JP2005037926A - Toner for electrostatic image development - Google Patents
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本発明は、電子写真法、静電記録法、静電印刷法等において形成される潜像の現像に用いられる静電荷像現像用トナーに関する。 The present invention relates to an electrostatic image developing toner used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method or the like.
近年、電子写真分野における高速化・高画質化に伴い，トナーには耐久性、帯電安定性及び定着性が強く要望されている。これらの課題を考慮して、ポリエステルは耐久性が高く、着色剤の分散に優れることから広く使用されているが、帯電量や帯電安定性等の帯電特性はいまだ十分なものではなく、さらなる改善が求められている。そこで、ポリエステルを結着樹脂として含有したトナーの帯電性向上のため、複数種の荷電制御剤を含有したトナーが報告されている。 In recent years, with the increase in speed and image quality in the field of electrophotography, toners are strongly demanded for durability, charging stability and fixability. Considering these issues, polyester is widely used because of its high durability and excellent colorant dispersion, but the charging properties such as charge amount and charging stability are still not sufficient, and further improvements Is required. Therefore, a toner containing a plurality of types of charge control agents has been reported in order to improve the chargeability of the toner containing polyester as a binder resin.
例えば、耐刷時の帯電安定性の向上を課題として、ポリエステルと、着色剤と、正帯電性の荷電制御剤と、負帯電性の荷電制御剤とを含有し、特定の平均粒径分布を有する現像剤が提案されている（特許文献１参照）。また、特定のポリエステルと正帯電性の荷電制御剤と負帯電性の荷電制御剤とを含有し、正帯電性の荷電制御剤の使用量が負帯電性の荷電制御剤の使用量の１／２以下である電子写真用現像剤組成物が提案されている（特許文献２参照）。 For example, for the purpose of improving charging stability during printing durability, it contains polyester, a colorant, a positively chargeable charge control agent, and a negatively chargeable charge control agent, and has a specific average particle size distribution. A developer having the same has been proposed (see Patent Document 1). Further, it contains a specific polyester, a positively chargeable charge control agent and a negatively chargeable charge control agent, and the amount of use of the positively chargeable charge control agent is 1 / of the amount of use of the negatively chargeable charge control agent. An electrophotographic developer composition of 2 or less has been proposed (see Patent Document 2).
また、トナーの擦り落ちを改善するために、摩擦帯電量の向上を課題として、第１の電荷制御剤と第２の電荷制御剤とを含有し、第１の電荷制御剤として、フマル酸等のジカルボン酸を積極的に添加したトナーが提案されている（特許文献３参照）。 In addition, in order to improve toner rub-off, it is necessary to improve the triboelectric charge amount, and it contains a first charge control agent and a second charge control agent. As the first charge control agent, fumaric acid, etc. A toner to which a dicarboxylic acid is positively added has been proposed (see Patent Document 3).
しかし、上記トナーは、湿度や温度等の環境に影響を受けてしまい安定した帯電量を維持することができないという欠点を有する。そこで、帯電量の環境安定性を改善するため、荷電制御剤として４級アンモニウム塩を使用する技術、例えば、ポリエステル及び正帯電性荷電制御剤と負帯電性荷電制御剤からなる負帯電性トナーにおいて、正帯電性荷電制御剤として４級アンモニウム塩を含有したトナーが提案されている（特許文献４参照）。
連続印字におけるトナーへのシリカの埋め込みに起因する転写不良による画質劣化の点から、低分子量成分が少ないフマル酸及び／又はマレイン酸を原料モノマーとして用いられたポリエステルが結着樹脂として好適である。しかしながら、帯電の環境特性に関しては十分なものではなかった。 Polyester using fumaric acid and / or maleic acid with a low molecular weight component as a raw material monomer is suitable as the binder resin from the viewpoint of image quality deterioration due to transfer failure due to silica embedding in toner in continuous printing. However, the environmental characteristics of charging have not been sufficient.
本発明の目的は、環境の変化に対して良好な帯電安定性を有しており、長期にわたって、安定して良好な画像を得ることができる静電荷像現像用トナーを提供することにある。 An object of the present invention is to provide a toner for developing an electrostatic charge image that has good charging stability against environmental changes and can stably obtain a good image over a long period of time.
本発明は、結着樹脂、着色剤及び荷電制御剤を含有してなる静電荷像現像用トナーであって、前記結着樹脂が、少なくともフマル酸及び／又はマレイン酸を原料モノマーとして用いて得られたポリエステルであり、前記荷電制御剤が負帯電性荷電制御剤及び正帯電性荷電制御剤であり、トナー中の未反応のフマル酸及び／又はマレイン酸の総含有量が０．２０重量％以下である静電荷像現像用トナーに関する。 The present invention relates to a toner for developing an electrostatic image comprising a binder resin, a colorant and a charge control agent, wherein the binder resin is obtained using at least fumaric acid and / or maleic acid as a raw material monomer. The charge control agent is a negatively chargeable charge control agent and a positively chargeable charge control agent, and the total content of unreacted fumaric acid and / or maleic acid in the toner is 0.20% by weight. The present invention relates to the following electrostatic toner developing toner.
本発明の静電荷像現像用トナーは、環境の変化に対して良好な帯電安定性を有しており、長期にわたって、安定して良好な画像を得ることができるという優れた効果を奏する。 The toner for developing an electrostatic charge image of the present invention has good charging stability against changes in the environment, and has an excellent effect that a good image can be stably obtained over a long period of time.
本発明は、結着樹脂として、少なくともフマル酸及び／又はマレイン酸を原料モノマーとして用いて得られたポリエステルを含有した静電荷像現像用トナーにおいて、荷電制御剤として、負帯電性荷電制御剤と正帯電性荷電制御剤とが含有されており、さらに、トナー中の未反応のフマル酸及び／又はマレイン酸の総含有量が、特定の値以下である点に特徴を有しており、これにより、本発明のトナーは、シリカ等の外添剤がトナー表面に埋まりにくく、耐久性に優れ、かつ環境変化に対する帯電安定性も格段に向上する。 The present invention relates to a toner for developing electrostatic images containing at least a polyester obtained by using fumaric acid and / or maleic acid as a raw material monomer as a binder resin, and as a charge control agent, a negatively chargeable charge control agent and A positively chargeable charge control agent, and the total content of unreacted fumaric acid and / or maleic acid in the toner is below a specific value. As a result, the toner of the present invention is less likely to have an external additive such as silica embedded in the toner surface, is excellent in durability, and has a markedly improved charge stability against environmental changes.
原料モノマーとしてフマル酸やマレイン酸を含有したポリエステルは、他のジカルボン酸と比べて樹脂中のアルコール成分由来の低分子量成分が少なく、現像ローラー部等で強いシェア（外力）を受けた時でもシリカ等の外添剤がトナー中に埋まりにくいという効果を有する。 Polyester containing fumaric acid or maleic acid as a raw material monomer has fewer low molecular weight components derived from the alcohol component in the resin than other dicarboxylic acids, and even when it receives a strong share (external force) at the developing roller section etc. This has the effect that external additives such as are difficult to be embedded in the toner.
トナー中のフマル酸及びマレイン酸は、ポリエステルを製造した際に未反応モノマーとして残存したものであり、未反応のフマル酸及び／又はマレイン酸の総含有量は、トナー中、０．２０重量％以下であり、好ましくは０．０１〜０．１５重量％、より好ましくは０．０１〜０．１重量％である。フマル酸及び／又はマレイン酸の総含有量を低減することで環境安定性が向上する傾向にある。フマル酸及び／又はマレイン酸の総含有量を低減するには、カルボン酸成分とアルコール成分の仕込み量や反応時間を適宜調整すること、又は反応末期にエステル化触媒を添加することにより行うことが出来る。例えば、カルボン酸成分の全カルボキシル基に対するアルコール成分の全ヒドロキシ基のモル比を１よりも超えた仕込み比率にする方法や、反応時間を延長する方法等が挙げられる。トナー中のフマル酸及び／又はマレイン酸の総含有量は実施例に記載の方法により測定する。 The fumaric acid and maleic acid in the toner remain as unreacted monomers when the polyester is produced, and the total content of unreacted fumaric acid and / or maleic acid is 0.20% by weight in the toner. Or less, preferably 0.01 to 0.15% by weight, more preferably 0.01 to 0.1% by weight. Environmental stability tends to be improved by reducing the total content of fumaric acid and / or maleic acid. In order to reduce the total content of fumaric acid and / or maleic acid, it may be carried out by appropriately adjusting the charged amount of carboxylic acid component and alcohol component and the reaction time, or by adding an esterification catalyst at the end of the reaction. I can do it. For example, a method in which the molar ratio of the total hydroxy groups of the alcohol component to the total carboxyl groups of the carboxylic acid component exceeds the charge ratio of 1, and a method of extending the reaction time can be mentioned. The total content of fumaric acid and / or maleic acid in the toner is measured by the method described in Examples.
ポリエステルの含有量は、結着樹脂中、５０〜１００重量％が好ましく、８０〜１００重量％がより好ましく、１００重量％が特に好ましい。ポリエステル以外の結着樹脂としては、スチレン−アクリル樹脂、エポキシ樹脂、ポリカーボネート、ポリウレタン、２種以上の樹脂成分が部分的に化学結合したハイブリッド樹脂等が挙げられる。 The content of the polyester is preferably 50 to 100% by weight, more preferably 80 to 100% by weight, and particularly preferably 100% by weight in the binder resin. Examples of binder resins other than polyester include styrene-acrylic resins, epoxy resins, polycarbonates, polyurethanes, and hybrid resins in which two or more kinds of resin components are partially chemically bonded.
ポリエステルは、２価のカルボン酸化合物としてフマル酸及び／又はマレイン酸が用いられる以外は通常のポリエステルと同様に、アルコール成分として公知の２価以上のアルコールとカルボン酸成分として公知の２価以上のカルボン酸化合物からなる原料モノマーを縮重合させて得られる。ここで、フマル酸及び／又はマレイン酸の含有量は、樹脂のアルコール成分由来の低分子量成分を低減する観点から、全カルボン酸成分中、１〜１００モル％が好ましく、２０〜１００モル％がより好ましく、４０〜１００モル％がさらに好ましく、５０〜１００モル％がさらに好ましく、５５〜１００モル％がさらに好ましい。 The polyester is a divalent or higher alcohol known as an alcohol component and a divalent or higher known carboxylic acid component as in the case of a normal polyester except that fumaric acid and / or maleic acid is used as a divalent carboxylic acid compound. It is obtained by subjecting a raw material monomer comprising a carboxylic acid compound to condensation polymerization. Here, the content of fumaric acid and / or maleic acid is preferably 1 to 100 mol%, preferably 20 to 100 mol% in the total carboxylic acid component, from the viewpoint of reducing the low molecular weight component derived from the alcohol component of the resin. More preferably, 40-100 mol% is further more preferable, 50-100 mol% is further more preferable, and 55-100 mol% is further more preferable.
フマル酸及びマレイン酸以外の２価のカルボン酸化合物としては、フタル酸、イソフタル酸、テレフタル酸等のジカルボン酸、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、これらの酸の無水物及びアルキル（炭素数１〜１２）エステル等が挙げられる。 Divalent carboxylic acid compounds other than fumaric acid and maleic acid were substituted with dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, alkyl groups having 1 to 20 carbon atoms, or alkenyl groups having 2 to 20 carbon atoms. Examples thereof include succinic acid, anhydrides of these acids, and alkyl (carbon number 1 to 12) esters.
３価以上のカルボン酸化合物としては、１，２，４−ベンゼントリカルボン酸（トリメリット酸）及びその酸無水物、アルキル（炭素数１〜１２）エステル等が挙げられる。 Examples of the trivalent or higher carboxylic acid compounds include 1,2,4-benzenetricarboxylic acid (trimellitic acid), its acid anhydride, and alkyl (C1-12) ester.
２価のアルコールとしては、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、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）プロパン等のビスフェノールＡのアルキレン（炭素数２又は３）オキサイド付加物（平均付加モル数１〜１０）、エチレングリコール、プロピレングリコール、１，６−ヘキサンジオール、ビスフェノールＡ、水素添加ビスフェノールＡ等が挙げられる。 Examples of the divalent alcohol include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane. Bisphenol A alkylene (carbon number 2 or 3) oxide adduct (average addition mole number 1 to 10), ethylene glycol, propylene glycol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A and the like. .
３価以上のアルコールとしては、ソルビトール、１，４−ソルビタン、ペンタエリスリトール、グリセロール、トリメチロールプロパン等が挙げられる。 Examples of trihydric or higher alcohols include sorbitol, 1,4-sorbitan, pentaerythritol, glycerol, trimethylolpropane, and the like.
なお、３価以上の多価モノマーの含有量、即ち３価以上のアルコール及び３価以上のカルボン酸化合物の総含有量は、低分子量成分を低減する観点から、ポリエステルの原料モノマー中、１０モル％以下好ましく、５モル％以下がより好ましい。 The content of the trivalent or higher polyvalent monomer, that is, the total content of the trivalent or higher alcohol and the trivalent or higher carboxylic acid compound is 10 mol in the polyester raw material monomer from the viewpoint of reducing low molecular weight components. % Or less, more preferably 5 mol% or less.
なお、アルコール成分及びカルボン酸成分には、１価のアルコール及び１価のカルボン酸化合物が、分子量調整の観点から、適宜含有されていてもよい。 In addition, the alcohol component and the carboxylic acid component may appropriately contain a monovalent alcohol and a monovalent carboxylic acid compound from the viewpoint of molecular weight adjustment.
ポリエステルは、例えば、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、要すればエステル化触媒を用いて、さらには減圧下、１８０〜２５０℃の温度で縮重合することにより製造することができる。 Polyester is produced by, for example, polycondensation of an alcohol component and a carboxylic acid component in an inert gas atmosphere, if necessary, using an esterification catalyst, and at a temperature of 180 to 250 ° C. under reduced pressure. be able to.
ポリエステルの軟化点は、８０〜１６５℃が好ましく、ガラス転移点は５０〜８５℃が好ましい。また、着色剤の分散性及び転写性の観点から、酸価は０．５〜６０ｍｇＫＯＨ／ｇが好ましく、水酸基価は１〜６０ｍｇＫＯＨ／ｇが好ましい。 The softening point of the polyester is preferably 80 to 165 ° C, and the glass transition point is preferably 50 to 85 ° C. Further, from the viewpoint of dispersibility and transferability of the colorant, the acid value is preferably from 0.5 to 60 mgKOH / g, and the hydroxyl value is preferably from 1 to 60 mgKOH / g.
本発明のトナーは荷電制御剤として負帯電性荷電制御剤と正帯電性荷電制御剤とを含有するものである。この両者を併用することにより、環境安定性が向上する傾向にあり、これは、トナー中の荷電制御剤の分布が均一になるためと考えられる。負帯電性荷電制御剤としては、含金属アゾ染料、例えば「バリファーストブラック３８０４」、「ボントロンＳ−３１」（以上、オリエント化学工業社製）、「Ｔ−７７」（保土谷化学工業社製）、「ボントロンＳ−３２」、「ボントロンＳ−３４」、「ボントロンＳ−３６」（以上、オリエント化学工業社製）、「アイゼンスピロンブラックＴＲＨ」（保土谷化学工業社製）等；銅フタロシアニン染料、サリチル酸のアルキル誘導体の金属錯体、例えば「ボントロンＥ−８１」、「ボントロンＥ−８２」、「ボントロンＥ−８４」、「ボントロンＥ−８５」（以上、オリエント化学工業社製）等；ニトロイミダゾール誘導体；ベンジル酸ホウ素錯体、例えば、「ＬＲ−１４７」（日本カーリット社製）等が挙げられ、これらの中では、帯電量の安定性及び環境安定性の観点から、含金属アゾ染料及びサリチル酸のアルキル誘導体の金属錯体が好ましく、含金属アゾ染料がより好ましい。 The toner of the present invention contains a negatively chargeable charge control agent and a positively chargeable charge control agent as charge control agents. By using both of these, the environmental stability tends to be improved, which is considered to be because the distribution of the charge control agent in the toner becomes uniform. Examples of the negatively chargeable charge control agent include metal-containing azo dyes such as “Varifast Black 3804”, “Bontron S-31” (manufactured by Orient Chemical Co., Ltd.), “T-77” (Hodogaya Chemical Co., Ltd.). ), “Bontron S-32”, “Bontron S-34”, “Bontron S-36” (manufactured by Orient Chemical Co., Ltd.), “Eisenspiron Black TRH” (Hodogaya Chemical Co., Ltd.), etc .; copper Metal complexes of phthalocyanine dyes, alkyl derivatives of salicylic acid, such as “Bontron E-81”, “Bontron E-82”, “Bontron E-84”, “Bontron E-85” (above, manufactured by Orient Chemical Industries); Nitroimidazole derivatives; boron benzylate complexes such as “LR-147” (manufactured by Nippon Carlit Co., Ltd.) From the viewpoint of stability and environmental stability, the metal complexes of the metal-containing azo dyes and alkyl derivatives of salicylic acid are preferable, metal-containing azo dyes are more preferred.
負帯電性荷電制御剤の含有量は、結着樹脂１００重量部に対して、０．５〜５重量部が好ましく、１〜３重量部がより好ましい。 The content of the negatively chargeable charge control agent is preferably 0.5 to 5 parts by weight and more preferably 1 to 3 parts by weight with respect to 100 parts by weight of the binder resin.
正帯電性荷電制御剤としては、ニグロシン染料、例えば「ニグロシンベースＥＸ」、「オイルブラックＢＳ」、「オイルブラックＳＯ」、「ボントロンＮ−０１」、「ボントロンＮ−０７」、「ボントロンＮ−０９」、「ボントロンＮ−１１」（以上、オリエント化学工業社製）等；３級アミンを側鎖として含有するトリフェニルメタン系染料、４級アンモニウム塩化合物、例えば「ボントロンＰ−５１」、「ボントロンＰ−５２」（以上、オリエント化学工業社製）、「ＴＰ−４１５」（保土谷化学工業社製）、セチルトリメチルアンモニウムブロミド、「COPY CHARGE PX VP435」（ヘキスト社製）等；ポリアミン樹脂、例えば「ＡＦＰ−Ｂ」（オリエント化学工業社製）等；イミダゾール誘導体、例えば「ＰＬＺ−２００１」、「ＰＬＺ−８００１」（以上、四国化成社製）等が挙げられ、これらの中では、分散性及びトナーの帯電量の安定化の観点から、ニグロシン染料及びトリフェニルメタン系染料が好ましく、ニグロシン染料がより好ましい。 Examples of positively chargeable charge control agents include nigrosine dyes such as “Nigrosine Base EX”, “Oil Black BS”, “Oil Black SO”, “Bontron N-01”, “Bontron N-07”, “Bontron N-09”. , “Bontron N-11” (manufactured by Orient Chemical Co., Ltd.), etc .; triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salt compounds such as “Bontron P-51”, “Bontron” “P-52” (manufactured by Orient Chemical Co., Ltd.), “TP-415” (manufactured by Hodogaya Chemical Co., Ltd.), cetyltrimethylammonium bromide, “COPY CHARGE PX VP435” (manufactured by Hoechst), etc .; “AFP-B” (manufactured by Orient Chemical Co., Ltd.) and the like; imidazole derivatives such as “PLZ-2001”, “PLZ-80” 1 "(manufactured by Shikoku Kasei Co., Ltd.) and the like. Among these, nigrosine dyes and triphenylmethane dyes are preferable, and nigrosine dyes are more preferable from the viewpoints of dispersibility and stabilization of toner charge amount. .
正帯電性荷電制御剤の含有量は、結着樹脂１００重量部に対して、０．０５〜５重量部が好ましく、０．０５〜１重量部がより好ましい。 The content of the positively chargeable charge control agent is preferably 0.05 to 5 parts by weight and more preferably 0.05 to 1 part by weight with respect to 100 parts by weight of the binder resin.
負帯電性荷電制御剤と正帯電性荷電制御剤の重量比（負帯電性荷電制御剤／正帯電性荷電制御剤）は、特に限定されないが、６０／１〜３／１が好ましい。負帯電性荷電制御剤と正帯電性荷電制御剤の重量比の好適範囲は、その組み合わせによって異なるが、負帯電性荷電制御剤として含金属アゾ染料が、正帯電性荷電制御剤としてニグロシン染料がそれぞれ含有されている場合は、これらの重量比（含金属アゾ染料／ニグロシン染料）は、３０／１〜３／１が好ましく、２０／１〜５／１がより好ましい。 The weight ratio of the negatively chargeable charge control agent to the positively chargeable charge control agent (negatively chargeable charge control agent / positively chargeable charge control agent) is not particularly limited, but is preferably 60/1 to 3/1. The preferred range of the weight ratio between the negatively chargeable charge control agent and the positively chargeable charge control agent differs depending on the combination, but the metal-containing azo dye is used as the negatively chargeable charge control agent, and the nigrosine dye is used as the positively chargeable charge control agent. When each is contained, the weight ratio (metal-containing azo dye / nigrosine dye) is preferably 30/1 to 3/1, and more preferably 20/1 to 5/1.
本発明における着色剤としては、トナー用着色剤として用いられている染料、顔料等のすべてを使用することができ、カーボンブラック、フタロシアニンブルー、パーマネントブラウンFG、ブリリアントファーストスカーレット、ピグメントグリーンＢ、ローダミン−Ｂベース、ソルベントレッド49、ソルベントレッド146 、ソルベントブルー35、キナクリドン、カーミン６Ｂ、ジスアゾエロー等が挙げられ、これらは単独で又は２種以上を混合して用いることができ、本発明のトナーは、黒トナー、モノカラートナー、フルカラートナーのいずれであってもよい。着色剤の使用量は、結着樹脂１００重量部に対して、１〜４０重量部が好ましく、３〜１０重量部がより好ましい。 As the colorant in the present invention, all of dyes and pigments used as toner colorants can be used, such as carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, rhodamine- B base, Solvent Red 49, Solvent Red 146, Solvent Blue 35, Quinacridone, Carmine 6B, Disazo Yellow and the like can be used alone or in combination of two or more. The toner of the present invention is black. Any of toner, mono-color toner, and full-color toner may be used. The amount of the colorant used is preferably 1 to 40 parts by weight and more preferably 3 to 10 parts by weight with respect to 100 parts by weight of the binder resin.
本発明のトナーには、トナー飛散を抑制する観点から、磁性粉が含有されていてもよい。磁性粉としては、マグネタイト、ヘマタイト、フェライト等の合金や鉄、コバルト、ニッケル等の強磁性金属粉末等が挙げられる。磁性粉の含有量は、結着樹脂１００重量部に対し、０．５〜１０重量部が好ましい。 The toner of the present invention may contain magnetic powder from the viewpoint of suppressing toner scattering. Examples of the magnetic powder include alloys such as magnetite, hematite, and ferrite, and ferromagnetic metal powders such as iron, cobalt, and nickel. The content of the magnetic powder is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the binder resin.
本発明のトナーには、さらに、離型剤、流動性向上剤、導電性調整剤、体質顔料、繊維状物質等の補強充填剤、酸化防止剤、老化防止剤、クリーニング性向上剤等の添加剤が適宜内添又は外添されていてもよい。特に、外添剤として、二酸化ケイ素、ケイ酸アルミニウム、ケイ酸ナトリウム、ケイ酸カリウム、ケイ酸亜鉛、ケイ酸マグネシウム等からなるシリカ系微粒子が好ましい。 The toner of the present invention further includes a release agent, a fluidity improver, a conductivity modifier, an extender pigment, a reinforcing filler such as a fibrous substance, an antioxidant, an anti-aging agent, and a cleaning property improver. The agent may be appropriately added internally or externally. In particular, silica-based fine particles composed of silicon dioxide, aluminum silicate, sodium silicate, potassium silicate, zinc silicate, magnesium silicate and the like are preferable as the external additive.
本発明のトナーの製造方法は、混練粉砕法、乳化転相法、重合法等の従来より公知のいずれの方法であってもよいが、製造が容易なことから、混練粉砕法が好ましい。例えば、混練粉砕法による粉砕トナーの場合、結着樹脂、荷電制御剤、着色剤等をヘンシェルミキサー等の混合機で均一に混合した後、密閉式ニーダー又は１軸もしくは２軸の押出機等で溶融混練し、冷却、粉砕、分級して製造することができる。トナーの体積平均粒径は３〜１５μｍが好ましい。 The method for producing the toner of the present invention may be any conventionally known method such as a kneading and pulverizing method, an emulsification phase inversion method, and a polymerization method, but the kneading and pulverizing method is preferred because it is easy to produce. For example, in the case of a pulverized toner by a kneading pulverization method, a binder resin, a charge control agent, a colorant, and the like are uniformly mixed with a mixer such as a Henschel mixer, and then sealed with a closed kneader or a single or twin screw extruder. It can be manufactured by melt-kneading, cooling, pulverizing and classifying. The volume average particle diameter of the toner is preferably 3 to 15 μm.
本発明のトナーは、磁性体微粉末を含有するときは単独で現像剤として、また磁性体微粉末を含有しないときは非磁性一成分系現像剤として、もしく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。 When the toner of the present invention contains a magnetic fine powder, it is used alone as a developer, and when it does not contain a magnetic fine powder, it is used as a non-magnetic one-component developer or mixed with a carrier to develop a two-component developer. It can be used as an agent.
本発明のトナーは、シリカ等の外添剤がトナー表面に埋まりにくく、高温、高湿下の環境においても安定した帯電性を維持することができる。そのため、非接触現像用トナーとして好適に用いることができる。 In the toner of the present invention, external additives such as silica are not easily embedded in the toner surface, and stable chargeability can be maintained even in an environment of high temperature and high humidity. Therefore, it can be suitably used as a non-contact developing toner.
〔樹脂の軟化点〕
高化式フローテスター「ＣＦＴ−５００Ｄ」（島津製作所製）を用い、樹脂の半分が流出する温度を軟化点とする（試料：１ｇ、昇温速度：６℃／分、荷重：１．９６ＭＰａ、ノズル：１ｍｍφ×１ｍｍ）。
[Softening point of resin]
Using Koka-type flow tester “CFT-500D” (manufactured by Shimadzu Corporation), the temperature at which half of the resin flows out is defined as the softening point (sample: 1 g, heating rate: 6 ° C./min, load: 1.96 MPa, Nozzle: 1 mmφ × 1 mm).
〔樹脂のガラス転移点〕
示差走査熱量計「ＤＳＣ２１０」（セイコー電子工業（株）製）を用いて１５ｍｇの試料を昇温速度１０℃／分で測定する。
[Glass transition point of resin]
Using a differential scanning calorimeter “DSC210” (manufactured by Seiko Denshi Kogyo Co., Ltd.), a 15 mg sample is measured at a heating rate of 10 ° C./min.
〔樹脂の酸価及び水酸基価〕
ＪＩＳ Ｋ００７０に従って測定する。
[Acid value and hydroxyl value of resin]
Measured according to JIS K0070.
〔フマル酸及び／又はマレイン酸の総含有量〕
１．試料溶液の調製
(1) 試料（トナー）を０．２ｇ秤量し、トルエンを添加して２０ｍｌの溶液に調製する。
(2) 調製した溶液から、２ｍｌをふた付き試験管に移し入れ、続いてイオン交換水５ｍｌを加える。
(3) 試験管内の混合液を、タッチミキサーを用いてよく攪拌し、遠心分離機を用いて分相させ、下層（水相）を試料溶液として分取する。
[Total content of fumaric acid and / or maleic acid]
1. Sample solution preparation
(1) Weigh 0.2 g of the sample (toner) and add toluene to prepare a 20 ml solution.
(2) Transfer 2 ml from the prepared solution to a test tube with a lid, and then add 5 ml of ion exchange water.
(3) Stir the mixed solution in the test tube well using a touch mixer, separate the phases using a centrifuge, and separate the lower layer (aqueous phase) as a sample solution.
２．検量線の作成
フマル酸及びマレイン酸を、それぞれ約０．１ｇ秤量し、イオン交換水で正確に１００ｍｌとする。１〜１５ｍｇ／ｌの検量線溶液を用いて検量線を作成した。
2. Preparation of calibration curve About 0.1 g each of fumaric acid and maleic acid are weighed and made exactly 100 ml with ion-exchanged water. A calibration curve was prepared using a calibration curve solution of 1 to 15 mg / l.
３．溶離液の調製
リン酸０．１％水溶液１ｍｌをイオン交換水１リットルに溶解させたものを溶離液とした。
3. Preparation of eluent An eluent was prepared by dissolving 1 ml of a 0.1% phosphoric acid aqueous solution in 1 liter of ion-exchanged water.
４．高速液体クロマトグラフィー測定
装置：東ソー社製、８０２０シリーズ
オートサンプラー：注入量 ２０μｌ、分析時間 １０分
ポンプ：流速 １．０ｍｌ／ｍｉｎ
カラムオーブン：４０℃
カラム：化学物質評価研究機構 Ｌ−カラム ＯＤＳ（４．０φ×１０＋４．６φ×１５０ｍｍ）
検出器：ＵＶＤ ２１０ｎｍ
4). High-performance liquid chromatography measurement apparatus: Tosoh Corporation, 8020 series Autosampler: injection volume 20 μl, analysis time 10 minutes Pump: flow rate 1.0 ml / min
Column oven: 40 ° C
Column: Chemical Substance Evaluation Research Organization L-Column ODS (4.0φ × 10 + 4.6φ × 150 mm)
Detector: UVD 210nm
５．フマル酸及びマレイン酸の含有量の算出
測定した試料のチャートと検量線とを対比し、面積比を求めることにより、トナー中に含まれるフマル酸及びマレイン酸の残存量が、重量分率（重量％）として求められる。
5. Calculation of the content of fumaric acid and maleic acid By comparing the chart of the measured sample with a calibration curve and determining the area ratio, the remaining amount of fumaric acid and maleic acid contained in the toner is expressed as a weight fraction (weight %).
樹脂製造例１
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１０５０ｇ、フマル酸３５５ｇ、ハイドロキノン（重合禁止剤）１ｇ及びジブチル錫オキサイド（エステル化触媒）１．４ｇを窒素雰囲気下、常圧下、２１０℃で５時間反応させた後、減圧下２１０℃で７時間反応させて樹脂Ａを得た。得られた樹脂の軟化点は１０２．０℃、酸価は１９．８ｍｇＫＯＨ／ｇ、ガラス転移点は５８．０℃であった。
Resin production example 1
1050 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 355 g of fumaric acid, 1 g of hydroquinone (polymerization inhibitor) and 1.4 g of dibutyltin oxide (esterification catalyst) under a nitrogen atmosphere The mixture was reacted at 210 ° C. for 5 hours under normal pressure, and then reacted at 210 ° C. for 7 hours under reduced pressure to obtain Resin A. The obtained resin had a softening point of 102.0 ° C., an acid value of 19.8 mgKOH / g, and a glass transition point of 58.0 ° C.
樹脂製造例２
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１０５０ｇ、フマル酸３５５ｇ、ハイドロキノン（重合禁止剤）１ｇ及びジブチル錫オキサイド（エステル化触媒）１．４ｇを窒素雰囲気下、常圧下、２１０℃で６時間反応させた後、減圧下２１０℃で１０時間反応させて樹脂Ｂを得た。得られた樹脂の軟化点は１０９．１℃、酸価は８．７ｍｇＫＯＨ／ｇ、ガラス転移点は６０．６℃であった。
Resin production example 2
1050 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 355 g of fumaric acid, 1 g of hydroquinone (polymerization inhibitor) and 1.4 g of dibutyltin oxide (esterification catalyst) under a nitrogen atmosphere The mixture was reacted at 210 ° C. under normal pressure for 6 hours and then reacted at 210 ° C. under reduced pressure for 10 hours to obtain Resin B. The obtained resin had a softening point of 109.1 ° C, an acid value of 8.7 mgKOH / g, and a glass transition point of 60.6 ° C.
樹脂製造例３
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１０４０ｇ、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１０ｇ、テレフタル酸１９９ｇ及びジブチル錫オキサイド（エステル化触媒）４ｇを窒素雰囲気下、常圧下２３０℃で５時間反応させ、さらに減圧下で反応させた。その後、２１０℃まで冷却し、フマル酸２０９ｇ及びハイドロキノン１ｇを添加し、５時間反応させた後、さらに減圧下で６時間反応させて樹脂Ｃを得た。得られた樹脂の軟化点は１０９．５℃、酸価は２１．３ｍｇＫＯＨ／ｇ、ガラス転移点は６４．４℃であった。
Resin production example 3
1040 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 10 g of polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, 199 g of terephthalic acid and 4 g of dibutyltin oxide (esterification catalyst) was reacted at 230 ° C. under normal pressure for 5 hours under a nitrogen atmosphere, and further reacted under reduced pressure. Thereafter, the mixture was cooled to 210 ° C., 209 g of fumaric acid and 1 g of hydroquinone were added, reacted for 5 hours, and further reacted for 6 hours under reduced pressure to obtain Resin C. The obtained resin had a softening point of 109.5 ° C, an acid value of 21.3 mgKOH / g, and a glass transition point of 64.4 ° C.
樹脂製造例４
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１０５０ｇ、フマル酸３５５ｇ、ハイドロキノン（重合禁止剤）１ｇ及びジブチル錫オキサイド（エステル化触媒）１．４ｇを窒素雰囲気下、常圧下、２１０℃で４．５時間反応させた後、減圧下２１０℃で反応させて２時間反応させて樹脂Ｄを得た。得られた樹脂の軟化点は９７．２℃、酸価は２４．６ｍｇＫＯＨ／ｇ、ガラス転移点は５５．４℃であった。
Resin production example 4
1050 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 355 g of fumaric acid, 1 g of hydroquinone (polymerization inhibitor) and 1.4 g of dibutyltin oxide (esterification catalyst) under a nitrogen atmosphere After reacting at 210 ° C. for 4.5 hours under normal pressure, the reaction was performed at 210 ° C. under reduced pressure for 2 hours to obtain Resin D. The obtained resin had a softening point of 97.2 ° C, an acid value of 24.6 mgKOH / g, and a glass transition point of 55.4 ° C.
樹脂製造例５
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８３０ｇ、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３２０ｇ、テレフタル酸２３３ｇ、ドデセニル無水コハク酸２４５ｇ、無水トリメリット酸１４０ｇ及びジブチル錫オキサイド（エステル化触媒）４ｇを窒素雰囲気下、常圧下２３０℃で８時間反応させ、さらに減圧下で５時間反応させて樹脂Ｅを得た。得られた樹脂の軟化点は１３８．５℃、酸価は２５．８ｍｇＫＯＨ／ｇ、ガラス転移点は６５．８℃であった。
Resin production example 5
830 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 320 g of polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, 233 g of terephthalic acid, Resin E was obtained by reacting 245 g of dodecenyl succinic anhydride, 140 g of trimellitic anhydride and 4 g of dibutyltin oxide (esterification catalyst) at 230 ° C. for 8 hours under a nitrogen atmosphere and further for 5 hours under reduced pressure. . The resulting resin had a softening point of 138.5 ° C, an acid value of 25.8 mgKOH / g, and a glass transition point of 65.8 ° C.
実施例１〜５及び比較例１、２
表１に示す結着樹脂１００重量部、表１に示す負帯電性荷電制御剤「ボントロンＳ−３４」（オリエント化学工業社製）及び正帯電性荷電制御剤「ボントロンＮ−０７」（オリエント化学工業社製）、カーボンブラック「モーガルＬ」（キャボット社製）６重量部、ポリプロピレンワックス「ハイワックス ＮＰ−１０５」（三井化学社製）２重量部、マグネタイト「ＥＰＴ１００２」（戸田工業社製）１重量部を二軸混練機「ＰＣＭ−４５」（池貝社製）を用いて、フィード量４０ｋｇ／ｍｉｎ、回転数２００ｒｐｍ、混練温度１００℃で溶融混練し、ジェットミルで微粉砕し、気流分級機で分級して、体積平均粒子径８．５μｍの粉体を得た。
Examples 1 to 5 and Comparative Examples 1 and 2
100 parts by weight of the binder resin shown in Table 1, negatively chargeable charge control agent “Bontron S-34” (manufactured by Orient Chemical Co., Ltd.) and positively chargeable charge control agent “Bontron N-07” (Orient Chemical) Kogyo Co., Ltd.), carbon black “Mogal L” (Cabot Corp.) 6 parts by weight, polypropylene wax “High Wax NP-105” (Mitsui Chemicals Co., Ltd.) 2 parts by weight, magnetite “EPT1002” (Toda Kogyo Co., Ltd.) 1 Using a biaxial kneader “PCM-45” (manufactured by Ikegai Co., Ltd.), parts by weight are melt-kneaded at a feed rate of 40 kg / min, a rotation speed of 200 rpm, a kneading temperature of 100 ° C., finely pulverized with a jet mill, and an airflow classifier. To obtain a powder having a volume average particle diameter of 8.5 μm.
得られた粉体１００重量部に対して疎水性シリカ「アエロジルＲ−９７２」（日本アエロジル社製）０．９重量部をヘンシェルミキサーを用いて混合付着させ、負帯電性トナーを得た。 To 100 parts by weight of the obtained powder, 0.9 part by weight of hydrophobic silica “Aerosil R-972” (manufactured by Nippon Aerosil Co., Ltd.) was mixed and adhered using a Henschel mixer to obtain a negatively chargeable toner.
試験例１
トナー０．６ｇ及びキャリア９．４ｇを２０ｍｌ容のポリ容器に入れ、ターブラーミキサーで５分攪拌し、二成分現像剤を２個調製した。
調製した二成分現像剤の、それぞれの現像剤の帯電量（μＣ／ｇ）を、エッピング社製のＱ／Ｍメーターを用いた以下の方法により測定した後、一方を、温度２５℃、相対湿度５５％の通常（ＮＮ）環境下で、もう一方を温度４０℃、相対湿度９０％の高温高湿（ＨＨ）環境下で、それぞれ２時間放置した。
Test example 1
0.6 g of toner and 9.4 g of carrier were placed in a 20 ml plastic container and stirred for 5 minutes with a tumbler mixer to prepare two two-component developers.
The charge amount (μC / g) of each developer of the prepared two-component developer was measured by the following method using a Q / M meter manufactured by Epping Co., Ltd. The other was left under a normal (NN) environment of 55% and a high temperature and high humidity (HH) environment at a temperature of 40 ° C. and a relative humidity of 90% for 2 hours.
〔帯電量の測定方法〕
Ｑ／Ｍメーター付属のセルに規定量の現像剤を投入し、目開き３２μｍのふるい（ステンレス製、線径：０．０３５ｍｍ）に通して、トナーのみを９０秒間吸引する。そのとき発生したキャリア上の電圧変化をモニターし、〔９０秒後の総電気量（μＣ）〕／〔吸引されたトナーの重量（ｇ）〕の値を帯電量（μＣ／ｇ）として算出する。
[Measurement method of charge amount]
A specified amount of developer is put into a cell attached to the Q / M meter, and the mixture is passed through a sieve (made of stainless steel, wire diameter: 0.035 mm) having an opening of 32 μm, and only the toner is sucked for 90 seconds. The change in voltage on the carrier generated at that time is monitored, and the value of [total amount of electricity after 90 seconds (μC)] / [weight of attracted toner (g)] is calculated as the charge amount (μC / g). .
放置後、各二成分現像剤を再びターブラーミキサーで５分攪拌し、帯電量（μＣ／ｇ）を測定し、下記式に基づいて、ＨＨ／ＮＮ帯電量残存率を求め、以下の評価基準に従って、帯電安定性を評価した。結果を表１に示す。なお、ＮＮ環境下での帯電量の変化（放置後／放置前）は０．８〜０．９５の範囲内であった。 After being allowed to stand, each two-component developer is stirred again with a tumbler mixer for 5 minutes, the charge amount (μC / g) is measured, and the HH / NN charge amount remaining rate is calculated based on the following formula. The charging stability was evaluated according to The results are shown in Table 1. The change in the charge amount (after leaving / before leaving) in the NN environment was in the range of 0.8 to 0.95.
〔評価基準〕
ＨＨ／ＮＮ帯電量残存率が、
◎◎：７０％以上
◎ ：５０％以上、７０％未満
○ ：４０％以上、５０％未満
× ：４０％未満
〔Evaluation criteria〕
HH / NN charge remaining rate is
◎: 70% or more ◎: 50% or more, less than 70% ○: 40% or more, less than 50% ×: less than 40%
以上の結果より、負帯電性荷電制御剤と正帯電性荷電制御剤とを含有し、さらにフマル酸及び／又はマレイン酸の総含有量が所定の値以下である実施例のトナーは、比較例のトナーと対比して、温度や湿度の環境変化に対する帯電量の変化が小さく、良好な帯電安定性を有していることが分かる。 From the above results, the toner of the example containing the negatively chargeable charge control agent and the positively chargeable charge control agent, and the total content of fumaric acid and / or maleic acid is a predetermined value or less is a comparative example. It can be seen that the charge amount change with respect to the environmental change of temperature and humidity is small, and that the toner has good charge stability.
本発明の静電荷像現像用トナーは、電子写真法、静電記録法、静電印刷法等において形成される潜像の現像に用いられる。 The electrostatic image developing toner of the present invention is used for developing a latent image formed in electrophotography, electrostatic recording method, electrostatic printing method and the like.
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| JP2004186780A JP4225949B2 (en) | 2003-07-02 | 2004-06-24 | Toner for electrostatic image development |
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Cited By (8)
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| JP2007219216A (en) * | 2006-02-17 | 2007-08-30 | Konica Minolta Business Technologies Inc | Toner for electrostatic image development |
| JP2007322705A (en) * | 2006-05-31 | 2007-12-13 | Kao Corp | Positively charged toner |
| JP2008249886A (en) * | 2007-03-29 | 2008-10-16 | Kao Corp | Electrostatic charge image developing toner |
| JP2008276206A (en) * | 2007-03-30 | 2008-11-13 | Kao Corp | Toner for electrostatic image development |
| JP2010181845A (en) * | 2009-02-09 | 2010-08-19 | Kao Corp | Toner for electrostatic image development |
| JP2011008252A (en) * | 2009-06-24 | 2011-01-13 | Xerox Corp | Purified polyester resin for toner performance improvement |
| JP2019090900A (en) * | 2017-11-14 | 2019-06-13 | 株式会社リコー | Toner, toner storage unit, and image forming apparatus |
| JP2019095772A (en) * | 2017-11-24 | 2019-06-20 | 花王株式会社 | Method for producing binder resin composition |
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| JP6543973B2 (en) * | 2015-03-16 | 2019-07-17 | 株式会社リコー | Toner, developer, process cartridge, image forming apparatus |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4661623B2 (en) * | 2006-02-17 | 2011-03-30 | コニカミノルタビジネステクノロジーズ株式会社 | Toner for developing electrostatic image and method for producing toner for developing electrostatic image |
| JP2007219216A (en) * | 2006-02-17 | 2007-08-30 | Konica Minolta Business Technologies Inc | Toner for electrostatic image development |
| JP2007322705A (en) * | 2006-05-31 | 2007-12-13 | Kao Corp | Positively charged toner |
| JP2008249886A (en) * | 2007-03-29 | 2008-10-16 | Kao Corp | Electrostatic charge image developing toner |
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| JP2011008252A (en) * | 2009-06-24 | 2011-01-13 | Xerox Corp | Purified polyester resin for toner performance improvement |
| JP2019090900A (en) * | 2017-11-14 | 2019-06-13 | 株式会社リコー | Toner, toner storage unit, and image forming apparatus |
| JP2019095772A (en) * | 2017-11-24 | 2019-06-20 | 花王株式会社 | Method for producing binder resin composition |
| JP7112911B2 (en) | 2017-11-24 | 2022-08-04 | 花王株式会社 | Method for producing binder resin composition |
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