WO2014042201A1 - Copper foil provided with carrier - Google Patents
Copper foil provided with carrier Download PDFInfo
- 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
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- layer
- carrier
- copper foil
- resin
- copper
- Prior art date
Links
- 0 C*(*O)SC=Cc(cc1)ccc1N=**1CCC(*)CC1 Chemical compound C*(*O)SC=Cc(cc1)ccc1N=**1CCC(*)CC1 0.000 description 5
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Classifications
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- 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
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- 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
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- 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.
Abstract
Description
本発明に係るキャリア付き銅箔と絶縁基板とを準備する工程、
前記キャリア付き銅箔と絶縁基板を積層する工程、
前記キャリア付き銅箔と絶縁基板を積層した後に、前記キャリア付き銅箔のキャリアを剥がす工程を経て銅張積層板を形成し、
その後、セミアディティブ法、サブトラクティブ法、パートリーアディティブ法又はモディファイドセミアディティブ法の何れかの方法によって、回路を形成する工程を含むプリント配線板の製造方法である。 In another aspect of the present invention,
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, a copper clad laminate is formed through a step of peeling the carrier of the copper foil with carrier,
Thereafter, 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.
本発明に用いることのできるキャリアとしては銅箔を使用する。キャリアは典型的には圧延銅箔や電解銅箔の形態で提供される。一般的には、電解銅箔は硫酸銅めっき浴からチタンやステンレスのドラム上に銅を電解析出して製造され、圧延銅箔は圧延ロールによる塑性加工と熱処理を繰り返して製造される。銅箔の材料としてはタフピッチ銅や無酸素銅といった高純度の銅の他、例えばSn入り銅、Ag入り銅、Cr、Zr又はMg等を添加した銅合金、Ni及びSi等を添加したコルソン系銅合金のような銅合金も使用可能である。なお、本明細書において用語「銅箔」を単独で用いたときには銅合金箔も含むものとする。 <1. Career>
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. In general, 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. In addition to high-purity copper such as tough pitch copper and oxygen-free copper, 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. In addition, when the term “copper foil” is used alone in this specification, a copper alloy foil is also included.
キャリアの上には剥離層を設ける。剥離層としては、キャリア付き銅箔において当業者に知られた任意の剥離層とすることができる。例えば、剥離層はCr、Ni、Co、Fe、Mo、Ti、W、P、Cu、Al、又はこれらの合金、またはこれらの水和物、またはこれらの酸化物、あるいは有機物の何れか一種以上を含む層で形成することが好ましい。剥離層は複数の層で構成されても良い。 <2. Release layer>
A release layer is provided on the carrier. As 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. For example, 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.
剥離層の上には極薄銅層を設ける。極薄銅層は、硫酸銅、ピロリン酸銅、スルファミン酸銅、シアン化銅等の電解浴を利用した電気めっきにより形成することができ、一般的な電解銅箔で使用され、高電流密度での銅箔形成が可能であることから硫酸銅浴が好ましい。極薄銅層の厚みは特に制限はないが、一般的にはキャリアよりも薄く、例えば12μm以下である。典型的には0.5~12μmであり、より典型的には2~5μmである。 <3. 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 μm or less. Typically 0.5 to 12 μm, more typically 2 to 5 μm.
極薄銅層の表面には、例えば絶縁基板との密着性を良好にすること等のために粗化処理を施すことで粗化処理層を設ける。粗化処理は、例えば、銅又は銅合金で粗化粒子を形成することにより行うことができる。粗化処理層は、ファインピッチ形成の観点から微細な粒子で構成されるのが好ましい。粗化粒子を形成する際の電気めっき条件について、電流密度を高く、めっき液中の銅濃度を低く、又は、クーロン量を大きくすると粒子が微細化する傾向にある。 <4. Surface treatment such as roughening>
On the surface of the ultrathin copper layer, 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. Regarding 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.
本発明に係るキャリア付銅箔においては、粗化処理等の各種表面処理を施した後の極薄銅層の表面に更に樹脂層を備えても良い。例えば、粗化処理層、耐熱層、防錆層、クロメート処理層、又はシランカップリング処理層の上に樹脂層を備えても良い。前記樹脂層は絶縁樹脂層であってもよい。 <5. Resin layer>
In the copper foil with a carrier according to the present invention, a resin layer may be further provided on the surface of the ultrathin copper layer after various surface treatments such as roughening treatment. For example, 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.
前記リン含有エポキシ樹脂として公知のリンを含有するエポキシ樹脂を用いることができる。また、前記リン含有エポキシ樹脂は例えば、分子内に2以上のエポキシ基を備える9,10-ジヒドロ-9-オキサ-10-ホスファフェナントレン-10-オキサイドからの誘導体として得られるエポキシ樹脂であることが好ましい。 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. Also, 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 a hydrogenated product of the epoxy resin or Halogenated substances can be used.
As 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.
前記ポリアミンまたは芳香族ポリアミンとしては、公知のポリアミンまたは芳香族ポリアミンを用いることができる。例えば、ポリアミンまたは芳香族ポリアミンとして、m-フェニレンジアミン、p-フェニレンジアミン、4,4’-ジアミノジシクロヘキシルメタン、1,4-ジアミノシクロヘキサン、2,6-ジアミノピリジン、4,4’-ジアミノジフェニルメタン、2,2-ビス(4-アミノフェニル)プロパン、4,4’-ジアミノジフェニルエーテル、4,4’-ジアミノ-3-メチルジフェニルエーテル、4,4’-ジアミノジフェニルスルフィド、4,4’-ジアミノベンゾフェノン、4,4’-ジアミノジフェニルスルホン、ビス(4-アミノフェニル)フェニルアミン、m-キシレンジアミン、p-キシレンジアミン、1,3-ビス[4-アミノフェノキシ]ベンゼン、3-メチル-4,4’-ジアミノジフェニルメタン、3,3’-ジエチル-4,4’-ジアミノジフェニルメタン、3,3’-ジクロロ-4,4’-ジアミノジフェニルメタン、2,2’,5,5’-テトラクロロ-4,4’-ジアミノジフェニルメタン、2,2-ビス(3-メチル-4-アミノフェニル)プロパン、2,2-ビス(3-エチル-4-アミノフェニル)プロパン、2,2-ビス(2,3-ジクロロ-4-アミノフェニル)プロパン、ビス(2,3-ジメチル-4-アミノフェニル)フェニルエタン、エチレンジアミンおよびヘキサメチレンジアミン、2,2-ビス(4-(4-アミノフェノキシ)フェニル)プロパン並びに上記化合物と、上記化合物またはその他の化合物とを重合させたポリマー等を用いることができる。また、公知のポリアミンおよび/または芳香族ポリアミンまたは前述のポリアミンまたは芳香族ポリアミンを一種または二種以上用いることができる。
前記フェノキシ樹脂としては公知のフェノキシ樹脂を用いることができる。また、前記フェノキシ樹脂として、ビスフェノールと2価のエポキシ樹脂との反応により合成されるものを用いることができる。エポキシ樹脂としては、公知のエポキシ樹脂および/または前述のエポキシ樹脂を用いることができる。
前記ビスフェノールとしては、公知のビスフェノールを使用することができ、またビスフェノールA、ビスフェノールF、ビスフェノールS、テトラブロモビスフェノールA、4,4’-ジヒドロキシビフェニル、HCA(9,10-Dihydro-9-Oxa-10-Phosphaphenanthrene-10-Oxide)とハイドロキノン、ナフトキノン等のキノン類との付加物として得られるビスフェノール等を使用することができる。
前記架橋可能な官能基を有する線状ポリマーとしては、公知の架橋可能な官能基を有する線状ポリマーを用いることができる。例えば、前記架橋可能な官能基を有する線状ポリマーは水酸基、カルボキシル基等のエポキシ樹脂の硬化反応に寄与する官能基を備えることが好ましい。そして、この架橋可能な官能基を有する線状ポリマーは、沸点が50℃~200℃の温度の有機溶剤に可溶であることが好ましい。ここで言う官能基を有する線状ポリマーを具体的に例示すると、ポリビニルアセタール樹脂、フェノキシ樹脂、ポリエーテルスルホン樹脂、ポリアミドイミド樹脂等である。
前記樹脂層は架橋剤を含んでもよい。架橋剤には、公知の架橋剤を用いることができる。架橋剤として例えばウレタン系樹脂を用いることができる。
前記ゴム性樹脂は公知のゴム性樹脂を用いることができる。例えば前記ゴム性樹脂とは、天然ゴム及び合成ゴムを含む概念として記載しており、後者の合成ゴムにはスチレン-ブタジエンゴム、ブタジエンゴム、ブチルゴム、エチレン-プロピレンゴム、アクリロニトリルブタジエンゴム、アクリルゴム(アクリル酸エステル共重合体)、ポリブタジエンゴム、イソプレンゴム等がある。更に、形成する樹脂層の耐熱性を確保する際には、ニトリルゴム、クロロプレンゴム、シリコンゴム、ウレタンゴム等の耐熱性を備えた合成ゴムを選択使用することも有用である。これらのゴム性樹脂に関しては、芳香族ポリアミド樹脂またはポリアミドイミド樹脂と反応して共重合体を製造するようにするため、両末端に種々の官能基を備えるものであることが望ましい。特に、CTBN(カルボキシ基末端ブタジエンニトリル)を用いることが有用である。また、アクリロニトリルブタジエンゴムの中でも、カルボキシル変性体であると、エポキシ樹脂と架橋構造を取り、硬化後の樹脂層のフレキシビリティを向上させることができる。カルボキシル変性体としては、カルボキシ基末端ニトリルブタジエンゴム(CTBN)、カルボキシ基末端ブタジエンゴム(CTB)、カルボキシ変性ニトリルブタジエンゴム(C‐NBR)を用いることができる。
前記ポリアミドイミド樹脂としては公知のポリイミドアミド樹脂を用いることができる。また、前記ポリイミドアミド樹脂としては例えば、トリメリット酸無水物、ベンゾフェノンテトラカルボン酸無水物及びビトリレンジイソシアネートをN-メチル-2-ピロリドン又は/及びN,N-ジメチルアセトアミド等の溶剤中で加熱することで得られる樹脂や、トリメリット酸無水物、ジフェニルメタンジイソシアネート及びカルボキシル基末端アクリロニトリル-ブタジエンゴムをN-メチル-2-ピロリドン又は/及びN,N-ジメチルアセトアミド等の溶剤中で加熱することで得られるものを用いることができる。
前記ゴム変成ポリアミドイミド樹脂として、公知のゴム変成ポリアミドイミド樹脂を用いることができる。ゴム変成ポリアミドイミド樹脂は、ポリアミドイミド樹脂とゴム性樹脂とを反応させて得られるものである。ポリアミドイミド樹脂とゴム性樹脂とを反応させて用いるのは、ポリアミドイミド樹脂そのものの柔軟性を向上させる目的で行う。すなわち、ポリアミドイミド樹脂とゴム性樹脂とを反応させ、ポリアミドイミド樹脂の酸成分(シクロヘキサンジカルボン酸等)の一部をゴム成分に置換するのである。ポリアミドイミド樹脂には公知のポリアミドイミド樹脂を用いることができる。また、ゴム性樹脂には公知のゴム性樹脂または前述のゴム性樹脂を用いることができる。ゴム変成ポリアミドイミド樹脂を重合させる際に、ポリアミドイミド樹脂とゴム性樹脂との溶解に使用する溶剤には、ジメチルホルムアミド、ジメチルアセトアミド、N-メチル-2-ピロリドン、ジメチルスルホキシド、ニトロメタン、ニトロエタン、テトラヒドロフラン、シクロヘキサノン、メチルエチルケトン、アセトニトリル、γ-ブチロラクトン等を、1種又は2種以上を混合して用いることが好ましい。
前記フォスファゼン系樹脂として、公知のフォスファゼン系樹脂を用いることができる。フォスファゼン系樹脂は、リン及び窒素を構成元素とする二重結合を持つフォスファゼンを含む樹脂である。フォスファゼン系樹脂は、分子中の窒素とリンの相乗効果により、難燃性能を飛躍的に向上させることができる。また、9,10-ジヒドロ-9-オキサ-10-ホスファフェナントレン-10-オキサイド誘導体と異なり、樹脂中で安定して存在し、マイグレーションの発生を防ぐ効果が得られる。
前記フッ素樹脂として、公知のフッ素樹脂を用いることができる。また、フッ素樹脂として例えばPTFE(ポリテトラフルオロエチレン(4フッ化))、PFA(テトラフルオロエチレン・パーフルオロアルキルビニルエーテル共重合体)、FEP(テトラフルオロエチレン・ヘキサフルオロプロピレン共重合体(4.6フッ化))、ETFE(テトラフルオロエチレン・エチレン共重合体)、PVDF(ポリビニリデンフルオライド(2フッ化))、PCTFE(ポリクロロトリフルオロエチレン(3フッ化))、ポリアリルスルフォン、芳香族ポリスルフィドおよび芳香族ポリエーテルの中から選ばれるいずれか少なくとも1種の熱可塑性樹脂とフッ素樹脂とからなるフッ素樹脂等を用いてもよい。
また、前記樹脂層は樹脂硬化剤を含んでもよい。樹脂硬化剤としては公知の樹脂硬化剤を用いることができる。例えば樹脂硬化剤としてはジシアンジアミド、イミダゾール類、芳香族アミン等のアミン類、ビスフェノールA、ブロム化ビスフェノールA等のフェノール類、フェノールノボラック樹脂及びクレゾールノボラック樹脂等のノボラック類、無水フタル酸等の酸無水物、ビフェニル型フェノール樹脂、フェノールアラルキル型フェノール樹脂等を用いることができる。また、前記樹脂層は前述の樹脂硬化剤の1種又は2種以上を含んでもよい。これらの硬化剤はエポキシ樹脂に特に有効である。
前記ビフェニル型フェノール樹脂の具体例を化8に示す。
As the polyamine or aromatic polyamine, known polyamines or aromatic polyamines can be used. For example, as 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 ' -Diaminodiphenylmethane, 3,3'-diethyl-4 4′-diaminodiphenylmethane, 3,3′-dichloro-4,4′-diaminodiphenylmethane, 2,2 ′, 5,5′-tetrachloro-4,4′-diaminodiphenylmethane, 2,2-bis (3- Methyl-4-aminophenyl) propane, 2,2-bis (3-ethyl-4-aminophenyl) propane, 2,2-bis (2,3-dichloro-4-aminophenyl) propane, bis (2,3 -Dimethyl-4-aminophenyl) phenylethane, ethylenediamine and hexamethylenediamine, 2,2-bis (4- (4-aminophenoxy) phenyl) propane and the above compound were polymerized with the above compound or other compounds A polymer or the like can be used. Moreover, 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. Moreover, what is synthesize | combined by reaction of bisphenol and a bivalent epoxy resin can be used as said phenoxy resin. As an epoxy resin, a well-known epoxy resin and / or the above-mentioned epoxy resin can be used.
As 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.
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 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. For example, a urethane-based resin can be used as the crosslinking agent.
A known rubber resin can be used as the rubber resin. For example, 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. In particular, it is useful to use CTBN (carboxy group-terminated butadiene nitrile). Moreover, among acrylonitrile butadiene rubbers, a carboxyl-modified product can take a crosslinked structure with an epoxy resin and improve the flexibility of the cured resin layer. As the carboxyl-modified product, carboxy group-terminated nitrile butadiene rubber (CTBN), carboxy group-terminated butadiene rubber (CTB), and carboxy-modified nitrile butadiene rubber (C-NBR) can be used.
A known polyimide amide resin can be used as the polyamide imide resin. In addition, as the 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. By heating the resin obtained in this way, 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, γ-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. In addition, unlike 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives, they exist stably in the resin, and an effect of preventing the occurrence of migration can be obtained.
A known fluororesin can be used as the fluororesin. Examples of the fluororesin include PTFE (polytetrafluoroethylene (tetrafluoroethylene)), PFA (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer), FEP (tetrafluoroethylene / hexafluoropropylene copolymer (4.6). Fluoride)), ETFE (tetrafluoroethylene / ethylene copolymer), PVDF (polyvinylidene fluoride (difluoride)), PCTFE (polychlorotrifluoroethylene (trifluoride)), polyallylsulfone, aromatic 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. For example, 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. Products, biphenyl type phenol resins, phenol aralkyl type phenol resins and the like can be used. 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.
また、中でも、以下の化10に示す構造式を備えるイミダゾール類を用いる事が好ましい。この化10に示す構造式のイミダゾール類を用いることで、半硬化状態の樹脂層の耐吸湿性を顕著に向上でき、長期保存安定性に優れる。イミダゾール類は、エポキシ樹脂の硬化に際して触媒的な働きを行うものであり、硬化反応の初期段階において、エポキシ樹脂の自己重合反応を引き起こす反応開始剤として寄与するからである。
Of these, imidazoles having the structural formula shown in Chemical Formula 10 below are preferably used. By using the imidazole having the structural formula shown in Chemical Formula 10, 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.
前記樹脂層は硬化促進剤を含んでもよい。硬化促進剤としては公知の硬化促進剤を用いることができる。例えば、硬化促進剤としては、3級アミン、イミダゾール、尿素系硬化促進剤等を用いることができる。
前記樹脂層は反応触媒を含んでもよい。反応触媒としては公知の反応触媒を用いることができる。例えば反応触媒として微粉砕シリカ、三酸化アンチモン等を用いることができる。
The resin layer may contain a curing accelerator. A known curing accelerator can be used as the curing accelerator. For example, 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.
前記ポリビニルアセタール樹脂は酸基および水酸基以外のエポキシ樹脂またはマレイミド化合物と重合可能な官能基を有してもよい。また、前記ポリビニルアセタール樹脂はその分子内にカルボキシル基、アミノ基または不飽和二重結合を導入したものであってもよい。
前記芳香族ポリアミド樹脂ポリマーとしては、芳香族ポリアミド樹脂とゴム性樹脂とを反応させて得られるものが挙げられる。ここで、芳香族ポリアミド樹脂とは、芳香族ジアミンとジカルボン酸との縮重合により合成されるものである。このときの芳香族ジアミンには、4,4’-ジアミノジフェニルメタン、3,3’-ジアミノジフェニルスルホン、m-キシレンジアミン、3,3’-オキシジアニリン等を用いる。そして、ジカルボン酸には、フタル酸、イソフタル酸、テレフタル酸、フマル酸等を用いる。
前記芳香族ポリアミド樹脂と反応させる前記ゴム性樹脂とは、公知のゴム性樹脂または前述のゴム性樹脂を用いることができる。
この芳香族ポリアミド樹脂ポリマーは、銅張積層板に加工した後の銅箔をエッチング加工する際に、エッチング液によりアンダーエッチングによる損傷を受けないことを目的に用いたものである。 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.
Examples of the aromatic polyamide resin polymer include those obtained by reacting an aromatic polyamide resin and a rubber resin. Here, the aromatic polyamide resin is synthesized by condensation polymerization of an aromatic diamine and a dicarboxylic acid. As the aromatic diamine at this time, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylsulfone, m-xylenediamine, 3,3′-oxydianiline and the like are used. As the dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid or the like is used.
As the 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.
また、前記高分子ポリマー層は、エポキシ樹脂、マレイミド系樹脂、フェノール樹脂、ウレタン樹脂のいずれか1種又は2種以上を含むことが好ましい。また、前記半硬化樹脂層は厚さが10μm~50μmのエポキシ樹脂組成物で構成されていることが好ましい。 Moreover, when providing the copper foil with a carrier which has a resin layer suitable for a three-dimensional molded printed wiring board manufacture use, it is preferable that the said cured resin layer is a polymeric polymer layer which has hardened | cured flexibility. 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 μm to 10 μm.
Moreover, it is preferable that the said high molecular polymer layer contains any 1 type, or 2 or more types of 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 μm to 50 μm.
A成分: エポキシ当量が200以下で、室温で液状のビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールAD型エポキシ樹脂の群から選ばれる1種又は2種以上からなるエポキシ樹脂。
B成分: 高耐熱性エポキシ樹脂。
C成分: リン含有エポキシ系樹脂、フォスファゼン系樹脂のいずれか1種又はこれらを混合した樹脂であるリン含有難燃性樹脂。
D成分: 沸点が50℃~200℃の範囲にある溶剤に可溶な性質を備える液状ゴム成分で変成したゴム変成ポリアミドイミド樹脂。
E成分: 樹脂硬化剤。 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.
C成分のリン含有エポキシ樹脂として、前述のリン含有エポキシ樹脂を用いることができる。また、C成分のフォスファゼン系樹脂として前述のフォスファゼン系樹脂を用いることができる。
D成分のゴム変成ポリアミドイミド樹脂として、前述のゴム変成ポリアミドイミド樹脂を用いることができる。E成分の樹脂硬化剤として、前述の樹脂硬化剤を用いることができる。 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.
As 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.
なお、前記不織布及び織布を構成する繊維は、その表面の樹脂との濡れ性を向上させるため、シランカップリング剤処理を施す事が好ましい。このときのシランカップリング剤は、使用目的に応じて公知のアミノ系、エポキシ系等のシランカップリング剤または前述のシランカップリング剤を用いることができる。 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. Since 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.
In addition, in order to improve the wettability with the resin of the surface, it is preferable to perform the silane coupling agent process for the fiber which comprises the said nonwoven fabric and woven fabric. As the silane coupling agent at this time, 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.
前記樹脂層は誘電体(誘電体フィラー)を含んでもよい。
上記いずれかの樹脂層または樹脂組成物に誘電体(誘電体フィラー)を含ませる場合には、キャパシタ層を形成する用途に用い、キャパシタ回路の電気容量を増大させることができるのである。この誘電体(誘電体フィラー)には、BaTiO3、SrTiO3、Pb(Zr-Ti)O3(通称PZT)、PbLaTiO3・PbLaZrO(通称PLZT)、SrBi2Ta2O9(通称SBT)等のペブロスカイト構造を持つ複合酸化物の誘電体粉を用いる。 (When the resin layer contains a dielectric (dielectric filler))
The resin layer may include a dielectric (dielectric filler).
In the case where 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.
上述の実施の形態により、当該内層コア材の内層回路表面と誘電体を含む樹脂層との密着性を向上させ、低い誘電正接を備えるキャパシタ回路層を形成するための誘電体を含む樹脂層を有するキャリア付銅箔を提供することができる。 The dielectric (dielectric filler) may be powdery. When the dielectric (dielectric filler) is powdery, the powder characteristics of the dielectric (dielectric filler) are as follows. First, the particle size is 0.01 μm to 3.0 μm, preferably 0.02 μm to 2.0 μm. 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. It cannot be used because 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. In addition, 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.
According to the above-described embodiment, 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.
また、前記樹脂層はMIL規格におけるMIL-P-13949Gに準拠して測定したときのレジンフローが5%~35%の範囲にある半硬化樹脂膜であることが好ましい。
本件明細書において、レジンフローとは、MIL規格におけるMIL-P-13949Gに準拠して、樹脂厚さを55μmとした樹脂付銅箔から10cm角試料を4枚サンプリングし、この4枚の試料を重ねた状態(積層体)でプレス温度171℃、プレス圧14kgf/cm2、プレス時間10分の条件で張り合わせ、そのときの樹脂流出重量を測定した結果から数1に基づいて算出した値である。 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). On 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. For example, 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%. It is good also as a resin liquid. In addition, it is most preferable at this stage from an environmental standpoint to dissolve using a mixed solvent of methyl ethyl ketone and cyclopentanone. It is preferable to use a solvent having a boiling point in the range of 50 ° C. to 200 ° C.
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 μm. It is a value calculated based on Equation 1 from the result of measuring the resin outflow weight at the time of laminating under the conditions of a press temperature of 171 ° C., a press pressure of 14 kgf / cm 2 and a press time of 10 minutes in a stacked state (laminate). .
この樹脂層の厚みは0.1~120μmであることが好ましい。 In addition, when the prepreg material is not used, the material cost of the prepreg material is saved and the laminating process is simplified, which is economically advantageous. Moreover, 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 μm or less can be manufactured.
The thickness of this resin layer is preferably 0.1 to 120 μm.
なお、樹脂層を有するキャリア付銅箔が極薄の多層プリント配線板を製造することに用いられる場合には、前記樹脂層の厚みを0.1μm~5μm、より好ましくは0.5μm~5μm、より好ましくは1μm~5μmとすることが、多層プリント配線板の厚みを小さくするために好ましい。
また、樹脂層が誘電体を含む場合には、樹脂層の厚みは0.1~50μmであることが好ましく、0.5μm~25μmであることが好ましく、1.0μm~15μmであることがより好ましい。
また、前記硬化樹脂層、半硬化樹脂層との総樹脂層厚みは0.1μm~120μmであるものが好ましく、5μm~120μmであるものが好ましく、10μm~120μmであるものが好ましく、10μm~60μmのものがより好ましい。そして、硬化樹脂層の厚みは2μm~30μmであることが好ましく、3μm~30μmであることが好ましく、5~20μmであることがより好ましい。また、半硬化樹脂層の厚みは3μm~55μmであることが好ましく、7μm~55μmであることが好ましく、15~115μmであることがより望ましい。総樹脂層厚みが120μmを超えると、薄厚の多層プリント配線板を製造することが難しくなる場合があり、5μm未満では薄厚の多層プリント配線板を形成し易くなるものの、内層の回路間における絶縁層である樹脂層が薄くなりすぎ、内層の回路間の絶縁性を不安定にする傾向が生じる場合があるためである。また、硬化樹脂層厚みが2μm未満であると、銅箔粗化面の表面粗度を考慮する必要が生じる場合がある。逆に硬化樹脂層厚みが20μmを超えると硬化済み樹脂層による効果は特に向上することがなくなる場合があり、総絶縁層厚は厚くなる。 When the thickness of the resin layer is less than 0.1 μm, 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. On the other hand, if the thickness of the resin layer is greater than 120 μm, 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.
When the copper foil with a carrier having a resin layer is used for producing an extremely thin multilayer printed wiring board, the thickness of the resin layer is 0.1 μm to 5 μm, more preferably 0.5 μm to 5 μm, More preferably, the thickness is 1 μm to 5 μm in order to reduce the thickness of the multilayer printed wiring board.
When the resin layer contains a dielectric, the thickness of the resin layer is preferably 0.1 to 50 μm, more preferably 0.5 μm to 25 μm, and more preferably 1.0 μm to 15 μm. preferable.
The total resin layer thickness of the cured resin layer and the semi-cured resin layer is preferably 0.1 μm to 120 μm, preferably 5 μm to 120 μm, preferably 10 μm to 120 μm, and 10 μm to 60 μm. Are more preferred. The thickness of the cured resin layer is preferably 2 μm to 30 μm, preferably 3 μm to 30 μm, and more preferably 5 to 20 μm. The thickness of the semi-cured resin layer is preferably 3 μm to 55 μm, more preferably 7 μm to 55 μm, and even more preferably 15 to 115 μm. If the total resin layer thickness exceeds 120 μm, it may be difficult to produce a thin multilayer printed wiring board. If the total resin layer thickness is less than 5 μm, 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 μm, it may be necessary to consider the surface roughness of the roughened copper foil surface. Conversely, if the cured resin layer thickness exceeds 20 μm, the effect of the cured resin layer may not be particularly improved, and the total insulating layer thickness becomes thick.
なお、前述の樹脂層の厚みは、任意の10点において断面観察により測定した厚みの平均値をいう。 When the thickness of the resin layer is 0.1 μm to 5 μm, in order to improve the adhesion between the resin layer and the copper foil with carrier, a heat-resistant layer and / or a rust-proof layer is formed on the ultrathin copper layer. After providing the chromate treatment layer and / or the silane coupling treatment layer, it is preferable to form a resin layer on the heat-resistant layer, rust prevention layer, chromate treatment layer or silane coupling treatment layer.
In addition, the thickness of the above-mentioned resin layer says the average value of the thickness measured by cross-sectional observation in arbitrary 10 points | pieces.
このようにして、銅箔キャリアと、銅箔キャリア上に積層された剥離層と、剥離層の上に積層された極薄銅層と、随意的な樹脂層を備えたキャリア付き銅箔が製造される。キャリア付き銅箔自体の使用方法は当業者に周知であるが、例えば極薄銅層の表面を紙基材フェノール樹脂、紙基材エポキシ樹脂、合成繊維布基材エポキシ樹脂、ガラス布・紙複合基材エポキシ樹脂、ガラス布・ガラス不織布複合基材エポキシ樹脂及びガラス布基材エポキシ樹脂、ポリエステルフィルム、ポリイミドフィルム等の絶縁基板に貼り合わせて熱圧着後にキャリアを剥がして銅張積層板とし、絶縁基板に接着した極薄銅層を目的とする導体パターンにエッチングし、最終的にプリント配線板を製造することができる。更に、プリント配線板に電子部品類を搭載することで、プリント回路板が完成する。以下に、本発明に係るキャリア付き銅箔を用いたプリント配線板の製造工程の例を幾つか示す。 <6. Copper foil with carrier>
In this way, 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. For example, 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.
前記キャリア付き銅箔と絶縁基板を積層する工程、
前記キャリア付き銅箔と絶縁基板を積層した後に、前記キャリア付き銅箔のキャリアを剥がす工程、
前記キャリアを剥がして露出した極薄銅層を酸などの腐食溶液を用いたエッチングやプラズマなどの方法によりすべて除去する工程、
前記極薄銅層をエッチングにより除去することにより露出した絶縁基板及び存在する場合には樹脂層にスルーホールまたは/およびブラインドビアを設ける工程、
前記スルーホールまたは/およびブラインドビアを含む領域についてデスミア処理を行う工程、
前記樹脂および前記スルーホールまたは/およびブラインドビアを含む領域について無電解めっき層を設ける工程、
前記無電解めっき層の上にめっきレジストを設ける工程、
前記めっきレジストに対して露光し、その後、回路が形成される領域のめっきレジストを除去する工程、
前記めっきレジストが除去された前記回路が形成される領域に、電気めっき層を設ける工程、
前記めっきレジストを除去する工程、
前記回路が形成される領域以外の領域にある無電解めっき層をフラッシュエッチングなどにより除去する工程、
を含む。 Therefore, in one embodiment of a method for producing a printed wiring board according to the present invention using a semi-additive method, 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;
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 the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like;
including.
前記キャリア付き銅箔と絶縁基板を積層する工程、
前記キャリア付き銅箔と絶縁基板を積層した後に、前記キャリア付き銅箔のキャリアを剥がす工程、
前記キャリアを剥がして露出した極薄銅層を酸などの腐食溶液を用いたエッチングやプラズマなどの方法によりすべて除去する工程、
前記極薄銅層をエッチングにより除去することにより露出した絶縁基板又は存在する場合には樹脂層の表面について無電解めっき層を設ける工程、
前記無電解めっき層の上にめっきレジストを設ける工程、
前記めっきレジストに対して露光し、その後、回路が形成される領域のめっきレジストを除去する工程、
前記めっきレジストが除去された前記回路が形成される領域に、電気めっき層を設ける工程、
前記めっきレジストを除去する工程、
前記回路が形成される領域以外の領域にある無電解めっき層及び極薄銅層をフラッシュエッチングなどにより除去する工程、
を含む。 In another embodiment of the method for producing a printed wiring board according to the present invention using a semi-additive method, 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 plating resist;
Removing the electroless plating layer and the ultrathin copper layer in a region other than the region where the circuit is formed by flash etching or the like;
including.
前記キャリア付き銅箔と絶縁基板を積層する工程、
前記キャリア付き銅箔と絶縁基板を積層した後に、前記キャリア付き銅箔のキャリアを剥がす工程、
前記キャリアを剥がして露出した極薄銅層と絶縁基板にスルーホールまたは/およびブラインドビアを設ける工程、
前記スルーホールまたは/およびブラインドビアを含む領域についてデスミア処理を行う工程、
前記スルーホールまたは/およびブラインドビアを含む領域について無電解めっき層を設ける工程、
前記キャリアを剥がして露出した極薄銅層表面にめっきレジストを設ける工程、
前記めっきレジストを設けた後に、電気めっきにより回路を形成する工程、
前記めっきレジストを除去する工程、
前記めっきレジストを除去することにより露出した極薄銅層をフラッシュエッチングにより除去する工程、
を含む。 Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using the modified semi-additive method, 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.
前記キャリア付き銅箔と絶縁基板を積層する工程、
前記キャリア付き銅箔と絶縁基板を積層した後に、前記キャリア付き銅箔のキャリアを剥がす工程、
前記キャリアを剥がして露出した極薄銅層の上にめっきレジストを設ける工程、
前記めっきレジストに対して露光し、その後、回路が形成される領域のめっきレジストを除去する工程、
前記めっきレジストが除去された前記回路が形成される領域に、電気めっき層を設ける工程、
前記めっきレジストを除去する工程、
前記回路が形成される領域以外の領域にある極薄銅層をフラッシュエッチングなどにより除去する工程、
を含む。 In another embodiment of the method for manufacturing a printed wiring board according to the present invention using the modified semi-additive method, 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.
前記キャリア付き銅箔と絶縁基板を積層する工程、
前記キャリア付き銅箔と絶縁基板を積層した後に、前記キャリア付き銅箔のキャリアを剥がす工程、
前記キャリアを剥がして露出した極薄銅層と絶縁基板にスルーホールまたは/およびブラインドビアを設ける工程、
前記スルーホールまたは/およびブラインドビアを含む領域についてデスミア処理を行う工程、
前記スルーホールまたは/およびブラインドビアを含む領域について触媒核を付与する工程、
前記キャリアを剥がして露出した極薄銅層表面にエッチングレジストを設ける工程、
前記エッチングレジストに対して露光し、回路パターンを形成する工程、
前記極薄銅層および前記触媒核を酸などの腐食溶液を用いたエッチングやプラズマなどの方法により除去して、回路を形成する工程、
前記エッチングレジストを除去する工程、
前記極薄銅層および前記触媒核を酸などの腐食溶液を用いたエッチングやプラズマなどの方法により除去して露出した前記絶縁基板表面に、ソルダレジストまたはメッキレジストを設ける工程、
前記ソルダレジストまたはメッキレジストが設けられていない領域に無電解めっき層を設ける工程、
を含む。 Therefore, in one embodiment of a method for producing a printed wiring board according to the present invention using a partly additive method, 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 an acid 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 ultrathin copper layer and the catalyst core by a method such as etching or plasma using a corrosive solution such as an acid;
Providing an electroless plating layer in a region where the solder resist or plating resist is not provided,
including.
前記キャリア付き銅箔と絶縁基板を積層する工程、
前記キャリア付き銅箔と絶縁基板を積層した後に、前記キャリア付き銅箔のキャリアを剥がす工程、
前記キャリアを剥がして露出した極薄銅層と絶縁基板にスルーホールまたは/およびブラインドビアを設ける工程、
前記スルーホールまたは/およびブラインドビアを含む領域についてデスミア処理を行う工程、
前記スルーホールまたは/およびブラインドビアを含む領域について無電解めっき層を設ける工程、
前記無電解めっき層の表面に、電気めっき層を設ける工程、
前記電気めっき層または/および前記極薄銅層の表面にエッチングレジストを設ける工程、
前記エッチングレジストに対して露光し、回路パターンを形成する工程、
前記極薄銅層および前記無電解めっき層および前記電気めっき層を酸などの腐食溶液を用いたエッチングやプラズマなどの方法により除去して、回路を形成する工程、
前記エッチングレジストを除去する工程、
を含む。 Therefore, in one embodiment of a method for manufacturing a printed wiring board according to the present invention using a subtractive method, 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 and the electroplating layer by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit;
Removing the etching resist;
including.
前記キャリア付き銅箔と絶縁基板を積層する工程、
前記キャリア付き銅箔と絶縁基板を積層した後に、前記キャリア付き銅箔のキャリアを剥がす工程、
前記キャリアを剥がして露出した極薄銅層と絶縁基板にスルーホールまたは/およびブラインドビアを設ける工程、
前記スルーホールまたは/およびブラインドビアを含む領域についてデスミア処理を行う工程、
前記スルーホールまたは/およびブラインドビアを含む領域について無電解めっき層を設ける工程、
前記無電解めっき層の表面にマスクを形成する工程、
マスクが形成されいない前記無電解めっき層の表面に電気めっき層を設ける工程、
前記電気めっき層または/および前記極薄銅層の表面にエッチングレジストを設ける工程、
前記エッチングレジストに対して露光し、回路パターンを形成する工程、
前記極薄銅層および前記無電解めっき層を酸などの腐食溶液を用いたエッチングやプラズマなどの方法により除去して、回路を形成する工程、
前記エッチングレジストを除去する工程、
を含む。 In another embodiment of the method for producing a printed wiring board according to the present invention using a subtractive method, 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 circuit pattern;
Removing the ultra-thin copper layer and the electroless plating layer by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit;
Removing the etching resist;
including.
まず、図2-Aに示すように、表面に粗化処理層が形成された極薄銅層を有するキャリア付銅箔(1層目)を準備する。
次に、図2-Bに示すように、極薄銅層の粗化処理層上にレジストを塗布し、露光・現像を行い、レジストを所定の形状にエッチングする。
次に、図2-Cに示すように、回路用のめっきを形成した後、レジストを除去することで、所定の形状の回路めっきを形成する。
次に、図3-Dに示すように、回路めっきを覆うように(回路めっきが埋没するように)極薄銅層上に埋め込み樹脂を設けて樹脂層を積層し、続いて別のキャリア付銅箔(2層目)を極薄銅層側から接着させる。
次に、図3-Eに示すように、2層目のキャリア付銅箔からキャリアを剥がす。
次に、図3-Fに示すように、樹脂層の所定位置にレーザー穴あけを行い、回路めっきを露出させてブラインドビアを形成する。
次に、図4-Gに示すように、ブラインドビアに銅を埋め込みビアフィルを形成する。
次に、図4-Hに示すように、ビアフィル上に、上記図2-B及び図2-Cのようにして回路めっきを形成する。
次に、図4-Iに示すように、1層目のキャリア付銅箔からキャリアを剥がす。
次に、図5-Jに示すように、フラッシュエッチングにより両表面の極薄銅層を除去し、樹脂層内の回路めっきの表面を露出させる。
次に、図5-Kに示すように、樹脂層内の回路めっき上にバンプを形成し、当該はんだ上に銅ピラーを形成する。このようにして本発明のキャリア付銅箔を用いたプリント配線板を作製する。 Here, the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention is demonstrated in detail using drawing. Here, the carrier-attached copper foil having an ultrathin copper layer on which a roughened layer is formed will be described as an example. However, 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.
First, as shown in 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.
Next, as shown in FIG. 2-B, a resist is applied on the roughened layer of the ultrathin copper layer, exposed and developed, and etched into a predetermined shape.
Next, as shown in FIG. 2C, after forming a circuit plating, the resist is removed to form a circuit plating having a predetermined shape.
Next, as shown in FIG. 3-D, 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.
Next, as shown in FIG. 3E, the carrier is peeled off from the second layer copper foil with carrier.
Next, as shown in FIG. 3F, laser drilling is performed at a predetermined position of the resin layer to expose the circuit plating and form a blind via.
Next, as shown in FIG. 4-G, copper is embedded in the blind via to form a via fill.
Next, as shown in FIG. 4-H, circuit plating is formed on the via fill as shown in FIGS. 2-B and 2-C.
Next, as shown in FIG. 4-I, the carrier is peeled off from the first layer of copper foil with carrier.
Next, as shown in FIG. 5-J, the ultrathin copper layers on both surfaces are removed by flash etching, and the surface of the circuit plating in the resin layer is exposed.
Next, as shown in FIG. 5K, bumps are formed on the circuit plating in the resin layer, and copper pillars are formed on the solder. Thus, the printed wiring board using the copper foil with a carrier of this invention is produced.
(1)極薄銅層または粗化処理層または耐熱層または防錆層またはクロメート処理層またはシランカップリング処理層の表面のJISZ8730に基づく色差ΔE*abが45以上である。 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). In the present invention, 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 ΔE * 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.
また上述の色差は、極薄銅層の表面に粗化処理を施して粗化処理層を設けることで調整することもできる。粗化処理層を設ける場合には銅およびニッケル、コバルト、タングステン、モリブデンからなる群から選択される一種以上の元素とを含む電界液を用いて、従来よりも電流密度を高く(例えば40~60A/dm2)し、処理時間を短く(例えば0.1~1.3秒)することで調整することができる。極薄銅層の表面に粗化処理層を設けない場合には、Niの濃度をその他の元素の2倍以上としたメッキ浴を用いて、極薄銅層または耐熱層または防錆層またはクロメート処理層またはシランカップリング処理層の表面にNi合金メッキ(例えばNi-W合金メッキ、Ni-Co-P合金メッキ、Ni-Zn合金めっき)を従来よりも低電流密度(0.1~1.3A/dm2)で処理時間を長く(20秒~40秒)設定して処理することで達成できる。 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.
Moreover, 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. In the case of providing the roughened 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). When a roughening layer is not provided on the surface of the ultrathin copper layer, use a plating bath in which the concentration of Ni is twice or more that of other elements, and use an ultrathin copper layer, heat resistant layer, rust preventive layer or chromate. 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).
<実施例1>
銅箔キャリアとして、厚さ35μmの長尺の電解銅箔(JX日鉱日石金属社製JTC)を用意した。この銅箔のシャイニー面に対して、以下の条件でロール・トウ・ロール型の連続めっきラインで電気めっきすることにより4000μg/dm2の付着量のNi層を形成した。 1. Production of copper foil with carrier <Example 1>
As a copper foil carrier, a long electrolytic copper foil having a thickness of 35 μm (JTC manufactured by JX Nippon Mining & Metals) was prepared. An Ni layer having an adhesion amount of 4000 μg / 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.
硫酸ニッケル:250~300g/L
塩化ニッケル:35~45g/L
酢酸ニッケル:10~20g/L
クエン酸三ナトリウム:15~30g/L
光沢剤:サッカリン、ブチンジオール等
ドデシル硫酸ナトリウム:30~100ppm
pH:4~6
浴温:50~70℃
電流密度:3~15A/dm2 ・ Ni layer 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
・電解クロメート処理
液組成:重クロム酸カリウム1~10g/L、亜鉛0~5g/L
pH:3~4
液温:50~60℃
電流密度:0.1~2.6A/dm2
クーロン量:0.5~30As/dm2 After washing with water and pickling, a Cr layer having an adhesion amount of 11 μg / dm 2 was deposited on the Ni layer by electrolytic chromate treatment under the following conditions on a roll-to-roll type continuous plating line. .
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
・極薄銅層
銅濃度:30~120g/L
H2SO4濃度:20~120g/L
電解液温度:20~80℃
電流密度:10~100A/dm2 Subsequently, on the roll-to-roll type continuous plating line, an ultrathin copper layer having a thickness of 3 μm was formed on the Cr layer by electroplating under the following conditions to produce a copper foil with a carrier. In this example, a copper foil with a carrier having an ultrathin copper layer thickness of 2, 5, and 10 μm was also manufactured and evaluated in the same manner as in the example of the ultrathin copper layer thickness of 3 μm. The result was the same regardless of the thickness.
・ Ultra-thin copper layer Copper concentration: 30-120 g / L
H 2 SO 4 concentration: 20 to 120 g / L
Electrolyte temperature: 20-80 ° C
Current density: 10 to 100 A / dm 2
・粗化処理1
(液組成1)
Cu:10~30g/L
H2SO4:10~150g/L
W:0~50mg/L
ドデシル硫酸ナトリウム:0~50mg/L
As:0~200mg/L
(電気めっき条件1)
温度:30~70℃
電流密度:25~110A/dm2
粗化クーロン量:50~500As/dm2
めっき時間:0.5~20秒
・粗化処理2
(液組成2)
Cu:20~80g/L
H2SO4:50~200g/L
(電気めっき条件2)
温度:30~70℃
電流密度:5~50A/dm2
粗化クーロン量:50~300As/dm2
めっき時間:1~60秒
・防錆処理
(液組成)
NaOH:40~200g/L
NaCN:70~250g/L
CuCN:50~200g/L
Zn(CN)2:2~100g/L
As2O3:0.01~1g/L
(液温)
40~90℃
(電流条件)
電流密度:1~50A/dm2
めっき時間:1~20秒
・クロメート処理
K2Cr2O7(Na2Cr2O7或いはCrO3):2~10g/L
NaOH又はKOH:10~50g/L
ZnOH又はZnSO4・7H2O:0.05~10g/L
pH:7~13
浴温:20~80℃
電流密度:0.05~5A/dm2
時間:5~30秒
・シランカップリング処理
0.1vol%~0.3vol%の3-グリシドキシプロピルトリメトキシシラン水溶液をスプレー塗布した後、100~200℃の空気中で0.1~10秒間乾燥・加熱する。 Next, the following roughening treatment 1, roughening treatment 2, rust prevention treatment, chromate treatment, and silane coupling treatment were performed in this order on the surface of the ultrathin copper layer.
・ Roughening 1
(Liquid composition 1)
Cu: 10-30 g / L
H 2 SO 4 : 10 to 150 g / L
W: 0-50mg / L
Sodium dodecyl sulfate: 0 to 50 mg / L
As: 0 to 200 mg / L
(Electroplating condition 1)
Temperature: 30-70 ° C
Current density: 25 to 110 A / dm 2
Roughening coulomb amount: 50 to 500 As / dm 2
Plating time: 0.5-20 seconds, roughening treatment 2
(Liquid composition 2)
Cu: 20-80 g / L
H 2 SO 4 : 50 to 200 g / L
(Electroplating condition 2)
Temperature: 30-70 ° C
Current density: 5 to 50 A / dm 2
Roughening coulomb amount: 50 to 300 As / dm 2
Plating time: 1-60 seconds, anti-rust treatment (liquid composition)
NaOH: 40 to 200 g / L
NaCN: 70 to 250 g / L
CuCN: 50 to 200 g / L
Zn (CN) 2 : 2 to 100 g / L
As 2 O 3 : 0.01 to 1 g / L
(Liquid temperature)
40-90 ° C
(Current condition)
Current density: 1 to 50 A / dm 2
Plating time: 1 to 20 seconds, chromate treatment K 2 Cr 2 O 7 (Na 2 Cr 2 O 7 or CrO 3 ): 2 to 10 g / L
NaOH or KOH: 10-50 g / L
ZnOH or ZnSO 4 .7H 2 O: 0.05 to 10 g / L
pH: 7-13
Bath temperature: 20-80 ° C
Current density: 0.05 to 5 A / dm 2
Time: 5 to 30 seconds Silane coupling treatment 0.1 vol% to 0.3 vol% 3-glycidoxypropyltrimethoxysilane aqueous solution is spray-coated and then 0.1 to 10 in air at 100 to 200 ° C. Dry and heat for seconds.
実施例1と同様の条件で銅箔キャリア上に極薄銅層を形成した後、以下の粗化処理1、粗化処理2、防錆処理、クロメート処理、及び、シランカップリング処理をこの順に行った。なお、極薄銅箔の厚みは3μmとした。
・粗化処理1
液組成 :銅10~20g/L、硫酸50~100g/L
液温 :25~50℃
電流密度 :1~58A/dm2
クーロン量:4~81As/dm2
・粗化処理2
液組成 :銅10~20g/L、ニッケル5~15g/L、コバルト5~15g/L
pH :2~3
液温 :30~50℃
電流密度 :24~50A/dm2
クーロン量:34~48As/dm2
・防錆処理
液組成 :ニッケル5~20g/L、コバルト1~8g/L
pH :2~3
液温 :40~60℃
電流密度 :5~20A/dm2
クーロン量:10~20As/dm2
・クロメート処理
液組成 :重クロム酸カリウム1~10g/L、亜鉛0~5g/L
pH :3~4
液温 :50~60℃
電流密度 :0~2A/dm2(浸漬クロメート処理のため無電解での実施も可能)
クーロン量:0~2As/dm2(浸漬クロメート処理のため無電解での実施も可能)
・シランカップリング処理
ジアミノシラン水溶液の塗布(ジアミノシラン濃度:0.1~0.5wt%) <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 μm.
・ Roughening 1
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: 3-4
Liquid temperature: 50-60 ° C
Current density: 0-2A / dm 2 (Impregnation is possible because of immersion chromate treatment)
Coulomb amount: 0 to 2 As / dm 2 (can be electroless because of immersion chromate treatment)
・ Silane coupling treatment Application of diaminosilane aqueous solution (diaminosilane concentration: 0.1 to 0.5 wt%)
実施例1と同様の条件で銅箔キャリア上に極薄銅層を形成した後、次いで、極薄銅層表面に以下の粗化処理1、粗化処理2、防錆処理、クロメート処理、及び、シランカップリング処理をこの順に行った。なお、極薄銅箔の厚みは3μmとした。
・粗化処理1
(液組成1)
Cu:10~30g/L
H2SO4:10~150g/L
As:0~200mg/L
(電気めっき条件1)
温度:30~70℃
電流密度:25~110A/dm2
粗化クーロン量:50~500As/dm2
めっき時間:0.5~20秒
・粗化処理2
(液組成2)
Cu:20~80g/L
H2SO4:50~200g/L
(電気めっき条件2)
温度:30~70℃
電流密度:5~50A/dm2
粗化クーロン量:50~300As/dm2
めっき時間:1~60秒
・防錆処理
(液組成)
NaOH:40~200g/L
NaCN:70~250g/L
CuCN:50~200g/L
Zn(CN)2:2~100g/L
As2O3:0.01~1g/L
(液温)
40~90℃
(電流条件)
電流密度:1~50A/dm2
めっき時間:1~20秒
・クロメート処理
K2Cr2O7(Na2Cr2O7或いはCrO3):2~10g/L
NaOH又はKOH:10~50g/L
ZnOH又はZnSO4・7H2O:0.05~10g/L
pH:7~13
浴温:20~80℃
電流密度:0.05~5A/dm2
時間:5~30秒
・シランカップリング処理
0.1vol%~0.3vol%の3-グリシドキシプロピルトリメトキシシラン水溶液をスプレー塗布した後、100~200℃の空気中で0.1~10秒間乾燥・加熱する。 <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 μm.
・ Roughening 1
(Liquid composition 1)
Cu: 10-30 g / L
H 2 SO 4 : 10 to 150 g / L
As: 0 to 200 mg / L
(Electroplating condition 1)
Temperature: 30-70 ° C
Current density: 25 to 110 A / dm 2
Roughening coulomb amount: 50 to 500 As / dm 2
Plating time: 0.5-20 seconds, roughening treatment 2
(Liquid composition 2)
Cu: 20-80 g / L
H 2 SO 4 : 50 to 200 g / L
(Electroplating condition 2)
Temperature: 30-70 ° C
Current density: 5 to 50 A / dm 2
Roughening coulomb amount: 50 to 300 As / dm 2
Plating time: 1-60 seconds, anti-rust treatment (liquid composition)
NaOH: 40 to 200 g / L
NaCN: 70 to 250 g / L
CuCN: 50 to 200 g / L
Zn (CN) 2 : 2 to 100 g / L
As 2 O 3 : 0.01 to 1 g / L
(Liquid temperature)
40-90 ° C
(Current condition)
Current density: 1 to 50 A / dm 2
Plating time: 1 to 20 seconds, chromate treatment K 2 Cr 2 O 7 (Na 2 Cr 2 O 7 or CrO 3 ): 2 to 10 g / L
NaOH or KOH: 10-50 g / L
ZnOH or ZnSO 4 .7H 2 O: 0.05 to 10 g / L
pH: 7-13
Bath temperature: 20-80 ° C
Current density: 0.05 to 5 A / dm 2
Time: 5 to 30 seconds Silane coupling treatment 0.1 vol% to 0.3 vol% 3-glycidoxypropyltrimethoxysilane aqueous solution is spray-coated and then 0.1 to 10 in air at 100 to 200 ° C. Dry and heat for seconds.
実施例1と同様の条件で銅箔キャリア上にNi層及びCr層を形成した後、ロール・トウ・ロール型の連続めっきライン上で、Cr層の上に厚み3μmの極薄銅層を以下の条件で電気めっきすることにより形成し、キャリア付銅箔を製造した。なお、本実施例では極薄銅層の厚みを2、5、10μmとしたキャリア付銅箔についても製造し、極薄銅層の厚みが3μmの実施例と同様に評価した。結果は厚みによらずほとんど同じとなった。
・極薄銅層
銅濃度:30~120g/L
H2SO4濃度:20~120g/L
ビス(3スルホプロピル)ジスルフィド-濃度:10~100ppm
3級アミン化合物:10~100ppm
塩素:10~100ppm
電解液温度:20~80℃
電流密度:10~100A/dm2
なお、前述の3級アミン化合物として以下の化合物を用いた。
上記化合物は例えばナガセケムテックス株式会社製デコナール Ex-314とジメチルアミンを所定量混合させ、60℃で3時間反応を行うことで得ることができる。 <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 μm 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. In this example, a copper foil with a carrier having an ultrathin copper layer thickness of 2, 5, and 10 μm was also manufactured, and evaluated in the same manner as in the example with an ultrathin copper layer thickness of 3 μm. The result was almost the same regardless of the thickness.
・ Ultra-thin copper layer Copper concentration: 30-120 g / L
H 2 SO 4 concentration: 20 to 120 g / L
Bis (3sulfopropyl) disulfide concentration: 10 to 100 ppm
Tertiary amine compound: 10-100ppm
Chlorine: 10-100ppm
Electrolyte temperature: 20-80 ° C
Current density: 10 to 100 A / dm 2
In addition, the following compounds were used as the above-mentioned tertiary amine compound.
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.
・粗化処理1
液組成 :銅10~20g/L、硫酸50~100g/L
液温 :25~50℃
電流密度 :1~58A/dm2
クーロン量:4~81As/dm2
・粗化処理2
液組成 :銅10~20g/L、ニッケル5~15g/L、コバルト5~15g/L
pH :2~3
液温 :30~50℃
電流密度 :24~50A/dm2
クーロン量:34~48As/dm2
・防錆処理
液組成 :ニッケル5~20g/L、コバルト1~8g/L
pH :2~3
液温 :40~60℃
電流密度 :5~20A/dm2
クーロン量:10~20As/dm2
・クロメート処理
液組成 :重クロム酸カリウム1~10g/L、亜鉛0~5g/L
pH :3~4
液温 :50~60℃
電流密度 :0~2A/dm2(浸漬クロメート処理のため無電解での実施も可能)
クーロン量:0~2As/dm2(浸漬クロメート処理のため無電解での実施も可能)
・シランカップリング処理
ジアミノシラン水溶液の塗布(ジアミノシラン濃度:0.1~0.5wt%) After the ultrathin copper layer was formed on the copper foil carrier, the following roughening treatment 1, roughening treatment 2, rust prevention treatment, chromate treatment, and silane coupling treatment were performed in this order.
・ Roughening 1
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: 3-4
Liquid temperature: 50-60 ° C
Current density: 0-2A / dm 2 (Impregnation is possible because of immersion chromate treatment)
Coulomb amount: 0 to 2 As / dm 2 (can be electroless because of immersion chromate treatment)
・ Silane coupling treatment Application of diaminosilane aqueous solution (diaminosilane concentration: 0.1 to 0.5 wt%)
実施例1と同様の条件で銅箔キャリア上にNi層及びCr層を形成した後、ロール・トウ・ロール型の連続めっきライン上で、Cr層の上に厚み3μmの極薄銅層を以下の条件で電気めっきすることにより形成し、キャリア付銅箔を製造した。なお、本実施例では極薄銅層の厚みを2、5、10μmとしたキャリア付銅箔についても製造し、極薄銅層の厚みが3μmの実施例と同様に評価した。結果は厚みによらずほとんど同じとなった。
・極薄銅層
銅濃度:30~120g/L
H2SO4濃度:20~120g/L
ビス(3スルホプロピル)ジスルフィド-濃度:10~100ppm
3級アミン化合物:10~100ppm
塩素:10~100ppm
電解液温度:20~80℃
電流密度:10~100A/dm2
なお、前述の3級アミン化合物として以下の化合物を用いた。
上記化合物は例えばナガセケムテックス株式会社製デコナール Ex-314とジメチルアミンを所定量混合させ、60℃で3時間反応を行うことで得ることができる。) <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 μm 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. In this example, a copper foil with a carrier having an ultrathin copper layer thickness of 2, 5, and 10 μm was also manufactured, and evaluated in the same manner as in the example with an ultrathin copper layer thickness of 3 μm. The result was almost the same regardless of the thickness.
・ Ultra-thin copper layer Copper concentration: 30-120 g / L
H 2 SO 4 concentration: 20 to 120 g / L
Bis (3sulfopropyl) disulfide concentration: 10 to 100 ppm
Tertiary amine compound: 10-100ppm
Chlorine: 10-100ppm
Electrolyte temperature: 20-80 ° C
Current density: 10 to 100 A / dm 2
In addition, the following compounds were used as the above-mentioned tertiary amine compound.
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. )
・粗化処理1
(液組成1)
Cu:10~30g/L
H2SO4:10~150g/L
W:0.1~50mg/L
ドデシル硫酸ナトリウム:0.1~50mg/L
As:0.1~200mg/L
(電気めっき条件1)
温度:30~70℃
電流密度:25~110A/dm2
粗化クーロン量:50~500As/dm2
めっき時間:0.5~20秒
・粗化処理2
(液組成2)
Cu:20~80g/L
H2SO4:50~200g/L
(電気めっき条件2)
温度:30~70℃
電流密度:5~50A/dm2
粗化クーロン量:50~300As/dm2
めっき時間:1~60秒
・防錆処理
(液組成)
NaOH:40~200g/L
NaCN:70~250g/L
CuCN:50~200g/L
Zn(CN)2:2~100g/L
As2O3:0.01~1g/L
(液温)
40~90℃
(電流条件)
電流密度:1~50A/dm2
めっき時間:1~20秒
・クロメート処理
K2Cr2O7(Na2Cr2O7或いはCrO3):2~10g/L
NaOH又はKOH:10~50g/L
ZnOH又はZnSO4・7H2O:0.05~10g/L
pH:7~13
浴温:20~80℃
電流密度:0.05~5A/dm2
時間:5~30秒
・シランカップリング処理
0.1vol%~0.3vol%の3-グリシドキシプロピルトリメトキシシラン水溶液をスプレー塗布した後、100~200℃の空気中で0.1~10秒間乾燥・加熱する。 After the ultrathin copper layer was formed on the copper foil carrier, the following roughening treatment 1, roughening treatment 2, rust prevention treatment, chromate treatment, and silane coupling treatment were performed in this order.
・ Roughening 1
(Liquid composition 1)
Cu: 10-30 g / L
H 2 SO 4 : 10 to 150 g / L
W: 0.1-50mg / L
Sodium dodecyl sulfate: 0.1 to 50 mg / L
As: 0.1 to 200 mg / L
(Electroplating condition 1)
Temperature: 30-70 ° C
Current density: 25 to 110 A / dm 2
Roughening coulomb amount: 50 to 500 As / dm 2
Plating time: 0.5-20 seconds, roughening treatment 2
(Liquid composition 2)
Cu: 20-80 g / L
H 2 SO 4 : 50 to 200 g / L
(Electroplating condition 2)
Temperature: 30-70 ° C
Current density: 5 to 50 A / dm 2
Roughening coulomb amount: 50 to 300 As / dm 2
Plating time: 1-60 seconds, anti-rust treatment (liquid composition)
NaOH: 40 to 200 g / L
NaCN: 70 to 250 g / L
CuCN: 50 to 200 g / L
Zn (CN) 2 : 2 to 100 g / L
As 2 O 3 : 0.01 to 1 g / L
(Liquid temperature)
40-90 ° C
(Current condition)
Current density: 1 to 50 A / dm 2
Plating time: 1 to 20 seconds, chromate treatment K 2 Cr 2 O 7 (Na 2 Cr 2 O 7 or CrO 3 ): 2 to 10 g / L
NaOH or KOH: 10-50 g / L
ZnOH or ZnSO 4 .7H 2 O: 0.05 to 10 g / L
pH: 7-13
Bath temperature: 20-80 ° C
Current density: 0.05 to 5 A / dm 2
Time: 5 to 30 seconds Silane coupling treatment 0.1 vol% to 0.3 vol% 3-glycidoxypropyltrimethoxysilane aqueous solution is spray-coated and then 0.1 to 10 in air at 100 to 200 ° C. Dry and heat for seconds.
実施例1と同様の条件で銅箔キャリア上にNi層及びCr層を形成した後、ロール・トウ・ロール型の連続めっきライン上で、Cr層の上に厚み3μmの極薄銅層を以下の条件で電気めっきすることにより形成し、キャリア付き銅箔を製造した。
・極薄銅層
銅濃度:30~120g/L
H2SO4濃度:20~120g/L
電解液温度:20~80℃
電流密度:5~9A/dm2
・粗化処理1
(液組成1)
Cu:10~30g/L
H2SO4:10~150g/L
As:0~200mg/L
(電気めっき条件1)
温度:30~70℃
電流密度:25~110A/dm2
粗化クーロン量:50~500As/dm2
めっき時間:0.5~20秒
・粗化処理2
(液組成2)
Cu:20~80g/L
H2SO4:50~200g/L
(電気めっき条件2)
温度:30~70℃
電流密度:5~50A/dm2
粗化クーロン量:50~300As/dm2
めっき時間:1~60秒
・防錆処理
(液組成)
NaOH:40~200g/L
NaCN:70~250g/L
CuCN:50~200g/L
Zn(CN)2:2~100g/L
As2O3:0.01~1g/L
(液温)
40~90℃
(電流条件)
電流密度:1~50A/dm2
めっき時間:1~20秒
・クロメート処理
K2Cr2O7(Na2Cr2O7或いはCrO3):2~10g/L
NaOH又はKOH:10~50g/L
ZnOH又はZnSO4・7H2O:0.05~10g/L
pH:7~13
浴温:20~80℃
電流密度:0.05~5A/dm2
時間:5~30秒
・シランカップリング処理
0.1vol%~0.3vol%の3-グリシドキシプロピルトリメトキシシラン水溶液をスプレー塗布した後、100~200℃の空気中で0.1~10秒間乾燥・加熱する。 <Comparative Example 1>
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 μm 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.
・ Ultra-thin copper layer Copper concentration: 30-120 g / L
H 2 SO 4 concentration: 20 to 120 g / L
Electrolyte temperature: 20-80 ° C
Current density: 5-9 A / dm 2
・ Roughening 1
(Liquid composition 1)
Cu: 10-30 g / L
H 2 SO 4 : 10 to 150 g / L
As: 0 to 200 mg / L
(Electroplating condition 1)
Temperature: 30-70 ° C
Current density: 25 to 110 A / dm 2
Roughening coulomb amount: 50 to 500 As / dm 2
Plating time: 0.5-20 seconds, roughening treatment 2
(Liquid composition 2)
Cu: 20-80 g / L
H 2 SO 4 : 50 to 200 g / L
(Electroplating condition 2)
Temperature: 30-70 ° C
Current density: 5 to 50 A / dm 2
Roughening coulomb amount: 50 to 300 As / dm 2
Plating time: 1-60 seconds, anti-rust treatment (liquid composition)
NaOH: 40 to 200 g / L
NaCN: 70 to 250 g / L
CuCN: 50 to 200 g / L
Zn (CN) 2 : 2 to 100 g / L
As 2 O 3 : 0.01 to 1 g / L
(Liquid temperature)
40-90 ° C
(Current condition)
Current density: 1 to 50 A / dm 2
Plating time: 1 to 20 seconds, chromate treatment K 2 Cr 2 O 7 (Na 2 Cr 2 O 7 or CrO 3 ): 2 to 10 g / L
NaOH or KOH: 10-50 g / L
ZnOH or ZnSO 4 .7H 2 O: 0.05 to 10 g / L
pH: 7-13
Bath temperature: 20-80 ° C
Current density: 0.05 to 5 A / dm 2
Time: 5 to 30 seconds Silane coupling treatment 0.1 vol% to 0.3 vol% 3-glycidoxypropyltrimethoxysilane aqueous solution is spray-coated and then 0.1 to 10 in air at 100 to 200 ° C. Dry and heat for seconds.
実施例1と同様の条件で銅箔キャリア上にNi層及びCr層を形成した後、ロール・トウ・ロール型の連続めっきライン上で、Cr層の上に厚み3μmの極薄銅層を以下の条件で電気めっきすることにより形成し、キャリア付き銅箔を製造した。
・極薄銅層
銅濃度:30~120g/L
H2SO4濃度:20~120g/L
電解液温度:20~80℃
電流密度:10~100A/dm2
・粗化処理1
(液組成1)
Cu:10~30g/L
H2SO4:10~150g/L
W:0~50mg/L
ドデシル硫酸ナトリウム:0~50mg/L
As:0~200mg/L
(電気めっき条件1)
温度:30~70℃
電流密度:25~110A/dm2
粗化クーロン量:50~500As/dm2
めっき時間:40秒
・粗化処理2
(液組成2)
Cu:20~80g/L
H2SO4:50~200g/L
(電気めっき条件2)
温度:30~70℃
電流密度:5~50A/dm2
粗化クーロン量:50~300As/dm2
めっき時間:80秒
・防錆処理
(液組成)
NaOH:40~200g/L
NaCN:70~250g/L
CuCN:50~200g/L
Zn(CN)2:2~100g/L
As2O3:0.01~1g/L
(液温)
40~90℃
(電流条件)
電流密度:1~50A/dm2
めっき時間:1~20秒
・クロメート処理
K2Cr2O7(Na2Cr2O7或いはCrO3):2~10g/L
NaOH又はKOH:10~50g/L
ZnOH又はZnSO4・7H2O:0.05~10g/L
pH:7~13
浴温:20~80℃
電流密度:0.05~5A/dm2
時間:5~30秒
・シランカップリング処理
0.1vol%~0.3vol%の3-グリシドキシプロピルトリメトキシシラン水溶液をスプレー塗布した後、100~200℃の空気中で0.1~10秒間乾燥・加熱する。 <Comparative Example 2>
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 μm 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.
・ Ultra-thin copper layer Copper concentration: 30-120 g / L
H 2 SO 4 concentration: 20 to 120 g / L
Electrolyte temperature: 20-80 ° C
Current density: 10 to 100 A / dm 2
・ Roughening 1
(Liquid composition 1)
Cu: 10-30 g / L
H 2 SO 4 : 10 to 150 g / L
W: 0-50mg / L
Sodium dodecyl sulfate: 0 to 50 mg / L
As: 0 to 200 mg / L
(Electroplating condition 1)
Temperature: 30-70 ° C
Current density: 25 to 110 A / dm 2
Roughening coulomb amount: 50 to 500 As / dm 2
Plating time: 40 seconds, roughening treatment 2
(Liquid composition 2)
Cu: 20-80 g / L
H 2 SO 4 : 50 to 200 g / L
(Electroplating condition 2)
Temperature: 30-70 ° C
Current density: 5 to 50 A / dm 2
Roughening coulomb amount: 50 to 300 As / dm 2
Plating time: 80 seconds, rust prevention treatment (liquid composition)
NaOH: 40 to 200 g / L
NaCN: 70 to 250 g / L
CuCN: 50 to 200 g / L
Zn (CN) 2 : 2 to 100 g / L
As 2 O 3 : 0.01 to 1 g / L
(Liquid temperature)
40-90 ° C
(Current condition)
Current density: 1 to 50 A / dm 2
Plating time: 1 to 20 seconds, chromate treatment K 2 Cr 2 O 7 (Na 2 Cr 2 O 7 or CrO 3 ): 2 to 10 g / L
NaOH or KOH: 10-50 g / L
ZnOH or ZnSO 4 .7H 2 O: 0.05 to 10 g / L
pH: 7-13
Bath temperature: 20-80 ° C
Current density: 0.05 to 5 A / dm 2
Time: 5 to 30 seconds Silane coupling treatment 0.1 vol% to 0.3 vol% 3-glycidoxypropyltrimethoxysilane aqueous solution is spray-coated and then 0.1 to 10 in air at 100 to 200 ° C. Dry and heat for seconds.
上記のようにして得られたキャリア付き銅箔について、以下の方法で特性評価を実施した。結果を表1に示す。
(表面粗さ)
極薄銅層の表面粗さ(Ra、Rt、Rz、Ssk、Sku)を非接触式粗さ測定機(オリンパス製 LEXT OLS 4000)を用いて、Ra、RzについてはJIS B0601-1994に準拠して、RtについてはJIS B0601-2001に準拠して、またSsk、SkuについてはISO25178ドラフトに準拠して以下の測定条件で、測定した。
<測定条件>
カットオフ:無
基準長さ:257.9μm
基準面積:66524μm2
測定環境温度:23~25℃ 2. Evaluation of characteristics of copper foil with carrier The characteristics of the copper foil with carrier obtained as described above were evaluated by the following method. The results are shown in Table 1.
(Surface roughness)
The surface roughness (Ra, Rt, Rz, Ssk, Sku) of the ultra-thin copper layer was measured using a non-contact type roughness measuring machine (OLYMPUS LEXT OLS 4000), and Ra and Rz were in accordance with JIS B0601-1994. Rt was measured in accordance with JIS B0601-2001, and Ssk and Sku were measured in accordance with ISO 25178 draft under the following measurement conditions.
<Measurement conditions>
Cut-off: None Reference length: 257.9 μm
Reference area: 66524 μm 2
Measurement ambient temperature: 23-25 ° C
<測定条件>
カットオフ:0.25mm
基準長さ:0.8mm
測定環境温度:23~25℃ For comparison, 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). In accordance with the following measurement conditions, the surface roughness (Ra, Rt, Rz) of the ultrathin copper layer was measured.
<Measurement conditions>
Cut-off: 0.25mm
Standard length: 0.8mm
Measurement ambient temperature: 23-25 ° C
非接触式粗さ測定機(オリンパス製 LEXT OLS 4000)を用いて、以下の測定条件で、測定した。表面積比は、エリア及び実エリアを測定し、実エリア/エリアの値を表面積比とした。ここで、エリアとは測定基準面積を指し、実エリアとは測定基準面積中の表面積を指す。
<測定条件>
カットオフ:無
基準長さ:257.9μm
基準面積:66524μm2
測定環境温度:23~25℃ (Surface area ratio)
It measured on the following measurement conditions using the non-contact-type roughness measuring machine (OLYMPUS LEXT OLS 4000). For the surface area ratio, the area and the actual area were measured, and the value of the actual area / area was defined as the surface area ratio. Here, the area refers to the measurement reference area, and the actual area refers to the surface area in the measurement reference area.
<Measurement conditions>
Cut-off: None Reference length: 257.9 μm
Reference area: 66524 μm 2
Measurement ambient temperature: 23-25 ° C
非接触式粗さ測定機(レーザー顕微鏡、オリンパス製 LEXT OLS 4000)を用いて、以下の測定条件で、測定した。なお、粗化処理面の体積は以下の様に測定される。
(1)レーザー顕微鏡がサンプルの表面に焦点の合う高さに合わせる。
(2)明るさを調整し、全体照度が飽和点の約80%になるよう調節する。
(3)レーザー顕微鏡をサンプルに近づけ、画面照度が完全に消失した地点をゼロとする。
(4)レーザー顕微鏡をサンプルから遠ざけ、画面照度が完全に消失した地点を上限高さとする。
(5)高さゼロから上限までの粗化処理面の体積を測定する。
<測定条件>
カットオフ:無
基準長さ:257.9μm
基準面積:66524μm2
測定環境温度:23~25℃
(マイグレーション)
各キャリア付き銅箔をビスマス系樹脂に接着し、次いでキャリア箔を剥離除去した。露出した極薄銅層の厚みをソフトエッチングにより1.5μmとした。その後、洗浄、乾燥を行った後に、極薄銅層上に、DF(日立化成社製、商品名RY-3625)をラミネート塗布した。15mJ/cm2の条件で露光し、現像液(炭酸ナトリウム)を用いて38℃で1分間液噴射揺動し、表1に記載の各種ピッチでレジストパターンを形成した。次いで、硫酸銅めっき(荏原ユージライト製 CUBRITE21)を用いて15μmめっきUPしたのち、剥離液(水酸化ナトリウム)でDFを剥離した。その後、極薄銅層を硫酸-過酸化水素系のエッチャントでエッチング除去して表1に記載の各種ピッチの配線を形成した。
表中に記載されているピッチはライン及びスペースの合計値に相当する。
得られた配線に対して、マイグレーション測定機(IMV製 MIG-9000)を用いて、以下の測定条件で、配線パターン間の絶縁劣化の有無を評価した。
<測定条件>
閾値:初期抵抗60%ダウン
測定時間:1000h
電圧:60V
温度:85℃
相対湿度:85%RH (Roughening surface volume)
It measured on the following measuring conditions using the non-contact-type roughness measuring machine (a laser microscope, Olympus LEXT OLS 4000). 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.
<Measurement conditions>
Cut-off: None Reference length: 257.9 μm
Reference area: 66524 μm 2
Measurement ambient temperature: 23-25 ° C
(migration)
Each carrier-attached copper foil was bonded to a bismuth-based resin, and then the carrier foil was peeled off. The thickness of the exposed ultrathin copper layer was set to 1.5 μm by soft etching. After washing and drying, DF (manufactured by Hitachi Chemical Co., Ltd., trade name RY-3625) was laminated on the ultrathin copper layer. Exposure was carried out under the condition of 15 mJ / cm 2 , and liquid jet rocking was performed for 1 minute at 38 ° C. using a developer (sodium carbonate) to form resist patterns at various pitches shown in Table 1. Next, UP was plated by 15 μm using copper sulfate plating (CUBRITE 21 manufactured by Sugawara Eugleite), and then DF was peeled with a peeling solution (sodium hydroxide). Thereafter, the ultrathin copper layer was removed by etching with a sulfuric acid-hydrogen peroxide etchant to form wirings having various pitches shown in Table 1.
The pitch described in the table corresponds to the total value of lines and spaces.
The obtained wirings were evaluated for the presence or absence of insulation deterioration between the wiring patterns using a migration measuring machine (IMV MIG-9000) under the following measurement conditions.
<Measurement conditions>
Threshold: Initial resistance 60% down Measurement time: 1000h
Voltage: 60V
Temperature: 85 ° C
Relative humidity: 85% RH
Claims (29)
- 銅箔キャリアと、銅箔キャリア上に積層された剥離層と、剥離層の上に積層された極薄銅層とを備えたキャリア付き銅箔であって、極薄銅層は粗化処理されており、極薄銅層表面のRzは非接触式粗さ計で測定して1.6μm以下であるキャリア付き銅箔。 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 being roughened Rz on the surface of the ultrathin copper layer is 1.6 μm or less as measured with a non-contact type roughness meter.
- 銅箔キャリアと、銅箔キャリア上に積層された剥離層と、剥離層の上に積層された極薄銅層とを備えたキャリア付き銅箔であって、極薄銅層は粗化処理されており、極薄銅層表面のRaは非接触式粗さ計で測定して0.3μm以下であるキャリア付き銅箔。 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 being roughened The carrier-attached copper foil whose Ra on the surface of the ultrathin copper layer is 0.3 μm or less as measured with a non-contact type roughness meter.
- 銅箔キャリアと、銅箔キャリア上に積層された剥離層と、剥離層の上に積層された極薄銅層とを備えたキャリア付き銅箔であって、極薄銅層は粗化処理されており、極薄銅層表面のRtは非接触式粗さ計で測定して2.3μm以下であるキャリア付き銅箔。 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 being roughened The carrier-attached copper foil whose Rt on the surface of the ultrathin copper layer is 2.3 μm or less as measured with a non-contact type roughness meter.
- 極薄銅層表面のRzは非接触式粗さ計で測定して1.4μm以下である請求項1~3の何れか一項に記載のキャリア付き銅箔。 4. The copper foil with a carrier according to claim 1, wherein Rz on the surface of the ultrathin copper layer is 1.4 μm or less as measured with a non-contact roughness meter.
- 極薄銅層表面のRaは非接触式粗さ計で測定して0.25μm以下である請求項1~4の何れか一項に記載のキャリア付き銅箔。 The copper foil with a carrier according to any one of claims 1 to 4, wherein Ra on the surface of the ultrathin copper layer is 0.25 µm or less as measured with a non-contact roughness meter.
- 極薄銅層表面のRtは非接触式粗さ計で測定して1.8μm以下である請求項1~5の何れか一項に記載のキャリア付き銅箔。 6. The copper foil with a carrier according to claim 1, wherein Rt on the surface of the ultrathin copper layer is 1.8 μm or less as measured with a non-contact type roughness meter.
- 極薄銅層表面のRzは非接触式粗さ計で測定して1.3μm以下である請求項1~3の何れか一項に記載のキャリア付き銅箔。 The copper foil with a carrier according to any one of claims 1 to 3, wherein Rz on the surface of the ultrathin copper layer is 1.3 µm or less as measured with a non-contact roughness meter.
- 極薄銅層表面のRaは非接触式粗さ計で測定して0.20μm以下である請求項1~4の何れか一項に記載のキャリア付き銅箔。 The copper foil with a carrier according to any one of claims 1 to 4, wherein Ra on the surface of the ultrathin copper layer is 0.20 µm or less as measured with a non-contact roughness meter.
- 極薄銅層表面のRtは非接触式粗さ計で測定して1.5μm以下である請求項1~5の何れか一項に記載のキャリア付き銅箔。 6. The copper foil with a carrier according to claim 1, wherein Rt on the surface of the ultrathin copper layer is 1.5 μm or less as measured with a non-contact type roughness meter.
- 極薄銅層表面のRzは非接触式粗さ計で測定して0.8μm以下である請求項1~3の何れか一項に記載のキャリア付き銅箔。 The copper foil with a carrier according to any one of claims 1 to 3, wherein Rz on the surface of the ultrathin copper layer is 0.8 µm or less as measured with a non-contact roughness meter.
- 極薄銅層表面のRaは非接触式粗さ計で測定して0.16μm以下である請求項1~4の何れか一項に記載のキャリア付き銅箔。 The copper foil with a carrier according to any one of claims 1 to 4, wherein Ra on the surface of the ultrathin copper layer is 0.16 µm or less as measured with a non-contact roughness meter.
- 極薄銅層表面のRtは非接触式粗さ計で測定して1.0μm以下である請求項1~5の何れか一項に記載のキャリア付き銅箔。 6. The copper foil with a carrier according to claim 1, wherein Rt on the surface of the ultrathin copper layer is 1.0 μm or less as measured with a non-contact type roughness meter.
- 極薄銅層表面は、Sskが-0.3~0.3である請求項1~6の何れか一項に記載のキャリア付き銅箔。 The copper foil with a carrier according to any one of claims 1 to 6, wherein the surface of the ultrathin copper layer has Ssk of -0.3 to 0.3.
- 極薄銅層表面は、Skuが2.7~3.3である請求項1~7の何れか一項に記載のキャリア付き銅箔。 The copper foil with a carrier according to any one of claims 1 to 7, wherein the surface of the ultrathin copper layer has a Sku of 2.7 to 3.3.
- 銅箔キャリアと、銅箔キャリア上に積層された剥離層と、剥離層の上に積層された極薄銅層とを備えたキャリア付き銅箔であって、極薄銅層は粗化処理されており、極薄銅層表面の表面積比が1.05~1.5であるキャリア付き銅箔。 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 being roughened A copper foil with a carrier having a surface area ratio of 1.05 to 1.5 on the surface of the ultrathin copper layer.
- 極薄銅層表面の表面積比が1.05~1.5である請求項1~9の何れか一項に記載のキャリア付き銅箔(ここで、表面積比とは、レーザー顕微鏡にてエリア及び実エリアを測定したときの、実エリア/エリアの値である。エリアとは測定基準面積を指し、実エリアとは測定基準面積中の表面積を指す。)。 10. The copper foil with a carrier according to claim 1, wherein the surface area ratio of the surface of the ultrathin copper layer is 1.05 to 1.5 (here, the surface area ratio means the area and the area with a laser microscope). (The real area / area value when the real area is measured. The area refers to the measurement reference area, and the real area refers to the surface area in the measurement reference area.)
- 極薄銅層表面の面積66524μm2当たりのレーザー顕微鏡にて測定される体積が300000μm3以上である請求項1~16の何れか一項に記載のキャリア付き銅箔。 The copper foil with a carrier according to any one of claims 1 to 16, wherein the volume measured with a laser microscope per area of 66524 μm 2 on the surface of the ultrathin copper layer is 300000 μm 3 or more.
- 前記粗化処理された極薄銅層の上に、耐熱層、防錆層、クロメート処理層及びシランカップリング処理層からなる群から選択された1種以上の層を有する請求項1~17の何れか一項に記載のキャリア付き銅箔。 The one or more layers selected from the group consisting of a heat-resistant layer, a rust preventive layer, a chromate treatment layer, and a silane coupling treatment layer are provided on the roughened ultrathin copper layer. The copper foil with a carrier as described in any one of Claims.
- 前記粗化処理された極薄銅層の上に樹脂層を備える請求項1~17の何れか一項に記載のキャリア付き銅箔。 The carrier-attached copper foil according to any one of claims 1 to 17, further comprising a resin layer on the roughened ultrathin copper layer.
- 前記耐熱層、防錆層、クロメート処理層及びシランカップリング処理層からなる群から選択された1種以上の層の上に樹脂層を備える請求項18に記載のキャリア付き銅箔。 The copper foil with a carrier according to claim 18, comprising a resin layer on one or more layers selected from the group consisting of the heat-resistant layer, the rust-proof layer, the chromate-treated layer, and the silane coupling-treated layer.
- 請求項1~20の何れか一項に記載のキャリア付き銅箔を用いて製造した銅張積層板。 A copper clad laminate produced using the copper foil with a carrier according to any one of claims 1 to 20.
- 請求項1~20の何れか一項に記載のキャリア付き銅箔を用いて製造したプリント配線板。 A printed wiring board manufactured using the carrier-attached copper foil according to any one of claims 1 to 20.
- 請求項1~20の何れか一項に記載のキャリア付き銅箔を用いて製造したプリント回路板。 A printed circuit board manufactured using the carrier-attached copper foil according to any one of claims 1 to 20.
- 請求項1~20の何れか一項に記載のキャリア付き銅箔と絶縁基板とを準備する工程、
前記キャリア付き銅箔と絶縁基板を積層する工程、
前記キャリア付き銅箔と絶縁基板を積層した後に、前記キャリア付き銅箔のキャリアを剥がす工程を経て銅張積層板を形成し、
その後、セミアディティブ法、サブトラクティブ法、パートリーアディティブ法又はモディファイドセミアディティブ法の何れかの方法によって、回路を形成する工程を含むプリント配線板の製造方法。 Preparing a copper foil with a carrier according to any one of claims 1 to 20 and an insulating substrate;
Laminating the copper foil with carrier and an insulating substrate;
After laminating the copper foil with carrier and the insulating substrate, a copper clad laminate is formed through a step of peeling the carrier of the copper foil with carrier,
Then, the manufacturing method of a printed wiring board including the process of forming a circuit by any method of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method. - 請求項1~20のいずれか一項に記載のキャリア付き銅箔の前記極薄銅層側表面に回路を形成する工程、
前記回路が埋没するように前記キャリア付銅箔の前記極薄銅層側表面に樹脂層を形成する工程、
前記樹脂層上に回路を形成する工程、
前記樹脂層上に回路を形成した後に、前記キャリアを剥離させる工程、及び、
前記キャリアを剥離させた後に、前記極薄銅層を除去することで、前記極薄銅層側表面に形成した、前記樹脂層に埋没している回路を露出させる工程
を含むプリント配線板の製造方法。 Forming a circuit on the ultrathin copper layer side surface of the copper foil with a carrier according to any one of claims 1 to 20,
Forming a resin layer on the ultrathin copper layer side surface of the carrier-attached copper foil so that the circuit is buried;
Forming a circuit on the resin layer;
Forming the circuit on the resin layer, and then peeling the carrier; and
After the carrier is peeled off, the printed wiring board includes a step of exposing the circuit embedded in the resin layer formed on the surface of the ultrathin copper layer by removing the ultrathin copper layer Method. - 前記樹脂層上に回路を形成する工程が、前記樹脂層上に別のキャリア付銅箔を極薄銅層側から貼り合わせ、前記樹脂層に貼り合わせたキャリア付銅箔を用いて前記回路を形成する工程である請求項25に記載のプリント配線板の製造方法。 The step of forming a circuit on the resin layer includes attaching another carrier-attached copper foil on the resin layer from the ultrathin copper layer side, and using the carrier-attached copper foil attached to the resin layer to form the circuit. 26. The method for manufacturing a printed wiring board according to claim 25, which is a forming step.
- 前記樹脂層上に貼り合わせる別のキャリア付銅箔が、請求項1~20のいずれか一項に記載のキャリア付銅箔である請求項25に記載のプリント配線板の製造方法。 The method for producing a printed wiring board according to claim 25, wherein another copper foil with a carrier to be bonded onto the resin layer is the copper foil with a carrier according to any one of claims 1 to 20.
- 前記樹脂層上に回路を形成する工程が、セミアディティブ法、サブトラクティブ法、パートリーアディティブ法又はモディファイドセミアディティブ法のいずれかの方法によって行われる請求項25~27のいずれか一項に記載のプリント配線板の製造方法。 The print according to any one of claims 25 to 27, wherein the step of forming a circuit on the resin layer is performed by any one of a semi-additive method, a subtractive method, a partly additive method, and a modified semi-additive method. A method for manufacturing a wiring board.
- キャリアを剥離する前に、キャリア付銅箔のキャリア側表面に基板を形成する工程を更に含む請求項25~28のいずれか一項に記載のプリント配線板の製造方法。 The method for producing a printed wiring board according to any one of claims 25 to 28, further comprising a step of forming a substrate on the carrier side surface of the copper foil with a carrier before peeling the carrier.
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KR1020177011125A KR102050646B1 (en) | 2012-09-11 | 2013-09-11 | Copper foil provided with carrier |
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JP2015205481A (en) * | 2014-04-22 | 2015-11-19 | Jx日鉱日石金属株式会社 | Copper foil with carrier, copper-clad laminate, printed wiring board, electronic apparatus and manufacturing method of printed wiring board |
JP2015214750A (en) * | 2014-04-24 | 2015-12-03 | Jx日鉱日石金属株式会社 | Copper foil with carrier, printed wiring board, laminate, electronic apparatus and manufacturing method of printed wiring board |
WO2016031960A1 (en) * | 2014-08-28 | 2016-03-03 | 株式会社有沢製作所 | Three-layer flexible metal-clad laminate and double-sided three-layer flexible metal-clad laminate |
JP2016049773A (en) * | 2014-08-28 | 2016-04-11 | 株式会社有沢製作所 | Three-layer flexible metal-clad laminate and double-sided three-layer flexible metal-clad laminate |
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CN106358377B (en) * | 2015-07-16 | 2019-09-13 | Jx金属株式会社 | Copper foil with carrier, laminate, the manufacturing method of laminate, the manufacturing method of the manufacturing method of printing distributing board and e-machine |
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US10950768B2 (en) | 2017-04-27 | 2021-03-16 | Kyocera Corporation | Circuit board and light-emitting device provided with same |
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WO2022255421A1 (en) * | 2021-06-03 | 2022-12-08 | 三井金属鉱業株式会社 | Roughened copper foil, copper clad laminate, and printed wiring board |
Also Published As
Publication number | Publication date |
---|---|
JP5481577B1 (en) | 2014-04-23 |
CN104619889A (en) | 2015-05-13 |
KR102050646B1 (en) | 2019-11-29 |
TW201533280A (en) | 2015-09-01 |
CN109379858A (en) | 2019-02-22 |
CN108588766B (en) | 2020-02-18 |
MY167704A (en) | 2018-09-21 |
TWI504788B (en) | 2015-10-21 |
KR101766554B1 (en) | 2017-08-08 |
KR20170046822A (en) | 2017-05-02 |
JP2014139336A (en) | 2014-07-31 |
CN107641820A (en) | 2018-01-30 |
PH12015500529B1 (en) | 2015-04-27 |
CN104619889B (en) | 2018-10-09 |
PH12015500529A1 (en) | 2015-04-27 |
KR20150052315A (en) | 2015-05-13 |
TWI575120B (en) | 2017-03-21 |
TW201428144A (en) | 2014-07-16 |
MY188679A (en) | 2021-12-22 |
CN108588766A (en) | 2018-09-28 |
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