JP2004361520A - Full color toner - Google Patents

Abstract

An object of the present invention is to provide a full-color toner capable of obtaining a full-color image excellent in both fine line reproducibility and gloss uniformity.
A full-color toner comprising a black toner and at least one color toner, each containing a binder resin and a colorant, wherein the aromatic concentration of the binder resin contained in the black toner (black (Toner aromatic concentration) is lower than the aromatic concentration (color toner aromatic concentration) of the binder resin contained in any of the color toners, and the difference between the black toner aromatic concentration and the lowest color aromatic concentration is the color. A full-color toner wherein the difference between the aromatic concentration of the black toner and the aromatic concentration of any color toner is 1 to 14% by weight, which is greater than any of the differences between the toner aromatic concentrations.
[Selection diagram] None

Description

【００１９】
（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、好ましくは１．５〜５．０である）
で表されるビスフェノールＡのアルキレンオキサイド付加物、エチレングリコール、プロピレングリコール、グリセリン、ペンタエリスリトール、トリメチロールプロパン、水素添加ビスフェノールＡ、ソルビトール、又はそれらのアルキレン（炭素数２〜４）オキサイド（平均付加モル数１〜１６）付加物等が挙げられる。
【００２０】
また、カルボン酸成分としては、フタル酸、イソフタル酸、テレフタル酸、トリメリット酸等の芳香族カルボン酸、フマル酸、マレイン酸、アジピン酸、コハク酸、ドデセニルコハク酸、オクテニルコハク酸等の炭素数１〜２０のアルキル基又は炭素数２〜２０のアルケニル基で置換されたコハク酸等の脂肪族カルボン酸、それらの酸の無水物及びそれらの酸のアルキル（炭素数１〜３）エステル等が挙げられる。
【００２１】
本発明においては、帯電性、着色剤の分散性及び耐ブロッキング性の観点から、黒トナーとカラートナーのいずれにおいても、アルコール成分中に、式（Ｉ）で表されるビスフェノールＡのアルキレンオキサイド付加物が、好ましくは５０重量％以上、より好ましくは８０〜１００重量％、特に好ましくは１００重量％含有されていることが好ましく、黒トナーとカラートナーとの芳香族濃度差は、カルボン酸成分を構成するモノマーにより調整することが好ましい。
【００２２】
また、カルボン酸成分中の芳香族カルボン酸化合物の含有量は、黒トナーでは、好ましくは５０〜９０モル％、より好ましくは５０〜７５モル％であり、カラートナーでは、好ましくは８０〜１００モル％、より好ましくは９０〜１００モル％である。なお、芳香族カルボン酸化合物は、芳香族カルボン酸、及びそれらの酸の無水物、それらの酸のアルキル（炭素数１〜３）エステル等の芳香族カルボン酸の誘導体を含む。
【００２３】
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、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。
【００２４】
本発明のトナーを正帯電性トナーとして使用する場合、ポリエステルの酸価は、０．５〜１５ｍｇＫＯＨ／ｇが好ましく、１〜１２ｍｇＫＯＨ／ｇがより好ましく、１．５〜１０ｍｇＫＯＨ／ｇが特に好ましい。
【００２５】
また、トナーを負帯電性トナーとして使用する場合、ポリエステルの酸価は、５〜４０ｍｇＫＯＨ／ｇが好ましく、１０〜３５ｍｇＫＯＨ／ｇがより好ましく、１５〜３０ｍｇＫＯＨ／ｇが特に好ましい。
【００２６】
また、結着樹脂の軟化点は、８０〜１６５℃が好ましく、９５〜１５５℃がより好ましく、ガラス転移点は５０〜８５℃が好ましい。なお、より広い定着域を得る観点から、軟化点が１２０〜１６５℃の樹脂（高軟化点樹脂）と、軟化点が８０℃以上１２０℃未満の樹脂（低軟化点樹脂）が、好ましくは１０／９０〜９０／１０、より好ましくは３０／７０〜７０／３０の重量比（高軟化点樹脂／低軟化点樹脂）で、配合されているのが好ましい。
【００２７】
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る。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。
【００２８】
本発明においては、さらに、荷電制御剤、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を原料として配合してもよい。
【００２９】
荷電制御剤としては、ニグロシン染料、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、ポリアミン樹脂、イミダゾール誘導体等の正帯電性荷電制御剤と、含金属アゾ染料、芳香族ヒドロキシカルボン酸金属錯体、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、ベンジル酸ホウ素化合物等の負帯電性荷電制御剤が挙げられ、これらはトナーの帯電性に応じてそれぞれ単独で用いられていても、混合して用いられていてもよい。
【００３０】
離型剤としては、カルナウバワックス、ライスワックス等の天然エステル系ワックス、ポリプロピレンワックス、ポリエチレンワックス、フィッシャートロプッシュ等の合成ワックス、モンタンワックス等の石炭系ワックス、アルコール系ワックス等のワックスが挙げられ、これらは単独でまたは２種以上を混合して含有されていてもよい。
【００３１】
各トナーの製造方法は、混練粉砕法、転相乳化法、乳化分散法、懸濁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、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。
【００３２】
黒トナー及びカラートナーの軟化点は、定着性及び耐ブロッキング性の観点から、９５〜１４０℃が好ましく、１００〜１３０℃がより好ましい。
【００３３】
本発明のフルカラートナーは、黒トナーと少なくとも１種のカラートナーとから構成されるが、カラートナーとしては、マゼンタトナー、イエロートナー、シアントナー等が挙げられる。
【００３４】
本発明のフルカラートナーは、解像度が６００ｄｐｉ以上の静電像の現像器、好ましくは複写機又はプリンターに用いることにより、細線再現性における効果がより顕著に発揮される。
【００３５】
【実施例】
〔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）。
【００３６】
〔ガラス転移点〕
示差走査熱量計（セイコー電子工業社製、ＤＳＣ２１０）を用いて２００℃まで昇温し、その温度から降温速度１０℃／分で０℃まで冷却した試料を昇温速度１０℃／分で測定し、最大ピーク温度以下のベースラインの延長線とピークの立ち上がり部分から、ピークの頂点まで最大傾斜を示す接線との交点の温度をガラス転移点とする。
【００３７】
〔粘度〕
粘弾性測定装置（レオメーター）ＲＤＡ−ＩＩ型（レオメトリックス社製）を用い、以下の測定条件にて、１８０℃から１４０℃まで１０℃ごとに測定した際の１６０℃の値を採用する。
（測定条件）
治具：パラレルプレート（半径：５ｍｍ）
試料：１ｇ
周波数：２ラジアン／秒
歪：２°
【００３８】
樹脂製造例１
表１に示す無水トリメリット酸以外の原料及び酸化ジブチル錫４ｇを窒素導入管、脱水管、攪拌器及び熱伝対を装備した５リットル容の四つ口フラスコに入れ、２２０℃で８時間かけて反応させた後、８．３ｋＰａにて１時間反応させた。さらに２１０℃にて無水トリメリット酸を添加し、所定の軟化点に達するまで反応させて、樹脂Ａ〜Ｄを得た。
【００３９】
【表１】

【００４０】
黒トナー製造例
表２に示す結着樹脂１００重量部、カーボンブラック「ＭＯＧＵＬ−Ｌ」（キャボット社製）４．０重量部、荷電制御剤「Ｔ−７７」（保土谷化学工業社製）０．５重量部及び離型剤「カルナバワックスＣ１」（加藤洋行社製）１重量部を、ヘンシェルミキサーにて予備混合した後、二軸押出機で溶融混練し、冷却後、粉砕、分級工程を経て、体積平均粒子径が８μｍの粉体を得た。
【００４１】
得られた粉体１００重量部に、疎水性シリカ「アエロジルＲ−９７２」（日本アエロジル社製）１．０重量部をヘンシェルミキサーにより混合付着させ、黒トナーＡ〜Ｅを得た。
【００４２】
カラートナー製造例
表２に示す結着樹脂１００重量部、イエロー着色剤「パリオトールＤ１１５５」（ＢＡＳＦ社製）４．０重量部、荷電制御剤「ＬＲ−１４７」（日本カーリット社製）０．５重量部及び離型剤「カルナバワックスＣ１」（加藤洋行社製）１重量部を使用し、黒トナーと同様にして、イエロートナーＡ〜Ｃを得た。
【００４３】
また、イエロー着色剤の代わりに、マゼンタ着色剤「ＥＣＲ−１０１」（大日化学社製）４．０重量部又はシアン着色剤「ＥＣＢ−３０」（大日精化社製）４．０重量部を使用した以外は、イエロートナーと同様にして、マゼンタトナーＡ〜Ｃ及びシアントナーＡ〜Ｃを得た。
【００４４】
【表２】

【００４５】
実施例１〜６、比較例１、２
▲１▼ 反転現像によるデジタル方式のカラープリンタ「ＭＯＣＲＯＬＩＮＥ７３００」（沖データ社製）の各色トナー用現像器に、イエロートナー、マゼンタトナー、シアントナー及び黒トナーをそれぞれ実装し、各トナーの付着量をそれぞれ０．５５ｍｇ／ｃｍ^２ に調整して、各色ごとに、６００ｄｐｉの高解像モードで、Ｈａｍｍｅｒｍｉｌｌ（ＬａｓｅｒＰｒｉｎｔ，９０ｇ紙）上に５ｃｍ四方のベタ画像（定着温度１８０℃、定着速度は５０ｍｍ／ｓｅｃ）を得た。得られた定着画像の光沢度をグロスセンサー「ＶＧ−２Ｐ」（ＮＩＰＰＯＮＤＥＮＳＨＯＫＵ社製）を用いて測定し、以下の評価基準に従って、光沢の均一性を評価した。結果を表３に示す。なお、各実施例及び比較例におけるカラー画像間の光沢度の差はいずれも１０未満であった。
【００４６】
〔評価基準〕
黒画像と、カラー画像の中で黒画像ともっとも光沢度の差が大きなカラー画像の光沢度との差が、
◎： １０未満
○： １０以上、２０未満
×： ２０以上
【００４７】
▲２▼ ▲１▼と同じカラープリンタを用い、黒トナー、カラートナー（イエロートナー、マゼンタトナー、シアントナー）の現像条件を調整せず、初期条件で１ｄｏｔ・１ｓｐａｃｅで黒トナー、カラートナーを交互に印字・定着し、得られた画像を１０００倍に拡大して観察し、細線再現性を評価した。結果を表３に示す。
【００４８】
〔評価基準〕
◎： いずれのカラーラインもはっきり観測できる。
○： 黒トナーに隣接するカラーラインが若干にごっているが実使用上問題ない。
△： 黒トナーに隣接するカラーラインがにごっているのが確認できる。
×： 黒トナーに隣接するカラーラインがほとんど確認できない。
【００４９】
【表３】

【００５０】
以上の結果より、黒トナー芳香族濃度がカラートナー芳香族濃度よりも低く、かつ両者の差が一定の範囲内に調整された実施例１〜６のフルカラートナーは、比較例１、２のフルカラートナーと対比して、良好な細線再現性及び光沢の均一性を有していることが分かる。
【００５１】
【発明の効果】
本発明のフルカラートナーにより、細線再現性及び光沢の均一性のいずれにも優れたフルカラー画像が得られるという優れた効果が奏される。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a full-color toner used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, or the like.
[0002]
[Prior art]
In recent years, full-color toners using three primary color toners of yellow, cyan, and magenta and four toners of black toner have become widespread. However, due to differences in required characteristics such as transparency and colorants, the development characteristics of each toner are different. There is a demand for improvements in image quality such as gloss and fine line reproducibility, and digital methods that develop electrostatic latent images on a dot-by-dot basis by reversal development have high image quality, especially with no smearing. Therefore, improvement is desired.
[0003]
Therefore, as means for adjusting the development characteristics between the four color toners, external addition of a plurality of inorganic fine particles having specific physical properties to the toner (see Patent Document 1), the softening points of the color toner and the black toner, and the added wax Adjustment (see Patent Literature 2), transfer order of toner, regulation of the degree of compression (see Patent Literature 3), and the like are known, and although some effects are obtained, further improvement is desired.
[0004]
[Patent Document 1]
JP-A-10-10773 (Claims 1 and 4)
[Patent Document 2]
JP 2001-109198 A (Claim 1)
[Patent Document 3]
Japanese Patent Application Laid-Open No. 2001-194861 (Claim 1)
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a full-color toner capable of obtaining a full-color image excellent in both fine line reproducibility and gloss uniformity.
[0006]
[Means for Solving the Problems]
The present invention relates to a full-color toner comprising a black toner and at least one type of color toner, each containing a binder resin and a colorant, wherein the aromatic concentration of the binder resin contained in the black toner (black (Toner aromatic concentration) is lower than the aromatic concentration (color toner aromatic concentration) of the binder resin contained in any of the color toners, and the difference between the black toner aromatic concentration and the lowest color aromatic concentration is the color. It relates to a full-color toner in which the difference between the aromatic concentration of the black toner and the aromatic concentration of any of the color toners is greater than any of the differences between the aromatic concentrations of the toner and 1 to 14% by weight.
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
The full-color toner of the present invention contains a black toner and at least one type of color toner, and the aromatic concentration of the binder resin (black toner aromatic concentration) contained in the black toner is the same as the color toner. It is characterized by being lower than the aromatic concentration (aromatic concentration of color toner) of the contained binder resin and being adjusted to a specific concentration difference. Generally, in forming a full-color image, the color toners may be compatible with each other, but the color toner and the black toner are preferably incompatible. This is because the overlapping of colors between color toners causes a certain color to be reproduced and the effect on image quality is small, but when the color toner and black toner are mixed, the image quality becomes blurred or smudged. Prevention of color mixing of color toner and black toner is an important issue, particularly in a dot method in which the smear greatly affects image quality. However, in the present invention, the black toner aromatic concentration is lower than the color toner aromatic concentration, and the difference is adjusted to be larger than the aromatic concentration difference between the color toners. A high-quality full-color image with excellent fine line reproducibility can be obtained without mixing the toner and the color toner. It should be noted that as the binder resins of the respective toners are more dissimilar, the difference in gloss increases, and the two have generally contradictory physical properties. However, the present invention has solved these by a simple method.
[0008]
The difference between the aromatic density of the black toner and the aromatic density of any color toner is 14% by weight or less from the viewpoint of uniformity of gloss in an image, and 1% by weight or more from the viewpoint of fine line reproducibility. From these viewpoints, the difference between the black toner aromatic concentration and the color toner aromatic concentration is 1 to 14% by weight, and preferably 2 to 7% by weight.
[0009]
The difference in aromatic concentration between the color toners is preferably within 5% by weight, more preferably within 1% by weight, and more preferably 0% by weight, that is, it is particularly preferable that the same binder resin is contained in each color toner. .
[0010]
The aromatic concentration of the black toner is preferably from 30 to 50% by weight, more preferably from 35 to 45% by weight, particularly preferably from 37 to 43% by weight from the viewpoint of gloss and chargeability. From the viewpoints of gloss, chargeability and dispersibility of the colorant, the content is preferably 40 to 55% by weight, more preferably 45 to 50% by weight.
[0011]
In the present specification, the aromatic concentration of the binder resin is defined as the weight ratio (percentage) of aromatic rings such as benzene rings and naphthalene rings in the binder resin, preferably benzene rings. The weight of the aromatic ring is, for example, the sum of six carbon atoms of benzene and a hydrogen atom directly bonded to the carbon atom in a benzene ring. For example, the weight of the aromatic ring in phthalic acid is 76 and the weight of the aromatic ring in styrene is 77.
[0012]
That is, for each constituent unit of the binder resin, that is, for the monomer unit, [mol number] × [total molecular weight of benzene ring in one molecule of the constituent component] is calculated, and the obtained values are summed for all constituent components. To obtain a total value (g) (hereinafter referred to as AR). On the other hand, for each constituent component, the mole number is multiplied by the molecular weight, and the obtained values are summed for all the constituent components to obtain a total value (g) (hereinafter referred to as SUM). The aromatic concentration (%) is determined by calculation. In the case of a polycondensation resin, a value obtained by subtracting the amount (g) of depolymerized low molecular substances such as water and lower alcohol from the SUM is used as the SUM value.
[0013]
The difference in the melt viscosity at 160 ° C. of the binder resin contained in the black toner and the color toner is preferably 500 to 3000 Pa · s, more preferably 700 to 2000 Pa · s. Of the black toner and the color toner, the black toner preferably has a higher melt viscosity, and the binder resin contained in the black toner preferably has a melt viscosity at 160 ° C of 1500 to 8000 Pa · s, and 3500 to 6000 Pa · s. s is more preferred. The melt viscosity at 160 ° C. of the binder resin contained in the color toner is preferably 500 to 5000 Pa · s, and more preferably 3000 to 5000 Pa · s.
[0014]
The black toner and the color toner contain a binder resin and a colorant, respectively, similarly to a normal toner.
[0015]
Examples of the binder resin include polyester, polyamide, epoxy resin, styrene-acrylic resin, mixed resin of polyester and styrene-acrylic resin, and hybrid resin in which two or more resin components are partially chemically bonded. From the viewpoint of transparency and transparency, it is preferable to use polyester as a main component. The content of the polyester in the binder resin is preferably 50 to 100% by weight, more preferably 70 to 100% by weight, and particularly preferably 100% by weight. As the hybrid resin, a resin in which a condensation polymerization resin such as polyester, polyester / polyamide, polyamide and the like and an addition polymerization resin such as a vinyl polymerization resin are chemically bonded is preferable, and two or more kinds of resins are used as raw materials. Although it may be obtained or may be obtained from a mixture of raw material monomers of one type of resin and another type of resin, in order to obtain a hybrid resin efficiently, two or more types of resins may be used. Those obtained from a mixture of the raw material monomers are preferred.
[0016]
The raw material monomer of the polyester is not particularly limited, but a known alcohol component and a known carboxylic acid component such as carboxylic acid, carboxylic anhydride, and carboxylic ester are used.
[0017]
Examples of the alcohol component include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane. Formula (I):
[0018]
Embedded image

[0019]
(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, preferably 1.5 to 5.0)
An alkylene oxide adduct of bisphenol A, ethylene glycol, propylene glycol, glycerin, pentaerythritol, trimethylolpropane, hydrogenated bisphenol A, sorbitol, or an alkylene (2-4 carbon) oxide thereof (average addition mole) Formulas 1 to 16) adducts and the like.
[0020]
As the carboxylic acid component, phthalic acid, isophthalic acid, terephthalic acid, aromatic carboxylic acids such as trimellitic acid, fumaric acid, maleic acid, adipic acid, succinic acid, dodecenyl succinic acid, carbon number of 1 to 1 such as octenyl succinic acid. Examples thereof include aliphatic carboxylic acids such as succinic acid substituted with 20 alkyl groups or alkenyl groups having 2 to 20 carbon atoms, anhydrides of these acids, and alkyl (1 to 3 carbon atoms) esters of these acids. .
[0021]
In the present invention, from the viewpoints of chargeability, dispersibility of the colorant and blocking resistance, addition of the alkylene oxide of bisphenol A represented by the formula (I) to the alcohol component in any of the black toner and the color toner. Is preferably 50% by weight or more, more preferably 80 to 100% by weight, and particularly preferably 100% by weight. It is preferable to adjust according to the constituting monomer.
[0022]
Further, the content of the aromatic carboxylic acid compound in the carboxylic acid component is preferably 50 to 90 mol%, more preferably 50 to 75 mol% for the black toner, and preferably 80 to 100 mol% for the color toner. %, More preferably 90 to 100 mol%. The aromatic carboxylic acid compounds include aromatic carboxylic acids, anhydrides of these acids, and derivatives of aromatic carboxylic acids such as alkyl (C1 to C3) esters of these acids.
[0023]
The polyester can be produced, for example, by subjecting an alcohol component and a carboxylic acid component to polycondensation in an inert gas atmosphere, if necessary, using an esterification catalyst at a temperature of 180 to 250 ° C.
[0024]
When the toner of the present invention is used as a positively chargeable toner, the acid value of the polyester is preferably 0.5 to 15 mgKOH / g, more preferably 1 to 12 mgKOH / g, and particularly preferably 1.5 to 10 mgKOH / g.
[0025]
When the toner is used as a negatively chargeable toner, the acid value of the polyester is preferably 5 to 40 mgKOH / g, more preferably 10 to 35 mgKOH / g, and particularly preferably 15 to 30 mgKOH / g.
[0026]
The softening point of the binder resin is preferably from 80 to 165C, more preferably from 95 to 155C, and the glass transition point is preferably from 50 to 85C. From the viewpoint of obtaining a wider fixing range, a resin having a softening point of 120 to 165 ° C. (high softening point resin) and a resin having a softening point of 80 ° C. or more and less than 120 ° C. (low softening point resin) are preferable. / 90-90 / 10, more preferably 30 / 70-70 / 30, in a weight ratio (high softening point resin / low softening point resin).
[0027]
As the colorant, any of dyes and pigments used as toner colorants can be used, and 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, and these can be used alone or in combination of two or more. The amount of the colorant to be used is preferably 1 to 40 parts by weight, more preferably 3 to 10 parts by weight, based on 100 parts by weight of the binder resin.
[0028]
In the present invention, further, a charge control agent, a release agent, a fluidity improver, a conductivity adjuster, an extender, a reinforcing filler such as a fibrous substance, an antioxidant, an antioxidant, a cleaning improver, etc. May be blended as a raw material.
[0029]
Examples of the charge control agent include a nigrosine dye, a triphenylmethane dye containing a tertiary amine as a side chain, a quaternary ammonium salt compound, a polyamine resin, a positive charge control agent such as an imidazole derivative, and a metal-containing azo dye. Negatively chargeable charge control agents such as aromatic hydroxycarboxylic acid metal complexes, copper phthalocyanine dyes, metal complexes of alkyl derivatives of salicylic acid, and boron benzylate compounds, which are used alone depending on the chargeability of the toner. Or may be used as a mixture.
[0030]
Examples of the release agent include natural ester waxes such as carnauba wax and rice wax, synthetic waxes such as polypropylene wax, polyethylene wax and Fischer-Tropsch, coal waxes such as montan wax, and waxes such as alcohol waxes. These may be contained alone or as a mixture of two or more.
[0031]
The method for producing each toner may be any of the conventionally known methods such as a kneading and pulverizing method, a phase inversion emulsifying method, an emulsifying and dispersing method, and a suspension polymerization method. Is preferred. For example, in the case of a pulverized toner by a kneading and pulverizing method, a binder resin, a colorant, and the like are uniformly mixed by a mixer such as a Henschel mixer, and then melt-kneaded by a closed kneader or a single-screw or twin-screw extruder, It can be manufactured by cooling, pulverizing and classifying. The volume average particle size of the toner is preferably 3 to 15 μm.
[0032]
The softening point of the black toner and the color toner is preferably from 95 to 140 ° C, more preferably from 100 to 130 ° C, from the viewpoints of fixability and blocking resistance.
[0033]
The full-color toner of the present invention is composed of a black toner and at least one type of color toner. Examples of the color toner include a magenta toner, a yellow toner, and a cyan toner.
[0034]
When the full-color toner of the present invention is used in an electrostatic image developing device having a resolution of 600 dpi or more, preferably in a copying machine or a printer, the effect on fine line reproducibility is more remarkably exhibited.
[0035]
【Example】
(Softening point)
Using a Koka type flow tester “CFT-500D” (manufactured by Shimadzu Corporation), the temperature at which half of the resin flows out is taken as the softening point (sample: 1 g, heating rate: 6 ° C./min, load: 1.96 MPa, Nozzle: 1 mmφ × 1 mm).
[0036]
(Glass transition point)
The temperature was raised to 200 ° C. using a differential scanning calorimeter (DSC210, manufactured by Seiko Instruments Inc.), and the sample cooled from that temperature to 0 ° C. at a rate of 10 ° C./min was measured at a rate of 10 ° C./min. The temperature at the intersection of the extension line of the baseline below the maximum peak temperature and the tangent line showing the maximum slope from the rising portion of the peak to the peak of the peak is defined as the glass transition point.
[0037]
〔viscosity〕
Using a viscoelasticity measurement device (rheometer) RDA-II type (manufactured by Rheometrics), a value of 160 ° C. when measured at every 10 ° C. from 180 ° C. to 140 ° C. under the following measurement conditions is adopted.
(Measurement condition)
Jig: Parallel plate (radius: 5 mm)
Sample: 1g
Frequency: 2 radians / second Distortion: 2 °
[0038]
Resin production example 1
Raw materials other than trimellitic anhydride shown in Table 1 and 4 g of dibutyltin oxide were placed in a five-liter four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple, and heated at 220 ° C. for 8 hours. Then, the reaction was performed at 8.3 kPa for 1 hour. Further, trimellitic anhydride was added at 210 ° C. and reacted until a predetermined softening point was reached, to obtain resins A to D.
[0039]
[Table 1]

[0040]
Production Example of Black Toner 100 parts by weight of a binder resin shown in Table 2, 4.0 parts by weight of carbon black “MOGUL-L” (manufactured by Cabot), and 0 of charge control agent “T-77” (manufactured by Hodogaya Chemical Industry Co., Ltd.) After preliminarily mixing 0.5 parts by weight and 1 part by weight of a release agent "Carnauba wax C1" (manufactured by Kato Yoko Co., Ltd.) with a Henschel mixer, melt kneading with a twin screw extruder, cooling, pulverizing and classifying processes. As a result, a powder having a volume average particle diameter of 8 μm was obtained.
[0041]
To 100 parts by weight of the obtained powder, 1.0 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 black toners A to E.
[0042]
Production Example of Color Toner 100 parts by weight of binder resin shown in Table 2, 4.0 parts by weight of yellow colorant "Paliotor D1155" (manufactured by BASF), and 0.5 of charge control agent "LR-147" (manufactured by Nippon Carlit) The yellow toners A to C were obtained in the same manner as the black toner using 1 part by weight and 1 part by weight of the release agent "Carnauba wax C1" (manufactured by Kato Yoko Co., Ltd.).
[0043]
Instead of the yellow colorant, 4.0 parts by weight of a magenta colorant “ECR-101” (manufactured by Dainichi Kagaku) or 4.0 parts by weight of a cyan colorant “ECB-30” (manufactured by Dainichi Seika) Magenta toners A to C and cyan toners A to C were obtained in the same manner as for the yellow toner, except that was used.
[0044]
[Table 2]

[0045]
Examples 1 to 6, Comparative Examples 1 and 2
{Circle around (1)} The yellow toner, magenta toner, cyan toner, and black toner are mounted on the developing units for each color toner of the digital color printer “MOCROLINE 7300” (manufactured by Oki Data Co., Ltd.) by reversal development, and the adhesion amount of each toner is measured. Each was adjusted to 0.55 mg / cm ² , and for each color, in a 600 dpi high resolution mode, a 5 cm square solid image (fixing temperature 180 ° C., fixing speed 50 mm / sec) on Hammermill (LaserPrint, 90 g paper). ) Got. The glossiness of the obtained fixed image was measured using a gloss sensor “VG-2P” (manufactured by NIPPONDENSHOKU), and the uniformity of gloss was evaluated according to the following evaluation criteria. Table 3 shows the results. The difference in glossiness between color images in each of the examples and comparative examples was less than 10.
[0046]
〔Evaluation criteria〕
The difference between the glossiness of the black image and the color image with the largest glossiness difference between the black image and the color image is
◎: less than 10 ：: 10 or more, less than 20 ×: 20 or more
(2) Using the same color printer as (1), without adjusting the development conditions of black toner and color toner (yellow toner, magenta toner, cyan toner), alternate between black toner and color toner at 1 dot / 1 space under initial conditions The resulting image was magnified 1000 times and observed to evaluate fine line reproducibility. Table 3 shows the results.
[0048]
〔Evaluation criteria〕
A: Both color lines can be clearly observed.
：: The color line adjacent to the black toner is slightly smeared, but there is no practical problem.
Δ: The color line adjacent to the black toner is blurred.
X: The color line adjacent to the black toner is hardly observed.
[0049]
[Table 3]

[0050]
From the above results, the full-color toners of Examples 1 to 6 in which the black toner aromatic concentration was lower than the color toner aromatic concentration and the difference between the two was adjusted to be within a certain range were the full-color toners of Comparative Examples 1 and 2. It can be seen that the toner has excellent fine line reproducibility and gloss uniformity as compared with the toner.
[0051]
【The invention's effect】
The full-color toner of the present invention has an excellent effect that a full-color image excellent in both fine line reproducibility and gloss uniformity can be obtained.

Claims (5)

A full-color toner comprising a black toner and at least one type of color toner each containing a binder resin and a colorant, wherein the aromatic concentration of the binder resin contained in the black toner (the aromatic concentration of the black toner) ) Is lower than the aromatic concentration (color toner aromatic concentration) of the binder resin contained in any color toner, and the difference between the black toner aromatic concentration and the lowest color aromatic concentration is the color toner aromatic concentration. A full-color toner in which the difference between the aromatic concentration of the black toner and the aromatic concentration of any of the color toners is greater than any of the differences between 1 and 14% by weight. The full-color toner according to claim 1, wherein the difference between the aromatic concentrations of the color toner is within 5% by weight, and the aromatic concentration of the black toner is 30 to 50% by weight. The binder resin contained in the black toner contains a carboxylic acid component containing 50 to 90 mol% of an aromatic carboxylic acid compound and a formula (I):

(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)
Is a polyester obtained by condensation polymerization of an alcohol component containing at least 50% by weight of an alkylene oxide adduct of bisphenol A represented by the formula: wherein the binder resin contained in the color toner is an aromatic carboxylic acid compound Is obtained by subjecting a carboxylic acid component containing from 80 to 100 mol% to an alcohol component containing at least 50% by weight of an alkylene oxide adduct of bisphenol A represented by the formula (I) to obtain a polyester. Item 3. The full-color toner according to item 1 or 2. The full-color toner according to any one of claims 1 to 3, wherein a difference in a dissolution viscosity at 160 ° C of the binder resin contained in the black toner and the color toner is 500 to 3000 Pa · s. The full-color toner according to any one of claims 1 to 4, wherein the full-color toner is used in a developing device for an electrostatic image having a resolution of 600 dpi or more.