JPS62156202A - Ferromagnetic metallic powder treated with amines - Google Patents
Ferromagnetic metallic powder treated with aminesInfo
- Publication number
- JPS62156202A JPS62156202A JP60292875A JP29287585A JPS62156202A JP S62156202 A JPS62156202 A JP S62156202A JP 60292875 A JP60292875 A JP 60292875A JP 29287585 A JP29287585 A JP 29287585A JP S62156202 A JPS62156202 A JP S62156202A
- Authority
- JP
- Japan
- Prior art keywords
- iron powder
- powder
- magnetic
- air
- iron
- 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
Links
- 239000000843 powder Substances 0.000 title claims abstract description 28
- 230000005294 ferromagnetic effect Effects 0.000 title claims abstract description 26
- 150000001412 amines Chemical class 0.000 title claims abstract description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 40
- 150000001408 amides Chemical class 0.000 claims abstract description 11
- 150000003949 imides Chemical class 0.000 claims abstract description 10
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 238000006722 reduction reaction Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 98
- 230000005291 magnetic effect Effects 0.000 abstract description 64
- 239000007789 gas Substances 0.000 abstract description 17
- 229910052742 iron Inorganic materials 0.000 abstract description 14
- 229910000069 nitrogen hydride Inorganic materials 0.000 abstract description 10
- 238000005245 sintering Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000003449 preventive effect Effects 0.000 abstract description 3
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 abstract description 2
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 239000007792 gaseous phase Substances 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 150000002466 imines Chemical class 0.000 abstract 1
- 238000000034 method Methods 0.000 description 48
- 230000006866 deterioration Effects 0.000 description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 238000012360 testing method Methods 0.000 description 19
- 239000002245 particle Substances 0.000 description 16
- 239000003973 paint Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 239000011973 solid acid Substances 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 239000010419 fine particle Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 7
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000007605 air drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002923 metal particle Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 4
- 230000003679 aging effect Effects 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000005415 magnetization Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 239000000696 magnetic material Substances 0.000 description 3
- 239000006247 magnetic powder Substances 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- -1 Salt vinyl acetate Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000006249 magnetic particle Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- 229940013085 2-diethylaminoethanol Drugs 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- OIJMIQIDIZASII-UHFFFAOYSA-N benzene;benzoic acid Chemical compound C1=CC=CC=C1.OC(=O)C1=CC=CC=C1 OIJMIQIDIZASII-UHFFFAOYSA-N 0.000 description 1
- NHVSMPAFLCDMAU-UHFFFAOYSA-N benzene;butan-1-amine Chemical compound CCCCN.C1=CC=CC=C1 NHVSMPAFLCDMAU-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 1
- 229940087646 methanolamine Drugs 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、高密度記録に適した磁気記録媒体に於ける磁
性素材としての強磁性金属粉微粒子及びその製造方法に
関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to ferromagnetic metal powder particles as a magnetic material in a magnetic recording medium suitable for high-density recording, and a method for producing the same.
〈従来技術〉
磁気記録用磁性素材については、広い記録波長域での高
出力・低ノイズを計る為に、均一性の高い微細形状粒子
で、高い保磁力（Ｈｃ）を有し、飽和磁化（σＳ）・残
留磁化（σｒ）共に大キく、かつ角形比（Ｒｓ＝σｒ／
＝ｓ）も可及的に大きい磁気特性が基本的に要求され、
更に塗料用樹脂との親和性や分散性、塗膜での配向性・
充填性に優れた特性が要望され、しかも信頼性を保証す
る媒体寿命が充分である事が望まれている。近年は、高
密度記録が社会的に要請され、素材粉としての磁性粉を
始めとして、バインダー樹脂・各種添加剤・更には媒体
加工法等の多岐にわたった改良研究が成されている（：
例えば、明石丘部「磁気テープの進歩」、日本応用磁気
学会誌、７（３）、１８５ （１９８３）、）。<Prior art> In order to achieve high output and low noise in a wide recording wavelength range, magnetic materials for magnetic recording are made of highly uniform fine particles, have high coercive force (Hc), and have low saturation magnetization ( Both σS) and residual magnetization (σr) are large, and the squareness ratio (Rs=σr/
=s) is also basically required to have as large a magnetic property as possible,
Furthermore, the affinity and dispersibility with paint resins, the orientation and
It is desired that the media have excellent filling properties, and that the media has a sufficient life span to ensure reliability. In recent years, there has been a social demand for high-density recording, and a wide range of improvement research has been carried out, including magnetic powder as a material powder, binder resin, various additives, and even media processing methods (:
For example, Akashi Okabe, "Advances in magnetic tape," Journal of the Japan Society of Applied Magnetics, 7(3), 185 (1983),).
このうち、磁性素材としての磁性粉については、強磁性
金属粉がその優れた磁気特性から、１ずオーディオ用磁
気テープの素材として実用され、又、８朋ビデオ用素材
として実用化されている。Among these, as for magnetic powder as a magnetic material, ferromagnetic metal powder is first put into practical use as a material for audio magnetic tapes, and also as a material for 8-way video, due to its excellent magnetic properties.
鉄を主要成分とした針状性金属粉微粒子の場合、Ｈｃ−
値及びσ１値の充分な高さに基づく優れた磁気的ボテン
シャリテイが利用されている事となる訳であるが、通常
は１μ以下の微粒子である事から、空気に対する酸化活
性が極めて強く、磁気記録媒体としての適用性を確保し
、かつ信頼性を付与せしめる為の安定性が重要な物性と
して位置づけられている。In the case of acicular metal powder particles containing iron as the main component, Hc-
Excellent magnetic potency based on a sufficiently high value and σ1 value is utilized, but since they are usually fine particles of 1μ or less, their oxidizing activity against air is extremely strong. Stability is considered to be an important physical property in order to ensure applicability as a magnetic recording medium and provide reliability.
従来、この種の安定性を確保する手段として、（り微粒
子表層部に酸化層を設ける方法や、
（２）微粒子表面に特殊な層を被膜形成させる方法
更にこれ等の組合せの方法等が知られている。Conventionally, as means to ensure this kind of stability, methods such as (2) forming an oxidized layer on the surface of the fine particles, (2) forming a special layer on the surface of the fine particles, and combinations of these methods have been known. It is being
（１）に属する方法としては、酸化層を気相接触反応で
行う方法、及び液層反応で行う方法に分類され、前者の
例としては、特開昭５５−１２５２０５． ５６−６９
３０１ 、５６−１２７７０１ 、５７−９２１０１等
が挙げられる。Methods belonging to (1) are classified into a method in which the oxidation layer is formed by a gas phase contact reaction and a method in which the oxidation layer is formed by a liquid phase reaction. 56-69
301, 56-127701, 57-92101, etc.
後者の例としては、特開昭５２−８５０５４ 、 ５５
−１６４００１ 。An example of the latter is JP-A-52-85054, 55
-164001.
５７−８５９０１ 、５７−９５５０４ 、 ５８−１
１０４３３ 、５８−１５９３１１等が挙げられる。57-85901, 57-95504, 58-1
10433, 58-159311, etc.
更に、（２）に属する方法としては有機物を被着する方
法と無機物を被着する方法とに分けられ、前者はシリコ
ーン等に代表される特殊な界面活性剤的性格の強い低分
子量有機物全被着する方法として特開昭４６−５０５７
、 ５Ｏ−１０４１ｉ５４ 、５１−１２２６５５
、５１−１４０８６０ 、５２−１５５３９８ 、 ５
３−５７９８ 、５３−７６９５８ 。Furthermore, methods belonging to (2) can be divided into methods of depositing organic materials and methods of depositing inorganic materials. Japanese Patent Application Laid-Open No. 46-5057
, 5O-1041i54 , 51-122655
, 51-140860 , 52-155398 , 5
3-5798, 53-76958.
５４−２４０００．５５−３９６６０ 、 ５５−３９
６６１ ．５５−５９６６２ 。54-24000.55-39660, 55-39
661. 55-59662.
５６−２９８４１ 、 ５６−５４０１３ 、 ５６−
１４８７２６更に、樹脂類を被覆する方法として、
特開昭５３−１３９０６ 、５５−７８０９９ 、５４
−１３９５０８ 。56-29841, 56-54013, 56-
148726 Furthermore, as a method for coating resins, JP-A-53-13906, 55-78099, 54
-139508.
等がある。又、後者は珪酸アルミニウムや酸化アルミニ
ウムその他を被着する方法として、特開昭５３−８７９
８ 、５６−９８４０１ 、５７−９８０２ 、５７−
６５６０１ 、 ５８−１５９３０６ 、５８−１５９
３０７ 、５８−１５９３０８ 。etc. The latter method is described in Japanese Patent Application Laid-Open No. 53-879 as a method for depositing aluminum silicate, aluminum oxide, etc.
8, 56-98401, 57-9802, 57-
65601, 58-159306, 58-159
307, 58-159308.
５８−１６１７０８ 、５８−１６１７０９ 、５８−
１６１７２５等が挙げられる。58-161708, 58-161709, 58-
161725 and the like.
又、気化性防錆剤を使用する方法として、特許公報 昭
６０−４５６５
が挙げられる。Further, as a method of using a volatile rust preventive agent, Patent Publication No. 60-4565 can be mentioned.
父、アミン及び鉱物油を使用する方法として、特開昭５
３−７８０９６．５３−７８０９７が挙げられる。As a method using amine and mineral oil, JP-A No. 5
3-78096.53-78097.
〈本発明の解決しようとする問題点〉
鉄を主要成分とする強磁性金属粉微粒子の表面に、前記
の有機物乃至は無機物の被着もしくは被膜を形成せしめ
る方法は、金属と空気中の酸素および水を遮断すること
により酸化防止効果を持たせようとすることにある。し
かしながら有機物の被膜を作成し空気中の酸素及び水を
遮断しようとした場合、完全に遮断することは困難で充
分な酸化防止効果を持たせることは出来ない。また鉄粉
表面に酸化被膜を形成させる方法は、磁性粉自身に酸化
防止効果を持たせる有効な手段と言える。<Problems to be Solved by the Present Invention> The method of depositing or forming a film of an organic or inorganic substance on the surface of ferromagnetic metal powder fine particles containing iron as a main component is a The aim is to provide an antioxidant effect by blocking water. However, if an attempt is made to create a film of organic matter to block oxygen and water in the air, it is difficult to completely block out oxygen and water, and a sufficient antioxidant effect cannot be achieved. Furthermore, the method of forming an oxide film on the surface of iron powder can be said to be an effective means of imparting an antioxidant effect to the magnetic powder itself.
しかしながら、磁気記録用磁性微粒子として高密度記録
に適したものを得ようとした場合、粒子径短軸０９１〜
０．０２μｍ長軸径０．１〜０．２ μｍ比表面積４０
〜７０ｍ”／ｇ８度の極めて微細な粒子が必要となる。However, when trying to obtain magnetic particles suitable for high-density recording as magnetic fine particles for magnetic recording, the short axis of the particle diameter is 091~
0.02 μm major axis diameter 0.1-0.2 μm specific surface area 40
Very fine particles of ˜70 m”/g 8 degrees are required.
また同様に磁気特性に於いても高い飽和磁化が必要とな
り酸化被膜を薄くつけることが必要となる。８ｍｍＶＴ
Ｒ用磁気テープの素材としては、特に両者を満足する必
要がある。酸化被膜全形成し酸化防止を行う方法では、
一般に酸化被膜が厚い程酸化防止効果が高い為に、粒子
径の充分小さな磁性粒子では、飽和磁化及び耐候性の両
者を満足させるのは困難であった。この様なことから酸
化防止の画期的な方法が望１れていた。Similarly, regarding the magnetic properties, high saturation magnetization is required, and it is necessary to apply a thin oxide film. 8mmVT
The material for the R magnetic tape must particularly satisfy both requirements. In the method of completely forming an oxide film and preventing oxidation,
In general, the thicker the oxide film, the higher the antioxidant effect, so it has been difficult to satisfy both saturation magnetization and weather resistance with magnetic particles having sufficiently small particle diameters. For these reasons, an innovative method for preventing oxidation has been desired.
〈問題点を解決する為の手段〉
本発明者等は、上記の問題点の解決を計る為に、種々の
検討を加えた結果、焼結防止成分を添加したオキシ水酸
化鉄及び／又は酸化鉄を主成分とする出発原料を、Ｎ２
ガス等の還元性ガスによる接触式還元反応によって得た
鉄を主要成分とする強磁性金属粉微粒子の表面にＮＨ３
、アミン、アミド、イミドのうち少くとも一種で処理し
その表面に吸着させることにより、酸化被膜を形成した
強磁性金属粒子の耐候性を著しく改善することができる
ことを見い出し本発明に到達した。<Means for Solving the Problems> In order to solve the above problems, the present inventors have conducted various studies and found that iron oxyhydroxide and/or oxidized iron to which an anti-sintering component has been added. The starting material whose main component is iron is
NH3 on the surface of ferromagnetic metal powder particles containing iron as the main component obtained by catalytic reduction reaction with reducing gas such as gas.
The present inventors have discovered that the weather resistance of ferromagnetic metal particles on which an oxide film has been formed can be significantly improved by treating the particles with at least one of amine, amide, and imide and adsorbing the particles onto the surface of the particles.
本発明においてＮＨ３、アミン、アミド、イミドで処理
しこれを吸着させる方法としては、ＮＨ３及び一部の低
分子量のアミンに対しては、Ｎ２ガスにより希釈して混
合ガスとして接触せしめることにより吸着させる方法が
簡単でかつ有効な方法であり又一般のアミン、アミド、
イミドに関してはトルエン、ＭＥＫ等の溶媒に溶解した
後その中へ強磁性金属微粒子をディップ処理することで
吸着させる方法が簡単でかつ有効な方法である。両者の
方法共に、均一に吸着することがより一層の効果を持た
せることが出来る。その具体的な態様としてたとえば気
相接触吸着では、流動層等の粉体の混合が充分性われる
接触形式を利用することが有効である。又、液相の接触
吸着では、ディシルバー、ホモジナイザー等でスラリー
状とした後、混合を続けながら接触吸着せしめる方法が
有効である。又、強磁性金属粒子表面に安定層たる酸化
被膜を形成する前に吸着させても有効であり、同粒子に
酸化被膜を形成後吸着させても同効果は得られる。なお
、一般に酸化被膜の形成方法は、均一にゆっくりと酸化
することが酸化被膜を薄く形成することが可能であり磁
気特性を充分に引き出すことができる。又、本発明者等
が、特願昭５９−２７３７１１号で提案した酸化被膜全
熱処理し被膜の強化した強磁性金属粉微粒子についても
効果は大さい。ＮＨ３、アミン、アミドもしくはイミド
の添加量は、焼結防止剤の種類及び量、又その他の不純
物の種類及び量等により異なるが、要するにアミン等に
よる処理後の鉄粉の固体酸量がｏ、 ｉ ｍｅｑ／Ｌ？
未満になるように条件を決めればよいのである。但し、
一般的に、目やすとしてはＮＨ３又は／及び有機アミン
の持つ塩基量として粒子１ｇ当りＮＨ３として０．０１
ｍｅｑ 〜５．０ ｍｅｑ程度とすれば通常充分であ
り好ましくは１ｇ当たり０．１ ｍｅｑ〜１．。In the present invention, as a method for treating and adsorbing NH3, amine, amide, and imide, NH3 and some low molecular weight amines are adsorbed by diluting with N2 gas and contacting them as a mixed gas. The method is simple and effective, and can be used for general amines, amides,
As for imide, a simple and effective method is to dissolve it in a solvent such as toluene or MEK and then dip ferromagnetic metal particles therein to adsorb it. Both methods can be more effective if they are uniformly adsorbed. As a specific embodiment, for example, in gas phase catalytic adsorption, it is effective to use a contact format such as a fluidized bed that allows sufficient mixing of powders. In addition, for contact adsorption in the liquid phase, it is effective to make a slurry using a disilver, homogenizer, etc., and then perform contact adsorption while continuing mixing. It is also effective to adsorb the ferromagnetic metal particles before forming an oxide film as a stable layer on the surface of the particles, and the same effect can be obtained even if the particles are adsorbed after the oxide film is formed on the particles. In general, the method for forming an oxide film is to oxidize uniformly and slowly so that the oxide film can be formed thinly and the magnetic properties can be fully brought out. Furthermore, the ferromagnetic metal powder fine particles whose oxide coating is fully heat-treated and whose coating is strengthened as proposed by the present inventors in Japanese Patent Application No. 59-273711 are also highly effective. The amount of NH3, amine, amide or imide added varies depending on the type and amount of the sintering inhibitor, the type and amount of other impurities, etc., but in short, the amount of solid acid in the iron powder after treatment with amine etc. is o, i meq/L?
All you have to do is set the conditions so that it is less than or equal to. however,
Generally, as a guideline, the amount of base possessed by NH3 or/and organic amine is 0.01 as NH3 per 1g of particles.
meq to 5.0 meq is usually sufficient, preferably 0.1 meq to 1.0 meq per 1g. .
ｍｅｑがより一層効果が高い。meq is even more effective.
０．０１ ｍｅｑ未満では耐候性を向上する効果として
充分ではなく又特に分子量の大きいアミンの場合ＮＨ３
換算で５．０ ｍｅｑを越えるような添加°量では金属
磁性鉄粉として充分な磁気特性が損なわれる。If it is less than 0.01 meq, the effect of improving weather resistance is not sufficient, and especially in the case of amines with large molecular weight, NH3
If the added amount exceeds 5.0 meq in terms of conversion, sufficient magnetic properties as a metallic magnetic iron powder will be lost.
本発明において使用するアミンの種類としては、−級及
び二級アミンが一般に入手しやすく、たとえばメチルア
ミン、エチルアミン、プロピルアミン、ブチルアミン、
メタノールアミン、エタノールアミン、ジメチルアミン
、ジエチルアミン、２−ジメチルアミノエタノール、２
−ジエチルアミノエタノール等が挙げられる。またアミ
ドとしては、尿素、アセトアミド、メチルアクリルアミ
ド等が挙げられる。さらにイミドとしては、グアニジン
等が挙げられる。Regarding the types of amines used in the present invention, -class and secondary amines are generally easily available, such as methylamine, ethylamine, propylamine, butylamine,
Methanolamine, ethanolamine, dimethylamine, diethylamine, 2-dimethylaminoethanol, 2
-diethylaminoethanol and the like. Further, examples of amides include urea, acetamide, methylacrylamide, and the like. Furthermore, examples of the imide include guanidine and the like.
〈作 用〉
本発明は、鉄を主体とする強磁性金属粒子表面をＮＨ３
、アミン、アミド、イミドの少くとも一種で処理しこれ
を吸着させることを特徴とする。Ｐ、Ｓｉ、ＡｌＸＢ等
の焼結防止成分を含むＨ２還元によって得られた鉄を主
体とする強磁性微粒子表面は、鉄、酸化鉄及び水酸化鉄
ばかりでなく焼結防止剤等の種々の無機塩類及び金属が
存在する。本発明は強磁性粒子表面のかかる各種無機塩
類が強磁性金属粒子の耐候性に対する影響が大きいこと
を見い出すことによりなされた。固体触媒の活性等を支
配する因子として、触媒表面の固体酸及び固体塩基が当
業者では一般に知れている。本発明者らは、強磁性金属
微粒子表面を、触媒の当業者が調べる方法により解析し
た結果、驚くほど多くの酸点が表面に存在していること
を見出した。しかして水溶液中の金属鉄の混触な、ｐＨ
３以下の酸の場合と中性領域とｐＨ１０以上の塩基性の
場合で速度が著しく異なり特にｐＨ３以下の酸の場合湿
蝕は極端に進行する。又、固体酸触媒ではＦｅ２Ｏ３に
ＳＯ４根が存在すると超強酸が出現する。<Function> In the present invention, the surface of ferromagnetic metal particles mainly composed of iron is treated with NH3.
, an amine, an amide, and an imide to adsorb it. The surface of ferromagnetic fine particles mainly composed of iron obtained by H2 reduction containing anti-sintering components such as P, Si, and AlXB contains not only iron, iron oxide and iron hydroxide, but also various inorganic substances such as anti-sintering agents. Salts and metals are present. The present invention was accomplished by discovering that the various inorganic salts on the surface of ferromagnetic particles have a large effect on the weather resistance of ferromagnetic metal particles. Those skilled in the art generally know that the solid acid and solid base on the surface of the catalyst are factors that control the activity of the solid catalyst. The present inventors analyzed the surface of ferromagnetic metal fine particles using a method investigated by those skilled in the art of catalysts, and found that a surprisingly large number of acid sites were present on the surface. However, due to the mixing of metallic iron in aqueous solution, the pH
The rate is markedly different in the case of an acid with a pH of 3 or less, in a neutral region, and in the case of a basic pH of 10 or more, and especially in the case of an acid with a pH of 3 or less, damp corrosion progresses extremely. Furthermore, in the case of solid acid catalysts, when SO4 roots are present in Fe2O3, a super strong acid appears.
’！たＰＸ Ｓｉ、Ａｌ、Ｂ等の酸化物に於いても強酸
性を示すものが存在する。本発明者等は、このような観
点から上記方法により強磁性粒子の表面解析を行い、種
々検討した結果、ＮＨ３、アミン、アミド、イミドの少
くとも一種で表面処理しこれを吸着することで固体酸量
が著しく減少し、耐候性が著しく向上することを見い出
し友ものである。'! There are also oxides such as PX Si, Al, and B that exhibit strong acidity. From this point of view, the present inventors analyzed the surface of ferromagnetic particles using the method described above, and as a result of various studies, we found that by treating the surface with at least one of NH3, amine, amide, and imide and adsorbing this, solid We have discovered that the amount of acid is significantly reduced and weather resistance is significantly improved.
〈実施例〉
以下実施例及び比較例により更に詳細に本発明を説明す
る。なお、本発明はこれ等に限定されるものでは無い。<Examples> The present invention will be explained in more detail below using Examples and Comparative Examples. Note that the present invention is not limited to these.
〔実施例−１〕
く還元鉄粉の製造〉
特開昭５７−１０６５２７及び５７−９６５０４記載の
方法により、Ｐ、及びＳｉ−成分を重量比でＰ／Ｆｅ
＝ ０．３／１００、及びＳｉ／′Ｆｅ ＝ １．５
／ １００だけ含む針状性オキ７水酸化鉄微粒子を合成
した。[Example-1] Production of reduced iron powder> By the method described in JP-A-57-106527 and JP-A-57-96504, P and Si components were reduced to P/Fe in weight ratio.
= 0.3/100, and Si/'Fe = 1.5
/100 acicular iron-7-hydroxide particles were synthesized.
該００６．粒子の形状は、Ｎ２−ガスの吸着特性から算
出した比表面積ＭＳＡ）は８５２ｙｙｔ”／ｇ乙、又６
乃至９万倍の透過電子顕微鏡像から算出した長軸径（：
Ｌ）と短軸径（：Ｄ）との比即ち軸比（： Ｌ／Ｄ ）
は１６であった。Said 006. The shape of the particles has a specific surface area (MSA) calculated from the adsorption characteristics of N2 gas of 852 yyt"/g, and 6
The long axis diameter calculated from a transmission electron microscope image at a magnification of 90,000 to 90,000 times (:
L) and short axis diameter (:D), that is, the axial ratio (: L/D)
was 16.
次いで、特開昭５８−４８６１２記載の方法によりほう
酸亜鉛の被着変性処理を加え（：Ｂ／Ｆｅ＝１．０／１
００重量比）、乾燥・粉砕工程を経た後、Ｒ２−ガスに
よる気相接触還元反応（：温度＝４２０℃、ガス空間速
度＝ ２ＯＮ７７％−Ｈ２／ｋｇｒ−Ｆｅ、Ｈｒ 、
）により還元鉄粉とした。Next, adhesion modification treatment with zinc borate was applied by the method described in JP-A-58-48612 (:B/Fe=1.0/1
00 weight ratio), after drying and pulverization process, gas phase catalytic reduction reaction with R2-gas (temperature = 420°C, gas space velocity = 2ON77%-H2/kgr-Fe, Hr,
) to obtain reduced iron powder.
該鉄粉をＮ２−ガス雰囲気下で一部抜き出して、Ｎ２−
ガス法による比表面積及び東英工業社製振動式磁気特性
測定装置：ＶＳＭ−ＩＩＩ型による磁性の評価を行った
ところ、Ｓ Ａ＝６５．２７７１シ／ｇ ｒ５、Ｈｃ＝
１４５００ｅ、、σｓ＝１８２ｅｍｕ／ｇｒ 、、Ｒ５
＝Ｃ１，４９０でｔｐツた。A portion of the iron powder is extracted under an N2- gas atmosphere and
Specific surface area by gas method and magnetism were evaluated using a vibrating magnetic property measuring device manufactured by Toei Kogyo Co., Ltd.: Model VSM-III, and S A = 65.2771 sh/g r5, Hc =
14500e,,σs=182emu/gr,,R5
= C1,490 and tp.
〈アンモニア処理〉
該鉄粉を上記の気相接触還元反応に利用した反応器を用
いて、アンモニアの気相接触反応を行った。純度９９．
９％の窒素ガス中にアンモニアガスをｏ、 ５ ｖｏｌ
％に希釈し処理を行った。（：温度＝３５℃、ガス空
間速度１ ＯＮＥ／ｋｇｒ−Ｆｅ、Ｈｒ、） 処理時間
は１時間行った。次いで、該処理鉄粉をトルエンに浸漬
し取り出した。<Ammonia Treatment> A gas phase catalytic reaction of ammonia was carried out using the reactor in which the iron powder was used for the above gas phase catalytic reduction reaction. Purity 99.
O, 5 vol of ammonia gas in 9% nitrogen gas
% and processed. (Temperature=35°C, gas space velocity 1 ONE/kgr-Fe, Hr) The treatment time was 1 hour. Next, the treated iron powder was immersed in toluene and taken out.
く処理鉄粉の風乾〉
次に、該処理鉄粉５０ｇ乙をホーロー製バット上に１
ｃｍ程の厚味になる様移し、大気下でトルエンの飛散処
理を加えた。Air drying of treated iron powder> Next, 50g of the treated iron powder was placed on an enamel vat.
The mixture was transferred to a thickness of about cm, and subjected to toluene scattering treatment in the atmosphere.
溶剤臭が完全に無くなった段階で鉄粉を回収し、風乾鉄
粉とした。Once the solvent odor was completely gone, the iron powder was collected and made into air-dried iron powder.
該風乾鉄粉の物性評価を行ったところ、５Ａ＝５６、ｑ
ｍ”／ｇｒ−１Ｈｃ＝＝１５５ＧＯｅ、 σｓ＝１５５
ｅｍｕ／ｇｒ 、、Ｒｓ＝０．５２２であった。When the physical properties of the air-dried iron powder were evaluated, 5A = 56, q
m”/gr-1Hc==155GOe, σs=155
emu/gr, Rs=0.522.
く風乾鉄粉の劣化促進テスト〉
該処理風乾鉄粉を１０ｇｒ 、 をステンレス製シャ
ーレに入れ恒温恒湿槽にて５０℃、８［ＩＲＨ％の条件
で劣化促進テストを行った。Deterioration acceleration test of air-dried iron powder> 10g of the treated air-dried iron powder was placed in a stainless steel petri dish, and a deterioration acceleration test was conducted in a constant temperature and humidity chamber at 50° C. and 8 [IRH%].
６ＯＨｒ後の物性評価を行ったところ、５Ａ＝５ｏ６イ
／ｇｒ、、σｓ＝１１５ｅｍｕ／ｇｒ 、、劣化率１４
．８％であった。When we evaluated the physical properties after 6OHr, we found that 5A=5o6i/gr, σs=115emu/gr, deterioration rate 14
．． It was 8%.
一般的には、８ｍｍＶＴＲ用磁性鉄粉としては少くとも
初期のσＳが１２０ｅｍｕ／Ｓｉ’以上で、かつ、本条
件での劣化率が２０％以下とされているのでこの結果は
、８ｇｍＶＴＲ用磁性鉄粉として充分に耐候性をもつこ
とがわかった。Generally speaking, magnetic iron powder for 8 mm VTRs has at least an initial σS of 120 emu/Si' or more and a deterioration rate of 20% or less under these conditions. It was found to have sufficient weather resistance as a powder.
く風乾鉄粉の固体酸塩基量の測定〉
該処理鉄粉２ ｔｏｇｒ、 ｆ：、コニカルビーカーに
採取し、０．１ＮＩ７）Ｎ−ブチルアミン−ベンゼン溶
媒ヲ５０１ｆｔｌ加え撹拌しＮ−ブチルアミンの吸着を
行った。該鉄粉をろ別後、ろ液中の残Ｎ−ブチルアミン
をシーウ酸により定食した。アミンの吸着当量を該処理
鉄粉の固体酸量とした。固体酸量は、０１］１ ｍｅｑ
以下であった。又、該処理鉄粉を同方式で固体塩基量の
測定を行った。試薬は安息香酸−ベンゼン溶媒とＮａＯ
Ｈ溶液を使用した。固体塩基量は、０．１ ｉｍｅｑ／
ｇｒ 、であった。Measurement of solid acid base amount of air-dried iron powder> The treated iron powder 2 togr, f: was collected in a conical beaker, and 501 ftl of 0.1NI7) N-butylamine-benzene solvent was added and stirred to adsorb N-butylamine. Ta. After filtering off the iron powder, the remaining N-butylamine in the filtrate was diluted with shiulic acid. The adsorption equivalent of amine was defined as the amount of solid acid in the treated iron powder. The amount of solid acid is 01]1 meq
It was below. In addition, the amount of solid base of the treated iron powder was measured using the same method. Reagents are benzoic acid-benzene solvent and NaO
H solution was used. The amount of solid base is 0.1 imeq/
It was gr.
く風乾鉄粉の塗料化・塗工化及びテープ特性の評価〉
該風乾鉄粉１０ｇｒ、を採取して、下記材料と共に、内
容積５５０ｍ／のボットに投入し、米国・レッド・デビ
ル社製ペイント・シェーカーで５時間混合・分散を続け
る（二分散メディアとしては、２ｍ／ｒＴＩ径のα−ア
ルミナ・ピーズを用いた）。Making air-dried iron powder into paint/coating and evaluation of tape properties> 10g of the air-dried iron powder was collected and put into a bot with an internal volume of 550m/cm along with the following materials, and painted with paint manufactured by Red Devil Co., Ltd. in the United States. - Continue mixing and dispersion for 5 hours using a shaker (α-alumina beads with a diameter of 2 m/rTI were used as the bidispersion media).
・米・ＵＣＣ社製塩酢ビ系ポリマー ＶＡＧＨ：１．Ｏｇｒ。・Salt vinyl acetate polymer manufactured by UCC, USA VAGH:1. Ogr.
・三井東圧化学社製ポリウレタン ＮＬ−２４４８： １． Ｏｇｒ。・Polyurethane manufactured by Mitsui Toatsu Chemical Co., Ltd. NL-2448: 1. Ogr.
Φ大入化学社製燐酸エステル ＡＰ−１ｓ ： ０．２
ｇｒ。Phosphate ester AP-1s manufactured by Oiri Kagakusha: 0.2
gr.
・住友化学社製α−アルミナ ＡＫＰ−３０： ０．２
ｇｒ。・α-Alumina AKP-30 manufactured by Sumitomo Chemical Co., Ltd.: 0.2
gr.
・溶剤 トルエン＝１４ｇｒ１、ＭＥＫ： １４ｇｒ
。・Solvent Toluene = 14gr1, MEK: 14gr
.
以後、分散メディアを分離して磁性塗料とし、磁気テー
プ使用の精密コーターにてアプリケーターを利用して１
２μ厚の東し社製ポリエステル・フィルム：ルミラー（
：１２Ｂ−Ｌｌｏ）上に塗工する。After that, the dispersion media is separated to make a magnetic paint, and it is coated with an applicator in a precision coater using magnetic tape.
2μ thick polyester film made by Toshisha: Lumirror (
:12B-Llo).
その後、カレンダー・ロール処理して塗膜面の平滑化処
理を加え、次いで５０℃にて２日間熱処理を加えてポリ
ウレタン硬化反応を完結せしめる。Thereafter, the coated film surface is smoothed by calender roll treatment, and then heat treated at 50° C. for 2 days to complete the polyurethane curing reaction.
８．００ｍ／ｉｎに裁断して、現行の８ｍｍＶＴＲカセ
ット仕様サイズの磁気テープとする。該磁気テープの磁
気特性を、既述の測定装置にて測定・評価したところ、
Ｈｃ＝１４８００ｃＸＢｒ＝２３００Ｇ、Ｂｒ／Ｂｍ：
０．７５０であり、充分な特性値を示した。The magnetic tape is cut to 8.00 m/in to make a magnetic tape of the current 8 mm VTR cassette specification size. When the magnetic properties of the magnetic tape were measured and evaluated using the above-mentioned measuring device,
Hc=14800cXBr=2300G, Br/Bm:
0.750, indicating sufficient characteristic values.
く磁気テープの劣化促進テスト〉
該磁気テープを、６０℃・相対湿度９０％の環境下で一
週間、経時促進処理実験を行って、磁気特性、特にＢｍ
の劣化速度を評価した。助−値は２９１０Ｇで、初期値
から５０％低下していた。Test for accelerating deterioration of magnetic tape> The magnetic tape was subjected to an aging acceleration treatment experiment for one week in an environment of 60°C and 90% relative humidity to determine its magnetic properties, especially Bm.
The deterioration rate was evaluated. The assist value was 2910G, which was 50% lower than the initial value.
一般的にＢ「は２２００Ｇ以上、劣化率は本条件で１０
％以下とされているので、この値は、この種の磁気媒体
の示す劣化特性としては十二分に小さく、優れた経時性
を示したと言えるものである。Generally, B is 2200G or more, and the deterioration rate is 10 under these conditions.
% or less, this value is sufficiently small for the deterioration characteristics exhibited by this type of magnetic medium, and can be said to exhibit excellent aging properties.
〔実施例−２〕 く還元鉄粉の製造〉 実施例１記載の還元鉄粉を使用した。[Example-2] Production of reduced iron powder> The reduced iron powder described in Example 1 was used.
くアミン処理〉
内容積１１の攪拌器付き反応器を用意し、純度ｑ５ｎ％
の市販の２−ジメチルアミノエタノール０５ｇｒ、を溶
解し友トルエン４００ｇｒ 、を投入する。Amine treatment> Prepare a reactor with a stirrer with an internal volume of 11, and a purity of q5n%.
Dissolve 05g of commercially available 2-dimethylaminoethanol and add 400g of toluene.
次いで、該還元鉄粉１００ｇｒ 、を浸漬せしめ、反応
器の封入・雰囲気のＮ２−ガス置換を行い、５時間程攪
拌を継続する。Next, 100 grams of the reduced iron powder is immersed, the reactor is sealed, the atmosphere is replaced with N2 gas, and stirring is continued for about 5 hours.
く処理鉄粉の風乾〉 実施例１記載の方法により風乾処理を行った。Air drying of treated iron powder Air drying treatment was performed by the method described in Example 1.
該風乾鉄粉の物性評価を行ったところ、５Ａ＝５５．２
ｍ”／ｇｒ、、Ｈｃ＝１５６００ｅ、σｓ＝１３３ｅｍ
ｕ／ｇｒ 、、Ｒ８＝０．５２４であった。When the physical properties of the air-dried iron powder were evaluated, 5A=55.2
m”/gr,, Hc=15600e, σs=133em
u/gr,,R8=0.524.
〈風乾鉄粉の劣化促進テスト〉 実施例１記載の方法により劣化促進テストを行った。〈Accelerated deterioration test of air-dried iron powder〉 An accelerated deterioration test was conducted using the method described in Example 1.
６ＯＨｒ後の物性評価を行ったところ、５Ａ＝４８．３
ｍ’／ｇｒ、、（７Ｓ＝１１６ｅｍｕ／ｇｒ 、、劣化
率１２．８％であった。When the physical properties were evaluated after 6OHr, 5A=48.3
m'/gr, (7S=116 emu/gr), the deterioration rate was 12.8%.
この結果は、ＦＪｍｔｎＶＴＲ用磁性鉄粉として充分に
耐候性をもつことがわかった。The results showed that the magnetic iron powder for FJmtn VTR has sufficient weather resistance.
く風乾鉄粉の固体酸塩基量の測定〉 実施例１記載の方法により測定を行った。Measurement of solid acid-base content of air-dried iron powder> Measurement was performed by the method described in Example 1.
固体酸量は、０．０１ｍｅｑ 以下であった。固体塩基
量は、０．１４ｍｅｑ／ｇｒ 、であった。The amount of solid acid was 0.01 meq or less. The amount of solid base was 0.14 meq/gr.
この結果充分に酸点にアミンが吸着していることが、解
った。As a result, it was found that the amine was sufficiently adsorbed at the acid site.
〈風乾鉄粉の塗料化・塗工化及びテープ特性の評価〉
該風乾鉄粉１ Ｏｇｒ 、を採取して、実施例−１記載
と同様にして磁性塗料を調製し、塗工化・平滑化・ボス
トアニーリング処理・裁断を加えて現行８闘ＶＴＲ用カ
セツト仕様サイズの磁気テープとする。該磁気テープの
磁気特性を、既述の測定装置にて測定・評価したところ
、
Ｈｃ＝１４９００ｅＸＢｒ＝２３５０ＧＸＢｒ／Ｂｍ＝
０．７６５であった。<Formation of air-dried iron powder into paint/coating and evaluation of tape properties> 1 Ogr of the air-dried iron powder was collected, a magnetic paint was prepared in the same manner as described in Example-1, and it was coated and smoothed.・Add boss annealing and cutting to make magnetic tape sized to the current cassette size for VTRs. When the magnetic properties of the magnetic tape were measured and evaluated using the above-mentioned measuring device, Hc=14900eXBr=2350GXBr/Bm=
It was 0.765.
〈磁気テープの劣化促進テスト〉
該磁気テープを、実施例１記載の方法により劣化促進テ
ストを行った。<Accelerated deterioration test of magnetic tape> An accelerated deterioration test was conducted on the magnetic tape according to the method described in Example 1.
Ｂｍ値は２９３０Ｇで、初期値から４５％低下していた
。The Bm value was 2930G, which was 45% lower than the initial value.
この値は、８ｍｍＶＴＲ用テープの示す劣化特性として
は充分小さく、優れた経時性を示したと言えるものであ
る。This value is sufficiently small for the deterioration characteristics exhibited by an 8 mm VTR tape, and can be said to exhibit excellent aging properties.
〔比較例−１〕 く還元鉄粉の製造〉 実施例−１記載の還元鉄粉を使用した。[Comparative example-1] Production of reduced iron powder> The reduced iron powder described in Example-1 was used.
処理を行わずその１１トルエンに浸漬した。11 It was immersed in toluene without any treatment.
く処理鉄粉の風乾〉 実施例１記載の方法により風乾処理を行った。Air drying of treated iron powder Air drying treatment was performed by the method described in Example 1.
該風乾鉄粉の物性評価を行ったところ、ＳＡ ６０．３
ｍ／ｇ ｒ 、、Ｈｃ＝１５６５０ｅ、σｓ＝１３４
ｅｍｕ／ｇ ｒ 、、Ｒ３＝０５２４であった。When the physical properties of the air-dried iron powder were evaluated, SA 60.3
m/g r ,, Hc=15650e, σs=134
emu/g r , R3=0524.
〈風乾鉄粉の劣化促進テスト〉 実施例１記載の方法により劣化促進テストを行った。〈Accelerated deterioration test of air-dried iron powder〉 An accelerated deterioration test was conducted using the method described in Example 1.
６ＯＨｒ後の物性評価を行ったところ、ＥｔＡ＝４５．
５ｍ”／ｇｒ、、ａ ｓ＝１０５ ｅｍｕ／ｇ ｒ 、
、劣化率２１６チであった。When physical properties were evaluated after 6OHr, EtA=45.
5m”/gr,, a s=105 emu/gr,
, the deterioration rate was 216chi.
この結果は、ＢｆｆｉｌｌＶＴＲ用磁性鉄粉として耐磁
性鉄粉点をもつ結果となった。This result shows that the magnetic iron powder for Bffill VTR has anti-magnetic iron powder points.
〈風乾鉄粉の固体酸塩基量の測定〉 実施例１記載の方法により測定を行った。<Measurement of solid acid-base amount of air-dried iron powder> Measurement was performed by the method described in Example 1.
固体酸量は、０．３５ｍｅｑ／Ｇｒ以下であった。固体
塩基量は、０．０５ｍｅｑ／ｇｒ 、であった。The amount of solid acid was 0.35 meq/Gr or less. The amount of solid base was 0.05 meq/gr.
固体酸の多く含まれる鉄粉となっていた。The iron powder contained a large amount of solid acid.
〈風乾鉄粉の塗料化・塗工化及びテープ特性の評価〉該
風乾鉄粉ＩＤｇｒ、を採取して、実施例−１記載と同様
にして磁性塗料を調製し、塗工化・平滑化・ボストアニ
ーリング処理・裁断を加えて現行８ｍｆｎＶＴＲ用カセ
ント仕様サイズの磁気テープとする。該磁気テープの磁
気特性を、既述の測定装置にて測定・評価したところ
Ｈｃ＝１４９５０ｅＸＢｒ＝２３０００． Ｂｒ／Ｂｍ
＝０．７２０であった。<Preparation of air-dried iron powder into paint/coating and evaluation of tape properties> The air-dried iron powder IDgr was collected, magnetic paint was prepared in the same manner as described in Example-1, and coating, smoothing and tape properties were obtained. By adding boss annealing and cutting, it is made into a magnetic tape of the current 8mfn VTR cartridge specification size. The magnetic properties of the magnetic tape were measured and evaluated using the above-mentioned measuring device and found that Hc=14950eXBr=23000. Br/Bm
=0.720.
〈磁気テープの劣化促進テスト〉
該磁気テープを、実施例１記載の方法により劣化促進テ
ストを行った。<Accelerated deterioration test of magnetic tape> An accelerated deterioration test was conducted on the magnetic tape according to the method described in Example 1.
その結果Ｂｍ値は２６９０（）で、初期値から１２Ｄ％
低下していた。この結果は、９ｍｍＶＴＲ用テープとし
て耐候性に難点をもつ結果となった。As a result, the Bm value is 2690 (), which is 12D% from the initial value.
It was declining. As a result, the tape had poor weather resistance as a 9mm VTR tape.
〔実施例３〕 〈風乾鉄粉の製造〉 比較例１記載の風乾鉄粉を使用した。[Example 3] <Manufacture of air-dried iron powder> The air-dried iron powder described in Comparative Example 1 was used.
〈アンモニア処理〉
実施例１記載の方法により上記の風乾鉄粉にアンモニア
処理を行った。反応器から抜き出し物性評価を行ったと
ころ５Ａ＝５５．４ｍシ’ｇ ｒＸＨｃ＝１５６００ｅ
。<Ammonia treatment> The above air-dried iron powder was subjected to ammonia treatment by the method described in Example 1. When extracted from the reactor and evaluated for physical properties, 5A = 55.4m x Hc = 15600e
.
ａ ｓ＝１３３ ｅｍｕ／ｇ ｒＸＲｓ＝０．５２５
であった。a s=133 emu/g rXRs=0.525
Met.
〈処理鉄粉の劣化促進テスト〉 実施例１記載の方法により劣化促進テストを行った。〈Test for accelerated deterioration of treated iron powder〉 An accelerated deterioration test was conducted using the method described in Example 1.
その結果、５Ａ＝４９．５ｍシ／ｇ ｒ６、σｓ＝１１
５ｅｍｕ／ｇｒ 。As a result, 5A=49.5mshi/g r6, σs=11
5emu/gr.
劣化率は１３５％であった。この結果は、８１１！ＩＩ
ｖＴＲ用磁性鉄粉として充分に耐候性を持つことがわか
った。The deterioration rate was 135%. This result is 811! II
It was found that it has sufficient weather resistance as a magnetic iron powder for vTR.
く風乾鉄粉の固体酸塩基量の測定〉 実施例１記載の方法により測定を行った。Measurement of solid acid-base content of air-dried iron powder> Measurement was performed by the method described in Example 1.
固体酸量は、０．０１ｍｅｑ以下であった。固体塩基量
は、ｏ、１２ｍｅ ｑ／ｇ ｒ −であった。The amount of solid acid was 0.01 meq or less. The amount of solid base was 0.12 meq/g r -.
この結果充分に酸点にアンモニアが吸着していることが
、解った。As a result, it was found that ammonia was sufficiently adsorbed at the acid sites.
く風乾鉄粉の塗料化・塗工化及びテープ特性の評価〉該
風乾鉄粉１０ｇｒ、ｉ採取して、実施例−１記載と同様
にして磁性塗料を調製し、塗工化・平滑化・ボストアニ
ーリング処理・裁断を加えて現行８ｍｍＶＴＲ用力セク
ト仕様サイズの磁気テープとする。該磁気テープの磁気
特性を、既述の測定装置にて測定・評価したところ、
Ｈｃ＝１４８５０ｅＸＢｒ＝２３９０ＧＸＢｒ／Ｂｍ＝
０．７７５であった。Formation of air-dried iron powder into paint, coating, and evaluation of tape properties> 10g of the air-dried iron powder was collected, and a magnetic paint was prepared in the same manner as described in Example-1, and the coating, smoothing, and By adding boss annealing and cutting, it becomes a magnetic tape of the current 8mm VTR size specification. When the magnetic properties of the magnetic tape were measured and evaluated using the above-mentioned measuring device, Hc=14850eXBr=2390GXBr/Bm=
It was 0.775.
〈磁気テープの劣化促進テスト〉
該磁気テープを、実施例１記載の方法により劣化促進テ
ストを行った。<Accelerated deterioration test of magnetic tape> An accelerated deterioration test was conducted on the magnetic tape according to the method described in Example 1.
Ｂｍ値は２９６０Ｇで、初期値から４．０％低下してい
た。The Bm value was 2960G, which was 4.0% lower than the initial value.
この値［，８＋１ＩＩＩＶＴＲ用テープの示す劣化特性
としては充分小さく、優れた経時性を示したと言えるも
のである。This value [,8+1IIIVTR tape has sufficiently low deterioration characteristics and can be said to exhibit excellent aging properties.
〔実施例４〕 く風乾鉄粉の製造〉 比較例１記載の風乾鉄粉を使用した。[Example 4] Production of air-dried iron powder> The air-dried iron powder described in Comparative Example 1 was used.
〈アミ／処理〉
実施例２記載の方法により上記の風乾鉄粉に２−ジメチ
ルアミノエタノールの処理を行った。（鉄粉１００ｇｒ
、 トルエン４００ｇｒ、 ２−ジメチルアミノエタ
ノール０．５ｇｒ、 ）
〈処理鉄粉の乾燥〉
処理鉄粉を窒素雰囲気下で乾燥を行い、徐々に空気に触
れさせ空気中に取り出した。該処理鉄粉の物性評価を行
ったところ、５Ａ＝５４．５ｙｐｇ ｒ 。<Ami/Treatment> The above air-dried iron powder was treated with 2-dimethylaminoethanol by the method described in Example 2. (Iron powder 100g
, 400 gr of toluene, 0.5 gr of 2-dimethylaminoethanol, ) <Drying of treated iron powder> The treated iron powder was dried in a nitrogen atmosphere, gradually exposed to air, and taken out into the air. When the physical properties of the treated iron powder were evaluated, 5A=54.5ypg r .
Ｈｃ＝１５７００ｅ、 ０３＝＝１３２ｅｍｕ／ｇｒ
、 Ｒｓ＝０．５３０であった。Hc=15700e, 03==132emu/gr
, Rs=0.530.
〈処理鉄粉の劣化促進テスト〉 実施例１記載の方法により劣化促進テストを行った。〈Test for accelerated deterioration of treated iron powder〉 An accelerated deterioration test was conducted using the method described in Example 1.
その結果、５Ａ＝４７．５ｍシ／ｇ ｒ、σｓ＝１１４
ｅｍｕ／ｇｒ 。As a result, 5A = 47.5 mshi/g r, σs = 114
emu/gr.
劣化率は１３．６％であった。この結果は、１３＋１ｓ
ＶＴＲ用磁性鉄粉として充分に耐候性を持つことがわが
りた。The deterioration rate was 13.6%. This result is 13+1s
It was found that it has sufficient weather resistance as a magnetic iron powder for VTRs.
〈風乾鉄粉の固体酸塩基量の測定〉 実施例１記載の方法により測定を行った。<Measurement of solid acid-base amount of air-dried iron powder> Measurement was performed by the method described in Example 1.
固体酸量は、０．０１ｍｅｑ以下であった。固体塩基量
は、０．１４ｍｅ ｑ／ｇ ｒ 、でありた。The amount of solid acid was 0.01 meq or less. The amount of solid base was 0.14 meq/g r.
この結果充分に酸点にアミンが吸着していることが解っ
た。As a result, it was found that amine was sufficiently adsorbed at the acid sites.
く風乾鉄粉の塗料化・塗工化及びテープ特性の評価〉該
風乾鉄粉１ ｏｇｒ 、を採取して、実施例−１記載と
同様にして磁性塗料を調製し、塗工化・平滑化・ボスト
アニーリング処理・裁断を加えて現行８ｍｍＶＴＲ用力
セント仕様サイズの磁気テープとする。該磁気テープの
磁気特性を、既述の測定装置にて測定・評価したところ
、
Ｈｃ＝＝１４７５０ｅＸＢｒ＝２５６００． Ｂｒ／Ｂ
ｍ＝０．７７０であった。Formation of air-dried iron powder into paint/coating and evaluation of tape properties> 1 ogr of the air-dried iron powder was collected, a magnetic paint was prepared in the same manner as described in Example-1, and it was coated and smoothed.・Add boss annealing and cutting to create a magnetic tape of current 8mm VTR standard size. When the magnetic properties of the magnetic tape were measured and evaluated using the above-mentioned measuring device, Hc==14750eXBr=25600. Br/B
m=0.770.
〈磁気テープの劣化促進テスト〉
該磁気テープを、実施例１記載の方法により劣化促進テ
ストヲ行った。<Accelerated deterioration test of magnetic tape> An accelerated deterioration test was conducted on the magnetic tape according to the method described in Example 1.
Ｂｍ値は２８８０Ｇで、初期値から６θ％低下していた
。The Bm value was 2880G, which was 6θ% lower than the initial value.
この値は、ＢｍｔｌＶＴＲｍｔ−ＶＴＲす劣化特性とし
ては充分小さく、優れた経時性を示したと言えるもので
ある。This value is sufficiently small for the deterioration characteristics of BmtlVTRmt-VTR, and can be said to show excellent aging properties.
〔実施例５〕
アンモニアのガス濃度を０２５％とした以外は、実施例
１と同様の処理を行った。主な結果については、表１に
示す。[Example 5] The same treatment as in Example 1 was performed except that the ammonia gas concentration was changed to 0.25%. The main results are shown in Table 1.
〔実施例６〜８〕
アミンの添加量を変化した以外は、実施例２と同様の処
理を行った。主な結果については、表１に示す。磁気特
性、耐候性共に効果があられれた。[Examples 6 to 8] The same treatment as in Example 2 was performed except that the amount of amine added was changed. The main results are shown in Table 1. It was effective in both magnetic properties and weather resistance.
〔実施例９〕
Ｎメチルアセトアミドを使用した以外は、実施例２と同
様の処理を行った。主な結果については、表１に示す。[Example 9] The same treatment as in Example 2 was performed except that N-methylacetamide was used. The main results are shown in Table 1.
磁気特性、耐候性共に効果があられれた。It was effective in both magnetic properties and weather resistance.
〔実施例１０〕
グアニジンを使用し溶媒をメタノールに変更した以外は
、実施例２と同様の処理を行った。主な結果については
、表１に示す。磁気特性、耐候性共に効果があられれた
。[Example 10] The same treatment as in Example 2 was performed except that guanidine was used and the solvent was changed to methanol. The main results are shown in Table 1. It was effective in both magnetic properties and weather resistance.
〔実施例１１〕
比較例１記載の風乾鉄粉を窒素中で１５０’Ｃの加熱処
理を行った以外は実施例６と同様な処理を行った。主な
結果については、表１に示す。主な結果については、表
１に示す。磁気特性、耐候性共に効果があられれた。[Example 11] The same treatment as in Example 6 was performed except that the air-dried iron powder described in Comparative Example 1 was heat treated at 150'C in nitrogen. The main results are shown in Table 1. The main results are shown in Table 1. It was effective in both magnetic properties and weather resistance.
〔比較例−２〕
２−ジメチルアミノエタノールを０．００５ｇｒ、 ト
した以外は、実施例２と同様に処理を行った。主な結果
については、表１に示す。耐候性に効果が現れなかった
。[Comparative Example-2] The same process as in Example 2 was carried out except that 0.005 gr of 2-dimethylaminoethanol was added. The main results are shown in Table 1. There was no effect on weather resistance.
〔比較例−３〕
２−ジメチルアミノエタノールをＩＣｌｇｒ、 トＬ７
’Ｃ以外は、実施例２と同様に処理を行った。主な結果
については、表１に示す。充分な磁気特性を得られなか
った。[Comparative Example-3] 2-dimethylaminoethanol was added to IClgr, ToL7
The process was carried out in the same manner as in Example 2 except for 'C. The main results are shown in Table 1. Sufficient magnetic properties could not be obtained.
〔比較例−４〕
２−ジメチルアミノエタノールを１０ｇｒ、 トｔ、’
ｃ以外は、実施例４と同様に処理を行っ友。主な結果に
ついては、表１に示す。充分な磁気特性を得られなかっ
た。[Comparative Example-4] 10g of 2-dimethylaminoethanol, t,'
The process was carried out in the same manner as in Example 4 except for c. The main results are shown in Table 1. Sufficient magnetic properties could not be obtained.
Claims (5)
一種類で処理されたＦｅを主成分とした強磁性金属粉末
。(1) A ferromagnetic metal powder containing Fe as a main component and treated with at least one of ammonia, amine, amide, and imide.
分としてＰ、Ｓｉ、Ａｌ、Ｂのいずれかを含み、且つ還
元性ガスによる還元反応により得られた特許請求の範囲
第１項記載の強磁性金属粉末。(2) The ferromagnetic metal powder containing Fe as a main component contains any one of P, Si, Al, and B as a shape-retaining component, and is obtained by a reduction reaction with a reducing gas. ferromagnetic metal powder.
で、 Ｐ／Ｆｅ＝０．１／１００〜５／１００、 Ｓｉ／Ｆｅ＝０．１／１００〜５／１００、Ａｌ／Ｆｅ
＝０．１／１００〜５／１００、Ｂ／Ｆｅ＝０．１／１
００〜５／１００ の範囲にある特許請求の範囲第１項記載の強磁性金属粉
。(3) Content of P, Si, Al or B in weight ratio with Fe: P/Fe=0.1/100 to 5/100, Si/Fe=0.1/100 to 5/100, Al /Fe
=0.1/100~5/100, B/Fe=0.1/1
00 to 5/100.
処理量が、処理前の強磁性粉末１ｇ当たりの等量比で、
０．０１〜５．０ｍｅｑ（ＮＨ＿３基準）の範囲にある
特許請求の範囲第１項記載の強磁性金属粉末。(4) The amount of ammonia and/or amine, amide, imide treated is an equivalent ratio per 1 g of ferromagnetic powder before treatment,
The ferromagnetic metal powder according to claim 1, which is in the range of 0.01 to 5.0 meq (NH_3 standard).
１項記載の強磁性金属粉末。(5) The ferromagnetic metal powder according to claim 1, wherein the ferromagnetic metal powder has an oxide layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60292875A JPS62156202A (en) | 1985-12-27 | 1985-12-27 | Ferromagnetic metallic powder treated with amines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60292875A JPS62156202A (en) | 1985-12-27 | 1985-12-27 | Ferromagnetic metallic powder treated with amines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62156202A true JPS62156202A (en) | 1987-07-11 |
Family
ID=17787509
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60292875A Pending JPS62156202A (en) | 1985-12-27 | 1985-12-27 | Ferromagnetic metallic powder treated with amines |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62156202A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02260608A (en) * | 1989-03-31 | 1990-10-23 | Hitachi Maxell Ltd | Fine partice of ferromagnetic metallic iron, manufacture thereof, and magnetic recording medium using same |
| US6447618B1 (en) | 1998-07-31 | 2002-09-10 | Toda Kogyo Corporation | Magnetic acicular alloy particles containing iron as a main component |
| CN103357884A (en) * | 2013-07-07 | 2013-10-23 | 合肥工业大学 | Method for preparing porous nano-iron by brown iron ore |
-
1985
- 1985-12-27 JP JP60292875A patent/JPS62156202A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02260608A (en) * | 1989-03-31 | 1990-10-23 | Hitachi Maxell Ltd | Fine partice of ferromagnetic metallic iron, manufacture thereof, and magnetic recording medium using same |
| US6447618B1 (en) | 1998-07-31 | 2002-09-10 | Toda Kogyo Corporation | Magnetic acicular alloy particles containing iron as a main component |
| US6682813B2 (en) | 1998-07-31 | 2004-01-27 | Toda Kogyo Corporation | Magnetic acicular alloy particles containing iron as a main component |
| CN103357884A (en) * | 2013-07-07 | 2013-10-23 | 合肥工业大学 | Method for preparing porous nano-iron by brown iron ore |
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