201022177 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種MnZnLi系鐵氧體，更詳細而言，其 係用於開關式電源（switched-mode power supply，SMPS)等 電源變壓器等之磁心的MnZnLi系鐵氧體，特別是於較廣 之溫度範圍内磁損耗（磁心損失）小，且實現燒結體強度、 特別是抗折強度（抗彎強度）之提高的MnZnLi系鐵氧體。 【先前技術】 近年來，電子設備之小型化、高功率化急速發展。與之 相伴的是各種零件之高集體化、高速處理化不斷發展，從 而要求供給電力之電源線路大電流化。對於變壓器、扼流 圈之類的零件亦要求在大電流下驅動，進而由於汽車等之 使用環境的高溫化、驅動時放熱所導致之溫度上升，而要 求於100°C附近穩定驅動。 為了與大電流驅動對應，對於鐵氧體磁心，要求於高溫 下、例如100°C以上之溫度範圍内的高飽和磁通密度。進 而，為了確保優良之磁穩定性與高可靠性，期望有可降低 l〇〇°C附近之磁損耗（磁心損失）值、且可減少100°c附近之 磁損耗（磁心損失）值之溫度依存性、並且高溫貯存性優異 之鐵氧體的方案。 又，由於需對應鐵氧體磁心之小型·薄型化，故要求其 高抗折強度化。然而，主要用於變壓器之MnZn鐵氧體存 在抗折強度低之問題。又，於存在將變壓器浸潰於烊锡槽 中進行焊接之工序之情形時，要求磁心具有耐熱衝擊性。 143075.doc 201022177 認為與本申請相關之先前技術有如下之文獻。 於日本專利第3487243號中，公開了一種為了容易地使 飽和磁通密度高且磁心損失最小之溫度成為實用之溫度， 而添加必須成分Li、Ca、Si作為副成分之MnZn系鐵氧 體。 於曰本特開2007-238429號公報中，公開了一種為了提 供於100 c下具有更高之飽和磁通密度、且於1〇〇<>c下磁心 才貝失較低之鐵氧體材料，而添加Li作為副成分之河以^^鐵 氧體。 於日本專利第3924272號中，公開了一種為了提供於高 溫範圍内磁心損失小、進而即使於高溫下儲存磁心損失等 劣化亦較小的鐵氧體材料，而添加Co作為副成分之Mnzn 系鐵氧體。 於日本專利特公平4_3089中，公開了 一種於Li_ZnMn鐵 氧體中含有Co而成的鐵氧體材料。然而，Li含量比鋅與短 各自之含量均高，與本發明之範圍完全不同。進而，該先 前技術中之FhO3量少於化學計量組成（st〇ichi〇metric composition) ° 【發明内容】 對於上述之高飽和磁通密度特性、降低磁損耗（磁心損 失）值之溫度依存性的特性等之要求沒有止境，因而需要 可實現特性進一步提高之MnZnLi系鐵氧體之方案。 進而’上述各先前技術係關注高飽和磁通密度、1〇〇 附近之磁心損失之降低、以及於高溫貯存下之磁心損失劣 143075.doc 201022177 化等效果而進行組分調配之技術，而並非以提高特別是抗 折強度為目的而進行組分調配之技術。因此，先前之 MnZnLi系鐵氧體產品之抗折強度並不能令人十分滿意， 因此要求一種具有以下特性之新的MnZnLi系鐵氧體之方 案：可非常有效地防止例如變壓器用磁心之製造過程及變 壓器組裝工序中破裂、破損等之發生，實現產品良率之進 一步提高，進而磁心之而ί熱衝擊性優異。 本發明係基於此種現狀而發明者，其目的在於提供一種 新的MnZnLi系鐵氧體，其具有高飽和磁通密度特性、降 低磁損耗（磁心損失）值之溫度依存性的特性優異，進而實 現了抗折強度之提高且實現了產品良率之提高，進而磁心 之耐熱衝擊性優異。 為了解決上述課題，本發明之MnZnLi系鐵氧體係以如 下方式構成：作為主成分，含有以Fe203換算計為 54.0〜58.0 mol%之氧化鐵、以ZnO換算計為3.0-10.0 mol0/〇 之氧化辞、以Li〇0.5換算計為0.3〜1.5 mol%之氧化鋰、剩 餘部分（以MnO換算）為氧化錳；且含有相對於上述主成分 以CoO換算計為500〜2000重量ppm之Co作為副成分。 又，作為本發明之MnZnLi系鐵氧體之較好態樣，其以 如下方式構成：於對MnZnLi系鐵氧體施加100 kHz、200 mT之正弦波交流磁場，將使測定溫度作各種變化所得之 磁損耗（磁心損失）Pcv值利用與測定溫度之關係來表示的圖 表中，於令相當於圖表最低點之底部溫度Tb下的磁損耗值 (磁心損失）為Pcvb、比底部溫度Tb高20°C(Tb+20°C)之溫度 143075.doc 201022177 下的磁損耗值（磁心損失）為PcVb+2〇時’在此2 0 C之間的磁 損耗變化率的值S2 = [(Pcvb+2(rPcvb)/Pcvbxl00]為 15%以下。 又，作為本發明之MnZnLi系鐵氧體之較好態樣，其以 如下方式構成：於l〇〇°C下之飽和磁通密度Bs為430 mT以 上。 又，作為本發明MnZnLi系鐵氧體之較好態樣，其以如 下方式構成：底部溫度Tb為70°C以上。 本發明之變壓器用磁心包含前述MnZnLi系鐵氧體。 本發明之變壓器係使用有前述變壓器用磁心而構成。 本發明之MhZnLi系鐵氧體，作為主成分，含有以Fe203 換算計為54.0〜58.0 mol%之氧化鐵、以ZnO換算計為 3.0〜10.0 mol%之氧化鋅、以LiO〇.5換算計為0.3〜1.5 mol% 之氧化鋰、剩餘部分（以MnO換算）為氧化錳，相對於前述 主成分，含有以Co◦換算計為500-2000重量ppm之Co作為 副成分，因此表現出以下效果：高飽和磁通密度特性、降 低磁損耗（磁心損失）值之溫度依存性的特性優異、進而實 現抗折強度之提高、且可實現產品良率之進一步提高、進 而磁心之耐熱衝擊性優異。 【實施方式】 以下，對本發明之MnZnLi系鐵氧體加以詳細說明。 [本發明之MnZnLi系鐵氧體之說明] (關於主成分組分之說明） 本發明之MnZnLi系鐵氧體，作為主成分，含有以Fe203 換算計為54.0〜58.0 mol%(較好的是54.5〜57·5 mol%，更好 143075.doc 201022177 的是55.G〜57·〇则1%)之氧化鐵、以Zn⑽算計為3 〇〜動 咖1%(較好的是3.5〜9.0则1% ’更好的是4()~8g祕。)之 軋化鋅、以LiO0.5換算計為〇 3〜！ 5 _(較好的是 0H45 m〇1% ’更好的是〇 4〜i 4则叫之氧化經剩餘 部分（以Mn〇換算）為氧北錳。 ^ 於上述主成分組分中，若Fe2〇3之量超過58〇则1%，則 存在產生磁心損失增大之不良情況的傾向。又，若Fe2〇3 春之量不足54·0 m〇1%，則存在產生飽和磁通密度降低之2不3 良情況的傾向。 又，於上述主成分組分中，若Zn〇之量不足3〇祕， 則存^產生磁心損失之溫度特性變高之不良情況的傾向。 又，若Zn〇之量超過则则以，則存在產生飽和磁通密度 降低之不良情況的傾向。 於上述主成分組分中，若以〇〇5之量不足〇 3则以，則 存在產生抗折強度降低之不良情況的傾向。又，若Li% $ 拳之量超過m〇1%，則存在產生磁心損失變高之不良情況 的傾向。又，該LiOwf，可藉由與後述之⑽之量的 關係，而發揮關於提高磁心耐熱衝擊性的乘數效果 (multiplier effect)。 (關於副成分組分之說明） 本發明之MnZnLi系鐵氧體含有必須成分c〇而作為副成 分。作為副成分之原料，可使用氧化物或藉由加熱而變成 氧化物之化合物的粉末。具體而言，可根據添加時之形態 而使用CoO。 143075.doc 201022177 此種副成分含有相對於前述主成分以c〇〇換算計為 500〜2000重量Ppm(較好的是6〇〇〜18〇〇重量ppm，更好的是 700〜1500重量 ppm)之 c〇。 若CoO之量不足500重量ppm，則存在產生磁心損失之溫 度特性變大之不良情況的傾向。又，若c〇〇之量超過2〇〇〇 重量PPm，則存在產生磁心損失變大之不良情況的傾向。 該CoO之量，可藉由與Li〇〇5之關係，而發揮關於提高磁 心耐熱衝擊性的乘數效果。 又，於不偏離本發明之作用效果的範圍内，除上述副成 分之外’亦可添加 Zr02、Si02、CaC03、Nb205、V205、201022177 VI. Description of the Invention: TECHNICAL FIELD The present invention relates to a MnZnLi-based ferrite, and more particularly to a power transformer such as a switched-mode power supply (SMPS). The MnZnLi-based ferrite of the core is, in particular, a MnZnLi-based ferrite having a small magnetic loss (core loss) in a wide temperature range and an improvement in sintered body strength, particularly flexural strength (bending strength). [Prior Art] In recent years, miniaturization and high power of electronic devices have been rapidly developed. Along with this, high-level collectivization of various parts and high-speed processing have been progressing, and it is required to supply a large current to the power supply line. For parts such as transformers and choke coils, it is also required to drive at a high current, and the temperature rises due to the high temperature of the environment in which the automobile or the like is used and the heat generation during driving is required to be stably driven at around 100 °C. In order to correspond to a large current drive, for a ferrite core, a high saturation magnetic flux density at a high temperature, for example, a temperature range of 100 ° C or higher is required. Further, in order to secure excellent magnetic stability and high reliability, it is desirable to have a temperature which can reduce the value of magnetic loss (core loss) in the vicinity of 10 ° C and reduce the value of magnetic loss (magnetic core loss) near 100 ° c. A ferrite solution that is excellent in dependence and high in high-temperature storage property. Further, since the ferrite core is required to be small and thin, it is required to have a high bending strength. However, the MnZn ferrite mainly used for transformers has a problem of low bending strength. Further, in the case where the transformer is immersed in the tin bath to perform the soldering process, the core is required to have thermal shock resistance. 143075.doc 201022177 The prior art related to the present application is considered to have the following documents. Japanese Patent No. 3,748,423 discloses a MnZn-based ferrite in which an essential component of Li, Ca, and Si is added as an auxiliary component in order to easily make the temperature at which the saturation magnetic flux density is high and the core loss is at a practical temperature. In Japanese Laid-Open Patent Publication No. 2007-238429, a ferrite having a higher saturation magnetic flux density at 100 c and a lower core loss at 1 〇〇 <> Body material, while adding Li as a by-component river to ^ ferrite. Japanese Patent No. 3,924,272 discloses a Mnzn-based iron in which Co is added as an auxiliary component in order to provide a ferrite material which has a small core loss in a high temperature range and which has a small deterioration in storage core loss even at a high temperature. Oxygen. A ferrite material containing Co in a Li_ZnMn ferrite is disclosed in Japanese Patent Publication No. Hei 4-3089. However, the Li content is higher than the respective contents of zinc and short, and is completely different from the range of the present invention. Further, the amount of FhO3 in the prior art is less than the stoichiometric composition. [Invention] The temperature dependence of the high saturation magnetic flux density characteristic and the magnetic loss (magnetic core loss) value are reduced. The requirements for characteristics and the like are not endless, and thus a scheme of MnZnLi-based ferrite which can further improve characteristics can be realized. Further, each of the above prior art techniques focuses on high saturation magnetic flux density, reduction in core loss near 1 、, and magnetic core loss under high temperature storage, and the composition is compounded instead of A technique for compounding components for the purpose of improving the flexural strength in particular. Therefore, the flexural strength of the prior MnZnLi-based ferrite product is not very satisfactory, and therefore a new MnZnLi-based ferrite solution having the following characteristics is required: the manufacturing process of a magnetic core such as a transformer can be very effectively prevented. In the transformer assembly process, cracking, breakage, and the like occur, and the product yield is further improved, and the magnetic core is excellent in thermal shock resistance. The present invention has been made in view of such circumstances, and an object of the invention is to provide a novel MnZnLi-based ferrite which has high saturation magnetic flux density characteristics and excellent characteristics of temperature dependence for reducing magnetic loss (magnetic core loss), and further The improvement of the bending strength is achieved and the product yield is improved, and the magnetic core is excellent in thermal shock resistance. In order to solve the problem, the MnZnLi-based ferrite system of the present invention is configured to contain, as a main component, iron oxide in an amount of 54.0 to 58.0 mol% in terms of Fe203, and oxidation in an amount of 3.0 to 10.0 mol0/〇 in terms of ZnO. Lithium oxide in an amount of 0.3 to 1.5 mol% in terms of Li〇0.5, and the remainder (calculated as MnO) is manganese oxide; and Co is 500 to 2000 ppm by weight in terms of CoO based on the main component. ingredient. Moreover, as a preferable aspect of the MnZnLi-based ferrite of the present invention, a sinusoidal alternating magnetic field of 100 kHz and 200 mT is applied to the MnZnLi-based ferrite, and the measurement temperature is varied. The magnetic loss (core loss) Pcv value is expressed by the relationship with the measured temperature, and the magnetic loss value (core loss) at the bottom temperature Tb corresponding to the lowest point of the graph is Pcvb and is higher than the bottom temperature Tb by 20 °C (Tb + 20 ° C) temperature 143075.doc 201022177 The magnetic loss value (core loss) is PcVb + 2 ' 'The value of the rate of change of magnetic loss between 2 0 C S2 = [(Pcvb Further, as a preferred aspect of the MnZnLi-based ferrite of the present invention, it is constituted as follows: the saturation magnetic flux density Bs at 10 ° C is Further, as a preferred aspect of the MnZnLi-based ferrite of the present invention, the bottom temperature Tb is 70° C. or more. The magnetic core for a transformer of the present invention contains the MnZnLi-based ferrite. The transformer of the invention is constructed using the core for the transformer described above. The MhZnLi-based ferrite of the present invention contains, as a main component, iron oxide in an amount of 54.0 to 58.0 mol% in terms of Fe203, zinc oxide in an amount of 3.0 to 10.0 mol% in terms of ZnO, and 0.30 in terms of LiO〇.5. Lithium oxide of 1.5 mol% and the remainder (calculated as MnO) are manganese oxide, and Co is contained in an amount of 500 to 2000 ppm by weight in terms of Co 作为 as a subcomponent with respect to the main component, and thus exhibits the following effects: high saturation The magnetic flux density characteristic and the magnetic loss (magnetic core loss) value are excellent in temperature dependence, and the bending strength is improved, and the product yield is further improved, and the magnetic core is excellent in thermal shock resistance. The MnZnLi-based ferrite of the present invention will be described in detail below. [Description of the MnZnLi-based ferrite of the present invention] (Description of the main component) The MnZnLi-based ferrite of the present invention contains as a main component. In terms of Fe203, it is 54.0~58.0 mol% (preferably 54.5~57.5 mol%, more preferably 143075.doc 201022177 is 55.G~57·〇1%) of iron oxide, calculated by Zn(10) 3 〇 ~ mobile coffee 1% (better It is 3.5 to 9.0, then 1% 'better is 4 () ~ 8g secret.) Rolling zinc, in LiO0.5 conversion, 〇3~! 5 _ (better is 0H45 m〇1% 'more It is good that 〇4~i 4 is called oxidation. The remaining part (in terms of Mn〇) is oxybei manganese. ^ Among the above main component, if the amount of Fe2〇3 exceeds 58〇, then 1%, then there is There is a tendency to cause an increase in core loss. Further, when the amount of Fe2〇3 in spring is less than 54·0 m〇1%, there is a tendency that the saturation magnetic flux density is lowered. Further, in the above-mentioned main component, when the amount of Zn〇 is less than 3, the temperature characteristic of the core loss tends to be high. Further, when the amount of Zn〇 exceeds, there is a tendency that the saturation magnetic flux density is lowered. When the amount of 〇〇5 is less than 〇3 in the above-mentioned main component, there is a tendency that the bending strength is lowered. Further, if the amount of Li%$ punch exceeds m〇1%, there is a tendency that the core loss becomes high. Further, the LiOwf can exhibit a multiplier effect on improving the thermal shock resistance of the magnetic core by the relationship with the amount of (10) described later. (Description of Subcomponent Component) The MnZnLi-based ferrite of the present invention contains an essential component c〇 as a by-component. As a raw material of the subcomponent, an oxide or a powder of a compound which becomes an oxide by heating can be used. Specifically, CoO can be used depending on the form at the time of addition. 143075.doc 201022177 The subcomponent contains 500 to 2000 parts by weight of Ppm (preferably 6 to 18 weight ppm, more preferably 700 to 1500 ppm by weight) in terms of c? ) c〇. When the amount of CoO is less than 500 ppm by weight, there is a tendency that the temperature characteristics of the core loss become large. Further, when the amount of c〇〇 exceeds 2 重量 by weight, the amount of defects tends to increase the core loss. The amount of CoO can exert a multiplier effect on improving the thermal shock resistance of the core by the relationship with Li〇〇5. Further, Zr02, SiO2, CaC03, Nb205, V205 may be added in addition to the above-mentioned sub-components within a range not deviating from the effects of the present invention.
Ta205、NiO、Ti〇2、Sn02等其他副成分。 鐵氧體燒結體之燒結密度較好的是47〇 g/cm3以上。雖 然對上限並無特別限制，但通常為5 〇〇 g/cm3左右。若燒 結密度不足4.70 g/cm3，則存在產生飽和磁通密度降低且 抗折強度降低之不良情況的傾向。 (關於本發明之鐵氧體燒結體之物性的說明） 本發明之鐵氧體具有以下的物性。 (1) 抗折強度 本發明之抗折強度藉由以下要點而求出。利用精細陶瓷 之常溫3點彎曲試驗，基於JIS Rl6〇1而求出。數值越大則 抗折強度越高。 本發明之抗彎強度的目標值為14.0 Kgf/mm2以上。 (2) 磁損耗（磁心損失）值之溫度依存性 本發明之磁知耗值之溫度依存性藉由以下要點而求出。 143075.doc 201022177 對鐵氧體施加100 kHz、200 mT之正弦波交流磁場，並利 用與測定溫度之關係而將使測定溫度進行各種改變而得到 之磁損耗（磁心損失）Pcv值繪製成圖表。 於該圖表中，分別求出相當於圖表之最低點的底部溫度 Tb下的磁損耗值Pcvb、以及比底部溫度Tb高20°C的溫度 (Tb+20°C)下的磁損耗值Pcv b + 20。本發明之底部溫度Tb較 好的是70°c以上。 本發明之底部溫度Tb下的磁損耗（磁心損失）值Pcvb的目 標值為450 KW/m3以下。 使用該等值，算出於20°C之間的磁損耗變化率之值 82 = [(Pcvb+20-Pcvb)/PcvbxlOO]。於本發明中，於20°C 之間 的磁損耗變化率之值δ2為15%以下。 (3) 飽和磁通密度Bm 於100°C下之飽和磁通密度Bs為430 mT以上。 (4) 耐熱衝擊性 評價標準如下前述： 〇...浸潰於400°C之焊锡槽中，磁心並不產生龜裂。 X..·浸潰於400°C之焊锡槽中，磁心產生龜裂。 [MnZnLi系鐵氧體之製造方法] 繼而，就本發明之MnZnLi系鐵氧體的較好之製造工序 的一例加以說明。 (1)為了獲得目標鐵氧體，以金屬離子之比例成為規定成分 的方式進行稱量之工序 作為主成分之原料，可使用氧化物或藉由加熱而成為氧 143075.doc 201022177 化物之化合物，例如碳酸鹽、氫氧化物 蓉夕扒古右认& 早^鹽、确酸鹽 等者刀末至於各原料粉末之平均粒徑於〇1〜3〇帅之 範圍内適當選擇即可。再者，並不侷限於上述原料粉末， 亦可將含有2㈣上之金屬的複合氧化物粉末作為原料粉 末。分別稱量原料粉末以使其成為規定之組分。 再者’較好的是合物使用對水為不溶性或難溶性之 化合物。此處本發明之所謂的「對水為不溶性或難溶性之 化合物（以下簡稱為「水不溶性化合物」）」係指相對於则g 水（溫度為20。〇’化合物溶質之量（克數）為1 g以下的化合 物。作為此種水不溶性Li化合物，為了於河〇211系鐵氧體 中使用，較好的是含有Li與選自Fe、Mn、Zn中至少一種 以上成分之軋化物。較好的是⑴含有Li與Fe成分之 UFe02、UFe5〇8、Li2Fe3〇5、Li5Fe〇4 等氧化物或（2)含有 Li與Μη成分之LiMnsO4、LiMn02等氧化物。藉由使用此種 水不溶性Li化合物，可抑制產品批次間之特性偏差，從而 可實現產品良率之提高與產品品質之可靠性的提高。 (2)藉由濕式或乾燥之方式混合稱量物後之煅燒工序 藉由球磨機對原料粉末進行例如濕式混合、乾燥、粉 碎、篩分後’於700〜1〇〇〇。(：之溫度範圍内進行保持規定時 間之燉燒。煅燒之保持時間於1〜5小時之範圍内適當選擇 即可。 (3)锻燒粉末之粉碎工序 於煅燒後，將煅燒體末粉碎至例如平均粒徑為0.5〜5.0 μιη之程度。 143075.doc -10- 201022177 通常情況下，於該粉碎工序中 c〇〇。即’於㈣粉碎後得到之 的副成分 之副成分⑽而進行混合。再者，：:末中添加規定量 Γ了並不於調配工序 中，而疋於該粉碎工序中添加Li成分。 (4) 造粒•成形工序 為了順利地進行其後之成形工序， 將被粉碎的粉末造粒 為顆粒。此時，較好的是於粉碎粉末中添加少量之適絲 合劑’例如聚乙料（PVA)。較好的是所得之顆粒粒徑為 8㈣〇㈣左右。對造粒粉末進行加壓成形，成形為例如 環形（toroidal)之成形體。 (5) 燒成工序 將成形之成形體於燒成工序中進行燒成。 於燒成工序巾，必須控制燒纽度與燒成環境。藉由於 1150〜1350°C之範圍内保持規定時間而進行燒成。 [實施例I] β 以下’列舉具體之實施例對本發明加以更詳細之說明。 如下述表1之樣品M3所示，稱量成為主成分之主成分原 料，使最終組分中之氧化鐵以以203換算計為56 0 mol%， 氧化猛以MnO換算計為371 mc)1%，氧化鋅以Zn〇換算計為 6.0 molX氧化鐘以Li〇o.5換算計為0.9 mol。/。。再者，使 用LiFe〇2作為Li原料，考慮。以仏中以的量而調整以成 分0 使用濕式球磨機對所稱量之原料進行16小時之濕式混合 後，使其乾燥。 143075.doc 201022177 繼而於大氣中，於900°C下對乾燥物煅燒3小時後進行粉 將CoO粉末加入至所得之煅燒粉末中作為副成分之原 料，於混合粉碎所得之混合物粉末中加入黏合劑，進行顆 粒化之後進行成形，獲得環形之成形體。再者，以相對於 主成分原料，含有1000重量ppm之CoO的方式添加副成分 原料。再者，Li成分亦可於粉碎時加入。 於1350C之溫度下，一面控制氧分壓一面對環形之成形 物進行燒成，製作如下表1中所示之樣品號U的鐵氧體燒 成體。 以該樣品號1-3之鐵氧體燒成體的製作方法為基礎，基 此而製作如下表1中所示之各種樣品。 對該等表1中所示之各樣品，分別測定： (1) 底部溫度Tb、 (2) 底部溫度下的磁損耗（磁心損失）pcVb、 (3) 比底部溫度Tb高2〇°c (Tb+2〇〇c )之溫度下的磁損耗（磁 心損失）值Pcvb+20、 (4) 磁心損失之溫度依存性δ2、 (5) 抗折強度（3點抗彎強度）、 (6) 飽和磁通密度Bm、 (7) 耐熱衝擊性。 再者，各種測定要點如上前述。將結果示於如下表丄 中〇 143075.doc -12· 201022177 表ι(其一） 樣品號 主成分 副成分 FC2〇3 (mol%) MnO (mol%) ZnO (mol%) Li〇0.5 (mol%) CoO (wtppm) 1-1(比較） 54.8 39.2 6.0 0.0 1000 1-2 55.3 38.4 6.0 0.3 1000 1-3 56.0 37.1 6.0 0.9 1000 1-4 56.3 36.4 6.0 1.3 1000 1-5 56.6 35.9 6.0 1.5 1000 1-6(比較） 57.1 34.9 6.0 2.0 1000 1-7(比較） 57.1 40.0 2.0 0.9 1000 1-8 56.6 39.5 3.0 0.9 1000 1-9 55.0 34.1 10.0 0.9 1000 1-10(比較） 54.1 32.0 13.0 0.9 1000 1-11(比較） 53.0 40.1 6.0 0.9 1000 1-12 54.0 39.1 6.0 0.9 1000 1-13 57.5 35.6 6.0 0.9 1000 1-14(比較） 60.0 33.1 6.0 0.9 1000 1-15(比較） 56.0 38.3 4.3 1.4 0 1-16 56.0 38.3 4.3 1.4 500 1-17 56.0 38.3 4.3 1.4 2000 1-18(比較） 56.0 38.3 4.3 1.4 4000 1-19(比較） 54.8 39.2 6.0 0 500 1-20(比較） 54.8 39.2 6.0 0 1500 1-21(比較） 54.8 39.2 6.0 0 2000 1-22(比較） 54.8 39.2 6.0 0 5000 1-23(比較） 54.8 39.2 6.0 0 10000 143075.doc -13 - 201022177 表ι(其二）Other sub-components such as Ta205, NiO, Ti〇2, and Sn02. The sintered density of the ferrite sintered body is preferably 47 〇 g/cm 3 or more. Although the upper limit is not particularly limited, it is usually about 5 〇〇 g/cm3. When the sintered density is less than 4.70 g/cm3, there is a tendency that the saturation magnetic flux density is lowered and the bending strength is lowered. (Description of physical properties of the ferrite sintered body of the present invention) The ferrite of the present invention has the following physical properties. (1) Flexural strength The flexural strength of the present invention was determined by the following points. The room temperature three-point bending test using fine ceramics was determined based on JIS Rl6〇1. The larger the value, the higher the flexural strength. The target value of the bending strength of the present invention is 14.0 Kgf/mm2 or more. (2) Temperature dependence of magnetic loss (core loss) value The temperature dependence of the magnetic value of the present invention is obtained by the following points. 143075.doc 201022177 A sinusoidal alternating magnetic field of 100 kHz and 200 mT is applied to the ferrite, and the magnetic loss (core loss) Pcv value obtained by variously changing the measured temperature is plotted as a relationship with the measured temperature. In the graph, the magnetic loss value Pcvb at the bottom temperature Tb corresponding to the lowest point of the graph and the magnetic loss value Pcv b at a temperature (Tb+20 ° C) higher than the bottom temperature Tb by 20 ° C are respectively obtained. + 20. The bottom temperature Tb of the present invention is preferably 70 ° C or more. The magnetic loss (core loss) value Pcvb at the bottom temperature Tb of the present invention has a target value of 450 KW/m3 or less. Using these values, the value of the rate of change in magnetic loss between 20 ° C is calculated as 82 = [(Pcvb + 20 - Pcvb) / PcvbxlOO]. In the present invention, the value δ2 of the rate of change in magnetic loss between 20 ° C is 15% or less. (3) The saturation magnetic flux density Bm at 100 ° C has a saturation magnetic flux density Bs of 430 mT or more. (4) Thermal shock resistance The evaluation criteria are as follows: 〇...impregnated in a solder bath at 400 ° C, the core does not crack. X..·Immersed in a solder bath at 400 °C, the core is cracked. [Method for Producing MnZnLi-Based Ferrite] Next, an example of a preferable production process of the MnZnLi-based ferrite of the present invention will be described. (1) In order to obtain the target ferrite, a step of weighing the metal ion as a predetermined component is used as a raw material of the main component, and an oxide or a compound which is made into a compound of oxygen 143075.doc 201022177 by heating may be used. For example, the average particle diameter of each of the raw material powders of the carbonate, the hydroxide, the sulphate, the sputum, the salt, the acid salt, and the like may be appropriately selected within the range of 〇1 to 3 〇. Further, it is not limited to the above-mentioned raw material powder, and a composite oxide powder containing a metal of 2 (tetra) may be used as a raw material powder. The raw material powder was weighed separately to make it a prescribed component. Further, it is preferred that the compound be a compound which is insoluble or poorly soluble in water. The term "a compound which is insoluble or poorly soluble in water (hereinafter referred to as "water-insoluble compound")" as used herein means a quantity of g (water) which is relative to g water (temperature is 20 〇' compound solute) The compound which is 1 g or less. As such a water-insoluble Li compound, in order to use it in the 〇 211 series ferrite, it is preferable to contain a rolled product of Li and at least one or more selected from the group consisting of Fe, Mn, and Zn. Preferably, it is (1) an oxide such as UFeO 2 , UFe 5 〇 8 , Li 2 Fe 3 〇 5 or Li 5 Fe 〇 4 containing Li and Fe components, or (2) an oxide such as LiMnsO 4 or LiMn 02 containing Li and Μ η components. The insoluble Li compound can suppress the variation in characteristics between product batches, thereby improving the yield of the product and improving the reliability of the product quality. (2) The calcination process after the weighing device is mixed by wet or dry After the raw material powder is subjected to, for example, wet mixing, drying, pulverization, and sieving by a ball mill, it is subjected to stewing for a predetermined period of time in a temperature range of from 700 to 1. The holding time of the calcination is from 1 to 5 Within hours (3) Pulverization process of calcined powder After calcination, the calcined body is pulverized to a degree such as an average particle diameter of 0.5 to 5.0 μm. 143075.doc -10- 201022177 Usually, the pulverization is performed. In the step, c〇〇, that is, the subcomponent (10) of the subcomponent obtained after the (four) pulverization is mixed, and further, the addition of the predetermined amount to the end is not in the blending step, but is in the pulverizing step. (Li) granulation and molding step In order to smoothly carry out the subsequent molding step, the pulverized powder is granulated into granules. In this case, it is preferred to add a small amount of the sizing agent to the pulverized powder. For example, a polyethylene material (PVA) is preferred. The obtained particle size is about 8 (four) 〇 (4). The granulated powder is subjected to press molding to form a molded body such as a toroidal. (5) A firing step The formed molded body is fired in the firing step. In the firing step, it is necessary to control the firing rate and the firing environment, and to perform baking for a predetermined period of time in the range of 1150 to 1350 ° C. Example I] β below 'list specific EXAMPLES The present invention will be described in more detail. As shown in the sample M3 of the following Table 1, the main component raw material which is the main component is weighed, and the iron oxide in the final component is 560 mol% in terms of 203, and is oxidized. In terms of MnO, it is 371 mc) 1%, and zinc oxide is 6.0 molX in terms of Zn〇, which is 0.9 mol in terms of Li〇o.5. Further, LiFe〇2 is used as the Li raw material. It is considered that the raw material is adjusted to the content of 仏 by using a wet ball mill for 16 hours of wet mixing, and then dried. 143075.doc 201022177 Then, in the atmosphere, the dried product is calcined at 900 ° C for 3 hours, and then the CoO powder is added to the obtained calcined powder as a raw material of the auxiliary component, and the binder is added to the mixture powder obtained by mixing and pulverizing. After granulation, it is shaped to obtain a ring-shaped formed body. Further, the auxiliary component raw material was added so as to contain 1000 ppm by weight of CoO based on the main component raw material. Further, the Li component can also be added at the time of pulverization. At a temperature of 1350 °C, the molded body facing the ring was controlled while the partial pressure of oxygen was controlled, and a ferrite sintered body of sample No. U shown in Table 1 below was produced. Based on the method for producing the ferrite sintered body of Sample No. 1-3, various samples shown in Table 1 below were prepared. For each of the samples shown in Table 1, respectively, (1) bottom temperature Tb, (2) magnetic loss at the bottom temperature (core loss) pcVb, (3) 2 〇 °c higher than the bottom temperature Tb ( Magnetic loss (core loss) value at temperature Tb+2〇〇c) Pcvb+20, (4) Temperature dependence of core loss δ2, (5) Flexural strength (3 point bending strength), (6) Saturation flux density Bm, (7) Thermal shock resistance. In addition, various measurement points are as mentioned above. The results are shown in the following table 〇 143075.doc -12· 201022177 Table ι (1) Sample No. Main component Subcomponent FC2〇3 (mol%) MnO (mol%) ZnO (mol%) Li〇0.5 (mol %) CoO (wtppm) 1-1 (comparative) 54.8 39.2 6.0 0.0 1000 1-2 55.3 38.4 6.0 0.3 1000 1-3 56.0 37.1 6.0 0.9 1000 1-4 56.3 36.4 6.0 1.3 1000 1-5 56.6 35.9 6.0 1.5 1000 1 -6 (comparative) 57.1 34.9 6.0 2.0 1000 1-7 (comparative) 57.1 40.0 2.0 0.9 1000 1-8 56.6 39.5 3.0 0.9 1000 1-9 55.0 34.1 10.0 0.9 1000 1-10 (comparative) 54.1 32.0 13.0 0.9 1000 1- 11 (comparative) 53.0 40.1 6.0 0.9 1000 1-12 54.0 39.1 6.0 0.9 1000 1-13 57.5 35.6 6.0 0.9 1000 1-14 (comparative) 60.0 33.1 6.0 0.9 1000 1-15 (comparative) 56.0 38.3 4.3 1.4 0 1-16 56.0 38.3 4.3 1.4 500 1-17 56.0 38.3 4.3 1.4 2000 1-18 (comparative) 56.0 38.3 4.3 1.4 4000 1-19 (comparative) 54.8 39.2 6.0 0 500 1-20 (comparative) 54.8 39.2 6.0 0 1500 1-21 ( Compare) 54.8 39.2 6.0 0 2000 1-22 (comparative) 54.8 39.2 6.0 0 5000 1-23 (comparative) 54.8 39.2 6.0 0 10000 143075.doc -13 - 20102 2177 Table ι (Part 2)
樣品號 底部 溫度 TbfC) 底部溫 度下之 Pcvb (kW/m3) PcV+2〇 (kW/m3) 磁心損失 之溫度 依存性δ2 抗彎 強度 (Kgf/mm2) 100°C下之飽 和磁通密度 Bm(mT) 耐熱 衝擊性 1-1(比較） 100 320 343 7.2 12.5 435 X 1-2 100 336 364 8.4 14.1 440 〇 1-3 100 362 396 9.4 15.4 445 〇 1-4 100 391 431 10.3 15.6 450 〇 1-5 100 410 456 11.2 15.7 455 〇 1-6(比較） 100 488 535 9.6 15.8 460 X 1-7(比較） 75 431 501 16.2 14.8 472 〇 1-8 85 394 453 14.9 15.4 466 〇 1-9 110 292 304 4.2 16.6 434 〇 1-10(比較） 130 345 368 6.8 17.1 392 〇 1-11(比較） 120 336 365 8.6 15.7 410 〇 1-12 110 312 343 9.8 15.2 430 〇 1-13 90 398 427 7.2 15.1 464 〇 1-14(比較） 70 512 544 6.3 14.6 490 〇 1-15(比較） 110 392 503 28.4 15,8 452 X 1-16 100 415 476 14.7 15.5 455 〇 1-17 80 445 473 6.3 15.2 454 〇 1-18(比較） 60 514 531 3.3 15.4 451 X 1-19(比較） 90 293 335 14.3 12.4 435 X 1-20(比較） 70 332 363 9.4 12.3 439 X 1-21(比較） 60 387 400 3.4 12.2 438 X 1-22(比較） 0 612 706 15.4 12.5 434 X 1-23(比較） - 977 1269 29.9 12.8 436 X • 14· 143075.doc 201022177 根據上述表1所示之實施例I的結果，本發明之效果顯而 易見。即，本發明之MnZnLi系鐵氧體以如下方式構成： 含有以Fees換算計為54.0〜58·0 mol%之氧化鐵、以Zn〇換 算計為3.0〜1〇.〇 m〇l%之氧化鋅、以U〇〇 5換算計為0^ 5 mol%之氧化鋰、剩餘部分（以Mn〇換算）為氧化錳而作為主 成分’且相對於前述主成分，含有以c〇0換算計為 500〜2000重量ppm之CoO而作為副成分，因此其表現出如 φ 下效果：高飽和磁通密度特性、降低磁損耗（磁心損失）值 之溫度依存性的特性優異、進而實現抗折強度之提高、可 實現產品良率之進一步提高、進而磁心之耐熱衝擊性優 異。 [產業上之可利用性] 本發明之MnZnLi系鐵氧體的製造方法可廣泛地用於各 種電力零件產業中。 ❹ 143075.doc 15Sample No. bottom temperature TbfC) Pcvb (kW/m3) at bottom temperature PcV+2〇(kW/m3) Temperature dependence of core loss δ2 Bending strength (Kgf/mm2) Saturation flux density at 100°C Bm (mT) Thermal shock resistance 1-1 (comparative) 100 320 343 7.2 12.5 435 X 1-2 100 336 364 8.4 14.1 440 〇1-3 100 362 396 9.4 15.4 445 〇1-4 100 391 431 10.3 15.6 450 〇1 -5 100 410 456 11.2 15.7 455 〇1-6 (comparative) 100 488 535 9.6 15.8 460 X 1-7 (comparative) 75 431 501 16.2 14.8 472 〇1-8 85 394 453 14.9 15.4 466 〇1-9 110 292 304 4.2 16.6 434 〇 1-10 (comparative) 130 345 368 6.8 17.1 392 〇 1-11 (comparative) 120 336 365 8.6 15.7 410 〇 1-12 110 312 343 9.8 15.2 430 〇 1-13 90 398 427 7.2 15.1 464 〇1-14 (comparative) 70 512 544 6.3 14.6 490 〇1-15 (comparative) 110 392 503 28.4 15,8 452 X 1-16 100 415 476 14.7 15.5 455 〇1-17 80 445 473 6.3 15.2 454 〇1 -18 (comparative) 60 514 531 3.3 15.4 451 X 1-19 (comparative) 90 293 335 14.3 12.4 435 X 1-20 (comparative) 70 332 363 9.4 1 2.3 439 X 1-21 (comparative) 60 387 400 3.4 12.2 438 X 1-22 (comparative) 0 612 706 15.4 12.5 434 X 1-23 (comparative) - 977 1269 29.9 12.8 436 X • 14· 143075.doc 201022177 The effects of the present invention shown in Table 1 above are apparent from the effects of the present invention. In other words, the MnZnLi-based ferrite of the present invention is configured to contain iron oxide in an amount of 54.0 to 58·0 mol% in terms of Fees and 3.0 to 1 〇.〇m〇l% in terms of Zn〇. Zinc, which is 0^5 mol% of lithium oxide in terms of U〇〇5, and the remainder (calculated as Mn〇) is manganese oxide as a main component, and is contained in c〇0 as a ratio of the main component. Since 500 to 2000 ppm by weight of CoO is used as an accessory component, it exhibits an effect of φ: high saturation magnetic flux density characteristics, low magnetic loss (magnetic core loss) value, excellent temperature dependence, and further achievement of flexural strength. The improvement is achieved, and the product yield is further improved, and the magnetic core is excellent in thermal shock resistance. [Industrial Applicability] The method for producing a MnZnLi-based ferrite of the present invention can be widely used in various power component industries. ❹ 143075.doc 15