JP2016184703A - Method for producing magnetic fine particle - Google Patents
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- JP2016184703A JP2016184703A JP2015064959A JP2015064959A JP2016184703A JP 2016184703 A JP2016184703 A JP 2016184703A JP 2015064959 A JP2015064959 A JP 2015064959A JP 2015064959 A JP2015064959 A JP 2015064959A JP 2016184703 A JP2016184703 A JP 2016184703A
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- 239000010419 fine particle Substances 0.000 title claims abstract description 97
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims abstract description 34
- 125000000524 functional group Chemical group 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 33
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000002091 cationic group Chemical group 0.000 claims abstract description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 9
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 9
- 125000000129 anionic group Chemical group 0.000 claims abstract description 6
- 239000000696 magnetic material Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 17
- 239000007788 liquid Substances 0.000 abstract description 5
- 230000005415 magnetization Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 239000011148 porous material Substances 0.000 description 8
- 150000008040 ionic compounds Chemical class 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 5
- 230000004043 responsiveness Effects 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000779 poly(divinylbenzene) Polymers 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-ISLYRVAYSA-N V-65 Substances CC(C)CC(C)(C#N)\N=N\C(C)(C#N)CC(C)C WYGWHHGCAGTUCH-ISLYRVAYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910001172 neodymium magnet Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- Soft Magnetic Materials (AREA)
Abstract
Description
本発明は、磁性微粒子の製造方法に関し、特に湿式方法にて得られた磁性微粒子の分散液を乾燥させることを特徴とする磁性微粒子の製造方法に関する。 The present invention relates to a method for producing magnetic fine particles, and more particularly, to a method for producing magnetic fine particles characterized by drying a dispersion of magnetic fine particles obtained by a wet method.
従来、微粒子を磁性化する際には、例えば高分子微粒子を多孔質にしてその孔に磁性体をイオン的もしくは物理的に吸着させる、もしくは高分子微粒子と磁性体を乾式回転方法によって物理的に高分子微粒子表面に磁性体をコーティングする方法が用いられていた（特許文献１）。多孔質高分子微粒子を使用する場合には、孔の奥深くまで磁性体が浸透することによる磁気応答性の低下や、磁気応答性確保のために過剰な磁性体添加を原因とする比重増大による分散安定性の低下が起こる。また、高分子微粒子と磁性体を乾式回転方式にて実施する際には、高価な装置を必要として汎用性に欠けるという問題があった。 Conventionally, when magnetizing fine particles, for example, the fine polymer particles are made porous and the magnetic material is adsorbed ionically or physically in the pores, or the fine polymer particles and the magnetic material are physically separated by a dry rotation method. A method of coating the surface of polymer fine particles with a magnetic material has been used (Patent Document 1). When using porous polymer fine particles, dispersion due to decrease in magnetic response due to penetration of magnetic material deep into the hole and increase in specific gravity due to excessive addition of magnetic material to ensure magnetic response A decrease in stability occurs. Further, when the polymer fine particles and the magnetic material are carried out by a dry rotation method, there is a problem that an expensive apparatus is required and lacks versatility.
本発明は、微粒子に対して磁性化を行う際に、多孔質微粒子を用いなくても、また高価な装置を使わなくても磁性微粒子を製造することができる方法を提供するものである。 The present invention provides a method for producing magnetic fine particles without using porous fine particles or using an expensive apparatus when magnetizing fine particles.
本発明者は、鋭意検討の結果、以下の方法をとることで、上記問題点を解決しうることを見出し、本発明を完成した。 As a result of intensive studies, the present inventor has found that the above problems can be solved by taking the following method, and has completed the present invention.
即ち、本発明は以下のとおりである。
（１）湿式方法にて得られた磁性微粒子の分散液を乾燥させることを特徴とする、磁性微粒子の製造方法。
（２）（１）に記載の方法において、湿式方法にて得られた磁性微粒子の分散液が、金属酸化物被覆微粒子と磁性体とを反応させて得られたものである方法。
（３）（２）に記載の方法において、金属酸化物が酸化鉄である方法。
（４）（１）に記載の方法において、湿式法にて得られた磁性微粒子の分散液が、微粒子表面にあるイオン性官能基と、磁性体表面にあり、微粒子表面にあるイオン性官能基とは反対の電荷を有するイオン性官能基とを反応させて得られたものである方法。
（５）（１）乃至（４）いずれかに記載の方法において、磁性体表面にカチオン性官能基がある方法。
（６）（１）１乃至（４）いずれかに記載の方法において、磁性体表面にアニオン性官能基がある方法。
以下に本発明を更に詳細に説明する。
That is, the present invention is as follows.
(1) A method for producing magnetic fine particles, comprising drying a dispersion of magnetic fine particles obtained by a wet method.
(2) The method according to (1), wherein the dispersion of magnetic fine particles obtained by a wet method is obtained by reacting metal oxide-coated fine particles with a magnetic substance.
(3) The method according to (2), wherein the metal oxide is iron oxide.
(4) In the method described in (1), the dispersion liquid of the magnetic fine particles obtained by the wet method is present on the surface of the fine particles and the ionic functional group on the surface of the magnetic material. A method obtained by reacting an ionic functional group having a charge opposite to the above.
(5) The method according to any one of (1) to (4), wherein the magnetic surface has a cationic functional group.
(6) The method according to any one of (1) 1 to (4), wherein the magnetic surface has an anionic functional group.
The present invention is described in further detail below.
本発明の湿式方法にて得られた磁性微粒子の分散液とは、溶媒中で微粒子に磁性体を導入させて得られた磁性微粒子の分散液である。この際に、磁性体が均一に分散（コロイド状分散状態を含む）する溶媒を用いたものであり、水溶液、有機溶媒から適宜選択したものを用いればよい。 The dispersion of magnetic fine particles obtained by the wet method of the present invention is a dispersion of magnetic fine particles obtained by introducing a magnetic substance into fine particles in a solvent. At this time, a solvent in which the magnetic substance is uniformly dispersed (including a colloidal dispersion state) is used, and a solvent appropriately selected from an aqueous solution and an organic solvent may be used.
本発明で用いられる微粒子とは、ガラス、金属、セラミツクス等の無機物であってもよく、また高分子ポリマー等の有機物であってもよい。またそれらの微粒子は磁性体を含むものであってもよい。微粒子の粒子径は０．１から５０μｍが好ましく、さらには１から１０μｍが好ましい。また微粒子は細孔を有しても有さなくてもよいが、細孔を有さない表面が平滑なものであっても本発明の方法は適用できる点に特徴がある。なお微粒子の表面とは、微粒子の外表面ばかりでなく、細孔を有する微粒子の場合は細孔内表面を含めてもよい。 The fine particles used in the present invention may be inorganic substances such as glass, metal, ceramics, etc., and may be organic substances such as polymer polymers. The fine particles may contain a magnetic material. The particle diameter of the fine particles is preferably from 0.1 to 50 μm, more preferably from 1 to 10 μm. The fine particles may or may not have pores, but are characterized in that the method of the present invention can be applied even if the surface having no pores is smooth. The surface of the fine particles may include not only the outer surface of the fine particles, but also the inner surface of the fine pores in the case of fine particles having pores.
本発明の微粒子は、金属酸化物で被覆されたものであってもよい。金属酸化物とは、ＦｅＯ、Ｆｅ３Ｏ４、Ｆｅ２Ｏ３、Ｃｕ２Ｏ、ＣｕＯ、Ａｇ２Ｏ、ＡｇＯ、Ａｕ２Ｏ３、Ｔｉ２Ｏ、ＴｉＯ、ＲｕＯ２、ＲｕＯ４等があげられ、特に酸化鉄が好ましい。 The fine particles of the present invention may be coated with a metal oxide. Examples of the metal oxide include FeO, Fe 3 O 4 , Fe 2 O 3 , Cu 2 O, CuO, Ag 2 O, AgO, Au 2 O 3 , Ti 2 O, TiO, RuO 2 , and RuO 4. In particular, iron oxide is preferable.
また本発明の微粒子上にイオン性官能基があってもよい。イオン性官能基とは、アミノ基、イミノ基等のカチオン性官能基、スルホニル基、カルボキシル基、フェノール性水酸基、アルコール性水酸基等のアニオン性官能基があげられる。イオン性官能基は、微粒子が既にそのような官能基を表面に有している場合（例えばイオン性官能基を有する高分子ポリマー微粒子）は、それをそのまま利用すればよい。一方、そのような官能基を有していない微粒子の場合（例えばイオン性官能基を有さない高分子ポリマーやガラス、金属、セラミツクス等の微粒子）は、その微粒子表面に官能基を導入すればよい。その方法としては特に限定されるものではないが、例えば微粒子とイオン性化合物とを反応させ、微粒子表面上にイオン性官能基を導入すればよい。このとき用いられるイオン性化合物には特に限定はないが、例えばスルホン酸、カルボン酸などの酸性化合物もしくはアンモニウム塩、フェノール性水酸基塩、アルコール性水酸基塩などが好ましい。反応条件にも特に限定はなく、例えばイオン性化合物を含む溶液に高分子微粒子を分散・反応させることにより、イオン性官能基を導入すればよい。この際に水溶性の無機もしくは有機イオン性化合物を用いる場合には溶媒として水を用いることが好ましい。有機イオン性化合物が水および有機溶媒に溶解する場合には、どちらを用いても構わない。なお、イオン性官能基を導入したのちは、十分な洗浄を行い、過剰なイオン性化合物を除去することが好ましい。 Further, an ionic functional group may be present on the fine particles of the present invention. Examples of the ionic functional group include a cationic functional group such as an amino group and an imino group, and an anionic functional group such as a sulfonyl group, a carboxyl group, a phenolic hydroxyl group, and an alcoholic hydroxyl group. As for the ionic functional group, when the fine particle already has such a functional group on the surface (for example, polymer polymer fine particle having an ionic functional group), it may be used as it is. On the other hand, in the case of fine particles not having such a functional group (for example, a polymer polymer having no ionic functional group, fine particles of glass, metal, ceramics, etc.), if a functional group is introduced on the surface of the fine particles, Good. The method is not particularly limited. For example, the ionic functional group may be introduced onto the surface of the fine particles by reacting the fine particles with an ionic compound. The ionic compound used at this time is not particularly limited, but for example, acidic compounds such as sulfonic acid and carboxylic acid or ammonium salts, phenolic hydroxyl salts, alcoholic hydroxyl salts and the like are preferable. The reaction conditions are not particularly limited, and for example, ionic functional groups may be introduced by dispersing and reacting polymer fine particles in a solution containing an ionic compound. In this case, when a water-soluble inorganic or organic ionic compound is used, it is preferable to use water as a solvent. When the organic ionic compound is dissolved in water and an organic solvent, either of them may be used. In addition, after introducing an ionic functional group, it is preferable to perform sufficient washing to remove excess ionic compounds.
一方、本発明の磁性微粒子の製造に用いられる磁性体は、その組成に特に限定はなく、例えば、フェライト、マグネタイト、マグヘマイト等があげられる。その粒子径は１から１００ｎｍが好ましい。磁性体は細孔を有しても有さなくてもよい。磁性体の表面とは、微粒子の外表面ばかりでなく、細孔を有する磁性体の場合は細孔内表面を含めてもよい。磁性体表面には、イオン性官能基（アニオン性官能基、カチオン性官能基）や脂肪酸などがあってもよい。アニオン性官能基、カチオン性官能基としては、前述と同様のものが例示される。 On the other hand, the composition of the magnetic material used for producing the magnetic fine particles of the present invention is not particularly limited, and examples thereof include ferrite, magnetite, maghemite and the like. The particle diameter is preferably 1 to 100 nm. The magnetic body may or may not have pores. The surface of the magnetic body may include not only the outer surface of the fine particles but also the inner surface of the pore in the case of a magnetic body having pores. The surface of the magnetic material may have an ionic functional group (anionic functional group, cationic functional group), a fatty acid, and the like. Examples of the anionic functional group and the cationic functional group are the same as those described above.
本発明において、前述のような微粒子に磁性体が導入されるのは、磁性体表面にイオン性官能基がある場合には、そのイオン性官能基と微粒子を被覆している金属酸化物の電子の局在化又は電荷の偏りにより結合が生じると推測される。一方、磁性体表面にイオン性官能基がない場合や脂肪酸などがある場合は、物理的吸着により金属酸化物被覆微粒子と磁性体とが結合すると推測される。 In the present invention, the magnetic substance is introduced into the fine particles as described above, when there are ionic functional groups on the surface of the magnetic substance, the electrons of the metal oxide covering the ionic functional groups and the fine particles. It is presumed that the coupling occurs due to the localization or the bias of the charge. On the other hand, when there is no ionic functional group on the surface of the magnetic material or when there is a fatty acid, it is presumed that the metal oxide-coated fine particles and the magnetic material are bonded by physical adsorption.
本発明では、湿式方法で得られた磁性微粒子の分散液を乾燥させ、磁性微粒子を得る。この時の乾燥法には特に限定はなく、磁性微粒子に悪影響値を与えない温度（例えば２０〜８０℃）で乾燥するまで行えばよい。このようにして得られた磁性微粒子は、乾燥前の分散液状態のものと比べて磁気応答性が大きく向上する。 In the present invention, the magnetic fine particle dispersion obtained by the wet method is dried to obtain magnetic fine particles. There is no particular limitation on the drying method at this time, and it may be carried out until drying is performed at a temperature (for example, 20 to 80 ° C.) that does not adversely affect the magnetic fine particles. The magnetic fine particles thus obtained have a greatly improved magnetic responsiveness as compared with those in a dispersion state before drying.
本発明ではこのようにして得られた磁性微粒子を原料として用いて、湿式方法にて磁性微粒子の分散液を得て、それを用いて本発明の磁性微粒子の製造方法を繰り返して行うことができる。これは必要な回数繰り返して行うことができ、これによって微粒子の上に必要な量の磁性体をコートすることができ、かつ磁気応答性も大きく向上する。 In the present invention, the magnetic fine particles obtained as described above are used as raw materials, a dispersion of magnetic fine particles is obtained by a wet method, and the method for producing magnetic fine particles of the present invention can be repeated using the obtained dispersion. . This can be repeated as many times as necessary, whereby a necessary amount of magnetic material can be coated on the fine particles, and the magnetic response is greatly improved.
本発明により、磁気応答性が大きく向上した磁性微粒子を得ることができる。 According to the present invention, magnetic fine particles having greatly improved magnetic responsiveness can be obtained.
以下、実施例により本発明を詳細に説明する。しかし本発明はこれら実施例にのみ限定されるものではない。 Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited only to these examples.
（実施例１）
ポリジビニルベンゼン微粒子５．０ｇ（粒子径２．５μｍ、白色）、ポリビニルピロリドン１．２ｇ、１Ｎ−塩酸水溶液６ｍＬを純水１６０ｍＬに回転数１８０ｒｐｍで分散させた。窒素雰囲気下、８０℃に昇温した後に、尿素６ｇ、塩化鉄（ＩＩ）四水和物２ｇ、塩化鉄（ＩＩＩ）六水和物３ｇを添加し５時間反応させた。この微粒子分散液をろ過にて微粒子と反応液を分離した後に、再度微粒子を純水２００ｍＬに回転数１８０ｒｐｍで分散させた。窒素雰囲気下、８０℃に昇温した後に、０．２Ｎ−水酸化ナトリウム水溶液を滴下し１５時間反応させた。純水にて洗浄し、黄土色の酸化鉄被覆された微粒子５．７５ｇを得た。
Example 1
Polydivinylbenzene fine particles 5.0 g (particle diameter 2.5 μm, white), polyvinylpyrrolidone 1.2 g, 1N hydrochloric acid aqueous solution 6 mL were dispersed in pure water 160 mL at a rotation speed of 180 rpm. After heating up to 80 ° C. in a nitrogen atmosphere, 6 g of urea, 2 g of iron (II) chloride tetrahydrate and 3 g of iron (III) chloride hexahydrate were added and reacted for 5 hours. After the fine particle dispersion was separated from the reaction liquid by filtration, the fine particles were again dispersed in 200 mL of pure water at a rotation speed of 180 rpm. After raising the temperature to 80 ° C. in a nitrogen atmosphere, a 0.2N sodium hydroxide aqueous solution was added dropwise and reacted for 15 hours. It was washed with pure water to obtain 5.75 g of fine particles coated with ocher iron oxide.
このようにして得られた微粒子１ｇを純水５０ｍＬに室温にて回転数１００ｒｐｍで分散させた。この微粒子分散液に、表面にカチオン系分散剤を有する磁性体（材質：マグネタイト、粒子径：１０ｎｍ、商品名：ＥＭＧ６０７、フェローテック社製）０．３ｇを添加し、室温にて回転数１００ｒｐｍで２時間反応させた。純水にて洗浄し、さらに５０℃で１５時間乾燥させることにより、褐色の磁性化された微粒子を１．２８ｇ得た。 1 g of the fine particles thus obtained was dispersed in 50 mL of pure water at room temperature at a rotation speed of 100 rpm. To this fine particle dispersion, 0.3 g of a magnetic substance (material: magnetite, particle diameter: 10 nm, trade name: EMG607, manufactured by Ferrotec Co., Ltd.) having a cationic dispersant on the surface is added, and the rotation speed is 100 rpm at room temperature. The reaction was performed for 2 hours. After washing with pure water and further drying at 50 ° C. for 15 hours, 1.28 g of brown magnetized fine particles were obtained.
（実施例２）
実施例１にて得られた磁性化微粒子１．２ｇを純水５０ｍＬに室温にて回転数１００ｒｐｍで分散させた。この微粒子分散液に、表面にカチオン系分散剤を有する磁性体（材質：マグネタイト、粒子径：１０ｎｍ、商品名：ＥＭＧ６０７、フェローテック社製）０．３ｇを添加し、室温にて回転数１００ｒｐｍで２時間反応させた。純水にて洗浄し、さらに５０℃で１５時間乾燥させることにより、褐色の磁性化された微粒子を１．４７ｇ得た。
(Example 2)
1.2 g of the magnetized fine particles obtained in Example 1 were dispersed in 50 mL of pure water at room temperature at a rotation speed of 100 rpm. To this fine particle dispersion, 0.3 g of a magnetic substance (material: magnetite, particle diameter: 10 nm, trade name: EMG607, manufactured by Ferrotec Co., Ltd.) having a cationic dispersant on the surface is added, and the rotation speed is 100 rpm at room temperature. The reaction was performed for 2 hours. By washing with pure water and further drying at 50 ° C. for 15 hours, 1.47 g of brown magnetized fine particles were obtained.
（実施例３）
実施例２にて得られた磁性化微粒子１．４ｇを純水５０ｍＬに室温にて回転数１００ｒｐｍで分散させた。この微粒子分散液に、表面にカチオン系分散剤を有する磁性体（材質：マグネタイト、粒子径：１０ｎｍ、商品名：ＥＭＧ６０７、フェローテック社製）０．３ｇを添加し、室温にて回転数１００ｒｐｍで２時間反応させた。純水にて洗浄し、さらに５０℃で１５時間乾燥させることにより、褐色の磁性化された微粒子を１．６７ｇ得た。
Example 3
1.4 g of the magnetized fine particles obtained in Example 2 were dispersed in 50 mL of pure water at room temperature at a rotation speed of 100 rpm. To this fine particle dispersion, 0.3 g of a magnetic substance (material: magnetite, particle diameter: 10 nm, trade name: EMG607, manufactured by Ferrotec Co., Ltd.) having a cationic dispersant on the surface is added, and the rotation speed is 100 rpm at room temperature. The reaction was performed for 2 hours. After washing with pure water and further drying at 50 ° C. for 15 hours, 1.67 g of brown magnetized fine particles were obtained.
（実施例４）
１，４−ジオキサン５０ｍＬに、ポリジビニルベンゼン微粒子１．０ｇ（粒子径２．５μｍ、白色）を回転数１００ｒｐｍにて分散させた。グリシジルメタクリレート１．３５ｇ、エチレングリコールジメタクリレート０．１５ｇ、Ｖ−６５ ０．０３ｇを添加し、６０℃に加熱し、この状態を維持したまま１５時間反応させた。反応終了後、１，４−ジオキサンおよび純水にて洗浄した後に、純水５０ｍＬに回転数１００ｒｐｍにて分散させた。この微粒子分散液に亜硫酸ナトリウム２．０ｇを添加し、６０℃に加熱し、この状態を維持したまま１５時間反応させた。反応終了後、純水にて洗浄し、表面がスルホン化された微粒子を得た。
Example 4
In 50 mL of 1,4-dioxane, 1.0 g of polydivinylbenzene fine particles (particle diameter: 2.5 μm, white) was dispersed at a rotation speed of 100 rpm. 1.35 g of glycidyl methacrylate, 0.15 g of ethylene glycol dimethacrylate and 0.03 g of V-65 were added, heated to 60 ° C., and allowed to react for 15 hours while maintaining this state. After completion of the reaction, it was washed with 1,4-dioxane and pure water, and then dispersed in 50 mL of pure water at a rotation speed of 100 rpm. To this fine particle dispersion, 2.0 g of sodium sulfite was added, heated to 60 ° C., and allowed to react for 15 hours while maintaining this state. After completion of the reaction, it was washed with pure water to obtain fine particles whose surface was sulfonated.
この微粒子１ｇを純水５０ｍＬに室温にて回転数１００ｒｐｍで分散させた。この微粒子分散液に、表面にカチオン系分散剤を有する磁性体（材質：マグネタイト、粒子径：１０ｎｍ、商品名：ＥＭＧ６０７、フェローテック社製）０．５ｇを添加し、室温にて回転数１００ｒｐｍで２時間反応させた。純水にて洗浄し、さらに５０℃で１５時間乾燥させることにより、褐色の磁性化された微粒子１．４５ｇを得た。 1 g of the fine particles was dispersed in 50 mL of pure water at room temperature at a rotation speed of 100 rpm. To this fine particle dispersion, 0.5 g of a magnetic material (material: magnetite, particle size: 10 nm, trade name: EMG607, manufactured by Ferrotec Co., Ltd.) having a cationic dispersant on the surface is added, and the rotation speed is 100 rpm at room temperature. The reaction was performed for 2 hours. After washing with pure water and further drying at 50 ° C. for 15 hours, 1.45 g of brown magnetized fine particles were obtained.
（比較例１）
乾燥工程を行わなかった以外は実施例１と同様にして、褐色の磁性化された微粒子分散液を１２．６ｇ得た（スラリー濃度１０．１％、乾燥重量換算１．２７ｇ）。
(Comparative Example 1)
Except for not carrying out the drying step, 12.6 g of a brown magnetized fine particle dispersion was obtained in the same manner as in Example 1 (slurry concentration 10.1%, dry weight conversion 1.27 g).
（比較例２）
表面にカチオン系分散剤を有する磁性体の添加量を１．０ｇとし、かつ乾燥工程を行わなかった以外は実施例１と同様にして、褐色の磁性化された微粒子分散液を１８．８ｇ得た（スラリー濃度１０．２％、乾燥重量換算１．９２ｇ）。
(Comparative Example 2)
18.8 g of a brown magnetized fine particle dispersion was obtained in the same manner as in Example 1 except that the amount of the magnetic substance having a cationic dispersant on the surface was 1.0 g and the drying step was not performed. (Slurry concentration 10.2%, dry weight conversion 1.92g).
（比較例３）
乾燥工程を行わなかった以外は実施例４と同様にして、褐色の磁性化された微粒子分散液を１４．０ｇ得た（スラリー濃度１０．５％、乾燥重量換算１．４７ｇ）。
(Comparative Example 3)
14.0 g of a brown magnetized fine particle dispersion was obtained in the same manner as in Example 4 except that the drying step was not performed (slurry concentration: 10.5%, dry weight conversion: 1.47 g).
（試験例１）
実施例１〜４、比較例１〜３にて得られた磁性化された微粒子又はその分散液をスラリー濃度１．０％の分散液とした。これら分散液１ｍＬをプラスチック製容器に入れ、超音波洗浄機（出力２４０Ｗ、周波数４０ｋＨｚ）に１０分間投入した。実施例１〜４にて得られた磁性微粒子の分散液上澄みは無色透明で磁性体の流出が確認されなかった。比較例１〜３にて得られた磁性微粒子の分散液上澄みは茶色濁った液で磁性体の流出が確認された。
(Test Example 1)
The magnetized fine particles obtained in Examples 1 to 4 and Comparative Examples 1 to 3 or dispersions thereof were used as dispersions having a slurry concentration of 1.0%. 1 mL of these dispersions were put into a plastic container and put into an ultrasonic cleaning machine (output 240 W, frequency 40 kHz) for 10 minutes. The dispersion supernatant of the magnetic fine particles obtained in Examples 1 to 4 was colorless and transparent, and no outflow of the magnetic material was confirmed. The dispersion liquid of the magnetic fine particles obtained in Comparative Examples 1 to 3 was a brownish turbid liquid, and the outflow of the magnetic material was confirmed.
（試験例２）
実施例１〜４、比較例１〜３にて得られた磁性化された微粒子をスラリー濃度０．０５％の懸濁液とした。これら懸濁液２ｍＬをプラスチック製セルに入れ、分光光度計にセットした。セル側面にネオジウム磁石を設置して吸光度の変化を測定し、初期吸光度の１０分の１となるまでの時間を算出した。実施例１〜４にて得られた磁性微粒子の測定結果は、それぞれ１６０秒、１２０秒、８０秒、１２５秒であった。比較例１〜３にて得られた磁性微粒子の測定結果は、それぞれ２００秒、１４０秒、１７５秒であった。
(Test Example 2)
The magnetized fine particles obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were used as suspensions having a slurry concentration of 0.05%. 2 mL of these suspensions were placed in a plastic cell and set in a spectrophotometer. A neodymium magnet was installed on the side of the cell, the change in absorbance was measured, and the time until it became 1/10 of the initial absorbance was calculated. The measurement results of the magnetic fine particles obtained in Examples 1 to 4 were 160 seconds, 120 seconds, 80 seconds, and 125 seconds, respectively. The measurement results of the magnetic fine particles obtained in Comparative Examples 1 to 3 were 200 seconds, 140 seconds, and 175 seconds, respectively.
これらの結果から以下のことが明らかである。
１．実施例１と比較例１の結果から、また実施例４と比較例３との結果から、湿式方法で得られた磁性微粒子分散液を乾燥させて得られた磁性微粒子は、乾燥前の分散液状態のものより磁気応答性が大きく向上していた。
２．実施例３と比較例１の結果より、実施例３は用いた磁性体の合計量がより少ないにもかかわらず、湿式方法による磁性微粒子分散液の製造と乾燥工程を繰り返すことにより、磁気応答性が大きく向上していた。
３．実施例１〜３の結果より、湿式方法による磁性微粒子分散液の製造と乾燥工程の繰り返しにより、磁気応答性が大きく向上した。
From these results, the following is clear.
1. From the results of Example 1 and Comparative Example 1 and from the results of Example 4 and Comparative Example 3, the magnetic fine particles obtained by drying the magnetic fine particle dispersion obtained by the wet method are the dispersion before drying. The magnetic responsiveness was greatly improved compared to the state.
2. From the results of Example 3 and Comparative Example 1, in Example 3, although the total amount of the magnetic material used was smaller, magnetic responsiveness was obtained by repeating the production of the magnetic fine particle dispersion by the wet method and the drying step. Was greatly improved.
3. From the results of Examples 1 to 3, the magnetic responsiveness was greatly improved by the production of the magnetic fine particle dispersion by the wet method and the repetition of the drying process.
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