JP4942542B2 - Method for producing toner for electrophotography - Google Patents
Method for producing toner for electrophotography Download PDFInfo
- Publication number
- JP4942542B2 JP4942542B2 JP2007116792A JP2007116792A JP4942542B2 JP 4942542 B2 JP4942542 B2 JP 4942542B2 JP 2007116792 A JP2007116792 A JP 2007116792A JP 2007116792 A JP2007116792 A JP 2007116792A JP 4942542 B2 JP4942542 B2 JP 4942542B2
- Authority
- JP
- Japan
- Prior art keywords
- toner
- resin
- particles
- weight
- dispersion
- 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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- 238000001035 drying Methods 0.000 claims description 60
- 239000006185 dispersion Substances 0.000 claims description 57
- 239000011230 binding agent Substances 0.000 claims description 40
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- 239000012298 atmosphere Substances 0.000 claims description 7
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 35
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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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 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 229940044197 ammonium sulfate Drugs 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
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- 239000002994 raw material Substances 0.000 description 4
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 239000003093 cationic surfactant Substances 0.000 description 3
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- 238000001816 cooling Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
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- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 3
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- DSEKYWAQQVUQTP-XEWMWGOFSA-N (2r,4r,4as,6as,6as,6br,8ar,12ar,14as,14bs)-2-hydroxy-4,4a,6a,6b,8a,11,11,14a-octamethyl-2,4,5,6,6a,7,8,9,10,12,12a,13,14,14b-tetradecahydro-1h-picen-3-one Chemical compound C([C@H]1[C@]2(C)CC[C@@]34C)C(C)(C)CC[C@]1(C)CC[C@]2(C)[C@H]4CC[C@@]1(C)[C@H]3C[C@@H](O)C(=O)[C@@H]1C DSEKYWAQQVUQTP-XEWMWGOFSA-N 0.000 description 2
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- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
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- 125000003342 alkenyl group Chemical group 0.000 description 2
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Images
Description
本発明は、電子写真法、静電記録法、静電印刷法などに用いられる電子写真用トナーの製造方法、及び該方法により得られる電子写真用トナーに関する。 The present invention relates to a method for producing an electrophotographic toner used in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and the like, and an electrophotographic toner obtained by the method.
電子写真用トナーの分野においては、重合法や乳化分散法などのケミカル法により得られる、いわゆるケミカルトナーが提案されている。このような方法においては、トナーの原材料をサブミクロンレベルに分散した後、それらの粒子をトナー粒径まで凝集・合一するといった工程を経るが、一般に、合一後、更に洗浄工程、固液分離工程、及び乾燥工程等を経て、トナー粒子となる。
従来、上記乾燥工程において用いる乾燥方法としては、真空乾燥法（例えば、特許文献１参照）、スプレードライ法（例えば、特許文献２）、気流乾燥法、流動乾燥法等が検討されていた。
In the field of electrophotographic toners, so-called chemical toners obtained by chemical methods such as polymerization methods and emulsion dispersion methods have been proposed. In such a method, after the toner raw materials are dispersed to a submicron level, the particles are aggregated and united to the toner particle diameter. Through the separation process and the drying process, the toner particles are obtained.
Conventionally, vacuum drying methods (see, for example, Patent Document 1), spray drying methods (for example, Patent Document 2), airflow drying methods, fluidized drying methods, and the like have been studied as drying methods used in the drying step.
しかしながら、真空乾燥法の場合、乾燥時間が長く生産性が十分でなく、また、含水ケーキ状態から乾燥を行うことからトナーの凝集体が多く発生するため、乾燥後に解砕や分級工程が必要となり作業が煩雑となる。また、スプレードライ法、気流乾燥法の場合は、乾燥時間が短く生産性に優れるが、熱風のみで水分を蒸発させるため、乾燥温度を非常に高く設定する必要があり、トナーの融着、離型剤成分の滲出等により保存性、定着性が悪化するなどの問題がある。更に流動乾燥法の場合は、真空乾燥より乾燥時間は若干短いが、同様の問題がある。
本発明は、トナーの凝集や熱による融着がなく、一次粒子を維持した乾燥が可能であり、その結果、解砕工程等を設ける必要がなく、生産性を大幅に改善することができ、更に得られるトナーの定着性を向上しうる電子写真用トナーの製造方法に関する。
However, in the case of the vacuum drying method, the drying time is long and the productivity is not sufficient, and since the toner is agglomerated because it is dried from the water-containing cake state, a crushing and classification process is required after drying. Work becomes complicated. In the case of the spray drying method and the airflow drying method, the drying time is short and the productivity is excellent.However, since the moisture is evaporated only by hot air, the drying temperature must be set very high, and the toner can be fused and separated. There are problems such as deterioration of preservability and fixability due to exudation of the mold component. Further, in the case of the fluidized drying method, the drying time is slightly shorter than that of vacuum drying, but there is a similar problem.
The present invention is free from toner aggregation and heat fusion, and can be dried while maintaining primary particles. As a result, it is not necessary to provide a crushing step and the like, and the productivity can be greatly improved. Furthermore, the present invention relates to a method for producing an electrophotographic toner capable of improving the fixability of the obtained toner.
本発明は、（Ａ）水系媒体中で結着樹脂を含有するトナー粒子の分散液を得る工程、及び（Ｂ）工程（Ａ）で得られたトナー粒子の分散液をパルス燃焼による衝撃波の雰囲気中に噴霧して乾燥する工程、を有する電子写真用トナーの製造方法、及び該製造方法により得られる電子写真用トナーに関する。 The present invention includes (A) a step of obtaining a dispersion of toner particles containing a binder resin in an aqueous medium, and (B) an atmosphere of shock waves by pulse combustion using the dispersion of toner particles obtained in step (A). The present invention relates to a method for producing an electrophotographic toner having a step of spraying and drying therein, and an electrophotographic toner obtained by the production method.
本発明によれば、トナー粒子の凝集や熱による融着がなく、一次粒子を維持した乾燥が可能であり、その結果、解砕工程等を設ける必要がなく、生産性を大幅に改善することができ、更に得られるトナーの低温定着性を向上しうる電子写真用トナーの製造方法、及び該製造方法により得られる電子写真用トナーを提供することができる。 According to the present invention, there is no aggregation of toner particles or fusion by heat, and drying while maintaining primary particles is possible. As a result, it is not necessary to provide a crushing step or the like, and the productivity is greatly improved. In addition, it is possible to provide a method for producing an electrophotographic toner capable of improving the low-temperature fixability of the obtained toner, and an electrophotographic toner obtained by the production method.
［電子写真用トナーの製造方法］
本発明のトナーの製造方法は、（Ａ）水系媒体中で結着樹脂を含有するトナー粒子の分散液を得る工程、及び（Ｂ）工程（Ａ）で得られたトナー粒子の分散液をパルス燃焼による衝撃波の雰囲気中に噴霧して乾燥する工程、を有する。
[Method for producing toner for electrophotography]
The toner production method of the present invention comprises (A) a step of obtaining a dispersion of toner particles containing a binder resin in an aqueous medium, and (B) a pulse of the dispersion of toner particles obtained in step (A). Spraying into an atmosphere of a shock wave caused by combustion and drying.
（工程（Ａ））
＜水系媒体＞
工程（Ａ）に用いられる水系媒体は、水を主成分とするものであり、環境保全の観点から、水の含有量は、水系媒体中８０重量％以上が好ましく、９０重量％以上がより好ましく、１００重量％がさらに好ましい。
本発明では、実質的に有機溶剤を用いることなく水のみを用いて結着樹脂を分散させることが好ましい。
尚、水以外の成分としては、メタノール、エタノール、イソプロパノール、ブタノール、アセトン、メチルエチルケトン、テトラヒドロフラン等の水に溶解する有機溶媒が挙げられる。これらのなかでは、トナーへの混入を防止する観点から、結着樹脂を溶解しない有機溶媒である、メタノール、エタノール、イソプロパノール、ブタノール等のアルコール系有機溶媒が使用できる。
(Process (A))
<Aqueous medium>
The aqueous medium used in the step (A) is mainly composed of water. From the viewpoint of environmental conservation, the water content is preferably 80% by weight or more, more preferably 90% by weight or more in the aqueous medium. 100% by weight is more preferable.
In the present invention, it is preferable to disperse the binder resin using only water without substantially using an organic solvent.
Examples of components other than water include organic solvents that dissolve in water, such as methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, and tetrahydrofuran. Among these, alcohol-based organic solvents such as methanol, ethanol, isopropanol, and butanol, which are organic solvents that do not dissolve the binder resin, can be used from the viewpoint of preventing mixing into the toner.
＜結着樹脂＞
本発明において用いられる結着樹脂には、トナーの定着性及び耐久性の観点から、酸基を有するポリエステルが含有されていることが好ましい。酸基を有するポリエステルの含有量は、結着樹脂中、定着性及び耐久性の観点から、６０重量％以上が好ましく、７０重量％以上がより好ましく、８０重量％以上がさらに好ましく、実質１００重量％であることが更に好ましい。酸基を有するポリエステルは、結晶性ポリエステル及び非晶質ポリエステルのいずれであってもよい。
<Binder resin>
The binder resin used in the present invention preferably contains a polyester having an acid group from the viewpoint of toner fixability and durability. The content of the polyester having an acid group is preferably 60% by weight or more, more preferably 70% by weight or more, still more preferably 80% by weight or more, and substantially 100% by weight from the viewpoint of fixing property and durability in the binder resin. % Is more preferable. The polyester having an acid group may be a crystalline polyester or an amorphous polyester.
酸基をポリエステルの結晶化の度合いは、軟化点と示差走査熱量計による吸熱の最高ピーク温度との比（軟化点／吸熱の最高ピーク温度）で定義される結晶性指数によって表すことができ、一般にこの値が１．５を超えると樹脂は非晶質であり、０．６未満のときは結晶性が低く非晶質部分が多い。従って、本発明における結晶性ポリエステルとしては、この結晶性指数が０．６〜１．５のものが好ましく用いられ、低温定着性の観点からは、０．８〜１．３がより好ましく、さらに好ましくは０．９〜１．１である。
この結晶化の度合いは、原料モノマーの種類とその比率、及び製造条件（例えば、反応温度、反応時間、冷却速度）等により調整することができる。ここで、吸熱の最高ピーク温度とは、観測される吸熱ピークのうち、最も高温側にあるピークの温度を指す。吸熱の最高ピーク温度が軟化点と２０℃以内の差であれば、このピーク温度を融点とし、軟化点との差が２０℃を超える場合は、このピークをガラス転移に起因するピークとする。
酸基を有するポリエステル以外の結着樹脂としては、トナーに用いられる公知の樹脂、例えば、スチレン−アクリル共重合体、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。
The degree of crystallization of polyester based on acid groups can be represented by the crystallinity index defined by the ratio between the softening point and the highest endothermic peak temperature by the differential scanning calorimeter (softening point / the highest endothermic peak temperature), Generally, when this value exceeds 1.5, the resin is amorphous, and when it is less than 0.6, the crystallinity is low and there are many amorphous portions. Therefore, as the crystalline polyester in the present invention, those having a crystallinity index of 0.6 to 1.5 are preferably used, and from the viewpoint of low-temperature fixability, 0.8 to 1.3 is more preferable. Preferably it is 0.9-1.1.
The degree of crystallization can be adjusted by the type and ratio of raw material monomers, production conditions (for example, reaction temperature, reaction time, cooling rate) and the like. Here, the highest endothermic peak temperature refers to the temperature of the peak on the highest temperature side among the observed endothermic peaks. If the maximum endothermic peak temperature is within 20 ° C. from the softening point, this peak temperature is taken as the melting point, and if the difference from the softening point exceeds 20 ° C., this peak is taken as the peak due to glass transition.
Examples of the binder resin other than the polyester having an acid group include known resins used for toner, for example, a styrene-acrylic copolymer, an epoxy resin, a polycarbonate, a polyurethane, and the like.
酸基を有するポリエステルの原料モノマーは、特に限定されないが、公知のアルコール成分と、カルボン酸、カルボン酸無水物、カルボン酸エステル等の公知のカルボン酸成分が用いられる。
アルコール成分としては、ポリオキシプロピレン−２，２−ビス（４−ヒドロキシフェニル）プロパン、ポリオキシエチレン−２，２−ビス（４−ヒドロキシフェニル）プロパン等のビスフェノールＡのアルキレン（炭素数２〜３）オキサイド（平均付加モル数１〜１６）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。
このアルコール成分は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
Although the raw material monomer of the polyester which has an acid group is not specifically limited, Well-known alcohol components and well-known carboxylic acid components, such as carboxylic acid, a carboxylic acid anhydride, and carboxylic acid ester, are used.
Examples of the alcohol component include alkylenes of bisphenol A such as polyoxypropylene-2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene-2,2-bis (4-hydroxyphenyl) propane (carbon number of 2 to 3). ) Oxide (average addition mole number 1-16) adduct, ethylene glycol, propylene glycol, glycerin, pentaerythritol, trimethylolpropane, hydrogenated bisphenol A, sorbitol, or their alkylene (2-4 carbon atoms) oxide (average) Addition mole number 1-16) Additions etc. are mentioned.
This alcohol component may be used individually by 1 type, and may be used in combination of 2 or more type.
また、カルボン酸成分としては、フタル酸、イソフタル酸、テレフタル酸、フマル酸、マレイン酸、アジピン酸、コハク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１〜３）エステル等が挙げられる。
このカルボン酸成分は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
The carboxylic acid component includes dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, adipic acid and succinic acid, alkyl groups having 1 to 20 carbon atoms such as dodecenyl succinic acid and octenyl succinic acid, or carbon. Trivalent or higher polyvalent carboxylic acids such as succinic acid, trimellitic acid and pyromellitic acid substituted with alkenyl groups of 2 to 20, anhydrides of these acids and alkyls of these acids (1 to 3 carbon atoms) ) Esters and the like.
This carboxylic acid component may be used individually by 1 type, and may be used in combination of 2 or more type.
酸基を有するポリエステルは、例えば、上記アルコール成分とカルボン酸成分とを不活性ガス雰囲気中にて、必要に応じエステル化触媒を用いて、１８０〜２５０℃程度の温度で縮重合することにより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、ジオクチル酸錫等の錫化合物や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のエステル化触媒を使用することができる。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重量部が好ましく、０.１〜０.６重量部がより好ましい。
The polyester having an acid group is produced, for example, by subjecting the alcohol component and the carboxylic acid component to condensation polymerization at a temperature of about 180 to 250 ° C. in an inert gas atmosphere, if necessary, using an esterification catalyst. can do.
As the esterification catalyst, an esterification catalyst such as a tin compound such as dibutyltin oxide or tin dioctylate or a titanium compound such as titanium diisopropylate bistriethanolamate can be used. The amount of the esterification catalyst used is preferably 0.01 to 1 part by weight, more preferably 0.1 to 0.6 part by weight, based on 100 parts by weight of the total amount of the alcohol component and the carboxylic acid component.
トナーの保存性の観点から、酸基を有するポリエステルの軟化点は７０〜１６５℃が好ましく、ガラス転移点は５０〜８５℃が好ましい。酸価は、乳化する際の製造性の観点から、６〜３５ｍｇＫＯＨ／ｇが好ましく、１０〜３５ｍｇＫＯＨ／ｇがより好ましく、１５〜３５ｍｇＫＯＨ／ｇがさらに好ましい。軟化点や酸価は縮重合の温度、反応時間を調節することにより所望のものを得ることができる。
トナーの耐久性の観点から、ポリエステルの数平均分子量は１，０００〜１０，０００が好ましく、２，０００〜８，０００がより好ましい。
From the viewpoint of storage stability of the toner, the softening point of the polyester having an acid group is preferably 70 to 165 ° C, and the glass transition point is preferably 50 to 85 ° C. The acid value is preferably 6 to 35 mgKOH / g, more preferably 10 to 35 mgKOH / g, and still more preferably 15 to 35 mgKOH / g, from the viewpoint of manufacturability during emulsification. The desired softening point and acid value can be obtained by adjusting the condensation polymerization temperature and reaction time.
From the viewpoint of the durability of the toner, the number average molecular weight of the polyester is preferably 1,000 to 10,000, and more preferably 2,000 to 8,000.
尚、結着樹脂が複数の結着樹脂を含有する場合には、前記結着樹脂の軟化点、ガラス転移点、酸価、及び数平均分子量は、いずれも各結着樹脂の混合物としての値を意味する。
尚、本発明において、酸基を有するポリエステルには、前記ポリエステルのみならず、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も含まれる。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や、ポリエステルユニットを含む２種以上の樹脂ユニットを有する複合樹脂が挙げられる。
When the binder resin contains a plurality of binder resins, the softening point, glass transition point, acid value, and number average molecular weight of the binder resin are all values as a mixture of the binder resins. Means.
In the present invention, the polyester having an acid group includes not only the polyester but also 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. And a composite resin having two or more kinds of resin units including a polyester unit.
さらに、本発明のトナー用結着樹脂は、定着性及び耐久性の観点から、軟化点が異なる２種類の酸基を有するポリエステルを含有することができ、一方のポリエステル（ａ）の軟化点は７０以上１１５℃未満が好ましく、他方のポリエステル（ｂ）の軟化点は１１５℃以上１６５℃以下が好ましい。
ポリエステル（ａ）とポリエステル（ｂ）の重量比（ａ／ｂ）は、１０／９０〜９０／１０が好ましく、５０／５０〜９０／１０がより好ましい。
Furthermore, the binder resin for toner of the present invention can contain polyesters having two kinds of acid groups having different softening points from the viewpoint of fixability and durability, and the softening point of one polyester (a) is 70 to less than 115 ° C. is preferable, and the softening point of the other polyester (b) is preferably 115 to 165 ° C.
The weight ratio (a / b) between the polyester (a) and the polyester (b) is preferably 10/90 to 90/10, and more preferably 50/50 to 90/10.
＜工程（Ａ）＞
上記水系媒体中で上記結着樹脂を含有するトナー粒子の分散液を得る工程には、懸濁重合法、乳化重合法、シード重合法、分散重合法、乳化凝集法など公知の各方法がいずれも使用可能である。ここで、乳化重合法は、水にほとんど不溶の重合性単量体（モノマー）を、水溶性重合開始剤を含む水相中に乳化剤を用いて分散させ、重合を行う方法である。分散重合法は、重合性単量体は可溶であるが得られる重合体は不溶である有機溶剤を用い、重合の進行に伴い重合体微粒子を析出させる方法である。懸濁重合法は、機械的攪拌手段を用いて重合性単量体を水性媒体中に分散させながら重合を行って重合トナー粒子を得る方法である。シード重合法は、一旦得られた重合体微粒子に更に重合性単量体を吸収させた後、重合開始剤を用いて重合させる方法である。また、乳化凝集法は、乳化粒子を凝集させる工程を含むトナー粒子を製造する方法である。これらの方法の中では、小粒径でシャープな粒度分布を有するトナー粒子が得られる観点から、乳化凝集法が好ましい。本発明の乾燥工程を有する乳化凝集法により得られるトナーは、定着性に優れるものとなる。
<Process (A)>
In the step of obtaining a dispersion of toner particles containing the binder resin in the aqueous medium, any of known methods such as suspension polymerization, emulsion polymerization, seed polymerization, dispersion polymerization, and emulsion aggregation can be used. Can also be used. Here, the emulsion polymerization method is a method in which a polymerizable monomer (monomer) almost insoluble in water is dispersed using an emulsifier in an aqueous phase containing a water-soluble polymerization initiator, and polymerization is performed. The dispersion polymerization method is a method in which polymer fine particles are precipitated with the progress of polymerization using an organic solvent in which the polymerizable monomer is soluble but the obtained polymer is insoluble. The suspension polymerization method is a method of obtaining polymerized toner particles by performing polymerization while dispersing a polymerizable monomer in an aqueous medium using a mechanical stirring means. The seed polymerization method is a method in which the polymer fine particles once obtained are further absorbed with a polymerizable monomer and then polymerized using a polymerization initiator. The emulsion aggregation method is a method for producing toner particles including a step of aggregating the emulsion particles. Among these methods, the emulsion aggregation method is preferable from the viewpoint of obtaining toner particles having a small particle size and a sharp particle size distribution. The toner obtained by the emulsion aggregation method having the drying step of the present invention has excellent fixability.
本発明において、工程（Ａ）は、水系媒体中で結着樹脂を含有するトナー粒子の分散液を得る工程であるが、生産性及び得られるトナーの定着性の観点から、樹脂乳化液中の樹脂粒子を、凝集、合一する工程を含むことが好ましく、該樹脂乳化液としては、（１）酸基を有するポリエステルを含有する結着樹脂を塩基性水系媒体中において分散する工程、（２）得られた分散液を攪拌して中和させる工程、及び（３）中和された分散液に水性液を添加して水性媒体中で乳化する工程、を有する方法により得られるものを用いることが好ましい。以下、この態様について説明する。 In the present invention, the step (A) is a step of obtaining a dispersion of toner particles containing a binder resin in an aqueous medium. From the viewpoint of productivity and fixability of the obtained toner, the step (A) It is preferable to include a step of aggregating and coalescing the resin particles. As the resin emulsion, (1) a step of dispersing a binder resin containing a polyester having an acid group in a basic aqueous medium, (2 Use a method obtained by a method comprising: a step of stirring and neutralizing the obtained dispersion and (3) a step of adding an aqueous solution to the neutralized dispersion and emulsifying in an aqueous medium. Is preferred. Hereinafter, this aspect will be described.
工程（１）
工程（１）は、酸基を有するポリエステルを含有する結着樹脂を塩基性水系媒体中において分散させ樹脂分散液を得る工程である。
工程（１）で用いられる塩基性水系媒体とは、塩基性化合物を含む水系媒体を指し、水系媒体としては、前述のものが挙げられる。塩基性化合物としては、無機塩基性化合物及び有機塩基性化合物のいずれであってもよい。無機塩基性化合物としては、例えば水酸化ナトリウム、水酸化カリウム、水酸化リチウム等の水酸化アルカリ金属、それらの炭酸塩や酢酸塩などの弱酸の塩あるいは部分中和塩、及びアンモニアなどが挙げられる。有機塩基性化合物としては、例えばメチルアミン、ジメチルアミン、トリメチルアミン、エチルアミン、ジエチルアミン、トリエチルアミン等のアルキルアミン類、ジエタノールアミン等のアルカノールアミン類、コハク酸ナトリウム、ステアリン酸ナトリウムなどの脂肪酸塩等が挙げられる。これらの塩基性化合物は１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
塩基性水性媒体における塩基性化合物の含有量は、用いる塩基性化合物の種類により左右されるが、結着樹脂の加水分解の抑制の点から、通常１〜３０重量％、好ましくは３〜２０重量％、より好ましくは５〜１０重量％である。
Process (1)
Step (1) is a step of obtaining a resin dispersion by dispersing a binder resin containing a polyester having an acid group in a basic aqueous medium.
The basic aqueous medium used in step (1) refers to an aqueous medium containing a basic compound, and examples of the aqueous medium include those described above. As a basic compound, any of an inorganic basic compound and an organic basic compound may be sufficient. Examples of the inorganic basic compound include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, weak acid salts such as carbonates and acetates thereof, partially neutralized salts, and ammonia. . Examples of the organic basic compound include alkylamines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine and triethylamine, alkanolamines such as diethanolamine, and fatty acid salts such as sodium succinate and sodium stearate. These basic compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the basic compound in the basic aqueous medium depends on the type of the basic compound to be used, but is usually 1 to 30% by weight, preferably 3 to 20% from the viewpoint of suppressing hydrolysis of the binder resin. %, More preferably 5 to 10% by weight.
また、工程（１）においては、界面活性剤を加えることができる。その添加量は、分散工程での発泡抑制の観点及び得られる樹脂乳化液の乳化安定性の向上などを考慮して、樹脂に対して好ましくは５重量％以下、より好ましくは０．２〜５重量％、より好ましくは０．５〜４重量％、更に好ましくは１〜３重量％である。この界面活性剤としては、例えばドデシルベンゼンスルホン酸ナトリウム、オクタデシル硫酸ナトリウム、オレイン酸ナトリウム、ラウリン酸ナトリウム、ステアリン酸カリウム等のアニオン性界面活性剤；ラウリルアミンアセテート、ステアリルアミンアセテート、ラウリルトリメチルアンモニウムクロライド等のカチオン性界面活性剤；ラウリルジメチルアミンオキサイド等の両性界面活性剤；ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ソルビタンモノステアレート、ポリオキシエチレンアルキルアミン等のノニオン性界面活性剤が挙げられる。
これらの中で、乳化安定性などの観点から、アニオン性界面活性剤及びノニオン性界面活性剤が好ましい。これらの界面活性剤は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
In step (1), a surfactant can be added. The addition amount is preferably 5% by weight or less, more preferably 0.2 to 5% with respect to the resin in consideration of the suppression of foaming in the dispersion step and the improvement of the emulsion stability of the obtained resin emulsion. % By weight, more preferably 0.5 to 4% by weight, still more preferably 1 to 3% by weight. Examples of the surfactant include anionic surfactants such as sodium dodecylbenzenesulfonate, sodium octadecyl sulfate, sodium oleate, sodium laurate, and potassium stearate; laurylamine acetate, stearylamine acetate, lauryltrimethylammonium chloride, and the like. Cationic surfactants such as: Amphoteric surfactants such as lauryl dimethylamine oxide; Nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, sorbitan monostearate, and polyoxyethylene alkyl amine It is done.
Among these, anionic surfactants and nonionic surfactants are preferable from the viewpoint of emulsion stability and the like. These surfactants may be used individually by 1 type, and may be used in combination of 2 or more type.
工程（１）においては、結着樹脂に、必要に応じて着色剤、離型剤、荷電制御剤などの添加剤を加え、これらの混合物を分散処理することができる。
着色剤としては、特に制限はなく公知の着色剤がいずれも使用でき、適宜選択することができる。具体的には、カーボンブラック、無機系複合酸化物、クロムイエロー、ハンザイエロー、ベンジジンイエロー、スレンイエロー、キノリンイエロー、パーマネントオレンジＧＴＲ、ピラゾロンオレンジ、バルカンオレンジ、ウオッチヤングレッド、パーマネントレッド、ブリリアンカーミン３Ｂ、ブリリアンカーミン６Ｂ、デュポンオイルレッド、ピラゾロンレッド、リソールレッド、ローダミンＢレーキ、レーキレッドＣ、ベンガル、アニリンブルー、ウルトラマリンブルー、カルコオイルブルー、メチレンブルークロライド、フタロシアニンブルー、フタロシアニングリーン、マラカイトグリーンオクサレート等の種々の顔料やアクリジン系、キサンテン系、アゾ系、ベンゾキノン系、アジン系、アントラキノン系、インジコ系、チオインジコ系、フタロシアニン系、アニリンブラック系、チアゾール系等の各種染料を１種を単独で又は２種以上を組み合わせて使用することができる。
結着樹脂と着色剤との使用割合は、トナーの帯電性、耐久性、印字濃度などの観点から、重量比で７０：３０〜９７：３が好ましく、８０：２０〜９７：３がより好ましい。
In step (1), additives such as a colorant, a release agent, and a charge control agent can be added to the binder resin as necessary, and the mixture can be dispersed.
The colorant is not particularly limited, and any known colorant can be used and can be appropriately selected. Specifically, carbon black, inorganic composite oxide, chrome yellow, hansa yellow, benzidine yellow, selenium yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red, brilliantamine 3B, Brilliantamine 6B, Dupont Oil Red, Pyrazolone Red, Resol Red, Rhodamine B Lake, Lake Red C, Bengal, Aniline Blue, Ultramarine Blue, Calco Oil Blue, Methylene Blue Chloride, Phthalocyanine Blue, Phthalocyanine Green, Malachite Green Oxalate, etc. Various pigments, acridine, xanthene, azo, benzoquinone, azine, anthraquinone, indico, thioi Zico system, phthalocyanine, aniline black, can be used alone or in combination of two or more kinds of various dyes of thiazole, and the like.
The use ratio of the binder resin and the colorant is preferably 70:30 to 97: 3, and more preferably 80:20 to 97: 3, in terms of weight ratio, from the viewpoints of toner chargeability, durability, print density, and the like. .
離型剤の具体例としては、ポリエチレン、ポリプロピレン、ポリブテン等の低分子量ポリオレフィン類；加熱により軟化点を有するシリコーン類；オレイン酸アミド、エルカ酸アミド、リシノール酸アミド、ステアリン酸アミド等の脂肪酸アミド類；カルナウバワックス、ライスワックス、キャンデリラワックス、木ロウ、ホホバ油等の植物系ワックス；ミツロウ等の動物系ワックス；モンタンワックス、オゾケライト、セレシン、パラフィンワックス、マイクロクリスタリンワックス、フィッシャートロプシュワックス等の鉱物・石油系ワックスなどが挙げられる。これらの離型剤は、１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
離型剤の含有量は、添加効果及び帯電性への悪影響を考慮して、結着樹脂１００重量部に対して、通常１〜２０重量部程度、好ましくは２〜１５重量部である。
Specific examples of the release agent include low molecular weight polyolefins such as polyethylene, polypropylene and polybutene; silicones having a softening point by heating; fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide and stearic acid amide ; Plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil; animal waxes such as beeswax; minerals such as montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax・ Petroleum-based wax. These mold release agents may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the release agent is usually about 1 to 20 parts by weight, preferably 2 to 15 parts by weight with respect to 100 parts by weight of the binder resin in consideration of the addition effect and the adverse effect on the chargeability.
荷電制御剤としては、例えば安息香酸の金属塩、サリチル酸の金属塩、アルキルサリチル酸の金属塩、カテコールの金属塩、含金属ビスアゾ染料、テトラフェニルボレート誘導体、第四級アンモニウム塩、アルキルピリジニウム塩などが挙げられる。これらは１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
荷電制御剤の含有量は、結着樹脂１００重量部に対して、通常１０重量部以下、好ましくは０．０１〜５重量部である。
Examples of charge control agents include benzoic acid metal salts, salicylic acid metal salts, alkyl salicylic acid metal salts, catechol metal salts, metal-containing bisazo dyes, tetraphenylborate derivatives, quaternary ammonium salts, alkylpyridinium salts, and the like. Can be mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type.
The content of the charge control agent is usually 10 parts by weight or less, preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the binder resin.
工程（１）においては、結着樹脂と必要に応じて用いられる各種添加剤との混合物を均一に分散させる観点から、該結着樹脂のガラス転移点以下の温度で分散処理を行うことが好ましい。該結着樹脂のガラス転移点以下、好ましくはガラス転移点より１０℃低い温度（以下、「ガラス転移点−１０℃」と記す）以下の温度で分散処理することにより、結着樹脂粒子同士の融着を抑制し、均一な樹脂分散液を調製することができる。また、分散処理の下限温度は、媒体の流動性及び樹脂乳化液の製造エネルギーの観点から０℃より高い温度が好ましく、１０℃以上がより好ましい。混合樹脂を用いる場合は、その混合比率で混合し溶融した混合樹脂のガラス転移点を結着樹脂のガラス転移点とする。また、マスターバッチを使用する場合は、それに用いた樹脂をも含めた混合樹脂のガラス転移点とする。
具体的な分散処理方法としては、界面活性剤を含む塩基性水性媒体中において、例えば酸基を有するポリエステルを含む結着樹脂を必要に応じ着色剤などと共に、該結着樹脂のガラス転移点以下、例えば１０〜５０℃程度の温度で攪拌するなどの通常の方法により、均一な樹脂分散液を調製することができる。
In the step (1), from the viewpoint of uniformly dispersing the mixture of the binder resin and various additives used as necessary, it is preferable to perform a dispersion treatment at a temperature below the glass transition point of the binder resin. . By dispersing the binder resin particles at a temperature not higher than the glass transition point of the binder resin, preferably not higher than 10 ° C. below the glass transition point (hereinafter referred to as “glass transition point−10 ° C.”), Fusion can be suppressed and a uniform resin dispersion can be prepared. Further, the lower limit temperature of the dispersion treatment is preferably higher than 0 ° C., more preferably 10 ° C. or higher, from the viewpoint of fluidity of the medium and production energy of the resin emulsion. When a mixed resin is used, the glass transition point of the mixed resin mixed and melted at the mixing ratio is defined as the glass transition point of the binder resin. Moreover, when using a masterbatch, it is set as the glass transition point of the mixed resin including the resin used for it.
As a specific dispersion treatment method, in a basic aqueous medium containing a surfactant, for example, a binder resin containing a polyester having an acid group, together with a colorant, if necessary, below the glass transition point of the binder resin For example, a uniform resin dispersion can be prepared by an ordinary method such as stirring at a temperature of about 10 to 50 ° C.
工程（２）
工程（２）は、前記工程（１）で得られた樹脂分散液を、攪拌して中和させる工程である。樹脂分散液が着色剤等を含有している場合にはさらに着色剤を均一に中和する観点から、該攪拌時間は好ましくは３０分以上、より好ましくは１時間以上である。
中和は、前記結着樹脂のガラス転移点以上かつ軟化点以下の温度で行うことが好ましい。前記範囲の温度で行うことにより、中和が十分に行われ、次工程の乳化処理で大きな乳化粒子の生成が抑制され、また、加熱に特別な装置を必要としない。この点で、中和温度は、該樹脂のガラス転移点＋１０℃以上の温度であることが好ましく、また軟化点−５℃以下の温度であることがより好ましい。
Process (2)
Step (2) is a step of neutralizing the resin dispersion obtained in step (1) by stirring. When the resin dispersion contains a colorant or the like, the stirring time is preferably 30 minutes or longer, more preferably 1 hour or longer from the viewpoint of further neutralizing the colorant uniformly.
Neutralization is preferably performed at a temperature not lower than the glass transition point and not higher than the softening point of the binder resin. By carrying out at the temperature within the above range, neutralization is sufficiently carried out, generation of large emulsified particles is suppressed in the emulsification treatment in the next step, and no special apparatus is required for heating. In this respect, the neutralization temperature is preferably a glass transition point of the resin + 10 ° C. or more, and more preferably a softening point−5 ° C. or less.
この中和工程における中和の度合いは、次工程で樹脂粒子を作製するのに必要な親水性を樹脂に付与できる程度でよく、必ずしも１００％中和する必要はない。例えば、極性基を多く有する親水性の高い樹脂を用いる場合は、中和度は低くてもよく、逆に親水性の低い樹脂を用いる場合は、中和度は高くするほうが好ましい。本発明においては、上記中和度は、５０％以上であることが好ましく、６０〜１００％であることがより好ましく、７０〜１００％であることが更に好ましい。中和度は、一般に中和前後の酸基のモル数の比（中和後の酸基のモル数／中和前の酸基のモル数）で表わすことができる。 The degree of neutralization in this neutralization step may be such that hydrophilicity necessary for producing resin particles in the next step can be imparted to the resin, and it is not always necessary to neutralize 100%. For example, when a highly hydrophilic resin having many polar groups is used, the degree of neutralization may be low. Conversely, when a resin having low hydrophilicity is used, it is preferable to increase the degree of neutralization. In the present invention, the degree of neutralization is preferably 50% or more, more preferably 60 to 100%, and still more preferably 70 to 100%. The degree of neutralization can generally be represented by the ratio of the number of moles of acid groups before and after neutralization (number of moles of acid groups after neutralization / number of moles of acid groups before neutralization).
具体的には、前記工程（１）で得られた樹脂分散液を、攪拌しながら結着樹脂のガラス転移転移点以上かつ軟化点以下の温度、例えばガラス転移点が６０〜７０℃程度で軟化点が１１０〜１２０℃程度の有するカルボキシル基をもつポリエステルを用いた場合には、９０〜１００℃程度の温度に昇温し、所定の中和度に達するまで、その温度で適当な時間保持することにより中和を行う。 Specifically, the resin dispersion obtained in the step (1) is softened while stirring at a temperature not lower than the glass transition point of the binder resin and not higher than the softening point, for example, a glass transition point of about 60 to 70 ° C. When a polyester having a carboxyl group having a point of about 110 to 120 ° C. is used, the temperature is raised to a temperature of about 90 to 100 ° C. and kept at that temperature for an appropriate time until reaching a predetermined degree of neutralization. Neutralization.
工程（３）
工程（３）は、前記工程（２）で中和された分散液に水性液を添加して水性媒体中で乳化する工程であるが、該工程は、微細な樹脂乳化液を調製する観点から、工程（２）で中和された樹脂分散液を、該結着樹脂のガラス転移点以上かつ軟化点以下の温度に保持し、攪拌しながら、これに水性液を添加し、水性媒体中で乳化を行うことが好ましい。
乳化を前記範囲の温度で行うことにより、乳化がスムーズに行われ、又加熱に特別の装置を必要としない。このことから、乳化を行う際の温度は、ガラス転移点＋１０℃以上の温度であることが好ましく、また、軟化点−５℃以下の温度であることが好ましい。
Step (3)
Step (3) is a step of adding an aqueous liquid to the dispersion neutralized in the step (2) and emulsifying it in an aqueous medium. This step is from the viewpoint of preparing a fine resin emulsion. The aqueous dispersion neutralized in step (2) is maintained at a temperature not lower than the glass transition point and not higher than the softening point of the binder resin, and the aqueous liquid is added to the aqueous dispersion while stirring. It is preferable to carry out emulsification.
By carrying out the emulsification at a temperature within the above range, the emulsification is carried out smoothly and no special apparatus is required for heating. From this, the temperature at the time of emulsification is preferably a temperature of glass transition point + 10 ° C. or higher, and a temperature of softening point −5 ° C. or lower is preferable.
この乳化工程においては、乳化開始直前では、転相が容易である等の点から、分散液中の樹脂含有量が好ましくは５０〜９０重量％程度、より好ましくは５０〜８０重量％である。ここで乳化開始直前とは、系内の粘度が全工程中で最も高くなる時点をいう。
乳化開始時点は、用いる樹脂の酸価や中和度などにより任意に調整することができる。例えば、樹脂の酸価を高くしたり、中和度を高くすると樹脂の親水性が高くなり、少量の水性媒体と接触させることで乳化を開始させることができる。
In this emulsification step, the resin content in the dispersion is preferably about 50 to 90% by weight, more preferably 50 to 80% by weight, from the viewpoint of easy phase inversion immediately before the start of emulsification. Here, “immediately before the start of emulsification” refers to a point in time when the viscosity in the system is highest in all steps.
The emulsification start time can be arbitrarily adjusted depending on the acid value and the degree of neutralization of the resin used. For example, when the acid value of the resin is increased or the degree of neutralization is increased, the hydrophilicity of the resin is increased, and emulsification can be started by contacting with a small amount of an aqueous medium.
乳化に用いられる水性液としては、脱イオン水を挙げることができる。該水性液の添加速度は、乳化を効果的に実施し得る点から、樹脂１００ｇ当たり、好ましくは０．５〜５０ｇ／分、より好ましくは０．５〜３０ｇ／分、さらに好ましくは１〜２０ｇ／分である。この添加速度は、一般にＯ／Ｗ型の乳化液を実質的に形成するまで維持されていればよく、Ｏ／Ｗ型の乳化液を形成した後の水性液の添加速度に特に制限はない。 Examples of the aqueous liquid used for emulsification include deionized water. The addition rate of the aqueous liquid is preferably 0.5 to 50 g / min, more preferably 0.5 to 30 g / min, and further preferably 1 to 20 g per 100 g of resin from the viewpoint that emulsification can be effectively carried out. / Min. In general, the addition rate may be maintained until the O / W type emulsion is substantially formed, and the addition rate of the aqueous liquid after the formation of the O / W type emulsion is not particularly limited.
このようにして得られた樹脂乳化液の固形分濃度は、乳化液の安定性及び後で実施される凝集工程での樹脂乳化液の取り扱い性の観点から、７〜５０重量％が好ましく、７〜４５重量％がより好ましく、１０〜４０重量％がさらに好ましい。
また、Ｏ／Ｗ型の乳化液を形成した後の樹脂乳化液中の樹脂粒子の体積中位粒径（Ｄ50）は、凝集工程での均一な凝集を行うために、好ましくは０．０２〜２μｍ、より好ましくは０．０５〜１μｍ、さらに好ましくは０．０５〜０．６μｍである。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 solid content concentration of the resin emulsion thus obtained is preferably 7 to 50% by weight from the viewpoint of the stability of the emulsion and the handleability of the resin emulsion in the subsequent aggregation step. -45 wt% is more preferable, and 10-40 wt% is more preferable.
The volume median particle size (D 50 ) of the resin particles in the resin emulsion after forming the O / W emulsion is preferably 0.02 in order to perform uniform aggregation in the aggregation process. It is -2 micrometer, More preferably, it is 0.05-1 micrometer, More preferably, it is 0.05-0.6 micrometer. 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.
樹脂乳化液を得る他の方法としては、例えば、目的とする樹脂粒子原料として重縮合性単量体を水系媒体中に例えば機械的シェアや超音波などにより乳化分散させる方法が挙げられる。この際、必要に応じて、重縮合触媒、界面活性剤などの添加剤も水溶性媒体に添加する。そして、この溶液に対して例えば加熱などを施すことで、重縮合を進行させる。例えば、樹脂がポリエステルである場合は、前述のポリエステルの重縮合性単量体、重縮合触媒が使用でき、界面活性剤としては前述のものが同様に使用できる。
通常、重縮合樹脂は重合時に脱水を伴うために原理的に水系媒体中では進行しない。しかしながら、例えば、水系媒体中にミセルを形成せしめるような界面活性剤とともに重縮合性単量体を水系媒体中に乳化せしめた場合、単量体がミセル中のミクロな疎水場に置かれることによって、脱水作用が生じ、生成した水はミセル外の水系媒体中に排出せしめ重合を進行させることができる。このようにして、低エネルギーで、水系媒体中で重縮合樹脂の樹脂粒子が乳化分散した分散液が得られる。
As another method for obtaining a resin emulsion, for example, a method in which a polycondensable monomer is emulsified and dispersed in an aqueous medium as a target resin particle raw material by, for example, mechanical shearing or ultrasonic waves. At this time, if necessary, additives such as a polycondensation catalyst and a surfactant are also added to the water-soluble medium. And polycondensation is advanced by, for example, heating the solution. For example, when the resin is polyester, the above-mentioned polyester polycondensable monomer and polycondensation catalyst can be used, and the above-mentioned surfactants can be used similarly.
Usually, polycondensation resins do not proceed in an aqueous medium in principle because they are dehydrated during polymerization. However, for example, when a polycondensable monomer is emulsified in an aqueous medium together with a surfactant that causes micelles to form in the aqueous medium, the monomer is placed in a micro hydrophobic field in the micelle. Then, dehydration occurs, and the generated water can be discharged into an aqueous medium outside the micelles to allow polymerization to proceed. In this way, a dispersion in which the resin particles of the polycondensation resin are emulsified and dispersed in an aqueous medium is obtained with low energy.
本発明のトナーの製造方法においては、前記工程（１）〜（３）を有する方法により得られた樹脂分散液中の樹脂粒子を凝集・合一させることが好ましい。
凝集工程
凝集工程においては、樹脂乳化液中の固形分濃度は、均一な凝集を起こさせるため前述の値とすることが好ましい。混合液の分散安定性と、結着樹脂及び着色剤等の微粒子の凝集性とを両立させる観点から、系内のｐＨ値は２〜１０が好ましく、２〜９がより好ましく、３〜８がさらに好ましい。
In the method for producing a toner of the present invention, it is preferable that the resin particles in the resin dispersion obtained by the method having the steps (1) to (3) are aggregated and united.
Aggregation Step In the aggregation step, the solid content concentration in the resin emulsion is preferably set to the above-described value in order to cause uniform aggregation. From the viewpoint of achieving both the dispersion stability of the mixed solution and the cohesiveness of fine particles such as a binder resin and a colorant, the pH value in the system is preferably 2 to 10, more preferably 2 to 9, and 3 to 8 Further preferred.
凝集工程においては、凝集を効果的に行うために凝集剤を添加することが好ましい。
凝集剤としては、４級塩のカチオン性界面活性剤、ポリエチレンイミン等の有機系凝集剤、無機金属塩、アンモニウム塩、２価以上の金属錯体等の無機系凝集剤が用いられる。本発明においては、凝集剤として、高精度のトナーの粒径制御及びシャープな粒度分布を達成する観点から、１価の塩を用いることが好ましい。ここで１価の塩とは、該塩を構成する金属イオン又は陽イオンの価数が１であることを意味する。１価の塩としては、４級塩のカチオン性界面活性剤等の有機系凝集剤、無機金属塩、アンモニウム塩等の無機系凝集剤が用いられるが、本発明においては、高精度のトナーの粒径制御及びシャープな粒度分布を達成する観点から、分子量３５０以下の水溶性含窒素化合物が好ましく用いられる。
In the aggregation step, it is preferable to add an aggregating agent in order to effectively perform aggregation.
As the aggregating agent, a quaternary salt cationic surfactant, an organic aggregating agent such as polyethyleneimine, an inorganic aggregating agent such as an inorganic metal salt, an ammonium salt or a divalent or higher metal complex is used. In the present invention, it is preferable to use a monovalent salt as the flocculant from the viewpoint of achieving highly accurate toner particle size control and a sharp particle size distribution. Here, the monovalent salt means that the valence of the metal ion or cation constituting the salt is 1. As the monovalent salt, organic flocculants such as quaternary salt cationic surfactants, inorganic flocculants such as inorganic metal salts and ammonium salts are used. From the viewpoint of achieving particle size control and a sharp particle size distribution, a water-soluble nitrogen-containing compound having a molecular weight of 350 or less is preferably used.
分子量３５０以下の水溶性含窒素化合物は、樹脂粒子を速やかに凝集させる観点から、酸性を示す化合物であることが好ましく、その１０重量％水溶液の２５℃でのｐＨ値が４〜６であるものが好ましく、４．２〜６のものがより好ましい。また、高温高湿における帯電性等の観点から、その分子量が３５０以下のものが好ましく、３００以下のものがより好ましい。このような水溶性含窒素化合物としては、例えば、ハロゲン化アンモニウム、硫酸アンモニウム、酢酸アンモニウム、安息香酸アンモニウム、サリチル酸アンモニウム等のアンモニウム塩、テトラアルキルアンモニウムハライド等の４級アンモニウム塩等が挙げられるが、生産性の点から、硫酸アンモニウム（１０重量％水溶液の２５℃でのｐＨ値、以下「ｐＨ値」という：５．４）、塩化アンモニウム（ｐＨ値：４．６）、臭化テトラエチルアンモニウム（ｐＨ値：５．６）、臭化テトラブチルアンモニウム（ｐＨ値：５．８）が好ましく挙げられる。 The water-soluble nitrogen-containing compound having a molecular weight of 350 or less is preferably a compound that exhibits acidity from the viewpoint of rapidly agglomerating resin particles, and a pH value at 25 ° C. of a 10 wt% aqueous solution thereof is 4-6. Are preferable, and 4.2 to 6 are more preferable. From the viewpoint of chargeability at high temperature and high humidity, the molecular weight is preferably 350 or less, more preferably 300 or less. Examples of such water-soluble nitrogen-containing compounds include ammonium salts such as ammonium halide, ammonium sulfate, ammonium acetate, ammonium benzoate and ammonium salicylate, and quaternary ammonium salts such as tetraalkylammonium halide. From the viewpoint of properties, ammonium sulfate (pH value of a 10% by weight aqueous solution at 25 ° C., hereinafter referred to as “pH value”: 5.4), ammonium chloride (pH value: 4.6), tetraethylammonium bromide (pH value: 5.6) and tetrabutylammonium bromide (pH value: 5.8) are preferred.
凝集剤の使用量は、使用する凝集剤の電荷の価数により異なるが、１価の凝集剤を用いた場合、凝集性の観点から、結着樹脂１００重量部に対して、２〜５０重量部が好ましく、３．５〜４０重量部がより好ましく、３．５〜３０重量部がさらに好ましい。
凝集剤は、水性媒体に溶解させて添加することが好ましく、凝集剤の添加時及び添加終了後には十分な攪拌をすることが好ましい。
The amount of the flocculant used varies depending on the valence of the charge of the flocculant used, but when a monovalent flocculant is used, 2 to 50 wt. Part is preferable, 3.5 to 40 parts by weight is more preferable, and 3.5 to 30 parts by weight is further preferable.
The flocculant is preferably added after being dissolved in an aqueous medium, and it is preferable to sufficiently stir at the time of adding the flocculant and after the addition.
凝集剤の添加は、均一な凝集を行うために、系内のｐＨを調整した後で、かつ樹脂粒子を構成する樹脂のガラス転移点以下の温度、好ましくはガラス転移点―１０℃以下の温度で行うのが望ましい。凝集剤は、一時に添加しても良いし、断続的あるいは連続的に添加してもよい。さらに、凝集剤は、水性媒体に溶解させて添加することが好ましく、凝集剤の添加時及び添加終了後には十分な攪拌をすることが好ましい。 The addition of the flocculant is performed after adjusting the pH in the system in order to perform uniform aggregation, and at a temperature below the glass transition point of the resin constituting the resin particles, preferably at a glass transition point of −10 ° C. or lower. It is desirable to do in. The flocculant may be added at once, or may be added intermittently or continuously. Further, the flocculant is preferably added after being dissolved in an aqueous medium, and it is preferable that the flocculant is sufficiently stirred at the time of addition of the flocculant and after completion of the addition.
本発明においては、離型剤等の流出を防止したり、カラートナーにおいて、各色間の帯電量を同レベルにする等の観点から、凝集時に、得られた樹脂乳化液中の樹脂粒子に、他の樹脂微粒子を添加することができる（樹脂粒子をコア材、添加する他の樹脂微粒子をシェル材ともいう）。
添加される樹脂微粒子としては、特に制限はなく、本発明の樹脂乳化液に含有される樹脂粒子と同様にして調製されたものを使用することができる。
上記他の樹脂微粒子は、結着樹脂以外に、必要に応じて着色剤、荷電制御剤、さらには界面活性剤、定着性向上剤などの添加剤を適宜含有することができる。
上記他の樹脂微粒子は、本発明の樹脂粒子と同じものであってもよく、異なるものであってもよい。更にこの工程においては、上記他の樹脂微粒子を、本発明の樹脂乳化液に前述のように凝集剤を添加して得られた凝集粒子と混合させてもよい。
In the present invention, from the viewpoint of preventing the release of a release agent or the like, and in the color toner, the charge amount between each color is set to the same level, etc., the resin particles in the obtained resin emulsion at the time of aggregation, Other resin fine particles can be added (the resin particles are also referred to as a core material, and the other resin fine particles to be added are also referred to as a shell material).
The resin fine particles to be added are not particularly limited, and those prepared in the same manner as the resin particles contained in the resin emulsion of the present invention can be used.
In addition to the binder resin, the other resin fine particles can appropriately contain additives such as a colorant, a charge control agent, a surfactant, and a fixability improver as necessary.
The other resin fine particles may be the same as or different from the resin particles of the present invention. Further, in this step, the other resin fine particles may be mixed with the aggregated particles obtained by adding the flocculant as described above to the resin emulsion of the present invention.
本発明においては、上記他の樹脂微粒子の添加時期は、特に制限はないが、生産性の観点から凝集剤の添加終了後、合一工程までの間であることが好ましい。
上記他の樹脂微粒子の凝集粒子に対する添加量は、凝集粒子に対する樹脂粒子による均一な被覆を行う観点から、凝集粒子中の樹脂１００重量部に対して、添加する樹脂微粒子を構成する樹脂が、好ましくは５〜１００重量部、より好ましくは１０〜９０重量部、更に好ましくは２０〜８０重量部となるような量である。
当該工程においては、上記他の樹脂微粒子を１回又は複数回に分割して添加することができる。本発明においては、得られるトナーの狭い粒度分布の達成の観点から、複数回に分割して添加することが好ましい。
In the present invention, the addition timing of the other resin fine particles is not particularly limited. However, from the viewpoint of productivity, it is preferable that the addition of the flocculant is performed until the coalescence step.
The amount of the other resin fine particles added to the aggregated particles is preferably a resin constituting the resin fine particles to be added with respect to 100 parts by weight of the resin in the aggregated particles from the viewpoint of uniformly coating the aggregated particles with the resin particles. Is in an amount of 5 to 100 parts by weight, more preferably 10 to 90 parts by weight, and still more preferably 20 to 80 parts by weight.
In this step, the other resin fine particles can be added once or divided into a plurality of times. In the present invention, from the viewpoint of achieving a narrow particle size distribution of the obtained toner, it is preferable to add it divided into a plurality of times.
他の樹脂微粒子を1回又は複数回に分割して添加する場合、形成される凝集粒子の粒度分布の制御などの観点から、凝集粒子中の樹脂１００重量部に対して、添加する樹脂微粒子を構成する樹脂が３０重量部未満添加される場合は、凝集剤の添加は任意である。３０重量部以上添加する場合は、凝集性及び形成する凝集粒子の粒度分布の観点から、凝集剤を添加することが好ましく、凝集剤としては、前述のものを同様に用いることができる。この場合、樹脂粒子と凝集剤とを独立して同時に添加するか、又は交互に添加することがより好ましく、独立して同時に添加することがさらに好ましい。 When other fine resin particles are added in one or more portions, the resin fine particles to be added are added to 100 parts by weight of the resin in the aggregated particles from the viewpoint of controlling the particle size distribution of the formed aggregated particles. When less than 30 parts by weight of the constituent resin is added, the addition of the flocculant is optional. In the case of adding 30 parts by weight or more, it is preferable to add an aggregating agent from the viewpoint of aggregating property and the particle size distribution of the aggregated particles to be formed, and the above-mentioned aggregating agents can be used similarly. In this case, it is more preferable to add the resin particles and the flocculant independently at the same time or alternately, and it is more preferable to add them independently and simultaneously.
当該工程において、他の樹脂微粒子を複数回に分割して添加する場合、各々の樹脂微粒子の量は同量であることが好ましく、また、凝集剤を分割して添加する場合には、各々の凝集剤は同量であることが好ましい。
前記のように他の樹脂微粒子を複数回分割して添加する場合、その回数については特に制限はないが、形成される凝集粒子の粒度分布及び生産性などの観点から、２〜１０回が好ましく、２〜８回がより好ましい。
また、凝集性及び形成される凝集粒子の粒度分布などの観点から、複数回の樹脂微粒子の添加においては、添加の後５〜１５分間、更には５〜３０分間、特に５分〜２時間熟成させることが好ましく、複数回添加の各添加において、上記熟成時間を設けることがより好ましい。
In the step, when adding other resin fine particles in a plurality of times, the amount of each resin fine particle is preferably the same amount, and when adding the flocculant separately, The amount of the flocculant is preferably the same.
When the other resin fine particles are added in a plurality of divided portions as described above, the number of times is not particularly limited, but is preferably 2 to 10 times from the viewpoint of the particle size distribution and productivity of the formed aggregated particles. 2 to 8 times are more preferable.
In addition, from the viewpoint of cohesiveness and particle size distribution of the formed aggregated particles, in the addition of a plurality of resin fine particles, aging is performed for 5 to 15 minutes, further 5 to 30 minutes, particularly 5 to 2 hours after the addition. It is preferable to provide the aging time in each addition of a plurality of times.
本発明においては、樹脂微粒子を凝集させた後に、アルキルエーテル硫酸塩、アルキル硫酸塩、直鎖アルキルベンゼンスルホン酸塩などの界面活性剤を添加することが好ましい。
アルキルエーテル硫酸塩としては、下記式（１）で表わされるものが好ましい。
Ｒ1−Ｏ−（ＣＨ2ＣＨ2Ｏ）ｐＳＯ3Ｍ1 （１）
式中、Ｒ1はアルキル基を示し、凝集粒子への吸着性およびトナーへの残留性の観点から、好ましくは炭素数６〜２０、より好ましくは炭素数８〜１５のアルキル基が挙げられる。ｐは０〜１５の平均付加モル数を示し、粒径制御の観点から、好ましくは1〜１０、より好ましくは１〜５の数である。Ｍ1は1価のカチオンを示し、粒径制御の観点から、好ましくはナトリウム、カリウム、アンモニウムであり、より好ましくはナトリウム、アンモニウムである。
In the present invention, it is preferable to add a surfactant such as an alkyl ether sulfate, an alkyl sulfate, or a linear alkylbenzene sulfonate after the resin fine particles are aggregated.
As the alkyl ether sulfate, those represented by the following formula (1) are preferable.
R 1 —O— (CH 2 CH 2 O) pSO 3 M 1 (1)
In the formula, R 1 represents an alkyl group, and preferably an alkyl group having 6 to 20 carbon atoms, more preferably 8 to 15 carbon atoms, from the viewpoint of adsorptivity to aggregated particles and persistence to toner. p represents an average added mole number of 0 to 15, and is preferably 1 to 10, more preferably 1 to 5, from the viewpoint of particle size control. M 1 represents a monovalent cation, and is preferably sodium, potassium, or ammonium, more preferably sodium or ammonium, from the viewpoint of particle size control.
また、直鎖アルキルベンゼンスルホン酸塩としては、特に制限はないが、凝集粒子への吸着性およびトナーへの残留性の観点から、式（２）で表わされるものが好ましい。
Ｒ2−Ｐｈ−ＳＯ3Ｍ2 （２）
式中、Ｒ2は直鎖のアルキル基を示し、式（１）のＲ1のうち直鎖のものと同じである。Ｐｈはフェニル基、Ｍ2は1価のカチオンである。直鎖アルキルベンゼンスルホン酸塩としては、硫酸ナトリウム塩が好適に用いられる。
上記界面活性剤の添加量は、凝集停止性およびトナーへの残留性の観点から、凝集粒子を構成する樹脂１００重量部に対して、好ましくは０．１〜１５重量部、より好ましくは０．１〜１０重量部、さらに好ましくは０．１〜８重量部である。
The linear alkyl benzene sulfonate is not particularly limited, but is preferably a compound represented by the formula (2) from the viewpoint of adsorptivity to aggregated particles and persistence to toner.
R 2 -Ph-SO 3 M 2 (2)
In the formula, R 2 represents a linear alkyl group, and is the same as the linear one of R 1 in the formula (1). Ph is a phenyl group, and M 2 is a monovalent cation. As the linear alkylbenzene sulfonate, sodium sulfate is preferably used.
The amount of the surfactant added is preferably from 0.1 to 15 parts by weight, more preferably from 0.1 to 15 parts by weight, based on 100 parts by weight of the resin constituting the aggregated particles, from the viewpoints of aggregation stopping properties and persistence to the toner. 1 to 10 parts by weight, more preferably 0.1 to 8 parts by weight.
本発明においては、高画質化の観点から、凝集粒子の体積中位粒径（Ｄ50）は１〜１０μｍであることが好ましく、２〜９μｍがより好ましく、３〜８μｍが更に好ましい。
得られた凝集粒子は、凝集粒子を合一させる工程（合一工程）に供される。
In the present invention, from the viewpoint of improving the image quality, the volume median particle size (D 50 ) of the aggregated particles is preferably 1 to 10 μm, more preferably 2 to 9 μm, and further preferably 3 to 8 μm.
The obtained agglomerated particles are subjected to a step of coalescing the agglomerated particles (a coalescence step).
合一工程
この工程は、前記凝集工程で得られた凝集粒子を合一させる工程である。
本発明においては、前記凝集工程で得られた凝集粒子を加熱して合一させる。合一工程においては、系内の温度は凝集工程の系内の温度と同じかそれ以上であることが好ましいが，目的とするトナーの粒径、粒度分布、形状制御、及び粒子の融着性の観点から、結着樹脂のガラス転移点以上が好ましく、軟化点＋２０℃以下がより好ましく、ガラス転移点＋５℃以上、軟化点＋１５℃以下がより好ましく、ガラス転移点＋１０℃以上、軟化点＋１０℃以下が更に好ましい。また、攪拌速度は凝集粒子が沈降しない速度であることが好ましい。
合一工程は、例えば昇温を連続的に行うことにより、あるいは凝集かつ合一が可能な温度まで昇温後、その温度で攪拌を続けることにより、凝集工程と同時に行うこともできる。
高画質化の観点から、合一粒子の体積中位粒径（Ｄ50）は１〜１０μｍであることが好ましく、２〜９μｍがより好ましく、３〜８μｍが更に好ましい。
Coalescence process This process is a process of coalescing the aggregated particles obtained in the aggregation process.
In the present invention, the aggregated particles obtained in the aggregation step are heated and united. In the coalescence process, the temperature in the system is preferably equal to or higher than the temperature in the system in the aggregation process, but the target toner particle size, particle size distribution, shape control, and particle fusing property In view of the above, the glass transition point or higher of the binder resin is preferable, the softening point + 20 ° C. or lower is more preferable, the glass transition point + 5 ° C. or higher, the softening point + 15 ° C. or lower is more preferable, the glass transition point + 10 ° C. or higher, the softening point +10. More preferably, it is not higher than ° C. The stirring speed is preferably a speed at which the aggregated particles do not settle.
The coalescence process can be performed simultaneously with the aggregation process, for example, by continuously raising the temperature or by raising the temperature to a temperature at which aggregation and coalescence can be performed and then continuing stirring at that temperature.
From the viewpoint of high image quality, the volume-median particle size (D 50 ) of the coalesced particles is preferably 1 to 10 μm, more preferably 2 to 9 μm, and even more preferably 3 to 8 μm.
本発明においては、得られた合一粒子は、ろ過、遠心分離などの固液分離工程、洗浄工程、及び乾燥工程を経て、トナー粒子となるが、ここで、洗浄工程は、トナーとして十分な帯電特性及び信頼性を確保する目的で行われ、トナー表面の金属イオンを除去することを含む。洗浄は複数回行うことが好ましい。 In the present invention, the obtained coalesced particles become toner particles through a solid-liquid separation process such as filtration and centrifugal separation, a washing process, and a drying process. Here, the washing process is sufficient as a toner. It is performed for the purpose of ensuring charging characteristics and reliability, and includes removing metal ions on the toner surface. The washing is preferably performed a plurality of times.
（工程（Ｂ））
本発明においては、乾燥工程において、上記工程（Ａ）で得られたトナー粒子の分散液をパルス燃焼による衝撃波の雰囲気中に噴霧して乾燥する、パルス燃焼式乾燥方法が用いられる。ここで、パルス燃焼式乾燥方法とは、パルスエンジンにより強力なパルス衝撃波（空中超音波と熱風）を発生させ、分散液やスラリーなどの溶液を該衝撃波中に噴霧し、パルス衝撃波と熱により固体と液体を分離・乾燥させる方法である。この乾燥方法によれば、単純な熱のみによる蒸発乾燥だけでなく、圧力変動を利用した力学的な作用も伴うため、瞬間乾燥（例えば１／１００秒以下）、低温乾燥（例えば、６０℃以下）及び高い熱効率を実現できる。
(Process (B))
In the present invention, a pulse combustion type drying method is used in which the toner particle dispersion obtained in the above step (A) is sprayed and dried in a shock wave atmosphere by pulse combustion in the drying step. Here, the pulse combustion type drying method is a method in which a powerful pulse shock wave (airborne ultrasonic wave and hot air) is generated by a pulse engine, a solution such as a dispersion or slurry is sprayed into the shock wave, and the solid is generated by the pulse shock wave and heat. And the liquid is separated and dried. According to this drying method, not only a simple heat-evaporated drying but also a dynamic action utilizing pressure fluctuation is involved, so instantaneous drying (for example, 1/100 second or less), low-temperature drying (for example, 60 ° C. or less) ) And high thermal efficiency.
本発明においては、具体的には、トナー粒子は、洗浄後、水性液中にトナー粒子を分散させた分散液としてパルス衝撃波乾燥装置に導入され、パルスエンジンの燃焼ガス排出口付近に噴霧されてパルス燃焼波により乾燥、粉末化される。水性液としては、例えば脱イオン水を挙げることができる。
本発明に使用されるパルス衝撃波乾燥装置としては、例えば特公平６−２８６８１号公報等に記載されている装置が使用できる。図１に、本発明において使用することができるパルス衝撃波乾燥装置の一例の概略説明図を示す。
In the present invention, specifically, the toner particles are introduced into the pulse shock wave drying device as a dispersion liquid in which the toner particles are dispersed in the aqueous liquid after being washed, and sprayed near the combustion gas discharge port of the pulse engine. It is dried and powdered by the pulse combustion wave. Examples of the aqueous liquid include deionized water.
As the pulse shock wave drying apparatus used in the present invention, for example, an apparatus described in Japanese Patent Publication No. 6-28681 can be used. FIG. 1 is a schematic explanatory diagram of an example of a pulse shock wave drying apparatus that can be used in the present invention.
図１によれば、パルス衝撃波乾燥装置において、ドライチェンバー１中の熱源であるパルスエンジン２によりパルス衝撃波（空中超音波と熱風）を発生させる。パルスエンジン２は、燃料供給口３及び空気供給口４より、それぞれ燃料および空気を供給し、燃料を毎秒数十回〜数千回にわたって爆発させてパルスを発生せしめる燃焼器であり、単なる熱に加え、パルス衝撃波を発生せしめることができる。この燃焼ガス排出口付近のパルス燃焼により衝撃波雰囲気中に、トナー粒子分散液供給口６からトナー粒子の分散液を噴霧し、パルス衝撃波と熱により分散液中の固体が一次粒子にまで分散されることで、効率よく乾燥が行われる。分散液の噴霧、パルス燃焼、衝撃波雰囲気の各々の条件、程度については、所望の乾燥度が得られるものであれば特に制限はなく、適宜選択可能である。パルス衝撃波乾燥装置は、更に燃焼ガスを冷却するために供給される二次空気供給口５を有し、乾燥粉末は乾燥室７、サイクロン装置８およびバグフィルター９で捕集され、コンベアー１０に排出され、製品トナーとして得ることができる。
According to FIG. 1, in a pulse shock wave drying apparatus, a pulse shock wave (airborne ultrasonic wave and hot air) is generated by a
上記工程（Ｂ）においては、乾燥に供する分散液中の固形分濃度は、得られるトナーの定着性の観点から、１重量％以上５０重量％未満であることが好ましく、より好ましくは１重量％以上４５重量％以下である。乾燥前の分散液は必要に応じて適宜種々の分散液として乾燥に供することができる。また、乾燥の際の温度は、トナーの凝集体の発生を抑制し、定着性を高める観点から結着樹脂のガラス転移点＋２０℃以下であるころが好ましく、ガラス転移点＋１０℃以下がより好ましく、ガラス転移点以下がさらに好ましい。 In the step (B), the solid content concentration in the dispersion to be dried is preferably 1% by weight or more and less than 50% by weight, more preferably 1% by weight, from the viewpoint of the fixability of the obtained toner. It is 45 weight% or less. The dispersion before drying can be used for drying as various dispersions as needed. The temperature at the time of drying is preferably from about the glass transition point of the binder resin to 20 ° C. or less, more preferably from about 10 ° C. or less, from the viewpoint of suppressing the generation of toner aggregates and improving the fixability. The glass transition point or lower is more preferable.
乾燥後の水分含有量は、乾燥条件により適宜調整することができるが、得られるトナーの帯電性及び低定着性の観点から、水分割合（水分率）で、好ましくは１．５重量％以下、より好ましくは１．０重量％以下、更に好ましくは０．５重量％以下である。
上記乾燥方法により、本発明においては、衝撃波による分散効果で、トナー粒子は一次粒子にまで分散されるので、乾燥品には凝集体がほとんどなく、その後の解砕工程や分級工程を必要としない。また、トナー粒子中の空隙部分に含まれる水分も、衝撃波によりトナー粒子表面まで移動し易くなり、効果的に乾燥されるため低温定着性が向上する。
本発明においては、工程（Ｂ）の乾燥工程において、上記パルス燃焼式乾燥方法とともに、本発明の効果を損しない範囲において、必要に応じ、真空乾燥法、スプレードライ法、気流乾燥法、流動乾燥法等の方法を併用することができる。
The water content after drying can be appropriately adjusted depending on the drying conditions, but from the viewpoint of chargeability and low fixability of the obtained toner, the water content (water content) is preferably 1.5% by weight or less. More preferably, it is 1.0 weight% or less, More preferably, it is 0.5 weight% or less.
By the above drying method, in the present invention, the toner particles are dispersed to the primary particles by the dispersion effect due to the shock wave, so that the dried product has almost no aggregates and does not require the subsequent crushing step or classification step. . In addition, the moisture contained in the voids in the toner particles is easily moved to the toner particle surface by the shock wave and is effectively dried, so that the low-temperature fixability is improved.
In the present invention, in the drying step of step (B), together with the above-mentioned pulse combustion type drying method, as long as the effects of the present invention are not impaired, a vacuum drying method, a spray drying method, an air flow drying method, a fluidized drying method, as necessary Methods such as law can be used in combination.
本発明の方法で得られるトナーには、外添剤として流動化剤等の助剤を合一粒子表面に添加処理することができる（外添剤による表面処理前のトナーをトナー母粒子ともいう）。外添剤としては、表面を疎水化処理したシリカ微粒子、酸化チタン微粒子、アルミナ微粒子、酸化セリウム微粒子、カーボンブラック等の無機微粒子やポリカーボネート、ポリメチルメタクリレート、シリコーン等のポリマー微粒子等、公知の微粒子が使用できる。
外添剤の配合量は、トナー母粒子１００重量部に対して、１〜５重量部が好ましく、１．５〜３．５重量部がより好ましい。ただし、外添剤として疎水性シリカを用いる場合は、トナー母粒子１００重量部に対して、疎水性シリカを１〜３重量部用いることが好ましい。
To the toner obtained by the method of the present invention, an auxiliary agent such as a fluidizing agent can be added to the surface of the coalesced particles as an external additive (the toner before the surface treatment with the external additive is also referred to as toner base particles). ). Examples of the external additive include known fine particles such as silica fine particles whose surface is hydrophobized, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, carbon black and other inorganic fine particles, and polymer fine particles such as polycarbonate, polymethyl methacrylate and silicone. Can be used.
The amount of the external additive is preferably 1 to 5 parts by weight and more preferably 1.5 to 3.5 parts by weight with respect to 100 parts by weight of the toner base particles. However, when using hydrophobic silica as an external additive, it is preferable to use 1 to 3 parts by weight of hydrophobic silica with respect to 100 parts by weight of toner base particles.
トナー母粒子と外添剤を混合する際に用いられる混合機としては、ヘンシェルミキサー(三井三池社製)、スーパーミキサー(カワタ社製)、メカノフュージュンシステム(ホソカワミクロン社製)等の攪拌装置が挙げられるが、これらの中では攪拌力の点でヘンシェルミキサーが好ましい。本発明の製造工程の後に上記表面処理工程を行う製造方法は、トナーの凝集物を解砕効果が得られる点でも有効な製造方法である。 As a mixer used for mixing the toner base particles and the external additive, a stirrer such as a Henschel mixer (manufactured by Mitsui Miike), a super mixer (manufactured by Kawata), a mechano-fusion system (manufactured by Hosokawa Micron), etc. Among these, a Henschel mixer is preferable in terms of stirring power. The manufacturing method in which the surface treatment step is performed after the manufacturing step of the present invention is also an effective manufacturing method in that a toner agglomeration effect can be obtained.
［電子写真用トナー］
以下、前記電子写真用トナーの製造方法により得られる電子写真用トナーについて説明する。
トナーの軟化点は、低温定着性の観点から、６０〜１４０℃であることが好ましく、より好ましくは６０〜１３０℃、さらに好ましくは６０〜１２０℃である。また、ガラス転移点は、耐久性の観点から、３０〜８０℃が好ましく、４０〜７０℃がより好ましい。なお、軟化点及びガラス転移点の測定方法は、樹脂におけるこれらの測定方法に準ずる。
[Electrophotographic toner]
Hereinafter, the electrophotographic toner obtained by the method for producing the electrophotographic toner will be described.
The softening point of the toner is preferably 60 to 140 ° C., more preferably 60 to 130 ° C., and still more preferably 60 to 120 ° C. from the viewpoint of low-temperature fixability. Moreover, 30-80 degreeC is preferable from a durable viewpoint, and, as for a glass transition point, 40-70 degreeC is more preferable. In addition, the measuring method of a softening point and a glass transition point is based on these measuring methods in resin.
高画質化の観点から、トナーの体積中位粒径（Ｄ50）は１〜１０μｍであることが好ましく、２〜９μｍがより好ましく、２〜８μｍがより好ましく、３〜８μｍが更に好ましい。また、前述の凝集粒子、合一粒子及びトナー粒子の粒度分布の変動係数（ＣＶ値）は、下記式で求めることができ、いずれも３０以下が好ましく、２７以下がより好ましく、２５以下が更に好ましい。ここで、トナーの粒径及び粒度分布は、後述の方法で測定することができる。
変動係数（ＣＶ値）＝（粒径分布の標準偏差／体積中位粒径（Ｄ50））×１００
本発明により得られる電子写真用トナーは、一成分系現像剤として、又はキャリアと混合して二成分系現像剤として使用することができる。
From the viewpoint of high image quality, the volume median particle size (D 50 ) of the toner is preferably 1 to 10 μm, more preferably 2 to 9 μm, more preferably 2 to 8 μm, and even more preferably 3 to 8 μm. Further, the coefficient of variation (CV value) of the particle size distribution of the above-mentioned aggregated particles, coalesced particles and toner particles can be determined by the following formula, and all are preferably 30 or less, more preferably 27 or less, and further 25 or less. preferable. Here, the particle size and particle size distribution of the toner can be measured by the method described below.
Coefficient of variation (CV value) = (standard deviation of particle size distribution / volume median particle size (D 50 )) × 100
The toner for electrophotography obtained by the present invention can be used as a one-component developer or as a two-component developer by mixing with a carrier.
以下に実施例等により、本発明を更に具体的に説明する。以下の実施例等においては、各性状値は次の方法により測定、評価した。
［樹脂の酸価］
ＪＩＳ Ｋ００７０に従って測定する。但し、測定溶媒は、エタノールとエーテルの混合溶媒を、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))とした。
Hereinafter, the present invention will be described more specifically with reference to examples and the like. In the following examples and the like, each property value was measured and evaluated by the following method.
[Acid value of resin]
Measured according to JIS K0070. However, as a measurement solvent, a mixed solvent of ethanol and ether was a mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).
［結着樹脂、トナーの軟化点及びガラス転移点］
（１）軟化点
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のノズルから押し出す。温度に対し、フローテスターのブ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。
[Binder resin, toner softening point and glass transition point]
(1) Softening point Using a flow tester (Shimadzu Corporation, “CFT-500D”), a 1 g sample was heated at a heating rate of 6 ° C./min, a load of 1.96 MPa was applied by a plunger, a diameter of 1 mm, Extrude from a 1 mm long nozzle. Plot the flow tester drop by the flow tester against the temperature, and let the softening point be the temperature at which half the sample flowed out.
（２）ガラス転移点
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℃まで冷却した試料を昇温速度１０℃／分で測定する。軟化点より２０℃以上低い温度でピークが観測される場合にはそのピークの温度を、また軟化点より２０℃以上低い温度でピークが観測されずに段差が観測されるときは該段差部分の曲線の最大傾斜を示す接線と該段差の高温側のベースラインの延長線との交点の温度を、ガラス転移点として読み取る。なお、ガラス転移点は、樹脂の非晶質部分に特有の物性であり、一般には非晶質ポリエステルで観測されるが、結晶性ポリエステルでも非晶質部分が存在する場合には観測されることがある。
(2) Glass transition point The temperature was raised to 200 ° C. using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), and the sample was cooled from that temperature to 0 ° C. at a temperature lowering rate of 10 ° C./min. Measured in ° C / min. When a peak is observed at a temperature 20 ° C. or more lower than the softening point, the peak temperature is measured. When a peak is not observed at a temperature 20 ° C. or higher lower than the softening point, a step is observed. The temperature at the intersection of the tangent line indicating the maximum slope of the curve and the extension line of the base line on the high temperature side of the step is read as the glass transition point. The glass transition point is a physical property peculiar to the amorphous part of the resin, and is generally observed in amorphous polyester, but is observed when amorphous part exists even in crystalline polyester. There is.
［結着樹脂の数平均分子量］
以下の方法により、ゲルパーミエーションクロマトグラフィーにより分子量分布を測定し、数平均分子量を算出する。
（１）試料溶液の調製
濃度が０．５ｇ／１００ｍｌになるように、樹脂をクロロホルムに溶解させる。次いで、この溶液をポアサイズ２μｍのフッ素樹脂フィルター［住友電気工業（株）製、「ＦＰ−２００」］を用いて濾過して不溶解成分を除き、試料溶液とする。
（２）分子量分布測定
下記装置を用いて、クロロホルムを毎分１ｍｌの流速で流し、４０℃の恒温槽中でカラムを安定させる。そこに試料溶液１００μｌを注入して測定を行う。試料の分子量は、あらかじめ作成した検量線に基づき算出する。このときの検量線には、数種類の単分散ポリスチレン(東ソー(株)製の２.６３×１０3、２.０６×１０4、１.０２×１０5、ジーエルサイエンス社製の２.１０×１０3、７.００×１０3、５.０４×１０4)を標準試料として作成したものを用いる。
測定装置：ＣＯ−８０１０（東ソー社製）
分析カラム：ＧＭＨＬＸ＋Ｇ３０００ＨＸＬ（東ソー社製）
[Number average molecular weight of binder resin]
The molecular weight distribution is measured by gel permeation chromatography and the number average molecular weight is calculated by the following method.
(1) Preparation of sample solution The resin is dissolved in chloroform so that the concentration is 0.5 g / 100 ml. Subsequently, this solution is filtered using a fluororesin filter having a pore size of 2 μm [manufactured by Sumitomo Electric Industries, Ltd., “FP-200”] to remove insoluble components to obtain a sample solution.
(2) Molecular weight distribution measurement Using the following apparatus, chloroform is flowed at a flow rate of 1 ml per minute, and the column is stabilized in a constant temperature bath at 40 ° C. 100 μl of the sample solution is injected therein and measurement is performed. The molecular weight of the sample is calculated based on a calibration curve prepared in advance. In this calibration curve, several types of monodisperse polystyrene (2.63 × 10 3 , 2.06 × 10 4 , 1.02 × 10 5 manufactured by Tosoh Corporation), 2.10 × manufactured by GL Sciences Inc. 10 3 , 7.00 × 10 3 , 5.04 × 10 4 ) are used as standard samples.
Measuring device: CO-8010 (manufactured by Tosoh Corporation)
Analysis column: GMHLX + G3000HXL (manufactured by Tosoh Corporation)
［樹脂粒子及び離型剤粒子の粒径］
レーザー回折型粒径測定機（ＨＯＲＩＢＡ製、「ＬＡ−９２０」）を用いて、測定用セルに蒸留水を加え、水に対する相対屈折率を１．２として、吸光度が適正範囲になる濃度で得られた粒径分布からメジアン径（すなわち、体積中位粒径(Ｄ50)）、及び、体積平均粒径(Ｄ4)及び標準偏差を測定、算出する。また、樹脂粒子、及び離型剤粒子の体積基準の変動係数（ＣＶ値）は下記の式に従って算出する。
体積基準の変動係数（ＣＶ値）＝（粒径分布の標準偏差／体積平均粒径(Ｄ4)）×１００
[Particle size of resin particles and release agent particles]
Using a laser diffraction particle size measuring instrument (HORIBA, “LA-920”), distilled water is added to the measurement cell, the relative refractive index to water is 1.2, and the absorbance is obtained at a concentration within an appropriate range. From the obtained particle size distribution, the median diameter (that is, the volume median particle size (D 50 )), the volume average particle size (D 4 ), and the standard deviation are measured and calculated. The volume-based coefficient of variation (CV value) of the resin particles and the release agent particles is calculated according to the following formula.
Volume-based coefficient of variation (CV value) = (standard deviation of particle size distribution / volume average particle size (D 4 )) × 100
［乳化液、乾燥前の分散液中の固形分濃度］
赤外線水分計（株式会社ケツト科学研究所：ＦＤ−２３０）を用いて、乳化液５ｇを乾燥温度１５０℃，測定モード９６（監視時間２．５分／変動幅０．０５％）にて、ウェットベースの水分％を測定する。固形分濃度は下記の式に従って算出した。
固形分濃度（％）＝１００−Ｍ
Ｍ：ウェットベース水分（％）＝［（Ｗ−Ｗ０）／Ｗ］×１００
Ｗ：測定前の試料重量（初期試料重量）
Ｗ０：測定後の試料重量（絶対乾燥重量）
[Emulsified liquid, solid concentration in dispersion before drying]
Using an infrared moisture meter (Ketto Science Laboratory Co., Ltd .: FD-230), 5 g of the emulsion was wet at a drying temperature of 150 ° C. and in a measurement mode 96 (monitoring time 2.5 minutes / variation width 0.05%). Measure the moisture content of the base. The solid content concentration was calculated according to the following formula.
Solid content concentration (%) = 100-M
M: wet base moisture (%) = [(W−W0) / W] × 100
W: Sample weight before measurement (initial sample weight)
W0: Sample weight after measurement (absolute dry weight)
［凝集粒子，合一粒子及びトナーの粒径］
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を添加する。さらに、トナーの測定においては超音波分散機にて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。
また、トナーの粒度分布の変動係数（ＣＶ値）は下記の式に従って算出する。
変動係数（ＣＶ値）＝（粒径分布の標準偏差／体積中位粒径(Ｄ50)）×１００
[Agglomerated particles, coalesced particles and toner particle size]
Measuring machine: Coulter Multisizer II (Beckman Coulter, Inc.)
Aperture diameter: 50 μm
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, and then 25 ml of an electrolyte is added. Further, in the measurement of toner, a sample dispersion is prepared by dispersing for 1 minute with an ultrasonic disperser.
Measurement conditions: By adding the sample dispersion to 100 ml of the electrolyte solution, the particle size of 30,000 particles is adjusted to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured. Determine the volume median particle size (D 50 ).
The coefficient of variation (CV value) of the toner particle size distribution is calculated according to the following equation.
Coefficient of variation (CV value) = (standard deviation of particle size distribution / volume median particle size (D 50 )) × 100
製造例１ ポリエステルＡの製造
ポリオキシプロピレン（２．２）−２，２−ビス（４−ヒドロキシフェニル）プロパン８３２０ｇ、ポリオキシエチレン（２．０）−２，２−ビス（４−ヒドロキシフェニル）プロパン８０ｇ、テレフタル酸１５９２ｇ及びジブチル錫オキサイド（エステル化触媒）３２ｇを窒素導入管、脱水管、攪拌器及熱電対を装備した四つ口フラスコに入れ、窒素雰囲気下、常圧（１０１．３ｋＰａ）下２３０℃で５時間反応させ、更に減圧（８．３ｋＰａ）下で反応させた。２１０℃に冷却し、フマル酸１６７２ｇ、ハイドロキノン８ｇを加え、５時間反応させた後に、更に上記減圧下で反応させて、ポリエステルＡを得た。ポリエステルＡの軟化点は１１０℃、ガラス転移点は６６℃、酸価は２４．４ｍｇＫＯＨ／ｇ、数平均分子量は３７６０であった。
Production Example 1 Production of Polyester A 8320 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) 80 g of propane, 1592 g of terephthalic acid and 32 g of dibutyltin oxide (esterification catalyst) are placed in a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, and under atmospheric pressure (101.3 kPa) under a nitrogen atmosphere The reaction was carried out at 230 ° C. for 5 hours and further under reduced pressure (8.3 kPa). After cooling to 210 ° C., 1672 g of fumaric acid and 8 g of hydroquinone were added and reacted for 5 hours, and further reacted under the reduced pressure to obtain polyester A. Polyester A had a softening point of 110 ° C., a glass transition point of 66 ° C., an acid value of 24.4 mgKOH / g, and a number average molecular weight of 3760.
製造例２ ポリエステルＢの製造
ポリオキシプロピレン（２．２）−２，２−ビス（４−ヒドロキシフェニル）プロパン１７５００ｇ、ポリオキシエチレン（２．０）−２，２−ビス（４−ヒドロキシフェニル）プロパン１６２５０ｇ、テレフタル酸１１４５４ｇ、ドデセニルコハク酸無水物１６０８ｇ、トリメリット酸無水物４８００ｇ及びジブチル錫オキサイド１５ｇを窒素導入管、脱水管、攪拌器及び熱電対を装備した四つ口フラスコに入れ、窒素雰囲気下、２２０℃で攪拌し、ＡＳＴＭ Ｄ３６−８６に準拠して測定した軟化点が１２０℃に達するまで反応させて、ポリエステルＢを得た。ポリエステルＢの軟化点は１２１℃、ガラス転移点は６５℃、酸価は１８．５ｍｇＫＯＨ／ｇ、数平均分子量は３３９４であった。
Production Example 2 Production of Polyester B 17500 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) 16250 g of propane, 11454 g of terephthalic acid, 1608 g of dodecenyl succinic anhydride, 4800 g of trimellitic anhydride and 15 g of dibutyltin oxide were placed in a four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer and a thermocouple, and under a nitrogen atmosphere The polyester B was obtained by stirring at 220 ° C. and reacting until the softening point measured in accordance with ASTM D36-86 reached 120 ° C. Polyester B had a softening point of 121 ° C., a glass transition point of 65 ° C., an acid value of 18.5 mgKOH / g, and a number average molecular weight of 3394.
製造例３ マスターバッチ１の製造
製造例１で得たポリエステルＡの微粉末７０重量部及び大日精化製銅フタロシアニンのスラリー顔料（ＥＣＢ−３０１：固形分４６．２重量％）を顔料分３０重量部になる様にヘンシェルミキサーに仕込み５分間混合し湿潤させた。次にこの混合物をニーダー型ミキサーに仕込み徐々に加熱した。ほぼ９０〜１１０℃にて樹脂が溶融し、水が混在した状態で混練し、水を蒸発させながら２０分間９０〜１１０℃で混練を続けた。
更に１２０℃にて混練を続け残留している水分を蒸発させ、脱水乾燥させた。更に１２０〜１３０℃にて１０分間混練を続けた。冷却後更に加熱三本ロールにより混練し、冷却、粗砕して青色顔料を３０重量％の濃度で含有する高濃度着色組成物の粗砕品（マスターバッチ１）を得た。これをスライドグラスに乗せて加熱溶融させて顕微鏡で観察したところ、顔料粒子は全て微細に分散しており、粗大粒子は認められなかった。
Production Example 3 Production of Master Batch 1 70 parts by weight of fine powder of polyester A obtained in Production Example 1 and slurry pigment of copper phthalocyanine manufactured by Dainichi Seika (ECB-301: solid content 46.2% by weight) 30% by weight of pigment The mixture was mixed in a Henschel mixer for 5 minutes and moistened. Next, this mixture was charged into a kneader mixer and gradually heated. The resin was melted at approximately 90 to 110 ° C. and kneaded in a state where water was mixed, and kneading was continued at 90 to 110 ° C. for 20 minutes while water was evaporated.
Further, the kneading was continued at 120 ° C. to evaporate the remaining water, followed by dehydration drying. Further, kneading was continued at 120 to 130 ° C. for 10 minutes. After cooling, the mixture was further kneaded with a heated three roll, cooled and coarsely crushed to obtain a crushed product (master batch 1) of a high-concentration colored composition containing a blue pigment at a concentration of 30% by weight. When this was placed on a slide glass, heated and melted, and observed with a microscope, all pigment particles were finely dispersed, and no coarse particles were observed.
製造例４ 離型剤分散液の製造
２リットル容のビーカーで、脱イオン水８００ｇにアルケニルコハク酸ジカリウム水溶液「ラテムルＡＳＫ（花王（株）社製）、有効濃度２８％」７.１４gを溶解させた後、カルナウバロウワックス（加藤洋行社製、融点８５℃）２００ｇを分散させた。この分散液を９０〜９５℃に温度を保持しながら、Ｕｌｔｒａｓｏｎｉｃ Ｈｏｍｏｇｅｎｉｚｅｒ ６００Ｗ (日本精機社製)で３０分間分散処理を行い、体積中位粒径（Ｄ50）：０.５１μｍ、ＣＶ値：３２、固形分濃度：２２％の離型剤分散液を得た。
Production Example 4 Production of mold release agent dispersion In a 2-liter beaker, 7.14 g of an aqueous solution of dipotassium alkenyl succinate “Latemul ASK (manufactured by Kao Corporation), effective concentration 28%” was dissolved in 800 g of deionized water. After that, 200 g of carnauba wax (manufactured by Kato Yoko Co., Ltd., melting point 85 ° C.) was dispersed. While maintaining the temperature at 90 to 95 ° C., this dispersion was subjected to a dispersion treatment with an Ultrasonic Homogenizer 600W (manufactured by Nippon Seiki Co., Ltd.) for 30 minutes, a volume median particle size (D 50 ): 0.51 μm, and a CV value: 32 A release agent dispersion having a solid content concentration of 22% was obtained.
実施例１及び３、並びに参考例２、４及び５
（工程Ａ）
樹脂乳化液の製造
ポリエステルＡ ６４０ｇ、ポリエステルＢ ４２０ｇ、マスターバッチ１ ２００ｇ（ポリエステルＡ、ポリエステルＢ及びマスターバッチ１に用いた樹脂を前記配合割合で混合溶融した混合樹脂の軟化点は１１４℃、ガラス転移点は６４℃であった）、及び、アニオン性界面活性剤「ネオペレックス Ｇ−１５（花王社製）」ドデシルベンゼンスルホン酸ナトリウム（固形分：１５重量％）８０ｇ、および、非イオン性界面活性剤「エマルゲン ４３０（花王社製）」ポリオキシエチレン（２６ｍｏｌ）オレイルエーテル（ＨＬＢ：１６．２）１２ｇ、及び５重量％水酸化カリウム水溶液５５１ｇを、２軸の攪拌羽根が遊星運動を行う、プラネタリーミキサー（ＰＲＩＭＩＸ社製：５Ｌ容Ｔ．Ｋ.ハイビスミックス）にて、攪拌羽根が自転方向と逆向きに捻転した形状のブレード状の羽根を用い、攪拌周速１．２ｍ／ｓｅｃ（自転周速：０.７ｍ／ｓｅｃ、公転周速：０.５ｍ／ｓｅｃ）の攪拌下、２５℃で分散させた後、９５℃まで昇温して２時間中和を行った。続いて、脱イオン水を１２ｇ／ｍｉｎ（樹脂１００ｇあたり１ｇ/分）で２２７６ｇ滴下し、乳化を行った。得られた乳化液を室温まで冷却し２００メッシュ（目開き：１０５μｍ）の金網を通して、微粒化した樹脂乳化液（１）を得た。得られた樹脂乳化液（１）中の樹脂粒子の固形濃度は３１．２重量％、樹脂乳化液中の樹脂粒子の体積中位粒径(Ｄ50)は０．１３μｍ、体積基準の変動係数は２５であり、金網上に樹脂成分は何も残らなかった。
Examples 1 and 3 and Reference Examples 2, 4 and 5
(Process A)
Production of resin emulsion: 640 g of polyester A, 420 g of polyester B, 200 g of master batch 1 (the softening point of the mixed resin obtained by mixing and melting the resins used in polyester A, polyester B, and master batch 1 at the above blending ratio is 114 ° C., glass transition The point was 64 ° C.), and anionic surfactant “Neopelex G-15 (manufactured by Kao)” sodium dodecylbenzenesulfonate (solid content: 15% by weight) 80 g, and nonionic surfactant The agent “Emulgen 430 (manufactured by Kao)” polyoxyethylene (26 mol) oleyl ether (HLB: 16.2) 12 g and 5 wt% potassium hydroxide aqueous solution 551 g Stir with a Lee mixer (manufactured by PRIMIX: 5L TK Hibismix) Using a blade-like blade whose root is twisted in the direction opposite to the rotation direction, stirring agitation speed of 1.2 m / sec (spinning speed: 0.7 m / sec, revolution speed: 0.5 m / sec) Then, after dispersing at 25 ° C., the mixture was heated to 95 ° C. and neutralized for 2 hours. Subsequently, 2276 g of deionized water was added dropwise at 12 g / min (1 g / min per 100 g of resin) for emulsification. The obtained emulsion was cooled to room temperature and passed through a 200 mesh (mesh opening: 105 μm) wire mesh to obtain a finely divided resin emulsion (1). The solid concentration of the resin particles in the obtained resin emulsion (1) is 31.2% by weight, the volume median particle size (D 50 ) of the resin particles in the resin emulsion is 0.13 μm, and the coefficient of variation based on volume. And no resin component remained on the wire mesh.
トナー粒子の製造
１）凝集粒子の作成
（ａ）コア材の作成）
樹脂乳化液（１） ５００ｇ、製造例４で得た離型剤分散液３８ｇ、脱イオン水１３７ｇを脱水管、攪拌器及び熱電対を装備した２リットル容四つ口フラスコに入れ、室温下混合した。次に、カイ型の攪拌機で攪拌下、この混合物に硫酸アンモニウム（シグマアルドリッチジャパン社製 特級）３４ｇを２７９ｇの脱イオン水に溶解させた水溶液を室温で１０分かけて滴下した。その後、混合分散液を５５℃まで昇温し凝集粒子を形成させ、５５℃で３時間保持した。
（ｂ）シェル材の添加
シェル材として、樹脂乳化液（１）５０ｇと脱イオン水１３ｇを混合したものを２ｍＬ／ｍｉｎで滴下し、その後５５℃で２０分間保持した。この操作を更に２回繰り返した。さらに、樹脂乳化液（１）５０ｇと脱イオン水１１ｇを混合したもの、及び、硫酸アンモニウム３．４ｇを脱イオン水４６ｇに溶解させた水溶液を別々に同時に２ｍＬ／ｍｉｎで滴下し、その後５５℃で２０分間保持した。この操作を更に１回繰り返した。
その後、ポリオキシエチレン（２モル）ドデシルエーテル硫酸ナトリウム水溶液（固形分：２８重量％）４２ｇを脱イオン水３７５ｇで希釈した水溶液を添加した。この時、凝集粒子の体積中位粒径（Ｄ50）は４．７μｍ、ＣＶ値は２４であった。
Toner particle manufacturing
1) Production of aggregated particles (a) Production of core material)
Resin emulsion (1) 500 g, release agent dispersion 38 g obtained in Production Example 4 and 137 g of deionized water were placed in a 2 liter four-necked flask equipped with a dehydrating tube, a stirrer and a thermocouple, and mixed at room temperature. did. Next, an aqueous solution in which 34 g of ammonium sulfate (special grade made by Sigma-Aldrich Japan) was dissolved in 279 g of deionized water was added dropwise to this mixture at room temperature over 10 minutes while stirring with a Kai-type stirrer. Thereafter, the mixed dispersion was heated to 55 ° C. to form aggregated particles, and held at 55 ° C. for 3 hours.
(B) Addition of shell material As a shell material, a mixture of 50 g of resin emulsion (1) and 13 g of deionized water was added dropwise at 2 mL / min, and then held at 55 ° C for 20 minutes. This operation was repeated two more times. Further, 50 g of the resin emulsion (1) and 11 g of deionized water and an aqueous solution in which 3.4 g of ammonium sulfate was dissolved in 46 g of deionized water were separately dropped simultaneously at 2 mL / min, and then at 55 ° C. Hold for 20 minutes. This operation was repeated once more.
Thereafter, an aqueous solution obtained by diluting 42 g of polyoxyethylene (2 mol) aqueous sodium dodecyl ether sulfate (solid content: 28% by weight) with 375 g of deionized water was added. At this time, the volume-median particle size (D 50 ) of the aggregated particles was 4.7 μm, and the CV value was 24.
２）合一粒子の作成
ポリオキシエチレン（２モル）ドデシルエーテル硫酸ナトリウム水溶液を添加後、８０℃まで昇温した。８０℃で１時間保持した後、室温まで冷却した。その後、内容物を、吸引ろ過、洗浄を行い、トナー粒子の含水ケーキを得た。トナー粒子の体積中位粒径（Ｄ50）は４．９μm、ＣＶ値は２１であった。
2) Preparation of coalesced particles After adding an aqueous solution of polyoxyethylene (2 mol) sodium dodecyl ether sulfate, the temperature was raised to 80 ° C. After holding at 80 ° C. for 1 hour, it was cooled to room temperature. Thereafter, the contents were subjected to suction filtration and washing to obtain a water-containing cake of toner particles. The toner particles had a volume median particle size (D 50 ) of 4.9 μm and a CV value of 21.
工程（Ｂ）
乾燥工程
得られたトナー粒子の含水ケーキに脱イオン水を加え、表１に示す各々の固形分濃度に調整したトナー粒子を含むトナー粒子分散液をパルス燃焼乾燥装置（パルテック社製：蒸発量２ｋｇ／ｈｒハイパルコン）を用いて噴霧圧：０．４ＭＰａ、燃焼量：９．０９ＭＪ／ｈの条件で乾燥を行い、D50が４．９μｍのトナー母粒子を得た。
このトナー母粒子１００重量部に対して１．０重量部の疎水性シリカ（日本アエロジル社製、Ｒ９７２、個数平均粒子径１６ｎｍ）をヘンシェルミキサーを用いて外添しトナー（１）〜（７）とした。各トナーについて、下記方法により、乾燥後の水分率、凝集体割合及び定着性を測定した結果を表１に示す。
Process (B)
Deionized water is added to the water-containing cake of toner particles obtained in the drying step, and a toner particle dispersion containing toner particles adjusted to the respective solid content concentrations shown in Table 1 is converted into a pulse combustion drying device (manufactured by Partec:
Toners (1) to (7) are prepared by externally adding 1.0 part by weight of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., R972, number average particle diameter 16 nm) to 100 parts by weight of the toner base particles using a Henschel mixer. It was. Table 1 shows the results of measuring the moisture content after drying, the aggregate ratio, and the fixability of each toner by the following method.
比較例１（スプレードライ法）
実施例1と同様に調製したトナー粒子分散液を、スプレードライヤー（Ｌ−８型、大川原化工機社製）を用いて、乾燥室温度１００℃にて乾燥を行った。実施例１と同様にして乾燥後の水分率、凝集体割合及び定着性を測定した結果を表１に示す。
Comparative Example 1 (spray drying method)
The toner particle dispersion prepared in the same manner as in Example 1 was dried at a drying chamber temperature of 100 ° C. using a spray dryer (L-8 type, manufactured by Okawara Kako Co., Ltd.). The results of measuring the moisture content after drying, the aggregate ratio, and the fixability in the same manner as in Example 1 are shown in Table 1.
比較例2（真空乾燥法）
実施例１と同様にして、トナー粒子の含水率が３５重量％（固形分６５重量％）になるよう、濾過により固液分離してトナー粒子含水ケーキを調製した。
得られたトナー粒子含水ケーキを、自・公転する攪拌機構を有した真空乾燥機（ＮＸＶ−１型、ホソカワミクロン社製）を用いて、ジャケット温度４５℃，圧力−０．０９ＭＰａにて乾燥を行った。乾燥に要した時間は１３時間であった。実施例１と同様にして乾燥後の水分率、凝集体量及び定着性を測定した結果を表１に示す。
Comparative example 2 (vacuum drying method)
In the same manner as in Example 1, a toner particle water-containing cake was prepared by solid-liquid separation by filtration so that the water content of the toner particles was 35% by weight (solid content 65% by weight).
The obtained toner particle water-containing cake is dried at a jacket temperature of 45 ° C. and a pressure of −0.09 MPa using a vacuum dryer (NXV-1 type, manufactured by Hosokawa Micron Corporation) having a stirring mechanism that rotates and revolves. It was. The time required for drying was 13 hours. Table 1 shows the results of measuring the moisture content after drying, the amount of aggregates, and the fixability in the same manner as in Example 1.
［乾燥前のトナー粒子分散液、トナー粒子含水ケーキの固形分濃度、乾燥後のトナーの水分率］
赤外線水分計（株式会社ケツト科学研究所：ＦＤ−２３０）を用いて、乾燥前のトナー粒子分散液、トナー粒子含水ケーキ、または、乾燥後のトナー５ｇを乾燥温度１５０℃，測定モード９６（監視時間２．５分／変動幅０．０５％）にて、ウェットベースの水分％を測定する。水分率および固形分は下記の式に従って算出した。
水分率（Ｍ）（％）＝［（Ｗ−Ｗ０）／Ｗ］×１００
固形分（％）＝１００−Ｍ
Ｗ：測定前の試料重量（初期試料重量）
Ｗ０：測定後の試料重量（絶対乾燥重量）
なお、水分率が０．５重量％以上の場合、含水ケーキをバットに移し、温度４０℃、圧力０．０８ＭＰａにて１５時間棚乾燥を行った。
[Toner particle dispersion before drying, solid content concentration of toner particle water-containing cake, moisture content of toner after drying]
Using an infrared moisture meter (Ketto Science Laboratory Co., Ltd .: FD-230), a toner particle dispersion before drying, a water-containing cake containing toner particles, or 5 g of toner after drying is dried at a temperature of 150 ° C. and measurement mode 96 (monitoring) Moisture% in wet base is measured at time 2.5 minutes / variation width 0.05%). The moisture content and solid content were calculated according to the following formula.
Moisture content (M) (%) = [(W−W0) / W] × 100
Solid content (%) = 100-M
W: Sample weight before measurement (initial sample weight)
W0: Sample weight after measurement (absolute dry weight)
When the moisture content was 0.5% by weight or more, the water-containing cake was transferred to a vat and shelf-dried at a temperature of 40 ° C. and a pressure of 0.08 MPa for 15 hours.
［凝集体量］
乾燥後のトナー１００ｇを、開口径２mmの篩で篩った後、篩い上に残った凝集体の割合を評価した。凝集体の割合が少ないほど良好である。
[Aggregate amount]
After 100 g of the dried toner was sieved with a sieve having an opening diameter of 2 mm, the ratio of the aggregate remaining on the sieve was evaluated. The smaller the proportion of aggregates, the better.
［定着性］
市販のプリンタ（ＯＫＩ製、「ＭＬ５４００」）を用いて、トナーの紙上の付着量が０.４±０.０７ｍｇ/ｃｍ2となるベタ画像を３×２．５ｃｍの大きさで未定着画像のまま出力し、同プリンタに搭載されている定着器を温度可変に改造し、定着速度２０枚／分（Ａ４縦方向）で、１３０℃の温度で定着した。得られた定着画像の定着性はテープ剥離法によって評価した。メンディングテープ(３Ｍ製Ｓｃｏｔｃｈメンディングテープ８１０ 幅１８ｍｍ)を長さ１０ｃｍに切り、軽く未定着画像上に貼り付けた後、4つ折にしたＬｉｎｔ−ｆｒｅｅ−ｐａｐｅｒ（ＡＳＡＨＩ ＣＨＥＭＩＣＡＬ製ＢＥＭＣＯＴ サイズM−３）を１.０±０.２ｋｇの加重で１０往復押し当てた。その後、貼付したテープを２秒かけて剥がした際の画像濃度とテープの貼付前の画像濃度から定着率を算出した。ただし、
定着率＝（テープ剥離後の画像濃度／テープ貼付前の画像濃度）×１００
とし、テープ剥離後の画像濃度がテープ貼付前と同じだった時を１００とし、値が小さくなるにつれ定着性が低いことを示す。
定着率が９０以上を定着性良好とする。
[Fixability]
Using a commercially available printer (OKI, “ML5400”), a solid image with a toner adhesion amount of 0.4 ± 0.07 mg / cm 2 is 3 × 2.5 cm in size with an unfixed image. The fixing device mounted on the printer was modified so that the temperature was variable, and the fixing was performed at a fixing speed of 20 sheets / minute (A4 vertical direction) at a temperature of 130 ° C. The fixability of the obtained fixed image was evaluated by a tape peeling method. Cut a mending tape (3M Scotch Mending Tape 810 width 18mm) into a length of 10cm, lightly affix it on the unfixed image, and then fold it into four-folded Lint-free-paper (BEMCOT made by ASAHI CHEMICAL Size M-3 ) Was pressed 10 times with a load of 1.0 ± 0.2 kg. Thereafter, the fixing rate was calculated from the image density when the applied tape was peeled off over 2 seconds and the image density before the tape was applied. However,
Fixing rate = (image density after tape peeling / image density before tape application) × 100
When the image density after peeling the tape is the same as that before sticking the tape, the value is 100, and the lower the value, the lower the fixing property.
When the fixing rate is 90 or more, the fixing property is good.
本発明の製造方法は、電子写真法、静電記録法、静電印刷法などにおいて使用される電子写真用トナーの製造に好適に用いることができる。 The production method of the present invention can be suitably used for production of an electrophotographic toner used in electrophotography, electrostatic recording method, electrostatic printing method and the like.
１・・・ドライ チェンバー
２・・・パルスエンジン
３・・・燃料供給口
４・・・空気供給口
５・・・二次空気供給口
６・・・トナー粒子分散液供給口
７・・・乾燥室
８・・・サイクロン
９・・・バグフィルター
１０・・コンベアー
DESCRIPTION OF SYMBOLS 1 ...
Claims (2)
（Ｂ）工程（Ａ）で得られたトナー粒子の分散液をパルス燃焼による衝撃波の雰囲気中に噴霧して乾燥する工程
を有する電子写真用トナーの製造方法であって、
工程（Ｂ）における、乾燥に供する分散液中の固形分濃度が１〜３０重量％であり、
工程（Ｂ）における乾燥を結着樹脂のガラス転移点以下の温度で行い、乾燥後のトナー粒子の水分含有量が０．５重量％以下である、
電子写真用トナーの製造方法。 (A) a step of agglomerating and coalescing resin particles in the resin emulsion in an aqueous medium to obtain a dispersion of toner particles containing a binder resin; and
(B) A method for producing an electrophotographic toner comprising a step of spraying and drying the dispersion of toner particles obtained in step (A) in a shock wave atmosphere by pulse combustion ,
In the step (B), the solid content concentration in the dispersion to be dried is 1 to 30% by weight,
The drying in the step (B) is performed at a temperature not higher than the glass transition point of the binder resin, and the moisture content of the toner particles after drying is 0.5% by weight or less.
A method for producing an electrophotographic toner .
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