JPWO2006126614A1 - Pasty silver composition, its production method, solid silver production method, solid silver, adhesion method and circuit board production method - Google Patents
Pasty silver composition, its production method, solid silver production method, solid silver, adhesion method and circuit board production method Download PDFInfo
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- JPWO2006126614A1 JPWO2006126614A1 JP2007517877A JP2007517877A JPWO2006126614A1 JP WO2006126614 A1 JPWO2006126614 A1 JP WO2006126614A1 JP 2007517877 A JP2007517877 A JP 2007517877A JP 2007517877 A JP2007517877 A JP 2007517877A JP WO2006126614 A1 JPWO2006126614 A1 JP WO2006126614A1
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 419
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 399
- 239000004332 silver Substances 0.000 title claims abstract description 399
- 239000000203 mixture Substances 0.000 title claims abstract description 133
- 239000007787 solid Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 49
- 235000011837 pasties Nutrition 0.000 title claims description 62
- 239000002245 particle Substances 0.000 claims abstract description 186
- 239000002612 dispersion medium Substances 0.000 claims abstract description 84
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 62
- 238000010438 heat treatment Methods 0.000 claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 56
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 53
- 239000000758 substrate Substances 0.000 claims description 47
- 238000005245 sintering Methods 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 18
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- 239000012459 cleaning agent Substances 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- 235000019441 ethanol Nutrition 0.000 description 36
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 34
- 239000003822 epoxy resin Substances 0.000 description 28
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- 239000000047 product Substances 0.000 description 20
- 239000003990 capacitor Substances 0.000 description 19
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 18
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 14
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 14
- 238000009835 boiling Methods 0.000 description 14
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 14
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 13
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
- 238000007747 plating Methods 0.000 description 10
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 9
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 9
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- 239000008103 glucose Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 8
- 239000003638 chemical reducing agent Substances 0.000 description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 8
- 229910052737 gold Inorganic materials 0.000 description 8
- 239000010931 gold Substances 0.000 description 8
- 239000011164 primary particle Substances 0.000 description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 8
- 238000007665 sagging Methods 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 7
- 108010010803 Gelatin Proteins 0.000 description 7
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229920000159 gelatin Polymers 0.000 description 7
- 239000008273 gelatin Substances 0.000 description 7
- 235000019322 gelatine Nutrition 0.000 description 7
- 235000011852 gelatine desserts Nutrition 0.000 description 7
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 7
- 235000019252 potassium sulphite Nutrition 0.000 description 7
- 238000007670 refining Methods 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
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- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 230000002411 adverse Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
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- 238000002411 thermogravimetry Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
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- 150000001298 alcohols Chemical class 0.000 description 3
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- 229920002545 silicone oil Polymers 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000004962 Polyamide-imide Substances 0.000 description 2
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- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003985 ceramic capacitor Substances 0.000 description 2
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- 239000000843 powder Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
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- 239000005968 1-Decanol Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- 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
-
- 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
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
- H05K1/097—Inks comprising nanoparticles and specially adapted for being sintered at low temperature
-
- 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
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Nanotechnology (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Conductive Materials (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
[要約][課題]加熱すると銀粒子が容易に焼結して強度と電気伝導性と熱伝導性が優れた固形状銀となるペースト状銀組成物、その製造方法等を提供する。[解決手段]平均粒径が0.1〜6μmであり、炭素含有量が0.50重量%以下、好ましくは0.25重量%以下である球状銀粒子と揮発性分散媒とからなるペースト状物であり、加熱により該揮発性分散媒が揮散し該球状銀粒子同士が焼結して固形状銀になるペースト状銀組成物。その製造方法、該ペースト状銀組成物を加熱する固形状銀の製造方法、強度と電気伝導性と熱伝導性が優れた固形状銀、ペースト状銀組成物を使用する接着方法および回路板の製造方法。[Summary] [Problem] To provide a paste-like silver composition which is easily sintered when heated to form solid silver having excellent strength, electrical conductivity and thermal conductivity, and a method for producing the same. [Solution] A paste comprising spherical silver particles having an average particle diameter of 0.1 to 6 μm and a carbon content of 0.50% by weight or less, preferably 0.25% by weight or less and a volatile dispersion medium. A paste-like silver composition, which is a product, and the volatile dispersion medium is volatilized by heating and the spherical silver particles are sintered to form solid silver. Method for producing the same, method for producing solid silver for heating the paste-like silver composition, solid silver having excellent strength, electrical conductivity, and thermal conductivity, an adhesion method using the paste-like silver composition, and a circuit board Production method.
Description
本発明は、実質的に球状の銀粒子と揮発性分散媒からなり、加熱により焼結して優れた強度と電気伝導性と熱伝導性を有する固形状銀となるペースト状銀組成物、その製造方法、当該ペースト状銀組成物からの固形状銀の製造方法、優れた強度と電気伝導性と熱伝導性を有する固形状銀、当該ペースト状銀組成物を使用しての接着方法および回路板の製造方法に関する。 The present invention comprises a paste-like silver composition comprising substantially spherical silver particles and a volatile dispersion medium, which is sintered by heating to form solid silver having excellent strength, electrical conductivity and thermal conductivity, Production method, production method of solid silver from the paste-like silver composition, solid silver having excellent strength, electrical conductivity and thermal conductivity, adhesion method and circuit using the paste-like silver composition It is related with the manufacturing method of a board.
銀粉末を熱硬化性樹脂組成物中に分散させてなる導電性ペーストは、加熱により硬化して導電性被膜が形成されるので、プリント回路基板上の導電性回路の形成、抵抗器やコンデンサ等の各種電子部品及び各種表示素子の電極の形成、電磁波シールド用導電性被膜の形成、コンデンサ、抵抗、ダイオード、メモリ、演算素子(CPU)等のチップ部品の基板への接着、太陽電池の電極、特にアモルファスシリコン半導体を用いた高温処理のできない太陽電池の電極の形成、積層セラミックコンデンサ、積層セラミックインダクタ、積層セラミックアクチュエータ等のチップ型セラミック電子部品の外部電極の形成等に使用されている。
近年チップ部品の高性能化によりチップ部品からの発熱量が増え、電気伝導性はもとより、熱伝導性の向上が要求されるので、銀粒子の含有率を可能な限り増加して電気伝導性、熱伝導性を向上しようとすると、ペーストの粘度が上昇し、作業性が著しく低下するという問題がある。Conductive paste made by dispersing silver powder in thermosetting resin composition is cured by heating to form a conductive film, so that conductive circuit formation on printed circuit boards, resistors, capacitors, etc. Electrode formation of various electronic parts and display elements, formation of a conductive film for electromagnetic wave shielding, adhesion of chip parts such as capacitors, resistors, diodes, memories and arithmetic elements (CPUs) to substrates, solar cell electrodes, In particular, it is used for forming electrodes of solar cells that cannot be processed at high temperature using amorphous silicon semiconductors, forming external electrodes of chip-type ceramic electronic components such as multilayer ceramic capacitors, multilayer ceramic inductors, multilayer ceramic actuators, and the like.
In recent years, the amount of heat generated from chip parts has increased due to the high performance of chip parts, and it is required to improve the thermal conductivity as well as the electrical conductivity. When trying to improve the thermal conductivity, there is a problem that the viscosity of the paste increases and the workability is remarkably lowered.
一方、チップ部品、プラズマディスプレイパネル等の電極や回路を、大幅のファイン化、高密度、高精度、高信頼性で形成することのできる導電ペーストの製造に最適な高分散性球状銀粉末およびそれを使用した銀ペーストが特許文献1に教示されている。また、回路板への導電性ペーストの塗布方法としてスクリーン印刷法に加えてインクジェット法が使用されだしており、そのために走査型電子顕微鏡像の画像解析により得られる一次粒子の平均粒径DIAが0.6μm以下である銀粉とポリオール類、必要に応じてさらに粘度調整剤等からなる銀インクが提案されている(特許文献2参照)。On the other hand, highly dispersible spherical silver powder that is optimal for the production of conductive paste that can form electrodes and circuits for chip parts, plasma display panels, etc. with significant fineness, high density, high precision, and high reliability, and the
特許文献1では、銀粉は、硝酸銀水溶液とアンモニア水とを混合して反応させ銀アンミン錯体水溶液を得て、これとヒドロキノンと無水亜硫酸カリウムもしくはアンモニウムとゼラチンの水溶液を接触反応させて銀粉を還元析出させ、濾過し、残渣を水で洗浄し、加熱下乾燥させて調製している。特許文献1にはこのようにして調製した銀粉を使用して銀ペーストを調製したと記載されているが、その処方は不明である。そこで本発明者らは当該銀粉に少量の水を混ぜてペースト状とし加熱したところ、当該銀粉が十分に焼結しないという問題があること、あるいは、焼結して固形状の銀が生成しても、強度と電気伝導性と熱伝導性が予想外に小さいという問題があることに気が付いた。特許文献2では、銀粉は、硝酸銀水溶液とアンモニア水とを混合して反応させ銀アンミン錯体水溶液を得て、これと有機還元剤(ヒドロキノン、アスコルビン酸、グルコース等)、特にはヒドロキノンの水溶液を接触反応させて銀粉を還元析出させ、濾過し、残渣を水とメタノールで洗浄し、加熱下乾燥させて調製している。ところが、本発明者らは、このようにして調製された銀粉とポリオール類(例えば、1,4−ブタンジオール、ジプロピレングリコール)からなる銀インクを加熱したところ、当該銀粉が十分に焼結しないという問題があること、あるいは、焼結して固形状の銀が生成しても、強度と電気伝導性と熱伝導性が予想外に小さいという問題があることに気が付いた。
In
本発明者らは、上記問題のない球状銀粒子ペースト、すなわち、ペースト状銀組成物を開発すべく鋭意研究した結果、球状銀粒子の炭素含有量が焼結性と焼結して生成した固形状銀の強度と電気伝導性と熱伝導性に影響していることを見出し、本発明を完成するに至った。本発明の目的は、加熱すると球状銀粒子が容易に焼結して強度と電気伝導性と熱伝導性が優れた固形状銀となるペースト状銀組成物、その製造方法、ペースト状銀組成物から強度と電気伝導性と熱伝導性が優れた固形状銀を製造する方法、強度と電気伝導性と熱伝導性が優れた固形状銀、当該ペースト状銀組成物を使用して被着体を電気伝導性と熱伝導性よく強固に接着する方法および耐摩耗性と基板への接着性と電気伝導性と熱伝導性が優れた銀回路を有する回路板を製造する方法を提供することにある。 As a result of earnest research to develop a spherical silver particle paste without the above problems, that is, a paste-like silver composition, the present inventors have determined that the carbon content of the spherical silver particles is formed by sintering and sintering. It has been found that the strength, electrical conductivity, and thermal conductivity of shape silver are affected, and the present invention has been completed. An object of the present invention is to form a paste-like silver composition in which spherical silver particles are easily sintered when heated to form solid silver having excellent strength, electrical conductivity, and thermal conductivity, a method for producing the same, and a paste-like silver composition A method for producing solid silver excellent in strength, electrical conductivity and thermal conductivity, solid silver excellent in strength, electrical conductivity and thermal conductivity, and an adherend using the paste-like silver composition To provide a method for manufacturing a circuit board having a silver circuit excellent in abrasion resistance, adhesion to a substrate, electrical conductivity, and thermal conductivity. is there.
この目的は、
[1] 平均粒径が0.1〜6μmであり、炭素含有量が0.50重量%以下である球状銀粒子と揮発性分散媒とからなるペースト状物であり、加熱により該揮発性分散媒が揮散し該球状銀粒子同士が焼結することを特徴とするペースト状銀組成物。
[2] 炭素含有量が0.25重量%以下であることを特徴とする[1]記載のペースト状銀組成物。
[3] 球状銀粒子が還元法で作られたものであることを特徴とする[1]または[2]記載のペースト状銀組成物。
[4] 揮発性分散媒が水、揮発性の親水性溶剤または脂肪族炭化水素系溶剤であることを特徴とする[1]または[2]記載のペースト状銀組成物。
[5] 揮発性親水性溶剤が、揮発性アルコールまたは揮発性アルコールと水の混合物であることを特徴とする[4]記載のペースト状銀組成物。
[6] 還元法で作られた平均粒径が0.1〜6μmである球状銀粒子を洗浄してその炭素含有量を0.50重量%以下とし、揮発性分散媒と混合することを特徴とする、加熱により該揮発性分散媒が揮散し該球状銀粒子同士が焼結するペースト状銀組成物の製造方法。
[7] 球状銀粒子の炭素含有量を0.25重量%以下とすることを特徴とする[6]記載のペースト状銀組成物の製造方法。
[8] 洗浄剤が水、揮発性の親水性溶剤または脂肪族炭化水素系溶剤であり、揮発性分散媒が水、揮発性の親水性溶剤または脂肪族炭化水素系溶剤であることを特徴とする[6]記載のペースト状銀組成物の製造方法。
[9] [1]、[2]または[3]記載のペースト状銀組成物を100℃以上で加熱することにより該揮発性分散媒が揮散し該球状銀粒子同士が焼結することを特徴とする固形状銀の製造方法。
[10] 固形状銀の体積抵抗率が1×10-4Ω・cm以下であり、かつ、熱伝導度が5W/m・K以上であることを特徴とする[9]記載の固形状銀の製造方法。
[11] [1]、[2]または[3]記載のペースト状銀組成物を100℃以上で加熱することにより該揮発性分散媒が揮散し球状銀粒子が焼結してなる体積抵抗率が1×10-4Ω・cm以下であり、かつ、熱伝導度が5W/m・K以上であることを特徴とする固形状銀。
[12] 平均粒径が0.1〜6μmであり、炭素含有量が0.50重量%以下である球状銀粒子と揮発性分散媒とからなるペースト状物であり、100℃以上での加熱により該揮発性分散媒が揮散し該球状銀粒子同士が焼結するペースト状銀組成物を複数の被着体間に介在させ、100℃以上での加熱により該揮発性分散媒が揮散し該球状銀粒子同士が焼結して複数の被着体同士を接着させることを特徴とする接着方法。
[13] 球状銀粒子の炭素含有量が0.25重量%以下であることを特徴とする[12]記載の接着方法。
[14] 被着体が電子部品であることを特徴とする[12]記載の接着方法。
[15] 平均粒径が0.1〜6μmであり、炭素含有量が0.50重量%以下である球状銀粒子と揮発性分散媒とからなるペースト状物であり、100℃以上での加熱により該揮発性分散媒が揮散し該球状銀粒子同士が焼結するペースト状銀組成物を基板上に塗布し、100℃以上での加熱により該揮発性分散媒が揮散し該球状銀粒子同士が焼結して銀回路を形成することを特徴とする回路板の製造方法。
[16] 球状銀粒子の炭素含有量が0.25重量%以下であることを特徴とする[15]記載の回路板の製造方法。;により達成される。This purpose is
[1] A paste-like product composed of spherical silver particles having an average particle diameter of 0.1 to 6 μm and a carbon content of 0.50% by weight or less and a volatile dispersion medium. A paste-like silver composition, wherein the medium is volatilized and the spherical silver particles are sintered together.
[2] The pasty silver composition according to [1], wherein the carbon content is 0.25% by weight or less.
[3] The pasty silver composition according to [1] or [2], wherein the spherical silver particles are produced by a reduction method.
[4] The pasty silver composition according to [1] or [2], wherein the volatile dispersion medium is water, a volatile hydrophilic solvent or an aliphatic hydrocarbon solvent.
[5] The pasty silver composition according to [4], wherein the volatile hydrophilic solvent is volatile alcohol or a mixture of volatile alcohol and water.
[6] Characteristically, spherical silver particles having an average particle diameter of 0.1 to 6 μm produced by a reduction method are washed to reduce their carbon content to 0.50% by weight or less and mixed with a volatile dispersion medium. The method for producing a paste-like silver composition in which the volatile dispersion medium is volatilized by heating and the spherical silver particles are sintered together.
[7] The method for producing a pasty silver composition according to [6], wherein the spherical silver particles have a carbon content of 0.25% by weight or less.
[8] The cleaning agent is water, a volatile hydrophilic solvent or an aliphatic hydrocarbon solvent, and the volatile dispersion medium is water, a volatile hydrophilic solvent or an aliphatic hydrocarbon solvent. [6] The method for producing a pasty silver composition according to [6].
[9] The paste-like silver composition according to [1], [2], or [3] is heated at 100 ° C. or higher to volatilize the volatile dispersion medium and sinter the spherical silver particles. A method for producing solid silver.
[10] The solid silver according to [9], wherein the solid silver has a volume resistivity of 1 × 10 −4 Ω · cm or less and a thermal conductivity of 5 W / m · K or more. Manufacturing method.
[11] Volume resistivity obtained by heating the pasty silver composition according to [1], [2] or [3] at 100 ° C. or more to volatilize the volatile dispersion medium and sinter spherical silver particles. Is 1 × 10 −4 Ω · cm or less, and has a thermal conductivity of 5 W / m · K or more.
[12] A paste-like material comprising spherical silver particles having an average particle diameter of 0.1 to 6 μm and a carbon content of 0.50% by weight or less and a volatile dispersion medium, and heated at 100 ° C. or higher The volatile dispersion medium is volatilized and a paste-like silver composition in which the spherical silver particles are sintered is interposed between a plurality of adherends, and the volatile dispersion medium is volatilized by heating at 100 ° C. or higher. A bonding method characterized in that spherical silver particles are sintered to bond a plurality of adherends.
[13] The bonding method according to [12], wherein the spherical silver particles have a carbon content of 0.25% by weight or less.
[14] The bonding method according to [12], wherein the adherend is an electronic component.
[15] A paste-like material composed of spherical silver particles having an average particle diameter of 0.1 to 6 μm and a carbon content of 0.50% by weight or less and a volatile dispersion medium, and heated at 100 ° C. or higher. The paste-like silver composition in which the volatile dispersion medium is volatilized and the spherical silver particles are sintered is applied onto a substrate, and the volatile dispersion medium is volatilized by heating at 100 ° C. or higher to form the spherical silver particles. A method of manufacturing a circuit board, comprising sintering a silver circuit.
[16] The method for producing a circuit board according to [15], wherein the spherical silver particles have a carbon content of 0.25% by weight or less. Achieved by;
本発明のペースト状銀組成物は、加熱により該揮発性分散媒が揮散し、特には100℃以上での加熱により該球状銀粒子同士が焼結して強度と電気伝導性と熱伝導性が優れた固形状銀となる。本発明のペースト状銀組成物の製造方法は、加熱により該揮発性分散媒が揮散し、特には100℃以上での加熱により該球状銀粒子同士が焼結して強度と電気伝導性と熱伝導性が優れた固形状銀となるペースト状銀組成物を容易に製造することができる。本発明の固形状銀の製造方法は、加熱により該揮発性分散媒が揮散し、特には100℃以上での加熱により該球状銀粒子同士が焼結して強度と電気伝導性と熱伝導性が優れた固形状銀を容易に製造することができる。本発明の固形状銀は、精錬法により製造された銀並みの強度を有している。本発明の接着方法は、ペースト状銀組成物を複数の被着体間に介在させ、100℃以上での加熱により該揮発性分散媒が揮散し該球状銀粒子同士が焼結して複数の被着体同士を電気伝導性と熱伝導性よく強固に接着させることができる。本発明の回路板の製造方法は、ペースト状銀組成物を基板上に印刷し、100℃以上での加熱により該揮発性分散媒が揮散し該球状銀粒子同士が焼結して耐摩耗性と基板への接着性と電気伝導性と熱伝導性が優れた銀回路を有する回路板を容易に製造することができる。 In the paste-like silver composition of the present invention, the volatile dispersion medium is volatilized by heating, and the spherical silver particles are particularly sintered by heating at 100 ° C. or higher, resulting in strength, electrical conductivity, and thermal conductivity. Excellent solid silver. In the method for producing a paste-like silver composition of the present invention, the volatile dispersion medium is volatilized by heating, and the spherical silver particles are particularly sintered by heating at 100 ° C. or higher, resulting in strength, electrical conductivity, and heat. A pasty silver composition that becomes solid silver having excellent conductivity can be easily produced. In the method for producing solid silver according to the present invention, the volatile dispersion medium is volatilized by heating, and particularly the spherical silver particles are sintered by heating at 100 ° C. or higher, whereby strength, electrical conductivity, and thermal conductivity. Can easily produce solid silver. The solid silver of the present invention has the same strength as silver produced by a refining method. In the bonding method of the present invention, a paste-like silver composition is interposed between a plurality of adherends, the volatile dispersion medium is volatilized by heating at 100 ° C. or higher, and the spherical silver particles are sintered to form a plurality of The adherends can be firmly bonded to each other with good electrical conductivity and thermal conductivity. The method for producing a circuit board according to the present invention comprises printing a paste-like silver composition on a substrate, volatilizing the volatile dispersion medium by heating at 100 ° C. or higher, and sintering the spherical silver particles to wear resistance. In addition, a circuit board having a silver circuit having excellent adhesion to the substrate, electrical conductivity, and thermal conductivity can be easily manufactured.
A 固着強度測定用試験体
1 ガラス繊維強化エポキシ樹脂基板
2 チップコンデンサ
3 チップコンデンサの端子電極
4 電極ランド(パッド)部
5 ペースト状銀組成物A Test specimen for fixing
本発明のペースト状銀組成物は、平均粒径が0.1〜6μmであり、炭素含有量が0.50重量%以下である球状銀粒子と揮発性分散媒とからなる。当該球状銀粒子の平均粒径は、走査型電子顕微鏡像の画像解析により得られる一次粒子の平均粒径である。球は、真球だけでなく、多少歪な球や、楕円球を含むものである。平均粒径が6μmを越えると球状銀同士の焼結性が小さくなり、優れた強度と電気伝導性、熱伝導性、接着性を得にくい。そのため平均粒子径は小さい方がより好ましく、特には3μm以下であることが好ましい。いわゆるナノサイズとなる0.1μm未満の場合、球状銀粒子の表面活性が強すぎてペースト状銀組成物の保存安定性が低下する恐れがあるため、0.1μm以上である。
当該球状銀粒子の炭素含有量は、0.50重量%以下であり、下限値は0重量%である。加熱時の球状銀粒子の焼結性と、焼結してできた固形状銀の強度と電気伝導性と熱伝導性の点で好ましくは0.25重量%以下、より好ましくは0.13重量%以下である。ここで炭素含有量は、球状銀粒子を酸素気流中で加熱して球状銀粒子に付着していた有機化合物中の炭素を炭酸ガスに変えて赤外線吸収スペクトル法により定量したものである。なお熱重量測定法(TGA)による減少量から炭素含有量を算出しても良い。The pasty silver composition of the present invention comprises spherical silver particles having an average particle diameter of 0.1 to 6 μm and a carbon content of 0.50% by weight or less and a volatile dispersion medium. The average particle diameter of the spherical silver particles is the average particle diameter of primary particles obtained by image analysis of a scanning electron microscope image. The sphere includes not only a true sphere but also a slightly distorted sphere or an elliptic sphere. When the average particle size exceeds 6 μm, the sinterability between spherical silver particles becomes small, and it is difficult to obtain excellent strength, electrical conductivity, thermal conductivity, and adhesion. Therefore, it is more preferable that the average particle size is small, and it is particularly preferable that the average particle size is 3 μm or less. When the so-called nano-size is less than 0.1 μm, the surface activity of the spherical silver particles is too strong, and the storage stability of the pasty silver composition may be lowered.
The carbon content of the spherical silver particles is 0.50% by weight or less, and the lower limit is 0% by weight. In terms of the sinterability of spherical silver particles during heating and the strength, electrical conductivity, and thermal conductivity of the solid silver obtained by sintering, it is preferably 0.25% by weight or less, more preferably 0.13% by weight. % Or less. Here, the carbon content is determined by an infrared absorption spectrum method in which spherical silver particles are heated in an oxygen stream and carbon in an organic compound adhering to the spherical silver particles is changed to carbon dioxide. Note that the carbon content may be calculated from the decrease by thermogravimetry (TGA).
当該球状銀粒子は、特には還元法で作られた球状銀粒子である。前記特許文献に記載されているように、還元法では、通常、硝酸銀水溶液とアンモニア水とを混合して反応させ銀アンミン錯体水溶液を得て、これとヒドロキノンと無水亜硫酸カリウムもしくはアンモニウムとゼラチンの水溶液を接触反応させて銀粉を還元析出させ、濾過し、残渣を水で洗浄し、加熱下乾燥させて調製している。あるいは、硝酸銀水溶液とアンモニア水とを混合して反応させ銀アンミン錯体水溶液を得て、これと有機還元剤(ヒドロキノン、アスコルビン酸、グルコース等)の水溶液を接触反応させて銀粉を還元析出させ、濾過し、洗浄し、乾燥させて調製している。濾過残渣はアンモニアとヒドロキノンと無水亜硫酸カリウムもしくはアンモニウムとゼラチンを含有しており、銀粉表面にアンモニアとヒドロキノンと無水亜硫酸カリウムもしくはアンモニウムとゼラチンが付着しているため、清浄な水で繰り返し洗浄している。あるいは、濾過残渣はアンモニアと有機還元剤(ヒドロキノン、アスコルビン酸またはグルコース)を含有しており、銀粒子表面にアンモニアと有機還元剤(ヒドロキノン、アスコルビン酸またはグルコース)が付着しているため、清浄な水とメタノールで繰り返し洗浄している。 The spherical silver particles are particularly spherical silver particles produced by a reduction method. As described in the above-mentioned patent document, in the reduction method, an aqueous silver ammine complex solution is usually obtained by mixing and reacting an aqueous silver nitrate solution and aqueous ammonia, and an aqueous solution of hydroquinone, anhydrous potassium sulfite or ammonium and gelatin. The silver powder is reduced and deposited by contact reaction, filtered, and the residue is washed with water and dried under heating. Alternatively, a silver nitrate aqueous solution and aqueous ammonia are mixed and reacted to obtain a silver ammine complex aqueous solution, which is contacted with an aqueous solution of an organic reducing agent (hydroquinone, ascorbic acid, glucose, etc.) to cause silver powder to be reduced and precipitated, and filtered. It is prepared by washing and drying. The filtration residue contains ammonia, hydroquinone, anhydrous potassium sulfite or ammonium, and gelatin. Since ammonia, hydroquinone, anhydrous potassium sulfite, ammonium, and gelatin adhere to the silver powder surface, it is repeatedly washed with clean water. . Alternatively, the filtration residue contains ammonia and an organic reducing agent (hydroquinone, ascorbic acid or glucose), and since ammonia and an organic reducing agent (hydroquinone, ascorbic acid or glucose) are attached to the surface of the silver particles, the filtration residue is clean. Washed repeatedly with water and methanol.
しかし、ヒドロキノンのような水溶性が小さく、メタノールへの溶解性が小さい有機還元剤が付着した球状銀粒子を水、あるいは、水とメタノールで繰り返し洗浄しても有機還元剤を十分には除去できるものではない。特に凝集した球状銀粒子間に存在するヒドロキノンは、水とメタノールへの溶解性が小さいので、水とメタノールで繰り返し洗浄しても容易に除去できるものではない。また、アスコルビン酸やグルコースは水溶性であるが、凝集した球状銀粒子間に存在するアスコルビン酸またはグルコースは、水、あるいは、水とメタノールで繰り返し洗浄しても容易に除去できるものではない。 However, the organic reducing agent can be sufficiently removed even if spherical silver particles with a small water solubility such as hydroquinone and poorly soluble in methanol adhere to water or repeatedly washed with water and methanol. It is not a thing. In particular, hydroquinone present between aggregated spherical silver particles has low solubility in water and methanol, and thus cannot be easily removed even by repeated washing with water and methanol. Further, ascorbic acid and glucose are water-soluble, but ascorbic acid or glucose present between the aggregated spherical silver particles cannot be easily removed even by repeated washing with water or water and methanol.
市販の還元法による球状銀粒子は、水でよく洗浄された球状銀粒子、あるいは、水とメタノールで洗浄された球状銀粒子であってもその炭素含有量は通常0.50重量%を大幅に上回るので、本発明では、これをエタノールのような炭素原子数2以上の低級アルコールにより洗浄することにより、あるいは水とメタノールにより洗浄することによりその炭素含有量が0.50重量%以下、好ましくは0.25重量%以下となった球状銀粒子を使用するものである。それも、単に洗浄するだけでなく、凝集物が1次粒子またはそれに近い状態に分散するよう物理的、機械的な力を加えつつ洗浄し、濾過して洗浄液を捨て、残渣を再度エタノールのような炭素原子数2以上の低級アルコール、あるいは水とメタノールにより洗浄することによりその炭素含有量が0.50重量%以下、好ましくは0.25重量%以下、より好ましくは0.13重量%以下となった球状銀粒子を使用するものである。特には乳鉢等により球状銀粒子の凝集物を壊すように攪拌することにより球状銀粒子の1次粒子またはそれに近い状態で洗浄したものを使用するものである。洗浄後の球状銀粒子は乾燥させることが好ましい。乾燥条件は限定されないが、乾燥中に球状銀粒子同士の融着を防止するため100℃未満で乾燥することが好ましく、特には常温であることが好ましい。乾燥を促進するため減圧下や、通風下に置いても良い。 Commercially available spherical silver particles obtained by the reduction method are spherical silver particles that have been washed well with water, or spherical silver particles that have been washed with water and methanol. In the present invention, the carbon content is 0.50% by weight or less, preferably by washing with a lower alcohol having 2 or more carbon atoms such as ethanol, or by washing with water and methanol. Spherical silver particles having a concentration of 0.25% by weight or less are used. It is not only washed, but also washed with physical and mechanical force so that the aggregates are dispersed in or near the primary particles, filtered and discarded, and the residue again like ethanol. By washing with a lower alcohol having 2 or more carbon atoms, or water and methanol, the carbon content is 0.50% by weight or less, preferably 0.25% by weight or less, more preferably 0.13% by weight or less. The resulting spherical silver particles are used. In particular, the primary particles of spherical silver particles or those washed in the vicinity thereof are used by stirring so as to break up aggregates of spherical silver particles with a mortar or the like. The spherical silver particles after washing are preferably dried. The drying conditions are not limited, but it is preferable to dry at less than 100 ° C., particularly at room temperature, in order to prevent fusion of spherical silver particles during drying. It may be placed under reduced pressure or ventilation to promote drying.
しかるに、市販の還元法によるよく洗浄された球状銀粒子製品の一部の製品には、多数のロットのうちの一部のロットには炭素含有量が0.50重量%以下のものがあることが見出されたので、本発明では、入手した球状銀粒子製品の炭素含有量を検査して0.50重量%以下である球状銀粒子を選定して、ペースト状銀組成物の調製に使用してもよい。 However, some of the well-cleaned spherical silver particle products that are commercially available by the reduction method have a carbon content of less than 0.50% by weight in some of the lots. Therefore, in the present invention, the carbon content of the obtained spherical silver particle product is inspected and selected to be 0.50% by weight or less, and used to prepare a paste-like silver composition. May be.
かくして得られた球状銀粒子の炭素含有量は0.50重量%以下、好ましくは0.25重量%以下、より好ましくは0.13重量%以下であるので、100℃以上の温度で加熱時の銀粒子の焼結性と、焼結してできた固形状銀の強度と電気伝導性と熱伝導性が優れている。球状銀粒子の表面は、少々酸化されていてもよい。酸化銀の割合が高いと加熱時に多量の酸素が発生し、焼結してできた固形状銀中にボイドが発生する原因となる恐れがあるため、表面が酸化銀である割合は球状銀粒子の全表面の50%以下が好ましく、特には20%以下、更には2%以下が好ましい。特にメモリやCPUのような大型チップ接続のため比較的大きな接合面積で半密閉系となるダイボンド剤のような使用例では、酸化銀の存在はボイド発生により接着強度の低下の原因となり好ましくない。 The carbon content of the spherical silver particles thus obtained is 0.50% by weight or less, preferably 0.25% by weight or less, and more preferably 0.13% by weight or less. The sinterability of silver particles and the strength, electrical conductivity, and thermal conductivity of solid silver obtained by sintering are excellent. The surface of the spherical silver particles may be slightly oxidized. If the ratio of silver oxide is high, a large amount of oxygen is generated during heating, which may cause voids in the solid silver produced by sintering. 50% or less of the entire surface is preferable, particularly 20% or less, and more preferably 2% or less. In particular, in use cases such as a die bond agent that becomes a semi-sealed system with a relatively large bonding area for connecting a large chip such as a memory or a CPU, the presence of silver oxide is not preferable because it causes a decrease in adhesive strength due to the generation of voids.
本発明のペースト状銀組成物は、炭素含有量が0.50重量%以下、好ましくは0.25重量%以下、より好ましくは0.13重量%以下の実質的に球状の銀粒子と揮発性分散媒との混合物であり、粉末状の球状銀粒子が揮発性分散媒の作用によりペースト化している。ペースト化することによりシリンダーやノズルから細い線状に吐出しやすくなり、電極の形に適用しやすくなる。非揮発性分散媒ではなく、揮発性分散媒を使用するのは、加熱により球状銀粒子が焼結する際に分散媒が揮散すると、球状銀粒子が焼結しやすく、その結果固形状銀の強度と電気伝導性や熱伝導性が大きくなりやすいからである。揮発性分散媒は、球状銀粒子表面を変質させず、その沸点は70℃以上であり、250℃以下であることが好ましい。沸点が70℃未満であるとペースト状銀組成物を調製する作業中に溶媒が揮散しやすく、沸点が250℃より大であると、球状銀粒子が焼結後も揮発性分散媒が残留しかねないからである。そのような揮発性分散媒として、水;エチルアルコール、プロピルアルコール、ブチルアルコール、ペンチルアルコール、ヘキシルアルコール、ヘプチルアルコール、オクチルアルコール、ノニルアルコール、デシルアルコール、ベンジルアルコール等の揮発性一価アルコール;低級n−パラフィン、低級イソパラフィン等の揮発性脂肪族炭化水素;トルエン、キシレン等の揮発性芳香族炭化水素;アセトン、メチルエチルケトン等の揮発性ケトン;酢酸エチルエステルのような揮発性低級脂肪族カルボン酸エステル、低分子量の揮発性シリコーンオイルが例示される。球状銀粒子との混合時および加熱時の安全性ならびにVOCの発生が実質的にゼロという点で水がもっとも好ましく、ついで、エチルアルコール、プロピルアルコール、ブチルアルコール、ペンチルアルコール、ヘキシルアルコール、ヘプチルアルコール、オクチルアルコール、ノニルアルコール、デシルアルコール、ベンジルアルコール等の揮発性一価アルコールが好ましい。これら炭素原子数が2〜10である揮発性一価直鎖状アルコールはペースト状銀組成物にしたときにメタルマスクやシリンジからの押出性、吐出性に優れているからである。;ついで低級n−パラフィン、低級イソパラフィン等の揮発性脂肪族炭化水素が好ましい。水は純水が好ましく、その電気伝導度は100μs/cm以下が好ましく、10μs/cm以下、さらには3μs/cm以下がより好ましい。純水の製造方法は通常の方法で良く、イオン交換法、逆浸透法、蒸留法などが例示される。
揮発性分散媒が水である場合、炭素原子数が4〜10である一価アルコールを水に添加すると、高温域で表面張力が上昇する(マランゴニ効果)ので、塗布形状保持性を制御しやすくなる。ペースト状銀組成物中の水に対し重量比で0.01〜5倍量のブチルアルコール、ペンチルアルコール、ヘキシルアルコール、ヘプチルアルコール、オクチルアルコール、ノニルアルコール、デシルアルコールまたはベンジルアルコールを添加することが例示される。The pasty silver composition of the present invention has substantially spherical silver particles and volatility having a carbon content of 0.50% by weight or less, preferably 0.25% by weight or less, more preferably 0.13% by weight or less. It is a mixture with a dispersion medium, and powdery spherical silver particles are made into a paste by the action of a volatile dispersion medium. By making a paste, it becomes easy to discharge from a cylinder or nozzle in a thin line shape, and it becomes easy to apply to the shape of an electrode. The volatile dispersion medium is used instead of the non-volatile dispersion medium because the spherical silver particles are easily sintered when the dispersion medium volatilizes when the spherical silver particles are sintered by heating. This is because strength, electrical conductivity, and thermal conductivity tend to increase. The volatile dispersion medium does not alter the surface of the spherical silver particles and has a boiling point of 70 ° C. or higher and preferably 250 ° C. or lower. When the boiling point is less than 70 ° C., the solvent easily evaporates during the preparation of the paste-like silver composition, and when the boiling point is greater than 250 ° C., the volatile dispersion medium remains after the spherical silver particles are sintered. Because it might be. As such a volatile dispersion medium, water; volatile monohydric alcohols such as ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, benzyl alcohol; -Volatile aliphatic hydrocarbons such as paraffin and lower isoparaffin; volatile aromatic hydrocarbons such as toluene and xylene; volatile ketones such as acetone and methyl ethyl ketone; volatile lower aliphatic carboxylic esters such as ethyl acetate; Low molecular weight volatile silicone oils are exemplified. Water is most preferable in terms of safety when mixed with spherical silver particles and heating, and generation of VOC is substantially zero, followed by ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, Volatile monohydric alcohols such as octyl alcohol, nonyl alcohol, decyl alcohol and benzyl alcohol are preferred. This is because these volatile monovalent linear alcohols having 2 to 10 carbon atoms are excellent in extrudability and dischargeability from a metal mask or syringe when made into a paste-like silver composition. Then volatile aliphatic hydrocarbons such as lower n-paraffins and lower isoparaffins are preferred. The water is preferably pure water, and its electric conductivity is preferably 100 μs / cm or less, more preferably 10 μs / cm or less, and even more preferably 3 μs / cm or less. A pure water production method may be a normal method, and examples include an ion exchange method, a reverse osmosis method, and a distillation method.
When the volatile dispersion medium is water, adding monohydric alcohol having 4 to 10 carbon atoms to water increases the surface tension in the high temperature range (Marangoni effect), making it easy to control the coating shape retention. Become. Illustrative is adding 0.01 to 5 times the amount of butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol or benzyl alcohol in a weight ratio to the water in the pasty silver composition. Is done.
揮発性分散媒の配合量は、該球状銀粒子をペースト状にするのに十分な量でよく、目安として該球状銀粒子100重量部あたり、5〜20重量部であり、好ましくは6〜16重量部である。本発明のペースト状銀組成物には、本発明の目的に反しない限り銀以外の金属系や非金属系の粉体、チクソ剤、安定剤、着色剤等の添加物を少量ないし微量添加しても良い。 The blending amount of the volatile dispersion medium may be an amount sufficient to make the spherical silver particles into a paste, and as a guide, it is 5 to 20 parts by weight, preferably 6 to 16 parts per 100 parts by weight of the spherical silver particles. Parts by weight. The paste-like silver composition of the present invention may be added with a small amount or a small amount of additives such as metal-based or non-metallic powder other than silver, thixotropic agent, stabilizer, colorant, etc., unless it is contrary to the object of the present invention. May be.
本発明のペースト状銀組成物は、加熱することにより揮発性分散媒が揮散し、該球状銀粒子同士が焼結することにより強度と電気伝導性と熱伝導性が優れた固形状の銀となる。この際、揮発性分散媒が揮散し、ついで球状銀粒子同士が焼結してもよく、揮発性分散媒の揮散と共に球状銀粒子同士が焼結してもよいが、後者の方が焼結性が優れている。銀は本来大きな強度と極めて高い電気伝導性と熱伝導性を有するため、本発明の該球状銀粒子同士の焼結物も大きな強度ときわめて高い電気伝導性と熱伝導性を有する。この際の加熱温度は、揮発性分散媒が揮散し、球状銀粒子が焼結できる温度であればよく、通常100℃以上であり、150℃以上がより好ましく、180℃以上がさらに好ましい。しかし、300℃以上では揮発性分散媒が突沸的に蒸発して固形状銀の形状に悪影響が出る可能性があるため250℃以下であることが好ましい。
該球状銀粒子が焼結してできた、本発明の固形状銀は、その電気伝導性が体積抵抗率で1×10-4Ω・cm以下であるが、1×10-5Ω・cm以下であることが好ましい。その熱伝導性は、5W/m・K以上であるが、10W/m・K以上であることが好ましい。該球状銀粒子が焼結してできた、本発明の固形状銀の形状は特に限定されず、シート状、フィルム状、テープ状、回路状、円盤状、ブロック状が例示される。The paste-like silver composition of the present invention is a solid silver having excellent strength, electrical conductivity, and thermal conductivity by volatilization of the volatile dispersion medium by heating and sintering of the spherical silver particles. Become. At this time, the volatile dispersion medium is volatilized, and then the spherical silver particles may be sintered together, or the spherical silver particles may be sintered together with the volatilization of the volatile dispersion medium. The property is excellent. Since silver inherently has high strength and extremely high electrical and thermal conductivity, the sintered product of the spherical silver particles of the present invention also has high strength and extremely high electrical and thermal conductivity. The heating temperature at this time should just be the temperature which a volatile dispersion medium volatilizes and a spherical silver particle can be sintered, and is 100 degreeC or more normally, 150 degreeC or more is more preferable, 180 degreeC or more is further more preferable. However, at 300 ° C. or higher, the volatile dispersion medium may suddenly evaporate and the solid silver shape may be adversely affected.
The solid silver of the present invention formed by sintering the spherical silver particles has an electric conductivity of 1 × 10 −4 Ω · cm or less in terms of volume resistivity, but 1 × 10 −5 Ω · cm. The following is preferable. Its thermal conductivity is 5 W / m · K or more, but preferably 10 W / m · K or more. The shape of the solid silver of the present invention formed by sintering the spherical silver particles is not particularly limited, and examples thereof include a sheet shape, a film shape, a tape shape, a circuit shape, a disk shape, and a block shape.
本発明のペースト状銀組成物は、100℃以上で加熱すると揮発性分散媒が揮散し球状銀粒子同士が焼結することにより大きな強度と極めて高い電気伝導性と熱伝導性を有する固形状の銀となるので、回路板用基板に塗布して加熱することにより耐摩耗性と基板への接着性に優れた銀回路を形成することができる。本発明の回路板の製造方法は、回路板用基板に本発明のペースト状銀組成物を塗布し、100℃以上で加熱することよりなる。加熱温度は、150℃以上がより好ましく、180℃以上がさらに好ましい。しかし、300℃以上では揮発性分散媒が突沸的に蒸発して銀回路の形状に悪影響が出る可能性があるため250℃以下であることが好ましい。塗布する方法は特に制限されず、ディスペンス塗布、印刷塗布、スプレー塗布、はけ塗り等がある。回路板用基板として、ガラス繊維強化エポキシ樹脂板が代表的であるが、その他にポリイミドフィルム、ポリアミドイミドフィルム、BTレジン板、アルミナセラミック板、ガラス板等が例示される。 When the paste-like silver composition of the present invention is heated at 100 ° C. or higher, the volatile dispersion medium is volatilized and the spherical silver particles are sintered together, so that the solid silver paste has a large strength, extremely high electrical conductivity and thermal conductivity. Since it becomes silver, a silver circuit excellent in wear resistance and adhesion to the substrate can be formed by applying to a circuit board substrate and heating. The manufacturing method of the circuit board of this invention consists of apply | coating the pasty silver composition of this invention to the board | substrate for circuit boards, and heating at 100 degreeC or more. The heating temperature is more preferably 150 ° C. or higher, and further preferably 180 ° C. or higher. However, when the temperature is 300 ° C. or higher, the volatile dispersion medium may be suddenly evaporated to adversely affect the shape of the silver circuit. The method of applying is not particularly limited, and includes dispensing application, printing application, spray application, brush application, and the like. A typical example of the circuit board substrate is a glass fiber reinforced epoxy resin plate, but other examples include a polyimide film, a polyamideimide film, a BT resin plate, an alumina ceramic plate, and a glass plate.
本発明のペースト状銀組成物は100℃以上で加熱すると揮発性分散媒が揮散し該球状銀粒子が焼結することにより、強度と電気伝導性、熱伝導性が優れ、接触していた基材、例えば銀板、銀メッキ金属板への接着性を有する固形状銀となるので、複数の被着体間に介在させ、100℃以上で加熱することにより複数の被着体、特には銀、金、銅、銀メッキ、金メッキのような金属系の接着体同士を強固に接着・接合させるのに有用である。したがって、本発明の接着方法は、銀、金、銅、銀メッキ、金メッキのような金属部材を有する電子部品や電子装置の接着・接合に有用である。図1、図2はそのような接着・接合の一実施形態でもある。そのような接合として、コンデンサ、抵抗等のチップ部品と回路基板との接合;ダイオード、メモリ、CPU等の半導体チップとリードフレームもしくは回路基板との接合;高発熱のCPUチップと冷却板との接合が例示される。なお、回路基板として単層プリント配線基板、多層プリント配線基板が例示される。 When the paste-like silver composition of the present invention is heated at 100 ° C. or higher, the volatile dispersion medium is volatilized and the spherical silver particles are sintered, whereby the strength, electrical conductivity, and thermal conductivity are excellent, and the contacted group Since it becomes solid silver having adhesiveness to a material, for example, a silver plate or a silver-plated metal plate, it is interposed between a plurality of adherends and heated at 100 ° C. or more, so that a plurality of adherends, particularly silver It is useful for firmly bonding and joining metal adhesives such as gold, copper, silver plating, and gold plating. Therefore, the bonding method of the present invention is useful for bonding / joining electronic components and electronic devices having metal members such as silver, gold, copper, silver plating, and gold plating. 1 and 2 also show an embodiment of such adhesion and bonding. Such bonding includes bonding of chip components such as capacitors and resistors and circuit boards; bonding of semiconductor chips such as diodes, memories, and CPUs to lead frames or circuit boards; bonding of high heat generating CPU chips and cooling plates. Is exemplified. Examples of the circuit board include a single-layer printed wiring board and a multilayer printed wiring board.
なお、本発明のペースト状銀組成物は、加熱して銀粒子を焼結した後の洗浄は不要であるが、少量ないし微量の有機系添加剤を含む場合は、有機系添加剤を溶解可能な溶媒で洗浄することが好ましい。特に揮発性分散媒が水である場合は水で洗浄することができ、アルコール等の有機溶媒による洗浄の場合のようなVOC発生の問題がない。基本的に本発明のペースト状銀組成物の各成分は不純物が少ないため容易に洗浄ができる。 The pasty silver composition of the present invention does not require cleaning after heating to sinter the silver particles, but it can dissolve the organic additive if it contains a small or trace amount of organic additive. It is preferable to wash with an appropriate solvent. In particular, when the volatile dispersion medium is water, it can be washed with water, and there is no problem of VOC generation as in the case of washing with an organic solvent such as alcohol. Basically, each component of the pasty silver composition of the present invention can be easily cleaned because it contains few impurities.
本発明のペースト状銀組成物は、揮発性分散媒を含有するので、密閉容器に保存することが好ましい。長期間保存後に使用するときは、容器を振とうしてから、あるいは容器内を攪拌してから使用することが好ましい。保存安定性を向上する目的で冷蔵保管をしても良く、保管温度として5℃以下が例示される。 Since the pasty silver composition of the present invention contains a volatile dispersion medium, it is preferably stored in a sealed container. When used after long-term storage, it is preferable to use the container after shaking or stirring the container. Refrigerated storage may be performed for the purpose of improving storage stability, and the storage temperature is exemplified by 5 ° C. or less.
本発明の実施例と比較例を掲げる。実施例と比較例中、部とあるのは重量部を意味する。球状銀粒子中の炭素含有量、ならびに、ペースト状銀組成物を加熱して焼結することにより生成した固形状銀の固着強度、体積抵抗率および熱伝導率は、下記の方法により25℃で測定した。 Examples and comparative examples of the present invention will be given. In the examples and comparative examples, “parts” means “parts by weight”. The carbon content in the spherical silver particles, and the fixing strength, volume resistivity and thermal conductivity of the solid silver produced by heating and sintering the paste-like silver composition are 25 ° C. by the following methods. It was measured.
[炭素含有量]
球状銀粒子を酸素気流中で高周波により加熱して球状銀粒子に付着していた有機化合物中の炭素を炭酸ガスに変えて赤外線吸収スペクトル法により定量した。[Carbon content]
Spherical silver particles were heated by high frequency in an oxygen stream, and carbon in the organic compound adhering to the spherical silver particles was changed to carbon dioxide gas and quantified by infrared absorption spectroscopy.
[固着強度]
100mm×40mmのガラス繊維強化エポキシ樹脂基板上に1mmの間隔をおいて設けられた2つの0.8mm×1.2mmの電極ランド(パッド)部(銀メッキ仕上げ)に150μm厚のメタルマスクを用いてペースト状銀組成物を塗布し、チップマウンタにより2012チップコンデンサ(両端部は銀メッキ仕上げ)を搭載後、強制循環式オーブン内で200℃で30分間加熱したところ、水、低級イソパラフィンまたはアルコールの揮散とともに球状銀粒子が焼結してランド(パッド)部と2012チップコンデンサ(両端部銀メッキ仕上げ)が接合した。かくして得られた接合試験体を固着強度試験機により押厚速度23mm/分で加圧し、せん断破壊したときの荷重をもって固着強度(単位;kgf)とした。[Fixing strength]
A 150 μm-thick metal mask is used for two 0.8 mm × 1.2 mm electrode land (pad) portions (silver plating finish) provided on a 100 mm × 40 mm glass fiber reinforced epoxy resin substrate with a 1 mm interval. After applying a paste-like silver composition and mounting a 2012 chip capacitor (silver plated on both ends) with a chip mounter, heating in a forced circulation oven at 200 ° C. for 30 minutes resulted in water, lower isoparaffin or alcohol. The spherical silver particles were sintered together with the volatilization, and the land (pad) part and the 2012 chip capacitor (both ends silver plating finish) were joined. The bonded specimen thus obtained was pressed at a pressing speed of 23 mm / min with a bond strength tester, and the load when sheared was used as the bond strength (unit: kgf).
[体積抵抗率]
幅10mm、長さ50mmの開口部を有する厚さ100μmの金属製のマスクを用い、電気絶縁性のFR−4ガラス繊維強化エポキシ樹脂基板上にペースト状銀組成物を印刷塗布し、強制循環式オーブン内で200℃で30分間加熱したところ、水、低級イソパラフィンまたはアルコールの揮散とともに球状銀粒子が焼結してフィルム状となった。フィルム状の銀について、50mm長の測定端間で10ボルトの電圧を印加して抵抗を測定し、体積抵抗率(単位;Ω・cm)を算出した。[Volume resistivity]
Using a metal mask having a thickness of 10 mm and an opening having a length of 50 mm and a thickness of 100 μm, a paste-like silver composition is printed and applied onto an electrically insulating FR-4 glass fiber reinforced epoxy resin substrate. When heated in an oven at 200 ° C. for 30 minutes, spherical silver particles were sintered together with a volatilization of water, lower isoparaffin or alcohol to form a film. About film-form silver, the voltage of 10 volts was applied between the measurement ends of 50 mm length, resistance was measured, and volume resistivity (unit; ohm * cm) was computed.
[熱伝導率]
10mmX10mm角のシリコンウエハー間に40μmまたは80μm厚となるようペースト状銀組成物を塗布し、強制循環式オーブン内で200℃で30分間加熱したところ、水、低級イソパラフィンまたはアルコールの揮散とともに球状銀粒子が焼結してフィルム状となった。フィルム状の銀について、各々の厚さにおける熱抵抗(単位;℃/W)を測定した。各厚さ(単位;m)と熱抵抗の関係をグラフにプロットして直線を引き、その傾きを熱伝導率(単位;W/mK)として算出した。[Thermal conductivity]
A pasty silver composition was applied between 10 mm × 10 mm square silicon wafers to a thickness of 40 μm or 80 μm and heated in a forced circulation oven at 200 ° C. for 30 minutes. Sintered into a film. The film-like silver was measured for thermal resistance (unit: ° C./W) at each thickness. The relationship between each thickness (unit: m) and thermal resistance was plotted on a graph, a straight line was drawn, and the slope was calculated as thermal conductivity (unit: W / mK).
[実施例1]
市販の還元法で製造された球状銀粒子多数の炭素含有量を検査することにより見出したA社品、すなわち、還元法で製造されよく洗浄された、走査型電子顕微鏡像の画像解析により得られる1次粒子の平均粒径が0.4μmであり実質的に球状の銀粒子(炭素含有量が0.21重量%であり、銀表面に酸化銀は検出されない)20部に、純度99.5%のエタノール(和光純薬工業株式会社発売の試薬1級エタノール)20部を添加し、乳鉢を用いて1分間攪拌混合した。1分間静置後、上澄み液を可能な限りスポイトで系外へ抜き出した。その後更に純度99.5%のエタノールを用いて同様に2回洗浄し、その後常温で放置しエタノール臭がしなくなるまで風乾したところ球状銀粒子の炭素含有量は0.11重量%であった。
この球状銀粒子粉末に電気伝導度が5μs/cmであるイオン交換水1.5部を添加し、ヘラを用いて均一に混合しペースト状銀組成物を調製した。
このペースト状銀組成物をメタルマスクによりガラス繊維強化エポキシ樹脂基板上に塗布したところ、ダレ、流れ等はなく良好な形状に塗布できた。この塗布したガラス繊維強化エポキシ樹脂基板を強制循環式オーブン内で200℃で30分間加熱したところ、加熱焼結物である固形状銀は、精錬法による銀と遜色ない強度を有していた。上記ペースト状銀組成物について、加熱焼結物である固形状銀の固着強度、体積抵抗率、熱伝導率を測定し、結果を表1にまとめて示した。以上の結果より、このペースト状銀組成物が被着体を電気伝導性と熱伝導性よく強固に接着させるのに有用であり、耐摩耗性と基板への接着性と電気伝導性と熱伝導性が優れた銀回路を形成するのに有用であることがわかる。[Example 1]
Products obtained by inspecting the carbon content of a large number of spherical silver particles produced by a commercially available reduction method, that is, obtained by image analysis of a scanning electron microscope image produced by the reduction method and washed well The primary particles have an average particle size of 0.4 μm and substantially spherical silver particles (carbon content is 0.21% by weight and no silver oxide is detected on the silver surface). 20 parts of ethanol (reagent primary ethanol sold by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred and mixed for 1 minute using a mortar. After standing for 1 minute, the supernatant liquid was extracted out of the system with a dropper as much as possible. Thereafter, it was further washed twice using ethanol having a purity of 99.5%, and then allowed to stand at room temperature and air-dried until no ethanol odor was found. The carbon content of the spherical silver particles was 0.11% by weight.
To this spherical silver particle powder, 1.5 parts of ion-exchanged water having an electric conductivity of 5 μs / cm was added and mixed uniformly using a spatula to prepare a pasty silver composition.
When this pasty silver composition was applied onto a glass fiber reinforced epoxy resin substrate using a metal mask, it could be applied in a good shape without sagging or flowing. When the coated glass fiber reinforced epoxy resin substrate was heated at 200 ° C. for 30 minutes in a forced circulation oven, the solid silver as the heat-sintered product had a strength comparable to silver by a refining method. About the said paste-form silver composition, the fixed strength, volume resistivity, and thermal conductivity of solid silver which is a heat-sintered product were measured, and the results are shown in Table 1. From the above results, this pasty silver composition is useful for firmly adhering an adherend with good electrical and thermal conductivity, and has excellent wear resistance, adhesion to a substrate, electrical conductivity and thermal conductivity. It can be seen that it is useful for forming a silver circuit having excellent properties.
[実施例2]
実施例1において実質的に球状の銀粒子(炭素含有量が0.21重量%であり、銀表面に酸化銀は検出されない)をエタノールで洗浄しない以外は実施例1と同様にしてペースト状銀組成物を調製した。
このペースト状銀組成物をメタルマスクによりガラス繊維強化エポキシ樹脂基板上に塗布したところ、ダレ、流れ等はなく良好な形状に塗布できた。この塗布したガラス繊維強化エポキシ樹脂基板を強制循環式オーブン内で200℃で30分間加熱したところ、加熱焼結物である固形状銀は、精錬法による銀と遜色ない強度を有していた。上記ペースト状銀組成物について、加熱焼結物である固形状銀の固着強度、体積抵抗率、熱伝導率を測定し、結果を表1にまとめて示した。以上の結果より、このペースト状銀組成物が被着体を電気伝導性と熱伝導性よく強固に接着させるのに有用であり、耐摩耗性と基板への接着性と電気伝導性と熱伝導性が優れた銀回路を形成するのに有用であることがわかる。[Example 2]
Paste silver in the same manner as in Example 1 except that substantially spherical silver particles (carbon content is 0.21% by weight and silver oxide is not detected on the silver surface) are not washed with ethanol in Example 1. A composition was prepared.
When this pasty silver composition was applied onto a glass fiber reinforced epoxy resin substrate using a metal mask, it could be applied in a good shape without sagging or flowing. When the coated glass fiber reinforced epoxy resin substrate was heated at 200 ° C. for 30 minutes in a forced circulation oven, the solid silver as the heat-sintered product had a strength comparable to silver by a refining method. About the said paste-form silver composition, the fixed strength, volume resistivity, and thermal conductivity of solid silver which is a heat-sintered product were measured, and the results are shown in Table 1. From the above results, this pasty silver composition is useful for firmly adhering an adherend with good electrical and thermal conductivity, and has excellent wear resistance, adhesion to a substrate, electrical conductivity and thermal conductivity. It can be seen that it is useful for forming a silver circuit having excellent properties.
[実施例3]
実施例1において、イオン交換水の代りに蒸留範囲が106℃から202℃である低級イソパラフィン(新日本石油化学株式会社製、商品名アイソゾール300)を使用した以外は実施例1と同様にしてペースト状銀組成物を調製した。
このペースト状銀組成物をメタルマスクによりガラス繊維強化エポキシ樹脂基板上に塗布したところ、ダレ、流れ等はなく良好な形状に塗布できた。この塗布したガラス繊維強化エポキシ樹脂基板を強制循環式オーブン内で200℃で30分間加熱したところ、加熱焼結物である固形状銀は、精錬法による銀と遜色ない強度を有していた。上記ペースト状銀組成物について、加熱焼結物である固形状銀の固着強度、体積抵抗率、熱伝導率を測定し、結果を表1にまとめて示した。以上の結果より、このペースト状銀組成物が被着体を電気伝導性と熱伝導性よく強固に接着させるのに有用であり、耐摩耗性と基板への接着性と電気伝導性と熱伝導性が優れた銀回路を形成するのに有用であることがわかる。[Example 3]
In Example 1, paste was used in the same manner as in Example 1 except that lower isoparaffin having a distillation range of 106 ° C. to 202 ° C. (trade name Isosol 300, manufactured by Nippon Petrochemical Co., Ltd.) was used instead of ion-exchanged water. A silver-like composition was prepared.
When this pasty silver composition was applied onto a glass fiber reinforced epoxy resin substrate using a metal mask, it could be applied in a good shape without sagging or flowing. When the coated glass fiber reinforced epoxy resin substrate was heated at 200 ° C. for 30 minutes in a forced circulation oven, the solid silver as the heat-sintered product had a strength comparable to silver by a refining method. About the said paste-form silver composition, the fixed strength, volume resistivity, and thermal conductivity of solid silver which is a heat-sintered product were measured, and the results are shown in Table 1. From the above results, this pasty silver composition is useful for firmly adhering an adherend with good electrical and thermal conductivity, and has excellent wear resistance, adhesion to a substrate, electrical conductivity and thermal conductivity. It can be seen that it is useful for forming a silver circuit having excellent properties.
[実施例4]
実施例1においてイオン交換水1.5部の代りに、0.5部のn−デシルアルコール(1−デカノール)および1.0部のイオン交換水を使用した以外は実施例1と同様にしてペースト状組成物を調製した。
このペースト状銀組成物をメタルマスクによりガラス繊維強化エポキシ樹脂基板上に塗布したところ、ダレ、流れ等はなく良好な形状に塗布できた。この塗布したガラス繊維強化エポキシ樹脂基板を強制循環式オーブン内で200℃で30分間加熱したところ、加熱焼結物である固形状銀は、精錬法による銀と遜色ない強度を有していた。上記ペースト状銀組成物について、加熱焼結物である固形状銀の固着強度、体積抵抗率、熱伝導率を測定し、結果を表1にまとめて示した。以上の結果より、このペースト状銀組成物が被着体を電気伝導性と熱伝導性よく強固に接着させるのに有用であたり、耐摩耗性と基板への接着性と電気伝導性と熱伝導性が優れた銀回路を形成するのに有用であることがわかる。[Example 4]
In the same manner as in Example 1 except that 0.5 part of n-decyl alcohol (1-decanol) and 1.0 part of ion exchange water were used instead of 1.5 parts of ion exchange water in Example 1. A pasty composition was prepared.
When this pasty silver composition was applied onto a glass fiber reinforced epoxy resin substrate using a metal mask, it could be applied in a good shape without sagging or flowing. When the coated glass fiber reinforced epoxy resin substrate was heated at 200 ° C. for 30 minutes in a forced circulation oven, the solid silver as the heat-sintered product had a strength comparable to silver by a refining method. About the said paste-form silver composition, the fixed strength, volume resistivity, and thermal conductivity of solid silver which is a heat-sintered product were measured, and the results are shown in Table 1. From the above results, this paste-like silver composition is useful for firmly adhering adherends with good electrical and thermal conductivity, and wear resistance, adhesion to substrates, electrical conductivity and thermal conductivity. It can be seen that it is useful for forming a silver circuit having excellent properties.
[実施例5]
市販の還元法で製造され、走査型電子顕微鏡像の画像解析により得られる1次粒子の平均粒径が1.8μmであり実質的に球状の銀粒子(B社品、炭素含有量が0.88重量%であり、銀表面に酸化銀は検出されない)20部に、電気伝導度が5μs/cmである純水を20部添加し、乳鉢を用いて1分間攪拌混合した。1分間静置後、上澄み液を可能な限りスポイトで系外へ抜き出した。その後同様に純水により5回球状銀粒子を洗浄した。その後、純度99.8%のメタノール20部を添加して同様に攪拌混合し、1分間静置後、上澄み液を可能な限りスポイトで系外へ抜き出した。常温で放置しメタノール臭がしなくなるまで風乾したところ、球状銀粒子の炭素含有量は0.46重量%であった。
この実質的に球状の銀粒子20部に純度99%の1−オクタノール2部を添加し、ヘラを用いて均一に混合してペースト状銀組成物を調製した。
このペースト状銀組成物をメタルマスクによりガラス繊維強化エポキシ樹脂基板上に塗布したところ、ダレ、流れ等はなく良好な形状に塗布できた。この塗布したガラス繊維強化エポキシ樹脂基板を強制循環式オーブン内で200℃で30分間加熱したところ、加熱焼結物である固形状銀は、精錬法による銀と遜色ない強度を有していた。上記ペースト状銀組成物について、加熱焼結物である固形状銀の固着強度、体積抵抗率、熱伝導率を測定し、結果を表1にまとめて示した。以上の結果より、このペースト状銀組成物が被着体を電気伝導性と熱伝導性よく強固に接着させるのに有用であり、耐摩耗性と基板への接着性と電気伝導性と熱伝導性が優れた銀回路を形成するのに有用であることがわかる。[Example 5]
The primary particles produced by a commercially available reduction method and obtained by image analysis of a scanning electron microscope image have an average particle diameter of 1.8 μm and are substantially spherical silver particles (B company product, carbon content is 0.5. 20 parts of pure water having an electric conductivity of 5 μs / cm was added to 20 parts, and the mixture was stirred and mixed for 1 minute using a mortar. After standing for 1 minute, the supernatant liquid was extracted out of the system with a dropper as much as possible. Thereafter, spherical silver particles were washed five times with pure water in the same manner. Thereafter, 20 parts of methanol having a purity of 99.8% was added and stirred and mixed in the same manner. After allowing to stand for 1 minute, the supernatant was taken out of the system with a dropper as much as possible. When it was allowed to stand at room temperature and air-dried until it did not smell of methanol, the carbon content of the spherical silver particles was 0.46% by weight.
To 20 parts of these substantially spherical silver particles, 2 parts of 1-octanol having a purity of 99% was added and mixed uniformly using a spatula to prepare a pasty silver composition.
When this pasty silver composition was applied onto a glass fiber reinforced epoxy resin substrate using a metal mask, it could be applied in a good shape without sagging or flowing. When the coated glass fiber reinforced epoxy resin substrate was heated at 200 ° C. for 30 minutes in a forced circulation oven, the solid silver as the heat-sintered product had a strength comparable to silver by a refining method. About the said paste-form silver composition, the fixed strength, volume resistivity, and thermal conductivity of solid silver which is a heat-sintered product were measured, and the results are shown in Table 1. From the above results, this pasty silver composition is useful for firmly adhering an adherend with good electrical and thermal conductivity, and has excellent wear resistance, adhesion to a substrate, electrical conductivity and thermal conductivity. It can be seen that it is useful for forming a silver circuit having excellent properties.
[実施例6]
実施例5において、炭素含有量が0.46重量%の実質的に球状の銀粒子の代りに、実施例1で調製した炭素含有量が0.11重量%の実質的に球状の銀粒子10部と炭素含有量が0.46重量%の実質的に球状の銀粒子10部とを混合して得た、平均炭素含有量が0.285重量%の球状銀粒子20部を使用した他は、実施例5と同一条件でペースト状銀組成物を調製して、塗布性、焼結性および加熱硬化後の固着強度、体積抵抗率、熱伝導率を測定し、結果を表1にまとめて示した。以上の結果より、このペースト状銀組成物が、被着体を電気伝導性と熱伝導性よく強固に接着したり、耐摩耗性と基板への接着性と電気伝導性と熱伝導性が優れた銀回路を形成するのに有用であることがわかる。[Example 6]
In Example 5, instead of the substantially spherical silver particles having a carbon content of 0.46% by weight, the substantially spherical silver particles 10 having a carbon content of 0.11% by weight prepared in Example 1 were used. Except that 20 parts of spherical silver particles having an average carbon content of 0.285% by weight obtained by mixing 10 parts of substantially spherical silver particles having a carbon content of 0.46% by weight were used. Then, a paste-like silver composition was prepared under the same conditions as in Example 5, and coating properties, sintering properties, fixing strength after heat curing, volume resistivity, and thermal conductivity were measured. The results are summarized in Table 1. Indicated. From the above results, this pasty silver composition has excellent adherence to the adherend with good electrical and thermal conductivity, and excellent wear resistance, adhesion to the substrate, electrical and thermal conductivity. It can be seen that it is useful for forming a silver circuit.
[比較例1]
実施例1で得られたエタノール洗浄した実質的に球状の銀粒子(炭素含有量が0.21重量%であり、銀表面に酸化銀は検出されない)85部、粘度が2500mmPa・sである液状エポキシ樹脂(ビスフェノールA:ビスフェノールF=1:1)14部、2−メチルイミダゾール1部を混合してエポキシ樹脂がバインダーであるペースト状銀組成物の調製を試みたが、このペースト状銀組成物は粘度が高く均一に混合するのが困難であった。結果を表2にまとめて示した。[Comparative Example 1]
85 parts by weight of ethanol-washed substantially spherical silver particles obtained in Example 1 (carbon content is 0.21 wt%, silver oxide is not detected on the silver surface), and the viscosity is 2500 mmPa · s An attempt was made to prepare a pasty silver composition in which 14 parts of an epoxy resin (bisphenol A: bisphenol F = 1: 1) and 1 part of 2-methylimidazole were mixed and the epoxy resin was a binder. Was highly viscous and difficult to mix uniformly. The results are summarized in Table 2.
[比較例2]
実施例1で得られたエタノール洗浄した実質的に球状の銀粒子(炭素含有量が0.21重量%であり、銀表面に酸化銀は検出されない)80部、粘度が2500mmPa・sである液状エポキシ樹脂(ビスフェノールA:ビスフェノールF=1:1)19部、2−メチルイミダゾール1部を均一に混合してエポキシ樹脂がバインダーであるペースト状銀組成物を調製した。
このペースト状銀組成物は粘度が非常に高い(300Pa・S以上)が、メタルマスクによりガラス繊維強化エポキシ樹脂基板上に塗布したところ、ダレ、流れ等はなく良好な形状に塗布できた。200℃で30分間加熱したところ、エポキシ樹脂状の硬い硬化物であった。
加熱硬化後の固着強度、体積抵抗率、熱伝導率を測定し、結果を表2にまとめて示した。[Comparative Example 2]
80 parts by weight of ethanol-washed substantially spherical silver particles obtained in Example 1 (carbon content is 0.21 wt%, silver oxide is not detected on the silver surface), and the viscosity is 2500 mmPa · s 19 parts of epoxy resin (bisphenol A: bisphenol F = 1: 1) and 1 part of 2-methylimidazole were uniformly mixed to prepare a pasty silver composition in which the epoxy resin is a binder.
This pasty silver composition had a very high viscosity (300 Pa · S or more), but when applied to a glass fiber reinforced epoxy resin substrate with a metal mask, it could be applied in a good shape without sagging or flowing. When heated at 200 ° C. for 30 minutes, it was an epoxy resin-like hard cured product.
The fixing strength, volume resistivity, and thermal conductivity after heat curing were measured, and the results are summarized in Table 2.
[比較例3]
B社品である還元法で製造され、走査型電子顕微鏡像の画像解析により得られる1次粒子の平均粒径が1.8μmで実質的に球状の銀粒子(炭素含有量が0.88重量%であり、銀表面に酸化銀は検出されない)20部に、純度99.8%のメタノールと電気伝導度が5μs/cmである純水が重量比で1:1である混合洗浄液を20部添加し、乳鉢を用いて1分間攪拌混合した。1分間静置後、上澄み液を可能な限りスポイトで系外へ抜き出した。その後更に前記混合洗浄液を用いて同様に2回洗浄し、その後常温で放置しメタノール臭がしなくなるまで風乾したところ、実質的に球状の銀粒子の炭素含有量は0.61重量%であった。
この実質的に球状の銀粒子に電気伝導度が5μs/cmであるイオン交換水1.5部を添加し、ヘラを用いて均一に混合してペースト状銀組成物を調製した。
このペースト状銀組成物をメタルマスクにてよりガラス繊維強化エポキシ樹脂基板上に塗布したところ、ダレ、流れ等はなく良好な形状に塗布できた。ところが、200℃で30分間加熱しても球状銀粒子が充分に焼結せず、フィルム状ではあるが、もろく指で触ると容易に壊れた。結果を表2にまとめて示した。[Comparative Example 3]
A primary particle produced by a reduction method, which is a product of Company B, obtained by image analysis of a scanning electron microscope image and having an average particle diameter of 1.8 μm and substantially spherical silver particles (carbon content is 0.88 wt. 20 parts of a mixed cleaning solution in which methanol having a purity of 99.8% and pure water having an electric conductivity of 5 μs / cm is 1: 1 in a weight ratio is 20 parts. The mixture was added and stirred and mixed for 1 minute using a mortar. After standing for 1 minute, the supernatant liquid was extracted out of the system with a dropper as much as possible. Thereafter, the mixture was further washed twice in the same manner as described above, and then allowed to stand at room temperature and air-dried until it did not smell of methanol. As a result, the carbon content of the substantially spherical silver particles was 0.61% by weight. .
To the substantially spherical silver particles, 1.5 parts of ion-exchanged water having an electric conductivity of 5 μs / cm was added and mixed uniformly using a spatula to prepare a pasty silver composition.
When this pasty silver composition was applied onto a glass fiber reinforced epoxy resin substrate with a metal mask, it could be applied in a good shape without sagging or flowing. However, even when heated at 200 ° C. for 30 minutes, the spherical silver particles did not sinter sufficiently, and although they were film-like, they were easily broken when touched with a fragile finger. The results are summarized in Table 2.
[比較例4]
実施例1において、炭素含有量が0.11重量%の実質的に球状の銀粒子にイオン交換水を添加しないでガラス繊維強化エポキシ樹脂基板上に塗布し、200℃で30分間加熱したところ、この実質的に球状の銀粒子は焼結せず、粒子状のままであった。結果を表2にまとめて示した。[Comparative Example 4]
In Example 1, a substantially spherical silver particle having a carbon content of 0.11% by weight was coated on a glass fiber reinforced epoxy resin substrate without adding ion exchange water and heated at 200 ° C. for 30 minutes. The substantially spherical silver particles did not sinter and remained particulate. The results are summarized in Table 2.
[比較例5]
実施例5において、炭素含有量が0.46重量%の実質的に球状の銀粒子の代りに、未洗浄の炭素含有量が0.88重量%の実質的に球状の銀粒子を使用した以外は実施例5と同様にしてペースト状銀組成物を調製した。
このペースト状銀組成物をメタルマスクによりガラス繊維強化エポキシ樹脂基板上に塗布したところ、ダレ、流れ等はなく良好な形状に塗布できた。ところが、200℃で30分間加熱しても実質的に球状の銀粒子は充分に焼結せず、フィルム状となったが、もろく指で触ると容易に壊れた。結果を表2にまとめて示した。[Comparative Example 5]
In Example 5, instead of substantially spherical silver particles having a carbon content of 0.46% by weight, substantially spherical silver particles having an unwashed carbon content of 0.88% by weight were used. Prepared a pasty silver composition in the same manner as in Example 5.
When this pasty silver composition was applied onto a glass fiber reinforced epoxy resin substrate using a metal mask, it could be applied in a good shape without sagging or flowing. However, even when heated at 200 ° C. for 30 minutes, the substantially spherical silver particles did not sinter sufficiently and became a film, but they were easily broken when touched with a finger. The results are summarized in Table 2.
以上の結果により、本発明のペースト状銀組成物が、加熱焼結性に優れ、被着体を電気伝導性と熱伝導性よく強固に接着させるのに有用であり、耐磨耗性を基板への接着性と電気伝導性と熱伝導性が優れた銀回路を形成するのに有用であることがわかる。 Based on the above results, the paste-like silver composition of the present invention has excellent heat sinterability, is useful for firmly bonding an adherend with good electrical and thermal conductivity, and has excellent wear resistance. It can be seen that it is useful for forming a silver circuit having excellent adhesion, electrical conductivity and thermal conductivity.
本発明のペースト状銀組成物、固形状銀の製造方法、固形状銀および接着方法は、プリント回路基板上の導電性回路の形成、抵抗器やコンデンサ等の各種電子部品及び各種表示素子の電極の形成、電磁波シールド用導電性被膜の形成、コンデンサ、抵抗、ダイオード、メモリ、演算素子(CPU)等のチップ部品の基板への接着、太陽電池の電極の形成、積層セラミックコンデンサ、積層セラミックインダクタ、積層セラミックアクチュエータ等のチップ型セラミック電子部品の外部電極の形成等に有用である。本発明のペースト状銀組成物の製造方法は、ペースト状銀組成物を効率よく製造するのに有用であり、本発明の回路板の製造方法は、回路板を効率よく製造するのに有用である。
The paste-like silver composition, solid silver production method, solid silver, and adhesion method of the present invention include formation of conductive circuits on a printed circuit board, various electronic components such as resistors and capacitors, and electrodes of various display elements. Formation of conductive films for electromagnetic wave shielding, adhesion of chip components such as capacitors, resistors, diodes, memories, arithmetic elements (CPUs) to substrates, formation of solar cell electrodes, multilayer ceramic capacitors, multilayer ceramic inductors, This is useful for forming external electrodes of chip-type ceramic electronic components such as multilayer ceramic actuators. The method for producing a paste-like silver composition of the present invention is useful for efficiently producing a paste-like silver composition, and the method for producing a circuit board of the present invention is useful for efficiently producing a circuit board. is there.
【0005】
を容易に製造することができる。本発明の固形状銀の製造方法は、加熱により該揮発性分散媒が揮散し、特には100℃以上での加熱により該球状銀粒子同士が焼結して強度と電気伝導性と熱伝導性が優れた固形状銀を容易に製造することができる。本発明の固形状銀は、精錬法により製造された銀並みの強度を有している。本発明の接着方法は、ペースト状銀組成物を複数の被着体間に介在させ、100℃以上での加熱により該揮発性分散媒が揮散し該球状銀粒子同士が焼結して複数の被着体同士を電気伝導性と熱伝導性よく強固に接着させることができる。本発明の回路板の製造方法は、ペースト状銀組成物を基板上に印刷し、100℃以上での加熱により該揮発性分散媒が揮散し該球状銀粒子同士が焼結して耐摩耗性と基板への接着性と電気伝導性と熱伝導性が優れた銀回路を有する回路板を容易に製造することができる。
図面の簡単な説明
[0009]
[図1]実施例における固着強度測定用試験体Aの平面図である。チップコンデンサ端子電極3と電極ランド(パッド)部4がハンダ付けされることにより、チップコンデンサ2がガラス繊維強化エポキシ樹脂基板1に搭載されている固着強度測定用試験体Aを固定し、チップコンデンサ2の側面を矢印の方向に押圧して、チップコンデンサ2とガラス繊維強化エポキシ樹脂基板1との接合部分の固着強度を測定するものである。
[図2]図1におけるY−Y´断面図である。
符号の説明
[0010]
A 固着強度測定用試験体
1 ガラス繊維強化エポキシ樹脂基板
2 チップコンデンサ
3 チップコンデンサの端子電極
4 電極ランド(パッド)部
5 ペースト状銀組成物
発明を実施するための最良の形態
[0011]
本発明のペースト状銀組成物は、(A)平均粒径が0.1〜6μmであり,炭素含有量が0.5[0005]
Can be easily manufactured. In the method for producing solid silver according to the present invention, the volatile dispersion medium is volatilized by heating, and particularly the spherical silver particles are sintered by heating at 100 ° C. or higher, whereby strength, electrical conductivity, and thermal conductivity. Can easily produce solid silver. The solid silver of the present invention has the same strength as silver produced by a refining method. In the bonding method of the present invention, a paste-like silver composition is interposed between a plurality of adherends, the volatile dispersion medium is volatilized by heating at 100 ° C. or higher, and the spherical silver particles are sintered to form a plurality of The adherends can be firmly bonded to each other with good electrical conductivity and thermal conductivity. The method for producing a circuit board according to the present invention comprises printing a paste-like silver composition on a substrate, volatilizing the volatile dispersion medium by heating at 100 ° C. or higher, and sintering the spherical silver particles to wear resistance. In addition, a circuit board having a silver circuit having excellent adhesion to the substrate, electrical conductivity, and thermal conductivity can be easily manufactured.
BRIEF DESCRIPTION OF THE DRAWINGS [0009]
FIG. 1 is a plan view of a test specimen A for measurement of adhesion strength in an example. The chip
2 is a cross-sectional view taken along line YY ′ in FIG.
Explanation of symbols [0010]
A Specimen for
The pasty silver composition of the present invention has (A) an average particle diameter of 0.1 to 6 μm and a carbon content of 0.5.
【0006】
0重量%以下である球状銀粒子と、(B)水,沸点が70〜250℃である揮発性一価アルコールおよび沸点が70〜250℃である非アルコール系の揮発性分散媒から選択される揮発性分散媒とからなる。当該球状銀粒子の平均粒径は、走査型電子顕微鏡像の画像解析により得られる一次粒子の平均粒径である。球は、真球だけでなく、多少歪な球や、楕円球を含むものである。平均粒径が6μmを越えると球状銀同士の焼結性が小さくなり、優れた強度と電気伝導性、熱伝導性、接着性を得にくい。そのため平均粒子径は小さい方がより好ましく、特には3μm以下であることが好ましい。いわゆるナノサイズとなる0.1μm未満の場合、球状銀粒子の表面活性が強すぎてペースト状銀組成物の保存安定性が低下する恐れがあるため、0.1μm以上である。
当該球状銀粒子の炭素含有量は、0.50重量%以下であり、下限値は0重量%である。加熱時の球状銀粒子の焼結性と、焼結してできた固形状銀の強度と電気伝導性と熱伝導性の点で好ましくは0.25重量%以下、より好ましくは0.13重量%以下である。ここで炭素含有量は、球状銀粒子を酸素気流中で加熱して球状銀粒子に付着していた有機化合物中の炭素を炭酸ガスに変えて赤外線吸収スペクトル法により定量したものである。なお熱重量測定法(TGA)による減少量から炭素含有量を算出しても良い。
[0012]
当該球状銀粒子は、特には還元法で作られた球状銀粒子である。前記特許文献に記載されているように、還元法では、通常、硝酸銀水溶液とアンモニア水とを混合して反応させ銀アンミン錯体水溶液を得て、これとヒドロキノンと無水亜硫酸カリウムもしくはアンモニウムとゼラチンの水溶液を接触反応させて銀粉を還元析出させ、濾過し、残渣を水で洗浄し、加熱下乾燥させて調製している。あるいは、硝酸銀水溶液とアンモニア水とを混合して反応させ銀アンミン錯体水溶液を得て、これと有機還元剤(ヒドロキノン、アスコルビン酸、グルコース等)の水溶液を接触反応させて銀粉を還元析出させ、濾過し、洗浄し、乾燥させて調製している。濾過残渣はアンモニアとヒドロキノンと無水亜硫酸カリウムもしくはアンモニウムとゼラチンを含有しており、銀粉表面にアンモニアとヒドロキノンと無水亜硫酸カリウムもしくはアンモニウムとゼラチンが付着しているため、清浄な水で繰り返し洗浄している。あるいは、濾過残渣はアンモニアと有機還元剤(ヒドロキノン、アスコルビン酸またはグルコース)を含有しており、銀粒子表面にアンモニアと有機還元剤(ヒドロキノン、アスコルビン酸またはグルコース)が付[0006]
Spherical silver particles of 0 wt% or less, (B) water, volatile monohydric alcohol having a boiling point of 70 to 250 ° C., and non-alcohol volatile dispersion medium having a boiling point of 70 to 250 ° C. It consists of a volatile dispersion medium. The average particle diameter of the spherical silver particles is the average particle diameter of primary particles obtained by image analysis of a scanning electron microscope image. The sphere includes not only a true sphere but also a slightly distorted sphere or an elliptic sphere. When the average particle size exceeds 6 μm, the sinterability between spherical silver particles becomes small, and it is difficult to obtain excellent strength, electrical conductivity, thermal conductivity, and adhesion. Therefore, it is more preferable that the average particle size is small, and it is particularly preferable that the average particle size is 3 μm or less. When the so-called nano-size is less than 0.1 μm, the surface activity of the spherical silver particles is too strong, and the storage stability of the pasty silver composition may be lowered, so that it is 0.1 μm or more.
The carbon content of the spherical silver particles is 0.50% by weight or less, and the lower limit is 0% by weight. In terms of the sinterability of spherical silver particles during heating, and the strength, electrical conductivity, and thermal conductivity of the solid silver obtained by sintering, it is preferably 0.25% by weight or less, more preferably 0.13% by weight. % Or less. Here, the carbon content is determined by an infrared absorption spectrum method in which spherical silver particles are heated in an oxygen stream and carbon in an organic compound adhering to the spherical silver particles is changed to carbon dioxide. Note that the carbon content may be calculated from the decrease by thermogravimetry (TGA).
[0012]
The spherical silver particles are particularly spherical silver particles produced by a reduction method. As described in the above-mentioned patent document, in the reduction method, an aqueous silver ammine complex solution is usually obtained by mixing and reacting an aqueous silver nitrate solution and aqueous ammonia, and an aqueous solution of hydroquinone, anhydrous potassium sulfite or ammonium and gelatin. The silver powder is reduced and deposited by contact reaction, filtered, and the residue is washed with water and dried under heating. Alternatively, a silver nitrate aqueous solution and aqueous ammonia are mixed and reacted to obtain a silver ammine complex aqueous solution, which is contacted with an aqueous solution of an organic reducing agent (hydroquinone, ascorbic acid, glucose, etc.) to cause silver powder to be reduced and precipitated, and filtered. It is prepared by washing and drying. The filtration residue contains ammonia, hydroquinone, anhydrous potassium sulfite or ammonium, and gelatin. Since ammonia, hydroquinone, anhydrous potassium sulfite, ammonium, and gelatin adhere to the silver powder surface, it is repeatedly washed with clean water. . Alternatively, the filtration residue contains ammonia and an organic reducing agent (hydroquinone, ascorbic acid or glucose), and ammonia and an organic reducing agent (hydroquinone, ascorbic acid or glucose) are attached to the surface of the silver particles.
【0003】
製造方法、ペースト状銀組成物から強度と電気伝導性と熱伝導性が優れた固形状銀を製造する方法、強度と電気伝導性と熱伝導性が優れた固形状銀、当該ペースト状銀組成物を使用して被着体を電気伝導性と熱伝導性よく強固に接着する方法および耐摩耗性と基板への接着性と電気伝導性と熱伝導性が優れた銀回路を有する回路板を製造する方法を提供することにある。
課題を解決するための手段
[0007]
この目的は、
[1](A)平均粒径が0.1〜6μmであり,炭素含有量が0.50重量%以下である還元法で作られた球状銀粒子と、(B)水,沸点が70〜250℃である揮発性一価アルコールおよび沸点が70〜250℃である非アルコール系の揮発性分散媒から選択される揮発性分散媒とからなるペースト状物であり、加熱により,該揮発性分散媒が揮散し該球状銀粒子同士が焼結することを特徴とする、ペースト状銀組成物。
[2]炭素含有量が0.25重量%以下であることを特徴とする、[1]記載のペースト状銀組成物。
[3]球状銀粒子同士の焼結物は、体積抵抗率が1×10−5Ω・cm以下であり,かつ,熱伝導度が10W/m・K以上であることを特徴とする、[1]または[2]記載のペースト状銀組成物。
[4]揮発性一価アルコールがエチルアルコール、プロピルアルコール、ブチルアルコール、ペンチルアルコール、ヘキシルアルコール、ヘプチルアルコール、オクチルアルコール、ノニルアルコール、デシルアルコールまたはベンジルアルコールであり、非アルコール系の揮発性分散媒が揮発性脂肪族炭化水素、揮発性芳香族炭化水素、揮発性ケトン、揮発性低級脂肪族カルボン酸エステルまたは低分子量の揮発性シリコーンオイルであることを特徴とする、[1]または[2]記載のペースト状銀組成物。
[5]揮発性一価アルコールがエチルアルコール、プロピルアルコール、ブチルアルコール、ペンチルアルコール、ヘキシルアルコール、ヘプチルアルコール、オクチルアルコール、ノニルアルコール、デシルアルコールまたはベンジルアルコールであり、非アルコール系の揮発性分散媒が揮発性脂肪族炭化水素、揮発性芳香族炭化水素、揮発性ケトン、揮発性低級脂肪族カルボン酸エステルまたは低分子量の揮発性シリコーンオイルであることを特徴とする、[3]記載のペースト状銀組成物。
[6]揮発性分散媒が、水と、ブチルアルコール、ペンチルアルコール、ヘキシルアルコール、ヘプチルアルコール、オクチルアルコール、ノニルアルコール、デシルアルコールまたはベンジルアルコールとの混合物であることを特徴とする、[4]記載のペースト状銀組成物の製造方法。
[7]揮発性分散媒が、水と、ブチルアルコール、ペンチルアルコール、ヘキシルアルコール、ヘプチルアルコール、オクチルアルコール、ノニルアルコール、デシルアルコールまたはベンジルアルコールとの混合物であることを特徴とする、[5]記載のペースト状銀組成物。
[8]平均粒径が0.1〜6μmである還元法で作られた球状銀粒子を洗浄して,その炭素含有量を0.50重量%以下とし、(B)水,沸点が70〜250℃である揮発性一価アルコールおよび沸点が70〜250℃である非アルコール系の揮発性分散媒から選択される揮発性分散媒と混合することを特徴とする、加熱により,該揮発性分散媒が揮散し該球状銀粒子同士が焼結する、ペースト状銀組成物の製造方法。
[9]球状銀粒子の炭素含有量を0.25重量%以下とすることを特徴とする、[8]記載のペースト状銀組成物の製造方法。[0003]
Production method, method for producing solid silver excellent in strength, electrical conductivity and thermal conductivity from paste-like silver composition, solid silver excellent in strength, electrical conductivity and thermal conductivity, said paste-like silver composition A circuit board having a silver circuit excellent in wear resistance, adhesion to a substrate, electrical conductivity, and thermal conductivity It is to provide a method of manufacturing.
Means for Solving the Problems [0007]
This purpose is
[1] (A) Spherical silver particles made by a reduction method having an average particle diameter of 0.1 to 6 μm and a carbon content of 0.50% by weight or less, and (B) water having a boiling point of 70 to A paste-like material comprising a volatile monohydric alcohol having a temperature of 250 ° C. and a volatile dispersion medium selected from a non-alcohol volatile dispersion medium having a boiling point of 70 to 250 ° C. A paste-like silver composition, wherein the medium is volatilized and the spherical silver particles are sintered together.
[2] The pasty silver composition according to [1], wherein the carbon content is 0.25% by weight or less.
[3] The sintered product of spherical silver particles has a volume resistivity of 1 × 10 −5 Ω · cm or less and a thermal conductivity of 10 W / m · K or more. The pasty silver composition according to [1] or [2].
[4] The volatile monohydric alcohol is ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol or benzyl alcohol, and the non-alcohol volatile dispersion medium is [1] or [2], which is a volatile aliphatic hydrocarbon, volatile aromatic hydrocarbon, volatile ketone, volatile lower aliphatic carboxylic acid ester, or low molecular weight volatile silicone oil Pasty silver composition.
[5] The volatile monohydric alcohol is ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol or benzyl alcohol, and the non-alcohol volatile dispersion medium is Pasty silver according to [3], which is a volatile aliphatic hydrocarbon, volatile aromatic hydrocarbon, volatile ketone, volatile lower aliphatic carboxylic acid ester or low molecular weight volatile silicone oil Composition.
[6] The volatile dispersion medium is a mixture of water and butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol or benzyl alcohol, A process for producing a pasty silver composition.
[7] The volatile dispersion medium is a mixture of water and butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol or benzyl alcohol, [5] Pasty silver composition.
[8] Spherical silver particles produced by a reduction method having an average particle diameter of 0.1 to 6 μm are washed to have a carbon content of 0.50% by weight or less, and (B) water having a boiling point of 70 to Mixing with a volatile dispersion medium selected from a volatile monohydric alcohol having a boiling point of 250 ° C. and a non-alcohol-based volatile dispersion medium having a boiling point of 70 to 250 ° C. A method for producing a paste-like silver composition, wherein the medium is volatilized and the spherical silver particles are sintered together.
[9] The method for producing a pasty silver composition according to [8], wherein the carbon content of the spherical silver particles is 0.25% by weight or less.
【0004】
[10]洗浄剤が水,揮発性の親水性溶剤または脂肪族炭化水素系溶剤であることを特徴とする、[8]記載のペースト状銀組成物の製造方法。
[11][1],[2]または[3]記載のペースト状銀組成物を100℃以上で加熱することにより、該揮発性分散媒が揮散し,該球状銀粒子同士が焼結することを特徴とする、固形状銀の製造方法。
[12]固形状銀の体積抵抗率が1×10−5Ω・cm以下であり,かつ,熱伝導度が10W/m・K以上であることを特徴とする、[11]記載の固形状銀の製造方法。
[13](A)平均粒径が0.1〜6μmであり,炭素含有量が0.50重量%以下である還元法で作られた球状銀粒子と、(B)水,沸点が70〜250℃である揮発性一価アルコールおよび沸点が70〜250℃である非アルコール系の揮発性分散媒から選択される揮発性分散媒とからなるペースト状物であり、100℃以上での加熱により,該揮発性分散媒が揮散し該球状銀粒子同士が焼結するペースト状銀組成物を、複数の被着体間に介在させ、100℃以上での加熱により、該揮発性分散媒が揮散し,該球状銀粒子同士が焼結して,複数の被着体同士を接着させることを特徴とする、接着方法。
[14]球状銀粒子の炭素含有量が0.25重量%以下であることを特徴とする、[13]記載の接着方法。
[15]球状銀粒子同士の焼結物の体積抵抗率が1×10−5Ω・cm以下であり,かつ,熱伝導度が10W/m・K以上であることを特徴とする、[13]または[14]記載の接着方法。
[16]ペースト状銀組成物が[4]または[6]記載のペースト状銀組成物であることを特徴とする、[13]記載の接着方法。
[17]ペースト状銀組成物が[5]または[7]記載のペースト状銀組成物であることを特徴とする、[14]または[15]記載の接着方法。
[18]被着体が電子部品であることを特徴とする、[13]記載の接着方法。
[19](A)平均粒径が0.1〜6μmであり,炭素含有量が0.50重量%以下である還元法で作られた球状銀粒子と、(B)水,沸点が70〜250℃である揮発性一価アルコールおよび沸点が70〜250℃である非アルコール系の揮発性分散媒から選択される揮発性分散媒とからなるペースト状物であり、100℃以上での加熱により,該揮発性分散媒が揮散し,該球状銀粒子同士が焼結するペースト状銀組成物を、基板上に塗布し、100℃以上での加熱により,該揮発性分散媒が揮散し該球状銀粒子同士が焼結して銀回路を形成することを特徴とする、回路板の製造方法。
[20]球状銀粒子の炭素含有量が0.25重量%以下であることを特徴とする、[19]記載の回路板の製造方法。
;により達成される。
発明の効果
[0008]
本発明のペースト状銀組成物は、加熱により該揮発性分散媒が揮散し、特には100℃以上での加熱により該球状銀粒子同士が焼結して強度と電気伝導性と熱伝導性が優れた固形状銀となる。本発明のペースト状銀組成物の製造方法は、加熱により該揮発性分散媒が揮散し、特には100℃以上での加熱により該球状銀粒子同士が焼結して強度と電気伝導性と熱伝導性が優れた固形状銀となるペースト状銀組成物[0004]
[10] The method for producing a pasty silver composition according to [8], wherein the cleaning agent is water, a volatile hydrophilic solvent or an aliphatic hydrocarbon solvent.
[11] When the pasty silver composition according to [1], [2] or [3] is heated at 100 ° C. or higher, the volatile dispersion medium is volatilized and the spherical silver particles are sintered together. A method for producing solid silver.
[12] The solid state according to [11], wherein the solid silver has a volume resistivity of 1 × 10 −5 Ω · cm or less and a thermal conductivity of 10 W / m · K or more. Silver production method.
[13] (A) Spherical silver particles produced by a reduction method having an average particle diameter of 0.1 to 6 μm and a carbon content of 0.50% by weight or less; and (B) water having a boiling point of 70 to A paste-like material comprising a volatile monohydric alcohol at 250 ° C. and a volatile dispersion medium selected from a non-alcohol volatile dispersion medium having a boiling point of 70 to 250 ° C., and is heated by heating at 100 ° C. or higher. The paste-like silver composition in which the volatile dispersion medium is volatilized and the spherical silver particles are sintered is interposed between a plurality of adherends, and the volatile dispersion medium is volatilized by heating at 100 ° C. or higher. The spherical silver particles are sintered to bond a plurality of adherends to each other.
[14] The bonding method according to [13], wherein the spherical silver particles have a carbon content of 0.25% by weight or less.
[15] The volume resistivity of the sintered product of spherical silver particles is 1 × 10 −5 Ω · cm or less, and the thermal conductivity is 10 W / m · K or more, [13 ] Or the bonding method according to [14].
[16] The bonding method according to [13], wherein the pasty silver composition is the pasty silver composition according to [4] or [6].
[17] The bonding method according to [14] or [15], wherein the pasty silver composition is the pasty silver composition according to [5] or [7].
[18] The bonding method according to [13], wherein the adherend is an electronic component.
[19] (A) Spherical silver particles made by a reduction method having an average particle diameter of 0.1 to 6 μm and a carbon content of 0.50% by weight or less; and (B) water having a boiling point of 70 to A paste-like material comprising a volatile monohydric alcohol having a temperature of 250 ° C. and a volatile dispersion medium selected from a non-alcohol volatile dispersion medium having a boiling point of 70 to 250 ° C. The paste-like silver composition in which the volatile dispersion medium is volatilized and the spherical silver particles are sintered is applied onto a substrate, and the volatile dispersion medium is volatilized and heated by heating at 100 ° C. or higher. A method for producing a circuit board, wherein silver particles are sintered to form a silver circuit.
[20] The method for producing a circuit board according to [19], wherein the carbon content of the spherical silver particles is 0.25% by weight or less.
Achieved by;
Effect of the Invention [0008]
In the paste-like silver composition of the present invention, the volatile dispersion medium is volatilized by heating, and the spherical silver particles are particularly sintered by heating at 100 ° C. or higher, so that the strength, electrical conductivity, and thermal conductivity are increased. Excellent solid silver. In the method for producing a paste-like silver composition of the present invention, the volatile dispersion medium is volatilized by heating, and the spherical silver particles are particularly sintered by heating at 100 ° C. or higher, resulting in strength, electrical conductivity, and heat. Pasty silver composition that is solid silver with excellent conductivity
【0010】
性と熱伝導性を有する。この際の加熱温度は、揮発性分散媒が揮散し、球状銀粒子が焼結できる温度であればよく、通常100℃以上であり、150℃以上がより好ましく、180℃以上がさらに好ましい。しかし、300℃以上では揮発性分散媒が突沸的に蒸発して固形状銀の形状に悪影響が出る可能性があるため250℃以下であることが好ましい。
該球状銀粒子が焼結してできた固形状銀は、その電気伝導性が体積抵抗率で1×10−5Ω・cm以下である。その熱伝導性は、10W/m・K以上である。該球状銀粒子が焼結してできた固形状銀の形状は特に限定されず、シート状、フィルム状、テープ状、回路状、円盤状、ブロック状が例示される。
[0020]
本発明のペースト状銀組成物は、100℃以上で加熱すると揮発性分散媒が揮散し球状銀粒子同士が焼結することにより大きな強度と極めて高い電気伝導性と熱伝導性を有する固形状の銀となるので、回路板用基板に塗布して加熱することにより耐摩耗性と基板への接着性に優れた銀回路を形成することができる。本発明の回路板の製造方法は、回路板用基板に本発明のペースト状銀組成物を塗布し、100℃以上で加熱することよりなる。加熱温度は、150℃以上がより好ましく、180℃以上がさらに好ましい。しかし、300℃以上では揮発性分散媒が突沸的に蒸発して銀回路の形状に悪影響が出る可能性があるため250℃以下であることが好ましい。塗布する方法は特に制限されず、ディスペンス塗布、印刷塗布、スプレー塗布、はけ塗り等がある。回路板用基板として、ガラス繊維強化エポキシ樹脂板が代表的であるが、その他にポリイミドフィルム、ポリアミドイミドフィルム、BTレジン板、アルミナセラミック板、ガラス板等が例示される。
[0021]
本発明のペースト状銀組成物は100℃以上で加熱すると揮発性分散媒が揮散し該球状銀粒子が焼結することにより、強度と電気伝導性、熱伝導性が優れ、接触していた基材、例えば銀板、銀メッキ金属板への接着性を有する固形状銀となるので、複数の被着体間に介在させ、100℃以上で加熱することにより複数の被着体、特には銀、金、銅、銀メッキ、金メッキのような金属系の接着体同士を強固に接着・接合させるのに有用である。したがって、本発明の接着方法は、銀、金、銅、銀メッキ、金メッキ[0010]
And heat conductivity. The heating temperature at this time should just be the temperature which a volatile dispersion medium volatilizes and a spherical silver particle can be sintered, and is 100 degreeC or more normally, 150 degreeC or more is more preferable, 180 degreeC or more is further more preferable. However, at 300 ° C. or higher, the volatile dispersion medium may suddenly evaporate and the solid silver shape may be adversely affected.
Solid silver formed by sintering the spherical silver particles has an electric conductivity of 1 × 10 −5 Ω · cm or less in terms of volume resistivity. Its thermal conductivity is 10 W / m · K or more. The shape of the solid silver formed by sintering the spherical silver particles is not particularly limited, and examples thereof include a sheet shape, a film shape, a tape shape, a circuit shape, a disk shape, and a block shape.
[0020]
When the paste-like silver composition of the present invention is heated at 100 ° C. or higher, the volatile dispersion medium is volatilized and the spherical silver particles are sintered together, so that the solid silver paste has a large strength, extremely high electrical conductivity and thermal conductivity. Since it becomes silver, a silver circuit excellent in wear resistance and adhesion to the substrate can be formed by applying to a circuit board substrate and heating. The manufacturing method of the circuit board of this invention consists of apply | coating the pasty silver composition of this invention to the board | substrate for circuit boards, and heating at 100 degreeC or more. The heating temperature is more preferably 150 ° C. or higher, and further preferably 180 ° C. or higher. However, when the temperature is 300 ° C. or higher, the volatile dispersion medium may be suddenly evaporated to adversely affect the shape of the silver circuit. The method of applying is not particularly limited, and includes dispensing application, printing application, spray application, brush application, and the like. A typical example of the circuit board substrate is a glass fiber reinforced epoxy resin plate, but other examples include a polyimide film, a polyamideimide film, a BT resin plate, an alumina ceramic plate, and a glass plate.
[0021]
When the paste-like silver composition of the present invention is heated at 100 ° C. or higher, the volatile dispersion medium is volatilized and the spherical silver particles are sintered, whereby the strength, electrical conductivity, and thermal conductivity are excellent, and the contacted group Since it becomes solid silver having adhesiveness to a material, for example, a silver plate or a silver-plated metal plate, it is interposed between a plurality of adherends and heated at 100 ° C. or more, so that a plurality of adherends, particularly silver It is useful for firmly bonding and joining metal adhesives such as gold, copper, silver plating, and gold plating. Therefore, the bonding method of the present invention is silver, gold, copper, silver plating, gold plating.
Claims (16)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP2007517877A JP4347381B2 (en) | 2005-05-25 | 2006-05-24 | Paste silver composition for adhesion of metal-based adherend, method for producing the same, and method for bonding metal-based adherend |
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JP2007517877A JP4347381B2 (en) | 2005-05-25 | 2006-05-24 | Paste silver composition for adhesion of metal-based adherend, method for producing the same, and method for bonding metal-based adherend |
PCT/JP2006/310400 WO2006126614A1 (en) | 2005-05-25 | 2006-05-24 | Paste-like silver composition, method for producing same, method for producing solid silver, solid silver, bonding method, and method for manufacturing circuit board |
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JP5207281B2 (en) * | 2008-01-17 | 2013-06-12 | 国立大学法人大阪大学 | Conductive paste |
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JP2014098186A (en) * | 2012-11-14 | 2014-05-29 | Mitsui Mining & Smelting Co Ltd | Silver powder |
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WO2017006531A1 (en) * | 2015-07-08 | 2017-01-12 | バンドー化学株式会社 | Joining composition and joining method |
JP6796937B2 (en) * | 2016-03-16 | 2020-12-09 | 日東電工株式会社 | Manufacturing method of joint |
JP6920029B2 (en) | 2016-04-04 | 2021-08-18 | 日亜化学工業株式会社 | Metal powder sintered paste and its manufacturing method, conductive material manufacturing method |
JP6796448B2 (en) * | 2016-10-20 | 2020-12-09 | Dowaエレクトロニクス株式会社 | Conductive paste and its manufacturing method, and solar cell |
JP2018206826A (en) * | 2017-05-31 | 2018-12-27 | Dowaエレクトロニクス株式会社 | Bonding material, bonding body, and bonding method |
JP6958434B2 (en) | 2018-03-06 | 2021-11-02 | 三菱マテリアル株式会社 | Metal particle agglomerates and a method for producing the same, and a paste-like metal particle agglomerate composition and a method for producing a bonded body using the same. |
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