JP2007094270A - Electrophotographic oil-less magenta toner - Google Patents

Electrophotographic oil-less magenta toner Download PDF

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JP2007094270A
JP2007094270A JP2005286356A JP2005286356A JP2007094270A JP 2007094270 A JP2007094270 A JP 2007094270A JP 2005286356 A JP2005286356 A JP 2005286356A JP 2005286356 A JP2005286356 A JP 2005286356A JP 2007094270 A JP2007094270 A JP 2007094270A
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mass
parts
magenta toner
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colorant
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JP4475213B2 (en
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Hideki Ikeda
英樹 池田
Akira Fujisawa
亮 藤澤
Kenji Kihira
顕治 紀平
Tadahiro Tsubaki
忠洋 椿
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Casio Computer Co Ltd
Casio Electronics Co Ltd
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Casio Electronics Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic oil-less magenta toner having high chroma, excellent color reproducibility, high environmental stability, hue stability, oil-less fixing property and light resistance. <P>SOLUTION: The electrophotographic toner contains a binder resin, a colorant and a charge control agent, wherein the colorant contains a red pigment comprising a compound expressed by formula (1) (wherein each of X and Y independently represents a halogen atom or an alkyl group) and a red pigment comprising a predetermined quinacridone compound, and the charge control agent contains a metal compound of a predetermined salicylic acid derivative. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、電子写真用オイルレスマゼンタトナーに係り、特に、複数の赤色顔料の組合せにより優れた特性を示す電子写真用粉砕式オイルレスマゼンタトナーに関する。   The present invention relates to an oilless magenta toner for electrophotography, and more particularly to a pulverized oilless magenta toner for electrophotography that exhibits excellent characteristics by a combination of a plurality of red pigments.

一般に、電子写真用トナーは、結着樹脂、着色剤、及び荷電制御剤を含む原料混合物を溶融混練し、粉砕し、分級することにより製造される。電子写真方式のカラープリンターでは、このようなトナーを用いて画像形成が行われる。即ち、現像ローラを用いて、トナーを静電像担持体の表面に形成された静電潜像に供給することにより、静電潜像を現像して可視化し、現像により得られたトナー像を用紙に転写した後、加熱ローラーにて用紙に溶融結着することにより定着する。   In general, an electrophotographic toner is produced by melt-kneading, pulverizing, and classifying a raw material mixture containing a binder resin, a colorant, and a charge control agent. In an electrophotographic color printer, image formation is performed using such toner. That is, by using a developing roller to supply toner to the electrostatic latent image formed on the surface of the electrostatic image carrier, the electrostatic latent image is developed and visualized, and the toner image obtained by the development is visualized. After being transferred to the paper, it is fixed by melting and bonding to the paper with a heating roller.

トナーの定着方式として、近年、オイル塗布装置を用いないオイルレス定着方式が採用されるようになったため、高い剥離性がトナーに求められるようになった。また、印刷物は、太陽光線に曝されても退色することが無く、長期保存が可能であり、且つ高彩度で色再現性、定着性、色相変化特性等の様々な特性を満足する必要がある。しかし、これらの特性をすべて満足するオイルレストナー、特にマゼンタトナーは、これまで見出されていない。   In recent years, an oil-less fixing method that does not use an oil application device has been adopted as a toner fixing method, and thus high releasability has been demanded of the toner. Further, the printed material does not fade even when exposed to sunlight, can be stored for a long period of time, and needs to satisfy various characteristics such as high color saturation, color reproducibility, fixability, and hue change characteristics. However, no oilless toner, particularly magenta toner, that satisfies all of these characteristics has been found so far.

例えば、従来知られている高耐光性高級顔料であるC.I. Pigment Red 122 、C.I. Pigment Red 202、またはC.I. Pigment Violet 19を用いた粉砕式マゼンタトナー(例えば、特許文献1及び2参照)は、着色力が低いため、着色剤添加量が多くなり、ホットオフセットが発生し易くなるため、オイル塗布機構を備えていないプリンターでは、良好な定着性が得られなかった。   For example, a pulverized magenta toner using CI Pigment Red 122, CI Pigment Red 202, or CI Pigment Violet 19 which are conventionally known high light fastness high pigments (for example, see Patent Documents 1 and 2) has a coloring power. Therefore, the amount of the colorant added is increased and hot offset is likely to occur. Therefore, in a printer not provided with an oil application mechanism, good fixability could not be obtained.

また、着色剤としてC.I. Pigment Red 57.1、C.I. Pigment Red 48.2、C.I. Pigment Red 146、C.I. Pigment Red 150、C.I. Pigment Red 269、C.I. Pigment Red 238、C.I. Pigment Red 31、C.I. Pigment Red 185、C.I. Pigment Red 184を用いたマゼンタトナーは、耐光性が弱く、紫外線暴露による退色が発生し、荷電制御剤の種類によっては連続印刷による色相変化が大きくなったり、環境安定性が悪いという問題がある。
特許第3563925号公報 特許第3437436号公報
Also, CI Pigment Red 57.1, CI Pigment Red 48.2, CI Pigment Red 146, CI Pigment Red 150, CI Pigment Red 269, CI Pigment Red 238, CI Pigment Red 31, CI Pigment Red 185, CI Pigment Red 184 as colorants The magenta toner used has low light resistance, fading due to exposure to ultraviolet rays, and there is a problem that the hue change due to continuous printing increases depending on the type of charge control agent, and environmental stability is poor.
Japanese Patent No. 3563925 Japanese Patent No. 3437436

本発明は、以上の事情の下になされ、高彩度で色再現性に優れているとともに、高い環境安定性、色相安定性、オイルレス定着性、及び耐光性を有する電子写真用オイルレスマゼンタトナーを提供することを目的とする。   The present invention is an oilless magenta toner for electrophotography that has been made under the circumstances described above, has high saturation and excellent color reproducibility, and has high environmental stability, hue stability, oilless fixing property, and light resistance. The purpose is to provide.

上記課題を解決するため、第1の発明は、結着樹脂、着色剤、及び電荷制御剤を含む電子写真用オイルレスマゼンタトナーであって、前記着色剤は、下記式(1)により表される化合物からなる赤色顔料と、下記式(2)、(3)又は(4)により表される化合物の少なくとも1種からなる赤色顔料とを含有し、前記電荷制御剤は、下記式(5)又は(6)により表される化合物の少なくとも1種を含有することを特徴とする電子写真用オイルレスマゼンタトナーを提供する。

Figure 2007094270
In order to solve the above problems, a first invention is an oilless magenta toner for electrophotography including a binder resin, a colorant, and a charge control agent, wherein the colorant is represented by the following formula (1). And a red pigment comprising at least one compound represented by the following formula (2), (3) or (4), and the charge control agent comprises the following formula (5): Alternatively, the present invention provides an oilless magenta toner for electrophotography, comprising at least one compound represented by (6).
Figure 2007094270

(式中、X、Yは、それぞれ独立してハロゲン原子又はアルキル基を示す。)

Figure 2007094270
Figure 2007094270
Figure 2007094270
Figure 2007094270
(In the formula, X and Y each independently represent a halogen atom or an alkyl group.)
Figure 2007094270
Figure 2007094270
Figure 2007094270
Figure 2007094270

(式中、R、R及びRはそれぞれ独立して水素原子、直鎖もしくは分岐鎖状の炭素数1〜10のアルキル基またはアリル基、Mは亜鉛、ジルコニウム、クロム、アルミニウム、銅、ニッケル又はコバルト、mは2以上の整数、nは1以上の整数を示す)

Figure 2007094270
(Wherein R 1 , R 2 and R 3 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or an allyl group, M is zinc, zirconium, chromium, aluminum, copper) Nickel or cobalt, m is an integer of 2 or more, and n is an integer of 1 or more)
Figure 2007094270

(式中、Mはホウ素又はアルミニウム、mは2以上の整数、nは1以上の整数を示す)
第2の発明は、結着樹脂、着色剤、及び電荷制御剤を含む電子写真用オイルレスマゼンタトナーであって、前記着色剤は、下記式(1)により表される化合物からなる赤色顔料と、下記式(7)又は(8)により表される化合物の少なくとも1種からなる赤色顔料とを含有し、前記電荷制御剤は、下記式(5)又は(6)により表される化合物の少なくとも1種を含有することを特徴とする電子写真用オイルレスマゼンタトナーを提供する。

Figure 2007094270
(In the formula, M is boron or aluminum, m is an integer of 2 or more, and n is an integer of 1 or more)
A second invention is an oilless magenta toner for electrophotography comprising a binder resin, a colorant, and a charge control agent, wherein the colorant comprises a red pigment comprising a compound represented by the following formula (1): And a red pigment comprising at least one compound represented by the following formula (7) or (8), wherein the charge control agent is at least a compound represented by the following formula (5) or (6): Provided is an oilless magenta toner for electrophotography characterized by containing one kind.
Figure 2007094270

(式中、X、Yは、それぞれ独立してハロゲン原子又はアルキル基を示す。)

Figure 2007094270
(In the formula, X and Y each independently represent a halogen atom or an alkyl group.)
Figure 2007094270

Figure 2007094270
Figure 2007094270

Figure 2007094270
Figure 2007094270

(式中、R、R及びRはそれぞれ独立して水素原子、直鎖もしくは分岐鎖状の炭素数1〜10のアルキル基またはアリル基、Mは亜鉛、ジルコニウム、クロム、アルミニウム、銅、ニッケル又はコバルト、mは2以上の整数、nは1以上の整数を示す)

Figure 2007094270
(Wherein R 1 , R 2 and R 3 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or an allyl group, M is zinc, zirconium, chromium, aluminum, copper) Nickel or cobalt, m is an integer of 2 or more, and n is an integer of 1 or more)
Figure 2007094270

(式中、Mはホウ素又はアルミニウム、mは2以上の整数、nは1以上の整数を示す)
第3の発明は、結着樹脂、着色剤、及び電荷制御剤を含む電子写真用オイルレスマゼンタトナーであって、前記着色剤は、下記式(1)により表される化合物からなる赤色顔料と、下記式(2)、(3)又は(4)により表される化合物の少なくとも1種からなる赤色顔料との固溶体を含有し、前記電荷制御剤は、下記式(5)又は(6)により表される化合物の少なくとも1種を含有することを特徴とするオイルレスマゼンタ電子写真用トナー。

Figure 2007094270
(In the formula, M is boron or aluminum, m is an integer of 2 or more, and n is an integer of 1 or more)
A third invention is an oilless magenta toner for electrophotography comprising a binder resin, a colorant, and a charge control agent, wherein the colorant comprises a red pigment comprising a compound represented by the following formula (1): And a solid solution with a red pigment comprising at least one compound represented by the following formula (2), (3) or (4), wherein the charge control agent is represented by the following formula (5) or (6): An oilless magenta electrophotographic toner comprising at least one of the compounds represented.
Figure 2007094270

(式中、X、Yは、それぞれ独立してハロゲン原子又はアルキル基を示す。)

Figure 2007094270
(In the formula, X and Y each independently represent a halogen atom or an alkyl group.)
Figure 2007094270

Figure 2007094270
Figure 2007094270

Figure 2007094270
Figure 2007094270

Figure 2007094270
Figure 2007094270

(式中、R、R及びRはそれぞれ独立して水素原子、直鎖もしくは分岐鎖状の炭素数1〜10のアルキル基またはアリル基、Mは亜鉛、ジルコニウム、クロム、アルミニウム、銅、ニッケル又はコバルト、mは2以上の整数、nは1以上の整数を示す)

Figure 2007094270
(Wherein R 1 , R 2 and R 3 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or an allyl group, M is zinc, zirconium, chromium, aluminum, copper) Nickel or cobalt, m is an integer of 2 or more, and n is an integer of 1 or more)
Figure 2007094270

(式中、Mはホウ素又はアルミニウム、mは2以上の整数、nは1以上の整数を示す)
以上の第1〜第3の発明において、前記結着樹脂は、下記式(9)により表される化合物を含有するアルコール成分と、ジカルボン酸化合物及び3価以上の多価カルボン酸化合物を含有するカルボン酸成分とを縮重合して得たポリエステルであることが望ましい。

Figure 2007094270
(In the formula, M is boron or aluminum, m is an integer of 2 or more, and n is an integer of 1 or more)
In the first to third inventions described above, the binder resin contains an alcohol component containing a compound represented by the following formula (9), a dicarboxylic acid compound, and a trivalent or higher polyvalent carboxylic acid compound. A polyester obtained by condensation polymerization with a carboxylic acid component is desirable.
Figure 2007094270

(式中、Rは炭素数2又は3のアルキレン基、x及びyは正の数を示し、xとyの和は1〜16である)   (Wherein R is an alkylene group having 2 or 3 carbon atoms, x and y are positive numbers, and the sum of x and y is 1 to 16)

本発明によると、所定の複数の赤色顔料の混合物又は複数の赤色顔料の固溶体と、所定の荷電制御剤とを組合せることにより、高彩度で色再現性に優れているとともに、高い環境安定性、色相安定性、オイルレス定着性、及び耐光性を有する電子写真用オイルレスマゼンタトナーが提供される。   According to the present invention, by combining a predetermined mixture of a plurality of red pigments or a solid solution of a plurality of red pigments and a predetermined charge control agent, it has high chroma and excellent color reproducibility, and high environmental stability. Provided is an oilless magenta toner for electrophotography having hue stability, oilless fixing property, and light resistance.

以下、発明を実施するための最良の形態について説明する。   The best mode for carrying out the invention will be described below.

本発明の第1の実施形態に係る電子写真用オイルレスマゼンタトナーは、上述した式(1)により表される化合物からなる赤色顔料と、上述した式(2)〜(4)により表されるキナクリドン化合物の少なくとも1種からなる赤色顔料との組合せを着色剤として含むものである。   The oilless magenta toner for electrophotography according to the first embodiment of the present invention is represented by the red pigment composed of the compound represented by the above-described formula (1) and the above-described formulas (2) to (4). A combination with a red pigment comprising at least one quinacridone compound is included as a colorant.

上述した式(1)により表される化合物は、環境安定性、オイルレス定着性、及び耐光性のいずれにおいても優れている赤色顔料であるが、その色相はオレンジ色を呈し、単独ではマゼンタトナー用着色剤としては使用できない。   The compound represented by the above formula (1) is a red pigment that is excellent in all of environmental stability, oilless fixing property, and light resistance, but its hue is orange, and it is a magenta toner by itself. It cannot be used as a coloring agent.

この赤色顔料を、単独では特性に難点がある上述した式(2)〜(4)により表されるキナクリドン化合物からなる赤色顔料と組合わせるとともに、所定の荷電制御剤と併用することにより、環境安定性、オイルレス定着性、色相安定性、及び耐光性のいずれにおいても優れた特性を示すオイルレスマゼンタトナーが得られる。   By combining this red pigment with a red pigment composed of the quinacridone compounds represented by the above formulas (2) to (4), which have disadvantages in their characteristics, environmental stability is achieved by using them together with a predetermined charge control agent. An oilless magenta toner exhibiting excellent properties in all of properties, oilless fixing properties, hue stability, and light resistance can be obtained.

なお、式(2)により表される化合物はキナクリドン(C.I.Pigment Violet 19)であり、式(3)により表される化合物は2,9−ジメチルキナクリドン(C.I.Pigment Red 122)であり、式(4)により表される化合物は4,15−ジクロルキナクリドン(C.I.Pigment Red 202)である。   The compound represented by the formula (2) is quinacridone (CIPigment Violet 19), the compound represented by the formula (3) is 2,9-dimethylquinacridone (CIPigment Red 122), and the formula (4 ) Is 4,15-dichloroquinacridone (CIPigment Red 202).

式(1)において、X、Yは、ハロゲン原子又はアルキル基であるが、Cl又はメチル基であるのが好ましい。具体例として、X、YがClであるCROMOPHTAL Red 2030(C.I.Pigment Red 256、チバスペシャリティーケミカルズ(株)社製)を挙げることができる。   In the formula (1), X and Y are a halogen atom or an alkyl group, but are preferably Cl or a methyl group. Specific examples include CROMOPHTAL Red 2030 (C.I. Pigment Red 256, manufactured by Ciba Specialty Chemicals Co., Ltd.) in which X and Y are Cl.

本発明の第2の実施形態に係る電子写真用オイルレスマゼンタトナーは、上述した式(1)により表される化合物からなる赤色顔料と、上述した式(5)及び(6)により表される化合物の少なくとも1種からなる赤色顔料との組合せを含むものである。   The oilless magenta toner for electrophotography according to the second embodiment of the present invention is represented by the red pigment composed of the compound represented by the above formula (1) and the above formulas (5) and (6). It includes a combination with a red pigment comprising at least one compound.

なお、式(5)により表される化合物はアゾレーキ系顔料であり、式(6)により表される化合物はナフトール系顔料である。   The compound represented by the formula (5) is an azo lake pigment, and the compound represented by the formula (6) is a naphthol pigment.

以上の実施形態において、式(1)により表される化合物からなる赤色顔料(A)と、他の赤色顔料(B)との配合比(A:B)は、1:9〜9:1であるのが好ましい。  In the above embodiment, the compounding ratio (A: B) of the red pigment (A) composed of the compound represented by the formula (1) and the other red pigment (B) is 1: 9 to 9: 1. Preferably there is.

本発明の第3の実施形態に係る電子写真用オイルレスマゼンタトナーは、上述した式(1)により表される化合物からなる赤色顔料と、上述した式(2)〜(4)により表されるキナクリドン化合物の少なくとも1種からなる赤色顔料との固溶体を含むものである。   The oilless magenta toner for electrophotography according to the third embodiment of the present invention is represented by the red pigment composed of the compound represented by the above formula (1) and the above formulas (2) to (4). It contains a solid solution with a red pigment comprising at least one quinacridone compound.

2種の赤色顔料の固溶体であっても、混合物の場合と同様に、式(1)により表される化合物と組合わせることにより、マゼンタトナー用着色剤として優れた効果を発揮する。
なお、2種の赤色顔料の固溶体の原料配合比は、固溶体を形成する配合比であればよい。
Even in the case of a solid solution of two kinds of red pigments, an excellent effect as a colorant for magenta toner is exhibited by combining with the compound represented by the formula (1) as in the case of the mixture.
In addition, the raw material compounding ratio of the solid solution of 2 types of red pigments should just be a compounding ratio which forms a solid solution.

以上の本発明の第1〜3の実施形態に係る電子写真用オイルレスマゼンタトナーのいずれにおいても、電荷制御剤としては、上述した式(7)又は(8)により表される化合物の少なくとも1種が使用される。   In any of the oilless magenta toners for electrophotography according to the first to third embodiments of the present invention, the charge control agent is at least one of the compounds represented by the above formula (7) or (8). A seed is used.

以下に、本発明の実施例及び比較例を示し、本発明の効果を具体的に説明する。なお、各例で得たトナーについての環境安定性、オイルレス定着性、色相安定性、及び耐光性の評価基準は、次の通りである。   Examples of the present invention and comparative examples will be shown below to specifically explain the effects of the present invention. The evaluation criteria for environmental stability, oilless fixability, hue stability, and light resistance of the toner obtained in each example are as follows.

〔環境安定性評価基準〕
通常環境(22℃、50%RH)、高温高湿(28℃、80%RH)、及び低温低湿(10℃、20%RH)の下で、[MODEL210HSQ/Mメーター」(トレックス社製)を用い、メイン電源を入れてアイドル状態になった時の現像ロール上の帯電量を測定した。通常環境下の帯電量に対する高温高湿下及び低温低湿下での帯電量変化率の平均値〔(高温高湿下での帯電量変化率+低温低湿下での帯電量変化率)/2〕を算出し、以下の評価基準に従って環境安定性を評価する。
[Environmental stability evaluation criteria]
Under normal environment (22 ° C, 50% RH), high temperature and high humidity (28 ° C, 80% RH), and low temperature and low humidity (10 ° C, 20% RH), [MODEL210HSQ / M meter] (manufactured by Torex) The charge amount on the developing roll was measured when the main power supply was turned on and the engine became idle. Average rate of change in charge amount under high temperature and high humidity and low temperature and low humidity relative to the charge amount under normal environment [(charge amount change rate under high temperature and high humidity + charge amount change rate under low temperature and low humidity) / 2] And the environmental stability is evaluated according to the following evaluation criteria.

◎:平均値が5%未満であり、実使用上、特に良好である。   A: The average value is less than 5%, which is particularly good in practical use.

○:平均値が5%以上、10%未満であり、実使用上良好である。   A: The average value is 5% or more and less than 10%, which is good in practical use.

△:平均値が10%以上、15%未満であり、実使用上問題はない。   (Triangle | delta): An average value is 10% or more and less than 15%, and there is no problem in actual use.

×:平均値が15%以上であり、実使用不可である。   X: The average value is 15% or more, and actual use is impossible.

〔オイルレス定着性評価基準〕
定着オイル供給装置を外した「スピーディアN5300」(カシオ計算機(株)社製)にマゼンタトナーを実装し、未定着画像を得た後、取り出した定着器の温度を100℃から220℃へと順次上昇させて、装置外で未定着画像を定着させた際の定着可能温度域を測定し、定着性を以下の評価基準に従って評価する。
[Oilless fixability evaluation criteria]
The magenta toner was mounted on “Speedia N5300” (manufactured by Casio Computer Co., Ltd.) with the fixing oil supply device removed, and after obtaining an unfixed image, the temperature of the taken out fixing device was changed from 100 ° C. to 220 ° C. The temperature is gradually increased to measure the fixable temperature range when the unfixed image is fixed outside the apparatus, and the fixability is evaluated according to the following evaluation criteria.

◎:定着可能温度域が50℃以上であり、実使用上、特に良好である。   A: Fixable temperature range is 50 ° C. or more, which is particularly good in practical use.

○:定着可能温度域が40℃以上、50℃未満であり、実使用上良好である。   ○: Fixable temperature range is 40 ° C. or higher and lower than 50 ° C., which is good for practical use.

△:定着可能温度域が30℃以上、40℃未満であり、実使用上問題がない。   (Triangle | delta): The temperature range which can be fixed is 30 degreeC or more and less than 40 degreeC, and there is no problem in actual use.

×:定着可能温度域が30℃未満であり、実使用不可である。   X: The fixable temperature range is less than 30 ° C. and cannot be used in practice.

〔色相安定性評価基準〕
定着オイル供給装置を外した「スピーディアN5300」(カシオ計算機(株)社製)にマゼンタトナーを実装し、普通紙「XEROX−L」を用いて、1枚当たりの印字率が5%の印刷を連続して6000枚行い、1枚目と6000枚印字後の色相変化の差(ΔE)を「SPECTRODENSITOMETER 938」(X−rite社製)を用いて測定し、色相変化の程度を以下の評価基準に従って評価する。
[Hue Stability Evaluation Criteria]
Printing with a printing rate of 5% per sheet using magenta toner mounted on "Speedia N5300" (manufactured by Casio Computer Co., Ltd.) with the fixing oil supply device removed, and plain paper "XEROX-L" The difference in hue (ΔE) after printing the first and 6000 sheets was measured using “SPECTRODENSITOMETER 938” (manufactured by X-rite), and the degree of hue change was evaluated as follows. Assess according to criteria.

◎:ΔEが5未満であり、実使用上、特に良好である。   A: ΔE is less than 5, which is particularly good in practical use.

○:ΔEが5以上、10未満であり、実使上良好である。   ◯: ΔE is 5 or more and less than 10, which is good in practical use.

△:ΔEが10以上、20未満であり、実使用可能である。   Δ: ΔE is 10 or more and less than 20, and can be actually used.

×:ΔEが20以上であり、使用不可である。   X: ΔE is 20 or more and cannot be used.

〔耐光性評価基準〕
定着オイル供給装置を外した「スピーディアN5300」(カシオ計算機(株)社製)にマゼンタトナーを実装し、普通紙「XEROX−L」を用いて印刷した画像を、「スーパーキセノンウェザーメータ SX−75」(スガ試験機社製)を用い、光源として7.5KWキセノンランプ/アウター:#275/インナー:石英を使用し、ブラックパネル温度63℃にて促進耐光性試験を行い、200時間連続照射前後の色相変化の差(ΔE)を「SPECTRODENSITOMETER938」(X−rite社製)を用いて測定し、退色の度合いを以下の評価基準に従って評価する。
(Light resistance evaluation criteria)
An image printed with “Serdia N5300” (manufactured by Casio Computer Co., Ltd.) with magenta toner and using plain paper “XEROX-L” was removed from the “Super Xenon Weather Meter SX-”. 75 "(manufactured by Suga Test Instruments Co., Ltd.), 7.5KW xenon lamp / outer: # 275 / inner: quartz as the light source, accelerated light resistance test at a black panel temperature of 63 ° C, and continuous irradiation for 200 hours The difference (ΔE) in the hue change before and after is measured using “SPECTRODENSITOMETER 938” (manufactured by X-rite), and the degree of fading is evaluated according to the following evaluation criteria.

◎:ΔEが2.0未満であり、実使用上、特に良好である。   (Double-circle): (DELTA) E is less than 2.0 and is especially favorable on actual use.

○:ΔEが2.0以上、5.0未満であり、実使上良好である。   A: ΔE is 2.0 or more and less than 5.0, which is good in practical use.

△:ΔEが5.0以上、10.0未満であり、実使用可能である。   (Triangle | delta): (DELTA) E is 5.0 or more and less than 10.0, and can be actually used.

×:ΔEが10.0以上であり、使用不可である。   X: ΔE is 10.0 or more and cannot be used.

実施例1
結着樹脂100質量部、第1の着色剤(CROMOPHTAL Red 2030(C.I. Pigment Red 256):チバスペシャリティーケミカルズ(株)社製)2.0質量部、第2の着色剤(PV FAST PINK E(C.I.Pigment Red 122):クラリアントジャパン社製)2.0部、荷電制御剤(LR147:日本カーリット(株)社製)1.5質量部、及び雛形剤(カルナウバワックスC1:加藤洋行社輸入品)5質量部をヘンシェルミキサーを用いて混合した後、二軸押出機により溶融混練した。
Example 1
Binder resin 100 parts by mass, first colorant (CROMOPHTAL Red 2030 (CI Pigment Red 256): Ciba Specialty Chemicals Co., Ltd.) 2.0 parts by mass, second colorant (PV FAST PINK E ( CIPigment Red 122): 2.0 parts manufactured by Clariant Japan), 1.5 parts by mass of charge control agent (LR147: manufactured by Nippon Carlit Co., Ltd.), and template (carnauba wax C1: imported by Yoko Kato) After 5 parts by mass were mixed using a Henschel mixer, the mixture was melt-kneaded with a twin screw extruder.

次いで、得られた溶融混練物を冷却し、衝突板式粉砕機(ディスパージョンセパレーター:日本ニューマチック工業(株)社製)を用いて粉砕した後、分級工程を経て、質量平均粒子経8.5μm、変動係数25.4%の着色微粒子を得た。   Next, the obtained melt-kneaded product is cooled and pulverized using a collision plate type pulverizer (dispersion separator: manufactured by Nippon Pneumatic Industry Co., Ltd.), followed by a classification step, and a mass average particle diameter of 8.5 μm. Colored fine particles having a coefficient of variation of 25.4% were obtained.

次に、得られた着色微粒子100質量部に疎水性シリカ(NAX−50:日本アエロジル社製、平均粒子経:35nm)2.5質量部を添加し、10リットル容のヘンシェルミキサーにより3200r/minの回転速度で180秒間撹拌し、着色微粒子に外添処理を施して、マゼンタトナーを得た。   Next, 2.5 parts by mass of hydrophobic silica (NAX-50: manufactured by Nippon Aerosil Co., Ltd., average particle size: 35 nm) was added to 100 parts by mass of the obtained colored fine particles, and 3200 r / min by a 10 liter Henschel mixer. The mixture was stirred for 180 seconds at a rotational speed of, and externally added to the colored fine particles to obtain a magenta toner.

得られたマゼンタトナーを「スピーディアN5300」(カシオ計算機(株)社製)に実装し、オイル塗布ユニットを取り外して、画像印刷を行い、環境安定性、オイルレス定着性、色相安定性、及び耐光性について評価した。その結果を下記表1に示す。   The obtained magenta toner is mounted on “Speedia N5300” (manufactured by Casio Computer Co., Ltd.), the oil application unit is removed, image printing is performed, environmental stability, oilless fixing property, hue stability, and The light resistance was evaluated. The results are shown in Table 1 below.

実施例2
結着樹脂100質量部、第1の着色剤(CROMOPHTAL Red 2030:チバスペシャリティーケミカルズ(株)社製)2.0質量部、第2の着色剤(PV FAST RED E5B(C.I.Pigment Violet 19):クラリアントジャパン社製)2.0部、荷電制御剤(LR147:日本カーリット(株)社製)1.5質量部、及び離型剤(カルナウバワックスC1:加藤洋行社輸入品)5質量部を、ヘンシェルミキサーを用いて混合した後、二軸押出機により溶融混練した。
Example 2
Binder resin 100 parts by mass, first colorant (CROMOPHTAL Red 2030: Ciba Specialty Chemicals Co., Ltd.) 2.0 parts by mass, second colorant (PV FAST RED E5B (CIPigment Violet 19): Clariant 2.0 parts by Japan), 1.5 parts by weight of charge control agent (LR147: made by Nippon Carlit Co., Ltd.), and 5 parts by weight of release agent (carnauba wax C1: imported by Kato Yoko Co., Ltd.) After mixing using a Henschel mixer, the mixture was melt kneaded with a twin screw extruder.

次いで、得られた溶融混練物を冷却し、衝突板式粉砕機(ディスパージョンセパレーター:日本ニューマチック工業(株)社製)を用いて粉砕した後、分級工程を経て、質量平均粒子経8.5μm、変動係数25.4%の着色微粒子を得た。   Next, the obtained melt-kneaded product is cooled and pulverized using a collision plate type pulverizer (dispersion separator: manufactured by Nippon Pneumatic Industry Co., Ltd.), followed by a classification step, and a mass average particle diameter of 8.5 μm. Colored fine particles having a coefficient of variation of 25.4% were obtained.

次に、得られた着色微粒子100質量部に疎水性シリカ「NAX−50」(日本アエロジル社製、平均粒子経:35nm)2.5質量部を添加し、10リットル容のヘンシェルミキサーにより3200r/minの回転速度で180秒間撹拌し、着色微粒子に外添処理を施して、マゼンタトナーを得た。   Next, 2.5 parts by mass of hydrophobic silica “NAX-50” (manufactured by Nippon Aerosil Co., Ltd., average particle diameter: 35 nm) was added to 100 parts by mass of the obtained colored fine particles, and 3200 r / s by a 10 liter Henschel mixer. The mixture was stirred for 180 seconds at a rotation speed of min, and the color fine particles were externally added to obtain a magenta toner.

以上のようにして得られたマゼンタトナーを用いて、実施例1と同様にして画像印刷を行い、環境安定性、オイルレス定着性、色相安定性、及び耐光性について評価した。その結果を下記表1に示す。   Using the magenta toner obtained as described above, image printing was performed in the same manner as in Example 1, and environmental stability, oil-less fixing property, hue stability, and light resistance were evaluated. The results are shown in Table 1 below.

実施例3
結着樹脂100質量部、第1の着色剤(CROMOPHTAL Red 2030:チバスペシャリティーケミカルズ(株)社製)2.0質量部、第2の着色剤(CINQUASIA Magenta RT−235−D(C.I.Pigment Red 202):チバスペシャリティーケミカルズ(株)社製)2.0部、荷電制御剤(LR147:日本カーリット(株)社製)1.5質量部、及び離型剤(カルナウバワックスC1:加藤洋行社輸入品)5質量部をヘンシェルミキサーを用いて混合した後、二軸押出機により溶融混練した。
Example 3
Binder resin 100 parts by mass, first colorant (CROMOPHTAL Red 2030: manufactured by Ciba Specialty Chemicals Co., Ltd.) 2.0 parts by mass, second colorant (CINQUASIA Magenta RT-235-D (CIPigment Red 202 ): 2.0 parts by Ciba Specialty Chemicals Co., Ltd.), 1.5 parts by mass of charge control agent (LR147: made by Nippon Carlit Co., Ltd.), and mold release agent (Carnauba wax C1: Hiroyuki Kato) (Imported product) 5 parts by mass was mixed using a Henschel mixer, and then melt-kneaded by a twin screw extruder.

次いで、得られた溶融混練物を冷却し、衝突板式粉砕機(ディスパージョンセパレーター:日本ニューマチック工業(株)社製)を用いて粉砕した後、分級工程を経て、質量平均粒子経8.5μm、変動係数25.4%の着色微粒子を得た。   Next, the obtained melt-kneaded product is cooled and pulverized using a collision plate type pulverizer (dispersion separator: manufactured by Nippon Pneumatic Industry Co., Ltd.), followed by a classification step, and a mass average particle diameter of 8.5 μm. Colored fine particles having a coefficient of variation of 25.4% were obtained.

次に、得られた着色微粒子100質量部に疎水性シリカ「NAX−50」(日本アエロジル社製、平均粒子経:35nm)2.5質量部を添加し、10リットル容のヘンシェルミキサーにより3200r/minの回転速度で180秒間撹拌し、着色微粒子に外添処理を施して、マゼンタトナーを得た。   Next, 2.5 parts by mass of hydrophobic silica “NAX-50” (manufactured by Nippon Aerosil Co., Ltd., average particle diameter: 35 nm) was added to 100 parts by mass of the obtained colored fine particles, and 3200 r / s by a 10 liter Henschel mixer. The mixture was stirred for 180 seconds at a rotation speed of min, and the color fine particles were externally added to obtain a magenta toner.

以上のようにして得られたマゼンタトナーを用いて、実施例1と同様にして画像印刷を行い、環境安定性、オイルレス定着性、色相安定性、及び耐光性について評価した。その結果を下記表1に示す。   Using the magenta toner obtained as described above, image printing was performed in the same manner as in Example 1, and environmental stability, oil-less fixing property, hue stability, and light resistance were evaluated. The results are shown in Table 1 below.

実施例4
結着樹脂100質量部、第1の着色剤(CROMOPHTAL Red 2030:チバスペシャリティーケミカルズ(株)社製)2.0質量部、第2の着色剤(ECR−101(C.I.Pigment Red 57.1):大日精化工業(株)社製)2.0部と、荷電制御剤(LR147:日本カーリット(株)社製)1.5質量部、及び離型剤(カルナウバワックスC1:加藤洋行社輸入品)5質量部をヘンシェルミキサーを用いて混合した後、二軸押出機により溶融混練した。
Example 4
Binder resin 100 parts by mass, first colorant (CROMOPHTAL Red 2030: Ciba Specialty Chemicals Co., Ltd.) 2.0 parts by mass, second colorant (ECR-101 (CIPigment Red 57.1): Dainichi Kato Kogyo Co., Ltd.) 2.0 parts, charge control agent (LR147: Nippon Carlit Co., Ltd.) 1.5 parts by mass, and mold release agent (Carnauba wax C1: imported by Kato Yoko Co., Ltd.) After 5 parts by mass were mixed using a Henschel mixer, the mixture was melt-kneaded with a twin screw extruder.

次いで、得られた溶融混練物を冷却し、衝突板式粉砕機(ディスパージョンセパレーター:日本ニューマチック工業(株)社製)を用いて粉砕した後、分級工程を経て、質量平均粒子経8.5μm、変動係数25.4%の着色微粒子を得た。   Next, the obtained melt-kneaded product is cooled and pulverized using a collision plate type pulverizer (dispersion separator: manufactured by Nippon Pneumatic Industry Co., Ltd.), followed by a classification step, and a mass average particle diameter of 8.5 μm. Colored fine particles having a coefficient of variation of 25.4% were obtained.

次に、得られた着色微粒子100質量部に疎水性シリカ「NAX−50」(日本アエロジル社製、平均粒子経:35nm)2.5質量部を添加し、10リットル容のヘンシェルミキサーにより3200r/minの回転速度で180秒間撹拌し、着色微粒子に外添処理を施して、マゼンタトナーを得た。   Next, 2.5 parts by mass of hydrophobic silica “NAX-50” (manufactured by Nippon Aerosil Co., Ltd., average particle diameter: 35 nm) was added to 100 parts by mass of the obtained colored fine particles, and 3200 r / s by a 10 liter Henschel mixer. The mixture was stirred for 180 seconds at a rotation speed of min, and the color fine particles were externally added to obtain a magenta toner.

以上のようにして得られたマゼンタトナーを用いて、実施例1と同様にして画像印刷を行い、環境安定性、オイルレス定着性、色相安定性、及び耐光性について評価した。その結果を下記表1に示す。   Using the magenta toner obtained as described above, image printing was performed in the same manner as in Example 1, and environmental stability, oil-less fixing property, hue stability, and light resistance were evaluated. The results are shown in Table 1 below.

実施例5
結着樹脂100質量部、第1の着色剤(CROMOPHTAL Red 2030:チバスペシャリティーケミカルズ(株)社製)2.0質量部、第2の結着剤(TOSHIKI RED 1022(C.I.Pigment Red 269):大日本インキ化学工業(株)社製)2.0部、荷電制御剤(LR147:日本カーリット(株)社製)1.5質量部、及び離型剤(カルナウバワックスC1:加藤洋行社輸入品)5質量部をヘンシェルミキサーを用いて混合した後、二軸押出機により溶融混練した。
Example 5
Binder resin 100 parts by mass, first colorant (CROMOPHTAL Red 2030: Ciba Specialty Chemicals Co., Ltd.) 2.0 parts by mass, second binder (TOSHIKI RED 1022 (CIPigment Red 269): large 2.0 parts by Nippon Ink Chemical Co., Ltd.), 1.5 parts by mass of charge control agent (LR147: made by Nippon Carlit Co., Ltd.), and release agent (Carnauba wax C1: imported by Yoko Kato) ) After 5 parts by mass were mixed using a Henschel mixer, the mixture was melt-kneaded with a twin screw extruder.

次いで、得られた溶融混練物を冷却し、衝突板式粉砕機(ディスパージョンセパレーター:日本ニューマチック工業(株)社製)を用いて粉砕した後、分級工程を経て、質量平均粒子経8.5μm、変動係数25.4%の着色微粒子を得た。   Next, the obtained melt-kneaded product is cooled and pulverized using a collision plate type pulverizer (dispersion separator: manufactured by Nippon Pneumatic Industry Co., Ltd.), followed by a classification step, and a mass average particle diameter of 8.5 μm. Colored fine particles having a coefficient of variation of 25.4% were obtained.

次に、得られた着色微粒子100質量部に疎水性シリカ「NAX−50」(日本アエロジル社製、平均粒子経:35nm)2.5質量部を添加し、10リットル容のヘンシェルミキサーにより3200r/minの回転速度で180秒間撹拌し、着色微粒子に外添処理を施して、マゼンタトナーを得た。   Next, 2.5 parts by mass of hydrophobic silica “NAX-50” (manufactured by Nippon Aerosil Co., Ltd., average particle diameter: 35 nm) was added to 100 parts by mass of the obtained colored fine particles, and 3200 r / s by a 10 liter Henschel mixer. The mixture was stirred for 180 seconds at a rotation speed of min, and the color fine particles were externally added to obtain a magenta toner.

以上のようにして得られたマゼンタトナーを用いて、実施例1と同様にして画像印刷を行い、環境安定性、オイルレス定着性、色相安定性、及び耐光性について評価した。その結果を下記表1に示す。   Using the magenta toner obtained as described above, image printing was performed in the same manner as in Example 1, and environmental stability, oil-less fixing property, hue stability, and light resistance were evaluated. The results are shown in Table 1 below.

実施例6
結着樹脂100質量部、CROMOPHTAL Red 2030とPV FAST RED E5Bとの固溶体である着色剤(Magenta ST:チバスペシャリティーケミカルズ(株)社製)4質量部、及び荷電制御剤(LR147:日本カーリット(株)社製)1.5質量部、および離型剤(カルナバワックスC1:加藤洋行社輸入品)5質量部をヘンシェルミキサーで十分に混合した後、2軸押出機で溶融混練した。
Example 6
100 parts by mass of a binder resin, 4 parts by mass of a colorant (Magenta ST: manufactured by Ciba Specialty Chemicals Co., Ltd.), which is a solid solution of CROMOPHTAL Red 2030 and PV FAST RED E5B, and a charge control agent (LR147: Nippon Carlit ( 1.5 parts by mass (manufactured by Co., Ltd.) and 5 parts by mass of a release agent (Carnauba wax C1: imported from Kato Yoko Co., Ltd.) were sufficiently mixed with a Henschel mixer and then melt-kneaded with a twin screw extruder.

次いで、得られた溶融混練物を冷却し、衝突板式粉砕機(ディスパージョンセパレーター:日本ニューマチック工業(株)社製)を用いて粉砕した後、分級工程を経て、質量平均粒子経8.5μmの着色微粒子を得た。   Next, the obtained melt-kneaded product is cooled and pulverized using a collision plate type pulverizer (dispersion separator: manufactured by Nippon Pneumatic Industry Co., Ltd.), followed by a classification step, and a mass average particle diameter of 8.5 μm. Colored fine particles were obtained.

次に、得られた着色微粒子100質量部に疎水性シリカ「RX−200」(日本アエロジル社製)1.5質量部を添加し、10リットル容のヘンシェルミキサーにより3200r/minの回転速度で180秒間撹拌し、着色微粒子に外添処理を施して、マゼンタトナーを得た。   Next, 1.5 parts by mass of hydrophobic silica “RX-200” (manufactured by Nippon Aerosil Co., Ltd.) was added to 100 parts by mass of the obtained colored fine particles, and 180 rpm at a rotation speed of 3200 r / min with a 10 liter Henschel mixer. The mixture was stirred for 2 seconds, and the colored fine particles were externally treated to obtain a magenta toner.

以上のようにして得られたマゼンタトナーを用いて、実施例1と同様にして画像印刷を行い、環境安定性、オイルレス定着性、色相安定性、及び耐光性について評価した。その結果を下記表1に示す。   Using the magenta toner obtained as described above, image printing was performed in the same manner as in Example 1, and environmental stability, oil-less fixing property, hue stability, and light resistance were evaluated. The results are shown in Table 1 below.

比較例1
結着樹脂100質量部、着色剤(CROMOPHTAL Red 2030:チバスペシャリティーケミカルズ(株)社製)4.0質量部、荷電制御剤(LR147:日本カーリット(株)社製)1.5質量部、及び離型剤(カルナウバワックスC1:加藤洋行社輸入品)5質量部をヘンシェルミキサーを用いて混合した後、二軸押出機により溶融混練した。
Comparative Example 1
Binder resin 100 parts by weight, colorant (CROMOPHTAL Red 2030: Ciba Specialty Chemicals Co., Ltd.) 4.0 parts by weight, charge control agent (LR147: Nippon Carlit Co., Ltd.) 1.5 parts by weight, Then, 5 parts by mass of a release agent (Carnauba wax C1: imported from Kato Yoko Co., Ltd.) was mixed using a Henschel mixer, and then melt-kneaded using a twin screw extruder.

次いで、得られた溶融混練物を冷却し、衝突板式粉砕機(ディスパージョンセパレーター:日本ニューマチック工業(株)社製)を用いて粉砕した後、分級工程を経て、質量平均粒子経8.5μm、変動係数25.4%の着色微粒子を得た。   Next, the obtained melt-kneaded product is cooled and pulverized using a collision plate type pulverizer (dispersion separator: manufactured by Nippon Pneumatic Industry Co., Ltd.), followed by a classification step, and a mass average particle diameter of 8.5 μm. Colored fine particles having a coefficient of variation of 25.4% were obtained.

次に、得られた着色微粒子100質量部に、疎水性シリカ(RX200:日本アエロジル社製)1.5質量部を添加し、10リットル容のヘンシェルミキサーにより3200r/minの回転速度で180秒間撹拌し、着色微粒子に外添処理を施して、マゼンタトナーを得た。   Next, 1.5 parts by mass of hydrophobic silica (RX200: manufactured by Nippon Aerosil Co., Ltd.) is added to 100 parts by mass of the obtained colored fine particles, and stirred for 180 seconds at a rotation speed of 3200 r / min with a 10 liter Henschel mixer. The colored fine particles were subjected to an external addition process to obtain a magenta toner.

以上のようにして得られたマゼンタトナーを用いて、実施例1と同様にして画像印刷を行い、環境安定性、オイルレス定着性、色相安定性、及び耐光性について評価した。その結果を下記表1に示す。   Using the magenta toner obtained as described above, image printing was performed in the same manner as in Example 1, and environmental stability, oil-less fixing property, hue stability, and light resistance were evaluated. The results are shown in Table 1 below.

比較例2
結着樹脂100質量部、着色剤(ECR−101:大日本精化工業(株)社製)4質量部、荷電制御剤(LR147:日本カーリット(株)社製)1.5質量部、及び離型剤(カルナウバワックスC1:加藤洋行社輸入品)5質量部をヘンシェルミキサーを用いて混合した後、二軸押出機により溶融混練した。
Comparative Example 2
100 parts by mass of binder resin, 4 parts by mass of colorant (ECR-101: manufactured by Dainippon Seika Kogyo Co., Ltd.), 1.5 parts by mass of charge control agent (LR147: manufactured by Nippon Carlit Co., Ltd.), and After 5 parts by mass of a release agent (Carnauba wax C1: imported from Kato Yoko Co., Ltd.) was mixed using a Henschel mixer, it was melt-kneaded using a twin screw extruder.

次いで、得られた溶融混練物を冷却し、衝突板式粉砕機(ディスパージョンセパレーター:日本ニューマチック工業(株)社製)を用いて粉砕した後、分級工程を経て、質量平均粒子経8.5μm、変動係数25.4%の着色微粒子を得た。   Next, the obtained melt-kneaded product is cooled and pulverized using a collision plate type pulverizer (dispersion separator: manufactured by Nippon Pneumatic Industry Co., Ltd.), followed by a classification step, and a mass average particle diameter of 8.5 μm. Colored fine particles having a coefficient of variation of 25.4% were obtained.

次に、得られた着色微粒子100質量部に、疎水性シリカ(NAX−50:日本アエロジル社製、平均粒子経:35nm)2.5質量部を添加し、10リットル容のヘンシェルミキサーにより3200r/minの回転速度で180秒間撹拌し、着色微粒子に外添処理を施して、マゼンタトナーを得た。   Next, 2.5 parts by mass of hydrophobic silica (NAX-50: manufactured by Nippon Aerosil Co., Ltd., average particle size: 35 nm) was added to 100 parts by mass of the obtained colored fine particles, and 3200 r / s by a 10 liter Henschel mixer. The mixture was stirred for 180 seconds at a rotation speed of min, and the color fine particles were externally added to obtain a magenta toner.

以上のようにして得られたマゼンタトナーを用いて、実施例1と同様にして画像印刷を行い、環境安定性、オイルレス定着性、色相安定性、及び耐光性について評価した。その結果を下記表1に示す。   Using the magenta toner obtained as described above, image printing was performed in the same manner as in Example 1, and environmental stability, oil-less fixing property, hue stability, and light resistance were evaluated. The results are shown in Table 1 below.

比較例3.
結着樹脂100質量部、着色剤(PV FAST RED E5B:クラリアントジャパン社製)7.0部、荷電制御剤(LR147:日本カーリット(株)社製)1.5質量部、及び離型剤(カルナウバワックスC1:加藤洋行社輸入品)5質量部をヘンシェルミキサーを用いて混合した後、二軸押出機により溶融混練した。
Comparative Example 3
Binder resin 100 parts by mass, colorant (PV FAST RED E5B: made by Clariant Japan) 7.0 parts, charge control agent (LR147: made by Nippon Carlit Co., Ltd.) 1.5 parts by mass, and release agent ( Carnauba wax C1: imported from Kato Yoko Co., Ltd.) 5 parts by mass were mixed using a Henschel mixer, and then melt-kneaded using a twin screw extruder.

次いで、得られた溶融混練物を冷却し、衝突板式粉砕機(ディスパージョンセパレーター:日本ニューマチック工業(株)社製)を用いて粉砕した後、分級工程を経て、質量平均粒子経8.5μm、変動係数25.4%の着色微粒子を得た。   Next, the obtained melt-kneaded product is cooled and pulverized using a collision plate type pulverizer (dispersion separator: manufactured by Nippon Pneumatic Industry Co., Ltd.), followed by a classification step, and a mass average particle diameter of 8.5 μm. Colored fine particles having a coefficient of variation of 25.4% were obtained.

次に、得られた樹脂微粒子100質量部に、疎水性シリカ(NAX−50:日本アエロジル社製、平均粒子経:35nm)2.5質量部を添加し、10リットル容のヘンシェルミキサーにより3200r/minの回転速度で180秒間撹拌し、着色微粒子に外添処理を施して、マゼンタトナーを得た。   Next, 2.5 parts by mass of hydrophobic silica (NAX-50: manufactured by Nippon Aerosil Co., Ltd., average particle diameter: 35 nm) was added to 100 parts by mass of the obtained resin fine particles, and 3200 r / s by a 10 liter Henschel mixer. The mixture was stirred for 180 seconds at a rotation speed of min, and the color fine particles were externally added to obtain a magenta toner.

以上のようにして得られたマゼンタトナーを用いて、実施例1と同様にして画像印刷を行い、環境安定性、オイルレス定着性、色相安定性、及び耐光性について評価した。その結果を下記表1に示す。   Using the magenta toner obtained as described above, image printing was performed in the same manner as in Example 1, and environmental stability, oil-less fixing property, hue stability, and light resistance were evaluated. The results are shown in Table 1 below.

比較例4
結着樹脂100質量部、第1の着色剤(CROMOPHTAL Red 2030:チバスペシャリティーケミカルズ(株)社製)2.0質量部、第2の着色剤(TOSHIKI RED 1022:大日本インキ化学工業(株)社製)2.0部、荷電制御剤(ボントロンE−89:オリエント化学工業社製)1.5質量部、及び離型剤(カルナウバワックスC1:加藤洋行社輸入品)5質量部をヘンシェルミキサーを用いて混合した後、二軸押出機により溶融混練した。
Comparative Example 4
Binder resin 100 parts by mass, first colorant (CROMOPHTAL Red 2030: Ciba Specialty Chemicals Co., Ltd.) 2.0 parts by mass, second colorant (TOSHIKI RED 1022: Dainippon Ink & Chemicals, Inc. ) 2.0 parts, 1.5 parts by mass of charge control agent (Bontron E-89: manufactured by Orient Chemical Co., Ltd.), and 5 parts by mass of release agent (carnauba wax C1: imported by Kato Yoko Co., Ltd.) After mixing using a Henschel mixer, the mixture was melt kneaded with a twin screw extruder.

次いで、得られた溶融混練物を冷却し、衝突板式粉砕機(ディスパージョンセパレーター:日本ニューマチック工業(株)社製)を用いて粉砕した後、分級工程を経て、質量平均粒子径8.5μm、変動係数25.4%の着色微粒子を得た。   Subsequently, the obtained melt-kneaded product was cooled and pulverized using a collision plate type pulverizer (dispersion separator: manufactured by Nippon Pneumatic Industry Co., Ltd.), followed by a classification step, and a mass average particle diameter of 8.5 μm. Colored fine particles having a coefficient of variation of 25.4% were obtained.

次に、得られた着色微粒子100質量部に疎水性シリカ(NAX−50:日本アエロジル社製、平均粒子径:35nm)2.5質量部を添加し、10リットル容のヘンシェルミキサーにより3200r/minの回転速度で180秒間攪拌し、着色微粒子に外添処理を施して、マゼンタトナーを得た。   Next, 2.5 parts by mass of hydrophobic silica (NAX-50: manufactured by Nippon Aerosil Co., Ltd., average particle size: 35 nm) was added to 100 parts by mass of the obtained colored fine particles, and 3200 r / min was added using a 10 liter Henschel mixer. The mixture was stirred at a rotational speed of 180 seconds for 180 seconds, and the colored fine particles were externally added to obtain a magenta toner.

以上のようにして得られたマゼンタトナーを用いて、実施例1と同様にして画像印刷を行い、環境安定性、オイルレス定着性、色相安定性、及び耐光性について評価した。その結果を下記表1に示す。

Figure 2007094270
Using the magenta toner obtained as described above, image printing was performed in the same manner as in Example 1, and environmental stability, oil-less fixing property, hue stability, and light resistance were evaluated. The results are shown in Table 1 below.
Figure 2007094270

上記表1から、所定の2種の赤色顔料の混合物と所定の荷電制御剤との組合せに係るトナー(実施例1〜5)、及び所定の2種の赤色顔料の固溶体と所定の荷電制御剤との組合せに係るトナー(実施例6)は、環境安定性、オイルレス定着性、色相安定性、及び耐光性のいずれにおいても優れていることがわかる。   From Table 1 above, a toner (Examples 1 to 5) relating to a combination of a mixture of two predetermined red pigments and a predetermined charge control agent, and a solid solution of two predetermined red pigments and a predetermined charge control agent It can be seen that the toner according to the combination (Example 6) is excellent in all of environmental stability, oil-less fixing property, hue stability, and light resistance.

これに対し、着色剤としてCROMOPHTAL Red 2030のみを用いたトナー(比較例1)は色相及び色相安定性が悪く、ECR−101のみを用いたトナー(比較例2)は環境安定性、色相・色相安定性、及び耐光性が悪く、PV FAST RED E5Bのみを用いたトナー(比較例3)は、PV FAST RED E5Bが着色力が低いために多量に配合したことによりオイルレス定着性が悪く、所定の2種の赤色顔料の混合物を用いているが、本発明の範囲外の荷電制御剤(ボントロンE−89)を用いたトナー(比較例4)は、色相及び色相安定性において劣っている。   On the other hand, the toner using only CROMOPHTAL Red 2030 as the colorant (Comparative Example 1) has poor hue and hue stability, and the toner using only ECR-101 (Comparative Example 2) has environmental stability, hue and hue. The stability and light resistance are poor, and the toner using only PV FAST RED E5B (Comparative Example 3) has poor oilless fixability because PV FAST RED E5B is blended in a large amount because the coloring power is low. The toner (Comparative Example 4) using the charge control agent (Bontron E-89) outside the scope of the present invention is inferior in hue and hue stability.

実施例7
結着樹脂100質量部、第1の着色剤(CROMOPHTAL Red 2030:チバスペシャリティーケミカルズ(株)社製)2.0質量部、第2の着色剤(PV FAST PINK E:クラリアントジャパン社製)2.0部、荷電制御剤(ボントロンE−84:オリエント化学工業社製)1.5質量部、及び離型剤(カルナウバワックスC1:加藤洋行社輸入品)5質量部をヘンシェルミキサーを用いて混合した後、二軸押出機により溶融混練した。
Example 7
Binder resin 100 parts by mass, first colorant (CROMOPHTAL Red 2030: Ciba Specialty Chemicals Co., Ltd.) 2.0 parts by mass, second colorant (PV FAST PINK E: manufactured by Clariant Japan) 2 0.0 part, 1.5 parts by mass of charge control agent (Bontron E-84: manufactured by Orient Chemical Co., Ltd.) and 5 parts by mass of mold release agent (carnauba wax C1: imported by Kato Yoko Co., Ltd.) using a Henschel mixer After mixing, the mixture was melt kneaded with a twin screw extruder.

次いで、得られた溶融混練物を冷却し、衝突板式粉砕機(ディスパージョンセパレーター:日本ニューマチック工業(株)社製)を用いて粉砕した後、分級工程を経て、質量平均粒子径8.5μm、変動係数25.4%の着色微粒子を得た。   Subsequently, the obtained melt-kneaded product was cooled and pulverized using a collision plate type pulverizer (dispersion separator: manufactured by Nippon Pneumatic Industry Co., Ltd.), followed by a classification step, and a mass average particle diameter of 8.5 μm. Colored fine particles having a coefficient of variation of 25.4% were obtained.

次に、得られた樹脂微粒子100質量部に疎水性シリカ「NAX−50」(日本アエロジル社製、平均粒子径:35nm)2.5質量部を添加し、10リットル容のヘンシェルミキサーで3200r/min、180秒間攪拌し、着色微粒子に外添処理を施して、マゼンタトナーを得た。   Next, 2.5 parts by mass of hydrophobic silica “NAX-50” (manufactured by Nippon Aerosil Co., Ltd., average particle size: 35 nm) was added to 100 parts by mass of the obtained resin fine particles, and 3200 r / min with a 10 liter Henschel mixer. The mixture was stirred for min for 180 seconds, and the colored fine particles were externally added to obtain a magenta toner.

以上のようにして得られたマゼンタトナーを用いて、実施例1と同様にして画像印刷を行い、環境安定性、オイルレス定着性、色相安定性、及び耐光性について評価した。その結果を下記表2に示す。   Using the magenta toner obtained as described above, image printing was performed in the same manner as in Example 1, and environmental stability, oil-less fixing property, hue stability, and light resistance were evaluated. The results are shown in Table 2 below.

実施例8
結着樹脂100質量部、第1の着色剤(CROMOPHTAL Red 2030:チバスペシャリティーケミカルズ(株)社製)2.0質量部、第2の着色剤(PV FAST RED E5B:クラリアントジャパン社製)2.0部、荷電制御剤(ボントロンE−84:オリエント化学工業社製)1.5質量部、及び離型剤(カルナウバワックスC1:加藤洋行社輸入品)5質量部をヘンシェルミキサーを用いて混合した後、二軸押出機により溶融混練した。
Example 8
Binder resin 100 parts by mass, first colorant (CROMOPHTAL Red 2030: manufactured by Ciba Specialty Chemicals Co., Ltd.) 2.0 parts by mass, second colorant (PV FAST RED E5B: manufactured by Clariant Japan) 2 0.0 part, 1.5 parts by mass of charge control agent (Bontron E-84: manufactured by Orient Chemical Co., Ltd.) and 5 parts by mass of mold release agent (carnauba wax C1: imported by Kato Yoko Co., Ltd.) using a Henschel mixer After mixing, the mixture was melt kneaded with a twin screw extruder.

次いで、得られた溶融混練物を冷却し、衝突板式粉砕機(ディスパージョンセパレーター:日本ニューマチック工業(株)社製)を用いて粉砕した後、分級工程を経て、質量平均粒子径8.5μm、変動係数25.4%の着色微粒子を得た。   Subsequently, the obtained melt-kneaded product was cooled and pulverized using a collision plate type pulverizer (dispersion separator: manufactured by Nippon Pneumatic Industry Co., Ltd.), followed by a classification step, and a mass average particle diameter of 8.5 μm. Colored fine particles having a coefficient of variation of 25.4% were obtained.

次に、得られた着色微粒子100質量部に疎水性シリカ(NAX−50:日本アエロジル社製、平均粒子径:35nm)2.5質量部を添加し、10リットル容のヘンシェルミキサーにより3200r/minの回転速度で180秒間攪拌し、着色微粒子に外添処理を施して、マゼンタトナーを得た。   Next, 2.5 parts by mass of hydrophobic silica (NAX-50: manufactured by Nippon Aerosil Co., Ltd., average particle size: 35 nm) was added to 100 parts by mass of the obtained colored fine particles, and 3200 r / min was added using a 10 liter Henschel mixer. The mixture was stirred at a rotational speed of 180 seconds for 180 seconds, and the colored fine particles were externally added to obtain a magenta toner.

以上のようにして得られたマゼンタトナーを用いて、実施例1と同様にして画像印刷を行い、環境安定性、オイルレス定着性、色相安定性、及び耐光性について評価した。その結果を下記表2に示す。   Using the magenta toner obtained as described above, image printing was performed in the same manner as in Example 1, and environmental stability, oil-less fixing property, hue stability, and light resistance were evaluated. The results are shown in Table 2 below.

実施例9
結着樹脂100質量部、第1の着色剤(CROMOPHTAL Red 2030:チバスペシャリティーケミカルズ(株)社製)、第2の着色剤(CINQUASIA Magenta RT−235−D:チバスペシャリティーケミカルズ(株)社製)2.0部、荷電制御剤(ボントロンE−84:オリエント化学工業社製)1.5質量部、及び離型剤(カルナウバワックスC1:加藤洋行社輸入品)1.5質量部をヘンシェルミキサーを用いて混合した後、二軸押出機により溶融混練した。
Example 9
Binder resin 100 parts by mass, first colorant (CROMOPHTAL Red 2030: manufactured by Ciba Specialty Chemicals Co., Ltd.), second colorant (CINQUASIA Magenta RT-235-D: Ciba Specialty Chemicals Co., Ltd.) 2.0 parts, charge control agent (Bontron E-84: manufactured by Orient Chemical Co., Ltd.) 1.5 parts by mass, and release agent (carnauba wax C1: imported by Kato Yoko Co., Ltd.) 1.5 parts by mass After mixing using a Henschel mixer, the mixture was melt kneaded with a twin screw extruder.

次いで、衝突板式粉砕機(ディスパージョンセパレーター:日本ニューマチック工業(株)社製)を用いて粉砕した後、分級工程を経て、質量平均粒子径8.5μm、変動係数25.4%の着色微粒子を得た。   Next, after pulverization using a collision plate type pulverizer (dispersion separator: manufactured by Nippon Pneumatic Industry Co., Ltd.), a fine particle having a mass average particle size of 8.5 μm and a coefficient of variation of 25.4% is obtained through a classification step. Got.

次に、得られた着色微粒子100質量部に疎水性シリカ(NAX−50:日本アエロジル社製、平均粒子径:35nm)2.5質量部を添加し、10リットル容のヘンシェルミキサーにより3200r/minの回転速度で180秒間攪拌し、着色微粒子に外添処理を施して、マゼンタトナーを得た。   Next, 2.5 parts by mass of hydrophobic silica (NAX-50: manufactured by Nippon Aerosil Co., Ltd., average particle size: 35 nm) was added to 100 parts by mass of the obtained colored fine particles, and 3200 r / min was added using a 10 liter Henschel mixer. The mixture was stirred at a rotational speed of 180 seconds for 180 seconds, and the colored fine particles were externally added to obtain a magenta toner.

以上のようにして得られたマゼンタトナーを用いて、実施例1と同様にして画像印刷を行い、環境安定性、オイルレス定着性、色相安定性、及び耐光性について評価した。その結果を下記表2に示す。   Using the magenta toner obtained as described above, image printing was performed in the same manner as in Example 1, and environmental stability, oil-less fixing property, hue stability, and light resistance were evaluated. The results are shown in Table 2 below.

実施例10
結着樹脂100質量部、第1の着色剤(CROMOPHTAL Red 2030:チバスペシャリティーケミカルズ(株)社製)2.0質量部、第2の着色剤(ECR−101:大日本精化工業(株)社製)2.0部、荷電制御剤(ボントロンE−84:オリエント化学工業社製)1.5質量部、及び離型剤(カルナウバワックスC1:加藤洋行社輸入品)5質量部をヘンシェルミキサーを用いて混合した後、二軸押出機により溶融混練した。
Example 10
Binder resin 100 parts by mass, first colorant (CROMOPHTAL Red 2030: Ciba Specialty Chemicals Co., Ltd.) 2.0 parts by mass, second colorant (ECR-101: Dainippon Seika Kogyo Co., Ltd.) ) 2.0 parts, charge control agent (Bontron E-84: manufactured by Orient Chemical Industry Co., Ltd.) 1.5 parts by mass, and release agent (Carnauba wax C1: imported by Kato Yoko Co., Ltd.) 5 parts by mass After mixing using a Henschel mixer, the mixture was melt kneaded with a twin screw extruder.

次いで、得られた溶融混練物を冷却し、衝突板式粉砕機(ディスパージョンセパレーター:日本ニューマチック工業(株)社製)を用いて粉砕した後、分級工程を経て、質量平均粒子径8.5μm、変動係数25.4%の着色微粒子を得た。   Subsequently, the obtained melt-kneaded product was cooled and pulverized using a collision plate type pulverizer (dispersion separator: manufactured by Nippon Pneumatic Industry Co., Ltd.), followed by a classification step, and a mass average particle diameter of 8.5 μm. Colored fine particles having a coefficient of variation of 25.4% were obtained.

次に、得られた着色微粒子100質量部に疎水性シリカ(NAX−50:日本アエロジル社製、平均粒子径:35nm)2.5質量部を添加し、10リットル容のヘンシェルミキサーにより3200r/minの回転速度で180秒間攪拌し、着色微粒子に外添処理を施して、マゼンタトナーを得た。   Next, 2.5 parts by mass of hydrophobic silica (NAX-50: manufactured by Nippon Aerosil Co., Ltd., average particle size: 35 nm) was added to 100 parts by mass of the obtained colored fine particles, and 3200 r / min was added using a 10 liter Henschel mixer. The mixture was stirred at a rotational speed of 180 seconds for 180 seconds, and the colored fine particles were externally added to obtain a magenta toner.

以上のようにして得られたマゼンタトナーを用いて、実施例1と同様にして画像印刷を行い、環境安定性、オイルレス定着性、色相安定性、及び耐光性について評価した。その結果を下記表2に示す。   Using the magenta toner obtained as described above, image printing was performed in the same manner as in Example 1, and environmental stability, oil-less fixing property, hue stability, and light resistance were evaluated. The results are shown in Table 2 below.

実施例11
結着樹脂100質量部、第1の着色剤(CROMOPHTAL Red 2030:チバスペシャリティーケミカルズ(株)社製)2.0質量部、第2の着色剤(TOSHIKI RED 1022:大日本インキ化学工業(株)社製)2.0部と、荷電制御剤(ボントロンE−84:オリエント化学工業社製)1.5質量部、及び離型剤(カルナウバワックスC1:加藤洋行社輸入品)5質量部をヘンシェルミキサーを用いて混合した後、二軸押出機により溶融混練した。
Example 11
Binder resin 100 parts by mass, first colorant (CROMOPHTAL Red 2030: Ciba Specialty Chemicals Co., Ltd.) 2.0 parts by mass, second colorant (TOSHIKI RED 1022: Dainippon Ink & Chemicals, Inc. 2.0 parts by charge), 1.5 parts by weight of charge control agent (Bontron E-84: manufactured by Orient Chemical Co., Ltd.), and 5 parts by weight of release agent (carnauba wax C1: imported by Kato Yoko Co., Ltd.) Were mixed using a Henschel mixer and then melt-kneaded by a twin screw extruder.

次いで、得られた溶融混練物を冷却し、衝突板式粉砕機(ディスパージョンセパレーター:日本ニューマチック工業(株)社製)を用いて粉砕した後、分級工程を経て、質量平均粒子径8.5μm、変動係数25.4%の着色微粒子を得た。   Subsequently, the obtained melt-kneaded product was cooled and pulverized using a collision plate type pulverizer (dispersion separator: manufactured by Nippon Pneumatic Industry Co., Ltd.), followed by a classification step, and a mass average particle diameter of 8.5 μm. Colored fine particles having a coefficient of variation of 25.4% were obtained.

次に、得られた着色微粒子100質量部に疎水性シリカ(NAX−50:日本アエロジル社製、平均粒子径:35nm)2.5質量部を添加し、10リットル容のヘンシェルミキサーにより3200r/minの回転速度で180秒間攪拌し、着色微粒子に外添処理を施して、マゼンタトナーを得た。   Next, 2.5 parts by mass of hydrophobic silica (NAX-50: manufactured by Nippon Aerosil Co., Ltd., average particle size: 35 nm) was added to 100 parts by mass of the obtained colored fine particles, and 3200 r / min was added using a 10 liter Henschel mixer. The mixture was stirred at a rotational speed of 180 seconds for 180 seconds, and the colored fine particles were externally added to obtain a magenta toner.

以上のようにして得られたマゼンタトナーを用いて、実施例1と同様にして画像印刷を行い、環境安定性、オイルレス定着性、色相安定性、及び耐光性について評価した。その結果を下記表2に示す。   Using the magenta toner obtained as described above, image printing was performed in the same manner as in Example 1, and environmental stability, oil-less fixing property, hue stability, and light resistance were evaluated. The results are shown in Table 2 below.

実施例12
結着樹脂100質量部、CROMOPHTAL Red 2030とPV FAST RED E5Bとの固溶体である着色剤(Magenta ST:チバスペシャリティーケミカルズ(株)社製)4質量部、荷電制御剤(ボントロンE−84:オリエント化学工業社製)1.5質量部、および離型剤(カルナバワックスC1:加藤洋行社輸入品)5質量部をヘンシェルミキサーで十分に混合した後、2軸押出機で溶融混練した。
Example 12
100 parts by mass of binder resin, 4 parts by mass of a colorant (Magenta ST: manufactured by Ciba Specialty Chemicals Co., Ltd.) which is a solid solution of CROMOPHTAL Red 2030 and PV FAST RED E5B, charge control agent (Bontron E-84: Orient 1.5 parts by mass (made by Kagaku Kogyo Co., Ltd.) and 5 parts by mass of a release agent (carnauba wax C1: imported from Kato Yoko Co., Ltd.) were sufficiently mixed with a Henschel mixer, and then melt-kneaded with a twin screw extruder.

次いで、得られた溶融混練物を冷却し、衝突板式粉砕機(ディスパージョンセパレーター:日本ニューマチック工業(株)社製)を用いて粉砕した後、分級工程を経て、質量平均粒子径9.0μmの着色微粒子を得た。   Subsequently, the obtained melt-kneaded product is cooled and pulverized using a collision plate type pulverizer (dispersion separator: manufactured by Nippon Pneumatic Industry Co., Ltd.), followed by a classification step, and a mass average particle diameter of 9.0 μm. Colored fine particles were obtained.

次に、得られた粉体100質量部に、外添剤として疎水性シリカ(RX200:日本アエロジル社製)1.5質量部を添加し、10リットル容のヘンシェルミキサーにより3200r/minの回転速度で180秒間攪拌し、着色微粒子に外添処理を施して、マゼンタトナーを得た。   Next, 1.5 parts by mass of hydrophobic silica (RX200: manufactured by Nippon Aerosil Co., Ltd.) as an external additive is added to 100 parts by mass of the obtained powder, and the rotational speed is 3200 r / min using a 10 liter Henschel mixer. The mixture was stirred for 180 seconds, and the color fine particles were externally added to obtain a magenta toner.

以上のようにして得られたマゼンタトナーを用いて、実施例1と同様にして画像印刷を行い、環境安定性、オイルレス定着性、色相安定性、及び耐光性について評価した。   Using the magenta toner obtained as described above, image printing was performed in the same manner as in Example 1, and environmental stability, oil-less fixing property, hue stability, and light resistance were evaluated.

比較例5
結着樹脂100質量部、着色剤(CROMOPHTAL Red 2030:チバスペシャリティーケミカルズ(株)社製)4.0質量部、荷電制御剤(ボントロンE−84:オリエント化学工業社製)1.5質量部、及び離型剤(カルナウバワックスC1:加藤洋行社輸入品)5質量部をヘンシェルミキサーを用いて混合した後、二軸押出機により溶融混練した。
Comparative Example 5
100 parts by mass of binder resin, 4.0 parts by mass of colorant (CROMOPHTAL Red 2030: manufactured by Ciba Specialty Chemicals Co., Ltd.), 1.5 parts by mass of charge control agent (Bontron E-84: manufactured by Orient Chemical Industries) , And 5 parts by mass of a release agent (carnauba wax C1: imported from Kato Yoko Co., Ltd.) were mixed using a Henschel mixer, and then melt-kneaded using a twin screw extruder.

次いで、得られた溶融混練物を冷却し、衝突板式粉砕機(ディスパージョンセパレーター:日本ニューマチック工業(株)社製)を用いて粉砕した後、分級工程を経て、質量平均粒子径8.5μm、変動係数25.4%の着色微粒子を得た。   Subsequently, the obtained melt-kneaded product was cooled and pulverized using a collision plate type pulverizer (dispersion separator: manufactured by Nippon Pneumatic Industry Co., Ltd.), followed by a classification step, and a mass average particle diameter of 8.5 μm. Colored fine particles having a coefficient of variation of 25.4% were obtained.

次に、得られた着色微粒子100質量部に疎水性シリカ(RX200:日本アエロジル社製)1.5質量部を添加し、10リットル容のヘンシェルミキサーにより3200r/minの回転速度で180秒間攪拌し、着色微粒子に外添処理を施して、マゼンタトナーを得た。   Next, 1.5 parts by mass of hydrophobic silica (RX200: manufactured by Nippon Aerosil Co., Ltd.) is added to 100 parts by mass of the obtained colored fine particles, and the mixture is stirred for 180 seconds at a rotation speed of 3200 r / min with a 10 liter Henschel mixer. The colored fine particles were externally added to obtain a magenta toner.

以上のようにして得られたマゼンタトナーを用いて、実施例1と同様にして画像印刷を行い、環境安定性、オイルレス定着性、色相安定性、及び耐光性について評価した。   Using the magenta toner obtained as described above, image printing was performed in the same manner as in Example 1, and environmental stability, oil-less fixing property, hue stability, and light resistance were evaluated.

比較例6
結着樹脂100質量部、着色剤(ECR−101:大日本精化工業(株)社製)4.0質量部、荷電制御剤(ボントロンE−84:オリエント化学工業社製)1.5質量部、及び離型剤(カルナウバワックスC1:加藤洋行社輸入品)5質量部をヘンシェルミキサーを用いて混合した後、二軸押出機により溶融混練した。
Comparative Example 6
100 parts by weight of binder resin, 4.0 parts by weight of colorant (ECR-101: manufactured by Dainippon Seika Kogyo Co., Ltd.), 1.5 parts by weight of charge control agent (Bontron E-84: manufactured by Orient Chemical Industries) And 5 parts by mass of a release agent (Carnauba wax C1: imported from Kato Yoko Co., Ltd.) were mixed using a Henschel mixer, and then melt-kneaded using a twin screw extruder.

次いで、得られた溶融混練物を冷却し、衝突板式粉砕機「ディスパージョンセパレーター」(日本ニューマチック工業(株)社製)を用いて粉砕した後、分級工程を経て、質量平均粒子径8.5μm、変動係数25.4%の着色微粒子を得た。   Next, the obtained melt-kneaded product is cooled and pulverized using a collision plate type pulverizer “Dispersion Separator” (manufactured by Nippon Pneumatic Industry Co., Ltd.), followed by a classification step, and a mass average particle size of 8. Colored fine particles having 5 μm and a coefficient of variation of 25.4% were obtained.

次に、得られた着色微粒子100質量部に疎水性シリカ(NAX−50:日本アエロジル社製、平均粒子径:35nm)2.5質量部を添加し、10リットル容のヘンシェルミキサーにより3200r/minの回転速度で180秒間攪拌し、着色微粒子に外添処理を施して、マゼンタトナーを得た。   Next, 2.5 parts by mass of hydrophobic silica (NAX-50: manufactured by Nippon Aerosil Co., Ltd., average particle size: 35 nm) was added to 100 parts by mass of the obtained colored fine particles, and 3200 r / min was added using a 10 liter Henschel mixer. The mixture was stirred at a rotational speed of 180 seconds for 180 seconds, and the colored fine particles were externally added to obtain a magenta toner.

以上のようにして得られたマゼンタトナーを用いて、実施例1と同様にして画像印刷を行い、環境安定性、オイルレス定着性、色相安定性、及び耐光性について評価した。   Using the magenta toner obtained as described above, image printing was performed in the same manner as in Example 1, and environmental stability, oil-less fixing property, hue stability, and light resistance were evaluated.

比較例7
結着樹脂100質量部、着色剤CROMOPHTAL Red 2030とPV FAST RED E5Bとの固溶体である着色剤(Magenta ST:チバスペシャリティーケミカルズ(株)社製)4質量部、荷電制御剤(TN−105:保土ヶ谷化学社製)1.5質量部、及び離型剤(カルナウバワックスC1:加藤洋行社輸入品)5質量部をヘンシェルミキサーを用いて混合した後、二軸押出機により溶融混練した。
Comparative Example 7
100 parts by mass of binder resin, 4 parts by mass of a colorant (Magenta ST: manufactured by Ciba Specialty Chemicals Co., Ltd.), which is a solid solution of colorant CROMOPHTAL Red 2030 and PV FAST RED E5B, charge control agent (TN-105: 1.5 parts by mass of Hodogaya Chemical Co., Ltd.) and 5 parts by mass of a release agent (Carnauba wax C1: imported from Kato Yoko Co., Ltd.) were mixed using a Henschel mixer, and then melt-kneaded using a twin screw extruder.

次いで、得られた混練物を冷却し、衝突板式粉砕機(ディスパージョンセパレーター:日本ニューマチック工業(株)社製)を用いて粉砕した後、分級工程を経て、質量平均粒子径8.5μm、変動係数25.4%の着色微粒子得た。   Next, the obtained kneaded product was cooled and pulverized using a collision plate type pulverizer (dispersion separator: manufactured by Nippon Pneumatic Industry Co., Ltd.), followed by a classification step, and a mass average particle diameter of 8.5 μm, Colored fine particles having a coefficient of variation of 25.4% were obtained.

次に、得られた樹脂微粒子100質量部に疎水性シリカ(NAX−50:日本アエロジル社製、平均粒子径:35nm)2.5質量部を添加し、10リットル容のヘンシェルミキサーにより3200r/minの回転速度で180秒間攪拌し、着色微粒子に外添処理を施して、マゼンタトナーを得た。   Next, 2.5 parts by mass of hydrophobic silica (NAX-50: manufactured by Nippon Aerosil Co., Ltd., average particle size: 35 nm) was added to 100 parts by mass of the obtained resin fine particles, and 3200 r / min by a 10 liter Henschel mixer. The mixture was stirred at a rotational speed of 180 seconds for 180 seconds, and the colored fine particles were externally added to obtain a magenta toner.

以上のようにして得られたマゼンタトナーを用いて、実施例1と同様にして画像印刷を行い、環境安定性、オイルレス定着性、色相安定性、及び耐光性について評価した。その結果を下記表2に示す。

Figure 2007094270
Using the magenta toner obtained as described above, image printing was performed in the same manner as in Example 1, and environmental stability, oil-less fixing property, hue stability, and light resistance were evaluated. The results are shown in Table 2 below.
Figure 2007094270

上記表2から、所定の2種の赤色顔料の混合物と所定の荷電制御剤との組合せに係るトナー(実施例7〜11)、及び所定の2種の赤色顔料の固溶体と所定の荷電制御剤との組合せに係るトナー(実施例12)は、環境安定性、オイルレス定着性、色相安定性、及び耐光性のいずれにおいても優れていることがわかる。   From Table 2 above, toners (Examples 7 to 11) relating to a combination of a mixture of two predetermined red pigments and a predetermined charge control agent, and a solid solution of the two predetermined red pigments and a predetermined charge control agent It can be seen that the toner according to the combination (Example 12) is excellent in all of environmental stability, oil-less fixing property, hue stability, and light resistance.

これに対し、着色剤としてCROMOPHTAL Red 2030のみを用いたトナー(比較例5)は色相及び色相安定性が悪く、ECR−101のみを用いたトナー(比較例6)は環境安定性、色相・色相安定性、及び耐光性が悪く、所定の2種の赤色顔料の固溶体を用いているが、本発明の範囲外の荷電制御剤を用いたトナー(比較例7)は、オイルレス定着性において劣っている。   In contrast, a toner using only CROMOPHTAL Red 2030 as a colorant (Comparative Example 5) has poor hue and hue stability, and a toner using only ECR-101 (Comparative Example 6) has environmental stability, hue and hue. Although the stability and light resistance are poor and a solid solution of two predetermined red pigments is used, the toner using the charge control agent outside the scope of the present invention (Comparative Example 7) is inferior in oilless fixing property. ing.

Claims (4)

結着樹脂、着色剤、及び電荷制御剤を含む電子写真用オイルレスマゼンタトナーであって、前記着色剤は、下記式(1)により表される化合物からなる赤色顔料と、下記式(2)、(3)又は(4)により表される化合物の少なくとも1種からなる赤色顔料とを含有し、前記電荷制御剤は、下記式(5)又は(6)により表される化合物の少なくとも1種を含有することを特徴とする電子写真用オイルレスマゼンタトナー。
Figure 2007094270
(式中、X、Yは、それぞれ独立してハロゲン原子又はアルキル基を示す。)
Figure 2007094270
Figure 2007094270
Figure 2007094270
Figure 2007094270
(式中、R、R及びRはそれぞれ独立して水素原子、直鎖もしくは分岐鎖状の炭素数1〜10のアルキル基またはアリル基、Mは亜鉛、ジルコニウム、クロム、アルミニウム、銅、ニッケル又はコバルト、mは2以上の整数、nは1以上の整数を示す)
Figure 2007094270
(式中、Mはホウ素又はアルミニウム、mは2以上の整数、nは1以上の整数を示す)
An oilless magenta toner for electrophotography comprising a binder resin, a colorant, and a charge control agent, wherein the colorant comprises a red pigment comprising a compound represented by the following formula (1), and the following formula (2): And a red pigment comprising at least one compound represented by (3) or (4), wherein the charge control agent is at least one compound represented by the following formula (5) or (6): An oilless magenta toner for electrophotography, comprising:
Figure 2007094270
(In the formula, X and Y each independently represent a halogen atom or an alkyl group.)
Figure 2007094270
Figure 2007094270
Figure 2007094270
Figure 2007094270
(Wherein R 1 , R 2 and R 3 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or an allyl group, M is zinc, zirconium, chromium, aluminum, copper) Nickel or cobalt, m is an integer of 2 or more, and n is an integer of 1 or more)
Figure 2007094270
(In the formula, M is boron or aluminum, m is an integer of 2 or more, and n is an integer of 1 or more)
結着樹脂、着色剤、及び電荷制御剤を含む電子写真用オイルレスマゼンタトナーであって、前記着色剤は、下記式(1)により表される化合物からなる赤色顔料と、下記式(7)又は(8)により表される化合物の少なくとも1種からなる赤色顔料とを含有し、前記電荷制御剤は、下記式(5)又は(6)により表される化合物の少なくとも1種を含有することを特徴とする電子写真用オイルレスマゼンタトナー。
Figure 2007094270
(式中、X、Yは、それぞれ独立してハロゲン原子又はアルキル基を示す。)
Figure 2007094270
Figure 2007094270
Figure 2007094270
(式中、R、R及びRはそれぞれ独立して水素原子、直鎖もしくは分岐鎖状の炭素数1〜10のアルキル基またはアリル基、Mは亜鉛、ジルコニウム、クロム、アルミニウム、銅、ニッケル又はコバルト、mは2以上の整数、nは1以上の整数を示す)
Figure 2007094270
(式中、Mはホウ素又はアルミニウム、mは2以上の整数、nは1以上の整数を示す)
An oilless magenta toner for electrophotography comprising a binder resin, a colorant, and a charge control agent, wherein the colorant comprises a red pigment comprising a compound represented by the following formula (1), and the following formula (7): Or a red pigment comprising at least one compound represented by (8), and the charge control agent comprises at least one compound represented by the following formula (5) or (6): An oilless magenta toner for electrophotography.
Figure 2007094270
(In the formula, X and Y each independently represent a halogen atom or an alkyl group.)
Figure 2007094270
Figure 2007094270
Figure 2007094270
(Wherein R 1 , R 2 and R 3 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or an allyl group, M is zinc, zirconium, chromium, aluminum, copper) Nickel or cobalt, m is an integer of 2 or more, and n is an integer of 1 or more)
Figure 2007094270
(In the formula, M is boron or aluminum, m is an integer of 2 or more, and n is an integer of 1 or more)
結着樹脂、着色剤、及び電荷制御剤を含む電子写真用オイルレスマゼンタトナーであって、前記着色剤は、下記式(1)により表される化合物からなる赤色顔料と、下記式(2)、(3)又は(4)により表される化合物の少なくとも1種からなる赤色顔料との固溶体を含有し、前記電荷制御剤は、下記式(5)又は(6)により表される化合物の少なくとも1種を含有することを特徴とする電子写真用オイルレスマゼンタトナー。
Figure 2007094270
(式中、X、Yは、それぞれ独立してハロゲン原子又はアルキル基を示す。)
Figure 2007094270
Figure 2007094270
Figure 2007094270
Figure 2007094270
(式中、R、R及びRはそれぞれ独立して水素原子、直鎖もしくは分岐鎖状の炭素数1〜10のアルキル基またはアリル基、Mは亜鉛、ジルコニウム、クロム、アルミニウム、銅、ニッケル又はコバルト、mは2以上の整数、nは1以上の整数を示す)
Figure 2007094270
(式中、Mはホウ素又はアルミニウム、mは2以上の整数、nは1以上の整数を示す)
An oilless magenta toner for electrophotography comprising a binder resin, a colorant, and a charge control agent, wherein the colorant comprises a red pigment comprising a compound represented by the following formula (1), and the following formula (2): , (3) or a solid solution with a red pigment composed of at least one of the compounds represented by (4), wherein the charge control agent is at least a compound represented by the following formula (5) or (6) An oilless magenta toner for electrophotography, comprising one kind.
Figure 2007094270
(In the formula, X and Y each independently represent a halogen atom or an alkyl group.)
Figure 2007094270
Figure 2007094270
Figure 2007094270
Figure 2007094270
(Wherein R 1 , R 2 and R 3 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or an allyl group, M is zinc, zirconium, chromium, aluminum, copper) Nickel or cobalt, m is an integer of 2 or more, and n is an integer of 1 or more)
Figure 2007094270
(In the formula, M is boron or aluminum, m is an integer of 2 or more, and n is an integer of 1 or more)
前記結着樹脂は、下記式(9)により表される化合物を含有するアルコール成分と、ジカルボン酸化合物及び3価以上の多価カルボン酸化合物を含有するカルボン酸成分とを縮重合して得たポリエステルであることを特徴とする請求項1〜3のいずれかに記載の電子写真用オイルレスマゼンタトナー。
Figure 2007094270
(式中、Rは炭素数2又は3のアルキレン基、x及びyは正の数を示し、xとyの和は1〜16である)
The binder resin was obtained by polycondensing an alcohol component containing a compound represented by the following formula (9) and a carboxylic acid component containing a dicarboxylic acid compound and a trivalent or higher polyvalent carboxylic acid compound. The oilless magenta toner for electrophotography according to any one of claims 1 to 3, which is polyester.
Figure 2007094270
(In the formula, R is an alkylene group having 2 or 3 carbon atoms, x and y are positive numbers, and the sum of x and y is 1 to 16)
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EP2607954A1 (en) 2011-12-22 2013-06-26 Fuji Xerox Co., Ltd. Magenta toner for electrophotography, developer, toner cartridge, process cartridge, image forming apparatus, and image forming method
WO2018181189A1 (en) * 2017-03-31 2018-10-04 日本ゼオン株式会社 Magenta toner
US10146147B2 (en) * 2017-03-31 2018-12-04 Konica Minolta, Inc. Magenta toner for electrostatic charge image development

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WO2012045708A1 (en) * 2010-10-06 2012-04-12 Basf Se Pigment composition for mass colouration of aliphatic polyamide
EP2607954A1 (en) 2011-12-22 2013-06-26 Fuji Xerox Co., Ltd. Magenta toner for electrophotography, developer, toner cartridge, process cartridge, image forming apparatus, and image forming method
KR20130079089A (en) 2011-12-22 2013-07-10 후지제롯쿠스 가부시끼가이샤 Magenta toner for electrophotography, developer, toner cartridge, process cartridge, image forming apparatus, and image forming method
US8771911B2 (en) 2011-12-22 2014-07-08 Fuji Xerox, Co., Ltd. Magenta toner for electrophotography, developer, toner cartridge, process cartridge, image forming apparatus, and image forming method
WO2018181189A1 (en) * 2017-03-31 2018-10-04 日本ゼオン株式会社 Magenta toner
US10146147B2 (en) * 2017-03-31 2018-12-04 Konica Minolta, Inc. Magenta toner for electrostatic charge image development
JPWO2018181189A1 (en) * 2017-03-31 2020-05-14 日本ゼオン株式会社 Magenta toner
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