JPS61179802A - Treatment of metallic powder - Google Patents
Treatment of metallic powderInfo
- Publication number
- JPS61179802A JPS61179802A JP60021407A JP2140785A JPS61179802A JP S61179802 A JPS61179802 A JP S61179802A JP 60021407 A JP60021407 A JP 60021407A JP 2140785 A JP2140785 A JP 2140785A JP S61179802 A JPS61179802 A JP S61179802A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- metal powder
- metallic powder
- titanate
- coupling agent
- 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.)
- Granted
Links
- 239000000843 powder Substances 0.000 title claims abstract description 58
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000007822 coupling agent Substances 0.000 claims abstract description 27
- 150000001412 amines Chemical class 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims description 55
- 239000002184 metal Substances 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000000057 synthetic resin Substances 0.000 abstract description 25
- 229920003002 synthetic resin Polymers 0.000 abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 23
- 238000003756 stirring Methods 0.000 abstract description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004381 surface treatment Methods 0.000 abstract description 4
- IEKHISJGRIEHRE-UHFFFAOYSA-N 16-methylheptadecanoic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O IEKHISJGRIEHRE-UHFFFAOYSA-N 0.000 abstract description 3
- 229960004418 trolamine Drugs 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- -1 cyamylamine Chemical compound 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 230000002265 prevention Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- KKOHCQAVIJDYAF-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O KKOHCQAVIJDYAF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- SRORDPCXIPXEAX-UHFFFAOYSA-N CCCCCCCCCCCCCP(CCCCCCCCCCCCC)(O)(OCCCCCCCC)OCCCCCCCC.CCCCCCCCCCCCCP(CCCCCCCCCCCCC)(O)(OCCCCCCCC)OCCCCCCCC Chemical compound CCCCCCCCCCCCCP(CCCCCCCCCCCCC)(O)(OCCCCCCCC)OCCCCCCCC.CCCCCCCCCCCCCP(CCCCCCCCCCCCC)(O)(OCCCCCCCC)OCCCCCCCC SRORDPCXIPXEAX-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical group CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical group CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical group CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 1
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paints Or Removers (AREA)
- Powder Metallurgy (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野〕
本発明は合成樹脂に金属粉を充填して機能性を有する複
合材料を得るために最適な金属粉の処理方法に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for processing metal powder most suitable for filling a synthetic resin with metal powder to obtain a functional composite material.
具体的な利用分野の例を上げると、金属粉を充填した合
成樹脂成形材料としては、高比重材料、放射線遮蔽材料
、軸受材料、感圧スイッチ材料、導電材料、熱伝導材料
、耐摩耗材料1などが有る。To give examples of specific fields of use, synthetic resin molding materials filled with metal powder include high specific gravity materials, radiation shielding materials, bearing materials, pressure-sensitive switch materials, conductive materials, heat conductive materials, and wear-resistant materials1. etc.
また金属粉を配合した合成樹脂塗料の例としては、導電
性、電磁波シールド性、耐摩耗性を有するものが上げら
れる。Further, examples of synthetic resin paints containing metal powder include those having electrical conductivity, electromagnetic shielding properties, and abrasion resistance.
本発明により処理した金属粉は、合成樹脂との親和性が
良好で、かつ合成樹脂と有害な化学反応を起こさないた
め、金属粉を大量に充填しても合成樹脂複合材料の物理
的性質の劣化が少なく、また金属粉による合成樹脂の酸
化劣化の問題が生巳ない。さらに導電性など金属特有の
特性が維持されるため、新しい機能を有する複合材料の
開発が可能となる。The metal powder treated according to the present invention has good affinity with synthetic resins and does not cause harmful chemical reactions with synthetic resins, so even when filled with a large amount of metal powder, the physical properties of synthetic resin composite materials are There is little deterioration, and there is no problem of oxidative deterioration of the synthetic resin due to metal powder. Furthermore, since properties unique to metals, such as electrical conductivity, are maintained, it becomes possible to develop composite materials with new functions.
金属と合成樹脂とは一船に互に親和性に乏しく、また金
属粉の腐食、金属粉による合成樹脂の酸化劣化の問題が
生じるため種々の表面処理方法、添加剤が考案されてい
る。Metals and synthetic resins have poor affinity for each other, and there are problems of corrosion of metal powder and oxidative deterioration of synthetic resins due to metal powder, so various surface treatment methods and additives have been devised.
従来の技術としてベンゾトリアゾール、トリルトリアゾ
ールなどの有機インヒビターで金属粉に防錆効果を与え
る方法があげられるが、それらの保護被覆は導電性を悪
くし、導電性を目的とする用途には使用できない。合成
樹脂との親和性、分散性を改善するものとしてチオール
・S・トリアジン及びその誘導体を添加する方法(例え
ば特開昭53−45346号公報)、あるいはチタネー
ト系カップリング剤を使用する方法(例えば特開昭57
−207651号公報)がある。しかしこれらの方法は
改善効果は認められるものの不十分であり、金属粉の有
する特性を阻害する傾向も有り、合成樹脂に充填する金
属粉の処理方法として優れた方法とは言えない。Conventional techniques include applying rust prevention to metal powder using organic inhibitors such as benzotriazole and tolyltriazole, but these protective coatings impair electrical conductivity and cannot be used in applications where electrical conductivity is desired. . To improve the affinity and dispersibility with synthetic resins, there is a method of adding thiol/S/triazine and its derivatives (for example, JP-A-53-45346), or a method of using a titanate coupling agent (for example, Japanese Unexamined Patent Publication No. 1983
-207651). However, although these methods have an improvement effect, they are insufficient and tend to impede the properties of the metal powder, so they cannot be said to be excellent methods for treating metal powder to be filled into synthetic resins.
金属粉の腐食、金属粉による合成樹脂の酸化劣化を防止
するためには、なんらかの防錆処理が必要である。しか
し従来の技術では防錆のための保護被膜は金属酸化膜を
介して結合するものや、絶縁性のものが多(、導電性を
目的とした用途には使用できない。したがって導電性な
ど金属の特性を悪くしない防錆処理方法が必要である。In order to prevent corrosion of metal powder and oxidative deterioration of synthetic resin due to metal powder, some kind of rust prevention treatment is required. However, in conventional technology, protective coatings for rust prevention are often bonded through metal oxide films or are insulating (and cannot be used for conductive purposes. There is a need for a rust-preventing treatment method that does not impair properties.
一方、無機物と合成樹脂との親和性を良(するためのカ
ップリング剤としてシラン系、アルdニウム系、チタネ
ート系などが市販されている。シリカ、ガラスにはシラ
ン系が良く、炭酸カルシウムにはチタネート系が有効で
あることは知られているが、金属粉に対しては有効な処
理方法が見出されてなく、カップリング剤として十分な
効果が生かされていない。On the other hand, silane-based, aldium-based, and titanate-based coupling agents are commercially available to improve the affinity between inorganic materials and synthetic resins. It is known that titanate-based compounds are effective, but no effective treatment method has been found for metal powder, and their effectiveness as coupling agents has not been fully utilized.
したがって本発明者等は、表面処理後も金属の有する導
電性などの特性を維持あるいは改善し、かつ合成樹脂と
有害な化学反応を起こさせず、合成樹脂との親和性が良
い金属粉の処理方法を見出すために種々の研究を行った
結果、本発明を完成したものである。Therefore, the present inventors have developed a method for processing metal powder that maintains or improves the properties of metals such as conductivity even after surface treatment, does not cause harmful chemical reactions with synthetic resins, and has good affinity with synthetic resins. The present invention was completed as a result of various researches to find a method.
即ち、本発明は、金属粉をアミン及びその誘導体の少な
くとも1種を溶解した水溶液で処理し、次いで該金属粉
を乾燥し、チタネート系カップリング剤を該金属粉に混
合被覆することを特徴とする金属粉の処理方法である。That is, the present invention is characterized in that metal powder is treated with an aqueous solution in which at least one of amines and derivatives thereof is dissolved, then the metal powder is dried, and a titanate coupling agent is mixed and coated on the metal powder. This is a method for processing metal powder.
金属粉とは、銅、鉄、ニッケル、鉛、錫、銀、並びにこ
れらの合金粉が含まれるが、特に銅粉、銅合金粉、鉄粉
、ニッケル粉等の金属粉に本発明方法を実施すると、き
わめて良好な結果が得られる。Metal powders include copper, iron, nickel, lead, tin, silver, and alloy powders thereof, but the method of the present invention is particularly applied to metal powders such as copper powder, copper alloy powder, iron powder, and nickel powder. This gives very good results.
本発明の方法に使用するアミンとは、アンモニアの水素
原子を炭化水素残5Rで置換した化合物であって、例え
ばエチルアミン、アミルアミン、シアミルアミン、トリ
エタノールアミンユアリリルアミン、シクロヘキシルア
ミンなどが挙げられる。アミンの誘導体としては塩酸塩
、硫酸塩および有機酸塩などであるが、水に可溶なア、
ミン化合物であれば使用可能である。The amine used in the method of the present invention is a compound in which the hydrogen atom of ammonia is replaced with a hydrocarbon residue 5R, and examples thereof include ethylamine, amylamine, cyamylamine, triethanolamine, arylylamine, and cyclohexylamine. Derivatives of amines include hydrochloride, sulfate and organic acid salts, but water-soluble a
Any compound can be used.
アミンの金属粉に対する添加量は、使用する水溶液の量
、処理方法、金属粉の粒子の大きさより異なるが、一般
に処理する金属粉に対して重量で0.01%から効果が
あり10%以下が望ましい。処理方法としては、水溶液
をスプレー添加する方法、水溶液中にて金属粉を攪拌す
る方法、少量の水溶液でペースト状態にして湿潤する方
法などが有る。The amount of amine added to the metal powder varies depending on the amount of aqueous solution used, the processing method, and the particle size of the metal powder, but generally it is effective from 0.01% by weight to the metal powder being treated, and 10% or less is effective. desirable. As a treatment method, there are a method of spraying an aqueous solution, a method of stirring metal powder in an aqueous solution, a method of making a paste state with a small amount of an aqueous solution and moistening it.
処理時間は短時間で良く、処理時間は自由に選定するこ
とができる。The processing time may be short, and the processing time can be freely selected.
本発明の方法に使用するチタネート系カップリング剤と
は、例えばイソプロピルトリイソステアロイルチタネー
ト、イソプロピルトリドデシルベンゼンスルホニルチタ
ネート、イソプロピルトリス(ジオクチルパイロホスフ
ェート)チタネート、テトラオクチルビス(ジトリデシ
ルホスファ・イト)チタネート、ビス(ジオクチルパイ
ロホスフェート)オキシアセテートチタネートなどが挙
げられる。The titanate coupling agents used in the method of the present invention include, for example, isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, and tetraoctyl bis(ditridecyl phosphite) titanate. , bis(dioctylpyrophosphate)oxyacetate titanate, and the like.
チタネート系カップリング剤の添加量は金属粉。The amount of titanate coupling agent added is metal powder.
の粒子の大きさ、金属組成によって異なるが、一般に、
処理する金属粉に対して重量で0.1%から効果があり
10%以下が望ましい。It varies depending on the particle size and metal composition, but in general,
It is effective from 0.1% by weight to the metal powder to be treated, and preferably 10% or less.
チタネート系カップリング剤の処理方法としては、直接
金属粉に添加し、ミキサーあるいはボールミルなどで撹
拌混合する方法が工業的に筒車である。チタネート系カ
ップリング剤を相溶性の良いトルエン、メチルエチルケ
トンなどの溶剤に希釈して攪拌混合する方法は短時間に
均一な被覆が得られ効果的な方法である。The industrially preferred method for treating titanate coupling agents is to add them directly to metal powder and stir and mix with a mixer or ball mill. A method in which a titanate coupling agent is diluted in a highly compatible solvent such as toluene or methyl ethyl ketone and mixed with stirring is an effective method that can provide a uniform coating in a short time.
本発明の処理方法が優れた特性を有する理由については
、どのような機構で、どのような結合、あるいは相互作
用をしているか十分に明らかになっていないが次のよう
なことが考えられる。As for the reason why the treatment method of the present invention has excellent properties, it is not fully clear what kind of mechanism, what kind of bonding, or what kind of interaction occurs, but the following may be considered.
金属粉をアミンの水溶液で処理することは金属粉表面を
清浄する効果があり、処理した金属粉を乾燥することに
より金属粉表面にキレ−、ト化合物が生成し、ある程度
の防錆効果が得られる。Treating metal powder with an aqueous solution of amine has the effect of cleaning the surface of the metal powder, and drying the treated metal powder generates a chemical compound on the surface of the metal powder, which has a certain degree of rust prevention effect. It will be done.
さらに金属粉を水溶液中で処理し乾燥することは金属粉
表面に水酸基を強制的に付与したことになり、チタネー
ト系カップリング剤が金属粉表面と結合するのに最適な
状態となり、優れた力、プリング剤の効果が生ずる。つ
まりチタネート系カップリング剤の遷移金属であるTi
元素が金属表面と十分に結合したのち、イソステアリン
酸残基、オクチルアルコール酸基及び亜リン酸エステル
のトリデシルアルコール残基などの疎水基が外側に向き
金属粉表面を疎水化する。これらの疎水基はを機構と親
和する部分が有るため、合成樹脂との親和性も良くなる
と考えられる。Furthermore, treating the metal powder in an aqueous solution and drying it means that hydroxyl groups are forcibly added to the surface of the metal powder, creating an optimal state for the titanate coupling agent to bond to the surface of the metal powder, resulting in excellent strength. , the effect of the pulling agent occurs. In other words, Ti, which is a transition metal in titanate coupling agents,
After the elements are sufficiently bonded to the metal surface, hydrophobic groups such as isostearic acid residues, octyl alcohol acid groups, and tridecyl alcohol residues of phosphite esters face outward to make the metal powder surface hydrophobic. Since these hydrophobic groups have a part that is compatible with the mechanism, it is thought that the affinity with synthetic resins is also improved.
他のカップリング剤を使用しても機構的には同じと考え
られるが、シラン系は導電性を著しく悪くし、アル゛ミ
ニウム系は耐湿性に劣るなどの欠点があることが本発明
者等の研究で判明し、チタネート系カップリング剤を使
用した。Although it is thought that the mechanism is the same even if other coupling agents are used, the present inventors have found that silane-based coupling agents have drawbacks such as significantly poor conductivity and aluminum-based coupling agents have poor moisture resistance. This was discovered through research and a titanate-based coupling agent was used.
金属粉に水を添加してカップリング効果を向上する方法
も有るが、乾燥中に金属粉が酸化する問題がある。また
乾燥せずにカップリング剤を添加したり、カップリング
剤と水を同時に添加して処理した場合には、残留水分が
多く有るため種々の問題を生じる。本発明の処理方法に
おいて、アミンの水溶液で処理し乾燥した金属粉の残留
水分を測定した結果、重量で0.005部程度であった
。金属粉の種類により含水量に差は有るが、このくらい
の量がチタネート系カップリング剤の親木基が加水分解
し金属と結合するのに必要かつ不可欠な量であろう。金
属粉を充填した合成樹脂複合材料の導電性が良くなるの
は防錆性と親和性の相乗効果によるものと考えられる。Although there is a method of adding water to metal powder to improve the coupling effect, there is a problem that the metal powder oxidizes during drying. Furthermore, if a coupling agent is added without drying, or if a coupling agent and water are added at the same time for treatment, there will be a large amount of residual moisture, which will cause various problems. In the treatment method of the present invention, the residual water content of the metal powder treated with an aqueous amine solution and dried was measured and found to be approximately 0.005 parts by weight. Although there are differences in water content depending on the type of metal powder, this amount is probably necessary and essential for the parent wood group of the titanate coupling agent to hydrolyze and bond to the metal. The improved conductivity of synthetic resin composite materials filled with metal powder is thought to be due to the synergistic effect of rust prevention and affinity.
以下実施例により本発明を具体的に説明する。 The present invention will be specifically explained below using Examples.
なお文中に部とあるのはすべて重量部である。All parts in the text are parts by weight.
実施例1
水100部にトリエタノールアミンを0.01部溶解し
た水溶液に平均粒径50μの噴霧銅粉を100部浸漬し
、1分間攪拌した。その後ろ紙で銅粉と水を分離し、熱
風乾燥器にて80℃120分間加熱乾燥した。乾燥後室
温にてしばらく放置した後、チタネート系カップリング
剤であるイソプロピルトリイソステアロイルチタネート
を0.1部トルエン2部に溶解して、銅粉に添加した。Example 1 100 parts of atomized copper powder having an average particle size of 50 μm was immersed in an aqueous solution prepared by dissolving 0.01 part of triethanolamine in 100 parts of water, and stirred for 1 minute. After that, the copper powder and water were separated using paper and dried by heating at 80° C. for 120 minutes in a hot air dryer. After drying, the mixture was left at room temperature for a while, and then 0.1 part of isopropyl triisostearoyl titanate, which is a titanate coupling agent, was dissolved in 2 parts of toluene and added to the copper powder.
ミキサーで6Orpm10分間混合し、銅粉表面にチタ
ネート系カップリング剤を被覆した。The mixture was mixed using a mixer at 6 rpm for 10 minutes to coat the surface of the copper powder with the titanate coupling agent.
このようにして処理した銅粉は金属銅の色を呈しており
かつ疎水性を有していた。The copper powder treated in this manner had the color of metallic copper and was hydrophobic.
合成樹脂との親和性、反応性を見るために、このように
して得た処理銅粉をポリブヂレンテレフタレート樹脂に
重量で75%充填し、射出成形機にてフライホイールを
成形した。In order to examine the affinity and reactivity with synthetic resins, 75% by weight of the treated copper powder thus obtained was filled into polybutylene terephthalate resin, and a flywheel was molded using an injection molding machine.
本発明の処理を行なわない銅粉を使用して成形したもの
と比べて非常に成形性が良く、かつ表面外観も赤変色せ
ず銅色を呈していた。成形品の物理的性質、電気的性質
を表1に、無処理銅粉を充填したものを比較例1として
示す。Compared to molding using copper powder not treated according to the present invention, the moldability was very good, and the surface appearance was copper-colored without turning red. The physical properties and electrical properties of the molded product are shown in Table 1 as Comparative Example 1, which is filled with untreated copper powder.
表1
実施例2
水100部にトリエタノールアミンを2部溶解した水溶
液に平均粒径2μの電解銅粉100部浸漬し、60分間
混合撹拌した。その後ろ紙で銅粉と水を分離し、熱風乾
燥器にて80℃120分間加熱乾燥した。Table 1 Example 2 100 parts of electrolytic copper powder having an average particle size of 2 μm was immersed in an aqueous solution prepared by dissolving 2 parts of triethanolamine in 100 parts of water, and mixed and stirred for 60 minutes. After that, the copper powder and water were separated using paper and dried by heating at 80° C. for 120 minutes in a hot air dryer.
乾燥後室温にてしばらく放置した後、チタネート系カッ
プリング剤であるビス(ジオクチルパイロホスフェート
)オキシアセテートチタネートを5部銅粉に添加しミキ
サーで6Orpm60分間混合し、銅粉表面にチクネー
ト系カップリング剤を被覆した。After drying and leaving it for a while at room temperature, 5 parts of bis(dioctylpyrophosphate) oxyacetate titanate, which is a titanate coupling agent, was added to the copper powder and mixed with a mixer at 6 rpm for 60 minutes to coat the surface of the copper powder with the titanate coupling agent. coated.
このようにして処理した銅粉は金属銅の色を呈しており
かつ疎水性があり、水中に30日間浸漬しても無処理銅
粉は黒弯色するが変色しなかった。The copper powder treated in this manner had the color of metallic copper and was hydrophobic, and did not change color even when immersed in water for 30 days, although the untreated copper powder turned blackish.
合成樹脂との親和性、反応性、電気伝導性を見るために
、このようにして得た処理銅粉をアクリル樹脂固形分に
対して重1で80%になる。ように配合し、トルエンで
希釈した導電塗料を製造した。In order to examine the affinity, reactivity, and electrical conductivity with the synthetic resin, the treated copper powder thus obtained was 80% by weight based on the solid content of the acrylic resin. A conductive paint was prepared by diluting with toluene.
この導電塗料によって得られた塗膜は無処理銅粉を使用
して製造したものと比べて塗膜外観にザラツキがなく、
塗膜から銅粉の脱落がなく、また長期間塗料を放置して
もゲル化が生じなかった。The coating film obtained with this conductive paint has a less rough appearance than that produced using untreated copper powder, and
No copper powder fell off from the paint film, and gelation did not occur even if the paint was left for a long time.
塗膜の電気的性能を表2に無処理銅粉を充填したものを
比較例2として示す。なお塗膜厚は50ミクロンである
。The electrical performance of the coating film filled with untreated copper powder is shown in Table 2 as Comparative Example 2. The coating film thickness was 50 microns.
表2
実施例3
水100部にシクロヘキシルアミンのカルボン酸塩を1
0部添加溶解した水溶液を平均粒径5μの粉砕鉄粉にス
プレー添加し、直ちに鉄粉を水と分離し、真空乾燥器に
て180分間乾燥した。その後、チタネート系カップリ
ング剤であるテトラオクチルビス(ジトリデシルホスフ
ァイト)チタネートを10部添加し、ボールミルにて3
Orpm 30分間混合した。Table 2 Example 3 Add 1 part of cyclohexylamine carboxylate to 100 parts of water.
The dissolved aqueous solution was sprayed onto crushed iron powder having an average particle size of 5 μm, and the iron powder was immediately separated from water and dried in a vacuum dryer for 180 minutes. Then, 10 parts of tetraoctyl bis(ditridecyl phosphite) titanate, which is a titanate-based coupling agent, was added, and 3 parts were added using a ball mill.
Orpm Mixed for 30 minutes.
このようにして処理した鉄粉は疎水性を有しており、無
処理鉄粉が酸化する塩水中でも錆の発生が防止できた。The iron powder treated in this way has hydrophobicity, and was able to prevent rusting even in salt water where untreated iron powder would oxidize.
合成樹脂との親和性を見るためにABS樹脂に重量で4
0%充填した射出成形板のアイゾツト衝撃強度(インチ
有り)を測定した結果、無処理鉄粉を充填したものは2
.3kg、cm/cmであったが本発明の実施例3の処
理鉄粉を充填したものは5 kg、cm/cmと2倍以
上の値となり、十分使用に耐えるものとなった。4 by weight on ABS resin to check its affinity with synthetic resins.
As a result of measuring the Izotsu impact strength (in inches) of the injection molded plate filled with 0%, the one filled with untreated iron powder was 2.
.. The weight was 3 kg, cm/cm, but the one filled with the treated iron powder of Example 3 of the present invention had a weight of 5 kg, cm/cm, more than double the value, and was sufficiently usable.
実施例4
水10部にアミルアミンを0.5部溶解した水溶液を平
均粒径5μのニッケル粉100部に添加し、ミキサーで
6Orpm 30分間混合攪拌した。その後熱風乾燥器
にて120℃180分間加熱乾燥した。乾燥後室温にて
しばらく放置した後、チタネート系カップリング剤であ
るイソプロピルトリドデシルベンゼンスルホニルチタネ
ートを3部二ソヶル扮に添加し、ミキサーで5Qrpm
60分間混合し、ニッケル粉表面にチタネート系カッ
プリング剤を被覆した。Example 4 An aqueous solution prepared by dissolving 0.5 parts of amylamine in 10 parts of water was added to 100 parts of nickel powder having an average particle size of 5 μm, and the mixture was mixed and stirred using a mixer at 6 Orpm for 30 minutes. Thereafter, it was dried by heating at 120° C. for 180 minutes in a hot air dryer. After drying and leaving it at room temperature for a while, 3 parts of isopropyl tridodecylbenzenesulfonyl titanate, which is a titanate coupling agent, was added to the Nisogal and mixed at 5 Qrpm with a mixer.
The mixture was mixed for 60 minutes to coat the surface of the nickel powder with the titanate coupling agent.
このようにして処理したニッケル粉の親和性、電気伝導
性を見るためにエポキシ樹脂に重量で80%充填した。In order to examine the affinity and electrical conductivity of the nickel powder thus treated, it was filled in an epoxy resin at 80% by weight.
その結果、均一に分散することが容易となり、かつ無処
理ニッケル粉を充電した場合の電気伝導性が10−1Ω
・cmであったが本発明の実施例4の処理ニッケル粉を
充填した場合は10− ”Ω・cmの体積固有抵抗値が
得られた。As a result, it is easy to disperse uniformly, and the electrical conductivity when charging untreated nickel powder is 10-1Ω.
·cm, but when filled with the treated nickel powder of Example 4 of the present invention, a volume resistivity of 10-''Ω·cm was obtained.
以上詳細に説明した通り本発明の処理方法は、表面処理
後も金属粉の有する導電性などの特性が良くなり、かつ
合成樹脂と有害な化学反応を起こさせず、しかも合成樹
脂との親和性が非常に改善される効果が有る。As explained in detail above, the treatment method of the present invention improves the properties of metal powder such as conductivity even after surface treatment, does not cause harmful chemical reactions with synthetic resins, and has good compatibility with synthetic resins. This has the effect of greatly improving the
したがって、金属の特徴をいかした新しい金属粉含有合
成樹脂複合材料を得ることが可能となった。Therefore, it has become possible to obtain a new metal powder-containing synthetic resin composite material that takes advantage of the characteristics of metal.
Claims (1)
した水溶液で処理し、次いで該金属粉を乾燥し、チタネ
ート系カップリング剤を該金属粉に混合被覆することを
特徴とする金属粉の処理方法。A method for treating metal powder, which comprises treating metal powder with an aqueous solution containing at least one of amines and derivatives thereof, then drying the metal powder, and coating the metal powder with a titanate coupling agent. .
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60021407A JPS61179802A (en) | 1985-02-05 | 1985-02-05 | Treatment of metallic powder |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60021407A JPS61179802A (en) | 1985-02-05 | 1985-02-05 | Treatment of metallic powder |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS61179802A true JPS61179802A (en) | 1986-08-12 |
JPH024643B2 JPH024643B2 (en) | 1990-01-30 |
Family
ID=12054179
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP60021407A Granted JPS61179802A (en) | 1985-02-05 | 1985-02-05 | Treatment of metallic powder |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS61179802A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63225657A (en) * | 1986-10-28 | 1988-09-20 | Calp Corp | Composite polymer composition |
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 |
JP2008195904A (en) * | 2007-02-15 | 2008-08-28 | Diatex Co Ltd | Electroconductive adhesive composition, electroconductive adhesive sheet, and electroconductive adhesive tape |
-
1985
- 1985-02-05 JP JP60021407A patent/JPS61179802A/en active Granted
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63225657A (en) * | 1986-10-28 | 1988-09-20 | Calp Corp | Composite polymer composition |
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 |
JP2008195904A (en) * | 2007-02-15 | 2008-08-28 | Diatex Co Ltd | Electroconductive adhesive composition, electroconductive adhesive sheet, and electroconductive adhesive tape |
Also Published As
Publication number | Publication date |
---|---|
JPH024643B2 (en) | 1990-01-30 |
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