JP2005225731A - Ferrous black particle powder and black toner containing the same - Google Patents
Ferrous black particle powder and black toner containing the same Download PDFInfo
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- JP2005225731A JP2005225731A JP2004037122A JP2004037122A JP2005225731A JP 2005225731 A JP2005225731 A JP 2005225731A JP 2004037122 A JP2004037122 A JP 2004037122A JP 2004037122 A JP2004037122 A JP 2004037122A JP 2005225731 A JP2005225731 A JP 2005225731A
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- 239000002245 particle Substances 0.000 title claims abstract description 132
- 239000000843 powder Substances 0.000 title claims abstract description 90
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- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 229910002593 Fe-Ti Inorganic materials 0.000 claims abstract description 16
- IXQWNVPHFNLUGD-UHFFFAOYSA-N iron titanium Chemical compound [Ti].[Fe] IXQWNVPHFNLUGD-UHFFFAOYSA-N 0.000 claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 137
- 229910052742 iron Inorganic materials 0.000 claims description 54
- 239000001055 blue pigment Substances 0.000 claims description 13
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- 230000005415 magnetization Effects 0.000 abstract description 24
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- 239000003973 paint Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 239000010936 titanium Substances 0.000 description 22
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 20
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 20
- 239000000203 mixture Substances 0.000 description 14
- 150000003609 titanium compounds Chemical class 0.000 description 12
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 8
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- 238000004519 manufacturing process Methods 0.000 description 7
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- -1 FeTiO 3 Substances 0.000 description 5
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- 229910052719 titanium Inorganic materials 0.000 description 5
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- 238000000034 method Methods 0.000 description 4
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- 239000011029 spinel Substances 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
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- 238000010335 hydrothermal treatment Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 3
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 2
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- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
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- 229910000349 titanium oxysulfate Inorganic materials 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
- 238000004438 BET method Methods 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 101000845012 Macrovipera lebetina Disintegrin lebein-1-alpha Proteins 0.000 description 1
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- 238000005273 aeration Methods 0.000 description 1
- AOADSHDCARXSGL-ZMIIQOOPSA-M alkali blue 4B Chemical compound CC1=CC(/C(\C(C=C2)=CC=C2NC2=CC=CC=C2S([O-])(=O)=O)=C(\C=C2)/C=C/C\2=N\C2=CC=CC=C2)=CC=C1N.[Na+] AOADSHDCARXSGL-ZMIIQOOPSA-M 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
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- ZZNMWGVMOBOREI-VQTJNVASSA-N chembl464952 Chemical compound C1([C@H]2OC=3C4=C(C=5C=CC(C)(C)OC=5C=3C(=O)[C@@H]2O)OC(C=C4)(C)C)=CC=CC=C1 ZZNMWGVMOBOREI-VQTJNVASSA-N 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
- 239000000084 colloidal system Substances 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
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- 229920001971 elastomer Polymers 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- 239000010419 fine particle Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- YWXYYJSYQOXTPL-SLPGGIOYSA-N isosorbide mononitrate Chemical compound [O-][N+](=O)O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 YWXYYJSYQOXTPL-SLPGGIOYSA-N 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
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- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
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- Dry Development In Electrophotography (AREA)
- Developing Agents For Electrophotography (AREA)
- Compounds Of Iron (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
Description
本発明は、黒色度に優れると共に、可及的に磁化値が低い鉄系黒色粒子粉末を提供する。 The present invention provides an iron-based black particle powder having excellent blackness and a magnetization value as low as possible.
本発明に係る鉄系黒色粒子粉末は、黒色を呈する顔料及び塗料、樹脂組成物の着色用材料等として使用することができ、殊に、非磁性黒色トナーに用いた場合には、黒色度に優れ、しかも磁化値が低い黒色トナーを提供することができる。 The iron-based black particle powder according to the present invention can be used as a pigment and paint exhibiting black color, a coloring material for a resin composition, and the like, and particularly when used for a non-magnetic black toner, An excellent black toner having a low magnetization value can be provided.
マグネタイト粒子粉末、イルメナイト粒子粉末、カーボンブラック等の黒色顔料は、塗料用、印刷インク用、化粧品用、ゴム・樹脂組成物用等の着色剤として古くから汎用されている。 Black pigments such as magnetite particle powder, ilmenite particle powder, and carbon black have long been widely used as colorants for paints, printing inks, cosmetics, rubber / resin compositions, and the like.
特に、マグネタイト粒子粉末等の黒色磁性酸化鉄粒子粉末を樹脂中に混合分散させた複合体粒子は、電子写真用現像剤として用いる磁性トナーに多用されている。 In particular, composite particles obtained by mixing and dispersing black magnetic iron oxide particles such as magnetite particles in a resin are frequently used in magnetic toners used as electrophotographic developers.
近時、レーザービームプリンターやデジタル複写機の高速化及び高画質化に伴って、現像剤である黒色トナーの特性向上が強く要求されており、その為には、黒色トナーが十分な黒色度を有していることが強く要求される。 Recently, with the increase in the speed and image quality of laser beam printers and digital copying machines, there has been a strong demand for improving the characteristics of black toner as a developer. For this purpose, black toner has sufficient blackness. It is strongly required to have it.
更に、近年では、フルカラー化が進められており、対応するプリンターや複写機としては非磁性トナーが用いられている。 Furthermore, in recent years, full-color printing has been promoted, and non-magnetic toner is used as a corresponding printer or copying machine.
そこで、黒色トナーにおいても、非磁性又は可及的に磁化値が小さく、現在のシステムに適合できる黒色非磁性トナーが要求されている。 Therefore, there is a demand for black toner that is non-magnetic or has a magnetization value as small as possible and can be adapted to the current system.
上述した通り、黒色非磁性トナーの諸特性の向上は強く要求されているところである。黒色非磁性トナーは、殊に、トナー中に含有する黒色顔料が、現像特性に大きく影響することが知られており、黒色非磁性トナーの諸特性と黒色非磁性トナー中に混合分散されている黒色顔料の諸特性とは密接な関係があり、黒色非磁性トナーに用いられる黒色顔料についても、更に一層の特性改善が強く望まれている。 As described above, improvement of various characteristics of the black nonmagnetic toner is strongly demanded. In black nonmagnetic toner, it is known that the black pigment contained in the toner has a great influence on the development characteristics, and various characteristics of the black nonmagnetic toner and the black nonmagnetic toner are mixed and dispersed. There is a close relationship with various characteristics of the black pigment, and further improvement of the characteristics of the black pigment used in the black nonmagnetic toner is strongly desired.
即ち、黒色度に優れた黒色非磁性トナーを得るためには、黒色粒子粉末が十分な黒色度を有し、分散性がより優れていることが要求されている。さらに、現行の非磁性トナーを用いるシステムに適合させるためには、黒色粒子粉末としても、非磁性又は可及的に磁化値が低い粒子粉末が要求されている。 That is, in order to obtain a black non-magnetic toner with excellent blackness, it is required that the black particle powder has sufficient blackness and better dispersibility. Furthermore, in order to adapt to the current system using non-magnetic toner, as the black particle powder, non-magnetic or particle powder having a magnetization value as low as possible is required.
一方、カーボンブラックは非磁性ではあるが、粒子サイズが平均粒子径０．００５〜０．０５μｍ程度の微粒子粉末であるため、ビヒクル中や樹脂組成物中への分散が困難であり、また、かさ密度が０．１ｇ／ｃｍ３程度とかさ高い粉末であるため、取り扱いが困難で、作業性が悪いことが知られている。 On the other hand, although carbon black is non-magnetic, it is a fine particle powder having an average particle size of about 0.005 to 0.05 μm, so that it is difficult to disperse in a vehicle or a resin composition. It is known that since it is a bulky powder with a density of about 0.1 g / cm 3 , handling is difficult and workability is poor.
そこで、黒色度に優れ、しかも、非磁性又は磁化値が可及的に低い黒色粒子粉末が要求されている。 Therefore, there is a demand for black particle powder that is excellent in blackness and that is as non-magnetic or as low in magnetization as possible.
黒色を呈した鉄系粒子粉末として、水熱処理することによって得られたイルメナイト粒子粉末（特許文献１）、Ｆｅ２ＴｉＯ５とＦｅ２Ｏ３−ＦｅＴｉＯ３固溶体との混合組成からなる黒色顔料（特許文献２）、磁化値σ１０００が２０〜５０Ａｍ２／ｋｇであって全Ｆｅに対して０．５〜１０．０原子％のチタンを含有する黒色磁性酸化鉄粒子粉末（特許文献３）が知られている。 Ilmenite particle powder (Patent Document 1) obtained by hydrothermal treatment as a black iron-based particle powder, a black pigment comprising a mixed composition of Fe 2 TiO 5 and Fe 2 O 3 —FeTiO 3 solid solution (patent Document 2), black magnetic iron oxide particle powder (Patent Document 3) having a magnetization value σ 1000 of 20 to 50 Am 2 / kg and containing 0.5 to 10.0 atomic% of titanium with respect to total Fe is known. It has been.
黒色度に優れるとともに、可及的に磁化値が低い鉄系黒色粒子粉末は、現在最も要求されているところであるが、未だ得られていない。 An iron-based black particle powder that is excellent in blackness and has a magnetization value as low as possible is currently most demanded, but has not yet been obtained.
即ち、前出特許文献１には、Ｔｉ３＋を用いて水熱処理によってイルメナイト粒子粉末を得ることが記載されているが、水熱処理によって製造しており、工業的とは言い難い。 That is, in the above-mentioned Patent Document 1, it is described that ilmenite particle powder is obtained by hydrothermal treatment using Ti 3+ , but it is manufactured by hydrothermal treatment and is not industrially useful.
前出特許文献２記載の非磁性粒子粉末は、Ｆｅ２ＴｉＯ５とＦｅ２Ｏ３−ＦｅＴｉＯ３固溶体であり、後出比較例に示す通り、着色力が低く、黒色度を満足するものとは言い難いものである。 The non-magnetic particle powder described in the above-mentioned Patent Document 2 is a solid solution of Fe 2 TiO 5 and Fe 2 O 3 -FeTiO 3, and it is difficult to say that the coloring power is low and the blackness is satisfied as shown in the following comparative example. is there.
前出特許文献３記載の黒色磁性酸化鉄粒子粉末は、Ｔｉ含有量が０．５〜１０原子％であり、また、磁場１ｋＯｅにおける磁化値σ１０００が２０〜５０ｅｍｕ／ｇであるが、Ｎａ−Ｆｅ−Ｔｉ化合物は含まれておらず黒色度が十分とは言い難いものである。 The black magnetic iron oxide particle powder described in the aforementioned Patent Document 3 has a Ti content of 0.5 to 10 atomic% and a magnetization value σ 1000 at a magnetic field of 1 kOe is 20 to 50 emu / g. Fe-Ti compound is not included, and it is difficult to say that the blackness is sufficient.
そこで、本発明は、黒色度に優れると共に、磁化値が低い鉄系黒色粒子粉末を得ることを技術的課題とする。 Then, this invention makes it a technical subject to obtain the iron-type black particle powder which is excellent in blackness and has a low magnetization value.
前記技術的課題は、次の通りの本発明によって達成できる。 The technical problem can be achieved by the present invention as follows.
即ち、本発明は、鉄チタン複合酸化物とＮａ−Ｆｅ−Ｔｉ化合物とを有することを特徴とする鉄系黒色粒子粉末である（本発明１）。 That is, the present invention is an iron-based black particle powder characterized by having an iron-titanium composite oxide and a Na—Fe—Ti compound (Invention 1).
また、本発明は、前記鉄系黒色粒子粉末において、Ｎａ−Ｆｅ−Ｔｉ化合物と鉄チタン複合酸化物とのＸ線回折のピーク強度比が０．００２〜１．００であることを特徴とする鉄系黒色粒子粉末である（本発明２）。 In the iron-based black particle powder according to the present invention, a peak intensity ratio of X-ray diffraction between the Na—Fe—Ti compound and the iron-titanium composite oxide is 0.002 to 1.00. This is iron-based black particle powder (Invention 2).
また、本発明は、０．１〜２０重量％の青色顔料を含有する請求項１又は２記載の鉄系黒色粒子粉末である（本発明３）。 Moreover, this invention is an iron-type black particle powder of Claim 1 or 2 containing a 0.1-20 weight% blue pigment (this invention 3).
また、本発明は、本発明１乃至本発明３のいずれかの鉄系黒色粒子粉末を用いることを特徴とする黒色トナーである（本発明４）。 In addition, the present invention is a black toner using the iron-based black particle powder of any one of the first to third aspects (Invention 4).
本発明に係る鉄系黒色粒子粉末は、黒色度に優れ、可及的に磁化値が低いので、黒色を呈する顔料及び塗料、樹脂組成物の着色用材料、充填材等として好適である。 Since the iron-based black particle powder according to the present invention has excellent blackness and has a magnetization value as low as possible, it is suitable as a pigment and paint exhibiting black, a coloring material for a resin composition, a filler, and the like.
本発明に係る鉄系黒色粒子粉末を用いて製造した黒色非磁性トナーは、高い黒色度を有すると共に、磁化値が低いので、非磁性トナーとして好適である。 The black nonmagnetic toner produced using the iron-based black particle powder according to the present invention has a high blackness and a low magnetization value, and therefore is suitable as a nonmagnetic toner.
本発明の構成をより詳しく説明すれば次の通りである。 The configuration of the present invention will be described in more detail as follows.
先ず、本発明に係る鉄系黒色粒子粉末について述べる。 First, the iron-based black particle powder according to the present invention will be described.
本発明に係る鉄系黒色粒子粉末は、鉄チタン複合酸化物とＮａ−Ｆｅ−Ｔｉ化合物との混合組成からなる。Ｎａ−Ｆｅ−Ｔｉ化合物を有することにより、黒色度が向上する。 The iron-based black particle powder according to the present invention has a mixed composition of an iron-titanium composite oxide and a Na—Fe—Ti compound. By having the Na—Fe—Ti compound, the blackness is improved.
本発明における鉄チタン複合酸化物は、ＦｅＴｉＯ３−Ｆｅ２Ｏ３固溶体、Ｆｅ２ＴｉＯ５、Ｆｅ２ＴｉＯ４−Ｆｅ３Ｏ４固溶体、ＦｅＴｉＯ３、Ｆｅ２ＴｉＯ４等が挙げられ、上記化合物の二種以上の混合物であってもよい。また、原料であるＦｅ３Ｏ４や、γ−Ｆｅ２Ｏ３等のスピネル酸化鉄が存在してもよい。 Examples of the iron-titanium composite oxide in the present invention include FeTiO 3 —Fe 2 O 3 solid solution, Fe 2 TiO 5 , Fe 2 TiO 4 —Fe 3 O 4 solid solution, FeTiO 3 , Fe 2 TiO 4, etc. It may be a mixture of two or more. Also, Fe 3 O 4 and a raw material, spinel iron oxide such as γ-Fe 2 O 3 may be present.
本発明におけるＮａ−Ｆｅ−Ｔｉ化合物としては、ＮａＦｅＴｉ３Ｏ８、Ｎａ２Ｆｅ２Ｔｉ３Ｏ１０、ＮａＦｅＴｉＯ４，Ｎａ０．７５Ｆｅ０．７５Ｔｉ０．２５Ｏ２等が挙げられる。 Examples of the Na—Fe—Ti compound in the present invention include NaFeTi 3 O 8 , Na 2 Fe 2 Ti 3 O 10 , NaFeTiO 4 , Na 0.75 Fe 0.75 Ti 0.25 O 2 and the like.
本発明に係る鉄系黒色粒子粉末において、鉄チタン複合酸化物とＮａ−Ｆｅ−Ｔｉ化合物とのＸ線回折のピーク強度比は、各化合物の最強ピークの比で、０．００２〜１．００であることが好ましい。０．００２未満の場合には、黒色度に与える影響が小さい。１．００を超える場合には、スピネル酸化鉄量が多くなり、所望の磁化値を得ることが困難である。より好ましくは０．０１〜０．８０である。 In the iron-based black particle powder according to the present invention, the peak intensity ratio of X-ray diffraction between the iron-titanium composite oxide and the Na—Fe—Ti compound is the ratio of the strongest peak of each compound, and is 0.002 to 1.00. It is preferable that When it is less than 0.002, the influence on the blackness is small. When it exceeds 1.00, the amount of spinel iron oxide increases, and it is difficult to obtain a desired magnetization value. More preferably, it is 0.01-0.80.
本発明に係る鉄系黒色粒子粉末のＴｉ含有量は全Ｆｅに対して２．０〜１００．０原子％が好ましい。２．０原子％未満の場合には、磁化値が高くなり、現行の非磁性トナーを用いるシステムに適合させることが困難である。１００原子％を越える場合には、未反応のＴｉ化合物が残存するため、所望の黒色度と着色力とが得られない。より好ましくは３．０〜５０．０原子％であり、更により好ましくは５．０〜４０．０原子％である。 The Ti content of the iron-based black particle powder according to the present invention is preferably 2.0 to 100.0 atomic% with respect to the total Fe. If it is less than 2.0 atomic%, the magnetization value becomes high, and it is difficult to adapt to the current system using non-magnetic toner. If it exceeds 100 atomic%, the unreacted Ti compound remains, so that the desired blackness and coloring power cannot be obtained. More preferably, it is 3.0-50.0 atomic%, More preferably, it is 5.0-40.0 atomic%.
本発明に係る鉄系黒色粒子粉末の飽和磁化値は６０Ａｍ２／ｋｇ以下である。６０Ａｍ２／ｋｇを越える場合には、現行の非磁性トナーを用いるシステムに適合させることが困難であり、所望の画像濃度を得にくくなり、またカブリの発生が見られるようになる。好ましくは０〜５０Ａｍ２／ｋｇ、より好ましくは０〜４０Ａｍ２／ｋｇである。 The saturation magnetization value of the iron-based black particle powder according to the present invention is 60 Am 2 / kg or less. If it exceeds 60 Am 2 / kg, it is difficult to adapt to the current system using non-magnetic toner, it becomes difficult to obtain a desired image density, and occurrence of fogging is observed. Preferably it is 0-50 Am < 2 > / kg, More preferably, it is 0-40 Am < 2 > / kg.
本発明に係る鉄系黒色粒子粉末の黒色度Ｌ＊は６〜１２．５である。黒色度Ｌ＊が１２．５を越える場合には、黒色度に優れるとは言い難く黒色顔料として使用することができない。６未満の場合には工業的に製造することができない。好ましくは６〜１１．０である。 The blackness L * of the iron-based black particle powder according to the present invention is 6 to 12.5. When the blackness L * exceeds 12.5, it cannot be said that the blackness is excellent and cannot be used as a black pigment. If it is less than 6, it cannot be produced industrially. Preferably it is 6-11.0.
本発明に係る鉄系黒色粒子粉末の平均粒子径は０．０１〜０．５０μｍが好ましい。平均粒子径が０．０１μｍ未満の場合には、所望の黒色度が得られない。０．５０μｍを越える場合には、所望の着色力が得られない。より好ましくは０．０１５〜０．４０μｍである。 The average particle size of the iron-based black particle powder according to the present invention is preferably 0.01 to 0.50 μm. When the average particle size is less than 0.01 μm, the desired blackness cannot be obtained. If it exceeds 0.50 μm, the desired coloring power cannot be obtained. More preferably, it is 0.015-0.40 micrometer.
本発明に係る鉄系黒色粒子粉末のＢＥＴ比表面積値は２〜１００ｍ２／ｇが好ましい。ＢＥＴ比表面積値が２ｍ２／ｇ未満の場合には、非磁性黒色粒子粉末が粗大であったり、粒子及び粒子相互間で焼結が生じた粗大粒子となり着色力が低下する。１００ｍ２／ｇを越える場合には、所望の黒色度を得ることが困難となる。より好ましくは３〜９０ｍ２／ｇである。 The BET specific surface area value of the iron-based black particle powder according to the present invention is preferably 2 to 100 m 2 / g. When the BET specific surface area value is less than 2 m 2 / g, the nonmagnetic black particle powder is coarse or becomes coarse particles in which the particles and particles are sintered together, and the coloring power is reduced. When it exceeds 100 m 2 / g, it becomes difficult to obtain a desired blackness. More preferably, it is 3-90 m < 2 > / g.
本発明に係る鉄系黒色粒子粉末の着色力は、後述する評価法の展色で示した場合、３５．０〜４４．５が好ましい。着色力が４４．５を越える場合には、該非磁性黒色粒子粉末を用いた非磁性黒色トナーの使用した場合に、十分な画像濃度を得ることが困難である。着色力が３５．０未満の非磁性黒色粒子粉末は工業的に製造することができない。より好ましくは３５．０〜４１．５である。 The coloring power of the iron-based black particle powder according to the present invention is preferably 35.0 to 44.5 when expressed by the color development of the evaluation method described later. When the coloring power exceeds 44.5, it is difficult to obtain a sufficient image density when the nonmagnetic black toner using the nonmagnetic black particle powder is used. Nonmagnetic black particle powder having a coloring power of less than 35.0 cannot be produced industrially. More preferably, it is 35.0-41.5.
本発明３に係る鉄系黒色粒子粉末は、鉄チタン複合酸化物とＮａ−Ｆｅ−Ｔｉ化合物の混合組成物に、さらに青色顔料を含有することが好ましい。青色顔料を含有させることによって、黒色度と着色力がより向上する。 The iron-based black particle powder according to the present invention 3 preferably further contains a blue pigment in the mixed composition of the iron-titanium composite oxide and the Na—Fe—Ti compound. By containing a blue pigment, the blackness and coloring power are further improved.
本発明３に係る鉄系黒色粒子粉末の青色顔料の含有量は０．１〜２０重量％が好ましい。０．１重量％未満では黒色度に与える影響が小さい。２０重量％を越えるとその青色顔料の色相に近くなる。より好ましくは０．５〜１０重量％である。 As for content of the blue pigment of the iron-type black particle powder which concerns on this invention 3, 0.1 to 20 weight% is preferable. If it is less than 0.1% by weight, the influence on the blackness is small. If it exceeds 20% by weight, it will be close to the hue of the blue pigment. More preferably, it is 0.5 to 10% by weight.
本発明３に係る鉄系黒色粒子粉末は、組成、平均粒子径、磁化値は前記とほぼ同程度であり、黒色度Ｌ＊は６〜１２が好ましく、より好ましくは６〜１０であり、着色力は、後述する評価法の展色で示した場合、３０〜４２が好ましい。 The iron-based black particle powder according to the present invention 3 has a composition, an average particle diameter, and a magnetization value substantially the same as those described above, and the blackness L * is preferably 6 to 12, more preferably 6 to 10, and coloring. The force is preferably 30 to 42 when expressed by the color developed by the evaluation method described later.
本発明における青色顔料は公知のもので良く、例えばアルカリブルー、フタロシアニンブルー、コバルトブルー、ウルトラマリンブルー等が挙げられる。 The blue pigment in the present invention may be a known one, and examples thereof include alkali blue, phthalocyanine blue, cobalt blue, and ultramarine blue.
なお、本発明に係る鉄系黒色粒子粉末は、鉄、チタン以外にＭｇ、Ａｌ、Ｓｉ、Ｋ、Ｐ、Ｍｎ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ及びＺｒから選ばれる１種又２種以上の元素を鉄とチタンの全量に対して０〜１０原子％含んでも良い。 The iron-based black particle powder according to the present invention is one or more elements selected from Mg, Al, Si, K, P, Mn, Co, Ni, Cu, Zn and Zr in addition to iron and titanium. May be contained in an amount of 0 to 10 atomic% based on the total amount of iron and titanium.
次に、本発明に係る鉄系黒色粒子粉末の製造法について述べる。 Next, a method for producing the iron-based black particle powder according to the present invention will be described.
本発明に係る鉄系黒色粒子粉末は、マグネタイト粒子の粒子表面をチタン化合物で被覆した後、ナトリウム化合物を添加して濾別・乾燥する、又は、マグネタイト粒子の粒子表面をチタン化合物で被覆した後、濾別・乾燥し、ナトリウム化合物を乾式混合し、次いで、前記ナトリウム化合物を含有する混合物を非酸化性雰囲気下で６５０〜８８０℃の温度範囲で加熱焼成した後、粉砕して得ることができる。 The iron-based black particle powder according to the present invention is obtained by coating the particle surface of the magnetite particles with a titanium compound, adding a sodium compound, filtering and drying, or coating the particle surface of the magnetite particles with a titanium compound. It can be obtained by filtering, drying, and dry-mixing the sodium compound, and then heat-firing the mixture containing the sodium compound in a non-oxidizing atmosphere at a temperature range of 650 to 880 ° C. and then pulverizing. .
本発明に用いるマグネタイト粒子粉末は、平均粒子径０．００７〜０．４μｍが好ましく、より好ましくは０．０１〜０．３μｍであり、ＢＥＴ比表面積値３〜１８０ｍ２／ｇが好ましく、より好ましくは４〜１００ｍ２／ｇである。 The magnetite particle powder used in the present invention preferably has an average particle size of 0.007 to 0.4 μm, more preferably 0.01 to 0.3 μm, and a BET specific surface area value of 3 to 180 m 2 / g is more preferable. Is 4 to 100 m 2 / g.
前記マグネタイト粒子粉末は、常法によって得ることができるが、例えば、第一鉄塩水溶液とアルカリ水溶液とを反応して得られた水酸化第一鉄塩コロイドを含む第一鉄塩反応溶液に酸素含有ガスを通気することによって得ることができる。 The magnetite particle powder can be obtained by a conventional method. For example, oxygen is added to a ferrous salt reaction solution containing a ferrous hydroxide colloid obtained by reacting a ferrous salt aqueous solution and an alkaline aqueous solution. It can be obtained by aeration of the contained gas.
本発明に用いるチタン化合物としては、硫酸チタニル、四塩化チタン、三塩化チタンを挙げることができる。 Examples of the titanium compound used in the present invention include titanyl sulfate, titanium tetrachloride, and titanium trichloride.
前記チタン化合物の添加量は、Ｆｅに対して３〜５０原子％が好ましく、より好ましくは５〜４０原子％である。 The addition amount of the titanium compound is preferably 3 to 50 atomic%, more preferably 5 to 40 atomic% with respect to Fe.
マグネタイト粒子粉末に対するチタン化合物の被覆は、マグネタイト粒子を含有する水懸濁液に前記チタン化合物を添加し、水酸化アルカリ水溶液、炭酸アルカリ水溶液等を用いて、マグネタイト粒子の粒子表面にチタン化合物を被覆させる。なお、被覆反応では反応溶液のｐＨ値を低下させないで、チタン化合物の添加直後の反応ｐＨを維持させても良い。 The magnetite particle powder is coated with a titanium compound by adding the titanium compound to an aqueous suspension containing magnetite particles and coating the surface of the magnetite particles with an aqueous alkali hydroxide solution or an aqueous alkali carbonate solution. Let In the coating reaction, the reaction pH immediately after the addition of the titanium compound may be maintained without lowering the pH value of the reaction solution.
なお、前記異種金属元素を含有させる場合には、予めマグネタイト粒子中に含有させておいても良く、又はマグネタイト粒子の表面にチタン化合物を被覆させた水溶液に各種金属元素からなる塩、又は各種金属元素を含有する溶液を添加しても良い。 When the different metal element is contained, it may be previously contained in the magnetite particles, or a salt composed of various metal elements in an aqueous solution in which a titanium compound is coated on the surface of the magnetite particles, or various metals. A solution containing an element may be added.
本発明に用いるナトリウム化合物としては、水酸化ナトリウム、硫酸ナトリウム、炭酸ナトリウム又は塩化ナトリウム等が挙げられる。なお、ナトリウム化合物としては、チタン化合物の被覆において、水懸濁液のｐＨ値を低下させることなく、チタン化合物の添加直後の水懸濁液のｐＨ値を維持するために使用される水酸化アルカリ水溶液、炭酸アルカリ水溶液としての水酸化ナトリウム又は炭酸ナトリウムであってもよい。 Examples of the sodium compound used in the present invention include sodium hydroxide, sodium sulfate, sodium carbonate, and sodium chloride. The sodium compound is an alkali hydroxide used to maintain the pH value of the aqueous suspension immediately after the addition of the titanium compound without lowering the pH value of the aqueous suspension in the coating of the titanium compound. It may be sodium hydroxide or sodium carbonate as an aqueous solution or an aqueous alkali carbonate solution.
前記ナトリウム化合物の存在量は、マグネタイト粒子にチタン化合物を被覆させた粉末に対して０．０３〜１０重量％が好ましい。０．０３重量％未満の場合には、Ｎａ−Ｆｅ−Ｔｉ化合物の生成量が少なくなる。１０重量％を超える場合には、焼成後のスピネル酸化鉄量が多くなり、所望の磁化値を得ることが困難となる。より好ましくは０．０５〜７重量％である。 The abundance of the sodium compound is preferably 0.03 to 10% by weight based on the powder obtained by coating magnetite particles with a titanium compound. When it is less than 0.03% by weight, the amount of Na-Fe-Ti compound produced is reduced. If it exceeds 10% by weight, the amount of spinel iron oxide after firing increases, making it difficult to obtain a desired magnetization value. More preferably, it is 0.05-7 weight%.
本発明における加熱焼成の雰囲気は非酸化性雰囲気下が好ましく、酸化性雰囲気下では、高い黒色度を有する鉄系黒色粒子粉末を得ることが困難である。 The heating and firing atmosphere in the present invention is preferably a non-oxidizing atmosphere, and it is difficult to obtain an iron-based black particle powder having high blackness under an oxidizing atmosphere.
本発明における加熱焼成の温度範囲は６５０〜８８０℃が好ましく、６５０℃未満の場合には、マグネタイト粒子とＴｉ化合物の固相反応が不十分となり、目的とする鉄系黒色粒子粉末を得ることが困難であり、８８０℃を越える場合には、粗大粒子が生成するため好ましくない。より好ましくは７００〜８５０℃である。 The temperature range of the heating and baking in the present invention is preferably 650 to 880 ° C. When the temperature range is less than 650 ° C., the solid phase reaction between the magnetite particles and the Ti compound becomes insufficient, and the intended iron-based black particle powder can be obtained. When it exceeds 880 ° C., coarse particles are generated, which is not preferable. More preferably, it is 700-850 degreeC.
本発明２に係る鉄系黒色粒子粉末は、前記粉砕時に青色顔料を添加して混合・粉砕して得ることができる。 The iron-based black particle powder according to the present invention 2 can be obtained by adding a blue pigment at the time of pulverization, mixing and pulverizing.
本発明３に係る青色顔料を含有する鉄系黒色粒子粉末は、Ｎａ−Ｆｅ−Ｔｉ化合物及び鉄チタン複合酸化物の混合組成物と青色顔料とが混在していても良く、又は、Ｎａ−Ｆｅ−Ｔｉ化合物と鉄チタン複合酸化物の粒子表面に付着していてもよい。更に、鉄系黒色粒子粉末の粒子表面に糊剤を付着させ、該付着糊剤を介して青色顔料を付着又は被覆させても良い。なお、糊剤としては、アルコキシシランから生成するオルガノシラン化合物又はポリシロキサンを使用することができる。 The iron-based black particle powder containing the blue pigment according to the present invention 3 may be a mixture of a Na-Fe-Ti compound and an iron-titanium composite oxide and a blue pigment, or Na-Fe. -You may adhere to the particle | grain surface of a Ti compound and iron titanium complex oxide. Furthermore, a paste may be attached to the particle surface of the iron-based black particle powder, and the blue pigment may be attached or coated via the attached paste. In addition, as a paste agent, the organosilane compound or polysiloxane produced | generated from an alkoxysilane can be used.
次に、本発明に係る鉄系黒色粒子粉末を配合した非磁性トナーについて述べる。 Next, a non-magnetic toner containing the iron-based black particle powder according to the present invention will be described.
本発明における黒色磁性トナーは、本発明に係る鉄系黒色粒子及び結着剤樹脂からなり、必要に応じて離型剤、着色剤、荷電制御剤、その他の添加剤等を含有してもよい。 The black magnetic toner according to the present invention is composed of the iron-based black particles according to the present invention and a binder resin, and may contain a release agent, a colorant, a charge control agent, and other additives as necessary. .
黒色非磁性トナーは、平均粒子径が通常３〜１５μｍ、好ましくは５〜１２μｍである。 The black nonmagnetic toner has an average particle size of usually 3 to 15 μm, preferably 5 to 12 μm.
結着剤樹脂と鉄系黒色粒子との割合は、結着剤樹脂１００重量部に対して鉄系黒色粒子粉末通常０．１〜９００重量部、好ましくは１７〜１８５重量部である。 The ratio of the binder resin to the iron-based black particles is usually 0.1 to 900 parts by weight, preferably 17 to 185 parts by weight, based on 100 parts by weight of the binder resin.
結着剤樹脂としては、ポリエステル樹脂やスチレン−アクリル共重合樹脂、スチレン、アクリル酸アルキルエステル及びメタクリル酸アルキルエステル等のビニル系単量体を重合又は共重合したビニル系重合体が使用できる。上記スチレン単量体としては、例えばスチレン及びその置換体がある。上記アクリル酸アルキルエステル単量体としては、例えばアクリル酸、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル等がある。上記共重合体は、スチレン系成分を５０〜９５重量％含むことが好ましい。 As the binder resin, a vinyl polymer obtained by polymerizing or copolymerizing vinyl monomers such as polyester resin, styrene-acrylic copolymer resin, styrene, alkyl acrylate ester and alkyl methacrylate ester can be used. Examples of the styrene monomer include styrene and substituted products thereof. Examples of the alkyl acrylate monomer include acrylic acid, methyl acrylate, ethyl acrylate, and butyl acrylate. The copolymer preferably contains 50 to 95% by weight of a styrene component.
結着剤樹脂は、必要により、上記ビニル系重合体とともに、ポリエステル系樹脂、エポキシ系樹脂、ポリウレタン系樹脂等を併用することができる。 The binder resin can be used in combination with a polyester resin, an epoxy resin, a polyurethane resin, or the like, if necessary, together with the vinyl polymer.
次に、本発明における黒色非磁性トナーの製造法について述べる。 Next, a method for producing the black nonmagnetic toner in the present invention will be described.
本発明における黒色非磁性トナーは、所定量の結着剤樹脂と所定量の非磁性黒色粒子とを混合、加熱、混練、粉砕による公知の方法によって行うことができる。具体的には、非磁性黒色粒子と結着剤樹脂とを、必要により更に離型剤、着色剤、荷電制御剤、その他の添加剤等を添加した混合物を混合機により十分に混合した後、加熱混練機によって結着剤樹脂中に非磁性黒色粒子等を分散させ、次いで、冷却固化して樹脂混練物を得、該樹脂混練物を粉砕及び分級を行って所望の粒子サイズとすることにより得られる。 The black nonmagnetic toner in the present invention can be obtained by a known method by mixing, heating, kneading, and pulverizing a predetermined amount of a binder resin and a predetermined amount of nonmagnetic black particles. Specifically, after the non-magnetic black particles and the binder resin are mixed sufficiently with a mixer, a mixture further added with a release agent, a colorant, a charge control agent, and other additives as necessary, By dispersing non-magnetic black particles and the like in the binder resin with a heating kneader, then cooling and solidifying to obtain a resin kneaded product, and crushing and classifying the resin kneaded product to obtain a desired particle size can get.
前記混合機としては、ヘンシェルミキサー、ボールミル等を使用することができる。前記加熱混練機としては、ロールミル、ニーダー、二軸エクストルーダー等を使用することが出来る。前記粉砕は、カッターミル、ジェットミル等の粉砕機によって行うことができ、公知の風力分級等により行うことが出来る。 As the mixer, a Henschel mixer, a ball mill, or the like can be used. As the heating kneader, a roll mill, a kneader, a biaxial extruder, or the like can be used. The pulverization can be performed by a pulverizer such as a cutter mill or a jet mill, and can be performed by a known air classification or the like.
黒色磁性トナーを得る他の方法として、懸濁重合法又は乳化重合法がある。懸濁重合法においては、重合性単量体と黒色磁性酸化鉄粒子とを、必要により更に、着色剤、重合開始剤、架橋剤、荷電制御剤、その他の添加剤を添加した混合物を溶解又は分散させた単量体組成物を、懸濁安定剤を含む水相中に攪拌しながら添加して造粒し、重合させて所望の粒子サイズとすることにより得られる。乳化重合法においては、単量体と非磁性黒色粒子とを、必要により更に着色剤、重合開始剤などを水中に分散させて重合を行う過程に乳化剤を添加することによって所望の粒子サイズとすることにより得られる。 As another method for obtaining the black magnetic toner, there is a suspension polymerization method or an emulsion polymerization method. In the suspension polymerization method, a polymerizable monomer and black magnetic iron oxide particles are dissolved or mixed with a colorant, a polymerization initiator, a crosslinking agent, a charge control agent, and other additives as necessary. The dispersed monomer composition is added to an aqueous phase containing a suspension stabilizer while stirring, granulated, and polymerized to obtain a desired particle size. In the emulsion polymerization method, the monomer and the non-magnetic black particles are further dispersed in water, if necessary, by adding a colorant, a polymerization initiator, etc. in water, and an emulsifier is added in the process of polymerization to obtain a desired particle size. Can be obtained.
＜作用＞
本発明に係る鉄系黒色粒子粉末が黒色度に優れるのは、Ｎａ−Ｆｅ−Ｔｉ化合物が存在することによるものと推定している。
<Action>
It is presumed that the blackness of the iron-based black particle powder according to the present invention is due to the presence of the Na—Fe—Ti compound.
本発明に係る鉄系黒色粒子粉末が黒色度に優れるとともに、磁化値が低い理由として、スピネル酸化鉄の存在量を可及的に少なくしたことによるものと推定している。 It is presumed that the iron-based black particle powder according to the present invention is excellent in blackness and has a low magnetization value because the amount of spinel iron oxide is reduced as much as possible.
更に、本発明においては、青色顔料を混在させることによって、黒色度と着色力がより向上するものである。 Furthermore, in the present invention, the blackness and coloring power are further improved by mixing a blue pigment.
本発明の代表的な実施の形態は、次の通りである。 A typical embodiment of the present invention is as follows.
粒子の平均粒子径は、いずれも電子顕微鏡写真に示される粒子３５０個の粒子径をそれぞれ測定し、その平均値で示した。 The average particle size of each particle was measured by measuring the particle size of 350 particles shown in the electron micrograph, and the average value was shown.
粒子の構成相は、Ｘ線回折（管球：Ｃｕ）によって同定した。また、Ｎａ−Ｆｅ−Ｔｉ化合物とＦｅＴｉＯ３−Ｆｅ２Ｏ３固溶体のピーク強度比は、ＦｅＴｉＯ３−Ｆｅ２Ｏ３固溶体の（１０４）面のピーク強度に対するＮａ−Ｆｅ−Ｔｉ化合物のメインピーク強度から計算して求めた。ここで言うメインピークとは、Ｘ線回折のピーク強度が最大のピークを意味する。例えば、ＮａＦｅＴｉ３Ｏ８は、面間隔ｄが３．６３Åでのピーク強度、ＮａＦｅＴｉＯ４は（１１２）面でのピーク強度、Ｎａ０．７５Ｆｅ０．７５Ｔｉ０．２５Ｏ２は（１０４）面でのピーク強度を表す。 The constituent phases of the particles were identified by X-ray diffraction (tube: Cu). The peak intensity ratio between the Na—Fe—Ti compound and the FeTiO 3 —Fe 2 O 3 solid solution is the main peak intensity of the Na—Fe—Ti compound relative to the peak intensity of the (104) plane of the FeTiO 3 —Fe 2 O 3 solid solution. Calculated from The main peak here means a peak having the maximum peak intensity of X-ray diffraction. For example, NaFeTi 3 O 8 has a peak intensity at an interplanar spacing d of 3.63 mm, NaFeTiO 4 has a peak intensity at the (112) plane, and Na 0.75 Fe 0.75 Ti 0.25 O 2 has a (104) Represents the peak intensity at the surface.
比表面積値は、「Ｍｏｎｏ Ｓｏｒｂ ＭＳ−ＩＩ」（湯浅アイオニックス（株）製）を用いてＢＥＴ法により測定した値で示した。 The specific surface area value was represented by a value measured by the BET method using “Mono Sorb MS-II” (manufactured by Yuasa Ionics Co., Ltd.).
鉄系黒色粒子粉末の磁気特性は「振動試料型磁力計ＶＳＭ−３Ｓ−１５」（東英工業（株）製）を用いて磁場７９６ｋＡ／ｍ（１０ｋＯｅ）下で測定した値である。 The magnetic characteristics of the iron-based black particle powder are values measured under a magnetic field of 796 kA / m (10 kOe) using a “vibrating sample magnetometer VSM-3S-15” (manufactured by Toei Industry Co., Ltd.).
鉄系黒色粒子粉末のＴｉ及びＡｌ、Ｓｉ、Ｋ等の異種金属元素の含有量は、「蛍光Ｘ線分析装置 ＲＩＸ−２１００型」（理学電機工業（株）製）を用い検量線法により、測定した。 The content of different metal elements such as Ti and Al, Si, K, etc. in the iron-based black particle powder is determined by a calibration curve method using a “fluorescence X-ray analyzer RIX-2100 type” (manufactured by Rigaku Corporation). It was measured.
鉄系黒色粒子粉末の黒色度は、試料０．５ｇとヒマシ油０．５ｍｌとをフーバー式マーラーで練ってペースト状とし、このペーストにクリアラッカー４．５ｇを加え、混練、塗料化してキャストコート紙上に１５０μｍ（６ｍｉｌ）のアプリケーターを用いて塗布した塗布片（塗膜厚み：約３０μｍ）を作製し、該塗布片について、分光色彩計カラーガイド（ＢＹＫ−Ｇａｒｄｎｅｒ ＧｍｂＨ製）を用いて測色し、ＪＩＳ Ｚ ８９２９に定めるところに従って表色指数（Ｌ＊値）で示した。 The blackness of the iron-based black particle powder was determined by mixing 0.5 g of the sample and 0.5 ml of castor oil into a paste by kneading with a Hoover-type Mahler, adding 4.5 g of clear lacquer to this paste, kneading and coating, A coated piece (coating thickness: about 30 μm) coated on a paper using a 150 μm (6 mil) applicator was prepared, and the coated piece was measured using a spectrocolorimeter color guide (manufactured by BYK-Gardner GmbH). The color index (L * value) is shown in accordance with JIS Z 8929.
鉄系黒色粒子粉末の着色力は、試料０．５ｇ、ヒマシ油０．５ｍｌ及び二酸化チタン１．５ｇをフーバー式マーラーで練ってペースト状とし、このペーストにクリアラッカー４．５ｇを加え、混練、塗料化してキャストコート紙上に１５０μｍ（６ｍｉｌ）のアプリケーターを用いて塗布した塗布片（塗膜厚み：約３０μｍ）を作製し、該塗布片について、分光色彩計カラーガイド（ＢＹＫ−Ｇａｒｄｎｅｒ ＧｍｂＨ製）を用いて測色し、ＪＩＳ Ｚ ８９２９に定めるところに従って表色指数（Ｌ＊値）で示した。 The coloring power of the iron-based black particle powder is as follows: 0.5 g of sample, 0.5 ml of castor oil and 1.5 g of titanium dioxide are kneaded with a Hoover type Mahler to form a paste, and 4.5 g of clear lacquer is added to this paste, An application piece (coating thickness: about 30 μm) was prepared by applying a 150 μm (6 mil) applicator on cast-coated paper, and a spectral colorimeter color guide (by BYK-Gardner GmbH) was applied to the application piece. The color was used and measured, and the color index (L * value) was indicated according to JIS Z 8929.
黒色トナーを用いた画像濃度は、製造した黒色トナーを電子写真プリンター（沖電気工業製 ＭＩＣＲＯＬＩＮＥ６００ＣＬ）を用いてベタ黒（Ａ４）を印刷したものを用いて、そのベタ黒の画像濃度をＲＤ９１４（商品名、ＭＡＣＢＥＴＨ社製）により測定した。数値が高い方がより画像濃度に優れることを示す。 The image density using black toner is obtained by printing solid black (A4) using the produced black toner using an electrophotographic printer (MICROLINE600CL manufactured by Oki Electric Industry Co., Ltd.). Name, manufactured by MACBETH). Higher values indicate better image density.
黒色トナーを用いたカブリは、上述の電子写真用トナーの黒色度の測定に使用したベタ黒（Ａ４）を用い、カブリの有無を目視により観察し、下記４段階で評価した。
◎：非常に良好（未発生）
○：良好（ほとんど発生せず）
△：実用可（軽微な発生が見られる）
×：実用不可
As the fog using the black toner, the solid black (A4) used for the measurement of the blackness of the above-described electrophotographic toner was used, and the presence or absence of fog was visually observed and evaluated in the following four stages.
A: Very good (not generated)
○: Good (almost no occurrence)
Δ: Practical use possible (slight occurrence is observed)
×: Not practical
＜鉄系黒色粒子粉末の製造＞
実施例１
球状マグネタイト粒子粉末（平均粒子径０．１５μｍ、ＢＥＴ比表面積１０．８ｍ２／ｇ）１０ｋｇを含有する水懸濁液に、硫酸チタニル３８．９ｍｏｌを含有する水溶液（マグネタイト粒子粉末の全Ｆｅに対してＴｉ換算で３０原子％に相当する。）を添加する。次いで、混合溶液のｐＨ値を８．０に調整してマグネタイト粒子の粒子表面にチタンの含水酸化物を沈着させた後、濾別、水洗、乾燥し、粒子表面がチタンの含水酸化物で被覆されている球状黒色磁性酸化鉄粒子粉末を得た。
<Manufacture of iron-based black particle powder>
Example 1
An aqueous suspension containing 10 kg of spherical magnetite particle powder (average particle diameter 0.15 μm, BET specific surface area 10.8 m 2 / g) containing 38.9 mol of titanyl sulfate (based on the total Fe of the magnetite particle powder) Equivalent to 30 atomic% in terms of Ti). Next, after adjusting the pH value of the mixed solution to 8.0 and depositing the hydrous titanium oxide on the surface of the magnetite particles, the mixture is separated by filtration, washed with water, and dried, and the particle surface is coated with the hydrous titanium oxide. A spherical black magnetic iron oxide particle powder was obtained.
得られた粒子表面がチタンの含水酸化物で被覆されている球状黒色磁性酸化鉄粒子に硫酸ナトリウム４２０ｇを加えて混合した。次いで得られた混合物１０ｋｇをＮ２ガス流下７５０℃で６０分間加熱焼成した後、粉砕し、鉄系黒色粒子粉末を得た。 420 g of sodium sulfate was added to and mixed with spherical black magnetic iron oxide particles whose surface was coated with a hydrous oxide of titanium. Next, 10 kg of the obtained mixture was heated and fired at 750 ° C. for 60 minutes under a N 2 gas flow, and then pulverized to obtain iron-based black particle powder.
得られた鉄系黒色粒子粉末のＴｉ量は全Ｆｅに対して２９．８原子％であった。飽和磁化値σｓは１２．０Ａｍ２／ｋｇであり、黒色度を表すＬ＊値が９．２であり、着色力は４０．２であった。平均粒子径は電子顕微鏡観察の結果、０．１６μｍであり、図１のＸ線回折図に示す通り、ＦｅＴｉＯ３−Ｆｅ２Ｏ３固溶体とＦｅ３Ｏ４−γ‐Ｆｅ２Ｏ３固溶体とＮａＦｅＴｉ３Ｏ８の混合物であった。ＦｅＴｉＯ３−Ｆｅ２Ｏ３の（１０４）面に対するＮａＦｅＴｉ３Ｏ８のメインピーク強度の比は１：０．０８であった。 The amount of Ti of the obtained iron-based black particle powder was 29.8 atomic% with respect to the total Fe. The saturation magnetization value σs was 12.0 Am 2 / kg, the L * value representing blackness was 9.2, and the coloring power was 40.2. As a result of observation with an electron microscope, the average particle diameter is 0.16 μm. As shown in the X-ray diffraction diagram of FIG. 1, the FeTiO 3 —Fe 2 O 3 solid solution, the Fe 3 O 4 —γ-Fe 2 O 3 solid solution, and the NaFeTi It was a mixture of 3 O 8 . The ratio of the main peak intensity of NaFeTi 3 O 8 to the (104) plane of FeTiO 3 —Fe 2 O 3 was 1: 0.08.
実施例２〜１１、比較例２
マグネタイトの種類、チタン化合物の添加量、加熱焼成処理の温度を種々変化させた以外は前記実施例１と同様にして鉄系黒色粒子粉末を得た。
Examples 2-11, Comparative Example 2
An iron-based black particle powder was obtained in the same manner as in Example 1 except that the kind of magnetite, the addition amount of the titanium compound, and the temperature of the heat-firing treatment were variously changed.
このときの製造条件を表１に、得られた非磁性黒色粒子粉末の諸特性を表２に示す。 The production conditions at this time are shown in Table 1, and various characteristics of the obtained nonmagnetic black particle powder are shown in Table 2.
比較例１（特開平３−２２７６号公報の実施例１の追試実験）
粒状マグネタイト粒子粉末（平均粒子径０．２μｍ、磁化値８５．０ｅｍｕ／ｇ）１００ｇをＴｉＯＳＯ４を０．２６ｍｏｌ含有する水溶液中（Ｔｉ／Ｆｅ＝２０．０原子％に相当する。）に分散混合し、次いで、該混合液中にＮａＯＨを添加して中和し、ｐＨ８において粒子表面にＴｉの水酸化物を沈着させた後、濾別、乾燥した。得られた粒子表面がＴｉの水酸化物で被覆されている粒状マグネタイト粒子粉末のＴｉ（ＩＶ）量は、蛍光Ｘ線分析の結果、Ｆｅ（ＩＩ）及びＦｅ（ＩＩＩ）に対し２１．０原子％であった。
Comparative Example 1 (Follow-up experiment of Example 1 of JP-A-3-2276)
100 g of granular magnetite particle powder (average particle diameter 0.2 μm, magnetization value 85.0 emu / g) is dispersed and mixed in an aqueous solution containing 0.26 mol of TiOSO 4 (corresponding to Ti / Fe = 20.0 atomic%). Then, NaOH was added to the mixed solution to neutralize it, and a hydroxide of Ti was deposited on the particle surface at pH 8, followed by filtration and drying. The amount of Ti (IV) in the granular magnetite particles whose surface is coated with a hydroxide of Ti is 21.0 atoms with respect to Fe (II) and Fe (III) as a result of X-ray fluorescence analysis. %Met.
上記粒子表面がＴｉの水酸化物で被覆されている粒状マグネタイト粒子粉末５０ｇをＮ２ガス流下７５０℃で１２０分間加熱焼成した後、粉砕して黒色粒子粉末を得た。 50 g of the granular magnetite powder whose particle surface was coated with a hydroxide of Ti was heated and fired at 750 ° C. for 120 minutes under a N 2 gas flow, and then pulverized to obtain a black particle powder.
得られた黒色粒子粉末のＴｉ量は全Ｆｅに対して２１．０原子％であった。また飽和磁化値σｓが０．６Ａｍ２／ｋｇであり、黒色度を表すＬ＊値が１４．１であり、着色力は４６．９であった。平均粒子径は０．２５μｍであり、図２のＸ線回折図に示す通り、Ｆｅ２Ｏ３−ＦｅＴｉＯ３固溶体とＦｅ２ＴｉＯ５との混合物であった。 The amount of Ti of the obtained black particle powder was 21.0 atomic% with respect to the total Fe. The saturation magnetization value σs was 0.6 Am 2 / kg, the L * value representing blackness was 14.1, and the coloring power was 46.9. The average particle diameter was 0.25 μm, and was a mixture of Fe 2 O 3 —FeTiO 3 solid solution and Fe 2 TiO 5 as shown in the X-ray diffraction diagram of FIG.
このときの製造条件を表１に、得られた鉄系黒色粒子粉末の諸特性を表２に示す。 The production conditions at this time are shown in Table 1, and various characteristics of the obtained iron-based black particle powder are shown in Table 2.
実施例１２〜１４
前記実施例１〜３の粉砕処理時に各青色顔料を添加した以外は前記実施例１乃至３と同様にして非磁性黒色粒子粉末を得た。
Examples 12-14
A nonmagnetic black particle powder was obtained in the same manner as in Examples 1 to 3 except that each blue pigment was added during the pulverization treatment in Examples 1 to 3.
このときの製造条件及び得られた鉄系黒色粒子粉末の諸特性を表３に示す。 Table 3 shows the production conditions and various characteristics of the obtained iron-based black particle powder.
＜電子写真用トナーの製造＞
実施例１５
実施例１で得た鉄系黒色粒子粉末を用いて、下記混合割合でヘンシェルミキサーにより混合した組成物を、二軸押し出し混練機（栗本鉄鋼社製 商品名：Ｓ−１）を用いて溶融混練し、混練物を冷却後、微粉砕した。これを体積平均粒子径８〜１０μｍ（コールカウンター社製 商品名：Ｍｕｌｔｉｓｉｚｅｒで測定）に分級し、さらに得られたトナー粉１００重量部に対して、疎水性シリカ微粉末（日本アエロジル社製 商品名：ＲＸ−２００）０．５重量部を外添処理し、電子写真用トナーを得た。
<Manufacture of toner for electrophotography>
Example 15
Using the iron-based black particle powder obtained in Example 1, the composition mixed by the Henschel mixer at the following mixing ratio was melt-kneaded using a biaxial extrusion kneader (trade name: S-1 manufactured by Kurimoto Steel). The kneaded product was cooled and then finely pulverized. This was classified into a volume average particle diameter of 8 to 10 μm (trade name manufactured by Colecounter, Inc., measured by Multisizer). : RX-200) 0.5 part by weight was externally added to obtain an electrophotographic toner.
スチレン−アクリル系共重合樹脂 １００重量部、
（ハイマーＳＢ−３０８：三洋化成工業株式会社製）
鉄系黒色粒子粉末 ２５重量部、
負荷電制御剤 ０．５重量部、
（ＢＯＮＴＲＯＮ Ｅ−８４：オリエント化学工業株式会社製）
低分子量ワックス ５重量部。
（ビスコール５５０−Ｐ：三洋化成工業株式会社製）
100 parts by weight of styrene-acrylic copolymer resin,
(Heimer SB-308: Sanyo Chemical Industries, Ltd.)
25 parts by weight of iron-based black particle powder,
0.5 parts by weight of negative charge control agent,
(BONTRON E-84: manufactured by Orient Chemical Co., Ltd.)
5 parts by weight of low molecular weight wax.
(Biscol 550-P: Sanyo Chemical Industries, Ltd.)
得られた電子写真用トナーは、初期画像濃度は１．５０で、カブリの発生は無かった（４段階のうち◎）。 The obtained electrophotographic toner had an initial image density of 1.50 and no fogging (A among four steps).
実施例１６〜２８、比較例３及び４
非磁性黒色粒子粉末の種類を種々変化させた以外は、前記実施例１５と同様にして非磁性トナーを得た。
Examples 16 to 28, Comparative Examples 3 and 4
A nonmagnetic toner was obtained in the same manner as in Example 15 except that the type of nonmagnetic black particle powder was variously changed.
このときの処理条件及び得られた非磁性黒色トナーの諸特性を表４に示す。 Table 4 shows the treatment conditions and various characteristics of the obtained nonmagnetic black toner.
本発明に係る鉄系黒色粒子粉末は、黒色度に優れ、可及的に磁化値が低いので、黒色を呈する顔料及び塗料、樹脂組成物の着色用材料、充填材等として好適である。 Since the iron-based black particle powder according to the present invention has excellent blackness and has a magnetization value as low as possible, it is suitable as a pigment and paint exhibiting black, a coloring material for a resin composition, a filler, and the like.
本発明に係る鉄系黒色粒子粉末を用いて製造した黒色非磁性トナーは、高い黒色度を有すると共に、磁化値が低いので、非磁性トナーとして好適である。 The black nonmagnetic toner produced using the iron-based black particle powder according to the present invention has a high blackness and a low magnetization value, and therefore is suitable as a nonmagnetic toner.
Claims (4)
A black toner comprising the iron-based black particle powder according to claim 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008096782A (en) * | 2006-10-13 | 2008-04-24 | Canon Inc | Black toner |
| JP2009040636A (en) * | 2007-08-09 | 2009-02-26 | Mitsui Mining & Smelting Co Ltd | Black oxide particle powder, and method for producing the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06263449A (en) * | 1993-03-13 | 1994-09-20 | Toda Kogyo Corp | Non-magnetic blackish brown hydrated iron oxide particle powder, production thereof and substrate for magnetic recording medium using the powder |
| JPH0834617A (en) * | 1994-07-22 | 1996-02-06 | Toda Kogyo Corp | Black magnetic iron oxide particle-shaped powder |
| JPH08133745A (en) * | 1994-11-01 | 1996-05-28 | Toda Kogyo Corp | Granular magnetite particle powder and its production |
| JP2002068749A (en) * | 2000-05-25 | 2002-03-08 | National Institute Of Advanced Industrial & Technology | Silver-containing particulate magnetic oxide particle and method of producing the same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06263449A (en) * | 1993-03-13 | 1994-09-20 | Toda Kogyo Corp | Non-magnetic blackish brown hydrated iron oxide particle powder, production thereof and substrate for magnetic recording medium using the powder |
| JPH0834617A (en) * | 1994-07-22 | 1996-02-06 | Toda Kogyo Corp | Black magnetic iron oxide particle-shaped powder |
| JPH08133745A (en) * | 1994-11-01 | 1996-05-28 | Toda Kogyo Corp | Granular magnetite particle powder and its production |
| JP2002068749A (en) * | 2000-05-25 | 2002-03-08 | National Institute Of Advanced Industrial & Technology | Silver-containing particulate magnetic oxide particle and method of producing the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008096782A (en) * | 2006-10-13 | 2008-04-24 | Canon Inc | Black toner |
| JP2009040636A (en) * | 2007-08-09 | 2009-02-26 | Mitsui Mining & Smelting Co Ltd | Black oxide particle powder, and method for producing the same |
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