JPS63282749A - Electrostatic charge image developing toner - Google Patents
Electrostatic charge image developing tonerInfo
- Publication number
- JPS63282749A JPS63282749A JP62116798A JP11679887A JPS63282749A JP S63282749 A JPS63282749 A JP S63282749A JP 62116798 A JP62116798 A JP 62116798A JP 11679887 A JP11679887 A JP 11679887A JP S63282749 A JPS63282749 A JP S63282749A
- Authority
- JP
- Japan
- Prior art keywords
- particle
- toner
- obtd
- particles
- agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002245 particle Substances 0.000 claims abstract description 60
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 239000003086 colorant Substances 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 239000000839 emulsion Substances 0.000 claims abstract description 14
- 230000002378 acidificating effect Effects 0.000 claims abstract description 12
- 239000011164 primary particle Substances 0.000 claims abstract description 7
- 239000011163 secondary particle Substances 0.000 claims description 10
- 229920005672 polyolefin resin Polymers 0.000 claims description 3
- 238000003756 stirring Methods 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000000975 dye Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- -1 polyethylene Polymers 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 229910002012 Aerosil® Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- 239000012860 organic pigment Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- 239000004229 Alkannin Substances 0.000 description 1
- 235000011293 Brassica napus Nutrition 0.000 description 1
- 240000008100 Brassica rapa Species 0.000 description 1
- 235000000540 Brassica rapa subsp rapa Nutrition 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000004129 EU approved improving agent Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- QECVIPBZOPUTRD-UHFFFAOYSA-N N=S(=O)=O Chemical class N=S(=O)=O QECVIPBZOPUTRD-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003984 copper intrauterine device Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- VRIVJOXICYMTAG-IYEMJOQQSA-L iron(ii) gluconate Chemical compound [Fe+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O VRIVJOXICYMTAG-IYEMJOQQSA-L 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229920003146 methacrylic ester copolymer Polymers 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000005608 naphthenic acid group Chemical class 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920005670 poly(ethylene-vinyl chloride) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- VSRBKQFNFZQRBM-UHFFFAOYSA-N tuaminoheptane Chemical compound CCCCCC(C)N VSRBKQFNFZQRBM-UHFFFAOYSA-N 0.000 description 1
- 229960003986 tuaminoheptane Drugs 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/0825—Developers with toner particles characterised by their structure; characterised by non-homogenuous distribution of components
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/0802—Preparation methods
- G03G9/0804—Preparation methods whereby the components are brought together in a liquid dispersing medium
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Developing Agents For Electrophotography (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、電子写真、静電記録、静電印刷などにおける
静電荷像を現像するためのトナー及びその製法に関する
。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a toner for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc., and a method for producing the toner.
従来技術
従来、一般に広く用いられて来たトナーは懸濁重合によ
り得られるスチレン/アクリレート系共重合体粉末にカ
ーがンブラックのような着色剤、随意帯電制御剤及び/
又は磁性体をトライブレンドして後押出し機等で溶融混
練し、次いで粉砕・分級することによりて製造されて来
た(特開昭51−23354号参照)。Prior Art Toners that have been widely used in the past include styrene/acrylate copolymer powder obtained by suspension polymerization, a colorant such as carbon black, an optional charge control agent, and/or a colorant such as carbon black.
Alternatively, it has been produced by tri-blending a magnetic material, melt-kneading it in a post-extruder, etc., and then crushing and classifying it (see JP-A-51-23354).
しかし、上記のような溶融混練−粉砕法で得られる従来
のトナーは、トナー粒径の制御に限界があり、実質的に
10μ以下、特に8μ以下、殊に5μ以下の平均粒径の
トナーを歩留りよく製造することが困難なばかりでなく
、現像剤にした場合画像の定着性が悪く、またはオフセ
ット現像などにより画像が汚染されたり、また、解像度
が低くかつかぶりが発生などの欠点を避けることが困難
であった。However, the conventional toner obtained by the above-mentioned melt-kneading-pulverization method has a limit in controlling the toner particle size, and it is practically impossible to control toner with an average particle size of 10μ or less, particularly 8μ or less, especially 5μ or less. Not only is it difficult to manufacture with a high yield, but when used as a developer, the image fixation is poor, the image is stained by offset development, etc., and it is also difficult to avoid drawbacks such as low resolution and fogging. was difficult.
本発明の目的
本発明は従来一般に広く用いられて来たトナーの有した
上記の欠点を大巾に改善し、しかも新規な製法を用いる
ことによって従来法のトナーよりも安価なトナーを提供
することを目的とするものである。OBJECTS OF THE INVENTION The present invention provides a toner that greatly improves the above-mentioned drawbacks of toners that have been widely used in the past, and that is cheaper than toners of conventional methods by using a new manufacturing method. The purpose is to
本発明の特徴
本発明の静電荷像現像用トナーは、酸性極性基又は塩基
性極性基を有する重合体(以下「極性基を有する重合体
」という)、好ましくは酸性極性基を有する重合体の一
次粒子及び着色剤粒子並びに定着性改良剤粒子並びに随
意帯電制御剤を含有してなる二次粒子の会合粒子である
仁とを特徴とする静電荷像現像用トナーである。Features of the present invention The toner for developing electrostatic images of the present invention is made of a polymer having an acidic polar group or a basic polar group (hereinafter referred to as a "polymer having a polar group"), preferably a polymer having an acidic polar group. The present invention is a toner for developing an electrostatic image, which is an associated particle of primary particles, colorant particles, fixing property improver particles, and secondary particles containing an optional charge control agent.
本発明で用いられる極性基を有する重合体の一次粒子及
び定着性改良剤粒子は0.05〜0.5μ、好ましくは
0.1〜0.3μの平均粒径を有する熱可塑性重合体の
粒子でありて、一般に乳化重合法によって好適に得られ
る。本発明のトナーである上記会合粒子を構成する二次
粒子は、0.01〜0.5、好ましくは0.03〜0.
1μの平均粒径をもつ着色剤粒子と極性基を有する重合
体の一次粒子と定着性改良剤粒子とがイオン性結合、水
素結合、金属配位結合、弱酸−器差結合、或いはファン
デアワールスカ等の結合力によって凝集している粒子で
あって、一般に0.5〜5μ、好ましくは1μ〜4μの
平均粒径をもっている。The primary particles of the polymer having a polar group and the particles of the fixing property improver used in the present invention are thermoplastic polymer particles having an average particle size of 0.05 to 0.5 μ, preferably 0.1 to 0.3 μ. It is generally preferably obtained by an emulsion polymerization method. The secondary particles constituting the above-mentioned associated particles that are the toner of the present invention are 0.01 to 0.5, preferably 0.03 to 0.5.
The colorant particles having an average particle size of 1μ, the primary particles of the polymer having a polar group, and the fixing property improver particles are bonded together by ionic bonds, hydrogen bonds, metal coordination bonds, weak acid-instrument bonding, or van der Waalska bonds. These particles are aggregated by a bonding force such as, and generally have an average particle size of 0.5 to 5 μm, preferably 1 μ to 4 μm.
本発明の会合粒子は上記二次粒子が凝集して生成した不
定形の粒子であって、その平均粒径は一般に3〜25μ
、好ましくは5〜15μ、最も好ましくは5〜13μで
ある。The associated particles of the present invention are amorphous particles produced by agglomeration of the above-mentioned secondary particles, and the average particle size thereof is generally 3 to 25 μm.
, preferably 5-15μ, most preferably 5-13μ.
本発明の好適な態様では、上記会合粒子を構成する二次
粒子間の接触部分の少くとも一部、好ましくは二次粒子
間の接触部分の大半、が造膜融着している会合粒子が用
いられる。In a preferred embodiment of the present invention, the associated particles have at least part of the contact areas between the secondary particles constituting the associated particles, preferably most of the contact areas between the secondary particles are fused to form a film. used.
本発明のトナーである会合粒子は、極性基を有する重合
体と着色剤の合計当り、極性基を有する重合体を20〜
99.9重量%、好ましくは30〜98重量%、最も好
ましくは40〜95重量%及び着色剤を80〜0.11
Et%、好ましくは70〜2重量%、最も好ましくは6
0〜5重量%及び定着性改良剤としては、極性基を有す
る重合体と着色剤の合計100重量当り、定着性改良剤
を0.1〜40重量部、好ましくは、0.5〜30重量
部、更に好ましくは、1〜20重葉部含有してなるもの
である。The associated particles, which are the toner of the present invention, contain 20 to 20 to
99.9% by weight, preferably 30-98% by weight, most preferably 40-95% by weight and 80-0.11% by weight of colorant.
Et%, preferably 70-2% by weight, most preferably 6
0 to 5% by weight and the fixability improver is 0.1 to 40 parts by weight, preferably 0.5 to 30 parts by weight, per 100 weight of the total weight of the polymer having a polar group and the colorant. part, more preferably 1 to 20 parts.
本発明で用いられる極性基を有する重合体の好ましい例
はスチレン類、アルキル(メタ)アクリレート及び酸性
極性基又は塩基性極性基を有するコモノマーの共重合体
である。Preferred examples of the polymer having a polar group used in the present invention are copolymers of styrenes, alkyl (meth)acrylates, and comonomers having an acidic polar group or a basic polar group.
本明細書で「着色剤」の語は、静電荷偉現儂剤として必
要な色彩を該現像剤に与える着色性の添加剤と言う意味
で用いられるもので、マグネタイトのような磁性体やニ
グロシン染料のような帯電制御剤のように磁性又は帯電
制御性のような着色剤以外の性能を現像剤に賦与する添
加剤も現像剤に所期の着色性を与えるならば「着色剤」
に含まれるものである。In this specification, the term "colorant" is used to mean a coloring additive that gives the developer the necessary color as an electrostatically charged developer. Additives that impart properties other than colorants, such as magnetism or charge control properties, to the developer, such as charge control agents such as dyes, can also be considered "colorants" if they impart desired coloring properties to the developer.
It is included in
本発明で用いられる着色剤としては、無機顔料又は、有
機顔料及び有機染料、好ましくは、無機顔料又は、有機
顔料が用いられるが、一種、又は二種以上の顔料又は/
及び一種又は二種以上の染料を必要に応じて組合せて用
いてもよい。As the coloring agent used in the present invention, inorganic pigments, organic pigments and organic dyes, preferably inorganic pigments or organic pigments are used, and one or more types of pigments or/and organic pigments are used.
Also, one or more kinds of dyes may be used in combination as necessary.
本発明のトナーは、前記のように、必要に応じ、帯電制
御剤や磁性体等を含有するものである。このような帯電
制御剤としては、グラス用としてニグロシン系の電子供
与性染料、その他ナフテン酸または高級脂肪酸の金属塩
、アルコキシル化アミン、四級アンモニウム塩、アルキ
ルアミド、キレート、顔料、フッ素処理活性剤など、マ
イナス用として電子受容性の有機錯体、その低塩素化パ
ラフィン、塩素化プリエステル、数基過剰のポリエステ
ル、銅7タロシアニンのスルホニルアミンなどが例示で
きる。As described above, the toner of the present invention contains a charge control agent, a magnetic material, and the like, if necessary. Such charge control agents include nigrosine-based electron-donating dyes for glasses, metal salts of naphthenic acids or higher fatty acids, alkoxylated amines, quaternary ammonium salts, alkylamides, chelates, pigments, and fluorine treatment activators. Examples of negative electrodes include electron-accepting organic complexes, their less chlorinated paraffins, chlorinated preesters, polyesters with a few excess groups, and sulfonylamines of copper-7 talocyanine.
また、本発明のトナーは、必要により流動化剤等の添加
剤と共に用いることができ、そのような流動化剤として
は疎水性シリカ、酸化チタン、酸化アルミニウム等の微
粉末を例示でき、トナー100重量部当り0.01〜5
重量部、好ましくは0、1〜1重量部用いられる。Further, the toner of the present invention can be used together with additives such as a fluidizing agent, if necessary. Examples of such fluidizing agents include fine powders such as hydrophobic silica, titanium oxide, and aluminum oxide. 0.01-5 per part by weight
Parts by weight are used, preferably 0.1 to 1 part by weight.
本発明で用いられる定着性改良剤としては、一種又は二
種以上の定着性改良剤を組み合せてもかまわない。本発
明で用いられる定着性改良剤の好ましい例としては、オ
レフィン系樹脂(低分子量ポリエチレン、低分子量ポリ
プロピレン、酸化ポリエチレン、ポリ4弗化エチレンな
ど)、エポキシ樹脂、ポリエステル樹脂、スチレンーブ
タジエ□ン共重合体(モノマー比5〜30:95〜70
)、オレフィン共重合体(エチレン−アクリル酸共重合
体、エチレン−アクリル酸エステル共重合体、エチレン
−メタクリル酸共重合体、エチレン−メタクリル酸エス
テル共重合体、エチレン−塩化ビニル共重合体、エチレ
ン−酢酸ビニル共重合体、アイオノマー樹脂)、ポリビ
ニルピロリドン、メチルビニルエーテル−無水マレイン
酸共重合体、マレイン酸変性フェノール樹脂、フェノー
ル変性テルペン樹脂などがあげられ、好ましくはオレフ
ィン系樹脂などであるこれら樹脂は水分散エマルジョン
として使用されるのが好ましい。As the fixing property improving agent used in the present invention, one type or two or more types of fixing property improving agents may be used in combination. Preferred examples of the fixability improver used in the present invention include olefin resins (low molecular weight polyethylene, low molecular weight polypropylene, oxidized polyethylene, polytetrafluoroethylene, etc.), epoxy resins, polyester resins, styrene-butadiene resins, etc. Copolymer (monomer ratio 5-30:95-70
), olefin copolymers (ethylene-acrylic acid copolymer, ethylene-acrylic ester copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic ester copolymer, ethylene-vinyl chloride copolymer, ethylene -vinyl acetate copolymer, ionomer resin), polyvinylpyrrolidone, methyl vinyl ether-maleic anhydride copolymer, maleic acid-modified phenol resin, phenol-modified terpene resin, etc. These resins are preferably olefin resins. Preferably, it is used as an aqueous emulsion.
本発明において用いられる定着性改良剤の具体例として
は、
商品名r HYTECJ (東邦化学工業j1りとして
市販されているE−4A(ポリエチレンワックスエマル
ジョン)、E−4B(同)、E −5403A(同)、
E −5403B (同)、E−68A(同)、E−1
03A(同)、E−103°N(同)、E−433N(
ylすfロピレ/ワックスエマルジ1ン)などがあげら
れる。Specific examples of the fixability improver used in the present invention include E-4A (polyethylene wax emulsion), E-4B (same), and E-5403A (commercially available as Toho Chemical Industry Co., Ltd.) under the trade name HYTECJ. same),
E-5403B (same), E-68A (same), E-1
03A (same), E-103°N (same), E-433N (
Examples include wax emulsion/wax emulsion.
本発明のトナーの好適な製法を例示すれば、以下の通り
である。乳化重合により得られた酸性極性基又は塩基性
極性基を有する重合体のエマルジッンに所要量の着色剤
粉末並びに定着性改良剤並びに随意帯電制御剤を添加混
合して均一に分散させ0.5〜4時間、好ましくは1〜
3時間攪拌を続けると極性基を有する重合体の一次粒子
と定着性改良剤粒子と着色剤粒子は次第に凝集して0.
5〜5μの平均粒径をもった二次粒子に生長する。この
ような分散体を更にそのまま0.5〜3時間、好適には
1〜2時間攪拌を続けると二次粒子が更に凝集して5〜
25μの平均粒径をもった会合粒子に生長する。本発明
のトナーの最も好適な製法では、このようにして生成し
た分散液を、更に、極性基を有する重合体のガラス転移
点〜ガ2ス転移点より20℃高い温度に1〜6時間、好
適には2〜4時間攪拌を続けると、二次粒子間の接触部
分の少くとも一部が造膜融着した会合粒子が生成する。A preferred method for producing the toner of the present invention is as follows. A required amount of colorant powder, a fixing property improver, and an optional charge control agent are added and mixed to an emulsion of a polymer having an acidic polar group or a basic polar group obtained by emulsion polymerization, and the mixture is uniformly dispersed. 4 hours, preferably 1~
When stirring is continued for 3 hours, the primary particles of the polymer having polar groups, the fixing property improver particles, and the colorant particles gradually aggregate to a 0.
It grows into secondary particles with an average particle size of 5-5μ. If such a dispersion is continued to be stirred for 0.5 to 3 hours, preferably 1 to 2 hours, the secondary particles will further aggregate and become 5 to 3 hours.
It grows into associated particles with an average particle size of 25μ. In the most preferred method for producing the toner of the present invention, the dispersion liquid thus produced is further heated to a temperature 20° C. higher than the glass transition point to the gas transition point of the polymer having a polar group for 1 to 6 hours. When the stirring is preferably continued for 2 to 4 hours, associated particles in which at least some of the contact areas between the secondary particles are fused to form a film are produced.
このような会合粒子は、二次粒子間が造膜融着している
ので、貯蔵、輸送、現像剤製造時等に殆んど崩壊するこ
とが無いので静電荷像現像用現像剤としては特に好適で
ある。These associated particles are particularly useful as a developer for developing electrostatic images because they hardly disintegrate during storage, transportation, developer manufacturing, etc. because the secondary particles are fused together to form a film. suitable.
本発明のトナーは、鉄、ガラスピース等のキャリアと混
合されて現像剤とされるが、トナー自体がフェライト等
を既に着色剤として含有するような場合にはフェライト
等はキャリアの働きもするので、その場合にはトナーは
そのまま現像剤として用い得る。なお、上記キャリアと
しては、樹脂被覆、好ましくは弗素系樹脂被覆により負
の摩擦帯電特性を有する鉄粉が殊に好適である。The toner of the present invention is mixed with a carrier such as iron or glass piece to form a developer, but if the toner itself already contains ferrite etc. as a coloring agent, the ferrite etc. also acts as a carrier. In that case, the toner can be used as a developer as it is. Note that iron powder, which has negative triboelectrification characteristics due to resin coating, preferably fluorine-based resin coating, is particularly suitable as the carrier.
本発明の効果
本発明のトナーは、粒度分布が比較的狭く且つ平均粒径
が比較的小さいので、静電荷像現像剤にした場合、従来
品に較べ画像定着性がきわめて良いばかりでなく、オフ
セット現像もなく解像度が著しく向上し且つかぶりの発
生が殆んど無いといった優れた効果を奏し、更に粉砕分
級を要しない等製法が従来法に較べて簡略化され且つ必
要なトナ二粒分の収車も高いので経済性においても優れ
ているといった効果を奏するものでおる。Effects of the present invention The toner of the present invention has a relatively narrow particle size distribution and a relatively small average particle diameter, so when used as an electrostatic image developer, it not only has extremely good image fixing properties compared to conventional products, but also has an offset It has excellent effects such as significantly improved resolution and almost no fogging without the need for development.Furthermore, the manufacturing method is simplified compared to conventional methods, such as not requiring pulverization and classification, and the required amount of two toner particles can be reduced. Cars are also expensive, so this has the advantage of being economical.
以下に実施例により本発明を具体的に説明する。The present invention will be specifically explained below using Examples.
なお、特記しない限り数量は重量によって表示した。Note that unless otherwise specified, quantities are expressed by weight.
実施例1
酸性極性基含有重合樹脂の調整
スチレンモノマー(ST) 60 部アク
リル酸ゾチル(BA) 40 部アクリル
酸(AA) 8 部以上の七ツマー
混合物を
水 10
0 部ノニオン乳化剤 1 部(
エマルダン950)
アニオン乳化剤 1.5部(ネオ
cyn)
過硫酸カリウム 0.5部の水溶
液混合物に添加し、攪拌下70℃で8時間重合させて固
形分50チの酸性極性基含有樹脂エマルS)Mンを得た
。Example 1 Preparation of polymeric resin containing acidic polar groups Styrene monomer (ST) 60 parts Zotyl acrylate (BA) 40 parts Acrylic acid (AA) 8 parts or more of a heptamine mixture was mixed with water 10 parts
0 parts nonionic emulsifier 1 part (
Emuldan 950) Anionic emulsifier 1.5 parts (neocyn) Potassium persulfate 0.5 parts were added to an aqueous solution mixture and polymerized at 70°C for 8 hours with stirring to give an acidic polar group-containing resin emul S) with a solid content of 50 cm. I got Mn.
トナーの調整(1)
酸性極性基含有樹脂エマルジョン 120部マグ
ネタイト 40部ニグロシン
染料 5部(ボントロンN−
04)
カーボンブラック 5部(ダイ
ヤブラック+1oo )
ワックスエマルジヲン(HYTECE−433N )
20部(定着性改良剤)
水
380部以上の混合物をスラッシャ−で分散攪拌しな
がら約30℃に2時間保持した。その後、さらに攪拌し
ながら70℃に加温して3時間保持した。この間顕微値
で観察して、樹脂粒子と定着性改良剤粒子とマグネタイ
ト粒子とのコンブレックスが約10μに生長するのが確
認された。冷却して、得られた液状分散物をツフナーロ
過、水洗し、50℃真空乾燥10時間させた。Preparation of toner (1) Acidic polar group-containing resin emulsion 120 parts Magnetite 40 parts Nigrosine dye 5 parts (Bontron N-
04) Carbon black 5 parts (Diamond black + 1oo) Wax emulsion (HYTECE-433N)
20 parts (fixability improver) water
More than 380 parts of the mixture was dispersed and stirred using a slasher and maintained at about 30° C. for 2 hours. Thereafter, the mixture was heated to 70° C. with further stirring and maintained for 3 hours. During this time, microscopic observation revealed that a complex of resin particles, fixing property improver particles, and magnetite particles had grown to a size of about 10 μm. After cooling, the resulting liquid dispersion was filtered through a Tuftner filter, washed with water, and vacuum dried at 50° C. for 10 hours.
この得られたトナー100重量部に流動化剤としてシリ
カ(日本アエロジル社製アエロジルR972)を0.5
重量部を添加混合し、試験用現像剤とした。0.5 parts of silica (Aerosil R972 manufactured by Nippon Aerosil Co., Ltd.) was added as a fluidizing agent to 100 parts by weight of the obtained toner.
Parts by weight were added and mixed to prepare a test developer.
このトナーで用い九上記重合体のTgは43℃、グル化
度は8%、軟化点は142℃、トナーの平均粒径は、1
2μであった。The polymer used in this toner has a Tg of 43°C, a degree of gluing of 8%, a softening point of 142°C, and an average particle size of 1
It was 2μ.
上記現像剤を市販の複写機(キャノン製NP−270Z
)に入れ複写を行ったところ、濃度の高い、かぶ抄の少
ない複写画が得られた。結果を表−2に示した。The above developer was applied to a commercially available copying machine (Canon NP-270Z).
) and made a copy, a copy with high density and few turnips was obtained. The results are shown in Table-2.
実施例2〜7
表−1に示したモノマー組成と定着性改良剤を用い実施
例1と同様の操作を繰り返した。結果を表−2に示す。Examples 2 to 7 The same operations as in Example 1 were repeated using the monomer composition and fixability improver shown in Table 1. The results are shown in Table-2.
なお、表−1で用いた略記号の意味を以下に示す。The meanings of the abbreviations used in Table 1 are shown below.
2 ERA ニアクリル酸2エチルヘキシル胆 ;メタ
クリル酸
BQA;2−ヒドロキシグロビルーN、N、N−トリメ
、チルアンモニウムクロライドアクリレート
vP :ビニルピリジン
実施例5
実施例1と同様の酸性極性基含有樹脂エマルジョンをy
4tEした後、トナー調整時に以下の操作を行った。2 ERA 2-ethylhexyl diacrylate; BQA methacrylate; 2-hydroxyglobin-N,N,N-trimethylammonium chloride acrylate vP: vinylpyridine Example 5 The same acidic polar group-containing resin emulsion as in Example 1 was
After 4tE, the following operation was performed during toner adjustment.
トナーの調整(2)
実施例1の酸性極性基含有樹脂
エマル−)Nン 184部ク
ロム染料<eントロンE−81) 1カ
ーボンブラツク(リーガル330R)
7部ワ7りxエマルジョン (HYTECS−312
1) 15部(定着性改良剤)
水
307部以上の混合物を実施例1と同様の操作を行り
て、試験用トナーを調整した。得られた重合体のTgは
、42℃、rル化度996、軟化点132℃、トナーの
平均粒径は、10.5μmであった。このトナーを市販
の複写機(東芝製レオドライB D −4140)に入
れ、複写を行ったところ、濃度の高い、かぶりの少ない
複写画が得られた。結果を表−2に示す。Preparation of toner (2) Acidic polar group-containing resin emulsion of Example 1) N 184 parts Chromium dye <entron E-81) 1 Carbon black (Regal 330R)
Part 7 Wa 7 Ri x Emulsion (HYTECS-312
1) 15 parts (fixability improver) water
A test toner was prepared using 307 parts or more of the mixture in the same manner as in Example 1. The obtained polymer had a Tg of 42° C., a degree of chlorination of 996, a softening point of 132° C., and an average particle size of the toner of 10.5 μm. When this toner was put into a commercially available copying machine (ReoDry BD-4140 manufactured by Toshiba) and copied, a copy with high density and little fogging was obtained. The results are shown in Table-2.
実施例6,7
表−1に示すモノマー組成を用い実施例5と同様の操作
を繰り返した。結果を表−2に示す。Examples 6 and 7 The same operation as in Example 5 was repeated using the monomer composition shown in Table 1. The results are shown in Table-2.
実施例8
実施例1における会合粒子形成反応時、70℃、2時間
保持の代9に60℃加温2時間に保持したところ、粒子
成長が制御され収率6o%で平均粒径5μmのトナーが
得られた。このトナーにより複写試験を行ったところ、
非常に解像度の良好で、濃度が高く、かぶりの少ない画
像がえられた。Example 8 During the associated particle formation reaction in Example 1, when the temperature was maintained at 70°C for 2 hours, the particle growth was controlled and the toner with an average particle size of 5 μm was produced at a yield of 60%. was gotten. When a copying test was conducted using this toner,
Images with very good resolution, high density, and little fogging were obtained.
比較例1
表−1に示すように、実施例1の樹脂モノマー組成中酸
性極性基モノマーであるAAを添加せず重合した樹脂エ
マルジョンを用いたところ、会合粒子の成長がなく、試
験用トナーがえられなかった。Comparative Example 1 As shown in Table 1, when a polymerized resin emulsion was used without adding AA, which is an acidic polar group monomer, to the resin monomer composition of Example 1, there was no growth of associated particles and the test toner was I couldn't get it.
比較例2
実施例1にりける樹脂エマルジョンと定着性改良剤工、
マルジlンをスプレードライヤー(アシデワニロ7)マ
イデー製、モービルマイナー)で入口温度120℃、出
口温度90℃、供給量1.517m1n、アトマイデー
3 XI O’ rpmの運転条件にて乾燥させ、樹脂
を得た。この樹脂60部、マグネタイト40部、ニグロ
シン染料(&ントロンN−04”)5部、カーがンブラ
ック(ダイヤブラック$100 )5部を溶融混練、粉
砕して平均粒径5μmのトナーを得た。この時の収率は
、35チでありた。Comparative Example 2 Resin emulsion and fixing property improving agent used in Example 1,
The Margin was dried with a spray dryer (Aside Wanilo 7, manufactured by Mider, Mobile Minor) under the following operating conditions: inlet temperature 120 °C, outlet temperature 90 °C, supply amount 1.517 m1n, Atomide 3 XI O' rpm to obtain a resin. Ta. 60 parts of this resin, 40 parts of magnetite, 5 parts of nigrosine dye (&NTRON N-04''), and 5 parts of Cargan Black (Diablack $100) were melt-kneaded and pulverized to obtain a toner with an average particle size of 5 μm. The yield at this time was 35 cm.
この得られたトナー100重量部に流動化剤としてシリ
カ(日本アエロジル社%R−972)を0.5重量部を
添加混合し、試験用現像剤とした。To 100 parts by weight of the obtained toner, 0.5 parts by weight of silica (Nippon Aerosil Co., Ltd. %R-972) was added and mixed as a fluidizing agent to prepare a developer for testing.
この現像剤は、非常に流動性の悪いものであった。この
現像剤を用いて、実施例1と同様の複写試験を行ったと
ころ、非常にかぶりの多い画像がえられた。This developer had very poor fluidity. When a copying test similar to that in Example 1 was conducted using this developer, an image with very large fog was obtained.
比較例3
表−1に示すような樹脂組成で定着性改良剤を添加せず
実施例1と同様の操作でTg45℃、rル化度5%、較
化点147℃、平均粒径12.0μmのトナーを得7′
?、uこのトナーを用いて実施例1と同様の複写試験を
行ったところ非常に定着性の悪い画像がえられた。Comparative Example 3 A resin composition as shown in Table 1 was used in the same manner as in Example 1 without the addition of a fixing property improver, and a Tg of 45°C, a degree of oxidation of 5%, a comparison point of 147°C, and an average particle size of 12. Obtain 0μm toner7'
? , u When a copying test similar to that in Example 1 was conducted using this toner, an image with very poor fixability was obtained.
複写画解像度評価方法
データククエスト社テストパターンAR−4を複写し、
1箇あたりのライン数を目視確認して、解像度の評価と
した。本評価方法において、表−1の樹脂組成では、解
像度6.3以上で良好、3.6以下で不良と判断できる
。Copy image resolution evaluation method: Copy the test pattern AR-4 from Ququest Co., Ltd.
The resolution was evaluated by visually checking the number of lines per line. In this evaluation method, for the resin composition shown in Table 1, a resolution of 6.3 or higher can be judged as good, and a resolution of 3.6 or less can be judged as bad.
複写画かぶ抄評価法:
村上カラーラ?ラトリー社製CM−53Pの反射率計を
用いて、光角45°にて複写前の白紙の反射率と複写後
の非文字部分の反射率を比較し、反射率比にてかぶり濃
度(%)とした。かぶり濃度0.7以下でかぶり良好、
1.0以上で不良と判断できる。Copy Kabu-sho evaluation method: Murakami Carrara? Using a CM-53P reflectance meter manufactured by Latry Co., Ltd., the reflectance of the blank paper before copying and the reflectance of the non-text portion after copying were compared at a light angle of 45°, and the fog density (%) was calculated based on the reflectance ratio. ). Good fog with fog density below 0.7,
If it is 1.0 or more, it can be determined to be defective.
複写画定着率評価方法
前記テストパターンを複写し、黒ペタ部分を砂消ゴムで
5往復こすって、前記反射率計を用いて、こすり前とこ
すり後の反射率比にて定着率とした。Copy image fixation rate evaluation method: The test pattern was copied, and the black peta area was rubbed 5 times with a sand eraser, and using the reflectance meter, the fixation rate was calculated as the ratio of the reflectance before and after rubbing.
定着率85%以上で良好、70%以下で不良と判断でき
る。A fixing rate of 85% or more can be judged as good, and a fixing rate of 70% or less can be judged as bad.
平均粒子径
コールタ−カウンターTA−111:(株)日科機製〕
でトナー粒子10,000個の平均粒子径を測定する。Average particle diameter Coulter Counter TA-111: Manufactured by Nikkaki Co., Ltd.]
The average particle diameter of 10,000 toner particles is measured.
Claims (2)
一次粒子及び着色剤粒子及び定着性改良剤粒子並びに随
意帯電制御剤を含有してなる二次粒子の会合粒子である
ことを特徴とする静電荷像現像用トナー。(1) It is characterized by being an aggregate particle of a primary particle of a polymer having an acidic polar group or a basic polar group, and a secondary particle containing a colorant particle, a fixing property improver particle, and an optional charge control agent. A toner for developing electrostatic images.
ョンである特許請求の範囲第(1)項記載の静電荷像現
像用トナー。(2) The toner for developing electrostatic images according to claim (1), wherein the fixing property improver particles are an olefin resin emulsion.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62116798A JP2547014B2 (en) | 1987-05-15 | 1987-05-15 | Toner for electrostatic image development |
PCT/JP1988/000073 WO1988005930A1 (en) | 1987-01-29 | 1988-01-29 | Toner for developing electrostatically charged image |
DE3855939T DE3855939T2 (en) | 1987-01-29 | 1988-01-29 | TONER FOR DEVELOPING ELECTROSTATICALLY CHARGED IMAGES |
US07/261,829 US4996127A (en) | 1987-01-29 | 1988-01-29 | Toner for developing an electrostatically charged image |
EP88901304A EP0302939B1 (en) | 1987-01-29 | 1988-01-29 | Toner for developing electrostatically charged image |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62116798A JP2547014B2 (en) | 1987-05-15 | 1987-05-15 | Toner for electrostatic image development |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63282749A true JPS63282749A (en) | 1988-11-18 |
JP2547014B2 JP2547014B2 (en) | 1996-10-23 |
Family
ID=14695934
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62116798A Expired - Lifetime JP2547014B2 (en) | 1987-01-29 | 1987-05-15 | Toner for electrostatic image development |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2547014B2 (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03166551A (en) * | 1989-11-27 | 1991-07-18 | Tomoegawa Paper Co Ltd | Electrophotographic dry toner |
WO1993008510A1 (en) * | 1991-10-22 | 1993-04-29 | Nippon Carbide Kogyo Kabushiki Kaisha | Colored toner for developing electrostatic image |
JP2002072541A (en) * | 2000-09-05 | 2002-03-12 | Fuji Xerox Co Ltd | Electrostatic charge image developing toner, method for manufacturing the electrostatic charge image developing toner, developer for electrostatic charge image development, and image-forming method |
US6440627B2 (en) | 2000-02-21 | 2002-08-27 | Fuji Xerox Co., Ltd. | Toner for developing electrostatic image, process for preparation of the same, developer for electrostatic image, and process for forming image |
US6717602B2 (en) | 1999-07-02 | 2004-04-06 | Konica Corporation | Image forming method and image forming apparatus, and electrostatic latent image developing toner used by the same |
US6733944B2 (en) | 2001-08-17 | 2004-05-11 | Fuji Xerox Co., Ltd. | Image forming process |
US7422834B2 (en) | 2004-08-27 | 2008-09-09 | Fuji Xerox Co., Ltd. | Electrostatic latent image developing magenta toner, electrostatic latent image developer, toner manufacturing method, and image forming method |
US7741001B2 (en) | 2005-04-04 | 2010-06-22 | Sharp Kabushiki Kaisha | Toner for electrostatic image development and process for preparing the same |
US7901862B2 (en) | 2007-11-27 | 2011-03-08 | Kabushiki Kaisha Toshiba | Developing agent and method for manufacturing the same |
US8227167B2 (en) | 2008-07-14 | 2012-07-24 | Kabushiki Kaisha Toshiba | Developing agent and method for producing developing agent |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7169527B2 (en) | 2004-03-22 | 2007-01-30 | Kabushiki Kaisha Toshiba | Developing agent and method for manufacturing the same |
-
1987
- 1987-05-15 JP JP62116798A patent/JP2547014B2/en not_active Expired - Lifetime
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03166551A (en) * | 1989-11-27 | 1991-07-18 | Tomoegawa Paper Co Ltd | Electrophotographic dry toner |
WO1993008510A1 (en) * | 1991-10-22 | 1993-04-29 | Nippon Carbide Kogyo Kabushiki Kaisha | Colored toner for developing electrostatic image |
EP0609443A4 (en) * | 1991-10-22 | 1995-04-19 | Nippon Carbide Kogyo Kk | Colored toner for developing electrostatic image. |
US6717602B2 (en) | 1999-07-02 | 2004-04-06 | Konica Corporation | Image forming method and image forming apparatus, and electrostatic latent image developing toner used by the same |
US6440627B2 (en) | 2000-02-21 | 2002-08-27 | Fuji Xerox Co., Ltd. | Toner for developing electrostatic image, process for preparation of the same, developer for electrostatic image, and process for forming image |
JP2002072541A (en) * | 2000-09-05 | 2002-03-12 | Fuji Xerox Co Ltd | Electrostatic charge image developing toner, method for manufacturing the electrostatic charge image developing toner, developer for electrostatic charge image development, and image-forming method |
US6733944B2 (en) | 2001-08-17 | 2004-05-11 | Fuji Xerox Co., Ltd. | Image forming process |
US7422834B2 (en) | 2004-08-27 | 2008-09-09 | Fuji Xerox Co., Ltd. | Electrostatic latent image developing magenta toner, electrostatic latent image developer, toner manufacturing method, and image forming method |
US7741001B2 (en) | 2005-04-04 | 2010-06-22 | Sharp Kabushiki Kaisha | Toner for electrostatic image development and process for preparing the same |
US7901862B2 (en) | 2007-11-27 | 2011-03-08 | Kabushiki Kaisha Toshiba | Developing agent and method for manufacturing the same |
US8227167B2 (en) | 2008-07-14 | 2012-07-24 | Kabushiki Kaisha Toshiba | Developing agent and method for producing developing agent |
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JP2547014B2 (en) | 1996-10-23 |
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