CN108588766B

CN108588766B - Copper foil with carrier

Info

Publication number: CN108588766B
Application number: CN201810371406.9A
Authority: CN
Inventors: 古曳伦也; 永浦友太; 坂口和彦; 千叶徹
Original assignee: JX Nippon Mining and Metals Corp
Current assignee: JX Nippon Mining and Metals Corp
Priority date: 2012-09-11
Filing date: 2013-09-11
Publication date: 2020-02-18
Anticipated expiration: 2033-09-11
Also published as: JP5481577B1; CN104619889A; KR102050646B1; TW201533280A; CN109379858A; MY167704A; TWI504788B; KR101766554B1; KR20170046822A; JP2014139336A; CN107641820A; PH12015500529B1; CN104619889B; PH12015500529A1; KR20150052315A; TWI575120B; TW201428144A; WO2014042201A1; MY188679A; CN108588766A

Abstract

The present invention relates to a copper foil with a carrier. The invention provides a copper foil with a carrier, which is suitable for forming a narrow pitch. The copper foil with a carrier comprises a copper foil carrier, a release layer laminated on the copper foil carrier, and an extra thin copper layer laminated on the release layer, wherein the extra thin copper layer is roughened, and Rz of the surface of the extra thin copper layer is 1.6 μm or less as measured by a non-contact roughness meter.

Description

Copper foil with carrier

The application is a divisional application of Chinese patent application with the application number of 201380046519.7, the application date of 2013, 9 and 11 and the name of 'copper foil with carrier'.

Technical Field

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

Background

A printed wiring board is generally manufactured through the following steps: after a copper-clad laminate is produced by bonding an insulating substrate and a copper foil, a conductor pattern is formed on the surface of the copper foil by etching. With the recent increase in the demand for smaller and higher performance electronic devices, high-density packaging of mounted components and higher frequency of signals have been promoted, and printed wiring boards have been required to have finer conductor patterns (narrower pitches) and higher frequency response.

In recent years, copper foils with a thickness of 9 μm or less, and even 5 μm or less have been required to cope with the narrowing of pitches, but such extremely thin copper foils have low mechanical strength and are liable to crack or wrinkle during the production of printed wiring boards, and therefore carrier-attached copper foils have been developed in which an extremely thin copper layer is electrodeposited on a metal foil with a thickness as a carrier via a release layer. After the surface of the extremely thin copper layer is bonded to an insulating substrate and thermocompression bonded, the carrier is peeled and removed via the peeling layer. After forming a circuit pattern on the exposed extremely thin copper layer with a resist, the extremely thin copper layer is etched and removed with a sulfuric acid-hydrogen peroxide etching solution, and a fine circuit is formed by this method (MSAP: Modified-Semi-Additive-Process).

Here, the surface of the extra thin copper layer of the carrier-attached copper foil to be the surface to be bonded to the resin is mainly required to have sufficient peel strength between the extra thin copper layer and the resin base material, and the peel strength is also required to be sufficient even after high-temperature heating, wet treatment, welding, chemical treatment, or the like. The method of improving the peel strength between an extremely thin copper layer and a resin substrate is generally represented by the following methods: a large number of coarsened particles are attached to the extremely thin copper layer with an increased surface profile (roughness ).

However, even in the case of a printed wiring board, when such an extremely thin copper layer having a large profile (unevenness, roughness) is used for a semiconductor package substrate having a need to form a particularly fine circuit pattern, unnecessary copper particles remain during circuit etching, and a problem such as poor insulation between circuit patterns occurs.

Therefore, WO2004/005588 (patent document 1) has attempted to use a carrier-attached copper foil without roughening the surface of the extra thin copper layer as a carrier-attached copper foil for a fine circuit such as a semiconductor package substrate. Due to the influence of its low profile (roughness ), the adhesion (peel strength) of such an extra thin copper layer without roughening treatment to a resin tends to be lower than that of a copper foil for a general printed wiring board. Therefore, the carrier-attached copper foil must be further improved.

Therefore, japanese patent laid-open publication No. 2007-007937 (patent document 2) and japanese patent laid-open publication No. 2010-006071 (patent document 3) describe providing 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 on the surface of the carrier-attached ultra-thin copper foil in contact with (or in contact with) the polyimide-based resin substrate. By providing these surface-treated layers, the adhesion strength between the polyimide resin substrate and the carrier-attached ultra-thin copper foil can be obtained without roughening treatment or with a reduced degree of roughening treatment (miniaturization). Further, it is also described that surface treatment or rust prevention treatment is performed by using a silane coupling agent.

[ patent document 1] WO2004/005588

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

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

Disclosure of Invention

In the development of a copper foil with a carrier, it has been considered important to secure peel strength between an extremely thin copper layer and a resin base. Therefore, the narrowing of the pitch has not been sufficiently studied yet, and there is still room for improvement. Accordingly, an object of the present invention is to provide a copper foil with a carrier suitable for forming a narrow pitch. Specifically, an object of the present invention is to provide a copper foil with a carrier, which can form a wiring finer than the limit of L/S of 20 μm/20 μm which has been considered to be formable by MSAP.

The inventors of the present invention have made extensive studies to achieve the above object, and as a result, have found that a uniform roughened surface with low roughness can be formed by reducing the roughness of the surface of an extremely thin copper layer and forming fine roughened particles on the extremely thin copper layer. Further, it was found that the copper foil with carrier is extremely effective for narrow pitch formation.

The present invention has been made in view of the above-mentioned circumstances, and an aspect of the present invention is a copper foil with a carrier, which comprises a copper foil carrier, a release layer laminated on the copper foil carrier, and an extra thin copper layer laminated on the release layer, wherein the extra thin copper layer is roughened, and Rz of the surface of the extra thin copper layer is 1.6 μm or less as measured by a non-contact roughness meter.

In another aspect of the present invention, there is provided a copper foil with a carrier, comprising a copper foil carrier, a release layer laminated on the copper foil carrier, and an extra thin copper layer laminated on the release layer, wherein the extra thin copper layer is roughened, and Ra of the surface of the extra thin copper layer is 0.3 μm or less as measured by a non-contact roughness meter.

In still another aspect of the present invention, there is provided a copper foil with a carrier, comprising a copper foil carrier, a release layer laminated on the copper foil carrier, and an extra thin copper layer laminated on the release layer, wherein the extra thin copper layer is roughened, and Rt of the surface of the extra thin copper layer is 2.3 μm or less as measured by a non-contact roughness meter.

In one embodiment of the copper foil with carrier of the present invention, Rz of the surface of the extra thin copper layer is 1.4 μm or less as measured by a noncontact roughness meter.

In another embodiment of the copper foil with carrier of the present invention, Ra of the surface of the extra thin copper layer is 0.25 μm or less as measured by a noncontact roughness meter.

In still another embodiment of the copper foil with carrier of the present invention, Rt of the surface of the extra thin copper layer is 1.8 μm or less as measured by a noncontact roughness meter.

In still another embodiment of the copper foil with carrier of the present invention, the Ssk of the surface of the extra thin copper layer is-0.3 to 0.3.

In still another embodiment of the copper foil with carrier of the present invention, the surface of the extra thin copper layer has a Sku of 2.7 to 3.3.

In still another embodiment of the carrier-attached copper foil of the present invention, the carrier-attached copper foil comprises a copper foil carrier, a release layer laminated on the copper foil carrier, and an extra thin copper layer laminated on the release layer, wherein the extra thin copper layer is roughened, and the surface area ratio of the extra thin copper layer surface is 1.05 to 1.5.

In still another embodiment of the copper foil with carrier of the present invention, the surface area ratio of the surface of the extra thin copper layer is 1.05 to 1.5.

In still another embodiment of the copper foil with carrier of the present invention, the extremely thin copper layer surface is 66524 μm each²The volume of the area is 300000 mu m³The above.

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

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

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

In still another aspect of the present invention, there is provided a method for manufacturing a printed wiring board, comprising the steps of:

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

laminating the copper foil with carrier and the insulating substrate; and

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

thereafter, a step of forming a circuit by any one of a semi-additive method, a subtractive method, a partial additive method, or a Modified semi-additive method (Modified semi-additive method).

The copper foil with carrier of the present invention is suitable for narrow pitch formation, and for example, a wiring finer than the limit of L/S20 μm/20 μm that is considered to be formable by the MSAP step, for example, a fine wiring of L/S15 μm/15 μm can be formed.

Drawings

FIG. 1: SEM photographs of the M-plane of the very thin copper layers in examples 1 and 2.

FIG. 2: a to C are schematic diagrams of the cross-section of the wiring board in the steps from circuit plating to removal of the photoresist in the specific embodiment of the method for producing a printed wiring board using the carrier-attached copper foil of the present invention.

FIG. 3: d to F are schematic diagrams of the cross-section of the wiring board in the steps from the step of depositing the resin and the layer 2 copper foil with carrier to the step of laser drilling in the specific embodiment of the method for manufacturing the printed wiring board using the copper foil with carrier of the present invention.

FIG. 4: g to I are schematic diagrams of the cross-section of the wiring board in the steps from the formation of the via-filler to the peeling of the layer 1 carrier in the specific example of the method for producing a printed wiring board using the carrier-attached copper foil of the present invention.

FIG. 5: j to K are schematic diagrams of the cross-section of the wiring board in the steps from the rapid etching to the formation of the bump-copper pillar in the specific example of the method for manufacturing a printed wiring board using the carrier-attached copper foil of the present invention.

Detailed Description

< 1. vector >

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

The thickness of the carrier usable in the present invention is not particularly limited, and may be appropriately adjusted to an appropriate thickness so as to achieve the function as a carrier, and may be set to 12 μm or more, for example. However, if the thickness is too large, the production cost increases, so that it is generally preferable to be 70 μm or less. Therefore, the thickness of the carrier is typically 12 to 70 μm, and more typically 18 to 35 μm.

< 2 > peeling layer

A release layer is provided on the carrier. The release layer may be any release layer known to those skilled in the art in the carrier-attached copper foil. For example, the peeling layer is preferably formed of a layer containing at least one of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, an alloy thereof, a hydrate thereof, an oxide thereof, and an organic substance thereof. The release layer may be formed in multiple layers.

In an embodiment of the present invention, the peeling layer is a layer composed of a single metal layer composed of any one element of the element group of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, and Al, 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, and Al, and a layer composed of a hydrate or an oxide of one or more elements selected from the element group of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, and Al, laminated thereon, from the support side.

The exfoliation layer is preferably composed of 2 layers of Ni and Cr. In this case, the Ni layer and the Cr layer are laminated so as to be in contact with the interface with the copper foil carrier and the interface with the extra thin copper layer, respectively.

The peeling layer can be obtained by wet plating such as electroplating, electroless plating, and immersion plating, or dry plating such as sputtering, CVD, and PDV. Electroplating is preferred from the viewpoint of cost.

< 3. ultrathin copper layer >

An extremely thin copper layer is provided on the release layer. The extra thin copper layer is preferably formed by electroplating using an electrolytic bath containing copper sulfate, copper pyrophosphate, copper sulfamate, copper cyanide, or the like, and a copper sulfate bath is preferred in that a copper foil can be formed at a high current density by using a general electrolytic copper foil. The thickness of the extremely thin copper layer is not particularly limited, and is usually smaller than the carrier, for example, 12 μm or less. Typically 0.5 to 12 μm, more typically 2 to 5 μm.

< 4. surface treatment such as roughening treatment >

The surface of the extremely thin copper layer is provided with a roughened layer by roughening treatment applied thereto, for example, to improve adhesion to the insulating substrate. The roughening treatment may be performed by forming roughening particles with copper or a copper alloy, for example. From the viewpoint of forming a narrow pitch, the roughened layer is preferably formed of fine particles. The plating conditions for forming the roughened particles tend to make the particles finer if the current density is increased, the copper concentration in the plating solution is decreased, or the coulomb amount is increased.

The roughened layer may be formed of electrodeposited particles of a single substance selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt, and zinc, or an alloy containing at least one of these substances.

After the roughening treatment, secondary particles or tertiary particles and/or an anticorrosive layer and/or a heat-resistant layer are formed by using a simple substance or an alloy of nickel, cobalt, copper, zinc, or the like, and the surface treatment such as chromate treatment, silane coupling treatment, or the like may be further applied to the surface. That is, 1 or more kinds of layers selected from the group consisting of a rust-proof layer, a heat-resistant layer, a chromate treatment layer, and a silane coupling treatment layer may be formed on the surface of the roughened layer.

For example, a heat-resistant layer and/or a rust-preventive layer may be provided on the roughened layer, a chromate treatment layer may be provided on the heat-resistant layer and/or the rust-preventive layer, or a silane coupling treatment layer may be provided on the chromate treatment layer. Further, the order of forming the heat-resistant layer, the rust-proof layer, the chromate treatment layer, and the silane coupling treatment layer is not limited, and the above-mentioned layers may be formed in any order on the roughened layer.

The surface of the extremely thin copper layer after various surface treatments such as roughening treatment (also referred to as "roughened surface") is extremely advantageous in forming a narrow pitch from the viewpoint of Rz (ten-point average roughness) being 1.6 μm or less when measured by a non-contact roughness meter. Rz is preferably 1.5 μm or less, more preferably 1.4 μm or less, still more preferably 1.35 μm or less, still more preferably 1.3 μm or less, still more preferably 1.2 μm or less, still more preferably 1.0 μm or less, still more preferably 0.8 μm or less, and still more preferably 0.6 μm or less. However, when Rz is too small, the adhesion force with the resin decreases, and therefore, it is preferably 0.01 μm or more, more preferably 0.1 μm or more, and still more preferably 0.2 μm or more.

The surface of the extremely thin copper layer after various surface treatments such as roughening treatment (also referred to as "roughened surface") is extremely advantageous in that a narrow pitch is formed by setting Ra (arithmetic mean roughness) to 0.30 μm or less when measured by a non-contact roughness meter. Ra is preferably 0.27 μm or less, more preferably 0.26 μm or less, more preferably 0.25 μm or less, more preferably 0.24 μm or less, more preferably 0.23 μm or less, still more preferably 0.20 μm or less, still more preferably 0.18 μm or less, still more preferably 0.16 μm or less, still more preferably 0.15 μm or less, and still more preferably 0.13 μm or less. However, since the adhesion force with the resin decreases when Ra is too small, it is preferably 0.005 μm or more, more preferably 0.009 μm or more, 0.01 μm or more, 0.02 μm or more, more preferably 0.05 μm or more, and more preferably 0.10 μm or more.

When the surface of the extremely thin copper layer after various surface treatments such as roughening treatment (also referred to as "roughened surface") is measured by a non-contact roughness meter, it is extremely advantageous from the viewpoint of forming a narrow pitch to set Rt to 2.3 μm or less. Rt is preferably 2.2 μm or less, preferably 2.1 μm or less, preferably 2.07 μm or less, more preferably 2.0 μm or less, more preferably 1.9 μm or less, more preferably 1.8 μm or less, still more preferably 1.5 μm or less, still more preferably 1.2 μm or less, and still more preferably 1.0 μm or less. However, when Rt is too small, the adhesion force with the resin decreases, and therefore, Rt is preferably 0.01 μm or more, more preferably 0.1 μm or more, more preferably 0.3 μm or more, and more preferably 0.5 μm or more.

Further, when the surface of the extremely thin copper layer after various surface treatments such as roughening treatment is measured by a noncontact roughness meter, it is preferable to set the Ssk (skewness) to-0.3 to 0.3 in order to form a narrow pitch. The lower limit of Ssk is preferably-0.2 or more, more preferably-0.1 or more, more preferably-0.070 or more, more preferably-0.065 or more, more preferably-0.060 or more, more preferably-0.058 or more, and still more preferably 0 or more. The upper limit of Ssk is preferably 0.2 or less.

Further, when the surface of the extremely thin copper layer after various surface treatments such as roughening treatment is measured by a noncontact roughness meter, it is preferable to set Sku (kurtosis) to 2.7 to 3.3 in view of forming a narrow pitch. The lower limit of Sku is preferably 2.8 or more, more preferably 2.9 or more, and still more preferably 3.0 or more. The upper limit of Sku is preferably 3.2 or less.

In the present invention, the roughness parameters of Rz and Ra of the surface of the extremely thin copper layer are measured by a noncontact roughness meter in accordance with JIS B0601-1994, the roughness parameters of Rt are measured by a noncontact roughness meter in accordance with JIS B0601-2001, and the roughness parameters of Ssk and Sku are measured by a noncontact roughness meter in accordance with ISO25178 draft.

When an insulating substrate made of a resin such as a printed wiring board or a copper-clad laminate is bonded to the surface of the extra thin copper layer, the surface roughness (Ra, Rt, Rz) can be measured for the surface of the copper circuit or the copper foil by dissolving and removing the insulating substrate.

In order to form a narrow pitch, it is also important to control the volume of the roughened surface in order to reduce the etching amount of the roughened particle layer. The volume here is a value measured by a laser microscope, and is an index for evaluating the volume of the roughened particles present on the roughened surface. When the volume of the roughened surface is large, the adhesion force between the extremely thin copper layer and the resin tends to be high. Further, when the adhesion force between the extremely thin copper layer and the resin is increased, the migration resistance tends to be improved. Specifically, the thickness is preferably determined by a laser microscope, and is preferably determined every 66524 μm on the roughened surface²The area volume is 300000 mu m³Above, more preferably 350000 μm³The above. However, if the volume becomes too large, the etching amount increases, and a narrow pitch cannot be formed, so that the volume is preferably set to 500000 μm³Hereinafter, it is more preferably set to 450000 μm³The following.

Further, in order to form a narrow pitch, it is important to control the surface area ratio of the roughened surface in order to ensure adhesion to the resin due to the fine roughened particles. The surface area ratio herein refers to a value measured by a laser microscope, and refers to a value of an actual area/area when measuring an area and an actual area. The area refers to a measurement reference area, and the actual area refers to a surface area in the measurement reference area. When the surface area ratio is too large, the adhesion strength increases, but the etching amount increases, and thus a narrow pitch cannot be formed, while when the surface area ratio is too small, the adhesion strength cannot be secured, and therefore, the surface area ratio is preferably 1.05 to 1.5, preferably 1.07 to 1.47, preferably 1.09 to 1.4, and more preferably 1.1 to 1.3.

< 5. resin layer >

The carrier-attached copper foil of the present invention may further include a resin layer on the surface of the extra thin copper layer after various surface treatments such as roughening treatment. For example, a resin layer may be provided on the roughened layer, the heat-resistant layer, the rust-preventive layer, the chromate treatment layer, or the silane coupling treatment layer. The resin layer may be an insulating resin layer.

The resin layer may be an adhesive resin, i.e., an adhesive, or an insulating resin layer in a semi-cured state (B-stage state) for adhesion. The semi-cured state (B-stage state) includes the following states: the insulating resin layer is not sticky even when touched with a finger, can be stored in an overlapping manner, and is further subjected to a heat treatment to cause a curing reaction.

The resin layer may contain a thermosetting resin or a thermoplastic resin. The resin layer may contain a thermoplastic resin. The resin layer may contain a known resin, resin curing agent, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton material, and the like. The resin layer can be formed by using a method and a device for forming a resin layer and/or a substance (resin, resin curing agent, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton material, etc.) described in, for example, the following documents: international publication No. WO2008/004399, International publication No. WO2008/053878, International publication No. WO2009/084533, Japanese patent laid-open No. 11-5828, Japanese patent laid-open No. 11-140281, Japanese patent No. 3184485, International publication No. WO97/02728, Japanese patent No. 3676375, Japanese patent No. 2000-43188, Japanese patent No. 3612594, Japanese patent laid-open No. 2002-179772, Japanese patent laid-open No. 2002-359444, Japanese patent laid-open No. 2003-304068, Japanese patent No. 3992225, Japanese patent laid-open No. 2003-249739, Japanese patent No. 4136509, Japanese patent No. 2004-82687, Japanese patent No. 4025177, Japanese patent laid-open No. 2004-349654, Japanese patent No. 2005-4286060, Japanese patent laid-open No. 2005-262506, Japanese patent No. 4570070, Japanese patent No. 2005-53218, Japanese patent No. 3949676, Japanese patent No. 4178415, Japanese patent publication No. WO2004/005588, Japanese laid-open patent publication No. 2006-257153, Japanese laid-open patent publication No. 2007-326923, Japanese laid-open patent publication No. 2008-111169, Japanese patent publication No. 5024930, International publication No. WO2006/028207, Japanese patent publication No. 4828427, Japanese laid-open patent publication No. 2009-67029, International publication No. WO2006/134868, Japanese patent publication No. 5046927, Japanese laid-open patent publication No. 2009-173017, International publication No. WO2007/105635, Japanese patent publication No. 5180815, International publication No. WO2008/114858, International publication No. WO2009/008471, Japanese laid-open patent publication No. 2011-14727, International publication No. WO2009/001850, International publication No. WO2009/145179, International publication No. WO2011/068157, Japanese laid-open patent publication No. 2013-19056.

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

The epoxy resin has 2 or more epoxy groups in the molecule, and can be used without any problem as long as it is usable for electric and electronic materials. The epoxy resin is preferably an epoxy resin obtained by epoxidizing a compound having 2 or more glycidyl groups in the molecule. Further, it is possible to use, as a mixture, one selected from: 1 or 2 or more selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, novolak type epoxy resin, cresol novolak type epoxy resin, alicyclic epoxy resin, brominated epoxy resin, phenol novolak type epoxy resin, naphthalene type epoxy resin, brominated bisphenol A type epoxy resin, o-cresol novolak type epoxy resin, rubber modified bisphenol A type epoxy resin, glycidyl amine type epoxy resin, triglycidyl isocyanurate, N-diglycidylaniline and other glycidyl amine compounds, tetrahydrophthalic acid diglycidyl ester and other glycidyl ester compounds, phosphorus-containing epoxy resin, biphenyl type epoxy resin, biphenol novolak type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, or a hydrogenated or halogenated form of the above epoxy resin may be used.

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

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

[ chemical formula 1]

[ chemical formula 2]

The phosphorus-containing epoxy resin as the component E obtained from the compound as a raw material is preferably a mixture of 1 or 2 kinds of compounds having a structural formula represented by any one of chemical formulas 3 to 5 shown below. The reason for this is that the resin in a semi-cured state is excellent in stability of quality and has a high flame retardant effect.

[ chemical formula 3]

[ chemical formula 4]

[ chemical formula 5]

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

[ chemical formula 6]

[ chemical formula 7]

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

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

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

As the bisphenol, known bisphenols may be used, and bisphenols obtained as an adduct of bisphenol a, bisphenol F, bisphenol S, tetrabromobisphenol a, 4' -dihydroxybiphenyl, HCA (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) and a quinone such as hydroquinone and naphthoquinone may be used.

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

The resin layer may contain a crosslinking agent. The crosslinking agent may be a known crosslinking agent. For example, an amine ester-based resin can be used as the crosslinking agent.

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

As the polyamide-imide resin, a known polyimide-amide resin can be used. As the polyimide amide resin, for example: a resin obtained by heating trimellitic anhydride, benzophenone tetracarboxylic anhydride and 3, 3-dimethyl-4, 4-diphenyl diisocyanate in a solvent such as N-methyl-2-pyrrolidone or/and N, N-dimethylacetamide, or a resin obtained by heating trimellitic anhydride, diphenylmethane diisocyanate and carboxyl-terminated acrylonitrile-butadiene rubber in a solvent such as N-methyl-2-pyrrolidone or/and N, N-dimethylacetamide.

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

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

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

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

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

[ chemical formula 8]

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

[ chemical formula 9]

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

Among them, imidazoles having a structural formula represented by the following chemical formula 10 are preferably used. By using imidazoles of the structural formula represented by chemical formula 10, the moisture absorption resistance of the resin layer in a semi-cured state can be remarkably improved, and the long-term storage stability is excellent. This is because imidazoles play a catalytic role in curing an epoxy resin, and they function as a reaction initiator that causes a self-polymerization reaction of the epoxy resin in an initial stage of the curing reaction.

[ chemical formula 10]

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

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

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

The acid anhydride of the polycarboxylic acid is preferably a component that functions as a curing agent for the epoxy resin. The acid anhydride of the polycarboxylic acid is preferably phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydroxy phthalic anhydride, hexahydroxy phthalic anhydride, methylhexahydroxy phthalic anhydride, a soil-resistant acid, or a methyl soil-resistant acid.

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

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

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

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

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

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

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

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

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

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

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

And B component: high heat resistance epoxy resin.

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

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

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

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

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

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

A solvent is added to the resin composition described above to form a thermosetting resin layer as an adhesive layer of a printed wiring board, using the resin varnish. The resin varnish is a semi-cured resin film having a resin flow rate of 5 to 35% as measured by MIL-P-13949G in the MIL standard, wherein a solvent is added to the resin composition to prepare a resin solid content in the range of 30 to 70% by weight. As the solvent, a known solvent or a solvent described above can be used.

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

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

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

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

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

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

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

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

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

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

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

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

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

[ mathematical formula 1]

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

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

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

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

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

When the copper foil with a carrier having a resin layer is used for producing an extremely thin multilayer printed wiring board, it is preferable to reduce the thickness of the multilayer printed wiring board by setting the thickness of the resin layer to 0.1 to 5 μm, more preferably 0.5 to 5 μm, and still more preferably 1 to 5 μm.

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

The total thickness of the cured resin layer and the semi-cured resin layer is preferably 0.1 to 120 μm, more preferably 5 to 120 μm, even more preferably 10 to 120 μm, and yet more preferably 10 to 60 μm. The thickness of the cured resin layer is preferably 2 to 30 μm, more preferably 3 to 30 μm, and still more preferably 5 to 20 μm. The thickness of the semi-cured resin layer is preferably 3 to 55 μm, more preferably 7 to 55 μm, and still more preferably 15 to 115 μm. This is because if the total thickness of the resin layer exceeds 120 μm, it may be difficult to produce an extremely thin multilayer printed wiring board, and if it is less than 5 μm, the following may occur: although it is easy to form an extremely thin multilayer printed wiring board, the insulating layer, i.e., the resin layer, between the circuits in the inner layer tends to be too thin, and the insulation between the circuits in the inner layer tends to be unstable. If the thickness of the cured resin layer is less than 2 μm, the surface roughness of the roughened surface of the copper foil may be considered. On the other hand, if the thickness of the cured resin layer exceeds 20 μm, the effect of the cured resin layer may not be particularly improved, and the total insulating layer thickness may become thick.

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

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

Further, as still another product form of the resin-coated copper foil with carrier, it is possible to produce the resin-coated copper foil without carrier by coating the resin layer on the extra thin copper layer, or on the heat-resistant layer, the rust-preventive layer, the chromate treatment layer, or the silane coupling treatment layer to be semi-cured, and then peeling off the carrier.

< 6. copper foil with carrier

Thus, a copper foil with a carrier, which comprises a copper foil carrier, a release layer laminated on the copper foil carrier, an extra thin copper layer laminated on the release layer, and an arbitrary resin layer, is produced. The use of the copper foil with a carrier itself is known, and for example, a surface of an extremely thin copper layer is bonded to an insulating substrate such as a paper base phenol resin, a paper base epoxy resin, a synthetic fiber cloth base epoxy resin, a glass cloth-paper composite base epoxy resin, a glass cloth-glass nonwoven fabric composite base epoxy resin, a glass cloth base epoxy resin, a polyester film, or a polyimide film, and thermocompression bonded thereto, and then the carrier is peeled off to form a copper-clad laminate, and the extremely thin copper layer bonded to the insulating substrate is etched into a target conductor pattern, and finally a printed wiring board is produced. Further, electronic components are mounted on the printed wiring board, thereby completing the printed wiring board. Hereinafter, some examples of the steps for manufacturing a printed wiring board using the copper foil with a carrier of the present invention will be described.

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

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

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

laminating the copper foil with carrier and the insulating substrate;

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

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

a step of providing a through hole and/or a blind hole in the resin layer exposed by removing the extra thin copper layer by etching or in the presence of the resin layer;

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

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

a step of providing a plating resist on the electroless plating layer;

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

providing a plating layer in the region where the circuit is formed from which the plating resist is removed;

removing the plating resist; and

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

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

laminating the copper foil with carrier and the insulating substrate;

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

a step of providing a plating resist on the electroless plating layer;

removing the plating resist; and

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

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

Therefore, in one embodiment of the method for manufacturing a printed wiring board of the present invention using the modified semi-additive method, the following steps are included:

laminating the copper foil with carrier and the insulating substrate;

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

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

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

forming a circuit by electroplating after providing the plating resist;

removing the plating resist; and

and removing the extremely thin copper layer exposed by removing the plating resist by rapid etching.

In another embodiment of the method for manufacturing a printed wiring board of the present invention using the improved semi-additive method, the following steps are included:

laminating the copper foil with carrier and the insulating substrate;

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

removing the plating resist; and

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

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

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

laminating the copper foil with carrier and the insulating substrate;

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

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

exposing the etching resist to form a circuit pattern;

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

removing the etching resist;

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

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

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

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

laminating the copper foil with carrier and the insulating substrate;

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

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

exposing the etching resist to form a circuit pattern;

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

and removing the etching resist.

In another embodiment of the method for manufacturing a printed wiring board of the present invention using a subtractive process, the steps of:

laminating the copper foil with carrier and the insulating substrate;

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

a step of providing an electroplated layer on the surface of the electroless plating layer on which the mask is not formed;

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

exposing the etching resist to form a circuit pattern;

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

and removing the etching resist.

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

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

First, as shown in fig. 2-a, a carrier-attached copper foil (layer 1) having an extra thin copper layer on the surface thereof, on which a roughened layer is formed, is prepared.

Next, as shown in FIG. 2-B, a photoresist is coated on the roughened layer of the extremely thin copper layer, exposed, and developed, and the photoresist is etched into a predetermined shape.

Then, as shown in fig. 2-C, after the circuit plating is formed, the photoresist is removed, thereby forming a circuit plating layer having a specific shape.

Then, as shown in fig. 3-D, an embedding resin is provided on the extra thin copper layer so as to cover the circuit plating layer (so as to embed the circuit plating layer) to build up a resin layer, and then another copper foil with a carrier (layer 2) is bonded from the extra thin copper layer side.

Then, as shown in FIG. 3E, the carrier is peeled from the carrier-attached copper foil of the 2 nd layer.

Then, as shown in FIG. 3-F, laser drilling is performed at a predetermined position of the resin layer to expose the circuit plating layer and form a blind via.

Subsequently, as shown in fig. 4-G, a copper-buried via fill is formed in the blind via.

Subsequently, as shown in FIG. 4-H, a circuit plating layer is formed on the via-hole filler in the manner shown in FIGS. 2-B and 2-C.

Subsequently, as shown in FIG. 4-I, the carrier was peeled off from the carrier-attached copper foil of the 1 st layer.

Then, as shown in fig. 5-J, the extremely thin copper layers on both surfaces are removed by rapid etching to expose the surface of the circuit plating layer in the resin layer.

Then, as shown in fig. 5-K, bumps are formed on the circuit plating layer in the resin layer, and copper pillars are formed on the solder. Thus, a printed wiring board using the carrier-attached copper foil of the present invention was produced.

The other carrier-attached copper foil (layer 2) may be the carrier-attached copper foil of the present invention, an existing carrier-attached copper foil, or a general copper foil. Further, 1-layer or multi-layer circuits may be formed on the circuits of the 2 nd layer shown in fig. 4-H, and the circuits may be formed by any of a semi-additive method, a subtractive method, a partial additive method, or a modified semi-additive method.

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

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

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

(1) The color difference Δ E ﹡ ab based on JIS Z8730 of the surface of the extremely thin copper layer or the roughening-treated layer or the heat-resistant layer or the rust-preventive layer or the chromate-treated layer or the silane-coupling-treated layer is 45 or more.

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

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

The color difference can be adjusted by roughening the surface of the extremely thin copper layer and providing a roughened layer. When the roughened layer is formed, the current density can be further increased (e.g., 40 to 60A/dm) as compared with the conventional one by using an electric field liquid containing at least one element selected from the group consisting of copper, nickel, cobalt, tungsten and molybdenum²) The processing time (for example, 0.1 to 1.3 seconds) is shortened to perform adjustment. When the roughening treatment layer is not provided on the surface of the extremely thin copper layer, the current density can be set to be lower than that of the conventional current density (0.1 to 1.3A/dm) on the surface of the extremely thin copper layer, the heat-resistant layer, the rust-proof layer, the chromate treatment layer, or the silane coupling treatment layer by using a plating bath in which the Ni concentration is 2 times or more as high as that of other elements²) And the treatment time (20-40 seconds) is increased by treating the Ni-plated alloy (such as Ni-W alloy, Ni-Co-P alloy and Ni-Zn alloy).

When the color difference Δ E ﹡ ab based on jis z8730 on the surface of the extra thin copper layer is 45 or more, when a circuit is formed on the surface of the extra thin copper layer with the carrier copper foil, for example, the contrast between the extra thin copper layer and the circuit becomes clear, and as a result, the visibility becomes good, and the alignment of the circuit can be performed with high accuracy. The color difference Δ E ﹡ ab of jis z8730 on the surface of the extremely thin copper layer is preferably 50 or more, more preferably 55 or more, and still more preferably 60 or more.

When the color difference of the surface of the extremely thin copper layer, the roughened layer, the heat-resistant layer, the rust-preventive layer, the chromate treatment layer, or the silane coupling layer is controlled as described above, the contrast with the circuit plating layer becomes clear, and the visibility is good. Therefore, in the manufacturing steps shown in fig. 2-C, for example, of the printed wiring board as described above, the circuit plating layer can be formed at a predetermined position with high accuracy. Further, according to the method for manufacturing a printed wiring board as described above, since the circuit plating layer is embedded in the resin layer, when the extremely thin copper layer is removed by rapid etching as shown in fig. 5-J, for example, the circuit plating layer is protected by the resin layer and the shape thereof is maintained, thereby facilitating the formation of a fine circuit. In addition, in order to protect the circuit plating layer with the resin layer, the migration resistance is improved, and the conduction of the wiring of the circuit is favorably suppressed. Therefore, a fine circuit is easily formed. Further, when the extremely thin copper layer is removed by rapid etching as shown in fig. 5-J and 5-K, the exposed surface of the circuit plating layer is formed in a shape recessed from the resin layer, so that it is easy to form bumps on the circuit plating layer, respectively, and further, to form copper pillars thereon, thereby improving the manufacturing efficiency.

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

Examples

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

1. Production of copper foil with carrier

< example 1 >

A long electrolytic copper foil (JTC manufactured by JX Nikkiso Metal Co., Ltd.) having a thickness of 35 μm was prepared as a copper foil carrier. The glossy surface of the copper foil was covered with the following stripsUnder the roll, a continuous plating line of a roll type was electroplated with a roll, thereby forming 4000. mu.g/dm²The deposited amount of Ni layer.

Ni layer

Nickel sulfate: 250 to 300g/L

Nickel chloride: 35-45 g/L

Nickel acetate: 10 to 20g/L

Trisodium citrate: 15 to 30g/L

Gloss agent: saccharin, butynediol, and the like

Sodium lauryl sulfate: 30 to 100ppm of

pH：4～6

Bath temperature: 50-70 DEG C

Current density: 3 to 15A/dm²

After water washing and acid washing, 11. mu.g/dm were placed on a roll-to-roll type continuous plating line²The attached amount of Cr layer was subjected to electrolytic chromate treatment under the following conditions to be attached to the Ni layer.

Electrolytic chromate treatment

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

pH：3～4

Liquid temperature: 50-60 DEG C

Current density: 0.1 to 2.6A/dm²

Coulomb amount: 0.5 to 30As/dm²

Then, electroplating was performed on the roll-to-roll continuous plating line under the following conditions to form an extremely thin copper layer having a thickness of 3 μm on the Cr layer, thereby producing a copper foil with a carrier. In this example, carrier-attached copper foils having extremely thin copper layers of thicknesses of 2, 5, and 10 μm were also produced, and the same evaluation as in the example in which the extremely thin copper layer had a thickness of 3 μm was performed. As a result, evaluation was the same regardless of the thickness.

Very thin copper layer

Copper concentration: 30 to 120g/L

H₂SO₄Concentration: 20 to 120g/L

Temperature of the electrolyte: 20-80 DEG C

Current density: 10 to 100A/dm²

Then, the surface of the extremely thin copper layer is subjected to the following roughening treatment 1, roughening treatment 2, rust prevention treatment, chromate treatment, and silane coupling treatment in this order.

Roughening treatment 1

(liquid composition 1)

Cu：10～30g/L

H₂SO₄：10～150g/L

W：0～50mg/L

Sodium lauryl sulfate: 0 to 50mg/L

As：0～200mg/L

(plating Condition 1)

Temperature: 30-70 DEG C

Current density: 25 to 110A/dm²

Coarsening coulomb quantity: 50 to 500As/dm²

Plating time: 0.5 to 20 seconds

Roughening treatment 2

(liquid composition 2)

Cu：20～80g/L

H₂SO₄：50～200g/L

(plating Condition 2)

Temperature: 30-70 DEG C

Current density: 5 to 50A/dm²

Coarsening coulomb quantity: 50 to 300As/dm²

Plating time: 1 to 60 seconds

Anti-rust treatment

(liquid composition)

NaOH：40～200g/L

NaCN：70～250g/L

CuCN：50～200g/L

Zn(CN)₂：2～100g/L

As₂O₃：0.01～1g/L

(liquid temperature)

40～90℃

(Current Condition)

Current density: 1 to 50A/dm²

Plating time: 1 to 20 seconds

Chromate treatment

K₂Cr₂O₇(Na₂Cr₂O₇Or CrO₃)：2～10g/L

NaOH or KOH: 10 to 50g/L

ZnOH or ZnSO₄·7H₂O：0.05～10g/L

pH：7～13

Bath temperature: 20-80 DEG C

Current density: 0.05 to 5A/dm²

Time: 5 to 30 seconds

Silane coupling treatment

Spraying 0.1-0.3 vol% 3-glycidoxypropyltrimethoxysilane aqueous solution, and drying and heating in air at 100-200 deg.C for 0.1-10 seconds.

< example 2 >

After an extremely thin copper layer was formed on a copper foil carrier under the same conditions as in example 1, the following roughening treatment 1, roughening treatment 2, rust-proofing treatment, chromate treatment, and silane coupling treatment were sequentially performed. The thickness of the extra thin copper foil was set to 3 μm.

Roughening treatment 1

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

Liquid temperature: 25 to 50 DEG C

Current density: 1 to 58A/dm²

Coulomb amount: 4 to 81As/dm²

Roughening treatment 2

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

pH：2～3

Liquid temperature: 30 to 50 DEG C

Current density: 24 to 50A/dm²

Coulomb amount: 34 to 48As/dm²

Anti-rust treatment

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

pH：2～3

Liquid temperature: 40-60 DEG C

Current density: 5 to 20A/dm²

Coulomb amount: 10 to 20As/dm²

Chromate treatment

pH：3～4

Liquid temperature: 50-60 DEG C

Current density: 0 to 2A/dm²(since the treatment is carried out by immersion chromate treatment, electroless plating can be carried out)

Coulomb amount: 0 to 2As/dm²(since the treatment is carried out by immersion chromate treatment, electroless plating can be carried out)

Silane coupling treatment

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

< example 3 >

After an extremely thin copper layer was formed on a copper foil carrier under the same conditions as in example 1, the following roughening treatment 1, roughening treatment 2, rust prevention treatment, chromate treatment, and silane coupling treatment were sequentially performed on the surface of the extremely thin copper layer. The thickness of the extra thin copper foil was set to 3 μm.

Roughening treatment 1

(liquid composition 1)

Cu：10～30g/L

H₂SO₄：10～150g/L

As：0～200mg/L

(plating Condition 1)

Temperature: 30-70 DEG C

Current density: 25 to 110A/dm²

Coarsening coulomb quantity: 50 to 500As/dm²

Plating time: 0.5 to 20 seconds

Roughening treatment 2

(liquid composition 2)

Cu：20～80g/L

H₂SO₄：50～200g/L

(plating Condition 2)

Temperature: 30-70 DEG C

Current density: 5 to 50A/dm²

Coarsening coulomb quantity: 50 to 300As/dm²

Plating time: 1 to 60 seconds

Anti-rust treatment

(liquid composition)

NaOH：40～200g/L

NaCN：70～250g/L

CuCN：50～200g/L

Zn(CN)₂：2～100g/L

As₂O₃：0.01～1g/L

(liquid temperature)

40～90℃

(Current Condition)

Current density: 1 to 50A/dm²

Plating time: 1 to 20 seconds

Chromate treatment

K₂Cr₂O₇(Na₂Cr₂O₇Or CrO₃)：2～10g/L

NaOH or KOH: 10 to 50g/L

ZnOH or ZnSO₄·7H₂O：0.05～10g/L

pH：7～13

Bath temperature: 20-80 DEG C

Current density: 0.05 to 5A/dm²

Time: 5 to 30 seconds

Silane coupling treatment

< example 4 >

After forming an Ni layer and a Cr layer on a copper foil carrier under the same conditions as in example 1, an extremely thin copper layer having a thickness of 3 μm was formed on the Cr layer by electroplating on a roll-to-roll continuous plating line under the following conditions, thereby producing a carrier-attached copper foil. In this example, carrier-attached copper foils having extremely thin copper layers of thicknesses of 2, 5, and 10 μm were also produced, and the same evaluation as in the example in which the extremely thin copper layer had a thickness of 3 μm was performed. As a result, the evaluation was almost the same regardless of the thickness.

Very thin copper layer

Copper concentration: 30 to 120g/L

H₂SO₄Concentration: 20 to 120g/L

Bis (3 sulfopropyl) disulfide concentration: 10 to 100ppm of

Stage 3 amine compound: 10 to 100ppm of

Chlorine: 10 to 100ppm of

Temperature of the electrolyte: 20-80 DEG C

Current density: 10 to 100A/dm²

Further, the following compounds can be used as the above-mentioned 3-stage amine compound.

[ chemical formula 11]

(in the above chemical formula, R₁And R₂Is selected from the group consisting of hydroxyalkyl, ether, aryl, aromatic substituted alkyl, unsaturated hydrocarbon, and alkyl. Here, R₁And R₂Are both methyl. )

The compound can be obtained, for example, by mixing a predetermined amount of Denacol Ex-314 made by Nagase Chemtex Co., Ltd with dimethylamine and reacting at 60 ℃ for 3 hours.

After an extremely thin copper layer is formed on a copper foil carrier, the following roughening treatment 1, roughening treatment 2, rust prevention treatment, chromate treatment, and silane coupling treatment are performed in this order.

Roughening treatment 1

Liquid temperature: 25 to 50 DEG C

Current density: 1 to 58A/dm²

Coulomb amount: 4 to 81As/dm²

Roughening treatment 2

pH：2～3

Liquid temperature: 30 to 50 DEG C

Current density: 24 to 50A/dm²

Coulomb amount: 34 to 48As/dm²

Anti-rust treatment

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

pH：2～3

Liquid temperature: 40-60 DEG C

Current density: 5 to 20A/dm²

Coulomb amount: 10 to 20As/dm²

Chromate treatment

pH：3～4

Liquid temperature: 50-60 DEG C

Silane coupling treatment

< example 5 >

After forming an Ni layer and a Cr layer on a copper foil carrier under the same conditions as in example 1, an extremely thin copper layer having a thickness of 3 μm was formed on the Cr layer by electroplating on a roll-to-roll continuous plating line under the following conditions, thereby producing a carrier-attached copper foil. In this example, carrier-attached copper foils having extremely thin copper layers of thicknesses of 2, 5, and 10 μm were also produced, and the same evaluation as in the example in which the extremely thin copper layer had a thickness of 3 μm was performed. As a result, the evaluation was almost the same regardless of the degree of post-processing.

Very thin copper layer

Copper concentration: 30 to 120g/L

H₂SO₄Concentration: 20 to 120g/L

Bis (3 sulfopropyl) disulfide concentration: 10 to 100ppm of

Stage 3 amine compound: 10 to 100ppm of

Chlorine: 10 to 100ppm of

Temperature of the electrolyte: 20-80 DEG C

Current density: 10 to 100A/dm²

[ chemical formula 12]

Roughening treatment 1

(liquid composition 1)

Cu：10～30g/L

H₂SO₄：10～150g/L

W：0.1～50mg/L

Sodium lauryl sulfate: 0.1-50 mg/L

As：0.1～200mg/L

(plating Condition 1)

Temperature: 30-70 DEG C

Current density: 25 to 110A/dm²

Coarsening coulomb quantity: 50 to 500As/dm²

Plating time: 0.5 to 20 seconds

Roughening treatment 2

(liquid composition 2)

Cu：20～80g/L

H₂SO₄：50～200g/L

(plating Condition 2)

Temperature: 30-70 DEG C

Current density: 5 to 50A/dm²

Coarsening coulomb quantity: 50 to 300As/dm²

Plating time: 1 to 60 seconds

Anti-rust treatment

(liquid composition)

NaOH：40～200g/L

NaCN：70～250g/L

CuCN：50～200g/L

Zn(CN)₂：2～100g/L

As₂O₃：0.01～1g/L

(liquid temperature)

40～90℃

(Current Condition)

Current density: 1 to 50A/dm²

Plating time: 1 to 20 seconds

Chromate treatment

K₂Cr₂O₇(Na₂Cr₂O₇Or CrO₃)：2～10g/L

NaOH or KOH: 10 to 50g/L

ZnOH or ZnSO₄·7H₂O：0.05～10g/L

pH：7～13

Bath temperature: 20-80 DEG C

Current density: 0.05 to 5A/dm²

Time: 5 to 30 seconds

Silane coupling treatment

< comparative example 1 >

After forming an Ni layer and a Cr layer on a copper foil carrier under the same conditions as in example 1, an extremely thin copper layer having a thickness of 3 μm was formed on the Cr layer by electroplating on a roll-to-roll continuous plating line under the following conditions, thereby producing a carrier-attached copper foil.

Very thin copper layer

Copper concentration: 30 to 120g/L

H₂SO₄Concentration: 20 to 120g/L

Temperature of the electrolyte: 20-80 DEG C

Current density: 5 to 9A/dm²

Roughening treatment 1

(liquid composition 1)

Cu：10～30g/L

H₂SO₄：10～150g/L

As：0～200mg/L

(plating Condition 1)

Temperature: 30-70 DEG C

Current density: 25 to 110A/dm²

Coarsening coulomb quantity: 50 to 500As/dm²

Plating time: 0.5 to 20 seconds

Roughening treatment 2

(liquid composition 2)

Cu：20～80g/L

H₂SO₄：50～200g/L

(plating Condition 2)

Temperature: 30-70 DEG C

Current density: 5 to 50A/dm²

Coarsening coulomb quantity: 50 to 300As/dm²

Plating time: 1 to 60 seconds

Anti-rust treatment

(liquid composition)

NaOH：40～200g/L

NaCN：70～250g/L

CuCN：50～200g/L

Zn(CN)₂：2～100g/L

As₂O₃：0.01～1g/L

(liquid temperature)

40～90℃

(Current Condition)

Current density: 1 to 50A/dm²

Plating time: 1 to 20 seconds

Chromate treatment

K₂Cr₂O₇(Na₂Cr₂O₇Or CrO₃): 2-10 g/L NaOH or KOH: 10 to 50g/L

ZnOH or ZnSO₄·7H₂O：0.05～10g/L pH：7～13

Bath temperature: 20-80 DEG C

Current density: 0.05 to 5A/dm²

Time: 5 to 30 seconds

Silane coupling treatment

< comparative example 2 >

Very thin copper layer

Copper concentration: 30 to 120g/L

H₂SO₄Concentration: 20 to 120g/L

Temperature of the electrolyte: 20-80 DEG C

Current density: 10 to 100A/dm²

Roughening treatment 1

(liquid composition 1)

Cu：10～30g/L

H₂SO₄：10～150g/L

W：0～50mg/L

Sodium lauryl sulfate: 0 to 50mg/L

As：0～200mg/L

(plating Condition 1)

Temperature: 30-70 DEG C

Current density: 25 to 110A/dm²

Coarsening coulomb quantity: 50 to 500As/dm²

Plating time: 40 seconds

Roughening treatment 2

(liquid composition 2)

Cu：20～80g/L

H₂SO₄：50～200g/L

(plating Condition 2)

Temperature: 30-70 DEG C

Current density: 5 to 50A/dm²

Coarsening coulomb quantity: 50 to 300As/dm²

Plating time: 80 seconds

Anti-rust treatment

(liquid composition)

NaOH：40～200g/L

NaCN：70～250g/L

CuCN：50～200g/L

Zn(CN)₂：2～100g/L

As₂O₃：0.01～1g/L

(liquid temperature)

40～90℃

(Current Condition)

Current density: 1 to 50A/dm²

Plating time: 1 to 20 seconds

Chromate treatment

K₂Cr₂O₇(Na₂Cr₂O₇Or CrO₃)：2～10g/L

NaOH or KOH: 10 to 50g/L

ZnOH or ZnSO₄·7H₂O：0.05～10g/L

pH：7～13

Bath temperature: 20-80 DEG C

Current density: 0.05 to 5A/dm²

Time: 5 to 30 seconds

Silane coupling treatment

2. Evaluation of characteristics of copper foil with Carrier

The carrier-attached copper foil obtained as described above was subjected to characteristic evaluation by the following method. The results are shown in Table 1.

(surface roughness)

The surface roughness (Ra, Rt, Rz, Ssk, Sku) of the extremely thin copper layer was measured under the following measurement conditions in accordance with JIS B0601-1994 for Ra, Rz, JIS B0601-2001 for Rt, JIS B0601-2001 for Ssk, Sku, ISO25178draft for Ssk, Sku using a noncontact roughness measuring instrument (LEXT OLS 4000 manufactured by Olympus).

< measurement Condition >

Cutting: is free of

Reference length: 257.9 μm

Area of reference: 66524 μm²

Measuring the ambient temperature: 23 to 25 DEG C

For comparison, the surface roughness (Ra, Rt, Rz) of the extremely thin copper layer was measured under the following measurement conditions in accordance with JIS B0601-1994(Ra, Rz) and JIS B0601-2001(Rt) using a contact roughness measuring instrument (Surfcorder SE-3C manufactured by Osaka research corporation).

< measurement Condition >

Cutting: 0.25mm

Reference length: 0.8mm

Measuring the ambient temperature: 23 to 25 DEG C

(surface area ratio)

The measurement was performed using a non-contact roughness measuring instrument (LEXT OLS 4000 manufactured by olympus) under the following measurement conditions. The surface area ratio is a measured area and an actual area, and the value of the actual area/area is defined as the surface area ratio. Here, the area refers to a measurement reference area, and the actual area refers to a surface area in the measurement reference area.

< measurement Condition >

Cutting: is free of

Reference length: 257.9 μm

Area of reference: 66524 μm²

Measuring the ambient temperature: 23 to 25 DEG C

(volume of roughened surface)

The measurement was performed under the following measurement conditions using a non-contact roughness measuring instrument (laser microscope, LEXT OLS 4000 manufactured by olympus). The volume of the roughened surface was measured as follows.

(1) The laser microscope is matched with the focusing height of the sample surface.

(2) The brightness was adjusted to adjust the overall illumination to about 80% of the saturation point.

(3) The laser microscope is brought close to the sample, and the place where the screen illumination is completely lost is set to zero.

(4) The laser microscope is moved away from the sample, and the upper limit height is set to the place where the screen illumination is completely disappeared.

(5) The volume of the roughened surface was measured from zero height to the upper limit.

< measurement Condition >

Cutting: is free of

Reference length: 257.9 μm

Area of reference: 66524 μm²

Measuring the ambient temperature: 23 to 25 DEG C

(migration)

Each carrier-attached copper foil andthe bismuth-based resin is then peeled off to remove the carrier foil. The thickness of the exposed extremely thin copper layer was formed to be 1.5 μm by soft etching. Thereafter, the cleaning and drying were performed, and then DF was laminated and coated on the extra thin copper layer (trade name RY-3625 manufactured by hitachi chemical company). At 15mJ/cm²The resist pattern was formed at various pitches shown in table 1 by performing exposure using a developer (sodium carbonate) at 38 ℃ for 1 minute with liquid jetting and shaking. Next, DF was peeled off from the plating solution (sodium hydroxide) at 15 μm by plating UP using copper sulfate plating (CUBRITE 21 manufactured by Eisengylolite). Thereafter, the extremely thin copper layer was removed by etching with a sulfuric acid-hydrogen peroxide etching solution to form wirings with various pitches shown in table 1.

The pitches shown in the table correspond to the total values of the lines and the spaces.

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

< measurement Condition >

Threshold value: lower than the initial resistance by 60 percent

Measuring time: 1000h

Voltage: 60V

Temperature: 85 deg.C

Relative humidity: 85% RH

TABLE 1-1

Tables 1 to 2

Claims

1. A copper foil with a carrier, comprising a copper foil carrier, a peeling layer laminated on the copper foil carrier, and an extra thin copper layer laminated on the peeling layer, wherein the extra thin copper layer is roughened so that the surface area ratio of the surface of the extra thin copper layer is 1.05 to 1.5, and each 66524 [ mu ] m of the surface of the extra thin copper layer²Area ofThe volume of the sample measured by a laser microscope is 300000 mu m³The above; wherein the surface area ratio is a value of an actual area/an area when the area and the actual area are measured by a laser microscope; the area refers to a measurement reference area, and the actual area refers to a surface area in the measurement reference area.

2. A copper foil with a carrier, comprising a copper foil carrier, a release layer laminated on the copper foil carrier, and an extra thin copper layer laminated on the release layer, wherein the extra thin copper layer is roughened, the surface area ratio of the surface of the extra thin copper layer is 1.05 to 1.5, and the skewness Ssk of the surface of the extra thin copper layer, which is measured by a non-contact roughness meter according to ISO25178draft, is-0.058 to 0.3; wherein the surface area ratio is a value of an actual area/an area when the area and the actual area are measured by a laser microscope; the area refers to a measurement reference area, and the actual area refers to a surface area in the measurement reference area.

3. A copper foil with a carrier, comprising a copper foil carrier, a release layer laminated on the copper foil carrier, and an extra thin copper layer laminated on the release layer, wherein the extra thin copper layer is roughened, the surface area ratio of the extra thin copper layer surface is 1.05 to 1.5, and the kurtosis Sku of the extra thin copper layer surface measured by a non-contact roughness meter according to ISO25178draft is 2.8 to 3.3; wherein the surface area ratio is a value of an actual area/an area when the area and the actual area are measured by a laser microscope; the area refers to a measurement reference area, and the actual area refers to a surface area in the measurement reference area.

4. The copper foil with carrier according to any one of claims 1 to 3, wherein the surface area ratio of the surface of the extra thin copper layer is 1.1 to 1.3.

5. The copper foil with carrier according to any one of claims 1 to 3, wherein each 66524 μm of the surface of the extra thin copper layer²The volume of the area measured by a laser microscope was 350000 μm³The above.

6. The copper foil with carrier according to any one of claims 1 to 3, wherein Ssk of the surface of the extra thin copper layer is-0.058 to 0.3.

7. The copper foil with carrier according to claim 4, wherein Ssk of the surface of the extra thin copper layer is-0.058 to 0.3.

8. The copper foil with carrier according to any one of claims 1 to 3, wherein the Sku on the surface of the extra thin copper layer is 2.8 to 3.3.

9. The copper foil with carrier according to claim 4, wherein the Sku on the surface of the extra thin copper layer is 2.8 to 3.3.

10. The copper foil with carrier according to claim 5, wherein the Sku on the surface of the extra thin copper layer is 2.8 to 3.3.

11. The copper foil with carrier according to claim 6, wherein the Sku on the surface of the extra thin copper layer is 2.8 to 3.3.

12. The copper foil with carrier according to claim 7, wherein the Sku on the surface of the extra thin copper layer is 2.8 to 3.3.

13. A copper-clad laminate produced using the copper foil with a carrier according to any one of claims 1 to 12.

14. A printed wiring board produced using the carrier-attached copper foil according to any one of claims 1 to 12.

15. A printed circuit board manufactured using the carrier-attached copper foil according to any one of claims 1 to 12.

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

a step of preparing the carrier-attached copper foil according to any one of claims 1 to 12 and an insulating substrate;

laminating the copper foil with carrier and the insulating substrate; and

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