JP5427570B2 - Magenta toner - Google Patents
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- Publication number
- JP5427570B2 JP5427570B2 JP2009271844A JP2009271844A JP5427570B2 JP 5427570 B2 JP5427570 B2 JP 5427570B2 JP 2009271844 A JP2009271844 A JP 2009271844A JP 2009271844 A JP2009271844 A JP 2009271844A JP 5427570 B2 JP5427570 B2 JP 5427570B2
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- JP
- Japan
- Prior art keywords
- toner
- weight
- polyester
- preferable
- improving
- 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.)
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- 229920005989 resin Polymers 0.000 claims description 69
- 239000011347 resin Substances 0.000 claims description 69
- 229920000728 polyester Polymers 0.000 claims description 67
- -1 isophthalic acid compound Chemical class 0.000 claims description 57
- 239000003086 colorant Substances 0.000 claims description 40
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 36
- 239000002994 raw material Substances 0.000 claims description 36
- 239000011230 binding agent Substances 0.000 claims description 34
- 239000001993 wax Substances 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 239000000049 pigment Substances 0.000 claims description 18
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 16
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 11
- 229960004889 salicylic acid Drugs 0.000 claims description 11
- 150000004696 coordination complex Chemical class 0.000 claims description 8
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- 125000000217 alkyl group Chemical group 0.000 description 7
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- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 4
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- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 4
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- 239000004698 Polyethylene Substances 0.000 description 3
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Chemical group 0.000 description 3
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- 239000002904 solvent Substances 0.000 description 3
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- 239000004925 Acrylic resin Substances 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
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- GCOWTRMQPXDRQQ-UHFFFAOYSA-N [Mg].[Cu].[Zn] Chemical compound [Mg].[Cu].[Zn] GCOWTRMQPXDRQQ-UHFFFAOYSA-N 0.000 description 2
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Developing Agents For Electrophotography (AREA)
Description
本発明は、電子写真法、静電記録法、静電印刷法等において形成される潜像の現像に用いられるマゼンタトナーに関する。 The present invention relates to a magenta toner used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method or the like.
近年、プリント・オン・デマンド市場が成長しているなか、電子写真技術に対する高画質化、高精細化への要求はますます高まりつつある。特に、電子写真方式の印刷でオフセット印刷に置き換わるには、印刷並みの色調や耐光性の向上が必須である。 In recent years, with the growth of the print-on-demand market, there is an increasing demand for higher image quality and higher definition for electrophotographic technology. In particular, in order to replace offset printing with electrophotographic printing, it is essential to improve the color tone and light resistance equivalent to printing.
そこで、マゼンタトナー用顔料としてはいくつか提案されているが、色の鮮明性と透明性に優れ、かつ耐光性にも優れるという点でキナクリドン系の顔料が広く用いられている。例えば、キナクリドン系の顔料を含有したトナーにおいて、顔料の分散性を向上させて発色濃度を向上させることが開示されている（特許文献１参照）。 Thus, some pigments for magenta toner have been proposed, but quinacridone pigments are widely used in terms of excellent color sharpness and transparency, and excellent light resistance. For example, it is disclosed that in a toner containing a quinacridone pigment, the dispersibility of the pigment is improved to improve the color density (see Patent Document 1).
また、紫外線吸収剤である銅化合物を含有するトナーにおいて、トナー中の銅含有量を制御することにより、紫外線照射等による変色又は褪色を抑制する技術が開示されている（特許文献２参照）。 In addition, in a toner containing a copper compound that is an ultraviolet absorber, a technique for suppressing discoloration or fading due to ultraviolet irradiation or the like by controlling the copper content in the toner is disclosed (see Patent Document 2).
一方、スチレン系モノマー：200部、C.I.ピグメントレッド185：16部、サリチル酸アルミニウム：2部、プロピレンオキサイド変性ビスフェノールＡとイソフタル酸との重縮合物：7部等からなる重合性単量体組成物を重合して得られたトナーが、臭気がなく、光沢感があり均質な画像を形成できること（特許文献３参照）や、全面縁なし印刷における転写時・定着時の画像弊害を解決できること（特許文献４参照）を開示している。 On the other hand, a polymerizable monomer composition comprising styrene monomer: 200 parts, CI pigment red 185: 16 parts, aluminum salicylate: 2 parts, polycondensate of propylene oxide-modified bisphenol A and isophthalic acid: 7 parts, etc. The toner obtained by polymerization has no odor, can form a glossy and homogeneous image (see Patent Document 3), and can solve the bad effects of images at the time of transfer and fixing in borderless printing (Patent Document) 4).
しかしながら、ポリエステルを主成分としたマゼンタトナーの顔料としてキナクリドン系を使用すると耐光性は良好ではあるが、顔料の分散性が不十分であり、その結果、彩度が低くなる。また、紫外線吸収剤等を併用すると耐光性は向上するが、帯電性に大きな影響を及ぼすため均質な画像が得られないことが判明した。 However, when a quinacridone type is used as a pigment of a magenta toner containing polyester as a main component, the light resistance is good, but the dispersibility of the pigment is insufficient, and as a result, the saturation is lowered. Further, it has been found that when a UV absorber or the like is used in combination, the light resistance is improved, but a uniform image cannot be obtained because the chargeability is greatly affected.
本発明の課題は、高い彩度を有し、耐光性に優れたマゼンダトナーを提供することにある。 An object of the present invention is to provide a magenta toner having high saturation and excellent light resistance.
本発明は、結着樹脂、着色剤、荷電制御剤及びワックスを含有してなるマゼンタトナーであって、前記結着樹脂がポリエステルを50重量％以上含有し、該ポリエステルの少なくとも1種がイソフタル酸化合物を含有するカルボン酸成分とアルコール成分とを縮重合させて得られるポリエステルであり、前記着色剤がC.I.ピグメントレッド185を含有し、前記荷電制御剤がサリチル酸化合物の金属錯体を含有し、前記ワックスの融点が50〜120℃であるマゼンタトナーに関する。 The present invention relates to a magenta toner comprising a binder resin, a colorant, a charge control agent, and a wax, wherein the binder resin contains 50% by weight or more of polyester, and at least one of the polyesters is isophthalic acid. A polyester obtained by polycondensing a carboxylic acid component containing a compound and an alcohol component, wherein the colorant contains CI Pigment Red 185, the charge control agent contains a metal complex of a salicylic acid compound, and the wax Relates to a magenta toner having a melting point of 50 to 120 ° C.
本発明のマゼンダトナーは、高い彩度を有し、耐光性に優れた効果を奏するものである。 The magenta toner of the present invention has a high saturation and exhibits an effect of excellent light resistance.
本発明のマゼンタトナーは、結着樹脂、着色剤、荷電制御剤及びワックスを含有してなるマゼンタトナーであって、結着樹脂がポリエステルを50重量％以上含有し、該ポリエステルの少なくとも1種がイソフタル酸化合物を含有するカルボン酸成分とアルコール成分とを縮重合させて得られるポリエステルであり、着色剤がC.I.ピグメントレッド185を含有し、荷電制御剤がサリチル酸化合物の金属錯体を含有し、前記ワックスの融点が50〜120℃である点に大きな特徴を有しており、高い彩度を持ち、耐光性に優れた効果を奏するものである。 The magenta toner of the present invention is a magenta toner comprising a binder resin, a colorant, a charge control agent and a wax, wherein the binder resin contains 50% by weight or more of polyester, and at least one of the polyesters is A polyester obtained by polycondensation of a carboxylic acid component containing an isophthalic acid compound and an alcohol component, a colorant containing CI Pigment Red 185, a charge control agent containing a metal complex of a salicylic acid compound, and the wax It has a great feature in that its melting point is 50 to 120 ° C., has high saturation, and exhibits excellent light resistance.
本発明の効果が奏される理由の詳細は明らかではないが、イソフタル酸化合物を用いたポリエステルとサリチル酸化合物の金属錯体と特定の融点を持つワックスとの相互作用により、結着樹脂、着色剤、荷電制御剤、ワックス等を含有するトナー原料組成物の粘度が高くなり、溶融混練時における着色剤の分散が良好となるものと推定される。着色剤が結着樹脂中に良好に分散されることにより、彩度及び耐光性が向上する。さらに、本発明者らは、着色剤であるC.I.ピグメントレッド185自身の耐光性、及びイソフタル酸化合物を用いたポリエステル自身の耐光性が良好であることを見出し、これにより、さらにトナーの耐光性が向上するものと考えられる。 Although the details of the reason why the effect of the present invention is achieved are not clear, due to the interaction between the polyester using the isophthalic acid compound and the metal complex of the salicylic acid compound and the wax having a specific melting point, the binder resin, the colorant, It is presumed that the viscosity of the toner raw material composition containing a charge control agent, wax and the like is increased, and the colorant is favorably dispersed during melt kneading. By satisfactorily dispersing the colorant in the binder resin, saturation and light resistance are improved. Further, the present inventors have found that CI Pigment Red 185 itself, which is a colorant, has good light resistance, and that polyester using an isophthalic acid compound has good light resistance, thereby further improving the light resistance of the toner. It is thought to improve.
本発明のトナーの結着樹脂は、トナーの定着性を向上させる観点、着色剤の分散性を向上させ、それによりトナーの彩度、耐光性を向上させる観点から、ポリエステルを50重量％以上含有するものであり、ポリエステルの含有量は、結着樹脂中、70重量％以上が好ましく、90重量％以上がより好ましく、95重量％以上がさらに好ましい。 The binder resin of the toner of the present invention contains 50% by weight or more of polyester from the viewpoint of improving the fixability of the toner and the dispersibility of the colorant, thereby improving the saturation and light resistance of the toner. The polyester content in the binder resin is preferably 70% by weight or more, more preferably 90% by weight or more, and still more preferably 95% by weight or more.
また、本発明において、ポリエステルの少なくとも1種は、トナー原料組成物の粘度を向上させ、着色剤の分散性を向上させる観点、ポリエステル自身の耐光性を向上させ、トナーの耐光性を向上させる観点から、少なくともイソフタル酸化合物を含有するカルボン酸成分とアルコール成分とを縮重合させて得られるポリエステルである。 In the present invention, at least one of the polyesters is used to improve the viscosity of the toner raw material composition and improve the dispersibility of the colorant. From the viewpoint of improving the light resistance of the polyester itself and improving the light resistance of the toner. To polyester obtained by condensation polymerization of a carboxylic acid component containing at least an isophthalic acid compound and an alcohol component.
本発明において、イソフタル酸化合物とは、イソフタル酸、イソフタル酸のエステル、イソフタル酸無水物を含む。イソフタル酸のエステルとしては、低級アルキル(炭素数1〜6)エステル等が挙げられる。 In the present invention, the isophthalic acid compound includes isophthalic acid, an ester of isophthalic acid, and isophthalic anhydride. Examples of the esters of isophthalic acid include lower alkyl (C1-6) esters.
イソフタル酸化合物の含有量は、トナー原料組成物の粘度を向上させ、着色剤の分散性を向上させる観点、ポリエステルの耐光性を向上させ、トナーの耐光性を向上させる観点から、カルボン酸成分中、50モル％以上が好ましく、70モル％以上がより好ましく、90モル％以上がさらに好ましく、95モル％以上がよりさらに好ましい。 From the viewpoint of improving the viscosity of the toner raw material composition and improving the dispersibility of the colorant, improving the light resistance of the polyester, and improving the light resistance of the toner, the content of the isophthalic acid compound is 50 mol% or more is preferable, 70 mol% or more is more preferable, 90 mol% or more is more preferable, and 95 mol% or more is more preferable.
イソフタル酸化合物以外のカルボン酸成分としては、フタル酸、テレフタル酸、フマル酸、マレイン酸、コハク酸、アジピン酸等のジカルボン酸；ドデセニルコハク酸、オクテニルコハク酸等の炭素数1〜20のアルキル基又は炭素数2〜20のアルケニル基で置換されたコハク酸；トリメリット酸、ピロメリット酸等の3価以上の多価カルボン酸、それらの酸の無水物及びそれらの酸のアルキル(炭素数1〜6)エステル等が挙げられる。ポリエステル自身の耐光性を向上させ、トナーの耐光性を向上させる観点からは、フマル酸等の脂肪族ジカルボン酸化合物が好ましい。トナー原料組成物の粘度を向上させ、着色剤の分散性を向上させる観点からは、テレフタル酸等の芳香族ジカルボン酸化合物が好ましい。 Examples of carboxylic acid components other than isophthalic acid compounds include dicarboxylic acids such as phthalic acid, terephthalic acid, fumaric acid, maleic acid, succinic acid, and adipic acid; alkyl groups having 1 to 20 carbon atoms such as dodecenyl succinic acid and octenyl succinic acid, Succinic acid substituted with an alkenyl group of 2 to 20; a trivalent or higher polyvalent carboxylic acid such as trimellitic acid or pyromellitic acid, anhydrides of these acids, and alkyls of these acids (1 to 6 carbon atoms) ) Esters and the like. From the viewpoint of improving the light resistance of the polyester itself and improving the light resistance of the toner, an aliphatic dicarboxylic acid compound such as fumaric acid is preferred. From the viewpoint of improving the viscosity of the toner raw material composition and improving the dispersibility of the colorant, an aromatic dicarboxylic acid compound such as terephthalic acid is preferred.
ポリエステルのアルコール成分としては、式(I)： As an alcohol component of polyester, the formula (I):
（式中、Ｒ1Ｏ及びＯＲ1はオキシアルキレン基であり、Ｒ1はエチレン及び／又はプロピレン基であり、ｘ及びｙはアルキレンオキサイドの付加モル数を示し、それぞれ正の数であり、ｘとｙの和の平均値は1〜16が好ましく、1〜8がより好ましく、1.5〜4がさらに好ましい）
で表されるビスフェノールＡのアルキレンオキサイド付加物、エチレングリコール、プロピレングリコール、グリセリン、ペンタエリスリトール、トリメチロールプロパン、水素添加ビスフェノールＡ、ソルビトール、又はそれらのアルキレン(炭素数2〜4)オキサイド(平均付加モル数1〜16)付加物等が挙げられる。
(In the formula, R 1 O and OR 1 are oxyalkylene groups, R 1 is an ethylene and / or propylene group, x and y indicate the number of added moles of alkylene oxide, and each is a positive number; The average value of the sum of y and y is preferably 1 to 16, more preferably 1 to 8, and even more preferably 1.5 to 4)
An alkylene oxide adduct of bisphenol A represented by the formula: ethylene glycol, propylene glycol, glycerin, pentaerythritol, trimethylolpropane, hydrogenated bisphenol A, sorbitol, or their alkylene (2 to 4 carbon atoms) oxide (average addition mole) (Equation 1 to 16) include adducts.
これらの中では、トナー原料組成物の粘度を向上させ、着色剤の分散性を向上させる観点、トナーの耐刷時の耐久性及び帯電安定性を向上させる観点から、式(I)で表されるビスフェノールＡのアルキレンオキサイド付加物が好ましい。 Among these, from the viewpoint of improving the viscosity of the toner raw material composition and improving the dispersibility of the colorant, and improving the durability at the time of printing and the charge stability of the toner, it is represented by the formula (I). An alkylene oxide adduct of bisphenol A is preferred.
式(I)で表されるビスフェノールＡのアルキレンオキサイド付加物の含有量は、トナー原料組成物の粘度を向上させ、着色剤の分散性を向上させる観点、トナーの耐刷時の耐久性及び帯電安定性を向上させる観点から、アルコール成分中、50モル％以上が好ましく、80モル％以上がより好ましく、実質的に100モル％がさらに好ましい。 The content of the alkylene oxide adduct of bisphenol A represented by the formula (I) improves the viscosity of the toner raw material composition and improves the dispersibility of the colorant. From the viewpoint of improving stability, the content of the alcohol component is preferably 50 mol% or more, more preferably 80 mol% or more, and still more preferably 100 mol%.
また、アルコール成分には1価のアルコールが、カルボン酸成分には1価のカルボン酸化合物が、分子量調整等の観点から、適宜含有されていてもよい。 In addition, a monovalent alcohol may be appropriately contained in the alcohol component, and a monovalent carboxylic acid compound may be appropriately contained in the carboxylic acid component from the viewpoint of adjusting the molecular weight.
本発明に用いるポリエステルは、イソフタル酸化合物を含有するカルボン酸成分とアルコール成分から得られるポリエステル以外のポリエステルを含有してもよい。イソフタル酸化合物を含有するカルボン酸成分とアルコール成分から得られるポリエステル以外のポリエステルは、上記イソフタル酸化合物以外のカルボン酸化合物と、上記アルコール成分とから得られるものである。ポリエステル自身の耐光性を向上させ、トナーの耐光性を向上させる観点から、フマル酸等の脂肪族ジカルボン酸化合物を含有するカルボン酸成分とアルコール成分から得られるポリエステルが好ましい。また、トナー原料組成物の粘度を向上させ、着色剤の分散性を向上させる観点から、テレフタル酸等の芳香族ジカルボン酸化合物を含有するカルボン酸成分とアルコール成分から得られるポリエステルが好ましい。 The polyester used in the present invention may contain a polyester other than a polyester obtained from a carboxylic acid component containing an isophthalic acid compound and an alcohol component. The polyester other than the polyester obtained from the carboxylic acid component containing the isophthalic acid compound and the alcohol component is obtained from the carboxylic acid compound other than the isophthalic acid compound and the alcohol component. From the viewpoint of improving the light resistance of the polyester itself and improving the light resistance of the toner, a polyester obtained from a carboxylic acid component containing an aliphatic dicarboxylic acid compound such as fumaric acid and an alcohol component is preferable. Further, from the viewpoint of improving the viscosity of the toner raw material composition and improving the dispersibility of the colorant, a polyester obtained from a carboxylic acid component containing an aromatic dicarboxylic acid compound such as terephthalic acid and an alcohol component is preferable.
結着樹脂として用いるポリエステルにおいて、イソフタル酸化合物を含有するカルボン酸成分とアルコール成分とを縮重合させて得られるポリエステルの含有量は、トナー原料組成物の粘度を向上させ、着色剤の分散性を向上させる観点、ポリエステルの耐光性を向上させて、トナーの耐光性を向上させる観点から、全てのポリエステル中の、20重量％以上が好ましく、40重量％以上がより好ましく、60重量％以上がさらに好ましく、90重量％以上がよりさらに好ましく、95重量％以上がよりさらに好ましい。 In the polyester used as the binder resin, the content of the polyester obtained by polycondensing a carboxylic acid component containing an isophthalic acid compound and an alcohol component improves the viscosity of the toner raw material composition and improves the dispersibility of the colorant. From the viewpoint of improving the light resistance of the polyester by improving the light resistance of the polyester, it is preferably 20% by weight or more, more preferably 40% by weight or more, and more preferably 60% by weight or more in all polyesters. Preferably, 90% by weight or more is more preferable, and 95% by weight or more is more preferable.
結着樹脂として用いるポリエステルにおいて、全てのポリエステルの原料モノマー総モル量、すなわち、カルボン酸成分モノマーとアルコール成分モノマーの総モル量中、イソフタル酸化合物の含有量は、トナー原料組成物の粘度を向上させ、着色剤の分散性を向上させる観点、ポリエステルの耐光性を向上させて、トナーの耐光性を向上させる観点から、10モル％以上が好ましく、20モル％以上がより好ましく、30モル％以上がさらに好ましく、40モル％以上がよりさらに好ましい。また、トナーの定着性、及び耐刷時の耐久性を向上させる観点から、50モル％以下が好ましい。すなわち、これらの観点を総合すると、10〜50モル％が好ましく、20〜50モル％がより好ましく、30〜50モル％がさらに好ましく、40〜50モル％がよりさらに好ましい。 In the polyester used as the binder resin, the content of the isophthalic acid compound improves the viscosity of the toner raw material composition in the total molar amount of raw material monomers of all polyesters, that is, the total molar amount of carboxylic acid component monomer and alcohol component monomer. From the viewpoint of improving the dispersibility of the colorant, improving the light resistance of the polyester, and improving the light resistance of the toner, it is preferably 10 mol% or more, more preferably 20 mol% or more, more preferably 30 mol% or more. Is more preferable, and 40 mol% or more is even more preferable. Further, from the viewpoint of improving toner fixability and durability at the time of printing, 50 mol% or less is preferable. That is, taking these viewpoints together, 10 to 50 mol% is preferable, 20 to 50 mol% is more preferable, 30 to 50 mol% is more preferable, and 40 to 50 mol% is even more preferable.
また、結着樹脂中におけるポリエステルを構成するイソフタル酸化合物ユニットの総含有量は、トナー原料組成物の粘度を向上させ、着色剤の分散性を向上させる観点、ポリエステルの耐光性を向上させて、トナーの耐光性を向上させる観点から、10モル％以上が好ましく、20モル％以上がより好ましく、30モル％以上がさらに好ましく、40モル％以上がよりさらに好ましい。また、トナーの定着性、及び耐刷時の耐久性を向上させる観点から、50モル％以下が好ましい。すなわち、これらの観点を総合すると、10〜50モル％が好ましく、20〜50モル％がより好ましく、30〜50モル％がさらに好ましく、40〜50モル％がよりさらに好ましい。なお、結着樹脂が複数の樹脂からなる場合、結着樹脂中におけるポリエステルを構成するイソフタル酸化合物ユニットの総含有量は、各樹脂の［原料モノマーの総モル量中、イソフタル酸化合物の含有量（モル％）］と［結着樹脂中の当該樹脂の含有割合］の積の和で求められる。具体的には、結着樹脂が、イソフタル酸化合物の含有量が40モル％のポリエステル50重量％、イソフタル酸化合物の含有量が30モル％のポリエステル20重量％、ポリエステル以外の樹脂30重量％からなる場合、上記イソフタル酸化合物ユニットの総含有量は、40×0.5＋30×0.2＋0×0.3＝26％と算出できる。 Further, the total content of the isophthalic acid compound unit constituting the polyester in the binder resin is to improve the viscosity of the toner raw material composition, improve the dispersibility of the colorant, improve the light resistance of the polyester, From the viewpoint of improving the light resistance of the toner, it is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, and still more preferably 40 mol% or more. Further, from the viewpoint of improving toner fixability and durability at the time of printing, 50 mol% or less is preferable. That is, taking these viewpoints together, 10 to 50 mol% is preferable, 20 to 50 mol% is more preferable, 30 to 50 mol% is more preferable, and 40 to 50 mol% is even more preferable. When the binder resin is composed of a plurality of resins, the total content of the isophthalic acid compound unit constituting the polyester in the binder resin is [the content of the isophthalic acid compound in the total molar amount of raw material monomers] of each resin. (Mol%)] and [the content ratio of the resin in the binder resin]. Specifically, the binder resin is composed of 50% by weight of polyester having an isophthalic acid compound content of 40 mol%, 20% by weight of polyester having an isophthalic acid compound content of 30 mol%, and 30% by weight of resin other than polyester. In this case, the total content of the isophthalic acid compound unit can be calculated as 40 × 0.5 + 30 × 0.2 + 0 × 0.3 = 26%.
ポリエステルは、不活性ガス雰囲気中にて、必要に応じて、エステル化触媒、重合禁止剤等の存在下、180〜250℃程度の温度で縮重合させて製造することができる。エステル化触媒としては、酸化ジブチル錫、2-エチルヘキサン酸錫(II)等の錫化合物、チタンジイソプロピレートビストリエタノールアミネート等のチタン化合物等が挙げられ、エステル化助触媒としては、没食子酸等が挙げられる。エステル化触媒の使用量は、アルコール成分とカルボン酸成分の総量100重量部に対して、0.01〜1.5重量部が好ましく、0.1〜1.0重量部がより好ましい。エステル化助触媒の使用量は、アルコール成分とカルボン酸成分の総量100重量部に対して、0.001〜0.5重量部が好ましく、0.01〜0.1重量部がより好ましい。 Polyester can be produced by condensation polymerization in an inert gas atmosphere at a temperature of about 180 to 250 ° C. in the presence of an esterification catalyst, a polymerization inhibitor or the like, if necessary. Examples of the esterification catalyst include tin compounds such as dibutyltin oxide and tin (II) 2-ethylhexanoate, titanium compounds such as titanium diisopropylate bistriethanolamate, and the esterification cocatalyst includes gallic acid. Etc. The amount of the esterification catalyst used is preferably 0.01 to 1.5 parts by weight, more preferably 0.1 to 1.0 part by weight, based on 100 parts by weight of the total amount of the alcohol component and the carboxylic acid component. The amount of esterification promoter used is preferably 0.001 to 0.5 parts by weight, more preferably 0.01 to 0.1 parts by weight, based on 100 parts by weight of the total amount of the alcohol component and the carboxylic acid component.
イソフタル酸化合物を用いて得られるポリエステルの軟化点は、トナーの耐刷時の耐久性を向上させる観点から、90℃以上が好ましく、95℃以上がより好ましく、100℃以上がさらに好ましい。また、トナーの低温定着性を向上させる観点から、125℃以下が好ましく、120℃以下がより好ましく、115℃以下がさらに好ましい。すなわち、これらの観点を総合すると、90〜125℃が好ましく、95〜120℃がより好ましく、100〜115℃がさらに好ましい。 The softening point of the polyester obtained using the isophthalic acid compound is preferably 90 ° C. or higher, more preferably 95 ° C. or higher, and further preferably 100 ° C. or higher from the viewpoint of improving the durability of the toner during printing. Further, from the viewpoint of improving the low-temperature fixability of the toner, 125 ° C. or lower is preferable, 120 ° C. or lower is more preferable, and 115 ° C. or lower is further preferable. That is, when these viewpoints are put together, 90-125 degreeC is preferable, 95-120 degreeC is more preferable, and 100-115 degreeC is further more preferable.
イソフタル酸化合物を用いて得られるポリエステルのガラス転移点は、トナーの耐刷時の耐久性を向上させる観点から、50℃以上が好ましく、55℃以上がより好ましい。また、トナーの低温定着性を向上させる観点から、85℃以下が好ましく、80℃以下がより好ましい。すなわち、これらの観点を総合すると、50〜85℃が好ましく、55〜80℃がより好ましい。なお、ガラス転移点は、非晶質樹脂に特有の物性であり、結晶性樹脂では観測されない場合があるが、本発明におけるポリエステルは、結晶性ポリエステルであってもよい。 The glass transition point of the polyester obtained using the isophthalic acid compound is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, from the viewpoint of improving the durability of the toner during printing. Further, from the viewpoint of improving the low-temperature fixability of the toner, 85 ° C. or lower is preferable, and 80 ° C. or lower is more preferable. That is, when these viewpoints are put together, 50-85 degreeC is preferable and 55-80 degreeC is more preferable. The glass transition point is a physical property peculiar to an amorphous resin and may not be observed in a crystalline resin, but the polyester in the present invention may be a crystalline polyester.
イソフタル酸化合物を用いて得られるポリエステル以外のポリエステルの軟化点、ガラス転移点は、イソフタル酸化合物を用いて得られるポリエステルと同様であることが好ましい。 It is preferable that the softening point and glass transition point of the polyester other than the polyester obtained using the isophthalic acid compound are the same as those of the polyester obtained using the isophthalic acid compound.
イソフタル酸化合物を含有するカルボン酸成分とアルコール成分から得られるポリエステル、及びそれ以外のポリエステルの酸価は、着色剤の分散性を向上させる観点から、50mgKOH/g以下が好ましく、30mgKOH/g以下がより好ましく、20mgKOH/g以下がさらに好ましい。 From the viewpoint of improving the dispersibility of the colorant, the acid value of the polyester obtained from the carboxylic acid component containing the isophthalic acid compound and the alcohol component, and the other polyester is preferably 50 mg KOH / g or less, and 30 mg KOH / g or less. More preferred is 20 mg KOH / g or less.
軟化点、ガラス転移点及び酸価のいずれにおいても、複数のポリエステルからなる場合は、それらの加重平均値が上記範囲内となることが好ましい。 In any of the softening point, the glass transition point, and the acid value, when it is composed of a plurality of polyesters, the weighted average value thereof is preferably within the above range.
なお、本発明において、ポリエステルは、実質的にその特性を損なわない程度に変性されたポリエステルであってもよい。変性されたポリエステルとしては、例えば、特開平１１−１３３６６８号公報、特開平１０−２３９９０３号公報、特開平８−２０６３６号公報等に記載の方法によりフェノール、ウレタン、エポキシ等によりグラフト化やブロック化したポリエステルをいう。 In the present invention, the polyester may be a polyester modified to such an extent that the characteristics are not substantially impaired. Examples of the modified polyester include grafting and blocking with phenol, urethane, epoxy and the like by the methods described in JP-A-11-133668, JP-A-10-239903, JP-A-8-20636, and the like. Polyester.
ポリエステル以外の結着樹脂としては、ビニル系樹脂、エポキシ樹脂、ポリカーボネート、ポリウレタン等が挙げられる。これらの樹脂の中では、樹脂自身の耐光性に優れ、トナーの耐光性を向上させる観点から、ビニル系樹脂が好ましい。 Examples of binder resins other than polyester include vinyl resins, epoxy resins, polycarbonates, polyurethanes, and the like. Among these resins, vinyl resins are preferable from the viewpoint of excellent light resistance of the resin itself and improving light resistance of the toner.
ビニル系樹脂の原料モノマーとしては、スチレン、α−メチルスチレン等のスチレン化合物；エチレン、プロピレン等のエチレン性不飽和モノオレフィン類；ブタジエン等のジオレフィン類；塩化ビニル等のハロビニル類；酢酸ビニル、プロピオン酸ビニル等のビニルエステル類；(メタ)アクリル酸のアルキル(炭素数1〜18)エステル、(メタ)アクリル酸ジメチルアミノエチル等のエチレン性モノカルボン酸のエステル；ビニルメチルエーテル等のビニルエーテル類；ビニリデンクロリド等のビニリデンハロゲン化物；Ｎ−ビニルピロリドン等のＮ−ビニル化合物類等が挙げられる。 Examples of the raw material monomer for the vinyl resin include styrene compounds such as styrene and α-methylstyrene; ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; halovinyls such as vinyl chloride; vinyl acetate; Vinyl esters such as vinyl propionate; alkyl (1-18) esters of (meth) acrylic acid, esters of ethylenic monocarboxylic acids such as dimethylaminoethyl (meth) acrylate; vinyl ethers such as vinyl methyl ether Vinylidene halides such as vinylidene chloride; N-vinyl compounds such as N-vinylpyrrolidone; and the like.
樹脂自身の耐光性に優れ、トナーの耐光性を向上させる観点から、スチレン及び／又は(メタ)アクリル酸のアルキルエステルを含有するビニル系樹脂が好ましく、スチレン及び／又は(メタ)アクリル酸のアルキルエステルの含有量は、50重量％以上が好ましく、80〜100重量％がより好ましい。 From the viewpoint of improving the light resistance of the resin itself and improving the light resistance of the toner, a vinyl resin containing an alkyl ester of styrene and / or (meth) acrylic acid is preferable, and an alkyl of styrene and / or (meth) acrylic acid is preferred. The ester content is preferably 50% by weight or more, more preferably 80 to 100% by weight.
ビニル系樹脂の原料モノマーの重合反応は、例えば、ジクミルパーオキサイド等の重合開始剤、架橋剤等の存在下、有機溶媒存在下又は無溶媒下で、常法により行うことができる。温度条件としては、110〜200℃が好ましく、130〜170℃がより好ましい。 The polymerization reaction of the raw material monomer of the vinyl resin can be performed by a conventional method in the presence of a polymerization initiator such as dicumyl peroxide, a crosslinking agent, or the like, in the presence of an organic solvent or in the absence of a solvent. As temperature conditions, 110-200 degreeC is preferable and 130-170 degreeC is more preferable.
付加重合反応の際に有機溶媒を使用する場合、キシレン、トルエン、メチルエチルケトン、アセトン等を用いることができる。有機溶媒の使用量は、ビニル系樹脂の原料モノマー100重量部に対して、10〜50重量部程度が好ましい。 When an organic solvent is used in the addition polymerization reaction, xylene, toluene, methyl ethyl ketone, acetone or the like can be used. The amount of the organic solvent used is preferably about 10 to 50 parts by weight with respect to 100 parts by weight of the raw material monomer of the vinyl resin.
ビニル系樹脂の軟化点及びガラス転移点の好ましい範囲は、上記ポリエステルの場合と同様である。 The preferred range of the softening point and glass transition point of the vinyl resin is the same as that of the polyester.
また、結着樹脂全体としての軟化点及びガラス転移点も、上記範囲内であることが好ましい。 Moreover, it is preferable that the softening point and glass transition point as a whole binder resin are also in the said range.
本発明では、結着樹脂において、ポリエステルとビニル系樹脂は、ポリエステルの原料モノマーと付加重合系樹脂の原料モノマーのいずれとも反応し得る両反応性化合物を用いて、ハイブリッド化されていてもよい。 In the present invention, in the binder resin, the polyester and the vinyl resin may be hybridized using an amphoteric compound capable of reacting with either the polyester raw material monomer or the addition polymerization resin raw material monomer.
本発明のトナーの着色剤は、彩度及び耐光性を向上させる観点から、少なくともC.I.ピグメントレッド185を含有する。 The colorant of the toner of the present invention contains at least C.I. Pigment Red 185 from the viewpoint of improving saturation and light resistance.
さらに、本発明の効果が損なわれない程度に適宜、他の着色剤を併用してもよい。 Furthermore, other colorants may be used in combination as appropriate so long as the effects of the present invention are not impaired.
他の着色剤としては、縮合アゾ化合物、ジケトピロロピロール化合物、アントラキノン、キナクリドン化合物、塩基染料レーキ化合物、ナフトール化合物、ベンズイミダゾロン化合物、チオインジゴ化合物、ペリレン化合物等が挙げられる。具体的には、C.I.ピグメントレッド2、3、5〜7、23、48:2、48:3、48:4、57:1、81:1、122、146、166、169、177、184、202、206、220、221、254、C.I.ピグメントバイオレッド19等の顔料が挙げられる。 Examples of other colorants include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, CI Pigment Red 2, 3, 5-7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 166, 169, 177, 184, And pigments such as 202, 206, 220, 221, 254, CI Pigment Bio Red 19 and the like.
着色剤の含有量は、結着樹脂100重量部に対して、発色性を向上させる観点、彩度を向上させる観点から、1〜10重量部が好ましく、2〜8重量部がより好ましく、3〜6重量部がさらに好ましい。 The content of the colorant is preferably 1 to 10 parts by weight, more preferably 2 to 8 parts by weight, from the viewpoint of improving the color developability and the saturation, with respect to 100 parts by weight of the binder resin. More preferred is ˜6 parts by weight.
C.I.ピグメントレッド185の含有量は、結着樹脂100重量部に対して、発色性を向上させる観点、彩度を向上させる観点から、1〜10重量部が好ましく、2〜8重量部がより好ましく、3〜6重量部がさらに好ましい。 The content of CI Pigment Red 185 is preferably 1 to 10 parts by weight, more preferably 2 to 8 parts by weight, from the viewpoint of improving color developability and saturation, with respect to 100 parts by weight of the binder resin. 3 to 6 parts by weight is more preferable.
着色剤中、C.I.ピグメントレッド185の含有量は、彩度、耐光性を向上させる観点から、50重量％以上が好ましく、70重量％以上がより好ましく、90重量％以上がさらに好ましく、95重量％以上がよりさらに好ましい。 In the colorant, the content of CI Pigment Red 185 is preferably 50% by weight or more, more preferably 70% by weight or more, still more preferably 90% by weight or more, and 95% by weight from the viewpoint of improving saturation and light resistance. The above is even more preferable.
本発明のトナーの荷電制御剤は、トナー原料組成物の粘度を向上させ、着色剤の分散性を向上させる観点から、サリチル酸化合物の金属錯体を含有する。 The charge control agent of the toner of the present invention contains a metal complex of a salicylic acid compound from the viewpoint of improving the viscosity of the toner raw material composition and improving the dispersibility of the colorant.
サリチル酸化合物の金属錯体としては、亜鉛錯体、アルミニウム錯体、ジルコニウム錯体、クロム錯体等が挙げられる。トナー原料組成物の粘度を向上させ、着色剤の分散性を向上させる観点から、亜鉛錯体が好ましい。 Examples of metal complexes of salicylic acid compounds include zinc complexes, aluminum complexes, zirconium complexes, and chromium complexes. From the viewpoint of improving the viscosity of the toner raw material composition and improving the dispersibility of the colorant, a zinc complex is preferable.
サリチル酸化合物の金属錯体としては、例えば、式(II)： As a metal complex of a salicylic acid compound, for example, the formula (II):
（式中、Ｒ2、Ｒ3及びＲ4はそれぞれ独立して水素原子、直鎖又は分枝鎖状の炭素数1〜10のアルキル基又は炭素数2〜10のアルケニル基、Ｍはクロム、亜鉛、カルシウム、ジルコニウム又はアルミニウム、ｍは2以上の整数、ｎは1以上の整数を示す）
で表される化合物が挙げられる。
(Wherein R 2 , R 3 and R 4 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, M is chromium, Zinc, calcium, zirconium or aluminum, m is an integer of 2 or more, and n is an integer of 1 or more)
The compound represented by these is mentioned.
式(II)において、Ｒ3は水素原子が好ましく、Ｒ2及びＲ4は分岐鎖状のアルキル基が好ましくは、tert-ブチル基がより好ましい。 In the formula (II), R 3 is preferably a hydrogen atom, and R 2 and R 4 are preferably branched alkyl groups, more preferably tert-butyl groups.
式(II)で表される化合物の市販品としては、「ボントロンE-81」(Ｒ3：水素原子、Ｒ2及びＲ4：tert-ブチル基、Ｙ：クロム、オリエント化学工業(株)製)、「ボントロンE-84」(Ｒ3：水素原子、Ｒ2及びＲ4：tert-ブチル基、Ｙ：亜鉛、オリエント化学工業(株)製)、「ボントロンE-88」(Ｒ3：水素原子、Ｒ2及びＲ4：tert-ブチル基、Ｙ：アルミニウム、オリエント化学工業(株)製)、「ボントロンE-304」(Ｒ3：水素原子、Ｒ2及びＲ4：tert-ブチル基、Ｙ：亜鉛、オリエント化学工業(株)製)、「TN-105」(Ｒ3：水素原子、Ｒ2及びＲ4：tert-ブチル基、Ｙ：ジルコニウム、保土谷化学工業(株)製)等が挙げられる。これらの中では、トナー原料組成物の粘度を向上させ、着色剤の分散性を向上させる観点から「ボントロンE-84」「ボントロンE-304」（オリヱント化学工業社製）が好ましい。 As a commercial product of the compound represented by the formula (II), “Bontron E-81” (R 3 : hydrogen atom, R 2 and R 4 : tert-butyl group, Y: chromium, manufactured by Orient Chemical Industry Co., Ltd.) ), “Bontron E-84” (R 3 : hydrogen atom, R 2 and R 4 : tert-butyl group, Y: zinc, manufactured by Orient Chemical Co., Ltd.), “Bontron E-88” (R 3 : hydrogen) Atom, R 2 and R 4 : tert-butyl group, Y: aluminum, manufactured by Orient Chemical Industries, Ltd.), “Bontron E-304” (R 3 : hydrogen atom, R 2 and R 4 : tert-butyl group, Y: zinc, manufactured by Orient Chemical Industry Co., Ltd.), “TN-105” (R 3 : hydrogen atom, R 2 and R 4 : tert-butyl group, Y: zirconium, manufactured by Hodogaya Chemical Co., Ltd.), etc. Is mentioned. Among these, “Bontron E-84” and “Bontron E-304” (manufactured by Orient Chemical Industry Co., Ltd.) are preferable from the viewpoint of improving the viscosity of the toner raw material composition and improving the dispersibility of the colorant.
サリチル酸化合物の金属錯体の含有量は、結着樹脂100重量部に対して、トナー原料組成物の粘度を向上させ、着色剤の分散性を向上させる観点から、0.3〜6重量部が好ましく、0.5〜5重量部がより好ましく、1〜4重量部がさらに好ましい。 The content of the metal complex of the salicylic acid compound is preferably 0.3 to 6 parts by weight from the viewpoint of improving the viscosity of the toner raw material composition and improving the dispersibility of the colorant with respect to 100 parts by weight of the binder resin. -5 parts by weight is more preferable, and 1-4 parts by weight is more preferable.
さらに、本発明の効果が損なわれない程度に適宜、他の荷電制御剤を併用してもよい。 Furthermore, other charge control agents may be used in combination as appropriate so long as the effects of the present invention are not impaired.
他の荷電制御剤としては、具体的には、含金属アゾ染料、例えば「バリファーストブラック3804」、「ボントロンS-31」(以上、オリエント化学工業社製)、「T-77」(保土谷化学工業社製)、「ボントロンS-32」、「ボントロンS-34」、「ボントロンS-36」(以上、オリエント化学工業社製)、「アイゼンスピロンブラックTRH」(保土谷化学工業社製)等；銅フタロシアニン染料；ニトロイミダゾール誘導体；ベンジル酸化合物のホウ素錯体、例えば、「LR-147」(日本カーリット社製)等が挙げられる。 As other charge control agents, specifically, metal-containing azo dyes such as “Varifast Black 3804”, “Bontron S-31” (above, manufactured by Orient Chemical Industries), “T-77” (Hodogaya) Chemical Industry Co., Ltd.), Bontron S-32, Bontron S-34, Bontron S-36 (above, Orient Chemical Co., Ltd.), Eisenspiron Black TRH (Hodogaya Chemical Co., Ltd.) Copper phthalocyanine dyes; nitroimidazole derivatives; boron complexes of benzylic acid compounds such as “LR-147” (manufactured by Nippon Carlit).
荷電制御剤の含有量は、結着樹脂100重量部に対して、トナーへの帯電安定性を向上させる観点から、0.3〜6重量部が好ましく、0.5〜5重量部がより好ましく、1〜4重量部がさらに好ましい。 The content of the charge control agent is preferably 0.3 to 6 parts by weight, more preferably 0.5 to 5 parts by weight, and more preferably 1 to 4 from the viewpoint of improving the charging stability to the toner with respect to 100 parts by weight of the binder resin. Part by weight is more preferred.
荷電制御剤中、サリチル酸化合物の金属錯体の含有量は、トナー原料組成物の粘度を向上させ、着色剤の分散性を向上させる観点から、50重量％以上が好ましく、70重量％以上がより好ましく、90重量％以上がさらに好ましく、95重量％以上がよりさらに好ましい。 In the charge control agent, the content of the metal complex of the salicylic acid compound is preferably 50% by weight or more, more preferably 70% by weight or more from the viewpoint of improving the viscosity of the toner raw material composition and improving the dispersibility of the colorant. 90% by weight or more is more preferable, and 95% by weight or more is more preferable.
本発明のトナーのワックスの融点は、トナー原料組成物の粘度を向上させ、着色剤の分散性を向上させる観点、トナーの低温定着性を向上させる観点から、120℃以下であり、100℃以下が好ましく、90℃以下がより好ましい。また、トナーの保存安定性を向上させる観点、感光体へのフィルミングを抑制する観点、キャリアのトナースペントを抑制する観点から、50℃以上であり、60℃以上が好ましく、70℃以上がより好ましい。すなわち、これらの観点を総合すると、ワックスの融点は、50〜120℃であり、60〜100℃が好ましく、70〜90℃がより好ましい。 The melting point of the wax of the toner of the present invention is 120 ° C. or less from the viewpoint of improving the viscosity of the toner raw material composition and improving the dispersibility of the colorant, and improving the low-temperature fixability of the toner. Is preferable, and 90 ° C. or lower is more preferable. Further, from the viewpoint of improving the storage stability of the toner, from the viewpoint of suppressing filming on the photoreceptor, and from the viewpoint of suppressing the toner spent on the carrier, it is 50 ° C or higher, preferably 60 ° C or higher, and more preferably 70 ° C or higher. preferable. That is, taking these viewpoints together, the melting point of the wax is 50 to 120 ° C, preferably 60 to 100 ° C, more preferably 70 to 90 ° C.
ワックスとしては、低分子量ポリプロピレン、低分子量ポリエチレン、低分子量ポリプロピレンポリエチレン共重合体、マイクロクリスタリンワックス、パラフィンワックス、フィッシャートロプシュワックス等の脂肪族炭化水素系ワックス及びそれらの酸化物、カルナウバワックス、モンタンワックス、サゾールワックス及びそれらの脱酸ワックス、脂肪酸エステルワックス等のエステル系ワックス、脂肪酸アミド類、脂肪酸類、高級アルコール類、脂肪酸金属塩等が挙げられる。これらのなかでは、トナー原料組成物の粘度を向上させ、着色剤の分散性を向上させる観点からカルナウバワックスが好ましい。ワックスは単独で、又は2種以上を混合して含有されていてもよい。 Examples of the wax include aliphatic hydrocarbon waxes such as low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polypropylene polyethylene copolymer, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax, and oxides thereof, carnauba wax, and montan wax. And ester waxes such as sazol wax and their deoxidized waxes and fatty acid ester waxes, fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts and the like. Among these, carnauba wax is preferable from the viewpoint of improving the viscosity of the toner raw material composition and improving the dispersibility of the colorant. Waxes may be contained alone or in admixture of two or more.
ワックスの含有量は、トナー原料組成物の粘度を向上させ、着色剤の分散性を向上させる観点、トナーの低温定着性を向上させる観点から、結着樹脂100重量部に対して、0.3重量部以上が好ましく、0.5重量部以上がより好ましく、1.0重量部以上がさらに好ましい。トナーの保存安定性を向上させる観点、感光体へのフィルミングを抑制する観点、キャリアのトナースペントを抑制する観点から、結着樹脂100重量部に対して、4.0重量部以下が好ましく、3.5重量部以下がより好ましく、3.0重量部以下がさらに好ましい。すなわち、これらの観点を総合すると、ワックスの含有量は、結着樹脂100重量部に対して、0.3〜4.0重量部が好ましく、0.5〜3.5重量部がより好ましく、1.0〜3.0重量部がさらに好ましい。 The content of the wax is 0.3 parts by weight with respect to 100 parts by weight of the binder resin from the viewpoint of improving the viscosity of the toner raw material composition, improving the dispersibility of the colorant, and improving the low-temperature fixability of the toner. The above is preferable, 0.5 part by weight or more is more preferable, and 1.0 part by weight or more is further preferable. From the viewpoint of improving the storage stability of the toner, from the viewpoint of suppressing filming on the photoreceptor, and from the viewpoint of suppressing the toner spent of the carrier, 4.0 parts by weight or less is preferable with respect to 100 parts by weight of the binder resin, and 3.5 parts by weight. Part or less is more preferable, and 3.0 parts by weight or less is more preferable. That is, taking these viewpoints together, the content of the wax is preferably 0.3 to 4.0 parts by weight, more preferably 0.5 to 3.5 parts by weight, and even more preferably 1.0 to 3.0 parts by weight with respect to 100 parts by weight of the binder resin. .
本発明のトナーは、さらに、磁性粉、流動性向上剤、導電性調整剤、体質顔料、繊維状物質等の補強充填剤、酸化防止剤、老化防止剤、クリーニング性向上剤等の添加剤を適宜含有していてもよい。 The toner of the present invention further includes additives such as magnetic powder, fluidity improver, conductivity modifier, extender pigment, fibrous filler and other reinforcing fillers, antioxidants, anti-aging agents, and cleaning improvers. You may contain suitably.
本発明のトナーは、溶融混練法、乳化転相法、重合法等の従来より公知のいずれの方法により得られたトナーであってもよいが、生産性や着色剤の分散性の観点から、溶融混練法による粉砕トナーが好ましい。溶融混練法による粉砕トナーの場合、例えば、結着樹脂、着色剤、荷電制御剤、ワックス等の原料をヘンシェルミキサー等の混合機で均一に混合した後、密閉式ニーダー、１軸もしくは２軸の押出機、オープンロール型混練機等で溶融混練し、冷却、粉砕、分級して製造することができる。一方、トナーの小粒径化の観点からは、重合法によるトナーが好ましい。 The toner of the present invention may be a toner obtained by any conventionally known method such as a melt-kneading method, an emulsion phase inversion method, or a polymerization method, but from the viewpoint of productivity and dispersibility of the colorant, A pulverized toner obtained by melt kneading is preferred. In the case of the pulverized toner by the melt-kneading method, for example, a raw material such as a binder resin, a colorant, a charge control agent, and wax is uniformly mixed with a mixer such as a Henschel mixer, and then a hermetically sealed kneader, uniaxial or biaxial It can be produced by melt-kneading with an extruder, an open roll kneader or the like, cooling, pulverizing and classifying. On the other hand, from the viewpoint of reducing the particle size of the toner, a toner by a polymerization method is preferable.
本発明のトナーの体積中位粒径(Ｄ50)は、彩度、現像性を向上させる観点から、3〜15μｍが好ましく、4〜10μmがより好ましい。なお、本明細書において、体積中位粒径(Ｄ50)とは、体積分率で計算した累積体積頻度が粒径の小さい方から計算して50％になる粒径を意味する。 The volume median particle size (D 50 ) of the toner of the present invention is preferably from 3 to 15 μm, more preferably from 4 to 10 μm, from the viewpoint of improving saturation and developability. In the present specification, the volume-median particle size (D 50 ) means a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% when calculated from the smaller particle size.
本発明のトナーには、帯電性や流動性、転写性を向上させるために、無機微粒子を外添剤として用いるのが好ましい。具体的には、シリカ、アルミナ、チタニア、ジルコニア、酸化錫、及び酸化亜鉛からなる群から選ばれる１種以上が好ましく挙げられ、これらの中では、シリカが好ましく、埋め込み防止の観点から、比重の小さいシリカが含有されているのがより好ましい。 In the toner of the present invention, inorganic fine particles are preferably used as an external additive in order to improve chargeability, fluidity, and transferability. Specifically, at least one selected from the group consisting of silica, alumina, titania, zirconia, tin oxide, and zinc oxide is preferable. Among these, silica is preferable, and from the viewpoint of preventing embedding, the specific gravity is More preferably, small silica is contained.
シリカは、トナーの転写性の観点から、疎水化処理された疎水性シリカであるのが好ましい。 Silica is preferably hydrophobic silica that has been subjected to a hydrophobic treatment, from the viewpoint of toner transferability.
外添剤の平均粒径は、転写性向上及び脱離防止、トナー凝集防止の観点から、10〜100nmが好ましく、平均粒径の異なる2種以上の外添剤を併用して用いてもよい。 The average particle diameter of the external additive is preferably 10 to 100 nm from the viewpoint of improving transferability, preventing detachment, and preventing toner aggregation, and two or more external additives having different average particle diameters may be used in combination. .
2種の外添剤を併用する場合、流動性付与と埋め込み防止の観点から、平均粒径10nm以上30nm未満の外添剤(小外添剤)と平均粒径30〜100nmの外添剤(大外添剤)を併用するのが好ましい。小外添剤と大外添剤の重量比(小外添剤／大外添剤)は、1/10〜10/1が好ましく、1/5〜5/1より好ましい。 When two types of external additives are used in combination, from the viewpoint of imparting fluidity and preventing embedding, an external additive (small external additive) having an average particle size of 10 nm or more and less than 30 nm and an external additive having an average particle size of 30 to 100 nm ( A large external additive) is preferably used in combination. The weight ratio of the small external additive and the large external additive (small external additive / large external additive) is preferably 1/110 to 10/1, more preferably 1/5 to 5/1.
外添剤の含有量は、外添剤で処理する前のトナー粒子100重量部に対して、好ましくは0.05〜5重量部であり、より好ましくは0.1〜3重量部であり、さらに好ましくは0.3〜3重量部である。 The content of the external additive is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, and still more preferably 0.3 to 100 parts by weight of toner particles before being processed with the external additive. ~ 3 parts by weight.
本発明のトナーの軟化点は、トナーの耐刷時の耐久性を向上させる観点から、90℃以上が好ましく、95℃以上がより好ましく、100℃以上がさらに好ましい。また、トナーの低温定着性を向上させる観点から、120℃以下が好ましく、115℃以下がより好ましく、110℃以下がさらに好ましい。すなわち、これらの観点を総合すると、90〜120℃が好ましく、より好ましくは95〜115℃、さらに好ましくは100〜110℃である。 The softening point of the toner of the present invention is preferably 90 ° C. or higher, more preferably 95 ° C. or higher, and further preferably 100 ° C. or higher from the viewpoint of improving the durability of the toner during printing durability. Further, from the viewpoint of improving the low-temperature fixability of the toner, 120 ° C. or lower is preferable, 115 ° C. or lower is more preferable, and 110 ° C. or lower is further preferable. That is, when these viewpoints are put together, 90-120 degreeC is preferable, More preferably, it is 95-115 degreeC, More preferably, it is 100-110 degreeC.
本発明のトナーのガラス転移点は、トナーの耐刷時の耐久性を向上させる観点から、50℃以上が好ましく、55℃以上がより好ましい。また、トナーの低温定着性を向上させる観点から、85℃以下が好ましく、80℃以下がより好ましい。すなわち、これらの観点を総合すると、50〜85℃が好ましく、55〜80℃がより好ましい。 The glass transition point of the toner of the present invention is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, from the viewpoint of improving the durability of the toner during printing durability. Further, from the viewpoint of improving the low-temperature fixability of the toner, 85 ° C. or lower is preferable, and 80 ° C. or lower is more preferable. That is, when these viewpoints are put together, 50-85 degreeC is preferable and 55-80 degreeC is more preferable.
また、本発明のトナーの現像方式は特に限定されないが、彩度に優れることから、非接触定着方式の画像形成装置を用いた画像形成方法にも好適に用いることができ、線速が800mm/sec以上、好ましくは1000〜3000mm/secの高速の非接触定着方式の画像形成装置にも好適に用いることができる。 Further, the developing method of the toner of the present invention is not particularly limited, but since it is excellent in saturation, it can be suitably used for an image forming method using a non-contact fixing type image forming apparatus, and the linear velocity is 800 mm / It can also be suitably used for a high-speed non-contact fixing type image forming apparatus of sec or more, preferably 1000 to 3000 mm / sec.
本発明のトナーは、そのまま一成分現像用トナーとして、又はキャリアと混合して二成分現像剤として用いることができるが、キャリアとの攪拌条件下で特に安定した帯電性が得られる観点から、非磁性現像方式、特に非磁性二成分現像方式の画像形成装置に好適に用いられる。 The toner of the present invention can be used as a one-component developing toner as it is or as a two-component developer by mixing with a carrier. However, from the viewpoint of obtaining a particularly stable chargeability under stirring conditions with a carrier, It is suitably used for an image forming apparatus of a magnetic development method, particularly a non-magnetic two-component development method.
従って、本発明のトナーは、非磁性二成分現像方式、かつ非接触現像方式の高速の画像形成装置を用いた画像形成方法にも好適に用いることができる。 Therefore, the toner of the present invention can be suitably used in an image forming method using a high-speed image forming apparatus of a non-magnetic two-component developing method and a non-contact developing method.
本発明において、キャリアとしては、画像特性の観点から、磁気ブラシのあたりが弱くなる飽和磁化の低いキャリアが好ましい。キャリアの飽和磁化は、40〜100Am2/kgが好ましく、50〜90Am2/kgがより好ましい。飽和磁化は、磁気ブラシの固さを調節し、階調再現性を保持する観点から、100Am2/kg以下が好ましく、キャリア付着やトナー飛散を防止する観点から、40Am2/kg以上が好ましい。 In the present invention, from the viewpoint of image characteristics, the carrier is preferably a carrier with low saturation magnetization that weakens the area around the magnetic brush. Saturation magnetization of the carrier is preferably 40~100Am 2 / kg, 50~90Am 2 / kg is more preferable. The saturation magnetization is preferably 100 Am 2 / kg or less from the viewpoint of adjusting the hardness of the magnetic brush and maintaining gradation reproducibility, and preferably 40 Am 2 / kg or more from the viewpoint of preventing carrier adhesion and toner scattering.
キャリアのコア材としては、公知の材料からなるものを特に限定することなく用いることができ、例えば、鉄、コバルト、ニッケル等の強磁性金属、マグネタイト、ヘマタイト、フェライト、銅-亜鉛-マグネシウムフェライト、マンガンフェライト、マグネシウムフェライト等の合金や化合物、ガラスビーズ等が挙げられ、これらの中では、帯電性の観点から、マグネタイト、フェライト、銅-亜鉛-マグネシウムフェライト及びマンガンフェライトが好ましい。 As the core material of the carrier, those made of known materials can be used without particular limitation, for example, ferromagnetic metals such as iron, cobalt, nickel, magnetite, hematite, ferrite, copper-zinc-magnesium ferrite, Examples thereof include alloys and compounds such as manganese ferrite and magnesium ferrite, and glass beads. Among these, magnetite, ferrite, copper-zinc-magnesium ferrite, and manganese ferrite are preferable from the viewpoint of chargeability.
キャリアの表面は、スペント防止の観点から樹脂で被覆されていてもよい。キャリア表面を被覆する樹脂としては、トナー材料により異なるが、例えばポリテトラフルオロエチレン、モノクロロトリフルオロエチレン重合体、ポリフッ化ビニリデン等のフッ素樹脂、ポリジメチルシロキサン等のシリコーン樹脂、ポリエステル、スチレン系樹脂、アクリル系樹脂、ポリアミド、ポリビニルブチラール、アミノアクリレート樹脂等が挙げられ、これらは単独であるいは２種以上を併用して用いることができるが、樹脂によるコア材の被覆方法は、例えば、樹脂等の被覆材を溶剤中に溶解もしくは懸濁させて塗布し、コア材に付着させる方法、単に粉体で混合する方法等、特に限定されない。 The surface of the carrier may be coated with a resin from the viewpoint of preventing spent. The resin that coats the carrier surface varies depending on the toner material. For example, fluororesin such as polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resin such as polydimethylsiloxane, polyester, styrenic resin, Acrylic resin, polyamide, polyvinyl butyral, amino acrylate resin, etc. can be mentioned, and these can be used alone or in combination of two or more. There is no particular limitation such as a method in which the material is dissolved or suspended in a solvent and applied to the core material, or a method of simply mixing with powder.
トナーとキャリアとを混合して得られる二成分現像剤において、トナーの含有量は、現像剤の流動性及びカブリやダスト低減の観点から、キャリア100重量部に対して、0.5〜10重量部が好ましく、2〜8重量部がより好ましい。 In the two-component developer obtained by mixing the toner and the carrier, the toner content is 0.5 to 10 parts by weight with respect to 100 parts by weight of the carrier from the viewpoint of developer fluidity and reduction of fog and dust. Preferably, 2 to 8 parts by weight is more preferable.
〔樹脂及びトナーの軟化点(Tm)〕
フローテスター（島津製作所、CFT-500D）を用い、1gの試料を昇温速度6℃/分で加熱しながら、プランジャーにより1.96MPaの荷重を与え、直径1mm、長さ1mmのノズルから押出す。温度に対し、フローテスターのプランジャー降下量をプロットし、試料の半量が流出した温度を軟化点とする。
[Softening point of resin and toner (Tm)]
Using a flow tester (Shimadzu Corporation, CFT-500D), a 1 g sample was heated at a heating rate of 6 ° C / min, and a 1.96 MPa load was applied by a plunger and extruded from a nozzle with a diameter of 1 mm and a length of 1 mm. . The amount of plunger drop of the flow tester is plotted against the temperature, and the temperature at which half of the sample flows out is taken as the softening point.
〔樹脂及びトナーのガラス転移点(Tg)〕
示差走査熱量計(セイコー電子工業社製、DSC210)を用いて200℃まで昇温し、その温度から降温速度10℃/分で0℃まで冷却したサンプルを昇温速度10℃/分で昇温し、吸熱の最高ピーク温度以下のベースラインの延長線とピークの立ち上がり部分からピークの頂点までの最大傾斜を示す接線との交点の温度とする。
[Glass transition point (Tg) of resin and toner]
Using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), the temperature was increased to 200 ° C, and the sample was cooled to 0 ° C at a temperature decrease rate of 10 ° C / min. The temperature at the intersection of the extended line of the baseline below the maximum peak temperature of endotherm and the tangent line indicating the maximum slope from the peak rising portion to the peak apex.
〔樹脂の酸価〕
JIS K0070の方法により測定する。但し、測定溶媒のみJIS K0070の規定のエタノールとエーテルの混合溶媒から、アセトンとトルエンの混合溶媒(アセトン：トルエン＝1:1(容量比))に変更する。
[Acid value of the resin]
Measured by the method of JIS K0070. However, only the measurement solvent is changed from the mixed solvent of ethanol and ether specified in JIS K0070 to the mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).
〔ワックスの融点〕
示差走査熱量計（セイコー電子工業社製、DSC210）を用いて200℃まで昇温し、その温度から降温速度10℃／分で0℃まで冷却したサンプルを昇温速度10℃／分で昇温し、融解熱の最大ピーク温度を融点とする。
[Melting point of wax]
Using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), the temperature was raised to 200 ° C, and the sample was cooled to 0 ° C at a temperature drop rate of 10 ° C / min. The maximum peak temperature of heat of fusion is taken as the melting point.
〔トナーの体積中位粒径（Ｄ50）〕
測定機：コールターマルチサイザーII（ベックマンコールター社製）
アパチャー径：50μm
解析ソフト：コールターマルチサイザーアキュコンプ バージョン 1.19（ベックマンコールター社製）
電解液：アイソトンII（ベックマンコールター社製）
分散液：エマルゲン109Ｐ（花王社製、ポリオキシエチレンラウリルエーテル、HLB：13.6）を5重量％の濃度となるよう前記電解液に溶解させて分散液を得る。
分散条件：前記分散液5mlに測定試料10mgを添加し、超音波分散機にて1分間分散させ、その後、電解液25mlを添加し、さらに、超音波分散機にて1分間分散させて、試料分散液を調製する。
測定条件：前記試料分散液を前記電解液100mlに加えることにより、3万個の粒子の粒径を20秒で測定できる濃度に調整した後、3万個の粒子を測定し、その粒度分布から体積中位粒径（Ｄ50）を求める。
[Volume-median particle diameter of toner (D 50 )]
Measuring machine: Coulter Multisizer II (Beckman Coulter, Inc.)
Aperture diameter: 50μm
Analysis software: Coulter Multisizer AccuComp version 1.19 (Beckman Coulter)
Electrolyte: Isoton II (Beckman Coulter, Inc.)
Dispersion: Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB: 13.6) is dissolved in the electrolytic solution to a concentration of 5% by weight to obtain a dispersion.
Dispersion conditions: 10 mg of a measurement sample is added to 5 ml of the dispersion, and dispersed for 1 minute with an ultrasonic disperser, then 25 ml of an electrolyte is added, and further dispersed for 1 minute with an ultrasonic disperser. Prepare a dispersion.
Measurement conditions: After adjusting the particle size of 30,000 particles to a concentration that can be measured in 20 seconds by adding the sample dispersion to 100 ml of the electrolyte solution, 30,000 particles are measured, Determine the volume median particle size (D 50 ).
〔外添剤の平均粒子径〕
平均粒子径とは平均一次粒子径を指し、走査型電子顕微鏡(SEM)写真から500個の粒子の粒径(長径と短径の平均値)を測定し、それらの平均値を平均粒子径とする。
[Average particle diameter of external additive]
The average particle size refers to the average primary particle size, and the particle size (average value of major axis and minor axis) of 500 particles is measured from a scanning electron microscope (SEM) photograph, and the average value is referred to as the average particle size. To do.
〔キャリアの飽和磁化〕
(1) 外径7mm(内径6mm)、高さ5mmの蓋付プラスティックケースにキャリアをタッピングしながら充填し、プラスティックケースの重量とキャリアを充填したプラスティックケースの重量の差から、キャリアの質量を求める。
(2) 理研電子(株)の磁気特性測定装置「BHV-50H」(V.S.MAGNETOMETER)のサンプルホルダーにキャリアを充填したプラスティックケースをセットし、バイブレーション機能を使用して、プラスティックケースを加振しながら、79.6kA/mの磁場を印加して飽和磁化を測定する。得られた値は充填されたキャリアの質量を考慮し、単位質量当たりの飽和磁化に換算する。
[Carrier saturation magnetization]
(1) Fill a plastic case with a lid of 7 mm outer diameter (6 mm inner diameter) and 5 mm height while tapping the carrier, and calculate the mass of the carrier from the difference between the weight of the plastic case and the weight of the plastic case filled with the carrier. .
(2) Set the plastic case filled with the carrier in the sample holder of the magnetic property measuring device `` BHV-50H '' (VSMAGNETOMETER) of RIKEN ELECTRONICS CO., LTD., While vibrating the plastic case using the vibration function, Saturation magnetization is measured by applying a magnetic field of 79.6 kA / m. The obtained value is converted into saturation magnetization per unit mass in consideration of the mass of the filled carrier.
樹脂製造例１〔樹脂Ａ、Ｃ〕
表１に示す原料モノマーと、エステル化触媒(酸化ジブチル錫)19.5gを、窒素導入管、脱水管、攪拌器及び熱電対を装備した5リットル容の四つ口フラスコに入れ、窒素雰囲気下、230℃にて、反応率が90％に達するまで反応させた後、さらに8.3kPaにて1時間反応させて、樹脂Ａ、Ｃを得た。得られた樹脂の樹脂物性を表１に示す。なお、本発明において反応率とは、反応水量(mol)/理論生成水量(mol)×100の値をいう。
Resin production example 1 [resins A and C]
The raw material monomer shown in Table 1 and 19.5 g of an esterification catalyst (dibutyltin oxide) were placed in a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple. After reacting at 230 ° C. until the reaction rate reached 90%, the reaction was further continued at 8.3 kPa for 1 hour to obtain Resins A and C. Table 1 shows the resin physical properties of the obtained resin. In the present invention, the reaction rate means a value of reaction water amount (mol) / theoretical product water amount (mol) × 100.
樹脂製造例２〔樹脂Ｂ〕
表１に示す原料モノマーと、エステル化触媒(酸化ジブチル錫)19.5g、及び重合禁止剤（ハイドロキノン）2gを、窒素導入管、脱水管、攪拌器及び熱電対を装備した5リットル容の四つ口フラスコに入れ、窒素雰囲気下、230℃にて、反応率が90％に達するまで反応させた後、さらに8.3kPaにて1時間反応させて、樹脂Ｂを得た。得られた樹脂Ｂの樹脂物性を表１に示す。
Resin Production Example 2 [Resin B]
Raw material monomers shown in Table 1, 19.5 g of esterification catalyst (dibutyltin oxide), and 2 g of polymerization inhibitor (hydroquinone), 4 in 5 liters equipped with nitrogen introduction tube, dehydration tube, stirrer and thermocouple The mixture was placed in a neck flask, reacted at 230 ° C. in a nitrogen atmosphere until the reaction rate reached 90%, and further reacted at 8.3 kPa for 1 hour to obtain Resin B. Table 1 shows the resin physical properties of the obtained resin B.
樹脂製造例３〔樹脂Ｄ〕
表１に示す原料モノマーと、エステル化触媒(酸化ジブチル錫)19.5gとエステル化助触媒（没食子酸）1.2gを、窒素導入管、脱水管、攪拌器及び熱電対を装備した5リットル容の四つ口フラスコに入れ、窒素雰囲気下、230℃にて、反応率が90％に達するまで反応させた後、さらに8.3kPaにて1時間反応させて、樹脂Ｄを得た。得られた樹脂Ｄの樹脂物性を表１に示す。
Resin Production Example 3 [Resin D]
Raw material monomers shown in Table 1, 19.5 g of esterification catalyst (dibutyltin oxide) and 1.2 g of esterification cocatalyst (gallic acid), 5 liter capacity equipped with nitrogen introduction tube, dehydration tube, stirrer and thermocouple The mixture was placed in a four-necked flask and reacted at 230 ° C. in a nitrogen atmosphere until the reaction rate reached 90%, and further reacted at 8.3 kPa for 1 hour to obtain Resin D. Table 1 shows the resin physical properties of the obtained resin D.
樹脂製造例４〔樹脂Ｅ〕
キシレン2123ｇを窒素導入管、脱水管、攪拌器及び熱電対を装備した10リットル容の四つ口フラスコに入れ、135℃に昇温した。さらに表１に示す原料モノマーと、ラジカル開始剤パーブチルＥ(日油社製)15gを予め混合した溶液を、1.5時間かけてキシレン中に滴下した。滴下終了後、135℃にて、2時間、溶液重合を行った。その後、160℃まで昇温し、160℃にて1時間還流させた。さらに、200℃に昇温し、200℃にて、常圧下で1時間、さらに減圧下(8.3kPa) で2時間、キシレンを留去し、樹脂Ｅを得た。得られた樹脂Ｅの樹脂物性を表１に示す。
Resin Production Example 4 [Resin E]
2123 g of xylene was placed in a 10-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, and the temperature was raised to 135 ° C. Further, a solution prepared by previously mixing raw material monomers shown in Table 1 and 15 g of a radical initiator perbutyl E (manufactured by NOF Corporation) was dropped into xylene over 1.5 hours. After completion of the dropwise addition, solution polymerization was performed at 135 ° C. for 2 hours. Thereafter, the temperature was raised to 160 ° C. and refluxed at 160 ° C. for 1 hour. Further, the temperature was raised to 200 ° C., and xylene was distilled off at 200 ° C. under normal pressure for 1 hour and further under reduced pressure (8.3 kPa) for 2 hours to obtain Resin E. Table 1 shows the resin physical properties of the obtained resin E.
実施例１〜１０及び比較例１〜７
表２に示す結着樹脂100重量部、着色剤4重量部、荷電制御剤3重量部、ワックス2重量部を添加し、ヘンシェルミキサーにて180秒間混合した。得られた混合物を連続式二本オープンロール型混練機「ニーデックス」(三井鉱山(株)製)を用いて、以下の示す条件で溶融混練した。
Examples 1-10 and Comparative Examples 1-7
100 parts by weight of a binder resin shown in Table 2, 4 parts by weight of a colorant, 3 parts by weight of a charge control agent, and 2 parts by weight of wax were added and mixed for 180 seconds with a Henschel mixer. The obtained mixture was melt-kneaded under the following conditions using a continuous two-open roll type kneader “NIDEX” (manufactured by Mitsui Mining Co., Ltd.).
使用した連続式二本オープンロール型混練機は、ロール外径が0.14m、有効ロール長が0.8mのものであり、運転条件は、高回転側ロール(前ロール)の回転数が75r/min(周速度：32.97m/min)、低回転側ロール(後ロール)の回転数が35r/min(周速度：15.38m/min)、混練物供給口側端部のロール間隙が0.1mmであった。ロール内の加熱媒体温度及び冷却媒体温度は、高回転ロールの原料投入側の温度を100℃、混練物排出側の温度を85℃、低回転ロールの原料投入側の温度を35℃及び混練物排出側の温度を35℃に設定した。また、原料混合物の供給速度は10kg/hrであった。 The continuous two-open roll type kneader used has a roll outer diameter of 0.14 m and an effective roll length of 0.8 m, and the operating condition is that the rotation speed of the high rotation side roll (front roll) is 75 r / min. (Peripheral speed: 32.97 m / min), the rotation speed of the low-rotation side roll (rear roll) is 35 r / min (peripheral speed: 15.38 m / min), and the roll gap at the end of the kneaded product supply port is 0.1 mm. It was. The heating medium temperature and cooling medium temperature in the roll are 100 ° C on the raw material input side of the high-rotation roll, 85 ° C on the kneaded product discharge side, 35 ° C on the low-rotation roll raw material input side, and the kneaded material The temperature on the discharge side was set to 35 ° C. The feed rate of the raw material mixture was 10 kg / hr.
得られた溶融混練物を冷却後、ハンマーミルを用いて1mm程度に粗粉砕した。得られた粗粉砕物を流動層式ジェットミル「AFG-400」(アルピネ社製)で微粉砕し、ローター式分級機「TTSP」(アルピネ社製)で分級して、体積中位粒径(Ｄ50)が7.5μmの負帯電性のトナー母粒子を得た。 The obtained melt-kneaded product was cooled and then roughly pulverized to about 1 mm using a hammer mill. The resulting coarsely pulverized product is finely pulverized with a fluidized bed jet mill `` AFG-400 '' (Alpine), and classified with a rotor classifier `` TTSP '' (Alpine). Negatively charged toner base particles having a D 50 ) of 7.5 μm were obtained.
得られたトナー母粒子100重量部(10kg)と、疎水性シリカ「R-972」(日本アエロジル社製、平均粒子径：16nm)0.9重量部(90g)と疎水性シリカ「NAX-50」(日本アエロジル社製、平均粒子径：30nm)1.0重量部(100g)とを75Lヘンシェルミキサー(三井鉱山社製)で、1500r/minで3分間混合して、トナーを得た。なお、ヘンシェルミキサーの上羽根はST型で下羽根はA0型である。 The obtained toner base particles 100 parts by weight (10 kg), hydrophobic silica “R-972” (manufactured by Nippon Aerosil Co., Ltd., average particle size: 16 nm) 0.9 parts by weight (90 g) and hydrophobic silica “NAX-50” ( Toner was obtained by mixing 1.0 part by weight (100 g) manufactured by Nippon Aerosil Co., Ltd., with an average particle size of 30 nm, with a 75 L Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) at 1500 r / min for 3 minutes. The upper blade of the Henschel mixer is ST type and the lower blade is A0 type.
表２に記載のトナー原料は下記の通り。 The toner raw materials listed in Table 2 are as follows.
PR185：Novoperm Carmine HF4C-JP(クラリアント社製)
PR122：スーパーマゼンタＲ(DIC社製)
PR57:1 ：ECR-101(DIC社製)
PR185: Novoperm Carmine HF4C-JP (manufactured by Clariant)
PR122: Super Magenta R (manufactured by DIC)
PR57: 1: ECR-101 (manufactured by DIC)
荷電制御剤ａ：サリチル酸化合物のアルミニウム錯体(ボントロン E-84；オリヱント化学工業社製)
荷電制御剤ｂ：サリチル酸化合物のジルコニウム錯体(TN-105；保土ヶ谷化学社製)
荷電制御剤ｃ：ベンジル酸化合物のホウ素錯体(LR147；日本カーリット社製)
Charge control agent a: Aluminum complex of salicylic acid compound (Bontron E-84; manufactured by Orient Chemical Co., Ltd.)
Charge control agent b: Zirconium complex of salicylic acid compound (TN-105; manufactured by Hodogaya Chemical Co., Ltd.)
Charge control agent c: Boron complex of benzylic acid compound (LR147; manufactured by Nippon Carlit)
ワックスα：カルナウバワックス(カルナバワックスC1、融点83℃；加藤洋行社製)
ワックスβ：エステルワックス(WEP-8、融点80℃；日油社製)
ワックスγ：フィッシャートロプシュワックス(SP-105、融点105℃；サゾール社製)
ワックスδ：ポリプロピレンーポリエチレンワックス(NP-105、融点151℃；日油社製)
Wax α: Carnauba wax (Carnauba wax C1, melting point 83 ° C .; manufactured by Kato Yoko)
Wax β: ester wax (WEP-8, melting point 80 ° C .; manufactured by NOF Corporation)
Wax γ: Fischer-Tropsch wax (SP-105, melting point 105 ° C; manufactured by Sasol)
Wax δ: Polypropylene-polyethylene wax (NP-105, melting point 151 ° C .; manufactured by NOF Corporation)
試験例１〔着色剤の分散性〕
トナーを、ホットプレート上で、180℃で10秒間加熱して溶融させた後、デジタルマイクロスコープ(キーエンス社製)を用いトナーの溶融写真を撮影した。写真映像を2値化変換後、視野中にある着色剤の面積分率(％)の測定を行った。値が小さいほど分散性が優れる。結果を表２に示す。
Test Example 1 [Dispersibility of colorant]
The toner was melted by heating at 180 ° C. for 10 seconds on a hot plate, and then a fused photograph of the toner was taken using a digital microscope (manufactured by Keyence Corporation). After binarizing the photographic image, the area fraction (%) of the colorant in the field of view was measured. The smaller the value, the better the dispersibility. The results are shown in Table 2.
試験例２〔彩度〕
得られたトナー6重量部と、フェライトキャリア「KK01-C35」(オセ・プリンティングシステムズ社製、体積平均粒子径：60μm、飽和磁化：68Am2/kg)94重量部とを混合し、二成分現像剤を得た。得られた二成分現像剤を非接触現像・非接触定着方式の画像形成装置「Vario stream 9000」(オセ・プリンティングシステムズ社製)に実装し、トナー濃度6％、印字率9％、線速1000mm/secで2時間耐刷した。色相を色彩計「GretagMacbeth Spectroeye」(グレタグ社製)で画像印字部を10点測定し、その平均値を彩度Ｃ*とし算出し、彩度を得た。値が大きいほど、彩度に優れる。結果を表２に示す。
Test Example 2 [Saturation]
6 parts by weight of the obtained toner and 94 parts by weight of ferrite carrier “KK01-C35” (Oce Printing Systems, volume average particle size: 60 μm, saturation magnetization: 68 Am 2 / kg) are mixed, and two-component development An agent was obtained. The resulting two-component developer is mounted on a non-contact developing and non-contact fixing type image forming apparatus “Vario stream 9000” (manufactured by Ose Printing Systems), toner density 6%, printing rate 9%, linear speed 1000 mm Printed for 2 hours at / sec. The hue was measured at 10 points on the image printing portion with a color meter “GretagMacbeth Spectroeye” (manufactured by Gretag), and the average value was calculated as saturation C * to obtain saturation. The higher the value, the better the saturation. The results are shown in Table 2.
試験例３〔耐光性〕
非磁性一成分現像方式の画像形成装置「MICROLINE 3050」(沖データ社製)にトナーを実装し、トナー付着量が6.0g/m2になるように現像ロールの印加バイアスを調整した後、4cm×5cmのベタ画像をシャープ社製の厚紙「CopyBond SF-70NA」に印字した。定着機を通過する前にベタ画像を取り出し、未定着画像を得た。得られた未定着画像を、非接触定着方式の画像形成装置「Vario stream 9000」(オセ・プリンティングシステムズ社製)用の定着機を改造した外部定着機を使用し、線速1000mm/secで紙上の温度を150℃にて定着画像を得た。
Test Example 3 [Light resistance]
After mounting the toner on the non-magnetic one-component development type image forming device MICROLINE 3050 (Oki Data Co., Ltd.) and adjusting the bias applied to the developing roll so that the toner adhesion amount is 6.0 g / m 2 , 4 cm A solid image of × 5 cm was printed on Sharp's cardboard “CopyBond SF-70NA”. A solid image was taken out before passing through the fixing machine to obtain an unfixed image. The obtained non-fixed image is printed on paper at a linear speed of 1000 mm / sec using an external fixing machine modified from the fixing machine for the non-contact fixing type image forming device "Vario stream 9000" (manufactured by Ose Printing Systems). A fixed image was obtained at a temperature of 150 ° C.
得られた定着画像を下記条件のキセノンウェザーメーターにより耐光試験を行った。 The obtained fixed image was subjected to a light resistance test using a xenon weather meter under the following conditions.
・照射試験機：スガ試験機社製、SX75
・光源：キセノンランプ
・フィルター：内側＝石英フィルター、外側＝＃275
・パネル温度：50℃
・槽内湿度：35〜50%RH
・照射強度：50(W/m2)、300〜400(nm)での測定値
・積算照度：40000(kJ/m2)、300〜400(nm)での積算値
・ Irradiation tester: SX75, manufactured by Suga Test Instruments
Light source: Xenon lamp Filter: Inside = quartz filter, outside = # 275
・ Panel temperature: 50 ℃
-Humidity inside the tank: 35-50% RH
・ Irradiation intensity: Measured value at 50 (W / m 2 ), 300 to 400 (nm) ・ Integrated illuminance: Integrated value at 40000 (kJ / m 2 ), 300 to 400 (nm)
色彩計「GretagMacbeth Spectroeye」(グレタグ社製)を用い、下記式に基づいて色相変化量ΔＥab*を算出した。結果を表２に示す。色相変化量ΔＥab*が小さいほど、耐光性に優れる。 Using a color meter “GretagMacbeth Spectroeye” (manufactured by Gretag), the hue change amount ΔE ab * was calculated based on the following formula. The results are shown in Table 2. The smaller the hue change amount ΔE ab * is, the better the light resistance is.
色相変化量ΔＥab*＝［(Ｌ* 1−Ｌ* 2)2＋(ａ* 1−ａ* 2）2＋(ｂ* 1−ｂ* 2)2］1/2
Ｌ* 1、ａ* 1、ｂ* 1：照射前Ｌ*ａ*ｂ*値
Ｌ* 2、ａ* 2、ｂ* 2：照射後Ｌ*ａ*ｂ*値
Hue change amount ΔE ab * = [(L * 1 −L * 2 ) 2 + (a * 1 −a * 2 ) 2 + (b * 1 −b * 2 ) 2 ] 1/2
L * 1 , a * 1 , b * 1 : L * a * b * value before irradiation L * 2 , a * 2 , b * 2 : L * a * b * value after irradiation
以上の結果より、実施例１〜１０のトナーは、比較例１〜７のトナーと比べて、着色剤の分散性に優れ、彩度も良好であり、さらに耐光性にも優れていることが分かる。 From the above results, it can be seen that the toners of Examples 1 to 10 are superior in colorant dispersibility, saturation, and light resistance as compared with the toners of Comparative Examples 1 to 7. I understand.
本発明のマゼンタトナーは、電子写真法、静電記録法、静電印刷法等において形成される潜像の現像等に好適に用いられる。 The magenta toner of the present invention is suitably used for developing latent images formed in electrophotography, electrostatic recording, electrostatic printing, and the like.
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| JPH0282267A (en) * | 1988-09-19 | 1990-03-22 | Arakawa Chem Ind Co Ltd | Electrophotographic toner composition superior in low temperature fixability |
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| JP3623849B2 (en) * | 1996-04-10 | 2005-02-23 | 三菱レイヨン株式会社 | Polyester resin for toner |
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