JP5932638B2 - Copper powder for conductive paste and conductive paste - Google Patents
Copper powder for conductive paste and conductive paste Download PDFInfo
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- JP5932638B2 JP5932638B2 JP2012515777A JP2012515777A JP5932638B2 JP 5932638 B2 JP5932638 B2 JP 5932638B2 JP 2012515777 A JP2012515777 A JP 2012515777A JP 2012515777 A JP2012515777 A JP 2012515777A JP 5932638 B2 JP5932638 B2 JP 5932638B2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 116
- 239000002245 particle Substances 0.000 claims description 54
- 238000005245 sintering Methods 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 26
- 229910052698 phosphorus Inorganic materials 0.000 claims description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 18
- 239000011574 phosphorus Substances 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 238000009826 distribution Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000009692 water atomization Methods 0.000 claims description 8
- 238000005259 measurement Methods 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 238000000691 measurement method Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000002344 surface layer Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 description 17
- 230000003647 oxidation Effects 0.000 description 16
- 238000007254 oxidation reaction Methods 0.000 description 16
- 239000011231 conductive filler Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- 239000004020 conductor Substances 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 239000003985 ceramic capacitor Substances 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 239000012798 spherical particle Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910000881 Cu alloy Inorganic materials 0.000 description 4
- -1 application Substances 0.000 description 4
- 238000000889 atomisation Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- YWXYYJSYQOXTPL-SLPGGIOYSA-N isosorbide mononitrate Chemical compound [O-][N+](=O)O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 YWXYYJSYQOXTPL-SLPGGIOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000003685 thermal hair damage Effects 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
-
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/10—Alloys based on copper with silicon as the next major constituent
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/10—Copper
Description
本発明は、導電性ペースト用銅粉及びそれを用いた導電性ペーストに関する。詳しくは、電気回路の形成や、セラミックコンデンサの外部電極の形成などに好適に用いることができる導電性ペースト及びその導電フィラーとして好適な銅粉に関する。 The present invention relates to a copper powder for conductive paste and a conductive paste using the same. Specifically, the present invention relates to a conductive paste that can be suitably used for forming an electric circuit, forming an external electrode of a ceramic capacitor, and the like and a copper powder suitable as a conductive filler.
導電性ペーストは、樹脂系バインダーと溶媒からなるビヒクル中に導電フィラーを分散させた流動性組成物であり、電気回路の形成や、セラミックコンデンサの外部電極の形成などに広く用いられている。 The conductive paste is a fluid composition in which a conductive filler is dispersed in a vehicle composed of a resin binder and a solvent, and is widely used for forming an electric circuit, an external electrode of a ceramic capacitor, and the like.
この種の導電性ペーストには、樹脂の硬化によって導電性フィラーが圧着され導通を確保する樹脂硬化型と、焼成によって有機成分が揮発し導電性フィラーが焼結して導通を確保する焼成型とがある。 This type of conductive paste includes a resin-curing type in which a conductive filler is pressure-bonded by hardening of the resin to ensure conduction, and a baking type in which organic components are volatilized by baking and the conductive filler is sintered to ensure conduction. There is.
前者の樹脂硬化型導電性ペーストは、一般的に、金属粉末からなる導電フィラーと、エポキシ樹脂等の熱硬化性樹脂からなる有機バインダーとを含んだペースト状組成物であって、熱を加えることによって熱硬化型樹脂が導電フィラーとともに硬化収縮して、樹脂を介して導電フィラー同士が圧着され接触状態となり、導通性が確保されるものである。この樹脂硬化型導電性ペーストは１００℃から精々２００℃までの比較的低温域で処理可能であり、熱ダメージが少ないため、プリント配線基板や熱に弱い樹脂基板などに使用されている。 The former resin-curable conductive paste is generally a paste-like composition containing a conductive filler made of metal powder and an organic binder made of a thermosetting resin such as an epoxy resin, and is applied with heat. As a result, the thermosetting resin is cured and shrunk together with the conductive filler, and the conductive fillers are pressure-bonded through the resin so as to be in contact with each other, thereby ensuring conductivity. This resin-curable conductive paste can be processed in a relatively low temperature range from 100 ° C. to 200 ° C. and has little thermal damage, and is therefore used for printed wiring boards and heat-sensitive resin boards.
他方、後者の焼成型導電性ペーストは、一般に導電フィラー（金属粉末）とガラスフリットとを有機ビヒクル中に分散させてなるペースト状組成物であり、４００〜８００℃にて焼成することにより、有機ビヒクルが揮発し、さらに導電フィラーが焼結することによって導通性が確保されるものである。この際、ガラスフリットは、この導電膜を基板に接着させる作用を有し、有機ビヒクルは、金属粉末およびガラスフリットを印刷可能にするための有機液体媒体として作用する。
焼成型導電性ペーストは、焼成温度が高いため、プリント配線基板や樹脂材料には使用できないが、焼結して金属が一体化することから低抵抗化を実現することができ、例えば積層セラミックコンデンサの外部電極などに使用されている。On the other hand, the latter fired conductive paste is a paste-like composition in which a conductive filler (metal powder) and glass frit are generally dispersed in an organic vehicle. By firing at 400 to 800 ° C., organic Conductivity is ensured by volatilization of the vehicle and further sintering of the conductive filler. At this time, the glass frit has a function of adhering the conductive film to the substrate, and the organic vehicle functions as an organic liquid medium for enabling printing of the metal powder and the glass frit.
Firing-type conductive paste cannot be used for printed wiring boards or resin materials because of its high firing temperature, but it can be reduced in resistance because it is sintered and the metal is integrated. It is used for external electrodes.
樹脂硬化型導電性ペースト及び高温焼成型導電性ペーストのいずれにおいても、導電フィラーとして、従来は、銀粉が多用されてきたが、銅粉を用いた方が安価である上、マイグレーションが生じ難く、耐ハンダ性にも優れているため、銅粉を用いた導電性ペーストが汎用化されつつある。しかし、銅粉は、空気中で酸化し易く、銅粉表面の酸化膜は接続抵抗の増大をもたらすという課題を抱えていた。
そこで、導電性ペーストに用いる銅粉に関しては、従来から、銅粉表面の酸化を防止する方法が種々提案されている。In both the resin curable conductive paste and the high-temperature fired conductive paste, silver powder has been conventionally used as a conductive filler, but it is cheaper to use copper powder and migration is less likely to occur. Since the soldering resistance is also excellent, conductive paste using copper powder is being widely used. However, copper powder easily oxidizes in the air, and the oxide film on the surface of the copper powder has a problem of increasing the connection resistance.
Therefore, various methods for preventing oxidation of the copper powder surface have been conventionally proposed for the copper powder used in the conductive paste.
例えば特許文献１では、導電性ペースト内に還元作用を有する物質を配合し、銅表面の酸化を抑制することが提案されている。
また、特許文献２では、粒子表面を耐酸化性のある銀でコートすることが提案され、特許文献３では、無機酸化物でコートすることが提案されている。For example, Patent Document 1 proposes that a substance having a reducing action is blended in the conductive paste to suppress oxidation of the copper surface.
Patent Document 2 proposes coating the particle surface with silver having oxidation resistance, and Patent Document 3 proposes coating with an inorganic oxide.
特許文献４には、主成分であるＣｕに、ＺｎとＳｎの少なくともいずれか一方を添加して合金化した銅合金粉であって、当該銅合金粉中のＺｎ及び／又はＳｎの含有量が０．０２〜１．２質量％であり、しかも当該銅合金粉が０．００５〜０．０５質量％のＰを含有する導電材ペースト用銅合金が開示されている。 Patent Document 4 discloses a copper alloy powder that is alloyed by adding at least one of Zn and Sn to Cu as a main component, and the content of Zn and / or Sn in the copper alloy powder is as follows. The copper alloy for electrically conductive material pastes which is 0.02-1.2 mass% and whose copper alloy powder contains 0.005-0.05 mass% P is indicated.
さらにまた、特許文献５には、銅粉粒子内部にＳｉを０．１ａｔｍ％〜１０ａｔｍ％含有させることにより、粒度微細ながら耐酸化性に優れ、かつ導電性のバランスもとることができることが開示されている。 Furthermore, Patent Document 5 discloses that by containing 0.1 atm% to 10 atm% of Si inside the copper powder particles, it is excellent in oxidation resistance while having a fine particle size, and can be balanced in conductivity. ing.
近年、電気回路などにおいてファインピッチ化が進むのに伴い、導電性ペースト用の銅粉末も微粉化され、銅粉末の比表面積が大きくなってきており、導電性ペースト用の銅粉はさらに酸化し易い状態となってきている。 In recent years, with the progress of fine pitches in electrical circuits, etc., copper powder for conductive paste has also been made finer, and the specific surface area of copper powder has increased, and copper powder for conductive paste has further oxidized. It is becoming easy.
焼成型導電性ペーストに用いる銅粉は、加熱により焼結膜を形成することで導電性を確保するものである。これの焼結温度は、基板、用途、ペーストの配合組成などにより、５００〜９００℃の範囲で自在に調整できるのが理想である。
従来の銅粉は、焼成工程で銅粉が酸化すると焼成を阻害するため、基板、用途、ペーストの配合組成などにより様々に求められる焼結温度特性を満足するようにコントロールすることが難しいという課題を抱えていた。The copper powder used for the baked conductive paste ensures conductivity by forming a sintered film by heating. Ideally, the sintering temperature can be freely adjusted in the range of 500 to 900 ° C. depending on the substrate, application, paste composition and the like.
Since conventional copper powder inhibits firing when copper powder is oxidized in the firing process, it is difficult to control so as to satisfy various sintering temperature characteristics required depending on the substrate, application, paste composition, etc. Was holding.
そこで本発明は、耐酸化性を維持しつつも、焼結温度特性を５００〜９００℃の範囲で自在にコントロールすることができる、新たな導電性ペースト用銅粉及び導電性ペーストを提供することにある。 Therefore, the present invention provides a new copper powder for conductive paste and a conductive paste capable of freely controlling the sintering temperature characteristics within a range of 500 to 900 ° C. while maintaining oxidation resistance. It is in.
本発明は、Ｓｉ（ケイ素）及びＰ（リン）を含有する導電性ペースト用銅粉であって、Ｓｉ濃度が０．０１ａｔｍ％以上１．２ａｔｍ％未満であり、且つ、当該Ｓｉ濃度（ａｔｍ％）と、レーザー回折散乱式粒度分布測定法により測定して得られる体積基準粒度分布によるＤ５０（μｍ）との積によって算出されるＳｉ換算量（Ｓｉ濃度×Ｄ５０）が３．５０以下であることを特徴とする導電性ペースト用銅粉を提案する。 The present invention is a copper powder for conductive paste containing Si (silicon) and P (phosphorus), wherein the Si concentration is 0.01 atm% or more and less than 1.2 atm%, and the Si concentration (atm%) ) And D50 (μm) based on the volume-based particle size distribution obtained by measurement by the laser diffraction / scattering particle size distribution measurement method, the Si equivalent amount (Si concentration × D50) is 3.50 or less. We propose copper powder for conductive paste characterized by
本発明の導電性ペースト用銅粉は、耐酸化性を維持しつつも、焼結温度特性をコントロールすることができる。すなわち、Ｓｉ濃度が０．０１ａｔｍ％以上１．２ａｔｍ％未満の範囲内において、Ｓｉ濃度（ａｔｍ％）とＤ５０（μｍ）との積（Ｓｉ濃度×Ｄ５０）の値を３．５０以下に規定することにより、焼結開始温度を５００〜９００℃の範囲で調整することができる。よって、基板、用途、ペーストの配合組成などに応じて焼結温度特性をコントロールすることができるから、導電性ペースト用銅粉として優れている。例えばスクリーン印刷アディティブ法による導体回路形成用や、積層セラミックコンデンサの外部電極用等の各種電気的接点部材用の導電性ペーストの導電材料等に極めて良好に適用することができる。 The copper powder for conductive paste of the present invention can control the sintering temperature characteristics while maintaining oxidation resistance. That is, the product of Si concentration (atm%) and D50 (μm) (Si concentration × D50) is defined as 3.50 or less within a Si concentration range of 0.01 atm% or more and less than 1.2 atm%. Thereby, sintering start temperature can be adjusted in the range of 500-900 degreeC. Therefore, since the sintering temperature characteristics can be controlled according to the substrate, application, paste composition, etc., it is excellent as a copper powder for conductive paste. For example, the present invention can be applied very well to conductive materials such as conductive pastes for various electrical contact members such as conductor circuit formation by screen printing additive method and external electrodes of multilayer ceramic capacitors.
次に、実施の形態例に基づいて本発明を説明するが、本発明が次に説明する実施形態に限定されるものではない。 Next, the present invention will be described based on exemplary embodiments, but the present invention is not limited to the embodiments described below.
＜導電性ペースト用銅粉＞
本実施形態に係る導電性ペースト用銅粉（以下、「本銅粉」と称する）は、Ｓｉ（ケイ素）及びＰ（リン）を含有する導電性ペースト用銅粉である。Ｓｉ（ケイ素）及びＰ（リン）を含有する組成の銅粉であればよいから、Ｓｉ（ケイ素）及びＰ（リン）以外の金属元素を含有していてもよいが、典型的にはＣｕ−Ｐ−Ｓｉ型銅粉である。<Copper powder for conductive paste>
The copper powder for conductive paste according to the present embodiment (hereinafter referred to as “the present copper powder”) is a copper powder for conductive paste containing Si (silicon) and P (phosphorus). Since copper powder having a composition containing Si (silicon) and P (phosphorus) may be used, metal elements other than Si (silicon) and P (phosphorus) may be contained, but typically Cu- P-Si type copper powder.
本銅粉の特徴は、Ｓｉ濃度が０．０１ａｔｍ％以上１．２ａｔｍ％未満であり、且つ、当該Ｓｉ濃度（ａｔｍ％）と、レーザー回折散乱式粒度分布測定法により測定して得られる体積基準粒度分布によるＤ５０（μｍ）との積によって算出されるＳｉ換算量（Ｓｉ濃度×Ｄ５０）が３．５０以下であることにある。
Ｐ（リン）を含有する銅粉にＳｉ（ケイ素）を添加すると、Ｓｉ（ケイ素）濃度０．０１ａｔｍ％以上１．２ａｔｍ％未満の範囲内であれば、Ｓｉ濃度を高めることにより焼結開始温度を高くすることができる傾向があることを見出すことができた。また、粒径が小さければ、焼結開始温度が低下する傾向があることも確認することができた。しかし、Ｓｉ（ケイ素）濃度と粒径の何れかを規定するだけでは、焼結性、具体的には焼結開始温度を確実に制御できないことも確認された。そこで、両者の積、すなわち、Ｓｉ濃度とＤ５０の積（Ｓｉ濃度×Ｄ５０）を基準値として検討したところ、少なくもＳｉ濃度が一定範囲内においては焼結開始温度を段階的に制御できることを見出すことができた。
かかる観点から、本銅粉のＳｉ濃度×Ｄ５０は、３．５０以下であることが重要であり、好ましくは０．００１〜３．４０、特に０．００５〜３．００、中でも特に０．０１〜２．８０であるのがさらによい。
このような銅粉は、後の製造方法の項目において説明するように、実施例に基づいてアトマイズ条件を調整することにより製造することができる。但し、この方法に限定するものではない。The feature of this copper powder is that the Si concentration is 0.01 atm% or more and less than 1.2 atm%, and the Si concentration (atm%) and the volume standard obtained by measurement by the laser diffraction scattering type particle size distribution measuring method. The Si equivalent amount (Si concentration × D50) calculated by the product of D50 (μm) based on the particle size distribution is 3.50 or less.
When Si (silicon) is added to copper powder containing P (phosphorus), if the Si (silicon) concentration is in the range of 0.01 atm% or more and less than 1.2 atm%, the sintering start temperature is increased by increasing the Si concentration. I found out that there is a tendency to be high. It was also confirmed that if the particle size is small, the sintering start temperature tends to decrease. However, it has also been confirmed that the sinterability, specifically, the sintering start temperature cannot be reliably controlled only by defining either the Si (silicon) concentration or the particle size. Therefore, when the product of both, that is, the product of Si concentration and D50 (Si concentration × D50) was studied as a reference value, it was found that the sintering start temperature could be controlled stepwise at least when the Si concentration was within a certain range. I was able to.
From this viewpoint, it is important that the Si concentration x D50 of the present copper powder is 3.50 or less, preferably 0.001 to 3.40, particularly 0.005 to 3.00, and particularly 0.01 It is even better to be -2.80.
Such copper powder can be manufactured by adjusting the atomizing conditions based on the examples, as will be described later in the item of the manufacturing method. However, it is not limited to this method.
本銅粉、すなわちＳｉ濃度×Ｄ５０が３．５０以下である銅粉を分析した結果、銅粉粒子の表面にＳｉが濃化していることが分かった。より具体的な目安としては、銅粉粒子表面から深さ１０ｎｍにおけるＳｉ濃度に比べて、表面から深さ２ｎｍにおけるＳｉ濃度が高くなっていることが確認された。
Ｓｉ濃度が極めて低いために定量的に分析することは難しいが、銅粉粒子全体の表面に酸化ケイ素の薄い膜ができるため、内部に酸素が入り難くなり、その結果として焼結性を高めることができ、しかも、耐酸化性も高くなるのではないかと推察することができる。
なお、本銅粉において、表面にＳｉが濃化している銅粉粒子（「本銅粉粒子」と称する）が主材料であれば、１００％全ての銅粉粒子が表面にＳｉが濃化している銅粉粒子でなくても、同様の効果が得られると考えることができる。よって、本銅粉においては、表面にＳｉが濃化している銅粉粒子が全体の５０ｗｔ％以上、好ましくは８０ｗｔ％以上、特に９０ｗｔ％以上（１００ｗｔ％を含む）を占めるのが好ましい。
このように銅粉粒子の表面にＳｉを濃化させるためには、後の製造方法の項目において説明するように、実施例に基づいてアトマイズ条件を調整する方法を挙げることができる。但し、この方法に限定するものではない。As a result of analyzing this copper powder, that is, a copper powder having a Si concentration × D50 of 3.50 or less, it was found that Si was concentrated on the surface of the copper powder particles. As a more specific measure, it was confirmed that the Si concentration at a depth of 2 nm from the surface was higher than the Si concentration at a depth of 10 nm from the surface of the copper powder particles.
Although it is difficult to analyze quantitatively because the Si concentration is extremely low, a thin film of silicon oxide is formed on the entire surface of the copper powder particles, making it difficult for oxygen to enter inside, and as a result, improving the sinterability In addition, it can be inferred that the oxidation resistance may be increased.
In addition, in this copper powder, if the copper powder particle (referred to as “the present copper powder particle”) having Si concentrated on the surface is the main material, 100% of all the copper powder particles are concentrated on the surface. It can be considered that the same effect can be obtained even if the copper powder particles are not present. Therefore, in this copper powder, it is preferable that the copper powder particle | grains with which Si is concentrated on the surface occupy 50 wt% or more of the whole, Preferably it is 80 wt% or more, Especially 90 wt% or more (100 wt% is included).
In order to concentrate Si on the surface of the copper powder particles as described above, a method of adjusting the atomizing conditions based on the examples can be mentioned as described in the item of the manufacturing method later. However, it is not limited to this method.
本銅粉粒子のＳｉ濃度は、０．０１ａｔｍ％以上１．２ａｔｍ％未満の範囲であることが重要である。かかる範囲でＳｉ濃度量を調整することにより、耐酸化性を維持しつつ焼結開始温度を５００〜９００℃の範囲でより好ましく調整することができる。
このように耐酸化性維持と焼結開始温度の制御の観点から、本銅粉粒子のＳｉ濃度は、０．０１ａｔｍ％以上１．０ａｔｍ％未満の範囲であるのが好ましく、特に０．０３ａｔｍ％以上、中でも０．０５ａｔｍ％以上、或いは、特に０．２ａｔｍ％未満、中でも０．１ａｔｍ％未満であるのがより一層好ましい。It is important that the Si concentration of the copper powder particles is in the range of 0.01 atm% or more and less than 1.2 atm%. By adjusting the Si concentration in such a range, the sintering start temperature can be more preferably adjusted in the range of 500 to 900 ° C. while maintaining oxidation resistance.
Thus, from the viewpoint of maintaining oxidation resistance and controlling the sintering start temperature, the Si concentration of the present copper powder particles is preferably in the range of 0.01 atm% or more and less than 1.0 atm%, and particularly 0.03 atm%. Above all, 0.05 atm% or more, or particularly less than 0.2 atm%, especially less than 0.1 atm% is even more preferable.
本銅粉粒子のＰ（りん）濃度は、特に限定するものではないが、Ｐ（りん）の含有量は０．０１〜０．３ａｔｍ％、特に０．０２ａｔｍ％以上、或いは、０．１ａｔｍ％以下、その中でも０．０２ａｔｍ％以上、或いは、０．０６ａｔｍ％以下の割合で含有するのが好ましい。
このような範囲でＰ（りん）を含有すれば、粒度微細、耐酸化性を有し、導電性を損なわず、形状や粒度のバラツキが小さく、酸素濃度を低くすることができる。
かかる観点から、本銅粉粒子は、粒子内部にＰ（りん）を０．０２ａｔｍ％以上、０．０４ａｔｍ％以下の割合で含有するのがより一層好ましい。The P (phosphorus) concentration of the present copper powder particles is not particularly limited, but the content of P (phosphorus) is 0.01 to 0.3 atm%, particularly 0.02 atm% or more, or 0.1 atm%. In the following, it is preferable to contain at a ratio of 0.02 atm% or more or 0.06 atm% or less.
If P (phosphorus) is contained in such a range, it has fine particle size and oxidation resistance, does not impair electrical conductivity, has small variations in shape and particle size, and can reduce oxygen concentration.
From this viewpoint, the present copper powder particles more preferably contain P (phosphorus) in the particles at a ratio of 0.02 atm% or more and 0.04 atm% or less.
本銅粉粒子は、粒状、特に球状を呈するのが好ましい。ここで、粒状とは、アスペクト比（平均長径を平均短径で除した値）が１〜１．２５程度で揃っている形状をいい、アスペクト比が１〜１．１程度で揃っている形状を特に球状という。なお、形状が揃っていない状態は、不定形状という。このような粒状をなす銅粉は、相互のからみが少なくなり、導電性ペーストの導電材料等に使用した場合、ペースト中での分散性が向上するので、非常に好ましい。 The copper powder particles are preferably granular, particularly spherical. Here, granular means a shape in which the aspect ratio (value obtained by dividing the average major axis by the average minor axis) is about 1 to 1.25, and the aspect ratio is about 1 to 1.1. Is called spherical. A state where the shapes are not aligned is called an indefinite shape. Such a granular copper powder is very preferable because it causes less mutual entanglement and improves dispersibility in the paste when used as a conductive material for a conductive paste.
本銅粉において、レーザー回折散乱式粒度分布測定法により測定して得られる体積基準粒度分布によるＤ５０は、Ｓｉ濃度と、Ｓｉ濃度×Ｄ５０との値からその範囲は規定されるが、中でも０．１μｍ〜１０μｍであるのが好ましい。
かかる範囲でＤ５０を調整することにより、耐酸化性を維持しつつ焼結開始温度を５００〜９００℃の範囲でより好ましく調整することができる。
耐酸化性維持と焼結開始温度の制御の観点から、本銅粉粒子のＤ５０は、０．１μｍ〜１０μｍであるのが好ましく、特に０．３μｍ以上、或いは５μｍ以下、中でも０．５μｍ以上、或いは、３μｍ以下であるのがより一層好ましい。In the present copper powder, D50 based on the volume-based particle size distribution obtained by measurement by the laser diffraction / scattering particle size distribution measurement method is defined by the Si concentration and the value of Si concentration × D50. It is preferable that it is 1 micrometer-10 micrometers.
By adjusting D50 within such a range, the sintering start temperature can be more preferably adjusted within a range of 500 to 900 ° C. while maintaining oxidation resistance.
From the viewpoint of maintaining oxidation resistance and controlling the sintering start temperature, the D50 of the present copper powder particles is preferably 0.1 μm to 10 μm, particularly 0.3 μm or more, or 5 μm or less, especially 0.5 μm or more. Or it is still more preferable that it is 3 micrometers or less.
本銅粉の（初期）酸素濃度は、８００ｐｐｍ〜５０００ｐｐｍであるのが好ましい。酸素濃度がかかる範囲であれば、導電性ペーストの導電材料としての導電性及び耐酸化性を良好な範囲にすることができる。
本銅粉粒子は、上述のように、銅粉粒子の表面にＳｉが濃化しており、銅粉粒子全体の表面に酸化ケイ素の薄い膜ができており、粒子内部に酸素が入り難いため、初期酸素濃度が比較的高くても、表面の酸化ケイ素被膜によって耐酸化性を良好に維持することができるものと考えることができる。
かかる観点から、本銅粉の（初期）酸素濃度は８００ｐｐｍ〜５０００ｐｐｍであるのが好ましく、特に１０００ｐｐｍ以上、或いは４０００ｐｐｍ以下、中でも特に１２００ｐｐｍ以上、或いは３０００ｐｐｍ以下であるのがさらに好ましい。The (initial) oxygen concentration of the copper powder is preferably 800 ppm to 5000 ppm. When the oxygen concentration is within such a range, the conductivity and oxidation resistance as the conductive material of the conductive paste can be made good.
As described above, the copper powder particles are concentrated on the surface of the copper powder particles, a thin film of silicon oxide is formed on the entire surface of the copper powder particles, and it is difficult for oxygen to enter the particles. Even if the initial oxygen concentration is relatively high, it can be considered that the oxidation resistance can be satisfactorily maintained by the silicon oxide film on the surface.
From this viewpoint, the (initial) oxygen concentration of the present copper powder is preferably 800 ppm to 5000 ppm, more preferably 1000 ppm or more, or 4000 ppm or less, and particularly preferably 1200 ppm or more, or 3000 ppm or less.
本銅粉の焼結開始温度は５００〜９００℃であるのが好ましい。焼結開始温度をかかる温度範囲内で調整できれば、基板、用途、ペーストの配合組成などに応じて焼結温度特性をコントロールすることができ、極めて便利である。 The sintering start temperature of the copper powder is preferably 500 to 900 ° C. If the sintering start temperature can be adjusted within such a temperature range, the sintering temperature characteristics can be controlled according to the substrate, application, paste composition, etc., which is very convenient.
なお、本銅粉は、Ｓｉ（ケイ素）及びＰ（リン）以外に、例えばＮｉ、Ｔｉ、Ｆｅ、Ｃｏ、Ｃｒ、Ｍｇ、Ｍｎ、Ｍｏ、Ｗ、Ｔａ、Ｉｎ、Ｚｒ、Ｎｂ、Ｂ、Ｇｅ、Ｓｎ、Ｚｎ、Ｂｉ等のうちの少なくとも一種以上の元素成分を含有してもよい。
これらを添加することにより、例えば融点を低下させて焼結性を向上させるなど、導電性ペーストに求められる諸特性を調整することができる。In addition to Si (silicon) and P (phosphorus), the present copper powder is, for example, Ni, Ti, Fe, Co, Cr, Mg, Mn, Mo, W, Ta, In, Zr, Nb, B, Ge, You may contain at least 1 type or more of element components among Sn, Zn, Bi, etc.
By adding these, it is possible to adjust various characteristics required for the conductive paste, for example, to improve the sinterability by lowering the melting point.
＜製法＞
次に、本銅粉の好ましい具体的な製造方法について説明する。<Production method>
Next, the preferable specific manufacturing method of this copper powder is demonstrated.
本銅粉は、溶融した銅に、Ｓｉ成分、さらにその他の添加元素成分を、母合金又は化合物等の形態で所定量添加した後、所定のアトマイズ法により粉体化することにより製造することができる。
この種の銅粉は、銅塩を含む溶液などから還元剤により析出させる湿式還元法や、銅塩を加熱気化させて気相中で還元させる気相還元法や、溶融した銅地金を不活性ガスや水等の冷媒で急冷して粉末化するアトマイズ法などにより、製造することが可能である。これらの中でアトマイズ法は、一般的に広く利用されている湿式還元法に比べて、得られる銅粉中の不純物の残留濃度を小さくすることができると共に、得られる銅粉の粒子の表面から内部に至る細孔を少なくすることができるという利点を有している。このため、アトマイズ法により製造された銅粉は、導電性ペーストの導電材料に使用した場合、ペースト硬化時のガス発生量を少なくできると共に、酸化の進行を大幅に抑制できるという利点を有している。This copper powder can be produced by adding a predetermined amount of Si component and other additive element components in the form of a mother alloy or a compound to molten copper and then pulverizing it by a predetermined atomization method. it can.
This type of copper powder can be applied to a wet reduction method in which a copper salt-containing solution or the like is deposited with a reducing agent, a vapor phase reduction method in which the copper salt is heated and vaporized and reduced in the gas phase, or a molten copper ingot. It can be produced by an atomizing method in which it is rapidly cooled with a refrigerant such as active gas or water to form a powder. Among these, the atomization method can reduce the residual concentration of impurities in the obtained copper powder as compared with the wet reduction method that is generally widely used, and also from the surface of the obtained copper powder particles. This has the advantage that the number of pores reaching the inside can be reduced. For this reason, the copper powder produced by the atomization method has the advantage that, when used as a conductive material of a conductive paste, the amount of gas generated during paste curing can be reduced and the progress of oxidation can be greatly suppressed. Yes.
アトマイズ法としては、水アトマイズ法を好ましく採用することができる。水アトマイズすることにより、粒子表面にＳｉをより効果的に濃化することができるばかりか、粒子の微細化を図ることもできる。また、水アトマイズする際に、水中の溶存酸素が粒子内に取り込まれるため、酸素濃度が高まる傾向が認められる。 As the atomizing method, a water atomizing method can be preferably employed. By water atomization, not only can the Si be more effectively concentrated on the particle surface, but also the particles can be made finer. In addition, when water atomization is performed, dissolved oxygen in water is taken into the particles, so that a tendency to increase the oxygen concentration is recognized.
水アトマイズ法の中でも、高圧アトマイズ法によれば、粒子を微細かつ均一に製造することができるので好ましい。
高圧アトマイズ法とは、水アトマイズ法においては、５０ＭＰａ〜１５０ＭＰａ程度の水圧力でアトマイズする方法である。Among the water atomizing methods, the high pressure atomizing method is preferable because the particles can be produced finely and uniformly.
The high pressure atomizing method is a method of atomizing at a water pressure of about 50 MPa to 150 MPa in the water atomizing method.
アトマイズにより得られた銅粉は、還元処理してもよい。還元処理により、酸化の進行しやすい銅粉の表面の酸素濃度をさらに低減することができる。 The copper powder obtained by atomization may be reduced. By the reduction treatment, it is possible to further reduce the oxygen concentration on the surface of the copper powder that is easily oxidized.
このような還元処理としては、作業性の観点から、ガスによる還元が好ましい。この還元処理用ガスは、特に限定されることはないが、例えば、水素ガス、アンモニアガス、ブタンガス等を挙げることができる。
上記還元処理は、１５０〜３００℃の温度で行うのが好ましく、特に１７０〜２１０℃の温度で行うとより好ましい。なぜなら、上記温度が１５０℃未満であると、還元速度が遅くなってしまい、処理効果を充分に発現することができず、上記温度が３００℃を超えると、銅粉の凝集や焼結を引き起こしてしまうおそれがあり、上記温度が１７０℃〜２１０℃であると、酸素濃度の効率のよい低減化を図りながらも、銅粉の凝集や焼結を確実に抑制することができるからである。As such a reduction treatment, reduction with a gas is preferable from the viewpoint of workability. The reducing gas is not particularly limited, and examples thereof include hydrogen gas, ammonia gas, and butane gas.
The reduction treatment is preferably performed at a temperature of 150 to 300 ° C, and more preferably performed at a temperature of 170 to 210 ° C. This is because if the temperature is less than 150 ° C., the reduction rate becomes slow, and the treatment effect cannot be sufficiently exhibited, and if the temperature exceeds 300 ° C., it causes aggregation and sintering of copper powder. This is because when the temperature is 170 ° C. to 210 ° C., aggregation and sintering of copper powder can be reliably suppressed while efficiently reducing the oxygen concentration.
粉体化した後の銅粉は、分級するのが好ましい。
この分級は、適切な分級装置を用いて、目的とする粒度が中心となるように、粗粉や微粉を分離することにより容易に実施することができる。The powdered copper powder is preferably classified.
This classification can be easily carried out by separating coarse powder and fine powder using an appropriate classifier so that the target particle size is at the center.
（形状加工）
本銅粉は、そのまま利用することも可能であるが、本銅粉を形状加工処理した上で、利用することもできる。
例えば、球状粒子粉末（：８０％以上が球状粒子からなる粉末）を、機械的に形状加工して、フレーク状、鱗片状、平板状などの非球状粒子粉末（：８０％以上が非球状粒子からなる粉末）に加工することができる。
より具体的には、ビーズミル、ボールミル、アトライター、振動ミルなどを用いて機械的に偏平化加工（圧伸延または展伸）することにより、フレーク状粒子粉末（：８０％以上がフレーク状粒子からなる粉末）に形状加工することができる。この際、粒子同士の凝集や結合を防止しながら各粒子を独立した状態で加工するために、例えばステアリン酸などの脂肪酸や、界面活性剤などの助剤を添加するのが好ましい。
そして、このような形状加工処理した銅粉を利用することもできるし、また、形状加工しない元粉とこれとを混合して利用することもできる。(Shape processing)
Although this copper powder can be used as it is, it can also be used after the copper powder is subjected to shape processing.
For example, a spherical particle powder (powder consisting of 80% or more of spherical particles) is mechanically processed into non-spherical particle powders such as flakes, scales, and flat plates (: 80% or more of non-spherical particles) Powder).
More specifically, flaky particle powder (: 80% or more from flaky particles) is mechanically flattened (rolled or stretched) using a bead mill, ball mill, attritor, vibration mill or the like. Shape powder). At this time, in order to process each particle independently while preventing aggregation and bonding of the particles, it is preferable to add a fatty acid such as stearic acid or an auxiliary agent such as a surfactant.
And the copper powder which carried out such shape processing can also be utilized, and the original powder which is not shape-processed and this can also be mixed and utilized.
＜用途＞
本銅粉は、例えば樹脂硬化型導電性ペースト及び焼成型導電性ペーストのいずれに用いる導電フィラーとしても好適である。
よって、例えばエポキシ樹脂等の熱硬化性樹脂からなる有機バインダーに本銅粉を配合して樹脂硬化型導電性ペーストを調製することもできるし、また、有機ビヒクル中に本銅粉を配合して焼成型導電性ペーストを調製することもできる。<Application>
The copper powder is suitable as a conductive filler used for, for example, any of a resin curable conductive paste and a fired conductive paste.
Therefore, for example, the present copper powder can be blended with an organic binder made of a thermosetting resin such as an epoxy resin to prepare a resin curable conductive paste, or the present copper powder can be blended into an organic vehicle. A fired conductive paste can also be prepared.
本銅粉を導電フィラーとして用いた導電性ペースト用銅粉は、例えばスクリーン印刷アディティブ法による導体回路形成用や、積層セラミックコンデンサの外部電極用等の各種電気的接点部材用の導電性ペーストとして好適に使用することができる。 Copper powder for conductive paste using this copper powder as a conductive filler is suitable as a conductive paste for various electrical contact members such as for forming conductive circuits by screen printing additive method and for external electrodes of multilayer ceramic capacitors. Can be used for
その他、本発明の導電性ペースト用銅粉は、積層セラミックコンデンサの内部電極、インダクタやレジスター等のチップ部品、単板コンデンサ電極、タンタルコンデンサ電極、樹脂多層基板、セラミック（ＬＴＣＣ）多層基板、フレキブルプリント基板（ＦＰＣ）、アンテナスイッチモジュール、ＰＡモジュールや高周波アクティブフィルター等のモジュール、ＰＤＰ前面板及び背面板やＰＤＰカラーフィルター用電磁遮蔽フィルム、結晶型太陽電池表面電極及び背面引き出し電極、導電性接着剤、ＥＭＩシールド、ＲＦ−ＩＤ、及びＰＣキーボード等のメンブレンスイッチ、異方性導電膜（ＡＣＦ／ＡＣＰ）等にも使用可能である。 In addition, the copper powder for conductive paste of the present invention is used for internal electrodes of multilayer ceramic capacitors, chip parts such as inductors and resistors, single plate capacitor electrodes, tantalum capacitor electrodes, resin multilayer substrates, ceramic (LTCC) multilayer substrates, flexible Printed circuit boards (FPC), antenna switch modules, modules such as PA modules and high-frequency active filters, PDP front and back plates, electromagnetic shielding films for PDP color filters, crystalline solar cell surface electrodes and rear lead electrodes, conductive adhesives It can also be used for EMI shield, RF-ID, membrane switch such as PC keyboard, anisotropic conductive film (ACF / ACP) and the like.
＜語句の説明＞
本明細書において「Ｘ〜Ｙ」（Ｘ，Ｙは任意の数字）と表現する場合、特にことわらない限り「Ｘ以上Ｙ以下」の意と共に、「好ましくはＸより大きい」或いは「好ましくはＹより小さい」の意も包含する。
また、「Ｘ以上」（Ｘは任意の数字）或いは「Ｙ以下」（Ｙは任意の数字）と表現した場合、「Ｘより大きいことが好ましい」或いは「Ｙ未満であることが好ましい」旨の意図も包含する。<Explanation of words>
In the present specification, when expressed as “X to Y” (X and Y are arbitrary numbers), unless otherwise specified, “X is preferably greater than X” or “preferably Y”. It also includes the meaning of “smaller”.
In addition, when expressed as “X or more” (X is an arbitrary number) or “Y or less” (Y is an arbitrary number), it is “preferably greater than X” or “preferably less than Y”. Includes intentions.
以下、本発明を下記実施例及び比較例に基づいてさらに詳述する。
実施例および比較例で得られた銅粉に関して、以下に示す方法で諸特性を評価した。Hereinafter, the present invention will be further described in detail based on the following examples and comparative examples.
With respect to the copper powder obtained in the examples and comparative examples, various properties were evaluated by the following methods.
（１）元素含有量
試料を酸で溶解し、ＩＣＰにて分析した。(1) Element content Samples were dissolved with acid and analyzed by ICP.
（２）酸素濃度
酸素・窒素分析装置（堀場製作所株式会社製「ＥＭＧＡ−５２０（型番）」）を用いて銅粉(サンプル)の酸素濃度（初期酸素濃度ともいう）を分析した。(2) Oxygen concentration The oxygen concentration (also referred to as initial oxygen concentration) of the copper powder (sample) was analyzed using an oxygen / nitrogen analyzer ("EMGA-520 (model number)" manufactured by Horiba, Ltd.).
（３）粒度分布
銅粉(サンプル)０．２ｇを純水１００ｍｌ中に入れて超音波を照射して（３分間）分散させた後、粒度分布測定装置（日機装株式会社製「マイクロトラック（商品名）ＦＲＡ（型番）」）により、体積累積粒径Ｄ５０を測定した。(3) Particle size distribution After putting 0.2g of copper powder (sample) in 100ml of pure water and irradiating with ultrasonic waves (3 minutes), the particle size distribution measuring device ("MICROTRACK" manufactured by Nikkiso Co., Ltd.) Name) FRA (model number) ”), volume cumulative particle size D50 was measured.
（４）ＢＥＴ比表面積（ＳＳＡ）
ユアサアイオニクス（株）製のモノソーブ（商品名）を用いて、ＪＩＳ Ｒ １６２６-1996（ファインセラミックス粉体の気体吸着ＢＥＴ法による比表面積の測定方法）の「６．２流動法の（３．５）一点法」に準拠して、ＢＥＴ比表面積（ＳＳＡ）の測定を行った。その際、キャリアガスであるヘリウムと、吸着質ガスである窒素の混合ガスを使用した。(4) BET specific surface area (SSA)
Using monosorb (trade name) manufactured by Yuasa Ionics Co., Ltd., JIS R 1626-1996 (Method of measuring specific surface area of fine ceramic powder by gas adsorption BET method), “6.2 flow method (3. The BET specific surface area (SSA) was measured according to “5) One-point method”. At that time, a mixed gas of helium as a carrier gas and nitrogen as an adsorbate gas was used.
（５）焼結開始温度及び焼結性の評価
セイコーインスツルメンツ社製の熱機械分析装置（ＴＭＡ装置）であるＴＭＡ／ＳＳ６０００を用いて焼結開始温度を調べた。
焼結性に関しては、Ｐ（リン）を含有した銅よりも適当に焼結が遅れる、すなわちＰ（リン）を含有した銅の焼結開始温度（４９０℃前後）よりも焼結開始温度が適当に高い方が本発明の銅粉においては好ましい。そのため、本実施例での「焼結性の評価」は、５００〜９００℃の範囲内のものを「○」、中でも低温領域の５００〜５５０℃の範囲のものを「◎」、５００〜９００℃の範囲外のものを「×」と評価した。(5) Evaluation of sintering start temperature and sinterability The sintering start temperature was examined using TMA / SS6000 which is a thermomechanical analyzer (TMA apparatus) manufactured by Seiko Instruments Inc.
With regard to sinterability, sintering is delayed more appropriately than copper containing P (phosphorus), that is, the sintering start temperature is more appropriate than the sintering start temperature (around 490 ° C.) of copper containing P (phosphorus). Higher is preferable in the copper powder of the present invention. Therefore, “sinterability evaluation” in this example is “◯” when the temperature is in the range of 500 to 900 ° C., especially “◎” when the temperature is in the low temperature range of 500 to 550 ° C. The thing outside the range of ° C. was evaluated as “x”.
＜サンプルの調製：実施例・比較例＞
電気銅（銅純度：Ｃｕ９９．９５％）を溶解した溶湯（１３５０℃）に、純金属としてのＳｉ、さらには銅−りんの母合金（Ｐ１５ｗｔ％）を添加して充分に攪拌混合して１００ｋｇの溶湯を作製した。
次いで、水アトマイズ装置におけるタンディッシュ中に上記溶湯１００ｋｇを注入し（保持温度１３００℃）、タンディッシュ底部のノズル（口径５ｍｍ）から溶湯を落下させながら（流量５ｋｇ／ｍｉｎ）、フルコーン型のノズル（口径２６ｍｍ）の噴射孔から水を逆円錐状の水流形状のなるように上記溶湯にジェット噴射（水圧１００ＭＰａ、水量３５０Ｌ／ｍｉｎ）して水アトマイズすることにより銅粉を製造した。
次に、得られた銅粉を、分級装置（日清エンジニアリング株式会社製「ターボクラシファイアー（商品名）ＴＣ−２５（型番）」により、分級して銅粉（サンプル）を得た。<Sample preparation: Examples and Comparative Examples>
100 kg of molten copper (copper purity: Cu 99.95%) dissolved in molten copper (1350 ° C.) with Si as a pure metal and further a copper-phosphorus mother alloy (P15 wt%) mixed thoroughly and mixed. A molten metal was prepared.
Next, 100 kg of the molten metal was poured into the tundish in the water atomizing device (holding temperature 1300 ° C.), and the molten metal was dropped from the nozzle (caliber 5 mm) at the bottom of the tundish (flow rate 5 kg / min). Copper powder was manufactured by jetting water (water pressure: 100 MPa, water amount: 350 L / min) into the molten metal so as to form an inverted conical water flow shape from an injection hole having a diameter of 26 mm).
Next, the obtained copper powder was classified by a classifier (“Turbo Classifier (trade name) TC-25 (model number)” manufactured by Nissin Engineering Co., Ltd.) to obtain a copper powder (sample).
なお、実施例６−７については、水アトマイズして得られた銅粉を、分級装置（日清エンジニアリング株式会社製「ターボクラシファイアー（商品名）ＴＣ−２５（型番）」により、分級して得られた銅粉を、ビーズミルを用いて機械的に偏平化加工した。 In addition, about Example 6-7, the copper powder obtained by carrying out water atomization was classified with the classification apparatus (Nisshin Engineering Co., Ltd. "Turbo classifier (brand name) TC-25 (model number)". The obtained copper powder was mechanically flattened using a bead mill.
実施例１−５で得られた銅粉を電子顕微鏡などで観察し分析した結果、ほとんどが球状粒子であり、銅粉粒子表面から深さ１０ｎｍにおけるＳｉ濃度に比べて、表面から深さ２ｎｍにおけるＳｉ濃度が高く、Ｓｉが表面層に濃化していることが分かった。
また、実施例６−７で得られた銅粉を電子顕微鏡などで観察し分析した結果、ほとんどがフレーク状粒子であり、銅粉粒子表面から深さ１０ｎｍにおけるＳｉ濃度に比べて、表面から深さ２ｎｍにおけるＳｉ濃度が高く、Ｓｉが表面層に濃化していることが分かった。As a result of observing and analyzing the copper powder obtained in Example 1-5 with an electron microscope or the like, most were spherical particles, and compared with the Si concentration at a depth of 10 nm from the surface of the copper powder particles, at a depth of 2 nm from the surface. It was found that the Si concentration was high and Si was concentrated in the surface layer.
Moreover, as a result of observing and analyzing the copper powder obtained in Example 6-7 with an electron microscope or the like, most were flaky particles, and the depth from the surface was higher than the Si concentration at a depth of 10 nm from the surface of the copper powder particles. It was found that the Si concentration at 2 nm was high, and Si was concentrated in the surface layer.
実施例・比較例を比較検討すると、Ｐ（リン）を含有する銅粉にＳｉ（ケイ素）を添加すると、Ｓｉ（ケイ素）濃度が０．０１ａｔｍ％以上１．２ａｔｍ％未満の範囲であれば、Ｓｉ濃度を高めることにより焼結開始温度を高くすることができる傾向が認められた。但し、焼結性の観点からは、実施例１及び２が特に優れているため、かかる観点ではＳｉ（ケイ素）濃度が０．１０ａｔｍ％未満であるのが好ましいと考えることができる。
また、他の試験により、粒径が小さければ、焼結開始温度が低下する傾向があることが確認されている。しかし、Ｓｉ（ケイ素）濃度と粒径の何れかを規定するだけでは、焼結開始温度を制御できないことが確認された。その一方、Ｓｉ濃度とＤ５０の積（Ｓｉ濃度×Ｄ５０）を基準値として検討したところ、焼結開始温度を５００〜９００℃の範囲で制御できることが判明した。かかる観点から、本銅粉のＳｉ濃度×Ｄ５０は、３．５０以下であることが重要であり、好ましくは０．００１〜３．４０、特に０．００５〜３．００、中でも特に０．０１〜２．８０であるのがさらによいと考えることができる。Comparing the examples and comparative examples, when Si (silicon) is added to copper powder containing P (phosphorus), the Si (silicon) concentration is in the range of 0.01 atm% or more and less than 1.2 atm%, There was a tendency to increase the sintering start temperature by increasing the Si concentration. However, from the viewpoint of sinterability, since Examples 1 and 2 are particularly excellent, it can be considered that the Si (silicon) concentration is preferably less than 0.10 atm% from this viewpoint.
Further, it has been confirmed by other tests that if the particle size is small, the sintering start temperature tends to decrease. However, it has been confirmed that the sintering start temperature cannot be controlled only by defining either the Si (silicon) concentration or the particle size. On the other hand, when the product of Si concentration and D50 (Si concentration × D50) was examined as a reference value, it was found that the sintering start temperature could be controlled in the range of 500 to 900 ° C. From this viewpoint, it is important that the Si concentration x D50 of the present copper powder is 3.50 or less, preferably 0.001 to 3.40, particularly 0.005 to 3.00, and particularly 0.01 It can be considered that ˜2.80 is even better.
本実施例の銅粉のように、焼結温度特性をコントロールすることができる理由に関しては、試験的に確認できている訳ではないが、銅粉粒子表面に存在する微量のＳｉ（ケイ素）が焼成時に優先的に酸化物になる結果、酸化物成分すなわちセラミック成分を偏析させることができ、この偏析の程度によって焼結温度特性を変えることができるものと考えることができる。しかもこの際、酸化物成分は焼結後に粒界に偏析するため、導電性を妨げることがない点でも優れている。 As for the reason why the sintering temperature characteristic can be controlled like the copper powder of this example, although it is not necessarily confirmed experimentally, a small amount of Si (silicon) present on the surface of the copper powder particles is present. As a result of preferentially becoming an oxide during firing, the oxide component, that is, the ceramic component can be segregated, and it can be considered that the sintering temperature characteristics can be changed depending on the degree of segregation. Moreover, since the oxide component segregates at the grain boundary after sintering, it is excellent in that it does not hinder the conductivity.
実施例では、Ｄ５０を固定し、Ｓｉ濃度を変化させることにより、Ｓｉ濃度×Ｄ５０の値を変化させているが、Ｄ５０を０．１μｍ〜１０μｍ程度の範囲で変化させてＳｉ濃度×Ｄ５０の値を変化させても同様の効果を得ることができる。
また、このような効果は、Ｐ（りん）濃度には影響されないことが確かめられている。Ｐ（りん）濃度は、微粒子化や耐酸化性に影響するため、Ｐ（りん）の含有量は０．０１〜０．３ａｔｍ％の割合で含有するのが好ましいと考えることができる。
In the embodiment, the value of Si concentration × D50 is changed by fixing D50 and changing the Si concentration. However, the value of Si concentration × D50 is changed by changing D50 in the range of about 0.1 μm to 10 μm. The same effect can be obtained even if the value is changed.
Further, it has been confirmed that such an effect is not influenced by the P (phosphorus) concentration. Since the P (phosphorus) concentration affects the micronization and oxidation resistance, it can be considered that the P (phosphorus) content is preferably 0.01 to 0.3 atm%.
Claims (6)
Ｐ（りん）の含有量が０．０１〜０．３ａｔｍ％であり、且つ、
Ｓｉ濃度が０．０１ａｔｍ％以上１．２ａｔｍ％未満であり、且つ、当該Ｓｉ濃度（ａｔｍ％）と、レーザー回折散乱式粒度分布測定法により測定して得られる体積基準粒度分布によるＤ５０（μｍ）との積によって算出されるＳｉ換算量（Ｓｉ濃度×Ｄ５０）が３．５０以下であり、
銅粉粒子表面から深さ１０ｎｍにおけるＳｉ濃度に比べて、表面から深さ２ｎｍにおけるＳｉ濃度が高く、Ｓｉが表面層に濃化してなる銅粉粒子を主材としてなることを特徴とする導電性ペースト用銅粉。 A copper powder for conductive paste made of Cu (copper), Si (silicon) and P (phosphorus),
The content of P (phosphorus) is 0.01 to 0.3 atm%, and
Si concentration is 0.01 atm% or more and less than 1.2 atm%, and D50 (μm) based on the Si concentration (atm%) and a volume-based particle size distribution obtained by measurement by a laser diffraction scattering particle size distribution measurement method. Si equivalent amount calculated by the product of (Si concentration × D50) is 3.50 or less,
Compared to the Si concentration at a depth of 10 nm from the surface of the copper powder particles, the Si concentration at a depth of 2 nm from the surface is high, and the copper powder particles formed by concentration of Si in the surface layer are used as a main material. Copper powder for paste.
水アトマイズ法により製造することを特徴とする導電性ペースト用銅粉の製造方法。 It is a manufacturing method of the copper powder for conductive pastes in any one of Claims 1-3 ,
The manufacturing method of the copper powder for electrically conductive paste characterized by manufacturing by the water atomization method.
形状加工処理を行うことを特徴とする導電性ペースト用銅粉の製造方法。 It is a manufacturing method of the copper powder for conductive pastes in any one of Claims 1-3 ,
The manufacturing method of the copper powder for electrically conductive paste characterized by performing a shape processing process.
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| JP (1) | JP5932638B2 (en) |
| KR (1) | KR20130079315A (en) |
| TW (1) | TWI432588B (en) |
| WO (1) | WO2011145378A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5598739B2 (en) * | 2012-05-18 | 2014-10-01 | 株式会社マテリアル・コンセプト | Conductive paste |
| CN107921532B (en) * | 2015-09-03 | 2020-05-08 | 同和电子科技有限公司 | Phosphorus-containing copper powder and method for producing same |
| JP6854114B2 (en) * | 2016-01-04 | 2021-04-07 | Ｊｘ金属株式会社 | Surface-treated copper foil |
| CN105834418B (en) * | 2016-03-17 | 2018-01-05 | 西安工程大学 | The ethyl cellulose microcapsule processing method of copper powder in a kind of electric slurry |
| WO2019039058A1 (en) * | 2017-08-21 | 2019-02-28 | Ｊｘ金属株式会社 | Copper alloy powder for lamination shaping, lamination shaped product production method, and lamination shaped product |
| CN110578070B (en) * | 2019-10-30 | 2021-04-13 | 吉林大学 | Method for improving oxidation resistance of copper by using authigenic non-metallic oxide composite film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000328232A (en) * | 1999-05-18 | 2000-11-28 | Nisshin Steel Co Ltd | Electrically conductive powder, its production and coating material using it |
| WO2010004852A1 (en) * | 2008-07-11 | 2010-01-14 | 三井金属鉱業株式会社 | Copper powder for conductive paste, and conductive paste |
| JP2010013726A (en) * | 2007-12-28 | 2010-01-21 | Mitsui Mining & Smelting Co Ltd | Copper powder for electroconductive paste, and electroconductive paste |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3690552B2 (en) * | 1997-05-02 | 2005-08-31 | 株式会社アルバック | Metal paste firing method |
| JP2004263205A (en) * | 2003-01-31 | 2004-09-24 | Toho Titanium Co Ltd | Metallic impalpable powder, manufacturing method therefor, and conductive paste using the metallic impalpable powder |
| JP2009079269A (en) * | 2007-09-26 | 2009-04-16 | Dowa Electronics Materials Co Ltd | Copper powder for electroconductive paste, production method therefor and electroconductive paste |
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2011
- 2011-03-01 JP JP2012515777A patent/JP5932638B2/en active Active
- 2011-03-01 WO PCT/JP2011/054598 patent/WO2011145378A1/en active Application Filing
- 2011-03-01 KR KR1020127021007A patent/KR20130079315A/en not_active Application Discontinuation
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000328232A (en) * | 1999-05-18 | 2000-11-28 | Nisshin Steel Co Ltd | Electrically conductive powder, its production and coating material using it |
| JP2010013726A (en) * | 2007-12-28 | 2010-01-21 | Mitsui Mining & Smelting Co Ltd | Copper powder for electroconductive paste, and electroconductive paste |
| WO2010004852A1 (en) * | 2008-07-11 | 2010-01-14 | 三井金属鉱業株式会社 | Copper powder for conductive paste, and conductive paste |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2011145378A1 (en) | 2011-11-24 |
| JPWO2011145378A1 (en) | 2013-07-22 |
| TWI432588B (en) | 2014-04-01 |
| KR20130079315A (en) | 2013-07-10 |
| TW201211283A (en) | 2012-03-16 |
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