JPS60138563A - Toner for developing electrostatic latent image - Google Patents

Abstract

PURPOSE:To obtain a copy image of high quality which causes neither variation in the charging amount of toner nor sticking transfer to a vinyl chloride sheet due to the repetition of copying operation by using specific carbon black as the black pigment of the toner. CONSTITUTION:Carbon black which has <=50ml/100g DBP oil absorption, >=40mum mean grain size (primary grain size), and <=6.0pH carbon black is used as the black pigment of the toner. The carbon black is acidic, so less carbon black is absorbed by polyester resin having an acid group during kneading, the carbon black is exposed easily in particle surfaces, and the excessive accumulation of a charge in the toner is evaded, so that there is no decrease in image density due to the repetition of copying operation. Further, the carbon black is made acidic to improve the dispersibility of the polyester resin, and the use of the carbon black having small oil absorption prevents the localization of the toner and defect in fixation, thereby obtaining a copy image of high quality.

Description

【発明の詳細な説明】 本発明は、ポリエステル樹脂を主体とする熱可塑性樹脂
と黒色着色剤を主成分とする静電潜像現像用トナーに関
する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a toner for developing electrostatic latent images whose main components are a thermoplastic resin mainly composed of a polyester resin and a black colorant.

ポリエステル樹脂は、定着性にすぐれ、かつ、酸基を有
することから負帯電性に富み、更に、複写機で複写した
後のコピー紙を塩ビシートにファイルした場合でも、定
着されたトナーが塩ビジー）に付着転写しないなど種々
の利点を有しておシ、トナーの材料として多用されてい
る。Polyester resin has excellent fixing properties and is highly negatively charged due to the presence of acid groups.Furthermore, even when copy paper is filed on a PVC sheet after copying with a copying machine, the fixed toner remains free of chlorine. ) It has various advantages such as not adhering and transferring, and is widely used as a toner material.

また、上記トナーとしては、十分帯電、させるためには
高抵抗のものが好ましいが、その反面、感光体に形成さ
れたトナー像を転写紙へと容易に転写させるためには、
転写チャージによりｆｆｉ光体と転写紙との間に印加し
た電界を有効に働かせる上からある程度の導電性を必要
とする。In addition, the above-mentioned toner is preferably one with high resistance in order to be sufficiently charged, but on the other hand, in order to easily transfer the toner image formed on the photoreceptor to transfer paper,
A certain degree of electrical conductivity is required in order for the electric field applied between the FFI light body and the transfer paper to work effectively due to the transfer charge.

そのため、従来一般に、導電性を有するカーボンブラッ
クを黒色着色剤としてルい、そのカーボンブラックを熱
可塑性樹脂に分散していたが、カーボンブラックどうし
の再凝集を生じ、トナー中での分散性が悪くなるととも
に、帯電性が不均一になってトナー飛散や現像画像中に
画像カスレを生じる欠点があった。　またトナー製造時
における混練に伴ってカーボンブラックか熱可塑性樹脂
で被覆された状態になりやすく、混練を数十時間行って
均一に分散させたにせよ、コピーの繰返しに伴い、電荷
がトナー中に蓄積して帯電量が上昇１２、画像濃度が低
下する欠点があった。Therefore, in the past, conductive carbon black was generally used as a black colorant and the carbon black was dispersed in thermoplastic resin, but this caused reaggregation of the carbon blacks, resulting in poor dispersibility in the toner. At the same time, the charging property becomes non-uniform, resulting in toner scattering and image blurring in the developed image. Furthermore, during the kneading process during toner manufacturing, the toner tends to become coated with carbon black or thermoplastic resin. There was a drawback that the amount of charge increased due to accumulation12 and the image density decreased.

本発明は、上記の点に鑑み、ポリエステル樹脂の特性に
着目し、ＰＲ並びに平均粒子径を合理的に設定すること
により、分散性を良好にできながらトナーの定着面から
見て有利な吸油量の小さいカーボンブラックを用い、コ
ヒー繰り返しに伴うトナーの帯電量の変動を招くことな
く、塩ビシートへの付着転写を生じない質の高いコピー
画像を得られるトナーを提供することを目的とする。In view of the above points, the present invention focuses on the characteristics of polyester resin, and by rationally setting the PR and average particle diameter, it is possible to achieve good dispersibility and an oil absorption amount that is advantageous from the viewpoint of toner fixation. To provide a toner that uses carbon black with a small carbon black and can provide a high-quality copy image that does not cause adhesion and transfer to a vinyl chloride sheet without causing fluctuations in the amount of charge of the toner due to repeated cohesion.

本発明は、上２目的を達成するために、冒頭に記載した
静電潜像現像用トナーにおいて、前記黒色着色剤として
、ＤＢＰ吸油量が５０ゴ７ｉｏｏｙ以下で、平均粒子径
（−次粒子径）がｌＩｏｍμ以上、かつ、　ＰＨが乙Ｏ
以下のカーボンブラックを含有することを特徴とし、そ
れにより次のような効果を奏する。In order to achieve the above two objects, the present invention provides the toner for developing electrostatic latent images described at the beginning, in which DBP oil absorption is 50 go 7iooy or less, the average particle diameter (-order particle diameter ) is lIomμ or more, and PH is O
It is characterized by containing the following carbon black, thereby producing the following effects.

即ち、カーポンプフックを酸性にするから、混線に際し
て、酸基を有するポリエステル樹脂中に取り込まれるこ
とが少なく、カーボンブラックがトナー粒子の表面に露
出した状態になシやすく、このことから、電荷のトナー
中での過剰蓄積を回避できてコピーの繰り返しに伴う帯
電量の上昇を抑制でき、コピーの繰り返しにかかわらず
画像濃度の低下は生じない。In other words, since the car pump hook is made acidic, it is less likely to be incorporated into the polyester resin having acid groups when cross-wired, and the carbon black is more likely to be exposed on the surface of the toner particles. Excessive accumulation in the toner can be avoided, and an increase in the amount of charge caused by repeated copying can be suppressed, and image density does not decrease regardless of repeated copying.

また、カーボンブラックを酸性にしてポリエステル樹脂
との分散性を高めることＫよシ、トナーの帯電性が均一
にされるとともに、吸油量が小さいカーボンブラックが
使用されることによシ、定着時の加熱溶融後の冷却に伴
うトナー７０部の局在化や溶融粘性の悪影響に起因する
定着不良のいずれをも回避し、キメが細かく、定着性が
良好で質の高いコピー画像が得られるようＫなった。In addition, by making the carbon black acidic to improve its dispersibility with the polyester resin, the charging properties of the toner can be made uniform, and by using carbon black with a small oil absorption, it is possible to To avoid localization of the toner 70 parts caused by cooling after heating and melting and poor fixing due to the adverse effects of melt viscosity, it is possible to obtain high-quality copy images with fine texture and good fixing properties. became.

本発明の熱可塑性樹脂としては、ポリエステル樹脂のみ
のものに限らず、一部に他の樹脂を加えても良く、要す
るにポリエステル樹脂を主体とするものであれば良い。The thermoplastic resin of the present invention is not limited to only a polyester resin, but may include a portion of other resins, and in short, any thermoplastic resin may be used as long as it is mainly composed of a polyester resin.

　なお、加える他の樹脂としては、例えば、メタクリｉ
ｖｍ、アクリル酸、マレイン酸などをスチレン−アクリ
ル系樹脂と共重合して酸基を有するようにしたものが好
適である。In addition, other resins to be added include, for example, methacrylic i
Preferred are those obtained by copolymerizing vm, acrylic acid, maleic acid, etc. with a styrene-acrylic resin to have an acid group.

また、本発明のトナーを磁性トナーとして用いるために
、磁性粉を含有させても良い。　このような磁性粉とし
ては、磁場の中に置かれて磁化される物質が用いられ、
鉄、コバルト、ニッケルなどの強磁性金属の粉本もしく
はマグネタイト、ヘマタイト、フェライトなどの合金や
化合物がある。Further, in order to use the toner of the present invention as a magnetic toner, magnetic powder may be included. As such magnetic powder, a substance that is magnetized when placed in a magnetic field is used.
There are powders of ferromagnetic metals such as iron, cobalt, and nickel, and alloys and compounds such as magnetite, hematite, and ferrite.

この磁性粉の含有量はトナー重量に対して７５〜７０重
量％であることが好ましい。The content of this magnetic powder is preferably 75 to 70% by weight based on the weight of the toner.

以下、実施例、比較例並びに比較実験結果について説明
する。Examples, comparative examples, and comparative experiment results will be described below.

（実施例１〕 ポリエステル樹脂（軟化点／　２００Ｃ、ガラス転移点
乙ｔ’ｃ　、酸価／　ｇ　ｘｏＨＷ／７　）　１０　ｏ
部カーボンブラック （スベシャＡ／−ブラック−２ｓＯ（デグサ社製）ＤＢ
Ｐ吸油量＜ｚ　＋　ｘｔｔ７ｉｏｏｙ平均粒子径（−次
粒子径）　３１ｒ　ｎｓμＰＨ３，３“　フ　、Ｓ“　
部 上記の材料をポールミμで十分に混合した後、７３０°
ＣＫ熱した３本ロールで混練した。　混練物を放置冷却
後、フェザーミ〜で粗粉′砕した後、ジェット気流を用
いた微粉砕機で粉砕し、さらに風力分級し平均粒子径ｉ
３ｍμの負帯電性トナーを得た。　また、ヌチレンーア
クリル樹脂プライオライドＡＣＬ（グツドイヤー社製）
７００部に磁性粉マピコブラックＢＬ−３００（チタン
工業社！！！りカーボン・ブラックＭＡ　−７００（三
菱化成工業社製）５部をボールミμで十分に混合した後
、／１ｌＯ０Ｃに熱した３本ロールで混練後、放口冷却
しフェザ−ミルで粗粉砕後、ピンミ′ルにて微粉砕し風
力分級機で分級し平均粒径りＯμ、体積抵抗１０１′Ｉ
Ω・ｍの正帯電性キャリアを得た。(Example 1) Polyester resin (softening point/200C, glass transition point t'c, acid value/g xoHW/7) 10 o
Carbon black (Subeshya A/-Black-2sO (manufactured by Degussa) DB
P oil absorption <z + xtt7iooy average particle diameter (-order particle diameter) 31r nsμPH3,3"F,S"
After thoroughly mixing the above materials with a Paul Miμ, 730°
The mixture was kneaded using three rolls heated by CK. After cooling the kneaded material, it is crushed into coarse powder with a feather mill, then crushed with a fine crusher using a jet stream, and further classified by air to obtain an average particle size i.
A negatively chargeable toner of 3 mμ was obtained. In addition, Nutylene-acrylic resin Prioride ACL (manufactured by Gutdeyer Co., Ltd.)
700 parts of magnetic powder Mapico Black BL-300 (Titan Kogyo Co., Ltd.) and 5 parts of Carbon Black MA-700 (manufactured by Mitsubishi Chemical Industries, Ltd.) were thoroughly mixed in a ball mill μ, and the mixture was heated to /1lO0C. After kneading with this roll, it is cooled at the outlet, coarsely pulverized with a feather mill, finely pulverized with a pin mill, and classified with an air classifier, with an average particle size of Oμ and a volume resistance of 101'I
A positively chargeable carrier of Ω·m was obtained.

ｊ■述の試料として製造したトナー７０部とキャリアタ
Ｏ部の割合で混合【２て二成分現像剤を調製した。A two-component developer was prepared by mixing 70 parts of the toner prepared as the sample described above with 0 parts of the carrier.

上記現像剤を用い、（→帯電性Ｓｅｉ感光体とテフロン
コーディングした加熱定着ロールとを備えた複写機を用
い、正の静電荷像を磁気ブラシ現像法によシ現像すると
ともに、転写チャージャによる転写、及び、加熱定着ロ
ールによる定着の各工程を経て転写紙上に複写した。　
その複写画像において、画像濃度が７．１１３；と高く
、カブリが全くなく、かつ、解像力も高くて良好な画像
が得られた。　また、ｇ　ｏ、ｏ　ｏ　ｏ枚の連続コピ
ーを行ったが、そのｔｏ、ｏ　ｏ　ｏ枚後の画像も初期
画像と比較して何ら変りがなく、かつ、帯電量も初期で
一／３．ｓμｃ／（／であるのに対し。Using the above developer, a positive electrostatic charge image is developed by a magnetic brush development method using a copying machine equipped with a chargeable Sei photoreceptor and a Teflon-coated heat fixing roll, and transferred by a transfer charger. , and fixing with a heat fixing roll, and then copied onto transfer paper.
In the copied image, a good image was obtained with a high image density of 7.113, no fog, and high resolution. Further, although continuous copying was performed for go, o o o sheets, the images after the to, o o o sheets were no different from the initial image, and the amount of charge was 1/3 at the initial stage. whereas sμc/(/.

／　０．０００枚後で−／３．３ｔｔｃ／ｆ　、　ｌＩ
ｏ、ｏｏｏ枚後で７／３．２μｃ／ｆと安定した結果が
得られた。/ After 0.000 sheets -/3.3ttc/f, lI
After o and ooo sheets, a stable result of 7/3.2 μc/f was obtained.

〔実施例２〕 ポリエステル樹脂として酸価が／　ＯＫＯＨＭｆ／ｆの
ものを用いた以外Ｆｉ実施例１と同様にして現像剤を調
整した。[Example 2] A developer was prepared in the same manner as in Example 1 except that a polyester resin having an acid value of /OKOHMf/f was used.

〔実施例８〕 ポリエステル樹脂として酸価が、２８　ＫＯＩ（１９７
ｆのものを用いた以外は実施例１と同様にして現声゛剤
を調整した。[Example 8] As a polyester resin, the acid value was 28 KOI (197
A developing agent was prepared in the same manner as in Example 1, except that compound No. f was used.

〔実施側番〕[Implementation side number]

ポリエステル樹脂として酸価が３　ＫＯＨ１ｌｌｆ／ｆ
のものを用いた以外は実施例１と同様にして現像剤を調
製した。As a polyester resin, the acid value is 3 KOH1llf/f
A developer was prepared in the same manner as in Example 1 except that a developer was used.

〔実施例５〕 ポリエステル樹脂として酸価が３０ＫｏＨり７ｇのもの
を用いた以外は実施例１と同様にして現像剤を調製した
。[Example 5] A developer was prepared in the same manner as in Example 1 except that a polyester resin having an acid value of 30 KoH and 7 g was used.

〔実施例６〕 ポリエステル樹脂として酸価が＋　ＯＫＯＨ１４ｆ／ｆ
のものを用すた以外は’ＮＭ例１と同ＷｅＫして現像剤
を調整した。[Example 6] Polyester resin with acid value + OKOH14f/f
A developer was prepared in the same manner as in NM Example 1 except that the same WeK was used.

ここで、実施例２〜ｇで夫々調製された現像剤を用い、
実施例１と同様にして複写したところ、初期帯電量の点
を除き、実施例１とほぼ同一の結果が得られた。Here, using the developers prepared in Examples 2 to g,
When copies were made in the same manner as in Example 1, almost the same results as in Example 1 were obtained except for the initial charge amount.

〔比較例−１〕 カーボンブラック（スペシャル・ブラック−２！０）の
かわシにＭＡ−１０ｏ（三菱化成工業社製）（ＤＢＰ吸
油！　／　０１ｍｌ／１００１．　平均粒子径（−次粒
子径）　２２　ｎｔｐ、ＰＨ３，０）を５部添加した他
は、実施例１と同様に現像剤を調製した。　また、実施
例１と同様にして複写したところ、得られた画像濃度は
ｉ、ｓｔｔと高いものの、その画質は極めて悪いもので
あった一且、解像力の悪い画像が得らｈた。　なお、初
期帯電量も一乙、／μｃ／ｆと低いのであるが、連続コ
ピーを行なトナー飛散が発生１１１、画像のカスレ、カ
ブリも生じた。[Comparative Example-1] MA-10o (manufactured by Mitsubishi Chemical Industries, Ltd.) (DBP oil absorption! / 01ml/1001. Average particle size (-order particle size) 22 A developer was prepared in the same manner as in Example 1, except that 5 parts of ntp, pH 3,0) were added. Further, when copying was performed in the same manner as in Example 1, although the obtained image density was as high as i, stt, the image quality was extremely poor, and an image with poor resolution was obtained. Although the initial charge amount was as low as 1/μc/f, continuous copying resulted in toner scattering 111 and image blurring and fogging.

〔比較例−２〕 カーボンブラック（スペシャル・ブラック−２３０）の
かわりに＃５（三菱化成工業社製）（ＤＢＰ吸油量６り
ｔｔｔｌ／　／　ＯＯｙ、平均粒子径（−次粒子径＞ｇ
ｓ硝、ＰＨｇ、０）を５部添加した他は実施例１と同様
に現像剤を調製した。　また、実施例１と同様にして複
写したところ、得られ念画像濃度が／、ダざと高く、カ
ブリ及び解像力も良好であったが、定着画像中における
カーボンブラックどうしの凝集が観察され１画質の荒さ
が日立りものであった。[Comparative Example-2] Instead of carbon black (Special Black-230), #5 (manufactured by Mitsubishi Chemical Industries, Ltd.) (DBP oil absorption 6 tttl/ / OOy, average particle size (-order particle size > g
A developer was prepared in the same manner as in Example 1, except that 5 parts of S-nitrate, PHg, 0) were added. Further, when copying was performed in the same manner as in Example 1, the image density obtained was quite high, and the fog and resolution were also good, but aggregation of carbon black was observed in the fixed image, resulting in poor image quality. The roughness was typical of Hitachi.

〔比較例−８〕 カーポンプフック（スベシャμ・ブラック−コＳＯ）の
かわ夛にスペシャル・ブラック乙（デグサ・ジャパン社
５１１１）（ＤＢＰ吸油量／り０ｔｘｌ／１００９．平
均粒子径（−次粒子径）７３隼、ＰＨ，２，５）を５部
添加した他は実施例１と同様に現像剤を調製した。[Comparative Example-8] Car Pump Hook (Subesya μ Black-CO SO) Special Black Otsu (Degussa Japan Co., Ltd. 5111) (DBP Oil Absorption / 0txl / 1009. Average Particle Size (- A developer was prepared in the same manner as in Example 1, except that 5 parts of Diameter) 73 Hayabusa, PH, 2,5) were added.

また、実施例１と同様にして複写したところ、得らｈま
た画像濃度が／、乙２と高いものの、解像力などが悪く
、かつ、初期帯電量が低くて当初からトナー飛散が問題
となった。In addition, when copies were made in the same manner as in Example 1, although the obtained image density was as high as / and O2, the resolution was poor and the initial charge amount was low, causing toner scattering to be a problem from the beginning. .

〔比較例−４〕 カーボン・ブラック（スペシャル・ブラック−，２！；
０）のかわフに、プリンラックス−，２５（デグサ社製
）（ＤＢＰ吸油景ＩＩ　ｔ＠ｌ／１０Ｏｆ　。[Comparative Example-4] Carbon Black (Special Black-, 2!)
0), Purinlux-, 25 (manufactured by Degussa) (DBP Oil Absorption II t@l/10Of).

平均粒子径（−次粒子径）５ｇｍμ、ＰＨり、５　）を
５部添加した他は実施例１と同様に現像剤を調製した。A developer was prepared in the same manner as in Example 1, except that the average particle diameter (-order particle diameter) was 5 gmμ, and 5 parts of PH 5) were added.

　また、実施例１と同様にして複写したところ、得られ
た画像濃度が７゜３Ｓで、カブリ及び解像力も良好であ
ったが、トナー中でのカーボンブラックの分散の不均一
さから画質の荒れが目立った。Further, when copies were made in the same manner as in Example 1, the obtained image density was 7°3S, and the fog and resolution were also good, but the image quality was rough due to uneven dispersion of carbon black in the toner. was noticeable.

〔比較例−５〕 ポリエステル樹脂に代えて、 ０７、チレンーメタクリル酸ｎ−グチル（７０：３０）
共重合体 （軟化点７２３°Ｃ１ガラス転移点乙０°Ｃ１酸価０Ｋ
Ｏ１１ｑ／ｆ　）　／　Ｏ０部 ・０負帯電制御剤ボントロンＳ−３’ｌ（オリエント化
学工業社製）　５部 を用いた他は実施例１と同様に現像剤を調製し念。　ま
た、実施例１と同様にして複写し念ところ、得られた画
像濃度が７．５２で、カプリ及び解像力も良好であった
が、画質の点で実施例１と比較して劣り、得られた画像
は塩ビシートに容易に付着転写するものであった。　な
お、実施例１〜６、比較例１〜４．６〜ＩＯにおいては
塩ビシートへの付着転写は事実上観察されていない。[Comparative Example-5] Instead of polyester resin, 07, tyrene-n-glythyl methacrylate (70:30)
Copolymer (softening point 723°C1 glass transition point 0°C1 acid value 0K
A developer was prepared in the same manner as in Example 1, except that 5 parts of the negative charge control agent Bontron S-3'l (manufactured by Orient Chemical Industry Co., Ltd.) was used. In addition, copies were made in the same manner as in Example 1, and the obtained image density was 7.52, and the capri and resolution were also good, but the image quality was inferior compared to Example 1. The image was easily adhered to and transferred to the PVC sheet. In addition, in Examples 1 to 6 and Comparative Examples 1 to 4.6 to IO, adhesion and transfer to the vinyl chloride sheet was virtually not observed.

〔比較例−６〕 カーボンブラック（スペシャルブラックー、２ｓｏ）の
かわシに１旭＃ｔＯＦＥＦ　（旭カーボン社製）（ＤＢ
Ｐ吸油量３７ａｔ／１００ｆ　、平均粒子径（−次粒子
径）Ｉ１０ｍμ、ＰＨ７，’７）を５部添加した他は実
施例１と同様に現像剤を調製した。[Comparative Example-6] 1 Asahi #tOFEF (manufactured by Asahi Carbon Co., Ltd.) (DB
A developer was prepared in the same manner as in Example 1, except that 5 parts of P oil absorption amount 37 at/100f, average particle diameter (-order particle diameter) I 10 mμ, and PH 7,'7) were added.

〔比較例−７〕 カーボンブラック（スペシャルブラック−２！；０）の
かわりに、＃２３００　（三菱化成工業社ｐ！り（ＤＢ
Ｐ吸油量ぶ夕１１ｔ／１００ｆ　、平均粒子径（−次粒
子径）／５隼、ＰＨ８，０）を５部添加した他は実施例
１と同様に現像剤を調製した。[Comparative Example-7] Instead of carbon black (Special Black-2!;0), #2300 (Mitsubishi Chemical Corporation p!ri (DB
A developer was prepared in the same manner as in Example 1, except that 5 parts of P oil absorption amount 11t/100f, average particle diameter (-order particle diameter)/5 Hayabusa, pH 8.0) were added.

〔比較例−８〕 カーポンプフック（スペシャルブラック−，２ｓｏ）の
かわシに、プリンラックス−しくデグサ社製）（ＤＢＰ
吸油量／／り解ｌ／１００ｆ、平均粒子径（−次粒子径
）２部ｍμ、ＰＨ，！ｒ、３）を５部添加した他は実施
例１と同様に現像剤を調製した。[Comparative Example-8] Car pump hook (Special Black-, 2so) was attached to Pudding Luxe (manufactured by Degussa) (DBP).
Oil absorption/resolution l/100f, average particle diameter (-order particle diameter) 2 parts mμ, PH,! A developer was prepared in the same manner as in Example 1, except that 5 parts of r, 3) were added.

〔比較例−９〕 カーボンブラック（スペシャルブラック−２５０）のか
わりに、ＭＡ＃ざ（三菱化成工業社製）（ＤＢＰ吸油量
５　ｇ　ｘｉ／／　００　ｆ、平均粒子径（−次粒子径
）２１１ｍｐ、　ＰＨ３，０３を５部添加した他は実施
例１と同様に現像剤を調製した。[Comparative Example-9] Instead of carbon black (Special Black-250), MA #za (manufactured by Mitsubishi Chemical Industries, Ltd.) (DBP oil absorption 5 g xi//00 f, average particle size (-order particle size) 211 mp A developer was prepared in the same manner as in Example 1, except that 5 parts of PH3,03 were added.

〔比較例１０〕 カーポンプフック（スペシャルブラック−２ＳＯ）のか
わりに＃＋４Ｚ（三菱化成工業社ｐ９　）（Ｄ　Ｂ　ｐ
吸油量？ｔｔｄ／１００ｆ、平均粒子径（−次粒子径）
、ｚｉｍμ、ＰＨ，！ｒ、０）を５部添加した他は実施
例１と同様に現像剤を調製した。[Comparative Example 10] #+4Z (Mitsubishi Chemical Industries, Ltd. p9) (D B p
Oil absorption amount? ttd/100f, average particle diameter (-order particle diameter)
,zimμ,PH,! A developer was prepared in the same manner as in Example 1, except that 5 parts of r, 0) were added.

上記比較例６〜１０夫々の現像剤を用い、実施例１と同
様にして複写並びに連続コピーを行ったところ、例えば
、比較例７では、７０．０００枚で−／Ｑ、７μｃ／ｆ
　（初期帯電量）から−ｇ、　。Copying and continuous copying were carried out in the same manner as in Example 1 using the developers of Comparative Examples 6 to 10 above. For example, in Comparative Example 7, -/Q, 7 μc/f
(initial charge amount) to -g, .

ｐｃ／ｆに、比較例９では、／Ｓ、０００枚で−／／、
２μｃ／ｆ　（初期帯電量）から−ｇ、コμＣ／ｇに、
そして、比較例１０では、ｓ、ｏ　ｏ　ｏ枚で一タ６ｇ
μｃ／ｆ（、初期帯電量）から−７，０μｃ／ｆになる
など、いずれも、コピーの繰り返しに伴う帯電量の変動
が激しく、早期に画像が不鮮明になった。　なお、比較
例８においては、初期帯電量が−５，２μｃ　／　ｆ　
と低く、初期からトナー飛散の問題を生じていた。For pc/f, in Comparative Example 9, /S, 000 sheets -//,
From 2 μc/f (initial charge amount) to −g, μC/g,
In Comparative Example 10, s, o o o pieces weighs 6g.
In both cases, the charge amount fluctuated drastically with repeated copying, such as from μc/f (initial charge amount) to −7.0 μc/f, and the image became unclear at an early stage. In addition, in Comparative Example 8, the initial charge amount was -5.2 μc/f
This caused the problem of toner scattering from the beginning.

以上の実施例１〜６、並びに、比較例１〜１０夫々にお
ける黒色着色剤のＤＢＰ吸油量、平均粒子径（−次粒子
径）、ＰＨ，及び、熱可塑性樹脂の酸価、並びに、現像
剤としての初−期帯電量夫々について表に１とめて次頁
、−示１゜上記実施例において、いずれも実用上支障は
無いが、実施例８にお込で、多少トナー飛散を生じやす
い傾向が見らり、％また、実施例６では、熱可塑性樹脂
が固くて膣〈なり、トナー製造時において微粉を生じや
すい傾向が見られた。The DBP oil absorption, average particle size (-order particle size), PH, and acid value of the thermoplastic resin of the black colorant in Examples 1 to 6 and Comparative Examples 1 to 10 above, and the developer The initial charge amounts are listed in Table 1 and shown on the next page. In the above examples, there is no practical problem in any of them, but in Example 8, there is a tendency to cause toner scattering to some extent. Furthermore, in Example 6, the thermoplastic resin was hard and rough, and there was a tendency to generate fine powder during toner production.

また、酸価を種々変更してみたところ、上記問題を実用
上回避する上から、酸価を２〜ダＳにすることが望まし
く、殊に、上２問題を確実に回避する念めには、酸価を
ｇ〜２Ｓにすることが好適であることが明らかであった
。In addition, after trying various changes in the acid value, we found that in order to practically avoid the above problems, it is desirable to set the acid value to between 2 and 2S.Especially, in order to avoid the above two problems reliably, It was clear that it is suitable to set the acid value to g to 2S.

また、カーボンブラックにおいても、ＤＢＰ吸油量が３
０ｔｌｌ／１００１　を越えると定着画像中におけるカ
ーボンブラックどうしの凝集の問題炉′発生し、そして
、平均粒子径（−次粒子径）がり０隼未満になると初期
帯電量が低下しやすくなる欠点があシ、更に、ＰＨが６
．０を越えるとトナー中でのカーボンブラックの分散が
不均一になり、現像画像の画質劣化をもたらすばかりで
なく、コピー繰返しに伴うトナー帯電量が大幅に変動し
やすぐなることも別途確認されておｐ１本発明のカーボ
ンブラックとしては、ＤＢＰ吸油量が３０ｔｘｌ／１０
０９以下で、平均粒子径がりＯｍμ以上、かつ、ＰＨが
ｇ、θ以下にする必要のあることが明らかであった。Also, in carbon black, the DBP oil absorption is 3
If it exceeds 0tll/1001, the problem of agglomeration of carbon black in the fixed image will occur, and if the average particle size (-order particle size) becomes less than 0tll/1001, the initial charge amount will tend to decrease. Shi, furthermore, the pH is 6
．． It has been separately confirmed that if it exceeds 0, the dispersion of carbon black in the toner becomes uneven, which not only causes deterioration in the image quality of the developed image, but also causes the toner charge amount to fluctuate significantly with repeated copying. P1 The carbon black of the present invention has a DBP oil absorption of 30txl/10
09 or less, the average particle diameter should be Omμ or more, and the pH should be g, θ or less.

代理人　弁理士　北　村　修 手続補正書 特許庁　長官　殿 ２、発明の名称 静電潜像現像用トナー ３　補正をする者 事件との関保　特　許出願人 住所　大阪府大阪市東区安土町−丁目３０番地大阪国際
ビル 名称　（６０７）　ミノルタカメラ株式会社４代理人 昭和　年　月　日（発送日） ７、補正の内容 ＋ｌ）　明細書中、第６負第２行目の「（チタン工業社
製）」の後に「２００部と」を挿入する。Agent Patent Attorney Kitamura Commissioner of the Patent Office for amendments 2 Name of the invention Toner for developing electrostatic latent images 3 Connection with the case of the person making the amendment Patent applicant address Azuchi-cho-chome, Higashi-ku, Osaka-shi, Osaka Prefecture No. 30 Osaka Kokusai Building Name (607) Minolta Camera Co., Ltd. 4th Agent Showa Year, Month, Day (Delivery date) 7. Contents of amendment + l) "(Manufactured by Titanium Kogyo Co., Ltd.)" in the 6th negative 2nd line of the specification ” and then insert “200 copies.”

（２）同、第１頁第７２行目の１−調整した。」を「調
製した。」に訂正する。(2) Same as above, page 1, line 72, 1-Adjusted. " was corrected to "prepared."

（３）同、第１／頁第２行目の「ｎ−グチル」を「ｎ−
ブチル」に訂正する。(3) Same, ``n-butyl'' in the second line of page 1 is changed to ``n-
butyl”.

Claims (1)

【特許請求の範囲】[Claims] ポリエステル樹脂を主体とする熱可塑性樹脂と黒色着色
剤を主成分とする静電潜像現像用トナーにおいて、前記
黒色着色剤として、ＤＢＰ啜油食油量ｏｍｖｉｏｏｙ以
下で、平均粒子径（−次粒子径）が’ｔｔｔ　ｏ　ｍμ
以上、かつ、ＰＨが乙、０以下のカーボンブラックを含
有する静電潜像現像用トナー。In a toner for developing an electrostatic latent image whose main components are a thermoplastic resin mainly composed of a polyester resin and a black colorant, the black colorant is DBP sour oil in an amount of omviooy or less, and an average particle size (-order particle size). ) is 'ttt o mμ
A toner for developing an electrostatic latent image, which contains carbon black having a pH of O and 0 or less.