WO2014042201A1 - キャリア付き銅箔 - Google Patents

キャリア付き銅箔 Download PDF

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Publication number
WO2014042201A1
WO2014042201A1 PCT/JP2013/074585 JP2013074585W WO2014042201A1 WO 2014042201 A1 WO2014042201 A1 WO 2014042201A1 JP 2013074585 W JP2013074585 W JP 2013074585W WO 2014042201 A1 WO2014042201 A1 WO 2014042201A1
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WO
WIPO (PCT)
Prior art keywords
layer
carrier
copper foil
resin
copper
Prior art date
Application number
PCT/JP2013/074585
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
倫也 古曳
友太 永浦
和彦 坂口
徹 千葉
Original Assignee
Jx日鉱日石金属株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=50278311&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2014042201(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Jx日鉱日石金属株式会社 filed Critical Jx日鉱日石金属株式会社
Priority to KR1020177011125A priority Critical patent/KR102050646B1/ko
Priority to KR1020157009363A priority patent/KR101766554B1/ko
Priority to CN201380046519.7A priority patent/CN104619889B/zh
Publication of WO2014042201A1 publication Critical patent/WO2014042201A1/ja
Priority to PH12015500529A priority patent/PH12015500529B1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/04—Wires; Strips; Foils
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • H05K3/025—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates by transfer of thin metal foil formed on a temporary carrier, e.g. peel-apart copper
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating

Definitions

  • the present invention relates to a copper foil with a carrier.
  • this invention relates to the copper foil with a carrier used as a material of a printed wiring board.
  • a printed wiring board is generally manufactured through a process of forming a copper-clad laminate by bonding an insulating substrate to copper foil and then forming a conductor pattern on the copper foil surface by etching.
  • higher density mounting of components and higher frequency of signals have progressed, and conductor patterns have become finer (fine pitch) and higher frequency than printed circuit boards. Response is required.
  • the ultrathin copper layer is etched away with a sulfuric acid-hydrogen peroxide etchant (MSAP: Modified-Semi-Additive-Process). Is formed.
  • MSAP sulfuric acid-hydrogen peroxide etchant
  • the peel strength between the ultrathin copper layer and the resin base material is mainly sufficient, and the peel strength Is required to be sufficiently retained after high-temperature heating, wet processing, soldering, chemical processing, and the like.
  • a method of increasing the peel strength between the ultrathin copper layer and the resin base material generally, a large amount of roughened particles are adhered on the ultrathin copper layer having a large surface profile (unevenness, roughness). The method is representative.
  • Patent Document 1 a copper foil with a carrier that is not subjected to a roughening treatment on the surface of an ultrathin copper layer is used as a copper foil with a carrier for use in a fine circuit including a semiconductor package substrate. It has been tried.
  • the adhesion (peeling strength) between the ultrathin copper layer not subjected to such roughening treatment and the resin is affected by the low profile (unevenness, roughness, roughness) of the general copper foil for printed wiring boards. There is a tendency to decrease when compared. Therefore, the further improvement is calculated
  • the surface of the ultrathin copper foil with carrier that contacts (adheres) the polyimide resin substrate is Ni. It is described that a layer or / and a Ni alloy layer are provided, a chromate layer is provided, a Cr layer or / and a Cr alloy layer are provided, a Ni layer and a chromate layer are provided, and a Ni layer and a Cr layer are provided. Has been.
  • the adhesion strength between the polyimide resin substrate and the ultra-thin copper foil with carrier is not roughened, or the desired adhesive strength is achieved while reducing the degree of the roughening treatment (miniaturization). It has gained. Further, it is described that the surface treatment is performed with a silane coupling agent or the rust prevention treatment is performed.
  • the present inventors have conducted intensive research, and as a result, the surface of the ultrathin copper layer is reduced in roughness, and finely roughened particles are formed in the ultrathin copper layer. It has been found that a roughened surface with low roughness can be formed. And it discovered that the said copper foil with a carrier was very effective for fine pitch formation.
  • the present invention has been completed on the basis of the above knowledge, and in one aspect, includes a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultrathin copper layer laminated on the release layer.
  • a copper foil with a carrier, the ultrathin copper layer is roughened, and the Rz of the surface of the ultrathin copper layer is 1.6 ⁇ m or less as measured by a non-contact type roughness meter. is there.
  • the present invention is a copper foil with a carrier comprising a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultrathin copper layer laminated on the release layer,
  • the ultrathin copper layer is roughened, and Ra on the surface of the ultrathin copper layer is a copper foil with a carrier as measured by a non-contact type roughness meter and is 0.3 ⁇ m or less.
  • the present invention is a copper foil with a carrier comprising a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultrathin copper layer laminated on the release layer.
  • the ultrathin copper layer is roughened, and Rt on the surface of the ultrathin copper layer is a copper foil with a carrier that is 2.3 ⁇ m or less as measured with a non-contact type roughness meter.
  • Rz on the surface of the ultrathin copper layer is 1.4 ⁇ m or less as measured by a non-contact type roughness meter.
  • Ra on the surface of the ultrathin copper layer is 0.25 ⁇ m or less as measured with a non-contact roughness meter.
  • the Rt of the ultrathin copper layer surface is 1.8 ⁇ m or less as measured by a non-contact type roughness meter.
  • the surface of the ultrathin copper layer has Ssk of ⁇ 0.3 to 0.3.
  • the surface of the ultrathin copper layer has a Sku of 2.7 to 3.3.
  • a copper foil carrier In yet another embodiment of the copper foil with a carrier according to the present invention, a copper foil carrier, a release layer laminated on the copper foil carrier, and an ultrathin copper layer laminated on the release layer were provided.
  • the ultrathin copper layer In the copper foil with a carrier, the ultrathin copper layer is roughened, and the surface area ratio of the surface of the ultrathin copper layer is 1.05 to 1.5.
  • the surface area ratio of the surface of the ultrathin copper layer is 1.05 to 1.5.
  • the volume per area 66524 ⁇ m 2 of the surface of the ultrathin copper layer is 300000 ⁇ m 3 or more.
  • the present invention is a copper clad laminate manufactured using the copper foil with a carrier according to the present invention.
  • the present invention is a printed wiring board manufactured using the carrier-attached copper foil according to the present invention.
  • the present invention is a printed circuit board manufactured using a copper foil with a carrier.
  • the printed wiring board manufacturing method includes a step of forming a circuit by any one of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method.
  • FIGS. 8A to 8C are schematic views of a cross section of a wiring board in a process up to circuit plating and resist removal according to a specific example of a method of manufacturing a printed wiring board using the carrier-attached copper foil of the present invention.
  • D to F are schematic views of the cross section of the wiring board in the process from the lamination of the resin and the second-layer copper foil with a carrier to the laser drilling according to a specific example of the method for manufacturing a printed wiring board using the copper foil with a carrier of the present invention. It is.
  • GI are schematic views of the cross section of the wiring board in the steps from via fill formation to first layer carrier peeling, according to a specific example of the method for producing a printed wiring board using the copper foil with carrier of the present invention.
  • J to K are schematic views of a cross section of a wiring board in steps from flash etching to bump / copper pillar formation according to a specific example of a method of manufacturing a printed wiring board using the carrier-attached copper foil of the present invention.
  • a copper foil is used as a carrier that can be used in the present invention.
  • the carrier is typically provided in the form of rolled copper foil or electrolytic copper foil.
  • the electrolytic copper foil is produced by electrolytic deposition of copper from a copper sulfate plating bath onto a drum of titanium or stainless steel, and the rolled copper foil is produced by repeating plastic working and heat treatment with a rolling roll.
  • the copper foil material is, for example, Sn-containing copper, Ag-containing copper, copper alloy added with Cr, Zr, Mg, etc., and Corson-based added with Ni, Si, etc. Copper alloys such as copper alloys can also be used.
  • a copper alloy foil is also included.
  • the thickness of the carrier that can be used in the present invention is not particularly limited, but may be appropriately adjusted to a thickness suitable for serving as a carrier, for example, 12 ⁇ m or more. However, if it is too thick, the production cost increases, so it is generally preferable that the thickness is 70 ⁇ m or less. Accordingly, the thickness of the carrier is typically 12-70 ⁇ m, more typically 18-35 ⁇ m.
  • a release layer is provided on the carrier.
  • a peeling layer it can be set as the arbitrary peeling layers known to those skilled in the art in copper foil with a carrier.
  • the release layer may be one or more of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, alloys thereof, hydrates thereof, oxides thereof, or organic substances. It is preferable to form with the layer containing.
  • the release layer may be composed of a plurality of layers.
  • the release layer is a single metal layer made of any one element of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, and Al elements from the carrier side, Or, an alloy layer made of one or more elements selected from the element group of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, and Al, and Cr, Ni, Co, It is comprised from the layer which consists of a hydrate or oxide of 1 or more elements selected from the element group of Fe, Mo, Ti, W, P, Cu, and Al.
  • the release layer is preferably composed of two layers of Ni and Cr.
  • the Ni layer is laminated in contact with the interface with the copper foil carrier and the Cr layer is in contact with the interface with the ultrathin copper layer.
  • the release layer can be obtained by, for example, wet plating such as electroplating, electroless plating, and immersion plating, or dry plating such as sputtering, CVD, and PDV. Electroplating is preferable from the viewpoint of cost.
  • Ultra-thin copper layer An ultrathin copper layer is provided on the release layer.
  • the ultra-thin copper layer can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfamate, copper cyanide, etc., and is used in general electrolytic copper foil with high current density. Since a copper foil can be formed, a copper sulfate bath is preferable.
  • the thickness of the ultrathin copper layer is not particularly limited, but is generally thinner than the carrier, for example, 12 ⁇ m or less. Typically 0.5 to 12 ⁇ m, more typically 2 to 5 ⁇ m.
  • a roughening treatment layer is provided by performing a roughening treatment, for example, for improving the adhesion to the insulating substrate.
  • the roughening treatment can be performed, for example, by forming roughened particles with copper or a copper alloy.
  • the roughening treatment layer is preferably composed of fine particles from the viewpoint of fine pitch formation.
  • the electroplating conditions for forming the roughened particles if the current density is increased, the copper concentration in the plating solution is decreased, or the amount of coulomb is increased, the particles tend to become finer.
  • the roughening layer is composed of electrodeposited grains made of any single element selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, cobalt, and zinc, or an alloy containing at least one of them. can do.
  • secondary particles and tertiary particles and / or a rust-preventing layer and / or a heat-resistant layer are formed of nickel, cobalt, copper, zinc alone or an alloy, and further, chromate treatment is performed on the surface thereof.
  • Surface treatment such as silane coupling treatment may be performed. That is, you may form 1 or more types of layers selected from the group which consists of a rust prevention layer, a heat-resistant layer, a chromate processing layer, and a silane coupling processing layer on the surface of a roughening processing layer.
  • a heat-resistant layer and / or a rust-preventing layer may be provided on the roughened layer
  • a chromate-treated layer may be provided on the heat-resistant layer and / or the rust-proof layer
  • a silane cup is provided on the chromate-treated layer.
  • a ring treatment layer can be provided.
  • the order of forming the heat-resistant layer, the rust-preventing layer, the chromate treatment layer, and the silane coupling treatment layer is not limited to each other, and these layers may be formed in any order on the roughening treatment layer. .
  • the surface of the ultrathin copper layer after various surface treatments such as roughening treatment is Rz (10-point average roughness) when measured with a non-contact type roughness meter. ) Of 1.6 ⁇ m or less is extremely advantageous from the viewpoint of fine pitch formation.
  • Rz is preferably 1.5 ⁇ m or less, more preferably 1.4 ⁇ m or less, even more preferably 1.35 ⁇ m or less, even more preferably 1.3 ⁇ m or less, and even more preferably 1.2 ⁇ m or less. More preferably 1.0 ⁇ m or less, still more preferably 0.8 ⁇ m or less, and even more preferably 0.6 ⁇ m or less.
  • Rz is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more, and further preferably 0.2 ⁇ m or more, because if the Rz is too small, the adhesion with the resin is reduced. Is more preferable.
  • the surface of the ultrathin copper layer after being subjected to various surface treatments such as roughening treatment is Ra (arithmetic mean roughness) when measured with a non-contact type roughness meter. Is 0.30 ⁇ m or less from the viewpoint of fine pitch formation. Ra is preferably 0.27 ⁇ m or less, more preferably 0.26 ⁇ m or less, more preferably 0.25 ⁇ m or less, more preferably 0.24 ⁇ m or less, more preferably 0.23 ⁇ m or less, and even more preferably 0.20 ⁇ m.
  • Ra is preferably 0.005 ⁇ m or more, more preferably 0.009 ⁇ m or more, 0.01 ⁇ m or more, or 0.02 ⁇ m or more, because if it becomes too small, the adhesive strength with the resin is reduced.
  • the thickness is more preferably 0.05 ⁇ m or more, and more preferably 0.10 ⁇ m or more.
  • the surface of the ultrathin copper layer after being subjected to various surface treatments such as roughening treatment has an Rt of 2.3 ⁇ m or less when measured with a non-contact type roughness meter. This is extremely advantageous from the viewpoint of fine pitch formation.
  • Rt is preferably 2.2 ⁇ m or less, preferably 2.1 ⁇ m or less, preferably 2.07 ⁇ m or less, more preferably 2.0 ⁇ m or less, more preferably 1.9 ⁇ m or less, and more preferably 1.8 ⁇ m or less. Even more preferably, it is 1.5 ⁇ m or less, still more preferably 1.2 ⁇ m or less, and even more preferably 1.0 ⁇ m or less.
  • Rt is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more, and more preferably 0.3 ⁇ m or more, since the adhesive strength with the resin decreases if Rt is too small.
  • it is 0.5 ⁇ m or more.
  • the surface of the ultrathin copper layer after various surface treatments such as roughening treatment has an Ssk (skewness) of ⁇ 0.3 to 0.3 when measured with a non-contact type roughness meter. Is preferable from the viewpoint of fine pitch formation.
  • 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 It is -0.060 or more, more preferably -0.058 or more, and further preferably 0 or more.
  • the upper limit of Ssk is preferably 0.2 or less.
  • the surface of the ultrathin copper layer after various surface treatments such as roughening treatment may have a Sku (Cultosis) of 2.7 to 3.3 when measured with a non-contact type roughness meter. It is preferable from the viewpoint of fine pitch formation.
  • the lower limit of Sku is preferably 2.8 or more, more preferably 2.9 or more, and more preferably 3.0 or more.
  • the upper limit of Sku is preferably 3.2 or less.
  • the roughness parameters of Rz and Ra on the surface of the ultrathin copper layer conform to JIS B0601-1994, and the roughness parameter of Rt conforms to JIS B0601-2001, the roughness of Ssk and Sku.
  • the parameters are measured with a non-contact type roughness meter in accordance with ISO 25178 draft.
  • the volume here refers to a value measured with a laser microscope and serves as an index for evaluating the volume of the roughened particles present on the roughened surface.
  • the volume is preferably 300,000 ⁇ m 3 or more, more preferably 350,000 ⁇ m 3 or more per area 66524 ⁇ m 2 of the roughened surface as measured by a laser microscope.
  • volume may preferably be 500000Myuemu 3 or less, and more preferably, 450000Myuemu 3 or less.
  • the surface area ratio here is a value measured by a laser microscope, and is a value of actual area / area when the area and the actual area are measured.
  • the area refers to the measurement reference area
  • the actual area refers to the surface area in the measurement reference area. If the surface area ratio becomes too large, the adhesion strength increases, but the etching amount increases and fine pitch cannot be formed. On the other hand, if the surface area ratio becomes too small, the adhesion strength cannot be secured, and is preferably 1.05 to 1.5. 0.07 to 1.47 is preferable, 1.09 to 1.4 is preferable, and 1.1 to 1.3 is more preferable.
  • a resin layer may be further provided on the surface of the ultrathin copper layer after various surface treatments such as roughening treatment.
  • a resin layer may be provided on the roughening treatment layer, the heat-resistant layer, the rust prevention 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, that is, an adhesive, or may be a semi-cured (B-stage) insulating resin layer for adhesion.
  • the semi-cured state (B stage state) is a state in which there is no sticky feeling even if the surface is touched with a finger, the insulating resin layer can be stacked and stored, and a curing reaction occurs when subjected to heat treatment. Including that.
  • the resin layer may contain a thermosetting resin or a thermoplastic resin.
  • the resin layer may include 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 may be, for example, International Publication No. WO2008 / 004399, International Publication No. WO2008 / 053878, International Publication No. WO2009 / 084533, JP-A-11-5828, JP-A-11-140281, Patent 3184485, International Publication. No. WO 97/02728, Japanese Patent No. 3676375, Japanese Patent Application Laid-Open No.
  • Japanese Patent No. 3612594 Japanese Patent Application Laid-Open No. 2002-179721, Japanese Patent Application Laid-Open No. 2002-309444, Japanese Patent Application Laid-Open No. 2003-302068, Japanese Patent No. 3992225, Japanese Patent Application Laid-Open No. -249739, Japanese Patent No. 4136509, Japanese Patent Application Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Application Laid-Open No. 2004-349654, Japanese Patent No. 4286060, Japanese Patent Application Laid-Open No. 2005-262506, Japanese Patent No. 4570070, and Japanese Patent Application Laid-Open No. 4570070. No. 5-53218, Japanese Patent No.
  • WO 2008/114858 International Publication Number WO 2009/008471, JP 2011-14727, International Publication Number WO 2009/001850, International Publication Number WO 2009/145179, International Publication Number Nos. WO2011 / 068157 and JP2013-19056 (resins, resin curing agents, compounds, curing accelerators, dielectrics, reaction catalysts, crosslinking agents, polymers, prepregs, skeletal materials, etc.) and / or You may form using the formation method and formation apparatus of a resin layer.
  • the type of the resin layer is not particularly limited.
  • epoxy resin polyimide resin, polyfunctional cyanate ester compound, maleimide compound, polymaleimide compound, maleimide resin, aromatic maleimide resin , Polyvinyl acetal resin, urethane resin, polyethersulfone (also referred to as polyethersulfone or polyethersulfone), polyethersulfone (also referred to as polyethersulfone or polyethersulfone) resin, aromatic polyamide resin, aromatic Polyamide resin polymer, rubber resin, polyamine, aromatic polyamine, polyamideimide resin, rubber modified epoxy resin, phenoxy resin, carboxyl group-modified acrylonitrile-butadiene resin, polyphenylene oxide, bismaleimide triazine Resins, thermosetting polyphenylene oxide resins, cyanate ester resins, carboxylic acid anhydrides, polyvalent carboxylic acid anhydrides, linear polymers having crosslinkable functional groups, polyphenylene ether resins, 2,2-
  • the epoxy resin has two or more epoxy groups in the molecule and can be used without any problem as long as it can be used for electric / electronic materials.
  • the epoxy resin is preferably an epoxy resin epoxidized using a compound having two or more glycidyl groups in the molecule.
  • bisphenol A type epoxy resin bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, brominated (brominated) epoxy Resin, phenol novolac type epoxy resin, naphthalene type epoxy resin, brominated bisphenol A type epoxy resin, orthocresol novolac type epoxy resin, rubber modified bisphenol A type epoxy resin, glycidylamine type epoxy resin, triglycidyl isocyanurate, N, N -Glycidyl amine compounds such as diglycidyl aniline, glycidyl ester compounds such as diglycidyl tetrahydrophthalate, phosphorus-containing epoxy resins, biphenyl type epoxy resins, One or two or more types selected from the group of phenyl novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetraphenylethane type epoxy resin can be used, or
  • the phosphorus-containing epoxy resin a known epoxy resin containing phosphorus can be used.
  • the phosphorus-containing epoxy resin is, for example, an epoxy resin obtained as a derivative from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide having two or more epoxy groups in the molecule. Is preferred.
  • the epoxy resin obtained as a derivative from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is converted to 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
  • a compound represented by the following chemical formula 1 (HCA-NQ) or chemical formula 2 (HCA-HQ) an epoxy resin is reacted with the OH group portion to obtain a phosphorus-containing epoxy resin. Is.
  • the phosphorus-containing epoxy resin which is the component E obtained using the above-mentioned compound as a raw material, is a mixture of one or two compounds having the structural formula shown in any one of the following chemical formulas 3 to 5. Is preferred. This is because the resin quality in a semi-cured state is excellent in stability, and at the same time, the flame retardant effect is high.
  • the brominated (brominated) epoxy resin a known brominated (brominated) epoxy resin can be used.
  • the brominated (brominated) epoxy resin is a brominated epoxy resin having the structural formula shown in Chemical formula 6 obtained as a derivative from tetrabromobisphenol A having two or more epoxy groups in the molecule. It is preferable to use one or two brominated epoxy resins having the structural formula shown in FIG.
  • maleimide resin aromatic maleimide resin, maleimide compound or polymaleimide compound
  • known maleimide resins aromatic maleimide resins, maleimide compounds or polymaleimide compounds
  • maleimide resin or aromatic maleimide resin or maleimide compound or polymaleimide compound 4,4′-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3′-dimethyl -5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1, It is possible to use 3-bis (3-maleimidophenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene and a polymer obtained
  • the maleimide resin may be an aromatic maleimide resin having two or more maleimide groups in the molecule, and an aromatic maleimide resin having two or more maleimide groups in the molecule and a polyamine or aromatic polyamine. Polymerization adducts obtained by polymerizing and may be used. As the polyamine or aromatic polyamine, known polyamines or aromatic polyamines can be used.
  • polyamine or aromatic polyamine m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 2,6-diaminopyridine, 4,4′-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, 4,4′-diaminodiphenyl ether, 4,4′-diamino-3-methyldiphenyl ether, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, bis (4-aminophenyl) phenylamine, m-xylenediamine, p-xylenediamine, 1,3-bis [4-aminophenoxy] benzene, 3-methyl-4,4 '
  • 1 type, or 2 or more types of well-known polyamine and / or aromatic polyamine or the above-mentioned polyamine or aromatic polyamine can be used.
  • a known phenoxy resin can be used as the phenoxy resin.
  • combined by reaction of bisphenol and a bivalent epoxy resin can be used as said phenoxy resin.
  • an epoxy resin a well-known epoxy resin and / or the above-mentioned epoxy resin can be used.
  • the bisphenol known bisphenols can be used, and bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, 4,4′-dihydroxybiphenyl, HCA (9,10-Dihydro-9-Oxa- Bisphenol obtained as an adduct of 10-phosphophenanthrene-10-oxide) and quinones such as hydroquinone and naphthoquinone can be used.
  • the linear polymer having a crosslinkable functional group a known linear polymer having a crosslinkable functional group can be used.
  • the linear polymer having a crosslinkable functional group preferably has a functional group that contributes to the curing reaction of an epoxy resin such as a hydroxyl group or a carboxyl group.
  • the linear polymer having a crosslinkable functional group is preferably soluble in an organic solvent having a boiling point of 50 ° C. to 200 ° C.
  • Specific examples of the linear polymer having a functional group mentioned here include polyvinyl acetal resin, phenoxy resin, polyethersulfone resin, polyamideimide resin and the like.
  • the resin layer may contain a crosslinking agent.
  • a known crosslinking agent can be used as the crosslinking agent.
  • a urethane-based resin can be used as the crosslinking agent.
  • a known rubber resin can be used as the rubber resin.
  • the rubbery resin is described as a concept including natural rubber and synthetic rubber.
  • the latter synthetic rubber includes styrene-butadiene rubber, butadiene rubber, butyl rubber, ethylene-propylene rubber, acrylonitrile butadiene rubber, acrylic rubber ( Acrylic ester copolymer), polybutadiene rubber, isoprene rubber and the like. Furthermore, when ensuring the heat resistance of the resin layer to be formed, it is also useful to select and use a synthetic rubber having heat resistance such as nitrile rubber, chloroprene rubber, silicon rubber, urethane rubber or the like. Regarding these rubber resins, it is desirable to have various functional groups at both ends in order to produce a copolymer by reacting with an aromatic polyamide resin or a polyamideimide resin.
  • CTBN carboxy group-terminated butadiene nitrile
  • C-NBR carboxy-modified nitrile butadiene rubber
  • a known polyimide amide resin can be used as the polyamide imide resin.
  • polyimide amide resin for example, trimellitic anhydride, benzophenonetetracarboxylic anhydride and vitorylene diisocyanate are heated in a solvent such as N-methyl-2-pyrrolidone and / or N, N-dimethylacetamide.
  • trimellitic anhydride, diphenylmethane diisocyanate and carboxyl group-terminated acrylonitrile-butadiene rubber in a solvent such as N-methyl-2-pyrrolidone and / or N, N-dimethylacetamide. What is obtained can be used.
  • a known rubber-modified polyamideimide resin can be used as the rubber-modified polyamideimide resin.
  • the rubber-modified polyamideimide resin is obtained by reacting a polyamideimide resin and a rubber resin.
  • the reaction of the polyamide-imide resin and the rubber resin is performed for the purpose of improving the flexibility of the polyamide-imide resin itself. That is, the polyamideimide resin and the rubber resin are reacted to replace a part of the acid component (cyclohexanedicarboxylic acid or the like) of the polyamideimide resin with the rubber component.
  • a known polyamideimide resin can be used as the polyamideimide resin.
  • As the rubber resin a known rubber resin or the aforementioned rubber resin can be used.
  • Solvents used for dissolving the polyamideimide resin and the rubbery resin when polymerizing the rubber-modified polyamideimide resin include dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, nitromethane, nitroethane, tetrahydrofuran , Cyclohexanone, methyl ethyl ketone, acetonitrile, ⁇ -butyrolactone and the like are preferably used alone or in combination.
  • a known phosphazene resin can be used as the phosphazene resin.
  • the phosphazene resin is a resin containing phosphazene having a double bond having phosphorus and nitrogen as constituent elements.
  • the phosphazene resin can dramatically improve the flame retardancy due to the synergistic effect of nitrogen and phosphorus in the molecule.
  • a known fluororesin can be used as the fluororesin.
  • fluororesin examples include PTFE (polytetrafluoroethylene (tetrafluoroethylene)), PFA (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer), FEP (tetrafluoroethylene / hexafluoropropylene copolymer (4.6).
  • PTFE polytetrafluoroethylene (tetrafluoroethylene)
  • PFA tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer
  • FEP tetrafluoroethylene / hexafluoropropylene copolymer (4.6).
  • a fluororesin composed of at least one thermoplastic resin selected from polysulfide and aromatic polyether and a fluororesin may be used.
  • the resin layer may contain a resin curing agent.
  • a known resin curing agent can be used as the resin curing agent.
  • resin curing agents include amines such as dicyandiamide, imidazoles and aromatic amines, phenols such as bisphenol A and brominated bisphenol A, novolaks such as phenol novolac resins and cresol novolac resins, and acid anhydrides such as phthalic anhydride.
  • amines such as dicyandiamide, imidazoles and aromatic amines
  • phenols such as bisphenol A and brominated bisphenol A
  • novolaks such as phenol novolac resins and cresol novolac resins
  • acid anhydrides such as phthalic anhydride.
  • the resin layer may contain one or more of the aforementioned resin curing agents. These curing agents are particularly effective for epoxy resins.
  • a specific example of the biphenyl type phenol resin is shown in Chemical Formula 8.
  • imidazoles can be used, such as 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 etc. are mentioned, These can be used individually or in mixture. Of these, imidazoles having the structural formula shown in Chemical Formula 10 below are preferably used.
  • the moisture absorption resistance of the semi-cured resin layer can be remarkably improved, and the long-term storage stability is excellent. This is because imidazoles function as a catalyst during curing of the epoxy resin and contribute as a reaction initiator that causes a self-polymerization reaction of the epoxy resin in the initial stage of the curing reaction.
  • amine resin curing agent known amines can be used.
  • the amine resin curing agent for example, the above-mentioned polyamines and aromatic polyamines can be used, and aromatic polyamines, polyamides, and these are obtained by polymerizing or condensing with epoxy resins or polyvalent carboxylic acids.
  • One or more selected from the group of amine adducts to be used may be used.
  • the resin curing agent for the amines examples include 4,4′-diaminodiphenylene sulfone, 3,3′-diaminodiphenylene sulfone, 4,4-diaminodiphenylel, 2,2-bis [4 It is preferable to use at least one of-(4-aminophenoxy) phenyl] propane and bis [4- (4-aminophenoxy) phenyl] sulfone.
  • the resin layer may contain a curing accelerator.
  • a known curing accelerator can be used as the curing accelerator.
  • tertiary amine, imidazole, urea curing accelerator and the like can be used.
  • the resin layer may include a reaction catalyst.
  • a known reaction catalyst can be used as the reaction catalyst. For example, finely pulverized silica or antimony trioxide can be used as a reaction catalyst.
  • the anhydride of the polyvalent carboxylic acid is preferably a component that contributes as a curing agent for the epoxy resin.
  • the anhydride of the polyvalent carboxylic acid is phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydroxyphthalic anhydride, hexahydroxyphthalic anhydride, methylhexahydroxyphthalic anhydride, nadine. Acid and methyl nadic acid are preferred.
  • 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 functional group polymerizable with an epoxy resin or a maleimide compound other than an acid group and a hydroxyl group.
  • the polyvinyl acetal resin may have a carboxyl group, an amino group or an unsaturated double bond introduced into the molecule.
  • the aromatic polyamide resin polymer include those obtained by reacting an aromatic polyamide resin and a rubber resin.
  • the aromatic polyamide resin is synthesized by condensation polymerization of an aromatic diamine and a dicarboxylic acid.
  • aromatic diamine As the aromatic diamine at this time, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylsulfone, m-xylenediamine, 3,3′-oxydianiline and the like are used.
  • dicarboxylic acid phthalic acid, isophthalic acid, terephthalic acid, fumaric acid or the like is used.
  • rubber resin to be reacted with the aromatic polyamide resin a known rubber resin or the aforementioned rubber resin can be used. This aromatic polyamide resin polymer is used for the purpose of not being damaged by under-etching by an etchant when etching a copper foil after being processed into a copper-clad laminate.
  • the resin layer is a cured resin layer (the “cured resin layer” means a cured resin layer) and a half in order from the copper foil side (that is, the ultrathin copper layer side of the copper foil with carrier).
  • the resin layer which formed the cured resin layer sequentially may be sufficient.
  • the cured resin layer may be composed of a resin component of any one of a polyimide resin, a polyamideimide resin, and a composite resin having a thermal expansion coefficient of 0 ppm / ° C. to 25 ppm / ° C.
  • a semi-cured resin layer having a coefficient of thermal expansion after curing of 0 ppm / ° C. to 50 ppm / ° C. may be provided on the cured resin layer.
  • the thermal expansion coefficient of the entire resin layer after the cured resin layer and the semi-cured resin layer are cured may be 40 ppm / ° C. or less.
  • the cured resin layer may have a glass transition temperature of 300 ° C. 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.
  • epoxy resin a known epoxy resin or an epoxy resin described in this specification can be used.
  • maleimide resins aromatic maleimide resins, linear polymers having crosslinkable functional groups, known maleimide resins, aromatic maleimide resins, linear polymers having crosslinkable functional groups, or the aforementioned maleimide resins.
  • An aromatic maleimide resin or a linear polymer having a crosslinkable functional group can be used.
  • the said cured resin layer is a polymeric polymer layer which has hardened
  • the polymer layer is preferably made of a resin having a glass transition temperature of 150 ° C. or higher so that it can withstand the solder mounting process.
  • the polymer polymer layer is preferably made of one or a mixture of two or more of a polyamide resin, a polyether sulfone resin, an aramid resin, a phenoxy resin, a polyimide resin, a polyvinyl acetal resin, and a polyamideimide resin.
  • the thickness of the polymer layer is preferably 3 ⁇ m to 10 ⁇ m.
  • the said high molecular polymer layer contains any 1 type, or 2 or more types of an epoxy resin, a maleimide-type resin, a phenol resin, and a urethane resin.
  • the semi-cured resin layer is preferably composed of an epoxy resin composition having a thickness of 10 ⁇ m to 50 ⁇ m.
  • the epoxy resin composition preferably contains the following components A to E.
  • Component A An epoxy resin having one 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 that have an epoxy equivalent of 200 or less and are liquid at room temperature.
  • B component High heat-resistant epoxy resin.
  • Component C Phosphorus-containing flame-retardant resin, which is any one of phosphorus-containing epoxy resin and phosphazene-based resin, or a mixture of these.
  • Component D A rubber-modified polyamideimide resin modified with a liquid rubber component having a property of being soluble in a solvent having a boiling point in the range of 50 ° C. to 200 ° C.
  • E component Resin curing agent.
  • the B component is a “high heat resistant epoxy resin” having a high so-called glass transition point Tg.
  • the “high heat-resistant epoxy resin” referred to here is preferably a polyfunctional epoxy resin such as a novolac-type epoxy resin, a cresol novolac-type epoxy resin, a phenol novolac-type epoxy resin, or a naphthalene-type epoxy resin.
  • the phosphorus-containing epoxy resin of component C the aforementioned phosphorus-containing epoxy resin can be used.
  • the phosphazene resin described above can be used as the C component phosphazene resin.
  • the rubber-modified polyamide-imide resin described above can be used as the rubber-modified polyamide-imide resin of component D.
  • the resin curing agent described above can be used as the E component resin curing agent.
  • a solvent is added to the resin composition shown above and used as a resin varnish to form a thermosetting resin layer as an adhesive layer of a printed wiring board.
  • the resin varnish is prepared by adding a solvent to the resin composition described above so that the resin solid content is in the range of 30 wt% to 70 wt%, and the resin flow when measured in accordance with MIL-P-13949G in the MIL standard.
  • a semi-cured resin film in the range of 5% to 35% can be formed.
  • the solvent a known solvent or the aforementioned solvent can be used.
  • the resin layer is a resin layer having a first thermosetting resin layer and a second thermosetting resin layer located on the surface of the first thermosetting resin layer in order from the copper foil side
  • the curable resin layer is formed of a resin component that does not dissolve in chemicals during desmear processing in the wiring board manufacturing process, and the second thermosetting resin layer dissolves in chemicals during desmear processing in the wiring board manufacturing process. Then, it may be formed using a resin that can be washed and removed.
  • the first thermosetting resin layer may be formed using a resin component obtained by mixing one or more of polyimide resin, polyethersulfone, and polyphenylene oxide.
  • the second thermosetting resin layer may be formed using an epoxy resin component.
  • the thickness t1 ( ⁇ m) of the first thermosetting resin layer is Rz ( ⁇ m) of the roughened surface roughness of the copper foil with carrier, and the thickness of the second thermosetting resin layer is t2 ( ⁇ m). Then, t1 is preferably a thickness that satisfies the condition of Rz ⁇ t1 ⁇ t2.
  • 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 for manufacturing a printed wiring board.
  • the skeleton material may include aramid fibers, glass fibers, or wholly aromatic polyester fibers.
  • the skeleton material is preferably an aramid fiber, a glass fiber, or a nonwoven fabric or woven fabric of wholly aromatic polyester fibers.
  • the wholly aromatic polyester fiber is preferably a wholly aromatic polyester fiber having a melting point of 300 ° C. or higher.
  • the wholly aromatic polyester fiber having a melting point of 300 ° C. or higher is a fiber produced using a resin called a so-called liquid crystal polymer, and the liquid crystal polymer includes 2-hydroxyl-6-naphthoic acid and p-hydroxybenzoic acid.
  • the main component is an acid polymer.
  • this wholly aromatic polyester fiber has a low dielectric constant and low dielectric loss tangent, it has excellent performance as a constituent material of an electrically insulating layer and can be used in the same manner as glass fiber and aramid fiber. is there.
  • the silane coupling agent process for the fiber which comprises the said nonwoven fabric and woven fabric.
  • a known amino-based or epoxy-based silane coupling agent or the aforementioned silane coupling agent can be used depending on the purpose of use.
  • the prepreg is a prepreg obtained by impregnating a thermosetting resin into a nonwoven fabric using an aramid fiber or glass fiber having a nominal thickness of 70 ⁇ m or less, or a skeleton material made of glass cloth having a nominal thickness of 30 ⁇ m or less. Also good.
  • the resin layer may include a dielectric (dielectric filler).
  • a dielectric (dielectric filler) is included in any of the above resin layers or resin compositions, it can be used for the purpose of forming the capacitor layer and increase the capacitance of the capacitor circuit.
  • the dielectric (dielectric filler) includes a composite oxide having a perovskite structure such as BaTiO3, SrTiO3, Pb (Zr-Ti) O3 (commonly called PZT), PbLaTiO3 / PbLaZrO (commonly known as PLZT), SrBi2Ta2O9 (commonly known as SBT), and the like.
  • Dielectric powder is used.
  • the dielectric (dielectric filler) may be powdery.
  • the powder characteristics of the dielectric (dielectric filler) are as follows. First, the particle size is 0.01 ⁇ m to 3.0 ⁇ m, preferably 0.02 ⁇ m to 2.0 ⁇ m. Must be in range.
  • the particle size referred to here is indirect in which the average particle size is estimated from the measured values of the laser diffraction scattering type particle size distribution measurement method and the BET method because the particles form a certain secondary aggregation state.
  • the accuracy is inferior in measurement, and it refers to the average particle diameter obtained by directly observing a dielectric (dielectric filler) with a scanning electron microscope (SEM) and image analysis of the SEM image. It is. In this specification, the particle size at this time is indicated as DIA.
  • the image analysis of the dielectric (dielectric filler) powder observed using a scanning electron microscope (SEM) in this specification is performed using an IP-1000PC manufactured by Asahi Engineering Co., Ltd. Circular particle analysis was performed with a threshold value of 10 and an overlapping degree of 20, and the average particle diameter DIA was obtained.
  • the resin layer containing the dielectric for forming the capacitor circuit layer having a low dielectric loss tangent is improved by improving the adhesion between the inner layer circuit surface of the inner layer core material and the resin layer containing the dielectric.
  • the copper foil with a carrier which has can be provided.
  • Examples of the resin and / or resin composition and / or compound contained in the resin layer include methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene, methanol, ethanol, propylene glycol monomethyl ether , Dimethylformamide, dimethylacetamide, cyclohexanone, ethyl cellosolve, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like to obtain a resin liquid (resin varnish).
  • MEK methyl ethyl ketone
  • cyclopentanone dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene
  • methanol ethanol
  • propylene glycol monomethyl ether Dimethylformamide, dimethylacetamide, cyclohexanone, ethyl cellosolve
  • the ultrathin copper layer or on the heat-resistant layer, rust-preventing layer, chromate-treated layer, or silane coupling agent layer, for example, it is applied by a roll coater method or the like, and then heat-dried as necessary. Removing the solvent Te and to B-stage.
  • a hot air drying furnace may be used for drying, and the drying temperature may be 100 to 250 ° C., preferably 130 to 200 ° C.
  • the resin layer composition is dissolved using a solvent, and the resin solid content is 3 wt% to 70 wt%, preferably 3 wt% to 60 wt%, preferably 10 wt% to 40 wt%, more preferably 25 wt% to 40 wt%.
  • the resin layer is preferably a semi-cured resin film having a resin flow in the range of 5% to 35% when measured according to MIL-P-13949G in the MIL standard. In this specification, the resin flow is based on MIL-P-13949G in the MIL standard. Four 10 cm square samples were sampled from a resin-coated copper foil with a resin thickness of 55 ⁇ m.
  • the copper foil with a carrier provided with the resin layer (copper foil with a carrier with resin) is superposed on the base material, and the whole is thermocompression bonded to thermally cure the resin layer, and then the carrier is peeled off.
  • the ultrathin copper layer is exposed (which is naturally the surface on the intermediate layer side of the ultrathin copper layer), and a predetermined wiring pattern is formed thereon.
  • this resin-attached copper foil with a carrier can reduce the number of prepreg materials used when manufacturing a multilayer printed wiring board.
  • the copper-clad laminate can be manufactured even if the resin layer is made thick enough to ensure interlayer insulation or no prepreg material is used. At this time, the surface smoothness can be further improved by undercoating the surface of the substrate with an insulating resin.
  • the material cost of the prepreg material is saved and the laminating process is simplified, which is economically advantageous.
  • the multilayer printed wiring board manufactured by the thickness of the prepreg material is used. The thickness is reduced, and there is an advantage that an extremely thin multilayer printed wiring board in which the thickness of one layer is 100 ⁇ m or less can be manufactured.
  • the thickness of this resin layer is preferably 0.1 to 120 ⁇ m.
  • the thickness of the resin layer is less than 0.1 ⁇ m, the adhesive strength is reduced, and when the copper foil with a carrier with the resin is laminated on the base material provided with the inner layer material without interposing the prepreg material, the circuit of the inner layer material It may be difficult to ensure interlayer insulation between the two.
  • the thickness of the resin layer is greater than 120 ⁇ m, it is difficult to form a resin layer having a target thickness in a single coating process, which may be economically disadvantageous because of extra material costs and man-hours.
  • the thickness of the resin layer is 0.1 ⁇ m to 5 ⁇ m, more preferably 0.5 ⁇ m to 5 ⁇ m, More preferably, the thickness is 1 ⁇ m to 5 ⁇ m in order to reduce the thickness of the multilayer printed wiring board.
  • the thickness of the resin layer is preferably 0.1 to 50 ⁇ m, more preferably 0.5 ⁇ m to 25 ⁇ m, and more preferably 1.0 ⁇ m to 15 ⁇ m. preferable.
  • the total resin layer thickness of the cured resin layer and the semi-cured resin layer is preferably 0.1 ⁇ m to 120 ⁇ m, preferably 5 ⁇ m to 120 ⁇ m, preferably 10 ⁇ m to 120 ⁇ m, and 10 ⁇ m to 60 ⁇ m. Are more preferred.
  • the thickness of the cured resin layer is preferably 2 ⁇ m to 30 ⁇ m, preferably 3 ⁇ m to 30 ⁇ m, and more preferably 5 to 20 ⁇ m.
  • the thickness of the semi-cured resin layer is preferably 3 ⁇ m to 55 ⁇ m, more preferably 7 ⁇ m to 55 ⁇ m, and even more preferably 15 to 115 ⁇ m. If the total resin layer thickness exceeds 120 ⁇ m, it may be difficult to produce a thin multilayer printed wiring board.
  • the total resin layer thickness is less than 5 ⁇ m, it is easy to form a thin multilayer printed wiring board, but an insulating layer between inner layer circuits This is because the resin layer may become too thin and the insulation between the circuits of the inner layer tends to become unstable. Moreover, when the cured resin layer thickness is less than 2 ⁇ m, it may be necessary to consider the surface roughness of the roughened copper foil surface. Conversely, if the cured resin layer thickness exceeds 20 ⁇ m, the effect of the cured resin layer may not be particularly improved, and the total insulating layer thickness becomes thick.
  • the thickness of the resin layer is 0.1 ⁇ m to 5 ⁇ m, in order to improve the adhesion between the resin layer and the copper foil with carrier, a heat-resistant layer and / or a rust-proof layer is formed on the ultrathin copper layer.
  • a heat-resistant layer and / or a rust-proof layer is formed on the ultrathin copper layer.
  • the thickness of the above-mentioned resin layer says the average value of the thickness measured by cross-sectional observation in arbitrary 10 points
  • this copper foil with a carrier with a resin, on the ultra-thin copper layer, or on the heat-resistant layer, rust-preventing layer, chromate-treated layer, or silane coupling-treated layer
  • the carrier can then be peeled off and manufactured in the form of a copper foil with resin without the carrier.
  • Copper foil with carrier a copper foil with a carrier provided with a copper foil carrier, a release layer laminated on the copper foil carrier, an ultrathin copper layer laminated on the release layer, and an optional resin layer is produced. Is done.
  • the method of using the copper foil with carrier itself is well known to those skilled in the art.
  • the surface of the ultra-thin copper layer is made of paper base phenol resin, paper base epoxy resin, synthetic fiber cloth base epoxy resin, glass cloth / paper composite. Base epoxy resin, glass cloth / glass nonwoven fabric composite base epoxy resin and glass cloth base epoxy resin, polyester film, polyimide film, etc.
  • the printed wiring board can be finally manufactured by etching the ultrathin copper layer adhered to the substrate into a desired conductor pattern. Furthermore, a printed circuit board is completed by mounting electronic components on the printed wiring board. Below, some examples of the manufacturing process of the printed wiring board using the copper foil with a carrier which concerns on this invention are shown.
  • a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention a step of laminating the copper foil with a carrier and an insulating substrate, and with the carrier
  • a copper-clad laminate is formed through a process of peeling the carrier of the copper foil with carrier, and then a semi-additive method, a modified semi-conductor
  • the semi-additive method refers to a method in which a thin electroless plating is performed on an insulating substrate or a copper foil seed layer, a pattern is formed, and then a conductive pattern is formed using electroplating and etching.
  • a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention Laminating the copper foil with carrier and an insulating substrate; After laminating the copper foil with carrier and the insulating substrate, the step of peeling the carrier of the copper foil with carrier, Removing all of the ultrathin copper layer exposed by peeling the carrier by a method such as etching or plasma using a corrosive solution such as acid, A step of providing a through hole or / and a blind via in the insulating substrate exposed by removing the ultrathin copper layer by etching and, if present, a resin layer; Performing a desmear process on the region including the through hole or / and the blind via, Providing an electroless plating layer for the region including the resin and the through hole or / and the blind via; Providing a plating resist on the electroless plating layer; Expos
  • a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention Laminating the copper foil with carrier and an insulating substrate; After laminating the copper foil with carrier and the insulating substrate, the step of peeling the carrier of the copper foil with carrier, Removing all of the ultrathin copper layer exposed by peeling the carrier by a method such as etching or plasma using a corrosive solution such as acid, A step of providing an electroless plating layer on the surface of the insulating substrate exposed by removing the ultrathin copper layer by etching or, if present, the resin layer; Providing a plating resist on the electroless plating layer; Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed; Providing an electroplating layer in a region where the circuit from which the plating resist has been removed is formed; Removing the plat
  • the modified semi-additive method is a method in which a metal foil is laminated on an insulating layer, a non-circuit forming part is protected by a plating resist, and the copper is thickened in the circuit forming part by electroplating, and then the resist is removed. Then, a method of forming a circuit on the insulating layer by removing the metal foil other than the circuit forming portion by (flash) etching is indicated.
  • the step of preparing the copper foil with carrier and the insulating substrate according to the present invention Laminating the copper foil with carrier and an insulating substrate; After laminating the copper foil with carrier and the insulating substrate, the step of peeling the carrier of the copper foil with carrier, Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier; Performing a desmear process on the region including the through hole or / and the blind via, Providing an electroless plating layer for the region including the through hole or / and the blind via; Providing a plating resist on the surface of the ultrathin copper layer exposed by peeling the carrier, Forming a circuit by electroplating after providing the plating resist; Removing the plating resist; Removing the ultra-thin copper layer exposed by removing the plating resist by flash etching; including.
  • the step of preparing the copper foil with carrier and the insulating substrate according to the present invention Laminating the copper foil with carrier and an insulating substrate; After laminating the copper foil with carrier and the insulating substrate, the step of peeling the carrier of the copper foil with carrier, Providing a plating resist on the exposed ultrathin copper layer by peeling off the carrier; Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed; Providing an electroplating layer in a region where the circuit from which the plating resist has been removed is formed; Removing the plating resist; Removing an ultrathin copper layer in a region other than the region where the circuit is formed by flash etching or the like; including.
  • the partial additive method means that a catalyst circuit is formed on a substrate provided with a conductor layer, and if necessary, a substrate provided with holes for through holes or via holes, and etched to form a conductor circuit. Then, after providing a solder resist or a plating resist as necessary, it refers to a method of manufacturing a printed wiring board by thickening through holes, via holes, etc. on the conductor circuit by electroless plating.
  • a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention Laminating the copper foil with carrier and an insulating substrate; After laminating the copper foil with carrier and the insulating substrate, the step of peeling the carrier of the copper foil with carrier, Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier; Performing a desmear process on the region including the through hole or / and the blind via, Applying catalyst nuclei to the region containing the through-holes and / or blind vias; Providing an etching resist on the surface of the ultrathin copper layer exposed by peeling the carrier, Exposing the etching resist to form a circuit pattern; Removing the ultrathin copper layer and the catalyst nucleus by a method such as etching or plasma using a corrosive solution such as
  • the subtractive method refers to a method of selectively removing unnecessary portions of the copper foil on the copper clad laminate by etching or the like to form a conductor pattern.
  • a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention Laminating the copper foil with carrier and an insulating substrate; After laminating the copper foil with carrier and the insulating substrate, the step of peeling the carrier of the copper foil with carrier, Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier; Performing a desmear process on the region including the through hole or / and the blind via, Providing an electroless plating layer for the region including the through hole or / and the blind via; Providing an electroplating layer on the surface of the electroless plating layer; Providing an etching resist on the surface of the electroplating layer or / and the ultrathin copper layer; Exposing the etching resist to form a circuit pattern; Removing the ultrathin copper layer and the electroless plating layer
  • a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention Laminating the copper foil with carrier and an insulating substrate; After laminating the copper foil with carrier and the insulating substrate, the step of peeling the carrier of the copper foil with carrier, Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier; Performing a desmear process on the region including the through hole or / and the blind via, Providing an electroless plating layer for the region including the through hole or / and the blind via; Forming a mask on the surface of the electroless plating layer; Providing an electroplating layer on the surface of the electroless plating layer on which no mask is formed; Providing an etching resist on the surface of the electroplating layer or / and the ultrathin copper layer; Exposing the etching resist to form a
  • ⁇ Through holes and / or blind vias and subsequent desmear steps may not be performed.
  • the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention is demonstrated in detail using drawing.
  • the carrier-attached copper foil having an ultrathin copper layer on which a roughened layer is formed will be described as an example.
  • the present invention is not limited thereto, and the carrier has an ultrathin copper layer on which a roughened layer is not formed.
  • the following method for producing a printed wiring board can be similarly performed using an attached copper foil.
  • a copper foil with a carrier (first layer) having an ultrathin copper layer having a roughened layer formed on the surface is prepared.
  • FIG. 2-A a copper foil with a carrier (first layer) having an ultrathin copper layer having a roughened layer formed on the surface is prepared.
  • a resist is applied on the roughened layer of the ultrathin copper layer, exposed and developed, and etched into a predetermined shape.
  • the resist is removed to form a circuit plating having a predetermined shape.
  • an embedded resin is provided on the ultrathin copper layer so as to cover the circuit plating (so that the circuit plating is buried), and then the resin layer is laminated, and then another carrier is attached.
  • a copper foil (second layer) is bonded from the ultrathin copper layer side.
  • the carrier is peeled off from the second layer copper foil with carrier.
  • the other carrier-attached copper foil may be the carrier-attached copper foil of the present invention, a conventional carrier-attached copper foil, or a normal copper foil.
  • one or more circuits may be formed on the second layer circuit shown in FIG. 4-H, and these circuits may be formed by a semi-additive method, a subtractive method, a partial additive method, or a modified semi-conductor method. You may carry out by any method of an 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.
  • substrate or resin layer since the copper foil with a carrier used for the 1st layer is supported and it becomes difficult to wrinkle, there exists an advantage that productivity improves.
  • the substrate any substrate can be used as long as it has an effect of supporting the carrier-attached copper foil used in the first layer.
  • the carrier, prepreg, resin layer or known carrier, prepreg, resin layer, metal plate, metal foil, inorganic compound plate, inorganic compound foil, organic compound plate, organic compound A foil can be used.
  • the timing for forming the substrate on the carrier side surface is not particularly limited, but it is necessary to form the substrate before peeling off the carrier.
  • it is preferably formed before the step of forming a resin layer on the ultrathin copper layer side surface of the copper foil with carrier, and the step of forming a circuit on the ultrathin copper layer side surface of the copper foil with carrier More preferably, it is formed before.
  • the copper foil with a carrier according to the present invention is preferably controlled so that the color difference on the surface of the ultrathin copper layer satisfies the following (1).
  • the “color difference on the surface of the ultrathin copper layer” means the color difference on the surface of the ultrathin copper layer, or the color difference on the surface of the surface treatment layer when various surface treatments such as roughening treatment are applied. . That is, in the copper foil with a carrier according to the present invention, the color difference of the surface of the ultrathin copper layer, the roughening treatment layer, the heat resistance layer, the rust prevention layer, the chromate treatment layer or the silane coupling layer satisfies the following (1). It is preferably controlled. (1)
  • the color difference ⁇ E * ab based on JISZ8730 on the surface of the ultrathin copper layer, the roughened layer, the heat resistant layer, the rust preventive layer, the chromate layer or the silane coupling layer is 45 or more.
  • the color differences ⁇ L, ⁇ a, and ⁇ b are respectively measured with a color difference meter, and are shown using the L * a * b color system based on JIS Z8730, taking into account black / white / red / green / yellow / blue. It is a comprehensive index and is expressed as ⁇ L: black and white, ⁇ a: reddish green, ⁇ b: yellow blue.
  • ⁇ E * ab is expressed by the following formula using these color differences.
  • the above-described color difference can be adjusted by increasing the current density when forming the ultrathin copper layer, decreasing the copper concentration in the plating solution, and increasing the linear flow rate of the plating solution.
  • the above-mentioned color difference can also be adjusted by performing a roughening process on the surface of an ultra-thin copper layer and providing a roughening process layer.
  • the current density is higher than that of the prior art (for example, 40 to 60 A) using an electrolytic solution containing copper and one or more elements selected from the group consisting of nickel, cobalt, tungsten, and molybdenum. / Dm 2 ) and the processing time can be shortened (for example, 0.1 to 1.3 seconds).
  • Ni alloy plating (for example, Ni—W alloy plating, Ni—Co—P alloy plating, Ni—Zn alloy plating) is applied to the surface of the treatment layer or the silane coupling treatment layer at a lower current density (0.1 to 1.. 3A / dm 2 ), and the processing time can be set long (20 to 40 seconds).
  • the contrast between the ultrathin copper layer and the circuit is As a result, the visibility is improved and the circuit can be accurately aligned.
  • the color difference ⁇ E * ab based on JISZ8730 on the surface of the ultrathin copper layer is preferably 50 or more, more preferably 55 or more, and even more preferably 60 or more.
  • the circuit plating can be accurately formed at a predetermined position. Further, according to the printed wiring board manufacturing method as described above, since the circuit plating is embedded in the resin layer, for example, removal of the ultrathin copper layer by flash etching as shown in FIG. At this time, the circuit plating is protected by the resin layer and the shape thereof is maintained, thereby facilitating the formation of a fine circuit.
  • the circuit plating is protected by the resin layer, the migration resistance is improved, and the continuity of the circuit wiring is satisfactorily suppressed. For this reason, formation of a fine circuit becomes easy. Also, as shown in FIGS. 5-J and 5-K, when the ultrathin copper layer is removed by flash etching, the exposed surface of the circuit plating has a shape recessed from the resin layer, so that bumps are formed on the circuit plating. In addition, copper pillars can be easily formed thereon, and the production efficiency is improved.
  • a known resin or prepreg can be used as the embedding resin (resin).
  • a prepreg that is a glass cloth impregnated with BT (bismaleimide triazine) resin or BT resin, an ABF film or ABF manufactured by Ajinomoto Fine Techno Co., Ltd. can be used.
  • the resin layer and / or resin and / or prepreg as described in this specification can be used for the embedding resin (resin).
  • Example 1 Production of copper foil with carrier ⁇ Example 1> As a copper foil carrier, a long electrolytic copper foil having a thickness of 35 ⁇ m (JTC manufactured by JX Nippon Mining & Metals) was prepared. An Ni layer having an adhesion amount of 4000 ⁇ g / dm 2 was formed on the shiny surface of the copper foil by electroplating using a roll-to-roll type continuous plating line under the following conditions.
  • JTC manufactured by JX Nippon Mining & Metals
  • Nickel sulfate 250-300 g / L Nickel chloride: 35 to 45 g / L Nickel acetate: 10-20g / L Trisodium citrate: 15-30 g / L Brightener: Saccharin, butynediol, etc.
  • Sodium dodecyl sulfate 30 to 100 ppm pH: 4-6 Bath temperature: 50-70 ° C Current density: 3 to 15 A / dm 2
  • Electrolytic chromate treatment Liquid composition: potassium dichromate 1-10 g / L, zinc 0-5 g / L pH: 3-4 Liquid temperature: 50-60 ° C Current density: 0.1 to 2.6 A / dm 2 Coulomb amount: 0.5-30 As / dm 2
  • an ultrathin copper layer having a thickness of 3 ⁇ m was formed on the Cr layer by electroplating under the following conditions to produce a copper foil with a carrier.
  • a copper foil with a carrier having an ultrathin copper layer thickness of 2, 5, and 10 ⁇ m was also manufactured and evaluated in the same manner as in the example of the ultrathin copper layer thickness of 3 ⁇ m. The result was the same regardless of the thickness.
  • Current density 10 to 100 A / dm 2
  • Example 2 After forming an ultrathin copper layer on the 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 performed in this order. went.
  • the thickness of the ultrathin copper foil was 3 ⁇ m.
  • Liquid composition Copper 10-20 g / L, sulfuric acid 50-100 g / L Liquid temperature: 25-50 ° C Current density: 1 to 58 A / dm 2 Coulomb amount: 4 to 81 As / dm 2 ⁇ Roughening 2 Liquid composition: Copper 10-20 g / L, Nickel 5-15 g / L, Cobalt 5-15 g / L pH: 2-3 Liquid temperature: 30-50 ° C Current density: 24 to 50 A / dm 2 Coulomb amount: 34 to 48 As / dm 2 ⁇ Rust prevention treatment Liquid composition: Nickel 5-20g / L, Cobalt 1-8g / L pH: 2-3 Liquid temperature: 40-60 ° C Current density: 5 to 20 A / dm 2 Coulomb amount: 10-20 As / dm 2 ⁇ Chromate treatment Liquid composition: Potassium dichromate 1-10g / L, Zinc 0-5g / L pH: 3
  • Example 3 After forming the ultrathin copper layer on the 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 The silane coupling treatment was performed in this order.
  • the thickness of the ultrathin copper foil was 3 ⁇ m.
  • Example 4 After forming the Ni layer and the Cr layer on the copper foil carrier under the same conditions as in Example 1, the ultrathin copper layer having a thickness of 3 ⁇ m was formed on the Cr layer on the roll-to-roll continuous plating line.
  • the copper foil with a carrier was manufactured by electroplating under the conditions described above.
  • a copper foil with a carrier having an ultrathin copper layer thickness of 2, 5, and 10 ⁇ m was also manufactured, and evaluated in the same manner as in the example with an ultrathin copper layer thickness of 3 ⁇ m. The result was almost the same regardless of the thickness.
  • R 1 And R 2 were both methyl groups.
  • the above compound can be obtained, for example, by mixing a predetermined amount of Deconal Ex-314 manufactured by Nagase ChemteX Corporation and dimethylamine and reacting at 60 ° C. for 3 hours.
  • Example 5 After forming the Ni layer and the Cr layer on the copper foil carrier under the same conditions as in Example 1, the ultrathin copper layer having a thickness of 3 ⁇ m was formed on the Cr layer on the roll-to-roll continuous plating line.
  • the copper foil with a carrier was manufactured by electroplating under the conditions described above.
  • a copper foil with a carrier having an ultrathin copper layer thickness of 2, 5, and 10 ⁇ m was also manufactured, and evaluated in the same manner as in the example with an ultrathin copper layer thickness of 3 ⁇ m. The result was almost the same regardless of the thickness.
  • R 1 And R 2 were both methyl groups.
  • the above compound can be obtained, for example, by mixing a predetermined amount of Deconal Ex-314 manufactured by Nagase ChemteX Corporation and dimethylamine and reacting at 60 ° C. for 3 hours. )
  • a contact-type roughness measuring device (contact roughness meter Surfcorder SE-3C manufactured by Kosaka Laboratory Ltd.) was used for JIS B0601-1994 (Ra, Rz) and JIS B0601-2001 (Rt).
  • the surface roughness (Ra, Rt, Rz) of the ultrathin copper layer was measured.
  • the volume of the roughened surface is measured as follows. (1) The laser microscope is adjusted to a height at which the surface of the sample is focused. (2) Adjust the brightness so that the overall illuminance is about 80% of the saturation point. (3) The laser microscope is brought close to the sample, and the point where the screen illuminance completely disappears is set to zero. (4) The laser microscope is moved away from the sample, and the point where the screen illuminance completely disappears is set as the upper limit height. (5) Measure the volume of the roughened surface from zero height to the upper limit.

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JP2014139336A (ja) 2014-07-31
CN109379858A (zh) 2019-02-22
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CN104619889A (zh) 2015-05-13
JP5481577B1 (ja) 2014-04-23
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MY188679A (en) 2021-12-22
CN104619889B (zh) 2018-10-09
KR102050646B1 (ko) 2019-11-29
PH12015500529B1 (en) 2015-04-27
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