JP5072104B2 - Method for producing toner for developing electrostatic image - Google Patents
Method for producing toner for developing electrostatic image Download PDFInfo
- Publication number
- JP5072104B2 JP5072104B2 JP2008164484A JP2008164484A JP5072104B2 JP 5072104 B2 JP5072104 B2 JP 5072104B2 JP 2008164484 A JP2008164484 A JP 2008164484A JP 2008164484 A JP2008164484 A JP 2008164484A JP 5072104 B2 JP5072104 B2 JP 5072104B2
- Authority
- JP
- Japan
- Prior art keywords
- toner
- acid
- base particles
- resin
- mass
- 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.)
- Expired - Fee Related
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- 239000002245 particle Substances 0.000 claims description 64
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- 239000003795 chemical substances by application Substances 0.000 claims description 37
- 239000000377 silicon dioxide Substances 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 25
- 239000011230 binding agent Substances 0.000 claims description 23
- 125000003118 aryl group Chemical group 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 19
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 18
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 17
- -1 aromatic hydride Chemical class 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 229910052726 zirconium Inorganic materials 0.000 claims description 16
- 150000003755 zirconium compounds Chemical class 0.000 claims description 14
- 239000003086 colorant Substances 0.000 claims description 13
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
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- 229910052783 alkali metal Inorganic materials 0.000 description 2
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- 125000000217 alkyl group Chemical group 0.000 description 2
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- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
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- 238000001914 filtration Methods 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
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- 238000003860 storage Methods 0.000 description 2
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- OSNILPMOSNGHLC-UHFFFAOYSA-N 1-[4-methoxy-3-(piperidin-1-ylmethyl)phenyl]ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1CN1CCCCC1 OSNILPMOSNGHLC-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- XZELPCGHGANHPQ-UHFFFAOYSA-N 2-hydroxy-3,5-di(propan-2-yloxy)benzoic acid Chemical compound C(C)(C)OC1=C(C(C(=O)O)=CC(=C1)OC(C)C)O XZELPCGHGANHPQ-UHFFFAOYSA-N 0.000 description 1
- AAUQLHHARJUJEH-UHFFFAOYSA-N 2-hydroxy-5-methoxybenzoic acid Natural products COC1=CC=CC(O)=C1C(O)=O AAUQLHHARJUJEH-UHFFFAOYSA-N 0.000 description 1
- HJWYBFFQDXNWHV-UHFFFAOYSA-N 2-methylcyclotrisiloxane Chemical compound C[SiH]1O[SiH2]O[SiH2]O1 HJWYBFFQDXNWHV-UHFFFAOYSA-N 0.000 description 1
- CNJGWCQEGROXEE-UHFFFAOYSA-N 3,5-Dichlorosalicylicacid Chemical compound OC(=O)C1=CC(Cl)=CC(Cl)=C1O CNJGWCQEGROXEE-UHFFFAOYSA-N 0.000 description 1
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- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- QPQKUYVSJWQSDY-UHFFFAOYSA-N 4-phenyldiazenylaniline Chemical compound C1=CC(N)=CC=C1N=NC1=CC=CC=C1 QPQKUYVSJWQSDY-UHFFFAOYSA-N 0.000 description 1
- LISHFIBGTPXYDR-UHFFFAOYSA-N 7-butyl-3-hydroxynaphthalene-2-carboxylic acid Chemical compound CCCCc1ccc2cc(O)c(cc2c1)C(O)=O LISHFIBGTPXYDR-UHFFFAOYSA-N 0.000 description 1
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- 125000000041 C6-C10 aryl group Chemical group 0.000 description 1
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- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011802 pulverized particle Substances 0.000 description 1
- 235000012752 quinoline yellow Nutrition 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 229940051201 quinoline yellow Drugs 0.000 description 1
- 239000004172 quinoline yellow Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- MEZLKOACVSPNER-GFCCVEGCSA-N selegiline Chemical compound C#CCN(C)[C@H](C)CC1=CC=CC=C1 MEZLKOACVSPNER-GFCCVEGCSA-N 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920003066 styrene-(meth)acrylic acid ester copolymer Polymers 0.000 description 1
- 229920005792 styrene-acrylic resin Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- 238000006227 trimethylsilylation reaction Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- XOSXWYQMOYSSKB-LDKJGXKFSA-L water blue Chemical compound CC1=CC(/C(\C(C=C2)=CC=C2NC(C=C2)=CC=C2S([O-])(=O)=O)=C(\C=C2)/C=C/C\2=N\C(C=C2)=CC=C2S([O-])(=O)=O)=CC(S(O)(=O)=O)=C1N.[Na+].[Na+] XOSXWYQMOYSSKB-LDKJGXKFSA-L 0.000 description 1
- 239000011240 wet gel Substances 0.000 description 1
- 239000001052 yellow pigment Substances 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
- G03G9/087—Binders for toner particles
- G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
- G03G9/08793—Crosslinked polymers
-
- 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
- G03G9/0827—Developers with toner particles characterised by their shape, e.g. degree of sphericity
-
- 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
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09783—Organo-metallic compounds
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Developing Agents For Electrophotography (AREA)
Description
本発明は、静電荷像現像用トナー及びその製造方法に関する。さらに詳しくは、本発明は、定着時の耐ホットオフセット性が向上し、定着器巻き付き性が改善されると共に、帯電量の立ち上がりが良好で濃度が高く、カブリの少ない高品位の画像が得られ、また、カラートナーにおいても鮮明な色彩色が得られるなど、優れた特性を有する静電荷像現像用トナー、及びその製造方法に関するものである。 The present invention relates to an electrostatic image developing toner and a method for producing the same. More specifically, the present invention improves the hot offset resistance at the time of fixing, improves the wrapping property of the fixing device, and provides a high-quality image with a good rise in charge amount, high density, and low fog. Further, the present invention relates to a toner for developing an electrostatic image having excellent characteristics, such as a clear color that can be obtained with a color toner, and a method for producing the same.
電子写真方式を利用した画像形成方法においては、感光体を一様に帯電させ、次いで感光体を露光して露光部分の電荷を消散させることにより静電荷的な潜像を形成し、静電荷像にトナーを付着させることにより可視化して現像し、可視化像を紙などの材料に転写し、転写された像を加熱などの手段により定着させる。このような方式に用いられる上記トナーは、静電荷像現像用トナーと呼ばれる。
ところで、最近のフルカラーの画像形成装置には、中間転写体を有する機種が多く、トナーの転写性能が重要となってきている。したがって、従来の混練粉砕トナーのような角ばった形状の粒子では、感光体や中間転写体との接触面積が大きくなり、トナーの付着力が大きいため、転写性の点で不利となる。さらに、現像ローラー上でもトナーの付着性が大きくなるために帯電量が不均一となり、適正な画像濃度が得られなかったり、白紙部のカブリが発生することがある。
一方、２本のローラー間で加熱定着を行う定着装置で定着する場合には、ホットオフセットや高印字率のフルカラー画像を形成する際に用紙が定着ローラーへ巻き付く、いわゆる定着器巻き付きが発生しやすい。これを回避するためにある一定以上の粘弾性をもつバインダー樹脂が求められる。
また、加熱処理を行う工程においては、バインダー樹脂の粘弾性が高いほど、トナーは熱変形しにくく、その結果加熱温度が上昇し、トナー同士のカップリングの発生も増加するために処理量があがらず加工費が上昇するなどの問題が生じる。
このように、静電荷像現像用トナーにおいては耐ホットオフセット性や耐定着器巻き付き性と加熱処理時の処理量など生産性を両立させることが課題となっている。
In the image forming method using the electrophotographic method, the photosensitive member is uniformly charged, and then the photosensitive member is exposed to dissipate the charge on the exposed portion to form an electrostatic latent image. The toner image is visualized and developed by adhering to the toner, the visualized image is transferred to a material such as paper, and the transferred image is fixed by means such as heating. The toner used in such a system is called an electrostatic image developing toner.
By the way, many recent full-color image forming apparatuses have an intermediate transfer member, and toner transfer performance has become important. Therefore, the particles having an angular shape such as the conventional kneaded and pulverized toner have a large contact area with the photosensitive member or the intermediate transfer member, and have a large toner adhesion, which is disadvantageous in terms of transferability. Further, the toner adherence increases even on the developing roller, so that the charge amount becomes non-uniform, and an appropriate image density may not be obtained or fogging of a blank paper portion may occur.
On the other hand, when fixing with a fixing device that heat-fixes between two rollers, so-called fixing device wrapping occurs, in which the paper wraps around the fixing roller when forming a full color image with hot offset or high printing rate. Cheap. In order to avoid this, a binder resin having a certain level of viscoelasticity is required.
In the heat treatment step, the higher the viscoelasticity of the binder resin, the more difficult the toner is thermally deformed. As a result, the heating temperature rises and the occurrence of coupling between the toners increases, resulting in an increase in throughput. Problems such as increased processing costs occur.
As described above, in the electrostatic image developing toner, it is a problem to satisfy both the hot offset resistance and the fixing device wrapping property and the productivity such as the processing amount during the heat treatment.
特許文献１においては、転写性能や画像濃度の持続性、カブリの抑制など画像品質を向上させる方法として、加熱処理によりトナーを球形化する手段が開示されている。この方法では、熱処理によりトナーを球形化することで良好な現像ならびに転写特性が得られるが、溶融粘度の低いポリエステル樹脂を用いた場合には、ホットオフセットや定着器巻き付きなどの定着不良が生じる場合がある。
また、特許文献２には、電荷制御剤として、芳香族オキシカルボン酸又はその塩と、ジルコニウムを含む化合物とから得られるジルコニウム化合物を含む電子写真用トナーが開示されている。このトナーにおいては、高温高湿下でも帯電量の低下を抑え、カブリを抑制する効果は見られるものの、円形度が低いトナーの場合には、転写性が悪く、所望の画像濃度が得られにくいという問題があった。
Patent Document 2 discloses an electrophotographic toner containing a zirconium compound obtained from an aromatic oxycarboxylic acid or a salt thereof and a compound containing zirconium as a charge control agent. In this toner, although the effect of suppressing the decrease in the charge amount and suppressing fogging can be seen even under high temperature and high humidity, in the case of the toner having low circularity, the transferability is poor and it is difficult to obtain a desired image density. There was a problem.
本発明は、このような事情のもとで、定着時の耐ホットオフセット性が向上し、定着器巻き付き性が改善されると共に、帯電量の立ち上がりが良好で濃度が高く、カブリの少ない高品位の画像が得られ、また、カラートナーにおいても鮮明な色彩色が得られるなど、優れた特性を有する静電荷像現像用トナー、及びその製造方法を提供することを目的とするものである。 Under such circumstances, the present invention improves the hot offset resistance during fixing, improves the wrapping property of the fixing device, has a good rise in charge amount, high density, and high quality with little fogging. It is an object of the present invention to provide an electrostatic charge image developing toner having excellent characteristics such as that a clear color can be obtained with a color toner, and a method for producing the same.
本発明者らは、前記目的を達成するために鋭意研究を重ねた結果、バインダー樹脂と、芳香族ヒドロキシカルボン酸又はその塩と含ジルコニウム化合物との反応生成物を少なくとも含む電荷制御剤と、着色剤を含有する粉体を、平均円形度が特定の範囲になるように、浮遊状態で加熱架橋処理することにより得られたトナー母粒子を含有することにより、その目的を達成し得ることを見出し、この知見に基づいて、本発明を完成するに至った。
すなわち、本発明は、
［１］酸価が２〜２５ｍｇＫＯＨ／ｇであるポリエステル系樹脂からなるバインダー樹脂と、芳香族ヒドロキシカルボン酸又はその塩と含ジルコニウム化合物との反応生成物からなる電荷制御剤と、着色剤を含む粉体を、溶融混練後粉砕して分級して、トナー粒度分布がシャープなトナー母粒子を得て、該トナーに平均一次粒子径は０.００５〜０.０２μｍの疎水性シリカをトナー母粒子中に０.２５〜５質量％になるように添加して混合したのち、球形化装置によって、浮遊状態における熱風による加熱架橋処理により、該ポリエステル系樹脂のカルボン酸と前記電荷制御剤との加熱架橋を形成して、平均円形度が０.９３０〜０.９８０になるように球形化して、球形化トナー母粒子を調製する製造工程であって、前記電荷制御剤として、芳香族ヒドロキシカルボン酸又はその塩と含ジルコニウム化合物との反応生成物をトナー母粒子中に０.１〜１.０質量％含有させ、さらに、前記バインダー樹脂の、下記の測定方法で測定されたフロー軟化温度Ｔ１／２が１００〜１５０℃の範囲である静電荷像現像用トナーの製造方法、
＜フロー軟化温度Ｔ１／２の測定＞
ＪＩＳ Ｋ ７１９９に規定するキャピラリーレオメータを用い、シリンダ内径１１.３２９ｍｍ、キャピラリーダイ内径１ｍｍ、長さ１ｍｍとし、シリンダ内に樹脂１.０ｇを充填し、ピストンに荷重９８Ｎをかけ、５０℃から５℃／分で昇温し、充填された樹脂の２分の１が流出したときの温度を、フロー軟化温度Ｔ１／２とする、及び
［２］芳香族ヒドロキシカルボン酸又はその塩が、サリチル酸又はその塩である上記[１]項に記載の静電荷像現像用トナーの製造方法、
を提供するものである。
As a result of intensive studies to achieve the above object, the present inventors have obtained a binder resin, a charge control agent containing at least a reaction product of an aromatic hydroxycarboxylic acid or a salt thereof and a zirconium-containing compound, and coloring. It has been found that the object can be achieved by including toner base particles obtained by heat-crosslinking a powder containing an agent in a floating state so that the average circularity is in a specific range. Based on this finding, the present invention has been completed.
That is, the present invention
[1] A binder resin comprising a polyester resin having an acid value of 2 to 25 mg KOH / g, a charge control agent comprising a reaction product of an aromatic hydroxycarboxylic acid or salt thereof and a zirconium-containing compound, and a colorant The powder is melt-kneaded and then pulverized and classified to obtain toner base particles having a sharp toner particle size distribution, and hydrophobic silica having an average primary particle size of 0.005 to 0.02 μm is added to the toner base particles. After adding and mixing so that it may become 0.25-5 mass% in inside, the heating of the carboxylic acid of this polyester-type resin and the said charge control agent is carried out by the heat-crosslinking process by the hot air in a floating state with a spheronizer. A manufacturing process for forming spherical toner base particles by forming cross-links and spheronizing to have an average circularity of 0.930 to 0.980. The reaction products of group hydroxycarboxylic acid or a salt thereof and containing a zirconium compound is 0.1 to 1.0 mass% in the toner particles, further, the binder resin was measured by the following measurement methods Flow A method for producing a toner for developing an electrostatic image having a softening temperature T1 / 2 in the range of 100 to 150 ° C .;
<Measurement of flow softening temperature T1 / 2>
Using a capillary rheometer specified in JIS K 7199, the cylinder inner diameter is 11.329 mm, the capillary die inner diameter is 1 mm, the length is 1 mm, the cylinder is filled with 1.0 g of resin, a load of 98 N is applied to the piston, and 50 to 5 ° C. The temperature when 1/2 of the charged resin flows out is defined as a flow softening temperature T1 / 2, and [ 2 ] aromatic hydroxycarboxylic acid or a salt thereof is salicylic acid or its The method for producing a toner for developing an electrostatic charge image according to item [1], wherein the toner is a salt,
Is to provide.
本発明によれば、定着時の耐ホットオフセット性が向上し、定着器巻き付き性が改善されると共に、帯電量の立ち上がりが良好で濃度が高く、カブリの少ない高品位の画像が得られ、また、カラートナーにおいても鮮明な色彩色が得られるなど、優れた特性を有する静電荷像現像用トナー、及びその製造方法を提供することができる。 According to the present invention, the hot offset resistance during fixing is improved, the wrapping property of the fixing device is improved, the charge amount rises well, the density is high, and a high-quality image with little fog is obtained. In addition, it is possible to provide a toner for developing an electrostatic charge image having excellent characteristics such as that a clear color can be obtained even in a color toner, and a method for producing the same.
本発明の静電荷像現像用トナー（以下、単にトナーと称することがある。）は、バインダー樹脂と、電荷制御剤と、着色剤を含む粉体を、浮遊状態における加熱架橋処理により、平均円形度が０.９３０〜０.９８０になるように球形化して得られたトナー母粒子を含有し、かつ前記電荷制御剤が、芳香族ヒドロキシカルボン酸又はその塩と含ジルコニウム化合物との反応生成物を少なくとも含むものであることを特徴とする。 The electrostatic image developing toner of the present invention (hereinafter sometimes simply referred to as “toner”) has an average circular shape obtained by subjecting a powder containing a binder resin, a charge control agent, and a colorant to heat crosslinking in a floating state. Containing toner base particles obtained by spheronization to a degree of 0.930 to 0.980, and the charge control agent is a reaction product of an aromatic hydroxycarboxylic acid or a salt thereof and a zirconium-containing compound It is characterized by including at least.
［トナー母粒子］
本発明の静電荷像現像用トナーは、バインダー樹脂と、電荷制御剤と、着色剤を必須成分とするトナー母粒子を含有する。
（バインダー樹脂）
本発明で用いるバインダー樹脂に特に制限はなく、例えば、ポリエステル系樹脂、ポリアミド系樹脂、ポリウレタン系樹脂、アクリル系樹脂、ポリエチレン、ポリプロピレンなどのオレフィン系樹脂、エチレン−ノルボルネン共重合体などの環状オレフィン共重合体、ジエン系樹脂、シリコーン系樹脂、ケトン樹脂、マレイン酸樹脂、クマロン樹脂、フェノール樹脂、エポキシ樹脂、テルペン樹脂、石油樹脂、ポリスチレン、スチレン−ブタジエン共重合体、スチレン−マレイン酸共重合体、スチレン−(メタ)アクリル酸エステル共重合体などのスチレン系樹脂、ポリ(メタ)アクリル酸ブチル、ポリビニルブチラールなどを挙げることができる。これらの中で、ポリエステル系樹脂を好適に用いることができる。ポリエステル系樹脂としては、例えば、芳香族ジカルボン酸とアルキレンエーテル化ビスフェノールＡとの重縮合ポリエステルなどを挙げることができる。
[Toner mother particles]
The toner for developing an electrostatic image of the present invention contains toner base particles containing a binder resin, a charge control agent, and a colorant as essential components.
(Binder resin)
The binder resin used in the present invention is not particularly limited, and examples thereof include polyester resins, polyamide resins, polyurethane resins, acrylic resins, olefin resins such as polyethylene and polypropylene, and cyclic olefin copolymers such as ethylene-norbornene copolymers. Polymer, diene resin, silicone resin, ketone resin, maleic acid resin, coumarone resin, phenol resin, epoxy resin, terpene resin, petroleum resin, polystyrene, styrene-butadiene copolymer, styrene-maleic acid copolymer, Examples thereof include styrene resins such as styrene- (meth) acrylic acid ester copolymers, butyl poly (meth) acrylate, and polyvinyl butyral. Among these, a polyester resin can be suitably used. Examples of polyester resins include polycondensation polyesters of aromatic dicarboxylic acids and alkylene etherified bisphenol A.
このポリエステル系樹脂は、酸価が２〜２５ｍｇＫＯＨ／ｇの範囲にあることが好ましい。この酸価が上記範囲にあると、後述の電荷制御剤として用いられる芳香族ヒドロキシカルボン酸又はその塩と含ジルコニウム化合物との反応生成物のバインダー樹脂に対するなじみがよく、分散性に優れ、該反応生成物のトナー母粒子からの脱落が防止され、帯電均一化と、帯電の耐久安定性を得ることができる。該酸価が２５ｍｇＫＯＨ／ｇを超えると、高湿下での帯電安定性が低下するおそれが生じる。より好ましい酸価は２〜１５ｍｇＫＯＨ／ｇの範囲である。
また、当該ポリエステル系樹脂のフロー軟化温度Ｔ１／２は１００〜１５０℃の範囲にあることが好ましい。このフロー軟化温度が１００℃未満では、ホットオフセットや定着器巻き付きが発生しやすく、一方１５０℃を超えると、球形化処理時の温度が上昇し、生産性の低下や定着不良が発生するおそれが生じる。前記フロー軟化温度Ｔ１／２は１２０〜１４０℃の範囲にあることがより好ましい。
なお、前記フロー軟化温度Ｔ１／２は、以下のようにして測定した値である。
＜フロー軟化温度Ｔ１／２の測定＞
ＪＩＳ Ｋ ７１９９に規定するキャピラリーレオメータを用い、シリンダ内径１１.３２９ｍｍ、キャピラリーダイ内径１ｍｍ、長さ１ｍｍとし、シリンダ内に樹脂１.０ｇを充填し、ピストンに荷重９８Ｎをかけ、５０℃から５℃／分で昇温し、充填された樹脂の２分の１が流出したときの温度を、フロー軟化温度Ｔ１／２とする。
This polyester resin preferably has an acid value in the range of 2 to 25 mgKOH / g. When this acid value is in the above range, the reaction product of an aromatic hydroxycarboxylic acid or a salt thereof and a zirconium-containing compound used as a charge control agent, which will be described later, is familiar to the binder resin, excellent in dispersibility, and the reaction. The product is prevented from falling off from the toner base particles, and it is possible to obtain uniform charge and durable charge stability. When the acid value exceeds 25 mgKOH / g, the charging stability under high humidity may be lowered. A more preferred acid value is in the range of 2 to 15 mg KOH / g.
Moreover, it is preferable that the flow softening temperature T1 / 2 of the said polyester-type resin exists in the range of 100-150 degreeC. If the flow softening temperature is less than 100 ° C., hot offset or winding of the fixing device tends to occur. Arise. The flow softening temperature T1 / 2 is more preferably in the range of 120 to 140 ° C.
The flow softening temperature T1 / 2 is a value measured as follows.
<Measurement of flow softening temperature T1 / 2>
Using a capillary rheometer specified in JIS K 7199, the cylinder inner diameter is 11.329 mm, the capillary die inner diameter is 1 mm, the length is 1 mm, the cylinder is filled with 1.0 g of resin, a load of 98 N is applied to the piston, and 50 to 5 ° C. The temperature when the temperature is raised at 1 / min and one-half of the filled resin flows out is defined as a flow softening temperature T1 / 2.
（電荷制御剤）
＜有機ジルコニウム化合物＞
本発明においては、電荷制御剤として、芳香族ヒドロキシカルボン酸又はその塩と含ジルコニウム化合物との反応生成物（以下、有機ジルコニウム化合物と略称することがある。）を、少なくとも用いることが必要である。
前記電荷制御剤として、この有機ジルコニウム化合物を用いることで、バインダー樹脂、電荷制御剤及び着色剤を含む粉体の球形化処理時において、該有機ジルコニウム化合物と、バインダー樹脂として好適に用いられるポリエステル系樹脂のカルボン酸との加熱架橋が生じ、その結果得られるトナー母粒子が増粘し、定着時の耐ホットオフセット性やヒートローラーへの耐巻き付き性が向上する。
本発明においては、トナー母粒子中の当該有機ジルコニウム化合物の含有量は、前記効果と電荷制御剤としての性能バランスの観点から、０.１〜３.０質量％の範囲が好ましく、０.２〜２.０質量％の範囲がより好ましく、０.３〜１.０質量％の範囲がさらに好ましい。
当該有機ジルコニウム化合物の原料の１つとして用いられる芳香族ヒドロキシカルボン酸又はその塩としては、例えば下記一般式（１）
で表される化合物を与えることができる。
前記一般式（１）において、Ａｒで示される置換基を有していてもよい芳香族炭化水素基としては、置換基を有していてもよいベンゼン−１,２−ジイル基及びナフタレン−２,３−ジイル基などを挙げることができる。また、該置換基としては、炭素数１〜１０の直鎖状、分岐状、環状のアルキル基若しくはアルケニル基、炭素数６〜１０のアリール基、炭素数７〜１０のアラルキル基、ハロゲン原子、水酸基、カルボキシル基などを挙げることができ、これらは芳香環上に１つ以上導入されていてもよい。
また、Ｍのうちのアルカリ金属としてはナトリウム、カリウムなどが挙げられ、Ｒで示される１〜３のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基を挙げることができる。
(Charge control agent)
<Organic zirconium compound>
In the present invention, it is necessary to use at least a reaction product of an aromatic hydroxycarboxylic acid or a salt thereof and a zirconium-containing compound (hereinafter sometimes abbreviated as an organic zirconium compound) as a charge control agent. .
By using this organic zirconium compound as the charge control agent, the organic zirconium compound and a polyester system suitably used as the binder resin at the time of spheroidizing treatment of the powder containing the binder resin, the charge control agent and the colorant Heat crosslinking with the carboxylic acid of the resin occurs, resulting in thickening of the toner base particles, and resistance to hot offset during fixing and resistance to wrapping around a heat roller are improved.
In the present invention, the content of the organozirconium compound in the toner base particles is preferably in the range of 0.1 to 3.0% by mass from the viewpoint of the above effect and the performance balance as the charge control agent, and is 0.2. The range of -2.0 mass% is more preferable, and the range of 0.3-1.0 mass% is more preferable.
As an aromatic hydroxycarboxylic acid or salt thereof used as one of the raw materials for the organic zirconium compound, for example, the following general formula (1)
The compound represented by these can be given.
In the general formula (1), examples of the aromatic hydrocarbon group which may have a substituent represented by Ar include a benzene-1,2-diyl group which may have a substituent and naphthalene-2. , 3-diyl group and the like. Moreover, as this substituent, a C1-C10 linear, branched, cyclic alkyl group or alkenyl group, a C6-C10 aryl group, a C7-C10 aralkyl group, a halogen atom, A hydroxyl group, a carboxyl group, etc. can be mentioned, One or more of these may be introduce | transduced on the aromatic ring.
Examples of the alkali metal in M include sodium and potassium, and examples of the alkyl group 1 to 3 represented by R include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
前記一般式（１）で表される芳香族ヒドロキシカルボン酸又はその塩の具体例としては、サリチル酸、３,５−ジ−ｔ−ブチルサリチル酸、５−メトキシサリチル酸、２−ヒドロキシ−３−ナフトエ酸、３,５−ジイソプロポキシサリチル酸、３,５−ジ−ｔ−ブチル−２−メトキシ安息香酸、６−ブチル−２−ヒドロキシ−３−ナフトエ酸、３−ｔ−ブチル−２−メトキシ−５−メチル安息香酸、３,５−ジクロロサリチル酸及びそれらのナトリウム塩やカリウム塩などを挙げることができる。
本発明においては、これらの中で、サリチル酸又はそのナトリウム塩やカリウム塩を好ましく挙げることができる。一方、前記の芳香族ヒドロキシカルボン酸又はその塩と反応させる含ジルコニウム化合物としては、例えばＺｒＯＣｌ2、ＺｒＯＦ2、ＺｒＯＢｒ2などのオキシハロゲン化ジルコニウム、あるいはＺｒ(ｉ−Ｐｒｏ)4（ｉ−Ｐｒｏ＝イソプロポキシ基）などのテトラアルコキシジルコニウムなどを用いることができる。
含ジルコニウム化合物として、前記オキシハロゲン化ジルコニウムを用いる場合には、芳香族ヒドロキシカルボン酸又はその塩１モルに対して、４／５モルのジルコニウム原子が導入されてなる、下記一般式（２）
で表される有機ジルコニウム化合物が得られる。
具体的には、水媒体中において、水酸化アルカリ金属の存在下、芳香族ヒドロキシカルボン酸と、化学量論的量より若干過剰のオキシハロゲン化ジルコニウムとを４０〜６０℃程度で適当な時間反応させたのち、反応物をろ過、水洗、乾燥処理することにより、前記一般式（２）で表される有機ジルコニウム化合物を得ることができる。一方、含ジルコニウム化合物として、前記テトラアルコキシジルコニウムを用いる場合には、芳香族ヒドロキシカルボン酸又はその塩１モルに対して、１／４モルのジルコニウム原子が導入されてなる、下記一般式（３）
で表される有機ジルコニウム化合物が得られる。
具体的には、トルエンなどの適当な有機溶媒中において、芳香族ヒドロキシカルボン酸と、化学量論的量より若干過剰のテトラアルコキシジルコニウムとを、１００〜１５０℃程度の温度で適当な時間反応させたのち、反応物をろ過、洗浄、乾燥することにより、前記一般式（３）で表される有機ジルコニウム化合物を得ることができる。
Specific examples of the aromatic hydroxycarboxylic acid represented by the general formula (1) or a salt thereof include salicylic acid, 3,5-di-t-butylsalicylic acid, 5-methoxysalicylic acid, and 2-hydroxy-3-naphthoic acid. 3,5-diisopropoxysalicylic acid, 3,5-di-t-butyl-2-methoxybenzoic acid, 6-butyl-2-hydroxy-3-naphthoic acid, 3-t-butyl-2-methoxy-5 -Methylbenzoic acid, 3,5-dichlorosalicylic acid and their sodium and potassium salts.
In these, salicylic acid or its sodium salt and potassium salt can be mentioned preferably in these. Meanwhile, examples of the aromatic hydroxycarboxylic acid or containing zirconium compound is reacted with a salt, for example ZrOCl 2, ZrOF 2, oxyhalide, zirconium, such ZrOBr 2 or Zr (i-Pro) 4, (i-Pro = Tetraalkoxy zirconium such as isopropoxy group) can be used.
When the zirconium oxyhalide is used as the zirconium-containing compound, 4/5 mol of zirconium atoms are introduced per 1 mol of the aromatic hydroxycarboxylic acid or salt thereof.
The organic zirconium compound represented by these is obtained.
Specifically, in an aqueous medium, in the presence of an alkali metal hydroxide, an aromatic hydroxycarboxylic acid and a slight excess of zirconium oxyhalide in excess of the stoichiometric amount are reacted at about 40 to 60 ° C. for an appropriate time. Then, the organic zirconium compound represented by the general formula (2) can be obtained by filtering, washing, and drying the reaction product. On the other hand, when tetraalkoxyzirconium is used as the zirconium-containing compound, 1/4 mol of zirconium atom is introduced per 1 mol of the aromatic hydroxycarboxylic acid or salt thereof.
The organic zirconium compound represented by these is obtained.
Specifically, in an appropriate organic solvent such as toluene, an aromatic hydroxycarboxylic acid and a slightly excess of tetraalkoxyzirconium in excess of the stoichiometric amount are reacted at a temperature of about 100 to 150 ° C. for an appropriate time. Then, the organozirconium compound represented by the general formula (3) can be obtained by filtering, washing and drying the reaction product.
＜その他電荷制御剤＞
本発明において、前記の有機ジルコニウム化合物と併用することができるその他電荷制御剤としては、例えば、モノアゾ金属化合物、アセチルアセトン金属化合物、芳香族ヒドロキシカルボン酸、他の含金属サリチル酸系化合物、ホウ素錯体化合物、カリックスアレーンなどを挙げることができる。
トナー母粒子に、このような電荷制御剤を含有させることにより、静電荷像現像用トナーの帯電特性を安定させ、カブリの発生を防止することができる。
本発明においては、電荷制御剤として、前記有機ジルコニウム化合物を１種用いてもよいし、２種以上を組み合わせて用いてもよく、また、この有機ジルコニウム化合物１種以上と、前記のその他電荷制御剤１種以上とを併用してもよい。
当該電荷制御剤の配合量は、その種類にもよるが、前述のバインダー樹脂１００質量部に対して、トナーの帯電特性を安定させ、カブリの発生を防止する観点から、通常０.２〜３.０質量部程度、好ましくは０.５〜２.０質量部である。
<Other charge control agents>
In the present invention, other charge control agents that can be used in combination with the organic zirconium compound include, for example, monoazo metal compounds, acetylacetone metal compounds, aromatic hydroxycarboxylic acids, other metal-containing salicylic acid compounds, boron complex compounds, Examples include calix arene.
By including such a charge control agent in the toner base particles, the charging characteristics of the electrostatic image developing toner can be stabilized and fogging can be prevented.
In the present invention, one kind of the above-mentioned organic zirconium compound may be used as a charge control agent, or two or more kinds thereof may be used in combination. One or more agents may be used in combination.
Although the amount of the charge control agent depends on the type, it is usually 0.2 to 3 from the viewpoint of stabilizing the charging characteristics of the toner and preventing fogging with respect to 100 parts by mass of the binder resin. About 0.0 parts by mass, preferably 0.5 to 2.0 parts by mass.
（着色剤）
本発明で用いる着色剤に特に制限はなく、無機又は有機の各種の顔料、染料などを用いることができる。黒色顔料としては、例えば、カーボンブラック、酸化銅、四三酸化鉄、二酸化マンガン、アニリンブラックなどを挙げることができる。黄色顔料としては、例えば、パーマネントイエロー、クロムイエロー、キノリンイエロー、ベンジジンイエロー、黄色酸化鉄、Ｃ.Ｉ.ピグメント・イエロー９７、Ｃ.Ｉ.ピグメント・イエロー１７、Ｃ.Ｉ.ピグメント・イエロー１８０、Ｃ.Ｉ.ソルベント・イエロー１６２などを挙げることができる。赤色顔料としては、例えば、ベンガラ、レーキレッド、ローダミン６Ｂ、キナクリドン、カーミン６Ｂ、Ｃ.Ｉ.ピグメント・レッド４８：１、Ｃ.Ｉ.ピグメント・レッド１２２、Ｃ.Ｉ.ピグメント・レッド５７：１、Ｃ.Ｉ.ピグメント・レッド１８４などを挙げることができる。青色顔料としては、例えば、紺青、コバルトブルー、フタロシアニンブルー、アニリンブルー、Ｃ.Ｉ.ピグメント・ブルー１５：１、Ｃ.Ｉ.ピグメント・ブルー１５：３などを挙げることができる。本発明において、静電荷像現像用トナー中の着色剤の含有量は１〜２０質量％であることが好ましく、２〜８質量％であることがより好ましい。着色剤の含有量が１質量％未満であると、必要な画像濃度が得られないおそれがある。着色剤の含有量が２０質量％を超えると、トナーの定着性が低下するおそれがある。
(Coloring agent)
There is no restriction | limiting in particular in the coloring agent used by this invention, Various inorganic or organic pigments, dyes, etc. can be used. Examples of the black pigment include carbon black, copper oxide, triiron tetroxide, manganese dioxide, and aniline black. Examples of yellow pigments include permanent yellow, chrome yellow, quinoline yellow, benzidine yellow, yellow iron oxide, CI pigment yellow 97, CI pigment yellow 17, CI pigment yellow 180, And CI Solvent Yellow 162. Examples of red pigments include Bengala, Lake Red, Rhodamine 6B, Quinacridone, Carmine 6B, CI Pigment Red 48: 1, CI Pigment Red 122, CI Pigment Red 57: 1. CI Pigment Red 184, and the like. Examples of blue pigments include bitumen, cobalt blue, phthalocyanine blue, aniline blue, CI pigment blue 15: 1, and CI pigment blue 15: 3. In the present invention, the content of the colorant in the electrostatic image developing toner is preferably 1 to 20% by mass, more preferably 2 to 8% by mass. If the content of the colorant is less than 1% by mass, the required image density may not be obtained. When the content of the colorant exceeds 20% by mass, the toner fixability may be lowered.
（任意成分）
本発明におけるトナー母粒子には、前述のバインダー樹脂、電荷制御剤及び着色剤以外に、ワックスやシリカ粉末などを含有させることができる。
＜ワックス＞
本発明において、トナー母粒子に用いるワックスは、熱ロール定着時の離型性を良くする目的で用いられるものであり、このようなものとしては、例えばカルナウバワックス、ライスワックスなどの植物ワックス、パラフィンワックス、マイクロクリスタリンワックスなどの石油ワックス、モンタンワックス、キャンデリアワックスなどの鉱物ワックス、カーボワックス、ポリエチレンワックス、ポリプロピレンワックス、エチレン−プロピレン共重合体ワックス、塩素化ナフタレンワックスなどの合成ワックス、ステアリン酸、アラキン酸、ベヘン酸などの高級脂肪酸、セリルアルコール、メリシルアルコールなどの高級アルコール、ステアリン酸アミド、ベヘン酸アミドなどのアミド系ワックス、脂肪酸エステル、グリセリンモノステアレート、グリセリンジステアレートなどの多価アルコールエステル、シリコーンワニスなどを挙げることができる。これらのワックスは、１種を単独で用いることができ、あるいは、２種以上を組み合わせて用いることもできる。
(Optional component)
The toner base particles in the present invention may contain wax, silica powder, etc. in addition to the binder resin, charge control agent and colorant described above.
<Wax>
In the present invention, the wax used for the toner base particles is used for the purpose of improving the releasability at the time of heat roll fixing, and examples thereof include plant waxes such as carnauba wax and rice wax, Petroleum wax such as paraffin wax and microcrystalline wax, mineral wax such as montan wax and canderia wax, synthetic wax such as carbowax, polyethylene wax, polypropylene wax, ethylene-propylene copolymer wax, chlorinated naphthalene wax, stearic acid , Higher fatty acids such as arachidic acid and behenic acid, higher alcohols such as seryl alcohol and melyl alcohol, amide waxes such as stearic acid amide and behenic acid amide, fatty acid esters, glycerin monostearate Over DOO, polyhydric alcohol esters such as glycerin distearate, and the like silicone varnish. These waxes can be used alone or in combination of two or more.
このワックスの融点は好ましくは５０〜１６０℃であり、より好ましくは６０〜１５０℃である。ワックスの融点が５０℃未満であると、トナーの保存性が低下するおそれがあり、ワックスの融点が１５０℃を超えると、トナーの低温定着性が不充分となるおそれがある。ワックスの融点は、示差走査熱量計（ＤＳＣ）を用いる分析において、１０℃／分で昇温したときの吸熱ピーク温度として求めることができる。
本発明においては、トナー母粒子中のワックスの含有量は、０.５〜５質量％であることが好ましく、１〜３質量％であることがより好ましい。このワックスの含有量が０.５質量％未満であると、トナーの低温定着性が不充分となるおそれがある。ワックスの含有量が５質量％を超えると、製造工程において粒子の付着や堆積が生じやすい、特に熱処理球形化の際にトナー表面にワックス成分がにじみ出やすくなり、トナーの帯電性能を低下させる。また、トナーの流動性や保存性が低下するおそれがある。
The melting point of this wax is preferably 50 to 160 ° C, more preferably 60 to 150 ° C. If the melting point of the wax is less than 50 ° C., the storage stability of the toner may be reduced, and if the melting point of the wax exceeds 150 ° C., the low-temperature fixability of the toner may be insufficient. The melting point of the wax can be determined as an endothermic peak temperature when the temperature is raised at 10 ° C./min in an analysis using a differential scanning calorimeter (DSC).
In the present invention, the wax content in the toner base particles is preferably 0.5 to 5% by mass, more preferably 1 to 3% by mass. If the wax content is less than 0.5% by mass, the low-temperature fixability of the toner may be insufficient. When the wax content exceeds 5% by mass, adhesion and deposition of particles are likely to occur in the production process. In particular, the wax component tends to ooze out during the heat treatment spheroidization, thereby lowering the charging performance of the toner. In addition, the fluidity and storage stability of the toner may be reduced.
＜シリカ粉末＞
トナー母粒子にシリカ粉末を含有させることにより、バインダー樹脂と親和性の低いワックスがシリカ粒子の凝集体に吸着され、バインダー樹脂中に均一に分散し、トナー粒子の表面への滲み出しが抑制される。その結果、粉砕されたトナー粒子の流動性が向上し、製造装置内での付着と堆積が防止される。
本発明に用いるシリカ粉末の平均一次粒子径は０.００５〜０.０２μｍであることが好ましく、０.００７〜０.０１６μｍであることがより好ましい。
このシリカ粉末に特に制限はなく、例えば、乾式法シリカ、湿式沈降法シリカ、湿式ゲル法シリカなどを挙げることができる。また、多数のシラノール基を有する親水性シリカ、シラノール基のトリメチルシリル化やシリコーンオイルなどにより疎水化処理した疎水性シリカのいずれをも用いることができる。これらの中で、疎水性シリカは、バインダー樹脂との親和性が大きいので、特に好適に用いることができる。
トナー母粒子中のシリカ粉末の含有量は、通常０.２５〜５質量％程度である。シリカ粉末の含有量が０.２５質量％未満であると、ワックスを吸着し保持する効果が十分に発現しないおそれがある。シリカ粉末の含有量が５質量％を超えると、トナーの定着性が阻害されると共に、カラートナーの場合は、トナーの透明性が低下するおそれがある。
<Silica powder>
By including silica powder in the toner base particles, the wax having low affinity with the binder resin is adsorbed on the aggregate of silica particles, and uniformly dispersed in the binder resin, and the seepage of the toner particles to the surface is suppressed. The As a result, the fluidity of the pulverized toner particles is improved, and adhesion and accumulation in the manufacturing apparatus are prevented.
The average primary particle diameter of the silica powder used in the present invention is preferably 0.005 to 0.02 μm, and more preferably 0.007 to 0.016 μm.
The silica powder is not particularly limited, and examples thereof include dry method silica, wet precipitation method silica, and wet gel method silica. Also, any of hydrophilic silica having a large number of silanol groups and hydrophobic silica hydrophobized with trimethylsilylation of silanol groups or silicone oil can be used. Among these, hydrophobic silica is particularly suitable because it has a high affinity with the binder resin.
The content of silica powder in the toner base particles is usually about 0.25 to 5% by mass. If the content of the silica powder is less than 0.25% by mass, the effect of adsorbing and holding the wax may not be sufficiently exhibited. When the content of the silica powder exceeds 5% by mass, the fixing property of the toner is inhibited, and in the case of a color toner, the transparency of the toner may be lowered.
内添剤として好ましい疎水性シリカ粉末の材料としては、四塩化ケイ素などのハロゲン化シランを、蒸気相酸化により生成され、ヒュームドシリカと称せられる乾式シリカ粉末、及び水ガラスなどから製造されるいわゆる湿式シリカ粉末のいずれも使用することができるが、表面及び内部にあるシラノール基が少なく、またＮａ2Ｏ、ＳＯ3 -などの製造残渣の少ない乾式シリカ粉末が好ましい。
上記シリカ粉末の疎水化処理に用いられる処理剤としては、シリコーンワニス、各種変性シリコーンワニス、シリコーンオイル、各種変性シリコーンオイル、シラザン化合物、環状ジメチルシロキサン、シランカップリング剤などを挙げることができる。これらの中で、シリコーンオイル、シラザン化合物、環状ジメチルシロキサン、シランカップリング剤が好ましい。
As a material of a hydrophobic silica powder preferable as an internal additive, a halogenated silane such as silicon tetrachloride is produced by vapor phase oxidation, so-called dry silica powder called fumed silica, and so-called water glass is used. Although either can be used wet silica powder, less silanol groups on the surface and inside, also Na 2 O, SO 3 - less dry silica powder of manufacture residues such as is preferred.
Examples of the treatment agent used for the hydrophobic treatment of the silica powder include silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silazane compounds, cyclic dimethylsiloxane, and silane coupling agents. Among these, silicone oil, silazane compound, cyclic dimethylsiloxane, and silane coupling agent are preferable.
シリコーンオイルとしては、ジメチルシリコーンオイル、メチルフェニルシリコーンオイル、α−メチルスチレン変性シリコーンオイル、フッ素変性シリコーンオイルなどが、シラザン化合物としては、例えばヘキサメチルジシラザンなどが、環状ジメチルシロキサンとしては、例えばヘキサメチルシクロトリシロキサン、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサンなどが挙げられる。シランカップリング剤としては、例えばビニルトリメトキシシラン、ビニルトリエトキシシラン、γ−メタクリルオキシプロピルトリメトキシシラン、ビニルトリアセトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、イソブチルトリメトキシシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン、トリメチルメトキシシラン、ヒドロキシプロピルトリメトキシシラン、フェニルトリメトキシシラン、ｎ−ヘキサデシルトリメトキシシラン、ｎ−オクタデシルトリメトキシシラン等を挙げることができる。 Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene-modified silicone oil, fluorine-modified silicone oil, etc., examples of the silazane compound include hexamethyldisilazane, and examples of the cyclic dimethylsiloxane include hexagonal dimethylsiloxane. Examples include methylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and the like. Examples of silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane. Dimethyldiethoxysilane, trimethylmethoxysilane, hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane and the like.
（トナー母粒子の作製）
本発明においては、トナー母粒子は、以下に示す方法によって作製することができる。
まず、バインダー樹脂、着色剤、電荷制御剤及び所望によりワックスやシリカ粉末を溶融混練する。この溶融混練する方法に特に制限はなく、例えば、これらの材料をリボン型混合機、二重円錐型混合機、高速混合機、円錐型スクリュー混合機などを用いてあらかじめ混合したのち、バンバリーミキサー、二軸混練押出機などを用いて溶融混練することができる。
溶融混練物は、冷却後、粉砕される。用いる粉砕機としては、例えば、インパクトクラッシャー、ハンマークラッシャーなどの衝撃式粉砕機、ロッドミル、ボールミルなどの打撃式粉砕機、カウンタージェットミルなどの圧縮空気源を利用したジェット式粉砕機などを挙げることができる。粉砕された粒子は、分級することにより粗粒子と微粒子を除いて粒径分布の狭いトナー粒子とすることが好ましい。分級する方法に特に制限はなく、例えば、気流式分級装置などを用いて分級することができる。
本発明においては、分級により粒径分布が狭められた粉体をトナー母粒子として、浮遊状態で加熱処理することにより、粒子を球形化する。加熱処理に際しては、あらかじめシリカ粉末、好ましくは疎水性シリカ粉末を流動化剤として外添することにより、球形化工程の生産性を向上することができる。外添シリカの添加量は、トナー母粒子１００質量部に対して、０.１〜８質量部であることが好ましく、０.５〜６質量部であることがより好ましい。トナー母粒子を加熱処理する手段としては、例えば、流動床槽や、熱気流中にトナー母粒子を分散させて表面を溶融させて球形化する熱風球形化装置などを用いることができる。加熱処理により、トナー粒子の平均円形度を０.９３０〜０.９８０の範囲にする。
(Preparation of toner base particles)
In the present invention, the toner base particles can be produced by the following method.
First, a binder resin, a colorant, a charge control agent, and optionally wax or silica powder are melt-kneaded. There is no particular limitation on the method of melt-kneading, for example, these materials are mixed in advance using a ribbon mixer, a double cone mixer, a high speed mixer, a cone screw mixer, etc., and then a Banbury mixer, It can be melt-kneaded using a twin-screw kneading extruder or the like.
The melt-kneaded product is pulverized after cooling. Examples of the pulverizer used include impact pulverizers such as impact crushers and hammer crushers, impact pulverizers such as rod mills and ball mills, and jet pulverizers using a compressed air source such as counter jet mills. it can. The pulverized particles are preferably classified into toner particles having a narrow particle size distribution by removing coarse particles and fine particles. There is no restriction | limiting in particular in the classification method, For example, it can classify | categorize using an airflow classifier etc.
In the present invention, the particles are spheroidized by heat treatment in a floating state using the powder whose particle size distribution is narrowed by classification as toner base particles. In the heat treatment, the productivity of the spheronization step can be improved by externally adding silica powder, preferably hydrophobic silica powder, as a fluidizing agent in advance. The addition amount of the externally added silica is preferably 0.1 to 8 parts by mass, and more preferably 0.5 to 6 parts by mass with respect to 100 parts by mass of the toner base particles. As a means for heat-treating the toner mother particles, for example, a fluidized bed tank or a hot air spheronizing device for dispersing the toner mother particles in a hot air flow and melting the surface to spheroidize can be used. The average circularity of the toner particles is adjusted to a range of 0.930 to 0.980 by heat treatment.
この平均円形度が０.９３０未満では、トナーの転写性が低下したり、現像ローラー上で充分に帯電しないまま搬送されることで、カブリが発生したりする。一方、平均円形度が０.９８０を超えると、感光体あるいは中間転写体に付着したトナー粒子のクリーニングブレードによる掻き取りが困難となるおそれが生じる。好ましい平均円形度は０.９４５〜０.９７０である。なお、平均円形度の測定方法については後で説明する。
前記加熱処理において、電荷制御剤として用いられる前述した有機ジルコニウム化合物と、バインダー樹脂として好適に用いられるポリエステル系樹脂のカルボン酸との加熱架橋が生じ、その結果得られるトナー母粒子が増粘し、定着時の耐ホットオフセット性やヒートローラーへの耐巻き付き性が向上する。
加熱処理により球形化したトナー粒子には、最終外添剤として、疎水性シリカ、酸化チタンなどの無機酸化物の微粒子や、ポリメタクリル酸メチルなどの有機樹脂微粒子を添加して、トナーの帯電特性や流動性の調整を行うことが好ましい。最終外添剤の添加量は、トナー粒子１００質量部に対して０.１〜６質量部であることが好ましく、０.３〜５質量部であることがより好ましい。
When the average circularity is less than 0.930, the transferability of the toner is lowered, or the image is fogged by being conveyed on the developing roller without being sufficiently charged. On the other hand, if the average circularity exceeds 0.980, it may be difficult to scrape the toner particles adhering to the photosensitive member or the intermediate transfer member with the cleaning blade. A preferred average circularity is 0.945 to 0.970. A method for measuring the average circularity will be described later.
In the heat treatment, the above-described organozirconium compound used as a charge control agent and a heat-induced crosslinking of a carboxylic acid of a polyester resin suitably used as a binder resin occur, and the resulting toner base particles are thickened. Hot offset resistance during fixing and resistance to wrapping around a heat roller are improved.
Toner particles that have been spheroidized by heat treatment are added with fine particles of inorganic oxides such as hydrophobic silica and titanium oxide and organic resin fine particles such as polymethyl methacrylate as the final external additive. It is preferable to adjust the fluidity. The amount of the final external additive added is preferably 0.1 to 6 parts by mass and more preferably 0.3 to 5 parts by mass with respect to 100 parts by mass of the toner particles.
本発明はまた、バインダー樹脂と、電荷制御剤と、着色剤を含む粉体を、浮遊状態における加熱架橋処理により、平均円形度が０.９３０〜０.９８０になるように球形化して、トナー母粒子を調製する工程を含み、かつ前記電荷制御剤として、芳香族ヒドロキシカルボン酸又はその塩と含ジルコニウム化合物との反応生成物を少なくとも用いることを特徴とする、前述した本発明の静電荷像現像用トナーを製造する方法をも提供する。 The present invention also provides a toner in which a powder containing a binder resin, a charge control agent, and a colorant is spheroidized to have an average circularity of 0.930 to 0.980 by heat crosslinking in a floating state. The electrostatic charge image of the present invention as described above, which comprises a step of preparing mother particles, and at least a reaction product of an aromatic hydroxycarboxylic acid or a salt thereof and a zirconium-containing compound is used as the charge control agent. A method for producing a developing toner is also provided.
次に、本発明を実施例により、さらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。
なお、各例における諸特性は、下記の方法に従って求めた。
（１）球形化トナー母粒子の平均円形度
フロー式粒子像分析装置［シスメックス(株)製、「ＦＰＩＡ−２１００」］を用いて、円相当径３μｍ以上の粒子の平均円形度を求める。
円形度＝(粒子の投影面積と同じ面積を有する円の周長)／(粒子投影図の輪郭長さ)
（２）フロー軟化温度Ｔ１／２
明細書本文記載の方法に従って測定する。
（３）ＴＨＦ不溶分
トナーバインダー樹脂のテトラヒドロフラン（ＴＨＦ）不溶分を、以下に示す方法に従って測定する。
内径３.５ｃｍの円筒状のガラスろ過器「１ＧＰ１００」［柴田科学社製］に、「セライト５４５」［キシダ化学社製］を２ｇ入れ、セライト５４５の層の高さが変化しなくなるまで、ガラスろ過器をコルク台に軽くたたきつけた。この操作を４回繰り返して、セライト５４５の層の高さがフィルター面から２ｃｍとなるようにガラスろ過器へセライト５４５を充填した。このセライト５４５が充填されたガラスろ過器を１０５℃で３時間以上乾燥させて、その重さを秤量した（Ｙｇ）。次いで、サンプル約０.５ｇを三角フラスコ内に入れて精秤し（Ｘｇ）、次いでＴＨＦ５０ｍＬを加え、７０℃のウォーターバスにて３時間加熱してサンプルを溶解させた。この溶液を上記セライト５４５が充填されたガラスろ過器へ投入し、吸引ろ過した。ＴＨＦ不溶分を捕捉したガラスろ過器を８０℃で３時間以上乾燥させて、その重さを秤量し（Ｚｇ）、以下の式に従って、ＴＨＦ不溶分を算出した。
ＴＨＦ不溶分＝［(Ｚ−Ｙ)／Ｘ］×１００（質量％）
なお、このＴＨＦ不溶分は、ポリエステル樹脂中の架橋している成分量の目安となる。
（４）定着性
ベタ印刷面にセロハン粘着テープを貼着したのち剥離し、剥離前後の画像濃度をマクベス濃度計［マクベス社］で測定し、次式により定着性を算出する。
定着性 ＝（テープ剥離後の濃度／テープ剥離前の濃度）×１００（％）
○：９３.０％以上
△：９０.０％以上９３.０％未満
×：９０.０％未満
（５）定着器巻き付き性
用紙の定着器巻き付き性を、下記の基準で評価した。
○：良好
△：実用上問題ない
×：不良
（６）ＨＨ環境（３０℃／８０％ＲＨ）におけるカブリ性
目視により、下記の基準で評価した。
○：良好
△：実用上問題ない
×：不良
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
Various characteristics in each example were determined according to the following methods.
(1) Average Circularity of Spherical Toner Base Particles Using a flow type particle image analyzer [manufactured by Sysmex Corporation, “FPIA-2100”], the average circularity of particles having an equivalent circle diameter of 3 μm or more is determined.
Circularity = (circumference of a circle having the same area as the projected area of the particle) / (contour length of the particle projection)
(2) Flow softening temperature T1 / 2
It is measured according to the method described in the text of the specification.
(3) THF Insoluble Content The tetrahydrofuran (THF) insoluble content of the toner binder resin is measured according to the following method.
Place 2 g of “Celite 545” [Kishida Chemical Co., Ltd.] into a cylindrical glass filter “1GP100” [made by Shibata Kagaku Co., Ltd.] having an inner diameter of 3.5 cm, and glass until the height of the Celite 545 layer does not change. The filter was tapped against a cork table. This operation was repeated four times, and Celite 545 was filled into a glass filter so that the height of the Celite 545 layer was 2 cm from the filter surface. The glass filter filled with Celite 545 was dried at 105 ° C. for 3 hours or more and weighed (Yg). Next, about 0.5 g of the sample was put in an Erlenmeyer flask and precisely weighed (Xg), and then 50 mL of THF was added and heated in a 70 ° C. water bath for 3 hours to dissolve the sample. This solution was put into a glass filter packed with Celite 545 and suction filtered. The glass filter capturing the THF-insoluble matter was dried at 80 ° C. for 3 hours or more, the weight was weighed (Zg), and the THF-insoluble matter was calculated according to the following formula.
THF insoluble matter = [(Z−Y) / X] × 100 (mass%)
This THF-insoluble matter is a measure of the amount of cross-linked components in the polyester resin.
(4) Fixing property A cellophane adhesive tape is applied to the solid printing surface and then peeled off. The image density before and after peeling is measured with a Macbeth densitometer [Macbeth Co., Ltd.], and the fixing property is calculated by the following formula.
Fixability = (concentration after tape peeling / concentration before tape peeling) x 100 (%)
○: 93.0% or more Δ: 90.0% or more and less than 93.0% ×: less than 90.0% (5) Fixing device winding property The fixing device winding property of the paper was evaluated according to the following criteria.
○: Good Δ: No problem in practical use ×: Defect (6) Fog in HH environment (30 ° C./80% RH) Visually evaluated according to the following criteria.
○: Good △: No problem in practical use ×: Bad
実施例１
ポリエステル樹脂（酸価：６.０ｍｇＫＯＨ／ｇ、フロー軟化温度Ｔ１／２：１３０℃）９１.００質量部、カーボンブラック［キャボット社製、商品名「Ｂｌａｃｋ Ｐｅａｒｌｓ Ｌ」］５.００質量部、電荷制御剤［保土ヶ谷化学社製、商品名「ＴＮ１０５」、サリチル酸ジルコニウム系］０.７５質量部と［オリエント工業社製、商品名「Ｅ−３０４」］１.００質量部、離型剤ライスワックス［ボーソー油脂社製、「ＬＡＸ−Ｎ−３００Ａ」、ＤＳＣ吸熱ピーク：８０℃］１.００質量部と［三洋化成工業社製、商品名「ユーメックス１１０ＴＳ」］２.００質量部を、二軸押出機で溶融混練（湿練物の温度１５０℃）したのち、ジェット式粉砕機で体積平均粒径７.５μｍに粉砕し、さらに粗粉と微粉を分級装置で分級して、粒度分布がシャープなトナー母粒子を得た。
このトナー母粒子１００質量部に疎水性シリカ［日本アエロジル社製、商品名「ＲＸ−５０」］３.０質量部を添加し、ヘンシェルミキサーを用いて混合したのち、球形化装置［日本ニューマチック工業(株)製、機種名「ＳＦＳ−３型」］を用い、熱風温度３０５℃、フィード量５.０ｋｇ／ｈで球形化処理し、平均円形度０.９６２の球形化トナー母粒子を得た。この球形化トナー母粒子の体積平均粒径は７.９μｍであった。
得られた球形化トナー粒子を分級装置［日鉄鉱業(株)製、機種名「エルボージェットＥＪ−ＰＵＲＯ」］を用いて分級し、カップリング粒子を除去して、体積平均粒径７.８μｍの分級トナー粒子を得た。
この分級トナー粒子１００質量部に、疎水性シリカ［キャボット社製、商品名「ＴＳ−５３０」］０.５質量部及びチタン酸ストロンチウム（ＢＥＴ法窒素吸着比表面積：１.８５ｍ2／ｇ）１.０質量部を添加し、ヘンシェルミキサーで混合したのち、目開き２００メッシュのスクリーンを備えた超音波振動篩いを通すことにより、静電荷像現像用トナーを製造した。このトナーのフロー軟化温度Ｔ１／２は１３２.６℃であった。
このトナーを用いて、下記のように印字試験を行い、定着器巻き付き性、ＨＨ（３０℃／８０％ＲＨ）環境におけるカブリ性、及び定着性を評価した。
＜印字試験＞
１成分現像システムを備えた市販のカラーレーザプリンタを用い、ブラックカートリッジに上記トナーを充填して３,０００枚の印字試験を行った。印字試験では印字率５％の画像パターンを連続印字した。
Example 1
Polyester resin (acid value: 6.0 mgKOH / g, flow softening temperature T1 / 2: 130 ° C.) 91.00 parts by mass, carbon black [manufactured by Cabot, trade name “Black Pearls L”] 5.00 parts by mass, charge Control agent [made by Hodogaya Chemical Co., Ltd., trade name “TN105”, zirconium salicylate] 0.75 parts by mass [Orient Kogyo Co., Ltd., trade name “E-304”] 1.00 parts by weight, release agent rice wax [ “LAX-N-300A” manufactured by Borso Oil & Fats Co., Ltd., 1.00 parts by mass of DSC endothermic peak: 80 ° C. and 2.00 parts by mass of [trade name “Yumex 110TS” manufactured by Sanyo Chemical Industries, Ltd.] After melt-kneading with a machine (temperature of wet kneaded material at 150 ° C.), the powder is pulverized to a volume average particle size of 7.5 μm with a jet type pulverizer, and then coarse and fine powders are classified with a classifier, so It was obtained the toner mother particles.
To 100 parts by mass of the toner base particles, 3.0 parts by mass of hydrophobic silica [manufactured by Nippon Aerosil Co., Ltd., trade name “RX-50”] is added and mixed using a Henschel mixer, and then the spheronizer [Nippon Pneumatic] Sphericalized toner base particles having an average circularity of 0.962 are obtained by spheronizing at a hot air temperature of 305 ° C. and a feed rate of 5.0 kg / h using a model name “SFS-3 type” manufactured by Kogyo Co., Ltd. It was. The volume average particle diameter of the spheroidized toner base particles was 7.9 μm.
The resulting spheroidized toner particles are classified using a classifier [manufactured by Nittetsu Mining Co., Ltd., model name “Elbow Jet EJ-PURO”], and the coupling particles are removed to obtain a volume average particle diameter of 7.8 μm. The classified toner particles were obtained.
To 100 parts by mass of the classified toner particles, 0.5 part by mass of hydrophobic silica [manufactured by Cabot, trade name “TS-530”] and strontium titanate (BET method nitrogen adsorption specific surface area: 1.85 m 2 / g) 1 After adding 0.0 parts by mass and mixing with a Henschel mixer, an electrostatic charge image developing toner was produced by passing through an ultrasonic vibration sieve equipped with a 200 mesh screen. This toner had a flow softening temperature T1 / 2 of 132.6.degree.
Using this toner, a printing test was conducted as described below, and the fixing device winding property, fogging property in a HH (30 ° C./80% RH) environment, and fixing property were evaluated.
<Print test>
Using a commercially available color laser printer equipped with a one-component development system, the above-mentioned toner was filled in a black cartridge, and a printing test on 3,000 sheets was performed. In the printing test, an image pattern with a printing rate of 5% was continuously printed.
実施例２
実施例１におけるトナー母粒子の作製において、電荷制御剤としてのオリエント工業社製「Ｅ３０４」を用いなかったこと以外は、実施例１と同様にしてトナーを製造し、印字試験を行った。なお、球形化処理における熱風温度は３００℃、フィード量は５.０ｋｇ／ｈであった。また、得られたトナーのフロー軟化温度Ｔ１／２は１３１.４℃であった。
実施例３
実施例１におけるトナー母粒子の作製において、電荷制御剤としての「ＴＮ１０５」の量を０.２５質量部に変更した以外は、実施例１と同様にしてトナーを製造し、印字試験を行った。なお、球形化処理における熱風温度は２９０℃、フィード量は５.０ｋｇ／ｈであった。また、得られたトナーのフロー軟化温度Ｔ１／２は１３０.６℃であった。
Example 2
A toner was manufactured in the same manner as in Example 1 except that “E304” manufactured by Orient Kogyo Co., Ltd. as a charge control agent was not used in the production of toner base particles in Example 1, and a printing test was performed. In addition, the hot air temperature in the spheroidization treatment was 300 ° C., and the feed amount was 5.0 kg / h. The obtained toner had a flow softening temperature T1 / 2 of 131.4 ° C.
Example 3
A toner was produced in the same manner as in Example 1 except that the amount of “TN105” as the charge control agent was changed to 0.25 parts by mass in the production of the toner base particles in Example 1, and a printing test was performed. . The hot air temperature in the spheronization treatment was 290 ° C., and the feed amount was 5.0 kg / h. The obtained toner had a flow softening temperature T1 / 2 of 130.6 ° C.
比較例１
実施例１におけるトナー母粒子の作製において、ポリエステル樹脂として、フロー軟化温度Ｔ１／２が１５７℃、酸価６.０ｍｇＫＯＨ／ｇのものを用い、かつ電荷制御剤としての「ＴＮ１０５」を用いなかったこと以外は、実施例１と同様にしてトナーを製造し、印字試験を行った。
なお、球形化処理における温度は３９０℃で、処理量は２.５ｋｇ／ｈであり、生産性は満足の得られるものではなかった。耐ホットオフセット性は良好であったが、ワックスブリードが発生し、帯電ブレードへのトナー融着現象がみられた。また、得られたトナーのフロー軟化温度Ｔ１／２は１６０.２℃であった。
比較例２
実施例１におけるトナー母粒子の作製において、ポリエステル樹脂の代わりに、スチレンアクリル樹脂（フロー軟化温度Ｔ１／２＝１４３℃、酸価５ｍｇＫＯＨ／ｇ）を用い、かつ電荷制御剤としての「ＴＮ１０５」を用いなかったこと以外は、実施例１と同様にしてトナーを製造し、印字試験を行った。
なお、球形化処理における温度は３９０℃で、処理量は２.５ｋｇ／ｈであり、生産性は満足の得られるものではなかった。また、得られたトナーのフロー軟化温度Ｔ１／２は１３２.８℃であった。
比較例３
実施例１におけるトナー母粒子の作製において、電荷制御剤としての「ＴＮ１０５」を用いなかったこと以外は、実施例１と同様にしてトナーを製造し、印字試験を行った。なお、熱処理温度は３００℃で、処理量は５.１ｋｇ／ｈであり、生産性は満足し得るものであったが、ヒートローラーへの定着器巻き付きが発生した。また、得られたトナーのフロー軟化温度Ｔ１／２は１３４℃であった。
上記実施例１〜３及び比較例１〜３の評価結果を第１表に示す。
Comparative Example 1
In the production of the toner base particles in Example 1, a polyester resin having a flow softening temperature T1 / 2 of 157 ° C., an acid value of 6.0 mgKOH / g, and “TN105” as a charge control agent was not used. Except for this, a toner was produced in the same manner as in Example 1, and a printing test was conducted.
Note that the temperature in the spheronization treatment was 390 ° C., the treatment amount was 2.5 kg / h, and the productivity was not satisfactory. Although the hot offset resistance was good, wax bleed occurred and a toner fusing phenomenon to the charging blade was observed. The obtained toner had a flow softening temperature T1 / 2 of 160.2 ° C.
Comparative Example 2
In the production of the toner base particles in Example 1, a styrene acrylic resin (flow softening temperature T1 / 2 = 143 ° C., acid value 5 mgKOH / g) is used instead of the polyester resin, and “TN105” as a charge control agent is used. A toner was produced in the same manner as in Example 1 except that it was not used, and a printing test was performed.
Note that the temperature in the spheronization treatment was 390 ° C., the treatment amount was 2.5 kg / h, and the productivity was not satisfactory. Further, the flow softening temperature T1 / 2 of the obtained toner was 132.8 ° C.
Comparative Example 3
A toner was produced in the same manner as in Example 1 except that “TN105” as a charge control agent was not used in the production of toner base particles in Example 1, and a printing test was performed. The heat treatment temperature was 300 ° C., the throughput was 5.1 kg / h, and the productivity was satisfactory, but the fixing device was wound around the heat roller. The obtained toner had a flow softening temperature T1 / 2 of 134 ° C.
The evaluation results of Examples 1 to 3 and Comparative Examples 1 to 3 are shown in Table 1.
本発明の静電荷像現像用トナーによれば、定着時の耐ホットオフセット性が向上し、定着器巻き付き性が改善されると共に、帯電量の立ち上がりが良好で濃度が高く、カブリの少ない高品位の画像が得られ、また、カラートナーにおいても鮮明な色彩色が得られる。 According to the toner for developing an electrostatic image of the present invention, the hot offset resistance during fixing is improved, the fixing device wrapping property is improved, the charge amount rises well, the density is high, and the fog is high. In addition, a clear color can be obtained with a color toner.
Claims (2)
＜フロー軟化温度Ｔ１／２の測定＞
ＪＩＳ Ｋ ７１９９に規定するキャピラリーレオメータを用い、シリンダ内径１１.３２９ｍｍ、キャピラリーダイ内径１ｍｍ、長さ１ｍｍとし、シリンダ内に樹脂１.０ｇを充填し、ピストンに荷重９８Ｎをかけ、５０℃から５℃／分で昇温し、充填された樹脂の２分の１が流出したときの温度を、フロー軟化温度Ｔ１／２とする。 A powder comprising a binder resin comprising a polyester resin having an acid value of 2 to 25 mg KOH / g, a charge control agent comprising a reaction product of an aromatic hydroxycarboxylic acid or a salt thereof and a zirconium-containing compound, and a colorant The toner base particles having a sharp toner particle size distribution are obtained after melt-kneading and pulverizing, and hydrophobic silica having an average primary particle size of 0.005 to 0.02 μm is added to the toner base particles. . After adding and mixing so that it may become 25-5 mass%, the heat crosslinking of the carboxylic acid of this polyester resin and the said charge control agent is formed by the heat-crosslinking process by the hot air in a floating state with a spheronizer. Then, a manufacturing process for preparing spherical toner base particles by spheronizing so as to have an average circularity of 0.930 to 0.980 , wherein the aromatic hydride is used as the charge control agent. Rokishikarubon acid or reaction products thereof with a salt and containing zirconium compound in the toner base particles is 0.1 to 1.0 mass%, further, of the binder resin, flow softening measured by the following measurement methods A method for producing a toner for developing an electrostatic charge image, wherein the temperature T1 / 2 is in the range of 100 to 150 ° C.
<Measurement of flow softening temperature T1 / 2>
Using a capillary rheometer specified in JIS K 7199, the cylinder inner diameter is 11.329 mm, the capillary die inner diameter is 1 mm, the length is 1 mm, the cylinder is filled with 1.0 g of resin, a load of 98 N is applied to the piston, and 50 to 5 ° C. The temperature when the temperature is raised at 1 / min and one-half of the filled resin flows out is defined as a flow softening temperature T1 / 2.
2. The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the aromatic hydroxycarboxylic acid or a salt thereof is salicylic acid or a salt thereof.
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| JP2008164484A JP5072104B2 (en) | 2008-06-24 | 2008-06-24 | Method for producing toner for developing electrostatic image |
| PCT/JP2009/061808 WO2009157582A1 (en) | 2008-06-24 | 2009-06-23 | Toner for electrostatic-image development and process for producing the same |
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| JP2008164484A JP5072104B2 (en) | 2008-06-24 | 2008-06-24 | Method for producing toner for developing electrostatic image |
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| JP2004151438A (en) * | 2002-10-31 | 2004-05-27 | Canon Inc | Toner, image forming method, and image forming apparatus |
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