JP2017179316A - Coating liquid for forming silica-based insulation film and manufacturing method therefor - Google Patents
Coating liquid for forming silica-based insulation film and manufacturing method therefor Download PDFInfo
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- 239000011248 coating agent Substances 0.000 title claims abstract description 165
- 238000000576 coating method Methods 0.000 title claims abstract description 165
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 158
- 239000007788 liquid Substances 0.000 title claims abstract description 97
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 79
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 41
- 238000009413 insulation Methods 0.000 title abstract description 17
- 229920002050 silicone resin Polymers 0.000 claims abstract description 95
- 239000002904 solvent Substances 0.000 claims abstract description 59
- 238000003756 stirring Methods 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000003377 acid catalyst Substances 0.000 claims description 9
- 239000006247 magnetic powder Substances 0.000 abstract description 88
- 230000007547 defect Effects 0.000 abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 133
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 76
- 239000000843 powder Substances 0.000 description 53
- 239000002245 particle Substances 0.000 description 39
- 239000010410 layer Substances 0.000 description 33
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 30
- 229910004298 SiO 2 Inorganic materials 0.000 description 28
- 239000000428 dust Substances 0.000 description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 27
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 27
- 238000010438 heat treatment Methods 0.000 description 27
- 229910052742 iron Inorganic materials 0.000 description 23
- 238000004090 dissolution Methods 0.000 description 20
- 239000000203 mixture Substances 0.000 description 20
- 229910000398 iron phosphate Inorganic materials 0.000 description 19
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 19
- 238000000465 moulding Methods 0.000 description 19
- 239000012298 atmosphere Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 238000004458 analytical method Methods 0.000 description 15
- 239000011812 mixed powder Substances 0.000 description 15
- 238000001035 drying Methods 0.000 description 13
- 239000011261 inert gas Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 10
- 229910019142 PO4 Inorganic materials 0.000 description 9
- 230000007423 decrease Effects 0.000 description 9
- 239000000314 lubricant Substances 0.000 description 9
- 239000013081 microcrystal Substances 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 9
- 239000010452 phosphate Substances 0.000 description 9
- 238000011282 treatment Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 238000010304 firing Methods 0.000 description 8
- 229910001004 magnetic alloy Inorganic materials 0.000 description 6
- 230000002093 peripheral effect Effects 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 5
- 230000004907 flux Effects 0.000 description 5
- 230000001133 acceleration Effects 0.000 description 4
- 239000000696 magnetic material Substances 0.000 description 4
- 239000006249 magnetic particle Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005211 surface analysis Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 229910020516 Co—V Inorganic materials 0.000 description 1
- 229910017061 Fe Co Inorganic materials 0.000 description 1
- 229910017060 Fe Cr Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910002544 Fe-Cr Inorganic materials 0.000 description 1
- 229910017082 Fe-Si Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910017133 Fe—Si Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000700 radioactive tracer Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
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- Paints Or Removers (AREA)
- Soft Magnetic Materials (AREA)
- Organic Insulating Materials (AREA)
Abstract
Description
本発明は、高抵抗かつ高磁束密度の圧粉磁心の製造に好適なシリカ系絶縁皮膜形成用コーティング液およびその製造方法に関する。 The present invention relates to a coating liquid for forming a silica-based insulating film suitable for producing a dust core having high resistance and high magnetic flux density, and a method for producing the same.
従来、モーター用コア、アクチュエーター、磁気センサーなどの磁心として、Ｆｅ粉末またはＦｅ合金粉末などの軟磁性粉末に樹脂粉末を添加して混合粉末を作製し、この混合粉末を圧縮成形した後、熱処理して得られた圧粉磁心が知られている。
前記軟磁性粉末を用いて圧粉磁心を製造する場合、軟磁性粉末単体では比抵抗が低いため、軟磁性粉末の表面に絶縁皮膜の被覆を行うか、有機化合物や絶縁材を混合するなどして軟磁性粉末どうしの焼結を防止し、比抵抗を上げる対策が講じられている。例えば、この種の圧粉磁心において、渦電流損失を抑制するため、軟磁性粉末の表面を非鉄金属の下層絶縁皮膜と無機化合物を含む上層絶縁皮膜で２重に覆ってから成形し、熱処理した構造が知られている。
Conventionally, as a magnetic core for motor cores, actuators, magnetic sensors, etc., a resin powder is added to soft magnetic powder such as Fe powder or Fe alloy powder to produce a mixed powder, and this mixed powder is compression molded and then heat treated. The powder magnetic core obtained by this is known.
When producing a powder magnetic core using the soft magnetic powder, the soft magnetic powder itself has a low specific resistance, so the surface of the soft magnetic powder is covered with an insulating film, or an organic compound or an insulating material is mixed. Therefore, measures are taken to prevent sintering of soft magnetic powders and increase specific resistance. For example, in this type of powder magnetic core, in order to suppress eddy current loss, the surface of the soft magnetic powder is covered with a non-ferrous metal lower insulating film and an upper insulating film containing an inorganic compound, and then molded and heat-treated. The structure is known.
前記圧粉磁心の一例として、軟磁性粉末の表面にリン酸塩被覆を形成した後、バインダーとしてシリコーン樹脂を添加して混合し、シリコーン樹脂被覆軟磁性粉末としてから圧縮成形し、熱処理した圧粉磁心が知られている。
この圧粉磁心（複合軟磁性材）は、軟磁性粉末粒子どうしがシリコーン樹脂被覆を介し接合された組織を有し、樹脂被覆層により軟磁性粉末粒子どうしの絶縁が確保されているので渦電流損失を抑制できる。
また、この種の圧粉磁心（複合軟磁性材）の一例として、リン酸塩被覆鉄粉の表面にプライマ処理を施し、プライマ処理後の鉄粉にフッ素樹脂粉末を添加し混合して混合粉末を作製し、この混合粉末を圧縮成形した後、熱処理を施して複合軟磁性材を得る技術が提案されている（特許文献１参照）。前記プライマ処理とは、ポリエーテルスルホン、ポリアミドイミド、ポリイミド、シリコーン樹脂等の１種以上とポリテトラフルオロエチレンを溶解または分散した液をリン酸塩被覆鉄粉の表面に塗布し、乾燥する処理を意味する。
As an example of the powder magnetic core, after forming a phosphate coating on the surface of the soft magnetic powder, a silicone resin is added and mixed as a binder, and then the silicone resin-coated soft magnetic powder is compression-molded and heat-treated. Magnetic core is known.
This powder magnetic core (composite soft magnetic material) has a structure in which soft magnetic powder particles are bonded via a silicone resin coating, and the insulation between the soft magnetic powder particles is ensured by the resin coating layer. Loss can be suppressed.
In addition, as an example of this type of powder magnetic core (composite soft magnetic material), the surface of the phosphate-coated iron powder is subjected to a primer treatment, and then the fluororesin powder is added to and mixed with the iron powder after the primer treatment. A technique has been proposed in which a composite soft magnetic material is obtained by applying heat treatment after compression molding of the mixed powder (see Patent Document 1). The primer treatment is a treatment in which a solution obtained by dissolving or dispersing one or more of polyethersulfone, polyamideimide, polyimide, silicone resin and the like and polytetrafluoroethylene is applied to the surface of the phosphate-coated iron powder and dried. means.
ところで、電子機器用電磁気部品は、電子機器の小型化、高性能化に伴い、より優れた材料特性が求められ、更に実使用状態において問題を生じない電磁気部品であることが必要になってきている。このような電磁気部品に用いられる軟磁性材について検討すると、シリコーンレジンに代表される絶縁性樹脂で軟磁性粉末を覆った混合粉末を用いて製造した圧粉磁心は耐熱性に不足を生じ易く、比抵抗も十分に高くできないという問題がある。例えば、５００〜６００℃もの高温で焼成すると、絶縁性樹脂が劣化するので、軟磁性粉末粒子どうしを良好に絶縁することが難しくなり、比抵抗が低下する問題がある。
シリコーンレジンで覆った構造の軟磁性粉末は、通常、溶媒にシリコーンレジンを添加混合してコーティング液を作製し、このコーティング液を軟磁性粉末に塗布し、乾燥させることで得ている。このコーティング液中にはシリコーンレジンが含まれているので、塗布乾燥後に軟磁性粉末を覆った被覆層にはシリコーンレジンが含まれ、この被覆層が絶縁性を発揮するが、従来の被覆層では上述したように比抵抗を十分に高くできない問題があった。
By the way, with the miniaturization and high performance of electronic devices, electromagnetic components for electronic devices are required to have better material properties, and have become necessary to be electromagnetic components that do not cause problems in actual use conditions. Yes. When examining the soft magnetic material used for such electromagnetic parts, the dust core produced by using the mixed powder in which the soft magnetic powder is covered with an insulating resin typified by silicone resin is likely to have insufficient heat resistance, There is a problem that the specific resistance cannot be sufficiently high. For example, when the baking is performed at a high temperature of 500 to 600 ° C., the insulating resin deteriorates, so that it is difficult to satisfactorily insulate the soft magnetic powder particles, and there is a problem that the specific resistance is lowered.
A soft magnetic powder having a structure covered with a silicone resin is usually obtained by adding a silicone resin to a solvent to prepare a coating solution, applying the coating solution to the soft magnetic powder, and drying the coating solution. Since this coating liquid contains a silicone resin, the coating layer that covers the soft magnetic powder after coating and drying contains the silicone resin, and this coating layer exhibits insulation properties. As described above, there is a problem that the specific resistance cannot be sufficiently increased.
本発明は前記の問題に鑑み創案されたものであり、その目的は、耐熱性に優れ比抵抗が高いシリカ系絶縁皮膜を形成するためのコーティング液の提供とその製造方法を提供することにある。 The present invention was devised in view of the above problems, and an object of the present invention is to provide a coating liquid for forming a silica-based insulating film having excellent heat resistance and high specific resistance, and a method for producing the same. .
（１）上記目的を達成するために本発明のコーティング液は、Ｓｉアルコキシドとシリコーンレジンが溶媒中に混合され、２５℃、５０ｒｐｍで測定した粘度が２．８〜５．５ｍＰａ・ｓであることを特徴とする。
Ｓｉアルコキシドとシリコーンレジンが溶媒中に含まれ、粘度を２．８〜５．５ｍＰａ・ｓの範囲としたコーティング液であるならば、比抵抗が高く、耐熱性に優れたシリカ系絶縁皮膜を得ることができる。２５℃、５０ｒｐｍで測定したコーティング液の粘度が２．８〜５．５ｍＰａ・ｓであるならば、粉末表面に塗布した場合、コーティング液の付き回り性が良く、この範囲の粘度値を有するコーティング液を表面に有する軟磁性粉末を用いて作製した圧粉磁心は比抵抗が高く、耐熱性に優れる。
この範囲の粘度に調整されているならば、Ｓｉアルコキシドとシリコーンレジンが溶媒中に十分緻密に分散されているので、この粘度範囲のコーティング液を乾燥して得た皮膜は欠陥が少なく緻密な皮膜となる。
（２）本発明のコーティング液において、前記溶媒に酸触媒と水が添加されたことが好ましい。
溶媒中に酸触媒と水が添加されていることで加水分解液（シリカ系絶縁皮膜形成用コーティング液）とすることができ、溶媒中にＳｉアルコキシドとシリコーンレジンを均一分散できる。
(1) In order to achieve the above object, the coating liquid of the present invention is prepared by mixing Si alkoxide and silicone resin in a solvent and having a viscosity measured at 25 ° C. and 50 rpm is 2.8 to 5.5 mPa · s. It is characterized by.
If the coating liquid contains Si alkoxide and silicone resin in a solvent and has a viscosity in the range of 2.8 to 5.5 mPa · s, a silica-based insulating film having high specific resistance and excellent heat resistance is obtained. be able to. If the viscosity of the coating solution measured at 25 ° C. and 50 rpm is 2.8 to 5.5 mPa · s, the coating solution has good throwing power when applied to the powder surface and has a viscosity value in this range. A dust core made of soft magnetic powder having a liquid on its surface has high specific resistance and excellent heat resistance.
If the viscosity is adjusted within this range, the Si alkoxide and the silicone resin are sufficiently densely dispersed in the solvent. Therefore, the coating obtained by drying the coating liquid in this viscosity range is a dense coating with few defects. It becomes.
(2) In the coating liquid of the present invention, it is preferable that an acid catalyst and water are added to the solvent.
By adding an acid catalyst and water to the solvent, a hydrolyzed solution (silica-based insulating film forming coating solution) can be obtained, and the Si alkoxide and the silicone resin can be uniformly dispersed in the solvent.
（３）本発明のコーティング液において、溶媒にＳｉアルコキシドとシリコーンレジンが混合された液であって、粘度値が最終的な粘度到達値の±２％の範囲内であることが好ましい。
この範囲の粘度値であるならば、Ｓｉアルコキシドとシリコーンレジンが溶媒中に十分に均一混合されているので、コーティング液から形成した塗膜は耐熱性に優れた比抵抗の高いシリカ系絶縁皮膜となる。
(3) The coating liquid of the present invention is a liquid in which a Si alkoxide and a silicone resin are mixed in a solvent, and the viscosity value is preferably within a range of ± 2% of the final viscosity reached value.
If the viscosity value is within this range, since the Si alkoxide and the silicone resin are sufficiently uniformly mixed in the solvent, the coating film formed from the coating liquid is a silica-based insulating film having excellent heat resistance and high specific resistance. Become.
（４）本発明のコーティング液の製造方法は、Ｓｉアルコキシドとシリコーンレジンを溶媒に添加して撹拌、混合することにより２５℃、５０ｒｐｍで測定した粘度を２．８〜５．５ｍＰａ・ｓとすることを特徴とする。
Ｓｉアルコキシドとシリコーンレジンが溶媒中に含まれ、粘度を２．８〜５．５ｍＰａ・ｓの範囲としたコーティング液であるならば、比抵抗が高く、耐熱性に優れたシリカ系絶縁皮膜を得ることができる。
（５）本発明のコーティング液の製造方法において、前記溶媒に酸触媒と水を添加することが好ましい。
溶媒中に酸触媒と水が添加されていることで加水分解液（シリカ系絶縁皮膜形成用コーティング液）とすることができ、溶媒中にＳｉアルコキシドとシリコーンレジンを均一分散できる。
（６）本発明のコーティング液の製造方法は、前記Ｓｉアルコキシドとシリコーンレジンを溶媒に添加後、２時間以上撹拌混合することを特徴とする。
２時間以上混合撹拌することでＳｉアルコキシドとシリコーンレジンを溶媒中に十分に均一分散させ、混合することができる。２時間以上混合することにより粘度値を安定した範囲としたコーティング液にできる。
(4) In the method for producing the coating liquid of the present invention, the viscosity measured at 25 ° C. and 50 rpm is adjusted to 2.8 to 5.5 mPa · s by adding Si alkoxide and silicone resin to a solvent and stirring and mixing. It is characterized by that.
If the coating liquid contains Si alkoxide and silicone resin in a solvent and has a viscosity in the range of 2.8 to 5.5 mPa · s, a silica-based insulating film having high specific resistance and excellent heat resistance is obtained. be able to.
(5) In the manufacturing method of the coating liquid of this invention, it is preferable to add an acid catalyst and water to the said solvent.
By adding an acid catalyst and water to the solvent, a hydrolyzed solution (silica-based insulating film forming coating solution) can be obtained, and the Si alkoxide and the silicone resin can be uniformly dispersed in the solvent.
(6) The method for producing a coating liquid of the present invention is characterized in that the Si alkoxide and the silicone resin are added to a solvent and then stirred and mixed for 2 hours or more.
By mixing and stirring for 2 hours or more, the Si alkoxide and the silicone resin can be sufficiently uniformly dispersed and mixed in the solvent. By mixing for 2 hours or more, a coating liquid having a stable viscosity value can be obtained.
本発明のコーティング液によれば、比抵抗が高く、耐熱性に優れたシリカ系絶縁皮膜を提供できる。よって、このシリカ系絶縁皮膜を有する軟磁性粉末であれば、６５０℃などに高温加熱されても比抵抗の低下が少なく、耐熱性に優れる軟磁性粉末を提供できる。
また、本発明のコーティング液によるシリカ系絶縁皮膜を有する軟磁性粉末からなる圧粉磁心であるならば、高温の熱処理を経たとしても絶縁性に優れているので、比抵抗の高い耐熱性に優れた圧粉磁心を提供できる。
According to the coating liquid of the present invention, a silica-based insulating film having high specific resistance and excellent heat resistance can be provided. Therefore, if it is a soft magnetic powder having this silica-based insulating film, it is possible to provide a soft magnetic powder that has little decrease in specific resistance and is excellent in heat resistance even when heated to 650 ° C. at a high temperature.
In addition, if it is a dust core made of a soft magnetic powder having a silica-based insulating film with the coating liquid of the present invention, it is excellent in insulation even after being subjected to high-temperature heat treatment, so it has excellent heat resistance with high specific resistance. Can provide a dust core.
以下に本発明を詳細に説明するが、本発明は以下に説明する実施形態に限定されるものではない。
図１は本発明に係るコーティング液を用いて製造されたシリカ系絶縁被覆軟磁性粉末を示すもので、この形態のシリカ系絶縁被覆軟磁性粉末Ｂは、純鉄粉末などの軟磁性粉末５の周囲にリン酸塩皮膜６が被覆され、その周囲にシリカ系絶縁皮膜７が被覆されている。
軟磁性粉末５は一例として純鉄粉末粒子からなり、平均粒径（Ｄ５０）：５〜５００μｍの範囲内にある純鉄粉末５を主体とすることが好ましい。その理由は、平均粒径が５μｍより小さすぎると、純鉄粉末粒子の圧縮性が低下し、純鉄粉末粒子の体積割合が低くなるために磁束密度の値が低下する傾向があり、一方、平均粒径が５００μｍより大きすぎると、純鉄粉末内部の渦電流が増大して高周波における透磁率が低下するなどの理由によるものである。
なお、純鉄系の軟磁性粉末の平均粒径はレーザー回折法による測定で得られる粒径である。
リン酸塩皮膜６は、例えば、リン酸鉄皮膜、リン酸亜鉛皮膜、リン酸マンガン皮膜、リン酸カルシウム皮膜などからなる。なお、このリン酸塩皮膜６は本実施形態において必須ではなく、略しても良い。
The present invention will be described in detail below, but the present invention is not limited to the embodiments described below.
FIG. 1 shows a silica-based insulating coated soft magnetic powder produced by using the coating liquid according to the present invention. The silica-based insulating coated soft magnetic powder B of this embodiment is a soft magnetic powder 5 such as pure iron powder. A phosphate film 6 is coated around the periphery, and a silica-based insulating film 7 is coated therearound.
As an example, the soft magnetic powder 5 is composed of pure iron powder particles, and it is preferable that the soft magnetic powder 5 is mainly composed of pure iron powder 5 having an average particle diameter (D50) in the range of 5 to 500 μm. The reason is that if the average particle size is too small than 5 μm, the compressibility of the pure iron powder particles decreases, and the volume ratio of the pure iron powder particles tends to decrease, so the value of the magnetic flux density tends to decrease, If the average particle size is too large, the eddy current inside the pure iron powder increases and the magnetic permeability at high frequency decreases.
The average particle size of the pure iron-based soft magnetic powder is a particle size obtained by measurement by a laser diffraction method.
The phosphate film 6 is made of, for example, an iron phosphate film, a zinc phosphate film, a manganese phosphate film, a calcium phosphate film, or the like. The phosphate film 6 is not essential in the present embodiment, and may be omitted.
なお、軟磁性粉末５を構成する粒子は、純鉄粉末粒子に限るものではなく、Ｆｅ−Ｓｉ系鉄基軟磁性合金粉末粒子、Ｆｅ−Ｓｉ−Ａｌ系鉄基軟磁性合金粉末粒子、Ｆｅ−Ｎｉ系合金粉末粒子、Ｆｅ−Ｃｏ系鉄基軟磁性合金粉末粒子、Ｆｅ−Ｃｏ−Ｖ系鉄基軟磁性合金粉末粒子、Ｆｅ−Ｐ系鉄基軟磁性合金粉末粒子、Ｆｅ−Ｃｒ系Ｆｅ基合金粉末粒子などの軟磁性合金粒子一般に広く適用できるのは勿論である。 The particles constituting the soft magnetic powder 5 are not limited to pure iron powder particles. Fe-Si-based iron-based soft magnetic alloy powder particles, Fe-Si-Al-based iron-based soft magnetic alloy powder particles, Fe-- Ni-based alloy powder particles, Fe-Co-based iron-based soft magnetic alloy powder particles, Fe-Co-V-based iron-based soft magnetic alloy powder particles, Fe-P-based iron-based soft magnetic alloy powder particles, Fe-Cr-based Fe group Of course, soft magnetic alloy particles such as alloy powder particles can be widely applied in general.
図２は図１に示す第１実施形態のシリカ系絶縁被覆軟磁性粉末Ｂを圧縮成形し、熱処理することで得られた圧粉磁心の組織構造の一例を示す模式図であり、この実施形態の圧粉磁心Ａは、複数の軟磁性粉末粒子１１をそれらの間に粒界層１２を介在させて結合することで構成されている。また、各軟磁性粉末粒子１１の外周には上述のリン酸塩皮膜からなる下地皮膜１３が形成されている。
図２においては２つの軟磁性粉末粒子１１の一部分とそれらの間に存在する粒界層１２の一部分のみ表しているが圧粉磁心Ａは多数の軟磁性粉末粒子１１を個々に粒界層１２を介し接合して一体化し、目的の形状に成形されている。
FIG. 2 is a schematic diagram showing an example of the structure of a dust core obtained by compression-molding and heat-treating the silica-based insulation-coated soft magnetic powder B of the first embodiment shown in FIG. The powder magnetic core A is configured by joining a plurality of soft magnetic powder particles 11 with a grain boundary layer 12 interposed therebetween. Further, a base coating 13 made of the above-described phosphate coating is formed on the outer periphery of each soft magnetic powder particle 11.
In FIG. 2, only a part of two soft magnetic powder particles 11 and a part of the grain boundary layer 12 existing between them are shown, but the dust core A has a large number of soft magnetic powder particles 11 individually connected to the grain boundary layer 12. Are joined and integrated into a desired shape.
圧粉磁心Ａの電磁気部品への適用例として図３に示す平面視レーストラック形状かつ環状のリアクトルコア１４ａを例示できる。リアクトルコア１４ａの直線部分に巻線によるコイル部１４ｂ、１４ｂを形成し、リアクトル１４が構成されている。
図２に示すリアクトルコア１４ａは、後述する複数のシリカ系絶縁被覆軟磁性粉末と結着材を混合して金型に投入し、金型を用いて目的の環状に圧縮成形し、成形後に焼成することで得られる。
As an example of application of the dust core A to an electromagnetic component, a planar racetrack shape and annular reactor core 14a shown in FIG. 3 can be exemplified. Reactor 14 is formed by forming coil portions 14b and 14b by windings in a straight portion of the reactor core 14a.
The reactor core 14a shown in FIG. 2 is a mixture of a plurality of silica-based insulating coated soft magnetic powders and a binder, which will be described later, and put into a mold, compression-molded into a target ring using the mold, and fired after molding. It is obtained by doing.
圧粉磁心Ａの粒界層１２は、以下に説明する方法により製造されたシリカ系絶縁皮膜の焼成物からなる。圧粉磁心Ａは、シリコーンレジンとＴＥＯＳ（テトラエトキシシラン：Ｓｉ（ＯＣ２Ｈ５）４：Ｓｉアルコキシド）を溶媒に溶解または分散させた後述するコーティング液を下地皮膜付きの軟磁性粉末に塗布し、この粉末を乾燥後、潤滑剤とともに成形用の金型に必要量投入し、目的の形状に成形後、熱処理して得られる。 The grain boundary layer 12 of the dust core A is made of a fired product of a silica-based insulating film produced by the method described below. The powder magnetic core A is obtained by applying a coating liquid, which will be described later, in which a silicone resin and TEOS (tetraethoxysilane: Si (OC 2 H 5 ) 4 : Si alkoxide) are dissolved or dispersed in a solvent to a soft magnetic powder with an undercoat. The powder is dried, put into a molding die together with a lubricant, in a required amount, molded into a desired shape, and then heat treated.
以下、圧粉磁心Ａを製造する工程について詳しく説明する。
圧粉磁心Ａを製造するには、まず、軟磁性粉末の外周に塗布するコーティング液を作製する。コーティング液を作製するには、図４、図５（Ａ）に示すようにＩＰＡ（２−プロパノール）などの溶媒１５を２５〜５０℃程度の温度に加熱しながらこの溶媒を２〜２４時間程度攪拌しつつこの溶媒１５にシリコーンレジン１６を溶解する（溶解工程）。
Hereinafter, the process of manufacturing the dust core A will be described in detail.
In order to manufacture the powder magnetic core A, first, a coating liquid to be applied to the outer periphery of the soft magnetic powder is prepared. In order to prepare the coating liquid, as shown in FIGS. 4 and 5A, the solvent 15 such as IPA (2-propanol) is heated to a temperature of about 25 to 50 ° C. for about 2 to 24 hours. The silicone resin 16 is dissolved in the solvent 15 with stirring (dissolution step).
この溶解工程で用いる溶媒１５は、ＩＰＡの他にエタノール、１−ブタノールなどであっても良い。
加熱温度は、２５℃未満であると、シリコーンレジン１６の溶解が不十分となる可能性があり、５０℃を超える場合は溶媒の蒸発が進みやすくなり、シリコーンレジン１６が溶媒中に十分に分散しない状態となることが問題となる。
溶解撹拌時間は２時間以上とすることが望ましいが、溶解撹拌時間が短時間では溶解が不十分となり易く、２４時間を超える溶解撹拌時間を設定しても、時間が無駄になる。このため、溶解撹拌時間は２〜１２時間程度が望ましい。
溶媒１５に対するシリコーンレジン１６の溶解量は、溶媒１Ｌに対しシリコーンレジン２０ｇ〜３５０ｇ程度が好ましい。
The solvent 15 used in this dissolution step may be ethanol, 1-butanol, etc. in addition to IPA.
If the heating temperature is less than 25 ° C., the silicone resin 16 may not be sufficiently dissolved. If the heating temperature exceeds 50 ° C., the solvent tends to evaporate, and the silicone resin 16 is sufficiently dispersed in the solvent. It becomes a problem to be in a state where it does not.
The dissolution stirring time is desirably 2 hours or more. However, if the dissolution stirring time is short, dissolution tends to be insufficient, and even if a dissolution stirring time exceeding 24 hours is set, time is wasted. For this reason, the dissolution stirring time is desirably about 2 to 12 hours.
The amount of the silicone resin 16 dissolved in the solvent 15 is preferably about 20 g to 350 g of the silicone resin with respect to 1 L of the solvent.
シリコーンレジン１６を溶媒１５に十分に溶解した後、図４、図５（Ｂ）に示すように溶媒１５中にＴＥＯＳ（テトラエトキシシラン：Ｓｉ（ＯＣ２Ｈ５）４）１７を添加して混合し十分に攪拌する（ＴＥＯＳ添加工程）。
混合撹拌時間は４時間以上とすることが望ましいが、溶解時間が短時間では溶解が不十分となり易く、２４時間を超える溶解時間を設定しても、時間が無駄になる。このため、混合撹拌時間は４〜１２時間程度が望ましい。
このＴＥＯＳ１７の混合量は溶媒に対しモル比で[溶媒]／[ＴＥＯＳ]＝４〜１５程度、好ましくは７〜１３の範囲であることが望ましい。溶媒１５にＴＥＯＳ１７を溶解する場合の温度は室温で良いが前述のシリコーンレジン１６を溶解する場合と同程度の温度域に加熱しても良い。
混合撹拌時間は、溶媒にシリコーンレジンを加えて２時間以上必要、その後にＴＥＯＳを加えて４時間以上必要である。レジン溶解・撹拌時間とは、シリコーンレジンの溶解撹拌時間のことである。
After the silicone resin 16 is sufficiently dissolved in the solvent 15, TEOS (tetraethoxysilane: Si (OC 2 H 5 ) 4 ) 17 is added to the solvent 15 and mixed as shown in FIGS. 4 and 5B. Stir well (TEOS addition step).
The mixing and stirring time is desirably 4 hours or longer, but if the dissolution time is short, dissolution tends to be insufficient, and even if a dissolution time exceeding 24 hours is set, time is wasted. For this reason, the mixing and stirring time is desirably about 4 to 12 hours.
The TEOS 17 is mixed in a molar ratio of [solvent] / [TEOS] = 4 to 15, preferably 7 to 13, with respect to the solvent. The temperature for dissolving the TEOS 17 in the solvent 15 may be room temperature, but it may be heated to a temperature range similar to that for dissolving the silicone resin 16 described above.
The mixing and stirring time is 2 hours or more after adding the silicone resin to the solvent, and then 4 hours or more after adding TEOS. The resin dissolution / stirring time is the dissolution stirring time of the silicone resin.
ＴＥＯＳ１７を添加後、図４、図５（Ｃ）に示すように溶媒に酸触媒としての塩酸１８と水１９を添加後、２５〜５０℃、例えば３５℃で４時間以上、例えば、４〜２４時間程度攪拌する（触媒添加工程）。塩酸１８を添加することで加水分解反応を優先的に進行させ、縮合重合反応を進行させる。ここで用いる酸触媒は、塩酸の他、硝酸、酢酸、ギ酸、リン酸等を用いることができる。
以上の工程により図４、図５（Ｄ）に示すようにゾル‐ゲルコーティング液（シリカ系絶縁皮膜形成用コーティング液）２０を得ることができる。このゾル‐ゲルコーティング液２０はＴＥＯＳを溶媒中に添加した液体中に目視できない程度の微細なシリコーンレジンの微粒子が分散された状態を呈する。
このコーティング液２０は、ＴＥＯＳとシリコーンレジンが溶媒中に十分かつ微細に分散混合され、２５℃、５０ｒｐｍで測定した粘度が２．８〜５．５ｍＰａ・ｓであることを特徴とする。
After the addition of TEOS 17, as shown in FIGS. 4 and 5C, hydrochloric acid 18 and water 19 as acid catalysts are added to the solvent, and then 25 to 50 ° C., for example, 35 ° C. for 4 hours or more, for example, 4 to 24 Stir for about an hour (catalyst addition step). By adding hydrochloric acid 18, the hydrolysis reaction proceeds preferentially and the condensation polymerization reaction proceeds. As the acid catalyst used here, nitric acid, acetic acid, formic acid, phosphoric acid and the like can be used in addition to hydrochloric acid.
Through the above steps, a sol-gel coating liquid (silica-based insulating film forming coating liquid) 20 can be obtained as shown in FIGS. 4 and 5D. The sol-gel coating solution 20 is in a state in which fine particles of silicone resin that cannot be visually observed are dispersed in a liquid in which TEOS is added to a solvent.
This coating liquid 20 is characterized in that TEOS and silicone resin are sufficiently and finely dispersed and mixed in a solvent, and the viscosity measured at 25 ° C. and 50 rpm is 2.8 to 5.5 mPa · s.
コーティング液２０を作製したならば、図４の工程に示すように下地皮膜付きの軟磁性粉末２１とともにヘンシェルミキサーなどの流動式混合機に投入して軟磁性粉末の外周に所定の厚さのコーティング液２０を塗布する（塗布工程２２）。
なお、この塗布工程２２で用いる軟磁性粉末２１は下地皮膜１３を設けていない軟磁性粉末２１でも良く、下地皮膜１３は略しても差し支えない。
混合時の加熱温度は９０℃〜１０５℃、例えば９５℃に設定し、混合終了後、１７５〜２５０℃程度の温度、例えば２００℃に数１０分程度加熱して軟磁性粉末外周のコーティング液を乾燥させ、コーティング液の乾燥皮膜で軟磁性粉末の外周を覆った構造の成形用コーティング粉末を得ることができる（乾燥工程２３）。
前記乾燥時に１７５℃未満の温度で乾燥すると乾燥時間が長くかかるので製造効率が悪く、２５０℃を超える温度で乾燥すると皮膜に亀裂が入りやすくなるという問題を生じる。
When the coating liquid 20 is prepared, as shown in the step of FIG. 4, the outer periphery of the soft magnetic powder is coated on the outer periphery of the soft magnetic powder by introducing it into a fluid mixer such as a Henschel mixer together with the soft magnetic powder 21 with the undercoat. The liquid 20 is applied (application step 22).
Note that the soft magnetic powder 21 used in the coating step 22 may be the soft magnetic powder 21 not provided with the base film 13, and the base film 13 may be omitted.
The heating temperature at the time of mixing is set to 90 ° C. to 105 ° C., for example, 95 ° C. After the mixing is completed, the coating liquid around the soft magnetic powder is heated by heating to a temperature of about 175 to 250 ° C., for example, 200 ° C. for several tens of minutes. It is possible to obtain a molding coating powder having a structure in which the outer periphery of the soft magnetic powder is covered with a dry film of the coating liquid (drying step 23).
When drying at a temperature of less than 175 ° C. during the drying, the drying time is long, so the production efficiency is poor, and when drying at a temperature of more than 250 ° C., the film tends to crack.
次に、前記コーティング粉末にシリコーンレジン粉末を０質量％〜０．９質量％の割合、例えば０．０３質量％あるいは０．０９質量％、０．１８質量％の割合で混合し、成形用原料混合粉末を得、この成形用原料混合粉末に０質量％〜０．８質量％、例えば、０．４質量％あるいは０．６質量％の割合でワックス系潤滑剤を混合する（混合工程２４）。
得られた原料混合粉末をプレス成形機の金型に投入し、目的の形状、例えば円環状、ロッド状、円盤状などの形状に圧縮成形する（成形工程２５）。
成形時の加圧力は例えば７００〜１５７０ＭＰａ程度の圧力、例えば７９０ＭＰａで８０℃温間成形により圧縮成形することができる。
Next, a silicone resin powder is mixed with the coating powder in a proportion of 0% by mass to 0.9% by mass, for example, 0.03% by mass, 0.09% by mass, or 0.18% by mass. A mixed powder is obtained, and a wax-based lubricant is mixed in the raw material mixed powder for molding at a ratio of 0% by mass to 0.8% by mass, for example, 0.4% by mass or 0.6% by mass (mixing step 24). .
The obtained raw material mixed powder is put into a die of a press molding machine and compression-molded into a desired shape, for example, an annular shape, a rod shape, or a disk shape (molding step 25).
The pressing force at the time of molding is, for example, about 700 to 1570 MPa, for example, 790 MPa, and compression molding can be performed by 80 ° C. warm molding.
得られた成形体に対し、真空雰囲気あるいは窒素ガス雰囲気などの非酸化性雰囲気中において、５００℃〜９００℃の温度範囲に、例えば、６５０℃に数１０分〜数時間程度、例えば、３０分間程度加熱して焼成する熱処理工程２６により、複数の軟磁性粉末からなる軟磁性粉末粒子１１を粒界層１２で結合した組織を有する目的の圧粉磁心Ａを得ることができる。
以上説明した製造方法により得られた圧粉磁心Ａは、前述の溶媒中にシリコーンレジンを十分に溶解し、ＴＥＯＳを十分に分散させたコーティング液の乾燥物が圧密され、この層を焼成して生成された粒界層１２によって複数の軟磁性粉末粒子１１が結合された組織を呈する。
溶媒中にシリコーンレジンを十分に溶解し、ＴＥＯＳを十分に分散させたゾル‐ゲルコーティング液（シリカ系絶縁皮膜形成用コーティング液）の乾燥物を焼成してなる粒界層１２は、層内にゾル‐ゲルコーティング液由来のＳｉ−Ｏ骨格とシリコーンレジン由来の樹脂骨格の複合化がなされた複合酸化物層であると想定できる。
２５℃、５０ｒｐｍで測定したコーティング液の粘度が２．８〜５．５ｍＰａ・ｓであるならば、粉末表面に塗布した場合、コーティング液の付き回り性が良く、この範囲の粘度値を有するコーティング液を表面に有する軟磁性粉末を用いて作製した圧粉磁心は比抵抗が高く、耐熱性に優れる。
With respect to the obtained molded body, in a non-oxidizing atmosphere such as a vacuum atmosphere or a nitrogen gas atmosphere, in a temperature range of 500 ° C. to 900 ° C., for example, at 650 ° C. for several tens of minutes to several hours, for example, 30 minutes The target dust core A having a structure in which the soft magnetic powder particles 11 made of a plurality of soft magnetic powders are bonded together by the grain boundary layer 12 can be obtained by the heat treatment step 26 of heating to a certain degree and firing.
The powder magnetic core A obtained by the manufacturing method described above is prepared by sufficiently dissolving a silicone resin in the above-described solvent and compacting a dried coating liquid in which TEOS is sufficiently dispersed. The produced grain boundary layer 12 exhibits a structure in which a plurality of soft magnetic powder particles 11 are combined.
A grain boundary layer 12 formed by firing a dried product of a sol-gel coating solution (a coating solution for forming a silica-based insulating film) in which a silicone resin is sufficiently dissolved in a solvent and TEOS is sufficiently dispersed is formed in the layer. It can be assumed that this is a composite oxide layer in which a Si—O skeleton derived from a sol-gel coating liquid and a resin skeleton derived from a silicone resin are combined.
If the viscosity of the coating solution measured at 25 ° C. and 50 rpm is 2.8 to 5.5 mPa · s, the coating solution has good throwing power when applied to the powder surface and has a viscosity value in this range. A dust core made of soft magnetic powder having a liquid on its surface has high specific resistance and excellent heat resistance.
前述のゾル‐ゲルコーティング液（シリカ系絶縁皮膜形成用コーティング液）２０であるならば、溶媒に対しシリコーンレジンとＴＥＯＳを十分に攪拌混合し、酸触媒と水を添加して加水分解反応と縮合重合反応を促進している。そして、シリコーンレジンとＴＥＯＳを有するゾル‐ゲルコーティング液（シリカ系絶縁皮膜形成用コーティング液）であれば必然的に分子間に樹脂であるシリコーンレジンが存在し、これが焼成時に部分的に焼失することで粒界層内に原子レベルの空孔を生み出している。ここに焼成時にＦｅ系の軟磁性粉末からＦｅが拡散されて原子レベルの空孔に鉄原子が捕らわれる結果、Ｓｉの複合酸化物中にＦｅが拡散した構造の粒界層１２が生成され、この粒界層１２が原因となって軟磁性粉末粒子１１を強固に接合した強度の高い圧粉磁心Ａを得ることができる。なお、後述する実施例試料の解析から粒界層１２の内部にＦｅが拡散されていることは確認できている。
また、この粒界層１２で周囲を囲んでいる軟磁性粉末粒子１１であるならば、減圧不活性ガス雰囲気中で５００℃〜６５０℃の高温まで昇温しても軟磁性粉末粒子１１の周面に酸化鉄の微結晶が生成し難くなり、これが原因となって高温で焼成された圧粉磁心Ａであっても、比抵抗の低下を抑制できた圧粉磁心Ａを提供できる。即ち、得られた軟磁性粉末粒子１１の周面に酸化鉄の微結晶の析出が少ないため、高温になっても高い比抵抗を維持することができる。減圧不活性ガス雰囲気中での昇温時に酸化鉄の微結晶の析出が少ないことは、焼成前の皮膜に存在する欠陥の数が少ないことを意味している。
If the sol-gel coating liquid (silica-based insulating film forming coating liquid) 20 is used, the silicone resin and TEOS are sufficiently stirred and mixed in the solvent, and the acid catalyst and water are added to the hydrolysis reaction and condensation. The polymerization reaction is promoted. And if it is a sol-gel coating liquid (silica-based insulating film forming coating liquid) containing a silicone resin and TEOS, there is inevitably a silicone resin that is an intermolecular resin, and this partly burns out during firing. This creates atomic-level vacancies in the grain boundary layer. Here, as a result of Fe being diffused from the Fe-based soft magnetic powder at the time of firing and iron atoms being trapped in the atomic level vacancies, a grain boundary layer 12 having a structure in which Fe is diffused into the Si complex oxide is generated. The powder magnetic core A having high strength in which the soft magnetic powder particles 11 are firmly bonded due to the grain boundary layer 12 can be obtained. In addition, it has confirmed that Fe was diffused inside the grain boundary layer 12 from the analysis of the Example sample mentioned later.
Further, if the soft magnetic powder particles 11 are surrounded by the grain boundary layer 12, the circumference of the soft magnetic powder particles 11 is increased even when the temperature is raised to a high temperature of 500 ° C. to 650 ° C. in a reduced-pressure inert gas atmosphere. It becomes difficult to produce iron oxide microcrystals on the surface, and even if this is the dust core A fired at a high temperature, it is possible to provide the dust core A in which the decrease in specific resistance can be suppressed. That is, since there is little precipitation of iron oxide microcrystals on the peripheral surface of the obtained soft magnetic powder particles 11, a high specific resistance can be maintained even at high temperatures. Less precipitation of iron oxide microcrystals during heating in a reduced-pressure inert gas atmosphere means that the number of defects present in the film before firing is small.
以上説明の如く製造された圧粉磁心Ａは、高強度であり、比抵抗が高い特徴を有する。更に、圧粉磁心Ａは５００〜６５０℃に加熱されても比抵抗が低下し難い特徴を有し、耐熱性に優れる。
また、圧粉磁心Ａを適用した図３に示すリアクトル１４では、リアクトルコア１４ａの比抵抗が大きく、リアクトル１４として高い性能を得ることができる。
なお、前記リアクトル１４は本発明に係る圧粉磁心Ａを電磁気回路部品に適用した一例であって、本発明に係る圧粉Ａをその他種々の電磁気回路部品に適用できるのは勿論である。例えば、モーターコア、アクチュエーターのコア、トランスのコア、チョークコア、磁気センサコア、ノイズフィルターのコア、スイッチング電源用のコア、ＤＣ／ＤＣコンバーター用のコア等、種々の電磁気回路部品に適用することができる。
The dust core A manufactured as described above is characterized by high strength and high specific resistance. Further, the dust core A has a characteristic that the specific resistance is not easily lowered even when heated to 500 to 650 ° C., and has excellent heat resistance.
Moreover, in the reactor 14 shown in FIG. 3 to which the dust core A is applied, the specific resistance of the reactor core 14 a is large, and high performance as the reactor 14 can be obtained.
The reactor 14 is an example in which the dust core A according to the present invention is applied to an electromagnetic circuit component, and the dust A according to the present invention can be applied to various other electromagnetic circuit components. For example, it can be applied to various electromagnetic circuit components such as motor cores, actuator cores, transformer cores, choke cores, magnetic sensor cores, noise filter cores, switching power supply cores, DC / DC converter cores, etc. .
平均粒径５０μｍ（Ｄ５０）の純鉄粉末にリン酸鉄被覆を施したリン酸鉄被覆鉄粉または純鉄粉を用意した。
前記リン酸鉄被覆純鉄粉末（軟磁性粉末）３００ｇに対しＴＥＯＳ由来のＳｉＯ２皮膜厚として１６．９ｎｍ、軟磁性粉末に対しコーティング液中のシリコーンレジンとして０．２０質量％含有する第１実施例作製用の成形用原料混合粉末を以下の工程に従い作製した。
前記リン酸鉄被覆純鉄粉末（軟磁性粉末）３００ｇに対しＴＥＯＳ由来のＳｉＯ２皮膜厚３３．８ｎｍ、軟磁性粉末に対しコーティング液中のシリコーンレジンとして０．４１質量％含有する第２実施例作製用または第３実施例作製用の成形用原料混合粉末を以下の工程に従い作製した。
前記リン酸鉄被覆純鉄粉末（軟磁性粉末）３００ｇに対しＴＥＯＳ由来のＳｉＯ２皮膜厚６７．５ｎｍ、軟磁性粉末に対しコーティング液中のシリコーンレジンとして０．５４質量％含有する第４実施例作製用の成形用原料混合粉末を以下の工程に従い作製した。
前記純鉄粉末（軟磁性粉末）３００ｇに対しＴＥＯＳ由来のＳｉＯ２皮膜厚３３．８ｎｍ、軟磁性粉末に対しコーティング液中のシリコーンレジンとして０．４１質量％含有する第５実施例作製用の成形用原料混合粉末を以下の工程に従い作製した。この粉末は下地皮膜を略した軟磁性粉末を用いた例に相当する。
An iron phosphate-coated iron powder or a pure iron powder prepared by applying iron phosphate coating to pure iron powder having an average particle size of 50 μm (D50) was prepared.
1st implementation containing TEOS-derived SiO 2 film thickness of 16.9 nm with respect to 300 g of the iron phosphate-coated pure iron powder (soft magnetic powder) and 0.20% by mass as the silicone resin in the coating liquid with respect to the soft magnetic powder. A molding raw material mixed powder for producing an example was produced according to the following steps.
Second embodiment containing 300 g of iron phosphate-coated pure iron powder (soft magnetic powder) with a TEOS-derived SiO 2 film thickness of 33.8 nm and 0.41% by mass as a silicone resin in the coating solution with respect to the soft magnetic powder. A molding raw material mixed powder for production or for production of the third example was produced according to the following steps.
Example 4 containing TEOS-derived SiO 2 film thickness of 67.5 nm with respect to 300 g of the iron phosphate-coated pure iron powder (soft magnetic powder) and 0.54% by mass as the silicone resin in the coating liquid with respect to the soft magnetic powder. A molding raw material mixed powder for production was produced according to the following steps.
Molding of the pure iron powder (soft magnetic powder) 300 g SiO 2 film thickness from TEOS to 33.8Nm, fifth embodiment for manufacturing containing 0.41 wt% as the silicone resin in the coating liquid to the soft magnetic powder A raw material mixed powder was prepared according to the following steps. This powder corresponds to an example using a soft magnetic powder in which the undercoat is omitted.
各々の成形用原料混合粉末の作製手順を以下に説明する。
メチル系シリコーンレジンを液温４５℃の２−プロパノール（ＩＰＡ）に混合し２時間攪拌して溶解し、この溶液にテトラエトキシシラン（ＴＥＯＳ）を室温にて４時間攪拌して混合した。
撹拌はマグネチックスターラーを用い、攪拌子を１５０ｒｐｍで回転させる方法で実施した。
この後、１２ＮＨＣｌを添加し、（マグネチックスターラーを用い、攪拌子を１５０ ｒｐｍで回転させる方法で２４時間攪拌し（液温３５℃保持）、シリカゾル‐ゲルコーティング液を得た。
The procedure for producing each molding raw material mixed powder will be described below.
Methyl silicone resin was mixed with 2-propanol (IPA) having a liquid temperature of 45 ° C. and stirred for 2 hours to dissolve, and tetraethoxysilane (TEOS) was stirred and mixed at room temperature for 4 hours.
Stirring was carried out by using a magnetic stirrer and rotating the stirrer at 150 rpm.
Thereafter, 12N HCl was added, and the mixture was stirred for 24 hours by using a magnetic stirrer and rotating the stirrer at 150 rpm (the liquid temperature was maintained at 35 ° C.) to obtain a silica sol-gel coating liquid.
第１実施例作製用のシリカゾル‐ゲルコーティング液は、シリコーンレジン：０．６１ｇ、ＩＰＡ：６．７０ｇ、ＴＥＯＳ：１．８６ｇ、水：０．３２ｇ、１２ＮＨＣｌ：０．００８ｇ、合計９．４９６ｇの割合で各成分を混合した。このコーティング液の粘度は３．８７ｍＰａ・ｓであった。
第２実施例作製用と第３実施例作製用のシリカゾル‐ゲルコーティング液は、シリコーンレジン：１．２２ｇ、ＩＰＡ：１３．３９ｇ、ＴＥＯＳ：３．７３ｇ、水：０．６５ｇ、１２ＮＨＣｌ：０．０１７ｇ、合計１８．９９２ｇの割合で各成分を混合した。これらのコーティング液の粘度は３．０６ｍＰａ・ｓであった。
第４実施例作製用のシリカゾル‐ゲルコーティング液は、シリコーンレジン：１．６２ｇ、ＩＰＡ：８．５９７ｇ、ＴＥＯＳ：７．４５ｇ、水：１．２８８ｇ、１２ＮＨＣｌ：０．０６６ｇ、合計１９．０２１ｇの割合で各成分を混合した。このコーティング液の粘度は４．３２ｍＰａ・ｓであった。
第５実施例作製用のシリカゾル‐ゲルコーティング液は、シリコーンレジン：１．２２ｇ、ＩＰＡ：１３．３９ｇ、ＴＥＯＳ：３．７３ｇ、水：０．６５ｇ、１２ＮＨＣｌ：０．０１７ｇ、合計１８．９９２ｇの割合で各成分を混合した。このコーティング液の粘度は３．０６ｍＰａ・ｓであった。
これらシリカゾル‐ゲルコーティング液中のシリコーンレジンは、鉄粉に対し０．２０質量％（第１実施例作製用）、０．４１質量％（第２、第３実施例作製用）、０．５４質量％（第４実施例作製用）、０．４１質量％（第５実施例作製用）に設定している。シリコーンレジンは粒径１ｍｍ以下のグレード品を用いた。
The silica sol-gel coating solution for producing the first example was a silicone resin: 0.61 g, IPA: 6.70 g, TEOS: 1.86 g, water: 0.32 g, 12N HCl: 0.008 g, and a total of 9.496 g. Each component was mixed in proportions. The viscosity of this coating liquid was 3.87 mPa · s.
The silica sol-gel coating solution for the production of the second example and the production of the third example was 1.22 g of silicone resin, 13.39 g of IPA, 3.73 g of TEOS, 0.65 g of water, and 0.1N of 12N HCl. Each component was mixed at a ratio of 017 g, total 18.992 g. The viscosity of these coating solutions was 3.06 mPa · s.
The silica sol-gel coating solution for preparing the fourth example was composed of silicone resin: 1.62 g, IPA: 8.597 g, TEOS: 7.45 g, water: 1.288 g, 12N HCl: 0.066 g, total 19.021 g. Each component was mixed in proportions. The viscosity of this coating liquid was 4.32 mPa · s.
The silica sol-gel coating solution for producing the fifth example was silicone resin: 1.22 g, IPA: 13.39 g, TEOS: 3.73 g, water: 0.65 g, 12N HCl: 0.017 g, and a total of 18.992 g. Each component was mixed in proportions. The viscosity of this coating liquid was 3.06 mPa · s.
The silicone resin in these silica sol-gel coating solutions is 0.20% by mass (for producing the first example), 0.41% by mass (for producing the second and third examples), 0.54 with respect to the iron powder. It is set to mass% (for manufacturing the fourth embodiment) and 0.41 mass% (for manufacturing the fifth embodiment). A silicone resin having a particle size of 1 mm or less was used.
第２比較例作製用のシリカゾル‐ゲルコーティング液は、シリコーンレジン：３．６０ｇ、ＩＰＡ：１２．８９ｇ、ＴＥＯＳ：１．２４ｇ、水：０．２２ｇ、１２ＮＨＣｌ：０．００５ｇ、合計１７．９５５ｇの割合で各成分を混合した。このコーティング液の粘度は６．００ｍＰａ・ｓであった。
第３比較例作製用のシリカゾル‐ゲルコーティング液は、シリコーンレジン：０．９８ｇ、ＩＰＡ：１７．１９ｇ、ＴＥＯＳ：２．９８ｇ、水：１．０３ｇ、１２ＮＨＣｌ：０．０３ｇ、合計２２．２１ｇの割合で各成分を混合した。このコーティング液の粘度は２．７５ｍＰａ・ｓであった。
The silica sol-gel coating solution for producing the second comparative example was silicone resin: 3.60 g, IPA: 12.89 g, TEOS: 1.24 g, water: 0.22 g, 12N HCl: 0.005 g, a total of 17.955 g. Each component was mixed in proportions. The viscosity of this coating liquid was 6.00 mPa · s.
The silica sol-gel coating solution for preparing the third comparative example was silicone resin: 0.98 g, IPA: 17.19 g, TEOS: 2.98 g, water: 1.03 g, 12N HCl: 0.03 g, and a total of 22.21 g. Each component was mixed in proportions. The viscosity of this coating liquid was 2.75 mPa · s.
[ＩＰＡ]／[ＴＥＯＳ]の割合は、第１〜第３実施例作製用のシリカゾル‐ゲルコーティング液（シリカ系絶縁皮膜形成用コーティング液）において順次モル比で１２（第１実施例作製用）、１２（第２、第３実施例作製用）、４（第４実施例作製用）、１２（第５実施例作製用）に設定している。
ＴＥＯＳ添加量は、ＴＥＯＳ由来のＳｉＯ２皮膜厚として計算し、比表面積が４．０×１０−２ｍ２／ｇの軟磁性粉末をベースに換算した。
ＴＥＯＳ由来のＳｉＯ２皮膜の膜厚は、比表面積（ＢＥＴ３点法による測定値）、ＳｉＯ２密度（水晶の物性値２．６５ｇ／ｃｍ３）を用いて以下の式から算出した。
ＳｉＯ２皮膜の膜厚（ｎｍ）＝ＴＥＯＳの物質量（ｍｏｌ）×ＳｉＯ２原子量（ｇ／ｍｏｌ）／ＳｉＯ２密度（ｇ／ｃｍ３）／軟磁性粉末の比表面積（ｍ２／ｇ）／軟磁性粉末重量（ｇ）（＊）
The ratio of [IPA] / [TEOS] is 12 in order of the molar ratio in the silica sol-gel coating liquid (silica-based insulating film forming coating liquid) for producing the first to third embodiments (for producing the first embodiment). 12 (for manufacturing the second and third embodiments), 4 (for manufacturing the fourth embodiment), and 12 (for manufacturing the fifth embodiment).
The amount of TEOS added was calculated as the thickness of the TEOS-derived SiO 2 film, and converted based on soft magnetic powder having a specific surface area of 4.0 × 10 −2 m 2 / g.
The film thickness of the TEOS-derived SiO 2 film was calculated from the following equation using the specific surface area (measured value by the BET three-point method) and SiO 2 density (physical property value of crystal 2.65 g / cm 3 ).
SiO 2 film thickness (nm) = TEOS substance amount (mol) × SiO 2 atomic weight (g / mol) / SiO 2 density (g / cm 3 ) / specific surface area of soft magnetic powder (m 2 / g) / Soft magnetic powder weight (g) (*)
（計算例）
ＴＥＯＳ重量７．４５ｇ、鉄粉比表面積４．０×１０−２ｍ２／ｇ、鉄粉重量３００ｇの場合、上記計算式（＊）にＴＥＯＳ原子量２０８．１ｇ／ｍｏｌ、ＳｉＯ２原子量６０．１ｇ／ｍｏｌを代入して、ＳｉＯ２被膜の膜厚＝７．４５（ｇ）／２０８．１（ｇ／ｍｏｌ）×６０．１（ｇ／ｍｏｌ）／２．６５（ｇ／ｃｍ３）／４．０×１０−２（ｍ２／ｇ） ／３００（ｇ）＝６．７６×１０−８（ｍ）＝６７．６（ｎｍ）
(Calculation example)
When the TEOS weight is 7.45 g, the iron powder specific surface area is 4.0 × 10 −2 m 2 / g, and the iron powder weight is 300 g, the TEOS atomic weight is 208.1 g / mol and the SiO 2 atomic weight is 60.1 g. / Mol is substituted, and the film thickness of the SiO 2 film = 7.45 (g) /208.1 (g / mol) × 60.1 (g / mol) /2.65 (g / cm 3 ) / 4 0.0 × 10 −2 (m 2 / g) / 300 (g) = 6.76 × 10 −8 (m) = 67.6 (nm)
水の添加量は、［Ｈ２Ｏ］／［ＴＥＯＳ］＝２とした。
⇒（Ｈ２Ｏ質量）＝（ＴＥＯＳ質量／（２０８．３３ｇ／ｍｏｌ（ＴＥＯＳ原子量）））×２×１８．０１６ｇ／ｍｏｌ（Ｈ２Ｏの分子量）
希塩酸の添加量は、［１２ＮＨＣｌ］／［ＴＥＯＳ］＝０．０２５とした。
⇒［１００％ＨＣｌ］／［ＴＥＯＳ］＝０．００９
⇒（１２ＮＨＣｌ質量）＝（ＴＥＯＳ質量／（２０８．３３ｇ／ｍｏｌ（ＴＥＯＳ分子量）））×０．０２５×３６．４５８ｇ／ｍｏｌ（ＨＣｌの分子量）
あるいは、（１２ＮＨＣｌ質量）＝（ＴＥＯＳ質量／（２０８．３３ｇ／ｍｏｌ（ＴＥＯＳ分子量）））×０．００９×３６．４５８ｇ／ｍｏｌ（ＨＣｌの分子量）×１００／３６で計算できる。
なお、１２ＮＨＣｌ質量を表す二つ目の式は、塩酸試薬１２ＮＨＣｌのＨＣｌ濃度を３６％として計算する。
The amount of water added was [H 2 O] / [TEOS] = 2.
⇒ (H 2 O mass) = (TEOS mass / (208.33 g / mol (TEOS atomic weight))) × 2 × 18.016 g / mol (molecular weight of H 2 O)
The amount of dilute hydrochloric acid added was [12NHCl] / [TEOS] = 0.025.
=> [100% HCl] / [TEOS] = 0.009
⇒ (12NHCl mass) = (TEOS mass / (208.33 g / mol (TEOS molecular weight))) × 0.025 × 36.458 g / mol (HCl molecular weight)
Alternatively, (12NHCl mass) = (TEOS mass / (208.33 g / mol (TEOS molecular weight))) × 0.009 × 36.458 g / mol (HCl molecular weight) × 100/36.
Note that the second equation representing the mass of 12NHCl is calculated assuming that the HCl concentration of the hydrochloric acid reagent 12NHCl is 36%.
前記リン酸鉄被覆鉄粉もしくは前記純鉄粉にヘンシェルミキサーを用いて前記シリカゾル‐ゲルコーティング液（シリカ系絶縁皮膜形成用コーティング液）を塗布した。
９５℃に加熱したヘンシェルミキサーの容器内で撹拌されているリン酸鉄被覆鉄粉（３００ｇ）に対し前述の工程で得たコーティング液９．４９６ｇの１／３（３．１６５ｇ）を供給して減圧乾燥し、リン酸鉄被覆鉄粉温度がコーティング開始温度の例えば９４℃まで回復してから撹拌と加熱をさらに３分間続ける一連の操作を繰り返した。上述の比率で鉄粉とコーティング液を用いることでＴＥＯＳ由来のＳｉＯ２皮膜厚１６．９ｎｍのコーティング鉄粉（実施例１作製用）を得た。
ヘンシェルミキサーでの鉄粉へのゾル‐ゲルコーティングにおいて、鉄粉表面を覆うゾル‐ゲルコーティング液（シリカ系絶縁皮膜形成用コーティング液）の塗布を大気中９５℃で３分間加熱し続けると、繰り返しコーティング液を供給する度にゾル‐ゲルコーティング液膜が溶解することなく鉄粉上に塗り重ねられて定着していく。９５℃３分間未満の加熱時間であると、ゾル‐ゲルコーティング液膜が鉄粉表面上に定着せずに剥離しやすくなるので、３分間以上処理することが好ましい。
The silica sol-gel coating solution (a coating solution for forming a silica-based insulating film) was applied to the iron phosphate-coated iron powder or the pure iron powder using a Henschel mixer.
Supply 1/3 (3.165 g) of the coating liquid obtained in the above-mentioned step to the iron phosphate-coated iron powder (300 g) stirred in a Henschel mixer container heated to 95 ° C. After drying under reduced pressure, a series of operations in which stirring and heating were continued for another 3 minutes after the iron phosphate-coated iron powder temperature recovered to the coating start temperature, for example, 94 ° C., were repeated. By using the iron powder and the coating liquid at the above-mentioned ratio, a coated iron powder (for preparation of Example 1) having a thickness of 16.9 nm from the TEOS-derived SiO 2 film was obtained.
In sol-gel coating on iron powder with a Henschel mixer, the application of the sol-gel coating liquid (coating liquid for forming a silica-based insulating film) covering the surface of the iron powder is repeatedly heated at 95 ° C in the atmosphere for 3 minutes. Each time the coating solution is supplied, the sol-gel coating solution film is applied and fixed on the iron powder without dissolving. When the heating time is less than 95 ° C. for 3 minutes, the sol-gel coating liquid film is not fixed on the surface of the iron powder and is easily peeled off.
次に、９５℃に加熱したヘンシェルミキサーの容器内で撹拌されているリン酸鉄被覆鉄粉（３００ｇ）に対し前述の工程で得たコーティング液１８．９９２ｇの１／６（３．１６５ｇ）を供給し、上記と同等の処理により、上述の比率で鉄粉とコーティング液を用いることでＴＥＯＳ由来のＳｉＯ２皮膜厚３３．８ｎｍのコーティング鉄粉（実施例２、３作製用）を得た。 Next, 1/6 (3.165 g) of the coating liquid 18.992 g obtained in the above-mentioned process is applied to iron phosphate-coated iron powder (300 g) stirred in a Henschel mixer vessel heated to 95 ° C. By supplying the iron powder and the coating liquid at the above-mentioned ratio by supplying the same treatment as described above, a coated iron powder (for preparation of Examples 2 and 3) having a SiO 2 film thickness of 33.8 nm was obtained.
また、以下の手順で実施例４、５のコーティング鉄粉を得た。
９５℃に加熱したヘンシェルミキサーの容器内で撹拌されているリン酸鉄被覆鉄粉（３００ｇ）に対し前述の工程で得たコーティング液１９．０２１ｇの１／６（３．１７ｇ）を供給し、上記と同等の処理により、上述の比率で鉄粉とコーティング液を用いることでＴＥＯＳ由来のＳｉＯ２皮膜厚６７．５ｎｍのコーティング鉄粉（実施例４作製用）を得た。
９５℃に加熱したヘンシェルミキサーの容器内で撹拌されている純鉄粉（３００ｇ）に対し前述の工程で得たコーティング液１８．９９２ｇの１／６（３．１６５ｇ）を供給し、上記と同等の処理により、上述の比率で鉄粉とコーティング液を用いることでＴＥＯＳ由来のＳｉＯ２皮膜厚３３．８ｎｍのコーティング鉄粉（実施例５作製用）を得た。
Moreover, the coating iron powder of Example 4, 5 was obtained in the following procedures.
Supply 1/6 (3.17 g) of the coating liquid 19.021 g obtained in the above-mentioned process to iron phosphate-coated iron powder (300 g) stirred in a Henschel mixer container heated to 95 ° C., By the treatment equivalent to the above, the coated iron powder (for preparation of Example 4) having a thickness of 67.5 nm from the TEOS-derived SiO 2 film was obtained by using the iron powder and the coating liquid in the above-described ratio.
1/6 (3.165 g) of 18.992 g of the coating liquid obtained in the previous step is supplied to pure iron powder (300 g) stirred in a Henschel mixer container heated to 95 ° C., equivalent to the above As a result of the treatment, a coated iron powder (for production of Example 5) having a TEOS-derived SiO 2 film thickness of 33.8 nm was obtained by using the iron powder and the coating liquid in the above-described ratio.
この後、ゾル‐ゲルコーティング液膜を塗布したリン酸鉄被覆鉄粉もしくは純鉄粉を大気中で２００℃に０．５時間加熱し乾燥することでシリカゾル‐ゲル被覆鉄粉を得た。
実施例１作製用のシリカゾル‐ゲル被覆鉄粉に対しシリコーンレジン粉末を０．０９質量％添加し、ワックス系潤滑剤を鉄粉に対し０．６質量％添加して実施例１の原料混合粉末を得た。
実施例２作製用のシリカゾル‐ゲル被覆鉄粉に対しシリコーンレジン粉末を０．０３質量％添加し、ワックス系潤滑剤を鉄粉に対し０．６質量％添加して実施例２の原料混合粉末を得た。
実施例３作製用のシリカゾル‐ゲル被覆鉄粉に対しシリコーンレジン粉末を０．１８質量％添加し、ワックス系潤滑剤を軟磁性粉末に対し０．６質量％添加して実施例３の原料混合粉末を得た。
実施例４作製用のシリカゾル‐ゲル被覆鉄粉に対しシリコーンレジン粉末を０．０３質量％添加し、ワックス系潤滑剤を軟磁性粉末に対し０．４質量％添加して実施例４の原料混合粉末を得た。
実施例５作製用のシリカゾル‐ゲル被覆鉄粉に対しシリコーンレジン粉末を０．１８質量％添加し、ワックス系潤滑剤を軟磁性粉末に対し０．６質量％添加して実施例５の原料混合粉末を得た。
Thereafter, the iron phosphate-coated iron powder or pure iron powder coated with the sol-gel coating liquid film was heated in air to 200 ° C. for 0.5 hours and dried to obtain a silica sol-gel coated iron powder.
Example 1 0.09% by mass of a silicone resin powder is added to the silica sol-gel coated iron powder for preparation, and 0.6% by mass of a wax-based lubricant is added to the iron powder. Got.
Example 2 0.03% by mass of a silicone resin powder is added to the silica sol-gel coated iron powder for production, and 0.6% by mass of a wax-based lubricant is added to the iron powder. Got.
Example 3 0.18% by mass of a silicone resin powder is added to the silica sol-gel coated iron powder for production, and 0.6% by mass of a wax-based lubricant is added to the soft magnetic powder. A powder was obtained.
Example 4 Addition of 0.03% by mass of silicone resin powder to silica sol-gel coated iron powder for preparation, and addition of 0.4% by mass of wax-based lubricant to soft magnetic powder, mixing raw materials of Example 4 A powder was obtained.
Example 5 0.18% by mass of a silicone resin powder is added to the silica sol-gel coated iron powder for preparation, and 0.6% by mass of a wax-based lubricant is added to the soft magnetic powder. A powder was obtained.
これら実施例１〜５の原料混合粉末をそれぞれ用い、成形圧７９０ＭＰａ（８ｔ／ｃｍ２）で８０℃温間成形によりリング状の成形体を得た。
前記リング状の成形体を窒素雰囲気中において６５０℃に加熱し３０分間焼成し、焼成後徐冷して圧粉磁心を得た。リング状圧粉磁心のサイズは、ＯＤ３５×ＩＤ２５×Ｈ５ｍｍである。
なお、純鉄粉末の表面に被覆したコーティング液膜は６５０℃の焼成により一部の成分が消失するが液膜中のＳｉが主体として残留し、ＳｉとＦｅのそれぞれの酸化物あるいはＳｉとＦｅと酸素を含有する複合酸化物となって隣接する純鉄粉末粒子間の粒界に粒界層として残留する。
Each of the raw material mixed powders of Examples 1 to 5 was used, and a ring-shaped molded body was obtained by 80 ° C. warm molding at a molding pressure of 790 MPa (8 t / cm 2 ).
The said ring-shaped molded object was heated at 650 degreeC in nitrogen atmosphere, baked for 30 minutes, and after baking, it annealed and obtained the powder magnetic core. The size of the ring-shaped dust core is OD35 × ID25 × H5 mm.
The coating liquid film coated on the surface of the pure iron powder loses some components by baking at 650 ° C., but Si in the liquid film remains mainly, and each of the oxides of Si and Fe or Si and Fe It becomes a composite oxide containing oxygen and oxygen, and remains as a grain boundary layer at the grain boundary between adjacent pure iron powder particles.
＜比較例１＞
また、比較例１として、シリコーンレジン皮膜のみを備えた試料を作製した。前記リン酸鉄被覆純鉄粉末（軟磁性粉末）３００ｇに対し０．７２質量％のシリコーンレジンを添加してコーティングを行いコーティング鉄粉を得た後、大気中で乾燥処理を施し、その後に潤滑剤添加、成形、熱処理して比較例１のリング状成形試料を得た。成形条件と熱処理条件は実施例１〜５と同等条件としている。
＜比較例２＞
比較例２として、コーティング液の条件：ＴＥＯＳ由来のＳｉＯ２皮膜厚１１．３ｎｍ、コーティング液中のシリコーンレジンとして１．２質量％、軟磁性粉末としてリン酸鉄被覆鉄粉を用い、比較例２作製用のシリカゾル‐ゲル被覆鉄粉に対しシリコーンレジン粉末を０．１８質量％添加し、ワックス系潤滑剤を軟磁性粉末に対し０．６質量％添加して原料混合粉末を得た。比較例２を製造する場合のコーティング条件、コーティング後の乾燥条件、成形条件、焼成条件等は、実施例と同等である。
この比較例２の粘度測定値は、６．００ｍＰａ・ｓであった。
<Comparative Example 1>
Further, as Comparative Example 1, a sample having only a silicone resin film was prepared. After coating by adding 0.72 mass% silicone resin to 300 g of the iron phosphate-coated pure iron powder (soft magnetic powder), drying treatment is performed in the atmosphere, followed by lubrication. The ring-shaped molded sample of Comparative Example 1 was obtained by adding the agent, molding, and heat treatment. The molding conditions and heat treatment conditions are the same as those in Examples 1-5.
<Comparative example 2>
As Comparative Example 2, the coating solution conditions: TEOS-derived SiO 2 film thickness 11.3 nm, 1.2% by mass as the silicone resin in the coating solution, and iron phosphate-coated iron powder as the soft magnetic powder, Comparative Example 2 0.18% by mass of a silicone resin powder was added to the silica sol-gel coated iron powder for production, and 0.6% by mass of a wax-based lubricant was added to the soft magnetic powder to obtain a raw material mixed powder. The coating conditions, the drying conditions after coating, the molding conditions, the firing conditions, etc. in the case of producing Comparative Example 2 are the same as in the examples.
The measured viscosity value of Comparative Example 2 was 6.00 mPa · s.
＜比較例３＞
比較例３として、コーティング液の条件：ＴＥＯＳ由来のＳｉＯ２皮膜厚２７．０ｎｍ、コーティング液中のシリコーンレジンとして０．３２質量％、軟磁性粉末としてリン酸鉄被覆鉄粉を用い、比較例３作製用のシリカゾル‐ゲル被覆鉄粉に対しシリコーンレジン粉末を０．１８質量％添加し、ワックス系潤滑剤を軟磁性粉末に対し０．６質量％添加して原料混合粉末を得た。比較例３を製造する場合のコーティング条件、コーティング後の乾燥条件、成形条件、焼成条件等は、実施例と同等である。
この比較例３の粘度測定値は、２．７５ｍＰａ・ｓであった。
<Comparative Example 3>
As Comparative Example 3, the conditions of the coating solution: TEOS-derived SiO 2 film thickness 27.0 nm, 0.32% by mass as the silicone resin in the coating solution, and iron phosphate-coated iron powder as the soft magnetic powder, Comparative Example 3 0.18% by mass of a silicone resin powder was added to the silica sol-gel coated iron powder for production, and 0.6% by mass of a wax-based lubricant was added to the soft magnetic powder to obtain a raw material mixed powder. The coating conditions, the drying conditions after coating, the molding conditions, the firing conditions, etc. in the case of producing Comparative Example 3 are the same as in the examples.
The measured viscosity value of Comparative Example 3 was 2.75 mPa · s.
上述の如く得られた各リング状試料を用いて磁束密度（磁界１０ｋＡ／ｍ）と比抵抗（μΩｍ）と鉄損（Ｗ／ｋｇ）と抗折強度（ＭＰａ）を測定した。また、粒界層に存在するＦｅの平均値（ａｔ％）も測定した。
前記１０ｋＡ／ｍでの磁束密度の測定は、リング状試料を用いてＢ−Ｈトレーサ（横河電機（株）製直流磁化測定装置Ｂ積分ユニット ＴＹＰＥ３２５７）で行った。
以上の結果を以下の表１に示す。
The magnetic flux density (magnetic field 10 kA / m), specific resistance (μΩm), iron loss (W / kg), and bending strength (MPa) were measured using each of the ring samples obtained as described above. Moreover, the average value (at%) of Fe existing in the grain boundary layer was also measured.
The magnetic flux density at 10 kA / m was measured with a BH tracer (DC magnetization measuring device B integration unit TYPE 3257 manufactured by Yokogawa Electric Corporation) using a ring sample.
The above results are shown in Table 1 below.
粒界層に存在するＦｅ量は、それぞれの試料（圧粉磁心）断面の粒界層について１０箇所の元素分析を実施した。粒界層に存在するＦｅの値は、１０箇所での分析値の平均値である。なお、後述する実施例３のＴＥＭ分析結果は具体的な例として示しており、この他の実施例、比較例に示す粒界層に存在するＦｅの値は、１０箇所の元素分析を行った平均値である。よって、実施例３において、粒界層に存在するＦｅの（平均）値は０．６０ａｔ％となる。 For the amount of Fe present in the grain boundary layer, elemental analysis was conducted at 10 locations on the grain boundary layer of each sample (dust core) cross section. The value of Fe existing in the grain boundary layer is an average value of the analysis values at 10 locations. In addition, the TEM analysis result of Example 3 mentioned later is shown as a specific example, and the value of Fe existing in the grain boundary layer shown in other examples and comparative examples was subjected to elemental analysis at 10 locations. Average value. Therefore, in Example 3, the (average) value of Fe existing in the grain boundary layer is 0.60 at%.
表１に示す結果から、シリコーンレジンとＴＥＯＳを溶媒に添加したゾル‐ゲルコーティング液（シリカ系絶縁皮膜形成用コーティング液）を軟磁性粉末に塗布し、これを乾燥後、圧縮成形し焼成して得た圧粉磁心は、比抵抗が高く、磁束密度、鉄損ともに優れ、軟磁気特性に優れていることがわかる。
また、これらの試料はいずれも６５０℃に焼成して得られているので、耐熱性に優れ、５００〜６５０℃程度に加熱しても、比抵抗が低下せず、優れた軟磁気特性を有することが明かである。
なお、粒界層に存在するＦｅの（平均）値が６ａｔ％を超過するほどに粒界層に多くのＦｅが拡散されていると、圧粉磁心の強度は向上するが、それに伴って圧粉磁心の比抵抗が低下し、磁気特性（鉄損）も悪化する傾向となることが判る。
From the results shown in Table 1, a sol-gel coating liquid (silica-based insulating film forming coating liquid) in which silicone resin and TEOS are added to a solvent is applied to a soft magnetic powder, dried, compression-molded and fired. It can be seen that the obtained dust core has a high specific resistance, excellent magnetic flux density and iron loss, and excellent soft magnetic properties.
In addition, since these samples are all obtained by firing at 650 ° C., they have excellent heat resistance, and even when heated to about 500 to 650 ° C., the specific resistance does not decrease and has excellent soft magnetic properties. It is clear.
If the Fe (average) value of Fe existing in the grain boundary layer exceeds 6 at%, if the amount of Fe is diffused in the grain boundary layer, the strength of the dust core is improved. It can be seen that the specific resistance of the powder magnetic core decreases and the magnetic properties (iron loss) tend to deteriorate.
図６は上述の実施例３の圧粉磁心の粒界層を含む軟磁性粒子の部分断面を低加速電圧走査電子顕微鏡により観察した結果（ＳＥＭ観察結果）を示す組織写真である。
ＳＥＭは、Ｃａｒｌ Ｚｅｉｓｓ製 Ｕｌｔｒａ５５、ＥＤＳソフトウェア：ＮｏｒａｎＳｙｓｔｅｍ Ｓｅｖｅｎを用い、観察条件：加速電圧 １ｋＶ、ＥＤＳ面分析条件：加速電圧４ｋＶ、電流量１ｎＡ、ＷＤ３ｍｍにて分析を行った。
FIG. 6 is a structure photograph showing a result (SEM observation result) of a partial cross section of the soft magnetic particles including the grain boundary layer of the dust core of Example 3 described above observed with a low acceleration voltage scanning electron microscope.
The SEM was analyzed using Carl Zeiss Ultra 55, EDS software: Noran System Seven, observation conditions: acceleration voltage 1 kV, EDS surface analysis conditions: acceleration voltage 4 kV, current amount 1 nA, WD 3 mm.
図６から軟磁性粒子の周面に薄いリン酸鉄被覆が形成されており、隣接する軟磁性粒子間に粒界層が形成されていることがわかる。一例として挙げた図６の視野におけるこの実施例の粒界層は１〜２μｍ程度の厚さであることがわかる。また、粒界層の所々に最大径０．５μｍ程度の略楕円形状の濃淡模様が分散されていることがわかる。なお、図６に示す濃淡模様の略楕円形領域はＥＤＳ面分析（エネルギー分散型Ｘ線分析）結果から、Ｃの濃度が薄い領域であることがわかった。 FIG. 6 shows that a thin iron phosphate coating is formed on the peripheral surface of the soft magnetic particles, and a grain boundary layer is formed between adjacent soft magnetic particles. It can be seen that the grain boundary layer of this example in the visual field of FIG. 6 given as an example has a thickness of about 1 to 2 μm. It can also be seen that a substantially elliptical shading pattern having a maximum diameter of about 0.5 μm is dispersed in the grain boundary layers. It was found from the result of EDS surface analysis (energy dispersive X-ray analysis) that the light and shade pattern substantially elliptical region shown in FIG. 6 is a region having a low C concentration.
図７は先の実施例４で作製したゾル‐ゲルコーティング液（シリカ系絶縁皮膜形成用コーティング液）を塗布したリン酸鉄被覆鉄粉を大気中で２００℃に０．５時間加熱し乾燥することで得たシリカゾル‐ゲル被覆鉄粉（シリカ系絶縁皮膜被覆鉄粉）のＳＥＭ拡大写真である。倍率を２０００倍としてＳＥＭ画像一杯に１つのシリカゾル‐ゲル被覆鉄粉が入る拡大率とした。
このシリカゾル‐ゲル被覆鉄粉に対し、減圧不活性ガス雰囲気中で６５０℃に３０分間加熱する熱処理を施したＳＥＭ画像を図８に示す。熱処理は、減圧不活性ガス雰囲気中（試料を収容したチャンバー内を３００Ｐａ程度となるように減圧し、常時微量（３０ｃｃ／ｍｉｎ）の窒素ガスを流入している雰囲気）において６５０℃に保持することで行った。昇温速度は２〜１０℃／分としている。試料外周面の状態は殆ど変わらないが、詳細に観察すると、熱処理後の鉄粉外面の底部側には微細な凹凸部分が若干生成されている。
この微細な凹凸はシリカゾル‐ゲル被覆鉄粉の表面に生成した酸化鉄の微結晶である。その個数を測定した。個数の計測方法は、試料の中から任意選択したシリカ系絶縁被覆鉄粉１０個のそれぞれに対し、２０００倍の写真から画像解析を行い、鉄粉の周面に存在する粒径５００ｎｍ以上の酸化鉄微細結晶の数を計測し、その平均値を算出した。酸化鉄微結晶数の平均値は、不活性ガス雰囲気で加熱する前のシリカ系絶縁被覆鉄粉表面の皮膜に存在する欠陥の数と等価であると考えられる。
計測結果の平均値は５２個であった。
FIG. 7 shows that iron phosphate-coated iron powder coated with the sol-gel coating solution (silica-based insulating film forming coating solution) prepared in Example 4 is heated to 200 ° C. for 0.5 hours in the air and dried. It is a SEM enlarged photograph of the silica sol-gel coating iron powder (silica type insulating film coating iron powder) obtained by this. The magnification was set to 2000 ×, and the magnification was such that one silica sol-gel-coated iron powder would fill the SEM image.
FIG. 8 shows an SEM image in which this silica sol-gel coated iron powder was heat-treated by heating to 650 ° C. for 30 minutes in a reduced-pressure inert gas atmosphere. The heat treatment is to be maintained at 650 ° C. in a reduced pressure inert gas atmosphere (the pressure in the chamber containing the sample is reduced to about 300 Pa, and a constant amount of nitrogen gas is flowing in). I went there. The heating rate is 2 to 10 ° C./min. Although the state of the outer peripheral surface of the sample is hardly changed, a minute uneven portion is slightly generated on the bottom side of the outer surface of the iron powder after heat treatment when observed in detail.
The fine irregularities are fine crystals of iron oxide formed on the surface of the silica sol-gel coated iron powder. The number was measured. The number of particles is measured by performing image analysis on each of the 10 silica-based insulating coated iron powders arbitrarily selected from the samples from a 2000-fold photograph, and oxidizing the particles having a particle diameter of 500 nm or more present on the peripheral surface of the iron powder. The number of fine iron crystals was measured and the average value was calculated. It is considered that the average value of the number of iron oxide microcrystals is equivalent to the number of defects present in the film on the surface of the silica-based insulating coated iron powder before heating in an inert gas atmosphere.
The average value of the measurement results was 52.
図９は実施例４で用いたゾル‐ゲルコーティング液（シリカ系絶縁皮膜形成用コーティング液）の代わりに、溶媒にシリコーンレジンのみを添加し、ＴＥＯＳ、塩酸、水の添加を略し、その他は同等の工程を経て得た、従来のシリコーン被覆鉄粉のＳＥＭ拡大写真である。この鉄粉に対し、減圧不活性ガス雰囲気中で６５０℃に３０分間加熱する熱処理を施したＳＥＭ画像を図１０に示す。加熱条件は図８に示す試料の条件と同等である。
外周面の状態は容易に判別できるほど変化が現れ、熱処理後の鉄粉外面の底部側には微細な凹凸部分が多数新たに生成されている。
これらの微細凹凸は酸化鉄の結晶が成長したものである。このように純鉄の軟磁性粉末の外周面に微細な酸化鉄微結晶が多数生成すると、この軟磁性粉末の粒子からなる圧粉磁心では比抵抗が大幅に低下する原因になると推定できる。
FIG. 9 shows that instead of the sol-gel coating solution (silica-based insulating film forming coating solution) used in Example 4, only silicone resin was added to the solvent, TEOS, hydrochloric acid and water were omitted, and the others were the same. It is a SEM enlarged photograph of the conventional silicone covering iron powder obtained through the process of. FIG. 10 shows an SEM image in which this iron powder was heat-treated at 650 ° C. for 30 minutes in a reduced-pressure inert gas atmosphere. The heating conditions are the same as the sample conditions shown in FIG.
A change appears so that the state of an outer peripheral surface can be discriminate | determined easily, and many fine uneven | corrugated parts are newly produced | generated by the bottom part side of the iron powder outer surface after heat processing.
These fine irregularities are the growth of iron oxide crystals. When a large number of fine iron oxide crystallites are formed on the outer peripheral surface of the pure magnetic soft magnetic powder in this way, it can be estimated that the specific resistance is greatly reduced in the dust core made of the soft magnetic powder particles.
このため、図８に示す熱処理後のシリカゾル‐ゲル被覆鉄粉において酸化鉄微結晶の析出が殆ど見られないことから、このシリカゾル‐ゲル被覆鉄粉を圧縮して粒界層と共に焼成した圧粉磁心は、６５０℃程度に加熱されたとしても、比抵抗の低下が起こりにくく、このため本発明の圧粉磁心は優れた耐熱性を具備していることがわかる。 For this reason, since precipitation of iron oxide microcrystals is hardly seen in the silica sol-gel coated iron powder after the heat treatment shown in FIG. 8, this silica sol-gel coated iron powder is compressed and fired together with the grain boundary layer. Even when the magnetic core is heated to about 650 ° C., the specific resistance is unlikely to decrease, and thus it can be seen that the powder magnetic core of the present invention has excellent heat resistance.
前述のシリカゾル‐ゲル被覆鉄粉を製造する場合、メチル系シリコーンレジンを液温４５℃の２−プロパノール（ＩＰＡ）に混合し２時間攪拌して溶解し、この溶液にテトラエトキシシラン（ＴＥＯＳ）を室温にて４時間攪拌して混合していた。
これに対し、メチル系シリコーンレジンを液温４５℃の２−プロパノール（ＩＰＡ）に混合する場合の攪拌時間を３０分に変更し、その他の処理は同等とした場合に得られた試料の昇温観察結果（ＥＳＥＭ画像）を図１１に示す。図１１は減圧不活性ガス雰囲気中において５００℃到達時、６００℃到達時、６５０℃到達時、６５０℃で０．５時間保持後のそれぞれの時点での試料の表面状態を示している。加熱条件は図８に示す試料の条件と同等である。
この試料の熱履歴において、６５０℃で０.５時間加熱する条件においては多少酸化鉄微結晶の析出を確認できた。この試料において先に説明した方法と同じ方法で酸化鉄微結晶の平均個数を求めた。その結果、酸化鉄微結晶の平均析出個数は２６８個であった。この結果から、シリカゾル‐ゲル被覆鉄粉を製造する場合、シリコーンレジンとテトラエトキシシラン（ＴＥＯＳ）を溶媒に混合する工程が重要であると思われる。
When manufacturing the above-mentioned silica sol-gel coated iron powder, methyl silicone resin is mixed with 2-propanol (IPA) at a liquid temperature of 45 ° C. and stirred for 2 hours to dissolve, and tetraethoxysilane (TEOS) is dissolved in this solution. The mixture was stirred for 4 hours at room temperature.
In contrast, when the methyl silicone resin was mixed with 2-propanol (IPA) having a liquid temperature of 45 ° C., the stirring time was changed to 30 minutes, and other treatments were made equivalent, and the temperature of the sample obtained was increased. An observation result (ESEM image) is shown in FIG. FIG. 11 shows the surface condition of the sample at each time after reaching 500 ° C., reaching 600 ° C., reaching 650 ° C., and holding at 650 ° C. for 0.5 hours in a reduced-pressure inert gas atmosphere. The heating conditions are the same as the sample conditions shown in FIG.
In the thermal history of this sample, the precipitation of iron oxide microcrystals was somewhat confirmed under the condition of heating at 650 ° C. for 0.5 hour. In this sample, the average number of iron oxide microcrystals was determined by the same method as described above. As a result, the average number of precipitated iron oxide microcrystals was 268. From this result, when producing silica sol-gel coated iron powder, it seems that the process of mixing silicone resin and tetraethoxysilane (TEOS) in a solvent is important.
図１２は比較のために、先の実施例を製造する工程において溶媒に対しシリコーンレジンのみを溶解し、この溶液をコーティング液としてリン酸鉄被覆鉄粉に塗布し、これを乾燥して得たコーティング鉄粉の加熱試験結果を示す。試料製造条件において、その他の条件は先の実施例の場合と同様である。
また、図１２に先の実施例を製造する工程において溶媒に対しシリコーンレジンを略してＴＥＯＳゾル‐ゲルを混合撹拌し、この溶液をコーティング液としてリン酸鉄被覆鉄粉に塗布し、これを乾燥して得たコーティング鉄粉の加熱試験結果を示す。試料製造条件において、その他の条件は先の実施例の場合と同様である。
各試料とも、減圧不活性ガス雰囲気中において５００℃到達時、６００℃到達時、６５０℃到達時、６５０℃×０．５時間保持直後のそれぞれの時点での試料の表面状態を昇温観察したＥＳＥＭ画像で示す。昇温条件は図８に示す試料の条件と同等である。
図１２に示すＥＳＥＭ画像では６５０℃到達時の段階から酸化鉄微細結晶が大量に生成していることがわかる。このことから、シリコーンレジンのみ、あるいは、ＴＥＯＳのみを溶媒と混合撹拌して得たコーティング鉄粉は昇温とともに皮膜に欠陥が生じやすいため特性が低下すると想定できる。
For comparison, FIG. 12 was obtained by dissolving only the silicone resin in the solvent in the process of producing the previous example, applying this solution to the iron phosphate-coated iron powder as a coating solution, and drying the solution. The heating test result of coating iron powder is shown. In the sample manufacturing conditions, other conditions are the same as in the previous embodiment.
Further, in the process of manufacturing the previous embodiment in FIG. 12, the silicone resin is abbreviated with respect to the solvent and the TEOS sol-gel is mixed and stirred, and this solution is applied to the iron phosphate-coated iron powder as a coating solution and dried. The heating test result of the coated iron powder obtained in this way is shown. In the sample manufacturing conditions, other conditions are the same as in the previous embodiment.
For each sample, the surface condition of the sample at each time immediately after holding at 650 ° C. × 0.5 hours was observed at elevated temperatures when reaching 500 ° C., reaching 600 ° C., reaching 650 ° C. in a vacuum inert gas atmosphere. Shown in ESEM image. The temperature raising conditions are the same as the sample conditions shown in FIG.
In the ESEM image shown in FIG. 12, it can be seen that a large amount of iron oxide fine crystals are generated from the stage when the temperature reaches 650 ° C. From this, it can be assumed that the coating iron powder obtained by mixing and stirring only a silicone resin or only TEOS with a solvent tends to cause defects in the film as the temperature rises, so that the characteristics can be assumed to deteriorate.
図１３は比較例２で用いたゾル‐ゲルコーティング液（シリカ系絶縁皮膜形成用コーティング液）の代わりに、シリコーンレジン添加量を０．５４質量％、０．７２質量％にそれぞれ設定し、（シリコーンレジンと溶媒との混合撹拌時間を２時間に変更し、さらにこれらにＴＥＯＳを添加した後の撹拌混合時間を４時間）に変更し、その他の条件は同等として製造したコーティング液を塗布し乾燥させたコーティング鉄粉のＥＳＥＭでの昇温観察の結果を示す。昇温条件は先の例と同等である。
図１３に示すＥＳＥＭ画像では５００〜６５０℃加熱において酸化鉄微結晶の析出を殆ど確認できなかった。６５０℃×０．５時間加熱では多少の酸化鉄微結晶の析出を確認できたが、この試料の酸化鉄微細結晶の数は５２個であり、極めて少ない数であった。
このことからも、溶媒に添加する際のシリコーンレジン、ＴＥＯＳの攪拌混合を十分に行うことが重要であることがわかった。
In FIG. 13, instead of the sol-gel coating liquid (silica-based insulating film forming coating liquid) used in Comparative Example 2, the silicone resin addition amount was set to 0.54 mass% and 0.72 mass%, respectively ( Change the mixing and stirring time of the silicone resin and solvent to 2 hours, change the stirring and mixing time after adding TEOS to 4 hours, and apply the coating solution prepared under the same conditions. The result of the temperature rising observation by the ESEM of the coated iron powder made is shown. The temperature raising conditions are the same as in the previous example.
In the ESEM image shown in FIG. 13, almost no precipitation of iron oxide microcrystals was observed when heated at 500 to 650 ° C. Although some precipitation of iron oxide fine crystals could be confirmed by heating at 650 ° C. × 0.5 hours, the number of iron oxide fine crystals in this sample was 52, which was an extremely small number.
Also from this fact, it was found that it is important to sufficiently mix and mix the silicone resin and TEOS when added to the solvent.
次に、前述の如く製造されたコーティング液の粘度について説明する。
コーティング液を製造する場合、以下の３通りの条件にて組成例（１）、（２）、（３）のコーティング液を製造した。
○組成（１）
シリコーンレジンＡ１：１．２２ｇ（６．４２質量％）、ＩＰＡ：１３．３９ｇ（７０．４５質量％）、ＴＥＯＳ：３．７３ｇ（１９．６２質量％）、Ｈ２Ｏ：０．６５ｇ（３．４２質量％）、１２ＮＨＣｌ：０．０１７ｇ（０．０９質量％）。ＴＥＯＳ由来のＳｉＯ２膜厚：３３．８ｎｍ、０．４１％シリコーンレジンＡ１と表記。
○組成（２）
シリコーンレジンＡ１：１．６２ｇ（８．５３質量％）、ＩＰＡ：８．６０ｇ（４５．２８質量％）、ＴＥＯＳ：７．４５ｇ（３９．２３質量％）、Ｈ２Ｏ：１．２９ｇ（６．７９質量％）、１２ＮＨＣｌ：０．０３３ｇ（０．１７質量％）。ＴＥＯＳ由来のＳｉＯ２膜厚：６７．５ｎｍ、０．５４％シリコーンレジンＡ１と表記。
Next, the viscosity of the coating solution produced as described above will be described.
When manufacturing a coating liquid, the coating liquid of the composition example (1), (2), (3) was manufactured on the following three conditions.
○ Composition (1)
Silicone resin A 1 : 1.22 g (6.42 mass%), IPA: 13.39 g (70.45 mass%), TEOS: 3.73 g (19.62 mass%), H 2 O: 0.65 g ( 3.42% by mass), 12N HCl: 0.017 g (0.09% by mass). TEOS-derived SiO 2 film thickness: 33.8 nm, expressed as 0.41% silicone resin A 1
○ Composition (2)
Silicone resin A 1 : 1.62 g (8.53 mass%), IPA: 8.60 g (45.28 mass%), TEOS: 7.45 g (39.23 mass%), H 2 O: 1.29 g ( 6.79% by mass), 12N HCl: 0.033 g (0.17% by mass). TEOS-derived SiO 2 film thickness: 67.5 nm, expressed as 0.54% silicone resin A 1
○組成（３）
シリコーンレジンＢ１：０．６１ｇ（６．４２質量％）、ＩＰＡ：６．７０ｇ（７０．４５質量％）、ＴＥＯＳ：１．８６ｇ（１９．６２質量％）、Ｈ２Ｏ：０．３２ｇ（３．４２質量％）、ＨＣｌ：０．００８ｇ（０．０９質量％）。ＴＥＯＳ由来のＳｉＯ２膜厚：１６．９ｎｍ、０．２０％シリコーンレジンＢ１と表記。
・［Ｈ２Ｏ］／［ＴＥＯＳ］＝２（モル比）
・［１２ＮＨＣｌ］／［ＴＥＯＳ］＝０．０２５（モル比）
前記組成（１）は先に記載の第２実施例作製用コーティング液、第３実施例作製用コーティング液、第５実施例作製用コーティング液に相当し、組成（２）は第４実施例作製用コーティング液に相当し、組成（３）は第１実施例作製用コーティング液に相当する。
○ Composition (3)
Silicone resin B 1 : 0.61 g (6.42 mass%), IPA: 6.70 g (70.45 mass%), TEOS: 1.86 g (19.62 mass%), H 2 O: 0.32 g ( 3.42% by mass), HCl: 0.008 g (0.09% by mass). TEOS-derived SiO 2 film thickness: 16.9 nm, expressed as 0.20% silicone resin B 1
[H 2 O] / [TEOS] = 2 (molar ratio)
[12NHCl] / [TEOS] = 0.025 (molar ratio)
The composition (1) corresponds to the coating liquid for preparation of the second embodiment, the coating liquid for preparation of the third embodiment, and the coating liquid for preparation of the fifth embodiment, and the composition (2) is preparation of the fourth embodiment. The composition (3) corresponds to the coating liquid for producing the first embodiment.
ＴＥＯＳ由来のＳｉＯ２皮膜の膜厚は、軟磁性粉末の比表面積（ＢＥＴ３点法による測定値）、ＳｉＯ２密度（水晶の物性値２．６５ｇ／ｃｍ３）を用いて以下の式から算出した。 ＳｉＯ２皮膜の膜厚（ｎｍ）＝ＴＥＯＳの物質量（ｍｏｌ）×ＳｉＯ２分子量（ｇ／ｍｏｌ）／ＳｉＯ２密度（ｇ／ｃｍ３）／軟磁性粉末の比表面積（ｍ２／ｇ）／軟磁性粉末重量（ｇ） （＊）
（計算例）ＴＥＯＳ重量７．４５ｇ、鉄粉比表面積４．０×１０−２ｍ２／ｇ、鉄粉重量３００ｇの場合
上記計算式（＊）にＴＥＯＳ分子量２０８．１ｇ／ｍｏｌ、ＳｉＯ２分子量６０．１ｇ／ｍｏｌを代入して、ＳｉＯ２被膜の膜厚＝７．４５（ｇ）／２０８．１（ｇ／ｍｏｌ）×６０．１（ｇ／ｍｏｌ）／２．６５（ｇ／ｃｍ３）／４．０×１０−２（ｍ２／ｇ）／ ３００（ｇ）＝６．７６×１０−８（ｍ）＝６７．６（ｎｍ）。
The film thickness of the TEOS-derived SiO 2 film was calculated from the following equation using the specific surface area of the soft magnetic powder (measured by the BET three-point method) and the SiO 2 density (physical property value of crystal 2.65 g / cm 3 ). . SiO 2 film thickness (nm) = TEOS substance amount (mol) × SiO 2 molecular weight (g / mol) / SiO 2 density (g / cm 3 ) / specific surface area of soft magnetic powder (m 2 / g) / Soft magnetic powder weight (g) (*)
(Calculation example) TEOS weight 7.45 g, iron powder specific surface area 4.0 × 10 −2 m 2 / g, iron powder weight 300 g TEOS molecular weight 208.1 g / mol, SiO 2 molecular weight in the above formula (*) Substituting 60.1 g / mol, the film thickness of the SiO 2 film = 7.45 (g) /208.1 (g / mol) × 60.1 (g / mol) /2.65 (g / cm 3 ) /4.0×10 −2 (m 2 / g) / 300 (g) = 6.76 × 10 −8 (m) = 67.6 (nm).
それぞれのコーティング液を製造する場合、シリコーンレジンを溶媒に溶解するための撹拌時間と得られたコーティング液の粘度との関係を調べた。具体的には試料温度２５℃、コーンスピンドル回転数５０ｒｐｍの条件で粘度測定を行った。
粘度測定は、コーンプレート型粘度計（ブルックフィールド社製、ＬＶ−ＤＶ２Ｔ ＣＰ）、スピンドルはＣＰＡ−４０Ｚを用い、循環恒温槽はフーバー社製、ＭＰＣ−Ｋ６を用いた。
組成（１）、組成（２）、組成（３）のそれぞれのコーティング液の撹拌時間と粘度の関係を求めた。それらの関係を以下の表２に記載した。
When manufacturing each coating liquid, the relationship between the stirring time for dissolving the silicone resin in the solvent and the viscosity of the obtained coating liquid was examined. Specifically, the viscosity was measured under the conditions of a sample temperature of 25 ° C. and a cone spindle rotation speed of 50 rpm.
For the viscosity measurement, a cone plate viscometer (Brookfield, LV-DV2T CP), a spindle using CPA-40Z, and a circulating thermostat using Hoover, MPC-K6 were used.
The relationship between the stirring time and the viscosity of each coating liquid of composition (1), composition (2), and composition (3) was determined. Their relationships are listed in Table 2 below.
表２に示す組成（１）、（２）、（３）のそれぞれの試料について、レジン溶解・撹拌時間の関係を以下の図１４、図１５、図１６に示す。
図１４は組成（１）の試料における粘度とレジン溶解・撹拌時間の関係を示し、図１５は組成（２）の試料における粘度とレジン溶解・撹拌時間の関係を示し、図１６は組成（３）の試料における粘度とレジン溶解・撹拌時間の関係を示す。
これらの図に示す結果から、いずれの組成においても、撹拌時間１００分程度までは粘度の値が安定しないことがわかる。粘度が安定するのは１２０分程度以降と認識できるので、粘度を安定化するためのレジン溶解・撹拌時間は２時間以上必要であることがわかった。
また、いずれの組成においても、２時間以上経過後は、粘度が２．８〜５．５ｍＰａ・ｓの範囲内、より詳しくは、３．０〜４．５ｍＰａ・ｓの範囲内に収まっていることがわかる。粘度値がこの範囲になるならば、コーティング液内のシリコーンレジンとＴＥＯＳの分散状態が安定化状態に入ったと推定できる。更に、１２０分経過後はいずれの試料も粘度が安定しており、粘度値の偏差は±２％の範囲内に納まっていることが判る。
本明細書において、最終的な粘度到達値は、以下のように定義する。
最終的な粘度到達値：シリカ系絶縁皮膜形成用コーティング液調製工程において、シリコーンレジンを溶媒に添加して混合撹拌（溶解撹拌）を２４時間行うという操作（図５（Ａ）に該当）を経た後の液にＴＥＯＳ、塩酸、水を添加して得られたコーティング液の粘度値。
FIG. 14, FIG. 15 and FIG. 16 show the relationship between the resin dissolution and stirring time for each of the compositions (1), (2) and (3) shown in Table 2.
FIG. 14 shows the relationship between viscosity and resin dissolution / stirring time in the sample of composition (1), FIG. 15 shows the relationship between viscosity and resin dissolution / stirring time in the sample of composition (2), and FIG. ) Shows the relationship between viscosity and resin dissolution / stirring time.
From the results shown in these figures, it can be seen that in any composition, the viscosity value is not stable until the stirring time is about 100 minutes. Since it can be recognized that the viscosity is stabilized after about 120 minutes, it was found that the resin dissolution / stirring time for stabilizing the viscosity requires 2 hours or more.
In any composition, after 2 hours or more, the viscosity is within the range of 2.8 to 5.5 mPa · s, more specifically within the range of 3.0 to 4.5 mPa · s. I understand that. If the viscosity value falls within this range, it can be estimated that the dispersed state of the silicone resin and TEOS in the coating solution has entered a stabilized state. Further, it can be seen that after 120 minutes, the viscosity of all the samples is stable and the deviation of the viscosity value is within ± 2%.
In this specification, the final viscosity reached value is defined as follows.
Final viscosity reached value: In the step of preparing a coating liquid for forming a silica-based insulating film, an operation (corresponding to FIG. 5 (A)) in which a silicone resin was added to a solvent and mixed and stirred (dissolved stirring) was performed for 24 hours. Viscosity value of the coating solution obtained by adding TEOS, hydrochloric acid and water to the later solution.
次に、前述の実施例３で得られた圧粉磁心の粒界層の一部を分析した結果を示す。
実施例３で得られた圧粉磁心の粒界層について、任意の１０カ所を選択し、ＳＴＥＭでのＥＤＳによる元素分析を行った結果を以下に示す。以下の分析値で％はａｔ％を示す。
第１の分析位置「Ｏ：５７．１７％、Ｓｉ：４１．８６％、Ｆｅ：０．９７％」
第２の分析位置「Ｏ：６５．４０％、Ｓｉ：３３．９６％、Ｐ：０．２０％、Ｆｅ：０．４４％」
第３の分析位置「Ｏ：６４．１６％、Ｓｉ：３５．４１％、Ｐ：０．１１％、Ｆｅ：０．３２％」
第４の分析位置「Ｏ：６４．２０％、Ｓｉ：３５．４０％、Ｆｅ：０．４０％」
第５の分析位置「Ｏ：６１．３２％、Ｓｉ：３８．３７％、Ｆｅ：０．３１％」
第６の分析位置「Ｏ：６７．６４％、Ｓｉ：３１．６％、Ｆｅ：０．７６％」
第７の分析位置「Ｏ：６８．８９％、Ｓｉ：２９．７３％、Ｆｅ：１．３７％」
第８の分析位置「Ｏ：６８．２６％、Ｓｉ：３１．３６％、Ｆｅ：０．３８％」
第９の分析位置「Ｏ：７０．０９％、Ｓｉ：２９．４７％、Ｆｅ：０．４４％」
第１０の分析位置「Ｏ：７０．３６％、Ｓｉ：２９．０６％、Ｆｅ：０．５８％」
Next, the result of analyzing a part of the grain boundary layer of the dust core obtained in Example 3 will be shown.
Regarding the grain boundary layer of the dust core obtained in Example 3, arbitrary 10 locations were selected, and the results of elemental analysis by EDS in STEM are shown below. In the following analysis values,% indicates at%.
First analysis position “O: 57.17%, Si: 41.86%, Fe: 0.97%”
Second analysis position “O: 65.40%, Si: 33.96%, P: 0.20%, Fe: 0.44%”
Third analysis position “O: 64.16%, Si: 35.41%, P: 0.11%, Fe: 0.32%”
Fourth analysis position “O: 64.20%, Si: 35.40%, Fe: 0.40%”
Fifth analysis position “O: 61.32%, Si: 38.37%, Fe: 0.31%”
Sixth analysis position “O: 67.64%, Si: 31.6%, Fe: 0.76%”
Seventh analysis position “O: 68.89%, Si: 29.73%, Fe: 1.37%”
Eighth analysis position “O: 68.26%, Si: 31.36%, Fe: 0.38%”
Ninth analysis position “O: 70.09%, Si: 29.47%, Fe: 0.44%”
Tenth analysis position “O: 70.36%, Si: 29.06%, Fe: 0.58%”
これらの分析結果から、粒界層のいずれの部分においてもＦｅの存在を確認することができ、粒界層にＦｅの軟磁性粒子からＦｅが拡散されていることで、圧粉磁心において上述の如く優れた磁気特性が得られたと推定できる。 From these analysis results, the presence of Fe can be confirmed in any part of the grain boundary layer, and Fe is diffused from the soft magnetic particles of Fe in the grain boundary layer. It can be estimated that excellent magnetic properties were obtained.
Ａ…圧粉磁心、Ｂ…シリカ系絶縁被覆軟磁性粉末、５…軟磁性粉末、６…リン酸塩被覆、７…シリカ系絶縁皮膜、１１…軟磁性粉末粒子、１２…粒界層、１３…リン酸塩被覆、１４…リアクトル（電磁気回路部品）、１４ａ…リアクトルコア、１４ｂ…コイル部。 A ... dust core, B ... silica-based insulating coating soft magnetic powder, 5 ... soft magnetic powder, 6 ... phosphate coating, 7 ... silica-based insulating coating, 11 ... soft magnetic powder particles, 12 ... grain boundary layer, 13 ... Phosphate coating, 14 ... Reactor (electromagnetic circuit component), 14a ... Reactor core, 14b ... Coil part.
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| JPH02220308A (en) * | 1989-02-20 | 1990-09-03 | Sumitomo Electric Ind Ltd | Coating material composition and insulated wire |
| JPH0845724A (en) * | 1994-07-28 | 1996-02-16 | Tdk Corp | Dust core |
| JP2006057157A (en) * | 2004-08-23 | 2006-03-02 | Mitsubishi Materials Corp | Method for producing metal soft magnetic core material and metal soft magnetic core material produced by the method |
| JP2007197824A (en) * | 2005-12-28 | 2007-08-09 | Jfe Steel Kk | Electromagnetic steel sheet with insulating coating film |
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| JP2017073447A (en) * | 2015-10-06 | 2017-04-13 | Ntn株式会社 | Powder-compact magnetic core material, powder-compact magnetic core, and manufacturing method therefor |
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