WO2022154102A1 - Surface-treated copper foil, copper-cladded laminate plate, and printed wiring board - Google Patents
Surface-treated copper foil, copper-cladded laminate plate, and printed wiring board Download PDFInfo
- Publication number
- WO2022154102A1 WO2022154102A1 PCT/JP2022/001216 JP2022001216W WO2022154102A1 WO 2022154102 A1 WO2022154102 A1 WO 2022154102A1 JP 2022001216 W JP2022001216 W JP 2022001216W WO 2022154102 A1 WO2022154102 A1 WO 2022154102A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- copper foil
- treated
- layer
- treatment layer
- base material
- Prior art date
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 190
- 239000011889 copper foil Substances 0.000 title claims abstract description 175
- 239000010410 layer Substances 0.000 claims description 142
- 239000000463 material Substances 0.000 claims description 72
- 239000011347 resin Substances 0.000 claims description 63
- 229920005989 resin Polymers 0.000 claims description 63
- 239000002335 surface treatment layer Substances 0.000 claims description 46
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 21
- 229910052721 tungsten Inorganic materials 0.000 claims description 21
- 239000010937 tungsten Substances 0.000 claims description 21
- 238000005530 etching Methods 0.000 claims description 6
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 description 55
- 238000007747 plating Methods 0.000 description 51
- 239000000243 solution Substances 0.000 description 51
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 39
- 238000009713 electroplating Methods 0.000 description 30
- 238000000034 method Methods 0.000 description 27
- 239000010949 copper Substances 0.000 description 23
- 239000000203 mixture Substances 0.000 description 22
- 238000007788 roughening Methods 0.000 description 18
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 17
- 230000008878 coupling Effects 0.000 description 17
- 238000010168 coupling process Methods 0.000 description 17
- 238000005859 coupling reaction Methods 0.000 description 17
- 229910000077 silane Inorganic materials 0.000 description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- 229910052802 copper Inorganic materials 0.000 description 15
- 239000006087 Silane Coupling Agent Substances 0.000 description 14
- 238000009826 distribution Methods 0.000 description 14
- 238000005259 measurement Methods 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 239000011701 zinc Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 229910018605 Ni—Zn Inorganic materials 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000011651 chromium Substances 0.000 description 8
- 239000004020 conductor Substances 0.000 description 8
- 229910000881 Cu alloy Inorganic materials 0.000 description 6
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229920001721 polyimide Polymers 0.000 description 6
- 150000003658 tungsten compounds Chemical class 0.000 description 6
- 208000012868 Overgrowth Diseases 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000002500 effect on skin Effects 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 239000009719 polyimide resin Substances 0.000 description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 4
- 239000011135 tin Substances 0.000 description 4
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 description 3
- 229920000106 Liquid crystal polymer Polymers 0.000 description 3
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000003908 quality control method Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000010731 rolling oil Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000010485 coping Effects 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
- 239000006059 cover glass Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- UREBDLICKHMUKA-CXSFZGCWSA-N dexamethasone Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@@H](C)[C@@](C(=O)CO)(O)[C@@]1(C)C[C@@H]2O UREBDLICKHMUKA-CXSFZGCWSA-N 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- -1 that is Substances 0.000 description 1
- 125000003396 thiol group Chemical class [H]S* 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
-
- 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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight 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
- C25D5/16—Electroplating with layers of varying thickness
-
- 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
-
- 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
Definitions
- the present inventors have found that Sk of the surface-treated layer is involved in the adhesiveness with the resin substrate. rice field. From the viewpoint of stably obtaining the adhesive force to the resin base material, the Sku of the surface treatment layer is preferably 2.80 to 4.00, and more preferably 2.90 to 3.75. The Sk of the surface treatment layer is measured in accordance with ISO 25178-2: 2012.
- the lower limit value of Sq of the surface treatment layer is preferably 0.29 ⁇ m, more preferably 0.30 ⁇ m, still more preferably 0.34 ⁇ m, and the upper limit value is preferably 0. It is .48 ⁇ m, more preferably 0.43 ⁇ m.
- the surface treatment layer has a Sa of 0.20 to 0.32 ⁇ m and an Sq of 0.26 to 0. It is preferably .40 ⁇ m.
- the copper-clad laminate according to the embodiment of the present invention includes the above-mentioned surface-treated copper foil and a resin base material adhered to the surface-treated layer of the surface-treated copper foil.
- This copper-clad laminate can be manufactured by adhering a resin base material to the surface-treated layer of the above-mentioned surface-treated copper foil.
- the resin base material is not particularly limited, and those known in the art can be used. Examples of resin base materials include paper base material phenol resin, paper base material epoxy resin, synthetic fiber cloth base material epoxy resin, glass cloth / paper composite base material epoxy resin, glass cloth / glass non-woven composite base material epoxy resin, and glass. Examples thereof include cloth-based epoxy resin, polyester film, polyimide resin, liquid crystal polymer, and fluororesin. Among these, the resin base material is preferably a polyimide resin.
- Chromate-treated layer ⁇ Conditions for forming electrolytic chromate-treated layer> Chromate solution composition: 3 g / L K 2 Cr 2 O 7 , 0.33 g / L Zn Chromate solution pH: 3.7 Chromate liquid temperature: 55 ° C Electrolysis conditions: Current density 1.4 A / dm 2 , Time 0.7 seconds Chromate treatment count: 2 times
- Example 3 A surface-treated copper foil was obtained under the same conditions as in Example 1 except that the amount of tungsten in the plating solution composition was changed to 3 ppm under the conditions for forming the roughened particles.
- Roughening treatment layer ⁇ Conditions for forming roughened particles> Plating solution composition: 12 g / L Cu, 50 g / L sulfuric acid, 5 ppm tungsten (derived from sodium tungstate dihydrate) Plating liquid temperature: 27 ° C Electroplating conditions: Current density 48.3A / dm 2 , Time 0.81 seconds Number of electroplating processes: 2 times
- Example 1 The rolled copper foil (copper foil without surface treatment) used in Example 1 was used as a comparison.
- the surface-treated copper foils of Examples 1 to 10 Comparing the surface-treated copper foils of Examples 1 to 10 with the copper foils of Comparative Example 1, it can be seen that Str is a very close value.
- the surface-treated copper foils of Examples 1 to 10 have already been described in view of the fact that the copper foil of Comparative Example 1 is surface-treated and that Str exhibits surface anisotropy and isotropic properties.
- the surface-treated layer particularly the roughened particle layer, is uniformly formed along the minute uneven portion (oil pit in the case of rolled copper foil) on the surface of the copper foil. You can see that it has been done. If the roughened particle layer is not formed along the minute uneven portion, the Str value should be significantly different before and after the surface treatment.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electroplating Methods And Accessories (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
導体損失は、高周波域では表皮効果があり、電流は導体の表面を流れるという特性を有するため、銅箔表面が粗いと複雑な経路を辿って、電流が流れることになる。したがって、高周波信号の導体損失を少なくするためには、銅箔の表面粗さを小さくすることが望ましい。以下、本明細書において、単に「伝送損失」及び「導体損失」と記載した場合は、「高周波信号の伝送損失」及び「高周波信号の導体損失」を主に意味する。 The causes of signal power loss (transmission loss) in electronic circuits can be broadly divided into two. The first is the conductor loss, that is, the loss due to the copper foil, and the second is the dielectric loss, that is, the loss due to the resin base material.
The conductor loss has a skin effect in the high frequency region and has the characteristic that the current flows on the surface of the conductor. Therefore, if the surface of the copper foil is rough, the current will flow along a complicated path. Therefore, in order to reduce the conductor loss of the high frequency signal, it is desirable to reduce the surface roughness of the copper foil. Hereinafter, when the terms "transmission loss" and "conductor loss" are simply used in the present specification, they mainly mean "transmission loss of high frequency signal" and "conductor loss of high frequency signal".
そこで、銅箔と樹脂基材との間を接着剤の使用なしに接着するために、銅箔の少なくとも一方の面に表面処理層を形成することが提案されている。例えば、特許文献1には、銅箔上に粗化粒子から形成される粗化処理層を設けるとともに、最表層にシランカップリング処理層を形成する方法が提案されている。 On the other hand, since the dielectric loss depends on the type of the resin base material, it is possible to use a resin base material formed of a low dielectric material (for example, a liquid crystal polymer or a low dielectric polyimide) in a circuit board through which a high frequency signal flows. desirable. Further, since the dielectric loss is also affected by the adhesive that adheres between the copper foil and the resin base material, it is desirable to adhere between the copper foil and the resin base material without using an adhesive.
Therefore, it has been proposed to form a surface treatment layer on at least one surface of the copper foil in order to bond the copper foil and the resin base material without using an adhesive. For example, Patent Document 1 proposes a method of providing a roughening treatment layer formed of roughened particles on a copper foil and forming a silane coupling treatment layer on the outermost surface layer.
銅箔に微小な凹凸部が存在すると、例えば、粗化処理層を形成する際に、凸部では電流が集中して粗化粒子が過成長する一方、凹部では電流が十分に供給されず、粗化粒子が成長し難くなる。その結果、銅箔の凸部に粗大な粗化粒子が形成される一方、銅箔の凹部は粗化粒子が過小になるという状態、すなわち、銅箔表面の粗化粒子が均一に形成されていない状態になる。粗大な粗化粒子が多い表面処理銅箔では、樹脂基材との接合後、表面処理銅箔を剥離させる力を付与すると、粗大な粗化粒子に応力が集中して折れ易くなる結果、樹脂基材に対する接着力が低下することがある。また、粗化粒子の大きさが不十分な表面処理銅箔では、粗化粒子によるアンカー効果が低下してしまい、銅箔と樹脂基材との接着性が十分に得られないことがある。
特に、液晶ポリマー、低誘電ポリイミドなどの低誘電材料から形成された樹脂基材は、従来の樹脂基材よりも銅箔と接着し難いため、銅箔と樹脂基材との間の接着性を高める手法の開発が望まれている。
また、シランカップリング処理層は、銅箔と樹脂基材との間の接着性を向上させる効果を有するものの、その種類によっては、接着性の向上効果が十分ではないこともある。 The surface of the copper foil on which the surface treatment layer is formed generally has minute irregularities. For example, in the case of rolled copper foil, oil pits formed by rolling oil during rolling are formed on the surface as minute uneven portions. Further, in the case of the electrolytic copper foil, the polishing streaks of the rotating drum formed during polishing cause minute uneven portions on the surface of the electrolytic copper foil on the rotating drum side, which are deposited and formed on the rotating drum.
If the copper foil has minute irregularities, for example, when forming the roughening treatment layer, the current is concentrated in the convex portions and the roughened particles are overgrown, while the current is not sufficiently supplied in the concave portions. It becomes difficult for the roughened particles to grow. As a result, coarse roughened particles are formed in the convex portion of the copper foil, while the roughened particles are too small in the concave portion of the copper foil, that is, the roughened particles on the surface of the copper foil are uniformly formed. It will be in a non-existent state. In the surface-treated copper foil having many coarse coarse particles, if a force for peeling the surface-treated copper foil is applied after bonding with the resin base material, stress is concentrated on the coarse roughened particles and the resin is easily broken. Adhesive strength to the substrate may decrease. Further, in the surface-treated copper foil in which the size of the roughened particles is insufficient, the anchor effect due to the roughened particles is lowered, and the adhesiveness between the copper foil and the resin base material may not be sufficiently obtained.
In particular, a resin base material formed of a low dielectric material such as a liquid crystal polymer or a low dielectric polyimide is more difficult to adhere to a copper foil than a conventional resin base material, so that the adhesiveness between the copper foil and the resin base material is improved. It is desired to develop a method to enhance it.
Further, although the silane coupling treatment layer has an effect of improving the adhesiveness between the copper foil and the resin base material, the effect of improving the adhesiveness may not be sufficient depending on the type.
また、本発明の実施形態は、別の側面において、樹脂基材、特に高周波用途に好適な樹脂基材と表面処理銅箔との間の接着性に優れた銅張積層板を提供することを目的とする。
さらに、本発明の実施形態は、別の側面において、樹脂基材、特に高周波用途に好適な樹脂基材と回路パターンとの間の接着性に優れたプリント配線板を提供することを目的とする。 The embodiment of the present invention has been made to solve the above-mentioned problems, and in one aspect, it is possible to enhance the adhesiveness with a resin base material, particularly a resin base material suitable for high frequency applications. It is an object of the present invention to provide a surface-treated copper foil.
Further, in another aspect, the embodiment of the present invention provides a copper-clad laminate having excellent adhesion between a resin base material, particularly a resin base material suitable for high-frequency applications, and a surface-treated copper foil. The purpose.
Further, an embodiment of the present invention aims to provide a printed wiring board having excellent adhesion between a resin base material, particularly a resin base material suitable for high frequency applications, and a circuit pattern, in another aspect. ..
また、本発明の実施形態は、別の側面において、前記表面処理銅箔と、前記表面処理銅箔の前記表面処理層に接着された樹脂基材とを備える銅張積層板に関する。
さらに、本発明の実施形態は、別の側面において、前記銅張積層板の前記表面処理銅箔をエッチングして形成された回路パターンを備えるプリント配線板に関する。 That is, the embodiment of the present invention has a copper foil and a surface-treated layer formed on at least one surface of the copper foil on one side surface, and the surface-treated layer has Sku of 2.50 to 2.50. It relates to a surface-treated copper foil having 4.50 and a Str of 0.20 to 0.40.
In another aspect, an embodiment of the present invention relates to a copper-clad laminate comprising the surface-treated copper foil and a resin base material adhered to the surface-treated layer of the surface-treated copper foil.
Further, an embodiment of the present invention relates to a printed wiring board having a circuit pattern formed by etching the surface-treated copper foil of the copper-clad laminate on another side surface.
また、本発明の実施形態によれば、別の側面において、樹脂基材、特に高周波用途に好適な樹脂基材と表面処理銅箔との間の接着性に優れた銅張積層板を提供することができる。
さらに、本発明の実施形態によれば、別の側面において、樹脂基材、特に高周波用途に好適な樹脂基材と回路パターンとの間の接着性に優れたプリント配線板を提供することができる。 According to the embodiment of the present invention, it is possible to provide a surface-treated copper foil capable of enhancing the adhesiveness with a resin base material, particularly a resin base material suitable for high frequency applications, on one side.
Further, according to the embodiment of the present invention, on another aspect, a copper-clad laminate having excellent adhesiveness between a resin base material, particularly a resin base material suitable for high-frequency applications and a surface-treated copper foil is provided. be able to.
Further, according to the embodiment of the present invention, on another aspect, it is possible to provide a printed wiring board having excellent adhesion between a resin base material, particularly a resin base material suitable for high frequency applications, and a circuit pattern. ..
表面処理層は、銅箔の一方の面のみに形成されていてもよいし、銅箔の両方の面に形成されていてもよい。銅箔の両方の面に表面処理層が形成される場合、表面処理層の種類は同一であっても異なっていてもよい。 The surface-treated copper foil according to the embodiment of the present invention has a copper foil and a surface-treated layer formed on at least one surface of the copper foil.
The surface treatment layer may be formed on only one surface of the copper foil, or may be formed on both surfaces of the copper foil. When the surface treatment layer is formed on both surfaces of the copper foil, the type of the surface treatment layer may be the same or different.
表面処理層のSkuが2.50~4.50であることは、高さ分布が正規分布又はそれに近い分布状態であることを意味する。一方、表面処理層のSkuが2.50未満であることは、表面処理層の高さ(銅箔表面からの高さ)が低い部分と高い部分とが様々に入り交じった結果、高さ分布が偏っていない分布状態であることを意味する。表面処理層のSkuが4.50より大きいことは、高さ分布が偏っている分布状態であること、すなわち、表面処理層の表面は、ある高さの部分が突出して多くを占めている状態であることを意味する。
表面処理層の高さ分布が正規分布又はそれに近い分布状態は、例えば、銅箔の表面に粗化処理層を形成する場合に、銅箔の凸部において過成長した粗化粒子、すなわち粗大な粗化粒子や、銅箔の凹部において粗化粒子が形成されていない箇所が少ないことを意味する。したがって、表面処理層のSkuが2.50~4.50であることは、銅箔の凸部に形成される粗化粒子の過成長が抑制され、また、銅箔の凹部にも粗化粒子が形成されている状態を意味する。 The surface-treated copper foil according to the embodiment of the present invention has irregularities on the surface, and the irregularities contribute to the improvement of the adhesiveness between the copper foil and the resin base material. The Sk of the surface treatment layer is an index for evaluating the height distribution of the unevenness.
When the Sku of the surface treatment layer is 2.50 to 4.50, it means that the height distribution is a normal distribution or a distribution state close to it. On the other hand, the fact that the Sk of the surface treatment layer is less than 2.50 is a result of various mixing of low and high heights of the surface treatment layer (height from the copper foil surface), resulting in a height distribution. Means that is an unbiased distribution. The fact that the Sk of the surface treatment layer is larger than 4.50 means that the height distribution is uneven, that is, the surface of the surface treatment layer is in a state where a certain height portion protrudes and occupies a large part. Means that
The height distribution of the surface-treated layer is a normal distribution or a distribution state close to that, for example, when a roughened-treated layer is formed on the surface of the copper foil, the roughened particles overgrown in the convex portion of the copper foil, that is, coarse particles. This means that there are few roughened particles or recesses of the copper foil where the roughened particles are not formed. Therefore, when the Sku of the surface treatment layer is 2.50 to 4.50, the overgrowth of the roughened particles formed on the convex portion of the copper foil is suppressed, and the roughened particles are also suppressed on the concave portion of the copper foil. Means the state in which is formed.
樹脂基材に対する接着力を安定して得る観点から、表面処理層のSkuは、2.80~4.00であることが好ましく、2.90~3.75であることがより好ましい。
なお、表面処理層のSkuは、ISO 25178-2:2012に準拠して測定される。 Neither a surface-treated copper foil having a large amount of coarse roughened particles nor a surface-treated copper foil having a portion where roughened particles are formed is preferable from the viewpoint of adhesiveness to a resin base material. For example, in a surface-treated copper foil having many coarse roughened particles, if a force is applied to peel off the surface-treated copper foil after bonding with a resin base material, stress is concentrated on the coarse roughened particles and the particles are easily broken. On the contrary, it is considered that the adhesive force to the resin base material is reduced. Further, in the surface-treated copper foil in which the roughened particles are not formed, the anchor effect due to the roughened particles cannot be sufficiently secured, and the adhesive force between the surface-treated copper foil and the resin base material is lowered. Conceivable. As a result of measuring and analyzing the peel strength of the surface-treated copper foils of Examples and Comparative Examples described later, the present inventors have found that Sk of the surface-treated layer is involved in the adhesiveness with the resin substrate. rice field.
From the viewpoint of stably obtaining the adhesive force to the resin base material, the Sku of the surface treatment layer is preferably 2.80 to 4.00, and more preferably 2.90 to 3.75.
The Sk of the surface treatment layer is measured in accordance with ISO 25178-2: 2012.
表面処理層のStrが0.20~0.40であると、表面処理層の表面は異方性が適度にある状態となる。この状態は、銅箔の表面の微小な凹凸部に沿って表面処理層が均一に形成されていることを意味する。したがって、例えば、銅箔の表面に粗化処理層を形成する場合に、凸部において過成長した粗化粒子や、凹部において粗化粒子が形成されていない箇所が少ないことを意味する。すなわち、表面処理層のStrが0.20~0.40であることは、銅箔の凸部に形成される粗化粒子の過成長が抑制され、銅箔の凹部にも粗化粒子が形成されている状態を意味する。その結果、粗化粒子によるアンカー効果を十分に確保することができるため、表面処理銅箔と樹脂基材との接着力が高くなる。このような効果を安定して得る観点から、表面処理層のStrは0.26~0.35であることが好ましい。
なお、表面処理層のStrは、ISO 25178-2:2012に準拠して測定される。 The surface treatment layer has a Str (texture aspect ratio) of 0.20 to 0.40. Str is a spatial parameter defined in ISO 25178-2: 2012 and represents the strength of surface anisotropy and isotropic. Str is in the range of 0 to 1, and the closer it is to 0, the stronger the anisotropy (for example, the larger the streaks). On the contrary, the closer the Str is to 1, the stronger the isotropic property.
When the Str of the surface treatment layer is 0.20 to 0.40, the surface of the surface treatment layer has an appropriate anisotropy. This state means that the surface treatment layer is uniformly formed along the minute uneven portions on the surface of the copper foil. Therefore, for example, when the roughening treatment layer is formed on the surface of the copper foil, it means that there are few roughened particles overgrown in the convex portions and few roughened particles are not formed in the concave portions. That is, when the Str of the surface treatment layer is 0.20 to 0.40, the overgrowth of the roughened particles formed in the convex portion of the copper foil is suppressed, and the roughened particles are also formed in the concave portion of the copper foil. It means the state of being done. As a result, the anchoring effect of the roughened particles can be sufficiently ensured, so that the adhesive force between the surface-treated copper foil and the resin base material is increased. From the viewpoint of stably obtaining such an effect, the Str of the surface treatment layer is preferably 0.26 to 0.35.
The Str of the surface treatment layer is measured according to ISO 25178-2: 2012.
表面処理層のSaが大きいと、表面処理層の表面が粗くなるため、表面処理銅箔を樹脂基材に接着した場合にアンカー効果が発揮され易くなる。一方で、表面処理層のSaが大きすぎる(すなわち、表面が粗い)表面処理銅箔と樹脂基材とを接着した銅張積層板を加工して回路基板を作製した場合、表面処理銅箔の表皮効果によって伝送損失が大きくなる。そのため、表面処理層のSaを上記の範囲とすることにより、樹脂基材に対する表面処理銅箔の接着力の確保と伝送損失の抑制とのバランスを確保することができる。このような効果を安定して得る観点から、表面処理層のSaは、下限値が好ましくは0.20μm、より好ましくは0.23μm、更に好ましくは0.24μmであり、上限値が好ましくは0.40μm、より好ましくは0.35μmである。 The surface treatment layer preferably has a Sa (arithmetic mean height) of 0.18 to 0.43 μm. Sa is a parameter in the height direction defined in ISO 25178-2: 2012, and represents the average height difference from the average plane.
If the Sa of the surface-treated layer is large, the surface of the surface-treated layer becomes rough, so that the anchor effect is likely to be exhibited when the surface-treated copper foil is adhered to the resin base material. On the other hand, when a circuit board is produced by processing a copper-clad laminate in which a surface-treated copper foil having an excessively large Sa (that is, a rough surface) and a resin base material are bonded to each other, the surface-treated copper foil has a surface-treated copper foil. The transmission loss increases due to the skin effect. Therefore, by setting Sa of the surface-treated layer in the above range, it is possible to secure a balance between securing the adhesive force of the surface-treated copper foil to the resin base material and suppressing transmission loss. From the viewpoint of stably obtaining such an effect, the lower limit value of Sa of the surface treatment layer is preferably 0.20 μm, more preferably 0.23 μm, still more preferably 0.24 μm, and the upper limit value is preferably 0. It is .40 μm, more preferably 0.35 μm.
表面処理層のSqが大きいと、表面処理層の表面における凸部の高さのバラツキが大きくなり、表面処理銅箔を樹脂基材に接着した場合にアンカー効果が発揮され易くなる。ただし、Sqが大きすぎる(凸部の高さのバラツキが大きすぎる)と、工業製品としての品質管理の観点から問題になる場合がある。そのため、表面処理層のSqを上記の範囲とすることにより、アンカー効果の確保と品質管理の観点とのバランスを確保することができる。このような効果を安定して得る観点から、表面処理層のSqは、下限値が好ましくは0.29μm、より好ましくは0.30μm、更に好ましくは0.34μmであり、上限値が好ましくは0.48μm、より好ましくは0.43μmである。
なお、表皮効果による伝送損失の抑制及び工業製品としての品質管理のし易さを重視した場合、表面処理層は、Saが0.20~0.32μmであり、且つSqが0.26~0.40μmであることが好ましい。 The surface treatment layer preferably has an Sq (root mean square height) of 0.26 to 0.53 μm. Sq is a parameter in the height direction defined in ISO 25178-2: 2012, and represents a variation in the height of the convex portion on the surface of the surface treatment layer.
When the Sq of the surface-treated layer is large, the height of the convex portion on the surface of the surface-treated layer varies widely, and the anchor effect is likely to be exhibited when the surface-treated copper foil is adhered to the resin base material. However, if Sq is too large (the height variation of the convex portion is too large), it may cause a problem from the viewpoint of quality control as an industrial product. Therefore, by setting the Sq of the surface treatment layer within the above range, it is possible to secure a balance between ensuring the anchor effect and the viewpoint of quality control. From the viewpoint of stably obtaining such an effect, the lower limit value of Sq of the surface treatment layer is preferably 0.29 μm, more preferably 0.30 μm, still more preferably 0.34 μm, and the upper limit value is preferably 0. It is .48 μm, more preferably 0.43 μm.
When the suppression of transmission loss due to the skin effect and the ease of quality control as an industrial product are emphasized, the surface treatment layer has a Sa of 0.20 to 0.32 μm and an Sq of 0.26 to 0. It is preferably .40 μm.
表面処理層のSdrが大きすぎると、表面処理層の表面が緻密で起伏が激しくなるため、表面処理銅箔を樹脂基材に接着した場合にアンカー効果が発揮され易くなる一方、表皮効果によって伝送損失が大きくなる。そのため、表面処理層のSdrを上記の範囲とすることにより、アンカー効果の確保と伝送損失の抑制とのバランスを確保することができる。 The surface treatment layer preferably has an Sdr (developed interface area ratio) of 30 to 79%, more preferably 38 to 79%. Sdr is a composite parameter defined in ISO 25178-2: 2012 and represents the rate of increase in the surface. In other words, it represents the rate of increase in the actual surface area with respect to the area when a surface is viewed in a plan view.
If the Sdr of the surface-treated layer is too large, the surface of the surface-treated layer becomes dense and undulating, so that the anchor effect is likely to be exhibited when the surface-treated copper foil is adhered to the resin base material, while transmission is performed by the skin effect. The loss will be large. Therefore, by setting the Sdr of the surface treatment layer within the above range, it is possible to secure a balance between ensuring the anchor effect and suppressing transmission loss.
表面処理層の例としては、粗化処理層、耐熱処理層、防錆処理層、クロメート処理層、シランカップリング処理層などが挙げられる。これらの層は、単一又は2種以上を組み合わせて用いることができる。その中でも表面処理層は、樹脂基材との接着性の観点から、粗化処理層を含有することが好ましい。
また、表面処理層が、耐熱処理層、防錆処理層、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る1種以上の層を含有する場合、これらの層は粗化処理層上に設けられることが好ましい。 The type of the surface treatment layer is not particularly limited, and various surface treatment layers known in the art can be used.
Examples of the surface treatment layer include a roughening treatment layer, a heat resistance treatment layer, a rust prevention treatment layer, a chromate treatment layer, a silane coupling treatment layer and the like. These layers can be used alone or in combination of two or more. Among them, the surface treatment layer preferably contains a roughening treatment layer from the viewpoint of adhesiveness to the resin base material.
When the surface treatment layer contains one or more layers selected from the group consisting of a heat resistant treatment layer, a rust prevention treatment layer, a chromate treatment layer and a silane coupling treatment layer, these layers are roughened treatment layers. It is preferably provided on top.
図1に示されるように、銅箔10の一方の面に形成された粗化処理層は、粗化粒子20と、粗化粒子20の少なくとも一部を被覆するかぶせめっき層30とを含む。粗化粒子20は、銅箔10の凸部11だけでなく凹部12にも形成されている。また、銅箔10の凸部11に形成された粗化粒子20は、めっき液に微量のタングステン化合物を添加することにより、過成長が抑制されている。そのため、この粗化粒子20は粒径が大きい粒子に過成長しておらず、各方向に向かって成長した複雑な形状を有している。表面処理層のSkuやStrなどのパラメータを上記の範囲に制御することにより、このような構造をとることができると考えられる。 Here, as an example, FIG. 1 shows a schematic enlarged cross-sectional view of a surface-treated copper foil having a roughening-treated layer on one surface of the copper foil.
As shown in FIG. 1, the roughening-treated layer formed on one surface of the
かぶせめっき層30としては、特に限定されないが、銅、銀、金、ニッケル、コバルト、亜鉛などから形成することができる。 The roughened
The
タングステン化合物としては、特に限定されないが、例えば、タングステン酸ナトリウム(Na2WO4)などを用いることができる。
めっき液におけるタングステン化合物の含有量としては、1ppm以上とすることが好ましい。このような含有量であれば、凸部11に形成された粗化粒子20の過成長を抑制するとともに、凹部12に粗化粒子20を形成させ易くすることができる。なお、タングステン化合物の含有量の上限値は、特に限定されないが、電気抵抗の増大を抑制する観点から、20ppmであることが好ましい。 The roughened layer can be formed by electroplating. In particular, the roughened
The tungsten compound is not particularly limited, but for example, sodium tungstate (Na 2 WO 4 ) or the like can be used.
The content of the tungsten compound in the plating solution is preferably 1 ppm or more. With such a content, it is possible to suppress the overgrowth of the roughened
(粗化粒子20の形成条件)
めっき液組成:5~15g/LのCu、40~100g/Lの硫酸、1~6ppmのタングステン酸ナトリウム
めっき液温度:20~50℃
電気めっき条件:電流密度30~90A/dm2、時間0.1~8秒 The electroplating conditions for forming the roughening treatment layer may be adjusted according to the electroplating apparatus to be used, and are not particularly limited, but typical conditions are as follows. Each electroplating may be performed once or a plurality of times.
(Conditions for forming roughened particles 20)
Plating solution composition: 5 to 15 g / L Cu, 40 to 100 g / L sulfuric acid, 1 to 6 ppm sodium tungstate Plating solution temperature: 20 to 50 ° C.
Electroplating conditions: current density 30-90 A / dm 2 , time 0.1-8 seconds
めっき液組成:10~30g/LのCu、70~130g/Lの硫酸
めっき液温度:30~60℃
電気めっき条件:電流密度4.8~15A/dm2、時間0.1~8秒 (Conditions for forming the cover plating layer 30)
Plating solution composition: 10 to 30 g / L Cu, 70 to 130 g / L sulfuric acid Plating solution temperature: 30 to 60 ° C.
Electroplating conditions: current density 4.8 to 15 A / dm 2 , time 0.1 to 8 seconds
耐熱処理層及び/又は防錆処理層としては、ニッケル、亜鉛、錫、コバルト、モリブデン、銅、タングステン、リン、ヒ素、クロム、バナジウム、チタン、アルミニウム、金、銀、白金族元素、鉄、タンタルの群から選択される1種以上の元素(金属、合金、酸化物、窒化物、硫化物などのいずれの形態であってもよい)を含む層とすることができる。その中でも耐熱処理層及び/又は防錆処理層はNi-Zn層であることが好ましい。 The heat-resistant treatment layer and the rust-prevention treatment layer are not particularly limited, and can be formed from materials known in the art. Since the heat-resistant treatment layer may also function as a rust-preventive treatment layer, one layer having both the functions of the heat-resistant treatment layer and the rust-preventive treatment layer is formed as the heat-resistant treatment layer and the rust-preventive treatment layer. May be good.
The heat-resistant layer and / or rust-preventive layer includes nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, and tantalum. It can be a layer containing one or more elements (which may be in any form such as metal, alloy, oxide, nitride, sulfide, etc.) selected from the group of. Among them, the heat-resistant treatment layer and / or the rust-prevention treatment layer is preferably a Ni—Zn layer.
めっき液組成:1~30g/LのNi、1~30g/LのZn
めっき液pH:2~5
めっき液温度:30~50℃
電気めっき条件:電流密度0.1~10A/dm2、時間0.1~5秒 The heat-resistant treatment layer and the rust-prevention treatment layer can be formed by electroplating. The conditions may be adjusted according to the electroplating apparatus used and are not particularly limited, but the conditions for forming the heat-resistant treatment layer (Ni—Zn layer) using a general electroplating apparatus are as follows. be. The electroplating may be performed once or a plurality of times.
Plating solution composition: 1 to 30 g / L Ni, 1 to 30 g / L Zn
Plating solution pH: 2-5
Plating liquid temperature: 30 to 50 ° C
Electroplating conditions: current density 0.1-10 A / dm 2 , time 0.1-5 seconds
ここで、本明細書において「クロメート処理層」とは、無水クロム酸、クロム酸、二クロム酸、クロム酸塩又は二クロム酸塩を含む液で形成された層を意味する。クロメート処理層は、コバルト、鉄、ニッケル、モリブデン、亜鉛、タンタル、銅、アルミニウム、リン、タングステン、錫、ヒ素、チタンなどの元素(金属、合金、酸化物、窒化物、硫化物などのいずれの形態であってもよい)を含む層であることができる。クロメート処理層の例としては、無水クロム酸又は二クロム酸カリウム水溶液で処理したクロメート処理層、無水クロム酸又は二クロム酸カリウム及び亜鉛を含む処理液で処理したクロメート処理層などが挙げられる。 The chromate-treated layer is not particularly limited and can be formed from a material known in the art.
Here, the term "chromate-treated layer" as used herein means a layer formed of a liquid containing chromic anhydride, chromic acid, chromic acid, chromate or dichromate. The chromate-treated layer can be any element (metal, alloy, oxide, nitride, sulfide, etc.) such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. It can be a layer containing (may be in the form). Examples of the chromate-treated layer include a chromate-treated layer treated with an aqueous solution of chromic anhydride or potassium dichromate, and a chromate-treated layer treated with a treatment solution containing chromic anhydride or potassium dichromate and zinc.
クロメート液組成:1~10g/LのK2Cr2O7、0.01~10g/LのZn
クロメート液pH:2~5
クロメート液温度:30~55℃
電解条件:電流密度0.1~10A/dm2、時間0.1~5秒(電解クロメート処理の場合) The chromate-treated layer can be formed by a known method such as immersion chromate treatment and electrolytic chromate treatment. These conditions are not particularly limited, but for example, the conditions for forming a general chromate-treated layer are as follows. The chromate treatment may be performed once or a plurality of times.
Chromate solution composition: 1 to 10 g / L K 2 Cr 2 O 7 , 0.01 to 10 g / L Zn
Chromate solution pH: 2-5
Chromate liquid temperature: 30-55 ° C
Electrolytic conditions: Current density 0.1 to 10 A / dm 2 , time 0.1 to 5 seconds (in the case of electrolytic chromate treatment)
ここで、本明細書において「シランカップリング処理層」とは、シランカップリング剤で形成された層を意味する。
シランカップリング剤としては、特に限定されず、当該技術分野において公知のものを用いることができる。シランカップリング剤の例としては、アミノ系シランカップリング剤、エポキシ系シランカップリング剤、メルカプト系シランカップリング剤、メタクリロキシ系シランカップリング剤、ビニル系シランカップリング剤、イミダゾール系シランカップリング剤、トリアジン系シランカップリング剤などが挙げられる。これらの中でも、アミノ系シランカップリング剤、エポキシ系シランカップリング剤が好ましい。上記のシランカップリング剤は、単独又は2種以上を組み合わせて用いることができる。
代表的なシランカップリング処理層の形成方法としては、上述のシランカップリング剤の1~3体積%水溶液を塗布し、乾燥させることでシランカップリング処理層を形成する方法が挙げられる。 The silane coupling treatment layer is not particularly limited, and can be formed from a material known in the art.
Here, the term "silane coupling-treated layer" as used herein means a layer formed of a silane coupling agent.
The silane coupling agent is not particularly limited, and those known in the art can be used. Examples of silane coupling agents include amino-based silane coupling agents, epoxy-based silane coupling agents, mercapto-based silane coupling agents, metharoxy-based silane coupling agents, vinyl-based silane coupling agents, and imidazole-based silane coupling agents. , Triazine-based silane coupling agent and the like. Among these, amino-based silane coupling agents and epoxy-based silane coupling agents are preferable. The above silane coupling agent can be used alone or in combination of two or more.
As a typical method for forming a silane coupling treatment layer, a method of forming a silane coupling treatment layer by applying a 1 to 3% by volume aqueous solution of the above-mentioned silane coupling agent and drying it can be mentioned.
電解銅箔は、硫酸銅めっき浴からチタン又はステンレスのドラム上に銅を電解析出させることによって一般に製造されるが、回転ドラム側に形成される平坦なS面(シャイン面)と、S面の反対側に形成されるM面(マット面)とを有する。電解銅箔のM面は、一般に微小な凹凸部を有している。また、電解銅箔のS面は、研磨時に形成された回転ドラムの研磨スジが転写されるため、微小な凹凸部を有する。
また、圧延銅箔は、圧延時に圧延油によってオイルピットが形成されるため、微小な凹凸部を表面に有する。 The
Electrolytic copper foil is generally manufactured by electrolytically depositing copper on a titanium or stainless steel drum from a copper sulfate plating bath, but a flat S surface (shine surface) formed on the rotating drum side and an S surface. It has an M surface (matte surface) formed on the opposite side of the surface. The M surface of the electrolytic copper foil generally has minute uneven portions. Further, the S surface of the electrolytic copper foil has minute uneven portions because the polishing streaks of the rotating drum formed during polishing are transferred.
Further, the rolled copper foil has minute uneven portions on the surface because oil pits are formed by rolling oil during rolling.
銅箔10が、プリント配線板の回路パターンとして通常使用される、タフピッチ銅、無酸素銅などの高純度の銅、Sn、Ag、Cr、Zr又はMgなどを添加した銅合金を加工したものである場合、銅箔10にWは通常含有されない。よって、銅箔10を含む表面処理銅箔を溶液化したものを分析することで得たタングステンの量を基に、銅箔10の厚みを考慮した計算を行うことで、表面処理層のタングステンの含有量を推定することができる。上記の計算式はその推定法である。
酸分解処理による溶液化は、10cm角の表面処理銅箔を硝酸とフッ化水素酸との混合液に溶解し、当該溶液を希釈することによって行う。
誘導結合プラズマ質量分析は、誘導結合プラズマ質量分析装置(ICP-MS)を用いて行うことができる。 The surface-treated copper foil according to the embodiment of the present invention has a tungsten content of 1.0 × when it is acid-decomposed to a solution and the tungsten content in the solution is measured by inductively coupled plasma mass spectrometry. It is preferably 12 / t to 4.0 × 12 / t [ppm] (t is the thickness of the copper foil 10). If the content of tungsten is within such a range, the Sku and Str of the surface treatment layer can be controlled within the above range.
The
The solution by acid decomposition treatment is carried out by dissolving a 10 cm square surface-treated copper foil in a mixed solution of nitric acid and hydrofluoric acid and diluting the solution.
Inductively coupled plasma mass spectrometry can be performed using an inductively coupled plasma mass spectrometer (ICP-MS).
この銅張積層板は、上記の表面処理銅箔の表面処理層に樹脂基材を接着することによって製造することができる。
樹脂基材としては、特に限定されず、当該技術分野において公知のものを用いることができる。樹脂基材の例としては、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、ガラス布基材エポキシ樹脂、ポリエステルフィルム、ポリイミド樹脂、液晶ポリマー、フッ素樹脂などが挙げられる。これらの中でも樹脂基材はポリイミド樹脂が好ましい。 The copper-clad laminate according to the embodiment of the present invention includes the above-mentioned surface-treated copper foil and a resin base material adhered to the surface-treated layer of the surface-treated copper foil.
This copper-clad laminate can be manufactured by adhering a resin base material to the surface-treated layer of the above-mentioned surface-treated copper foil.
The resin base material is not particularly limited, and those known in the art can be used. Examples of resin base materials include paper base material phenol resin, paper base material epoxy resin, synthetic fiber cloth base material epoxy resin, glass cloth / paper composite base material epoxy resin, glass cloth / glass non-woven composite base material epoxy resin, and glass. Examples thereof include cloth-based epoxy resin, polyester film, polyimide resin, liquid crystal polymer, and fluororesin. Among these, the resin base material is preferably a polyimide resin.
上記のようにして製造された銅張積層板は、プリント配線板の製造に用いることができる。 The method for adhering the surface-treated copper foil to the resin base material is not particularly limited, and can be performed according to a method known in the art. For example, the surface-treated copper foil and the resin base material may be laminated and thermocompression bonded.
The copper-clad laminate manufactured as described above can be used for manufacturing a printed wiring board.
このプリント配線板は、上記の銅張積層板の表面処理銅箔をエッチングして回路パターンを形成することによって製造することができる。回路パターンの形成方法としては、特に限定されず、サブトラクティブ法、セミアディティブ法などの公知の方法を用いることができる。その中でも、回路パターンの形成方法はサブトラクティブ法が好ましい。 The printed wiring board according to the embodiment of the present invention includes a circuit pattern formed by etching the surface-treated copper foil of the copper-clad laminate.
This printed wiring board can be manufactured by etching the surface-treated copper foil of the copper-clad laminate to form a circuit pattern. The method for forming the circuit pattern is not particularly limited, and a known method such as a subtractive method or a semi-additive method can be used. Among them, the subtractive method is preferable as the method for forming the circuit pattern.
なお、このサブトラクティブ法における各種条件は、特に限定されず、当該技術分野において公知の条件に準じて行うことができる。 When the printed wiring board is manufactured by the subtractive method, it is preferable to carry out as follows. First, a predetermined resist pattern is formed by applying, exposing and developing a resist on the surface of the surface-treated copper foil of the copper-clad laminate. Next, the surface-treated copper foil of the portion (unnecessary portion) where the resist pattern is not formed is removed by etching to form a circuit pattern. Finally, the resist pattern on the surface-treated copper foil is removed.
The various conditions in this subtractive method are not particularly limited, and can be performed according to the conditions known in the art.
圧延銅箔(厚さ12μm)を準備し、一方の面を脱脂及び酸洗した後、表面処理層として粗化処理層、耐熱処理層としてNi-Zn層、クロメート処理層、及びシランカップリング処理層を順次形成することによって表面処理銅箔を得た。各処理層の形成条件は次の通りとした。
(1)粗化処理層
<粗化粒子の形成条件>
めっき液組成:11g/LのCu、50g/Lの硫酸、1ppmのタングステン(タングステン酸ナトリウム2水和物由来)
めっき液温度:27℃
電気めっき条件:電流密度38.8A/dm2、時間1.3秒
電気めっき処理回数:2回 (Example 1)
A rolled copper foil (
(1) Roughening treatment layer <Conditions for forming roughened particles>
Plating solution composition: 11 g / L Cu, 50 g / L sulfuric acid, 1 ppm tungsten (derived from sodium tungstate dihydrate)
Plating liquid temperature: 27 ° C
Electroplating conditions: Current density 38.8 A / dm 2 , time 1.3 seconds Number of electroplating processes: 2 times
めっき液組成:20g/LのCu、100g/Lの硫酸
めっき液温度:50℃
電気めっき条件:電流密度8.2A/dm2、時間1.4秒
電気めっき処理回数:2回 <Conditions for forming the cover plating layer>
Plating solution composition: 20 g / L Cu, 100 g / L sulfuric acid Plating solution temperature: 50 ° C.
Electroplating conditions: Current density 8.2 A / dm 2 , Time 1.4 seconds Number of electroplating processes: 2 times
<Ni-Zn層の形成条件>
めっき液組成:23.5g/LのNi、4.5g/LのZn
めっき液pH:3.6
めっき液温度:40℃
電気めっき条件:電流密度0.6A/dm2、時間0.7秒
電気めっき処理回数:1回 (2) Heat-resistant treatment layer <Conditions for forming Ni-Zn layer>
Plating solution composition: 23.5 g / L Ni, 4.5 g / L Zn
Plating solution pH: 3.6
Plating liquid temperature: 40 ° C
Electroplating conditions: Current density 0.6A / dm 2 , time 0.7 seconds Number of electroplating processes: 1 time
<電解クロメート処理層の形成条件>
クロメート液組成:3g/LのK2Cr2O7、0.33g/LのZn
クロメート液pH:3.7
クロメート液温度:55℃
電解条件:電流密度1.4A/dm2、時間0.7秒
クロメート処理回数:2回 (3) Chromate-treated layer <Conditions for forming electrolytic chromate-treated layer>
Chromate solution composition: 3 g / L K 2 Cr 2 O 7 , 0.33 g / L Zn
Chromate solution pH: 3.7
Chromate liquid temperature: 55 ° C
Electrolysis conditions: Current density 1.4 A / dm 2 , Time 0.7 seconds Chromate treatment count: 2 times
N-2-(アミノエチル)-3-アミノプロピルトリメトキシシランの1.2体積%水溶液を塗布し、乾燥させることでシランカップリング処理層を形成した。 (4) Silane Coupling Treatment Layer A silane coupling treatment layer was formed by applying a 1.2% by volume aqueous solution of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane and drying it.
粗化粒子の形成条件において、めっき液組成のタングステンの量を2ppmに変更したこと以外は、実施例1と同様の条件で表面処理銅箔を得た。 (Example 2)
A surface-treated copper foil was obtained under the same conditions as in Example 1 except that the amount of tungsten in the plating solution composition was changed to 2 ppm under the conditions for forming the roughened particles.
粗化粒子の形成条件において、めっき液組成のタングステンの量を3ppmに変更したこと以外は、実施例1と同様の条件で表面処理銅箔を得た。 (Example 3)
A surface-treated copper foil was obtained under the same conditions as in Example 1 except that the amount of tungsten in the plating solution composition was changed to 3 ppm under the conditions for forming the roughened particles.
粗化粒子の形成条件において、めっき液組成のタングステンの量を4ppmに変更したこと以外は、実施例1と同様の条件で表面処理銅箔を得た。 (Example 4)
A surface-treated copper foil was obtained under the same conditions as in Example 1 except that the amount of tungsten in the plating solution composition was changed to 4 ppm under the conditions for forming the roughened particles.
粗化粒子の形成条件において、めっき液組成のタングステンの量を5ppmに変更したこと以外は、実施例1と同様の条件で表面処理銅箔を得た。 (Example 5)
A surface-treated copper foil was obtained under the same conditions as in Example 1 except that the amount of tungsten in the plating solution composition was changed to 5 ppm under the conditions for forming the roughened particles.
粗化粒子の形成条件において、めっき液組成のタングステンの量を6ppmに変更したこと以外は、実施例1と同様の条件で表面処理銅箔を得た。 (Example 6)
A surface-treated copper foil was obtained under the same conditions as in Example 1 except that the amount of tungsten in the plating solution composition was changed to 6 ppm under the conditions for forming the roughened particles.
実施例1と同じ圧延銅箔を準備し、一方の面を脱脂及び酸洗した後、表面処理層として粗化処理層、耐熱処理層としてNi-Zn層、クロメート処理層、及びシランカップリング処理層を順次形成することによって表面処理銅箔を得た。各処理層の形成条件は次の通りとした。
(1)粗化処理層
<粗化粒子の形成条件>
めっき液組成:11g/LのCu、50g/Lの硫酸、5ppmのタングステン(タングステン酸ナトリウム2水和物由来)
めっき液温度:27℃
電気めっき条件:電流密度46.8A/dm2、時間1.0秒
電気めっき処理回数:2回 (Example 7)
The same rolled copper foil as in Example 1 was prepared, and after degreasing and pickling one surface, a roughening treatment layer was used as a surface treatment layer, a Ni—Zn layer as a heat treatment layer, a chromate treatment layer, and a silane coupling treatment. A surface-treated copper foil was obtained by sequentially forming layers. The formation conditions of each treatment layer were as follows.
(1) Roughening treatment layer <Conditions for forming roughened particles>
Plating solution composition: 11 g / L Cu, 50 g / L sulfuric acid, 5 ppm tungsten (derived from sodium tungstate dihydrate)
Plating liquid temperature: 27 ° C
Electroplating conditions: Current density 46.8 A / dm 2 , time 1.0 seconds Number of electroplating processes: 2 times
めっき液組成:20g/LのCu、100g/Lの硫酸
めっき液温度:50℃
電気めっき条件:電流密度8.2A/dm2、時間1.4秒
電気めっき処理回数:2回 <Conditions for forming the cover plating layer>
Plating solution composition: 20 g / L Cu, 100 g / L sulfuric acid Plating solution temperature: 50 ° C.
Electroplating conditions: Current density 8.2 A / dm 2 , Time 1.4 seconds Number of electroplating processes: 2 times
<Ni-Zn層の形成条件>
めっき液組成:23.5g/LのNi、4.5g/LのZn
めっき液pH:3.6
めっき液温度:40℃
電気めっき条件:電流密度0.7A/dm2、時間0.7秒
電気めっき処理回数:1回 (2) Heat-resistant treatment layer <Conditions for forming Ni-Zn layer>
Plating solution composition: 23.5 g / L Ni, 4.5 g / L Zn
Plating solution pH: 3.6
Plating liquid temperature: 40 ° C
Electroplating conditions: Current density 0.7A / dm 2 , time 0.7 seconds Number of electroplating processes: 1 time
<電解クロメート処理層の形成条件>
クロメート液組成:3g/LのK2Cr2O7、0.33g/LのZn
クロメート液pH:3.7
クロメート液温度:55℃
電解条件:電流密度1.5A/dm2、時間0.7秒
クロメート処理回数:2回 (3) Chromate-treated layer <Conditions for forming electrolytic chromate-treated layer>
Chromate solution composition: 3 g / L K 2 Cr 2 O 7 , 0.33 g / L Zn
Chromate solution pH: 3.7
Chromate liquid temperature: 55 ° C
Electrolysis conditions: Current density 1.5 A / dm 2 , Time 0.7 seconds Chromate treatment count: 2 times
N-2-(アミノエチル)-3-アミノプロピルトリメトキシシランの1.2体積%水溶液を塗布し、乾燥させることでシランカップリング処理層を形成した。 (4) Silane Coupling Treatment Layer A silane coupling treatment layer was formed by applying a 1.2% by volume aqueous solution of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane and drying it.
かぶせめっき層の形成条件において、電流密度を9.6A/dm2に変更したこと以外は、実施例7と同様の条件で表面処理銅箔を得た。 (Example 8)
A surface-treated copper foil was obtained under the same conditions as in Example 7 except that the current density was changed to 9.6 A / dm 2 under the conditions for forming the cover plating layer.
粗化粒子の形成条件において電流密度を46.0A/dm2に、かぶせめっき層の形成条件において電流密度を9.6A/dm2に、及びNi-Zn層の形成条件において電流密度を0.9A/dm2にそれぞれ変更したこと以外は、実施例7と同様の条件で表面処理銅箔を得た。 (Example 9)
The current density was set to 46.0 A / dm 2 under the conditions for forming the roughened particles, the current density was set to 9.6 A / dm 2 under the conditions for forming the cover plating layer, and the current density was set to 0 under the conditions for forming the Ni—Zn layer. A surface-treated copper foil was obtained under the same conditions as in Example 7 except that the values were changed to 9 A / dm 2 .
圧延銅箔(厚さ12μm)を準備し、一方の面を脱脂及び酸洗した後、表面処理層として粗化処理層、耐熱処理層としてNi-Zn層、クロメート処理層、及びシランカップリング処理層を順次形成することによって表面処理銅箔を得た。各処理層の形成条件は次の通りとした。
(1)粗化処理層
<粗化粒子の形成条件>
めっき液組成:12g/LのCu、50g/Lの硫酸、5ppmのタングステン(タングステン酸ナトリウム2水和物由来)
めっき液温度:27℃
電気めっき条件:電流密度48.3A/dm2、時間0.81秒
電気めっき処理回数:2回 (Example 10)
A rolled copper foil (
(1) Roughening treatment layer <Conditions for forming roughened particles>
Plating solution composition: 12 g / L Cu, 50 g / L sulfuric acid, 5 ppm tungsten (derived from sodium tungstate dihydrate)
Plating liquid temperature: 27 ° C
Electroplating conditions: Current density 48.3A / dm 2 , Time 0.81 seconds Number of electroplating processes: 2 times
めっき液組成:20g/LのCu、100g/Lの硫酸
めっき液温度:50℃
電気めっき条件:電流密度11.9A/dm2、時間1.15秒
電気めっき処理回数:2回 <Conditions for forming the cover plating layer>
Plating solution composition: 20 g / L Cu, 100 g / L sulfuric acid Plating solution temperature: 50 ° C.
Electroplating conditions: Current density 11.9 A / dm 2 , Time 1.15 seconds Number of electroplating processes: 2 times
<Ni-Zn層の形成条件>
めっき液組成:23.5g/LのNi、4.5g/LのZn
めっき液pH:3.6
めっき液温度:40℃
電気めっき条件:電流密度1.07A/dm2、時間0.59秒
電気めっき処理回数:1回 (2) Heat-resistant treatment layer <Conditions for forming Ni-Zn layer>
Plating solution composition: 23.5 g / L Ni, 4.5 g / L Zn
Plating solution pH: 3.6
Plating liquid temperature: 40 ° C
Electroplating conditions: Current density 1.07 A / dm 2 , Time 0.59 seconds Number of electroplating processes: 1 time
<電解クロメート処理層の形成条件>
クロメート液組成:3g/LのK2Cr2O7、0.33g/LのZn
クロメート液pH:3.65
クロメート液温度:55℃
電解条件:電流密度1.91A/dm2、時間0.59秒
クロメート処理回数:2回 (3) Chromate-treated layer <Conditions for forming electrolytic chromate-treated layer>
Chromate solution composition: 3 g / L K 2 Cr 2 O 7 , 0.33 g / L Zn
Chromate solution pH: 3.65
Chromate liquid temperature: 55 ° C
Electrolysis conditions: Current density 1.91 A / dm 2 , Time 0.59 seconds Chromate treatment count: 2 times
N-2-(アミノエチル)-3-アミノプロピルトリメトキシシランの1.2体積%水溶液を塗布し、乾燥させることでシランカップリング処理層を形成した。 (4) Silane Coupling Treatment Layer A silane coupling treatment layer was formed by applying a 1.2% by volume aqueous solution of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane and drying it.
実施例1で用いた圧延銅箔(表面処理を行っていない銅箔)を比較として用いた。 (Comparative Example 1)
The rolled copper foil (copper foil without surface treatment) used in Example 1 was used as a comparison.
粗化粒子の形成条件において、めっき液組成のタングステンの量を0ppm(タングステン酸ナトリウムを添加しなかった)としたこと以外は、実施例1と同様の条件で表面処理銅箔を得た。 (Comparative Example 2)
A surface-treated copper foil was obtained under the same conditions as in Example 1 except that the amount of tungsten in the plating solution composition was 0 ppm (sodium tungstate was not added) under the conditions for forming the roughened particles.
<Sku、Str、Sa、Sq及びSdr>
オリンパス株式会社製のレーザー顕微鏡(LEXT OLS4000)を用いて画像撮影を行なった。撮影した画像の解析は、オリンパス株式会社製のレーザー顕微鏡(LEXT OLS4100)の解析ソフトを用いて行った。Sku、Str、Sa、Sq及びSdrの測定はISO 25178-2:2012にそれぞれ準拠して行った。また、これらの測定結果は、任意の5か所で測定した値の平均値を測定結果とした。なお、測定時の温度は23~25℃とした。また、レーザー顕微鏡及び解析ソフトにおける主要な設定条件は下記の通りである。
対物レンズ:MPLAPON50XLEXT(倍率:50倍、開口数:0.95、液浸タイプ:空気、機械的鏡筒長:∞、カバーガラス厚:0、視野数:FN18)
光学ズーム倍率:1倍
走査モード:XYZ高精度(高さ分解能:60nm、取込みデータの画素数:1024×1024)
取込み画像サイズ[画素数]:横257μm×縦258μm[1024×1024]
(横方向に測定するため、評価長さとしては257μmに相当)
DIC:オフ
マルチレイヤー:オフ
レーザー強度:100
オフセット:0
コンフォーカルレベル:0
ビーム径絞り:オフ
画像平均:1回
ノイズリダクション:オン
輝度むら補正:オン
光学的ノイズフィルタ:オン
カットオフ:λc=200μm、λs及びλfは無し
フィルタ:ガウシアンフィルタ
ノイズ除去:測定前処理
表面(傾き)補正:実施
明るさ:30~50の範囲になるように調整する
明るさは測定対称の色調によって適宜設定すべき値である。上記の設定はL*が-69~-10、a*が2~32、b*が221の表面処理銅箔の表面を測定する際に適切な値である。
ここで、λsフィルタはISO 25178-2:2012におけるSフィルタに相当する。また、λcフィルタはISO 25178-2:2012におけるLフィルタに相当する。 The following characteristic evaluations were performed on the surface-treated copper foils or copper foils obtained in the above Examples and Comparative Examples.
<Sku, Str, Sa, Sq and Sdr>
Images were taken using a laser microscope (LEXT OLS4000) manufactured by Olympus Corporation. The captured image was analyzed using the analysis software of a laser microscope (LEXT OLS4100) manufactured by Olympus Corporation. Measurements of Sku, Str, Sa, Sq and Sdr were performed in accordance with ISO 25178-2: 2012, respectively. Further, as these measurement results, the average value of the values measured at any five places was used as the measurement result. The temperature at the time of measurement was 23 to 25 ° C. The main setting conditions for the laser microscope and analysis software are as follows.
Objective lens: MPLAPON50XLEXT (magnification: 50x, numerical aperture: 0.95, immersion type: air, mechanical lens barrel length: ∞, cover glass thickness: 0, field of view: FN18)
Optical zoom magnification: 1x Scanning mode: XYZ High precision (height resolution: 60 nm, number of pixels of captured data: 1024 x 1024)
Captured image size [number of pixels]: 257 μm wide x 258 μm long [1024 x 1024]
(Since it is measured in the lateral direction, the evaluation length is equivalent to 257 μm)
DIC: Off Multilayer: Off Laser intensity: 100
Offset: 0
Confocal level: 0
Beam diameter Aperture: Off Image average: 1 time Noise reduction: On Brightness unevenness correction: On Optical noise filter: On Cutoff: λc = 200 μm, no λs and λf Filter: Gaussian filter Noise reduction: Pretreatment surface (tilt) ) Correction: Implementation Brightness: Adjust so that it is in the range of 30 to 50. Brightness is a value that should be set appropriately according to the color tone of measurement symmetry. The above setting is an appropriate value when measuring the surface of the surface-treated copper foil in which L * is −69 to −10, a * is 2 to 32, and b * is 221.
Here, the λs filter corresponds to the S filter in ISO 25178-2: 2012. Further, the λc filter corresponds to the L filter in ISO 25178-2: 2012.
測定器としてHunterLab社製のMiniScan(登録商標)EZ Model 4000Lを用い、JIS Z8730:2009に準拠してCIE L*a*b*表色系のL*、a*及びb*の測定を行った。具体的には、上記の実施例及び比較例で得られた表面処理銅箔又は銅箔の測定対象面を測定器の感光部に押し当て、外から光が入らないようにしつつ測定した。また、L*、a*及びb*の測定は、JIS Z8722:2009の幾何条件Cに基づいて行った。なお、測定器の主な条件は下記の通りである。
光学系:d/8°、積分球サイズ:63.5mm、観察光源:D65
測定方式:反射
照明径:25.4mm
測定径:20.0mm
測定波長・間隔:400~700nm・10nm
光源:パルスキセノンランプ・1発光/測定
トレーサビリティ標準:CIE 44及びASTM E259に基づく、米国標準技術研究所(NIST)準拠校正
標準観察者:10°
また、測定基準となる白色タイルは、下記の物体色のものを使用した。
D65/10°にて測定した場合に、CIE XYZ表色系での値がX:81.90、Y:87.02、Z:93.76 <Measurement of color tone of measurement target>
Using MiniScan (registered trademark) EZ Model 4000L manufactured by HunterLab as a measuring instrument, CIE L * a * b * color system L *, a * and b * were measured in accordance with JIS Z8730: 2009. .. Specifically, the surface-treated copper foil or the surface to be measured of the copper foil obtained in the above Examples and Comparative Examples was pressed against the photosensitive portion of the measuring instrument, and the measurement was performed while preventing light from entering from the outside. Further, the measurements of L *, a * and b * were performed based on the geometric condition C of JIS Z8722: 2009. The main conditions of the measuring instrument are as follows.
Optical system: d / 8 °, integrating sphere size: 63.5 mm, observation light source: D65
Measurement method: Reflective illumination diameter: 25.4 mm
Measurement diameter: 20.0 mm
Measurement wavelength / interval: 400-700 nm / 10 nm
Light source: Pulse xenon lamp, 1 emission / measurement Traceability standard: Based on CIE 44 and ASTM E259, National Institute of Standards and Technology (NIST) compliant calibration Standard observer: 10 °
In addition, as the white tile used as the measurement standard, the one with the following object color was used.
When measured at D65 / 10 °, the values in the CIE XYZ color system are X: 81.90, Y: 87.02, Z: 93.76.
表面処理銅箔又は銅箔を酸分解処理して溶液化し、その溶液中のタングステンの含有量を誘導結合プラズマ質量分析によって測定した。溶液化などの条件は、上記した通りとした。
なお、実施例7~9については、表面処理層中のW濃度は実施例5と同等と考えられるため、この評価は行わなかった。また、実施例10についてはこの評価を行わなかったため、表面処理層中のW濃度は不明である。 <Content of tungsten (W)>
The surface-treated copper foil or copper foil was acid-decomposed to form a solution, and the content of tungsten in the solution was measured by inductively coupled plasma mass spectrometry. The conditions such as solution formation were as described above.
Since the W concentration in the surface-treated layer of Examples 7 to 9 is considered to be the same as that of Example 5, this evaluation was not performed. Moreover, since this evaluation was not performed for Example 10, the W concentration in the surface-treated layer is unknown.
表面処理銅箔をポリイミド樹脂基材と貼り合わせた後、幅3mmの回路をMD方向(圧延銅箔の長手方向)に形成した。回路の形成は通常の方法に則って実施した。次に、回路(表面処理銅箔)を樹脂基材の表面に対して、50mm/分の速度で90°方向に、すなわち、樹脂基材の表面に対して鉛直上向きに、引き剥がすときの強さ(MD90°ピール強度)をJIS C6471:1995に準拠して測定した。測定は3回行い、その平均値をピール強度の結果とした。ピール強度は、0.50kgf/cm以上であれば、回路(表面処理銅箔)と樹脂基材との接着性が良好であるといえる。
なお、比較例1の銅箔については、ポリイミド樹脂基材と貼り合わせることができなかったため、この評価は行わなかった。 <Peel strength>
After the surface-treated copper foil was bonded to the polyimide resin base material, a circuit having a width of 3 mm was formed in the MD direction (longitudinal direction of the rolled copper foil). The formation of the circuit was carried out according to a usual method. Next, the strength when the circuit (surface-treated copper foil) is peeled off at a speed of 50 mm / min in the 90 ° direction with respect to the surface of the resin base material, that is, vertically upward with respect to the surface of the resin base material. (MD90 ° peel strength) was measured according to JIS C6471: 1995. The measurement was performed three times, and the average value was used as the result of peel strength. If the peel strength is 0.50 kgf / cm or more, it can be said that the adhesiveness between the circuit (surface-treated copper foil) and the resin base material is good.
The copper foil of Comparative Example 1 could not be bonded to the polyimide resin base material, so this evaluation was not performed.
一方、表面処理層のSaは実施例1~10の表面処理銅箔と同等であるものの、Skuが所定の範囲外である比較例2の表面処理銅箔はピール強度が低かった。一般に、表面処理層のSaが大きいほど樹脂基材との接着性が向上することに鑑みると、この結果、すなわちSaがほぼ同等でありながら、Sku及びStrを制御することでピール強度が向上するという結果は驚くべきものであった。
実施例1~10の表面処理銅箔と、比較例1の銅箔を比較すると、Strが非常に近い値であることが分かる。実施例1~10の表面処理銅箔は、比較例1の銅箔に表面処理を施したものであること、及びStrが表面の異方性及び等方性を表すことに鑑みると、既に述べたように本発明の実施形態に係る表面処理銅箔は、銅箔表面の微小な凹凸部(圧延銅箔の場合はオイルピット)に沿って表面処理層、特に粗化粒子層が均一に形成されていることが分かる。仮に、微小な凹凸部に沿って粗化粒子層が形成されない場合は、Strの値は表面処理前後で大きく相違するはずである。
なお、比較例2についてW含有量が0.4ppmとなっているが、これは比較例2の表面処理銅箔を製造した際、表面処理層の形成に用いるいずれかのめっき液に意図せずWが残留していたことが原因と考えられる。本発明者らは、粗化処理層の形成用めっき液にはWは残留しておらず、その他の表面処理層の形成用めっき液中に残留していたものと考えている。 As shown in Table 1, the surface-treated copper foils of Examples 1 to 10 in which the Sku and Str of the surface-treated layer were within a predetermined range had high peel strength.
On the other hand, although the Sa of the surface-treated layer was equivalent to that of the surface-treated copper foils of Examples 1 to 10, the surface-treated copper foil of Comparative Example 2 in which the Sku was out of the predetermined range had a low peel strength. In general, considering that the larger the Sa of the surface treatment layer, the better the adhesiveness with the resin base material, this result, that is, the peel strength is improved by controlling the Sku and Str while the Sa is almost the same. The result was amazing.
Comparing the surface-treated copper foils of Examples 1 to 10 with the copper foils of Comparative Example 1, it can be seen that Str is a very close value. The surface-treated copper foils of Examples 1 to 10 have already been described in view of the fact that the copper foil of Comparative Example 1 is surface-treated and that Str exhibits surface anisotropy and isotropic properties. As described above, in the surface-treated copper foil according to the embodiment of the present invention, the surface-treated layer, particularly the roughened particle layer, is uniformly formed along the minute uneven portion (oil pit in the case of rolled copper foil) on the surface of the copper foil. You can see that it has been done. If the roughened particle layer is not formed along the minute uneven portion, the Str value should be significantly different before and after the surface treatment.
Although the W content of Comparative Example 2 is 0.4 ppm, this is unintentionally applied to any of the plating solutions used for forming the surface-treated layer when the surface-treated copper foil of Comparative Example 2 is manufactured. It is considered that the cause was that W remained. The present inventors consider that W did not remain in the plating solution for forming the roughening treatment layer, but remained in the plating solution for forming the other surface treatment layer.
11 凸部
12 凹部
20 粗化粒子
30 かぶせめっき層 10
Claims (10)
- 銅箔と、前記銅箔の少なくとも一方の面に形成された表面処理層とを有し、
前記表面処理層は、Skuが2.50~4.50、Strが0.20~0.40である表面処理銅箔。 It has a copper foil and a surface treatment layer formed on at least one surface of the copper foil.
The surface-treated layer is a surface-treated copper foil having a Sku of 2.50 to 4.50 and a Str of 0.20 to 0.40. - 前記Skuが2.80~4.00、前記Strが0.26~0.35である、請求項1に記載の表面処理銅箔。 The surface-treated copper foil according to claim 1, wherein the Sku is 2.80 to 4.00 and the Str is 0.26 to 0.35.
- 前記表面処理層は、Saが0.18~0.43μmである、請求項1又は2に記載の表面処理銅箔。 The surface-treated copper foil according to claim 1 or 2, wherein the surface-treated layer has a Sa of 0.18 to 0.43 μm.
- 前記表面処理層は、Sqが0.26~0.53μmである、請求項1~3のいずれか一項に記載の表面処理銅箔。 The surface-treated copper foil according to any one of claims 1 to 3, wherein the surface-treated layer has an Sq of 0.26 to 0.53 μm.
- 前記表面処理層は、Saが0.20~0.32μmであり、Sqが0.26~0.40μmである、請求項1又は2に記載の表面処理銅箔。 The surface-treated copper foil according to claim 1 or 2, wherein the surface-treated layer has Sa of 0.20 to 0.32 μm and Sq of 0.26 to 0.40 μm.
- 前記表面処理層は、Sdrが30~79%である、請求項1~5のいずれか一項に記載の表面処理銅箔。 The surface-treated copper foil according to any one of claims 1 to 5, wherein the surface-treated layer has an Sdr of 30 to 79%.
- 前記表面処理銅箔を酸分解処理して溶液化し、その溶液中のタングステンの含有量を誘導結合プラズマ質量分析によって測定した場合に、前記タングステンの含有量が1.0×12/t~4.0×12/t[ppm](tは前記銅箔の厚みである)である、請求項1~6のいずれか一項に記載の表面処理銅箔。 When the surface-treated copper foil was acid-decomposed to form a solution and the content of tungsten in the solution was measured by inductively coupled plasma mass spectrometry, the content of tungsten was 1.0 × 12 / t to 4. The surface-treated copper foil according to any one of claims 1 to 6, wherein 0 × 12 / t [ppm] (t is the thickness of the copper foil).
- 前記表面処理層は粗化処理層を含有する、請求項1~7のいずれか一項に記載の表面処理銅箔。 The surface-treated copper foil according to any one of claims 1 to 7, wherein the surface-treated layer contains a roughened-treated layer.
- 請求項1~8のいずれか一項に記載の表面処理銅箔と、前記表面処理銅箔の前記表面処理層に接着された樹脂基材とを備える銅張積層板。 A copper-clad laminate comprising the surface-treated copper foil according to any one of claims 1 to 8 and a resin base material adhered to the surface-treated layer of the surface-treated copper foil.
- 請求項9に記載の銅張積層板の前記表面処理銅箔をエッチングして形成された回路パターンを備えるプリント配線板。 A printed wiring board having a circuit pattern formed by etching the surface-treated copper foil of the copper-clad laminate according to claim 9.
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WO2018110579A1 (en) * | 2016-12-14 | 2018-06-21 | 古河電気工業株式会社 | Surface treated copper foil and copper-clad laminate |
WO2018207786A1 (en) * | 2017-05-09 | 2018-11-15 | Jx金属株式会社 | Electrolytic copper foil, copper-clad laminate, printed wiring board, production method therefor, electronic device, and production method therefor |
Also Published As
Publication number | Publication date |
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WO2022153580A1 (en) | 2022-07-21 |
KR20230104700A (en) | 2023-07-10 |
JPWO2022154102A1 (en) | 2022-07-21 |
TW202229651A (en) | 2022-08-01 |
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