CN108277509A - Copper foil with carrier - Google Patents

Abstract

The invention discloses Copper foil with carrier.Specifically, the present invention provides a kind of Copper foil with carrier suitably forming thin space.The Copper foil with carrier of the present invention sequentially has carrier, peeling layer, very thin layers of copper and arbitrary resin layer, and the average value of the Rz on very thin layers of copper surface is to be measured according to JIS B0601 1982 using contact roughmeter and be 1.5 μm hereinafter, and the standard deviation of Rz is 0.1 μm or less.

Description

Copper foil with carrier

This application is a divisional application of the Chinese patent application with the application number 201380060497.X, the application date is November 20, 2013, and the invention title is "copper foil with carrier".

technical field

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

Background technique

A printed wiring board is usually manufactured by bonding copper foil and an insulating substrate to form a copper-clad laminate, and then forming a conductive pattern on the surface of the copper foil by etching. With the increasing demand for miniaturization and high performance of electronic equipment in recent years, high-density mounting of mounted components and high frequency of signals have progressed, and miniaturization of conductor patterns (fine pitch (fine pitch)) is required for printed wiring boards. ) of) or in response to high frequency, etc.

In response to finer pitches, copper foils with a thickness of 9 μm or less, and furthermore, copper foils with a thickness of 5 μm or less have recently been required. However, due to the low mechanical strength of such extremely thin copper foils, it is easy to be damaged or wrinkled during the manufacture of printed wiring boards. Copper foil with a carrier, which uses a thick metal foil as a carrier and electroplates an ultra-thin copper layer through a peeling layer. After bonding the surface of the ultra-thin copper layer to the insulating substrate and performing thermocompression bonding, the carrier is peeled and removed through the release layer. After forming a circuit pattern with a resist on the exposed ultra-thin copper layer, the method of etching and removing the ultra-thin copper layer with a sulfuric acid-hydrogen peroxide-based etchant (MSAP: Modified-Semi-Additive-Process, Modified Semi-Additive-Process into a manufacturing method) to form a microcircuit.

Here, for the surface of the ultra-thin copper layer of the copper foil with a carrier to be the bonding surface with the resin, it is mainly required that the peel strength between the ultra-thin copper layer and the resin base material is sufficient, and that it should not be damaged by high-temperature heating, wet processing, welding, chemical treatment, etc. After that, it can fully maintain its peel strength. As a method of improving the peeling strength between the ultra-thin copper layer and the resin base material, generally, a method of attaching a large number of roughening particles to the ultra-thin copper layer that increases the surface profile (unevenness, roughness) is typical.

However, if such an ultra-thin copper layer with a large outline (concave-convex, roughness) is used in printed wiring boards, especially semiconductor package substrates that must form fine circuit patterns, unnecessary copper will remain during circuit etching. Particles can cause problems such as poor insulation between circuit patterns.

Therefore, WO2004/005588 (Patent Document 1) attempts to use a copper foil with a carrier that does not roughen the surface of the ultra-thin copper layer as a copper foil with a carrier for fine circuits represented by semiconductor package substrates. The adhesion (peel strength) of the ultra-thin copper layer without roughening treatment to the resin is different from that of ordinary copper foil for printed wiring boards due to the influence of its low profile (concave-convex, roughness, roughness). tendency to decrease. Therefore, further improvement is required for the copper foil with a carrier.

Therefore, in Japanese Patent Application Laid-Open No. 2007-007937 (Patent Document 2) and Japanese Patent Laid-Open No. 2010-006071 (Patent Document 3), it is described that an ultra-thin copper foil with a carrier and a polyimide-based resin substrate A Ni layer or/and a Ni alloy layer, a chromate layer, a Cr layer or/and a Cr alloy layer, a Ni layer and a chromate layer, and a Ni layer and a Cr layer are provided on the contacting (adhering) surface. By providing these surface treatment layers, the adhesion strength between the polyimide-based resin substrate and the ultra-thin copper foil with a carrier can be obtained without roughening or by reducing the degree of roughening (miniaturization). strength. Furthermore, surface treatment with a silane coupling agent or antirust treatment are also described.

[Patent Document 1] WO2004/005588

[Patent Document 2] Japanese Unexamined Patent Publication No. 2007-007937

[Patent Document 3] Japanese Patent Laid-Open No. 2010-006071.

Contents of the invention

[Problem to be solved by the invention]

So far, the development of copper foil with a carrier has focused on ensuring the peel strength between the ultra-thin copper layer and the resin substrate. Therefore, sufficient research has not yet been conducted on finer pitches, and there is still room for improvement. Therefore, the subject of this invention is providing the copper foil with a carrier suitable for forming a fine pitch. Specifically, the object is to provide a copper foil with a carrier that can form finer wiring than L/S=20 μm/20 μm, which is considered to be the limit of MSAP formation so far.

[Technical means to solve the problem]

In order to achieve the above object, the inventors of the present invention have made intensive research and found that the surface of the ultra-thin copper layer can be reduced in roughness, and the fine roughened particles can be uniformly formed in the surface of the ultra-thin copper layer. Uniform and low-roughness roughened surface. Furthermore, it was found that this copper foil with a carrier is extremely effective in forming fine pitches.

The present invention was completed based on the above findings, and in one aspect, it is a copper foil with a carrier, which is sequentially provided with a carrier, a release layer, an ultra-thin copper layer, and an optional resin layer, and the surface of the ultra-thin copper layer is The average value of Rz is 1.5 micrometers or less, and the standard deviation of Rz is 0.1 micrometer or less as measured with a contact-type roughness meter based on JISB0601-1982.

Another aspect of the present invention is a copper foil with a carrier, which is sequentially provided with a carrier, a peeling layer, an ultra-thin copper layer, and an arbitrary resin layer, and the average value of Rt on the surface of the ultra-thin copper layer is determined by contact The type roughness meter measured based on JIS B0601-2001 was 2.0 μm or less, and the standard deviation of Rt was 0.1 μm or less.

In yet another aspect of the present invention, it is a copper foil with a carrier, which is sequentially provided with a carrier, a release layer, an ultra-thin copper layer, and an arbitrary resin layer, and the average value of Ra on the surface of the ultra-thin copper layer is obtained by using The contact-type roughness meter measured based on JISB0601-1982 was 0.2 micrometer or less, and the standard deviation of Ra was 0.03 micrometer or less.

In one Embodiment of the copper foil with a carrier of this invention, an ultra-thin copper layer is roughened.

This invention is a printed wiring board manufactured using the copper foil with a carrier of this invention in another another one.

This invention is another one side. It is a printed wiring board manufactured using the copper foil with a carrier of this invention.

This invention is a copper clad laminated board manufactured using the copper foil with a carrier of this invention in another one side.

[Effect of the invention]

The copper foil with a carrier of the present invention is suitable for forming a fine pitch, for example, it can form finer wiring than L/S=20μm/20μm, which is considered to be the limit that can be formed by the MSAP step, for example, a finer wiring of L/S=15μm/15μm wiring. In particular, in the present invention, since the in-plane uniformity of the surface roughness of the ultra-thin copper layer is high, the in-plane uniformity becomes good in the flash etching when forming a circuit by the MSAP method, and thus an improvement in yield can be expected. .

Description of drawings

Fig. 1 is a schematic diagram showing a foil conveying method using a drum.

Fig. 2 is a schematic diagram showing a foil conveying method using zigzag folding.

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

FIG. 4 shows steps D to F of a specific example of the method of 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 the method of manufacturing a printed wiring board using the copper foil with a carrier of the present invention.

Fig. 6 shows steps J to K of a specific example of the method of manufacturing a printed wiring board using the copper foil with a carrier of the present invention.

Detailed ways

<1. Carrier>

The carrier that can be used in the present invention is typically metal foil or resin film, such as copper foil, copper alloy foil, nickel foil, nickel alloy foil, iron foil, iron alloy foil, stainless steel foil, aluminum foil, aluminum alloy foil, insulating resin It is provided in the form of a film (for example, polyimide film, liquid crystal polymer (LCP) film, polyethylene terephthalate (PET) film, polyamide film, polyester film, fluororesin film, etc.).

As a carrier usable in the present invention, copper foil is preferably used. Typically, the carrier is provided in the form of rolled copper foil or electrolytic copper foil. Usually, electrolytic copper foil is produced by electrolytically desorbing copper from a copper sulfate plating bath on a titanium or stainless steel drum, and rolled copper foil is produced by repeating plastic working and heat treatment with a rolling roll. As the material of copper foil, in addition to high-purity copper such as refined copper or oxygen-free copper, for example, Sn-doped copper, Ag-doped copper, copper alloys added with Cr, Zr or Mg, etc. Copper alloys such as Carson's copper alloys. In addition, in this specification, when the term "copper foil" is used independently, copper alloy foil is also included.

The thickness of the carrier that can be used in the present invention is also not particularly limited, as long as it is properly adjusted to an appropriate thickness in order to achieve the effect as a carrier, for example, it can be set to 12 μm or more. However, if it is too thick, the production cost will increase, so it is generally preferable to set it to 70 μm or less. Thus, the thickness of the carrier is typically 12-70 μm, more typically 18-35 μm.

＜2. Peeling layer＞

A release layer is provided on the carrier. Another layer may be provided between the copper foil carrier and the release layer. As a peeling layer, the copper foil with a carrier may be provided with the arbitrary peeling layer known to a person in the industry. For example, the peeling layer is preferably made of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, or alloys thereof, or hydrates thereof, or oxides thereof, Or any one or more layers of organic substances are formed. The release layer may also be composed of a plurality of layers. Furthermore, the release layer may have an anti-diffusion function. Here, the so-called anti-diffusion function has a function of preventing elements from the base material from diffusing to the ultra-thin copper layer side.

In one embodiment of the present invention, the peeling layer is composed of the following layer from the carrier side: any one of the element groups of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn A single metal layer composed of a single element, or an alloy layer composed of more than one element selected from the element group of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn (the etc. have the anti-diffusion function), the hydrate of one or more elements selected from the group of elements selected from Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn or A layer composed of oxides or organic matter.

Also, for example, the release layer can be composed of the following layer from the carrier side: a single metal composed of any element in the element group of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn layer, or an alloy layer composed of one or more elements selected from the element group of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, followed by Cr, Ni, Co , Fe, Mo, Ti, W, P, Cu, Al, a single metal layer composed of any element in the element group of Zn, or a single metal layer selected from Cr, Ni, Co, Fe, Mo, Ti, W, An alloy layer composed of one or more elements in the element group of P, Cu, Al, and Zn. In addition, the total adhesion amount of each element can be set to 1-6000 microgram/dm ^<2> , for example. Moreover, the layer constitution which can be used as a peeling layer can also be used for another layer.

The peeling layer is preferably composed of two layers of Ni and Cr. In this case, the Ni layer is laminated so as to be in contact with the interface with the copper foil carrier, and the Cr layer is laminated so as to be in contact with the interface with the ultra-thin copper layer.

The release 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.

Also, for example, the release layer can be formed by sequentially laminating nickel, nickel-phosphorus alloy or nickel-cobalt alloy and chromium on the carrier. Since the adhesive force between nickel and copper is higher than that between chromium and copper, when the ultra-thin copper layer is peeled off, it is peeled at the interface between the ultra-thin copper layer and chromium. Moreover, the barrier effect which prevents the diffusion of a copper component from a carrier to an ultra-thin copper layer is expected for the nickel of a peeling layer. The nickel adhesion amount in the peeling layer is preferably 100 μg/dm ² to 40000 μg/dm ² , more preferably 100 μg/dm ² to 4000 μg/dm ² , more preferably 100 μg/dm ² to 2500 μg/dm ² , more preferably 100 μg/dm ² or more and less than 1000 μg/dm ² , and the chromium adhesion amount in the release layer is preferably 5 μg/dm ² or more and 100 μg/dm ² or less. When the release layer is provided on only one side, it is preferable to provide a rust-proof layer such as a Ni-plated layer on the surface opposite to the carrier.

Furthermore, the peeling layer can also be disposed on both sides of the carrier.

＜3. Ultra-thin copper layer＞

An extremely thin layer of copper is provided on the lift-off layer. Another layer may be provided between the release layer and the ultra-thin copper layer. The ultra-thin copper layer can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfamate, copper cyanide, etc., and copper foil can be formed at a high current density by using ordinary electrolytic copper foil. A copper sulfate bath is preferred in terms of aspect. The thickness of the ultra-thin copper layer is not particularly limited, and is generally thinner than the carrier, for example, less than 12 μm. Typically, it is 0.5 to 12 μm, and more typically, it is 2 to 5 μm. Furthermore, the ultra-thin copper layer can also be disposed on both sides of the carrier. Moreover, the layer constitution which can be used as a peeling layer can also be used for another layer.

＜4. Coarsening treatment＞

For the surface of the ultra-thin copper layer, for example, in order to improve the adhesiveness with an insulating substrate, etc., you may provide a roughening process layer by performing a roughening process. The roughening treatment can be formed, for example, by forming roughening particles using copper or a copper alloy. From the viewpoint of forming fine pitches, the roughening treatment layer is preferably composed of fine particles. Regarding the plating conditions for forming roughened particles, if the current density is increased, the copper concentration in the plating solution is decreased, or the coulomb quantity is increased, the particles tend to be miniaturized.

The roughening treatment layer can be composed of the following plating particles: a single substance selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt and zinc or an alloy containing any one or more constituted.

In order to improve the in-plane uniformity of the surface roughness of the surface treatment surface, it is effective to keep the anode-cathode distance at the time of forming the roughening treatment layer constant. It is not limited, but from the viewpoint of industrial production, it is effective to secure a fixed inter-electrode distance by a foil conveying method using a drum or the like as a supporting medium. Fig. 1 is a schematic diagram showing the foil conveying method. While supporting the carrier copper foil conveyed by conveying rollers with a drum, a roughened particle layer is formed on the surface of the ultra-thin copper layer by electrolytic plating. The treatment 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 installed to face the drum. On the other hand, in FIG. 2, the schematic diagram which shows the foil conveying method using the conventional bending is described. In this method, there is a problem that it is difficult to fix the distance between the anode and the cathode due to the influence of the electrolyte and the tension of the foil. Furthermore, in order to keep the anode-cathode distance fixedly when the roughening treatment layer is formed by using the foil conveying method by bending, it is more effective to increase the tension for conveying the foil and shorten the distance between the conveying rollers compared with the conventional one. .

As shown in Figure 1, the foil conveying method using a drum can be used not only for roughening treatment, but also for the formation of peeling layers and the formation of ultra-thin copper layers. The reason for this is that the thickness accuracy of the peeled layer or the ultra-thin copper layer can be improved by adopting the foil conveying method with a drum. Furthermore, in order to keep the anode-cathode distance fixedly when the peeling layer or the ultra-thin copper layer is formed by using the foil conveying method by bending, the tension for conveying the foil is increased and the distance between the conveying rollers is shortened compared with the conventional one. distance is more effective.

The inter-electrode distance is not limited. If it is too long, the production cost will increase. On the other hand, if it is too short, the in-plane unevenness will easily increase. Therefore, it is usually preferably 3 to 100 mm, and more preferably 5 to 80 mm.

In addition, after roughening treatment, secondary particles or tertiary particles and/or anti-rust layer can be formed from nickel, cobalt, copper, zinc monomer or alloy, etc., and then chromate treatment and silane coupling can be performed on the surface. processing etc. That is, one or more layers selected from the group consisting of an antirust layer, a chromate treatment layer, and a silane coupling treatment layer may be formed on the surface of the roughening treatment layer, and the surface of the ultra-thin copper layer may not be roughened. One or more layers selected from the group consisting of a rust-proof layer, a chromate-treated layer, and a silane-coupling-treated layer are formed by chemical treatment. Furthermore, these surface treatments have almost no effect on the surface roughness of the ultra-thin copper layer.

The surface of the ultra-thin copper layer (in the case of various surface treatments such as roughening treatment, refers to the surface of the ultra-thin copper layer after surface treatment (also called "surface treatment surface")) is measured using a contact roughness meter. When measuring in accordance with JIS B0601-1982, it is extremely advantageous from the viewpoint of forming a fine pitch that the average value of Rz (ten-point average roughness) is 1.5 μm or less. 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 value of Rz is too small, the adhesive force with the resin will decrease. From this point, it is preferably 0.01 μm or more, more preferably 0.1 μm or more, still more preferably 0.3 μm or more, most preferably 0.5 μm or more .

In the present invention, the average value of Rz is the average value of each Rz obtained when the standard deviation of Rz is obtained by the method described below. In the present invention, furthermore, the standard deviation of Rz on the surface of the ultra-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 μm. The standard deviation of Rz on the surface of the ultra-thin copper layer was obtained from the measurement data of 100 points in the plane. In addition, the measurement data of 100 points in the plane were obtained by dividing the 550 mm square sheet into 10 parts in the longitudinal direction and the transverse direction, and measuring each central part of the 100 divided regions. This application uses this method to maintain in-plane uniformity, but the verification method is not limited to this. For example, the same data can be collected even if a commonly used sample with a size of 550 mm×440 mm to 400 mm×200 mm is divided into 100 parts in the plane (divided into 10 parts vertically and horizontally).

Also, from the viewpoint of fine pitch formation, the surface of the ultra-thin copper layer is preferably such that the average value of Rt (maximum section height) is 2.0 μm or less when measured with a contact roughness meter in accordance with JIS B0601-2001, preferably It is 1.8 μm or less, preferably 1.5 μm or less, preferably 1.3 μm or less, preferably 1.1 μm or less. However, when the average value of Rt is too small, the adhesive force with resin will fall, and it is preferable that it is 0.5 micrometer or more, and it is more preferable that it is 0.6 micrometer or more, and it is still more preferable that it is 0.8 micrometer or more. In the present invention, the average value of Rt is the average value of each Rt obtained when the standard deviation of Rt is obtained by the method described below.

In the present invention, furthermore, the standard deviation of Rt on the surface of the ultra-thin copper layer can be set to 0.1 μm or less, preferably 0.05 μm or less, for example, 0.01 to 0.6 μm. The standard deviation of Rt on the surface of the ultra-thin copper layer was obtained from the measurement data of 100 points in the plane in the same way as Rz.

Also, from the viewpoint of fine-pitch formation, the surface of the ultra-thin copper layer is preferably such that the average value of Ra (arithmetic mean roughness) is 0.2 μm or less when measured with a contact roughness meter in accordance with JIS B0601-1982. More preferably, it is 0.18 μm or less, preferably 0.15 μm or less. However, if the average value of Ra is too small, the adhesive force with the resin will decrease. From this point of view, it is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.12 μm or more, most preferably 0.13 μm or more . In the present invention, the average value of Ra is the average value of each Ra obtained when the standard deviation of Ra is obtained by the method described below.

In the present invention, furthermore, the standard deviation of Ra on the surface of the ultra-thin copper layer can be set to 0.03 μm or less, preferably 0.02 μm or less, for example, 0.001 to 0.03 μm. The standard deviation of Ra on the surface of the ultra-thin copper layer was obtained from the measurement data of 100 points in the plane in the same manner as Rz.

Furthermore, when bonding an insulating substrate such as resin or a resin layer to the surface of an ultra-thin copper layer such as copper foil with a resin layer, a printed wiring board, or a copper-clad laminate, the insulating substrate is melted and By removing it, the above-mentioned surface roughness (Ra, Rt, Rz) can be measured on the copper circuit or copper foil surface.

＜5. Other surface treatment＞

After roughening treatment, nickel, cobalt, copper, zinc monomers or alloys can be used to form a heat-resistant layer or anti-rust layer, and then the surface is subjected to chromate treatment, silane coupling treatment and other treatments. Alternatively, a heat-resistant layer or an anti-rust layer may be formed using a single or alloy of nickel, cobalt, copper, or zinc without roughening, and then the surface may be treated with chromate treatment, silane coupling treatment, or the like. That is, one or more layers selected from the group consisting of a heat-resistant layer, an antirust layer, a chromate-treated layer, and a silane coupling-treated layer may be formed on the surface of the roughened layer, and an ultra-thin copper layer may be formed. One or more layers selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a silane coupling-treated layer are formed on the surface. In addition, the above-mentioned heat-resistant layer, rust-proof layer, chromate-treated layer, and silane-coupling-treated layer may each be formed of a plurality of layers, for example, two or more layers, three or more layers, or the like.

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 rust-proof layer may contain elements selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, The layer of one or more elements in the group of iron and tantalum may also be made of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, Metal layer or alloy layer composed of one or more elements in the group of platinum group elements, iron, and tantalum. In addition, the heat-resistant layer and/or rust-proof layer may also contain elements selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, and platinum group elements. Oxides, nitrides, and silicides of one or more elements in the group of , iron, and tantalum. Also, the heat-resistant layer and/or the rust-proof layer may be a layer containing a nickel-zinc alloy. Also, the heat-resistant layer and/or the rust-proof layer may be a nickel-zinc alloy layer. The above-mentioned nickel-zinc alloy layer may contain 50 wt% to 99 wt% of nickel and 50 wt% 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 5-1000 mg/m ² , preferably 10-500 mg/m ² , preferably 20-100 mg/m ² . In addition, the layer containing nickel-zinc alloy or the nickel-zinc alloy layer preferably has a ratio of nickel deposition amount to zinc deposition amount (=nickel deposition amount/zinc deposition amount) of 1.5-10. Also, the nickel deposition amount of the layer containing nickel-zinc alloy or the nickel-zinc alloy layer is preferably 0.5 mg/m ² to 500 mg/m ² , more preferably 1 mg/m ² to 50 mg/m ² . When the heat-resistant layer and/or the rust-proof layer is a layer containing a nickel-zinc alloy, when the inner wall portion of a through hole or via hole is brought into contact with a desmear solution, the interface between the copper foil and the resin substrate is not easy. Corroded by the desmear solution, the adhesion between the copper foil and the resin substrate is improved.

For example, the heat-resistant layer and/or the rust-proof layer can be sequentially laminated with a nickel or nickel alloy layer with an adhesion amount of 1 mg/m ² to 100 mg/m ² , preferably 5 mg/m ² to 50 mg/m ² , and the adhesion amount 1 mg/m ² ~ 80 mg/m ² , preferably 5 mg/m ² ~ 40 mg/m ² tin layer, the above-mentioned nickel alloy layer can be any of nickel-molybdenum, nickel-zinc, nickel-molybdenum-cobalt a composition. In addition, the heat-resistant layer and/or rust-proof layer preferably has a total adhesion amount of nickel or nickel alloy and tin of 2 mg/m ² to 150 mg/m ² , more preferably 10 mg/m ² to 70 mg/m ² . In addition, the heat-resistant layer and/or the antirust layer are preferably [Ni deposition amount in nickel or nickel alloy]/[Sn deposition amount]=0.25-10, more preferably 0.33-3. If the heat-resistant layer and/or the antirust layer are used, the copper foil with a carrier is processed into a printed wiring board, and the peel strength of the subsequent circuit, the chemical resistance degradation rate of the peel strength, and the like become favorable.

In addition, the silane coupling agent used for a silane coupling process can use a well-known silane coupling agent, For example, an amino-type silane coupling agent, an epoxy-type silane coupling agent, and a mercapto-type silane coupling agent can also be used. In addition, as the silane coupling agent, vinyltrimethoxysilane, vinylphenyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane can also be used. , 4-glycidylbutyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-3 - (4-(3-aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxysilane, imidazolylsilane, triazinesilane, γ-mercaptopropyltrimethoxysilane and the like.

The above-mentioned silane coupling treatment layer can be formed using a silane coupling agent such as epoxy-based silane, amino-based silane, methacryloxy-based silane, mercapto-based silane, or the like. In addition, such a silane coupling agent can also mix and use 2 or more types. Among them, those formed using an amino-based silane coupling agent or an epoxy-based silane coupling agent are preferable.

The so-called amino-based silane coupling agent here can be selected from N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-(N-styrylmethyl-2-amine (Ethylamino)propyltrimethoxysilane, 3-aminopropyltriethoxysilane, bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, aminopropyl Trimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, N-(3-propenyloxy-2-hydroxypropyl)-3-amine propyltriethoxysilane, 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-aminopropoxy)-3,3-dimethyl-1-propenyltrimethoxysilane, 3-aminopropyl Tris(methoxyethoxyethoxy)silane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, ω-aminoundecyltrimethoxysilane, 3-(2-N-Benzylaminoethylaminopropyl)trimethoxysilane, bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, (N,N-di Ethyl-3-aminopropyl)trimethoxysilane, (N,N-dimethyl-3-aminopropyl)trimethoxysilane, N-methylaminopropyltrimethoxysilane, N -Phenylaminopropyltrimethoxysilane, 3-(N-Styrylmethyl-2-aminoethylamino)propyltrimethoxysilane, γ-Aminopropyltriethoxysilane , N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-3-(4-(3-aminopropoxy)butoxy)propyl-3-amino The group consisting of propyltrimethoxysilane.

The silane coupling treatment layer is preferably set at 0.05 mg/m ² to 200 mg/m ² in terms of silicon atoms, preferably 0.15 mg/m ² to 20 mg/m ² , preferably 0.3 mg/m ² to 2.0 mg/m ² range. In the case of the said range, the adhesiveness of a base resin and a surface-treated copper foil can be improved more.

In addition, the surface of the ultra-thin copper layer, roughening treatment layer, heat-resistant layer, rust-proof layer, silane coupling treatment layer or chromate treatment layer can be treated with 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 JP-A-2013 - Surface treatment as described in No. 19056.

[Resin layer on extremely thin copper layer]

A resin layer may be provided on the ultra-thin copper layer of the copper foil with a carrier of the present invention (in the case of surface-treating the ultra-thin copper layer, the surface-treated layer formed on the ultra-thin copper layer by the surface treatment) . The above-mentioned resin layer may also be an insulating resin layer.

The above-mentioned resin layer may be an adhesive resin, that is, an adhesive agent, or may be an insulating resin layer in a semi-cured state (B-stage state) for adhesive. The semi-hardened state (B-stage state) includes a state in which the insulating resin layer can be stored in a stacked state without sticky feeling even if the surface is touched with a finger, and a hardening reaction occurs when further heat-treated.

Moreover, the said resin layer may contain a thermosetting resin, and may be a thermoplastic resin. Moreover, the said resin layer may contain a thermoplastic resin. The resin layer may contain known resins, resin hardeners, compounds, hardening accelerators, dielectrics, reaction catalysts, crosslinking agents, polymers, prepregs, framework materials, and the like. In addition, for the resin layer, for example, those described in the following documents (resin, resin curing agent, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, frame material, etc.) can be used. And/or forming method and forming device of the resin layer: 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 No., Japanese Patent No. 3184485, International Publication No. WO97/02728, Japanese Patent No. 3676375, Japanese Patent Application No. 2000-43188, Japanese Patent Application No. 3612594, Japanese Patent Application No. 2002-179772, and Japanese Patent Application No. 2002-359444 , JP 2003-304068, JP 3992225, JP 2003-249739, JP 4136509, JP 2004-82687, JP 4025177, JP 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, International Publication No. WO2004/005588, Japanese Patent No. No. 2006-257153, Japanese Patent Application No. 2007-326923, Japanese Patent Application No. 2008-111169, Japanese Patent No. 5024930, International Publication No. WO2006/028207, Japanese Patent No. 4828427, Japanese Patent Application No. 2009-67029, International Publication No. WO2006/134868, Japanese Patent No. 5046927, Japanese Patent Laid-Open No. 2009-173017, International Publication No. WO2007/105635, Japanese Patent No. 5180815, International Publication No. WO2008/114858, International Publication No. WO2009/008471, Japanese Patent Laid-Open 2011-14727, International Publication No. WO2009/001850, International Publication No. WO2009/145179, International Publication No. WO2011/068157, Japanese Patent Laid-Open No. 2013-19056.

Also, the type of the above-mentioned resin layer is not particularly limited, and as preferred ones, for example, resins containing one or more types selected from the group consisting of epoxy resins, polyimide resins, polyfunctional cyanate esters, etc. Compounds, maleimide compounds, polymaleimide compounds, maleimide-based resins, aromatic maleimide resins, polyvinyl acetal resins, urethane resins, polyethersulfone (also known as polyethersulphone, polyethersulfone), polyethersulfone (also known as polyethersulphone, polyethersulfone) resin, aromatic polyamide resin, aromatic polyamide resin polymer, rubbery resin, polyamine, aromatic polyamine, polyamide Imide resin, rubber-modified epoxy resin, phenoxy resin, carboxy-modified acrylonitrile-butadiene resin, polyphenylene ether, bismaleimide triazine resin, thermosetting polyphenylene ether resin, Cyanate ester resins, anhydrides of carboxylic acids, anhydrides of polycarboxylic acids, linear polymers with crosslinkable functional groups, polyphenylene ether resins, 2,2-bis(4-cyanate phenyl ) propane, phosphorus-containing phenolic compounds, manganese naphthenate, 2,2-bis(4-glycidylphenyl)propane, polyphenylene ether-cyanate resin, siloxane-modified polyamideimide Resin, cyanate resin, phosphazene resin, rubber-modified polyamideimide resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, phenoxy, polymer epoxy resin, aromatic Polyamide, fluororesin, bisphenol, block copolymerized polyimide resin and cyanate resin.

In addition, the above-mentioned epoxy resin has two or more epoxy groups in the molecule, and can be used without any problem as long as it can be used for electrical and electronic material applications. Moreover, it is preferable that the said epoxy resin is an epoxy resin obtained by epoxidizing using the compound which has 2 or more glycidyl groups in a molecule|numerator. In addition, one or two or more selected from the group consisting of the following components can be used in combination: bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD type epoxy resin, novolak type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, brominated (brominated) epoxy resin, phenolic novolak type epoxy resin, naphthalene type ring Oxygen resin, brominated bisphenol A type epoxy resin, o-cresol novolak type epoxy resin, rubber modified bisphenol A type epoxy resin, glycidylamine type epoxy resin, triglycidyl isocyanurate, Glycidylamine compounds such as N,N-diglycidylaniline, glycidyl ester compounds such as diglycidyl tetrahydrophthalate, phosphorus-containing epoxy resins, biphenyl type epoxy resins, biphenyl novolak type Epoxy resins, trihydroxyphenylmethane type epoxy resins, tetraphenylethane type epoxy resins, or hydrogenated or halogenated forms of the above epoxy resins can be used.

A known phosphorus-containing epoxy resin can be used as the above-mentioned phosphorus-containing epoxy resin. Also, the above-mentioned phosphorus-containing epoxy resin is preferably, for example, one having two or more epoxy groups in the molecule, derived from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9,10 -dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) derivatives of epoxy resins.

The epoxy resin, obtained in the form of a derivative from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, is made of 9,10-dihydro-9-oxa- After 10-phosphaphenanthrene-10-oxide reacts with naphthoquinone or hydroquinone to prepare the compound represented by the following chemical formula 1 (HCA-NQ) or chemical formula 2 (HCA-HQ), the part of its OH group React with epoxy resin to make phosphorus-containing epoxy resin.

[chemical formula 1]

[chemical formula 2]

It is preferable to mix and use one or two compounds having a structural formula represented by any one of Chemical Formula 3 to Chemical Formula 5 below as the above-mentioned E component, that is, the phosphorus-containing epoxy resin from which the above-mentioned compound is obtained. This is because the stability of resin quality in a semi-cured state is excellent, and the effect of flame retardancy is high.

[chemical formula 3]

[chemical formula 4]

[chemical formula 5]

In addition, known brominated epoxy resins can be used as the above-mentioned brominated epoxy resin. For example, the above-mentioned brominated epoxy resin is preferably mixed with one or two kinds of epoxy groups having two or more epoxy groups in the molecule and having the chemical formula 6 obtained in the form of derivatives from tetrabromobisphenol A. A brominated epoxy resin having a structural formula, and a brominated epoxy resin having a structural formula represented by Chemical Formula 7 shown below.

[chemical formula 6]

[chemical formula 7]

As the maleimide resin, aromatic maleimide resin, maleimide compound, or polymaleimide compound, known maleimide resins or aromatic maleimide resins can be used. An imide resin or a maleimide compound or a polymaleimide compound. For example, as maleimide-based resins, aromatic maleimide resins, maleimide compounds, or polymaleimide compounds, 4,4'-diphenylmethane bismaleimide Imide, polyphenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5 '-Diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenyl ether bismaleimide Maleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(4-maleimide imidephenoxy)benzene, polymers obtained by polymerizing the above-mentioned compound with the above-mentioned compound or other compounds, etc. In addition, the above-mentioned maleimide-based resin may be an aromatic maleimide resin having two or more maleimide groups in the molecule, or may be an aromatic maleimide resin having two or more maleimide groups in the molecule. Polymerized adducts of aromatic maleimide resins and polyamines or aromatic polyamines.

As said polyamine or aromatic polyamine, a well-known polyamine or aromatic polyamine can be used. For example, as polyamines or aromatic polyamines, it is possible to use: m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 2, 6-diaminopyridine, 4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 4,4'-diaminodiphenyl ether, 4,4 '-Diamino-3-methyldiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl sulfone, bis(4-aminophenyl)phenylamine, m-xylylenediamine, p-xylylenediamine, 1,3-bis[4-aminophenoxy]benzene, 3-methyl-4 ,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diamino Diphenylmethane, 2,2',5,5'-tetrachloro-4,4'-diaminodiphenylmethane, 2,2-bis(3-methyl-4-aminophenyl)propane , 2,2-bis(3-ethyl-4-aminophenyl)propane, 2,2-bis(2,3-dichloro-4-aminophenyl)propane, bis(2,3-di Methyl-4-aminophenyl)phenylethane, ethylenediamine and hexamethylenediamine, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, and the above compounds with Polymers obtained by polymerizing the above-mentioned compounds or other compounds, etc. In addition, one kind, two or more kinds of known polyamines and/or aromatic polyamines, or the above-mentioned polyamines or aromatic polyamines can be used.

As the above-mentioned phenoxy resin, known phenoxy resins can be used. Moreover, as said phenoxy resin, the thing synthesize|combined by reaction of bisphenol and divalent epoxy resin can be used. As the epoxy resin, known epoxy resins and/or the above-mentioned epoxy resins can be used.

As the above-mentioned bisphenol, known bisphenols can be used, and bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, 4,4'-dihydroxybiphenyl, HCA (9,10 - bisphenols obtained in the form of adducts of Dihydro-9-Oxa-10-Phosphaphenanthrene-10-Oxide) and quinones such as hydroquinone and naphthoquinone, etc.

As the above-mentioned linear polymer having a crosslinkable functional group, a known linear polymer having a crosslinkable functional group can be used. For example, the above-mentioned linear polymer having a crosslinkable functional group preferably has a functional group such as a hydroxyl group or a carboxyl group that contributes to the curing reaction of the epoxy resin. In addition, the linear polymer having a crosslinkable functional group is preferably soluble in an organic solvent having a boiling point of 50°C to 200°C. Specific examples of the linear polymers having functional groups referred to herein include polyvinyl acetal resins, phenoxy resins, polyethersulfone resins, polyamideimide resins, and the like.

The above-mentioned resin layer may contain a crosslinking agent. As the crosslinking agent, known crosslinking agents can be used. For example, a urethane resin can be used as a crosslinking agent.

As the aforementioned rubbery resin, known rubbery resins can be used. For example, the aforementioned rubbery resin is described as a concept including natural rubber and synthetic rubber. The latter synthetic rubber includes styrene-butadiene rubber, butadiene rubber, butyl rubber, ethylene-propylene rubber, propylene Nitrile butadiene rubber, acrylic rubber (acrylate copolymer), polybutadiene rubber, isoprene rubber, etc. Furthermore, when securing the heat resistance of the formed resin layer, it is also useful to select and use heat-resistant synthetic rubbers such as nitrile rubber, chloroprene rubber, silicone rubber, and urethane rubber. These rubbery resins preferably have various functional groups at both terminals in order to react with an aromatic polyamide resin or a polyamide-imide resin to produce a copolymer. In particular, it is useful to use CTBN (carboxy-terminated butadiene nitrile). Also, if the acrylonitrile-butadiene rubber is also a carboxyl-modified body, an epoxy resin and a cross-linked structure can be obtained, and the flexibility of the cured resin layer can be improved. As the carboxyl-modified body, carboxyl-terminated nitrile rubber (CTBN), carboxyl-terminated butadiene rubber (CTB), and carboxyl-modified nitrile rubber (C-NBR) can be used.

As said polyamide-imide resin, a well-known polyimide amide resin can be used. In addition, as the above-mentioned polyimide amide resin, it is possible to use, for example: trimellitic anhydride, diphenyl A resin obtained by heating ketonetetracarboxylic anhydride and bitolylene diisocyanate, or in a solvent such as N-methyl-2-pyrrolidone or/and N,N-dimethylacetamide It is obtained by heating trimellitic anhydride, diphenylmethane diisocyanate and carboxyl-terminated acrylonitrile-butadiene rubber.

As the rubber-modified polyamide-imide resin, known rubber-modified polyamide-imide resins can be used. The rubber-modified polyamide-imide resin is obtained by reacting a polyamide-imide resin with a rubbery resin. When polyamide-imide resin is reacted and used with rubbery resin, it is performed in order to improve the flexibility of polyamide-imide resin itself. That is, polyamide-imide resin and rubbery resin are made to react, and a part of the acid component (cyclohexanedicarboxylic acid etc.) of polyamide-imide resin is substituted with a rubber component. As the polyamide-imide resin, known polyamide-imide resins can be used. Also, as the rubbery resin, known rubbery resins or the aforementioned rubbery resins can be used. When polymerizing the rubber-modified polyamide-imide resin, the solvent for dissolving the polyamide-imide resin and the rubbery resin is preferably mixed with one or more kinds of dimethylformamide and dimethylacetamide. , N-methyl-2-pyrrolidone, dimethyl sulfoxide, nitromethane, nitroethane, tetrahydrofuran, cyclohexanone, methyl ethyl ketone, acetonitrile, γ-butyrolactone, etc.

As the above-mentioned phosphazene-based resin, known phosphazene-based resins can be used. The phosphazene-based resin is a resin containing a phosphazene having a double bond having phosphorus and nitrogen as constituent elements. Phosphazene-based resins can drastically improve flame retardancy due to the synergistic effect of nitrogen and phosphorus in the molecule. Also, unlike the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, it can stably exist in the resin to prevent migration.

As the above-mentioned fluororesin, known fluororesins can be used. In addition, as the fluororesin, for example, a compound selected from PTFE (polytetrafluoroethylene (tetrafluoride)), PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), FEP (tetrafluoroethylene-hexafluoropropylene) can be used. Copolymer (four, hexafluorinated)), ETFE (tetrafluoroethylene-ethylene copolymer), PVDF (polyvinylidene fluoride (difluorinated)), PCTFE (polychlorotrifluoroethylene (trifluorinated)), A fluororesin composed of a thermoplastic resin of at least one of polyarylsulfone, aromatic polysulfide, and aromatic polyether and a fluororesin, or the like.

In addition, the above-mentioned resin layer may contain a resin curing agent. As the resin curing agent, known resin curing agents can be used. For example, as the resin hardener, amines such as dicyandiamides, imidazoles, and aromatic amines, phenols such as bisphenol A and brominated bisphenol A, phenolic novolac resins, and cresol novolac resins can be used. Novolaks, acid anhydrides such as phthalic anhydride, biphenyl type phenolic resins, phenol aralkyl type phenolic resins, and the like. Moreover, the said resin layer may contain 1 type, or 2 or more types of said resin hardening agents. These hardeners are especially effective with epoxy resins.

Specific examples of the biphenyl-type phenolic resins are shown in Chemical Formula 8.

[chemical formula 8]

Moreover, the specific example of the said phenol aralkyl type phenolic resin is shown in Chemical formula 9.

[chemical formula 9]

Known imidazoles can be used, for example, 2-undecylimidazole, 2-heptadecyl imidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole , 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-benzene 4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc., which may be used alone or in combination.

Moreover, among these, it is preferable to use the imidazoles which have the structural formula represented by the following chemical formula 10. By using the imidazoles of the structural formula represented by the 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 can be excellent. The reason for this is that imidazoles act catalytically during curing of the epoxy resin, and act as a reaction initiator for causing self-polymerization of the epoxy resin in the initial stage of the curing reaction.

[chemical formula 10]

Known amines can be used as the above-mentioned amine-based resin curing agent. In addition, as the resin curing agent of the above-mentioned amines, for example, the above-mentioned polyamines or aromatic polyamines can be used, and a compound selected from aromatic polyamines, polyamides, and epoxy resins or polycarboxylic acids can also be used. One or more of the group of amine adducts obtained by polymerization or condensation. Also, as the above-mentioned amine-based resin hardener, it is preferable to use 4,4'-diaminobisphenylene sulfone, 3,3'-diaminobisphenylene sulfone, 4,4-diaminobisphenylene sulfone, Any one or more of benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, or bis[4-(4-aminophenoxy)phenyl]sulfone.

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

The above-mentioned resin layer may contain a reaction catalyst. As a reaction catalyst, a known reaction catalyst can be used. For example, finely pulverized silica, antimony trioxide and the like can be used as a reaction catalyst.

The anhydride of the above-mentioned polyvalent carboxylic acid is preferably a component functioning as a curing agent for an epoxy resin. In addition, the anhydrides of the polyvalent carboxylic acids are preferably phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydroxyphthalic anhydride, hexahydroxyphthalic anhydride, methylhexahydroxybenzenedicarboxylic anhydride, Formic anhydride, nadic acid, methyl nadic acid.

The aforementioned thermoplastic resin may be a thermoplastic resin having a functional group other than an alcoholic hydroxyl group that can be polymerized with an epoxy resin.

The polyvinyl acetaldehyde resin may have a hydroxyl group and a functional group other than a hydroxyl group that can be polymerized with an epoxy resin or a maleimide compound. In addition, the above-mentioned polyvinyl acetaldehyde resin may have 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. Here, the term "aromatic polyamide resin" refers to one synthesized by polycondensation of aromatic diamine and dicarboxylic acid. The aromatic diamine used at this time is 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, m-xylylenediamine, 3,3'-diaminodiphenyl Ether etc. In addition, as dicarboxylic acids, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, and the like are used.

As the above-mentioned rubbery resin capable of reacting with the above-mentioned aromatic polyamide resin, known rubbery resins or the above-mentioned rubbery resins can be used.

This aromatic polyamide resin polymer is used in order not to receive damage by an etchant due to underetching when etching a copper foil processed into a copper-clad laminate.

In addition, the above-mentioned resin layer may be formed sequentially from the copper foil side (that is, the side of the ultra-thin copper layer with carrier copper foil) with a cured resin layer (the so-called "cured resin layer" means a resin layer that has been cured), and a semi-cured resin layer. The resin layer of the resin layer. The cured resin layer may be composed of any resin component among polyimide resin, polyamideimide resin, and composite resins having a coefficient of thermal expansion of 0 ppm/°C to 25 ppm/°C.

In addition, a semi-cured resin layer having a coefficient of thermal expansion after curing of 0 ppm/°C to 50 ppm/°C may be provided on the cured resin layer. In addition, the thermal expansion coefficient of the entire resin layer obtained by curing the cured resin layer and the semi-cured resin layer may be 40 ppm/°C or less. The glass transition temperature of the cured resin layer may be 300° C. or higher. In addition, the semi-cured resin layer may be formed using a maleimide-based resin or an aromatic maleimide resin. The resin composition for forming the semi-hardened resin layer preferably includes a maleimide resin, an epoxy resin, and a linear polymer having a crosslinkable functional group. As the epoxy resin, known epoxy resins or epoxy resins described in this specification can be used. In addition, known maleimide resins, aromatic maleimide resins, and aromatic maleimide resins can be used as maleimide resins, aromatic maleimide resins, and linear polymers having crosslinkable functional groups. An imide resin, a linear polymer having a crosslinkable functional group, or the above-mentioned maleimide-based resin, an aromatic maleimide resin, or a linear polymer having a crosslinkable functional group.

Moreover, when providing the copper foil with a carrier which has a resin layer suitable for the manufacture of a three-dimensional molded printed wiring board, it is preferable that the said cured resin layer is a cured high molecular polymer layer which has flexibility. The above-mentioned polymer layer is preferably composed of a resin having a glass transition temperature of 150° C. or higher in order to withstand the solder mounting step. The above-mentioned polymer layer is preferably made of any of polyamide resin, polyethersulfone resin, aramid resin, phenoxy resin, polyimide resin, polyvinyl acetaldehyde resin, polyamideimide resin Composed of 1 or more mixed resins. Moreover, the thickness of the above-mentioned high molecular polymer layer is preferably 3 μm to 10 μm.

Moreover, it is preferable that the said high molecular polymer layer contains any 1 type, or 2 or more types of epoxy resins, maleimide resins, phenol resins, and urethane resins. In addition, the semi-cured resin layer is preferably composed of an epoxy resin composition having a thickness of 10 μm to 50 μm.

Moreover, it is preferable that the said epoxy resin composition contains each component of the following A component - E component.

Component A: an epoxy equivalent of 200 or less and consisting of one or two selected from the group consisting of bisphenol A type epoxy resins, bisphenol F type epoxy resins, and bisphenol AD type epoxy resins that are liquid at room temperature Epoxy resins composed of the above types.

B component: high heat resistance epoxy resin.

Component C: a phosphorous-containing flame-retardant resin that is a resin obtained by mixing any one of phosphorus-containing epoxy resins and phosphazene-based resins.

Component D: a rubber-modified polyamide-imide resin modified from a liquid rubber component having a property of being soluble in a solvent having a boiling point in the range of 50°C to 200°C.

E component: resin hardener.

Component B is a so-called "high heat-resistant epoxy resin" with a high glass transition point Tg. Here, the "high heat-resistant epoxy resin" is preferably a polyfunctional epoxy resin such as a novolac epoxy resin, a cresol novolac epoxy resin, a phenolic novolak epoxy resin, or a naphthalene epoxy resin. .

As the phosphorus-containing epoxy resin of C component, the above-mentioned phosphorus-containing epoxy resin can be used. Moreover, as a phosphazene-type resin of C component, the said phosphazene-type resin can be used.

As the rubber-modified polyamide-imide resin of the D component, the aforementioned rubber-modified polyamide-imide resin can be used. As the resin curing agent of the E component, the above-mentioned resin curing agents can be used.

A solvent is added to the resin composition shown above, and it is used as a resin varnish, and a thermosetting resin layer is formed as an adhesive layer of a printed wiring board. In this resin varnish, a solvent is added to the above resin composition, and the resin solid content is adjusted to a range of 30wt% to 70wt%. Flow) is a semi-hardened resin film in the range of 5% to 35%. As the solvent, known solvents or the above-mentioned solvents can be used.

The above-mentioned resin layer is a resin layer having a first thermosetting resin layer and a second thermosetting resin layer located on the surface of the first thermosetting resin layer in order from the copper foil side, and the first thermosetting resin layer It may also be formed of a resin component that is insoluble in the chemicals used in the desmearing process in the wiring board manufacturing method, and the second thermosetting resin layer may be used and soluble in the wiring board manufacturing method. The chemicals used in the desmearing treatment and washed to remove the resin formers. The first thermosetting resin layer may be formed using a resin component mixed with any one or two or more of polyimide resin, polyethersulfone, and polyphenylene ether. The second thermosetting resin layer may be formed using an epoxy resin component. The thickness t1 (μm) of the first thermosetting resin layer is preferably such that the roughened surface roughness of the copper foil with a carrier is Rz (μm) and the thickness of the second thermosetting resin layer is t2 (μm). ), t1 satisfies the thickness of Rz<t1<t2 condition.

The aforementioned resin layer may be a prepreg in which the frame material is impregnated with resin. The resin impregnated in the skeleton material is preferably a thermosetting resin. The said prepreg may be a well-known prepreg or the prepreg used for manufacture of a printed wiring board.

The above skeleton material may contain aramid fiber, glass fiber or wholly aromatic polyester fiber. The aforementioned framework material is preferably non-woven or woven fabric of aramid fiber, glass fiber or wholly aromatic polyester fiber. Moreover, it is preferable that the above-mentioned wholly aromatic polyester fiber is a wholly aromatic polyester fiber having a melting point of 300° C. or higher. The above-mentioned wholly aromatic polyester fiber having a melting point of 300°C or higher refers to a fiber made of a resin called a liquid crystal polymer, and the liquid crystal polymer is composed of 2-hydroxy-6-naphthoic acid and p-hydroxy The polymer of benzoic acid is the 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.

In addition, the fibers constituting the above-mentioned nonwoven fabric and woven fabric are preferably treated with a silane coupling agent in order to improve the wettability with the resin on the surface. As the silane coupling agent at this time, well-known silane coupling agents such as amino-based and epoxy-based silane coupling agents or the above-mentioned silane coupling agents can be used depending on the purpose of use.

In addition, the above-mentioned prepreg may be obtained by impregnating a thermosetting resin into a skeleton material composed of non-woven fabric of aramid fiber or glass fiber with a nominal thickness of 70 μm or less, or glass cloth with a nominal thickness of 30 μm or less. finished prepreg.

(When the resin layer contains a dielectric (dielectric filler))

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

When a dielectric (dielectric filler) is contained in any of the above-mentioned resin layers or resin compositions, it can be used to form a capacitor layer to increase the capacitance of a capacitor circuit. The dielectric (dielectric filler) is made of BaTiO ₃ , SrTiO ₃ , Pb(Zr-Ti)O ₃ (commonly called PZT), PbLaTiO ₃ -PbLaZrO (commonly called PLZT), SrBi ₂ Ta ₂ O ₉ (commonly called SBT) Dielectric powder such as composite oxides having a perovskite structure.

The dielectric (dielectric filler) may be powdery. When the dielectric (dielectric filler) is powdery, the powder properties of the dielectric (dielectric filler) must first have a particle size of 0.01 μm to 3.0 μm, preferably 0.02 μm to 2.0 μm range. The so-called particle size here refers to the indirect measurement such as estimating the average particle size from the measured value of the laser diffraction scattering particle size distribution measurement method or the BET method because the powder particles form a certain secondary aggregation state. The average particle diameter obtained by directly observing the dielectric (dielectric filler) with a scanning electron microscope (SEM) and analyzing the SEM image cannot be used due to poor precision. In the specification of the present application, the particle diameter at this time is represented as DIA. In addition, the image analysis of the powder of the dielectric body (dielectric body filler) observed using the scanning electron microscope (SEM) in this application specification used the IP-1000PC manufactured by Asahi Engineering Co., Ltd., and the roundness The threshold value is 10, the degree of overlap is 20, circular particle analysis is performed, and the average particle diameter DIA is calculated|required.

Through the above embodiments, it is possible to provide a copper foil with a carrier as follows, which can improve the adhesion between the inner layer circuit surface of the inner layer core material and the resin layer containing a dielectric, and has The dielectric resin layer of the dielectric loss tangent capacitor circuit layer.

The resin and/or resin composition and/or compound contained in the above-mentioned resin layer are dissolved in, for example, methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, N-formaldehyde pyrrolidone, toluene, methanol, ethanol, propylene glycol monomethyl ether, dimethylformamide, dimethylacetamide, cyclohexanone, ethyl cellosolve, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide and other solvents to make a resin solution (resin varnish), and apply it on the above-mentioned ultra-thin copper layer by, for example, roll coating , or the above-mentioned heat-resistant layer, rust-proof layer, or the above-mentioned chromate treatment layer, or the above-mentioned silane coupling agent layer, and then heat and dry to remove the solvent as necessary to become a B-stage state. For drying, for example, a hot air drying oven may be used, and the drying temperature may be 100 to 250°C, preferably 130 to 200°C. Using a solvent to dissolve the composition of the above resin layer can be made into a resin with a resin solid content of 3wt%-70wt%, preferably 3wt%-60wt%, preferably 10wt%-40wt%, more preferably 25wt%-40wt% liquid. Furthermore, from an environmental viewpoint, it is most preferable to dissolve using a mixed solvent of methyl ethyl ketone and cyclopentanone at the present stage. In addition, as a solvent, it is preferable to use the solvent whose boiling point is the range of 50 degreeC - 200 degreeC.

Moreover, it is preferable that the said resin layer is a semi-hardened resin film in which the resin overflow amount measured based on MIL-P-13949G in MIL standard is the range of 5 % - 35 %.

In this application specification, the so-called resin overflow refers to the MIL-P-13949G in the MIL standard, taking 4 pieces of 10 cm square samples from the resin-attached copper foil with a resin thickness of 55 μm. In the state where the sheet samples are overlapped (laminated body), the lamination was carried out under the conditions of a pressing temperature of 171°C, a pressing pressure of 14kgf/cm ² , and a pressing time of 10 minutes. According to the results obtained by measuring the resin outflow weight at this time, Value calculated based on Mathematical Expression 1.

[mathematical formula 1]

Copper foil with a carrier (copper foil with a resin attached to a resin) having the above-mentioned resin layer is used in such a manner that the resin layer is laminated on a substrate, the whole body is thermocompression-bonded, the resin layer is thermally cured, and then peeled off. The ultra-thin copper layer is exposed on the carrier (of course, the surface on the intermediate layer side of the ultra-thin copper layer is exposed), and a specific wiring pattern is formed thereon.

When the copper foil with a carrier with this resin is used, the number of sheets of the prepreg used at the time of manufacture of a multilayer printed wiring board can be reduced. Furthermore, it is also possible to manufacture a copper-clad laminate by setting the thickness of the resin layer to a thickness that ensures interlayer insulation, or without using a prepreg material at all. In addition, at this time, the smoothness of the surface can be further improved by applying an insulating resin primer to the surface of the substrate.

In addition, when the prepreg material is not used, the material cost of the prepreg material can be saved, and the lamination process is simplified, so it is economically advantageous. In addition, there are advantages in that only the prepreg material is manufactured. The thickness of the multilayer printed wiring board with a thickness of about 100 μm is reduced, and an extremely thin multilayer printed wiring board with a thickness of 100 μm or less can be produced.

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, there may be a case where the resin-coated copper foil with a carrier is laminated on a base material having an inner layer material without lowering the adhesive force and inserting a prepreg material. When it is above, it is difficult to ensure the interlayer insulation between the circuit and the inner layer material. On the other hand, if the thickness of the resin layer is thicker than 120 μm, it may be difficult to form the resin layer with the target thickness in one coating step, and unnecessary material costs and the number of steps are required, so it becomes economically disadvantageous. .

Furthermore, when using the copper foil with a carrier which has a resin layer for manufacture of an extremely thin multilayer printed wiring board, the thickness of the said resin layer shall be 0.1 micrometer - 5 micrometers, More preferably, it shall be 0.5 micrometer - 5 micrometers, More preferably, When it is preferably 1 μm to 5 μm, since the thickness of the multilayer printed wiring board can be reduced, it is preferable.

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

Also, the total resin layer thickness of the cured resin layer and the semi-cured resin layer is preferably 0.1 μm to 120 μm, preferably 5 μm to 120 μm, preferably 10 μm to 120 μm, more preferably 10 μm to 60 μm. In addition, the thickness of the cured resin layer is preferably 2 μm to 30 μm, preferably 3 μm to 30 μm, and more preferably 5 to 20 μm. Moreover, the thickness of the semi-cured resin layer is preferably 3 μm to 55 μm, preferably 7 μm to 55 μm, and more preferably 15 to 115 μm. The reason is that if the total thickness of the resin layer exceeds 120 μm, it may be difficult to manufacture an extremely thin multilayer printed wiring board, and if it is less than 5 μm, there may be cases where it is easy to form an extremely thin multilayer printed wiring board, However, the resin layer, which is the insulating layer between the circuits of the inner layer, becomes too thin, and the insulation between the circuits of the inner layer tends to be unstable. Moreover, when the thickness of a cured resin layer is less than 2 micrometers, it may be necessary to consider the surface roughness of the roughened surface of copper foil. Conversely, when the thickness of the cured resin layer exceeds 20 μm, the effect of the cured resin layer may not be particularly improved, and the total thickness of the insulating layer may become thick.

Furthermore, when the thickness of the resin layer is set to 0.1 μm to 5 μm, in order to improve the adhesiveness between the resin layer and the copper foil with a carrier, it is preferable to provide a heat-resistant layer and/or After the antirust layer and/or the chromate treatment layer and/or the silane coupling treatment layer, a resin layer is formed on the heat resistance layer or the antirust layer or the chromate treatment layer or the silane coupling treatment layer.

In addition, the thickness of the said resin layer means the average value of the thickness measured by observing a cross-section at arbitrary 10 points.

Furthermore, as another product form of the resin-coated copper foil with a carrier, a resin layer may be coated on the above-mentioned ultra-thin copper layer, or the above-mentioned heat-resistant layer, rust-proof layer, or the above-mentioned chromate treatment layer, or After the above-mentioned silane coupling treatment layer is in a semi-hardened state, the carrier is then peeled off, and the resin-coated copper foil without the carrier is produced.

＜6. Printed Wiring Board＞

Below, some examples of the manufacturing process of the printed wiring board using the surface-treated copper foil of this invention or the copper foil with a carrier are shown. Moreover, a printed wiring board is completed by mounting electronic components on a printed wiring board.

Through the above-mentioned manufacturing method, the copper foil with a carrier provided with a copper foil carrier, a release layer, and an ultra-thin copper layer in this order is manufactured. The use method of copper foil with carrier itself is well known in the industry. For example, the surface of the ultra-thin copper layer can be pasted on the paper substrate phenolic resin, paper substrate epoxy resin, synthetic fiber cloth substrate epoxy resin, glass cloth -Paper composite substrate epoxy resin, glass cloth-glass non-woven composite substrate epoxy resin and glass cloth substrate epoxy resin, polyester film, polyimide film and other insulating substrates are thermally bonded and peeled off Carrier, so that after forming a copper-clad laminate, the ultra-thin copper layer that is attached to the insulating substrate is etched into a target conductor pattern, and finally a printed wiring board is manufactured.

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

Furthermore, a printed wiring board is completed by mounting electronic components on a printed wiring board. By using the copper foil with a carrier of the present invention, for example, a printed circuit board including an insulating substrate and a copper circuit provided on the insulating substrate, wherein the circuit width of the copper circuit is less than 20 μm, and adjacent The gap width between copper circuits is less than 20 μm. Furthermore, the circuit width of the said copper circuit is 17 micrometers or less, and the printed wiring board in which the gap width between adjacent copper circuits is 17 micrometers or less can also be manufactured. Furthermore, the circuit width of the said copper circuit is 17 micrometers or less, and the printed wiring board which the gap width between adjacent copper circuits is 17 micrometers or less can also be manufactured. Furthermore, the circuit width of the said copper circuit is 15 micrometers or less, and the printed wiring board in which the gap width between adjacent copper circuits is 15 micrometers or less can also be manufactured. Furthermore, it is also possible to manufacture the above-mentioned copper circuit with a circuit width of 5 to 10 μm, preferably 5 to 9 μm, more preferably 5 to 8 μm, and a gap width between adjacent copper circuits of 5 to 10 μm, preferably 5 to 9 μm, more preferably It is a printed circuit board of 5-8 μm. Also, the distance between lines and 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. In addition, the lower limit of the line and space does not need to be specifically defined, For example, it is 6 micrometers or more, or 8 micrometers or more, or 10 micrometers or more.

Furthermore, the pitch between the lines and spaces refers to the distance from the center of the width of the copper circuit to the center of the width of the adjacent copper circuit.

Below, some examples of the manufacturing process of the printed wiring board using the copper foil with a carrier of this invention are shown.

One embodiment of the method of manufacturing a printed wiring board of the present invention includes the steps of: preparing the copper foil with a carrier and the insulating substrate of the present invention; laminating the copper foil with a carrier and the insulating substrate; After laminating the above-mentioned copper foil with carrier and the insulating substrate so that the side of the thin copper layer faces the insulating substrate, the step of peeling the carrier of the above-mentioned copper foil with carrier is performed to form a copper-clad laminate. The step of forming a circuit by any one of semi additive method, modified semi additive method, partly additive method and subtractive method. The insulating substrate can also be used as the entrance of the inner layer circuit.

In the present invention, the so-called semi-additive method refers to a method in which thin electroless plating is performed on an insulating substrate or a copper foil seed layer to form a pattern, and then electroplating and etching are used to form a conductive pattern.

Therefore, one embodiment of the manufacturing method of the printed wiring board of the present invention using the semi-additive method includes the following steps:

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

The step of laminating the above-mentioned copper foil with a carrier and an insulating substrate;

After laminating the above-mentioned copper foil with a carrier and the insulating substrate, the step of peeling off the carrier of the above-mentioned copper foil with a carrier;

A step of completely removing the extremely thin copper layer exposed by peeling off the above-mentioned carrier by using etching or plasma with a corrosive solution such as acid;

A step of providing through holes or/and blind vias on the resin layer and the insulating substrate exposed by removing the above-mentioned ultra-thin copper layer by etching;

A step of desmearing the area containing the above-mentioned through holes or/and blind holes;

a step of providing an electroless plating layer on the above resin and the area containing the above through holes or/and blind holes;

The step of disposing anti-plating agent on above-mentioned electroless plating layer;

Exposing the above-mentioned plating resist, thereafter, removing the plating resist in the region where the circuit is formed;

A step of providing an electrolytic plating layer on the region where the above-mentioned circuit has been formed where the above-mentioned plating resist has been removed;

the step of removing said plating resist; and

A step of removing the electroless plating layer in areas other than the areas where the above-mentioned circuits are formed by flash etching or the like.

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

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

The step of laminating the above-mentioned copper foil with a carrier and an insulating substrate;

After laminating the above-mentioned copper foil with a carrier and the insulating substrate, the step of peeling off the carrier of the above-mentioned copper foil with a carrier;

A step of completely removing the extremely thin copper layer exposed by peeling off the above-mentioned carrier by using etching or plasma with a corrosive solution such as acid;

A step of providing an electroless plating layer on the surface of the resin layer exposed by removing the above-mentioned ultra-thin copper layer by etching;

The step of disposing anti-plating agent on above-mentioned electroless plating layer;

Exposing the above-mentioned plating resist, thereafter, removing the plating resist in the region where the circuit is formed;

A step of providing an electrolytic plating layer on the region where the above-mentioned circuit has been formed where the above-mentioned plating resist has been removed;

the step of removing said plating resist; and

A step of removing the electroless plating layer in areas other than the areas where the above-mentioned circuits are formed by flash etching or the like.

In the present invention, the so-called improved semi-additive method refers to laminating metal foil on the insulating layer, protecting the non-circuit forming part with a plating resist, thickening the copper layer of the circuit forming part by electroplating, and removing the resist. , A method of forming a circuit on an insulating layer by (rapid) etching to remove the metal foil other than the above-mentioned circuit formation part.

Therefore, one embodiment of the manufacturing method of the printed wiring board of the present invention using the improved semi-additive method comprises the following steps:

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

The step of laminating the above-mentioned copper foil with a carrier and an insulating substrate;

After laminating the above-mentioned copper foil with a carrier and the insulating substrate, the step of peeling off the carrier of the above-mentioned copper foil with a carrier;

A step of providing through holes or/and blind holes on the exposed ultra-thin copper layer and the insulating substrate after peeling off the above-mentioned carrier;

A step of desmearing the area containing the above-mentioned through holes or/and blind holes;

A step of providing an electroless plating layer in the area including the above-mentioned through holes or/and blind holes;

A step of disposing an anti-plating agent on the surface of the extremely thin copper layer exposed by peeling off the above-mentioned carrier;

After the above-mentioned plating resist is provided, the step of forming a circuit by electroplating;

the step of removing said plating resist; and

The step of using flash etching to remove the very thin copper layer exposed by the removal of the above-mentioned plating resist.

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

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

The step of laminating the above-mentioned copper foil with a carrier and an insulating substrate;

After laminating the above-mentioned copper foil with a carrier and the insulating substrate, the step of peeling off the carrier of the above-mentioned copper foil with a carrier;

A step of providing a plating resist on the extremely thin copper layer exposed by peeling off the above-mentioned carrier;

Exposing the above-mentioned plating resist, thereafter, removing the plating resist in the region where the circuit is formed;

A step of providing an electrolytic plating layer on the region where the above-mentioned circuit has been formed where the above-mentioned plating resist has been removed;

the step of removing said plating resist; and

A step of removing the ultra-thin copper layer in areas other than the areas where the above-mentioned circuits are formed by flash etching or the like.

In the present invention, the so-called partial addition method refers to providing catalytic nuclei on a substrate formed by providing a conductor layer, or a substrate formed by passing through a through hole or a hole for a guide hole if necessary, and etching to form a conductor circuit. It is necessary to provide a solder resist or a plating resist, and then thicken a through hole or a guide hole by electroless plating on the above-mentioned conductor circuit, thereby manufacturing a printed wiring board.

Therefore, one embodiment of the manufacturing method of the printed wiring board of the present invention using the partial additive method includes the following steps:

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

The step of laminating the above-mentioned copper foil with a carrier and an insulating substrate;

After laminating the above-mentioned copper foil with a carrier and the insulating substrate, the step of peeling off the carrier of the above-mentioned copper foil with a carrier;

A step of providing through holes or/and blind holes on the exposed ultra-thin copper layer and the insulating substrate after peeling off the above-mentioned carrier;

A step of desmearing the area containing the above-mentioned through holes or/and blind holes;

The step of imparting a catalytic nucleus to the region containing the above-mentioned through holes or/and blind holes;

The step of providing an anti-etching agent on the surface of the ultra-thin copper layer exposed by peeling off the above-mentioned carrier;

The step of exposing the above-mentioned resist to form a circuit pattern;

The step of removing the above-mentioned extremely thin copper layer and the above-mentioned catalytic nucleus by using etching or plasma with a corrosive solution such as acid to form a circuit;

The step of removing the above-mentioned resist;

A step of providing a solder resist or a plating resist on the surface of the insulating substrate exposed by removing the ultra-thin copper layer and the catalytic nucleus by means of etching or plasma using a corrosive solution such as acid; and

A step of providing an electroless plating layer in an area where the above-mentioned solder resist or plating resist is not provided.

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

Therefore, one embodiment of the manufacturing method of the printed wiring board of the present invention using the subtractive method includes the following steps:

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

The step of laminating the above-mentioned copper foil with a carrier and an insulating substrate;

After laminating the above-mentioned copper foil with a carrier and the insulating substrate, the step of peeling off the carrier of the above-mentioned copper foil with a carrier;

A step of providing through holes or/and blind holes on the exposed ultra-thin copper layer and the insulating substrate after peeling off the above-mentioned carrier;

A step of desmearing the area containing the above-mentioned through holes or/and blind holes;

A step of providing an electroless plating layer in the area including the above-mentioned through holes or/and blind holes;

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

The step of providing an anti-etching agent on the surface of the above-mentioned electrolytic plating layer or/and the above-mentioned ultra-thin copper layer;

The step of exposing the above-mentioned resist to form a circuit pattern;

A step of forming a circuit by removing the above-mentioned ultra-thin copper layer, the above-mentioned electroless plating layer, and the above-mentioned electrolytic plating layer by etching or plasma using a corrosive solution such as acid; and

The step of removing the above-mentioned resist.

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

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

The step of laminating the above-mentioned copper foil with a carrier and an insulating substrate;

After laminating the above-mentioned copper foil with a carrier and the insulating substrate, the step of peeling off the carrier of the above-mentioned copper foil with a carrier;

A step of providing through holes or/and blind holes on the exposed ultra-thin copper layer and the insulating substrate after peeling off the above-mentioned carrier;

A step of desmearing the area containing the above-mentioned through holes or/and blind holes;

A step of providing an electroless plating layer in the area including the above-mentioned through holes or/and blind holes;

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

A step of providing an electrolytic plating layer on the surface of the above-mentioned electroless plating layer where no mask is formed;

The step of providing an anti-etching agent on the surface of the above-mentioned electrolytic plating layer or/and the above-mentioned ultra-thin copper layer;

The step of exposing the above-mentioned resist to form a circuit pattern;

A step of forming a circuit by removing the above-mentioned ultra-thin copper layer and the above-mentioned electroless plating layer by etching or plasma using a corrosive solution such as acid; and

The step of removing the above-mentioned resist.

The step of providing through holes and/or blind holes and the subsequent step of removing smear may also be omitted.

Here, the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention is demonstrated in detail using drawing. In addition, here, a copper foil with a carrier having an ultra-thin copper layer on which a roughening treatment layer is formed is described as an example, but it is not limited thereto. Carrier copper foil can also perform the manufacturing method of the following printed wiring board in the same manner.

First, as shown in A in FIG. 3 , a copper foil with a carrier (first layer) having an ultra-thin copper layer with a roughened layer formed on the surface is prepared.

Next, as shown in B in FIG. 3 , a resist is applied on the roughened layer of the ultra-thin copper layer, exposed and developed, and the resist is etched into a specific shape.

Next, as shown in C in FIG. 3 , after the circuit plating is formed, the resist is removed to form circuit plating of a specific shape.

Next, as shown in D in FIG. 4, an embedding resin is provided on the ultra-thin copper layer to form a laminated resin layer in such a way as to cover the circuit plating (in the manner of burying the circuit plating), and then, from the ultra-thin copper layer side, Then another copper foil with carrier (2nd layer).

Next, as shown in E in FIG. 4 , the carrier is peeled off from the second-layer copper foil with a carrier.

Then, as shown in F in FIG. 4 , laser drilling is performed at a specific position of the resin layer to expose the circuit plating to form a blind hole.

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

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

Next, as shown by I in FIG. 5 , the carrier is peeled off from the first-layer copper foil with carrier.

Next, as shown in J in FIG. 6 , the ultra-thin copper layers on both surfaces are removed by flash etching to expose the surface of the circuit plating in the resin layer.

Next, as shown by K in FIG. 6 , bumps are formed on the circuit plating in the resin layer, and copper pillars are formed on the solder. Thus, the printed wiring board which used the copper foil with a carrier of this invention was produced.

The copper foil with a carrier of this invention can be used for said another copper foil with a carrier (2nd layer), and the existing copper foil with a carrier can also be used, and also a normal copper foil can also be used. Also, one or more layers of circuits can be further formed on the circuit of the second layer represented by H in Fig. 5, and the semi-additive method, subtractive method, partial additive method or improved semi-additive method can be used. Either method forms the circuits.

Moreover, the copper foil with a carrier used for the said 1st layer may have a board|substrate on the carrier side surface of this copper foil with a carrier. By having the substrate or the resin layer, the copper foil with a carrier used for the first layer is supported, and wrinkles are less likely to be generated, so there is an advantage of improving productivity. In addition, as long as the said board|substrate has the effect of supporting the copper foil with a carrier used for the said 1st layer, all board|substrates can be used. For example, the carrier, prepreg, resin layer described in the specification of this application or known carrier, prepreg, resin layer, metal plate, metal foil, inorganic compound plate, inorganic compound foil, organic compound plate can be used , a foil of an organic compound as the above-mentioned substrate.

The timing of forming the substrate on the side surface of the carrier is not particularly limited, but must be formed before the carrier is peeled off. In particular, it is preferably formed before the step of forming a resin layer on the surface of the copper foil with a carrier on the side of the ultra-thin copper layer, more preferably before the step of forming a circuit on the surface of the copper foil with a carrier on the side of the ultra-thin copper layer. .

It is preferable that the copper foil with a carrier of this invention controls the color difference of the ultra-thin copper layer surface so that the following (1) may be satisfied. In the present invention, the "color difference on the surface of the ultra-thin copper layer" means the color difference on the surface of the ultra-thin copper layer, or the color difference on the surface of the surface treatment layer when various surface treatments such as roughening treatment are performed. That is, the copper foil with a carrier of the present invention is preferably such that the surface of the ultra-thin copper layer, the roughened layer, the heat-resistant layer, the rust-proof layer, the chromate-treated layer, or the silane coupling layer is controlled so that the following (1) is satisfied. chromatic aberration.

(1) The color difference ΔE*ab of the surface of the ultra-thin copper layer or roughened layer or heat-resistant layer or rust-proof layer or chromate-treated layer or silane coupling-treated layer based on JISZ 8730 is 45 or more.

Here, the color differences ΔL, Δa, and Δb are comprehensive indicators that are measured by a color difference meter, using black/white/red/green/yellow/blue, and expressed using the L*a*b color system based on JIS Z8730, and Expressed as ΔL: white and black, Δa: red and green, Δb: yellow and blue. In addition, ΔE*ab is represented by the following formula using these color differences.

[mathematical formula 2]

The above-mentioned color difference can be adjusted by increasing the current density when forming the ultra-thin copper layer, reducing the copper concentration in the plating solution, and increasing the linear flow rate of the plating solution.

Moreover, the said chromatic aberration can also be adjusted by roughening the surface of an ultra-thin copper layer, and providing a roughening process layer. When the roughening treatment layer is provided, it is possible to further increase the current density (for example, 40 to 100 Å) by using an electrolytic solution containing one or more elements selected from the group consisting of copper, nickel, cobalt, tungsten, and molybdenum. 60A/dm ² ), shorten the processing time (for example, 0.1 to 1.3 seconds) and adjust. When the roughening treatment layer is not provided on the surface of the ultra-thin copper layer, it can be achieved by using a plating bath in which the concentration of Ni is more than twice that of other elements, and the ultra-thin copper layer or heat-resistant layer Or the surface of the antirust layer or chromate treatment layer or silane coupling treatment layer, so that Ni alloy plating (such as Ni-W alloy plating, Ni-Co-P alloy plating, Ni-Zn alloy plating) is low The treatment was performed at a conventional current density (0.1-1.3 A/dm ² ) and with a relatively long treatment time (20 seconds to 40 seconds).

If the color difference ΔE*ab based on JIS Z8730 on the surface of the ultra-thin copper layer is 45 or more, for example, when a circuit is formed on the surface of the ultra-thin copper layer with a carrier copper foil, the contrast between the ultra-thin copper layer and the circuit becomes clear, and the result is visually Reliability becomes good, and the positional alignment of circuits can be performed with high precision. The color difference ΔE*ab based on JIS Z8730 of the surface of the ultra-thin copper layer is preferably 50 or more, more preferably 55 or more, and still more preferably 60 or more.

In the case of controlling the color difference of the surface of an ultra-thin copper layer or a roughened layer or a heat-resistant layer or an anti-rust layer or a chromate-treated layer or a silane coupling layer as described above, the contrast with circuit plating becomes clear , visibility becomes good. Therefore, circuit plating can be accurately formed at a specific position in the manufacturing process shown by C in FIG. 3, for example, in the above-mentioned printed wiring board. Moreover, according to the above-mentioned method of manufacturing a printed wiring board, since the circuit plating is embedded in the resin layer, for example, when the ultra-thin copper layer is removed by flash etching as shown by J in FIG. The protective circuit is plated and its shape is maintained, making it easy to form a fine circuit. Moreover, since the circuit plating is protected by the resin layer, the migration resistance is improved, and the conduction of the wiring of the circuit can be favorably suppressed. Therefore, it is easy to form a fine circuit. In addition, when the ultra-thin copper layer is removed by flash etching as shown by J in FIG. 6 and K in FIG. 6, the exposed surface of the circuit plating becomes a shape recessed from the resin layer, so it is easy to form a copper layer on the circuit plating respectively. Bumps, and copper pillars are formed on them, and the manufacturing efficiency is improved.

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

[Example]

Hereinafter, the present invention will be described in further detail through the examples of the present invention, but the present invention is not limited by these examples.

1. Manufacture of copper foil with carrier

<Example 1>

As a copper foil carrier, a 35-micrometer-thick long electrolytic copper foil (JTC manufactured by JX Nippon Mining & Metals Co., Ltd.) was prepared. Under the following conditions, the glossy surface (Rz: 1.2 to 1.4 μm) of the copper foil was electroplated using a roll-to-roll continuous plating line (using the bending method shown in Figure 2), thereby A Ni layer with an adhesion amount of 4000 μg/dm ² was formed.

·Ni layer

Nickel sulfate: 250～300g/L

Nickel chloride: 35～45g/L

Nickel acetate: 10～20g/L

Trisodium citrate: 15～30g/L

Gloss agent: saccharin, butynediol, etc.

Sodium lauryl sulfate: 30~100ppm

pH value: 4~6

Bath temperature: 50～70℃

Current density: 3～15A/ ^dm2

After washing with water and pickling, electrolytic chromic acid is then carried out on the Cr layer with a deposition amount of 11 μg/ ^dm2 on a roll-to-roll continuous plating line (using the bending method shown in Figure 2) under the following conditions salt treatment to make it adhere to the Ni layer.

·Electrolytic chromate treatment

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

pH value: 3~4

Liquid temperature: 50～60℃

Current density: 0.1～2.6A/ ^dm2

Coulomb quantity: 0.5～30As/dm ²

Next, an ultra-thin copper layer with a thickness of 3 μm is formed on the Cr layer by electroplating under the following conditions on a roll-to-roll continuous plating line (using the rotary drum method shown in Figure 1), thereby manufacturing With carrier copper foil. In addition, this Example also produced the copper foil with a carrier which made the thickness of an ultra-thin copper layer 1, 2, 5, and 10 micrometers, and performed the same evaluation about the Example whose thickness of an ultra-thin copper layer was 3 micrometers. The results were the same regardless of the thickness.

·Extremely thin copper layer

Copper concentration: 30～120g/L

H ₂ SO ₄ concentration: 20～120g/L

Electrolyte temperature: 20～80℃

Current density: 10～100A/ ^dm2

Then, the following roughening treatment 1, roughening treatment 2, antirust treatment, chromate treatment and silane coupling treatment are sequentially performed on the surface of the ultra-thin copper layer. Roughening treatment 1 and roughening treatment 2 adopt the foil conveying method using a drum shown in Figure 1 (the distance between electrodes is 50mm), and the antirust treatment, chromate treatment and silane coupling treatment adopt the bending method shown in Figure 2 Way.

·Coarsening treatment 1

(liquid composition 1)

Cu: 10～30g/L

_H2SO4 : 10～150g _/ L

W: 0~50mg/L

Sodium lauryl sulfate: 0～50mg/L

As: 0~200mg/L

(plating condition 1)

Temperature: 30～70℃

Current density: 25～110A/ ^dm2

Coarsening coulomb volume: 50～500As/dm ²

Plating time: 0.5 to 20 seconds

·Coarsening 2

(liquid composition 2)

Cu: 20～80g/L

_H2SO4 : 50 _～ 200g/L

(plating condition 2)

Temperature: 30～70℃

Current density: 5～50A/ ^dm2

Coarsening coulomb volume: 50～300As/dm ²

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

As ₂ O ₃ : 0.01～1g/L

(liquid temperature)

40～90℃

(current condition)

Current density: 1～50A/ ^dm2

Plating time: 1 to 20 seconds

·Chromate treatment

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

NaOH or KOH: 10～50g/L

ZnOH or ZnSO ₄ ·7H ₂ O: 0.05～10g/L

pH value: 7~13

Bath temperature: 20～80℃

Current density: 0.05～5A/ ^dm2

Time: 5-30 seconds

·Silane coupling treatment

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

After the above-mentioned surface treatment, a resin layer of "A" described below was formed on the ultra-thin copper layer side.

<Example 2>

After forming an ultra-thin copper layer on the copper foil carrier under the same conditions as in Example 1, the following roughening treatment 1, roughening treatment 2, antirust treatment, chromate treatment, and silane coupling treatment were sequentially performed. Roughening treatment 1 and roughening treatment 2 adopt the foil conveying method using a drum shown in Figure 1 (the distance between electrodes is 50mm), and the antirust treatment, chromate treatment and silane coupling treatment adopt the bending method shown in Figure 2 Way. In addition, the thickness of the ultra-thin copper foil was set to 3 μm.

·Coarsening treatment 1

Liquid composition: copper 10-20g/L, sulfuric acid 50-100g/L

Liquid temperature: 25～50℃

Current density: 1～58A/ ^dm2

Coulomb quantity: 4～81As/dm ²

·Coarsening 2

Liquid composition: copper 10~20g/L, nickel 5~15g/L, cobalt 5~15g/L

pH value: 2~3

Liquid temperature: 30～50℃

Current density: 24～50A/ ^dm2

Coulomb quantity: 34～48As/dm ²

·Anti-rust treatment

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

pH value: 2~3

Liquid temperature: 40～60℃

Current density: 5～20A/ ^dm2

Coulomb volume: 10～20As/dm ²

·Chromate treatment

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

pH value: 3~4

Liquid temperature: 50～60℃

Current density: 0～2A/dm ² (in order to carry out dipping and chromate treatment, it can also be carried out without electrolysis)

Coulomb capacity: 0～2As/dm ² (for dipping and chromate treatment, it can also be carried out without electrolysis)

·Silane coupling treatment

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

After the above-mentioned surface treatment, a resin layer of "B" described below was formed on the ultra-thin copper layer side.

<Example 3>

As a copper foil carrier, prepare a long strip of electrolytic copper foil (manufactured by JX Nippon Mining Nippon Metal Co., Ltd. HLP) with a thickness of 35 μm. Copper foil with carrier is produced sequentially. Among them, the resin layer forms the following "C".

<Example 4>

As a copper foil carrier, prepare a long strip of electrolytic copper foil (manufactured by JX Nippon Mining Nippon Metal Co., Ltd.) with a thickness of 35 μm, and the glossy surface (Rz: 0.1 to 0.3 μm) of the copper foil is treated with the same method as in Example 2. Copper foil with carrier is produced sequentially. Among them, the resin layer forms the following "D".

<Example 5>

As a copper foil carrier, a 35-micrometer-thick long electrodeposited copper foil (HLP by JX Nippon Mining & Metals Co., Ltd.) was prepared. Under the same conditions as in Example 1, the glossy surface (Rz: 0.1 to 0.3 μm) of the copper foil was electroplated using a roll-to-roll continuous plating line to form a Ni layer with an adhesion of 4000 μg/dm ² , Next, after forming an ultra-thin copper layer in the same procedure as in Example 1, the following anti-rust treatment (bending method) was performed without performing the roughening treatment.

·Anti-rust treatment

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

pH value: 2~3

Liquid temperature: 40～60℃

Current density: 5～20A/ ^dm2

Coulomb volume: 10～20As/dm ²

After the above-mentioned surface treatment, a resin layer of "E" described below was formed on the ultra-thin copper layer side.

＜Comparative example 1＞

After the ultra-thin copper layer is formed on the copper foil carrier under the same conditions as in Example 1, the following roughening treatment 1, roughening treatment 2, antirust treatment, and chromic acid are sequentially performed on the surface of the ultra-thin copper layer Salt treatment and silane coupling treatment. Roughening treatment 1 and roughening treatment 2 adopt the foil conveying method using a drum shown in Figure 1 (the distance between electrodes is 50mm), and the antirust treatment, chromate treatment and silane coupling treatment adopt the bending method shown in Figure 2 Way. In addition, the thickness of the ultra-thin copper foil was set to 3 μm.

·Coarsening treatment 1

(liquid composition 1)

Cu: 31～45g/L

_H2SO4 : 10～150g _/ L

As: 0.1～200mg/L

(plating condition 1)

Temperature: 30～70℃

Current density: 25～110A/ ^dm2

Coarsening coulomb volume: 50～500As/dm ²

Plating time: 0.5 to 20 seconds

·Coarsening 2

(liquid composition 2)

Cu: 20～80g/L

_H2SO4 : 50 _～ 200g/L

(plating condition 2)

Temperature: 30～70℃

Current density: 5～50A/ ^dm2

Coarsening coulomb volume: 50～300As/dm ²

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

As ₂ O ₃ : 0.01～1g/L

(liquid temperature)

40～90℃

(current condition)

Current density: 1～50A/ ^dm2

Plating time: 1 to 20 seconds

·Chromate treatment

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

NaOH or KOH: 10～50g/L

ZnOH or ZnSO ₄ ·7H ₂ O: 0.05～10g/L

pH value: 7~13

Bath temperature: 20～80℃

Current density: 0.05～5A/ ^dm2

Time: 5-30 seconds

·Silane coupling treatment

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

After the above surface treatment, no resin layer is formed.

＜Comparative example 2＞

Copper foil with a carrier was produced in the same procedure as in Example 1 except that the roughening treatment 1 and the roughening treatment 2 adopted the foil conveyance method by bending shown in FIG. 2 . However, no resin layer was formed.

＜Comparative example 3＞

Copper foil with a carrier was produced in the same procedure as in Example 2 except that the roughening treatment 1 and the roughening treatment 2 adopted the foil conveyance method by bending shown in FIG. 2 . However, no resin layer was formed.

＜Comparative example 4＞

On the ultra-thin copper layer side of the copper foil with a carrier of Comparative Example 1, the following resin layer "A" was formed.

＜Comparative example 5＞

The following resin layer "B" was formed in the ultra-thin copper layer side of the copper foil with a carrier of the comparative example 2.

＜Comparative example 6＞

The following resin layer "C" was formed in the ultra-thin copper layer side of the copper foil with a carrier of the comparative example 3.

<Example 6>

Copper foil with a carrier was produced by the procedure similar to Example 1 except not forming a resin layer.

<Example 7>

Copper foil with a carrier was produced by the procedure similar to Example 2 except not forming a resin layer.

<Example 8>

Copper foil with a carrier was produced by the procedure similar to Example 3 except not forming a resin layer.

<Example 9>

Copper foil with a carrier was produced by the procedure similar to Example 4 except not forming a resin layer.

<Example 10>

Except not having formed a resin layer, the copper foil with a carrier was produced by the procedure similar to Example 5.

＜Formation of resin layer＞

Formation of the resin layer was performed as follows.

"A"

(Resin synthesis example)

Add 3,4/3',4'-biphenyl four Carboxylic dianhydride 117.68g (400mmol), 1,3-bis(3-aminophenoxy)benzene 87.7g (300mmol), γ-valerolactone 4.0g (40mmol), pyridine 4.8g (60mmol), N -Methyl-2-pyrrolidone (hereinafter referred to as NMP) 300g, and toluene 20g, heated at 180°C for 1 hour, cooled to around room temperature, then added 3,4/3'4'-biphenyl tetra Carboxylic dianhydride 29.42g (100mmol), 2,2-bis{4-(4-aminophenoxy)phenyl}propane 82.12g (200mmol), NMP 200g, and toluene 40g, mixed at room temperature for 1 hour Thereafter, it was heated at 180° C. for 3 hours to obtain a block copolymerized polyimide having a solid content of 38%. In this block copolymerization polyimide, the following general formula (1): general formula (2) = 3:2, number average molecular weight: 70000, weight average molecular weight: 150000 represented.

The block copolymerized polyimide solution obtained in the synthesis example was further diluted with NMP to prepare a block copolymerized polyimide solution with a solid content of 10%. In this block copolymerization polyimide solution with bis (4-maleimide phenyl) methane (BMI-H, K-I Chemical Industry) solid content weight ratio 35, block copolymerization polyimide The solid content weight ratio of amine is 65 (that is, the weight of bis(4-maleimide phenyl) methane solid content contained in the resin solution: the solid content of block copolymerized polyimide contained in the resin solution Component weight = 35:65) was dissolved and mixed at 60° C. for 20 minutes to prepare a resin solution. Thereafter, use a reverse roll coater to apply the above-mentioned resin solution on the surface of the ultra-thin copper layer side surface of the copper foil with a carrier before setting the resin layer, dry it at 120°C for 3 minutes in a nitrogen atmosphere, and then dry it at 160°C After 3 minutes of dry processing at a lower temperature, heat processing was performed at 300 degreeC for 2 minutes finally, and the copper foil with a carrier was produced. In addition, the thickness of the resin layer was set to 2 micrometers.

"B"

B is a resin composition prepared with 69 parts by weight of epoxy resin, 11 parts by weight of hardener, 0.25 parts by weight of hardening accelerator, 15 parts by weight of polymer component, 3 parts by weight of crosslinking agent, and 3 parts by weight of rubbery resin.

Specifically, it expresses as follows.

[Composition of resin composition]

Components/Specific Components/Specific Chemical Name (manufacturing company)/Composition (parts by weight)

Epoxy resin/bisphenol A type/YD-907 (manufactured by Tohto Kasei)/15

Epoxy resin/bisphenol A type/YD-011 (manufactured by Tohto Kasei)/54

Hardener/aromatic amine/4,41-diaminodiphenyl sulfone (manufactured by Wakayama Seika Chemical Co., Ltd.)/12

Hardening accelerator/imidazole/2E4MZ (manufactured by Shikoku Kasei)/0.4

Polymer component/polyvinyl acetal resin/5000A (made in Denki Chemical Industry)/15

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

Rubber component/core-shell type nitrile rubber/XER-91 (manufactured by JSR Corporation)/3

Then, the above-mentioned resin composition was adjusted to 30% by weight of resin solid content 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 ultra-thin copper layer side surface of the copper foil with a carrier before the resin layer was provided using a gravure coater. Then, it air-dried for 5 minutes, and dried in the heating environment of 140 degreeC for 3 minutes after that, and formed the 1.5-micrometer-thick semi-cured resin layer (adhesive layer) of a semi-cured state, and manufactured copper foil with a carrier. The measurement of the resin overflow amount of the semi-hardened resin layer (adhesion layer) obtained at this time is to prepare a 18 μm thick copper foil with a 40 μm thick semi-hardened resin layer on one side of the resin composition solution for forming the resin layer. , and set it as a sample for resin overflow measurement. Then, four 10-cm-square samples were collected from this sample for resin overflow measurement, and the measurement of resin overflow was performed based on said MIL-P-13949G. As a result, the amount of resin overflow was 1.5%.

"C"

A resin solution constituting the resin layer is produced. When producing this resin solution, an epoxy resin (EPPN-502 manufactured by Nippon Kayaku Co., Ltd.) and a polyethersulfone resin (Sumikaexcel PES-5003P manufactured by Sumitomo Chemical Co., Ltd.) were used as raw materials. Then, imidazole-based 2E4MZ (manufactured by Shikoku Chemical Industry Co., Ltd.) was added as a curing accelerator to prepare a resin composition.

Resin composition: 50 parts by weight of epoxy resin

50 parts by weight of polyethersulfone resin

1 part by weight of hardening accelerator

This resin composition was further adjusted to a resin solid content of 30% by weight using dimethylformamide to prepare a resin solution. The resin solution produced as above was applied to the ultra-thin copper layer side surface of the copper foil with a carrier before the resin layer was provided using a gravure coater. And after that, drying process was performed for 3 minutes in the heating environment of 140 degreeC, the 1.5 micrometer thick resin layer of the semi-cured state was formed, and the copper foil with a carrier of this invention was obtained. On the other hand, in order to measure the amount of resin overflow, a resin-coated copper foil (copper foil thickness 18 μm) having an undercoat resin layer having a thickness of 40 μm was produced (hereinafter referred to as “sample for measuring resin overflow amount”). Then, four 10-cm-square samples were collected from this sample for resin overflow measurement, and the measurement of resin overflow was performed based on the above-mentioned MIL-P-13949G. As a result, the amount of resin overflow was 1.4%.

"D"

A polyimide resin layer is formed as a cured resin layer on the ultra-thin copper layer side surface of the copper foil with a carrier before the resin layer is placed, and the semi-hardened resin layer is formed using a carrier with a maleimide resin Example of copper foil.

Preparation of polyamic acid varnish: A polyamic acid varnish for forming a hardened resin layer by a casting method will be described. 1 mol of pyromellitic dianhydride and 1 mol of 4,4'-diaminodiphenyl ether were dissolved in N-methylpyrrolidone as a solvent, and mixed. The reaction temperature at this time was 25° C., and the reaction was carried out for 10 hours. Then, a polyamic acid varnish having a resin solid content of 20% by mass was obtained.

Formation of a cured resin layer: Next, a cured resin layer was formed by a casting method using the obtained polyamic acid varnish. Using a Multi Coater (manufactured by Hirano Tecseed: M-400), apply polyamic acid varnish on the surface of the ultra-thin copper layer side surface of the copper foil with a carrier before setting the resin layer, and heat in a hot air dryer at 110°C×6 Dry in minutes. The resin thickness of the cured resin layer after drying was 35 μm, and the residual solvent rate at this stage was 32 wt % with respect to the total amount of the resin layer. The composite of electrolytic copper foil coated with polyamic acid varnish was placed in a hot air oven replaced by nitrogen, and the temperature was raised from room temperature to 400°C over 15 minutes, and then kept at 400°C for 8 minutes, and then cooled. . In this way, the residual solvent is removed from the composite of copper foil with carrier coated with polyamic acid, and an ultra-thin copper layer on copper foil with carrier is produced by dehydrating and ring-closing imide reaction of polyamic acid. Copper-clad polyimide resin substrate with a cured resin layer layered on the side surface. The residual solvent rate of the copper-clad polyimide resin base material obtained by this final heat treatment was 0.5 wt % with respect to the total amount of resin attached to the copper foil with carrier.

Next, corona treatment was performed on the copper foil with a carrier (copper-clad polyimide resin base material) on which the cured resin layer was laminated, and the surface modification of the cured resin layer was performed. The corona treatment was carried out in air under the conditions of electric power 210W, speed 2m/min, discharge capacity 300W·min/m ² , and irradiation distance from the electrode 1.5mm. In addition, in order to measure the coefficient of thermal expansion of the cured resin layer, the copper foil with a carrier (corona-treated copper-clad polyimide resin substrate) was coated with copper Removed by foil stripping and etching. As a result, the cured resin layer (polyimide film) obtained by removing the copper foil with a carrier had a resin thickness of 27 μm and a thermal expansion coefficient of 25 ppm/° C.

Formation of a semi-hardened resin layer: Here, a semi-hardened resin layer is formed on the hardened resin layer of the corona-treated copper-clad polyimide resin substrate. First, a resin varnish was prepared by dissolving the resin composition shown below using N,N'-dimethylacetamide as a solvent so that the resin solid content became 30 wt%.

[Resin composition forming semi-hardened resin layer]

Maleimide resin: 4,4'-diphenylmethanebismaleimide (trade name: BMI-1000, manufactured by Daiwa Chemical Industry Co., Ltd.)/30 parts by weight

Aromatic polyamine resin: 1,3-bis[4-aminophenoxy]benzene (trade name: TPE-R, manufactured by Wakayama Seika Kogyo Co., Ltd.)/35 parts by weight

Epoxy resin: Bisphenol A type epoxy resin (trade name: EPICLON 850S, manufactured by Dainippon Ink Chemical Industry Co., Ltd.)/20 parts by weight

Linear polymer having a crosslinkable functional group: polyvinyl acetal resin (trade name: Denka Butyral 5000A, manufactured by Denki Kagaku Kogyo Co., Ltd.)/15 parts by weight

Apply the above-mentioned resin varnish to the polyimide resin surface of the copper-clad polyimide resin substrate after corona treatment, air-dry for 5 minutes at room temperature, and heat-dry at 160°C for 5 minutes , laminated to form a semi-hardened resin layer. The resin thickness of the semi-cured resin layer at this time was set to 20 μm.

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

The thickness of the whole resin layer of the copper foil with a carrier obtained in this way was 47 micrometers. Then, the copper foil was etched and removed from the resin-attached copper foil by the following method, and the resin layer composed of a cured resin layer and a semi-cured resin layer was subjected to curing heating at 200° C. for 2 hours, and the semi-cured resin layer was measured. The thermal expansion coefficient of the entire resin layer after the cured resin layer is cured. As a result, the coefficient of thermal expansion was 35 ppm/°C. Also, the peel strength was 1.0 kgf/cm.

"E"

First, the first resin composition constituting the resin layer is manufactured. When producing the first resin composition, o-cresol novolak type epoxy resin (YDCN-704 manufactured by Tohto Chemical Co., Ltd.), a solvent-soluble aromatic polyamide resin polymer, and As a mixed varnish of cyclopentanone as a solvent, BP3225-50P manufactured by Nippon Kayaku Co., Ltd. was commercially available as a raw material. Furthermore, VH-4170 manufactured by Dainippon Ink Co., Ltd. and 2E4MZ manufactured by Shikoku Chemicals Co., Ltd. as a hardening accelerator were added to a phenolic resin as a hardener, and the mixed varnish having the following properties was prepared. The first resin composition with a compounding ratio of .

Further, methyl ethyl ketone was used for this first resin composition, and the resin solid content was adjusted to 30% by weight to prepare a resin solution.

The ultra-thin copper layer side surface of the copper foil with a carrier before the resin layer is formed (in the case of surface-treating the ultra-thin copper layer, the surface treated surface) is immersed in the following solution: to become 5g/l Concentration method A solution obtained by adding γ-glycidoxypropyltrimethoxysilane to ion-exchanged water was subjected to adsorption treatment. Then, moisture was released in the furnace adjusted to 180 degreeC environment by the electric heater over 4 seconds, and the condensation reaction of the silane coupling agent progressed, and the silane coupling agent layer was formed.

The resin solution produced as above was applied to the surface on which the silane coupling agent layer of the copper foil with a carrier was formed using a gravure coater. Then, it was air-dried for 5 minutes, and then dried in a heating environment at 140° C. for 3 minutes to form a semi-cured resin layer with a thickness of 1.5 μm, thereby obtaining the copper foil with a carrier of the present invention. In addition, the measurement of the resin overflow amount produced the resin-coated copper foil (henceforth "the sample for the resin overflow amount measurement") which made the undercoat resin layer into 40 micrometers thickness.

And, four 10-cm-square samples were collected from this sample for resin overflow measurement, and the measurement of resin overflow was performed based on said MIL-P-13949G. As a result, the amount of resin overflow was 1.5%.

2. Characteristic evaluation of copper foil with carrier

The characteristic evaluation of the copper foil with a carrier obtained as mentioned above was implemented by the following method. The results are shown in Table 1. In addition, "3.91E-16" of "Ra" in the "column of standard deviation (μm)" of Table 1 indicates 3.91×10 ^-16 (μm), and "1.30E-02" indicates 1.30×10 ^-2 ( μm).

(Surface roughness)

Straight lines were drawn vertically and horizontally at a pitch of 55 mm from each copper foil with a carrier (550 mm x 550 mm square) before the resin layer was formed, and 100 sites were allocated for each 55 mm x 55 mm square area. Use a contact roughness measuring machine (contact roughness meter Surfcorder SE-3C manufactured by Kosaka Laboratories Co., Ltd.) for each area, according to JIS B0601-1982 (Ra, Rz) and JIS B0601-2001 (Rt), in the following Measure the surface roughness (Ra, Rt, Rz) of the ultra-thin copper layer under the measurement conditions, and measure the average value and standard deviation.

＜Measurement conditions＞

Cut-off point: 0.25mm

Reference length: 0.8mm

Measuring ambient temperature: 23～25℃

(migrate)

Each copper foil with a carrier (square of 550 mm x 550 mm) before forming a resin layer was adhered to a bismuth-based resin, and then the carrier foil was peeled off and removed. The exposed ultra-thin copper layer had a thickness of 1.5 μm by soft etching. Thereafter, after washing and drying, DF (manufactured by Hitachi Chemical Co., Ltd., trade name RY-3625) was laminated and applied on the ultra-thin copper layer. Exposure was performed under the condition of 15mJ/cm ² , liquid jet oscillation was performed at 38° C. for 1 minute using a developer solution (sodium carbonate), and a photoresist pattern was formed with line and space (L/S) = 15 μm/15 μm. Next, after plating to a height of 15 μm by copper sulfate plating (CUBRITE 21 manufactured by Ebara-Udylite), DF was peeled off with a stripping solution (sodium hydroxide). Thereafter, the ultra-thin copper layer was etched away with a sulfuric acid-hydrogen peroxide-based etchant to form wiring with L/S=15 μm/15 μm. From the obtained wiring boards, 100 wiring boards were cut out from each of the above-mentioned areas having a size of 55 mm×55 mm.

For each of the obtained wiring boards, the presence or absence of insulation deterioration between wiring patterns was evaluated under the following measurement conditions using a migration measuring machine (MIG-9000 manufactured by IMV). For 100 wiring boards, the number of boards where migration occurred was evaluated.

Furthermore, with regard to Example 2, further, the above-mentioned migration is performed by forming wiring with a pitch of 20 μm between lines and spaces (L/S=8 μm/12 μm, L/S=10 μm/10 μm, L/S=12 μm/8 μm) evaluation of. Also, regarding Example 3, further, the distance between lines and spaces is 20 μm (L/S=8 μm/12 μm, L/S=10 μm/10 μm, L/S=12 μm/8 μm), and the distance between lines and spaces is 15 μm. (L/S=5 μm/10 μm, L/S=8 μm/7 μm) wiring was used to perform the above-mentioned migration evaluation. In addition, when the pitch of a line and a space|gap is 15 micrometers, the thickness of a plating height shall be 10 micrometers. As a result, when the copper foil with a carrier of Example 2 was used to form the wiring of L/S=8μm/12μm, L/S=10μm/10μm, and L/S=12μm/8μm, the in-plane migration rate They are 2/100, 2/100, 3/100 respectively. Also, when using the copper foil with a carrier in Example 3, L/S=8 μm/12 μm, L/S=10 μm/10 μm, L/S=12 μm/8 μm, L/S=5 μm/10 μm, L/S=8 μm In the case of wiring of /7 μm, the in-plane migration occurrence rates were 1/100, 1/100, 2/100, 1/100, and 3/100, respectively.

＜Measurement conditions＞

Threshold: 60% drop in initial resistance

Measuring time: 1000h

Voltage: 60V

Temperature: 85°C

Relative humidity: 85%RH

(peel strength)

The peel strength from the resin base material of the ultra-thin copper layer was measured about the copper foil with a carrier produced with the resin layer (when the resin layer is not formed, however, there is no resin layer). Using a BT substrate (bismaleimide triazine resin, GHPL-830MBT manufactured by Mitsubishi Gas Chemical Co., Ltd.) Copper-clad laminates are produced by heat-compression bonding under the recommended conditions of Chemical Co., Ltd. Thereafter, after peeling off the carrier, a circuit having a width of 10 mm was prepared by wet etching, and ten measurement samples were prepared for each of the examples and comparative examples. Thereafter, the ultra-thin copper layer forming the circuit was peeled off, and the 90-degree peel strength was measured for 10 samples, and the average value, maximum value, minimum value, and unevenness of the peel strength ((maximum value - minimum value) /average value×100(%)). BT base material is a representative base material for semiconductor packaging substrates. The peel strength of the ultra-thin copper layer from the BT base material when laminating the BT base material is preferably 0.70 kN/m or more, more preferably 0.85 kN/m or more.

Claims (30)

1. a kind of Copper foil with carrier sequentially has carrier, peeling layer, very thin layers of copper and arbitrary resin layer, and very thin copper The average value of the Rt of layer surface be using contact roughmeter according to JIS B0601-2001 be measured and be 2.0 μm with Under, and the standard deviation of Rt is 0.1 μm or less.

2. Copper foil with carrier according to claim 1, wherein the average value of the Rz on very thin layers of copper surface is to utilize contact Roughmeter is measured according to JIS B0601-1982 and is 1.5 μm hereinafter, and the standard deviation of Rz is 0.1 μm or less.

3. Copper foil with carrier according to claim 1, wherein the average value of the Ra on very thin layers of copper surface is to utilize contact Roughmeter is measured according to JIS B0601-1982 and is 0.2 μm hereinafter, and the standard deviation of Ra is 0.03 μm or less.

4. Copper foil with carrier according to claim 2, wherein the average value of the Ra on very thin layers of copper surface is to utilize contact Roughmeter is measured according to JIS B0601-1982 and is 0.2 μm hereinafter, and the standard deviation of Ra is 0.03 μm or less.

5. Copper foil with carrier according to any one of claim 1 to 4, wherein the average value of the Rt on very thin layers of copper surface It is 1.0 μm or less.

6. a kind of Copper foil with carrier sequentially has carrier, peeling layer, very thin layers of copper and arbitrary resin layer, very thin layers of copper table The average value of the Rt in face be using contact roughmeter according to JIS B0601-2001 be measured and be 2.0 μm hereinafter, and The standard deviation of Rt is 0.1 μm hereinafter, and meeting following A)~L) in one, binomial, three, four, five, six, Seven, eight, nine, ten, 11 or ten binomials,

A) 1 in the group being made of project below：

1:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 1.5 μm hereinafter,

2:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 1.4 μm hereinafter,

3:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 1.3 μm hereinafter,

4:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 1.2 μm hereinafter,

5:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 1.0 μm hereinafter,

6:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 0.8 μm hereinafter,

7:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 0.5 μm hereinafter,

B) 1 in the group being made of project below：

1:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And it is 0.01 μm or more,

2:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And it is 0.1 μm or more,

3:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And it is 0.3 μm or more,

C) 1 in the group being made of project below：

1:The standard deviation of the Rz on very thin layers of copper surface be 0.1 μm hereinafter,

2:The standard deviation of the Rz on very thin layers of copper surface be 0.068 μm hereinafter,

3:The standard deviation of the Rz on very thin layers of copper surface be 0.05 μm hereinafter,

D):The standard deviation of the Rz on very thin layers of copper surface is 0.01 μm or more,

E) 1 in the group being made of project below：

1:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And be 1.8 μm hereinafter,

2:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And be 1.5 μm hereinafter,

3:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And be 1.3 μm hereinafter,

4:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And be 1.1 μm hereinafter,

5:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And be 1.0 μm hereinafter,

F) 1 in the group being made of project below：

1:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And it is 0.5 μm or more,

2:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And it is 0.6 μm or more,

3:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And it is 0.8 μm or more,

G) 1 in the group being made of project below：

1:The standard deviation of the Rt on very thin layers of copper surface be 0.060 μm hereinafter,

2:The standard deviation of the Rt on very thin layers of copper surface be 0.05 μm hereinafter,

H):The standard deviation of the Rt on very thin layers of copper surface is 0.01 μm or more,

I) 1 in the group being made of project below：

1:The average value of the Ra on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 0.2 μm hereinafter,

2:The average value of the Ra on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 0.18 μm hereinafter,

3:The average value of the Ra on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 0.15 μm hereinafter,

J) 1 in the group being made of project below：

1:The average value of the Ra on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And it is 0.01 μm or more,

2:The average value of the Ra on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And it is 0.05 μm or more,

3:The average value of the Ra on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And it is 0.12 μm or more,

4:The average value of the Ra on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And it is 0.13 μm or more,

K) 1 in the group being made of project below：

1:The standard deviation of the Ra on very thin layers of copper surface be 0.03 μm hereinafter,

2:The standard deviation of the Ra on very thin layers of copper surface be 0.026 μm hereinafter,

3:The standard deviation of the Ra on very thin layers of copper surface be 0.02 μm hereinafter,

L):The standard deviation of the Ra on very thin layers of copper surface is 0.001 μm or more.

7. a kind of Copper foil with carrier sequentially has carrier, peeling layer, very thin layers of copper and arbitrary resin layer person, and very thin The average value of the Ra on layers of copper surface be using contact roughmeter according to JIS B0601-1982 be measured and be 0.2 μm with Under, and the standard deviation of Ra is 0.03 μm or less.

8. Copper foil with carrier according to claim 7, wherein the average value of the Rz on very thin layers of copper surface is to utilize contact Roughmeter is measured according to JIS B0601-1982 and is 1.5 μm hereinafter, and the standard deviation of Rz is 0.1 μm or less.

9. Copper foil with carrier according to claim 7, wherein the average value of the Rt on very thin layers of copper surface is to utilize contact Roughmeter is measured according to JIS B0601-2001 and is 2.0 μm hereinafter, and the standard deviation of Rt is 0.1 μm or less.

10. Copper foil with carrier according to claim 8, wherein the average value of the Rt on very thin layers of copper surface is to utilize contact Formula roughmeter is measured according to JIS B0601-2001 and is 2.0 μm hereinafter, and the standard deviation of Rt is 0.1 μm or less.

11. Copper foil with carrier according to any one of claims 7 to 10, wherein the Ra's on very thin layers of copper surface is averaged Value is 0.15 μm or less.

12. a kind of Copper foil with carrier sequentially has carrier, peeling layer, very thin layers of copper and arbitrary resin layer, very thin layers of copper The average value of the Ra on surface be using contact roughmeter according to JIS B0601-1982 be measured and be 0.2 μm hereinafter, And the standard deviation of Ra is 0.03 μm hereinafter, and meeting following A)~L) in one, binomial, three, four, five, six Item, seven, eight, nine, ten, 11 or ten binomials,

A) 1 in the group being made of project below：

1:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 1.5 μm hereinafter,

2:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 1.4 μm hereinafter,

3:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 1.3 μm hereinafter,

4:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 1.2 μm hereinafter,

5:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 1.0 μm hereinafter,

6:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 0.8 μm hereinafter,

7:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 0.5 μm hereinafter,

B) 1 in the group being made of project below：

1:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And it is 0.01 μm or more,

2:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And it is 0.1 μm or more,

3:The average value of the Rz on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And it is 0.3 μm or more,

C) 1 in the group being made of project below：

1:The standard deviation of the Rz on very thin layers of copper surface be 0.1 μm hereinafter,

2:The standard deviation of the Rz on very thin layers of copper surface be 0.068 μm hereinafter,

3:The standard deviation of the Rz on very thin layers of copper surface be 0.05 μm hereinafter,

D):The standard deviation of the Rz on very thin layers of copper surface is 0.01 μm or more,

E) 1 in the group being made of project below：

1:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And be 2.0 μm hereinafter,

2:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And be 1.8 μm hereinafter,

3:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And be 1.5 μm hereinafter,

4:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And be 1.3 μm hereinafter,

5:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And be 1.1 μm hereinafter,

6:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And be 1.0 μm hereinafter,

F) 1 in the group being made of project below：

1:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And it is 0.5 μm or more,

2:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And it is 0.6 μm or more,

3:The average value of the Rt on very thin layers of copper surface is measured according to JIS B0601-2001 using contact roughmeter And it is 0.8 μm or more,

G) 1 in the group being made of project below：

1:The standard deviation of the Rt on very thin layers of copper surface be 0.1 μm hereinafter,

2:The standard deviation of the Rt on very thin layers of copper surface be 0.060 μm hereinafter,

3:The standard deviation of the Rt on very thin layers of copper surface be 0.05 μm hereinafter,

H):The standard deviation of the Rt on very thin layers of copper surface is 0.01 μm or more,

I) 1 in the group being made of project below：

1:The average value of the Ra on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 0.18 μm hereinafter,

2:The average value of the Ra on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And be 0.15 μm hereinafter,

J) 1 in the group being made of project below：

1:The average value of the Ra on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And it is 0.01 μm or more,

2:The average value of the Ra on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And it is 0.05 μm or more,

3:The average value of the Ra on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And it is 0.12 μm or more,

4:The average value of the Ra on very thin layers of copper surface is measured according to JIS B0601-1982 using contact roughmeter And it is 0.13 μm or more,

K) 1 in the group being made of project below：

1:The standard deviation of the Ra on very thin layers of copper surface be 0.026 μm hereinafter,

2:The standard deviation of the Ra on very thin layers of copper surface be 0.02 μm hereinafter,

L):The standard deviation of the Ra on very thin layers of copper surface is 0.001 μm or more.

13. according to the Copper foil with carrier described in Claims 1-4,6 to 10, any one of 12, wherein very thin layers of copper is by thick Change is handled.

14. a kind of printing distributing board is made using the Copper foil with carrier described in any one of claim 1 to 13.

15. printing distributing board according to claim 14, has：

Insulating substrate and

Copper circuit on above-mentioned insulating substrate is set,

The circuit width of above-mentioned copper circuit is not up to 20 μm, and the gap width between adjacent copper circuit is not up to 20 μm.

16. printing distributing board according to claim 14, has：

Insulating substrate and

Copper circuit on above-mentioned insulating substrate is set,

The circuit width of above-mentioned copper circuit is 17 μm hereinafter, the gap width between the copper circuit of adjoining is 17 μm or less.

17. printing distributing board according to claim 14, wherein the spacing in line and gap is not up to 40 μm.

18. printing distributing board according to claim 14, wherein the spacing in line and gap is 34 μm or less.

19. a kind of printed circuit board is made using the Copper foil with carrier described in any one of claim 1 to 13.

20. printed circuit board according to claim 19, has：

Insulating substrate and

Copper circuit on above-mentioned insulating substrate is set,

The circuit width of above-mentioned copper circuit is not up to 20 μm, and the gap width between adjacent copper circuit is not up to 20 μm.

21. printed circuit board according to claim 19, has：

Insulating substrate and

Copper circuit on above-mentioned insulating substrate is set,

The circuit width of above-mentioned copper circuit is 17 μm hereinafter, the gap width between the copper circuit of adjoining is 17 μm or less.

22. printed circuit board according to claim 19, wherein the spacing in line and gap is not up to 40 μm.

23. printed circuit board according to claim 19, wherein the spacing in line and gap is 34 μm or less.

24. a kind of copper-cover laminated plate is manufactured using the Copper foil with carrier described in any one of claim 1 to 13.

25. a kind of manufacturing method of printing distributing board, it includes following steps：

The step of preparing the Copper foil with carrier and insulating substrate described in any one of claim 1 to 13；

The step of by above-mentioned Copper foil with carrier and insulating substrate lamination；

After by above-mentioned Copper foil with carrier and insulating substrate lamination, by the step of carrier of above-mentioned Copper foil with carrier is removed Copper-cover laminated plate is formed,

Thereafter, circuit is formed by any one of semi-additive process, subtractive process, part addition process or improvement semi-additive process method Step.

26. a kind of manufacturing method of printing distributing board, it includes following steps：

The above-mentioned very thin layers of copper side surface of Copper foil with carrier described in any one of claim 1 to 13 forms the step of circuit Suddenly；

In a manner of burying foregoing circuit the step of the above-mentioned very thin layers of copper side surface of above-mentioned Copper foil with carrier forms resin layer；

In the step of forming circuit on above-mentioned resin layer；

After forming circuit on above-mentioned resin layer, above-mentioned carrier is removed；And

By removing above-mentioned very thin layers of copper after removing above-mentioned carrier, and make to be formed in being buried in for above-mentioned very thin layers of copper side surface The step of circuit of above-mentioned resin layer exposes.

27. the manufacturing method of printing distributing board according to claim 26, wherein form circuit on above-mentioned resin layer Step is to be fitted in another Copper foil with carrier on above-mentioned resin layer from very thin layers of copper side, using being fitted in the attached of above-mentioned resin layer Carrier copper foil forms the step of foregoing circuit.

28. the manufacturing method of printing distributing board according to claim 27, wherein be fitted in another on above-mentioned resin layer Copper foil with carrier is the Copper foil with carrier described in any one of claim 1 to 13.

29. the manufacturing method of the printing distributing board according to any one of claim 26 to 28, wherein in above-mentioned resin layer The step of upper formation circuit is by semi-additive process, subtractive process, part addition process or to improve any one of semi-additive process method It carries out.

30. the manufacturing method of the printing distributing board according to any one of claim 26 to 28 is further contained in stripping Before carrier, in the step of carrier side surface of Copper foil with carrier forms substrate.