JPH02197102A - Surface modification method for magnetic material - Google Patents
Surface modification method for magnetic materialInfo
- Publication number
- JPH02197102A JPH02197102A JP1017016A JP1701689A JPH02197102A JP H02197102 A JPH02197102 A JP H02197102A JP 1017016 A JP1017016 A JP 1017016A JP 1701689 A JP1701689 A JP 1701689A JP H02197102 A JPH02197102 A JP H02197102A
- Authority
- JP
- Japan
- Prior art keywords
- magnetic powder
- group
- epoxy group
- treated
- magnetic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000696 magnetic material Substances 0.000 title abstract description 7
- 238000002715 modification method Methods 0.000 title description 4
- 239000006247 magnetic powder Substances 0.000 claims abstract description 33
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 20
- -1 azo compound Chemical class 0.000 claims abstract description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000012986 modification Methods 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 abstract description 6
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 238000007645 offset printing Methods 0.000 abstract description 4
- 239000005977 Ethylene Substances 0.000 abstract 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 abstract 1
- 238000011282 treatment Methods 0.000 description 21
- 239000000843 powder Substances 0.000 description 17
- 229910000859 α-Fe Inorganic materials 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229910018605 Ni—Zn Inorganic materials 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 5
- 239000004926 polymethyl methacrylate Substances 0.000 description 5
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005291 magnetic effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 230000005294 ferromagnetic effect Effects 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 239000011553 magnetic fluid Substances 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005293 ferrimagnetic effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/10—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure
- H01F1/11—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure in the form of particles
- H01F1/113—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure in the form of particles in a bonding agent
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Hard Magnetic Materials (AREA)
- Soft Magnetic Materials (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は高分子＠を化学的に結合させることにより磁性
粉体の表面全改質する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for completely modifying the surface of magnetic powder by chemically bonding polymers.
特願昭６１−２９０５５２号および特願昭６２−０９０
７１５号では磁気を利用したオフセット印刷に用いる磁
性物を提案しているが、この磁性物は基本的には磁性粉
体に高分子鎖を化学的に結合させた本のであり、従来の
オフセット印刷用平版の機能を持つ画像を形成するとい
う極めて重要な役割を演する。すなわち、磁性粉体の表
面に結合させた高分子鎖が親水性であれば親インキ性の
磁気ドラム外表面での非画線部形成を、親インキ性であ
れば親水性の磁気ドラム外嵌面での画線部形成を担う。Patent Application No. 1983-290552 and Patent Application No. 62-090
No. 715 proposes a magnetic material for use in offset printing using magnetism, but this magnetic material is basically a magnetic powder with polymer chains chemically bonded to it, making it difficult to use in conventional offset printing. It plays an extremely important role in forming images that have the function of planographic printing. In other words, if the polymer chains bonded to the surface of the magnetic powder are hydrophilic, the non-image area can be formed on the outer surface of the ink-philic magnetic drum, and if the polymer chain is ink-philic, it can be formed on the outer surface of the hydrophilic magnetic drum. Responsible for forming the drawing area on the surface.
ところが、磁性粉体の表面に高分子鎖を化学的に結合さ
せることは必ずしも容易でなく、その方法も限られてい
た。However, it is not always easy to chemically bond polymer chains to the surface of magnetic powder, and the methods for doing so are also limited.
本発明は、磁性粉体の表面に高分子鎖を化学的に結合さ
せる、新規且つ有効な方法を提供するものである。The present invention provides a novel and effective method for chemically bonding polymer chains to the surface of magnetic powder.
本発明に係る磁性粉体の表面改質方法は磁性粉体をエポ
キシ基を有するアルコキシシランで処理した後、カルボ
キシル基を有するアゾ化合物で処理し、次いで、ラジカ
ル重合性エチレン誘導体で処理することを特徴とする。The method for surface modification of magnetic powder according to the present invention includes treating the magnetic powder with an alkoxysilane having an epoxy group, then treating it with an azo compound having a carboxyl group, and then treating it with a radically polymerizable ethylene derivative. Features.
磁性粉体ｒ、ｒ−グリシドキシグロビル） ＋７メトキ
シシラン、γ−グリシドキシプロビル（ジメトキシ）メ
チルシラン等の、エポキシ基を有するアルコキシシラン
で処理することにより、磁性粉体の表面に存在する水酸
基と該アルコキシシランのアルコキシ基とが縮合し、シ
ロキサン結合を介してエポキシ基が導入される。その後
、このエポキシ基が導入された磁性粉体をカルボキシル
基を有するアゾ化合物、例えば、 ４．４’−アゾビス
−（４−シアノ吉草酸）で処理することにより、該磁性
粉体に導入され几エポキシ基と該アゾ化合物のカルボキ
シル基とが付加反応し、該磁性粉体の表面にアゾ基が導
入される。アゾ基はラジカル重合の開始能力を有するの
で、上記の、アゾ基が導入された磁性粉体をメタクリル
酸エチル、スチレン等のラジカル重合性エチレン誘導体
で処理することにより、該磁性粉体の表面から該エチレ
ン誘導体のラジカル重合が開始され、高分子鎖が結合す
る。Magnetic powder r, r-glycidoxyglobil) exists on the surface of magnetic powder by treating with an alkoxysilane having an epoxy group, such as +7 methoxysilane or γ-glycidoxyprobyl(dimethoxy)methylsilane. The hydroxyl group and the alkoxy group of the alkoxysilane are condensed, and an epoxy group is introduced via a siloxane bond. Thereafter, by treating the magnetic powder into which the epoxy group has been introduced with an azo compound having a carboxyl group, for example, 4,4'-azobis-(4-cyanovaleric acid), the epoxy group is introduced into the magnetic powder. The epoxy group and the carboxyl group of the azo compound undergo an addition reaction, and an azo group is introduced onto the surface of the magnetic powder. Since the azo group has the ability to initiate radical polymerization, by treating the above-mentioned magnetic powder into which the azo group has been introduced with a radically polymerizable ethylene derivative such as ethyl methacrylate or styrene, the surface of the magnetic powder can be Radical polymerization of the ethylene derivative is initiated, and the polymer chains are bonded together.
本発明に用いられる磁性粉体とは、鉄、コバルト、ニッ
ケルおよびこれらの合金に代弄されるフェロ母性体やマ
グネタイト、フェライトに代表されるフェリ磁性体など
の強磁性体の粉末であるが、これらの磁性粉体の表面に
は、マグネタイト、フェライト等の金属酸化物以外であ
っても、大気中においては多かれ少なかれ酸化層が形成
されているので、水酸基が存在しており、本発明の表面
改質法が適用できる。The magnetic powder used in the present invention is a powder of ferromagnetic substances such as ferromagnetic substances represented by iron, cobalt, nickel, and alloys thereof, magnetite, and ferrimagnetic substances represented by ferrite. On the surface of these magnetic powders, even if they are not metal oxides such as magnetite or ferrite, an oxide layer is formed to a greater or lesser extent in the atmosphere, so hydroxyl groups are present on the surface of the present invention. Modification methods can be applied.
一方、エポキシ基を有するアルコキシシランとしては、
〔作用〕のところで述べ九前記のものが代表的であるが
、本発明に用いられる該アルコキシシランはこれらに限
定されるものではなく、少なくとも１分子中に１個以上
のエポキシ基と１個以上のアルコキシ基を有するシラン
化合物は一般に使用可能である。On the other hand, as an alkoxysilane having an epoxy group,
The alkoxysilanes mentioned in [Operation] are representative, but the alkoxysilanes used in the present invention are not limited to these, and at least one epoxy group and one or more epoxy groups in one molecule. Silane compounds having an alkoxy group of 1 are generally usable.
カルボキシル基を有するアゾ化合物としては、上記のも
のを除いて、入手の容易な市販品は見当たらないが、上
記のもの以外であっても、該アゾ化合物が入手できれば
、これを用いることは可能である。As for azo compounds having a carboxyl group, except for the ones mentioned above, there are no easily available commercially available products, but even if the azo compounds other than those mentioned above are available, it is possible to use them if they are available. be.
また、ラジカル重合性エチレン誘導体としては。Also, as a radically polymerizable ethylene derivative.
上記のもの以外に、メタクリル酸エチル、メタクリル酸
ｎ−グチル、アクリル酸メチル、アクリル酸エチル、ア
クリル酸１ｓｏ−ブチル、アクリル酸、メタクリル酸、
アクリロニトリル、アクリルアミド、酢酸ビニル等が用
いられるが、これらの２種類以上を組合せて用いれば、
共重合体鎖を磁性粉体の表面に結合させることもできる
。In addition to the above, ethyl methacrylate, n-butyl methacrylate, methyl acrylate, ethyl acrylate, 1so-butyl acrylate, acrylic acid, methacrylic acid,
Acrylonitrile, acrylamide, vinyl acetate, etc. are used, but if two or more of these are used in combination,
Copolymer chains can also be attached to the surface of magnetic powder.
本発明の方法による磁性粉体の表面改質手順を具体的に
述べると以下のとおシである。まず、エポキシ基を有す
るアルコキシシランによる処理として、磁性粉体と該ア
ルコキシシランとを混合するか、またはベンゼン、トル
エン等の有機溶媒中に加え、室温〜１２０℃で０．１〜
２４時間攪拌を行った後、カル２キシル基を有するアゾ
化合物による処理として、上記のエポキシ基を有するア
ルコキシシランで処理した磁性粉体と該アゾ化合物とを
ジメチルスルホキシド、ジメチルホルムアミド等の有機
溶媒中に加え、２０〜４０℃で０．１〜２４時間攪拌を
行い１次いで、ラジカル重合性エチレン誘導体による処
理として、上記のエポキシ基を有するアルコキシシラン
で処理した後、カルボキシル基を有するアゾ化合物で処
理した磁性粉体と該エチレン誘導体とを混合するか、ま
たは該エチレン誘導体およびその付加重合体が可溶で且
つラジカル重合を阻害しない溶媒中に加え、不活性ガス
雰囲気中、５０〜１５０℃で０．１〜２４時間攪拌を行
う。The procedure for surface modification of magnetic powder by the method of the present invention is specifically described below. First, as a treatment with an alkoxysilane having an epoxy group, magnetic powder and the alkoxysilane are mixed or added to an organic solvent such as benzene or toluene, and the mixture is heated from room temperature to 120°C to
After stirring for 24 hours, the magnetic powder treated with the alkoxysilane having an epoxy group and the azo compound are mixed in an organic solvent such as dimethyl sulfoxide or dimethyl formamide for treatment with an azo compound having a carboxylic group. In addition, the mixture was stirred at 20 to 40°C for 0.1 to 24 hours, and then treated with the above-mentioned alkoxysilane having an epoxy group as a treatment with a radically polymerizable ethylene derivative, and then treated with an azo compound having a carboxyl group. The magnetic powder and the ethylene derivative are mixed, or added to a solvent in which the ethylene derivative and its addition polymer are soluble and which does not inhibit radical polymerization, and the mixture is heated at 0 to 150°C in an inert gas atmosphere. .Stir for 1 to 24 hours.
上述の表面改質手順に示し比処理温度、処理時間はあく
までも一般的な条件であって、本発明の表面改質手順を
限定するものではない。すなわち、磁性粉体、および磁
性粉体の表面に結合させる高分子鎖の種類、結合させる
高分子鎖の量によって任意に決められるものである。同
様に、原料の量的な条件も特に限定されるべきものでは
ない。The specific treatment temperature and treatment time shown in the above-mentioned surface modification procedure are merely general conditions, and do not limit the surface modification procedure of the present invention. That is, it is arbitrarily determined by the magnetic powder, the type of polymer chain to be bonded to the surface of the magnetic powder, and the amount of the polymer chain to be bonded. Similarly, the quantitative conditions for the raw materials are not particularly limited either.
また、上述の、カルボキシル基を有するアゾ化合物によ
る処理においては反応促進剤としてα−ピコリン、ピリ
ジン等の３級アミンを少量添加してもよい。Further, in the above-mentioned treatment with an azo compound having a carboxyl group, a small amount of tertiary amine such as α-picoline or pyridine may be added as a reaction accelerator.
次に、本発明を実施例によってさらに説明する。Next, the present invention will be further explained by examples.
実施例１
本発明の方法によシ、Ｎｌ −Ｚｎフェライト粉（平均
粒径１５０Ｘ、表面水酸基量３．６ Ｘ １０−’モル
／Ｅｌ）全欠のように改質した。Example 1 According to the method of the present invention, Nl-Zn ferrite powder (average particle size 150X, surface hydroxyl group content 3.6 x 10-' mol/El) was modified to be completely depleted.
まず、上記のＮ１−Ｚｎフェライト粉１０．０ｇを、１
１０℃、１■Ｉ（ｇ以下の減圧下で２４時間の乾燥を行
った抜工Ｉキシ基を有するアルコキシシランによる処理
として、γ−グリシドキシグロピルトリメトキシシラン
１０．０ｇ（４，２Ｘ１０ モル）とと゛もに、脱水
、精製したトルエン１５０−中に加え、トルエンの沸点
で８時間攪拌を行った。この処理を行ったＮｉ −Ｚｎ
フェライト粉をメタノールで洗浄し、８０℃、１■Ｉｇ
以下の減圧下で６時間の乾燥を行った後、カルボキシル
基を存するアゾ化合物による処理として、 ４．４’−
アゾビス−（４−シアノ吉草酸） ３．０．ｉｉ＋ （
１，ｌＸ１Ｏモル）とともに、脱水、精製したジメチル
スルホキシド１５０−中に加え、さらに、α−ピコリン
０，０５ｄｅ浩卯して、２０℃で１０時間攪拌を行った
。この処理を行ったＮ１−Ｚｎフェライト粉をメタノー
ルで洗浄し、２０℃、１■Ｉｇ以下の減圧下で２４時間
の乾燥全行っ九後、このＮｔ −Ｚｎ ７工ライト粉１
ｇを分取し、ラジカル重合性エチレン誘導体による処理
として、常法により精製し念メタクリル酸メチル３０−
と混合して、７０℃で９時間攪拌上行り念。First, 10.0 g of the above N1-Zn ferrite powder was
10.0 g (4.2 x 10 mol) of γ-glycidoxyglopyltrimethoxysilane was treated with an alkoxysilane having an oxidized group, which was dried for 24 hours at 10°C and under a reduced pressure of 1. ) were added to dehydrated and purified toluene 150- and stirred for 8 hours at the boiling point of toluene.Ni-Zn subjected to this treatment
Wash the ferrite powder with methanol, 80℃, 1■Ig
After drying for 6 hours under the following reduced pressure, 4.4'-
Azobis-(4-cyanovaleric acid) 3.0. ii+ (
The mixture was added to dehydrated and purified dimethyl sulfoxide 150, along with 0.05 mol of α-picoline, and stirred at 20° C. for 10 hours. The N1-Zn ferrite powder subjected to this treatment was washed with methanol and dried for 24 hours at 20°C under a reduced pressure of 1 Ig or less.
g was collected and purified by a conventional method as a treatment with a radically polymerizable ethylene derivative to give 30-methyl methacrylate.
and carefully stirred at 70°C for 9 hours.
その後、上記の一連の表面改質処理を行ったＮｉ −Ｚ
ｎフェライト粉ｆ ７０００ｒ、ｐ、ｍ、 ３０分間の
遠心分離により沈降させ、上澄液を除去し友。次いで、
沈降し＆Ｎｉ−Ｚｎ７エライト粉をトルエンに分散させ
念後、７０００ｒ、ｐ、ｒｎ、 ３０分間の遠心分離に
より再度沈降させ、上澄ｇを除去する操作を５回繰り返
し友後、沈降したＮｌ −Ｚｎフェライト粉を１１０℃
、１ ｗ Ｈｇ以下の減圧下で２４時間の乾燥を行い、
元素分析を行った結果、Ｎｉ −Ｚｎフェライト粉ＩＩ
に対して０．４１ｇのポリメタクリル酸メチルが結合し
ていることが判明した。After that, Ni-Z was subjected to the above series of surface modification treatments.
Ferrite powder f 7000r, p, m, Sediment by centrifugation for 30 minutes, remove the supernatant and drain. Then,
After dispersing the precipitated & Ni-Zn7 elite powder in toluene, it was precipitated again by centrifugation at 7000 r, p, rn for 30 minutes, and the supernatant was removed. After repeating the procedure 5 times, the precipitated Nl-Zn Ferrite powder at 110℃
, dried for 24 hours under reduced pressure of 1 w Hg or less,
As a result of elemental analysis, Ni-Zn ferrite powder II
It was found that 0.41 g of polymethyl methacrylate was bound to the sample.
一方、上記の一連の表面改質処理に続く遠心分離の際に
沈降しないＮｉ−Ｚｎフェライトが上澄液相に認められ
次ので、この上澄液を濃縮し友ところ濃縮液は磁性流体
として挙動した。On the other hand, Ni-Zn ferrite that did not precipitate during centrifugation following the above series of surface modification treatments was found in the supernatant liquid phase, so this supernatant liquid was concentrated and the concentrate behaved as a magnetic fluid. did.
実施例２
実施例１に記載したＮ１− Ｚｎフェライト粉につき、
メタクリル酸メチルの代わＦ）Ｋスチレンを用いた以外
は実施例１と全く同様の一連の表面改質処理を行っ九後
、実施例１と全く同様に沈降分離、乾燥を行い、元素分
析を行っ友結果、Ｎｉ−Ｚｎフェライト１．Ｆに対して
０．１５！Ｉのポリスチレンが結合していることが判明
した。Example 2 Regarding the N1-Zn ferrite powder described in Example 1,
After carrying out a series of surface modification treatments exactly the same as in Example 1 except for using F) K styrene instead of methyl methacrylate, sedimentation separation and drying were carried out in the same manner as in Example 1, and elemental analysis was carried out. Friend result, Ni-Zn ferrite 1. 0.15 for F! It was found that the polystyrene of I was bonded.
比較例１
実施例１に記載したＮｉ −Ｚｎ ７エライト粉につき
、実施例１に記載し九エポキシ基を有するアルコキシシ
ランによる処理およびカルボキシル基を有するアゾ化合
物による処理を省略し、ラジカル重合性エチレン誘導体
による処理のみを実施例１と全く同様に行った後、実施
例１と全く同様に沈降分離、乾燥を行い、元素分析を行
った結果、Ｎｉ−Ｚｎフェライト粉にポリメタクリル酸
メチルが全く結合していないことが判明し友。Comparative Example 1 Regarding the Ni-Zn 7 elite powder described in Example 1, the treatment with an alkoxysilane having nine epoxy groups and the treatment with an azo compound having a carboxyl group as described in Example 1 were omitted, and a radically polymerizable ethylene derivative was used. After the treatment was carried out in exactly the same manner as in Example 1, sedimentation separation and drying were carried out in the same manner as in Example 1, and elemental analysis was performed. As a result, no polymethyl methacrylate was bonded to the Ni-Zn ferrite powder. It turns out not to be a friend.
比較例２
実施例１に記載し７ｊＮ１−Ｚｎ７エライト粉につき、
カルぎキシル基を有するアゾ化合物による処理を省略し
友以外は実施例１と全く同様にエポキシ基を有するアル
コキシシランによる処理、次いで、ラジカル重合性エチ
レン誘導体による処理を行った後、実施例１と全く同様
に沈降分離、乾燥を行い、元素分析を行った結果、Ｎｔ
−Ｚｎフェライト粉にポリメタクリル酸メチルが全く結
合していないことが判明し友。Comparative Example 2 Regarding the 7jN1-Zn7 elite powder described in Example 1,
After omitting the treatment with the azo compound having a carboxyl group and performing treatment with an alkoxysilane having an epoxy group in the same manner as in Example 1, and then treatment with a radically polymerizable ethylene derivative, the same procedure as in Example 1 was carried out. As a result of performing sedimentation separation, drying, and elemental analysis in exactly the same manner, Nt
- It was discovered that polymethyl methacrylate was not bonded to Zn ferrite powder at all.
比較例３
実施例１Ｋ：記載しｆｔ Ｎｉ −Ｚｎフェライト粉に
つき、エポキシ基を有するアルコキシシランによる処理
を省略し几以外は実施例１と全く同様にカルボキシル基
を有するアゾ化合物による処理、次いで、ラジカル重合
性エチレン誘導体による処理を行った後、実施例１と全
く同様に沈降分離、乾燥を行い、元素分析を行った結果
、Ｎｉ −Ｚｎフェライト粉１ｇに対して結合している
ポリメタクリル酸メチルは０．０ Ａ ｌｌと極めて少
ないことが判明した。この事実ＶｉＮｉ−Ｚｎ７エライ
ト粉に吸着した微量の４．４′−アゾビス−（４−シア
ノ吉草酸）がメタクリル酸メチルの重合を開始し次こと
を示唆するが、ポリメタクリル酸メチルの結合は化学的
々結合（共有結合）ではなく、吸着によるものである。Comparative Example 3 Example 1K: The described ft Ni-Zn ferrite powder was treated with an azo compound having a carboxyl group in the same manner as in Example 1, except that the treatment with an alkoxysilane having an epoxy group was omitted, and then the treatment with an azo compound having a carboxyl group was performed. After treatment with a polymerizable ethylene derivative, sedimentation separation and drying were performed in exactly the same manner as in Example 1, and elemental analysis revealed that polymethyl methacrylate bound to 1 g of Ni-Zn ferrite powder was It was found that the amount was extremely small at 0.0 All. This fact suggests that a trace amount of 4,4'-azobis-(4-cyanovaleric acid) adsorbed on the ViNi-Zn7 elite powder initiates the polymerization of methyl methacrylate, but the bonding of polymethyl methacrylate is chemically induced. This is due to adsorption rather than targeted bonding (covalent bonding).
本発明は前述のように構成されているので以下に述べる
ような効果を奏する。Since the present invention is configured as described above, it produces the following effects.
（１）本発明は磁性粉体の表面に高分子鎖を化学的に結
合させる、新規且つ有効な改質方法を提供する。(1) The present invention provides a novel and effective modification method for chemically bonding polymer chains to the surface of magnetic powder.
（２）本発明の底面改質方法の用途に関連して、磁気を
利用したオフセット印刷において従来の平版の機能を持
つ画像の形成に用いられる磁性物について述べ九が、本
発明はこれに限定して適用されるべきものではない。す
なわち、本発明の表面改質を施し之磁性粉体は、その底
面に高分子鎖が共有結合によシ化学結合している九め、
表面に結合し次高分子と同一ま友は類似の高分子中に容
易に、且つ均一に配合分散でき、例えば、プラスチック
研石の原料として好適である。(2) In connection with the application of the bottom surface modification method of the present invention, a magnetic material used to form an image having the function of a conventional lithographic plate in offset printing using magnetism will be described; however, the present invention is limited to this. It should not be applied as such. That is, the surface-modified magnetic powder of the present invention has polymer chains chemically bonded to the bottom surface by covalent bonds.
A surface-bound polymer that is the same as a polymer can be easily and uniformly mixed and dispersed in a similar polymer, and is suitable as a raw material for, for example, a plastic grinding stone.
（３）−万、該磁性粉体は表面に結合した高分子の艮溶
媒中で安定なコロイド分散相を形成するので、磁性塗料
あるいは磁性流体が製造できる等、本発明の用途は極め
て多岐にわたる。(3) - Since the magnetic powder forms a stable colloidal dispersed phase in a polymeric solvent bonded to the surface, the present invention has an extremely wide range of applications, including the production of magnetic paints and magnetic fluids. .
Claims (1)
した後、カルボキシル基を有するアゾ化合物で処理し、
次いで、ラジカル重合性エチレン誘導体で処理すること
を特徴とする磁性粉体の表面改質方法。After treating magnetic powder with an alkoxysilane having an epoxy group, treating it with an azo compound having a carboxyl group,
A method for surface modification of magnetic powder, which is then treated with a radically polymerizable ethylene derivative.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1017016A JPH02197102A (en) | 1989-01-26 | 1989-01-26 | Surface modification method for magnetic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1017016A JPH02197102A (en) | 1989-01-26 | 1989-01-26 | Surface modification method for magnetic material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02197102A true JPH02197102A (en) | 1990-08-03 |
Family
ID=11932200
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1017016A Pending JPH02197102A (en) | 1989-01-26 | 1989-01-26 | Surface modification method for magnetic material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02197102A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003041149A (en) * | 2001-07-27 | 2003-02-13 | Tokai Carbon Co Ltd | Carbon black for black matrix and method for producing the same |
| JP2007129079A (en) * | 2005-11-04 | 2007-05-24 | Kagawa Univ | Magnetic particulate, its manufacturing method, magnet using them, and its manufacturing method |
| JP2020132691A (en) * | 2019-02-14 | 2020-08-31 | 株式会社リコー | Ink, ink containing container, recording method, recording device, and method for producing ink |
-
1989
- 1989-01-26 JP JP1017016A patent/JPH02197102A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003041149A (en) * | 2001-07-27 | 2003-02-13 | Tokai Carbon Co Ltd | Carbon black for black matrix and method for producing the same |
| JP2007129079A (en) * | 2005-11-04 | 2007-05-24 | Kagawa Univ | Magnetic particulate, its manufacturing method, magnet using them, and its manufacturing method |
| JP2020132691A (en) * | 2019-02-14 | 2020-08-31 | 株式会社リコー | Ink, ink containing container, recording method, recording device, and method for producing ink |
| US11661523B2 (en) | 2019-02-14 | 2023-05-30 | Ricoh Company, Ltd. | Ink, ink accommodating unit, recording method, recording device, and method of manufacturing ink |
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