JP2001200169A - Resin composite material compounded with ferromagnetic metal powder - Google Patents
Resin composite material compounded with ferromagnetic metal powderInfo
- Publication number
- JP2001200169A JP2001200169A JP2000262322A JP2000262322A JP2001200169A JP 2001200169 A JP2001200169 A JP 2001200169A JP 2000262322 A JP2000262322 A JP 2000262322A JP 2000262322 A JP2000262322 A JP 2000262322A JP 2001200169 A JP2001200169 A JP 2001200169A
- Authority
- JP
- Japan
- Prior art keywords
- metal powder
- ferromagnetic metal
- composite material
- value
- resin composite
- 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.)
- Withdrawn
Links
- 239000000843 powder Substances 0.000 title claims abstract description 108
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 89
- 239000002184 metal Substances 0.000 title claims abstract description 89
- 230000005294 ferromagnetic effect Effects 0.000 title claims abstract description 85
- 239000000463 material Substances 0.000 title claims abstract description 30
- 239000000805 composite resin Substances 0.000 title claims abstract description 24
- 238000004381 surface treatment Methods 0.000 claims abstract description 24
- 125000000962 organic group Chemical group 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012153 distilled water Substances 0.000 claims abstract description 7
- 239000006228 supernatant Substances 0.000 claims abstract description 6
- 239000010409 thin film Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- 229910001463 metal phosphate Inorganic materials 0.000 claims description 7
- 238000005259 measurement Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 238000011282 treatment Methods 0.000 abstract description 23
- 238000000576 coating method Methods 0.000 abstract description 19
- 239000011248 coating agent Substances 0.000 abstract description 17
- 238000003756 stirring Methods 0.000 abstract description 13
- 239000007788 liquid Substances 0.000 abstract description 7
- 230000009467 reduction Effects 0.000 abstract description 4
- 150000002736 metal compounds Chemical class 0.000 abstract description 3
- 229910019142 PO4 Inorganic materials 0.000 abstract 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 94
- 235000011007 phosphoric acid Nutrition 0.000 description 47
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 45
- 238000000034 method Methods 0.000 description 20
- 238000012360 testing method Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 12
- 239000002245 particle Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 230000005291 magnetic effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000004898 kneading Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229910000859 α-Fe Inorganic materials 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 229910052712 strontium Inorganic materials 0.000 description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- -1 silane compound Chemical class 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- BUZRAOJSFRKWPD-UHFFFAOYSA-N isocyanatosilane Chemical compound [SiH3]N=C=O BUZRAOJSFRKWPD-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical group 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910001172 neodymium magnet Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229910018106 Ni—C Inorganic materials 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 101001062854 Rattus norvegicus Fatty acid-binding protein 5 Proteins 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical group N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910000828 alnico Inorganic materials 0.000 description 1
- JZQOJFLIJNRDHK-CMDGGOBGSA-N alpha-irone Chemical compound CC1CC=C(C)C(\C=C\C(C)=O)C1(C)C JZQOJFLIJNRDHK-CMDGGOBGSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910000938 samarium–cobalt magnet Inorganic materials 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/06—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys in the form of particles, e.g. powder
- H01F1/061—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys in the form of particles, e.g. powder with a protective layer
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Powder Metallurgy (AREA)
- Chemical Treatment Of Metals (AREA)
- Hard Magnetic Materials (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、強磁性金属粉末を樹脂
材に混合し混練してなる、樹脂−強磁性金属粉末複合材
料に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin-ferromagnetic metal powder composite material obtained by mixing and kneading a ferromagnetic metal powder with a resin material.
【０００２】[0002]
【従来の技術】１種または２種以上の強磁性粉末を樹脂
に配合して加熱混練し、ぺレット或いはシート状の樹脂
複合材料とし、又はこれを射出成形して製品を形成し、
これに着磁してボンド磁石(プラスチック磁石)とするこ
とが実施されている。上記樹脂複合材料は、製造時に混
練機内で強磁性粉末と樹脂材を攪拌する際、摩擦によっ
て高熱が発生し、樹脂複合材料は非常な高温に曝され
る。強磁性粉末がストロンチウムフェライトなどの金属
酸化物であれば、熱的に十分に安定なため、混練中の発
生熱による磁気特性の劣化はほとんど問題にならない。
しかし、熱的安定性が十分でない強磁性金属粉末の場合
には、攪拌混練の工程で発生する熱が強磁性金属粉末の
耐熱温度を越えており、強磁性金属粉末の酸化が起こ
り、そのような樹脂複合材料を原料としたボンド磁石製
品は磁気特性を損なう問題があった。特に強磁性金属粉
末に耐熱処理が施されていない場合には、混練工程の高
温による酸化で強磁性金属粉末のダメージが甚だしく、
得られるボンド磁石の品質を低下させる。2. Description of the Related Art One or more ferromagnetic powders are mixed with a resin and heated and kneaded to form a pellet or sheet-like resin composite material, or injection-molded to form a product.
This is magnetized to form a bond magnet (plastic magnet). When the ferromagnetic powder and the resin material are stirred in the kneader during the production of the resin composite material, high heat is generated due to friction, and the resin composite material is exposed to a very high temperature. If the ferromagnetic powder is a metal oxide such as strontium ferrite, it is thermally sufficiently stable, so that deterioration of magnetic properties due to heat generated during kneading hardly causes a problem.
However, in the case of a ferromagnetic metal powder having insufficient thermal stability, the heat generated in the stirring and kneading process exceeds the heat resistance temperature of the ferromagnetic metal powder, and oxidation of the ferromagnetic metal powder occurs. Bonded magnet products made of a resin composite material as a raw material have a problem of impairing magnetic properties. Especially when the heat-resistant treatment is not applied to the ferromagnetic metal powder, the ferromagnetic metal powder is significantly damaged by oxidation at a high temperature in the kneading step,
Decreases the quality of the resulting bonded magnet.
【０００３】この問題に対処するため出願人は強磁性金
属粉末の耐熱処理方法を特許第２６０２８８３号で明ら
かにした。又、出願人は、ホットランナー成形の様に、
樹脂材料へ過大な熱負荷が加わって熱酸化し、品質劣化
し易い材料を用い成形に適した、強磁性金属粉末を含む
樹脂複合材料を特許第１９０６９１１号で開示した。後
者特許の樹脂複合材料は、強磁性金属粉末の表面を、有
機基を含まない無機燐酸金属化合物の薄膜によって一様
に覆い、さらにシリルイソシアネート系シラン化合物に
よって表面処理したものである。この樹脂複合材料は溶
融流動性が高いため加工性の点で優れているが、成形品
を長期間高湿中で保有した場合、成形品は強度低下を来
すという耐候性の点で問題があり、更なる改良が望まれ
た。[0003] In order to address this problem, the applicant has disclosed a method for heat-treating ferromagnetic metal powder in Japanese Patent No. 2602883. Also, the applicant, like hot runner molding,
Japanese Patent No. 1906911 discloses a resin composite material containing a ferromagnetic metal powder, which is suitable for molding by using a material which easily undergoes thermal oxidation due to an excessive heat load applied to the resin material and which is easily deteriorated in quality. The resin composite material of the latter patent is obtained by uniformly covering the surface of a ferromagnetic metal powder with a thin film of an inorganic metal phosphate compound containing no organic group, and further treating the surface with a silyl isocyanate-based silane compound. This resin composite material is excellent in workability because of its high melt fluidity, but when the molded product is held in high humidity for a long period of time, there is a problem with the weather resistance that the molded product will lose its strength. Yes, further improvement was desired.
【０００４】強磁性金属粉末を燐酸被覆処理した場合に
は、粉末表面の酸性度が非常に高くなる。燐酸被覆処理
を行った強磁性金属粉末を含む樹脂複合材料を用いて製
造されたボンド磁石を高湿中で長期間保持すると、樹脂
の吸湿により樹脂複合材の内部へ水分が浸入する。浸入
した水分が強磁性金属粉末表面にまで達すると、強磁性
金属粉末の表面に存在する無機燐酸金属化合物が溶解
し、その水溶液は水素イオン濃度を示すｐＨ値が低いた
めに樹脂の劣化を促進させ、結果的にボンド磁石の強度
低下を招来する。When the ferromagnetic metal powder is coated with phosphoric acid, the acidity of the powder surface becomes very high. When a bonded magnet manufactured using a resin composite material containing a ferromagnetic metal powder that has been subjected to a phosphoric acid coating treatment is held for a long time in high humidity, moisture permeates into the resin composite material due to moisture absorption of the resin. When the infiltrated water reaches the surface of the ferromagnetic metal powder, the inorganic metal phosphate compound present on the surface of the ferromagnetic metal powder dissolves, and the aqueous solution has a low pH value indicating the hydrogen ion concentration, thereby accelerating the deterioration of the resin. As a result, the strength of the bonded magnet is reduced.
【０００５】[0005]
【解決しようとする課題】本出願人は、強磁性金属粉末
を配合した樹脂複合材料を原料として成形したボンド磁
石について耐候性を研究したところ、その過程で、無機
燐酸金属化合物で覆われた強磁性金属粉末の表面ｐＨ値
を高くする処理をした場合、これを用いて製造したボン
ド磁石は高湿中での強度低下が抑制されることを見い出
した。本発明は、有機基を含まない燐酸被覆処理された
強磁性金属粉末を配合した樹脂複材料について高湿中で
の劣化を少なくし、耐候性のより高いボンド磁石用樹脂
複合材料を提供することを目的とする。SUMMARY OF THE INVENTION The present applicant has studied the weather resistance of a bonded magnet formed from a resin composite material containing a ferromagnetic metal powder as a raw material. It has been found that when a treatment is performed to increase the surface pH value of the magnetic metal powder, the bond magnet manufactured using the same is suppressed from decreasing in strength in high humidity. An object of the present invention is to provide a resin composite material for bonded magnets which has less deterioration in high humidity and has higher weather resistance for a resin composite material containing a ferromagnetic metal powder coated with phosphoric acid which does not contain an organic group. With the goal.
【０００６】[0006]
【課題を解決する手段】本発明の強磁性金属粉末を配合
した樹脂複合材料は、有機基を含まない無機燐酸金属又
は該無機燐酸金属化合物の薄膜によって強磁性金属粉末
の粒子表面が覆われ、且つ、その表面のｐＨ値が間接測
定で一定値以上になるように表面処理を施した強磁性金
属粉末を含む樹脂複合材料であって、該強磁性金属粉末
の表面ｐＨ値は、該強磁性金属粉末を蒸留水に投入して
攪拌し、上澄み液又は濾液のｐＨ値が６以上になること
を特徴とする。In the resin composite material containing the ferromagnetic metal powder of the present invention, the particle surface of the ferromagnetic metal powder is covered with a thin film of an inorganic metal phosphate or an inorganic metal compound containing no organic group, Further, a resin composite material containing a ferromagnetic metal powder that has been subjected to a surface treatment so that the pH value of the surface thereof is equal to or more than a certain value by indirect measurement, wherein the surface pH value of the ferromagnetic metal powder is the ferromagnetic metal powder. The metal powder is put into distilled water and stirred, and the pH value of the supernatant or the filtrate is 6 or more.
【０００７】[0007]
【作用】強磁性金属粉末を配合した樹脂複合材料は、該
金属粉末に対し有機基を含まない無機燐酸によって燐酸
被覆処理し、且つ表面が間接測定でｐＨ６以上となる様
に表面処理した場合にのみ、特異的に樹脂複合材料の耐
候性が向上する。The resin composite material containing the ferromagnetic metal powder is treated with a phosphoric acid coating treatment with an inorganic phosphoric acid containing no organic group on the metal powder, and the surface treatment is performed such that the surface has a pH of 6 or more by indirect measurement. Only, the weather resistance of the resin composite material is specifically improved.
【０００８】[0008]
【効果】強磁性金属粉末を配合した樹脂複合材料を用い
た成形品の耐候性は著しく改善され、８０℃、湿度９０
％の雰囲気中に１０００時間保持した場合の物性値(曲
げ強度)の低下率は、発明者らが以前に提案したシリル
イソシアネート系シラン化合物によって表面処理した樹
脂複合材料(特許第１９０６９１１号)を用いた成形品に
比べて大幅に減小した。[Effect] The weather resistance of a molded article using a resin composite material containing a ferromagnetic metal powder is remarkably improved.
% Of the resin composite material (patent No. 1906911) surface-treated with a silyl isocyanate-based silane compound previously proposed by the inventors of the present invention, when the property value (flexural strength) is maintained in an atmosphere of 1000% for 1000 hours. It was greatly reduced compared to the molded product.
【０００９】[0009]
【実施の形態】この出願において「強磁性金属粉末」と
は、例えばＳｍ−Ｃｏ系合金に代表されるＲＭ5、Ｒ2Ｍ
17(ＲはＳｍ、Ｐｒ、Ｃｅ、 Ｌａ等の稀土類元素、Ｍは
Ｆｅ，Ｎｉ，Ｃｏ等の遷移金属元素)、Ａｌ−Ｎｉ−Ｃ
ｏ系合金、強磁性鉄系合金など強磁性合金粉末、また、
Ｎd−Ｆｅ−Ｂ系、Ｓｍ−Ｆｅ−Ｎ系、Ｍｎ−Ａｌ−Ｃ
系など金属間化合物粉末、強磁性金属等から成る硬磁性
相とα鉄など高磁化の軟磁性相の２相からなる交換スプ
リング磁性粉末を含む。又、「燐酸」とは、燐酸(Ｈ3ＰＯ
4)のみでなく、無機の燐塩、その他の無機燐化合物を含
むものとする。又、樹脂としては、例えば、エポキシ樹
脂、フェノール樹脂、キシレン樹脂などの熱硬化性樹
脂、ポリアミド、ポリカーボネート、ポリフェニレンサ
ルファイド、液晶ポリマー等の熱可塑性樹脂、アクリロ
ニトリル−ブタジエンゴムなどの合成ゴムが挙げられる
が、本発明はこれらに限定されない。[Embodiment] RM 5 is a "ferromagnetic metal powder" as used in this application, typified by example Sm-Co-based alloy, R 2 M
17 (R is a rare earth element such as Sm, Pr, Ce, La, etc., M is a transition metal element such as Fe, Ni, Co), Al-Ni-C
o-based alloys, ferromagnetic alloy powders such as ferromagnetic iron-based alloys,
Nd-Fe-B system, Sm-Fe-N system, Mn-Al-C
An exchange spring magnetic powder comprising two phases of a hard magnetic phase composed of an intermetallic compound powder such as a ferromagnetic metal and a soft magnetic phase having a high magnetization such as α-iron. “Phosphoric acid” refers to phosphoric acid (H 3 PO
4 ) In addition to inorganic phosphorus salts and other inorganic phosphorus compounds. Examples of the resin include thermosetting resins such as epoxy resin, phenol resin and xylene resin, thermoplastic resins such as polyamide, polycarbonate, polyphenylene sulfide and liquid crystal polymer, and synthetic rubbers such as acrylonitrile-butadiene rubber. However, the present invention is not limited to these.
【００１０】強磁性金属粉末は、発明者が以前に特許第
２６０２９７９号公報で提案した方法或いは他の公知の
方法によって微粉砕し、平均粒径１０μm、所望により
平均粒径１μmの超微粉とする。The ferromagnetic metal powder is finely pulverized by a method previously proposed by the inventor in Japanese Patent No. 2602979 or another known method to obtain an ultrafine powder having an average particle diameter of 10 μm and, if desired, an average particle diameter of 1 μm. .
【００１１】燐酸とアルコール溶剤とを混合した被覆処
理液と、前記微粉砕した強磁性金属粉末とを、不活性ガ
スの雰囲気中にて攪拌混合して金属粉末表面を燐酸被覆
する。The surface of the metal powder is coated with phosphoric acid by stirring and mixing the coating solution obtained by mixing phosphoric acid and an alcohol solvent and the finely ground ferromagnetic metal powder in an inert gas atmosphere.
【００１２】上記被覆処理液は、予め製造して準備する
のではなくて、金属粒を所望粒径に粉砕し被覆処理を行
う直前に、粒径に応じて決まる必要量の燐酸にアルコー
ル系溶剤を素早く攪拌混合して製り、燐酸のエステル化
を可及的に抑えたものである。The coating solution is not manufactured and prepared in advance, but immediately before the metal particles are crushed to a desired particle size and the coating process is performed, a necessary amount of phosphoric acid determined according to the particle size is added to an alcohol-based solvent. Is rapidly stirred and mixed to suppress phosphoric acid esterification as much as possible.
【００１３】燐酸が金属粉末に対して過剰であると、表
面処理後の乾燥工程中で、被覆処理液中の残留燐酸とア
ルコール系溶剤が反応してエステル化が進み、これが接
着作用を呈する様になり、金属粉末層が固化したり、取
扱中の容器に強固に付着して機器、容器の清掃に困難を
来す。従って処理される強磁性金属粉末の量と平均粒径
に応じて投入すべき燐酸量とを厳密に規定し、更にこの
燐酸を溶解すべきアルコール溶剤の量も、燐酸を均一分
散させるために必要な最小限度に制限することが重要で
ある。If the phosphoric acid is excessive with respect to the metal powder, during the drying step after the surface treatment, the residual phosphoric acid in the coating solution and the alcohol-based solvent react to promote esterification, which exhibits an adhesive effect. And the metal powder layer solidifies or adheres strongly to the container being handled, making it difficult to clean equipment and containers. Therefore, the amount of the ferromagnetic metal powder to be treated and the amount of phosphoric acid to be added are strictly specified according to the average particle size, and the amount of the alcohol solvent in which the phosphoric acid is to be dissolved is also necessary for uniformly dispersing the phosphoric acid. It is important to limit to a minimum.
【００１４】一般に燐酸は、平均粒径１０μm前後の強
磁性金属粉末に対し、燐酸重量は０.３〜１.０重量％、
望ましくは０.４〜０.５重量％の添加によって所望の耐
酸化膜が得られ。この制限された添加量によって、燐酸
のエステル化に伴う前記トラブルは回避でき、乾燥上が
りの製品金属粉末はサラサラして極めて流動性が良いば
かりでなく、単分子層に近い燐酸系金属化合物を金属微
粉末の表面に形成することに留めることが出来、磁気特
性を向上できる。In general, phosphoric acid has a phosphoric acid weight of 0.3 to 1.0% by weight based on a ferromagnetic metal powder having an average particle size of about 10 μm.
Desirably, a desired oxidation resistant film is obtained by adding 0.4 to 0.5% by weight. With this limited amount of addition, the above-mentioned troubles associated with the esterification of phosphoric acid can be avoided, and the product metal powder after drying is not only smooth and extremely fluid, but also a phosphoric metal compound close to a monomolecular layer can be metallized. It can be limited to the formation on the surface of the fine powder, and the magnetic properties can be improved.
【００１５】次に燐酸被覆処理された強磁性金属粉末に
対して、後述する間接測定による表面ｐＨ値を上げる化
合物を接触させて、ｐＨ値上昇の表面処理を行う。ｐＨ
値上昇表面処理に用いる化合物(以下、「表面処理用化合
物」という)としては、例えば、アミノ系、ビニル系、エ
ポキシ系、メルカプト系などのシランカップリング剤、
チタネート系カップリング剤、アルミネート系カップリ
ング剤、尿酸基を含むシランカップリング剤などが挙げ
られるが、燐酸被覆処理された強磁性金属粉末のｐＨ値
を６以上に調整することが可能であれば表面処理用化合
物の種類は問わない。Next, the ferromagnetic metal powder coated with phosphoric acid is brought into contact with a compound for increasing the surface pH value by an indirect measurement described later to perform a surface treatment for increasing the pH value. pH
Compounds used in the surface treatment for increasing the value (hereinafter, referred to as “surface treatment compounds”) include, for example, amino-based, vinyl-based, epoxy-based, mercapto-based silane coupling agents,
Examples include titanate-based coupling agents, aluminate-based coupling agents, and silane coupling agents containing a uric acid group. However, it is possible to adjust the pH value of the ferromagnetic metal powder coated with phosphoric acid to 6 or more. The type of the compound for surface treatment is not limited.
【００１６】燐酸被覆処理された１種または２種以上の
強磁性金属粉末の重量比１００部に対して、表面処理用
化合物を０.１〜２部を用いる。該化合物の添加量が多
くなると、未反応のまま強磁性金属粉末表面へ残留する
量が多くなり、成形時にガス発生の原因となり、成形品
内部に微細な空隙が発生し易くなるため好ましくない。
表面処理用化合物はそのままでも使用できるが、アルコ
ール等の溶剤に希釈しても可い。The surface treatment compound is used in an amount of 0.1 to 2 parts with respect to 100 parts by weight of one or more ferromagnetic metal powders subjected to the phosphoric acid coating treatment. If the amount of the compound increases, the amount of the compound remaining unreacted on the surface of the ferromagnetic metal powder increases, which causes gas generation at the time of molding and tends to generate fine voids inside the molded product, which is not preferable.
The surface treating compound can be used as it is, but may be diluted with a solvent such as alcohol.
【００１７】ｐＨ値上昇表面処理方法は、加熱と振動の
機能を有する乾燥機に、上記燐酸被覆処理した強磁性金
属粉末を投入し、５〜３０Ｈzの振動を続けながら、予
め溶剤に分散させておいた表面処理用化合物を添加し混
合する。１００℃になるまで３０分程度振動させた後、
振動を停止し、８０〜１２０℃で乾燥させる。その際、
乾燥室内を真空ポンプで強制排気しても可い。In the surface treatment method for increasing the pH value, the above-mentioned ferromagnetic metal powder coated with phosphoric acid is put into a drier having a function of heating and vibration, and is dispersed in a solvent in advance while continuing vibration at 5 to 30 Hz. Add the surface treating compound and mix. After vibrating for about 30 minutes until it reaches 100 ° C,
Stop vibration and dry at 80-120 ° C. that time,
The drying chamber may be evacuated by a vacuum pump.
【００１８】次に上記工程で得られたｐＨ値上昇処理済
みの強磁性金属粉末を、合成樹脂、合成ゴム等の樹脂材
料に対し５〜９６重量％を配合して、１５０〜３５０℃
に加熱して混練する。この加熱混練の際、樹脂材料及び
ストロンチウムフェライトは熱的に安定であるから、上
記強磁性金属粉末との混合物とすることに問題はない。Next, 5-96% by weight of the ferromagnetic metal powder obtained in the above step, which has been subjected to the pH raising treatment, is mixed with a resin material such as synthetic resin or synthetic rubber at 150-350 ° C.
And knead by heating. During this heating and kneading, the resin material and the strontium ferrite are thermally stable, so there is no problem in forming a mixture with the ferromagnetic metal powder.
【００１９】加熱混練した後、押出機によって押出して
射出成形用のペレットに成形し、或いは加熱ローラによ
ってシート状の半製品に成形する。又は混練押出機によ
って混練すると共に所定形状に押出し成形する。成形方
法は上記に限らず、その他の成形方法を採用出来ること
は勿論であり、必要であれば磁場中にて成形することも
可能である。After the heating and kneading, the mixture is extruded by an extruder and formed into pellets for injection molding, or formed into a sheet-like semi-finished product by a heating roller. Alternatively, the mixture is kneaded by a kneading extruder and extruded into a predetermined shape. The molding method is not limited to the above, and it goes without saying that other molding methods can be employed, and if necessary, molding can be performed in a magnetic field.
【００２０】以下に、強磁性金属粉末の燐酸被覆処理方
法、ｐＨ値上昇表面処理方法、処理済み強磁性金属粉末
を配合した樹脂複合材料を用いた試料製造の具体例を示
す。磁性金属粉末に燐酸被覆処理をするには、次の２つ
の方法を実施した。燐酸被覆処理法その１ (強磁性金属粉末に燐酸アルコール溶液を散布攪拌する
方法)強磁性金属粉末５００ｇを鋼球３kgと一緒にボー
ルミル内へ入れ、Ｎ2ガス(純度９９.９％以上)でミル内
で十分にパージした後に１００rpmで３時間乾式粉砕
し、平均粒径１０μmの微粉末を得る。オルソ燐酸４.５
ｇとＮＰＡ(ノルマルプロピルアルコール)２０ｇをスタ
ーラーで約１分間攪拌して調製した均一な燐酸アルコー
ル溶液を、前記平均粒径１０μmの微粉末５００ｇに散
布して攪拌し、排気ファン付き乾燥器中にて４０〜９０
℃で約１時間加熱乾燥する。有機基を含まない無機燐酸
金属化合物の薄膜によって被覆された強磁性金属粉末が
得られた。The following are specific examples of the method of coating the ferromagnetic metal powder with phosphoric acid, the method of surface treatment for increasing the pH value, and the production of a sample using a resin composite material containing the treated ferromagnetic metal powder. To coat the magnetic metal powder with phosphoric acid, the following two methods were performed. Phosphoric acid coating treatment method 1 (Method of spraying and stirring a phosphoric acid alcohol solution on ferromagnetic metal powder) 500 g of ferromagnetic metal powder is put into a ball mill together with 3 kg of steel balls, and N 2 gas (purity of 99.9% or more) is added to the ball mill. After sufficiently purging in a mill, the mixture is dry-pulverized at 100 rpm for 3 hours to obtain a fine powder having an average particle size of 10 μm. Orthophosphoric acid 4.5
g of NPA (normal propyl alcohol) and 20 g of NPA (normal propyl alcohol) were stirred with a stirrer for about 1 minute, and a uniform phosphoric acid alcohol solution was sprayed on 500 g of the fine powder having an average particle size of 10 μm and stirred. 40-90
Heat and dry at about 1 hour. A ferromagnetic metal powder coated with a thin film of an inorganic metal phosphate compound containing no organic group was obtained.
【００２１】燐酸被覆処理法その２ (強磁性金属粉末を収容した不活性ガス雰囲気の攪拌槽
に、不活性ガス雰囲気を維持したまま燐酸アルコール溶
液を注入する方法)鋼球３kgと、粉砕助剤としてｎ−ヘ
キサン４００ｇとを投入しておいた攪拌槽に強磁性金属
粉末５００ｇを投入し、密閉する。攪拌槽内をＮ2ガス
(純度９９.９％以上)で約１分間パージを行った後、回
転数２０５rpmにて９分間湿式粉砕を行い、平均粒径１
０μmの微粉末を得る。オルソ燐酸４.５ｇとＮＰＡ(ノ
ルマルプロピルアルコール)２０ｇをスターラーで約１
分間攪拌して調製した均一な燐酸アルコール溶液を処理
液タンクに容れて、該タンク内をＮ2ガス置換を行う。
前記の強磁性金属粉末の粉砕完了時に合わせて、攪拌槽
と処理液タンクを連通するパイプのバルブを開いて、Ｎ
2ガス圧(１６.７Ｐａ)をかけながらタンクから攪拌槽へ
燐酸アルコール溶液を注入する。攪拌槽は粉砕に引き続
き同一回転数(２０５rpm)で回転を持続し、強磁性金属
粉末と燐酸アルコール溶液を攪拌分散させ、４５秒後に
回転を停止する。次に、攪拌槽から強磁性金属微粉末を
含んだ液体を流出させて容器に取り出し、上澄液を除去
した微粉末を排気ファン付き乾燥機内で、４０〜９０℃
で約１時間加熱乾燥する。有機基を含まない無機燐酸金
属化合物の薄膜によって被覆された強磁性金属粉末が得
られた。 Phosphoric Acid Coating Method 2 (Method of Injecting a Phosphoric Alcohol Solution into a Stirring Tank Containing Ferromagnetic Metal Powder in an Inert Gas Atmosphere While Maintaining the Inert Gas Atmosphere) 3 kg of steel balls and grinding aid Then, 500 g of ferromagnetic metal powder is charged into a stirring tank into which 400 g of n-hexane has been charged, and sealed. N 2 gas in the stirring tank
(Purity of 99.9% or more) for about 1 minute, and then wet pulverization at 205 rpm for 9 minutes to obtain an average particle size of 1
A fine powder of 0 μm is obtained. 4.5 g of orthophosphoric acid and 20 g of NPA (normal propyl alcohol) are stirred for about 1
The homogeneous phosphoric acid alcohol solution prepared by stirring for a minute is placed in a treatment liquid tank, and the inside of the tank is replaced with N 2 gas.
At the same time as the completion of the pulverization of the ferromagnetic metal powder, the valve of the pipe connecting the stirring tank and the processing liquid tank is opened, and N
2. Inject the phosphoric acid alcohol solution from the tank to the stirring tank while applying gas pressure (16.7 Pa). After the pulverization, the stirring tank continues to rotate at the same rotation speed (205 rpm) to stir and disperse the ferromagnetic metal powder and the phosphoric acid alcohol solution. After 45 seconds, the rotation is stopped. Next, the liquid containing the ferromagnetic metal fine powder is discharged from the stirring tank, taken out into a container, and the fine powder from which the supernatant liquid has been removed is placed in a dryer with an exhaust fan at 40 to 90 ° C.
For about 1 hour. A ferromagnetic metal powder coated with a thin film of an inorganic metal phosphate compound containing no organic group was obtained.
【００２２】強磁性金属粉末のｐＨ値上昇処理法及び樹
脂−金属粉末複合材による試料製造方法 表１は、１種類の強磁性金属粉末を用いた場合の、本発
明と比較例の製造諸条件及び強磁性金属粉末の表面ｐＨ
値と試料の耐候性試験の強度を示すものである。表１に
示す１種類の強磁性金属粉末(ＮｄＦｅＢ)を含む場合に
於ける、本発明試料１〜１０と、比較例５１〜５４の試
料の製造手順。工程１． 燐酸被覆処理を、上記処理法その１又はその
２に従って行った２２５ｇ(電子天秤で精秤)の強磁性金
属粉末(以下「原料粉末」という)２２５ｇ(１００重量部)
を製る。２.２５ｇ(１.０重量部)の表面処理用化合物
(［００１５］参照)を２５ｇの溶剤(メチルアルコール
又はキシレン)と一緒にスターラーで３分間混合する。
得られた表面処理液を、乳鉢の中で前記原料粉末と十分
に混ぜる(約３分間)。工程２． 表面処理液と混合された原料粉末をバットに拡
げて約８０〜１２０℃で１時間程度オーブン乾燥させ
る。強磁性金属粉末のｐＨ値上昇表面処理は終了した。工程３． 強磁性金属粉末のｐＨ値上昇表面処理を終えた
原料粉末を、乳鉢でナイロン１２等の樹脂バインダー２
０ｇと十分に混合する(約５分間)。工程４． 工程３で得られた混合物を２４５ｇ精秤し、バ
ッチ式樹脂混合機により、２８０℃で約５分間混練す
る。出来た餅状のコンパウンドをカッターで切断して直
径２〜３mmのペレットを得る。工程５． 上記工程で得られたペレット９８０ｇを成形用
材料にして射出成形機で７５mm(幅)×１３mm(長さ)×３
mm(高さ)のテストピースを作り、強度測定用の試料とし
た。 Method for raising pH value of ferromagnetic metal powder and tree
Fat - sample preparation method Table 1 by the metal powder composite is one in the case of using a ferromagnetic metal powder, the surface pH of the preparation conditions and the ferromagnetic metal powder of Comparative Example with the present invention
It shows the value and the strength of the weather resistance test of the sample. Manufacturing procedure of samples 1 to 10 of the present invention and samples of comparative examples 51 to 54 when one kind of ferromagnetic metal powder (NdFeB) shown in Table 1 is included. Step 1. The phosphoric acid coating treatment was performed according to the above-mentioned treatment method 1 or 2, and 225 g (100 wt parts) of ferromagnetic metal powder (hereinafter referred to as “raw material powder”) of 225 g (accurately weighed by an electronic balance)
Is made. 2.25 g (1.0 parts by weight) of compound for surface treatment
(See [0015]) with 25 g of solvent (methyl alcohol or xylene) with a stirrer for 3 minutes.
The obtained surface treatment liquid is sufficiently mixed with the raw material powder in a mortar (about 3 minutes). Step 2. The raw material powder mixed with the surface treatment liquid is spread on a vat and oven-dried at about 80 to 120 ° C. for about 1 hour. The surface treatment for raising the pH value of the ferromagnetic metal powder has been completed. Step 3. The raw material powder, which has been subjected to the surface treatment for raising the pH value of the ferromagnetic metal powder, is put into a resin binder 2 such as nylon 12 in a mortar.
Mix well with 0 g (about 5 minutes). Step 4. 245 g of the mixture obtained in the step 3 is precisely weighed and kneaded at 280 ° C. for about 5 minutes by a batch type resin mixer. The resulting rice cake-like compound is cut with a cutter to obtain pellets having a diameter of 2 to 3 mm. Step 5. Using 980 g of the pellet obtained in the above process as a molding material, 75 mm (width) × 13 mm (length) × 3 with an injection molding machine.
A test piece of mm (height) was prepared and used as a sample for strength measurement.
【００２３】[0023]
【表１】 [Table 1]
【００２４】下記表２は、２種類の強磁性金属粉末を用
いた場合の、本発明と比較例の製造諸条件及び強磁性金
属粉末の表面ｐＨ値と試料の耐候性試験後の強度を示す
ものである。表２に示す如く、２種類の強磁性金属粉末
を含む場合に於ける、比較例５５〜５８と、本発明１１
〜１４の試料の製造手順は、表２に示す割合で燐酸被覆
処理した２種類の強磁性金属粉末を配合し、表１につい
て記載した方法と同様の工程で、ｐＨ値上昇表面処理及
び強度試験用の試料を製造した。Table 2 below shows the production conditions of the present invention and the comparative example, the surface pH value of the ferromagnetic metal powder, and the strength of the sample after the weather resistance test when two kinds of ferromagnetic metal powders were used. Things. As shown in Table 2, when containing two types of ferromagnetic metal powders, Comparative Examples 55 to 58 and the present invention 11
The production procedures of the samples Nos. To 14 are as follows. Two kinds of ferromagnetic metal powders coated with phosphoric acid are blended at the ratios shown in Table 2 and the pH value is increased by the same process as described in Table 1. Samples were prepared.
【００２５】[0025]
【表２】 [Table 2]
【００２６】下記表３は、燐酸被覆処理及びｐＨ値上昇
処理を施した１種類の強磁性金属粉末と、何れの処理も
施さない１種類の強磁性金属酸化物粉末(充填材)を用い
た場合の、比較例と本発明との製造諸条件と、ｐＨ値及
び強度の比較を示すものである。強磁性金属粉末(Ｎｄ
ＦｅＢ、ＳｍＣｏ、ＡｌＮｉＣｏ又はＭｎＡｌＣ)と充
填材(実施例では、ストロンチウムフェライト)を含む場
合に於ける本発明１５〜１９と比較例５９〜６３の試料
の製造手順。燐酸被覆処理とｐＨ値上昇処理を施した強
磁性金属粉末と、何れの処理も施していないストロンチ
ウムフェライトを表３に示す割合で配合し、上記同様の
方法で試料を得た。Table 3 below shows one type of ferromagnetic metal powder subjected to the phosphoric acid coating treatment and the pH value increasing treatment, and one type of ferromagnetic metal oxide powder (filler) not subjected to any of the treatments. FIG. 4 shows a comparison of various production conditions of the comparative example and the present invention, and a pH value and strength. Ferromagnetic metal powder (Nd
The manufacturing procedure of the sample of this invention 15-19 and the comparative examples 59-63 in the case of containing FeB, SmCo, AlNiCo, or MnAlC) and a filler (strontium ferrite in an Example). Ferromagnetic metal powder that had been subjected to the phosphoric acid coating treatment and the pH value increasing treatment and strontium ferrite that had not been subjected to any of the treatments were blended in the ratio shown in Table 3, and a sample was obtained in the same manner as described above.
【００２７】[0027]
【表３】 [Table 3]
【００２８】表１乃至表３に於いて、強磁性金属粉末の
ｐＨ値は、強磁性金属粉末の表面ｐＨ値を直接測定する
ことはできないので、下記の方法で間接的に測定したも
のである。In Tables 1 to 3, the pH value of the ferromagnetic metal powder is indirectly measured by the following method since the surface pH value of the ferromagnetic metal powder cannot be directly measured. .
【００２９】強磁性金属粉末の表面ｐＨ値の測定方法 測定する１種又は２種以上の混合物からなり、上記燐酸
被覆処理及びｐＨ値上昇表面処理を行った強磁性金属粉
末を、蒸留水に、該蒸留水の重量の約５％投入する。実
施例では、５.０ｇの粉末を、１００ｇの蒸留水に入れ
て１０分間攪拌し、上澄み液又は濾液のｐＨを測定す
る。このｐＨ値を粉末の表面ｐＨ値として評価に用い
た。この上澄み液又は濾液のｐＨ値が高いほど強磁性金
属粉末の表面ｐＨ値が高いことを示す。 Method for Measuring Surface pH Value of Ferromagnetic Metal Powder The ferromagnetic metal powder consisting of one or more mixtures to be measured and having been subjected to the above-mentioned phosphoric acid coating treatment and pH value raising surface treatment is added to distilled water. About 5% of the weight of the distilled water is introduced. In the examples, 5.0 g of powder is placed in 100 g of distilled water and stirred for 10 minutes, and the pH of the supernatant or filtrate is measured. This pH value was used for evaluation as the surface pH value of the powder. The higher the pH value of the supernatant or the filtrate, the higher the surface pH value of the ferromagnetic metal powder.
【００３０】耐候性試験後の強度 試料毎にテストピースを２０個づつ準備し、１０個は耐
候性試験前に強度測定した。残り１０個は耐候性試験を
行い、その後に強度測定を行なった。耐候性試験前の強
度値に対する試験後の相対的強度値を算出し、強度低下
の大きさを比較した。耐候性試験後の相対的強度値の数
値が低いほど強度低下の程度が大きいことを表す。 耐候試験条件： 試料を温度８０℃、湿度９０％の雰囲
気中で１０００時間保持した。 強度測定： ＡＳＴＭ−Ｄ７９８の規格に基づき、曲げ
試験機にて曲げ強度測定を行った。[0030] Twenty test pieces were prepared for each strength sample after the weather resistance test, and the strength of ten test pieces was measured before the weather resistance test. The remaining 10 pieces were subjected to a weather resistance test, and then the strength was measured. The relative strength value after the test with respect to the strength value before the weather resistance test was calculated, and the magnitude of the strength decrease was compared. The lower the numerical value of the relative strength value after the weather resistance test, the greater the degree of strength reduction. Weathering test conditions: The sample was kept in an atmosphere at a temperature of 80 ° C and a humidity of 90% for 1000 hours. Strength measurement: The bending strength was measured by a bending tester based on the standard of ASTM-D798.
【００３１】試験結果 表１の比較例は、燐酸被覆処理を行った強磁性金属粉末
に、ｐＨ値上昇表面処理を施さない試料５１、試料５
２、及びアミンでｐＨ値上昇表面処理した試料５３、イ
ソシアネート系シラン化合物でｐＨ値上昇表面処理を行
った試料５４は、何れも表面ｐＨ値が６よりも低い。耐
候試験後の相対強度値は、すべての比較例試料について
５０％以下であり、強度低下が非常に大きいことが判
る。これに対して本発明の様に、燐酸被覆処理を行った
強磁性金属粉末に対して、表面ｐＨ値が６以上になるよ
うにｐＨ値上昇表面処理することで、すべての試料１〜
１０について耐候性試験による強度低下の程度が、比較
例に較べて１／２以下になる場合もあり、耐候性が著し
く改善されていることが明らかである。 Test Results The comparative examples shown in Table 1 show that the ferromagnetic metal powder which has been subjected to the phosphoric acid coating treatment is not subjected to the surface treatment for increasing the pH value of Sample 51 and Sample 5.
2, and the sample 53 subjected to the surface treatment for increasing the pH value with the amine and the sample 54 subjected to the surface treatment for increasing the pH value with the isocyanate-based silane compound have a surface pH value lower than 6. The relative strength values after the weathering test were 50% or less for all the comparative samples, indicating that the strength reduction was extremely large. On the other hand, as in the present invention, by subjecting the ferromagnetic metal powder that has been subjected to the phosphoric acid coating treatment to surface treatment for increasing the pH value so that the surface pH value becomes 6 or more, all the samples 1 to
In the case of No. 10, the degree of strength reduction by the weather resistance test may be １ ／ or less as compared with the comparative example, and it is clear that the weather resistance is remarkably improved.
【００３２】表２に示す様に、燐酸被覆処理を施した２
種類の強磁性金属粉末を含む場合でも、表面ｐＨ値が６
以上となるようにｐＨ値上昇処理することによって、本
発明の場合強度低下の程度が比較例に比べて著しく小さ
くなっていることが明らかである。As shown in Table 2, the phosphoric acid-coated 2
Surface pH value of 6
It is clear that the degree of strength decrease in the present invention is significantly smaller than that in the comparative example by performing the pH value increasing treatment as described above.
【００３３】表３に示す如く、燐酸被覆処理を施した強
磁性金属粉末を、燐酸被覆処理を施していない充填材と
混合した場合でも、燐酸被覆処理を行った強磁性金属粉
末の表面ｐＨ値を６以上になるように表面処理すること
によって、耐候性試験による強度低下の程度が比較例に
比べて著しく小さくなっていることが判る。As shown in Table 3, even when the phosphoric acid-coated ferromagnetic metal powder was mixed with a filler not subjected to the phosphoric acid coating treatment, the surface pH value of the phosphoric acid-coated ferromagnetic metal powder was mixed. It can be seen that by performing the surface treatment so as to be 6 or more, the degree of the strength decrease in the weather resistance test is significantly smaller than that of the comparative example.
【００３４】表１の比較例の試料５３のｐＨ５.７と本
発明の試料８のｐＨ６.２の夫々の耐候性試験後の強度
の比較から、表面ｐＨ値は６を境にして特異的に強度が
変わっている。このような効果は、燐酸被覆処理を施し
た強磁性金属粉末を単に塩基性化合物で処理しただけで
は達成できず、又、たとえ他の化合物による表面処理を
施したとしても、強磁性金属粉末の表面ｐＨ値が６より
小なる場合には耐候試験での強度低下の程度を小さくす
ることはできない。燐酸被覆処理した強磁性金属粉末の
表面ｐＨ値を６以上となるような適当な表面処理用化合
物を選択することで初めて達成できる顕著な効果であ
る。From the comparison of the strength of the sample 53 of Comparative Example 53 at pH 5.7 and the sample 8 of the present invention at pH 6.2 after the weather resistance test, the surface pH value was specifically determined at the boundary of 6. The intensity has changed. Such an effect cannot be achieved by simply treating the ferromagnetic metal powder that has been subjected to the phosphoric acid coating treatment with a basic compound. If the surface pH value is smaller than 6, the degree of strength decrease in the weather resistance test cannot be reduced. This is a remarkable effect that can be achieved only by selecting an appropriate surface treatment compound so that the surface pH of the ferromagnetic metal powder coated with phosphoric acid becomes 6 or more.
【００３５】本発明は、上記実施例の構成に限定される
ことはなく、特許請求の範囲に記載の範囲で種々の変形
が可能である。The present invention is not limited to the configuration of the above embodiment, and various modifications are possible within the scope of the claims.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 松田 大輔 岡山県和気郡佐伯町佐伯526番地の３ 株 式会社メイト内 Ｆターム(参考） 4J002 AA001 AC071 CC031 CD001 CE001 CG001 CL001 CN011 DC006 FB076 FB086 FD016 FD206 GQ00 4K018 BA04 BA05 BA18 BC28 BD01 KA46 4K026 AA01 AA23 BA03 BB10 CA03 DA06 DA11 5E040 AA04 AA09 AA14 AA19 BB03 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Daisuke Matsuda F-term (reference) 4M002 AA001 AC071 CC031 CD001 CE001 CG001 CL001 CN011 DC006 FB076 FB086 FD016 FD206 GQ00 4K018 BA04 BA05 BA18 BC28 BD01 KA46 4K026 AA01 AA23 BA03 BB10 CA03 DA06 DA11 5E040 AA04 AA09 AA14 AA19 BB03
Claims (1)
機燐酸金属化合物の薄膜によって表面が覆われ、且つ、
表面のｐＨ値が間接測定で一定値以上になるように表面
処理が施された強磁性金属粉末と樹脂との複合材料であ
って、該強磁性金属粉末の表面ｐＨ値は、該強磁性金属
粉末を蒸留水に投入して攪拌し、上澄み液又は濾液のｐ
Ｈ値が６以上であることを特徴とする強磁性金属粉末を
配合した樹脂複合材料。Claims: 1. An inorganic metal phosphate containing no organic group or a surface thereof is covered with a thin film of the inorganic metal phosphate compound, and
A composite material of a ferromagnetic metal powder and a resin that has been subjected to a surface treatment so that the surface pH value is equal to or higher than a certain value in an indirect measurement, wherein the surface pH value of the ferromagnetic metal powder is The powder is poured into distilled water and stirred, and the supernatant or filtrate
A resin composite material containing a ferromagnetic metal powder having an H value of 6 or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000262322A JP2001200169A (en) | 1999-11-09 | 2000-08-31 | Resin composite material compounded with ferromagnetic metal powder |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31858999 | 1999-11-09 | ||
| JP11-318589 | 1999-11-09 | ||
| JP2000262322A JP2001200169A (en) | 1999-11-09 | 2000-08-31 | Resin composite material compounded with ferromagnetic metal powder |
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| Publication Number | Publication Date |
|---|---|
| JP2001200169A true JP2001200169A (en) | 2001-07-24 |
Family
ID=26569419
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000262322A Withdrawn JP2001200169A (en) | 1999-11-09 | 2000-08-31 | Resin composite material compounded with ferromagnetic metal powder |
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| Country | Link |
|---|---|
| JP (1) | JP2001200169A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003007521A (en) * | 2000-11-13 | 2003-01-10 | Sumitomo Metal Mining Co Ltd | High weather-resistant magnet powder and magnet using the same |
| JP2005154676A (en) * | 2003-11-28 | 2005-06-16 | Uchiyama Mfg Corp | Magnetic rubber composition |
| CN106191836A (en) * | 2016-08-03 | 2016-12-07 | 北方工业大学 | Preparation method of magnesium alloy reinforced chemical conversion film |
| CN106544657A (en) * | 2015-09-22 | 2017-03-29 | 中国科学院宁波材料技术与工程研究所 | Improve coating liquid, method and its application of material surface modifying layer performance |
| EP3706436B1 (en) * | 2017-11-01 | 2023-09-27 | FUJIFILM Corporation | Resin composition for acoustic matching layer, hardened product, acoustic matching sheet, acoustic wave probe, acoustic wave measurement device, acoustic wave probe production method |
-
2000
- 2000-08-31 JP JP2000262322A patent/JP2001200169A/en not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003007521A (en) * | 2000-11-13 | 2003-01-10 | Sumitomo Metal Mining Co Ltd | High weather-resistant magnet powder and magnet using the same |
| JP2005154676A (en) * | 2003-11-28 | 2005-06-16 | Uchiyama Mfg Corp | Magnetic rubber composition |
| CN106544657A (en) * | 2015-09-22 | 2017-03-29 | 中国科学院宁波材料技术与工程研究所 | Improve coating liquid, method and its application of material surface modifying layer performance |
| CN106544657B (en) * | 2015-09-22 | 2019-03-05 | 中国科学院宁波材料技术与工程研究所 | Improve coating liquid, the method and its application of material surface modifying layer performance |
| CN106191836A (en) * | 2016-08-03 | 2016-12-07 | 北方工业大学 | Preparation method of magnesium alloy reinforced chemical conversion film |
| CN106191836B (en) * | 2016-08-03 | 2018-10-23 | 北方工业大学 | Preparation method of magnesium alloy reinforced chemical conversion film |
| EP3706436B1 (en) * | 2017-11-01 | 2023-09-27 | FUJIFILM Corporation | Resin composition for acoustic matching layer, hardened product, acoustic matching sheet, acoustic wave probe, acoustic wave measurement device, acoustic wave probe production method |
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