both sides of the carrier. Further, a layer that can be used as a release layer may be used as another layer.

< 4. roughening treatment >

The surface of the extremely thin copper layer may be roughened to provide a roughened layer, for example, for satisfactory adhesion to the insulating substrate. The roughening treatment can be formed by forming roughening particles using copper or a copper alloy, for example. From the viewpoint of forming a fine pitch, the roughened layer is preferably made of fine particles. As for the plating conditions for forming the coarse particles, if the current density is increased, the copper concentration in the plating solution is decreased, or the coulomb size is increased, the particles tend to be finer.

The coarsening treatment layer can be composed of the following electroplating particles: is composed of a single substance selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt and zinc, or an alloy containing any 1 or more of these substances.

In order to improve the in-plane uniformity of the surface roughness of the surface-treated surface, it is effective to maintain the distance between the anode and the cathode at the time of forming the roughened layer in a fixed manner. In terms of industrial production, a method of securing a fixed inter-electrode distance by a foil transport system using a drum or the like as a support medium is effective. Fig. 1 is a schematic view showing the foil transportation system. A roughened particle layer is formed on the surface of an extremely thin copper layer by electrolytic plating while supporting a carrier copper foil conveyed by a conveying roller by a drum. The treated surface of the carrier copper foil supported by the drum also serves as a cathode, and each electrolytic plating is performed in a plating solution between the drum and an anode disposed so as to face the drum. On the other hand, fig. 2 shows a schematic view illustrating a foil transport method using a conventional bending method. This method has a problem that it is difficult to fix the distance between the anode and the cathode due to the influence of the electrolyte, foil transport tension, and the like. Further, in order to fixedly maintain the distance between the anode and the cathode at the time of forming the roughened layer by the folded foil transport method, it is effective to increase the tension for transporting the foil and to shorten the distance between the transport rollers as compared with the conventional method.

As shown in fig. 1, the foil transportation method using a drum can be used not only for roughening treatment but also for forming a peeling layer and forming an extremely thin copper layer. The reason for this is that the thickness accuracy of the release layer or the extremely thin copper layer can be improved by using a foil transporting method using a rotary drum. Further, in order to fixedly hold the distance between the anode and the cathode when the peeling layer or the extremely thin copper layer is formed by the folded foil transporting method, it is effective to increase the tension for transporting the foil and to shorten the distance between the transport rollers as compared with the conventional method.

The inter-electrode distance is not limited, and if it is too long, the production cost increases, while if it is too short, the in-plane unevenness is likely to increase, and therefore, it is generally preferably 3 to 100mm, and more preferably 5 to 80 mm.

After the roughening treatment, secondary particles, tertiary particles and/or a rust-preventive layer may be formed of a single material or an alloy of nickel, cobalt, copper, or zinc, and the surface may be subjected to a chromate treatment, a silane coupling treatment, or the like. That is, 1 or more layers selected from the group consisting of an anticorrosive layer, a chromate treatment layer and a silane coupling treatment layer may be formed on the surface of the roughened layer, or 1 or more layers selected from the group consisting of an anticorrosive layer, a chromate treatment layer and a silane coupling treatment layer may be formed on the surface of the extremely thin copper layer without roughening. Furthermore, these surface treatments have little effect on the surface roughness of the very thin copper layers.

The surface of the extremely thin copper layer (which is referred to as the surface of the extremely thin copper layer after surface treatment (also referred to as "surface-treated surface") when subjected to various surface treatments such as roughening treatment) is extremely advantageous from the viewpoint of forming a fine pitch, when the average value of Rz (ten-point average roughness) is 1.5 μm or less as measured by a contact roughness meter in accordance with JIS B0601-1982. The average value of Rz is preferably 1.4 μm or less, more preferably 1.3 μm or less, more preferably 1.2 μm or less, more preferably 1.0 μm or less, more preferably 0.8 μm or less. However, if the average Rz is too small, the adhesion force with the resin decreases, and in this respect, it is preferably 0.01 μm or more, more preferably 0.1 μm or more, further more preferably 0.3 μm or more, and most preferably 0.5 μm or more.

In the present invention, the average value of Rz is an average value of Rz obtained when the standard deviation of Rz is obtained by the method described below. In the present invention, the standard deviation of Rz of the surface of the extremely thin copper layer can be set to 0.1 μm or less, preferably 0.05 μm or less, for example, 0.01 to 0.7. mu.m. The standard deviation of Rz of the surface of the extremely thin copper layer was determined from the in-plane 100-point measurement data. The in-plane 100-point measurement data was obtained by dividing a 550 mm-square sheet into 10 parts in the longitudinal and transverse directions, and measuring the central portions of the 100 divided regions. This method is used in the present application to maintain in-plane uniformity, but the verification method is not limited thereto. For example, the same data can be obtained even when a sample having a size of 550mm × 440mm to 400mm × 200mm, which is generally used, is divided into 100 parts (divided into 10 parts in the vertical and horizontal directions) in a plane.

In addition, from the viewpoint of fine pitch formation, it is preferable that the extremely thin copper layer surface has an average value of Rt (maximum cross-sectional height) of 2.0 μm or less, preferably 1.8 μm or less, preferably 1.5 μm or less, preferably 1.3 μm or less, preferably 1.1 μm or less, as measured by a contact roughness meter in accordance with JIS B0601-2001. However, if the average value of Rt is too small, the adhesion force with the resin decreases, and in this respect, it is preferably 0.5 μm or more, more preferably 0.6 μm or more, and still more preferably 0.8 μm or more. In the present invention, the average value of Rt is an average value of Rt obtained when the standard deviation of Rt is obtained by the method described below.

In the present invention, the standard deviation of Rt of the surface of the extremely thin copper layer may be 0.1 μm or less, preferably 0.05 μm or less, for example, 0.01 to 0.6. mu.m. The standard deviation Rt of the surface of the extremely thin copper layer was determined from the in-plane 100-point measurement data in the same manner as Rz.

In view of fine pitch formation, the surface of the extra thin copper layer is preferably set to have an average value of Ra (arithmetic mean roughness) of 0.2 μm or less, more preferably 0.18 μm or less, and still more preferably 0.15 μm or less, as measured by a contact roughness meter in accordance with JIS B0601-1982. However, if the average value of Ra is too small, the adhesion force with the resin decreases, and in this respect, it is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.12 μm or more, and most preferably 0.13 μm or more. In the present invention, the average value of Ra is an average value of each Ra obtained when the standard deviation of Ra is obtained by the method described below.

In the present invention, the Ra standard deviation of the surface of the extremely thin copper layer may be 0.03 μm or less, preferably 0.02 μm or less, for example, 0.001 to 0.03 μm. The standard deviation of Ra of the surface of the extra thin copper layer was determined from the in-plane 100-point measurement data in the same manner as Rz.

Further, when an insulating substrate or a resin layer such as a resin is bonded to the surface of an extra thin copper layer such as a copper foil with a carrier having a resin layer, a printed wiring board, or a copper clad laminate, the insulating substrate is melted and removed, whereby the surface roughness (Ra, Rt, Rz) can be measured for the surface of the copper circuit or the copper foil.

< 5. other surface treatment >

After the roughening treatment, a heat-resistant layer or a rust-proof layer may be formed using a single material or an alloy of nickel, cobalt, copper, or zinc, and the surface thereof may be subjected to chromate treatment, silane coupling treatment, or the like. Alternatively, a heat-resistant layer or a rust-proof layer may be formed of a single material or an alloy of nickel, cobalt, copper, or zinc without roughening treatment, and the surface may be subjected to chromate treatment, silane coupling treatment, or the like. That is, 1 or more layers selected from the group consisting of a heat-resistant layer, a rust-preventive layer, a chromate treatment layer and a silane coupling treatment layer may be formed on the surface of the roughened layer, or 1 or more layers selected from the group consisting of a heat-resistant layer, a rust-preventive layer, a chromate treatment layer and a silane coupling treatment layer may be formed on the surface of the extremely thin copper layer. The heat-resistant layer, the rust-preventive layer, the chromate treatment layer, and the silane coupling treatment layer may be formed of a plurality of layers, for example, 2 or more layers and 3 or more layers, respectively.

As the heat-resistant layer and the rust-proof layer, known heat-resistant layers and rust-proof layers can be used. For example, the heat-resistant layer and/or the rust-preventive layer may be a layer containing 1 or more elements selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, and tantalum, or may be a metal layer or an alloy layer containing 1 or more elements selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, and tantalum. The heat-resistant layer and/or the rust-preventive layer may contain an oxide, nitride, or silicide containing 1 or more elements selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, and tantalum. Further, the heat-resistant layer and/or the rust-preventive layer may be a layer containing a nickel-zinc alloy. The heat-resistant layer and/or the rust-preventive layer may be a nickel-zinc alloy layer. The nickel-zinc alloy layer may contain 50 to 99 wt% of nickel and 50 to 1 wt% of zinc, in addition to unavoidable impurities. The total adhesion amount of zinc and nickel in the nickel-zinc alloy layer may be 5 to 1000mg/m²Preferably 10 to 500mg/m²Preferably 20 to 100mg/m². The ratio of the amount of nickel deposited to the amount of zinc deposited (i.e., the amount of nickel deposited/the amount of zinc deposited) in the layer comprising a nickel-zinc alloy or the nickel-zinc alloy layer is preferably 1.5 to 10. The nickel adhesion of the layer containing a nickel-zinc alloy or the nickel-zinc alloy layerThe amount is preferably 0.5mg/m²～500mg/m²More preferably 1mg/m²～50mg/m². When the heat-resistant layer and/or the rust-preventive layer are/is a layer containing a nickel-zinc alloy, the interface between the copper foil and the resin substrate is not easily corroded by the desmear solution when the inner wall portion of the through hole or via (via) is brought into contact with the desmear solution, and the adhesion between the copper foil and the resin substrate is improved.

For example, the heat-resistant layer and/or the rust-preventive layer may be laminated in this order at an adhesion amount of 1mg/m²～100mg/m²Preferably 5mg/m²～50mg/m²Nickel or nickel alloy layer of 1mg/m²～80mg/m²Preferably 5mg/m²～40mg/m²The nickel alloy layer may be made of any one of nickel-molybdenum, nickel-zinc, and nickel-molybdenum-cobalt. The heat-resistant layer and/or the rust-preventive layer preferably have a total adhesion amount of nickel or a nickel alloy and tin of 2mg/m²～150mg/m²More preferably 10mg/m²～70mg/m². Further, the heat-resistant layer and/or the rust-preventive layer are preferably [ the amount of nickel deposited in the nickel or nickel alloy ]]/[ amount of tin deposited]0.25 to 10, more preferably 0.33 to 3. When the heat-resistant layer and/or the rust-proof layer are used, the copper foil with a carrier is processed into a printed wiring board, and the peel strength of a circuit and the rate of deterioration of chemical resistance of the peel strength after processing are improved.

Further, as the silane coupling agent used for silane coupling treatment, a known silane coupling agent may be used, and for example, an amino silane coupling agent, an epoxy silane coupling agent, and a mercapto silane coupling agent may be used, and as the silane coupling agent, vinyltrimethoxysilane, vinylphenyltrimethoxysilane, γ -methacryloxypropyltrimethoxysilane, γ -glycidoxypropyltrimethoxysilane, 4-glycidylbutyltrimethoxysilane, γ -aminopropyltriethoxysilane, N- β - (aminoethyl) - γ -aminopropyltrimethoxysilane, N-3- (4- (3-aminopropylpropoxy) butoxy) propyl-3-aminopropyltrimethoxysilane, imidazolesilane, triazinesilane, and γ -mercaptopropyltrimethoxysilane may be used.

The silane coupling layer can be formed using a silane coupling agent such as epoxy silane, amino silane, methacryloxy silane, mercapto silane, or the like. Further, 2 or more kinds of such silane coupling agents may be used in combination. Among them, those formed using an amino silane coupling agent or an epoxy silane coupling agent are preferable.

The amino silane coupling agent may be selected from the group consisting of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, 3-aminopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- (2-aminoethyl-3-aminopropyl) trimethoxysilane, N- (2-aminoethyl-3-aminopropyl) tris (2-ethylhexyloxy) silane, 6- (aminohexylaminopropyl) trimethoxysilane, aminophenyltrimethoxysilane, 3- (1-aminopropyloxy) -3, 3-dimethyl-1-propenyltrimethoxysilane, 3-aminopropyltris (methoxyethoxyethoxy) silane, 3-aminopropyltriethoxysilane, 3-aminopropyl-3-aminopropyltrimethoxysilane, N- (3-aminopropyl) 3-aminopropyltrimethoxysilane, N- (2-aminopropyl) 3-aminopropyl) trimethoxysilane, N- (3-diethylaminoethyl) -3-aminopropyl) trimethoxysilane, N- (3-2-aminopropyl) trimethoxysilane, N- (3-2-aminopropyl) trimethoxysilane, N-2-aminopropyl) trimethoxysilane, N-3-2-3-2-aminopropyl) trimethoxysilane, N-2-3-2-aminopropyl-2-3-2-aminopropyl-2-3-aminopropyl.

The silane coupling layer is preferably set to 0.05mg/m in terms of silicon atom²～200mg/m²Preferably 0.15mg/m²～20mg/m²Preferably 0.3mg/m²～2.0mg/m²The range of (1). In the case of the above range, the adhesion between the base resin and the surface-treated copper foil can be further improved.

Further, the surface of the extremely thin copper layer, the roughened layer, the heat-resistant layer, the rust-preventive layer, the silane coupling-treated layer or the chromate-treated layer may be subjected to surface treatment as described in International publication No. WO2008/053878, Japanese patent laid-open No. 2008-111169, Japanese patent No. 5024930, International publication No. WO2006/028207, Japanese patent No. 4828427, International publication No. WO2006/134868, Japanese patent No. 5046927, International publication No. WO2007/105635, Japanese patent No. 5180815, or Japanese patent laid-open No. 2013-19056.

[ resin layer on extremely thin copper layer ]

The carrier-attached copper foil of the present invention may be provided with a resin layer on the extra thin copper layer (in the case of surface treatment of the extra thin copper layer, the surface treatment layer formed on the extra thin copper layer by the surface treatment). The resin layer may be an insulating resin layer.

The resin layer may be an adhesive resin or an insulating resin layer in a semi-cured state (B-stage state) for adhesion. The semi-hardened state (B-stage state) includes the following states: the insulating resin layer is not sticky even when the surface is touched by fingers, and can be stored in an overlapped manner, and when the insulating resin layer is further subjected to a heat treatment, a curing reaction is caused.

The resin layer may contain a thermosetting resin or a thermoplastic resin. The resin layer may contain a thermoplastic resin. The resin layer may contain a known resin, resin curing agent, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton material, and the like. The resin layer can be formed by using, for example, a method and an apparatus for forming a resin layer and/or a substance (resin, resin curing agent, compound, curing accelerator, dielectric substance, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton material, etc.) described in the following documents: international publication No. WO2008/004399, International publication No. WO2008/053878, International publication No. WO2009/084533, Japanese patent laid-open No. 11-5828, Japanese patent laid-open No. 11-140281, Japanese patent No. 3184485, International publication No. WO97/02728, Japanese patent No. 3676375, Japanese patent laid-open No. 2000-4 43188, Japanese patent No. 3612594, Japanese patent laid-open No. 2002-179772, Japanese patent laid-open No. 2002-359444, Japanese patent laid-open No. 2003-304068, Japanese patent No. 3992225, Japanese patent laid-open No. 2003-249739, Japanese patent No. 4136509, Japanese patent laid-open No. 2004-82687, Japanese patent No. 4025177, Japanese patent laid-open No. 2004-349654, Japanese patent No. 4286060, 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, Japanese patent publication No. WO2004/005588, Japanese laid-open patent publication No. 2006-257153, Japanese laid-open patent publication No. 2007-326923, Japanese laid-open patent publication No. 2008-111169, Japanese patent publication No. 5024930, International publication No. WO2006/028207, Japanese patent publication No. 4828427, Japanese laid-open patent publication No. 2009-67029, International publication No. WO2006/134868, Japanese patent publication No. 5046927, Japanese laid-open patent publication No. 2009-173017, International publication No. WO2007/105635, Japanese patent publication No. 5180815, International publication No. WO2008/114858, International publication No. WO2009/008471, Japanese laid-open patent publication No. 2011-14727, International publication No. WO2009/001850, International publication No. WO2009/145179, International publication No. WO2011/068157, Japanese laid-open patent publication No. 2013-19056.

The type of the resin layer is not particularly limited, and preferable examples thereof include resins containing one or more selected from the group consisting of: epoxy resin, polyimide resin, polyfunctional cyanate ester compound, maleimide compound, polymaleimide compound, maleimide-based resin, aromatic maleimide resin, polyvinyl acetaldehyde resin, urethane resin, polyethersulfone (also referred to as polyethylsulfone, polyethylsulfolane), polyethersulfone (also referred to as polyethylsulfolane, polyethylsulfolane) resin, aromatic polyamide resin polymer, rubbery resin, polyamine, aromatic polyamine, polyamideimide resin, rubber-modified epoxy resin, phenoxy resin, carboxyl-modified acrylonitrile-butadiene resin, polyphenylene oxide, bismaleimide triazine resin, thermosetting polyphenylene oxide resin, cyanate ester resin, carboxylic acid anhydride, polycarboxylic acid anhydride, linear polymer having crosslinkable functional group, polyphenylene ether resin, 2-bis (4-cyanate ylphenyl) propane resin, polyphenylene oxide resin, 2-bis (4-cyanate ester) propane resin, aromatic maleimide resin, polyvinyl acetal resin, polyether sulfone, aromatic polyamide resin polymer, rubber-based resin, polyamine, aromatic polyamine, polyamideimide resin, rubber-modified epoxy resin, Phosphorus-containing phenol compound, manganese naphthenate, 2-bis (4-glycidylphenyl) propane, polyphenylene ether-cyanate ester resin, silicone-modified polyamideimide resin, cyanoester resin, phosphazene resin, rubber-modified polyamideimide resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, phenoxy group, high-molecular epoxy resin, aromatic polyamide, fluororesin, bisphenol, block copolymerized polyimide resin, and cyanoester resin.

The epoxy resin has 2 or more epoxy groups in the molecule, and can be used without any problem as long as it is usable for electric and electronic materials. The epoxy resin is preferably an epoxy resin obtained by epoxidizing a compound having 2 or more glycidyl groups in the molecule. Further, 1 or 2 or more 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, novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, brominated epoxy resin, phenol novolac type epoxy resin, naphthalene type epoxy resin, brominated bisphenol A type epoxy resin, o-cresol novolac type epoxy resin, rubber modified bisphenol A type epoxy resin, glycidyl amine type epoxy resin, triglycidyl isocyanurate, N, glycidyl amine compounds such as N-diglycidylaniline, glycidyl ester compounds such as tetrahydrophthalic acid diglycidyl ester, phosphorus-containing epoxy resins, biphenyl-type epoxy resins, biphenol-aldehyde-varnish-type epoxy resins, trishydroxyphenylmethane-type epoxy resins, tetraphenylethane-type epoxy resins, and hydrogenated or halogenated products of the above epoxy resins can be used.

As the above-mentioned phosphorus-containing epoxy resin, a known phosphorus-containing epoxy resin can be used. The phosphorus-containing epoxy resin is preferably an epoxy resin obtained as a derivative from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) having 2 or more epoxy groups in the molecule, for example.

The epoxy resin obtained as a derivative from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is prepared by reacting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with naphthoquinone or hydroquinone to prepare a compound represented by the following chemical formula 1(HCA-NQ) or chemical formula 2(HCA-HQ), and then reacting the OH group portion thereof with an epoxy resin to prepare a phosphorus-containing epoxy resin.

[ chemical formula 1]

[ chemical formula 2]

The phosphorus-containing epoxy resin as the component E to obtain the compound is preferably a mixture of 1 or 2 compounds having a structural formula represented by any one of chemical formulas 3 to 5. This is because the resin in a semi-cured state has excellent stability of quality and a high flame retardant effect.

[ chemical formula 3]

[ chemical formula 4]

[ chemical formula 5]

As the brominated epoxy resin, a known brominated epoxy resin can be used. For example, the brominated (brominated) epoxy resin is preferably a brominated epoxy resin having 1 or 2 or more epoxy groups in a molecule and having a structural formula represented by chemical formula 6 obtained as a derivative of tetrabromobisphenol a, or a brominated epoxy resin having a structural formula represented by chemical formula 7 shown below.

[ chemical formula 6]

[ chemical formula 7]

As the maleimide-based resin, the aromatic maleimide-based resin, the maleimide compound or the polymaleimide compound, a known maleimide-based resin, an aromatic maleimide-based resin, a maleimide compound or a polymaleimide compound can be used. For example, as the maleimide-based resin or the aromatic maleimide-based resin or the maleimide compound or the polymaleimide compound, there can be used: 4,4 '-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, bisphenol a diphenyl ether bismaleimide, 3' -dimethyl-5, 5 '-diethyl-4, 4' -diphenylmethane bismaleimide, 4-methyl-1, 3-phenylene bismaleimide, 4 '-diphenyl ether bismaleimide, 4' -diphenylsulfone bismaleimide, 1, 3-bis (3-maleimidophenoxy) benzene, 1, 3-bis (4-maleimidophenoxy) benzene, and a polymer obtained by polymerizing the above compound with the above compound or another compound. The maleimide-based resin may be an aromatic maleimide resin having 2 or more maleimide groups in the molecule, or a polymer adduct obtained by polymerizing an aromatic maleimide resin having 2 or more maleimide groups in the molecule with a polyamine or an aromatic polyamide.

As the polyamine or the aromatic polyamine, a known polyamine or an aromatic polyamine can be used. For example, as the polyamine or the aromatic polyamine, there can be used: m-phenylenediamine, p-phenylenediamine, 4' -diaminodicyclohexylmethane, 1, 4-diaminocyclohexane, 2, 6-diaminopyridine, 4' -diaminodiphenylmethane, 2-bis (4-aminophenyl) propane, 4' -diaminodiphenyl ether, 4' -diamino-3-methyl diphenyl ether, 4' -diaminodiphenyl sulfide, 4' -diaminobenzophenone, 4' -diaminodiphenyl sulfone, bis (4-aminophenyl) phenylamine, m-xylylenediamine, p-xylylenediamine, 1, 3-bis [ 4-aminophenoxy ] benzene, 3-methyl-4, 4' -diaminodiphenylmethane, 3' -diethyl-4, 4 '-diaminodiphenylmethane, 3' -dichloro-4, 4 '-diaminodiphenylmethane, 2',5,5 '-tetrachloro-4, 4' -diaminodiphenylmethane, 2-bis (3-methyl-4-aminophenyl) propane, 2-bis (3-ethyl-4-aminophenyl) propane, 2, 2-bis (2, 3-dichloro-4-aminophenyl) propane, bis (2, 3-dimethyl-4-aminophenyl) phenylethane, ethylenediamine and hexamethylenediamine, 2-bis (4- (4-aminophenoxy) phenyl) propane, and polymers obtained by polymerizing the above compounds with the above compounds or other compounds. One or more kinds of known polyamines and/or aromatic polyamines, or the above-mentioned polyamines or aromatic polyamines can be used.

As the phenoxy resin, a known phenoxy resin can be used. The phenoxy resin may be synthesized by reacting bisphenol with a 2-valent epoxy resin. As the epoxy resin, a known epoxy resin and/or the above epoxy resin can be used.

As the bisphenol, known bisphenols may be used, and bisphenols obtained as an adduct of bisphenol a, bisphenol F, bisphenol S, tetrabromobisphenol a, 4' -dihydroxybiphenyl, HCA (9, 10-Dihydro-9-Oxa-10-photophenanthrene-10-Oxide) and quinones such as hydroquinone and naphthoquinone may be used.

As the linear polymer having a crosslinkable functional group, a known linear polymer having a crosslinkable functional group can be used. For example, the linear polymer having a crosslinkable functional group preferably has a functional group such as a hydroxyl group or a carboxyl group which contributes to a curing reaction of the epoxy resin. The linear polymer having a crosslinkable functional group is preferably soluble in an organic solvent having a boiling point of 50 to 200 ℃. Specifically, the linear polymer having a functional group as referred to herein is exemplified by a polyethylene-acetaldehyde resin, a phenoxy resin, a polyethersulfone resin, a polyamideimide resin, or the like.

The resin layer may contain a crosslinking agent. The crosslinking agent may be a known crosslinking agent. For example, a urethane resin can be used as the crosslinking agent.

The rubber resin may be a known rubber resin. For example, the above-mentioned rubbery resin is described as a concept including natural rubber and synthetic rubber, and the latter synthetic rubber includes styrene-butadiene rubber, butyl rubber, ethylene-propylene rubber, acrylonitrile-butadiene rubber, acrylic rubber (acrylate copolymer), polybutadiene rubber, isoprene rubber, and the like. Further, in order to secure heat resistance of the formed resin layer, it is also useful to select and use a synthetic rubber having heat resistance, such as nitrile rubber, chloroprene rubber, silicone rubber, or urethane rubber. These rubber resins preferably have various functional groups at both ends in order to produce a copolymer by reacting with an aromatic polyamide resin or a polyamideimide resin. In particular, CTBN (carboxy-terminal succinonitrile) is useful. Further, when the acrylonitrile butadiene rubber is also a carboxyl group-modified material, the epoxy resin and the crosslinked structure can be obtained, and the flexibility of the cured resin layer can be improved. As the carboxyl group-modified substance, carboxyl group-terminated nitrile rubber (CTBN), carboxyl group-terminated butadiene rubber (CTB) or carboxyl group-modified nitrile rubber (C-NBR) can be used.

As the polyamide-imide resin, a known polyimide-amide resin can be used. As the polyimide amide resin, for example, there can be used: a resin obtained by heating trimellitic anhydride, benzophenone tetracarboxylic anhydride, and xylylene diisocyanate (bitolylene diisocyanate) in a solvent such as N-methyl-2-pyrrolidone or/and N, N-dimethylacetamide, or a resin obtained by heating trimellitic anhydride, diphenylmethane diisocyanate, and carboxyl-terminated acrylonitrile-butadiene rubber in a solvent such as N-methyl-2-pyrrolidone or/and N, N-dimethylacetamide.

As the rubber-modified polyamideimide resin, a known rubber-modified polyamideimide resin can be used. The rubber-modified polyamideimide resin is obtained by reacting a polyamideimide resin with a rubber resin. The polyamide-imide resin is used by reacting with a rubber resin in order to improve flexibility of the polyamide-imide resin itself. That is, the polyamideimide resin is reacted with the rubber resin to replace a part of the acid component (cyclohexane dicarboxylic acid, etc.) of the polyamideimide resin with the rubber component. As the polyamideimide resin, a known polyamideimide resin can be used. The rubber resin may be a known rubber resin or the rubber resin. In the polymerization of the rubber-modified polyamideimide resin, it is preferable to use 1 or 2 or more of dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, nitromethane, nitroethane, tetrahydrofuran, cyclohexanone, methyl ethyl ketone, acetonitrile, γ -butyrolactone, and the like as a mixture of solvents for dissolving the polyamideimide resin and the rubbery resin.

As the phosphazene resin, a known phosphazene resin can be used. The phosphazene resin is a resin containing phosphazene having a double bond and containing phosphorus and nitrogen as constituent elements. The phosphazene resin can dramatically improve flame retardancy by a synergistic effect of nitrogen and phosphorus in a molecule. Further, unlike the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, an effect of stably existing in the resin to prevent migration can be obtained.

As the fluororesin, a known fluororesin may be used. As the fluororesin, for example, a fluororesin composed of at least 1 kind of thermoplastic resin selected from PTFE (polytetrafluoroethylene (tetrafluoride)), PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), FEP (tetrafluoroethylene-hexafluoropropylene copolymer (tetra, hexa-fluorinated)), ETFE (tetrafluoroethylene-ethylene copolymer), PVDF (polyvinylidene fluoride (difluoride)), PCTFE (polychlorotrifluoroethylene (trifluoride)), polyarylsulfone, aromatic polysulfide and aromatic polyether, and a fluororesin can be used.

The resin layer may contain a resin curing agent. As the resin hardener, a known resin hardener can be used. For example, amines such as dicyandiamide, imidazoles, and aromatic amines, phenols such as bisphenol a and brominated bisphenol a, novolak resins such as phenol novolak resin and cresol novolak resin, acid anhydrides such as phthalic anhydride, biphenyl-type phenol resins, and phenol aralkyl-type phenol resins can be used as the resin curing agent. The resin layer may contain 1 or 2 or more of the resin curing agents. These hardeners are particularly effective for epoxy resins.

Specific examples of the biphenyl type phenol resin are shown in chemical formula 8.

[ chemical formula 8]

Further, a specific example of the above-mentioned phenol aralkyl type phenol resin is shown in chemical formula 9.

[ chemical formula 9]

As imidazoles, known ones can be used, and examples thereof include: 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole and the like, which may be used alone or in combination.

Among them, imidazoles having a structural formula represented by the following chemical formula 10 are preferably used. By using imidazoles of the structural formula represented by chemical formula 10, the moisture absorption resistance of the resin layer in a semi-cured state can be significantly improved, and the long-term storage stability is excellent. This is because the imidazole system exerts a catalytic action when the epoxy resin is cured, and it acts as a reaction initiator which causes a self-polymerization reaction of the epoxy resin in an initial stage of the curing reaction.

[ chemical formula 10]

As the amine-based resin curing agent, known amines can be used. The amine-based resin curing agent may be, for example, the polyamine or aromatic polyamine, or 1 or 2 or more selected from the group consisting of aromatic polyamine, polyamide and amine adduct obtained by polymerizing or condensing the polyamine with an epoxy resin or a polycarboxylic acid. Further, as the amine-based resin curing agent, it is preferable to use at least one of 4,4 '-diaminodiphenylsulfone, 3' -diaminodiphenylsulfone, 4-diaminobiphenyl, 2-bis [4- (4-aminophenoxy) phenyl ] propane, and bis [4- (4-aminophenoxy) phenyl ] sulfone.

The resin layer may contain a hardening accelerator. As the hardening accelerator, a known hardening accelerator can be used. For example, tertiary amine, imidazole, urea-based curing accelerators and the like can be used as the curing accelerator.

The resin layer may contain a reaction catalyst. As the reaction catalyst, a known reaction catalyst can be used. For example, finely divided silica, antimony trioxide or the like can be used as the reaction catalyst.

The acid anhydride of the polycarboxylic acid is preferably a component which functions as a curing agent for the epoxy resin. The acid anhydride of the polycarboxylic acid is preferably phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydroxyphthalic anhydride, hexahydroxyphthalic anhydride, methylhexahydroxyphthalic anhydride, nadic acid (nadic acid), or methylnadic acid.

The thermoplastic resin may be a thermoplastic resin having a functional group other than an alcoholic hydroxyl group polymerizable with an epoxy resin.

The polyvinyl acetal resin may have a hydroxyl group and a functional group other than the hydroxyl group, which is polymerizable with an epoxy resin or a maleimide compound. The polyethylene-acetaldehyde resin may be one having carboxyl groups, amino groups, or unsaturated double bonds introduced into the molecule.

Examples of the aromatic polyamide resin polymer include those obtained by reacting an aromatic polyamide resin with a rubbery resin. The aromatic polyamide resin is synthesized by polycondensation of an aromatic diamine and a dicarboxylic acid. Examples of the aromatic diamine used in this case include 4,4' -diaminodiphenylmethane, 3' -diaminodiphenylsulfone, m-xylylenediamine, and 3,3' -diaminodiphenyl ether. As the dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, and the like are used.

The rubber resin which can react with the aromatic polyamide resin may be a known rubber resin or the rubber resin.

The aromatic polyamide resin polymer is used for preventing the etching solution from being damaged by underetching when the copper foil processed into the copper-clad laminate is etched.

The resin layer may be a resin layer in which a cured resin layer (the "cured resin layer" means a resin layer having been cured) and a semi-cured resin layer are formed in this order from the copper foil side (i.e., the extremely thin copper layer side of the copper foil with carrier). The cured resin layer may be formed of any resin component selected from the group consisting of polyimide resins, polyamideimide resins, and composite resins thereof, each having a coefficient of thermal expansion of 0 ppm/DEG C to 25 ppm/DEG C.

Further, a semi-cured resin layer having a thermal expansion coefficient of 0 ppm/DEG C to 50 ppm/DEG C after curing may be provided on the cured resin layer. The cured resin layer and the semi-cured resin layer may have a coefficient of thermal expansion of 40 ppm/DEG C or less as a whole. The glass transition temperature of the hardened resin layer may be 300 ℃ or higher. The semi-cured resin layer may be formed using a maleimide resin or an aromatic maleimide resin. The resin composition for forming the semi-cured resin layer preferably contains a maleimide resin, an epoxy resin, and a linear polymer having a crosslinkable functional group. As the epoxy resin, a known epoxy resin or an epoxy resin described in this specification can be used. As the maleimide-based resin, the aromatic maleimide-based resin, and the linear polymer having a crosslinkable functional group, known maleimide-based resins, aromatic maleimide-based resins, and linear polymers having a crosslinkable functional group, or the maleimide-based resins, the aromatic maleimide-based resins, and the linear polymers having a crosslinkable functional group can be used.

In addition, in the case of providing a copper foil with a carrier having a resin layer suitable for the production of a three-dimensional molded printed wiring board, the cured resin layer is preferably a cured flexible polymer layer. The polymer layer is preferably made of a resin having a glass transition temperature of 150 ℃ or higher so as to be able to withstand the solder mounting step. The polymer layer is preferably formed of 1 or 2 or more kinds of mixed resins selected from polyamide resin, polyether sulfone resin, aromatic polyamide resin, phenoxy resin, polyimide resin, polyethylene acetaldehyde resin, and polyamide imide resin. The thickness of the polymer layer is preferably 3 to 10 μm.

The polymer layer preferably contains 1 or 2 or more of epoxy resin, maleimide resin, phenol resin, and urethane resin. The semi-cured resin layer is preferably made of an epoxy resin composition having a thickness of 10 to 50 μm.

The epoxy resin composition preferably contains the following components A to E.

Component A: an epoxy resin having an epoxy equivalent of 200 or less and comprising 1 or 2 or more selected from the group consisting of a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a bisphenol AD type epoxy resin which are liquid at room temperature.

And B component: high heat resistance epoxy resin.

And C, component C: phosphorus-containing flame-retardant resins are obtained by mixing 1 or more of phosphorus-containing epoxy resins and phosphazene resins.

And (D) component: a rubber-modified polyamide-imide resin modified with a liquid rubber component having a property of being soluble in a solvent having a boiling point in the range of 50 to 200 ℃.

And E, component (E): a resin hardener.

The component B is a so-called "high heat-resistant epoxy resin" having a high glass transition point Tg. The "high heat-resistant epoxy resin" is preferably a polyfunctional epoxy resin such as a novolak-type epoxy resin, a cresol novolak-type epoxy resin, a phenol novolak-type epoxy resin, or a naphthalene-type epoxy resin.

As the phosphorus-containing epoxy resin as the component C, the above-mentioned phosphorus-containing epoxy resin can be used. The phosphazene resin as the component C can be the one described above.

As the rubber-modified polyamideimide resin of the component D, the above-mentioned rubber-modified polyamideimide resin can be used. As the resin curing agent of the component E, the above resin curing agent can be used.

A solvent is added to the resin composition described above to be used as a resin varnish, and a thermosetting resin layer is formed as an adhesive layer of the printed wiring board. The resin varnish is a semi-cured resin film having a resin overflow flow (resin flow) of 5 to 35% as measured by adding a solvent to the resin composition to adjust the amount of the solid resin component to a range of 30 to 70% by weight, based on MIL-P-13949G of the MIL standard. As the solvent, a known solvent or a solvent described above can be used.

The resin layer is a resin layer having, in order from the copper foil side, a 1 st thermosetting resin layer and a 2 nd thermosetting resin layer located on the surface of the 1 st thermosetting resin layer, the 1 st thermosetting resin layer may be formed of a resin component insoluble in a chemical used in a desmear treatment in a wiring board manufacturing method, and the 2 nd thermosetting resin layer may be formed of a resin which is removed by washing using a chemical soluble in a desmear treatment in a wiring board manufacturing method. The 1 st thermosetting resin layer may be formed by using a resin component mixed with 1 or 2 or more of polyimide resin, polyether sulfone and polyphenylene ether. The 2 nd thermosetting resin layer may be formed by using an epoxy resin component. The thickness t1(μm) of the 1 st thermosetting resin layer is preferably such that t1 satisfies the condition Rz < t1 < t2 when Rz (μm) is the roughness of the roughened surface of the carrier-attached copper foil and t2(μm) is the thickness of the 2 nd thermosetting resin layer.

The resin layer may be a prepreg in which a skeleton material is impregnated with a resin. The resin impregnated in the skeleton material is preferably a thermosetting resin. The prepreg may be a known prepreg or a prepreg used in the production of a printed wiring board.

The above-mentioned skeleton material may contain aramid fibers, glass fibers or wholly aromatic polyester fibers. The skeleton material is preferably a nonwoven fabric or woven fabric of aramid fibers, glass fibers, or wholly aromatic polyester fibers. The wholly aromatic polyester fiber is preferably a wholly aromatic polyester fiber having a melting point of 300 ℃. The wholly aromatic polyester fiber having a melting point of 300 ℃ or higher is a fiber produced using a resin called a liquid crystal polymer, and the liquid crystal polymer contains a polymer of 2-hydroxy-6-naphthoic acid and p-hydroxybenzoic acid as a main component. The wholly aromatic polyester fiber has a low dielectric constant and a low dielectric loss tangent, and therefore has excellent performance as a constituent material of an electrical insulating layer, and can be used similarly to glass fibers and aramid fibers.

The fibers constituting the nonwoven fabric and the woven fabric are preferably treated with a silane coupling agent in order to improve wettability with the resin on the surfaces thereof. In this case, a known silane coupling agent such as an amine-based silane coupling agent or an epoxy-based silane coupling agent or the silane coupling agent can be used depending on the purpose of use.

The prepreg may be a prepreg obtained by impregnating a thermosetting resin into a skeleton material made of a nonwoven fabric made of aramid fibers or glass fibers having a nominal thickness of 70 μm or less or a glass cloth having a nominal thickness of 30 μm or less.

(the case where the resin layer contains a dielectric substance (dielectric filler))

The resin layer may contain a dielectric material (dielectric filler).

Any of the above resin layers or resin compositions contains a dielectric substance (dielectric)Bulk filler) may be used in forming the capacitor layer to increase the capacitance of the capacitor circuit. The dielectric material (dielectric filler) is BaTiO₃、SrTiO₃、Pb(Zr-Ti)O₃(generic name PZT), PbLaTiO₃-PbLaZrO (PLZT), SrBi₂Ta₂O₉Dielectric powders of complex oxides having a perovskite structure such as (generally referred to as SBT).

The dielectric (dielectric filler) may be in powder form. When the dielectric material (dielectric filler) is in the form of powder, the powder property of the dielectric material (dielectric filler) must be such that the particle diameter is in the range of 0.01 μm to 3.0. mu.m, preferably 0.02 μm to 2.0. mu.m. The particle size here means an average particle size obtained by directly observing a dielectric material (dielectric filler) with a Scanning Electron Microscope (SEM) and analyzing an image of the SEM image, because the particle size is in a constant 2-fold aggregation state, and thus cannot be used in indirect measurement such as estimation of the average particle size from a measurement value such as a laser diffraction scattering particle size distribution measurement method or a BET method because of poor accuracy. In the present specification, the particle diameter at this time is represented as DIA. In the present specification, the powder of the dielectric material (dielectric filler) observed by a Scanning Electron Microscope (SEM) was analyzed by using IP-1000PC manufactured by Asahi Engineering corporation, and the average particle diameter DIA was determined by performing a circular particle analysis with a roundness threshold of 10 and an overlap degree of 20.

According to the above embodiment, there can be provided a copper foil with a carrier having a resin layer containing a dielectric for forming a capacitor circuit layer having a low dielectric loss tangent, which can improve the adhesion between the inner layer circuit surface of the inner layer core material and the resin layer containing a dielectric.

The resin and/or the resin composition and/or the compound contained in the resin layer are dissolved in a solvent such as Methyl Ethyl Ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene, methanol, ethanol, propylene glycol monomethyl ether, dimethylformamide, dimethylacetamide, cyclohexanone, ethylcellosolve, N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, etc. to prepare a resin solution (resin varnish), which is applied to the extremely thin copper layer, the heat-resistant layer, the rust-preventive layer, the chromate treatment layer, or the silane coupling agent layer by, for example, roll coating, and then dried by heating as necessary to remove the solvent, thereby obtaining a B-stage state. For example, the drying may be carried out using a hot air drying oven, and the drying temperature may be 100 to 250 ℃, preferably 130 to 200 ℃. The resin solution having a solid resin content of 3 to 70 wt%, preferably 3 to 60 wt%, preferably 10 to 40 wt%, and more preferably 25 to 40 wt% can be prepared by dissolving the composition of the resin layer in a solvent. From the viewpoint of environment, it is most preferable to dissolve the methyl ethyl ketone and cyclopentanone in a mixed solvent. The solvent preferably has a boiling point in the range of 50 to 200 ℃.

The resin layer is preferably a semi-cured resin film having a resin overflow amount in the range of 5% to 35% when measured according to MIL-P-13949G in the MIL standard.

In the present specification, the term "resin overflow amount" means that 4 samples of 10cm square are taken from a copper foil with a resin having a resin thickness of 55 μm according to MIL-P-13949G of the MIL standard, and the 4 samples are stacked (stacked body) at a pressing temperature of 171 ℃ and a pressing pressure of 14kgf/cm²And a value calculated based on the following equation 1 from the result of measuring the resin flow-out weight at the time of bonding under the condition of a pressing time of 10 minutes.

[ mathematical formula 1]

The carrier-attached copper foil (carrier-attached copper foil with resin) provided with the resin layer is used in the following manner: the resin layer is thermally cured by thermocompression bonding the entire body after the resin layer is superposed on the base material, and then the carrier is peeled off to expose the extremely thin copper layer (of course, the surface of the extremely thin copper layer on the intermediate layer side is exposed), and a specific wiring pattern is formed thereon.

The use of the resin-coated copper foil for a carrier can reduce the number of prepregs used in the production of a multilayer printed wiring board. Further, the copper-clad laminate can be produced by setting the thickness of the resin layer to a thickness that ensures interlayer insulation, or by not using a prepreg at all. In this case, the insulating resin primer may be applied to the surface of the substrate to improve the surface smoothness.

Further, when the prepreg is not used, the material cost of the prepreg can be saved, and the laminating step can be simplified, so that it is economically advantageous, and there are advantages in that: the thickness of the multilayer printed wiring board is reduced only by the thickness of the prepreg, and an extremely thin multilayer printed wiring board having a thickness of 100 μm or less can be manufactured by 1 layer.

The thickness of the resin layer is preferably 0.1 to 120 μm.

If the thickness of the resin layer is less than 0.1 μm, the following is the case: when the copper foil with the resin carrier is laminated on a base material provided with an inner layer material without lowering the adhesion force and the prepreg is inserted, it is difficult to secure interlayer insulation between the copper foil and a circuit of the inner layer material. On the other hand, if the thickness of the resin layer is larger than 120 μm, the following is the case: it is difficult to form a resin layer having a desired thickness in 1 coating step, and an extra material cost and the number of steps are required, which is economically disadvantageous.

When the copper foil with a carrier having a resin layer is used for producing an extremely thin multilayer printed wiring board, the thickness of the resin layer is preferably set to 0.1 to 5 μm, more preferably 0.5 to 5 μm, and still more preferably 1 to 5 μm, because the thickness of the multilayer printed wiring board can be reduced.

When the resin layer contains a dielectric material, the thickness of the resin layer is preferably 0.1 to 50 μm, more preferably 0.5 to 25 μm, and still more preferably 1.0 to 15 μm.

The total thickness of the resin layers of the cured resin layer and the semi-cured resin layer is preferably 0.1 to 120 μm, more preferably 5 to 120 μm, even more preferably 10 to 120 μm. The thickness of the cured resin layer is preferably 2 to 30 μm, more preferably 3 to 30 μm, and still more preferably 5 to 20 μm. The thickness of the semi-cured resin layer is preferably 3 to 55 μm, more preferably 7 to 55 μm, and still more preferably 15 to 115 μm. This is because if the total thickness of the resin layer exceeds 120 μm, it may be difficult to produce an extremely thin multilayer printed wiring board, and if it is less than 5 μm, the following may occur: although it is easy to form an extremely thin multilayer printed wiring board, the insulating layer, i.e., the resin layer, between the circuits in the inner layer tends to be too thin, and the insulation between the circuits in the inner layer tends to be unstable. If the thickness of the cured resin layer is less than 2 μm, the surface roughness of the roughened surface of the copper foil may be considered. On the other hand, if the thickness of the cured resin layer exceeds 20 μm, the effect of the cured resin layer may not be particularly improved, and the total thickness of the insulating layer may be increased.

When the thickness of the resin layer is 0.1 to 5 μm, it is preferable to form a resin layer on the heat-resistant layer or the rust-proof layer or the chromate treatment layer or the silane coupling treatment layer after providing the heat-resistant layer and/or the rust-proof layer and/or the chromate treatment layer and/or the silane coupling treatment layer on the extra thin copper layer in order to improve the adhesion between the resin layer and the copper foil with a carrier.

The thickness of the resin layer is an average value of thicknesses measured by observing a cross section at an arbitrary 10 points.

Further, as another product form of the resin-coated copper foil, a resin-coated copper foil in which no carrier is present can be produced by forming a semi-hardened state on the ultra-thin copper layer, the heat-resistant layer, the rust-preventive layer, the chromate treatment layer, or the silane coupling treatment layer by coating with a resin layer, and then peeling off the carrier.

< 6. printed Wiring Board

Hereinafter, some examples of the steps of manufacturing a printed wiring board using the surface-treated copper foil or the carrier-attached copper foil of the present invention will be described. Further, electronic components are mounted on the printed wiring board, thereby completing the printed wiring board.

A copper foil with a carrier comprising a copper foil carrier, a release layer and an extremely thin copper layer in this order is produced by the above-mentioned production method. The use of the copper foil with a carrier itself is known, and for example, a printed wiring board can be produced by bonding the surface of an extremely thin copper layer to an insulating substrate such as a paper base phenolic resin, a paper base epoxy resin, a synthetic fiber cloth base epoxy resin, a glass cloth-paper composite base epoxy resin, a glass cloth-glass nonwoven fabric composite base epoxy resin, a glass cloth base epoxy resin, a polyester film, or a polyimide film, thermocompression bonding the surface to the insulating substrate, and then peeling off the carrier to form a copper-clad laminate, and then etching the extremely thin copper layer bonded to the insulating substrate into a desired conductor pattern.

The copper foil with a carrier of the present invention is suitable for forming a fine pitch printed wiring board. For example, the following printed wiring board can be produced by using the carrier-attached copper foil of the present invention: the printed wiring board has an insulating substrate and a copper circuit provided on the insulating substrate, and the circuit width of the copper circuit is less than 20 μm and the gap width between adjacent copper circuits is less than 20 μm. Further, a printed wiring board in which the circuit width of the copper circuit is 17 μm or less and the gap width between adjacent copper circuits is 17 μm or less can be manufactured. Further, a printed wiring board in which the circuit width of the copper circuit is 15 μm or less and the gap width between adjacent copper circuits is 15 μm or less can be manufactured. Furthermore, a printed wiring board having a circuit width of the copper circuit of 5 to 10 μm and a gap width between adjacent copper circuits of 5 to 10 μm can be manufactured.

Further, electronic components are mounted on the printed wiring board, thereby completing the printed wiring board. By using the carrier-attached copper foil of the present invention, for example, the following printed wiring board can be manufactured: the printed circuit board comprises an insulating substrate and a copper circuit disposed on the insulating substrate, wherein the width of the copper circuit is less than 20 μm, and the width of the gap between adjacent copper circuits is less than 20 μm. Furthermore, a printed wiring board having a circuit width of 17 μm or less and a gap width between adjacent copper circuits of 17 μm or less can be manufactured. Further, a printed wiring board in which the circuit width of the copper circuit is 17 μm or less and the gap width between adjacent copper circuits is 17 μm or less can be manufactured. Furthermore, a printed wiring board having a circuit width of the copper circuit of 15 μm or less and a gap width between adjacent copper circuits of 15 μm or less can be manufactured. Furthermore, a printed wiring board having a circuit width of 5 to 10 μm, preferably 5 to 9 μm, and more preferably 5 to 8 μm, and a gap width between adjacent copper circuits of 5 to 10 μm, preferably 5 to 9 μm, and more preferably 5 to 8 μm, can be manufactured. The pitch between the lines and the spaces is preferably less than 40 μm, more preferably 34 μm or less, more preferably 30 μm or less, more preferably 20 μm or less, and more preferably 15 μm or less. The lower limit of the line and the gap is not particularly limited, and is, for example, 6 μm or more, 8 μm or more, or 10 μm or more.

The pitch between the line and the space is a distance from the center of the copper circuit width to the center of the adjacent copper circuit width.

Hereinafter, some examples of the steps for manufacturing a printed wiring board using the copper foil with a carrier of the present invention will be described.

One embodiment of the method for manufacturing a printed wiring board of the present invention comprises the steps of: preparing the copper foil with carrier and the insulating substrate of the present invention; laminating the copper foil with carrier and the insulating substrate; and a step of forming a copper-clad laminate by laminating the copper foil with a carrier and the insulating substrate so that the ultra-thin copper layer side faces the insulating substrate, and then peeling the carrier with the copper foil with the carrier, and thereafter forming a circuit by any one of a semi-additive method, a modified semi-additive method, a partial additive method, and a subtractive method. The insulating substrate may also be provided as an inner circuit access.

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

Accordingly, one embodiment of the method for manufacturing a printed wiring board of the present invention using a semi-additive method comprises the steps of:

preparing the copper foil with carrier and the insulating substrate of the present invention;

laminating the copper foil with carrier and the insulating substrate;

a step of peeling off the carrier with the carrier copper foil after laminating the carrier copper foil with the insulating substrate;

completely removing the ultra-thin copper layer exposed by peeling the carrier by etching using an etching solution such as an acid or by a plasma method;

a step of providing a through hole and/or a blind via (blindvia) in the resin layer and the insulating substrate exposed by removing the extra thin copper layer by etching;

removing glue residues from the area containing the through hole or/and the blind hole;

providing an electroless plating layer on the resin and the region including the through hole and/or the blind hole;

a step of providing an anti-plating agent on the electroless plating layer;

exposing the plating resist to light, and then removing the plating resist in a region where a circuit is formed;

providing an electrolytic plating layer on the region where the plating resist has been removed and the circuit has been formed;

removing the plating resist; and

and removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like.

Another embodiment of the method for manufacturing a printed wiring board of the present invention using a semi-additive method comprises the steps of:

laminating the copper foil with carrier and the insulating substrate;

a step of providing an electroless plating layer on the surface of the resin layer exposed by removing the extremely thin copper layer by etching;

a step of providing an anti-plating agent on the electroless plating layer;

removing the plating resist; and

In the present invention, the modified semi-additive method is a method of forming a circuit on an insulating layer by laminating a metal foil on the insulating layer, protecting a non-circuit forming portion with a plating resist, thickening a copper layer of the circuit forming portion by electroplating, removing a resist, and removing the metal foil other than the circuit forming portion by (rapid) etching.

Accordingly, one embodiment of the method for manufacturing a printed wiring board of the present invention using the modified semi-additive method comprises the steps of:

laminating the copper foil with carrier and the insulating substrate;

a step of providing a through hole and/or a blind hole in the ultra-thin copper layer and the insulating substrate exposed by peeling the carrier;

providing an electroless plating layer in a region including the through hole and/or the blind hole;

a step of providing an anti-plating agent on the surface of the extremely thin copper layer exposed by peeling the carrier;

forming a circuit by electroplating after the plating resist is provided;

removing the plating resist; and

and removing the extremely thin copper layer exposed by the removal of the plating resist by flash etching.

Another embodiment of the method for manufacturing a printed wiring board of the present invention using the modified semi-additive method comprises the steps of:

laminating the copper foil with carrier and the insulating substrate;

a step of providing an anti-plating agent on the extremely thin copper layer exposed by peeling the carrier;

removing the plating resist; and

and removing the extremely thin copper layer in a region other than the region where the circuit is formed by flash etching or the like.

In the present invention, the partial addition method is a method of manufacturing a printed wiring board by applying a catalyst core to a substrate on which a conductor layer is provided or a substrate through which a hole for a through hole or a via hole is optionally formed, etching the substrate to form a conductor circuit, providing a solder resist or a plating resist as required, and then thickening the through hole, the via hole, or the like on the conductor circuit by electroless plating.

Accordingly, one embodiment of the method for manufacturing a printed wiring board of the present invention using a partial addition method comprises the steps of:

laminating the copper foil with carrier and the insulating substrate;

a step of providing a catalytic core to a region including the through-hole and/or the blind-hole;

a step of providing an etching resist on the surface of the extremely thin copper layer exposed by peeling the carrier;

exposing the resist to form a circuit pattern;

removing the ultra-thin copper layer and the catalytic nuclei by etching using an etching solution such as an acid or plasma to form a circuit;

removing the etching resist;

a step of providing a solder resist or plating resist on the surface of the insulating substrate exposed by removing the extra thin copper layer and the catalytic nuclei by etching using an etching solution such as an acid or plasma; and

and a step of providing an electroless plating layer in a region where the solder resist or plating resist is not provided.

In the present invention, the subtractive process means a process of selectively removing unnecessary portions of the copper foil on the copper-clad laminate by etching or the like to form a conductor pattern.

Accordingly, one embodiment of the method for manufacturing a printed wiring board of the present invention using the subtractive process comprises the steps of:

laminating the copper foil with carrier and the insulating substrate;

a step of providing an electrolytic plating layer on the surface of the electroless plating layer;

providing an etching resist on the surface of the electrolytic plating layer and/or the surface of the extremely thin copper layer;

exposing the resist to form a circuit pattern;

forming a circuit by removing the extra thin copper layer, the electroless plating layer and the electrolytic plating layer by etching with an etching solution such as an acid or plasma; and

and removing the etching resist.

Another embodiment of the method for manufacturing a printed wiring board of the present invention using a subtractive process comprises the steps of:

laminating the copper foil with carrier and the insulating substrate;

forming a mask on the surface of the electroless plating layer;

providing an electrolytic plating layer on the surface of the electroless plating layer on which the mask is not formed;

exposing the resist to form a circuit pattern;

removing the ultra-thin copper layer and the electroless plating layer by etching using an etching solution such as an acid or plasma to form a circuit; and

and removing the etching resist.

The step of arranging the through holes or/and the blind holes and the subsequent step of removing the glue residue can also be omitted.

Here, a specific example of a method for manufacturing a printed wiring board using the carrier-attached copper foil of the present invention will be described in detail with reference to the drawings. Further, although the carrier-attached copper foil having the extra thin copper layer on which the roughened layer is formed is described as an example, the present invention is not limited thereto, and the following method for manufacturing a printed wiring board can be similarly performed by using a carrier-attached copper foil having an extra thin copper layer on which a roughened layer is not formed.

First, as shown in fig. 3a, a carrier-attached copper foil (layer 1) having an extremely thin copper layer with a roughened layer formed on the surface thereof is prepared.

Next, as shown in fig. 3B, a resist is applied to the roughened layer of the extremely thin copper layer, exposed, and developed, and the resist is etched into a specific shape.

Then, as shown in fig. 3C, after the circuit plating is formed, the resist is removed, thereby forming a circuit plating having a specific shape.

Then, as shown in D in fig. 4, an embedded resin is provided on the extra thin copper layer by coating circuit plating (by coating circuit plating) to build up a resin layer, and then another copper foil with a carrier (layer 2) is bonded from the extra thin copper layer side.

Then, as shown in fig. 4E, the carrier is peeled from the carrier-attached copper foil of the 2 nd layer.

Then, as shown in fig. 4F, laser drilling is performed on a specific position of the resin layer to expose the circuit plating and form a blind via.

Then, as shown in G in fig. 5, a copper-buried via is formed in the blind via.

Then, as shown in fig. 5H, circuit plating is formed on the filled hole in the manner shown in fig. 3B and 3C.

Then, as shown in fig. 5I, the carrier is peeled from the carrier-attached copper foil of the 1 st layer.

Then, as shown in J of fig. 6, the extremely thin copper layers on both surfaces are removed by flash etching, so that the surface of the circuit plating in the resin layer is exposed.

Then, as shown by K in fig. 6, a bump is formed on the circuit plating in the resin layer, and a copper pillar is formed on the solder. Thus, a printed wiring board using the carrier-attached copper foil of the present invention was produced.

The other carrier-attached copper foil (layer 2) may be the carrier-attached copper foil of the present invention, an existing carrier-attached copper foil, or a general copper foil. Further, a 1-layer or a plurality of-layer circuits may be formed over the circuit of the 2 nd layer shown in fig. 5 as H, and the circuits may be formed by any of a semi-addition method, a subtractive method, a partial addition method, or a modified semi-addition method.

The carrier-attached copper foil used for the 1 st layer may have a substrate on the carrier-side surface of the carrier-attached copper foil. By providing the substrate or the resin layer, the copper foil with a carrier used for the 1 st layer is supported, and hence wrinkles are less likely to occur, which is advantageous in that productivity is improved. All of the substrates can be used as long as the substrate has the effect of supporting the copper foil with carrier used in the 1 st layer. For example, the substrate may be a carrier, a prepreg, a resin layer, a known carrier, a prepreg, a resin layer, a metal plate, a metal foil, a plate of an inorganic compound, a foil of an inorganic compound, a plate of an organic compound, or a foil of an organic compound described in the specification of the present application.

The point of time when the substrate is formed on the side surface of the carrier is not particularly limited, but must be formed before peeling off the carrier. In particular, it is preferably formed before the step of forming the resin layer on the surface of the extra thin copper layer of the carrier-attached copper foil, and more preferably before the step of forming the circuit on the surface of the extra thin copper layer of the carrier-attached copper foil.

The copper foil with carrier of the present invention preferably controls the color difference of the surface of the extra thin copper layer so as to satisfy the following (1). In the present invention, the term "surface color difference of the extremely thin copper layer" means a color difference of the surface of the extremely thin copper layer or a color difference of the surface-treated layer when various surface treatments such as roughening treatment are performed. That is, the carrier-attached copper foil of the present invention is preferably such that the color difference of the surface of the extra thin copper layer, the roughened layer, the heat-resistant layer, the rust-proof layer, the chromate treatment layer, or the silane coupling layer is controlled so as to satisfy the following (1).

(1) The surface of the extremely thin copper layer, the roughened layer, the heat-resistant layer, the rust-preventive layer, the chromate treatment layer or the silane coupling treatment layer has a color difference Δ E ﹡ ab of 45 or more in JIS Z8730.

Here, the color differences Δ L, Δ a, Δ b are comprehensive indices expressed by using a color system of L ﹡ a ﹡ b according to JIS Z8730, which are measured by a color difference meter, and are expressed as Δ L: white black, Δ a: red green, Δ b: yellow and blue. Δ E ﹡ ab is expressed by the following equation using the chromatic aberration.

[ mathematical formula 2]

The color difference can be adjusted by increasing the current density at the time of forming the extremely thin copper layer, decreasing the copper concentration in the plating solution, and increasing the linear flow rate of the plating solution.

The color difference can be adjusted by roughening the surface of the extremely thin copper layer and providing a roughened layer. When the roughened layer is provided, the current density can be further increased (e.g., 40 to 60A/dm) as compared with the conventional one by using an electrolyte containing at least one element selected from the group consisting of copper and nickel, cobalt, tungsten, and molybdenum²) The processing time (for example, 0.1 to 1.3 seconds) is shortened to perform adjustment. When the roughening treatment layer is not provided on the surface of the extremely thin copper layer, the roughening treatment layer can be obtained by: plating a Ni alloy (e.g., Ni-W) on the surface of an extremely thin copper layer, a heat-resistant layer, a rust-preventive layer, a chromate-treated layer, or a silane-coupling-treated layer by using a plating bath in which the concentration of Ni is 2 times or more that of other elementsAlloy plating, Ni-Co-P alloy plating, Ni-Zn alloy plating) lower than the conventional current density (0.1 to 1.3A/dm)²) And the treatment is performed so that the treatment time (20 seconds to 40 seconds) is set to be long.

When the color difference Δ E ﹡ ab based on JIS Z8730 on the surface of the extra thin copper layer is 45 or more, for example, when a circuit is formed on the surface of the extra thin copper layer with the carrier copper foil, the contrast between the extra thin copper layer and the circuit becomes clear, and as a result, the visibility becomes good, and the alignment of the circuit can be performed with high accuracy. The color difference Δ E ﹡ ab in JIS Z8730 of the surface of the extremely thin copper layer is preferably 50 or more, more preferably 55 or more, and still more preferably 60 or more.

When the color difference of the surface of the extremely thin copper layer, the roughened layer, the heat-resistant layer, the rust-preventive layer, the chromate treatment layer, or the silane coupling layer is controlled as described above, the contrast with the circuit plating becomes clear, and the visibility becomes good. Therefore, in the manufacturing step of the printed wiring board as described above, for example, as shown by C in fig. 3, circuit plating can be formed at a specific position with high accuracy. Further, according to the method for manufacturing a printed wiring board as described above, since the circuit plating is embedded in the resin layer, when the extremely thin copper layer is removed by flash etching as shown by J in fig. 6, for example, the circuit plating is protected by the resin layer and the shape thereof is maintained, thereby facilitating the formation of a fine circuit. Further, since the circuit is protected by the resin layer and plated, the migration resistance is improved, and the conduction of the wiring of the circuit can be favorably suppressed. Therefore, a fine circuit is easily formed. Further, when the extremely thin copper layer is removed by flash etching as shown in J in fig. 6 and K in fig. 6, the exposed surface of the circuit plating is recessed from the resin layer, so that it is easy to form a bump on each circuit plating and further form a copper pillar thereon, thereby improving the manufacturing efficiency.

The embedding Resin (Resin) may be a known Resin or prepreg. For example, BT (bismaleimide triazine) resin, glass cloth impregnated with BT resin, prepreg, ABF film manufactured by Ajinomoto Fine-Technio Co., Ltd, or ABF can be used. The Resin layer and/or Resin and/or prepreg described in the present specification can be used as the embedding Resin (Resin).

[ examples ]

The present invention will be described in further detail with reference to examples of the present invention, but the present invention is not limited to these examples.

1. Production of copper foil with carrier

< example 1 >

As a copper foil carrier, a long electrolytic copper foil (JTC manufactured by JX Nikkiso Metal Co., Ltd.) having a thickness of 35 μm was prepared. The glossy surface (Rz: 1.2-1.4 μm) of the copper foil was electroplated using a roll-to-roll continuous plating line (bending method shown in FIG. 2) under the following conditions, thereby forming 4000 μ g/dm²An attached amount of Ni layer.

Ni layer

Nickel sulfate: 250 to 300g/L

Nickel chloride: 35-45 g/L

Nickel acetate: 10 to 20g/L

Trisodium citrate: 15 to 30g/L

Gloss agent: saccharin, butynediol, and the like

Sodium lauryl sulfate: 30 to 100ppm of

pH value: 4 to 6

Bath temperature: 50-70 DEG C

Current density: 3 to 15A/dm²

After the water washing and acid washing, the resultant was treated with 11. mu.g/dm under the following conditions on a roll-to-roll type continuous plating line (using a bending system shown in FIG. 2)²The Cr layer having the adhesion amount is subjected to electrolytic chromate treatment to adhere to the Ni layer.

Electrolytic chromate treatment

The liquid composition is as follows: 1-10 g/L potassium dichromate and 0-5 g/L zinc

pH value: 3 to 4

Liquid temperature: 50-60 DEG C

Current density: 0.1 to 2.6A/dm²

Coulomb quantity: 0.5 to 30As/dm²

Then, an extremely thin copper layer having a thickness of 3 μm was formed on the Cr layer by electroplating on a roll-to-roll continuous plating line (by the drum method shown in fig. 1) under the following conditions, thereby producing a copper foil with a carrier. In this example, carrier-attached copper foils having extremely thin copper layers of thicknesses of 1, 2, 5 and 10 μm were produced, and the same evaluation was performed for the examples having an extremely thin copper layer of thickness of 3 μm. The result is the same regardless of thickness.

Very thin copper layer

Copper concentration: 30 to 120g/L

H₂SO₄Concentration: 20 to 120g/L

Temperature of the electrolyte: 20-80 DEG C

Current density: 10 to 100A/dm²

Then, the surface of the extremely thin copper layer is subjected to the following roughening treatment 1, roughening treatment 2, rust prevention treatment, chromate treatment, and silane coupling treatment in this order. The roughening treatment 1 and the roughening treatment 2 were performed by the foil transport method (interpolar distance 50mm) using a drum shown in fig. 1, and the rust prevention treatment, the chromate treatment, and the silane coupling treatment were performed by the bending method shown in fig. 2.

Roughening treatment 1

(liquid composition 1)

Cu：10～30g/L

H₂SO₄：10～150g/L

W：0～50mg/L

Sodium lauryl sulfate: 0 to 50mg/L

As：0～200mg/L

(plating Condition 1)

Temperature: 30-70 DEG C

Current density: 25 to 110A/dm²

Coarsening coulomb quantity: 50 to 500As/dm²

Plating time: 0.5 to 20 seconds

Roughening treatment 2

(liquid composition 2)

Cu：20～80g/L

H₂SO₄：50～200g/L

(plating Condition 2)

Temperature: 30-70 DEG C

Current density: 5 to 50A/dm²

Coarsening coulomb quantity: 50 to 300As/dm²

Plating time: 1 to 60 seconds

Anti-rust treatment

(liquid composition)

NaOH：40～200g/L

NaCN：70～250g/L

CuCN：50～200g/L

Zn(CN)₂：2～100g/L

As₂O₃：0.01～1g/L

(liquid temperature)

40～90℃

(Current Condition)

Current density: 1 to 50A/dm²

Plating time: 1 to 20 seconds

Chromate treatment

K₂Cr₂O₇(N₂Cr₂O₇Or CrO₃)：2～10g/L

NaOH or KOH: 10 to 50g/L

ZnOH or ZnSO₄·7H₂O：0.05～10g/L

pH value: 7 to 13

Bath temperature: 20-80 DEG C

Current density: 0.05 to 5A/dm²

Time: 5 to 30 seconds

Silane coupling treatment

After spraying and coating 0.1-0.3 vol% of 3-glycidoxypropyltrimethoxysilane aqueous solution, drying and heating are carried out in air at 100-200 ℃ for 0.1-10 seconds.

After the surface treatment, a resin layer "A" described below was formed on the extremely thin copper layer side.

< example 2 >

After an extremely thin copper layer was formed on a copper foil carrier under the same conditions as in example 1, the following roughening treatment 1, roughening treatment 2, rust-proofing treatment, chromate treatment and silane coupling treatment were sequentially performed. The roughening treatment 1 and the roughening treatment 2 were performed by the foil transport method (interpolar distance 50mm) using a drum shown in fig. 1, and the rust prevention treatment, the chromate treatment, and the silane coupling treatment were performed by the bending method shown in fig. 2. The thickness of the extra thin copper foil was set to 3 μm.

Roughening treatment 1

The liquid composition is as follows: 10-20 g/L copper, 50-100 g/L sulfuric acid

Liquid temperature: 25 to 50 DEG C

Current density: 1 to 58A/dm²

Coulomb quantity: 4 to 81As/dm²

Roughening treatment 2

The liquid composition is as follows: 10-20 g/L of copper, 5-15 g/L of nickel and 5-15 g/L of cobalt

pH value: 2 to 3

Liquid temperature: 30 to 50 DEG C

Current density: 24 to 50A/dm²

Coulomb quantity: 34 to 48As/dm²

Anti-rust treatment

The liquid composition is as follows: 5-20 g/L of nickel and 1-8 g/L of cobalt

pH value: 2 to 3

Liquid temperature: 40-60 DEG C

Current density: 5 to 20A/dm²

Coulomb quantity: 10 to 20As/dm²

Chromate treatment

pH value: 3 to 4

Liquid temperature: 50-60 DEG C

Current density: 0 to 2A/dm²(for the immersion chromate treatment, it may be carried out without electrolysis)

Coulomb quantity: 0 to 2As/dm²(for the immersion chromate treatment, it may be carried out without electrolysis)

Silane coupling treatment

Application of aqueous solution of diaminosilane (concentration of diaminosilane: 0.1 to 0.5 wt%)

After the surface treatment, a resin layer of the following "B" was formed on the extremely thin copper layer side.

< example 3 >

A long electrolytic copper foil (HLP manufactured by JX Nikkiso Marble metals Co., Ltd.) having a thickness of 35 μm was prepared as a copper foil carrier, and a carrier-attached copper foil was produced by the same procedure as in example 1 with respect to the glossy surface (Rz: 0.1 to 0.3 μm) of the copper foil. Wherein the resin layer is formed as the following "C".

< example 4 >

A long electrolytic copper foil (HLP manufactured by JX Nikkiso Marble metals Co., Ltd.) having a thickness of 35 μm was prepared as a copper foil carrier, and a carrier-attached copper foil was produced by the same procedure as in example 2 with respect to the glossy surface (Rz: 0.1 to 0.3 μm) of the copper foil. Wherein the resin layer is formed as the following "D".

< example 5 >

As a copper foil carrier, a long electrolytic copper foil (HLP manufactured by JX Nissan metals Co., Ltd.) having a thickness of 35 μm was prepared. The glossy surface (Rz: 0.1 to 0.3 μm) of the copper foil was plated by a roll-to-roll continuous plating line under the same conditions as in example 1 to obtain 4000. mu.g/dm²The deposited Ni layer was then formed into an extremely thin copper layer in the same order as in example 1, and then subjected to the following rust-proofing treatment (bending method) without roughening treatment.

Anti-rust treatment

The liquid composition is as follows: 5-20 g/L of nickel and 1-8 g/L of cobalt

pH value: 2 to 3

Liquid temperature: 40-60 DEG C

Current density: 5 to 20A/dm²

Coulomb quantity: 10 to 20As/dm²

After the surface treatment, a resin layer of the following "E" was formed on the extremely thin copper layer side.

< comparative example 1 >

After an extremely thin copper layer was formed on a copper foil carrier under the same conditions as in example 1, the surface of the extremely thin copper layer was subjected to the following roughening treatment 1, roughening treatment 2, rust-proofing treatment, chromate treatment and silane coupling treatment in this order. The roughening treatment 1 and the roughening treatment 2 were performed by the foil transport method (interpolar distance 50mm) using a drum shown in fig. 1, and the rust prevention treatment, the chromate treatment, and the silane coupling treatment were performed by the bending method shown in fig. 2. The thickness of the extra thin copper foil was set to 3 μm.

Roughening treatment 1

(liquid composition 1)

Cu：31～45g/L

H₂SO₄：10～150g/L

As：0.1～200mg/L

(plating Condition 1)

Temperature: 30-70 DEG C

Current density: 25 to 110A/dm²

Coarsening coulomb quantity: 50 to 500As/dm²

Plating time: 0.5 to 20 seconds

Roughening treatment 2

(liquid composition 2)

Cu：20～80g/L

H₂SO₄：50～200g/L

(plating Condition 2)

Temperature: 30-70 DEG C

Current density: 5 to 50A/dm²

Coarsening coulomb quantity: 50 to 300As/dm²

Plating time: 1 to 60 seconds

Anti-rust treatment

(liquid composition)

NaOH：40～200g/L

NaCN：70～250g/L

CuCN：50～200g/L

Zn(CN)₂：2～100g/L

As₂O₃：0.01～1g/L

(liquid temperature)

40～90℃

(Current Condition)

Current density: 1 to 50A/dm²

Plating time: 1 to 20 seconds

Chromate treatment

K₂Cr₂O₇(N₂Cr₂O₇Or CrO₃)：2～10g/L

NaOH or KOH: 10 to 50g/L

ZnOH or ZnSO₄·7H₂O：0.05～10g/L

pH value: 7 to 13

Bath temperature: 20-80 DEG C

Current density: 0.05 to 5A/dm²

Time: 5 to 30 seconds

Silane coupling treatment

After the surface treatment, no resin layer was formed.

< comparative example 2 >

Carrier-attached copper foil was produced in the same manner as in example 1 except that the foil transport method using bending shown in fig. 2 was used for roughening treatment 1 and roughening treatment 2. However, no resin layer was formed.

< comparative example 3 >

Carrier-attached copper foil was produced in the same manner as in example 2 except that the foil transport method using bending shown in fig. 2 was used for roughening treatment 1 and roughening treatment 2. However, no resin layer was formed.

< comparative example 4 >

The following resin layer "a" was formed on the side of the extra thin copper layer of the copper foil with carrier of comparative example 1.

< comparative example 5 >

The following resin layer "B" was formed on the side of the extra thin copper layer of the copper foil with carrier of comparative example 2.

< comparative example 6 >

The following resin layer "C" was formed on the side of the extra thin copper layer of the copper foil with carrier of comparative example 3.

< example 6 >

A copper foil with a carrier was produced in the same procedure as in example 1, except that no resin layer was formed.

< example 7 >

A copper foil with a carrier was produced in the same procedure as in example 2, except that no resin layer was formed.

< example 8 >

A carrier-attached copper foil was produced in the same procedure as in example 3, except that no resin layer was formed.

< example 9 >

A carrier-attached copper foil was produced in the same procedure as in example 4, except that no resin layer was formed.

< example 10 >

A copper foil with a carrier was produced in the same procedure as in example 5, except that no resin layer was formed.

< formation of resin layer >

The resin layer is formed as follows.

·“A”

(example of resin Synthesis)

117.68g (400mmol) of 3,4/3',4' -biphenyltetracarboxylic dianhydride, 87.7g (300mmol) of 1, 3-bis (3-aminophenoxy) benzene, 4.0g (40mmol) of γ -valerolactone, 4.8g (60mmol) of pyridine, 300g of N-methyl-2-pyrrolidinone (hereinafter referred to as NMP), and 20g of toluene were added to a 2-liter three-necked flask equipped with a stainless steel ingot-type stirrer, a nitrogen gas introduction tube, and a stopcock, and a reflux cooler equipped with a spherical condenser were placed in a well, and after heating at 180 ℃ for 1 hour, the flask was cooled to near room temperature, 29.42g (100mmol) of 3,4/3',4' -biphenyltetracarboxylic dianhydride, 2-bis {4- (4-aminophenoxy) phenyl } propane 82.12g (200mmol), 200g of NMP, and 40g of toluene were added, after mixing at room temperature for 1 hour, the mixture was heated at 180 ℃ for 3 hours to obtain a block copolymerization polyimide having a solid content of 38%. In the block copolymerization polyimide, the following general formula (1): general formula (2) ═ 3: 2, number average molecular weight: 70000, weight average molecular weight: 150000.

the block copolymerization polyimide solution obtained in synthesis example was further diluted with NMP to prepare a block copolymerization polyimide solution having a solid content of 10%. The block copolymerization polyimide solution was dissolved and mixed at 60 ℃ for 20 minutes in the form of a solid content weight ratio of bis (4-maleimidophenyl) methane (BMI-H, K-I Chemical Industry) of 35 and a solid content weight ratio of block copolymerization polyimide of 65 (i.e., the solid content weight of bis (4-maleimidophenyl) methane contained in the resin solution: the solid content weight of block copolymerization polyimide contained in the resin solution: 35: 65) to prepare a resin solution. Thereafter, the resin solution was applied to the surface of the extra thin copper layer of the carrier-attached copper foil before the formation of the resin layer by using a reverse roll coater, and the carrier-attached copper foil was produced by drying the carrier-attached copper foil at 120 ℃ for 3 minutes and 160 ℃ for 3 minutes in a nitrogen atmosphere, and then heating the carrier-attached copper foil at 300 ℃ for 2 minutes. The thickness of the resin layer was set to 2 μm.

·“B”

B is a resin composition prepared from 69 parts by weight of an epoxy resin, 11 parts by weight of a curing agent, 0.25 part by weight of a curing accelerator, 15 parts by weight of a polymer component, 3 parts by weight of a crosslinking agent, and 3 parts by weight of a rubbery resin.

Specifically, the following is shown.

[ composition of resin composition ]

Constituent/specific chemical name (manufacturing company)/composition (parts by weight)

Epoxy resin/bisphenol A type/YD-907 (manufactured by Dondo chemical Co., Ltd.)/15

Epoxy resin/bisphenol A type/YD-011 (manufactured by Dongdu chemical Co.)/54

Hardener/aromatic amine/4, 41-diaminodiphenyl sulfone (from refining of Hill.)/12

Hardening accelerator/imidazole/2E 4MZ (manufactured by four kingdoms chemical industries)/0.4

Polymer component/polyvinyl acetal resin/5000A (manufactured by electrochemical industries)/15

Crosslinking agent/urethane resin/AP-Stable (manufactured by Nippon Polyurethane)/3

Rubber component/core-Shell nitrile rubber/XER-91 (manufactured by JSR Corp.)/3

Then, the resin solid content of the resin composition described above was adjusted to 30 wt% using methyl ethyl ketone and dimethylacetamide to prepare a resin composition solution for forming a resin layer. Then, the resin composition solution for forming the resin layer was applied to the surface of the carrier-attached copper foil on the very thin copper layer side before the resin layer was provided, using a gravure coater. Then, the copper foil was air-dried for 5 minutes, and then dried for 3 minutes in a heating atmosphere at 140 ℃ to form a semi-cured resin layer (adhesive layer) having a thickness of 1.5 μm in a semi-cured state, thereby producing a carrier-attached copper foil. The resin overflow amount of the semi-cured resin layer (adhesive layer) obtained at this time was measured by preparing a 18 μm thick copper foil from the resin composition solution for forming a resin layer and providing a 40 μm thick semi-cured resin layer on one surface thereof, and this was used as a sample for measuring the resin overflow amount. Then, 4 pieces of 10cm square samples were collected from the resin overflow amount measurement sample, and the resin overflow amount was measured based on the MIL-P-13949G. As a result, the overflow amount of the resin was 1.5%.

·“C”

A resin solution constituting the resin layer is produced. In the production of the resin solution, an epoxy resin (EPPN-502 manufactured by Nippon chemical Co., Ltd.) and a polyether sulfone resin (Sumikaexcel PES-5003P manufactured by Sumitomo chemical Co., Ltd.) were used as raw materials. Thereafter, imidazole-based 2E4MZ (manufactured by Shikoku Kogyo Co., Ltd.) was added as a curing accelerator to prepare a resin composition.

The resin composition comprises: 50 parts by weight of epoxy resin

Polyether sulfone resin 50 weight portions

1 part by weight of a hardening accelerator

The resin composition was further adjusted to a resin solid content of 30 wt% using dimethylformamide to prepare a resin solution. The resin solution prepared in the above manner was applied to the surface of the carrier-attached copper foil on the side of the extremely thin copper layer before the resin layer was provided, using a gravure coater. Then, the copper foil was dried at 140 ℃ for 3 minutes to form a semi-cured resin layer having a thickness of 1.5 μm, thereby obtaining a carrier-attached copper foil according to the present invention. On the other hand, in order to measure the resin overflow amount, a resin-coated copper foil (copper foil thickness: 18 μm) was produced in which the undercoat resin layer was 40 μm thick (hereinafter referred to as "resin overflow amount measurement sample"). Then, 4 pieces of 10cm square samples were collected from the resin overflow amount measurement sample, and the resin overflow amount was measured based on the MIL-P-13949G described above. As a result, the overflow amount of the resin was 1.4%.

·“D”

The polyimide resin layer as a cured resin layer is formed on the surface of the extremely thin copper layer side of the carrier-attached copper foil before the resin layer is provided, and the semi-cured resin layer is formed in the case of using the carrier-attached copper foil with a maleimide resin.

Preparation of polyamic acid varnish: the polyamic acid varnish to form a hardened resin layer by a casting method is explained. Pyromellitic dianhydride (1 mol) and 4,4' -diaminodiphenyl ether (1 mol) were dissolved in N-methylpyrrolidone (solvent), and mixed. The reaction temperature at this time was 25 ℃ and the reaction time was 10 hours. Then, a polyamic acid varnish having a resin solid content of 20 mass% was obtained.

Formation of a hardened resin layer: then, using the obtained polyamic acid varnish, a cured resin layer was formed by a casting method. A polyamic acid varnish was applied to the surface of the side of the extra thin copper layer of the copper foil with a carrier before the resin layer was provided by a Multi Coater (manufactured by Hirano Tecsed Co., Ltd.: M-400), and dried in a hot air dryer at 110 ℃ for 6 minutes. The resin thickness of the cured resin layer after drying was set to 35 μm, and the residual solvent ratio at this stage was 32 wt% based on the total amount of the resin layer. The composite of the electrolytic copper foil coated with the polyamic acid varnish was placed in a hot air oven replaced with nitrogen, heated from room temperature to 400 ℃ over 15 minutes, and thereafter held at 400 ℃ for 8 minutes, followed by cooling. Thus, the residual solvent is removed from the composite coated with the carrier copper foil of polyamic acid, and the polyamic acid is subjected to a dehydration ring-closing imide reaction to produce the copper-clad polyimide resin substrate in which the cured resin layer is laminated on the surface of the extremely thin copper layer of the carrier copper foil. The residual solvent content of the copper-clad polyimide resin substrate obtained by the final heat treatment was 0.5 wt% based on the total amount of the resin attached to the copper foil with a carrier.

Then, the copper foil with carrier (copper-clad polyimide resin substrate) laminated with the cured resin layer is subjected to corona treatment to modify the surface of the cured resin layer. The corona treatment was carried out in the air at an electric power of 210W and a speed of 2m/min and a discharge rate of 300 W.min/m²The irradiation distance from the electrode was 1.5 mm. In order to measure the thermal expansion coefficient of the cured resin layer, the copper foil with carrier (corona-treated copper-clad polyimide resin substrate) was removed by peeling and etching from the copper foil with carrier laminated with the cured resin layer after the surface modification treatment. As a result, the cured resin layer (polyimide film) obtained by removing the copper foil with carrier had a resin thickness of 27 μm and a coefficient of thermal expansion of 25 ppm/DEG C.

Formation of semi-cured resin layer: here, a semi-cured resin layer is formed on the cured resin layer of the corona-treated copper-clad polyimide resin substrate. First, a resin composition described below was dissolved using N, N' -dimethylacetamide as a solvent, and prepared as a resin varnish in which the resin solid content was 30 wt%.

[ resin composition for Forming semi-cured resin layer ]

Maleimide resin: 4,4' -diphenylmethane bismaleimide (trade name: BMI-1000, manufactured by Daihuazai chemical industries, Ltd.)/30 parts by weight of the total amount of the composition

Aromatic polyamine resin: 1, 3-bis [ 4-aminophenoxy ] benzene (trade name: TPE-R, manufactured by Harmony mountain industries, Ltd.)/35 parts by weight of a solvent

Epoxy resin: bisphenol A type epoxy resin (trade name: EPICLON 850S, manufactured by Dainippon ink chemical industries, Ltd.)/20 parts by weight of the epoxy resin

Linear polymer with crosslinkable functional groups: polyvinyl acetal resin (trade name: Denkabutyl 5000A, manufactured by electrochemical industries, Ltd.)/15 parts by weight

The resin varnish was applied to the polyimide resin surface of the copper-clad polyimide resin substrate subjected to corona treatment, air-dried at room temperature for 5 minutes, and heat-dried at 160 ℃ for 5 minutes to form a semi-cured resin layer. The resin thickness of the semi-cured resin layer at this time was set to 20 μm.

In order to measure the thermal expansion coefficient of the semi-cured resin layer after curing, the resin varnish for forming the semi-cured resin layer was applied to a fluorine-based heat-resistant film by the same method as described above, air-dried at room temperature for 5 minutes, dried by heating at 160 ℃ for 5 minutes, and further heated by curing at 200 ℃ for 2 hours to prepare a cured resin layer for a test having a thickness of 20 μm. That is, the cured resin layer for test corresponds to a case where the semi-cured resin layer of the copper foil with carrier of the present invention is cured. The coefficient of thermal expansion of the cured resin layer for the test was 45 ppm/DEG C.

The thickness of the entire resin layer with the copper foil for carrier obtained in the above manner was 47 μm. The copper foil was etched and removed from the resin-coated copper foil by the following method, and the resin layer composed of the cured resin layer and the semi-cured resin layer was heated at 200 ℃ for 2 hours to cure, and the coefficient of thermal expansion of the entire resin layer after curing the semi-cured resin layer was measured. The resulting coefficient of thermal expansion was 35 ppm/deg.C. The peel strength was 1.0 kgf/cm.

·“E”

The 1 st resin composition constituting the resin layer was initially produced. In the production of the 1 st resin composition, an o-cresol novolac type epoxy resin (YDCN-704, manufactured by Tokyo chemical Co., Ltd.), an aromatic polyamide resin polymer soluble in a solvent, and BP3225-50P, manufactured by Nippon chemical Co., Ltd., commercially available as a mixed varnish with cyclopentanone as a solvent, were used as raw materials. VH-4170 manufactured by japan ink corporation and 2E4MZ manufactured by four chemical industries ltd as a curing accelerator were added to a phenol resin as a curing agent to prepare a 1 st resin composition having a formulation ratio shown below in the mixed varnish.

The resin composition 1 was further prepared into a resin solution by adjusting the solid resin content to 30% by weight using methyl ethyl ketone.

The surface of the extra thin copper layer side of the carrier-attached copper foil before the formation of the resin layer (in the case of surface treatment of the extra thin copper layer, the surface treated surface) is immersed in the following solution: a solution obtained by adding gamma-glycidoxypropyltrimethoxysilane to ion-exchanged water so as to have a concentration of 5g/l was subjected to adsorption treatment. Then, water was released in a furnace adjusted to 180 ℃ by a heater for 4 seconds to cause condensation reaction of the silane coupling agent, thereby forming a silane coupling agent layer.

The resin solution prepared as described above was applied to the surface on which the silane coupling agent layer with carrier copper foil was formed using a gravure coater. Then, the copper foil was air-dried for 5 minutes, and then dried for 3 minutes in a heating atmosphere at 140 ℃ to form a semi-cured resin layer having a thickness of 1.5 μm, thereby obtaining a carrier-attached copper foil according to the present invention. The resin overflow amount was measured by manufacturing a resin-coated copper foil (hereinafter referred to as "resin overflow amount measurement sample") in which the thickness of the undercoat resin layer was 40 μm.

Then, 4 pieces of 10cm square samples were collected from the resin overflow amount measurement sample, and the resin overflow amount was measured based on the MIL-P-13949G described above. As a result, the overflow amount of the resin was 1.5%.

2. Evaluation of characteristics of copper foil with Carrier

The carrier-attached copper foil obtained in the above manner was subjected to characteristic evaluation by the following method. The results are shown in Table 1. Further, in the above-described case,"3.91E-16" in "Ra" in "Standard deviation (. mu.m)" column "of Table 1 represents 3.91X 10^-16(. mu.m), "1.30E-02" means 1.30X 10^-2(μm)。

(surface roughness)

Each carrier-attached copper foil (550 mm. times.550 mm square) before the formation of the resin layer was led straight in the vertical and horizontal directions at a pitch of 55mm, and 100 portions were allocated to each 55 mm. times.55 mm square region. The surface roughness (Ra, Rt, Rz) of the extremely thin copper layer was measured under the following measurement conditions using a contact roughness measuring machine (Surfcorder SE-3C, contact roughness meter manufactured by Osaka research institute, Ltd.) for each region in accordance with JIS B0601-1982(Ra, Rz) and JIS B0601-2001(Rt), and the average value and standard deviation thereof were measured.

< measurement Condition >

Cut-off point: 0.25mm

Reference length: 0.8mm

Measuring the ambient temperature: 23 to 25 DEG C

(migration)

Each of the copper foils with carrier (550 mm. times.550 mm square) before the formation of the resin layer was bonded to a bismuth-based resin, and then the carrier foil was peeled off and removed. The thickness of the exposed extremely thin copper layer was made to be 1.5 μm by soft etching. Thereafter, the glass was cleaned, dried, and then laminated and coated with DF (manufactured by Hitachi chemical Co., Ltd., trade name RY-3625) on the extra thin copper layer. At 15mJ/cm²The resist pattern was formed with a line-to-space (L/S) of 15 μm/15 μm by performing liquid jet oscillation at 38 ℃ for 1 minute using a developing solution (sodium carbonate). Then, after the film was plated to a height of 15 μm by copper sulfate plating (CUBRITE 21 manufactured by Ebara-Udylite), DF was peeled off by a peeling liquid (sodium hydroxide). Then, the extremely thin copper layer was etched and removed with a sulfuric acid-hydrogen peroxide etchant to form a wiring having an L/S of 15 μm/15 μm. 100 wiring substrates were cut out from the obtained wiring substrate in accordance with the above-described area of each size of 55mm × 55 mm.

The obtained wiring boards were evaluated for the presence or absence of insulation deterioration between wiring patterns under the following measurement conditions using a migration measuring instrument (MIG-9000 manufactured by IMV). The number of substrates on which migration occurred was evaluated for 100 wiring substrates.

In example 2, a wiring having a pitch of 20 μm between lines and spaces (L/S8 μm/12 μm, L/S10 μm/10 μm, and L/S12 μm/8 μm) was formed, and the migration was evaluated. In example 3, the above-described evaluation of migration was performed by forming a wiring having a pitch of 20 μm between lines and spaces (L/S8 μm/12 μm, L/S10 μm/10 μm, and L/S12 μm/8 μm), and a pitch of 15 μm between lines and spaces (L/S5 μm/10 μm, and L/S8 μm/7 μm). In the case where the pitch between the wire and the gap is 15 μm, the thickness of the plated layer is 10 μm. As a result, when the copper foil with carrier of example 2 was used to form a wiring having an L/S of 8 μm/12 μm, an L/S of 10 μm/10 μm, and an L/S of 12 μm/8 μm, the in-plane mobility generation rates were 2/100, 2/100, and 3/100, respectively. When the copper foil with carrier of example 3 was used to form a wiring having an L/S of 8 μm/12 μm, an L/S of 10 μm/10 μm, an L/S of 12 μm/8 μm, an L/S of 5 μm/10 μm, and an L/S of 8 μm/7 μm, the in-plane mobility generation rates were 1/100, 1/100, 2/100, 1/100, and 3/100, respectively.

< measurement Condition >

Threshold value: the initial resistance is reduced by 60 percent

Measuring time: 1000h

Voltage: 60V

Temperature: 85 deg.C

Relative humidity: 85% RH

(Peel Strength)

With respect to the prepared carrier-attached copper foil with a resin layer (in which, when no resin layer is formed), the peel strength of the extremely thin copper layer from the resin base material was measured. A copper-clad laminate was produced by using a BT substrate (bismaleimide triazine resin, GHPL-830MBT manufactured by mitsubishi gas chemical corporation) as a resin substrate, laminating the resin substrate on the side of the resin layer with a carrier copper foil, and performing thermocompression bonding under the conditions recommended by mitsubishi gas chemical corporation. Thereafter, after peeling off the carrier, a circuit having a width of 10mm was formed by wet etching, and 10 measurement samples were prepared for each of examples and comparative examples. Thereafter, the extremely thin copper layer forming the circuit was peeled off, and the peel strength was measured at 90 degrees for 10 samples to determine the average value, the maximum value, the minimum value of the peel strength, and the variation in peel strength ((maximum-minimum)/average value × 100 (%)). The BT base material is a typical base material for a semiconductor package substrate. The peel strength of an extremely thin copper layer from a BT substrate when the BT substrate is laminated is preferably 0.70kN/m or more, and more preferably 0.85kN/m or more.

Claims

1. A copper foil with a carrier, which comprises a carrier, a release layer, an extra thin copper layer, and an optional resin layer in this order, wherein the average value of Rt on the surface of the extra thin copper layer is 2.0 [ mu ] m or less as measured by a contact roughness meter in accordance with JIS B0601-2001, and the standard deviation of Rt is 0.1 [ mu ] m or less.

2. The copper foil with carrier according to claim 1, wherein the average value of Rz of the surface of the extra thin copper layer is 1.5 μm or less as measured by a contact roughness meter in accordance with JIS B0601-1982, and the standard deviation of Rz is 0.1 μm or less.

3. The copper foil with carrier according to claim 1, wherein the average value of Ra on the surface of the extra thin copper layer is 0.2 μm or less as measured by a contact roughness meter in accordance with JIS B0601-1982, and the standard deviation of Ra is 0.03 μm or less.

4. The copper foil with carrier according to claim 2, wherein the average value of Ra of the surface of the extra thin copper layer is 0.2 μm or less as measured by a contact roughness meter in accordance with JIS B0601-1982, and the standard deviation of Ra is 0.03 μm or less.

5. The copper foil with carrier according to any one of claims 1 to 4, wherein the average value of Rt on the surface of the extra thin copper layer is 1.0 μm or less.

6. A copper foil with a carrier, which comprises a carrier, a release layer, an extra thin copper layer, and an arbitrary resin layer in this order, wherein the average value of Rt on the surface of the extra thin copper layer is 2.0 μm or less as measured by a contact roughness meter in accordance with JIS B0601-2001, the standard deviation of Rt is 0.1 μm or less, and one, two, three, four, five, six, seven, eight, nine, ten, eleven, or twelve of the following A) to L) are satisfied,

A) 1 item selected from the group consisting of:

1 the average value of Rz of the surface of the extremely thin copper layer is 1.5 μm or less as measured by a contact roughness meter in accordance with JIS B0601-1982,

2 the average value of Rz of the surface of the extremely thin copper layer is 1.4 μm or less as measured by a contact roughness meter in accordance with JIS B0601-1982,

3 the average value of Rz of the surface of the extremely thin copper layer is 1.3 μm or less as measured by a contact roughness meter in accordance with JIS B0601-1982,

4 the average value of Rz of the surface of the extremely thin copper layer is 1.2 μm or less as measured by a contact roughness meter in accordance with JIS B0601-1982,

5 the average value of Rz of the surface of the extremely thin copper layer is 1.0 μm or less as measured by a contact roughness meter in accordance with JIS B0601-1982,

6 the average value of Rz of the surface of the extremely thin copper layer is 0.8 μm or less as measured by a contact roughness meter in accordance with JIS B0601-1982,

7 the average value of Rz of the surface of the extremely thin copper layer is 0.5 μm or less as measured by a contact roughness meter in accordance with JIS B0601-1982,

B) 1 item selected from the group consisting of:

1 the average value of Rz of the surface of the extremely thin copper layer is 0.01 μm or more as measured by a contact roughness meter in accordance with JIS B0601-1982,

2 the average value of Rz of the surface of the extremely thin copper layer is 0.1 μm or more as measured by a contact roughness meter in accordance with JIS B0601-1982,

3 the average value of Rz of the surface of the extremely thin copper layer is 0.3 μm or more as measured by a contact roughness meter in accordance with JIS B0601-1982,

C) 1 item selected from the group consisting of:

1, the standard deviation of Rz of the surface of the extremely thin copper layer is 0.1 μm or less,

2, the standard deviation of Rz of the surface of the extremely thin copper layer is 0.068 μm or less,

3, the standard deviation of Rz of the surface of the extremely thin copper layer is 0.05 μm or less,

D) the standard deviation of Rz of the surface of the extremely thin copper layer is 0.01 μm or more,

E) 1 item selected from the group consisting of:

1 the average value of Rt on the surface of the extremely thin copper layer is 1.8 μm or less as measured by a contact roughness meter in accordance with JIS B0601-2001,

2 the average value of Rt on the surface of the extremely thin copper layer is 1.5 μm or less as measured by a contact roughness meter in accordance with JIS B0601-2001,

3 the average value of Rt on the surface of the extremely thin copper layer is 1.3 μm or less as measured by a contact roughness meter in accordance with JIS B0601-2001,

4 the average value of Rt on the surface of the extremely thin copper layer is 1.1 μm or less as measured by a contact roughness meter in accordance with JIS B0601-2001,

5 the average value of Rt on the surface of the extremely thin copper layer is 1.0 μm or less as measured by a contact roughness meter in accordance with JIS B0601-2001,

F) 1 item selected from the group consisting of:

1 the average value of Rt on the surface of the extremely thin copper layer is 0.5 μm or more as measured by a contact roughness meter in accordance with JIS B0601-2001,

2 the average value of Rt on the surface of the extremely thin copper layer is 0.6 μm or more as measured by a contact roughness meter in accordance with JIS B0601-2001,

3 the average value of Rt on the surface of the extremely thin copper layer is 0.8 μm or more as measured by a contact roughness meter in accordance with JIS B0601-2001,

G) 1 item selected from the group consisting of:

1 standard deviation of Rt on the surface of the extremely thin copper layer of 0.060 μm or less,

2 standard deviation of Rt on the surface of the extremely thin copper layer is 0.05 μm or less,

H) the standard deviation of Rt of the surface of the extremely thin copper layer is 0.01 μm or more, I) 1 item selected from the group consisting of:

1 average value of Ra on the surface of the extra thin copper layer is 0.2 μm or less as measured by a contact roughness meter in accordance with JIS B0601-1982,

2 the average value of Ra on the surface of the extra thin copper layer is 0.18 μm or less as measured by a contact roughness meter in accordance with JIS B0601-1982,

3 the average value of Ra on the surface of the extra thin copper layer is 0.15 μm or less as measured by a contact roughness meter in accordance with JIS B0601-1982,

J) 1 item selected from the group consisting of:

1 the average value of Ra on the surface of the extra thin copper layer is 0.01 μm or more as measured by a contact roughness meter in accordance with JIS B0601-1982,

2 the average value of Ra on the surface of the extra thin copper layer is 0.05 μm or more as measured by a contact roughness meter in accordance with JIS B0601-1982,

3 the average value of Ra on the surface of the extra thin copper layer is 0.12 μm or more as measured by a contact roughness meter in accordance with JIS B0601-1982,

4 the average value of Ra on the surface of the extra thin copper layer is 0.13 μm or more as measured by a contact roughness meter in accordance with JIS B0601-1982,

K) 1 item selected from the group consisting of:

1 standard deviation of Ra of the surface of the extremely thin copper layer is 0.03 μm or less,

2 the standard deviation of Ra on the surface of the extremely thin copper layer is less than 0.026 mu m,

3 the standard deviation of Ra of the surface of the extremely thin copper layer is 0.02 mu m or less,

l) the standard deviation of Ra on the surface of the extremely thin copper layer is 0.001 μm or more.

7. A copper foil with a carrier, which comprises a carrier, a release layer, an extra thin copper layer, and an optional resin layer in this order, wherein the average value of Ra on the surface of the extra thin copper layer is 0.2 μm or less as measured by a contact roughness meter in accordance with JIS B0601-1982, and the standard deviation of Ra is 0.03 μm or less.

8. The copper foil with carrier according to claim 7, wherein the average value of Rz of the surface of the extra thin copper layer is 1.5 μm or less as measured by a contact roughness meter in accordance with JIS B0601-1982, and the standard deviation of Rz is 0.1 μm or less.

9. The copper foil with carrier according to claim 7, wherein the average value of Rt on the surface of the extra thin copper layer is 2.0 μm or less as measured by a contact roughness meter in accordance with JIS B0601-2001, and the standard deviation of Rt is 0.1 μm or less.

10. The copper foil with carrier according to claim 8, wherein the average value of Rt on the surface of the extra thin copper layer is 2.0 μm or less as measured by a contact roughness meter according to JIS B0601-2001, and the standard deviation of Rt is 0.1 μm or less.

11. The copper foil with carrier according to any one of claims 7 to 10, wherein an average value of Ra of the surface of the extra thin copper layer is 0.15 μm or less.

12. A copper foil with a carrier, which comprises a carrier, a release layer, an extra thin copper layer, and an arbitrary resin layer in this order, wherein the average value of Ra on the surface of the extra thin copper layer is 0.2 μm or less as measured by a contact roughness meter in accordance with JIS B0601-1982, the standard deviation of Ra is 0.03 μm or less, and one, two, three, four, five, six, seven, eight, nine, ten, eleven, or twelve of the following A) to L) are satisfied,

A) 1 item selected from the group consisting of:

B) 1 item selected from the group consisting of:

C) 1 item selected from the group consisting of:

E) 1 item selected from the group consisting of:

1 the average value of Rt on the surface of the extremely thin copper layer is 2.0 μm or less as measured by a contact roughness meter in accordance with JIS B0601-2001,

2 the average value of Rt on the surface of the extremely thin copper layer is 1.8 μm or less as measured by a contact roughness meter in accordance with JIS B0601-2001,

3 the average value of Rt on the surface of the extremely thin copper layer is 1.5 μm or less as measured by a contact roughness meter in accordance with JIS B0601-2001,

4 the average value of Rt on the surface of the extremely thin copper layer is 1.3 μm or less as measured by a contact roughness meter in accordance with JIS B0601-2001,

5 the average value of Rt on the surface of the extremely thin copper layer is 1.1 μm or less as measured by a contact roughness meter in accordance with JIS B0601-2001,

6 the average value of Rt on the surface of the extremely thin copper layer is 1.0 μm or less as measured by a contact roughness meter in accordance with JIS B0601-2001,

F) 1 item selected from the group consisting of:

G) 1 item selected from the group consisting of:

1 standard deviation of Rt on the surface of the extremely thin copper layer of 0.1 μm or less,

2 standard deviation of Rt on the surface of the extremely thin copper layer is 0.060 μm or less,

3 standard deviation of Rt on the surface of the extremely thin copper layer is 0.05 μm or less,

1 average value of Ra on the surface of the extra thin copper layer is 0.18 μm or less as measured by a contact roughness meter in accordance with JIS B0601-1982,

2 the average value of Ra on the surface of the extra thin copper layer is 0.15 μm or less as measured by a contact roughness meter in accordance with JIS B0601-1982,

J) 1 item selected from the group consisting of:

K) 1 item selected from the group consisting of:

1 standard deviation of Ra of the surface of the extremely thin copper layer is 0.026 mu m or less,

2 the standard deviation of Ra of the surface of the extremely thin copper layer is 0.02 mu m or less,

13. The carrier-attached copper foil according to any one of claims 1 to 4, 6 to 10, and 12, wherein the extra thin copper layer is subjected to roughening treatment.

14. A printed wiring board produced using the copper foil with a carrier according to any one of claims 1 to 13.

15. The printed wiring board according to claim 14, having:

insulating substrate, and

a copper circuit provided on the insulating substrate,

the circuit width of the copper circuit is less than 20 μm, and the gap width between adjacent copper circuits is less than 20 μm.

16. The printed wiring board according to claim 14, having:

insulating substrate, and

a copper circuit provided on the insulating substrate,

the copper circuit has a circuit width of 17 μm or less, and a gap width between adjacent copper circuits is 17 μm or less.

17. The printed wiring board of claim 14, wherein the wire-to-gap spacing is less than 40 μm.

18. The printed wiring board of claim 14, wherein the pitch of the wires and the gaps is 34 μm or less.

19. A printed circuit board produced using the carrier-attached copper foil according to any one of claims 1 to 13.

20. The printed circuit board of claim 19, having:

insulating substrate, and

a copper circuit provided on the insulating substrate,

21. The printed circuit board of claim 19, having:

insulating substrate, and

a copper circuit provided on the insulating substrate,

22. The printed circuit board of claim 19, wherein the line-to-gap spacing is less than 40 μ ι η.

23. The printed circuit board of claim 19, wherein the line-to-gap spacing is 34 μ ι η or less.

24. A copper-clad laminate produced using the copper foil with a carrier according to any one of claims 1 to 13.

25. A method for manufacturing a printed wiring board, comprising the steps of:

a step of preparing the copper foil with carrier and the insulating substrate according to any one of claims 1 to 13;

laminating the copper foil with carrier and the insulating substrate;

after the copper foil with carrier and the insulating substrate are laminated, the carrier with the copper foil with carrier is peeled off to form a copper-clad laminate,

and thereafter, a step of forming a circuit by any one of a semi-addition method, a subtraction method, a partial addition method, or a modified semi-addition method.

26. A method for manufacturing a printed wiring board, comprising the steps of:

a step of forming a circuit on the surface of the extra thin copper layer side of the copper foil with a carrier according to any one of claims 1 to 13;

forming a resin layer on the surface of the extra thin copper layer of the carrier-attached copper foil so as to bury the circuit;

forming a circuit on the resin layer;

peeling the carrier after forming a circuit on the resin layer; and

and removing the extremely thin copper layer after peeling the carrier, thereby exposing a circuit formed on a side surface of the extremely thin copper layer and buried in the resin layer.

27. The method for manufacturing a printed wiring board according to claim 26, wherein the step of forming a circuit on the resin layer is a step of bonding another carrier-attached copper foil to the resin layer from the extra thin copper layer side, and forming the circuit using the carrier-attached copper foil bonded to the resin layer.

28. The method for manufacturing a printed wiring board according to claim 27, wherein the other carrier-attached copper foil attached to the resin layer is the carrier-attached copper foil according to any one of claims 1 to 13.

29. The manufacturing method of a printed wiring board according to any one of claims 26 to 28, wherein the step of forming a circuit on the resin layer is performed by any one of a semi-additive method, a subtractive method, a partial additive method, or a modified semi-additive method.

30. The method for manufacturing a printed wiring board according to any one of claims 26 to 28, further comprising a step of forming a substrate on the carrier-side surface of the carrier-attached copper foil before peeling off the carrier.