JP2009046708A - Silver powder - Google Patents
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- JP2009046708A JP2009046708A JP2007211721A JP2007211721A JP2009046708A JP 2009046708 A JP2009046708 A JP 2009046708A JP 2007211721 A JP2007211721 A JP 2007211721A JP 2007211721 A JP2007211721 A JP 2007211721A JP 2009046708 A JP2009046708 A JP 2009046708A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 239000002245 particle Substances 0.000 claims description 103
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229920002050 silicone resin Polymers 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 4
- 239000010956 nickel silver Substances 0.000 abstract 1
- 239000011800 void material Substances 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 18
- 229910052709 silver Inorganic materials 0.000 description 18
- 239000004332 silver Substances 0.000 description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 10
- 239000002585 base Substances 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 238000006467 substitution reaction Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 229910001961 silver nitrate Inorganic materials 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- -1 that is Substances 0.000 description 4
- 230000000007 visual effect Effects 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 2
- 229910001958 silver carbonate Inorganic materials 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RBWNDBNSJFCLBZ-UHFFFAOYSA-N 7-methyl-5,6,7,8-tetrahydro-3h-[1]benzothiolo[2,3-d]pyrimidine-4-thione Chemical compound N1=CNC(=S)C2=C1SC1=C2CCC(C)C1 RBWNDBNSJFCLBZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 241000557876 Centaurea cineraria Species 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229920002113 octoxynol Polymers 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 1
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Abstract
Description
本発明は、特殊形状の銀粉粒子からなる銀粉に関する。 The present invention relates to a silver powder comprising silver powder particles having a special shape.
銀粉は、導電性ペースト、焼結助剤、プラズマディスプレイ用電極材料などの原料として広く利用されている。 Silver powder is widely used as a raw material for conductive pastes, sintering aids, electrode materials for plasma displays, and the like.
一般的な銀粉の製造方法としては、硝酸銀水溶液に水酸化ナトリウム又は炭酸ナトリウムを添加して酸化銀又は炭酸銀を生成させ、該酸化銀又は該炭酸銀をヒドラジン等の還元剤で還元する方法が挙げられ、このようにして得られる銀粉は粒状品（形状は球形若しくはそれに準じた形状）を呈するのが通常である。 As a general method for producing silver powder, there is a method in which sodium hydroxide or sodium carbonate is added to a silver nitrate aqueous solution to produce silver oxide or silver carbonate, and the silver oxide or silver carbonate is reduced with a reducing agent such as hydrazine. The silver powder obtained in this way usually has a granular shape (the shape is spherical or a shape similar to it).
銀粉粒子の形状としては、このような粒状のほか、樹枝状、板状、フレーク状、不定形状などが知られており、銀粉粒子の形状によって特性が異なるため、従来から、銀粉粒子の形状に着目した発明が多数開示されている。 As the shape of the silver powder particles, in addition to such granular shapes, dendritic shapes, plate shapes, flake shapes, irregular shapes, etc. are known, and the characteristics differ depending on the shape of the silver powder particles. A number of the inventions that have focused attention are disclosed.
例えば特許文献１には、平均粒径１μｍ以下の積層構造を有する銀粉、並びに、この積層構造を有する銀粉を単層状に粉砕して作られるフレーク状銀粉が開示されている。
特許文献２には、スクリーン印刷などで電気回路を形成する厚膜プロセス用金属ペースト材料および導電性塗料用に使用する銀粉として、平均粒径が０．５μｍ〜５０μｍの微細な鱗片状銀粉末が開示されている。
特許文献３には、六角板状結晶銀粒子からなる銀粉が開示されている。
For example, Patent Document 1 discloses silver powder having a laminated structure with an average particle size of 1 μm or less, and flaky silver powder produced by pulverizing silver powder having this laminated structure into a single layer.
Patent Document 2 discloses a fine scaly silver powder having an average particle size of 0.5 μm to 50 μm as a metal paste material for a thick film process for forming an electric circuit by screen printing or the like and a silver powder used for a conductive paint. It is disclosed.
Patent Document 3 discloses silver powder made of hexagonal plate-like crystal silver particles.
特許文献４には、チップ部品、ＰＤＰ等の微細な配線又は薄層で平滑な塗膜を形成するための導電ペースト用として、高分散性球状銀粉末が開示されている。
特許文献５には、湿式還元法で製造された銀に、粒子同士を機械的に衝突させる表面平滑化処理を施してなる銀粉が開示されている。
特許文献６には、球状でも薄板状でもない多数の突起を有する不定形な形状の銀粒子からなる銀粉が開示されている。
特許文献７には、平均厚みが５０ｎｍ以下の極薄板状銀粒子からなる銀粉が開示されている。
特許文献８には、無電解湿式プロセスにより得られるデンドライト状の銀粉が開示されている。
Patent Document 4 discloses a highly dispersible spherical silver powder for use in a conductive paste for forming a fine coating such as a chip component or PDP or a thin layer and a smooth coating.
Patent Document 5 discloses a silver powder obtained by subjecting silver produced by a wet reduction method to a surface smoothing treatment in which particles are mechanically collided with each other.
Patent Document 6 discloses a silver powder composed of irregularly shaped silver particles having a large number of protrusions that are neither spherical nor thin.
Patent Document 7 discloses silver powder composed of ultrathin plate-like silver particles having an average thickness of 50 nm or less.
Patent Document 8 discloses dendritic silver powder obtained by an electroless wet process.
本発明は、新たに得られた特殊形状の銀粉粒子からなる銀粉を提供せんとするものである。 The present invention is intended to provide a silver powder composed of newly obtained silver powder particles having a special shape.
本発明は、粒子内部が中空部である銀粉粒子（本発明では「中空銀粉粒子」と称する）を含有する銀粉を提案するものである。
ここで、「含有」するとは、中空銀粉粒子の機能を妨げない範囲で、中空銀粉粒子以外の粒子を含有することを許容する意を包含するものである。中空銀粉粒子の含有割合を特別に限定するものではないが、中空銀粉粒子が銀粉中の５０個数％以上、特に７０個数％以上、中でも特に９０個数％以上（１００個数％含む）を占めるのが好ましい。言い換えれば、本発明の銀粉は、中空銀粉粒子からなる銀粉（但し、中空銀粉粒子の機能を妨げない範囲で、中空銀粉粒子以外の銀粉粒子を含有してもよい。）と表現することも可能である。
The present invention proposes a silver powder containing silver powder particles whose inside is a hollow part (referred to as “hollow silver powder particles” in the present invention).
Here, “containing” includes the meaning of allowing particles other than the hollow silver powder particles to be contained within a range not impeding the function of the hollow silver powder particles. Although the content ratio of the hollow silver powder particles is not particularly limited, the hollow silver powder particles account for 50% by number or more, particularly 70% by number or more, particularly 90% by number or more (including 100% by number) in the silver powder. preferable. In other words, the silver powder of the present invention can also be expressed as silver powder composed of hollow silver powder particles (however, it may contain silver powder particles other than the hollow silver powder particles as long as the function of the hollow silver powder particles is not hindered). It is.
本発明の銀粉は、中空銀粉粒子を含有するがゆえに、例えば導電ペーストを作製する場合、中実な銀粉粒子からなる銀粉に比べて、所望の導電性を得るための銀粉量（質量）が少なくて済み、導電ペーストの製造コストを抑えることができる。さらに、粒子内部に中空部（空洞部）を有するから、中実な粒子に比べて変形させ易いという特性を有しており、例えばフレーク状粒子に容易に加工することができる。 Since the silver powder of the present invention contains hollow silver powder particles, for example, when producing a conductive paste, the amount (mass) of silver powder for obtaining desired conductivity is smaller than that of solid silver powder particles. The manufacturing cost of the conductive paste can be reduced. Furthermore, since it has a hollow part (cavity part) inside the particle, it has the property of being easily deformed as compared with a solid particle, and can be easily processed into, for example, flaky particles.
以下、本発明の実施形態について詳述するが、本発明の範囲が以下の実施形態に限定されるものではない。
なお、本明細書において、「Ｘ〜Ｙ」（Ｘ，Ｙは任意の数字）と記載した場合、特にことわらない限り「Ｘ以上Ｙ以下」の意と共に、「好ましくはＸより大きい」或いは「好ましくはＹより小さい」の意も包含する。
Hereinafter, although the embodiment of the present invention is described in detail, the scope of the present invention is not limited to the following embodiment.
In the present specification, when “X to Y” (X and Y are arbitrary numbers) is described, it means “preferably greater than X” or “within the meaning of“ X to Y ”unless otherwise specified” or “ The term “preferably smaller than Y” is also included.
本実施形態に係る銀粉（以下「本銀粉」という）は、中空銀粉粒子（以下「本銀粉粒子」ともいう）を含有する銀粉である。 The silver powder (hereinafter referred to as “the present silver powder”) according to the present embodiment is a silver powder containing hollow silver powder particles (hereinafter also referred to as “the present silver powder particles”).
本銀粉は、上記の如く中空銀粉粒子を含有する銀粉であり、中空銀粉粒子でない銀粉粒子、すなわち粒子内部が中実である銀粉粒子を含んでいてもよいが、中空銀粉粒子の比率、例えば、銀粉をシリコーン樹脂に混合して硬化させた樹脂体の断面を切断し、この断面をＳＥＭ（Scanning Electron Microscope、走査型電子顕微鏡、１０００倍）で観察した際、１視野における全銀粉粒子の全断面積合計に対する、１視野における全中空銀粉粒子の断面積合計の割合（全中空銀粉粒子合計断面積／全銀粉粒子合計断面積）が５〜３５％、特に１０〜３０％、中でも特に１５〜２５％であるのが好ましい。全中空銀粉粒子合計断面積／全銀粉粒子合計断面積が５％以上であれば、中空銀粉粒子の効果、例えば所望の導電性を得るための銀粉量（質量）が少なくて済むという効果を享受することができる。その一方、３０％を超えてもよいが、３５％を超える銀粉を作製することは困難である。 The present silver powder is a silver powder containing hollow silver powder particles as described above, and may contain silver powder particles that are not hollow silver powder particles, that is, silver powder particles that are solid inside, but the ratio of the hollow silver powder particles, for example, When a cross section of a resin body obtained by mixing silver powder into a silicone resin and curing is cut, and this cross section is observed with a SEM (Scanning Electron Microscope, scanning electron microscope, 1000 times), all the silver powder particles are completely cut in one field of view. The ratio of the total cross-sectional area of all hollow silver powder particles in one field of view to the total area (total hollow silver powder particle total cross-sectional area / total silver powder particle total cross-sectional area) is 5 to 35%, particularly 10 to 30%, especially 15 to 25. % Is preferred. If the total cross-sectional area of all the hollow silver powder particles / the total cross-sectional area of the total silver powder particles is 5% or more, the effect of the hollow silver powder particles, for example, the effect that the amount (mass) of silver powder for obtaining desired conductivity can be reduced. can do. On the other hand, although it may exceed 30%, it is difficult to produce silver powder exceeding 35%.
本銀粉粒子は、例えばＦＩＢ／ＳＥＭ断面加工観察装置（ＦＩＢ：Focus Ion Beam:収束イオンビーム法：絞ったイオンビームで表面をスパッタリング（削り取り）して微細な加工を可能にする装置）によって、得られた銀粉粒子の縦断面を観察すると、図２及び図３に示すように、粒子内部に中空部（空洞部）を有するものである。この中空部（空洞部）は、気泡等とは明らかに区別することができる。
本銀粉粒子の中空部は、図２及び図３に示されるように、中空部と外部とを連通する穴を有していてもよい。中空部（空洞部）が閉塞していると、本銀粉粒子を加熱した際に、中空部の内圧が高まって本銀粉粒子が破裂する可能性があるが、外部と連通する穴を備えていればそのような破裂を抑制することができる。
The silver powder particles can be obtained by, for example, a FIB / SEM cross-section processing observation apparatus (FIB: Focused Ion Beam method: an apparatus that enables fine processing by sputtering the surface with a focused ion beam). When the longitudinal section of the obtained silver powder particles is observed, as shown in FIGS. 2 and 3, the particles have hollow portions (hollow portions). This hollow portion (hollow portion) can be clearly distinguished from bubbles and the like.
As shown in FIGS. 2 and 3, the hollow part of the present silver powder particles may have a hole that communicates the hollow part with the outside. If the hollow part (cavity part) is closed, when the silver powder particles are heated, the internal pressure of the hollow part may increase and the silver powder particles may rupture. Such a burst can be suppressed.
中空部（空洞部）の大きさに関して言えば、例えば、銀粉をシリコーン樹脂に混合して硬化させた樹脂体の断面を切断し、この断面をＳＥＭ（Scanning Electron Microscope、走査型電子顕微鏡、１０００倍）で観察した際、１視野における全中空銀粉粒子の断面積合計に対する、１視野における中空部の断面積合計の割合（中空部合計断面積／全断面積）が５〜５０％、特に１０〜３５％、中でも特に１５〜２５％であるのが好ましい。中空部合計断面積／全断面積が５％以上であれば、中空銀粉粒子の効果、例えば所望の導電性を得るための銀粉量（質量）が少なくて済むという効果を享受することができる。その一方、５０％を超えてもよいが、５０％を超える銀粉を作製することは困難である。 Speaking of the size of the hollow part (hollow part), for example, a cross section of a resin body in which silver powder is mixed with a silicone resin and cured is cut, and this cross section is SEM (Scanning Electron Microscope, scanning electron microscope, 1000 times) ), The ratio of the total cross-sectional area of the hollow part in one visual field to the total cross-sectional area of all the hollow silver powder particles in one visual field (total cross-sectional area of the hollow part / total cross-sectional area) is 5 to 50%, particularly 10 It is preferably 35%, especially 15 to 25%. If the total cross-sectional area of the hollow part / total cross-sectional area is 5% or more, the effect of the hollow silver powder particles, for example, the effect that the amount (mass) of silver powder for obtaining desired conductivity is small can be enjoyed. On the other hand, although it may exceed 50%, it is difficult to produce silver powder exceeding 50%.
本銀粉の粒度分布に関しては、レーザー回折散乱式粒度分布測定装置で測定される中心粒径（Ｄ５０）が１μｍ〜５０μｍであるのが好ましく、より好ましくは１μｍ〜４０μｍ、中でも３μｍ〜３０μｍであるのが特に好ましい。
Ｄ１０は、１μｍ〜１６μｍであるのが好ましく、より好ましくは４μｍ〜１２μｍ、中でも６μｍ〜１０μｍであるのが特に好ましい。
Ｄ９０は、１０μｍ〜４０μｍであるのが好ましく、より好ましくは１５μｍ〜３５μｍ、中でも２０μｍ〜３５μｍであるのが特に好ましい。
Ｄmaxは、２０μｍ〜８０μｍであるのが好ましく、より好ましくは３０μｍ〜７５μｍ、中でも４０μｍ〜７５μｍであるのが特に好ましい。
ＣＶ（変動係数）が１０〜７０であるのが好ましく、より好ましくは２０〜６０、中でも３０〜５０であるのが特に好ましい。
Regarding the particle size distribution of the present silver powder, the center particle size (D50) measured with a laser diffraction / scattering particle size distribution measuring device is preferably 1 μm to 50 μm, more preferably 1 μm to 40 μm, and more preferably 3 μm to 30 μm. Is particularly preferred.
D10 is preferably 1 μm to 16 μm, more preferably 4 μm to 12 μm, and particularly preferably 6 μm to 10 μm.
D90 is preferably 10 μm to 40 μm, more preferably 15 μm to 35 μm, and particularly preferably 20 μm to 35 μm.
Dmax is preferably 20 μm to 80 μm, more preferably 30 μm to 75 μm, and particularly preferably 40 μm to 75 μm.
The CV (coefficient of variation) is preferably 10 to 70, more preferably 20 to 60, and particularly preferably 30 to 50.
本銀粉粒子は、中空銀粉粒子を含有するがゆえに、嵩密度が小さいという特徴を有しており、ＡＤ（嵩密度）としては０．５〜２．０ｇ／ｃｍ３、特に０．７〜１．４ｇ／ｃｍ３であるのが好ましい。
また、ＴＤ（タップ充填密度）としては１．０〜３．０ｇ／ｃｍ３、特に１．５〜２．５ｇ／ｃｍ３であるのが好ましい。
Since the present silver powder particles contain hollow silver powder particles, they have a feature that the bulk density is small, and AD (bulk density) is 0.5 to 2.0 g / cm 3 , particularly 0.7 to 1. It is preferably 4 g / cm 3 .
As the TD (tap bulk density) 1.0 to 3.0 g / cm 3, is preferably particularly 1.5~2.5g / cm 3.
本銀粉粒子は、熱機械分析装置（ＴＭＡ）を用いて４００℃から６００℃に加熱した際の体積収縮率（４００℃から６００℃の間の体積収縮率の差）が２〜２０％であるのが好ましく、特に４〜１５％、中でも特に６〜１０％であるのが好ましい。 The present silver powder particles have a volume shrinkage (difference in volume shrinkage between 400 ° C. and 600 ° C.) of 2 to 20% when heated from 400 ° C. to 600 ° C. using a thermomechanical analyzer (TMA). And is particularly preferably 4 to 15%, particularly preferably 6 to 10%.
また、本銀粉粒子の体積固有抵抗値は２．０×１０-5〜６．０×１０-5ｍΩ・ｃｍであるのが好ましく、特に２．５×１０-5〜５．５×１０-5ｍΩ・ｃｍ、中でも特に４．０×１０-5〜５．５×１０-5ｍΩ・ｃｍであるのが好ましい。 Further, the volume resistivity value of the present silver powder particles is preferably 2.0 × 10 −5 to 6.0 × 10 −5 mΩ · cm, particularly 2.5 × 10 −5 to 5.5 × 10 −. It is preferably 5 mΩ · cm, particularly 4.0 × 10 −5 to 5.5 × 10 −5 mΩ · cm.
（用途）
本銀粉は、例えば導電性ペースト、焼結助剤、プラズマディスプレイ用電極材料など、各種電子部品の電極や回路形成に用いることができる。特に、本銀粉から導電ペーストを作製すると、中空銀粉粒子を含有するがゆえに、所望の導電性を得るための銀粉量が少なくて済み、製造コストを抑えることができるから、導電ペーストを作製するのに利用するのが好ましい。
また、本銀粉は、中空銀粉粒子を含有するものであるから、中空部が収縮し難い温度領域で使われる用途に用いるのが好ましい。その意味で、例えば樹脂硬化型ペースト材料などの原料に用いるのが特に好ましい。
(Use)
This silver powder can be used for forming electrodes and circuits of various electronic components such as conductive pastes, sintering aids, and electrode materials for plasma displays. In particular, when a conductive paste is prepared from the present silver powder, the amount of silver powder for obtaining desired conductivity can be reduced because it contains hollow silver powder particles, and the manufacturing cost can be reduced. It is preferable to use it.
Moreover, since this silver powder contains hollow silver powder particle | grains, it is preferable to use for the use used in the temperature range where a hollow part does not shrink easily. In that sense, it is particularly preferable to use it as a raw material such as a resin curable paste material.
（製造方法）
本銀粉は、銀と置換し得る金属、中でも好ましくは銅粉、その中でも好ましくは電解銅粉（デンドライト状）を元粉とし、この元粉を水に分散させ、キレート化剤を添加した後、水に可溶な銀塩を加えて置換反応させ、元粉の金属を銀に置換させることにより製造することができる。
(Production method)
The present silver powder is a metal that can be replaced with silver, preferably copper powder, preferably electrolytic copper powder (dendritic) among them as a base powder, after dispersing this base powder in water and adding a chelating agent, It can be produced by adding a silver salt soluble in water to cause a substitution reaction and substituting the metal of the original powder with silver.
元粉は、必要に応じて、置換反応前に表面酸化物（酸化皮膜）を除去する処理を行なうのがよい。例えば、元粉を水に投入して攪拌混合した後、ヒドラジン等の還元剤を加えて攪拌混合して反応させればよい。この際、加えた還元剤を十分に洗浄して元粉から除去するのが好ましい。 If necessary, the base powder is preferably subjected to a treatment for removing the surface oxide (oxide film) before the substitution reaction. For example, the raw powder may be charged into water and mixed with stirring, and then a reducing agent such as hydrazine may be added and mixed with stirring to react. At this time, it is preferable to thoroughly wash the added reducing agent and remove it from the base powder.
キレート化剤としては、例えばエチレンジアミン四酢酸塩（以下「ＥＤＴＡ」という）、トリエチレンジアミン、ジエチレントリアミン五酢酸、イミノ二酢酸から選ばれた１種又は２種以上のものを挙げることができるが、中でもＥＤＴＡを用いるのが好ましい。 Examples of the chelating agent include one or more selected from ethylenediaminetetraacetate (hereinafter referred to as “EDTA”), triethylenediamine, diethylenetriaminepentaacetic acid, and iminodiacetic acid. Is preferably used.
銀塩を加える際、溶液のｐＨ、すなわち置換反応させる際の溶液のｐＨは３〜４に調整するのが好ましい。
銀塩としては、水に可溶な銀塩、すなわちＡｇイオン供給源としては、硝酸銀、過塩素酸銀、酢酸銀、シュウ酸銀、塩素酸銀、６フッ化リン酸銀、４フッ化ホウ酸銀、６フッ化ヒ酸銀、硫酸銀から選ばれた１種又は２種以上を挙げることができる。
When adding a silver salt, it is preferable to adjust the pH of the solution, that is, the pH of the solution at the time of the substitution reaction to 3 to 4.
Silver salts soluble in water, that is, Ag ion sources include silver nitrate, silver perchlorate, silver acetate, silver oxalate, silver chlorate, silver hexafluorophosphate, and boron tetrafluoride. One or more selected from acid silver, silver hexafluoroarsenate, and silver sulfate can be mentioned.
銀塩の添加量は、理論当量以上、例えば銅を元粉として用いる場合、銅１モルに対して銀２モル以上、特に２．１モル以上となるように添加するのが好ましい。２モルより少ないと、置換が不十分となり銀粉粒子中に銅が多く残留する。但し、２．５モル以上入れても不経済である。 The addition amount of the silver salt is preferably the theoretical equivalent or more, for example, when copper is used as the base powder, the silver salt is added so as to be 2 mol or more, particularly 2.1 mol or more with respect to 1 mol of copper. When the amount is less than 2 mol, the substitution is insufficient and a large amount of copper remains in the silver powder particles. However, it is not economical to add 2.5 mol or more.
銀塩は、攪拌しながらゆっくりと時間をかけて加えるのが好ましい。一度に多量に加えると、銀塩が大過剰となり、元粉と置換反応しない銀イオンが多量に生じ、銀が単独で析出するようになる。但し、あまり長時間になると、元粉が酸化して酸化皮膜を形成するため、適度な時間、例えば３０分〜１２０分かけて銀塩濃度が０．１〜１０ｇ／Ｌとなるように調整するのが好ましい。 The silver salt is preferably added slowly over time with stirring. When a large amount is added at once, the silver salt becomes excessively large, a large amount of silver ions that do not undergo a substitution reaction with the original powder is generated, and silver is precipitated alone. However, if the time is too long, the base powder is oxidized to form an oxide film, so that the silver salt concentration is adjusted to 0.1 to 10 g / L over an appropriate time, for example, 30 minutes to 120 minutes. Is preferred.
置換反応終了の目安としては、得られた銀粉粒子の銀の含有率が９９質量％以上（元粉金属の含有量１質量％未満）、好ましくは銀の含有率が９９．８質量％以上（元粉金属の含有量０．２質量％未満）、さらに好ましくは銀の含有率が９９．９質量％以上（元粉金属の含有量０．１質量％未満）に達した時点で終了させるのが好ましい。
銀粉粒子における銀の含有率は、銀塩の添加量、反応時間、反応速度、キレート化剤の添加量などによって調整することができる。
置換反応終了後は、銀粉粒子を十分に洗浄し、乾燥させるのが好ましい。
なお、得られた粒子の銀の含有率が９９質量％以上（元粉金属の含有量１質量％未満）であれば、得られた粒子を銀粉粒子と認めることができる。
本銀粉を上記のように製造する場合、元粉金属を完全置換することは難しいが、元粉金属の含有割合は０．０１質量％〜１質量％、特に０．０１質量％〜０．５質量％、中でも特に０．０１質量％〜０．３質量％であるのが好ましい。
As a measure of completion of the substitution reaction, the silver content of the obtained silver powder particles is 99% by mass or more (the content of the original powder metal is less than 1% by mass), preferably the silver content is 99.8% by mass or more ( The content of the base powder metal is less than 0.2% by mass), more preferably, when the silver content reaches 99.9% by mass or more (the content of the base powder metal is less than 0.1% by mass). Is preferred.
The silver content in the silver powder particles can be adjusted by the amount of silver salt added, the reaction time, the reaction rate, the amount of chelating agent added, and the like.
After completion of the substitution reaction, the silver powder particles are preferably thoroughly washed and dried.
In addition, if the content rate of silver of the obtained particle | grains is 99 mass% or more (content of the original powder metal is less than 1 mass%), the obtained particle | grains can be recognized as a silver powder particle.
When the present silver powder is produced as described above, it is difficult to completely replace the original powder metal, but the content ratio of the original powder metal is 0.01% by mass to 1% by mass, particularly 0.01% by mass to 0.5%. It is preferable that it is mass%, especially 0.01 mass%-0.3 mass% especially.
以下、本発明の実施例について説明するが、本発明が以下の実施例に限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited to the following examples.
＜中空部比率、中空銀粉粒子比率＞
銀粉１ｇをシリコーン樹脂２ｇに混合して硬化させた樹脂体の断面を切断し、この断面をＳＥＭ（Scanning Electron Microscope、走査型電子顕微鏡、１０００倍）で撮影し、得られたＳＥＭ写真を画像解析ソフト（（株）マウンテック社製「ＭＡＣ−ＶＩＥＷ」）で解析し、１視野における銀粉粒子の全断面積合計に対する、１視野における中空部の断面積合計の割合（中空部合計断面積／全断面積）を測定した。表１には、「中空部比率」として示した。この際、中空部が確認できない粒子は無視した。
<Hollow part ratio, hollow silver powder particle ratio>
A cross section of a cured resin body obtained by mixing 1 g of silver powder with 2 g of a silicone resin is cut, the cross section is photographed with an SEM (Scanning Electron Microscope, scanning electron microscope, 1000 times), and the obtained SEM photograph is subjected to image analysis. Analysis by software ("MAC-VIEW" manufactured by Mountec Co., Ltd.) The ratio of the total cross-sectional area of the hollow part in one field of view to the total cross-sectional area of silver powder particles in one field of view (total cross-sectional area of hollow part / total interruption) Area). In Table 1, it was shown as “hollow part ratio”. At this time, particles in which the hollow portion could not be confirmed were ignored.
また、同ＳＥＭ写真を同画像解析ソフトを用いて、１視野における全銀粉粒子の全断面積合計に対する、１視野における全中空銀粉粒子の断面積合計の割合（全中空銀粉粒子合計断面積／全銀粉粒子合計断面積）を測定した。表１には、「中空銀粉粒子比率」として示した。 Moreover, the ratio of the total cross-sectional area of all the hollow silver powder particles in one visual field to the total cross-sectional area of all silver powder particles in one visual field using the same image analysis software (the total cross-sectional area of all hollow silver powder particles / total Silver powder particle total cross-sectional area) was measured. In Table 1, it was shown as “hollow silver powder particle ratio”.
＜粒度測定＞
測定サンプル（銅粉）を少量ビーカーに取り、３％トリトンＸ溶液（関東化学製）を２、３滴添加し、粉末になじませてから、０．１％ＳＮディスパーサント４１溶液(サンノプコ製)５０ｍＬを添加し、その後、超音波分散器ＴＩＰφ２０（日本精機製作所製、OUTPUT：8、TUNING：5）を用いて５分間分散処理して測定用サンプルを調製した。
この測定用サンプルを、レーザー回折散乱式粒度分布測定装置ＭＴ３３００ (日機装製)を用いて、体積累積基準Ｄ１０、Ｄ９０、Ｄ５０、Ｄmax、ＣＶ（変動係数）を測定した。
<Particle size measurement>
Take a measurement sample (copper powder) in a small amount of beaker, add a few drops of 3% Triton X solution (manufactured by Kanto Chemical Co., Ltd.), and blend with the powder. Then 0.1% SN Dispersant 41 solution (manufactured by San Nopco) 50 mL was added, and then a measurement sample was prepared by dispersing for 5 minutes using an ultrasonic disperser TIPφ20 (Nippon Seiki Seisakusho, OUTPUT: 8, TUNING: 5).
This sample for measurement was measured for volume accumulation standards D10, D90, D50, Dmax, and CV (coefficient of variation) using a laser diffraction / scattering particle size distribution analyzer MT3300 (manufactured by Nikkiso).
＜体積固有抵抗値の測定方法＞
抵抗率測定は、試料１５ｇを筒状容器に入れプレス圧４０×１０６Ｐａ（４０８ｋｇｆ／ｃｍ2）で圧縮成形した測定サンプルを形成し、ロレスタＡＰ及びロレスタＰＤ−４１型（いずれも三菱化学（株）社製）により測定を行った。
<Measurement method of volume resistivity>
The resistivity measurement was performed by forming a measurement sample in which 15 g of a sample was put in a cylindrical container and compression-molded with a press pressure of 40 × 10 6 Pa (408 kgf / cm 2 ), and Loresta AP and Loresta PD-41 types (both Mitsubishi Chemical Corporation) The measurement was carried out.
＜体積収縮率の測定方法＞
熱機械分析装置(ＴＭＡ)を用いて体積収縮率を測定した。測定条件としては、空気を１５０ｍＬ／ｍｉｎで流通させ、温度範囲２０〜８７０℃、昇温速度１０℃／ｍｉｎでサンプルを加熱し、得られたＴＡＭのチャートから、４００℃から６００℃に加熱した時の体積収縮率（４００℃から６００℃の間の体積収縮率の差）を算出した。
<Measurement method of volumetric shrinkage>
Volume shrinkage was measured using a thermomechanical analyzer (TMA). As measurement conditions, air was circulated at 150 mL / min, the sample was heated at a temperature range of 20 to 870 ° C., and a heating rate of 10 ° C./min, and was heated from 400 ° C. to 600 ° C. from the obtained TAM chart. The volumetric shrinkage ratio (the difference in volumetric shrinkage ratio between 400 ° C. and 600 ° C.) was calculated.
（実施例１）
デンドライト状電解銅粉（図１参照、純度９９％以上、Ｄ５０：１５．８８μｍ）３００ｇを、５０℃に保温した３０００ｍｌの純水に投入し、５分間攪拌混合してスラリーとした。次いで、還元剤である１００％ヒドラジンを２７．６ｇ投入し、３０分間攪拌を維持して還元処理を行なった。その後、ブフナロートにて固液分離し、１．８Ｌの純水で洗浄した後、メタノールを０．５ｍＬ添加処理して前処理済銅粉を得た。
Example 1
300 g of dendritic electrolytic copper powder (see FIG. 1, purity 99% or more, D50: 15.88 μm) was put into 3000 ml of pure water kept at 50 ° C. and stirred for 5 minutes to obtain a slurry. Next, 27.6 g of 100% hydrazine as a reducing agent was added, and the reduction treatment was performed while maintaining stirring for 30 minutes. Then, after solid-liquid separation with a buchner funnel and washing with 1.8 L of pure water, 0.5 mL of methanol was added to obtain a pretreated copper powder.
次に、３０００ｍＬの純水を４０℃に加熱させ、上記得られた全ての前処理済銅粉を投入し、５分間攪拌混合してスラリーとした。次いで、ＥＤＴＡを１２７．８ｇ投入して１０分間攪拌した後、予め用意しておいた硝酸銀溶液４．２Ｌ（硝酸銀１６８０ｇ）を２時間かけて攪拌しながら滴下して置換反応を進めた後、５分間攪拌を止めて静置してエージング処理を行なった。その後、ブフナロートにて固液分離し、３０００ｍＬの純水で洗浄した後、メタノール５００ｍＬ添加処理後、続いてアセトン５００ｍＬで脱水処理を行い、得られたケーキをステンレス製バットに移し変えて１００℃の雰囲気で５時間乾燥させて銀粉粒子を得た。 Next, 3000 mL of pure water was heated to 40 ° C., and all of the pretreated copper powder obtained above were added and stirred for 5 minutes to form a slurry. Next, 127.8 g of EDTA was added and stirred for 10 minutes. Then, 4.2 L (1680 g of silver nitrate) prepared in advance was added dropwise with stirring over 2 hours, and the substitution reaction proceeded. Stirring was stopped for a minute and the mixture was allowed to stand for aging treatment. Then, after solid-liquid separation with a buchner funnel and washing with 3000 mL of pure water, 500 mL of methanol was added, followed by dehydration with 500 mL of acetone, and the resulting cake was transferred to a stainless steel vat at 100 ° C. Silver powder particles were obtained by drying in an atmosphere for 5 hours.
得られた銀粉粒子をＳＥＭ観察（２０００倍）及びＦＩＢ／ＳＥＭ断面加工観察（５０００倍）したところ、いずれの粒子も、粒子内部に空洞部を有すると共に、この空洞部と外部とを連通する孔を備えていた（図２、図３）。
また、Ｄ５０は１５．５４μｍ、Ｃｕ含有率は０．１３質量％（銀：９９．８７質量％）、体積固有抵抗値は４．０×１０-5ｍΩ・ｃｍであった。
When the obtained silver powder particles were observed by SEM (2000 times) and FIB / SEM cross-section processing observation (5000 times), each particle had a cavity inside the particle and a hole communicating this cavity with the outside. (FIGS. 2 and 3).
Further, D50 was 15.54 μm, the Cu content was 0.13 mass% (silver: 99.87 mass%), and the volume resistivity value was 4.0 × 10 −5 mΩ · cm.
（実施例２）
硝酸銀溶液の滴下時間を３０分間に変更した以外、実施例１と同様にして銀粉粒子を得た。
得られた銀粉粒子をＳＥＭ観察（２０００倍）及びＦＩＢ／ＳＥＭ断面加工観察（５０００倍）したところ、いずれの粒子も、粒子内部に空洞部を有すると共に、この空洞部と外部とを連通する孔を備えていた。
また、Ｄ５０は１４．９３μｍ、Ｃｕ含有率は０．１３質量％（銀：９９．８７質量％）、体積固有抵抗値は５．１×１０-5ｍΩ・ｃｍであった。
(Example 2)
Silver powder particles were obtained in the same manner as in Example 1 except that the dropping time of the silver nitrate solution was changed to 30 minutes.
When the obtained silver powder particles were observed by SEM (2000 times) and FIB / SEM cross-section processing observation (5000 times), each particle had a cavity inside the particle and a hole communicating this cavity with the outside. It was equipped with.
Further, D50 was 14.93 μm, the Cu content was 0.13 mass% (silver: 99.87 mass%), and the volume resistivity value was 5.1 × 10 −5 mΩ · cm.
（実施例３）
硝酸銀溶液の滴下時間を６０分間に変更した以外、実施例１と同様にして銀粉粒子を得た。
得られた銀粉粒子をＳＥＭ観察（２０００倍）及びＦＩＢ／ＳＥＭ断面加工観察（５０００倍）したところ、いずれの粒子も、粒子内部に空洞部を有すると共に、この空洞部と外部とを連通する孔を備えていた。
また、Ｄ５０は１９．４７μｍ、Ｃｕ含有率は０．１３質量％（銀：９９．８７質量％）、体積固有抵抗値は４．０×１０-5ｍΩ・ｃｍであった。
(Example 3)
Silver powder particles were obtained in the same manner as in Example 1 except that the dropping time of the silver nitrate solution was changed to 60 minutes.
When the obtained silver powder particles were observed by SEM (2000 times) and FIB / SEM cross-section processing observation (5000 times), each particle had a cavity inside the particle and a hole communicating this cavity with the outside. It was equipped with.
Further, D50 was 19.47 μm, the Cu content was 0.13 mass% (silver: 99.87 mass%), and the volume resistivity value was 4.0 × 10 −5 mΩ · cm.
（考察）
本実施例のように、電解銅粉（デンドライト状）を元粉として銀の置換反応を長時間実施することにより、図２及び図３に示されるように、粒子内部が中空部となった中空銀粉粒子が得られることが分った。また、この中空銀粉粒子の多く（少なくとも５０個％以上）は、図２及び図３に示されるように、中空部と外部とを連通する穴を有していることが確認された。
また、図４に示されるように、本実施例の銀粉は、ＴＭＡのチャートをみると、２５０℃付近（±１０℃）で一旦膨張し、その後４００℃付近（±１０℃）からゆっくりと収縮することが確認された。
(Discussion)
As shown in FIG. 2 and FIG. 3, by carrying out a silver substitution reaction for a long time using electrolytic copper powder (dendritic form) as a base powder as in this example, the inside of the particle became a hollow part. It was found that silver powder particles were obtained. Further, it was confirmed that many of the hollow silver powder particles (at least 50% or more) have holes that connect the hollow portion and the outside, as shown in FIGS.
Also, as shown in FIG. 4, the silver powder of this example, when viewed from the TMA chart, once expands around 250 ° C. (± 10 ° C.), and then slowly contracts from around 400 ° C. (± 10 ° C.). Confirmed to do.
Claims (7)
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| JP2007211721A JP2009046708A (en) | 2007-08-15 | 2007-08-15 | Silver powder |
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| JP2007211721A JP2009046708A (en) | 2007-08-15 | 2007-08-15 | Silver powder |
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| JP2009046708A true JP2009046708A (en) | 2009-03-05 |
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