JP6855164B2 - Copper foil with carrier foil and copper-clad laminate - Google Patents
Copper foil with carrier foil and copper-clad laminate Download PDFInfo
- Publication number
- JP6855164B2 JP6855164B2 JP2015515308A JP2015515308A JP6855164B2 JP 6855164 B2 JP6855164 B2 JP 6855164B2 JP 2015515308 A JP2015515308 A JP 2015515308A JP 2015515308 A JP2015515308 A JP 2015515308A JP 6855164 B2 JP6855164 B2 JP 6855164B2
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- Prior art keywords
- foil
- copper foil
- carrier foil
- carrier
- copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 218
- 239000011888 foil Substances 0.000 title claims description 213
- 239000011889 copper foil Substances 0.000 title claims description 191
- 238000010438 heat treatment Methods 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 31
- 238000004519 manufacturing process Methods 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 6
- -1 nitrogen-containing compound Chemical class 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- 239000010949 copper Substances 0.000 description 27
- 229910052802 copper Inorganic materials 0.000 description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 22
- 239000013078 crystal Substances 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 238000009792 diffusion process Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000005259 measurement Methods 0.000 description 10
- 239000000470 constituent Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000001887 electron backscatter diffraction Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 5
- 238000009713 electroplating Methods 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000007772 electroless plating Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- AZUHEGMJQWJCFQ-UHFFFAOYSA-N 1,1-bis(2h-benzotriazol-4-ylmethyl)urea Chemical compound C1=CC2=NNN=C2C(CN(CC=2C3=NNN=C3C=CC=2)C(=O)N)=C1 AZUHEGMJQWJCFQ-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- YUJRPTYFVGVHSW-UHFFFAOYSA-N [Co].P#[Sn] Chemical compound [Co].P#[Sn] YUJRPTYFVGVHSW-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- QZYDAIMOJUSSFT-UHFFFAOYSA-N [Co].[Ni].[Mo] Chemical compound [Co].[Ni].[Mo] QZYDAIMOJUSSFT-UHFFFAOYSA-N 0.000 description 1
- IGOJDKCIHXGPTI-UHFFFAOYSA-N [P].[Co].[Ni] Chemical compound [P].[Co].[Ni] IGOJDKCIHXGPTI-UHFFFAOYSA-N 0.000 description 1
- XLLNQZKHYSHONN-UHFFFAOYSA-N [Sn].[P].[Ni] Chemical compound [Sn].[P].[Ni] XLLNQZKHYSHONN-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- JPNWDVUTVSTKMV-UHFFFAOYSA-N cobalt tungsten Chemical compound [Co].[W] JPNWDVUTVSTKMV-UHFFFAOYSA-N 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- SIBIBHIFKSKVRR-UHFFFAOYSA-N phosphanylidynecobalt Chemical compound [Co]#P SIBIBHIFKSKVRR-UHFFFAOYSA-N 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
- H05K3/025—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates by transfer of thin metal foil formed on a temporary carrier, e.g. peel-apart copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/12—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/615—Microstructure of the layers, e.g. mixed structure
- C25D5/617—Crystalline layers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Electroplating Methods And Accessories (AREA)
Description
本件出願は、キャリア箔付銅箔に関する。特に、高温負荷を受けた後でも、キャリア箔を容易に引き剥がすことの可能なピーラブルタイプのキャリア箔付銅箔に関する。 This application relates to copper foil with carrier foil. In particular, the present invention relates to a peelable type copper foil with a carrier foil, which can easily peel off the carrier foil even after receiving a high temperature load.
従来より、本件出願人は、ファインピッチ回路を備えるプリント配線板の製造原料として特許文献1等に開示のキャリア箔付銅箔を提案してきた。特許文献1に開示のキャリア箔付銅箔は、いわゆるピーラブルタイプのキャリア箔付銅箔であり、キャリア箔の表面上に、有機系剤を用いて形成した接合界面層を形成し、その接合界面層上に電解銅箔層を析出形成させたことを特徴としている。当該キャリア箔付銅箔によれば、接合界面層の剥離強度を低く維持し、しかも安定化させることができるため、プレス成形した後のキャリア箔の引き剥がし強度の不安定さを解消し、小さな力で安定したキャリア箔の引き剥がしをすることが可能になる。
Conventionally, the applicant has proposed a copper foil with a carrier foil disclosed in
しかしながら、近年、プリント配線板製造プロセスにおいて、キャリア箔付銅箔と絶縁層構成材との張り合わせる際のプレス温度が、より高くなる傾向にある。特に、300℃を超える温度が負荷される場合もある。このような場合には、特許文献1に開示のキャリア箔付銅箔では、高温負荷によりキャリア箔と電解銅箔の金属同士が相互に拡散することにより、キャリア箔と電解銅箔とが連結して、電解銅箔からキャリア箔を引き剥がせなくなる。
However, in recent years, in the printed wiring board manufacturing process, the press temperature at the time of laminating the copper foil with the carrier foil and the insulating layer constituent material tends to be higher. In particular, a temperature exceeding 300 ° C. may be loaded. In such a case, in the copper foil with a carrier foil disclosed in
そこで、本件出願人は、300℃を越える温度が負荷される場合にも、小さな力で安定したキャリア箔の引き剥がしをすることが可能なキャリア箔付銅箔として、特許文献2に記載のキャリア箔付銅箔を提案してきた。この特許文献2に開示のキャリア付銅箔は、チオシアヌル酸を用いて接合界面層を形成することにより、加熱前及び225〜360℃の範囲での加熱後において、キャリア箔と電解銅箔との接合界面での引き剥がし強度が200gf/cm以下のレベルを実現している。当該キャリア箔付銅箔によれば、従来のピーラブルタイプのキャリア箔付銅箔に比べ極めて小さく、しかも安定したキャリア箔の除去が可能になる。
Therefore, the applicant has described the carrier described in
さらに、本件出願人は、特許文献3において、キャリア箔の表面に有機剤を用いて有機接合界面層を形成し、その有機接合界面層の上にニッケル、ニッケル合金、コバルト、コバルト合金のいずれかを用いた異種金属層を形成し、その異種金属層の上に電解銅箔層を備えるキャリア箔付銅箔の製造方法等を提案してきた。この製造方法により得られるキャリア箔付銅箔は、「キャリア箔/有機接合界面層/ニッケル、コバルト等の異種金属層/電解銅箔層」の層構成を備える。当該キャリア箔付銅箔は、異種金属層を備えることにより、300℃を超える温度が負荷される場合にキャリア箔と電解銅箔とが連結するのをより安定的に防止することができる。
Further, in
しかしながら、250℃以上の温度が負荷された場合には、特許文献2及び特許文献3に開示のキャリア箔付銅箔であっても、キャリア箔付銅箔のキャリア箔を電解銅箔から引き剥がす際の引き剥がし強さ(以下、単に「キャリア箔引き剥がし強さ」と称する。)に大きなロット内ばらつきが生じていた。そして、このようにキャリア箔付銅箔のキャリア箔引き剥がし強さが大きくなるときには、上述のようにキャリア箔と電解銅箔とが連結し、電解銅箔からキャリア箔を容易に引き剥がせなくなるという現象が確認できた。
However, when a temperature of 250 ° C. or higher is applied, the carrier foil of the copper foil with carrier foil is peeled off from the electrolytic copper foil even if the copper foil with carrier foil disclosed in
この様子を示すのが図2である。この図2は、従来のキャリア箔付銅箔に対して、250℃×60分の加熱処理を行った後、その断面を観察したものである。この図2の下段の拡大した接合界面層の中には、高温負荷により形成された、比較的大きな相互拡散部位が確認できる。このときの様子を模式的に分かりやすく示したのが図3である。この図3の中には、キャリア箔2と銅箔3との間の接合界面層4を貫通して、高温負荷により形成された相互拡散部位(以下、単に「連結部5」と称する。)を示している。この連結部5が大きく、且つ、多くなると、銅箔からキャリア箔を容易に引き剥がせなくなることが判明してきた。
FIG. 2 shows this situation. FIG. 2 shows a cross section of a conventional copper foil with a carrier foil after being heat-treated at 250 ° C. for 60 minutes. In the enlarged joint interface layer in the lower part of FIG. 2, a relatively large mutual diffusion site formed by a high temperature load can be confirmed. FIG. 3 schematically shows the situation at this time in an easy-to-understand manner. In FIG. 3, a mutual diffusion site formed by a high temperature load penetrating the
以上のことから、本件発明は、250℃以上の温度が負荷される銅張積層板製造に用いても、銅箔からキャリア箔を容易に引き剥がすことが可能であり、ロット内ばらつきの少ないキャリア箔付銅箔の提供を目的とする。 From the above, the present invention can easily peel off the carrier foil from the copper foil even when used for manufacturing a copper-clad laminate to which a temperature of 250 ° C. or higher is applied, and the carrier with little variation in lots. The purpose is to provide copper foil with foil.
そこで、本件発明者等の鋭意研究の結果、250℃以上の温度で加熱処理を行った後のキャリア箔付銅箔において、キャリア箔が以下に述べる一定の条件を備えることにより、キャリア箔と銅箔との間の接合界面層に連結部が形成されることが抑制され、銅箔からキャリア箔を容易に引き剥がすことが可能であることに想到した。以下、この技術思想について説明する。 Therefore, as a result of diligent research by the inventors of the present invention, the carrier foil and copper are provided with certain conditions described below in the copper foil with a carrier foil after being heat-treated at a temperature of 250 ° C. or higher. It was conceived that the formation of a connecting portion in the bonding interface layer between the foils was suppressed, and the carrier foil could be easily peeled off from the copper foil. Hereinafter, this technical idea will be described.
キャリア箔付銅箔: 本件出願に係るキャリア箔付銅箔は、キャリア箔/接合界面層/銅箔層の層構成を備えるキャリア箔付銅箔であって、当該キャリア箔として、250℃×60分の加熱処理を行った後に40kgf/mm 2 以上の引張強さを備える電解銅箔を用い、当該加熱処理を行った後に、当該接合界面層内に存在する当該キャリア箔と当該銅箔層との連結部において、当該キャリア箔付銅箔の厚さ方向に直交する方向を長さ方向としたときに、長さ2000nmに相当する接合界面層内に存在する連結部のトータル長さが500nm以下であることを特徴とする。 Copper foil with carrier foil: The copper foil with carrier foil according to the present application is a copper foil with a carrier foil having a layer structure of a carrier foil / a bonding interface layer / a copper foil layer, and the carrier foil is 250 ° C. × 60. After the heat treatment for a minute, an electrolytic copper foil having a tensile strength of 40 kgf / mm 2 or more was used, and after the heat treatment, the carrier foil existing in the bonding interface layer and the copper foil layer The total length of the connecting portion existing in the bonding interface layer corresponding to the length of 2000 nm is 500 nm or less when the direction orthogonal to the thickness direction of the copper foil with the carrier foil is defined as the length direction. It is characterized by being.
銅張積層板: 本件出願に係る銅張積層板は、上述のキャリア箔付銅箔を用いて得られることを特徴とする。 Copper-clad laminate: The copper-clad laminate according to the present application is characterized in that it is obtained by using the above-mentioned copper foil with a carrier foil.
プリント配線板の製造方法: 本件出願に係るプリント配線板の製造方法は、上述のキャリア箔付銅箔を用いて製造することを特徴とする。 Method for manufacturing a printed wiring board: production method of the present filed on the printed wiring board is characterized in that produced using the copper foil with carrier foil above.
本件出願に係るキャリア箔付銅箔は、250℃以上の温度が負荷されても、電解銅箔からキャリア箔を容易に引き剥がすことが可能であり、ロット内ばらつきを少なくすることができる。よって、250℃以上の温度が負荷される銅張積層板製造において好適に使用できる。 In the copper foil with a carrier foil according to the present application, the carrier foil can be easily peeled off from the electrolytic copper foil even when a temperature of 250 ° C. or higher is applied, and variations within the lot can be reduced. Therefore, it can be suitably used in the production of copper-clad laminates to which a temperature of 250 ° C. or higher is applied.
以下、本件出願に係る「キャリア箔付銅箔」及び「銅張積層板」の形態に関して説明する。 Hereinafter, the forms of the "copper foil with carrier foil" and the "copper-clad laminate" according to the present application will be described.
キャリア箔付銅箔の形態: 本件出願に係るキャリア箔付銅箔は、キャリア箔/接合界面層/銅箔層の層構成を備えている。そして、このキャリア箔として、250℃×60分の加熱処理を行った後に40kgf/mm2以上の引張強さを備える電解銅箔を用いることを特徴としている。なお、「250℃×60分」という加熱条件は、プリント配線板用銅箔とプリプレグ等の絶縁層構成材とを積層して銅張積層板を製造する際に一般に採用される加熱条件に相当する。Form of Copper Foil with Carrier Foil: The copper foil with carrier foil according to the present application has a layer structure of a carrier foil / a bonding interface layer / a copper foil layer. The carrier foil is characterized by using an electrolytic copper foil having a tensile strength of 40 kgf / mm 2 or more after being heat-treated at 250 ° C. for 60 minutes. The heating condition of "250 ° C. x 60 minutes" corresponds to the heating condition generally adopted when manufacturing a copper-clad laminate by laminating a copper foil for a printed wiring board and an insulating layer constituent material such as a prepreg. To do.
キャリア箔として「250℃×60分の加熱処理を行った後の引張強さが40kgf/mm2以上」の電解銅箔を採用すれば、加熱工程におけるキャリア箔の結晶成長を阻害することにより加熱工程におけるキャリア箔側の銅の拡散を遅くすることができ、連結部が形成されるのを防止することができる。その結果、ロット内ばらつきなく加熱後に銅箔層からキャリア箔を引き剥がす際の引き剥がし強さが安定して200gf/cm以下となり、好ましくは50gf/cm以下に抑制することができる。一方、キャリア箔として、250℃×60分の加熱処理を行った後の引張強さが40kgf/mm2未満の電解銅箔を用いると、ロットによっては、上記連結部が形成され、加熱後に銅箔層からキャリア箔を引き剥がす際の引き剥がし強さが200gf/cmを超える場合がある。また、連結部が形成された箇所においては、銅箔層が破れて、キャリア箔の表面に残留する場合もある。これらのことから、上記加熱条件で加熱処理を行った後の引張強さが40kgf/mm2未満の電解銅箔をキャリア箔として用いることは、引き剥がし作業が困難になる場合があるため好ましくない。 If an electrolytic copper foil having a tensile strength of 40 kgf / mm 2 or more after being heat-treated at 250 ° C. for 60 minutes is used as the carrier foil, it is heated by inhibiting the crystal growth of the carrier foil in the heating step. It is possible to slow down the diffusion of copper on the carrier foil side in the process and prevent the formation of a connecting portion. As a result, the peeling strength when peeling the carrier foil from the copper foil layer after heating without variation within the lot is stably 200 gf / cm or less, preferably 50 gf / cm or less. On the other hand, if an electrolytic copper foil having a tensile strength of less than 40 kgf / mm 2 after heat treatment at 250 ° C. for 60 minutes is used as the carrier foil, the connecting portion is formed depending on the lot, and copper is formed after heating. The peeling strength when peeling the carrier foil from the foil layer may exceed 200 gf / cm. Further, at the place where the connecting portion is formed, the copper foil layer may be torn and remain on the surface of the carrier foil. For these reasons, it is not preferable to use an electrolytic copper foil having a tensile strength of less than 40 kgf / mm 2 after the heat treatment under the above heating conditions as the carrier foil because the peeling operation may become difficult. ..
本件出願に係るキャリア箔は、上記加熱条件での加熱後の引張り強さが上記特定の範囲にあればよく、当該キャリア箔の加熱前の引張り強さは特に限定されるものではない。当該キャリア箔として、加熱前の状態において、亜鉛やスズ等の金属成分により被覆された電解銅箔も使用可能である。亜鉛やスズ等の金属成分により被覆された電解銅箔を250〜400℃程度で加熱すれば、被覆金属成分が電解銅箔内に拡散し、加熱工程におけるキャリア箔の結晶成長が阻害されるため、加熱前の機械的強度を維持することができる。従って、このような電解銅箔も本件出願に係るキャリア箔付銅箔のキャリア箔として好適である。 The carrier foil according to the present application may have a tensile strength after heating under the above heating conditions within the above-mentioned specific range, and the tensile strength before heating of the carrier foil is not particularly limited. As the carrier foil, an electrolytic copper foil coated with a metal component such as zinc or tin before heating can also be used. When an electrolytic copper foil coated with a metal component such as zinc or tin is heated at about 250 to 400 ° C., the coated metal component diffuses into the electrolytic copper foil and the crystal growth of the carrier foil in the heating step is hindered. , The mechanical strength before heating can be maintained. Therefore, such an electrolytic copper foil is also suitable as a carrier foil for the copper foil with a carrier foil according to the present application.
また、当該電解銅箔は、「250℃×60分の加熱処理を行った後の平均結晶粒径が1.0μm未満」であることが好ましい。電解銅箔の結晶組織と、引張り強さとの間には一定の相関関係があり、結晶組織を構成する結晶粒が微細であると、その電解銅箔の引張強さは比較的高い値を示す。平均結晶粒径が1.0μm未満という微細な結晶粒により構成される電解銅箔は、概ね40kgf/mm2以上の高い引張強さを示す。なお、本件出願における平均結晶粒径とは、EBSD法に準じて、電解銅箔の断面の結晶状態を表す画像データをEBSD解析することにより行う。なお、具体的な測定方法の一例については、実施例の中で説明する。Further, it is preferable that the electrolytic copper foil has an average crystal grain size of less than 1.0 μm after being heat-treated at 250 ° C. for 60 minutes. There is a certain correlation between the crystal structure of the electrolytic copper foil and the tensile strength, and when the crystal grains constituting the crystal structure are fine, the tensile strength of the electrolytic copper foil shows a relatively high value. .. The electrolytic copper foil composed of fine crystal grains having an average crystal grain size of less than 1.0 μm exhibits a high tensile strength of about 40 kgf / mm 2 or more. The average crystal grain size in the present application is determined by EBSD analysis of image data representing the crystal state of the cross section of the electrolytic copper foil according to the EBSD method. An example of a specific measurement method will be described in the examples.
本件出願に係るキャリア箔付銅箔は、当該接合界面層内にキャリア箔と銅箔層とを連結する連結部を備え、その最大連結部径が200nm以下であることが好ましい。この最大連結部径が200nmを超えた部位が存在すると、その部位でキャリア箔を引き剥がすことが困難になる場合があり、キャリア箔を無理に引き剥がすと、200nmを超えた連結部で銅箔層が破れて、キャリア箔の表面に残留する傾向が高くなる。但し、本件出願に係るキャリア箔付銅箔において連結部とは、上記加熱条件等により加熱された際に、キャリア箔と銅箔層との間で銅が相互に拡散することにより、当該接合界面層を貫通して、当該キャリア箔と当該銅箔層とを連結する相互拡散部位を示している。 The copper foil with a carrier foil according to the present application preferably includes a connecting portion for connecting the carrier foil and the copper foil layer in the bonding interface layer, and the maximum connecting portion diameter thereof is 200 nm or less. If there is a portion where the maximum connecting portion diameter exceeds 200 nm, it may be difficult to peel off the carrier foil at that portion. If the carrier foil is forcibly peeled off, the copper foil is formed at the connecting portion exceeding 200 nm. The layer is more likely to tear and remain on the surface of the carrier foil. However, in the copper foil with a carrier foil according to the present application, the connecting portion is the bonding interface due to mutual diffusion of copper between the carrier foil and the copper foil layer when heated under the above heating conditions and the like. The mutual diffusion site that penetrates the layer and connects the carrier foil and the copper foil layer is shown.
また、本件出願に係るキャリア箔付銅箔は、上述のように当該キャリア箔付銅箔の厚さ方向に直交する方向を長さ方向としたときに、2000nmに相当する接合界面層内に存在する連結部のトータル長さが500nm以下であることが好ましい。なお、この連結部のトータル長さは、2000nmの幅の接合界面層内に存在する各連結部の各連結部径の合計長さに相当する。この連結部のトータル長さが500nmを超えると、加熱による相互拡散が過剰に起きていることになり、キャリア箔の引き剥がしが困難になる場合があり好ましくない。Further, the copper foil with carrier foil according to the present application exists in the bonding interface layer corresponding to 2000 nm when the direction orthogonal to the thickness direction of the copper foil with carrier foil is defined as the length direction as described above. It is preferable that the total length of the connecting portion is 500 nm or less. The total length of the connecting portions corresponds to the total length of each connecting portion diameter of each connecting portion existing in the bonding interface layer having a width of 2000 nm. If the total length of the connecting portion exceeds 500 nm, mutual diffusion due to heating occurs excessively, which may make it difficult to peel off the carrier foil, which is not preferable.
そして、本件出願に係るキャリア箔付銅箔は、前記キャリア箔付銅箔に250℃×60分の加熱処理を行った後の当該接合界面層の断面において、長さ2000nmに相当する当該接合界面層内に存在する平均連結部径が50nm以下であることが好ましい。この平均連結部径が50nmを超えると、銅箔層からキャリア箔を引き剥がす際の引き剥がし強さが200gf/cmを超える場合があり、銅箔層が破れてキャリア箔の表面に残留するようになるため好ましくない。ここで、図3の符号5で示したのが、加熱によりキャリア箔2と銅箔層3との間で起きた銅の拡散により形成した「連結部」であり、図3に符号「R1,R2,R3,R4,R5,R6」で示したのが「連結部径」である。そして、図3の場合の「平均連結部径」とは、6つの連結部径R1,R2,R3,R4,R5,R6を足した和の値を、6で割った値となる。
The copper foil with carrier foil according to the present application has a bonding interface corresponding to a length of 2000 nm in the cross section of the bonding interface layer after the copper foil with carrier foil is heat-treated at 250 ° C. for 60 minutes. The average connecting portion diameter existing in the layer is preferably 50 nm or less. If the average connecting portion diameter exceeds 50 nm, the peeling strength when peeling the carrier foil from the copper foil layer may exceed 200 gf / cm, so that the copper foil layer is torn and remains on the surface of the carrier foil. It is not preferable because it becomes. Here,
以上に述べてきた本件出願に係るキャリア箔付銅箔の前記接合界面層は、厚さ5nm〜60nmであることが好ましい。この接合界面層が厚さ5nm未満になると、キャリア箔と銅箔層との距離が近くなり過ぎて、キャリア箔と銅箔層との間で起こる銅の拡散が容易になるため好ましくない。一方、接合界面層が厚さ60nmを超えると、キャリア箔が銅箔層を保持することが不安定になるため好ましくない。そして、当該接合界面層は、厚さ5nm〜30nmであることが、より好ましい。当該接合界面層が厚さ30nm以下の場合、接合界面層の厚さのばらつきが少なくなり、加熱によって接合界面内に形成される連結部の分布が極めて均一になるため、銅箔層からキャリア箔を引き剥がす際の引き剥がし強さが安定するからである。 The bonded interface layer of the copper foil with a carrier foil according to the present application described above preferably has a thickness of 5 nm to 60 nm. If the thickness of the bonding interface layer is less than 5 nm, the distance between the carrier foil and the copper foil layer becomes too close, and the diffusion of copper that occurs between the carrier foil and the copper foil layer becomes easy, which is not preferable. On the other hand, if the thickness of the bonding interface layer exceeds 60 nm, it becomes unstable for the carrier foil to hold the copper foil layer, which is not preferable. The bonded interface layer is more preferably 5 nm to 30 nm in thickness. When the bonding interface layer has a thickness of 30 nm or less, the variation in the thickness of the bonding interface layer is small, and the distribution of the connecting portions formed in the bonding interface by heating becomes extremely uniform. Therefore, the copper foil layer to the carrier foil This is because the peeling strength at the time of peeling is stable.
本件出願に係るキャリア箔付銅箔の前記接合界面層は、有機成分を用いて形成する「有機系接合界面層」と、無機成分を用いて形成する「無機系接合界面層」とがある。 The bonding interface layer of the copper foil with a carrier foil according to the present application includes an "organic bonding interface layer" formed by using an organic component and an "inorganic bonding interface layer" formed by using an inorganic component.
そして、「有機系接合界面層」を採用する場合は、有機成分として、窒素含有有機化合物、硫黄含有有機化合物及びカルボン酸からなる群から選択される化合物の少なくとも一つ以上を含むものを用いることが好ましい。ここでいう窒素含有有機化合物には、置換基を有する窒素含有有機化合物を含んでいる。具体的には、窒素含有有機化合物としては、置換基を有するトリアゾール化合物である1,2,3−ベンゾトリアゾール、カルボキシベンゾトリアゾール、N’,N’−ビス(ベンゾトリアゾリルメチル)ユリア、1H−1,2,4−トリアゾール及び3−アミノ−1H−1,2,4−トリアゾール等を用いることが好ましい。そして、硫黄含有有機化合物としては、メルカプトベンゾチアゾール、チオシアヌル酸及び2−ベンズイミダゾールチオール等を用いることが好ましい。また、カルボン酸としては、モノカルボン酸を用いることが好ましく、中でもオレイン酸、リノール酸及びリノレイン酸等を用いることが好ましい。これらの有機成分は、高温耐熱性に優れ、キャリア箔の表面に厚さ5nm〜60nmの接合界面層を形成することが容易だからである。 When the "organic bonding interface layer" is adopted, a compound containing at least one or more of compounds selected from the group consisting of nitrogen-containing organic compounds, sulfur-containing organic compounds and carboxylic acids should be used as organic components. Is preferable. The nitrogen-containing organic compound referred to here includes a nitrogen-containing organic compound having a substituent. Specifically, as the nitrogen-containing organic compound, 1,2,3-benzotriazole, carboxybenzotriazole, N', N'-bis (benzotriazolylmethyl) urea, 1H, which are triazole compounds having a substituent, are used. It is preferable to use -1,2,4-triazole, 3-amino-1H-1,2,4-triazole and the like. As the sulfur-containing organic compound, it is preferable to use mercaptobenzothiazole, thiothianulic acid, 2-benzimidazole thiol and the like. Further, as the carboxylic acid, it is preferable to use a monocarboxylic acid, and among them, oleic acid, linoleic acid, linoleic acid and the like are preferably used. This is because these organic components have excellent high-temperature heat resistance, and it is easy to form a bonded interface layer having a thickness of 5 nm to 60 nm on the surface of the carrier foil.
そして、「無機系接合界面層」を採用する場合には、無機成分としてNi、Mo、Co、Cr、Fe、Ti、W、P又は、これらを主成分とする合金又は化合物からなる群から選択される少なくとも一種以上を用いることが可能である。これらの無機系接合界面層の場合、電解めっき法、無電解めっき法等の湿式成膜法やスパッタ法、蒸着法等の乾式成膜法等の公知の手法を用いて形成することが可能である。 When the "inorganic bonding interface layer" is adopted, it is selected from the group consisting of Ni, Mo, Co, Cr, Fe, Ti, W, P as the inorganic component, or an alloy or compound containing these as main components. It is possible to use at least one or more of the following. These inorganic bonded interface layers can be formed by using a known method such as a wet film forming method such as an electroplating method or an electroless plating method, or a dry film forming method such as a sputtering method or a vapor deposition method. is there.
以上に述べてきた本件出願に係るキャリア箔付銅箔は、キャリア箔/接合界面層/銅箔層の層構成を備える。加熱後に銅箔層からキャリア箔を安定して引き剥がし可能とするには、上述のとおり、接合界面層を介してキャリア箔と銅箔層との間における銅の拡散を抑制する必要がある。この銅の拡散挙動をより効果的に抑制するため、本件出願に係るキャリア箔付銅箔は、キャリア箔と銅箔層との間に、加熱による銅の拡散を抑制するため耐熱金属層を設けることが好ましい。具体的には、本件出願に係るキャリア箔付銅箔は、「キャリア箔/接合界面層/耐熱金属層/銅箔層」、「キャリア箔/耐熱金属層/接合界面層/銅箔層」等の層構成を備えることが好ましい。 The copper foil with a carrier foil according to the present application described above has a layer structure of a carrier foil / a bonding interface layer / a copper foil layer. In order to enable the carrier foil to be stably peeled off from the copper foil layer after heating, it is necessary to suppress the diffusion of copper between the carrier foil and the copper foil layer via the bonding interface layer as described above. In order to more effectively suppress the diffusion behavior of copper, the copper foil with a carrier foil according to the present application is provided with a heat-resistant metal layer between the carrier foil and the copper foil layer in order to suppress the diffusion of copper due to heating. Is preferable. Specifically, the copper foil with carrier foil according to the present application includes "carrier foil / bonding interface layer / heat-resistant metal layer / copper foil layer", "carrier foil / heat-resistant metal layer / bonding interface layer / copper foil layer", etc. It is preferable to have a layer structure of.
そして、この耐熱金属層は、耐熱安定性を考慮して、ニッケルや、ニッケル−燐、ニッケル−クロム、ニッケル−モリブデン、ニッケル−モリブデン−コバルト、ニッケル−コバルト、ニッケル−タングステン、ニッケル−錫−燐等のニッケル合金、コバルト、コバルト−燐、コバルト−モリブデン、コバルト−タングステン、コバルト−銅、コバルト−ニッケル−燐、コバルト−錫−燐等のコバルト合金のいずれかで構成されたものを用いることが好ましい。この耐熱金属層は、電解めっき法、無電解めっき法等の湿式成膜法やスパッタ法、蒸着法等の乾式成膜法等の公知の手法を用いて形成することが可能である。そして、耐熱金属層の厚さは、1nm〜50nmとすることが好ましい。 In consideration of heat resistance stability, this heat-resistant metal layer is composed of nickel, nickel-phosphorus, nickel-chromium, nickel-molybdenum, nickel-molybdenum-cobalt, nickel-cobalt, nickel-tungsten, nickel-tin-phosphorus. , Cobalt, cobalt-phosphorus, cobalt-molybdenum, cobalt-tungsten, cobalt-copper, cobalt-nickel-phosphorus, cobalt-tin-phosphorus, etc. preferable. This heat-resistant metal layer can be formed by using a known method such as a wet film forming method such as an electroplating method or an electroless plating method, or a dry film forming method such as a sputtering method or a vapor deposition method. The thickness of the heat-resistant metal layer is preferably 1 nm to 50 nm.
なお、本件出願に係るキャリア箔付銅箔において、キャリア箔の厚さに関して、特段の限定は無く、キャリア箔としての機能可能な9μm〜200μmの厚さと考えれば足りる。また、銅箔層の厚さに関しても、特段の限定は無いが、キャリア箔を必要とする薄い銅箔と考え、0.1μm〜18μm程度の厚さと考えればよい。 In the copper foil with a carrier foil according to the present application, there is no particular limitation on the thickness of the carrier foil, and it is sufficient to consider it as a thickness of 9 μm to 200 μm that can function as a carrier foil. The thickness of the copper foil layer is also not particularly limited, but may be considered to be a thin copper foil that requires a carrier foil, and may be considered to have a thickness of about 0.1 μm to 18 μm.
以上に述べてきたキャリア箔付銅箔は、キャリア箔として「250℃×60分の加熱処理を行った後に40kgf/mm2以上の引張強さを備える電解銅箔」を用い、キャリア箔/接合界面層/銅箔層の層構成を備えればよく、銅箔層を構成する銅箔については特に限定されるものではなく、その製法についても限定はない。例えば、銅箔層は、電解めっき法、或いは、無電解めっき法等の湿式成膜法により形成された銅層であってもよいし、スパッタ法、蒸着法等の乾式成膜法により形成された銅層であってもよく、これらの製法を適宜併用して、銅箔層を製法の異なる複数の銅層により形成してもよい。しかしながら、乾式成膜法と比較すると製造コストが安価であることなどから、湿式成膜法により形成された銅層であることが好ましい。また、無電解めっき法と比較すると、所定の厚みの銅層を工業的製造速度に見合った速さで成膜することができるという観点から、電解めっき法により形成した電解銅箔層であることが好ましい。電解銅箔は、その結晶組織がエッチング加工に適したものとなり、プリント配線板等の回路形成層として用いるのに適している。銅箔層を電解めっき法により成膜する場合、本件出願に係るキャリア箔付銅箔は、例えば、上述の特許文献1に開示した製造方法で製造できる。即ち、キャリア箔表面を酸洗処理等で清浄化し、清浄化したキャリア箔の表面に接合界面層を形成し、その接合界面層の上に銅箔層を形成し、必要に応じて当該銅箔層の表面に粗化処理、防錆処理、シランカップリング剤処理等を施して、乾燥処理して製造することができる。As the copper foil with a carrier foil described above, "an electrolytic copper foil having a tensile strength of 40 kgf / mm 2 or more after heat treatment at 250 ° C. for 60 minutes" is used as the carrier foil, and the carrier foil / bonding is performed. The layer structure of the interface layer / copper foil layer may be provided, and the copper foil constituting the copper foil layer is not particularly limited, and the manufacturing method thereof is also not limited. For example, the copper foil layer may be a copper layer formed by a wet film forming method such as an electrolytic plating method or a electroless plating method, or may be formed by a dry film forming method such as a sputtering method or a vapor deposition method. It may be a copper layer, or a copper foil layer may be formed by a plurality of copper layers having different manufacturing methods by appropriately using these manufacturing methods in combination. However, the copper layer formed by the wet film forming method is preferable because the manufacturing cost is lower than that of the dry film forming method. Further, as compared with the electroless plating method, the electrolytic copper foil layer is formed by the electrolytic plating method from the viewpoint that a copper layer having a predetermined thickness can be formed at a speed commensurate with the industrial production speed. Is preferable. The electrolytic copper foil has a crystal structure suitable for etching, and is suitable for use as a circuit forming layer for a printed wiring board or the like. When the copper foil layer is formed by an electrolytic plating method, the copper foil with a carrier foil according to the present application can be produced, for example, by the production method disclosed in
本件出願に係るキャリア箔付銅箔は、後述する銅張積層板、プリント配線板を製造する際に用いることができる。また、コアレスビルドアップ多層プリント配線板を製造する際に、当該キャリア箔付銅箔を支持基板として用いることができる。具体的には、当該キャリア箔付銅箔とプリプレグ等とを積層した支持基板の表面に、ビルドアップ法により必要な層数のビルドアップ層を形成する。その後、当該キャリア箔付銅箔の接合界面層でキャリア箔と銅箔層とを剥離して、ビルドアップ層を分離する。このような工程により、コアレスビルドアップ多層プリント配線板を得ることができる。当該キャリア箔付銅箔を支持基板として用いれば、当該キャリア箔付銅箔上に絶縁層を積層する際等に、250℃以上の温度で加熱されても、上述したとおり、キャリア箔から銅箔層への銅の拡散が遅く、上記連結部が形成されるのを抑制することができる。このため、キャリア箔と銅箔層とを剥離する際に、キャリア箔を安定的に引き剥がすことができる。従って、ビルドアップ層を形成した後、キャリア箔と銅箔層とを剥離する際に銅箔層がキャリア箔側に残留する等の不具合が生じず、歩留まりの低下を抑制することができる。更に、本件出願に係るキャリア箔付銅箔は、上述したとおり、キャリア箔の引張強さが高いため、支持基板に要求される機械的強度を満足することができ、支持基板の反り等を防いでハンドリングを容易にすることができる。また、当該キャリア箔付銅箔のキャリア箔の厚さが薄くとも、支持基板に要求される機械的強度を満足することができるため、支持基板の反り等を防止するためにキャリア箔の厚さを厚くする必要がなく、資源の無駄な消費を抑制することができる。 The copper foil with carrier foil according to the present application can be used when manufacturing a copper-clad laminate and a printed wiring board, which will be described later. Further, when manufacturing a coreless build-up multilayer printed wiring board, the copper foil with a carrier foil can be used as a support substrate. Specifically, a build-up layer having a required number of layers is formed on the surface of a support substrate in which the copper foil with a carrier foil and a prepreg or the like are laminated by a build-up method. Then, the carrier foil and the copper foil layer are peeled off at the bonding interface layer of the copper foil with the carrier foil to separate the build-up layer. Through such a process, a coreless build-up multilayer printed wiring board can be obtained. When the copper foil with a carrier foil is used as a support substrate, even if the insulating layer is laminated on the copper foil with a carrier foil and heated at a temperature of 250 ° C. or higher, as described above, the copper foil is transferred from the carrier foil. The diffusion of copper into the layer is slow, and the formation of the connecting portion can be suppressed. Therefore, when the carrier foil and the copper foil layer are peeled off, the carrier foil can be stably peeled off. Therefore, after the build-up layer is formed, when the carrier foil and the copper foil layer are peeled off, problems such as the copper foil layer remaining on the carrier foil side do not occur, and a decrease in yield can be suppressed. Further, as described above, the copper foil with a carrier foil according to the present application has a high tensile strength of the carrier foil, so that the mechanical strength required for the support substrate can be satisfied and the support substrate is prevented from warping. Can be easily handled with. Further, even if the thickness of the carrier foil of the copper foil with the carrier foil is thin, the mechanical strength required for the support substrate can be satisfied, so that the thickness of the carrier foil is prevented in order to prevent warpage of the support substrate. It is not necessary to increase the thickness, and wasteful consumption of resources can be suppressed.
銅張積層板: 本件出願に係る銅張積層板は、上述の本件出願に係るキャリア箔付銅箔と絶縁層構成材とを張り合わせたものであり、リジッド銅張積層板、フレキシブル銅張積層板の双方を含む。即ち、ここでいう絶縁層構成材の種類に関しては、特段の限定は無い。本件出願に係るキャリア箔付銅箔を用いれば、絶縁層構成材に張り合わせる際に、250℃以上の温度で加熱されても、上述のとおり、連結部が形成されにくいため、キャリア箔を安定的に引き剥がすことができる。また、キャリア箔の厚さが薄くても、十分な機械的強度を有するため、当該銅張積層板をハンドリングする際に、銅張積層板が反り等の不具合が生じにくく、ハンドリングが容易になる。 Copper-clad laminate: The copper-clad laminate according to the present application is a laminate of the above-mentioned copper foil with carrier foil and the insulating layer constituent material according to the present application, and is a rigid copper-clad laminate and a flexible copper-clad laminate. Including both. That is, there is no particular limitation on the type of the insulating layer constituent material referred to here. If the copper foil with a carrier foil according to the present application is used, the carrier foil is stable because the connecting portion is difficult to form as described above even if it is heated at a temperature of 250 ° C. or higher when it is attached to the insulating layer constituent material. Can be peeled off. Further, even if the thickness of the carrier foil is thin, it has sufficient mechanical strength, so that when handling the copper-clad laminate, problems such as warping of the copper-clad laminate are less likely to occur, and handling becomes easier. ..
プリント配線板: 本件出願に係るプリント配線板は、上述の本件出願に係るキャリア箔付銅箔を用いて得られたものであり、リジッドタイプのプリント配線板、フレキシブルタイプのプリント配線板の双方を含む。また、本件出願に係るプリント配線板は、片面プリント配線板、両面プリント配線板、多層プリント配線板等、全てのプリント配線板を含む。 Printed wiring board: The printed wiring board according to the present application is obtained by using the above-mentioned copper foil with carrier foil according to the present application, and both a rigid type printed wiring board and a flexible type printed wiring board can be used. Including. In addition, the printed wiring board according to the present application includes all printed wiring boards such as a single-sided printed wiring board, a double-sided printed wiring board, and a multi-layer printed wiring board.
キャリア箔の製造: 銅濃度80g/L、フリー硫酸濃度250g/L、塩素濃度2mg/L、ゼラチン濃度2mg/L、液温50℃の硫酸系銅電解液を用いて、電流密度60A/dm2で電解し、厚さ18μmの電解銅箔を製造し、これをキャリア箔として用いた。このときの電解銅箔の常態の引張強さが43.8kgf/mm2、250℃×60分の加熱処理を行った後の引張強さは42.2kgf/mm2であった。なお、キャリア箔の常態および加熱後の引張強さの測定は、IPC−TM−650に準拠して行った。以下の実施例及び比較例において同様である。 Manufacture of carrier foil: A current density of 60 A / dm 2 using a sulfuric acid-based copper electrolytic solution having a copper concentration of 80 g / L, a free sulfuric acid concentration of 250 g / L, a chlorine concentration of 2 mg / L, a gelatin concentration of 2 mg / L, and a liquid temperature of 50 ° C. To produce an electrolytic copper foil having a thickness of 18 μm, which was used as a carrier foil. At this time, the normal tensile strength of the electrolytic copper foil was 43.8 kgf / mm 2 , and the tensile strength after heat treatment at 250 ° C. × 60 minutes was 42.2 kgf / mm 2 . The normal state of the carrier foil and the measurement of the tensile strength after heating were performed in accordance with IPC-TM-650. The same applies to the following examples and comparative examples.
接合界面層の形成: 上記キャリア箔の表面に接合界面層を次のようにして形成した。硫酸150g/L、銅濃度10g/L、カルボキシベンゾトリアゾール(CBTA)濃度800mg/L、液温30℃の有機剤含有希硫酸水溶液にキャリア箔を30秒間浸漬し、キャリア箔に付いた汚染成分を酸洗除去すると共に、キャリア箔の表面にCBTAを吸着させ、キャリア箔の表面にCBTAからなる接合界面層を形成し、「接合界面層を備えるキャリア箔」とした。 Formation of bonded interface layer: A bonded interface layer was formed on the surface of the carrier foil as follows. The carrier foil is immersed in an organic agent-containing dilute sulfuric acid aqueous solution having 150 g / L of sulfuric acid, 10 g / L of copper concentration, 800 mg / L of carboxybenzotriazole (CBTA) concentration, and a liquid temperature of 30 ° C. for 30 seconds to remove the contaminating components attached to the carrier foil. While removing by pickling, CBTA was adsorbed on the surface of the carrier foil to form a bonding interface layer made of CBTA on the surface of the carrier foil to obtain a "carrier foil having a bonding interface layer".
銅箔層の形成: 次に、銅電解液中で、「接合界面層を備えるキャリア箔」をカソード分極し、接合界面層の表面に、銅箔層を形成してキャリア箔付銅箔を得た。この銅箔層の形成は、銅濃度70g/L、フリー硫酸濃度150g/L、液温45℃の硫酸銅溶液を用いて、電流密度30A/dm2で電解し、厚さ3μmの銅箔層を形成した。Formation of copper foil layer: Next, in a copper electrolytic solution, the "carrier foil having a bonding interface layer" is cathodeally polarized, and a copper foil layer is formed on the surface of the bonding interface layer to obtain a copper foil with a carrier foil. It was. The copper foil layer is formed by electrolysis at a current density of 30 A / dm 2 using a copper sulfate solution having a copper concentration of 70 g / L, a free sulfuric acid concentration of 150 g / L, and a liquid temperature of 45 ° C. to form a copper foil layer having a thickness of 3 μm. Was formed.
銅箔層の表面処理: 上記で得られたキャリア箔付銅箔の銅箔層の表面に、粗化処理を施すことなく、亜鉛−ニッケル合金防錆層を形成し、電解クロメート処理、アミノ系シランカップリング剤処理を施し、表面処理したキャリア箔付銅箔を得た。 Surface treatment of copper foil layer: A zinc-nickel alloy rust preventive layer is formed on the surface of the copper foil layer of the copper foil with carrier foil obtained above without roughening treatment, and electrolytic chromate treatment and amino-based treatment are performed. A silane coupling agent treatment was applied to obtain a surface-treated copper foil with a carrier foil.
平均結晶粒の測定: キャリア箔の結晶粒径の測定には、EBSD評価装置(OIM Analysis、株式会社TSLソリューションズ製)を搭載したFE銃型の走査型電子顕微鏡(SUPRA 55VP、カールツァイス株式会社製)及び付属のEBSD解析装置を用いた。この装置を用いて、適切に断面加工された当該サンプルについて、EBSD法に準じて、銅箔の断面の結晶状態の画像データを得て、この画像データを、EBSD解析プログラム(OIM Analysis、株式会社TSLソリューションズ製)の分析メニューにて、平均結晶粒径の数値化を行った。本評価においては、方位差5°以上を、結晶粒界とみなした。また、観察時の走査型電子顕微鏡の条件は、加速電圧:20kV、アパーチャー径:60mm、High Current mode、試料角度:70°とした。この測定結果を表1に纏めて示す。 Measurement of average crystal grains: For the measurement of the crystal grain size of the carrier foil, an FE gun-type scanning electron microscope (SUPRA 55VP, manufactured by Karl Zeiss Co., Ltd.) equipped with an EBSD evaluation device (OIM Analysis, manufactured by TSL Solutions Co., Ltd.) ) And the attached EBSD analyzer were used. Using this device, image data of the crystalline state of the cross section of the copper foil was obtained for the sample whose cross section was appropriately processed according to the EBSD method, and this image data was used as an EBSD analysis program (OIM Analysis, Inc.). The average crystal grain size was quantified in the analysis menu of TSL Solutions). In this evaluation, an orientation difference of 5 ° or more was regarded as a grain boundary. The conditions of the scanning electron microscope at the time of observation were an acceleration voltage of 20 kV, an aperture diameter of 60 mm, a high current mode, and a sample angle of 70 °. The measurement results are summarized in Table 1.
引き剥がし強さの測定:常態及び加熱後のキャリア箔の引き剥がし強さを、IPC−TM−650に準拠して行った。測定の際には、次の方法で作製した板状試験片を用いた。まず、上述のキャリア箔付銅箔の銅箔層の表面に、接着剤を用いて絶縁樹脂層構成材を張り合わせて、銅張積層板を作製した。このとき、絶縁層構成材として、厚さ100μmの硬化したプリプレグを用いた。そして、この銅張積層板の表面にあるキャリア箔をカッティングして、幅10mm×長さ10cmの板状試験片を作製した。なお、常態引き剥がし強さ測定用の試料を作製する場合には、加熱処理前のキャリア箔付銅箔を用い、加熱後の引き剥がし強さ測定用の試料を作製する場合は、予め250℃×60分の加熱処理を行ったキャリア箔付銅箔を用いた。なお、加熱後のキャリア箔の引き剥がし強さに関しては、キャリア箔付銅箔の異なる5箇所から採取してそれぞれ測定を行い、5回の測定値の範囲を示した。この測定結果を表1に纏めて示す。 Measurement of peeling strength: The peeling strength of the carrier foil under normal conditions and after heating was measured in accordance with IPC-TM-650. At the time of measurement, a plate-shaped test piece prepared by the following method was used. First, an insulating resin layer constituent material was bonded to the surface of the copper foil layer of the above-mentioned copper foil with a carrier foil using an adhesive to prepare a copper-clad laminate. At this time, a cured prepreg having a thickness of 100 μm was used as the insulating layer constituent material. Then, the carrier foil on the surface of the copper-clad laminate was cut to prepare a plate-shaped test piece having a width of 10 mm and a length of 10 cm. When preparing a sample for measuring the normal peeling strength, a copper foil with a carrier foil before the heat treatment is used, and when preparing a sample for measuring the peeling strength after heating, the temperature is 250 ° C. in advance. A copper foil with a carrier foil that had been heat-treated for 60 minutes was used. The peeling strength of the carrier foil after heating was measured from five different locations of the copper foil with the carrier foil, and the range of the measured values of five times was shown. The measurement results are summarized in Table 1.
連結部径の測定:平均結晶粒の測定に用いた上記銅箔の断面の結晶状態の画像データに基づき、上記で得られたキャリア箔付銅箔に250℃×60分の加熱処理を行った後の接合界面層の断面において、図3に模式的に示した方法と同様にして、長さ2000nmに相当する接合界面層内に存在する連結部径を求め、平均連結部径、連結部のトータル長さ、最大連結部径を求めた。この測定結果を表1に纏めて示す。 Measurement of connecting portion diameter: Based on the image data of the crystalline state of the cross section of the copper foil used for measuring the average crystal grains, the copper foil with the carrier foil obtained above was heat-treated at 250 ° C. for 60 minutes. In the cross section of the later bonded interface layer, the diameter of the connecting portion existing in the bonded interface layer corresponding to the length of 2000 nm was obtained in the same manner as the method schematically shown in FIG. The total length and the maximum connecting diameter were calculated. The measurement results are summarized in Table 1.
実施例2は、実施例1の「接合界面層の形成」と「銅箔層の形成」との間に、「耐熱金属層の形成」の工程を設けた点が異なるのみである。よって、「耐熱金属層の形成」に関してのみ述べる。 The only difference between the second embodiment and the "formation of the bonding interface layer" and the "formation of the copper foil layer" of the first embodiment is that the step of "formation of the heat-resistant metal layer" is provided. Therefore, only "formation of heat-resistant metal layer" will be described.
耐熱金属層の形成: 次に、接合界面層の表面に耐熱金属層としてニッケル層を形成した。この耐熱金属層の形成は、ニッケル電解液として、硫酸ニッケル(NiSO4・6H2O)330g/L、塩化ニッケル(NiCl2・6H2O)45g/L、ホウ酸35g/L、液温45℃、pH3のワット浴を用い、電流密度2.5A/dm2で電解し、換算厚さ10nmのニッケル層を形成した。Formation of heat-resistant metal layer: Next, a nickel layer was formed as a heat-resistant metal layer on the surface of the bonding interface layer. The formation of the refractory metal layer, a nickel electrolyte, nickel sulfate (NiSO 4 · 6H 2 O) 330g / L, nickel chloride (NiCl 2 · 6H 2 O) 45g / L, boric acid 35 g / L, liquid temperature 45 Using a watt bath at ° C. and
以下、実施例1と同様に、「耐熱金属層及び接合界面層を備えるキャリア箔」の耐熱金属層及び接合界面層が存在する表面に銅箔層を形成し、その銅箔層の表面に表面処理を施してキャリア箔付銅箔を得た。実施例2で得たキャリア箔付電解銅箔の断面観察写真を図1に示す。 Hereinafter, as in Example 1, a copper foil layer is formed on the surface of the "carrier foil provided with the heat-resistant metal layer and the bonding interface layer" on which the heat-resistant metal layer and the bonding interface layer exist, and the surface is surfaced on the surface of the copper foil layer. Treatment was performed to obtain a copper foil with a carrier foil. FIG. 1 shows a cross-sectional observation photograph of the electrolytic copper foil with a carrier foil obtained in Example 2.
実施例3は、実施例1とキャリア箔が異なるのみである。よって、実施例1と異なるキャリア箔の製造に関してのみ述べる。 The third embodiment is different from the first embodiment only in the carrier foil. Therefore, only the production of a carrier foil different from that of Example 1 will be described.
キャリア箔の製造: 銅濃度80g/L、フリー硫酸濃度140g/L、塩素濃度0.25mg/L、ヨウ化カリウム(KI)を用いたヨウ素濃度5.0mg/L、溶液温度50℃の硫酸系銅電解液を用いて、電流密度75A/dm2で電解し、厚さ18μmの電解銅箔を製造し、これをキャリア箔として用いた。このときの電解銅箔の常態の引張強さは48.7kgf/mm2、250℃×60分の加熱処理を行った後の引張強さは45.0kgf/mm2であった。Manufacture of carrier foil: Copper concentration 80 g / L, free sulfuric acid concentration 140 g / L, chlorine concentration 0.25 mg / L, iodine concentration 5.0 mg / L using potassium iodide (KI), sulfuric acid system with solution temperature 50 ° C. Electrolysis was performed at a current density of 75 A / dm 2 using a copper electrolytic solution to produce an electrolytic copper foil having a thickness of 18 μm, which was used as a carrier foil. Tensile strength of normal electrodeposited copper foil in this case the tensile strength after the heat treatment of 48.7kgf / mm 2, 250 ℃ × 60 minutes was 45.0kgf / mm 2.
実施例4は、実施例1とキャリア箔が異なるのみである。よって、実施例1と異なるキャリア箔の製造に関してのみ述べる。 The fourth embodiment differs from the first embodiment only in the carrier foil. Therefore, only the production of a carrier foil different from that of Example 1 will be described.
キャリア箔の製造: 銅濃度80g/L、硫酸濃度140g/L、分子量10000のポリエチレンイミン53mg/L、塩素濃度2.2mg/L、液温50℃の硫酸系銅電解液を用いて、電流密度70A/dm2で電解し、厚さ18μmの電解銅箔を製造し、これをキャリア箔として用いた。このときの電解銅箔の常態の引張強さは62.2kgf/mm2、250℃×60分の加熱処理を行った後の引張強さは48.1kgf/mm2であった。Manufacture of carrier foil: Current density using a sulfuric acid-based copper electrolytic solution having a copper concentration of 80 g / L, a sulfuric acid concentration of 140 g / L, a molecular weight of 10000 polyethyleneimine 53 mg / L, a chlorine concentration of 2.2 mg / L, and a liquid temperature of 50 ° C. Electrolysis was performed at 70 A / dm 2 to produce an electrolytic copper foil having a thickness of 18 μm, which was used as a carrier foil. At this time, the normal tensile strength of the electrolytic copper foil was 62.2 kgf / mm 2 , and the tensile strength after heat treatment at 250 ° C. for 60 minutes was 48.1 kgf / mm 2 .
実施例5は、実施例1とキャリア箔が異なるのみである。よって、実施例1と異なるキャリア箔の製造に関してのみ述べる。 The fifth embodiment is different from the first embodiment only in the carrier foil. Therefore, only the production of a carrier foil different from that of Example 1 will be described.
キャリア箔の製造: 実施例5では、銅濃度80g/L、硫酸濃度140g/L、分子量10000のポリエチレンイミン100mg/L、塩素濃度1.0mg/L、液温50℃の硫酸酸性銅電解液を用いて、電流密度70A/dm2で電解し、厚さ18μmの電解銅箔を製造し、これをキャリア箔として用いた。このときの電解銅箔の常態の引張強さは79.0kgf/mm2、250℃×60分の加熱処理を行った後の引張強さは55.4kgf/mm2であった。Production of carrier foil: In Example 5, a sulfuric acid acidic copper electrolytic solution having a copper concentration of 80 g / L, a sulfuric acid concentration of 140 g / L, a molecular weight of 10000 polyethyleneimine 100 mg / L, a chlorine concentration of 1.0 mg / L, and a liquid temperature of 50 ° C. was used. It was electrolyzed at a current density of 70 A / dm 2 to produce an electrolytic copper foil having a thickness of 18 μm, which was used as a carrier foil. At this time, the normal tensile strength of the electrolytic copper foil was 79.0 kgf / mm 2 , and the tensile strength after heat treatment at 250 ° C. for 60 minutes was 55.4 kgf / mm 2 .
比較例では、実施例1でキャリア箔として使用した電解銅箔に代えて、常態の引張強さが40.3kgf/mm2、250℃×60分の加熱処理を行った後の引張強さが35.0kgf/mm2の電解銅箔をキャリア箔として用いた。その他の工程に関しては、実施例2と同様にして、比較例としてのキャリア箔付銅箔を得た。そして、実施例と同様にャリア箔の平均結晶粒、キャリア箔の引き剥がし強さ、連結部径を測定した。各測定結果を、表1に纏めて示す。また、比較例で得たキャリア箔付電解銅箔の断面観察写真を図1に示す。In the comparative example, instead of the electrolytic copper foil used as the carrier foil in Example 1, the normal tensile strength is 40.3 kgf / mm 2 , and the tensile strength after heat treatment at 250 ° C. × 60 minutes is An electrolytic copper foil of 35.0 kgf / mm 2 was used as the carrier foil. Regarding other steps, a copper foil with a carrier foil was obtained as a comparative example in the same manner as in Example 2. Then, the average crystal grains of the carrier foil, the peeling strength of the carrier foil, and the diameter of the connecting portion were measured in the same manner as in Examples. The measurement results are summarized in Table 1. Further, FIG. 1 shows a cross-sectional observation photograph of the electrolytic copper foil with a carrier foil obtained in the comparative example.
[実施例と比較例との対比]
この表1から理解できるように、実施例1〜実施例5に関しては、キャリア箔として「250℃×60分の加熱処理を行った後に40kgf/mm2以上の引張強さを備える電解銅箔」を用いている。これに対し、比較例は、250℃×60分の加熱処理を行った後に35.0kgf/mm2の引張強さしか備えていない。その結果、実施例1〜実施例5に関しては、「接合界面層中に存在する連結部の内、最大連結部径が200nm以下」、「長さ2000nmに相当する接合界面層中に存在する連結部のトータル長さが500nm以下」となった。ところが、比較例の場合、上記最大連結部径が200nmを超え、上記連結部のトータル長さも500nmを超えている。よって、比較例のキャリア箔の引き剥がし強さ及びばらつきが実施例に比べて極めて高い値になっていることが理解できる。この比較例レベルのキャリア箔の引き剥がし強さの場合、これらのばらつきが生じることからキャリア箔の引き剥がしが困難となる場合がある。As can be understood from this Table 1, with reference to Examples 1 to 5, "an electrolytic copper foil having a tensile strength of 40 kgf / mm 2 or more after being heat-treated at 250 ° C. for 60 minutes" as a carrier foil. Is used. On the other hand, the comparative example has only a tensile strength of 35.0 kgf / mm 2 after being heat-treated at 250 ° C. for 60 minutes. As a result, with respect to Examples 1 to 5, "the maximum connecting portion diameter of the connecting portions existing in the bonding interface layer is 200 nm or less" and "the connection existing in the bonding interface layer corresponding to the length of 2000 nm". The total length of the part is 500 nm or less. " However, in the case of the comparative example, the maximum connecting portion diameter exceeds 200 nm, and the total length of the connecting portion also exceeds 500 nm. Therefore, it can be understood that the peeling strength and variation of the carrier foil of the comparative example are extremely high values as compared with the examples. In the case of the peeling strength of the carrier foil at the level of this comparative example, it may be difficult to peel off the carrier foil due to these variations.
本件出願に係るキャリア箔付銅箔は、250℃以上の温度が負荷されても、電解銅箔からキャリア箔を容易に引き剥がすことが可能であるから、250℃以上の温度が負荷される銅張積層板製造において好適に使用できる。銅箔層からキャリア箔を引き剥がす際の引き剥がし強さが低位で安定するため、キャリア箔の引き剥がし作業が容易に行える。 In the copper foil with carrier foil according to the present application, the carrier foil can be easily peeled off from the electrolytic copper foil even when a temperature of 250 ° C. or higher is applied, so that copper to which a temperature of 250 ° C. or higher is applied. It can be suitably used in the production of stretched laminates. Since the peeling strength when peeling the carrier foil from the copper foil layer is stable at a low level, the carrier foil can be easily peeled off.
1 キャリア箔付銅箔
2 キャリア箔
3 銅箔層
4 接合界面層
5 連結部
1 Copper foil with
Claims (9)
当該キャリア箔として、250℃×60分の加熱処理を行った後に40kgf/mm 2 以上の引張強さを備える電解銅箔を用い、
当該加熱処理を行った後に、当該接合界面層内に存在する当該キャリア箔と当該銅箔層との連結部において、当該キャリア箔付銅箔の厚さ方向に直交する方向を長さ方向としたときに、長さ2000nmに相当する接合界面層内に存在する連結部のトータル長さが500nm以下であることを特徴とするキャリア箔付銅箔。 A copper foil with a carrier foil having a layer structure of a carrier foil / a bonding interface layer / a copper foil layer.
As the carrier foil, an electrolytic copper foil having a tensile strength of 40 kgf / mm 2 or more after being heat-treated at 250 ° C. for 60 minutes was used.
After the heat treatment, the length direction is defined as the direction orthogonal to the thickness direction of the copper foil with the carrier foil at the connecting portion between the carrier foil and the copper foil layer existing in the bonding interface layer. A copper foil with a carrier foil, characterized in that the total length of the connecting portion existing in the bonding interface layer corresponding to a length of 2000 nm is 500 nm or less.
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KR101385761B1 (en) * | 2010-07-01 | 2014-04-17 | 미쓰이금속광업주식회사 | Electrodeposited copper foil and process for production thereof |
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2014
- 2014-11-21 JP JP2015515308A patent/JP6855164B2/en active Active
- 2014-11-21 MY MYPI2016701883A patent/MY187285A/en unknown
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CN105745360A (en) | 2016-07-06 |
WO2015080052A1 (en) | 2015-06-04 |
JP2019178431A (en) | 2019-10-17 |
KR20210037020A (en) | 2021-04-05 |
JPWO2015080052A1 (en) | 2017-03-16 |
KR102356179B1 (en) | 2022-02-08 |
MY187285A (en) | 2021-09-19 |
TWI644995B (en) | 2018-12-21 |
KR102272762B1 (en) | 2021-07-05 |
KR20160090818A (en) | 2016-08-01 |
TW201536876A (en) | 2015-10-01 |
JP6784806B2 (en) | 2020-11-11 |
CN105745360B (en) | 2017-12-08 |
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