JP4247801B2 - Paste-like metal particle composition and joining method - Google Patents
Paste-like metal particle composition and joining method Download PDFInfo
- Publication number
- JP4247801B2 JP4247801B2 JP2008528275A JP2008528275A JP4247801B2 JP 4247801 B2 JP4247801 B2 JP 4247801B2 JP 2008528275 A JP2008528275 A JP 2008528275A JP 2008528275 A JP2008528275 A JP 2008528275A JP 4247801 B2 JP4247801 B2 JP 4247801B2
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- Prior art keywords
- dispersion medium
- volatile
- metal
- paste
- particle composition
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 160
- 239000002923 metal particle Substances 0.000 title claims description 153
- 238000000034 method Methods 0.000 title claims description 42
- 238000005304 joining Methods 0.000 title claims description 22
- 239000002612 dispersion medium Substances 0.000 claims description 233
- 239000002245 particle Substances 0.000 claims description 191
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 170
- 229910052709 silver Inorganic materials 0.000 claims description 166
- 239000004332 silver Substances 0.000 claims description 166
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 56
- 239000000126 substance Substances 0.000 claims description 56
- 229910052751 metal Inorganic materials 0.000 claims description 52
- 239000002184 metal Substances 0.000 claims description 52
- 239000005871 repellent Substances 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 35
- 229930195729 fatty acid Natural products 0.000 claims description 35
- 239000000194 fatty acid Substances 0.000 claims description 35
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 33
- 229910052802 copper Inorganic materials 0.000 claims description 33
- 239000010949 copper Substances 0.000 claims description 33
- -1 fatty acid ester Chemical class 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 229910052759 nickel Inorganic materials 0.000 claims description 28
- 150000004665 fatty acids Chemical class 0.000 claims description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 23
- 238000003825 pressing Methods 0.000 claims description 13
- 239000011368 organic material Substances 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 9
- 150000005846 sugar alcohols Polymers 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 239000011135 tin Substances 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 48
- 238000000926 separation method Methods 0.000 description 46
- 235000011837 pasties Nutrition 0.000 description 40
- 239000003153 chemical reaction reagent Substances 0.000 description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 27
- 235000019441 ethanol Nutrition 0.000 description 24
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 21
- 239000011164 primary particle Substances 0.000 description 21
- 239000000853 adhesive Substances 0.000 description 20
- 230000001070 adhesive effect Effects 0.000 description 20
- 238000003860 storage Methods 0.000 description 20
- 238000007561 laser diffraction method Methods 0.000 description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 13
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
- 238000001556 precipitation Methods 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- 230000005484 gravity Effects 0.000 description 11
- 235000021355 Stearic acid Nutrition 0.000 description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000008117 stearic acid Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 235000019445 benzyl alcohol Nutrition 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 230000002940 repellent Effects 0.000 description 7
- 238000004062 sedimentation Methods 0.000 description 7
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229940053080 isosol Drugs 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 5
- 239000012855 volatile organic compound Substances 0.000 description 5
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 4
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 3
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000015654 memory Effects 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 229910001923 silver oxide Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
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- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- JGHZJRVDZXSNKQ-UHFFFAOYSA-N methyl octanoate Chemical group CCCCCCCC(=O)OC JGHZJRVDZXSNKQ-UHFFFAOYSA-N 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229940067107 phenylethyl alcohol Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003139 primary aliphatic amines Chemical class 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 150000005619 secondary aliphatic amines Chemical class 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003510 tertiary aliphatic amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
-
- 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
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
- B22F7/08—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools with one or more parts not made from powder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/27—Manufacturing methods
- H01L2224/273—Manufacturing methods by local deposition of the material of the layer connector
- H01L2224/2733—Manufacturing methods by local deposition of the material of the layer connector in solid form
- H01L2224/27334—Manufacturing methods by local deposition of the material of the layer connector in solid form using preformed layer
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
- H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
- H01L2224/838—Bonding techniques
- H01L2224/8384—Sintering
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/10—Details of semiconductor or other solid state devices to be connected
- H01L2924/11—Device type
- H01L2924/12—Passive devices, e.g. 2 terminal devices
- H01L2924/1204—Optical Diode
- H01L2924/12044—OLED
Description
本発明は、金属粒子と揮発性分散媒からなり、該金属粒子の沈降，分離が抑制されたペースト状金属粒子組成物、および、当該ペースト状金属粒子組成物を使用した，金属製部材の接合方法に関する。 The present invention relates to a paste-like metal particle composition comprising metal particles and a volatile dispersion medium, in which sedimentation and separation of the metal particles are suppressed, and joining of metal members using the paste-like metal particle composition Regarding the method.
銀，銅，ニッケルなどの金属粉末を液状熱硬化性樹脂組成物中に分散させてなる導電性・熱伝導性ペーストは、加熱により硬化して導電性・熱伝導性被膜が形成される。したがって、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、特に，アモルファスシリコン半導体を用いているために，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。したがって、金属粒子の含有率を可能な限り増加することにより電気伝導性、熱伝導性を向上しようとする。ところが、そうすると、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。A conductive / thermal conductive paste obtained by dispersing a metal powder such as silver, copper, or nickel in a liquid thermosetting resin composition is cured by heating to form a conductive / thermal conductive film. Therefore, formation of conductive circuits on printed circuit boards, formation of various electronic components such as resistors and capacitors, and electrodes of various display elements, formation of conductive films for electromagnetic shielding, capacitors, resistors, diodes, memories, arithmetic elements (CPU), etc., bonding of chip components to the substrate, formation of solar cell electrodes, especially formation of solar cell electrodes that cannot be processed at high temperatures due to the use of amorphous silicon semiconductors, multilayer ceramic capacitors, multilayer ceramic inductors , Used to form external electrodes for chip-type ceramic electronic components such as multilayer ceramic actuators.
2. Description of the Related Art In recent years, chip components have increased in performance, and the amount of heat generated from the chip components has increased, and improvement in thermal conductivity as well as electrical conductivity is required. Therefore, it tries to improve electrical conductivity and thermal conductivity by increasing the content of metal particles as much as possible. However, when it does so, there exists a problem that the viscosity of a paste rises and workability | operativity falls remarkably.
このような問題を解決するため、本発明者らは、銀粉末と揮発性分散媒とからなるペースト状銀組成物は、加熱すると当該揮発性分散媒が揮発し銀粉末が焼結して、極めて高い導電性と熱伝導性を有する固形状銀となること、および、金属製部材の接合や，導電回路の形成に有用なことを見出して特許出願した（特願２００５−１５２８２７、特願２００５−３０９１２６）。しかしながら、銀，銅，ニッケルのような比重の大きい金属粒子と比重の小さい揮発性分散媒とからなるペースト状組成物は、両者の大きな比重差のため、経時的に金属粒子が分離して沈降するという問題があることに、本発明者らは気付いた。 In order to solve such a problem, the present inventors, when heated, the paste-like silver composition composed of silver powder and a volatile dispersion medium volatilizes the volatile dispersion medium and sinters the silver powder, A patent application was filed for finding solid silver having extremely high electrical conductivity and thermal conductivity, and useful for joining metal members and forming conductive circuits (Japanese Patent Application Nos. 2005-152827 and 2005). -309126). However, the paste-like composition consisting of metal particles with a high specific gravity such as silver, copper, nickel and a volatile dispersion medium with a low specific gravity, due to the large difference in specific gravity between them, causes the metal particles to separate and settle over time. The present inventors have found that there is a problem of doing so.
特開２００５−９３３８０には、銀粉末とポリオール類とからなる銀インク、および、銀粉末とポリオール類と粘度調整剤（水、ケトン類またはアルコール類）とからなる銀インクが提案されている。そして、ポリオール類と，ケトン類またはアルコール類との併用により、分散性が向上すると記載されている。ところが、銀，銅，ニッケルのような比重の大きい金属粒子と比重の小さいポリオール類、さらには粘度調整剤とからなるペースト状組成物は、両者の大きな比重差のため、経時的に金属粒子が分離して沈降するという問題があることに、本発明者らは気付いた。 Japanese Patent Application Laid-Open No. 2005-93380 proposes a silver ink composed of silver powder and polyols, and a silver ink composed of silver powder, polyols and a viscosity modifier (water, ketones or alcohols). It is described that dispersibility is improved by the combined use of polyols and ketones or alcohols. However, the paste-like composition composed of metal particles having a high specific gravity such as silver, copper, nickel, polyols having a low specific gravity, and a viscosity modifier, the metal particles gradually change over time due to the large specific gravity difference between the two. The present inventors have noticed that there is a problem of separation and sedimentation.
本発明者らは、上記問題のないペースト状金属粒子組成物、すなわち、金属粒子と揮発性分散媒が経時的に分離することが抑制され，比重の大きい金属粒子の沈降することが抑制された，ペースト状金属粒子組成物を開発すべく鋭意研究した。その結果、金属粒子表面の被覆剤と揮発性分散媒の選択により、ペースト状金属粒子組成物における金属粒子の分離，沈降を抑制できることを見出し、本発明を完成するに至った。本発明の目的は、長期間保管しても、比重の大きい金属粒子が揮発性分散媒から分離すること、および、金属粒子の沈降することが抑制された、すなわち、保存安定性に優れたペースト状金属粒子組成物、ならびに、当該ペースト状金属粒子組成物を使用して金属製部材を強固に接合する方法を提供することにある。 The present inventors have suppressed the above-mentioned problem of a paste-like metal particle composition, that is, the metal particles and the volatile dispersion medium are separated from each other over time, and the precipitation of metal particles having a large specific gravity is suppressed. Therefore, we have intensively studied to develop a paste-like metal particle composition. As a result, it has been found that the separation and sedimentation of the metal particles in the paste-like metal particle composition can be suppressed by selecting the coating agent and the volatile dispersion medium on the surface of the metal particles, and the present invention has been completed. An object of the present invention is a paste in which metal particles having a large specific gravity are separated from a volatile dispersion medium and settling of metal particles is suppressed even when stored for a long period of time, that is, excellent in storage stability. It is to provide a method for strongly joining metal members using the metal particle composition and the paste metal particle composition.
この目的は、
［１］(A)平均粒径０.００１〜５０μｍであり，その表面が撥水性有機物で被覆された金属粒子１００重量部と、(B)揮発性分散媒３〜３０重量部とからなり、該揮発性分散媒(B)が，誘電率の異なる揮発性分散媒(B1)と揮発性分散媒(B2)とからなり、かつ、揮発性分散媒(B1)と揮発性分散媒(B2)が，常温において完全には相溶しない混合比率であることを特徴とする、ペースト状金属粒子組成物。
［２］撥水性有機物が高級脂肪酸，高級脂肪酸アミドまたは高級脂肪酸エステルであり、金属粒子(A)の金属が金，銀，銅，パラジウム，ニッケル，スズ，アルミニウム，または，それらの合金であることを特徴とする、［１］記載のペースト状金属粒子組成物。
［３］金属粒子(A)が高級脂肪酸被覆銀粒子であることを特徴とする、［２］記載のペースト状金属粒子組成物。
［４］揮発性分散媒(B1)と揮発性分散媒(B2)が、水，揮発性１価アルコール，エーテル結合を有する揮発性一価アルコール、揮発性多価アルコール，揮発性炭化水素，揮発性エーテル，揮発性脂肪酸エステル，揮発性ケトン，揮発性脂肪酸アミド，揮発性脂肪族アミンおよびアルキルニトリルからなる群から選択され、かつ、該揮発性分散媒(B1)と該揮発性分散媒(B2)の２５℃における誘電率の差が２.０以上であることを特徴とする、［１］記載のペースト状金属粒子組成物。
［５］揮発性分散媒(B1)と揮発性分散媒(B2)の混合比率が９８：２から２：９８の範囲であることを特徴とする、［１］記載のペースト状金属粒子組成物。
［６］揮発性分散媒(B1)と揮発性分散媒(B2)の混合比率が９８：２から２：９８の範囲であることを特徴とする、［４］記載のペースト状金属粒子組成物。
［７］［１］〜［６］のいずれかに記載のペースト状金属粒子組成物を、複数の金属製部材間に介在させ、加熱により，加圧しつつ超音波振動印加により，または，加圧および加熱しつつ超音波振動印加により、揮発性分散媒を揮散させ，金属粒子(A)同士を焼結させることにより、複数の金属製部材同士を接合させることを特徴とする、金属製部材の接合方法。
［８］(A)平均粒径０.００１〜５０μｍであり、その表面が撥水性有機物で被覆された金属粒子１００重量部と、(C)２５℃における誘電率が３０〜７５であり，金属粒子(A)をはじかない揮発性分散媒３〜３０重量部とからなることを特徴とする、ペースト状金属粒子組成物。
［９］撥水性有機物が高級脂肪酸，高級脂肪酸アミドまたは高級脂肪酸エステルであり、金属粒子(A)の金属が金，銀，銅，パラジウム，ニッケル，スズ，アルミニウム，または，それらの合金であることを特徴とする、［８］記載のペースト状金属粒子組成物。
［１０］金属粒子(A)が高級脂肪酸被覆銀粒子であることを特徴とする、［９］記載のペースト状金属粒子組成物。
［１１］揮発性分散媒(C)が揮発性多価アルコール，ジメチルホルムアミドまたは揮発性一価アルコール水溶液であることを特徴とする、［８］記載のペースト状金属粒子組成物。
［１２］［７］〜［１１］のいずれかに記載のペースト状金属粒子組成物を，複数の金属製部材間に介在させ、加熱により，加圧しつつ超音波振動印加により，または，加圧および加熱しつつ超音波振動印加により、揮発性分散媒(C)を揮散させ，金属粒子(A)同士を焼結させることにより、複数の金属製部材同士を接合させることを特徴とする、金属製部材の接合方法。；により達成される。This purpose is
[1] (A) 100 parts by weight of metal particles having an average particle diameter of 0.001 to 50 μm, the surface of which is coated with a water-repellent organic substance, and (B) 3 to 30 parts by weight of a volatile dispersion medium, The volatile dispersion medium (B) comprises a volatile dispersion medium (B1) and a volatile dispersion medium (B2) having different dielectric constants, and the volatile dispersion medium (B1) and the volatile dispersion medium (B2). However, the paste-like metal particle composition is characterized in that the mixing ratio is not completely compatible at room temperature.
[2] The water-repellent organic material is a higher fatty acid, a higher fatty acid amide or a higher fatty acid ester, and the metal of the metal particles (A) is gold, silver, copper, palladium, nickel, tin, aluminum, or an alloy thereof. The paste-like metal particle composition according to [1], wherein
[3] The paste-like metal particle composition according to [2], wherein the metal particles (A) are higher fatty acid-coated silver particles.
[4] Volatile dispersion medium (B1) and volatile dispersion medium (B2) are water, volatile monohydric alcohol, volatile monohydric alcohol with ether bond, volatile polyhydric alcohol, volatile hydrocarbon, volatilization Selected from the group consisting of volatile ethers, volatile fatty acid esters, volatile ketones, volatile fatty acid amides, volatile aliphatic amines and alkyl nitriles, and the volatile dispersion medium (B1) and the volatile dispersion medium (B2 ) Is a paste-like metal particle composition according to [1], wherein the difference in dielectric constant at 25 ° C. is 2.0 or more.
[5] The paste-like metal particle composition according to [1], wherein the mixing ratio of the volatile dispersion medium (B1) and the volatile dispersion medium (B2) is in the range of 98: 2 to 2:98. .
[6] The paste-like metal particle composition according to [4], wherein the mixing ratio of the volatile dispersion medium (B1) and the volatile dispersion medium (B2) is in the range of 98: 2 to 2:98. .
[7] The paste-like metal particle composition according to any one of [1] to [6] is interposed between a plurality of metal members, and is applied by applying ultrasonic vibration while being pressurized by heating or by pressing. And by applying ultrasonic vibration while heating, the volatile dispersion medium is volatilized and the metal particles (A) are sintered together, thereby joining a plurality of metal members. Joining method.
[8] (A) 100 parts by weight of metal particles having an average particle diameter of 0.001 to 50 μm, the surface of which is coated with a water repellent organic substance, and (C) a dielectric constant at 25 ° C. of 30 to 75, A paste-like metal particle composition comprising 3 to 30 parts by weight of a volatile dispersion medium that does not repel particles (A).
[9] The water-repellent organic substance is a higher fatty acid, a higher fatty acid amide or a higher fatty acid ester, and the metal of the metal particles (A) is gold, silver, copper, palladium, nickel, tin, aluminum, or an alloy thereof. The paste-like metal particle composition according to [8], wherein
[10] The paste-like metal particle composition according to [9], wherein the metal particles (A) are higher fatty acid-coated silver particles.
[11] The paste-like metal particle composition according to [8], wherein the volatile dispersion medium (C) is a volatile polyhydric alcohol, dimethylformamide, or a volatile monohydric alcohol aqueous solution.
[12] The paste-like metal particle composition according to any one of [7] to [11] is interposed between a plurality of metal members, and is applied by applying ultrasonic vibration while being pressurized by heating or by pressing. A metal characterized in that, by applying ultrasonic vibration while heating, the volatile dispersion medium (C) is volatilized and the metal particles (A) are sintered together, thereby joining a plurality of metal members. A method for joining manufactured members. Achieved by;
本発明のペースト状金属粒子組成物は、長期間保存しても、比重の大きい金属粒子と比重の小さい揮発性分散媒(B)が分離すること，および，比重の大きい金属粒子(A)が沈降することが抑制され，均一なペースト状態を保つことができる。
本発明の接合方法によると、金属製部材間のペースト状金属粒子組成物は、加熱により該揮発性分散媒が揮散し、該金属粒子(A)の焼結温度以上の温度での加熱により，該金属粒子(A)同士が焼結して固体状となり、複数の金属製部材同士を強固に接合させることができる。The paste-like metal particle composition of the present invention is such that, even when stored for a long period of time, the metal particles having a large specific gravity and the volatile dispersion medium (B) having a small specific gravity are separated, and the metal particles (A) having a large specific gravity are separated. Sedimentation is suppressed and a uniform paste state can be maintained.
According to the joining method of the present invention, the paste-like metal particle composition between metal members is volatilized by the volatile dispersion medium by heating, and by heating at a temperature equal to or higher than the sintering temperature of the metal particles (A), The metal particles (A) are sintered to form a solid, and a plurality of metal members can be firmly bonded to each other.
Ａ 分離性試験器
１ ペースト状金属粒子組成物
２ 先端キャップ
３ シリンジ
４ プランジャー
５ エンドキャップA Separability tester 1 Paste-like
本発明のペースト状金属粒子組成物は、(A)平均粒径０.００１〜５０μｍであり，その表面が撥水性有機物で被覆された金属粒子１００重量部と(B)揮発性分散媒３〜３０重量部とからなること、該揮発性分散媒(B)が，誘電率の異なる揮発性分散媒(B1)と揮発性分散媒(B2)とからなること、かつ、揮発性分散媒(B1)と揮発性分散媒(B2)が，常温において完全には相溶しない混合比率であることを特徴とする。
The paste-like metal particle composition of the present invention has (A) an average particle diameter of 0.001 to 50 μm, and 100 parts by weight of metal particles whose surface is coated with a water-repellent organic substance, and (B) a
金属粒子(A)は、その表面が撥水性有機物で被覆されていることが必要である。該有機物は潤滑性も優れていることが好ましく、高級脂肪酸，高級脂肪酸金属塩（ただし、アルカリ金属塩を除く），高級脂肪酸アミドおよび高級脂肪酸エステルが好ましく、特には高級脂肪酸が好ましい。撥水性有機物の被覆量は、金属粒子の粒径、比表面積、形状などにより変わるが、金属粒子の０.０１〜３重量％が好ましく、０.２〜２重量％がより好ましい。少なすぎると保存安定性が低下し、多すぎると加熱焼結性が低下するからである。 The surface of the metal particles (A) needs to be coated with a water-repellent organic material. The organic material is preferably excellent in lubricity, and higher fatty acids, higher fatty acid metal salts (excluding alkali metal salts), higher fatty acid amides and higher fatty acid esters are preferable, and higher fatty acids are particularly preferable. The coating amount of the water-repellent organic substance varies depending on the particle size, specific surface area, shape, etc. of the metal particles, but is preferably 0.01 to 3% by weight, more preferably 0.2 to 2% by weight of the metal particles. This is because if the amount is too small, the storage stability is lowered, and if too much, the heat-sinterability is lowered.
金属粒子(A)の材質は、常温で固体であり、加熱，または，加熱と超音波振動印加により焼結しやすければよく、金，銀，銅，パラジウム，ニッケル，スズ，アルミニウム，および，それらの合金が例示される。これらのうちでは、銀，銅，ニッケルが好ましく、加熱焼結性，熱伝導性および導電性の点で、銀が特に好ましい。銀粒子は、その表面の一部または全部が酸化銀になっていてもよい。 The material of the metal particles (A) is solid at room temperature, and should be easy to sinter by heating or heating and applying ultrasonic vibration. Gold, silver, copper, palladium, nickel, tin, aluminum, and those The alloy of is illustrated. Among these, silver, copper, and nickel are preferable, and silver is particularly preferable from the viewpoints of heat sinterability, thermal conductivity, and conductivity. Silver particles may be partly or wholly made of silver oxide.
金属粒子(A)の平均粒径は０.００１〜５０μｍである。この平均粒径は、レーザー回折散乱式粒度分布測定法により得られる一次粒子の平均粒径である。平均粒径が５０μｍを越えると，金属粒子の沈降を防止できにくくなる。そのため、平均粒子径は小さい方が好ましく、２０μｍ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、表面活性が強すぎて，ペースト状金属粒子組成物の保存安定性が低下する恐れがある。そのため０.１μｍ以上であることが好ましく、０.１〜１０μｍがより好ましい。
金属粒子(A)の形状は、球状，略球状，略立方体状，フレーク状，不定形状などである。保存安定性の点で、好ましくはフレーク状である。
特に好ましくは、還元法で作られた銀粒子をフレーク化したものである。なお、還元法の銀粒子の製造方法は多く提案されているが、硝酸銀水溶液に水酸化ナトリウム水溶液を加えて酸化銀を作製し、これにホルマリンのような還元剤の水溶液を加えることにより酸化銀を還元して銀粒子を生成し、水洗，ろ過，乾燥等をおこなうことが一般的である。The average particle diameter of the metal particles (A) is 0.001 to 50 μm. This average particle diameter is an average particle diameter of primary particles obtained by a laser diffraction / scattering particle size distribution measurement method. When the average particle diameter exceeds 50 μm, it becomes difficult to prevent the metal particles from settling. Therefore, the one where an average particle diameter is smaller is preferable and it is preferable that it is 20 micrometers or less. When the so-called nanosize is less than 0.1 μm, the surface activity is too strong, and the storage stability of the paste-like metal particle composition may be lowered. Therefore, it is preferable that it is 0.1 micrometer or more, and 0.1-10 micrometers is more preferable.
The shape of the metal particles (A) includes a spherical shape, a substantially spherical shape, a substantially cubic shape, a flake shape, and an indefinite shape. From the viewpoint of storage stability, a flake shape is preferable.
Particularly preferably, the silver particles produced by the reduction method are made into flakes. Many methods for producing reduction silver particles have been proposed. Silver oxide is prepared by adding an aqueous sodium hydroxide solution to an aqueous silver nitrate solution, and then adding an aqueous solution of a reducing agent such as formalin to the silver oxide solution. It is common to produce silver particles by reducing the water, followed by washing with water, filtration, drying and the like.
撥水性有機物が付着したフレーク状金属粒子は、球状のような粒状の金属粒子に撥水性有機物を添加して、ボールミル等による粉砕をおこなうことにより製造することができる（特公昭４０−６９７１、特開２０００−２３４１０７の[０００４]参照）。
粒状の金属粒子と、高級脂肪酸，高級脂肪酸金属塩（ただし、アルカリ金属塩を除く），高級脂肪酸エステル，高級脂肪酸アミド等の撥水性有機物とを、セラミック製のボールとともに、回転式ドラム装置（例えばボールミル）に投入し、ボールで金属粒子を物理的にたたくことにより、容易にフレーク状（鱗片状）に加工できる。この際、潤滑性向上のための高級脂肪酸，高級脂肪酸金属塩（ただし、アルカリ金属塩を除く），高級脂肪酸エステル，高級脂肪酸アミド等の撥水性有機物が、フレーク状金属粒子に付着する。このような高級脂肪酸としては、ラウリン酸，ミリスチン酸，パルミチン酸，ステアリン酸，オレイン酸，リノール酸，リノレン酸が例示されるが、高級飽和脂肪酸であることが好ましい。このような高級飽和脂肪酸としては、ララウリン酸，ミリスチン酸，パルミチン酸，ステアリン酸が例示される。フレーク状金属表面は、このような高級脂肪酸等により半分以上が被覆されておればよいが、全部が被覆されていることが好ましい。このように金属表面が撥水性有機物により被覆された金属粒子は、撥水性を示す。撥水性有機物の付着量が少なすぎると、金属粒子が分離沈降しやすくなり、多すぎると焼結性が低下することがある。したがって、撥水性有機物の付着量は、０.０１〜３％が好ましく、０.１〜１％であることがより好ましい。撥水性有機物の付着量は通常の方法で測定できる。例えば、窒素ガス中で撥水性有機物の沸点以上に加熱して重量減少を測定する方法、金属粒子を酸素気流中で加熱して金属粒子に付着していた撥水性有機物中の炭素を炭酸ガスに変え，赤外線吸収スペクトル法により定量分析する方法が例示される。
表面を撥水性有機物で被覆した金属粒子(A)は、通常の方法でも製造することができる。例えば、撥水性有機物の溶液中に金属粒子を浸漬し、金属粒子を取り出して乾燥することにより製造することができる。The flaky metal particles to which the water-repellent organic material is adhered can be produced by adding the water-repellent organic material to a spherical metal particle and grinding it with a ball mill or the like (Japanese Patent Publication No. 40-6971, No. 2000-234107 [0004]).
A rotary drum device (for example, a granular metal particle and a water-repellent organic material such as a higher fatty acid, a higher fatty acid metal salt (excluding an alkali metal salt), a higher fatty acid ester, a higher fatty acid amide) together with ceramic balls. It can be easily processed into a flake shape (scale shape) by putting it into a ball mill) and physically hitting the metal particles with a ball. At this time, water-repellent organic substances such as higher fatty acids, higher fatty acid metal salts (excluding alkali metal salts), higher fatty acid esters, and higher fatty acid amides for improving lubricity adhere to the flaky metal particles. Examples of such higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and linolenic acid, and higher saturated fatty acids are preferred. Examples of such higher saturated fatty acids include lalauric acid, myristic acid, palmitic acid, and stearic acid. The surface of the flaky metal may be covered with more than half of such a higher fatty acid, but it is preferable that the entire surface is covered. Thus, the metal particle by which the metal surface was coat | covered with the water-repellent organic substance shows water repellency. If the amount of the water-repellent organic substance attached is too small, the metal particles tend to separate and settle, and if too much, the sinterability may be reduced. Therefore, the adhesion amount of the water repellent organic material is preferably from 0.01 to 3%, and more preferably from 0.1 to 1%. The adhesion amount of the water repellent organic substance can be measured by a usual method. For example, a method of measuring weight loss by heating above the boiling point of water-repellent organic material in nitrogen gas, carbon in water-repellent organic material attached to metal particles by heating metal particles in an oxygen stream to carbon dioxide gas Instead, a method of quantitative analysis by infrared absorption spectroscopy is exemplified.
The metal particles (A) whose surfaces are coated with a water-repellent organic substance can also be produced by a usual method. For example, it can be produced by immersing metal particles in a solution of a water-repellent organic substance, taking out the metal particles and drying.
揮発性分散媒(B)は、誘電率の異なる揮発性分散媒(B1)と揮発性分散媒(B2)とからなり、かつ、揮発性分散媒(B1)と揮発性分散媒(B2)が，常温において完全には相溶しない比率の混合物である。
完全には相溶しないかどうかは、次の方法で判定できる。
すなわち、ガラス容器内で揮発性分散媒(B1)と揮発性分散媒(B2)を攪拌混合し、泡が消えるまで静置後、目視観察する。二層に分離しているか，または，濁っている場合には、相溶していないと判定できる。混合液が一層であり透明であれば、相溶していると判定できる。
揮発性分散媒(B1)と揮発性分散媒(B2)が相溶して均一な状態であると、ペースト状金属組成物中の金属粒子(A)が分離するため，沈降することを防止できない。揮発性分散媒(B1)と揮発性分散媒(B2)の混合比率は、完全には相溶しなければ良く、その比率は９９：２〜２：９９の範囲内であることが好ましい。
本発明のペースト状金属粒子組成物を、加熱焼結性，あるいは，加熱・超音波振動焼結性の接合剤、接着剤として使用するためには、分散媒は非揮発性ではなく、揮発性であることが必要である。特に、金属粒子(A)が銀粒子の場合、焼結する際に分散媒が揮散すると，銀粒子が焼結しやすくなり，接合剤、接着剤として利用しやすくなるからである。揮発性分散媒の沸点は、６０℃〜３００℃であることが好ましい。沸点が６０℃未満であると、ペースト状金属粒子組成物を調製する作業中に溶媒が揮散しやすく、沸点が３００℃より大であると、加熱後も揮発性分散媒(B)が残留しかねないからである。The volatile dispersion medium (B) is composed of a volatile dispersion medium (B1) and a volatile dispersion medium (B2) having different dielectric constants, and the volatile dispersion medium (B1) and the volatile dispersion medium (B2). , A mixture with a ratio that is not completely compatible at room temperature.
Whether it is not completely compatible can be determined by the following method.
That is, the volatile dispersion medium (B1) and the volatile dispersion medium (B2) are stirred and mixed in a glass container, and left to stand until bubbles disappear, and then visually observed. When separated into two layers or cloudy, it can be determined that they are not compatible. If the mixed solution is one layer and transparent, it can be determined that the mixed solution is compatible.
If the volatile dispersion medium (B1) and the volatile dispersion medium (B2) are mixed and in a uniform state, the metal particles (A) in the paste-like metal composition are separated and cannot be prevented from settling. . The mixing ratio of the volatile dispersion medium (B1) and the volatile dispersion medium (B2) may not be completely compatible, and the ratio is preferably in the range of 99: 2 to 2:99.
In order to use the paste-like metal particle composition of the present invention as a heat-sinterable or heat / ultrasonic vibration-sinterable bonding agent or adhesive, the dispersion medium is not non-volatile but volatile. It is necessary to be. In particular, when the metal particles (A) are silver particles, if the dispersion medium is volatilized during sintering, the silver particles are easily sintered and can be easily used as a bonding agent and an adhesive. The boiling point of the volatile dispersion medium is preferably 60 ° C to 300 ° C. When the boiling point is less than 60 ° C., the solvent easily evaporates during the preparation of the paste-like metal particle composition, and when the boiling point is higher than 300 ° C., the volatile dispersion medium (B) remains even after heating. Because it might be.
そのような揮発性分散媒(B)は、水、炭素原子および水素原子からなる揮発性炭化水素化合物、炭素原子，水素原子および酸素原子からなる揮発性有機化合物、炭素原子，水素原子および窒素原子からなる揮発性有機化合物、炭素原子，水素原子，酸素原子および窒素原子からなる揮発性有機化合物などから選択される。これらはいずれも常温において液状である。
具体的には、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，デシルアルコール等の揮発性一価アルコール、エチレングリコールモノメチルエーテル（メチルセロソルブ，メチルカルビトール），エチレングリコールモノエチルエーテル（エメチルセロソルブ，エチルカルビトール），エチレングリコールモノプロピルエーテル（プロピルセロソルブ，プロピルカルビトール），エチレングリコールモノブチルエーテル（ブチルセロソルブ，ブチルカルビトール），プロピレングリコールモノメチルエーテル，メチルメトキシブタノール等のエーテル結合を有する揮発性一価アルコール、ベンジルアルコール、２−フェニルエチルアルコールなどの揮発性アラルキルアルコール、エチレングリコール，プロピレングリコール，グリセリンなどの揮発性多価脂肪族アルコール、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，メチルイゾブチルケトン，シクロヘキサノン，ジアセトンアルコール（４−ヒドロキシ−４−メチル−２−ペンタノン），２−オクタノン，イソホロン（３，５，５−トリメチル−２−シクロヘキセン−１−オン），ジイブチルケトン（２，６−ジメチル−４−ヘプタノン）等の揮発性脂肪族ケトン、酢酸エチル（エチルアセテート），酢酸ブチル，アセトキシエタン，酪酸メチル，ヘキサン酸メチル，オクタン酸メチル，デカン酸メチル，メチルセロソルブアセテート，プロピレングリコールモノメチルエーテルアセテートのような揮発性脂肪族カルボン酸エステル、テトラヒドロフラン，ジプロピルエーテル，エチレングリコールジメチルエーテル，エチレングリコールジエチルエーテル，エチレングリコールジブチルエーテル，プロピレングリコールジメチルエーテル，エトキシエチルエーテル等の揮発性脂肪族エーテル、低分子量の揮発性シリコーンオイルおよび揮発性有機変成シリコーンオイル、アセトアミド，N,N-ジメチルホルムアミドのような揮発性カルボン酸アミド、メチルアミン，エチルアミン，プロピルアミン，エチレンジアミンのような揮発性１級脂肪族アミン，ジメチルアミン，ジエチルアミンのような揮発性２級脂肪族アミン，トリメチルアミン，トリエチルアミンのような揮発性３級脂肪族アミン，その他の揮発性脂肪族アミン、アセトニトリル，プロピオニトリルのような揮発性アルキルニトリルが例示される。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，蒸留法が例示される。Such a volatile dispersion medium (B) includes water, volatile hydrocarbon compounds composed of carbon atoms and hydrogen atoms, volatile organic compounds composed of carbon atoms, hydrogen atoms and oxygen atoms, carbon atoms, hydrogen atoms and nitrogen atoms. Selected from the group consisting of volatile organic compounds consisting of carbon atoms, hydrogen atoms, oxygen atoms and nitrogen atoms. These are all liquid at room temperature.
Specifically, volatile monohydric alcohols such as water, ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, ethylene glycol monomethyl ether (methyl cellosolve, methyl Carbitol), ethylene glycol monoethyl ether (Emethyl cellosolve, ethyl carbitol), ethylene glycol monopropyl ether (propyl cellosolve, propyl carbitol), ethylene glycol monobutyl ether (butyl cellosolve, butyl carbitol), propylene glycol monomethyl ether, Volatile monohydric alcohol having an ether bond such as methylmethoxybutanol, benzyl alcohol, 2- Volatile aralkyl alcohols such as phenylethyl alcohol, volatile polyhydric aliphatic alcohols such as ethylene glycol, propylene glycol and glycerin, volatile aliphatic hydrocarbons such as lower n-paraffins and lower isoparaffins, and volatility such as toluene and xylene Aromatic hydrocarbon, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), 2-octanone, isophorone (3,5,5-trimethyl-2-cyclohexene -1-one), di-butyl ketone (2,6-dimethyl-4-heptanone), volatile aliphatic ketones, ethyl acetate (ethyl acetate), butyl acetate, acetoxyethane, methyl butyrate, methyl hexanoate, octanoic acid Methyl, deca Volatile aliphatic carboxylic acid esters such as methyl acid, methyl cellosolve acetate, propylene glycol monomethyl ether acetate, tetrahydrofuran, dipropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, ethoxyethyl ether Of volatile aliphatic ethers such as low molecular weight volatile silicone oil and volatile organic modified silicone oil, volatile carboxylic acid amides such as acetamide, N, N-dimethylformamide, methylamine, ethylamine, propylamine, ethylenediamine Volatile primary aliphatic amines such as dimethylamine, volatile secondary aliphatic amines such as diethylamine, trimethylamine Emissions, volatile tertiary aliphatic amines such as triethylamine, other volatile aliphatic amines, acetonitrile, volatile alkyl nitrites such as propionitrile and the like. The water is preferably pure water, and its electric conductivity is preferably 100 μS / cm or less, more preferably 10 μS / cm or less. The pure water production method may be a normal method, and examples include an ion exchange method, a reverse osmosis method, and a distillation method.
揮発性分散媒(B1)と揮発性分散媒(B2)は、上記揮発性分散媒(B)から、２５℃における誘電率の差が２以上になるようなものを選択する必要があり、好ましくは３以上，より好ましくは５以上になるようなものを選択する。
揮発性分散媒(B1)として、２５℃における誘電率の高い、水，揮発性１価アルコール，揮発性多価アルコール，揮発性アラルキルアルコール，N,N-ジメチルホルムアミド，揮発性脂肪族アミン，揮発性脂肪族エーテル，揮発性脂肪族カルボン酸エステルまたは揮発性脂肪族ケトンを選択すること、揮発性分散媒(B2)として、２５℃における誘電率が揮発性分散媒(B1)より２以上小さい，好ましくは３以上小さい，より好ましくは５以上小さい揮発性脂肪族エーテル，揮発性脂肪族カルボン酸エステル，揮発性脂肪族ケトン，揮発性脂肪族炭化水素，揮発性芳香族炭化水素または揮発性シリコーンオイルを選択することが好ましい。この際、揮発性分散媒(B1)と揮発性分散媒(B2)は、２５℃における誘電率の差が２以上，好ましくは３以上，より好ましくは５以上であれば、同種の有機化合物であってもよい。
揮発性分散媒(B1)と揮発性分散媒(B2)の２５℃における誘電率の差が２未満であると、両揮発性分散媒同士の相溶性が高くなり、ペースト状金属粒子組成物における金属粒子(A)の分離，沈降が防止できにくくなるからである。
２５℃における誘電率の差が２以上，好ましくは３以上，より好ましくは５以上であっても、選択した揮発性分散媒(B1)と揮発性分散媒(B2)とが、ある程度相溶するが、完全には相溶しないことが必要である。また、金属粒子(A)と配合する際に、揮発性分散媒(B1)と揮発性分散媒(B2)は、ある程度相溶するが，完全には相溶しないような混合比率であることが必要である。
なお、揮発性分散媒は(B1)、(B2)ともに２種類以上を併用しても良いが、(B1)と(B2)の混合時に相溶しない混合比率であることが必要である。The volatile dispersion medium (B1) and the volatile dispersion medium (B2) must be selected from the above volatile dispersion medium (B) so that the difference in dielectric constant at 25 ° C. is 2 or more. Is selected to be 3 or more, more preferably 5 or more.
As a volatile dispersion medium (B1), water, volatile monohydric alcohol, volatile polyhydric alcohol, volatile aralkyl alcohol, N, N-dimethylformamide, volatile aliphatic amine, volatile, having a high dielectric constant at 25 ° C Volatile aliphatic ether, volatile aliphatic carboxylic acid ester or volatile aliphatic ketone, and, as volatile dispersion medium (B2), the dielectric constant at 25 ° C. is 2 or more smaller than that of volatile dispersion medium (B1). Preferably volatile aliphatic ethers, volatile aliphatic carboxylic esters, volatile aliphatic ketones, volatile aliphatic hydrocarbons, volatile aromatic hydrocarbons or volatile silicone oils, preferably 3 or smaller, more preferably 5 or smaller Is preferably selected. At this time, the volatile dispersion medium (B1) and the volatile dispersion medium (B2) are organic compounds of the same type as long as the difference in dielectric constant at 25 ° C. is 2 or more, preferably 3 or more, more preferably 5 or more. There may be.
When the difference in dielectric constant at 25 ° C. between the volatile dispersion medium (B1) and the volatile dispersion medium (B2) is less than 2, the compatibility between the two volatile dispersion media increases, and the paste-like metal particle composition This is because it becomes difficult to prevent separation and sedimentation of the metal particles (A).
Even if the difference in dielectric constant at 25 ° C is 2 or more, preferably 3 or more, more preferably 5 or more, the selected volatile dispersion medium (B1) and volatile dispersion medium (B2) are compatible to some extent. However, it is necessary that they are not completely compatible. In addition, when blended with the metal particles (A), the volatile dispersion medium (B1) and the volatile dispersion medium (B2) have a mixing ratio that is compatible to some extent but not completely compatible. is necessary.
Two or more kinds of volatile dispersion media (B1) and (B2) may be used in combination, but it is necessary that the mixing ratio is incompatible with the mixing of (B1) and (B2).
揮発性分散媒(B)の配合量、すなわち、揮発性分散媒(B1)と揮発性分散媒(B2)の合計配合量は、金属粒子(A)１００重量部当たり３〜３０重量部であり、金属粒子(A)を常温においてペースト状にするのに十分な量である。本発明のペースト状金属粒子組成物には、本発明の目的に反しない限り、金属粒子(A)以外の非金属系の粉体，金属化合物，金属錯体，チクソ剤，安定剤，着色剤等の添加物を少量ないし微量含有しても良い。 The blending amount of the volatile dispersion medium (B), that is, the total blending amount of the volatile dispersion medium (B1) and the volatile dispersion medium (B2) is 3 to 30 parts by weight per 100 parts by weight of the metal particles (A). The amount is sufficient to make the metal particles (A) paste at room temperature. The paste-like metal particle composition of the present invention includes a non-metallic powder other than the metal particles (A), a metal compound, a metal complex, a thixotropic agent, a stabilizer, a coloring agent, etc. These additives may be contained in a small amount or a trace amount.
本発明のペースト状金属粒子組成物は、(A)平均粒径０.００１〜５０μｍであり，その表面が撥水性有機物で被覆された金属粒子１００重量部と，(B)揮発性分散媒３〜３０重量部を，ミキサーに投入し、均一になるまで撹拌混合することにより、容易に製造することができる。揮発性分散媒(B1)と揮発性分散媒(B2)は、予め混合して，ある程度相溶しているが，完全には相溶しない状態で、金属粒子(A)と混合しても良い。あるいは、揮発性分散媒(B1)と揮発性分散媒（B2）を別々に混合しても良い。
The paste-like metal particle composition of the present invention has (A) an average particle diameter of 0.001 to 50 μm, and 100 parts by weight of metal particles whose surface is coated with a water-repellent organic substance, and (B) a
本発明のペースト状金属粒子組成物は、金属粒子(A)と揮発性分散媒(B)との混合物であり、常温でペースト状である。なお、ペースト状はクリーム状を含む。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でき、また、メタルマスクによる印刷塗布が容易である。 The paste-like metal particle composition of the present invention is a mixture of metal particles (A) and a volatile dispersion medium (B) and is paste-like at room temperature. The paste form includes a cream form. By making it into a paste, it can be discharged in a thin line from a cylinder or nozzle, and printing with a metal mask is easy.
本発明の別の実施態様であるペースト状金属粒子組成物は、(A)平均粒径０.００１〜５０μｍであり，その表面が撥水性有機物で被覆された金属粒子１００重量部と、(C)２５℃における誘電率が３０〜７５である揮発性分散媒３〜３０重量部とからなることを特徴とする。金属粒子(A)が撥水性有機物で被覆されているので、誘電率が３０〜７５である揮発性分散媒との併用により、分離・沈降が抑制されている。金属粒子が撥水性有機物で被覆されていないと、揮発性分散媒(C)と併用しても、分離・沈降を抑制できない。
金属粒子(A)は、前述したとおりである。
揮発性分散媒(C)は、炭素原子，水素原子および酸素原子からなる揮発性有機化合物、炭素原子，水素原子および窒素原子からなる揮発性有機化合物、炭素原子，水素原子，酸素原子および窒素原子からなる揮発性有機化合物などから、２５℃における誘電率が３０〜７５であるものを選択することにより得られる。具体的には、２５℃における誘電率が３０〜７５である揮発性一価アルコール，揮発性多価アルコール，揮発性低級脂肪族カルボン酸アミド，揮発性アルキルニトリル，および，揮発性アルコール（例えば、揮発性一価アルコール，揮発性多価アルコール）の水溶液から選択される。
そのような揮発性分散媒(C)として、メチルアルコール等の揮発性一価低級アルコール、揮発性一価低級アルコール（例えば、エチルアルコール）の水溶液、エチレングリコール，プロピレングリコール，グリセリンなどの揮発性多価アルコール、アセトアミド，ジメチルホルムアミドなどの揮発性低級脂肪族カルボン酸アミド、アセトニトリル，プロピオニトリルのような揮発性アルキルニトリルが例示される。これらのうちでは、誘電率が３０〜７０である多価アルコールが好ましい。なお、分散媒は２種類以上を併用しても、その混合物の２５℃における誘電率が３０〜７５であれば良い。The paste-like metal particle composition according to another embodiment of the present invention comprises (A) 100 parts by weight of metal particles having an average particle diameter of 0.001 to 50 μm and the surface thereof coated with a water-repellent organic substance, (C And 3 to 30 parts by weight of a volatile dispersion medium having a dielectric constant at 25 ° C. of 30 to 75. Since the metal particles (A) are coated with a water-repellent organic substance, separation / sedimentation is suppressed by the combined use with a volatile dispersion medium having a dielectric constant of 30 to 75. If the metal particles are not coated with a water-repellent organic substance, separation / sedimentation cannot be suppressed even when used in combination with the volatile dispersion medium (C).
The metal particles (A) are as described above.
Volatile dispersion media (C) are volatile organic compounds composed of carbon atoms, hydrogen atoms and oxygen atoms, volatile organic compounds composed of carbon atoms, hydrogen atoms and nitrogen atoms, carbon atoms, hydrogen atoms, oxygen atoms and nitrogen atoms. It is obtained by selecting those having a dielectric constant at 25 ° C. of 30 to 75 from volatile organic compounds consisting of Specifically, volatile monohydric alcohol, volatile polyhydric alcohol, volatile lower aliphatic carboxylic acid amide, volatile alkyl nitrile having a dielectric constant at 25 ° C. of 30 to 75, and volatile alcohol (for example, Selected from aqueous solutions of volatile monohydric alcohols and volatile polyhydric alcohols.
Examples of such a volatile dispersion medium (C) include volatile monohydric lower alcohols such as methyl alcohol, aqueous solutions of volatile monohydric lower alcohols (for example, ethyl alcohol), volatile polymers such as ethylene glycol, propylene glycol, and glycerin. Examples thereof include volatile lower aliphatic carboxylic acid amides such as monohydric alcohol, acetamide and dimethylformamide, and volatile alkyl nitriles such as acetonitrile and propionitrile. Of these, polyhydric alcohols having a dielectric constant of 30 to 70 are preferred. In addition, even if it uses 2 or more types of dispersion media together, the dielectric constant in 25 degreeC of the mixture should just be 30-75.
揮発性分散媒(C)の配合量は、金属粒子(A)１００重量部当たり３〜３０重量部であり、金属粒子(A)をペースト状にするのに十分な量である。本発明の上記ペースト状金属粒子組成物は、本発明の目的に反しない限り、金属粒子以外の非金属系の粉体，金属化合物，金属錯体，チクソ剤，安定剤，着色剤等の添加物を少量ないし微量含有しても良い。 The compounding amount of the volatile dispersion medium (C) is 3 to 30 parts by weight per 100 parts by weight of the metal particles (A), which is sufficient to make the metal particles (A) into a paste form. The paste-like metal particle composition of the present invention is an additive such as a non-metallic powder other than metal particles, a metal compound, a metal complex, a thixotropic agent, a stabilizer, a colorant, etc. May be contained in small or trace amounts.
本発明の上記ペースト状金属粒子組成物は、(A)平均粒径０.００１〜５０μｍであり，その表面が撥水性有機物で被覆された金属粒子１００重量部と、(C)揮発性分散媒３〜３０重量部をミキサーに投入し、均一になるまで撹拌混合することにより、容易に製造することができる。 The paste-like metal particle composition of the present invention comprises (A) 100 parts by weight of metal particles having an average particle diameter of 0.001 to 50 μm and the surface coated with a water-repellent organic substance, and (C) a volatile dispersion medium. It can manufacture easily by throwing 3-30 weight part into a mixer and stirring and mixing until it becomes uniform.
本発明の上記ペースト状金属粒子組成物は、金属粒子(A)と揮発性分散媒(C)との混合物であり、常温でペースト状である。なお、ペースト状はクリーム状も含む。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でき、また、メタルマスクによる印刷塗布が容易である。 The paste-like metal particle composition of the present invention is a mixture of metal particles (A) and a volatile dispersion medium (C), and is paste-like at room temperature. The paste form includes a cream form. By making it into a paste, it can be discharged in a thin line from a cylinder or nozzle, and printing with a metal mask is easy.
本発明の上記２種のペースト状金属粒子組成物は、加熱することにより揮発性分散媒が揮散する。本発明の上記２種のペースト状金属粒子組成物は、金属粒子の焼結温度以上の温度に加熱することにより、あるいは、加圧しつつ超音波振動を印加することにより、特には加圧，加熱しつつ超音波振動を印加することにより、揮発性分散媒(B)もしくは揮発性分散媒(C)が揮散して，該金属粒子同士(A)が焼結し、強度と導電性と熱伝導性が優れた固形状の金属となる。ペースト状金属粒子組成物の加熱時に圧力を加えても良い。この際、揮発性分散媒(B)もしくは揮発性分散媒(C)が揮散し、ついで金属粒子(A)同士が焼結してもよく、揮発性分散媒(B)もしくは揮発性分散媒(C)の揮散と共に金属粒子(A)同士が焼結してもよい。特に金属粒子(A)が銀粒子の場合は、銀が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(B)もしくは揮発性分散媒(C)が揮散し、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℃以上がより好ましい。しかし、４００℃を越えると揮発性分散媒が突沸的に蒸発して、固形状金属の形状に悪影響が出る可能性があるため、４００℃以下であることが必要であり、より好ましくは３００℃以下である。加熱だけでは、焼結しにくい金属粒子(A)も、加圧しつつ超音波振動を印加することにより、あるいは加圧，加熱しつつ超音波振動を印加することにより、よく焼結する。 The two types of paste-like metal particle compositions of the present invention volatilize the volatile dispersion medium when heated. The above two types of paste-like metal particle compositions of the present invention are particularly pressurized and heated by heating to a temperature equal to or higher than the sintering temperature of the metal particles, or by applying ultrasonic vibration while applying pressure. However, by applying ultrasonic vibration, the volatile dispersion medium (B) or volatile dispersion medium (C) is volatilized, and the metal particles (A) sinter together, resulting in strength, conductivity and heat conduction. It becomes a solid metal with excellent properties. Pressure may be applied during the heating of the paste-like metal particle composition. At this time, the volatile dispersion medium (B) or the volatile dispersion medium (C) is volatilized, and then the metal particles (A) may be sintered together.The volatile dispersion medium (B) or the volatile dispersion medium ( The metal particles (A) may be sintered together with the volatilization of C). In particular, when the metal particles (A) are silver particles, since silver has inherently high strength and extremely high electrical and thermal conductivity, the sintered product of the silver particles of the present invention also has high strength and extremely high electrical conductivity. Conductive and thermal conductivity. The heating temperature at this time may be a temperature at which the volatile dispersion medium (B) or the volatile dispersion medium (C) can be volatilized and the silver particles can be sintered, and is usually 100 ° C. or higher, more preferably 150 ° C. or higher. preferable. However, if the temperature exceeds 400 ° C., the volatile dispersion medium may suddenly evaporate and the shape of the solid metal may be adversely affected. Therefore, the temperature must be 400 ° C. or less, more preferably 300 ° C. It is as follows. Metal particles (A) that are difficult to sinter by heating alone are also well sintered by applying ultrasonic vibration while applying pressure, or applying ultrasonic vibration while applying pressure and heating.
超音波振動の周波数は、２ｋＨｚ以上であり，１０ｋＨｚ以上であることが好ましい。その上限は特に制限されないが、装置の能力上５００ｋＨｚ位である。また、超音波振動の振幅は焼結性に影響するので、好ましくは０．１〜４０μｍ，より好ましくは０．３〜２０μｍ，さらに好ましくは０．５〜１２μｍである。なお、超音波振動がペースト状金属粒子組成物に確実に伝わるようにするため、ペースト状金属粒子組成物に直接超音波振動の発信部分を押し当てることが好ましい。あるいは、超音波振動を吸収しにくい素材からなるカバー材等を介して，超音波振動の発信部分を押し当てることが好ましい。ペースト状金属粒子組成物への押当て圧力は、好ましくは０.９ｋＰａ（０.０９ｇｆ／ｍｍ２）以上，より好ましくは９ｋＰａ（０.９２ｇｆ／ｍｍ２）以上，さらに好ましくは３９ｋＰａ（３.９８ｇｆ／ｍｍ２）以上である。押当て圧力の上限は、接合する部材が破壊されない圧力の最大値である。
加圧，加熱しつつ超音波振動を印加して焼結する場合の加熱温度は、常温より高く、揮発性分散媒(B)もしくは揮発性分散媒(C)が揮散し金属粒子(A)が焼結できる温度であればよい。しかし、加熱温度が４００℃を越えると、揮発性分散媒(B)もしくは揮発性分散媒(C)が突沸的に蒸発して、固形状金属の形状に悪影響が出る恐れがあるため、４００℃以下，かつ該金属粒子(A)の融点未満の温度であることが好ましく、３００℃以下であることがより好ましい。The frequency of the ultrasonic vibration is 2 kHz or more, and preferably 10 kHz or more. The upper limit is not particularly limited, but is about 500 kHz due to the capability of the apparatus. Moreover, since the amplitude of ultrasonic vibration influences sinterability, it is preferably 0.1 to 40 μm, more preferably 0.3 to 20 μm, and still more preferably 0.5 to 12 μm. In order to ensure that the ultrasonic vibration is transmitted to the paste-like metal particle composition, it is preferable to directly press the transmitting portion of the ultrasonic vibration against the paste-like metal particle composition. Alternatively, it is preferable to press the transmitting portion of the ultrasonic vibration through a cover material made of a material that hardly absorbs the ultrasonic vibration. The pressing pressure to the paste-like metal particle composition is preferably 0.9 kPa (0.09 gf / mm 2 ) or more, more preferably 9 kPa (0.92 gf / mm 2 ) or more, and further preferably 39 kPa (3.98 gf). / Mm 2 ) or more. The upper limit of the pressing pressure is the maximum pressure at which the members to be joined are not destroyed.
When sintering by applying ultrasonic vibration while applying pressure and heating, the heating temperature is higher than normal temperature, the volatile dispersion medium (B) or volatile dispersion medium (C) is volatilized, and the metal particles (A) Any temperature that can be sintered is acceptable. However, if the heating temperature exceeds 400 ° C., the volatile dispersion medium (B) or the volatile dispersion medium (C) may suddenly evaporate, which may adversely affect the shape of the solid metal. The temperature is preferably lower than the melting point of the metal particles (A), more preferably 300 ° C. or lower.
該金属粒子(A)が焼結してできた固形状金属の形状は特に限定されず、シート状、フィルム状、テープ状、線状、円盤状、ブロック状、スポット状、不定形状が例示される。 The shape of the solid metal formed by sintering the metal particles (A) is not particularly limited, and examples thereof include a sheet shape, a film shape, a tape shape, a linear shape, a disk shape, a block shape, a spot shape, and an indefinite shape. The
本発明の上記２種のペースト状金属粒子組成物は、加熱により、加圧しつつ超音波振動印加により、あるいは加圧，加熱しつつ超音波振動印加により、揮発性分散媒(B)もしくは揮発性分散媒(C)が揮散し，金属粒子が焼結する。焼結してできた固形状金属は、強度と電気伝導性，熱伝導性が優れ、接触していた金属製部材，例えば金メッキ基板，銀基板，銀メッキ金属基板，銅基板，アルミニウム基板，ニッケルメッキ基板，スズメッキ金属基板等の金属系基板への接着性、電気絶縁性基板上の電極等金属部分への接着性を有するので、金属系基板や金属部分を有する電子部品，電子装置，電気部品，電気装置等の接合に有用である。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。 The two types of paste-like metal particle compositions of the present invention can be produced by applying ultrasonic vibration while applying pressure by heating, or by applying ultrasonic vibration while applying pressure or heating. The dispersion medium (C) is volatilized and the metal particles are sintered. Solid metal made by sintering has excellent strength, electrical conductivity, and thermal conductivity, and metal parts that have been in contact, such as gold-plated substrate, silver substrate, silver-plated metal substrate, copper substrate, aluminum substrate, nickel Adhesiveness to metal substrates such as plated substrates and tin-plated metal substrates, and adhesion to metal parts such as electrodes on electrically insulating substrates. Therefore, electronic components, electronic devices and electrical components having metal substrates and metal portions This is useful for joining electrical devices. Such bonding includes bonding of chip components such as capacitors and resistors to 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.
本発明の上記２種のペースト状金属粒子組成物を焼結した後は、分散媒が残存しないので洗浄は不要であるが、水や有機溶媒で洗浄してもよい。 After sintering the above two types of paste-like metal particle compositions of the present invention, no dispersion medium remains, so no washing is required, but washing with water or an organic solvent may be used.
本発明の上記２種のペースト状金属粒子組成物は、揮発性分散媒(B)もしくは揮発性分散媒(C)を含有するので、密閉容器に保存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１０℃以下が例示される。 Since the two types of paste-like metal particle compositions of the present invention contain a volatile dispersion medium (B) or a volatile dispersion medium (C), they are preferably stored in a sealed container. Refrigerated storage may be performed for the purpose of improving storage stability, and the storage temperature is 10 ° 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、部と記載されているのは、重量部を意味する。金属粒子中の撥水性有機物量の測定方法、揮発性分散媒の誘電率の測定方法、ペースト状金属粒子組成物の保管中における金属粒子と揮発性分散媒の分離性の測定方法、および、ペースト状金属粒子組成物を加熱または超音波熱圧着して焼結することにより生成した固形状金属の接着強度は、下記の方法により測定した。なお、特に記載のない場合の温度は２５℃である。 Examples and comparative examples of the present invention will be given. In the examples and comparative examples, “parts” means “parts by weight”. Method for measuring amount of water-repellent organic substance in metal particle, method for measuring dielectric constant of volatile dispersion medium, method for measuring separation property of metal particle and volatile dispersion medium during storage of paste-like metal particle composition, and paste The adhesion strength of a solid metal produced by heating or sintering a metal particle composition by heating or ultrasonic thermocompression bonding was measured by the following method. Note that the temperature is 25 ° C. unless otherwise specified.
［撥水性有機物量］
ＴＧＡ法により以下のように測定した。金属粒子を窒素気流中で１０℃／分の割合で５００℃まで昇温し、そのまま５００℃で１時間保持した。[加熱前の重量−加熱後の重量]/[加熱前の重量]x１００＝撥水性有機物量（単位％）とした。[Water repellent organic content]
Measurement was performed by the TGA method as follows. The metal particles were heated to 500 ° C. at a rate of 10 ° C./min in a nitrogen stream and held at 500 ° C. for 1 hour. [Weight before heating−Weight after heating] / [Weight before heating] × 100 = Amount of water repellent organic substance (unit%).
［誘電率］
液体誘電率測定装置（Ｓｃｉｅｎｔｉｆｉｃａ社製、モデル８７０）により測定した。[Dielectric constant]
It measured with the liquid dielectric constant measuring apparatus (Scientificica company make, model 870).
［金属粒子と揮発性分散媒の分離性］
ペースト状金属粒子組成物１を、先端キャップ２を装着したシリンジ３（内径１２ｍｍ、長さ５５ｍｍ、内容積５ｃｃ、ＥＦＤ社製）に、シリンジ３の先端部を下向きにして３０ｍｍの高さまで入れた後、プランジャー４を装着し、最後にエンドキャップ５を装着して密閉した。シリンジ３の先端部を下向きにして垂直に保持して２４時間静置した。シリンジ３内のペースト状金属粒子組成物１の上部に分離した揮発性分散媒層の厚さ（ｍｍ）を測定した。[Separability of metal particles and volatile dispersion media]
The paste-like metal particle composition 1 was placed in a syringe 3 (inner diameter: 12 mm, length: 55 mm, internal volume: 5 cc, manufactured by EFD) with a
［接着強度Ａ］
幅２５ｍｍ×長さ７５ｍｍ×厚さ１ｍｍの銀メッキ銅板に、１００μｍ厚のメタルマスクを用いて、ペースト状金属粒子組成物を塗布し(塗布面積：５ｍｍ×５ｍｍ)、その上に幅５ｍｍ×長さ５ｍｍ×厚さ０.５ｍｍの銀製チップを搭載後、強制循環式オーブン内で２００℃で１時間加熱することにより、銀製チップを銀メッキ銅板に接着させた。かくして得られた接着強度測定用試験体をダイシェア強度測定試験機に取付け、銀製チップの側面を、ダイシェア強度測定試験機のダイシェアツールにより、速度２３ｍｍ／分で押圧した。銀製チップと銀メッキ銅板間の接合部がせん断破壊したときの荷重をもって、接着強度（単位；ｋｇｆ）とした。なお、接着強度試験は３回であり、その平均値を接着強度Ａとした。
［接着強度Ｂ］
幅２５ｍｍ×長さ７５ｍｍ×厚さ１ｍｍの銀メッキ銅板に、１００μｍ厚のメタルマスクを用いて、ペースト状金属粒子組成物を塗布し(塗布面積：５ｍｍ×５ｍｍ)、その上に幅５ｍｍ×長さ５ｍｍ×厚さ０.５ｍｍの銀製チップを搭載して接着強度測定用前躯体を作った。接着強度測定用前躯体を超音波熱圧着装置に取付け、超音波振動の周波数３０ｋＨｚ、超音波振動の振幅４μｍ、押当て圧力１００Ｎ／ｃｍ２という条件で、超音波熱圧着装置の圧着部（プローブ）を上方から該接着強度測定用前躯体の銀製チップの上部に押し当てて、超音波振動を印加しながら２００℃の温度で３０秒間圧着した。かくして得られた接着強度測定用試験体をダイシェア強度測定試験機に取付け、銀製チップの側面をダイシェア強度測定試験機のダイシェアツールにより速度２３ｍｍ／分で押圧し、銀製チップと銀メッキ銅板間の接合部がせん断破壊したときの荷重をもって接着強度（単位；ｋｇｆ）とした。なお、接着強度試験は３回であり、その平均値を接着強度Ｂとした。[Adhesive strength A]
A paste-like metal particle composition was applied to a silver-plated copper plate having a width of 25 mm × a length of 75 mm × a thickness of 1 mm using a 100 μm-thick metal mask (application area: 5 mm × 5 mm), and a width of 5 mm × length After mounting a silver chip having a thickness of 5 mm and a thickness of 0.5 mm, the silver chip was adhered to a silver-plated copper plate by heating at 200 ° C. for 1 hour in a forced circulation oven. The test body for measuring the adhesive strength thus obtained was attached to a die shear strength measurement tester, and the side surface of the silver chip was pressed at a speed of 23 mm / min by a die shear tool of the die shear strength measurement tester. The load when the joint between the silver chip and the silver-plated copper plate was subjected to shear failure was defined as the adhesive strength (unit: kgf). The adhesive strength test was performed three times, and the average value was defined as adhesive strength A.
[Adhesive strength B]
A paste-like metal particle composition was applied to a silver-plated copper plate having a width of 25 mm × a length of 75 mm × a thickness of 1 mm using a 100 μm-thick metal mask (application area: 5 mm × 5 mm), and a width of 5 mm × length A silver chip having a thickness of 5 mm and a thickness of 0.5 mm was mounted to prepare a precursor for measuring adhesive strength. An adhesive strength measurement precursor is attached to an ultrasonic thermocompression bonding device, and the ultrasonic thermocompression bonding device (probe) is operated under the conditions of an ultrasonic vibration frequency of 30 kHz, an ultrasonic vibration amplitude of 4 μm, and a pressing pressure of 100 N / cm 2. ) From above and pressed against the upper part of the silver chip of the precursor for adhesive strength measurement, and crimped for 30 seconds at a temperature of 200 ° C. while applying ultrasonic vibration. The test specimen for measuring the adhesive strength thus obtained was attached to a die shear strength measurement tester, the side of the silver chip was pressed at a speed of 23 mm / min with the die shear tool of the die shear strength measurement tester, and between the silver tip and the silver plated copper plate The adhesive strength (unit: kgf) was defined as the load when the joint was sheared. The adhesive strength test was performed three times, and the average value was defined as adhesive strength B.
[実施例１]
市販の，還元法で製造された銀粒子をフレーク化することにより作られた，１次粒子の平均粒径が３.０μｍ（レーザー回折法により測定）であるフレーク状の銀粒子（０.５重量％のステアリン酸で銀表面が被覆されており、この銀粒子は撥水性を有する）１００部に、揮発性分散媒(B1)としてベンジルアルコール（和光純薬工業株式会社発売の試薬、誘電率１３.０）１２部、および、揮発性分散媒(B2)として１−ヘキサン（和光純薬工業株式会社発売の試薬、誘電率２.０）３部を添加し、ヘラを用いて均一に混合することにより、ペースト状銀粒子組成物を調製した。揮発性分散媒(B1)としてのベンジルアルコール１２部と揮発性分散媒(B2)としての１−ヘキサン３部の混合物は、相溶しない比率である。両者を攪拌，混合すると白濁し、静置するとすぐに２層に分離した。
このペースト状銀粒子組成物は、シリンジ内において銀粒子と揮発性分散媒の分離が認められなかった。このペースト状銀粒子組成物の接着強度を測定し、結果を表１にまとめて示した。以上の結果より、このペースト状銀粒子組成物は、銀粒子と揮発性分散媒の分離がなく、保存安定性に優れており、金属製部材を強固に接合するのに有用なことがわかる。[Example 1]
Flaked silver particles (0.5 by the average particle diameter of primary particles made by flaking commercially available silver particles produced by a reduction method having a primary particle size of 3.0 μm (measured by laser diffraction method)) Silver surface is coated with 100% by weight of stearic acid, and the silver particles have water repellency. Benzyl alcohol (a reagent sold by Wako Pure Chemical Industries, Ltd., dielectric constant) as a volatile dispersion medium (B1) 13.0) 12 parts, and 3 parts of 1-hexane (a reagent sold by Wako Pure Chemical Industries, Ltd., dielectric constant 2.0) as a volatile dispersion medium (B2) are added and mixed uniformly using a spatula. By doing so, a paste-like silver particle composition was prepared. A mixture of 12 parts of benzyl alcohol as the volatile dispersion medium (B1) and 3 parts of 1-hexane as the volatile dispersion medium (B2) is in an incompatible ratio. When both were stirred and mixed, it became cloudy, and upon standing, it separated into two layers.
In this paste-like silver particle composition, separation of the silver particles and the volatile dispersion medium was not observed in the syringe. The adhesive strength of this pasty silver particle composition was measured, and the results are summarized in Table 1. From the above results, it can be seen that this pasty silver particle composition has no separation between the silver particles and the volatile dispersion medium, has excellent storage stability, and is useful for firmly joining metal members.
[実施例２]
実施例１において、銀粒子の代わりに、市販の，銅粒子をフレーク化することにより作られた，１次粒子の平均粒径が４.０μｍ（レーザー回折法により測定）であるフレーク状の銅粒子（０.５重量％のステアリン酸で銅表面が被覆されており、この銅粒子は撥水性を有する）を用いた以外は、実施例１と同様にして、ペースト状銅粒子組成物を調製した。このペースト状銅粒子組成物は、シリンジ内において銅粒子と揮発性分散媒の分離が認められなかった。結果を表１にまとめて示した。
以上の結果より、このペースト状銅粒子組成物は、銅粒子と揮発性分散媒の分離がなく、長時間の保存安定性が優れていることがわかる。[Example 2]
In Example 1, instead of silver particles, a flaky copper having an average primary particle size of 4.0 μm (measured by laser diffraction method) made by flaking commercially available copper particles. A paste-like copper particle composition was prepared in the same manner as in Example 1 except that the particles (the copper surface was coated with 0.5% by weight of stearic acid, which has water repellency) were used. did. In this paste-like copper particle composition, separation of the copper particles and the volatile dispersion medium was not observed in the syringe. The results are summarized in Table 1.
From the above results, it can be seen that this pasty copper particle composition has no separation of copper particles and volatile dispersion medium and is excellent in long-term storage stability.
[実施例３]
市販の，ニッケル粒子をフレーク化することにより作られた，１次粒子の平均粒径が６.０μｍ（レーザー回折法により測定）であるフレーク状のニッケル粒子（０.８重量％のオレイン酸でニッケル表面が被覆されており、このニッケル粒子は撥水性を有する）１００部に、揮発性分散媒(B1)としてＮ，Ｎ−ジメチルホルムアミド（和光純薬工業株式会社発売の試薬、誘電率３８.０）１２部、および、揮発性分散媒(B2)として１−ヘキサン（（和光純薬工業株式会社発売の試薬、誘電率２.０）３部を添加し、ヘラを用いて均一に混合することにより、ペースト状ニッケル粒子組成物を調製した。揮発性分散媒(B1)としてのＮ，Ｎ−ジメチルホルムアミド１２部と揮発性分散媒(B2)としての１−ヘキサン３部の混合物は、相溶しない比率である。両者を攪拌混合すると白濁し、静置するとすぐに２層に分離した。
このペースト状ニッケル粒子組成物は、シリンジ内においてニッケル粒子と揮発性分散媒の分離が認められなかった。結果を表１にまとめて示した。以上の結果より、このペースト状ニッケル粒子組成物は、ニッケル粒子と揮発性分散媒の分離がなく、長時間の保存安定性が優れていることがわかる。[Example 3]
Commercially available flake nickel particles made by flaking nickel particles with an average primary particle size of 6.0 μm (measured by laser diffraction method) (0.8% by weight oleic acid) The nickel surface is coated, and the nickel particles have water repellency. 100 parts of N, N-dimethylformamide (a reagent sold by Wako Pure Chemical Industries, Ltd., dielectric constant 38. 0) 12 parts and 3 parts of 1-hexane (a reagent sold by Wako Pure Chemical Industries, Ltd., dielectric constant 2.0) as a volatile dispersion medium (B2) are added and mixed uniformly using a spatula. A mixture of 12 parts of N, N-dimethylformamide as the volatile dispersion medium (B1) and 3 parts of 1-hexane as the volatile dispersion medium (B2) was prepared as a paste-like nickel particle composition. It is a ratio that does not melt. When the mixture was stirred and mixed, it became cloudy, and upon standing, it separated into two layers.
In this paste-like nickel particle composition, separation of the nickel particles and the volatile dispersion medium was not observed in the syringe. The results are summarized in Table 1. From the above results, it can be seen that this paste-like nickel particle composition is excellent in long-term storage stability without separation of nickel particles and volatile dispersion medium.
[実施例４]
市販の，還元法で製造された銀粒子をフレーク化することにより作られた，１次粒子の平均粒径が３.０μｍ（レーザー回折法により測定）であるフレーク状の銀粒子（０.５重量％のステアリン酸で銀表面が被覆されており、この銀粒子は撥水性を有する）１００部に、揮発性分散媒(B1)としてビス（２−エトキシエチル）エーテル（和光純薬工業株式会社発売の試薬、誘電率５.６）１１部、および、揮発性分散媒(B2)としてエチレングリコール（和光純薬工業株式会社発売の試薬、誘電率３９.０）４部を添加し、ヘラを用いて均一に混合することにより、ペースト状金属粒子組成物を調製した。揮発性分散媒(B1)であるビス（２−エトキシエチル）エーテル１１部と揮発性分散媒(B2)であるエチレングリコール４部の混合物は、相溶しない比率である。両者を攪拌混合すると白濁し、静置するとすぐに２層に分離した。
このペースト状金属粒子組成物は、シリンジ内において銀粒子と揮発性分散媒の分離が認められなかった。このペースト状銀粒子組成物の接着強度を測定し、結果を表１にまとめて示した。以上の結果より、このペースト状銀粒子組成物は、銀粒子と揮発性分散媒の分離がなく、保存安定性に優れており、金属製部材を強固に接合するのに有用なことがわかる。[Example 4]
Flaked silver particles (0.5 by the average particle diameter of primary particles made by flaking commercially available silver particles produced by a reduction method having a primary particle size of 3.0 μm (measured by laser diffraction method)) A silver surface is coated with wt% stearic acid, and the silver particles have water repellency. 100 parts of bis (2-ethoxyethyl) ether (Wako Pure Chemical Industries, Ltd.) as a volatile dispersion medium (B1) Add 11 parts of a commercially available reagent, dielectric constant 5.6), and 4 parts of ethylene glycol (a reagent sold by Wako Pure Chemical Industries, Ltd., dielectric constant 39.0) as a volatile dispersion medium (B2). A paste-like metal particle composition was prepared by using and mixing uniformly. A mixture of 11 parts of bis (2-ethoxyethyl) ether, which is a volatile dispersion medium (B1), and 4 parts of ethylene glycol, which is a volatile dispersion medium (B2), is in an incompatible ratio. When both were stirred and mixed, they became cloudy, and upon standing, they separated into two layers.
In this paste-like metal particle composition, separation of the silver particles and the volatile dispersion medium was not observed in the syringe. The adhesive strength of this pasty silver particle composition was measured, and the results are summarized in Table 1. From the above results, it can be seen that this pasty silver particle composition has no separation between the silver particles and the volatile dispersion medium, has excellent storage stability, and is useful for firmly joining metal members.
[実施例５]
市販の，沈殿法で製造された，１次粒子の平均粒径が１.１μｍ（レーザー回折法により測定）である粒状の銀粒子（１.５重量％のステアリン酸で銀表面が被覆されており、この銀粒子は撥水性を有する）１００部に、揮発性分散媒(B1)として１，２−ジアセトキシエタン（和光純薬工業株式会社発売の試薬、誘電率７.３）１４部、および、揮発性分散媒(B2)としてアイソゾール３００（新日本石油株式会社発売のイソパラフィン混合物、誘電率２.１）２部を添加し、ヘラを用いて均一に混合することにより、ペースト状銀粒子組成物を調製した。揮発性分散媒(B1)である１，２−ジアセトキシエタン１４部と揮発性分散媒(B2)であるアイソゾール３００２部の混合物は、相溶しない比率である。両者を攪拌混合すると白濁し、静置するとすぐに２層に分離した。
このペースト状銀粒子組成物は、シリンジ内において銀粒子と揮発性分散媒の分離が認められなかった。このペースト状銀粒子組成物の接着強度を測定し、結果を表１にまとめて示した。以上の結果より、このペースト状銀粒子組成物は、銀粒子と揮発性分散媒の分離がなく、保存安定性に優れており、金属製部材を強固に接合するのに有用なことがわかる。[Example 5]
Commercially available granular silver particles (prepared by precipitation method) with an average primary particle size of 1.1 μm (measured by laser diffraction method) (silver surface coated with 1.5% by weight stearic acid) The silver particles have water repellency) and 100 parts of 1,2-diacetoxyethane (a reagent sold by Wako Pure Chemical Industries, dielectric constant 7.3) as a volatile dispersion medium (B1), And by adding 2 parts of ISOSOL 300 (isoparaffin mixture, dielectric constant 2.1 released by Nippon Oil Corporation) as a volatile dispersion medium (B2) and mixing uniformly with a spatula, pasty silver particles A composition was prepared. A mixture of 14 parts of 1,2-diacetoxyethane, which is a volatile dispersion medium (B1), and 3002 parts of isazole, which is a volatile dispersion medium (B2), is in an incompatible ratio. When both were stirred and mixed, they became cloudy, and upon standing, they separated into two layers.
In this paste-like silver particle composition, separation of the silver particles and the volatile dispersion medium was not observed in the syringe. The adhesive strength of this pasty silver particle composition was measured, and the results are summarized in Table 1. From the above results, it can be seen that this pasty silver particle composition has no separation between the silver particles and the volatile dispersion medium, has excellent storage stability, and is useful for firmly joining metal members.
[実施例６]
実施例５において、揮発性分散媒(B1)として、１，２−ジアセトキシエタンの代わりにメチル−ｎ−ヘキシルケトン（和光純薬工業株式会社発売の試薬、誘電率１２.２）１４部を用い、揮発性分散媒(B2)の代わりに純水（蒸留水、誘電率８０.０）２部を用いた以外は実施例５と同様にして、ペースト状銀粒子組成物を調製した。揮発性分散媒(B1)であるメチル−ｎ−ヘキシルケトン１４部と揮発性分散媒(B2)である純水２部の混合物は、相溶しない比率であり、両者を攪拌混合すると白濁した。
このペースト状銀粒子組成物は、シリンジ内において銀粒子と揮発性分散媒の分離は認められなかった。このペースト状銀粒子組成物の接着強度を測定し、結果を表１にまとめて示した。以上の結果より、このペースト状銀粒子組成物は、銀粒子と揮発性分散媒の分離がなく、保存安定性に優れており、金属製部材を強固に接合するのに有用なことがわかる。[Example 6]
In Example 5, instead of 1,2-diacetoxyethane, 14 parts of methyl-n-hexyl ketone (a reagent sold by Wako Pure Chemical Industries, Ltd., dielectric constant 12.2) was used as the volatile dispersion medium (B1). A pasty silver particle composition was prepared in the same manner as in Example 5 except that 2 parts of pure water (distilled water, dielectric constant 80.0) was used instead of the volatile dispersion medium (B2). A mixture of 14 parts of methyl-n-hexylketone, which is a volatile dispersion medium (B1), and 2 parts of pure water, which is a volatile dispersion medium (B2), is in an incompatible ratio.
In this pasty silver particle composition, separation of the silver particles and the volatile dispersion medium was not observed in the syringe. The adhesive strength of this pasty silver particle composition was measured, and the results are summarized in Table 1. From the above results, it can be seen that this pasty silver particle composition has no separation between the silver particles and the volatile dispersion medium, has excellent storage stability, and is useful for firmly joining metal members.
[実施例７]
市販の，還元法で製造された銀粒子をフレーク化することにより作られた，１次粒子の平均粒径が３.０μｍレーザー回折法により得られるであるフレーク状の銀粒子（０.５重量％のステアリン酸で銀表面が被覆されており、この銀粒子は撥水性を有する）１００部に、揮発性分散媒(C)としてエチレングリコール（和光純薬工業株式会社発売の試薬、誘電率３９.０）１５部を添加し、回転式混練機を用いて均一に混合することにより、ペースト状銀粒子組成物を調製した。
このペースト状銀粒子組成物は、シリンジ内において銀粒子と分散媒の分離が認められなかった。このペースト状銀粒子組成物の接着強度を測定し、結果を表２にまとめて示した。以上の結果より、このペースト状銀粒子組成物は、銀粒子と分散媒の分離がなく、保存安定性に優れており、金属製部材を強固に接合するのに有用なことがわかる。[Example 7]
Flaked silver particles (0.5 wt. Weight) produced by flaking commercially available silver particles produced by a reduction method and having an average primary particle size of 3.0 μm obtained by laser diffraction The silver surface is coated with 100% of stearic acid, and the silver particles have water repellency. 100 parts of ethylene glycol as a volatile dispersion medium (C) (a reagent sold by Wako Pure Chemical Industries, Ltd., dielectric constant 39) 0.0) 15 parts was added and mixed uniformly using a rotary kneader to prepare a pasty silver particle composition.
In this paste-like silver particle composition, separation of the silver particles and the dispersion medium was not observed in the syringe. The adhesive strength of this pasty silver particle composition was measured, and the results are summarized in Table 2. From the above results, it can be seen that this paste-like silver particle composition is excellent in storage stability without separation of silver particles and dispersion medium, and useful for strongly joining metal members.
[実施例８]
市販の，銅粒子をフレーク化することにより作られた，１次粒子の平均粒径が４.０μｍ（レーザー回折法により測定）であるフレーク状の銅粒子（０.５重量％のステアリン酸で銅表面が被覆されており、この銅粒子は撥水性を有する）１００部に、揮発性分散媒(C)としてグリセリン（和光純薬工業株式会社発売の試薬、誘電率４７.０）１５部を添加し、回転式混練機を用いて均一に混合することにより、ペースト状銅粒子組成物を調製した。
このペースト状銅粒子組成物は、シリンジ内において銅粒子と分散媒の分離が認められなかった。結果を表２にまとめて示した。以上の結果より、このペースト状銅粒子組成物は、銅粒子と分散媒の分離がなく、長時間の保存安定性が優れていることがわかる。[Example 8]
Flaked copper particles (obtained with 0.5% by weight of stearic acid) having a mean particle size of 4.0 μm (measured by laser diffractometry), made by flaking commercially available copper particles. The copper surface is coated, and the copper particles have water repellency. 100 parts of glycerin (a reagent sold by Wako Pure Chemical Industries, Ltd., dielectric constant 47.0) is added as a volatile dispersion medium (C). The paste-like copper particle composition was prepared by adding and mixing uniformly using a rotary kneader.
In this paste-like copper particle composition, separation of the copper particles and the dispersion medium was not observed in the syringe. The results are summarized in Table 2. From the above results, it can be seen that this pasty copper particle composition has no separation of copper particles and dispersion medium and is excellent in long-term storage stability.
[実施例９]
実施例８において、銅粒子の代わりに，市販の，ニッケル粒子をフレーク化することにより作られた、１次粒子の平均粒径が６.０μｍ（レーザー回折法により測定）であるフレーク状のニッケル粒子（０.８重量％のオレイン酸でニッケル表面が被覆されており、このニッケル粒子は撥水性を有する）を用いた以外は、実施例８と同様にしてペースト状ニッケル粒子組成物を調製した。このペースト状ニッケル粒子組成物は、シリンジ内においてニッケル粒子と分散媒の分離が認められなかった。結果を表２にまとめて示した。以上の結果より、このペースト状ニッケル粒子組成物は、ニッケル粒子と分散媒の分離がなく、長時間の保存安定性が優れていることがわかる。[Example 9]
In Example 8, instead of copper particles, commercially available nickel particles in the form of flakes having an average primary particle size of 6.0 μm (measured by laser diffraction method) made by flaking nickel particles A paste-like nickel particle composition was prepared in the same manner as in Example 8 except that the particles (the nickel surface was coated with 0.8% by weight of oleic acid and the nickel particles had water repellency) were used. . In this paste-like nickel particle composition, separation of the nickel particles and the dispersion medium was not observed in the syringe. The results are summarized in Table 2. From the above results, it can be seen that this paste-like nickel particle composition is excellent in long-term storage stability without separation of nickel particles and dispersion medium.
[実施例１０]
市販の，沈殿法で製造された，１次粒子の平均粒径（レーザー回折法により測定）が１.１μｍである粒状の銀粒子（１.５重量％のステアリン酸で銀表面が被覆されており、この銀粒子は撥水性を有する）１００部に、揮発性分散媒(C)としてＮ，Ｎ−ジメチルホルムアミド（和光純薬工業株式会社発売の試薬、誘電率３８.０）１５部を添加し、回転式混練機を用いて均一に混合することにより、ペースト状銀粒子組成物を調製した。
このペースト状銀粒子組成物は、シリンジ内において銀粒子と分散媒の分離が認められなかった。このペースト状銀粒子組成物の接着強度を測定し、結果を表２にまとめて示した。以上の結果より、このペースト状銀粒子組成物は、銀粒子と分散媒の分離がなく、保存安定性に優れており、金属製部材を強固に接合するのに有用なことがわかる。[Example 10]
Commercially-produced precipitation-produced granular silver particles having an average primary particle size (measured by laser diffraction method) of 1.1 μm (silver surface coated with 1.5% by weight of stearic acid) In addition, 100 parts of these silver particles have water repellency) and 15 parts of N, N-dimethylformamide (a reagent sold by Wako Pure Chemical Industries, Ltd., dielectric constant 38.0) as a volatile dispersion medium (C) Then, a paste-like silver particle composition was prepared by uniformly mixing using a rotary kneader.
In this paste-like silver particle composition, separation of the silver particles and the dispersion medium was not observed in the syringe. The adhesive strength of this pasty silver particle composition was measured, and the results are summarized in Table 2. From the above results, it can be seen that this paste-like silver particle composition is excellent in storage stability without separation of silver particles and dispersion medium, and useful for strongly joining metal members.
[実施例１１]
実施例１において、揮発性分散媒(B1)として、ベンジルアルコールの代わりに純水（誘電率８０.０）１５部、および、揮発性分散媒(B2)として、１−ヘキサンの代わりにエタノール（和光純薬工業株式会社発売の試薬、誘電率２４.０）３部を用いた以外は、実施例１と同様にして、ペースト状銀粒子組成物を調製した。純水１５部とエタノール３部の混合溶液の誘電率は６８である。このペースト状銀粒子組成物は、シリンジ内において銀粒子と分散媒の分離が認められなかった。このペースト状銀粒子組成物の接着強度を測定し、結果を表２にまとめて示した。以上の結果より、このペースト状銀粒子組成物は、銀粒子と分散媒の分離がなく、保存安定性に優れており、金属製部材を強固に接合するのに有用なことがわかる。[Example 11]
In Example 1, as the volatile dispersion medium (B1), 15 parts of pure water (dielectric constant 80.0) instead of benzyl alcohol, and as the volatile dispersion medium (B2), ethanol (instead of 1-hexane) A paste-like silver particle composition was prepared in the same manner as in Example 1 except that 3 parts of a reagent marketed by Wako Pure Chemical Industries, Ltd., dielectric constant 24.0) was used. The dielectric constant of a mixed solution of 15 parts of pure water and 3 parts of ethanol is 68. In this paste-like silver particle composition, separation of the silver particles and the dispersion medium was not observed in the syringe. The adhesive strength of this pasty silver particle composition was measured, and the results are summarized in Table 2. From the above results, it can be seen that this paste-like silver particle composition is excellent in storage stability without separation of silver particles and dispersion medium, and useful for strongly joining metal members.
[比較例１]
実施例１において、揮発性分散媒(B2)である１−ヘキサンを添加せず、揮発性分散媒(B1) であるベンジルアルコールの量を１５部とした以外は、実施例１と同様にして、ペースト状銀粒子組成物を調製した。このペースト状銀粒子組成物は、シリンジ内において銀粒子と揮発性分散媒の分離が認められた。結果を表３にまとめて示した。[Comparative Example 1]
Example 1 was the same as Example 1 except that 1-hexane, which is a volatile dispersion medium (B2), was not added, and the amount of benzyl alcohol which was a volatile dispersion medium (B1) was 15 parts. A paste-like silver particle composition was prepared. In this pasty silver particle composition, separation of the silver particles and the volatile dispersion medium was observed in the syringe. The results are summarized in Table 3.
[比較例２]
実施例１において、揮発性分散媒(B1)としてベンジルアルコール１４．８部、および、揮発性分散媒(B2)として１−ヘキサン０．２部を用いた以外は、実施例１と同様にしてペースト状銀粒子組成物を調製した。揮発性分散媒(B1)のベンジルアルコール１４．８部と揮発性分散媒(B2)の１−ヘキサン０．２部を攪拌混合すると透明となり、静置しても２層に分離しなかった。このペースト状銀粒子組成物は、シリンジ内において銀粒子と揮発性分散媒の分離が認められた。結果を表３にまとめて示した。[Comparative Example 2]
In Example 1, the same procedure as in Example 1 was used, except that 14.8 parts of benzyl alcohol was used as the volatile dispersion medium (B1) and 0.2 part of 1-hexane was used as the volatile dispersion medium (B2). A pasty silver particle composition was prepared. When 14.8 parts of benzyl alcohol of the volatile dispersion medium (B1) and 0.2 part of 1-hexane of the volatile dispersion medium (B2) were stirred and mixed, the mixture became transparent and did not separate into two layers even when allowed to stand. In this pasty silver particle composition, separation of the silver particles and the volatile dispersion medium was observed in the syringe. The results are summarized in Table 3.
[比較例３]
実施例１において、揮発性分散媒(B1)としてベンジルアルコール０.２部、および、揮発性分散媒(B2)として１−ヘキサン１４.８部を用いた以外は、実施例１と同様にしてペースト状銀粒子組成物を調製した。揮発性分散媒(B1)としてのベンジルアルコール０.２部と揮発性分散媒(B2)としての１−ヘキサン１４.８部を攪拌混合すると透明となり、静置しても２層に分離しなかった。このペースト状銀粒子組成物は、シリンジ内において銀粒子と揮発性分散媒の分離が認められた。結果を表３にまとめて示した。[Comparative Example 3]
In the same manner as in Example 1, except that 0.2 part of benzyl alcohol was used as the volatile dispersion medium (B1) and 14.8 parts of 1-hexane was used as the volatile dispersion medium (B2). A pasty silver particle composition was prepared. When 0.2 parts of benzyl alcohol as the volatile dispersion medium (B1) and 14.8 parts of 1-hexane as the volatile dispersion medium (B2) are stirred and mixed, the mixture becomes transparent and does not separate into two layers even when left standing. It was. In this pasty silver particle composition, separation of the silver particles and the volatile dispersion medium was observed in the syringe. The results are summarized in Table 3.
[比較例４]
実施例１において、揮発性分散媒(B2)として、１−ヘキサンの代わりにシクロヘキサノール（和光純薬工業株式会社発売の試薬、誘電率１５.０）３部用いた以外は、実施例１と同様にしてペースト状銀粒子組成物を調製した。揮発性分散媒(B1)であるベンジルアルコール１２部と揮発性分散媒(B2)であるシクロヘキサノール３部を攪拌混合すると透明となり、静置しても２層に分離しなかった。このペースト状銀粒子組成物は、シリンジ内において銀粒子と揮発性分散媒の分離が認められた。結果を表３にまとめて示した。[Comparative Example 4]
In Example 1, as volatile dispersion medium (B2), Example 1 was used except that 3 parts of cyclohexanol (a reagent sold by Wako Pure Chemical Industries, Ltd., dielectric constant 15.0) was used instead of 1-hexane. Similarly, a paste-like silver particle composition was prepared. When 12 parts of benzyl alcohol, which is a volatile dispersion medium (B1), and 3 parts of cyclohexanol, which is a volatile dispersion medium (B2), were stirred and mixed, the mixture became transparent and did not separate into two layers upon standing. In this pasty silver particle composition, separation of the silver particles and the volatile dispersion medium was observed in the syringe. The results are summarized in Table 3.
[比較例５]
実施例５において、撥水性の銀粒子の代わりに、市販の，沈殿法で製造された、１次粒子の平均粒径）が１.１μｍ（レーザー回折法により測定）である粒状の銀粒子（撥水性有機物で被覆されておらず撥水性を有しない）を用いた以外は、実施例５と同様にしてペースト状銀粒子組成物を調製した。このペースト状銀粒子組成物はシリンジ内において銀粒子と揮発性分散媒の分離が認められた。結果を表３にまとめて示した。[Comparative Example 5]
In Example 5, instead of water-repellent silver particles, commercially available granular silver particles having an average particle diameter of primary particles produced by a precipitation method of 1.1 μm (measured by laser diffraction method) ( A pasty silver particle composition was prepared in the same manner as in Example 5 except that a non-water-repellent organic material was not used and water-repellent property was not used. In this paste-like silver particle composition, separation of the silver particles and the volatile dispersion medium was observed in the syringe. The results are summarized in Table 3.
[比較例６]
実施例１において、揮発性分散媒(B1)として、ベンジルアルコールの代わりにエチレングリコール（和光純薬工業株式会社発売の試薬、誘電率３９.０）４部、および、揮発性分散媒(B2)として、１−ヘキサンの代わりにアセトン（和光純薬工業株式会社発売の試薬、誘電率２１.０）１１部用いた以外は、実施例１と同様にしてペースト状銀粒子組成物を調製した。揮発性分散媒(B1)であるエチレングリコール４部と揮発性分散媒(B2)であるアセトン１１部を攪拌混合すると透明となり、静置しても２層に分離しなかった。このペースト状銀粒子組成物は、シリンジ内において銀粒子と揮発性分散媒の分離が認められた。結果を表３にまとめて示した。[Comparative Example 6]
In Example 1, as volatile dispersion medium (B1), instead of benzyl alcohol, 4 parts of ethylene glycol (a reagent sold by Wako Pure Chemical Industries, Ltd., dielectric constant 39.0), and volatile dispersion medium (B2) As in Example 1, a paste-like silver particle composition was prepared in the same manner as in Example 1 except that 11 parts of acetone (a reagent sold by Wako Pure Chemical Industries, Ltd., dielectric constant 21.0) was used instead of 1-hexane. When 4 parts of ethylene glycol, which is a volatile dispersion medium (B1), and 11 parts of acetone, which is a volatile dispersion medium (B2), were stirred and mixed, the mixture became transparent and did not separate into two layers even when allowed to stand. In this pasty silver particle composition, separation of the silver particles and the volatile dispersion medium was observed in the syringe. The results are summarized in Table 3.
[比較例７]
実施例１において、発性分散媒(B1)として、ベンジルアルコールの代わりにエチレングリコール（和光純薬工業株式会社発売の試薬、誘電率３９.０）４部、および、揮発性分散媒(B2)として、１−ヘキサンの代わりに純水（誘電率８０.０）１１部用いた以外は、実施例１と同様にしてペースト状銀粒子組成物を調製した。エチレングリコール４部と純水１１部の混合液の誘電率は６９である。揮発性分散媒(B1)であるエチレングリコール４部と揮発性分散媒(B2)である純水１１部を攪拌混合すると透明となり、静置しても２層に分離しなかった。分散媒が銀粒子にはじかれてペースト状にならなかった。結果を表４にまとめて示した。[Comparative Example 7]
In Example 1, instead of benzyl alcohol, 4 parts of ethylene glycol (a reagent sold by Wako Pure Chemical Industries, Ltd., dielectric constant 39.0), and volatile dispersion medium (B2) were used as the emitting dispersion medium (B1). In the same manner as in Example 1 except that 11 parts of pure water (dielectric constant 80.0) was used instead of 1-hexane, a pasty silver particle composition was prepared. The dielectric constant of a mixed solution of 4 parts of ethylene glycol and 11 parts of pure water is 69. When 4 parts of ethylene glycol, which is a volatile dispersion medium (B1), and 11 parts of pure water, which is a volatile dispersion medium (B2), were stirred and mixed, they became transparent and did not separate into two layers upon standing. The dispersion medium was repelled by the silver particles and did not become a paste. The results are summarized in Table 4.
[比較例８]
実施例５において、撥水性の銀粒子の代わりに、市販の，沈殿法で製造された，１次粒子の平均粒径が１.１μｍ（レーザー回折法により測定）である粒状の銀粒子（撥水性有機物で被覆されておらず撥水性を有しない）を用い、揮発性分散媒(B1)として、１，２−ジアセトキシエタンの代わりに、エチレングリコール（和光純薬工業株式会社発売の試薬、誘電率３９.０）４部、および、揮発性分散媒(B2)として、アイソゾール３００の代わりにアセトン（和光純薬工業株式会社発売の試薬、誘電率２１.０）１１部を用いた以外は、実施例５と同様にしてペースト状銀粒子組成物を調整した。このペースト状銀粒子組成物は、シリンジ内において銀粒子と揮発性分散媒の分離が認められた。結果を表４にまとめて示した。[Comparative Example 8]
In Example 5, instead of the water-repellent silver particles, commercially available silver particles (repellent particles) produced by a precipitation method and having an average primary particle size of 1.1 μm (measured by laser diffraction method) are used. A volatile dispersion medium (B1) using ethylene glycol (a reagent sold by Wako Pure Chemical Industries, Ltd.) instead of 1,2-diacetoxyethane. Except that 4 parts of dielectric constant 39.0) and 11 parts of acetone (a reagent sold by Wako Pure Chemical Industries, Ltd., dielectric constant 21.0) were used in place of Isosol 300 as the volatile dispersion medium (B2). In the same manner as in Example 5, a pasty silver particle composition was prepared. In this pasty silver particle composition, separation of the silver particles and the volatile dispersion medium was observed in the syringe. The results are summarized in Table 4.
[比較例９]
実施例５において、撥水性の銀粒子の代わりに、市販の沈殿法で製造された，１次粒子の平均粒径（レーザー回折法により測定）が１.１μｍである粒状の銀粒子（撥水性有機物で被覆されておらず撥水性を有しない）を用い、揮発性分散媒(B1)として、１，２−ジアセトキシエタンの代わりにエタノール（和光純薬工業株式会社発売の試薬、誘電率２４．０）６部を用い、および、揮発性分散媒(B2)としてアイソゾール３００の量を９部にした以外は、実施例５と同様にしてペースト状銀粒子組成物を調整した。このペースト状銀粒子組成物はシリンジ内において銀粒子と揮発性分散媒の分離が認められた。結果を表４にまとめて示した。[Comparative Example 9]
In Example 5, instead of water-repellent silver particles, granular silver particles produced by a commercially available precipitation method and having an average primary particle diameter (measured by laser diffraction method) of 1.1 μm (water-repellent) Instead of 1,2-diacetoxyethane, ethanol (a reagent sold by Wako Pure Chemical Industries, Ltd., dielectric constant 24) is used as a volatile dispersion medium (B1). 0.0) 6 parts and a paste-like silver particle composition was prepared in the same manner as in Example 5 except that the amount of Isosol 300 was 9 parts as the volatile dispersion medium (B2). In this paste-like silver particle composition, separation of the silver particles and the volatile dispersion medium was observed in the syringe. The results are summarized in Table 4.
[比較例１０]
実施例５において、撥水性の銀粒子の代わりに、市販の，沈殿法で製造された，１次粒子の平均粒径が１.１μｍ（レーザー回折法により測定）である粒状の銀粒子（撥水性有機物で被覆されておらず撥水性を有しない）を用い、揮発性分散媒(B1)として、１，２−ジアセトキシエタンの代わりに純水（誘電率８０.０）６部、および、揮発性分散媒(B2)として、アイソゾール３００の代わりにエタノール（和光純薬工業株式会社発売の試薬、誘電率２４.０）９部を用いた以外は、実施例５と同様にしてペースト状銀粒子組成物を調製した。純水６部とエタノール９部の混合液の誘電率は４６.４である。このペースト状銀粒子組成物は、シリンジ内において銀粒子と揮発性分散媒の分離が認められた。結果を表４にまとめて示した。[Comparative Example 10]
In Example 5, instead of the water-repellent silver particles, commercially available silver particles (repellent particles) produced by a precipitation method and having an average primary particle size of 1.1 μm (measured by laser diffraction method) are used. 6 parts of pure water (dielectric constant 80.0) instead of 1,2-diacetoxyethane as the volatile dispersion medium (B1), and Paste silver in the same manner as in Example 5 except that 9 parts of ethanol (a reagent sold by Wako Pure Chemical Industries, Ltd., dielectric constant 24.0) was used as the volatile dispersion medium (B2) instead of Isosol 300. A particle composition was prepared. The dielectric constant of a mixed solution of 6 parts of pure water and 9 parts of ethanol is 46.4. In this pasty silver particle composition, separation of the silver particles and the volatile dispersion medium was observed in the syringe. The results are summarized in Table 4.
[比較例１１]
実施例７において、揮発性分散媒として、エチレングリコールの代わりに純水（誘電率８０.０）１５部を用いた以外は、実施例７と同様にしてペースト状銀粒子組成物を調製した。揮発性分散媒が銀粒子にはじかれてペースト状にならなかった。結果を表４にまとめて示した。[Comparative Example 11]
In Example 7, a pasty silver particle composition was prepared in the same manner as in Example 7 except that 15 parts of pure water (dielectric constant 80.0) was used instead of ethylene glycol as the volatile dispersion medium. The volatile dispersion medium was repelled by the silver particles and did not become a paste. The results are summarized in Table 4.
[比較例１２]
実施例７において、揮発性分散媒として、エチレングリコールの代わりにアイソゾール３００（新日本石油株式会社発売のイソパラフィン混合物、誘電率２.１）１５部を用いた以外は、実施例７と同様にしてペースト状銀粒子組成物を調製した。このペースト状銀粒子組成物は、シリンジ内において銀粒子と揮発性分散媒の分離が認められた。結果を表４にまとめて示した。[Comparative Example 12]
In Example 7, the same procedure as in Example 7 was used, except that 15 parts of Isosol 300 (isoparaffin mixture released by Nippon Oil Co., Ltd., dielectric constant 2.1) was used as the volatile dispersion medium instead of ethylene glycol. A pasty silver particle composition was prepared. In this pasty silver particle composition, separation of the silver particles and the volatile dispersion medium was observed in the syringe. The results are summarized in Table 4.
[比較例１３]
実施例７において、揮発性分散媒として、エチレングリコールの代わりに１−オクタノール（和光純薬工業株式会社発売の試薬、誘電率１０.０）１５部を用いた以外は、実施例７と同様にしてペースト状銀粒子組成物を調製した。このペースト状銀粒子組成物は、シリンジ内において銀粒子と揮発性分散媒の分離が認められた。結果を表５にまとめて示した。[Comparative Example 13]
In Example 7, the same procedure as in Example 7 was used, except that 15 parts of 1-octanol (a reagent sold by Wako Pure Chemical Industries, Ltd., dielectric constant 10.0) was used as the volatile dispersion medium instead of ethylene glycol. Thus, a pasty silver particle composition was prepared. In this pasty silver particle composition, separation of the silver particles and the volatile dispersion medium was observed in the syringe. The results are summarized in Table 5.
[比較例１４]
市販の，沈殿法で製造された，１次粒子の平均粒径が１.１μｍ（レーザー回折法により測定）である粒状の銀粒子（撥水性有機物で被覆されておらず撥水性を有しない）１００部に、揮発性分散媒(C)として、１，４−ブタンジオール（和光純薬工業株式会社発売の試薬、誘電率３１.０）７５部を添加し、回転式混練機を用いて均一に混合してペースト状銀粒子組成物を調製した。
このペースト状銀粒子組成物はシリンジ内において銀粒子と揮発性分散媒の分離が認められた。結果を表５にまとめて示した。[Comparative Example 14]
Commercially available granular silver particles produced by the precipitation method and having an average primary particle size of 1.1 μm (measured by laser diffraction method) (not coated with a water-repellent organic substance and not water-repellent) To 100 parts, 75 parts of 1,4-butanediol (a reagent sold by Wako Pure Chemical Industries, Ltd., dielectric constant: 31.0) is added as a volatile dispersion medium (C), and uniform using a rotary kneader. To prepare a pasty silver particle composition.
In this paste-like silver particle composition, separation of the silver particles and the volatile dispersion medium was observed in the syringe. The results are summarized in Table 5.
[比較例１５]
市販の，沈殿法で製造された，１次粒子の平均粒径が１.１μｍ（レーザー回折法により測定）である粒状の銀粒子（撥水性有機物で被覆されておらず撥水性を有しない）１００部に、揮発性分散媒(C)としてプロピレングリコール（和光純薬工業株式会社発売の試薬、誘電率３４．０）７５部を添加し、回転式混練機を用いて均一に混合することにより、ペースト状銀粒子組成物を調製した。
このペースト状銀粒子組成物は、シリンジ内において銀粒子と揮発性分散媒の分離が認められた。結果を表５にまとめて示した。[Comparative Example 15]
Commercially available granular silver particles produced by the precipitation method and having an average primary particle size of 1.1 μm (measured by laser diffraction method) (not coated with a water-repellent organic substance and not water-repellent) By adding 75 parts of propylene glycol (a reagent sold by Wako Pure Chemical Industries, Ltd., dielectric constant 34.0) as a volatile dispersion medium (C) to 100 parts, and mixing uniformly using a rotary kneader A paste-like silver particle composition was prepared.
In this pasty silver particle composition, separation of the silver particles and the volatile dispersion medium was observed in the syringe. The results are summarized in Table 5.
[比較例１６]
市販の，沈殿法で製造された，１次粒子の平均粒径が１.１μｍ（レーザー回折法により測定）である粒状の銀粒子（撥水性有機物で被覆されておらず、撥水性を有しない）１００部に、揮発性分散媒(C)としてエチレングリコール（和光純薬工業株式会社発売の試薬、誘電率３９．０）７５部を添加し、回転式混練機を用いて均一に混合することにより、ペースト状銀粒子組成物を調製した。
このペースト状銀粒子組成物は、シリンジ内において銀粒子と揮発性分散媒の分離が認められた。結果を表５にまとめて示した。[Comparative Example 16]
Commercially available granular silver particles produced by a precipitation method and having an average primary particle size of 1.1 μm (measured by a laser diffraction method) (not coated with a water-repellent organic substance and have no water repellency) ) To 100 parts, add 75 parts of ethylene glycol (a reagent sold by Wako Pure Chemical Industries, Ltd., dielectric constant 39.0) as a volatile dispersion medium (C), and mix evenly using a rotary kneader. Thus, a paste-like silver particle composition was prepared.
In this pasty silver particle composition, separation of the silver particles and the volatile dispersion medium was observed in the syringe. The results are summarized in Table 5.
[比較例１７]
市販の，沈殿法で製造された，１次粒子の平均粒径が１.１μｍ（レーザー回折法により測定）である粒状の銀粒子（撥水性有機物で被覆されておらず、撥水性を有しない）１００部に、揮発性分散媒(B1)として純水（蒸留水、誘電率８０.０）７５部、揮発性分散媒(B2)として１，４−ブタンジオール（和光純薬工業株式会社発売の試薬、誘電率３１.０）７５部、および、揮発性分散媒(B2)としてアセトン（和光純薬工業株式会社発売の試薬、誘電率２１.０）３．７５部を添加し、回転式混練機を用いて均一に混合することにより、ペースト状銀粒子組成物を調製した。
このペースト状銀粒子組成物は、シリンジ内において銀粒子と揮発性分散媒の分離が認められた。結果を表６にまとめて示した。[Comparative Example 17]
Commercially available granular silver particles produced by a precipitation method and having an average primary particle size of 1.1 μm (measured by a laser diffraction method) (not coated with a water-repellent organic substance and have no water repellency) ) 100 parts, 75 parts of pure water (distilled water, dielectric constant 80.0) as volatile dispersion medium (B1), 1,4-butanediol (Wako Pure Chemical Industries, Ltd.) as volatile dispersion medium (B2) And 75 parts of acetone (dielectric constant 31.0) and 3.75 parts of acetone (a reagent sold by Wako Pure Chemical Industries, Ltd., dielectric constant 21.0) as a volatile dispersion medium (B2). A paste-like silver particle composition was prepared by mixing uniformly using a kneader.
In this pasty silver particle composition, separation of the silver particles and the volatile dispersion medium was observed in the syringe. The results are summarized in Table 6.
[比較例１８]
市販の，沈殿法で製造された，１次粒子の平均粒径が１.１μｍ（レーザー回折法により測定）である粒状の銀粒子（撥水性有機物で被覆されておらず撥水性を有しない）１００部に、揮発性分散媒(B1)として純水（蒸留水、誘電率８０.０）７５部、揮発性分散媒(B2)としてプロピレングリコール（和光純薬工業株式会社発売の試薬、誘電率３４.０）７５部、および、揮発性分散媒(B2)としてアセトン（和光純薬工業株式会社発売の試薬、誘電率２１.０）３.７５部を添加し、回転式混練機を用いて均一に混合することによりペースト状銀粒子組成物を調製した。
このペースト状銀粒子組成物は、シリンジ内において銀粒子と揮発性分散媒の分離が認められた。結果を表６にまとめて示した。[Comparative Example 18]
Commercially available granular silver particles produced by the precipitation method and having an average primary particle size of 1.1 μm (measured by laser diffraction method) (not coated with a water-repellent organic substance and not water-repellent) 100 parts, 75 parts of pure water (distilled water, dielectric constant 80.0) as the volatile dispersion medium (B1), propylene glycol (the reagent released by Wako Pure Chemical Industries, Ltd., dielectric constant) as the volatile dispersion medium (B2) 34.0) 75 parts and 3.75 parts of acetone (a reagent sold by Wako Pure Chemical Industries, Ltd., dielectric constant 21.0) as a volatile dispersion medium (B2) are added, and a rotary kneader is used. A paste-like silver particle composition was prepared by mixing uniformly.
In this pasty silver particle composition, separation of the silver particles and the volatile dispersion medium was observed in the syringe. The results are summarized in Table 6.
[比較例１９]
市販の，沈殿法で製造された，１次粒子の平均粒径が１．１μｍ（レーザー回折法により測定）である粒状の銀粒子（撥水性有機物で被覆されておらず、撥水性を有しない）１００部に、分散媒（揮発性分散媒(B1)）として純水（蒸留水、誘電率８０.０）７５部、揮発性分散媒(B2)としてエチレングリコール（和光純薬工業株式会社発売の試薬、誘電率３９.０）７５部、および、揮発性分散媒(B2)としてアセトン（和光純薬工業株式会社発売の試薬、誘電率２１.０）３.７５部を添加し、回転式混練機を用いて均一に混合することにより、ペースト状銀粒子組成物を調製した。
このペースト状銀粒子組成物は、シリンジ内において銀粒子と揮発性分散媒の分離が認められた。結果を表６にまとめて示した。[Comparative Example 19]
Commercially available granular silver particles with a primary particle size of 1.1 μm (measured by laser diffraction method) produced by a precipitation method (not coated with a water-repellent organic substance and have no water repellency) ) 100 parts, 75 parts of pure water (distilled water, dielectric constant 80.0) as dispersion medium (volatile dispersion medium (B1)), ethylene glycol (Wako Pure Chemical Industries, Ltd.) as volatile dispersion medium (B2) And 75 parts of acetone (dielectric constant 39.0) and 3.75 parts of acetone (a reagent sold by Wako Pure Chemical Industries, Ltd., dielectric constant 21.0) as a volatile dispersion medium (B2). A paste-like silver particle composition was prepared by mixing uniformly using a kneader.
In this pasty silver particle composition, separation of the silver particles and the volatile dispersion medium was observed in the syringe. The results are summarized in Table 6.
本発明のペースト状金属粒子組成物は、長時間にわたり金属粒子と揮発性分散媒の分離がなく、保存安定性が優れているので、金属製部材の接合に有用である。本発明の金属製部材の接合方法は、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合に有用である。 The paste-like metal particle composition of the present invention is useful for joining metal members because it does not separate the metal particles from the volatile dispersion medium for a long time and has excellent storage stability. The metal member bonding method of the present invention is useful for bonding chip components such as capacitors, resistors, diodes, memories, and arithmetic elements (CPUs) to a substrate.
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| JP2006317791 | 2006-11-24 | ||
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| PCT/JP2007/000276 WO2008062548A1 (en) | 2006-11-24 | 2007-03-20 | Pasty metal particle composition and method of joining |
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Cited By (6)
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| EP2428293A2 (en) * | 2010-09-03 | 2012-03-14 | Heraeus Materials Technology GmbH & Co. KG | Contacting medium and process for contacting electrical parts |
| WO2013185839A1 (en) * | 2012-06-15 | 2013-12-19 | Osram Opto Semiconductors Gmbh | Method for producing an optoelectronic semiconductor device comprising a connecting layer sintered under the action of heat, pressure and ultrasound |
| EP2915857A4 (en) * | 2012-10-31 | 2016-07-06 | Mitsuboshi Belting Ltd | Conductive adhesive for screen printing, joined body of inorganic material, and method for producing same |
| US10141283B2 (en) | 2014-12-26 | 2018-11-27 | Henkel Ag & Co. Kgaa | Sinterable bonding material and semiconductor device using the same |
| US10446518B2 (en) | 2014-12-26 | 2019-10-15 | Henkel Ag & Co. Kgaa | Sinterable bonding material and semiconductor device using the same |
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| TWI285568B (en) * | 2005-02-02 | 2007-08-21 | Dowa Mining Co | Powder of silver particles and process |
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| EP2428293A2 (en) * | 2010-09-03 | 2012-03-14 | Heraeus Materials Technology GmbH & Co. KG | Contacting medium and process for contacting electrical parts |
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| WO2013185839A1 (en) * | 2012-06-15 | 2013-12-19 | Osram Opto Semiconductors Gmbh | Method for producing an optoelectronic semiconductor device comprising a connecting layer sintered under the action of heat, pressure and ultrasound |
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| JPWO2008062548A1 (en) | 2010-03-04 |
| WO2008062548A1 (en) | 2008-05-29 |
| TW200822991A (en) | 2008-06-01 |
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