JPH0320341A - Copper powder for thick film composition - Google Patents

Copper powder for thick film composition

Info

Publication number
JPH0320341A
JPH0320341A JP1153831A JP15383189A JPH0320341A JP H0320341 A JPH0320341 A JP H0320341A JP 1153831 A JP1153831 A JP 1153831A JP 15383189 A JP15383189 A JP 15383189A JP H0320341 A JPH0320341 A JP H0320341A
Authority
JP
Japan
Prior art keywords
copper powder
thick film
weight
film composition
organic zirconate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP1153831A
Other languages
Japanese (ja)
Inventor
Kentaro Mito
三戸 兼太郎
Toru Iwasaki
透 岩崎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsui Mining and Smelting Co Ltd
Original Assignee
Mitsui Mining and Smelting Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsui Mining and Smelting Co Ltd filed Critical Mitsui Mining and Smelting Co Ltd
Priority to JP1153831A priority Critical patent/JPH0320341A/en
Publication of JPH0320341A publication Critical patent/JPH0320341A/en
Pending legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/09Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092Dispersed materials, e.g. conductive pastes or inks
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/09Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092Dispersed materials, e.g. conductive pastes or inks
    • H05K1/095Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder

Landscapes

  • Compositions Of Macromolecular Compounds (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Paints Or Removers (AREA)
  • Powder Metallurgy (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)

Abstract

PURPOSE:To obtain a copper powder for a thick film composition excellent in conductivity, a long-term stability and workability by coating the surface of a copper powder having a specified reduction loss with an organic zirconate compound. CONSTITUTION:A copper powder prepared by coating the surface of a copper powder having a reduction loss <=0.5wt.% based on the weight of the copper powder with 0.01-0.5wt.% organic zirconate compound based on the weight of the copper powder. Because the above copper powder has a specified low reduction loss, it is amenable to an effect of the additive present in a thick film composition. Because the surface of this copper powder is coated with a specified amount of an organic zirconate compound which can enhance the dispersibility of the copper powder in the thick film composition and promotes the development of the thixotropy of the composition. This is because the affinity of the organic zirconate compound for molecules of the resin binder in the thick film composition can be increased by the oleophilic group moiety of the organic zirconate compound in such a way that they can be bonded through electrostatic and chemical bonds such as the van der Waals force, ionic bonds, covalent bonds and coordination bonds.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は電磁放射対策用に用いられる厚膜綱組成物用銅
粉に関し、特に還元減量が低く、がつ有機ジルコネート
化合物で表面被覆された銅粉を用いることによって導電
性、経時性、作業性を向上させた電磁波シールド厚膜組
成物用銅粉に係る。
[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to copper powder for thick film compositions used for electromagnetic radiation countermeasures, and in particular has low reduction loss and has a surface coated with an organic zirconate compound. The present invention relates to copper powder for use in electromagnetic shielding thick film compositions that has improved conductivity, aging properties, and workability by using copper powder.

〔従来の技術〕[Conventional technology]

コンピュータ等の電子機器から放射される電磁波による
障害を防止し,この電磁波をシールドするため厚膜組成
物が多用されている.これら厚膜組成物は他の手段に比
べて工程の低減、工程の簡略化等の種々利点を有する. 一般に、このような厚膜組成物に用いられる導電性フィ
ラーは組成物の各種物性を決定付ける主要な因子であり
、その意味から廉価でかつシールド効果に優れた銅粉が
主流となっている。
Thick film compositions are often used to prevent interference from electromagnetic waves emitted from computers and other electronic devices, and to shield these electromagnetic waves. These thick film compositions have various advantages over other methods, such as reduction in process steps and simplification of processes. Generally, the conductive filler used in such thick film compositions is a major factor determining various physical properties of the composition, and for this reason, copper powder, which is inexpensive and has an excellent shielding effect, has become mainstream.

従来、厚膜組或物の各種特性を向上させるため、銅粉を
有機カルボン酸で処理する(特公昭64−20276)
 ,有機チタネート、シラン、アルミネート化合物で表
面被覆する(特公昭59−75931等)、あるいは各
種有機系添加剤を用いる(特公・昭63−83179.
59−36170. 59−158905等)等の発明
が公知である. 〔発明が解決しようとする問題点〕 しかしながら、これらの処理方法によった銅粉を用いた
組或物では初期導電性が改善されるものもあるが.ほと
んど環境試験によって経時性が不良となるものであった
,また、各種金属有機化合物や有機カルボン酸によって
銅粉表面を被覆処理した場合、極端に厚膜組成物の機械
的強度が低下したり、導電性の改善の面でもそのほとん
どが効果を示さないものであった。
Conventionally, in order to improve various properties of thick film composites, copper powder was treated with organic carboxylic acid (Japanese Patent Publication No. 64-20276).
, coating the surface with organic titanate, silane, or aluminate compound (Japanese Patent Publication No. 59-75931, etc.), or using various organic additives (Japanese Patent Publication No. 83179-1989).
59-36170. 59-158905, etc.) are publicly known. [Problems to be Solved by the Invention] However, some of the assemblies using copper powder produced by these treatment methods have improved initial conductivity. In most environmental tests, the aging properties were poor, and when the copper powder surface was coated with various metal organic compounds or organic carboxylic acids, the mechanical strength of the thick film composition was extremely reduced. Most of them showed no effect in terms of improving conductivity.

本発明は銅粉特有の導電性を改善ら、しかも経時性、作
業性を著しく向上させた厚膜組或物用銅粉を提供するこ
とを目的とするものである.〔問題点を解決するための
手段〕 上記課題を改善するものとして本出願人は先に銅粉表面
を有機ジルコネート化合物で被覆処理した銅粉を提案し
た(特願昭63−21630号).これにより、導電性
および耐環境性に優れた銅粉が得られるが、かかる技術
課題に対する本発明者らのその後の継続的研究により、
有機ジルコネート化合物による表面被覆を施す場合、銅
粉の還元減量および有機ジルコネート化合物の被覆量が
厚膜組成物の特性に著しい影響を及ぼすことを見出し、
本発明をなすに至った。
The object of the present invention is to provide a copper powder for use in thick film assemblies, which has improved conductivity peculiar to copper powder, and has significantly improved aging properties and workability. [Means for Solving the Problems] In order to improve the above-mentioned problems, the present applicant previously proposed a copper powder whose surface was coated with an organic zirconate compound (Japanese Patent Application No. 63-21630). As a result, copper powder with excellent conductivity and environmental resistance can be obtained, but as a result of subsequent continuous research by the present inventors to address these technical issues,
It was discovered that when surface coating is performed with an organic zirconate compound, the reduction loss of the copper powder and the amount of the organic zirconate compound coated have a significant effect on the properties of the thick film composition.
The present invention has been accomplished.

すなわち、本発明による厚膜組成物用銅粉は、銅粉重量
に対する還元減量が0.5重量%以下の銅粉表面に,有
機ジルコネート化合物が銅粉重量に対して0.01〜0
.5重量%被覆処理されたものである. 〔作  用〕 以上のように本発明の銅粉は,特定の還元減量の少ない
ものを用いるので、厚膜組成物中に存在する添加剤の効
果を受け易くする.すなわち、銅粉表面の酸化物が還元
反応によって除去され易くなり、表面が0価の銅となり
易くなる。
That is, the copper powder for a thick film composition according to the present invention has an organic zirconate compound on the surface of the copper powder whose reduction loss is 0.5% by weight or less based on the weight of the copper powder.
.. It was coated with 5% by weight coating. [Function] As described above, since the copper powder of the present invention has a small specific reduction loss, it is easily affected by the additives present in the thick film composition. In other words, oxides on the surface of the copper powder are easily removed by a reduction reaction, and the surface is likely to become zero-valent copper.

さらに、本発明ではこの銅粉表面が特定量の有機ジルコ
ネート化合物で被覆されているため、この有機ジルコネ
ート化合物が厚膜組成物中における銅粉の分散性を高め
,しがも厚膜組或物のチクソ性の発現を促進させる.こ
れは有機ジルコネート化合物の親油基部分が厚膜組成物
中の樹脂バインダー分子とファンデルヮース力、イオン
結合、共有結合、配位結合等の静電的、化学的結合によ
り親和力を増すためである。
Furthermore, in the present invention, since the surface of this copper powder is coated with a specific amount of an organic zirconate compound, this organic zirconate compound improves the dispersibility of the copper powder in the thick film composition, and thus the thick film composition. promotes the expression of thixotropy. This is because the lipophilic group portion of the organic zirconate compound increases its affinity with the resin binder molecules in the thick film composition through electrostatic and chemical bonds such as van der Waals forces, ionic bonds, covalent bonds, and coordinate bonds.

以下に本発明をより詳細に説明する. 本発明で用いられる銅粉は、電解法,アトマイズ法、化
学還元法等の製造方法で得られるものすべてが挙げられ
,特別限定する必要はない。
The present invention will be explained in more detail below. The copper powder used in the present invention includes all those obtained by manufacturing methods such as electrolytic method, atomization method, and chemical reduction method, and there is no need to specifically limit the copper powder.

銅粉物性は見掛密度1.5g/a1以上,好ましくは2
.0g/a#以上,タップ密度2.0g/ffl以上、
好ましくは3.0g/ai以上、そして粒度分布は50
μm以上の粒径を有する粉が存在しない方が良い.これ
は厚膜組威物を形成する際の銅粉充填幅の拡大と表面平
滑性を増すためである.本発明で用いられる銅粉特性で
最も重要な点は銅粉表面の還元減量であり、それが任意
な表面処理を施さない状態で1.0重量%以下、好まし
くは0.5重量%以下の還元減量を有する銅粉を用いる
必要がある.これは還元減量が0.5重量%以下であれ
ば、厚膜組戒物を形成する際に用いられる一般的な添加
剤の効果を受け易く良好な導電性を得られるためである
.これに反し還元減量が0.5重量%を越えるとその添
加剤の効果を除々に受けにくくなり、1.0重量%を越
えるとその傾向が著しくなり、全く効果を示さなくなる
。ここで述べている添加剤とは銅化合物、例えば酸化物
と還元反応をしてO価の銅にする一般的な物質である。
The physical properties of copper powder are an apparent density of 1.5 g/a1 or more, preferably 2
.. 0g/a# or more, tap density 2.0g/ffl or more,
Preferably 3.0g/ai or more, and particle size distribution is 50
It is better that there is no powder with a particle size of μm or more. This is to expand the copper powder filling width and improve surface smoothness when forming a thick film composite. The most important characteristic of the copper powder used in the present invention is the reduction loss on the surface of the copper powder, which is 1.0% by weight or less, preferably 0.5% by weight or less without any surface treatment. It is necessary to use copper powder that has a reduction loss. This is because if the reduction loss is 0.5% by weight or less, it is easy to be affected by the general additives used when forming thick film composite materials, and good conductivity can be obtained. On the other hand, if the reduction loss exceeds 0.5% by weight, the effects of the additive will gradually become less effective, and if it exceeds 1.0% by weight, this tendency will become more pronounced and no effect will be exhibited at all. The additives mentioned here are common substances that undergo a reduction reaction with copper compounds, such as oxides, to form O-valent copper.

なおJ本明細書において、還元減量とは,例えばH!ガ
ス、NH,ガス等の還元性ガスによって、高温雰囲気中
で銅粉が減量する程度,換言すれば銅粉の酸化量を意味
する.実際的には厚膜組成物中には、必ずといえる程、
還元剤効果を有する添加物が加えられており,バインダ
ーとしてのフェノール系樹脂の合成にも還元剤が用いら
れており、それが含まれていることもあり、本発明では
これらによって銅粉が還元される際の重量減量を規定す
るものである.また銅粉表面に被覆する有機ジルコネー
ト化合物は,ジルコニウムアルコキシドを飽和もしくは
不飽和の高級脂肪酸でアシレート化した親木基,例えば
アルコール基と親油基,例えばアシレート基を有するも
のである.特性上好ましいものとしてはテトラn−ブト
キシジルコニウムやテトライソプロポキシジルコニウム
に対して,数倍モルのカプロン酸,カブリン酸、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、リノレイン酸、リシノール酸
およびその異性体を反応させて得られるものである.こ
の有機ジルコネート化合物は銅粉重量に対して0.00
1〜1.0重量%表面被覆される.特性上,好ましくは
0.Ol〜0.5重量%表面被覆される。被覆量が0.
Ol重量%未溝になると厚膜組或物の導電性の低下とチ
クソ性の低下がみられるようになり,o.oot重量%
未満になるとその傾向が著しくなる.また、0.5重量
%を超えると、厚膜組或物と基材の密着性が低下するよ
うになり、1.0重量%を超えるとその傾向が著しくな
る. この有機ジルコネート化合物による銅粉の被覆処理は、
銅粉に対し溶剤に溶解した有機ジルコネート化合物を添
加し、その後に溶剤を除去する方法、銅粉に対し必要量
の有機ジルコネート化合物を添加し,混合撹拌する方法
等により行うことができる. このようにして得られた銅粉5は、基本的に樹脂バイン
ダー、溶剤を含有させて組成物となし、導電性塗料とし
て厚膜塗布され、実用に供せられる. 以下に実施例を示す. 〔実施例】 まず、具体的実施例を挙げる前に、これら実施例で用い
られた銅粉、有機ジルコネート化合物および比較サンプ
ルをそれぞれ第1表〜第3表に示す. TD:充填密度 但し、粒径は光透過法で測定し.Nal〜4のいずれも
粒径〉50μ暖の銅粉は存在していない。
Note that in this specification, reduced weight loss refers to, for example, H! It means the amount by which copper powder is reduced in weight in a high temperature atmosphere by a reducing gas such as gas, NH, gas, etc. In other words, it means the amount of oxidation of copper powder. In practice, thick film compositions almost always contain
Additives that have a reducing agent effect are added, and reducing agents are also used in the synthesis of phenolic resins as binders, so in the present invention, copper powder is reduced by these. This stipulates the weight loss when Furthermore, the organic zirconate compound coated on the surface of the copper powder has parenteral groups such as alcohol groups and lipophilic groups such as acylate groups, which are obtained by acylating zirconium alkoxide with saturated or unsaturated higher fatty acids. Preferred properties are caproic acid, cabric acid, lauric acid, myristic acid, pal. Mitic acid, stearic acid,
It is obtained by reacting oleic acid, linoleic acid, linoleic acid, ricinoleic acid, and their isomers. This organic zirconate compound is 0.00% based on the weight of copper powder.
1 to 1.0% by weight of surface coating. In terms of characteristics, preferably 0. Ol ~ 0.5% by weight surface coated. Coverage amount is 0.
When the Ol weight% becomes ungrooved, a decrease in the conductivity and thixotropy of the thick film assembly can be seen, and o. oot weight%
This tendency becomes more pronounced when the value is less than 20%. Furthermore, if the content exceeds 0.5% by weight, the adhesion between the thick film assembly and the base material will decrease, and if it exceeds 1.0% by weight, this tendency will become significant. Coating treatment of copper powder with this organic zirconate compound is as follows:
This can be done by adding an organic zirconate compound dissolved in a solvent to the copper powder and then removing the solvent, or by adding the required amount of the organic zirconate compound to the copper powder and mixing and stirring. The copper powder 5 thus obtained is basically made into a composition containing a resin binder and a solvent, and is applied in a thick film as a conductive paint for practical use. An example is shown below. [Examples] First, before giving specific examples, the copper powder, organic zirconate compound, and comparative samples used in these examples are shown in Tables 1 to 3, respectively. TD: Packing density However, the particle size is measured by a light transmission method. There is no copper powder with a particle size>50μ in any of Nal~4.

(以下余白) 実施例1 第1表の銅粉を用い、樹脂バインダーとしてレゾール型
フェノール樹脂溶液(固形分65重量%)、溶剤として
エチル力ルビトールを用いて混合分散機で厚膜組成物を
調製した.スクリーン印刷機で2.5cmX2.5cm
、膜厚30〜354厘の厚膜を形成して体積固有抵抗を
測定した.その結果を第4表に示す. (以下余白) 第4表 第6表 (60℃795%RH) この第4表から、還元減量の少ない銅粉ほど優れた導電
性を有していることがわかる.実施例2 実施例1の厚膜組或物を85℃の循環オーブンと60℃
795%Rl1の恒温恒湿槽に放置して導電性の経時変
化をw4察した.その結果を第5表および第6表に示す
. 第5表     (85℃) 第5表および第6表から,還元減量の少ない銅粉は優れ
た経時性を有していることがわかる。
(Left below) Example 1 A thick film composition was prepared using a mixing and dispersing machine using the copper powder shown in Table 1, a resol-type phenolic resin solution (solid content 65% by weight) as a resin binder, and ethyl rubitol as a solvent. did. 2.5cm x 2.5cm with screen printing machine
A thick film with a thickness of 30 to 354 mm was formed and the volume resistivity was measured. The results are shown in Table 4. (Leaving space below) Table 4 Table 6 (60°C, 795% RH) From Table 4, it can be seen that the copper powder with less reduction loss has better conductivity. Example 2 The thick film assembly of Example 1 was heated in a circulating oven at 85°C and at 60°C.
It was left in a constant temperature and humidity chamber at 795% Rl1, and changes in conductivity over time were observed w4. The results are shown in Tables 5 and 6. Table 5 (85° C.) From Tables 5 and 6, it can be seen that the copper powder with less reduction loss has excellent aging properties.

実施例3 第1表の銅粉に対し,第2表の有機ジルコネート化合物
を各々銅粉重量に対して0.01,0.05,0.5重
景%表面被覆し,実施例lと同様に厚膜組成物を調製し
,体積固有抵抗を測定した.その結果を第7表に示す. (以下余白) 第7表 第7表の結果から、還元減量の少ない銅粉ほど優れた導
電性を有していることがわかる.実施例4 Nlllの銅粉に有機ジルコネート化合物を処理量0.
1重量%被覆し、これを実施例1および実施例3と同様
にして厚膜組成物を調製し,そのチクソ性をE型粘度計
を用いて比較した.その結果を第8表に示す. 第8表      (20℃) ことがわかる.このことから、スクリーン印刷特性(作
業性)が優れていることがわかる。
Example 3 The surface of the copper powder shown in Table 1 was coated with the organic zirconate compounds shown in Table 2 at 0.01, 0.05, and 0.5 percent by weight based on the weight of the copper powder, and the same as in Example 1 was applied. A thick film composition was prepared and the volume resistivity was measured. The results are shown in Table 7. (Left below) Table 7 From the results in Table 7, it can be seen that the copper powder with less reduction loss has better conductivity. Example 4 A treatment amount of an organic zirconate compound was 0.00% to Nllll copper powder.
Thick film compositions were prepared in the same manner as in Examples 1 and 3, and their thixotropy was compared using an E-type viscometer. The results are shown in Table 8. It can be seen from Table 8 (20℃). This shows that the screen printing properties (workability) are excellent.

実施例5 第1表の&1および&4の銅粉を用いて,実施例1と同
様に厚膜組成物を調製し、体積固有抵抗を測定した。但
し、第3表の比較サンプルを銅粉重量に対し、0.1重
量%厚膜組或物中に添加した.その結果を第9表に示す
. 第9表 第8表の結果から、有機ジルコネート化合物で表面被覆
した銅粉は優れたチクソ性を有する以上の結果から、還
元減量の少ない銅粉は添加剤の効果を受けて導電性が向
上することがわかる。また,実施例3の結果と比較して
も有機ジルコネート化合物で表面被覆された銅粉は優れ
た導電性を有することがわかる. 〔発明の効果〕
Example 5 A thick film composition was prepared in the same manner as in Example 1 using the copper powders &1 and &4 in Table 1, and the volume resistivity was measured. However, 0.1% by weight of the comparative sample shown in Table 3 was added to the thick film composition based on the weight of the copper powder. The results are shown in Table 9. From the results in Table 9 and Table 8, it can be seen that copper powder whose surface is coated with an organic zirconate compound has excellent thixotropy.From the above results, copper powder with less reduction loss has improved conductivity due to the effect of additives. I understand that. Furthermore, when compared with the results of Example 3, it can be seen that the copper powder whose surface is coated with an organic zirconate compound has excellent conductivity. 〔Effect of the invention〕

Claims (1)

【特許請求の範囲】[Claims] 1.銅粉重量に対する還元減量が0.5重量%以下の銅
粉表面に、有機ジルコネート化合物が銅粉重量に対して
0.01〜0.5重量%被覆処理された厚膜組成物用銅
銅粉。
1. Copper powder for thick film compositions, in which the surface of the copper powder whose reduction loss relative to the weight of the copper powder is 0.5% by weight or less is coated with 0.01 to 0.5% by weight of an organic zirconate compound based on the weight of the copper powder. .
JP1153831A 1989-06-16 1989-06-16 Copper powder for thick film composition Pending JPH0320341A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP1153831A JPH0320341A (en) 1989-06-16 1989-06-16 Copper powder for thick film composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP1153831A JPH0320341A (en) 1989-06-16 1989-06-16 Copper powder for thick film composition

Publications (1)

Publication Number Publication Date
JPH0320341A true JPH0320341A (en) 1991-01-29

Family

ID=15571044

Family Applications (1)

Application Number Title Priority Date Filing Date
JP1153831A Pending JPH0320341A (en) 1989-06-16 1989-06-16 Copper powder for thick film composition

Country Status (1)

Country Link
JP (1) JPH0320341A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003023790A1 (en) * 2001-09-06 2003-03-20 Noritake Co.,Limited Conductor composition and method for production thereof
US6826031B2 (en) 2001-09-06 2004-11-30 Noritake Co., Limited Ceramic electronic component and production method therefor
KR100843163B1 (en) * 2007-04-23 2008-07-02 박상윤 Blood back flow prevention catheter

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003023790A1 (en) * 2001-09-06 2003-03-20 Noritake Co.,Limited Conductor composition and method for production thereof
US6826031B2 (en) 2001-09-06 2004-11-30 Noritake Co., Limited Ceramic electronic component and production method therefor
CN1316509C (en) * 2001-09-06 2007-05-16 诺利塔克股份有限公司 Conductor composition and method for production thereof
KR100866220B1 (en) * 2001-09-06 2008-10-30 가부시키가이샤 노리타케 캄파니 리미티드 Conductor composition and method for production thereof
KR100843163B1 (en) * 2007-04-23 2008-07-02 박상윤 Blood back flow prevention catheter

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