JPH043402A - Ferrite coating liquid - Google Patents
Ferrite coating liquidInfo
- Publication number
- JPH043402A JPH043402A JP2104584A JP10458490A JPH043402A JP H043402 A JPH043402 A JP H043402A JP 2104584 A JP2104584 A JP 2104584A JP 10458490 A JP10458490 A JP 10458490A JP H043402 A JPH043402 A JP H043402A
- Authority
- JP
- Japan
- Prior art keywords
- coating liquid
- ferrite coating
- ferrite
- organic solvent
- iron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 64
- 239000007788 liquid Substances 0.000 title claims abstract description 58
- 239000011248 coating agent Substances 0.000 title claims abstract description 54
- 238000000576 coating method Methods 0.000 title claims abstract description 54
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 17
- INPLRNDUHADSET-UHFFFAOYSA-N butan-1-olate;iron(2+) Chemical compound [Fe+2].CCCC[O-].CCCC[O-] INPLRNDUHADSET-UHFFFAOYSA-N 0.000 claims description 16
- YJIFTYXRIKMETG-UHFFFAOYSA-N C(C)OC([O-])C.[Zn+2].C(C)OC([O-])C Chemical compound C(C)OC([O-])C.[Zn+2].C(C)OC([O-])C YJIFTYXRIKMETG-UHFFFAOYSA-N 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 150000002902 organometallic compounds Chemical class 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 229940093475 2-ethoxyethanol Drugs 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- IMGSGUIQEGMPJI-UHFFFAOYSA-N CCOC([O-])C.[Ni+2].CCOC([O-])C Chemical compound CCOC([O-])C.[Ni+2].CCOC([O-])C IMGSGUIQEGMPJI-UHFFFAOYSA-N 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 claims 3
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 13
- 230000035699 permeability Effects 0.000 abstract description 11
- 239000010409 thin film Substances 0.000 abstract description 10
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 7
- 230000007062 hydrolysis Effects 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 3
- 229910000765 intermetallic Inorganic materials 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 238000004519 manufacturing process Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 10
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 150000004703 alkoxides Chemical class 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000010304 firing Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- -1 Transition metal alkoxides Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 2
- CAFAOQIVXSSFSY-UHFFFAOYSA-N 1-ethoxyethanol Chemical compound CCOC(C)O CAFAOQIVXSSFSY-UHFFFAOYSA-N 0.000 description 1
- 101000913968 Ipomoea purpurea Chalcone synthase C Proteins 0.000 description 1
- 101000907988 Petunia hybrida Chalcone-flavanone isomerase C Proteins 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 125000000218 acetic acid group Chemical class C(C)(=O)* 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/14—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates
- H01F41/16—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates the magnetic material being applied in the form of particles, e.g. by serigraphy, to form thick magnetic films or precursors therefor
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、薄膜インダクタ、薄膜磁気ヘッド、磁気セン
サー、磁気シールド等の磁性体薄膜として利用され、目
的物に塗布し焼成することによってフェライトの薄膜を
形成するフェライトコーティング液に関するものである
。Detailed Description of the Invention [Field of Industrial Application] The present invention is used as a magnetic thin film for thin film inductors, thin film magnetic heads, magnetic sensors, magnetic shields, etc. This invention relates to a ferrite coating liquid that forms a thin film.
〔従来の技術及び発明が解決しようとする課題〕従来、
溶液を塗布することによって磁性体薄膜を得る方法とし
ては、以下の方法があった。[Problems to be solved by conventional techniques and inventions] Conventionally,
The following methods have been used to obtain a magnetic thin film by applying a solution.
即ち、フェライトの成分に相当する無機金属塩の溶液を
目的物に塗布し、これを焼成することによって熱分解、
酸化させ、これによってフェライトの薄膜を得る方法で
ある。That is, by applying a solution of an inorganic metal salt corresponding to the components of ferrite to the target object and firing it, thermal decomposition,
This method involves oxidation, thereby obtaining a thin ferrite film.
しかしながらこの方法によっては、以下の問題点があっ
た。即ち、
ア）、無機金属塩を熱分解すると、強酸等の腐食性ガス
が発生し、製造装置、作業環境、目的物の他の部分に悪
影響を及ぼす。However, this method has the following problems. That is, a): When inorganic metal salts are thermally decomposed, corrosive gases such as strong acids are generated, which adversely affects manufacturing equipment, the working environment, and other parts of the target object.
イ）、無機金属塩の分解反応は、急激で制御が困難なた
め、−様で緻密な膜の形成が困難である。b) The decomposition reaction of inorganic metal salts is rapid and difficult to control, making it difficult to form a -like and dense film.
以上の問題点を解決するための方法として有機金属の１
種である金属アルコキシドを用いた方法がある。One way to solve the above problems is to use organic metals.
There is a method using a metal alkoxide as a seed.
即ち、フェライトの成分に相当する金属アルコキシドを
加水分解して得たゾル溶液を窒素置換雰囲気中で目的物
に塗布し、これを焼成してフェライトの薄膜を得る方法
である。That is, this is a method in which a sol solution obtained by hydrolyzing a metal alkoxide corresponding to a component of ferrite is applied to a target object in a nitrogen-substituted atmosphere, and then baked to obtain a ferrite thin film.
しかしながら、単に金属アルコキシドを加水分解させて
得たゾル溶液は成膜性が悪く、組成の均一性に欠け、保
存安定性も悪いため、フェライトコーティング液として
は実用性に乏しかった。However, sol solutions obtained by simply hydrolyzing metal alkoxides have poor film-forming properties, lack uniformity of composition, and poor storage stability, and are therefore of little practical use as ferrite coating solutions.
特に二種類の遷移金属を含むＦｅ−Ｎｉ系フェライト膜
を形成する目的では未だ成功例を見ないのが現状である
。その理由を以下に挙げる。ちなみにこのような液は酸
化鉄やフェライトの微粉末を製造する目的で利用されて
いる。In particular, the current situation is that there has been no success story yet for the purpose of forming a Fe--Ni-based ferrite film containing two types of transition metals. The reasons for this are listed below. Incidentally, this kind of liquid is used for the purpose of producing fine powders of iron oxide and ferrite.
ア）、空気中の水分又は酸素により容易に分解、凝集す
るため、塗布作業は湿度を完全に取り除いた状態、望ま
しくは窒素置換された雰囲気中で行なわなければならな
い。a) Since it is easily decomposed and agglomerated by moisture or oxygen in the air, the coating operation must be performed in a state where humidity is completely removed, preferably in an atmosphere purged with nitrogen.
イ）、フェライトに必要な鉄、ニッケル等の遷移金属ア
ルコキシドは、これらを加水分解して得られる酸化物が
粉末状になり易く、成膜性が悪い。b) Transition metal alkoxides such as iron and nickel necessary for ferrite tend to have poor film-forming properties because the oxides obtained by hydrolyzing these tend to be powdered.
つ）、アルコキシドの成分毎に反応速度が異なるため、
成分が偏析しやすく、組成が不均一に成り易い。従って
均質な複合酸化物の膜にはなりにくい。(1), since the reaction rate differs depending on the alkoxide component,
Components tend to segregate and the composition tends to become non-uniform. Therefore, it is difficult to form a homogeneous composite oxide film.
工）、遷移金属元素を含むゾルの分散が不安定で沈殿を
生じるため、液の保存性が悪い。そのために、ゾル溶液
の製造と塗布作業を連続して行なわなければならない。(Engineering), the dispersion of the sol containing transition metal elements is unstable and precipitation occurs, resulting in poor storage stability of the liquid. For this purpose, the production and application of the sol solution must be carried out continuously.
本発明は上述の点に鑑みてなされたものであり、大気中
での塗布が可能で特別な設備を使用する必要がなく、均
一で高純度な特性の良いフェライト薄膜が形成でき、し
かも液の保存性が良いフェライトコーティング液を提供
することにある。The present invention has been made in view of the above points, and can be applied in the atmosphere, does not require the use of special equipment, can form a uniform, highly pure ferrite thin film with good properties, and can The purpose is to provide a ferrite coating liquid with good storage stability.
〔課題を解決するための手段及び作用〕上記問題点を解
決するため本発明はフェライトコーティング液を、一般
式Ｆｅ［０Ｒ）ｓ（但しＲは炭素を含む原子団）で表わ
される有機金属化合物と一般式Ｍ（ＯＲＬ （但しＭは
２価の金属元素）で表わされる有機金属化合物と有機溶
媒より成る組成物に、有機溶媒で希釈した水を加えるこ
とによって加水分解して製造した。なおこの溶液には酸
を含有させる。この溶液はゾル溶液である。[Means and effects for solving the problems] In order to solve the above problems, the present invention uses a ferrite coating liquid with an organometallic compound represented by the general formula Fe[0R)s (where R is an atomic group containing carbon). It was produced by hydrolyzing a composition consisting of an organometallic compound represented by the general formula M (ORL (where M is a divalent metal element) and an organic solvent by adding water diluted with an organic solvent.This solution contains an acid.This solution is a sol solution.
なお前記２価の金属元素Ｍは、Ｎｉ、Ｚｎ、Ｍｎ、Ｃｏ
、Ｍｇ又はＣｕの内、少なくとも１種類以上の元素から
選ぶ。Note that the divalent metal element M is Ni, Zn, Mn, Co
, Mg, or Cu.
また前記Ｒは以下の化学式で示される原子団の内、少な
くとも１種類以上の原子団から選ぶ。Further, the R is selected from at least one type of atomic group among the atomic groups represented by the following chemical formula.
（ｂ−１） −ｎＣ４ＨＩ（ｎ−ブチル基）（ｂ−２
） −Ｃ，Ｈ，−０−Ｃ！Ｈｓ（ｂ−３）−Ｃ＝ＣＨ
−Ｃ＝０
ＣＨｓ ＣＨ。(b-1) -nC4HI (n-butyl group) (b-2
) -C,H,-0-C! Hs(b-3)-C=CH
-C=0 CHs CH.
このように有機金属の原子団Ｒを選定した結果、加水分
解反応の速度が調整され、均一で安定なゾル溶液が得ら
れた。As a result of selecting the organometallic atomic group R in this manner, the rate of the hydrolysis reaction was adjusted, and a uniform and stable sol solution was obtained.
また上記酸を酢酸で構成する場合、この酢酸はフェライ
トコーティング液全体に対して容量で０．５％以上２．
０％以下で配合することが望ましい。これによって沈殿
を解離させゾルの分散性を増すことができた。ここで酢
酸の量を０．５％以下とした場合はこの効果は発揮され
ず、また２、０％を越えるとこのフェライトコーティン
グ液を用いて焼成した膜に亀裂が生じた。In addition, when the above-mentioned acid is composed of acetic acid, this acetic acid is contained in an amount of 0.5% or more by volume based on the entire ferrite coating liquid.
It is desirable to mix it at 0% or less. This made it possible to dissociate the precipitate and increase the dispersibility of the sol. When the amount of acetic acid was 0.5% or less, this effect was not exhibited, and when it exceeded 2.0%, cracks appeared in the film fired using this ferrite coating liquid.
またこの酸は、加水分解用の水分と共に配合するのが好
ましい。これによって沈殿の発生そのものを押さえ、分
散安定性を更に高め、有機金属の濃度を高めることがで
きた。Moreover, this acid is preferably blended with water for hydrolysis. This made it possible to suppress the occurrence of precipitation itself, further improve dispersion stability, and increase the concentration of organic metals.
一方前記有機金属化合物を次のように選定すれば、膜の
均質性が向上し、緻密で高い透磁率を有するフェライト
薄膜を形成しうるフェライトコーティング液が得られる
。On the other hand, if the organometallic compound is selected as follows, the homogeneity of the film is improved, and a ferrite coating liquid capable of forming a dense ferrite thin film having high magnetic permeability can be obtained.
即ち、Ｆ ｅ （ＯＲ） ｓとして鉄ｎブトキシド、Ｎ
ｉ（ＯＲ）よとしてニッケルエトキシエトキシド又はニ
ッケルアセチルアセトネート、Ｚｎ（ＯＲ）、として亜
鉛エトキシエトキシド。That is, F e (OR) s as iron n-butoxide, N
i(OR) as nickel ethoxyethoxide or nickel acetylacetonate, Zn(OR) as zinc ethoxyethoxide.
次に前記有機金属化合物の配合手順を以下（ａ〜Ｃ）の
ようにすることによって、分散の均一なゾル溶液を得る
ことができた。Next, a uniformly dispersed sol solution could be obtained by blending the organometallic compound as shown below (a to C).
ａ１ニッケルエトキシエトキシドと亜鉛エトキシエトキ
シドと鉄ｎブトキシドを用いた場合は、最後に鉄ｎブト
キシドを混合することが望ましい。鉄ｎブトキシドは色
が濃いので、先に混合すると沈殿等の異常を監視するこ
とが困難になるためである。a1 When using nickel ethoxy ethoxide, zinc ethoxy ethoxide, and iron n-butoxide, it is desirable to mix the iron n-butoxide last. This is because iron n-butoxide is dark in color, so if it is mixed first, it will be difficult to monitor abnormalities such as precipitation.
ｂ５ニッケルアセチルアセトネートと亜鉛エトキシエト
キシドと鉄ｎブトキシドを用いた場合は、ニッケルアセ
チルアセトネートと鉄ｎブトキシドを混合した後に亜鉛
エトキシエトキシドを混合する。この手順によらないと
、沈殿が生じ、均一なゾル溶液が得られない。b5 When nickel acetylacetonate, zinc ethoxy ethoxide, and iron n-butoxide are used, zinc ethoxy ethoxide is mixed after mixing nickel acetylacetonate and iron n-butoxide. If this procedure is not followed, precipitation will occur and a homogeneous sol solution will not be obtained.
Ｃ１以上の有機金属化合物は予め用意された所要量の２
−エトキシエタノール中に混合することが望ましい。こ
の操作は沈殿の発生を防止し、ゾル溶液の分散を保つこ
とに寄与する。The organometallic compound of C1 or higher is prepared in advance in the required amount of 2
- Preferably mixed in ethoxyethanol. This operation prevents the occurrence of precipitation and contributes to maintaining the dispersion of the sol solution.
さらに有機金属化合物の総量を以下（ａ又はｂ）のよう
に選定することにより、分散安定性の良いゾル溶液が得
られる。この範囲を越えるとゾルが不安定になり、沈殿
を生じる。Furthermore, by selecting the total amount of organometallic compounds as shown in (a or b) below, a sol solution with good dispersion stability can be obtained. If this range is exceeded, the sol becomes unstable and precipitates.
ａ、ニッケルエトキシエトキシドと亜鉛エトキシエトキ
シドと鉄ｎブトキシドを用いた場合は、フェライトコー
ティング液１Ｎにつき０．６モル以下。a. When using nickel ethoxy ethoxide, zinc ethoxy ethoxide, and iron n-butoxide, the amount is 0.6 mol or less per 1N of ferrite coating liquid.
ｂ１ニッケルアセチルアセトネートと亜鉛エトキシエト
キシドと鉄ｎブトキシドを用いた場合は、フェライトコ
ーティング液１２につき０．３モル以下。When using b1 nickel acetylacetonate, zinc ethoxyethoxide, and iron n-butoxide, the amount is 0.3 mol or less per 12 of the ferrite coating liquid.
またニッケルアセチルアセトネートと亜鉛エトキシエト
キシドと鉄ｎブトキシドを用いた場合、ニッケルアセチ
ルアセトネートのモル数は、鉄ｎブトキシドのモル数の
３倍以下に設定することにより、分散安定性の良いゾル
溶液が得られた。In addition, when using nickel acetylacetonate, zinc ethoxyethoxide, and iron n-butoxide, the number of moles of nickel acetylacetonate is set to 3 times or less than the number of moles of iron n-butoxide, resulting in a sol with good dispersion stability. A solution was obtained.
ニッケルアセチルアセトネートの量がこれを越えると、
亜鉛エトキシエトキシドが反応を起こし、沈殿が生じる
ため、安定した分散性が得られない。If the amount of nickel acetylacetonate exceeds this,
Stable dispersibility cannot be obtained because zinc ethoxyethoxide reacts and precipitates.
また有機溶媒として２−エトキシエタノールを、フェラ
イトコーティング液全体に対して容量で４０％以上配合
した結果、大気中での溶媒の蒸発速度が調整きれ、塗布
作業性が著しく向上し、均一な膜を形成することができ
た。Furthermore, as a result of blending 2-ethoxyethanol as an organic solvent with a volume of at least 40% of the entire ferrite coating liquid, the evaporation rate of the solvent in the atmosphere can be adjusted, the coating workability is significantly improved, and a uniform film can be produced. was able to form.
次に本発明の第１実施例と第２実施例について詳細に説
明する。Next, a first embodiment and a second embodiment of the present invention will be described in detail.
く第１実施例〉
第１図は本実施例にかかるフェライトコーティング液を
製造する装置の概要を示す図である。First Example> FIG. 1 is a diagram showing an outline of an apparatus for producing a ferrite coating liquid according to this example.
同図に示すようにこの装置は、Ｎ、ガス供給装置１と、
除湿器２と、加熱攪拌装置３と、還流装置４によって構
成されている。As shown in the figure, this device includes a nitrogen gas supply device 1,
It is composed of a dehumidifier 2, a heating stirring device 3, and a reflux device 4.
また第２図はこの装置を用いて本実施例にかかるフェラ
イトコーティング液を製造する製造工程を示す図である
。Further, FIG. 2 is a diagram showing a manufacturing process for manufacturing the ferrite coating liquid according to this example using this apparatus.
以下第１図と第２図を用いてフェライトコーティング液
の製造方法を説明する。The method for producing a ferrite coating liquid will be explained below with reference to FIGS. 1 and 2.
まずＮ２ガス供給装置１のＮ２ガスを用いで加熱攪拌装
置３の内部の雰囲気を、除湿器２を通して乾燥させた窒
素で置換しておく。First, the atmosphere inside the heating and stirring device 3 is replaced with nitrogen that has been dried through the dehumidifier 2 using N2 gas from the N2 gas supply device 1.
次に加熱攪拌装置３内に、有機溶媒として２−エトキシ
エタノールを約１ｏｏｍｊ！投入する。Next, approximately 1 oomj of 2-ethoxyethanol was added as an organic solvent into the heating stirring device 3. throw into.
次いでこの液を攪拌しながら、該加熱攪拌装置３内に亜
鉛エトキシエトキシド、ニッケルエトキシエトキシド、
鉄ｎ−ブトキシドのそれぞれのトルエン溶液をこの順番
で投入する。Next, while stirring this liquid, zinc ethoxy ethoxide, nickel ethoxy ethoxide,
Each toluene solution of iron n-butoxide is added in this order.
なおそれぞれのトルエン溶液の濃度は第３図に示す通り
である。但し投入するそれぞれのトルエン溶液の量は同
一としなくてもよい。Note that the concentrations of each toluene solution are as shown in FIG. However, the amounts of each toluene solution to be added may not be the same.
そしてこの混合液を攪拌しながら１０８℃で加熱沸騰さ
せ、この状態を２時間保つ（この操作を「還流」と称す
る）。This mixed solution is then heated to boiling at 108° C. while stirring, and this state is maintained for 2 hours (this operation is referred to as “refluxing”).
その後攪拌を続けたまま約３０℃となるまで放冷する。Thereafter, the mixture is allowed to cool to about 30°C while stirring.
次に水と２−エトキシエタノールと酢酸を混合した溶液
を加熱攪拌装置３内に徐々に加え、加水分解を行なう。Next, a mixed solution of water, 2-ethoxyethanol, and acetic acid is gradually added into the heating stirring device 3 to perform hydrolysis.
ここでこの水の量は次式で与えられる量に等しいモル数
とする。即ち、
〔水の配合量（ｍｏｌ））
＝〔鉄ｎ−ブトキシド（ｍｏｌ） ］ Ｘ ３＋〔ニッ
ケルエトキシエトキシド（ｍｏｌ） ｊ Ｘ Ｑ＋［亜
鉛エトキシエトキシド（ｍｏｌ） ］ Ｘ ２また酢酸
の量は得られるべきフェライトコーティング液全体の量
に対して容量で２％となる量とする。Here, the amount of water is assumed to be the number of moles equal to the amount given by the following equation. That is, [amount of water (mol)) = [iron n-butoxide (mol)] X 3+ [nickel ethoxyethoxide (mol) j X Q+ [zinc ethoxyethoxide (mol)] The amount is 2% by volume of the total amount of ferrite coating liquid to be obtained.
また２−エトキシエタノールと水の混合比率は、容量で
１００：２とした。The mixing ratio of 2-ethoxyethanol and water was 100:2 in terms of volume.
これによって本実施例にかかるフェライトコーティング
液が得られる。As a result, the ferrite coating liquid according to this example is obtained.
次にこのフェライトコーティング液を評価するため、次
のような方法でその比透磁率μ′を測定した。Next, in order to evaluate this ferrite coating liquid, its relative magnetic permeability μ' was measured using the following method.
即ち、まずスピンコーターを用いてこのフェライトコー
ティング液をシリコンウェハー上に塗布し、５００℃で
１０分間仮焼成する。That is, first, this ferrite coating liquid is applied onto a silicon wafer using a spin coater, and pre-baked at 500° C. for 10 minutes.
この操作を１０回繰り返す。Repeat this operation 10 times.
次に第４図に示す温度条件で、大気中で本焼成を行なう
。Next, main firing is performed in the atmosphere under the temperature conditions shown in FIG.
このようにして得られたフェライト薄膜試料を振動式磁
化率測定計で磁化曲線を取り、これより比透磁率μ を
計算した。The magnetization curve of the thus obtained ferrite thin film sample was taken using a vibrating magnetic susceptibility meter, and the relative magnetic permeability μ was calculated from this curve.
ここで第５図にはフェライトコーティング液における有
機金属の配合割合と、該フェライトコーティング液を上
記の方法で膜厚７０００〜８０００人に焼成したときの
比透磁率μ′の関係を示す図である。Here, FIG. 5 is a diagram showing the relationship between the compounding ratio of organic metal in the ferrite coating liquid and the relative magnetic permeability μ' when the ferrite coating liquid is fired to a film thickness of 7000 to 8000 mm using the above method. .
同図に示すように本実施例にかかるフェライトコーティ
ング液によれば、高い比透磁率μ′が得られた。As shown in the figure, a high relative magnetic permeability μ' was obtained with the ferrite coating liquid according to this example.
〈第２実施例〉 第２実施例においても第１図に示す製造装置を用いた。<Second example> The manufacturing apparatus shown in FIG. 1 was also used in the second example.
また第６図はこの装置を用いて本実施例にかかるフェラ
イトコーティング液を製造する製造工程を示す図である
。Further, FIG. 6 is a diagram showing a manufacturing process for manufacturing a ferrite coating liquid according to this example using this apparatus.
以下第１図と第６図を用いてフェライトコーティング液
の製造方法を説明する。The method for producing a ferrite coating liquid will be described below with reference to FIGS. 1 and 6.
まず加熱攪拌装置３内に、ニッケルアセチルアセトネー
トの粉末と有機溶媒たる２−エトキシエタノール（約１
００ｍ１を投入する。First, nickel acetylacetonate powder and organic solvent 2-ethoxyethanol (approximately 1
Inject 00ml.
次いでＮ２ガス供給装置１を用いて加熱攪拌装置３内部
を乾燥窒素で雰囲気置換する。Next, the atmosphere inside the heating stirring device 3 is replaced with dry nitrogen using the N2 gas supply device 1.
次にこの液を１００℃に加熱し、攪拌しながら、前記ニ
ッケルアセチルアセトネートを溶解させた後、鉄ｎ−ブ
トキシドと亜鉛エトキシエトキシドの各トルエン溶液を
この順番で投入する。Next, this liquid is heated to 100°C and, while stirring, the nickel acetylacetonate is dissolved, and then toluene solutions of iron n-butoxide and zinc ethoxyethoxide are added in this order.
なおそれぞれのトルエン溶液の濃度は第７図に示す通り
である。Note that the concentrations of each toluene solution are as shown in FIG.
次にこの液を１０８°Ｃに保ち、２時間還流した後に、
液温８０°Ｃ〜１００°Ｃの状態で、水と２−エトキシ
エタノールと酢酸の混合溶液を加え、加水分解する。Next, this liquid was kept at 108°C and after refluxing for 2 hours,
At a liquid temperature of 80°C to 100°C, a mixed solution of water, 2-ethoxyethanol, and acetic acid is added for hydrolysis.
なおこの混合溶液の調合の方法は前記第１実施例の場合
と同じである。The method for preparing this mixed solution is the same as in the first embodiment.
但し水の配合量は、
〔水の配合量（ｍｏｌ））
＝〔鉄ｎ−ブトキシド（ｍｏｌ） ５ Ｘ ３＋〔ニッ
ケルアセチルアセトネート（ｍｏｌ） ］ Ｘ ２＋〔
亜鉛エトキシエトキシド（ｍｏｌ） ） Ｘ ２である
。However, the amount of water blended is as follows: [Amount of water (mol)] = [Iron n-butoxide (mol) 5 X 3+ [Nickel acetylacetonate (mol)] X 2+ [
Zinc ethoxyethoxide (mol)
そして以上のようにして得られたゾル溶液を室温まで冷
却すれば、本実施例にかかるフェライトコーティング液
が得られる。Then, by cooling the sol solution obtained as described above to room temperature, the ferrite coating liquid according to this example can be obtained.
このフェライトコーティング液の評価も、前記第１実施
例と同じ方法でその比透磁率μ′を測定することによっ
て行なった。This ferrite coating liquid was also evaluated by measuring its relative magnetic permeability μ' in the same manner as in the first example.
第８図にはフェライトコーティング液における有機金属
の配合割合と、該フェライトコーティング液を上記第１
実施例と同じ方法で膜厚３０００〜８０００人に焼成し
たときの比透磁率μ′の関係を示す図である。Figure 8 shows the blending ratio of organic metals in the ferrite coating liquid and the ferrite coating liquid
FIG. 3 is a diagram showing the relationship between relative magnetic permeability μ' when firing to a film thickness of 3,000 to 8,000 layers using the same method as in Examples.
同図に示すように本実施例にかかるフェライトコーティ
ング液によっても、高い比透磁率μ′が得られた。As shown in the figure, a high relative magnetic permeability μ' was also obtained with the ferrite coating liquid according to this example.
以上詳細に説明したように本発明に係るフェライトコー
ティング液によれば、以下のような優れた効果が得られ
た。As described in detail above, the ferrite coating liquid according to the present invention provided the following excellent effects.
（１）金属アルコキシドを含む有機金属を用いたので、
従来の無機金属塩を用いたもののような有害なガスを発
生することはない。(1) Since we used an organic metal containing a metal alkoxide,
Unlike conventional methods using inorganic metal salts, no harmful gases are emitted.
（２）また金属アルコキシドを含む有機金属を本発明の
ように選定したので、加水分解速度が調整され、均一で
安定な特性の良いフェライトコーティング液たるゾル溶
液が得られ、しかも液の保存性、成膜性もよく、大気中
での塗布が可能となった。(2) Furthermore, since an organic metal containing a metal alkoxide is selected as in the present invention, the hydrolysis rate can be adjusted, and a sol solution, which is a ferrite coating liquid that is uniform and stable, and has good properties can be obtained, and the storage stability of the liquid can be improved. It has good film-forming properties and can be applied in the atmosphere.
第１図は本発明にかかるフェライトコーティング液を製
造する装置の概要を示す図、第２図はこの装置を用いて
第１実施例にかかるフェライトコーティング液を製造す
る製造工程を示す図、第３図はそれぞれの有機金属トル
エン溶液の濃度を示す図、第４図はこのフェライトコー
ティング液を大気中で本焼成する場合の温度条件を示す
図、第５図はフェライトコーティング液における有機金
属化合物の配合割合と、該フェライトコーティンダ液を
膜厚７０００〜８０００人に焼成したときの比透磁率μ
′の関係を示す図、第６図は第２実施例にかかるフェラ
イトコーティング液を製造する製造工程を示す図、第７
図はそれぞれの有機金属トルエン溶液の濃度を示す図、
第８図はフェライトコーティング液における有機金属化
合物の配合割合と、該フェライトコーティング液を膜厚
３０００〜８０００人に焼成したときの比透磁率μ′の
関係を示す図である。
特許出願人 帝国通信工業株式会社
代理人 弁理士 熊 谷 隆（外１名）第３
第４
第５
第６
図
第７図
ネ順厚３α℃ト＆工０人
第８
図FIG. 1 is a diagram showing an outline of an apparatus for manufacturing a ferrite coating liquid according to the present invention, FIG. 2 is a diagram showing a manufacturing process for manufacturing a ferrite coating liquid according to a first embodiment using this apparatus, and FIG. The figure shows the concentration of each organometallic toluene solution, Figure 4 shows the temperature conditions when this ferrite coating liquid is fired in the air, and Figure 5 shows the composition of the organometallic compound in the ferrite coating liquid. ratio and relative magnetic permeability μ when the ferrite coating indica liquid is fired to a film thickness of 7,000 to 8,000
' Figure 6 is a diagram showing the manufacturing process for manufacturing the ferrite coating liquid according to the second embodiment;
The figure shows the concentration of each organometallic toluene solution,
FIG. 8 is a diagram showing the relationship between the blending ratio of the organometallic compound in the ferrite coating liquid and the relative magnetic permeability μ' when the ferrite coating liquid is fired to a film thickness of 3000 to 8000 mm. Patent Applicant Teikoku Tsushin Kogyo Co., Ltd. Agent Patent Attorney Takashi Kumagai (1 other person) No. 3 No. 4 No. 5 No. 6 Fig. 7
Claims (7)
子団）で表わされる有機金属化合物と一般式Ｍ〔ＯＲ〕
＿２（但しＭは２価の金属元素）で表わされる有機金属
化合物と有機溶媒より成る組成物に、有機溶媒で希釈し
た水を加えて加水分解して製造されるゾル溶液より成り
、以下の（Ａ）と（Ｂ）の要件を具備することを特徴と
するフェライトコーティング液。 （Ａ）前記Ｒは以下の（ａ−１）乃至（ａ−３）の化学
式で示される原子団の内、少なくとも１種類以上の原子
団から選ばれたものであること。 （ａ−１）−ｎＣ＿４Ｈ＿９（ｎ−ブチル基）（ａ−２
）−Ｃ＿２Ｈ＿４−Ｏ−Ｃ＿２Ｈ＿５（ａ−３）▲数式
、化学式、表等があります▼ （Ｂ）酸を含有すること。(1) Organometallic compound represented by the general formula Fe[OR]_3 (where R is an atomic group containing carbon) and the general formula M[OR]
It consists of a sol solution produced by adding water diluted with an organic solvent to a composition consisting of an organometallic compound represented by _2 (where M is a divalent metal element) and an organic solvent and hydrolyzing it, and the following ( A ferrite coating liquid characterized by meeting the requirements of A) and (B). (A) Said R is selected from at least one type of atomic group represented by the following chemical formulas (a-1) to (a-3). (a-1)-nC_4H_9 (n-butyl group) (a-2
)-C_2H_4-O-C_2H_5 (a-3) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (B) Contains acid.
ｏ，Ｍｇ又はＣｕの内、少なくとも１種類以上の元素か
ら選ばれたものであることを特徴とする請求項（１）記
載のフェライトコーティング液。(2) The divalent metal element M is Ni, Zn, Mn, C
2. The ferrite coating liquid according to claim 1, wherein the ferrite coating liquid is at least one element selected from among O, Mg, and Cu.
特徴とする請求項（１）又は（２）記載のフェライトコ
ーティング液。 （Ａ）前記Ｆｅ（ＯＲ）＿３は鉄ｎブトキシド｛Ｆｅ（
Ｏ・Ｃ＿４Ｈ＿９）＿３｝であり、前記Ｎｉ（ＯＲ）＿
２はニッケルエトキシエトキシド｛Ｎｉ（Ｏ・Ｃ＿２Ｈ
＿４・Ｏ・Ｃ＿２Ｈ＿５）＿２｝であり、前記Ｚｎ（Ｏ
Ｒ）＿２は亜鉛エトキシエトキシド｛Ｚｎ（Ｏ・Ｃ＿２
Ｈ＿４・Ｏ・Ｃ＿２Ｈ＿５）＿２｝であること。 （Ｂ）前記有機金属化合物の含有量の総量は、フェライ
トコーティング液１ｌにつき０．６モル以下であること
。(3) The ferrite coating liquid according to claim (1) or (2), which satisfies the following requirements (A) and (B). (A) The above Fe(OR)_3 is iron n-butoxide {Fe(
O・C_4H_9)_3}, and the Ni(OR)_
2 is nickel ethoxyethoxide {Ni(O・C_2H
_4・O・C_2H_5)_2}, and the Zn(O
R)_2 is zinc ethoxyethoxide {Zn(O・C_2
H_4・O・C_2H_5)_2}. (B) The total content of the organometallic compound is 0.6 mol or less per liter of ferrite coating liquid.
を具備することを特徴とする請求項（１）又は（２）記
載のフェライトコーティング液。 （Ａ）前記Ｆｅ（ＯＲ）＿３は鉄ｎブトキシド｛Ｆｅ（
Ｏ・Ｃ＿４Ｈ＿９）＿３｝であり、前記Ｎｉ（ＯＲ）＿
２はニッケルアセチルアセトネート ▲数式、化学式、表等があります▼ であり、前記Ｚｎ（ＯＲ）＿２は亜鉛エトキシエトキシ
ド｛Ｚｎ（Ｏ・Ｃ＿２Ｈ＿４・Ｏ・Ｃ＿２Ｈ＿５）＿２
｝であること。 （Ｂ）前記ニッケルアセチルアセトネートと鉄ｎブトキ
シドを混合した後に前記亜鉛エトキシエトキシドを混合
したこと。 （Ｃ）前記有機金属化合物の含有量の総量は、フェライ
トコーティング液１ｌにつき０．３モル以下であること
。 （Ｄ）前記ニッケルアセチルアセトネートの配合量は、
分子数にして鉄ｎブトキシドの３倍以下であること。(4) The ferrite coating liquid according to claim (1) or (2), which satisfies the following requirements (A), (B), (C), and (D). (A) The above Fe(OR)_3 is iron n-butoxide {Fe(
O・C_4H_9)_3}, and the Ni(OR)_
2 is nickel acetylacetonate▲There are mathematical formulas, chemical formulas, tables, etc.▼, and the above Zn(OR)_2 is zinc ethoxyethoxide {Zn(O・C_2H_4・O・C_2H_5)_2
}. (B) After mixing the nickel acetylacetonate and iron n-butoxide, the zinc ethoxyethoxide was mixed. (C) The total content of the organometallic compound is 0.3 mol or less per liter of ferrite coating liquid. (D) The blending amount of the nickel acetylacetonate is:
The number of molecules must be less than three times that of iron n-butoxide.
ティング液全体に対して、容量で０．５％以上、２％以
下であることを特徴とする請求項（１），（２），（３
）又は（４）記載のフェライトコーティング液。(5) Claims (1), (2), wherein the acid is acetic acid, and the amount thereof is 0.5% or more and 2% or less by volume based on the entire ferrite coating liquid. (3
) or the ferrite coating liquid described in (4).
ことを特徴とする請求項（１），（２），（３），（４
）又は（５）記載のフェライトコーティング液。(6) Claims (1), (2), (3), and (4) characterized in that the acid is blended with water diluted with the organic solvent.
) or the ferrite coating liquid described in (5).
に対して容量で４０％以上の２−エトキシエタノールを
含有していることを特徴とする請求項（１），（２），
（３），（４），（５）又は（６）記載のフェライトコ
ーティング液。(7) Claims (1), (2), wherein the organic solvent contains 2-ethoxyethanol in an amount of 40% or more by volume based on the entire ferrite coating liquid.
The ferrite coating liquid according to (3), (4), (5) or (6).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2104584A JPH0758645B2 (en) | 1990-04-20 | 1990-04-20 | Ferrite coating liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2104584A JPH0758645B2 (en) | 1990-04-20 | 1990-04-20 | Ferrite coating liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH043402A true JPH043402A (en) | 1992-01-08 |
| JPH0758645B2 JPH0758645B2 (en) | 1995-06-21 |
Family
ID=14384487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2104584A Expired - Lifetime JPH0758645B2 (en) | 1990-04-20 | 1990-04-20 | Ferrite coating liquid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0758645B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0743284A1 (en) * | 1995-05-15 | 1996-11-20 | Matsushita Electric Industrial Co., Ltd | Paste for manufacturing ferrite and ferrite |
| TWI550041B (en) * | 2012-03-29 | 2016-09-21 | Mitsubishi Materials Corp | A method for forming a ferrous film for fat and iron, and a method for forming a ferritic iron film and a fat iron film formed by the method |
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| JPS59213603A (en) * | 1983-05-13 | 1984-12-03 | Kanegafuchi Chem Ind Co Ltd | Manufacture of thin film of composite material |
| JPS61136683A (en) * | 1984-12-07 | 1986-06-24 | Fuji Photo Film Co Ltd | Production of thin hexagonal ferrite film |
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1990
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|---|---|---|---|---|
| JPS59213665A (en) * | 1983-05-13 | 1984-12-03 | 鐘淵化学工業株式会社 | Functional inorganic thin film and manufacture |
| JPS59213603A (en) * | 1983-05-13 | 1984-12-03 | Kanegafuchi Chem Ind Co Ltd | Manufacture of thin film of composite material |
| JPS61136683A (en) * | 1984-12-07 | 1986-06-24 | Fuji Photo Film Co Ltd | Production of thin hexagonal ferrite film |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0743284A1 (en) * | 1995-05-15 | 1996-11-20 | Matsushita Electric Industrial Co., Ltd | Paste for manufacturing ferrite and ferrite |
| US5698131A (en) * | 1995-05-15 | 1997-12-16 | Matsushita Electric Industrial Co., Ltd. | Paste for manufacturing ferrite and ferrite |
| TWI550041B (en) * | 2012-03-29 | 2016-09-21 | Mitsubishi Materials Corp | A method for forming a ferrous film for fat and iron, and a method for forming a ferritic iron film and a fat iron film formed by the method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0758645B2 (en) | 1995-06-21 |
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