JP3481171B2 - ELECTRONIC COMPONENT MANUFACTURING MATERIAL, PROCESS FOR PRODUCING THE SAME, PROCESS FOR PRODUCING HIGH-DENSITY FERRITE ELECTRONIC COMPONENT USING THE SAME - Google Patents
ELECTRONIC COMPONENT MANUFACTURING MATERIAL, PROCESS FOR PRODUCING THE SAME, PROCESS FOR PRODUCING HIGH-DENSITY FERRITE ELECTRONIC COMPONENT USING THE SAMEInfo
- Publication number
- JP3481171B2 JP3481171B2 JP27076999A JP27076999A JP3481171B2 JP 3481171 B2 JP3481171 B2 JP 3481171B2 JP 27076999 A JP27076999 A JP 27076999A JP 27076999 A JP27076999 A JP 27076999A JP 3481171 B2 JP3481171 B2 JP 3481171B2
- Authority
- JP
- Japan
- Prior art keywords
- ferrite
- granules
- density
- ester
- fatty acid
- 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.)
- Expired - Fee Related
Links
- 229910000859 α-Fe Inorganic materials 0.000 title claims description 112
- 239000000463 material Substances 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 238000000034 method Methods 0.000 title description 28
- 239000008187 granular material Substances 0.000 claims description 92
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 40
- 239000000194 fatty acid Substances 0.000 claims description 40
- 229930195729 fatty acid Natural products 0.000 claims description 40
- 150000002148 esters Chemical class 0.000 claims description 37
- 150000004665 fatty acids Chemical class 0.000 claims description 37
- 239000000843 powder Substances 0.000 claims description 22
- 238000005245 sintering Methods 0.000 claims description 21
- 238000005469 granulation Methods 0.000 claims description 14
- 230000003179 granulation Effects 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 235000009984 Pterocarpus indicus Nutrition 0.000 claims 1
- 241000533793 Tipuana tipu Species 0.000 claims 1
- 238000000465 moulding Methods 0.000 description 44
- 230000000052 comparative effect Effects 0.000 description 26
- 239000002245 particle Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- -1 fatty acid ester Chemical class 0.000 description 9
- 229960005078 sorbitan sesquioleate Drugs 0.000 description 9
- 239000007921 spray Substances 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 8
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 8
- CUNWUEBNSZSNRX-RKGWDQTMSA-N (2r,3r,4r,5s)-hexane-1,2,3,4,5,6-hexol;(z)-octadec-9-enoic acid Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O CUNWUEBNSZSNRX-RKGWDQTMSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000035699 permeability Effects 0.000 description 7
- 238000005452 bending Methods 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 235000021355 Stearic acid Nutrition 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 5
- 239000008117 stearic acid Substances 0.000 description 5
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 4
- 239000005642 Oleic acid Substances 0.000 description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 4
- 235000021314 Palmitic acid Nutrition 0.000 description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 4
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- 235000021313 oleic acid Nutrition 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 4
- 229910017518 Cu Zn Inorganic materials 0.000 description 3
- 229910017752 Cu-Zn Inorganic materials 0.000 description 3
- 229910017943 Cu—Zn Inorganic materials 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- JNYAEWCLZODPBN-KVTDHHQDSA-N (2r,3r,4r)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@@H](O)[C@H]1O JNYAEWCLZODPBN-KVTDHHQDSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000007088 Archimedes method Methods 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- FBPFZTCFMRRESA-UHFFFAOYSA-N hexane-1,2,3,4,5,6-hexol Chemical compound OCC(O)C(O)C(O)C(O)CO FBPFZTCFMRRESA-UHFFFAOYSA-N 0.000 description 1
- 150000002402 hexoses Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Landscapes
- Glanulating (AREA)
- Magnetic Ceramics (AREA)
- Press-Shaping Or Shaping Using Conveyers (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、フェライト顆粒被
覆体からなる新規な電子部品製造用材料、この材料の製
造方法及びこの材料を用いた高密度フェライト電子部品
の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel material for producing electronic parts, which comprises a ferrite granule coating, and the production of this material.
Manufacturing method and high-density ferrite electronic component using this material
The present invention relates to a manufacturing method of.
【０００２】[0002]
【従来の技術】フェライトは、一般的に、耐熱性、耐化
学薬品性、機械的性質などに優れ、かつ電気絶縁性が大
きいなどの性質を有することから、例えば電気絶縁部
品、電子製品部品などの各種電子部品の製造用材料とし
て広く用いられている。2. Description of the Related Art Ferrite generally has excellent heat resistance, chemical resistance, mechanical properties and the like, and has a large electric insulation property. Therefore, for example, electric insulation parts, electronic product parts, etc. It is widely used as a material for manufacturing various electronic components.
【０００３】このようなフェライト電子部品を製造する
方法としては、従来、様々な方法が採用されているが、
中でも乾式加圧成形法が一般的に広く行われている。例
えば、フェライト粉末とバインダーと水とから水性スラ
リーを調製し、これをスプレードライヤーで噴霧乾燥し
て作製した顆粒、又はフェライト粉末とバインダー溶液
とを撹拌混合し、乾燥とオシレーティング押出し造粒を
繰り返して作製した顆粒を加圧成形したのち焼結するこ
とにより、フェライト電子部品を製造している。As a method for manufacturing such a ferrite electronic component, various methods have hitherto been adopted.
Among them, the dry pressure molding method is generally widely used. For example, an aqueous slurry is prepared from ferrite powder, a binder, and water, and granules prepared by spray-drying this with a spray dryer, or ferrite powder and a binder solution are mixed by stirring, and drying and oscillating extrusion granulation are repeated. Ferrite electronic parts are manufactured by press-molding the granules produced as described above and then sintering.
【０００４】このような加圧成形法においては、フェラ
イト顆粒として、流動性が良好で、金型への充填性及び
低圧でのつぶれの良いものを使用することが、得られる
フェライト電子部品の品質及び生産性の面から重要であ
る。流動性が良く、低圧でのつぶれの良い顆粒を作製す
る技術としては、例えば分散剤を用いてスラリーを調製
し、顆粒を作製する方法（特開平５−１５９９１８号公
報、特公平７−１７４６０号公報）、バインダーの偏析
を低減させて顆粒を作製する方法（特公平３−３１６６
０号公報、特開平１０−５９７７６号公報）などが提案
されている。In such a pressure molding method, it is necessary to use, as the ferrite granules, one having good fluidity, good moldability and good crushability at low pressure. It is also important in terms of productivity. As a technique for producing granules having good fluidity and good crushability at low pressure, for example, a method of preparing a slurry by using a dispersant to prepare granules (Japanese Patent Application Laid-Open No. 5-159918 and Japanese Patent Publication No. 7-17460). Gazette), a method of producing granules by reducing segregation of binder (Japanese Patent Publication No. 3166/93).
No. 0, JP-A-10-59776) and the like have been proposed.
【０００５】しかしながら、これらの技術は、スプレー
ドライヤーを用いた噴霧乾燥造粒法による顆粒の作製に
適用される技術であって、オシレーティング押出し造粒
法による顆粒の作製には効果を発揮することができな
い。その上、この技術では、顆粒の流動性及び低圧での
つぶれ性は改善されるものの、得られる電子部品製造用
成形体の密度バラツキ、金型からの離型性、スプリング
バックによる成形体内部のヒビ、金型の長寿命化につい
ては、満足しうる効果が得られていない。However, these techniques are applied to the preparation of granules by the spray-drying granulation method using a spray dryer, and are effective in the preparation of granules by the oscillating extrusion granulation method. I can't. Moreover, with this technique, although the fluidity of the granules and the crushability at low pressure are improved, the density variation of the obtained molded article for electronic component production, the releasability from the mold, and the inside of the molded article due to springback are improved. Satisfactory effects have not been obtained with regard to cracks and longer life of the mold.
【０００６】[0006]
【発明が解決しようとする課題】このような事情のもと
で、本発明の第１の目的は、金型からの離型性がよく、
スプリングバックによるヒビなどの成形不良がない成形
体を与え、かつ均質で優れた電磁特性を示す高密度フェ
ライト電子部品を与えるフェライト顆粒被覆体を提供す
ることにある。また、本発明の第２の目的は、上記のフ
ェライト顆粒被覆体を用い、低い成形圧による加圧成形
により、金型の寿命を損なうことなく、上記性状を有す
るフェライト電子部品を与えるフェライト顆粒被覆体の
成形体を提供することにある。本発明の第３の目的は、
上記のフェライト顆粒被覆体及びその成形体を用いて優
れた電磁特性を示す高密度フェライト電子部品を提供す
ることにある。Under these circumstances, the first object of the present invention is to provide good mold releasability from the mold,
It is an object of the present invention to provide a ferrite granule coated body that gives a molded body free from molding defects such as cracks due to springback, and that provides a high-density ferrite electronic component that is homogeneous and exhibits excellent electromagnetic characteristics. A second object of the present invention is to provide a ferrite granule coating using the above-mentioned ferrite granule coated body, which gives a ferrite electronic component having the above-mentioned properties by pressure molding under a low molding pressure without impairing the life of the mold. It is to provide a molded body. The third object of the present invention is to
An object of the present invention is to provide a high-density ferrite electronic component exhibiting excellent electromagnetic characteristics by using the above ferrite granule coated body and its molded body.
【０００７】[0007]
【課題を解決するための手段】本発明者は、優れた電磁
特性をもつ、高密度フェライト電子部品を得るために鋭
意研究を重ねた結果、潤滑剤として特定の高級脂肪酸エ
ステルを用い、これによって少なくとも表面の一部が被
覆されたフェライト顆粒被覆体を型成形し、その成形体
を焼結することにより、その目的を達成しうることを見
出し、この知見に基づいて本発明をなすに至った。The present inventor has conducted extensive studies to obtain a high-density ferrite electronic component having excellent electromagnetic characteristics, and as a result, a specific higher fatty acid ester was used as a lubricant . It was found that the object can be achieved by molding a ferrite granule coated body at least a part of the surface of which is coated and sintering the molded body, and based on this finding, the present invention has been accomplished. .
【０００８】 すなわち、本発明は、造粒して得たフェ
ライト顆粒に高級脂肪酸のヘキシタンエステルを接触さ
せ、その表面の少なくとも一部を高級脂肪酸のヘキシタ
ンエステルで被覆したことを特徴とする高密度フェライ
ト電子部品製造用材料、フェライト粉末を造粒後、得ら
れた顆粒にその重量に基づき０．１〜３．０重量％の高
級脂肪酸のヘキシタンエステルを添加し、両者をよく接
触させ、次いで乾燥してフェライト顆粒の表面の少なく
とも一部を高級脂肪酸のヘキシタンエステルで被覆する
ことを特徴とする高密度フェライト電子部品製造用材料
の製造方法及びフェライト粉末を造粒後、得られた顆粒
にその重量に基づき０．１〜３．０重量％の高級脂肪酸
のヘキシタンエステルを溶液として添加し、両者をよく
接触させたのち乾燥して、フェライト顆粒の表面の少な
くとも一部を高級脂肪酸のヘキシタンエステルで被覆
し、次いでこのようにして得たフェライト顆粒被覆体を
所定の形状の金型に充填してプレス成形したのち、焼結
することを特徴とする高密度フェライト電子部品の製造
方法を提供するものである。 That is, the present invention provides a powder obtained by granulation.
The light granules are contacted with the higher fatty acid hexitane ester.
And at least a part of the surface of the ferrite powder was coated with a hexitane ester of a higher fatty acid .
The granules have a high content of 0.1 to 3.0% by weight based on their weight.
Add hexitane ester of primary fatty acid
Touch and then dry to reduce the surface area of the ferrite granules.
Both are partially coated with a hexitan ester of higher fatty acid
Material for producing high-density ferrite electronic parts characterized by
And the granules obtained after granulating the ferrite powder
0.1 to 3.0% by weight of higher fatty acid based on the weight of
Hexane ester of
After contacting and drying, the surface of the ferrite granules
At least a part of it is coated with a hexitan ester of a higher fatty acid
And then the ferrite granule coating thus obtained was
Sinter after filling in a mold of a predetermined shape and press molding
Manufacture of high-density ferrite electronic parts characterized by
It provides a method.
【０００９】[0009]
【発明の実施の形態】本発明において、高密度フェライ
ト電子部品製造用材料の主材として用いるフェライト顆
粒は、公知の方法、例えばスプレードライヤーによる噴
霧造粒法やオシレーティング押出し造粒法などで、フェ
ライト粉末を造粒することにより得られる。この際用い
るフェライトの種類及び粒径については特に制限はな
く、得られるフェライト電子部品の使用目的や用途に応
じて適宜選択することができる。このフェライト粉末の
粒径は、通常０．５〜５μｍ、好ましくは０．７〜３μ
ｍの範囲で選ばれる。本発明においては、このフェライ
ト粉末は単独で用いてもよいし、２種以上を組み合わせ
て用いてもよい。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, ferrite granules used as a main material of a material for producing high-density ferrite electronic parts can be prepared by a known method such as a spray granulation method using a spray dryer or an oscillating extrusion granulation method. It is obtained by granulating ferrite powder. The type and particle size of the ferrite used at this time are not particularly limited, and can be appropriately selected according to the intended purpose and application of the obtained ferrite electronic component. The particle size of this ferrite powder is usually 0.5 to 5 μm, preferably 0.7 to 3 μm.
It is selected in the range of m. In the present invention, this ferrite powder may be used alone or in combination of two or more kinds.
【００１０】このフェライト顆粒の造粒に際しては、通
常バインダーが用いられる。このバインダーとしては、
従来フェライト顆粒の造粒において使用されている公知
のものの中から、任意のものを適宜選択して用いること
ができる。このバインダーの例としては、ポリビニルア
ルコールやポリ酢酸ビニルの部分けん化物、ポリアクリ
ル酸、メチルセルロース、アクリルアミド類の単独重合
体や共重合体などが挙げられる。これらのバインダー
は、フェライト粉末１００重量部に対し、通常０．２〜
１０重量部、好ましくは０．５〜８重量部、より好まし
くは０．７〜５重量部の範囲で用いられる。A binder is usually used for granulating the ferrite granules. As this binder,
Any known material conventionally used in the granulation of ferrite granules can be appropriately selected and used. Examples of this binder include partially saponified products of polyvinyl alcohol and polyvinyl acetate, homopolymers and copolymers of polyacrylic acid, methyl cellulose, and acrylamides. These binders are usually 0.2 to 100 parts by weight of ferrite powder.
It is used in an amount of 10 parts by weight, preferably 0.5 to 8 parts by weight, more preferably 0.7 to 5 parts by weight.
【００１１】また、このフェライト顆粒を造粒する際に
は、本発明の目的が損なわれない範囲で、所望により、
各種の公知の添加成分、例えばポリカルボン酸塩、縮合
ナフタレンスルホン酸塩などの分散剤、グリセリン、グ
リコール類、トリオール類などの可塑剤、ワックス、ス
テアリン酸やその塩などの滑剤、さらにはポリエーテル
系、ウレタン変性ポリエーテル系、ポリアクリル酸系、
変性アクリル酸系などの有機系高分子凝集剤、硫酸アル
ミニウム、塩化アルミニウム、硝酸アルミニウムなどの
無機系凝集剤などを添加することができる。このように
して得られるフェライト顆粒の粒径は、従来電子部品の
製造に際し、一般に用いられているフェライト顆粒の場
合と同じ範囲内でよく、特に変える必要はない。この粒
径範囲は通常平均粒径で５０〜５００μｍ、好ましくは
７０〜３００μｍの範囲である。When granulating the ferrite granules, if desired, within the range where the object of the present invention is not impaired,
Various known additives, for example, polycarboxylic acid salts, dispersants such as condensed naphthalene sulfonates, plasticizers such as glycerin, glycols, triols, waxes, lubricants such as stearic acid and its salts, and polyethers. System, urethane modified polyether system, polyacrylic acid system,
An organic polymer flocculant such as a modified acrylic acid type or an inorganic flocculant such as aluminum sulfate, aluminum chloride or aluminum nitrate may be added. The particle size of the ferrite granules thus obtained may be in the same range as that of the ferrite granules that are generally used in the production of conventional electronic parts, and does not have to be particularly changed. This particle size range is usually an average particle size of 50 to 500 μm, preferably 70 to 300 μm.
【００１２】次に、本発明の高密度フェライト電子部品
製造用材料は、このようにして得たフェライト顆粒に高
級脂肪酸のヘキシタンエステルを添加し、両者をよく接
触させて、フェライト顆粒の表面の少なくとも一部、す
なわち一部又は全部を高級脂肪酸のヘキシタンエステル
で被覆することにより製造される。Next, in the material for producing high density ferrite electronic parts of the present invention, the hextan ester of a higher fatty acid is added to the ferrite granules thus obtained, and both are brought into contact with each other to form the surface of the ferrite granules. It is produced by coating at least a part, that is, a part or the whole, with a hexitan ester of a higher fatty acid.
【００１３】このフェライト顆粒の表面の少なくとも一
部を被覆するために用いられる高級脂肪酸のヘキシタン
エステルにおけるヘキシタンとは、ヘキシトールすなわ
ちヘキソースの糖アルコールから１分子脱水して得られ
る分子内エーテルであり、その高級脂肪酸のエステルと
は、ヘキシタン中の４個の水酸基の一部又は全部が高級
脂肪酸エステルを形成したものである。このヘキシタン
の例としては、ソルビタン、マンニタン、ズルシタンな
どを挙げることができるが、これらの中でソルビタン及
びマンニタンが好ましく、特にソルビタンが好ましい。Hexetan in the hextan ester of a higher fatty acid used for coating at least a part of the surface of the ferrite granules is an intramolecular ether obtained by dehydrating one molecule of hexitol, that is, sugar alcohol of hexose, The ester of higher fatty acid is one in which some or all of the four hydroxyl groups in hexitane form a higher fatty acid ester. Examples of this hexitan include sorbitan, mannitan, dulcitan, and the like. Among these, sorbitan and mannitan are preferable, and sorbitan is particularly preferable.
【００１４】また、高級脂肪酸としては炭素数１２〜１
８の脂肪酸が好ましく、これは飽和、不飽和のいずれで
あってもよいし、直鎖状、分枝状のいずれであってもよ
い。このような高級脂肪酸の例としては、ラウリン酸、
ミリスチン酸、パルミチン酸、ステアリン酸、オレイン
酸などが挙げられるが、これらの中でパルミチン酸、ス
テアリン酸及びオレイン酸が好適である。本発明におい
ては、この高級脂肪酸のヘキシタンエステルは部分エス
テル及び完全エステルのいずれであってもよい。また、
これらのエステルは単独で用いてもよいし、２種以上を
組み合わせて用いてもよい。The higher fatty acid has 12 to 1 carbon atoms.
The fatty acid of No. 8 is preferable, and it may be saturated or unsaturated, and may be linear or branched. Examples of such higher fatty acids include lauric acid,
Examples thereof include myristic acid, palmitic acid, stearic acid, and oleic acid, and among these, palmitic acid, stearic acid, and oleic acid are preferable. In the present invention, the hexitane ester of the higher fatty acid may be a partial ester or a complete ester. Also,
These esters may be used alone or in combination of two or more.
【００１５】本発明の高密度フェライト電子部品製造用
材料においては、フェライト顆粒の表面を被覆している
高級脂肪酸のヘキシタンエステルの量が、フェライト顆
粒の重量に基づき０．１〜３．０重量％であり、高級脂
肪酸のヘキシタンエステルが、炭素数１２〜１８の高級
脂肪酸のソルビタン又はマンニタンエステル、特に高級
脂肪酸のヘキシタンエステルが、オレイン酸、ステアリ
ン酸又はパルミチン酸のソルビタンエステルであるもの
が好ましい。In the material for producing high density ferrite electronic parts of the present invention, the amount of the hexitan ester of higher fatty acid coating the surface of the ferrite granules is 0.1 to 3.0 weight% based on the weight of the ferrite granules. %, The hexitane ester of a higher fatty acid is a sorbitan or mannitane ester of a higher fatty acid having 12 to 18 carbon atoms, and particularly the hexitane ester of a higher fatty acid is a sorbitan ester of oleic acid, stearic acid, or palmitic acid. Is preferred.
【００１６】この高級脂肪酸のヘキシタンエステルの量
がフェライト顆粒の重量に基づき０．１重量％未満で
は、以下に示す本発明の効果が十分に発揮されないし、
また３．０重量％を越えるとその量を増加しても効果の
向上が認められず、むしろ経済的に不利となる。効果及
び経済性などを考慮すると、この高級脂肪酸のヘキシタ
ンエステルの好ましい使用量は０．２〜２．０重量％の
範囲であり、特に０．３〜１．５重量％の範囲が好適で
ある。If the amount of the hexitane ester of higher fatty acid is less than 0.1% by weight based on the weight of the ferrite granules, the effects of the present invention shown below will not be sufficiently exhibited.
On the other hand, if it exceeds 3.0% by weight, the effect is not improved even if the amount is increased, which is rather economically disadvantageous. Considering the effect and economical efficiency, the preferred amount of the hextan ester of higher fatty acid used is in the range of 0.2 to 2.0% by weight, particularly 0.3 to 1.5% by weight. is there.
【００１７】次に、フェライト顆粒と高級脂肪酸のヘキ
シタンエステルとの接触は、フェライト顆粒を造粒させ
たのちに行うことが必要である。フェライト顆粒の造粒
前にフェライト粉末中に高級脂肪酸のヘキシタンエステ
ルを加え混合する方法によると、型成形の際の本発明の
効果が十分に発揮されない。この接触方法としては、例
えば高級脂肪酸のヘキシタンエステルを、アルコールや
トルエンなどの適当な溶剤に溶かした溶液を、フェライ
ト顆粒に添加してドラムミキサーなどで混合する方法、
あるいは転動流動層などのコーティング装置で顆粒を転
動させながら、上記高級脂肪酸のヘキシタンエステル溶
液を霧化添加する方法、上記高級脂肪酸のヘキシタンエ
ステルを固体状のまま添加し機械的に混合する方法など
がある。Next, it is necessary to contact the ferrite granules with the hexitane ester of higher fatty acid after granulating the ferrite granules. According to the method of adding the hexitane ester of a higher fatty acid into the ferrite powder before granulating the ferrite granules, the effect of the present invention at the time of molding cannot be sufficiently exhibited. As this contact method, for example, a hexitane ester of a higher fatty acid, a solution prepared by dissolving it in an appropriate solvent such as alcohol or toluene, is added to ferrite granules and mixed by a drum mixer or the like,
Alternatively, while tumbling the granules in a coating device such as a rolling fluidized bed, a method of atomizing and adding the hexitane ester solution of the higher fatty acid, or a method of adding the hexitane ester of the higher fatty acid in a solid state and mechanically mixing There are ways to do it.
【００１８】本発明のフェライト顆粒の製造方法の好適
な態様を説明すると、フェライト粉末を、例えば、スプ
レードライヤー法、噴霧造粒法又はオシレーティング押
出造粒法により造粒して、平均粒径１００〜３００μｍ
の顆粒を作製し、次いでこれにオレイン酸、ステアリン
酸又はパルミチン酸のソルビタンエステルを所定の割合
で加え、十分に接触させることによって、フェライト顆
粒表面の少なくとも一部をこれによって被覆させる。こ
の際の被覆はフェライト顆粒の表面全体が均質に覆われ
るように行うのが好ましいが、その一部例えば３０％以
上が覆われていれば十分である。この際、上記の高級脂
肪酸のヘキシタンエステルは、その一部がフェライト顆
粒の表層部に浸透することがあるが、本発明においては
そのようになっていても特に支障はない。A preferred embodiment of the method for producing ferrite granules according to the present invention will be described. Ferrite powder is granulated by, for example, a spray dryer method, a spray granulation method or an oscillating extrusion granulation method to obtain an average particle size of 100. ~ 300 μm
Granules are prepared, and then sorbitan ester of oleic acid, stearic acid or palmitic acid is added thereto at a predetermined ratio, and sufficient contact is made to cover at least a part of the surface of the ferrite granules. The coating at this time is preferably performed so that the entire surface of the ferrite granules is uniformly covered, but it is sufficient if a part thereof, for example, 30% or more is covered. At this time, a part of the above-mentioned hexitane ester of higher fatty acid may penetrate into the surface layer of the ferrite granules, but in the present invention, even if it does so, there is no particular problem.
【００１９】このようにして、フェライト顆粒に、高級
脂肪酸のヘキシタンエステルを上記の範囲で含有させる
ことにより、型成形により高級脂肪酸のヘキシタンエス
テルの界面活性剤としての作用によって、滑り性、流動
性、圧力伝達性が向上し、金型への充填が良好となり、
その結果、バラツキが少なく、低い圧力で成形体を与え
る、フェライト顆粒被覆体からなる高密度フェライト電
子部品製造用材料を得ることができる。In this way, by incorporating the hexitane ester of higher fatty acid in the above range in the ferrite granules, the hexitane ester of higher fatty acid acts as a surfactant by molding, so that slipperiness and fluidity can be obtained. Characteristics and pressure transferability are improved, filling into the mold is good,
As a result, it is possible to obtain a material for producing a high-density ferrite electronic component, which is composed of a ferrite granule coated body and has a small variation and gives a compact at a low pressure.
【００２０】次に、このようにして得た表面の少なくと
も一部が高級脂肪酸のヘキシタンエステルで被覆された
フェライト顆粒被覆体を成形して高密度フェライト電子
部品製造用成形体を製造するには、上記フェライト顆粒
被覆体を、通常の型成形法により所望の形状に成形する
が、特にフェライト顆粒被覆体を金型を用いて乾式プレ
ス成形を行うのが有利である。この際、プレス圧力は、
通常０．５〜５ｔｏｎ／ｃｍ2、好ましくは１〜４ｔｏ
ｎ／ｃｍ2の範囲で選ばれる。この際使用されるフェラ
イト顆粒被覆体には、離型性が付与されているため、金
型からの成形体取出時の抜き圧が低下し、金型の摩耗や
損傷は減少する。さらに、これらの効果により、金型か
らの成形体取出時のスプリングバック（成形体膨張）が
減少し、ヒビなどの成形不良の発生が防止される。Next, in order to produce a molded article for producing high-density ferrite electronic parts by molding a ferrite granule-coated body obtained by coating at least a part of the surface thus obtained with a hexitan ester of a higher fatty acid, The above-mentioned ferrite granule coated body is molded into a desired shape by a usual molding method, and it is particularly advantageous to dry-mold the ferrite granule coated body using a mold. At this time, the press pressure is
Usually 0.5 to 5 ton / cm 2 , preferably 1 to 4 to
It is selected in the range of n / cm 2 . Since the ferrite granule coated body used at this time is provided with releasability, the drawing pressure at the time of taking out the molded body from the mold is lowered, and the wear and damage of the mold are reduced. Further, due to these effects, the spring back (expansion of the molded product) at the time of taking out the molded product from the mold is reduced, and the occurrence of defective molding such as cracks is prevented.
【００２１】このようにして得た、高密度フェライト電
子部品製造用成形体を続いて焼結すれば、高密度フェラ
イト電子部品を得ることができる。この際の焼結温度
は、フェライトの種類により異なるが、一般的には８０
０〜１４００℃の範囲であり、好ましくは１０００〜１
３００℃の範囲である。その他の焼結条件及び焼結方法
は、従来のフェライト電子部品を製造する場合と全く同
じであり、特に変更する必要はない。If the thus obtained molded body for producing high density ferrite electronic parts is subsequently sintered, high density ferrite electronic parts can be obtained. The sintering temperature at this time varies depending on the type of ferrite, but is generally 80
It is in the range of 0 to 1400 ° C., preferably 1000 to 1
It is in the range of 300 ° C. Other sintering conditions and a sintering method are exactly the same as those in the case of manufacturing a conventional ferrite electronic component, and it is not particularly necessary to change them.
【００２２】本発明のフェライト電子部品製造用成形体
は、均質で高密度であり、例えばＮｉ−Ｃｕ−Ｚｎ系フ
ェライトの場合には、その密度は３．０〜４．０ｇ／ｃ
ｍ3程度である。また、これから得られる電子部品は成
形体の離型性がよいため、金型からの電子部品成形体の
取出時の抜き圧が低い上、排出時のスプリングバックが
減少し、ヒビなどの成形不良の発生が少ないので、電磁
特性が優れたものになる。The molded article for producing a ferrite electronic component of the present invention is homogeneous and has a high density. For example, in the case of Ni-Cu-Zn type ferrite, the density is 3.0 to 4.0 g / c.
It is about m 3 . Also, since the electronic parts obtained from this product have a good mold release property, the extraction pressure when taking out the electronic parts molded body from the mold is low, and the springback at the time of discharge is reduced, and molding defects such as cracks occur. The electromagnetic characteristics are excellent because there is little occurrence.
【００２３】[0023]
【実施例】次に、本発明を実施例により、さらに詳細に
説明するが、本発明は、これらの例によってなんら限定
されるものではない。EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples.
【００２４】実施例１
Ｎｉ−Ｃｕ−Ｚｎ系フェライト粉末（平均粒径１μｍ）
６６重量部、水３４重量部、ポリビニルアルコール（バ
インダー）１．０重量部及びポリカルボン酸アンモニウ
ム塩（分散剤）０．２５重量部を、湿式粉砕混合機で混
合して、フェライトスラリーを調製した。このスラリー
をスプレードライヤーで噴霧造粒し、平均粒径１２５μ
ｍの球形顆粒を得た。次いで、ソルビタンセスキオレイ
ン酸エステルの５０重量％エタノール溶液を、上記顆粒
に対して１．０重量％の割合で添加し、ドラムミキサー
で回転混合し、凝集粉のないフェライト顆粒被覆体を調
製した。Example 1 Ni-Cu-Zn ferrite powder (average particle size 1 μm)
66 parts by weight, 34 parts by weight of water, 1.0 part by weight of polyvinyl alcohol (binder) and 0.25 part by weight of polycarboxylic acid ammonium salt (dispersant) were mixed by a wet pulverization mixer to prepare a ferrite slurry. . This slurry is spray granulated with a spray dryer to give an average particle size of 125μ.
m spherical granules were obtained. Then, a 50 wt% ethanol solution of sorbitan sesquioleate was added at a ratio of 1.0 wt% with respect to the above granules, and the mixture was rotatively mixed with a drum mixer to prepare a ferrite granule coated body having no aggregated powder.
【００２５】次に、このようにして得たフェライト顆粒
被覆体を、所定の金型に充填し、成形圧力３ｔｏｎ／ｃ
ｍ2で乾式プレス成形することにより、均質で高密度の
ヒビのない円柱コア製造用成形体（直径１．３ｍｍ、長
さ１．５ｍｍ）が得られた。この際の金型からの抜き圧
は、従来のフェライト顆粒を用いた場合よりも低く、ま
たスプリングバックも減少していた。この円柱コア製造
用成形体の製造では金型の損傷は認められず、また摩耗
も少ないため１２０万ショットの連続成形を行うことが
できた。また、別に前記のフェライト顆粒被覆体１．２
ｇを直径６ｍｍの金型に充填し、成形圧力を０．５〜４
ｔｏｎ／ｃｍ2の間で変化させ、乾式プレス成形するこ
とにより、直径６ｍｍ、長さ１２〜１４ｍｍの円柱コア
製造用成形体を作製し、このサンプルについて、成形圧
力と成形体密度との関係を図１（ａ）に、成形体密度と
金型からの抜き圧との関係を図２（ａ）に、成形体密度
と膨張率との関係（スプリングバックの変化）を図３
（ａ）にそれぞれ実線グラフとして示した。別に前記の
フェライト顆粒被覆体２．０ｇから成形圧力を変化させ
て直径６ｍｍ、長さ２０〜２２ｍｍの円柱コア製造用成
形体を成形し、長さ方向で５等分し、プレス印加の方向
から順にＡ、Ｂ、Ｃ、Ｄ、Ｅに区分して、各区分におけ
る成形体密度を成形圧力を変化させて測定した。その結
果得られた成形圧力０．５、１．０及び２．０ｔｏｎ／
ｃｍ2における密度のバラツキを実線Ｉ、ＩＩ及びＩＩ
Ｉとして図４（ａ）に示す。Next, the ferrite granule coated body thus obtained is filled in a predetermined mold and the molding pressure is 3 ton / c.
By dry press molding with m 2 , a homogeneous and high-density molded body for producing a cylindrical core without cracks (diameter 1.3 mm, length 1.5 mm) was obtained. The drawing pressure from the mold at this time was lower than that when using conventional ferrite granules, and the spring back was also reduced. In the production of this molded body for producing a cylindrical core, damage to the mold was not recognized, and wear was small, so 1.2 million shots could be continuously molded. In addition, separately, the above-mentioned ferrite granule coated body 1.2
g in a mold with a diameter of 6 mm and a molding pressure of 0.5 to 4
By changing the pressure between ton / cm 2 and performing dry press molding, a molded body for producing a cylindrical core having a diameter of 6 mm and a length of 12 to 14 mm is produced. For this sample, the relationship between the molding pressure and the molded body density is shown. FIG. 1 (a) shows the relationship between the density of the compact and the drawing pressure from the mold, and FIG. 2 (a) shows the relationship between the density of the compact and the expansion coefficient (change in springback).
Each is shown as a solid line graph in (a). Separately, from 2.0 g of the above ferrite granule coated body, the molding pressure was changed to form a molded body for producing a cylindrical core having a diameter of 6 mm and a length of 20 to 22 mm, which was divided into 5 equal parts in the lengthwise direction, and from the direction of press application. It was divided into A, B, C, D and E in order, and the density of the molded body in each section was measured by changing the molding pressure. The resulting molding pressures of 0.5, 1.0 and 2.0 ton /
The density variation in cm 2 is represented by the solid lines I, II and II.
It is shown as I in FIG.
【００２６】実施例２〜４
表１に示す種類のソルビタン脂肪酸エステルと添加量を
変えた以外は、実施例１と同様にしてフェライト顆粒被
覆体を調製し、それを実施例１と同様に直径６ｍｍの金
型を用いて型成形して円柱コア製造用成形体を製造し
た。これらの成形圧力と成形体密度との関係、成形体密
度と金型からの抜き圧との関係、成形体密度と膨張率と
の関係を示すグラフは、実施例１の場合とほとんど同じ
であった。Examples 2 to 4 A ferrite granule coated body was prepared in the same manner as in Example 1 except that the amount of sorbitan fatty acid ester of the type shown in Table 1 was changed and the addition amount was changed. Molding was performed using a 6 mm mold to manufacture a molded body for manufacturing a cylindrical core. The graphs showing the relationship between the molding pressure and the molded body density, the relationship between the molded body density and the drawing pressure from the mold, and the relationship between the molded body density and the expansion coefficient are almost the same as those in Example 1. It was
【００２７】比較例１
実施例１と同様にして、平均粒径１２５μｍの球形フェ
ライト顆粒を製造した。この顆粒にソルビタンセスキオ
レイン酸エステルの被覆処理を施すことなく、実施例１
と同様の直径６ｍｍの金型を用いて型成形し、円柱コア
製造用成形体を製造した。このようにして得たソルビタ
ンセスキオレイン酸エステル無添加の顆粒からの成形体
は、滑り性、圧力伝達性が悪い上、低圧での成形体密度
が低いものとなった。また、このものは金型からの抜き
圧が実施例１よりもかなり高く、高圧での成形では、成
形体取出時に金型鳴きが発生し、成形体に断層ヒビが発
生した。実施例１と同様にして調べた成形圧力と成形体
密度との関係を図１（ａ）に、成形体密度と金型からの
抜き圧との関係を図２（ａ）に、成形体密度と膨張率と
の関係（スプリングバックの変化）を図３（ａ）にそれ
ぞれ破線グラフとして示す。また、実施例１と同様にし
て、円柱状成形体（直径６ｍｍ、長さ２０〜２２ｍｍ）
の長さ方向における各区分の成形体密度を測定した。そ
の結果得られた成形圧力０．５、１．０及び２．０ｔｏ
ｎ／ｃｍ2における密度のバラツキを実線Ｉ、ＩＩ及び
ＩＩＩとして図４（ｂ）に示す。Comparative Example 1 In the same manner as in Example 1, spherical ferrite granules having an average particle diameter of 125 μm were produced. These granules were subjected to Example 1 without coating with sorbitan sesquioleate.
Molding was carried out using a mold having a diameter of 6 mm similar to that described above to produce a molded body for manufacturing a cylindrical core. The molded product obtained from the granules thus obtained without adding sorbitan sesquioleate had poor slipperiness and pressure transfer properties, and also had a low molded product density at low pressure. In addition, this product had a considerably higher extraction pressure from the mold than in Example 1, and in molding at high pressure, mold squeaking occurred when the molded product was taken out, and a fault crack occurred in the molded product. The relationship between the molding pressure and the density of the molded body examined in the same manner as in Example 1 is shown in FIG. 1 (a), and the relationship between the density of the molded body and the drawing pressure from the mold is shown in FIG. 2 (a). The relationship between the expansion coefficient and the expansion rate (change in springback) is shown as a broken line graph in FIG. Further, in the same manner as in Example 1, a cylindrical molded body (diameter 6 mm, length 20 to 22 mm)
The density of the molded body in each section in the length direction of was measured. The resulting molding pressure 0.5, 1.0 and 2.0 to
The variations in density at n / cm 2 are shown in solid lines I, II and III in FIG. 4 (b).
【００２８】比較例２
実施例１におけるソルビタンセスキオレイン酸エステル
の５０重量％エタノール溶液の代わりに、ステアリン酸
亜鉛微粉末を、顆粒に対し０．１重量％の割合で添加し
た以外は、実施例１と同様にしてフェライト顆粒被覆体
を調製し、これを実施例１と同じ直径６ｍｍの金型を用
いて型成形した。ステアリン酸亜鉛の添加により、離型
性が付与され、金型からの抜き圧は低下したが、低圧で
の成形体密度が低く、密度バラツキも大きい成形体が得
られた。また、円柱状成形体（直径１．３ｍｍ、長さ
１．５ｍｍ）の連続成形では、金型の損傷は無いもの
の、摩耗が多く、８０万ショットで寸法及び外観の規格
を外れる成形体を生じた。実施例１と同様にして調べた
成形圧力と成形体密度との関係、成形体密度と膨張率と
の関係（スプリングバックの変化）は比較例１の場合と
ほとんど同じであった。一方、成形体密度と金型からの
抜き圧との関係を図２（ａ）に点線グラフで示す。ま
た、実施例１と同様にして、円柱状成形体（直径６ｍ
ｍ、長さ２０〜２２ｍｍ）の長さ方向における各区分の
成形体密度を測定した。その結果得られた成形圧力０．
５、１．０及び２．０ｔｏｎ／ｃｍ2における密度のバ
ラツキを実線Ｉ、ＩＩ及びＩＩＩとして図４（ｃ）に示
す。Comparative Example 2 Example 2 was repeated except that zinc stearate fine powder was added at a ratio of 0.1% by weight to the granules instead of the 50% by weight ethanol solution of sorbitan sesquioleate in Example 1. A ferrite granule coated body was prepared in the same manner as in Example 1, and this was molded using the same die having a diameter of 6 mm as in Example 1. By the addition of zinc stearate, mold releasability was imparted and the drawing pressure from the mold was reduced, but a compact having a low density at low pressure and a large density variation was obtained. Further, in continuous molding of a cylindrical molded body (diameter 1.3 mm, length 1.5 mm), although the mold is not damaged, a large amount of wear causes a molded body that deviates from the specifications of dimensions and appearance in 800,000 shots. It was The relationship between the molding pressure and the density of the molded body and the relationship between the density of the molded body and the expansion coefficient (change in springback) examined in the same manner as in Example 1 were almost the same as those in Comparative Example 1. On the other hand, the relationship between the compact density and the drawing pressure from the mold is shown by the dotted line graph in FIG. Further, in the same manner as in Example 1, a cylindrical molded body (diameter 6 m
m, length 20 to 22 mm), and the density of the molded body in each section in the length direction was measured. The resulting molding pressure of 0.
The variations in density at 5, 1.0 and 2.0 ton / cm 2 are shown in FIG. 4 (c) as solid lines I, II and III.
【００２９】実施例５
Ｎｉ−Ｃｕ−Ｚｎ系フェライト粉末（平均粒径１μｍ）
１００重量部に、固形分濃度６重量％のポリビニルアル
コール水溶液１７重量部を添加し、撹拌造粒機ＴＭミキ
サー（三井鉱山社製）で混合撹拌造粒を行い、造粒粉を
調製した。この造粒粉をベルト式乾燥機で乾燥処理し、
オシレーティング造粒解砕機（日本精機社製）で押出し
造粒を行い、シフターで整粒し、平均粒径２５０μｍの
オシレーティング押出し造粒顆粒を得た。次いで、実施
例１と同様に、ソルビタンセスキオレイン酸エステルの
５０重量％エタノール溶液を、上記顆粒に対し１．０重
量％の割合で添加し、ドラムミキサーで回転混合し、凝
集粉のないフェライト顆粒被覆体を調製した。Example 5 Ni-Cu-Zn system ferrite powder (average particle size 1 μm)
17 parts by weight of an aqueous polyvinyl alcohol solution having a solid content of 6% by weight was added to 100 parts by weight, and mixed and stirred and granulated by a stirring granulator TM mixer (manufactured by Mitsui Mining Co., Ltd.) to prepare granulated powder. Drying this granulated powder with a belt dryer,
Extrusion granulation was performed with an oscillating granulator and crusher (manufactured by Nippon Seiki Co., Ltd.) and sized with a shifter to obtain oscillating extruded granules having an average particle size of 250 μm. Then, as in Example 1, a 50 wt% ethanol solution of sorbitan sesquioleate was added at a ratio of 1.0 wt% with respect to the above granules, and the mixture was rotatively mixed with a drum mixer to obtain a coagulated powder-free ferrite granule. A coating was prepared.
【００３０】次に、このフェライト顆粒被覆体１．２ｇ
を用い、実施例１と同様に、成形圧力を０．５〜４ｔｏ
ｎ／ｃｍ2に変化させて乾式加圧成形することにより、
均質で高密度でヒビのない円柱状成形体（直径６ｍｍ、
長さ１２〜１４ｍｍ）を得た。この際、金型からの抜き
圧が低下し、スプリングバックも実施例１〜４のスプレ
ードライヤー造粒顆粒被覆体使用時よりもさらに減少し
た。Next, 1.2 g of this ferrite granule coated body
And the molding pressure was 0.5 to 4 tom as in Example 1.
By changing to n / cm 2 and performing dry pressure molding,
Homogeneous, high-density, crack-free cylindrical molded body (diameter 6 mm,
A length of 12-14 mm) was obtained. At this time, the extraction pressure from the mold was lowered, and the spring back was further reduced as compared with the case of using the spray dryer granulated granules of Examples 1 to 4.
【００３１】この例における成形圧力と成形体密度との
関係を図１（ｂ）に、成形体密度と金型からの抜き圧と
の関係を図２（ｂ）に、成形体密度と膨張率との関係
（スプリングバックの変化）を図３（ｂ）に、それぞれ
実線のグラフで示す。The relationship between the molding pressure and the density of the molded body in this example is shown in FIG. 1 (b), the relationship between the density of the molded body and the drawing pressure from the mold is shown in FIG. 2 (b), and the density of the molded body and the expansion coefficient. The relationship (change in springback) with and is shown by the solid line graphs in FIG.
【００３２】比較例３
実施例５と同様にして、平均粒径２５０μｍの顆粒を調
製した。この顆粒にソルビタンセスキオレイン酸エステ
ルの５０重量％エタノール溶液を添加せずに、そのまま
型成形したこと以外は実施例５と同様にして成形体を製
造した。このようにして、ソルビタンセスキオレイン酸
エステル無添加の顆粒を用いた場合は、滑り性、圧力伝
達性が悪い上、低圧での成形体密度が低く、かつ密度バ
ラツキの大きい成形体となった。また、金型からの抜き
圧が高く、高圧での成形では、成形体取出時に金型鳴き
が発生し、得られた成形体に断層ヒビが認められた。成
形圧力と成形体密度との関係を図１（ｂ）に、成形体密
度と金型からの抜き圧との関係を図２（ｂ）に、成形体
密度と膨張率との関係（スプリングバックの変化）を図
３（ｂ）に、それぞれ破線グラフで示す。Comparative Example 3 In the same manner as in Example 5, granules having an average particle diameter of 250 μm were prepared. A molded product was produced in the same manner as in Example 5 except that the 50% by weight sorbitan sesquioleate ester solution in ethanol was not added to the granules and the mixture was directly molded. Thus, in the case of using granules without addition of sorbitan sesquioleate, the slipperiness and pressure transferability were poor, and the density of the compact at low pressure was low and the density was large. In addition, the mold was squeaked when the molded product was taken out when the molding was taken out at a high pressure because of the high extraction pressure from the mold, and a crack was observed in the resulting molded product. The relationship between the molding pressure and the density of the molded body is shown in FIG. 1 (b), the relationship between the density of the molded body and the drawing pressure from the mold is shown in FIG. 2 (b), the relationship between the density of the molded body and the expansion coefficient (spring back). 3) is shown by a broken line graph.
【００３３】比較例４
実施例５におけるソルビタンセスキオレイン酸エステル
の５０重量％エタノール溶液の代わりに、ステアリン酸
亜鉛微粉末を、顆粒に対し０．１重量％の割合で添加し
た以外は、実施例５と同様にしてフェライト顆粒被覆体
を調製し、次いでこれを型成形して成形体を製造した。
ステアリン酸亜鉛の添加により、離型性が付与され、金
型からの抜き圧は低下したが、低圧での成形体密度が低
く、密度バラツキも大きい成形体となった。成形圧力と
成形体密度との関係を示すグラフは、比較例３の場合と
ほとんど重なっていた。また成形体密度と金型からの抜
き圧との関係を図２（ｂ）に、成形体密度と膨張率との
関係（スプリングバックの変化）を図３（ｂ）にそれぞ
れ点線グラフで示す。以上実施例１〜５及び比較例１〜
４のフェライト顆粒について造粒方法、添加成分、添加
量をまとめて表１に示す。Comparative Example 4 Instead of the 50 wt% ethanol solution of sorbitan sesquioleate in Example 5, zinc stearate fine powder was added at a ratio of 0.1 wt% to the granules. A ferrite granule coated body was prepared in the same manner as in No. 5, and then this was molded into a molded body.
By the addition of zinc stearate, mold releasability was imparted and the drawing pressure from the mold was reduced, but the density of the compact at low pressure was low, and the density of the compact was large. The graph showing the relationship between the molding pressure and the density of the molded body almost overlapped with the case of Comparative Example 3. 2B shows the relationship between the density of the molded body and the extraction pressure from the mold, and FIG. 3B shows the relationship between the density of the molded body and the expansion coefficient (change in springback) by a dotted line graph. As described above, Examples 1 to 5 and Comparative Examples 1 to 1
Table 1 summarizes the granulation method, additional components, and addition amount of the ferrite granules of No. 4.
【００３４】[0034]
【表１】 [Table 1]
【００３５】実施例６
前記実施例１〜５で得たフェライト顆粒被覆体を、それ
ぞれ１０００ｋｇｆ／ｃｍ2の圧力でプレス成形し、外
径２１ｍｍ、内径１２ｍｍ、厚さ７ｍｍのリング状成形
体を得た。次いで、これらを１０３０℃、１０５０℃、
１０７０℃又は１０９０℃の温度において２時間焼結
し、リング状コアを製造した。次に、これらのリング状
コアの密度をアルキメデス法に準じた方法で測定した。
また、これらのリング状コアについて１００ｋＨｚにお
ける初透磁率を、ＬＣＲメーター４２７４Ａ（ヒューレ
ット・パッカード社製、商品名）により測定した。この
ようにして得た電子部品の焼結温度と密度との関係及び
焼結温度と初透磁率との関係をそれぞれ図５（ａ）、
（ｂ）及び図６（ａ）、（ｂ）に実線グラフＡ〜Ｅとし
て示す。図中Ａは、実施例１、Ｂは実施例２、Ｃは実施
例３、Ｄは実施例４、Ｅは実施例５のフェライト顆粒成
形体を用いた結果である。なお、実施例２〜４の成形体
を用いた電子部品の焼結温度と初透磁率との関係を示す
グラフは実施例１のグラフＡとほとんど重なっていた。Example 6 The ferrite granule coated bodies obtained in Examples 1 to 5 were press-molded at a pressure of 1000 kgf / cm 2 to obtain a ring-shaped molded body having an outer diameter of 21 mm, an inner diameter of 12 mm and a thickness of 7 mm. It was Then, these are 1030 ℃, 1050 ℃,
A ring-shaped core was manufactured by sintering at a temperature of 1070 ° C or 1090 ° C for 2 hours. Next, the densities of these ring-shaped cores were measured by a method according to the Archimedes method.
The initial magnetic permeability at 100 kHz of these ring-shaped cores was measured by LCR meter 4274A (trade name, manufactured by Hewlett-Packard Co.). The relationship between the sintering temperature and the density and the relationship between the sintering temperature and the initial magnetic permeability of the electronic component thus obtained are shown in FIG.
The solid line graphs A to E are shown in (b) and FIGS. In the figure, A is the result of using the ferrite granule molding of Example 1, B is Example 2, C is Example 3, D is Example 4 and E is Example 5. The graph showing the relationship between the sintering temperature and the initial magnetic permeability of the electronic parts using the molded bodies of Examples 2 to 4 almost overlapped with the graph A of Example 1.
【００３６】比較例５
前記比較例１〜４で得たフェライト顆粒を用い、実施例
６と同様にして成形、焼結することによりリング状コア
を製造した。このようにして得たリング状コアについ
て、実施例６と同様にして密度及び初透磁率を測定し、
このようにして得た電子部品の焼結温度と密度との関係
及び焼結温度と初透磁率との関係をそれぞれ図５
（ａ）、（ｂ）及び図６（ａ）、（ｂ）に破線グラフＦ
（比較例１のフェライト顆粒）、Ｇ（比較例２のフェラ
イト顆粒）、Ｈ（比較例３のフェライト顆粒）及びＩ
（比較例４のフェライト顆粒）として示す。比較例４の
成形体を用いた電子部品の焼結温度と初透磁率との関係
を示すグラフは比較例３のグラフＨとほとんど重なって
いた。Comparative Example 5 Using the ferrite granules obtained in Comparative Examples 1 to 4, a ring-shaped core was manufactured by molding and sintering in the same manner as in Example 6. With respect to the ring-shaped core thus obtained, the density and the initial magnetic permeability were measured in the same manner as in Example 6,
The relationship between the sintering temperature and the density and the relationship between the sintering temperature and the initial magnetic permeability of the electronic component thus obtained are shown in FIG.
A broken line graph F is shown in (a), (b) and FIGS. 6 (a), (b).
(Ferrite granules of Comparative Example 1), G (Ferrite granules of Comparative Example 2), H (Ferrite granules of Comparative Example 3) and I
(Ferrite granules of Comparative Example 4). The graph showing the relationship between the sintering temperature and the initial magnetic permeability of the electronic component using the molded body of Comparative Example 4 almost overlapped with Graph H of Comparative Example 3.
【００３７】実施例７
前記実施例１〜５で得たフェライト顆粒被覆体をそれぞ
れ１０００ｋｇｆ／ｃｍ2の圧力でプレス成形し、長さ
５５ｍｍ、幅１２ｍｍ、高さ５ｍｍの直方体状のブロッ
ク成形体を得た。このブロック成形体を１０３０℃、１
０６０℃又は１０９０℃の温度において２時間焼結し、
ブロックコアを製造した。このようにして得た電子部品
について、荷重試験機（アイコーエンジニアリング社
製）を用いて抗折強度をＪＩＳ Ｒ１６０１に従い測定
した。これらのものの焼結温度と抗折強度の関係を図７
（ａ）、（ｂ）に実線グラフＡ〜Ｅとして示す。Example 7 The ferrite granule coated bodies obtained in the above-mentioned Examples 1 to 5 were press-molded at a pressure of 1000 kgf / cm 2 to obtain a rectangular block molded body having a length of 55 mm, a width of 12 mm and a height of 5 mm. Obtained. This block molded body is heated at 1030 ° C., 1
Sintering at a temperature of 060 ° C or 1090 ° C for 2 hours,
A block core was manufactured. The bending strength of the thus obtained electronic component was measured according to JIS R1601 using a load tester (manufactured by Aiko Engineering Co., Ltd.). Fig. 7 shows the relationship between the sintering temperature and the bending strength of these materials.
The solid line graphs A to E are shown in (a) and (b).
【００３８】比較例６
前記比較例１〜４で得たフェライト顆粒を用い、実施例
７と同様にして成形、焼結することによりブロックコア
を製造した。このようにして得たブロックコアについ
て、実施例７と同様にして抗折強度を測定した。これら
のものの焼結温度と抗折強度の関係を図７（ａ）、
（ｂ）に破線グラフＦ〜Ｉとして示す。Comparative Example 6 Using the ferrite granules obtained in Comparative Examples 1 to 4, a block core was manufactured by molding and sintering in the same manner as in Example 7. The bending strength of the block core thus obtained was measured in the same manner as in Example 7. The relationship between the sintering temperature and the bending strength of these materials is shown in FIG.
Shown as broken line graphs FI in FIG.
【００３９】比較例７
実施例５におけるソルビタンセスキオレイン酸エステル
の同量を最初からフェライト粉末に添加して造粒したこ
と以外は、実施例５と同様にしてフェライト顆粒被覆体
を調製した。実施例５で得たフェライト顆粒被覆体及び
上記のフェライト顆粒被覆体をそれぞれ用いて実施例６
及び７と同様にして成形体を製造し、１０３０℃におい
て２時間焼成した。このようにして得た電子部品につい
て実施例６及び７と同様にして密度及び抗折温度を測定
した結果を表２に示す。Comparative Example 7 A ferrite granule coated body was prepared in the same manner as in Example 5, except that the same amount of the sorbitan sesquioleate ester used in Example 5 was added to the ferrite powder from the beginning for granulation. Example 6 using the ferrite granule coated body obtained in Example 5 and the above-mentioned ferrite granular coated body respectively
A molded product was produced in the same manner as in Nos. 7 and 7, and was fired at 1030 ° C. for 2 hours. Table 2 shows the results of measuring the density and bending temperature of the electronic parts thus obtained in the same manner as in Examples 6 and 7.
【００４０】[0040]
【表２】 [Table 2]
【００４１】この表から分かるように、高級脂肪酸のヘ
キシタンエステルをフェライト粉末にあらかじめ添加し
て造粒した場合と造粒後添加した場合は明らかに後者の
方が優れた物性を示す。As can be seen from this table, the latter shows clearer physical properties when the hextan ester of higher fatty acid is added to the ferrite powder in advance and granulated and after the granulation.
【００４２】[0042]
【発明の効果】本発明によれば、高級脂肪酸のヘキシタ
ンエステルを含有するフェライト顆粒被覆体を乾式加圧
成形に用いることにより、滑り性、流動性、圧力伝達性
が向上し、金型への充填が良好となり、バラツキが少な
く、低い圧力でも均質な、かつ電磁特性の優れた高密度
フェライト電子部品製造用材料が得られる。また、同時
に離型性が向上し、金型からの成形体取出時の抜き圧が
低下し、金型の摩耗や損傷が減少する。さらに、これら
の効果により、金型からの成形体取出時のスプリングバ
ック（成形体膨張）が減少し、ヒビ等の成形不良の無い
高密度フェライト電子部品製造用成形体を得ることがで
きる。INDUSTRIAL APPLICABILITY According to the present invention, by using a ferrite granule coated body containing a hexitane ester of a higher fatty acid for dry pressure molding, slipperiness, fluidity and pressure transferability are improved, and a mold is formed. The material for producing high-density ferrite electronic parts is excellent in filling, has little variation, is homogeneous even at low pressure, and has excellent electromagnetic characteristics. At the same time, the releasability is improved, the drawing pressure at the time of taking out the molded product from the mold is reduced, and the wear and damage of the mold are reduced. Further, due to these effects, spring back (molding body expansion) at the time of taking out the molded body from the mold is reduced, and a molded body for producing high-density ferrite electronic parts free from molding defects such as cracks can be obtained.
【図１】 実施例１、５及び比較例１、３で得た成形体
の成形圧力と成形体密度との関係を示すグラフ。FIG. 1 is a graph showing the relationship between the molding pressure and the density of the molded bodies obtained in Examples 1 and 5 and Comparative Examples 1 and 3.
【図２】 実施例１、５及び比較例１〜４で得た成形体
の成形体密度と金型からの抜き圧との関係を示すグラ
フ。FIG. 2 is a graph showing the relationship between the compact density of the compacts obtained in Examples 1 and 5 and Comparative Examples 1 to 4 and the extraction pressure from the mold.
【図３】 実施例１、５及び比較例１、３、４で得た成
形体密度と膨張率との関係を示すグラフ。FIG. 3 is a graph showing the relationship between the density and the expansion coefficient of the molded bodies obtained in Examples 1 and 5 and Comparative Examples 1, 3 and 4.
【図４】 実施例１、比較例１及び比較例２で得た成形
体の密度バラツキを示すグラフ。FIG. 4 is a graph showing density variations of the molded bodies obtained in Example 1, Comparative Example 1 and Comparative Example 2.
【図５】 実施例６及び比較例５で得た電子部品の焼結
温度と密度との関係を示すグラフ。FIG. 5 is a graph showing the relationship between the sintering temperature and the density of the electronic components obtained in Example 6 and Comparative Example 5.
【図６】 実施例６及び比較例５で得た電子部品の焼結
温度と初透磁率との関係を示すグラフ。FIG. 6 is a graph showing the relationship between the sintering temperature and the initial magnetic permeability of the electronic components obtained in Example 6 and Comparative Example 5.
【図７】 実施例７及び比較例６で得た電子部品の焼結
温度と抗折強度との関係を示すグラフ。FIG. 7 is a graph showing the relationship between the sintering temperature and the bending strength of the electronic components obtained in Example 7 and Comparative Example 6.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C04B 35/00 - 35/84 B01J 2/00 B28B 3/02 H01F 1/12 - 1/375 ─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. 7 , DB name) C04B 35/00-35/84 B01J 2/00 B28B 3/02 H01F 1/12-1/375
Claims (4)
酸のヘキシタンエステルを接触させ、その表面の少なく
とも一部を高級脂肪酸のヘキシタンエステルで被覆した
ことを特徴とする高密度フェライト電子部品製造用材
料。1. Ferrite granules obtained by granulation, and higher fat
Acid hexitane ester was contacted and at least part of the surface was coated with higher fatty acid hexitane ester
A material for producing high-density ferrite electronic parts, which is characterized by
量がフェライト顆粒の重量に基づき０．１〜３．０重量
％の範囲にある請求項１記載の高密度フェライト電子部
品製造用材料。2. The high-density ferrite electronic component according to claim 1, wherein the coating amount of the hexitan ester of higher fatty acid is in the range of 0.1 to 3.0% by weight based on the weight of the ferrite granules. material.
にその重量に基づき０．１〜３．０重量％の高級脂肪酸
のヘキシタンエステルを添加し、両者をよく接触させ、
次いで乾燥してフェライト顆粒の表面の少なくとも一部
を高級脂肪酸のヘキシタンエステルで被覆することを特
徴とする高密度フェライト電子部品製造用材料の製造方
法。 3. After granulating the ferrite powder, 0.1 to 3.0% by weight based on the weight of the obtained granules, a hexitane ester of a higher fatty acid is added, and both are well contacted ,
Next, a method for producing a material for producing a high-density ferrite electronic component, which comprises drying and coating at least a part of the surface of the ferrite granules with a hexitane ester of a higher fatty acid .
にその重量に基づき０．１〜３．０重量％の高級脂肪酸
のヘキシタンエステルを溶液として添加し、両者をよく
接触させたのち乾燥して、フェライト顆粒の表面の少な
くとも一部を高級脂肪酸のヘキシタンエステルで被覆
し、次いでこのようにして得たフェライト顆粒被覆体を
所定の形状の金型に充填してプレス成形したのち、焼結
することを特徴とする高密度フェライト電子部品の製造
方法。4. After granulating the ferrite powder, hexane rosewood esters of 0.1 to 3.0 wt% of a higher fatty acid based on the weight obtained granules was added as a solution, after contacting well both After drying , at least a part of the surface of the ferrite granules is coated with a hexitane ester of a higher fatty acid, and then the ferrite granule coated body thus obtained is filled in a mold of a predetermined shape and press- molded, A method of manufacturing a high-density ferrite electronic component, which comprises sintering.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27076999A JP3481171B2 (en) | 1998-10-02 | 1999-09-24 | ELECTRONIC COMPONENT MANUFACTURING MATERIAL, PROCESS FOR PRODUCING THE SAME, PROCESS FOR PRODUCING HIGH-DENSITY FERRITE ELECTRONIC COMPONENT USING THE SAME |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10-280764 | 1998-10-02 | ||
| JP28076498 | 1998-10-02 | ||
| JP27076999A JP3481171B2 (en) | 1998-10-02 | 1999-09-24 | ELECTRONIC COMPONENT MANUFACTURING MATERIAL, PROCESS FOR PRODUCING THE SAME, PROCESS FOR PRODUCING HIGH-DENSITY FERRITE ELECTRONIC COMPONENT USING THE SAME |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000169238A JP2000169238A (en) | 2000-06-20 |
| JP3481171B2 true JP3481171B2 (en) | 2003-12-22 |
Family
ID=26549358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27076999A Expired - Fee Related JP3481171B2 (en) | 1998-10-02 | 1999-09-24 | ELECTRONIC COMPONENT MANUFACTURING MATERIAL, PROCESS FOR PRODUCING THE SAME, PROCESS FOR PRODUCING HIGH-DENSITY FERRITE ELECTRONIC COMPONENT USING THE SAME |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3481171B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN121248278B (en) * | 2025-12-02 | 2026-03-03 | 西安恒翔电子新材料有限公司 | Zinc oxide piezoresistor ceramic powder with positive temperature coefficient special for photovoltaic direct current and preparation method and application thereof |
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1999
- 1999-09-24 JP JP27076999A patent/JP3481171B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000169238A (en) | 2000-06-20 |
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