JP2001265059A - Method for manufacturing toner - Google Patents
Method for manufacturing tonerInfo
- Publication number
- JP2001265059A JP2001265059A JP2000073280A JP2000073280A JP2001265059A JP 2001265059 A JP2001265059 A JP 2001265059A JP 2000073280 A JP2000073280 A JP 2000073280A JP 2000073280 A JP2000073280 A JP 2000073280A JP 2001265059 A JP2001265059 A JP 2001265059A
- Authority
- JP
- Japan
- Prior art keywords
- toner
- mass
- parts
- water
- colored polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Developing Agents For Electrophotography (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電子印刷の如き画
像形成方法において、静電荷像を現像するためのトナ
ー、または、トナージェット方式の画像形成方法におけ
るトナー定着画像を形成するためのトナーの製造方法に
関し、特に、トナー像を転写材の如きプリントシートに
加熱定着させる定着方式に供されるトナーの製造方法に
関する。The present invention relates to a toner for developing an electrostatic image or a toner for forming a toner-fixed image in a toner jet image forming method in an image forming method such as electronic printing. More particularly, the present invention relates to a method for producing a toner used in a fixing method in which a toner image is heated and fixed on a print sheet such as a transfer material.
【０００２】[0002]
【従来の技術】電子写真法は米国特許第２，２９７，６
９１号明細書等に記載されている如く、多数の方法が知
られており、一般には光導電性物質を利用し、種々の手
段で感光体上に電気的潜像を形成し、次いで該潜像をト
ナーと呼ばれる着色樹脂組成物からなる微粒子を用いて
現像し、必要に応じて、感光体上から紙等の転写材にト
ナー像を転写した後、加熱、圧力、或いは溶剤蒸気等に
より転写材上に定着させて、複写物やプリントを得てい
る。また、上記の方法において、トナーを用いて潜像を
現像する方法や、或いはトナー像を転写材上に定着する
方法としては、従来より各種の方法が提案され、それぞ
れの画像形成プロセスに適した方法が採用されている。2. Description of the Prior Art Electrophotography is disclosed in U.S. Pat. No. 2,297,6.
As described in, for example, US Pat. No. 91/91, a number of methods are known. Generally, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means, and then the latent image is formed. The image is developed using fine particles of a colored resin composition called a toner, and if necessary, the toner image is transferred from a photoreceptor to a transfer material such as paper, and then transferred by heating, pressure, or solvent vapor. They are fixed on materials to obtain copies and prints. Further, in the above method, various methods have been conventionally proposed as a method of developing a latent image using a toner or a method of fixing a toner image on a transfer material, and the method is suitable for each image forming process. The method has been adopted.
【０００３】さらに、電気的潜像を現像するために用い
られるトナーは、従来、一般的には、熱可塑性樹脂中に
染料及び顔料の如き着色剤を溶融混合させ、これらの材
料を均一に分散した後、微粉砕装置により微粉砕物を
得、その後、微粉砕物を分級機を用いて分級し、所望の
粒径を有するトナー（樹脂着色剤分散体）を得る、所謂
粉砕法によって製造されている。Further, conventionally, a toner used for developing an electric latent image is generally prepared by melting and mixing a coloring agent such as a dye and a pigment in a thermoplastic resin, and uniformly dispersing these materials. After that, a finely pulverized product is obtained by a finely pulverizing device, and then the finely pulverized product is classified using a classifier to obtain a toner (resin colorant dispersion) having a desired particle size. ing.
【０００４】上記の粉砕法によるトナーの製造方法によ
れば、かなり優れたトナーを製造し得るが、ある種の制
限、即ちトナー用材料の選択範囲に制限がある。例えば
樹脂着色剤分散体が十分に脆く、経済的に可能な製造装
置で微粉砕し得るものでなくてはならない。ところが、
こういった要求を満たすために樹脂着色剤分散体を脆く
すると、実際に高速で微粉砕した場合に形成された粒子
の粒径範囲が広くなり易く、特に比較的大きな割合の微
粒子がこれに含まれるという問題が生ずる。さらに、こ
のように脆性の高い材料は、複写機等現像用に使用する
際、さらなる微粉砕ないしは粉化を受け易い。また、こ
の方法では、着色剤等の固体微粒子を樹脂中へ完全に均
一に分散することは困難であり、その分散の度合によっ
ては、カブリの増大、画像濃度の低下や混色性・透明性
の不良の原因となるので、分散に注意を払わなければな
らない。また、破断面に着色剤が露出することにより、
現像特性に変動を引き起こす場合もある。According to the above-mentioned method for producing a toner by a pulverization method, a considerably excellent toner can be produced, but there is a certain limitation, that is, a selection range of a toner material is limited. For example, the resin colorant dispersion must be sufficiently brittle and capable of being pulverized with economically feasible manufacturing equipment. However,
When the resin colorant dispersion is made brittle to satisfy these requirements, the particle size range of the particles formed when actually pulverized at a high speed tends to be widened, and particularly a relatively large proportion of the fine particles is included in this. The problem arises. Further, such a highly brittle material is liable to be further pulverized or powdered when used for development in a copying machine or the like. Further, in this method, it is difficult to completely and uniformly disperse solid fine particles such as a colorant in a resin, and depending on the degree of the dispersion, an increase in fog, a decrease in image density, and color mixing / transparency are difficult. Attention must be paid to dispersion, as it will cause defects. Also, by exposing the colorant to the fracture surface,
In some cases, the development characteristics may fluctuate.
【０００５】一方、これら粉砕法によるトナーの問題点
を克服するため、特公昭３６−１０２３１号、特公昭４
３−１０７９９号及び特公昭５１−１４８９５号公報等
に、懸濁重合法トナーやその製造方法が提案されてい
る。例えば、懸濁重合法においては、重合性単量体、着
色剤、重合開始剤さらに必要に応じて架橋剤、荷電制御
剤、その他添加剤を均一に溶解又は分散せしめて重合性
単量体組成物を作製した後、該単量体組成物を分散安定
剤を含有する連続相、例えば水相中に適当な撹拌機を用
いて分散させて、同時に重合反応を行って、所望の粒径
を有するトナー粒子を得ている。On the other hand, in order to overcome the problems of the toner by these pulverization methods, Japanese Patent Publication No. 36-10231 and Japanese Patent Publication No.
JP-A-3-10799 and JP-B-51-14895 have proposed a suspension polymerization method toner and a method for producing the same. For example, in the suspension polymerization method, a polymerizable monomer, a colorant, a polymerization initiator and, if necessary, a crosslinking agent, a charge control agent, and other additives are uniformly dissolved or dispersed to form a polymerizable monomer composition. After preparing the product, the monomer composition is dispersed in a continuous phase containing a dispersion stabilizer, for example, an aqueous phase using a suitable stirrer, and simultaneously a polymerization reaction is performed to obtain a desired particle size. Toner particles are obtained.
【０００６】このような重合方法を利用したトナーの製
造方法は、粉砕工程を含まないため、粉砕方法によって
製造する場合のように、トナーの形成材料に脆性が要求
されることがないので、軟質の材料を使用することがで
きる。また、分級工程の省略をも可能にするため、エネ
ルギーの節約、製造時間の短縮、工程収率の向上等、コ
スト削減効果が大きい。A method for producing a toner utilizing such a polymerization method does not include a pulverizing step, and therefore, unlike the case of producing by a pulverizing method, the material for forming the toner does not require brittleness. Materials can be used. In addition, since the classification step can be omitted, the cost reduction effect is large, such as saving energy, shortening the manufacturing time, and improving the process yield.
【０００７】また、近年の複写機やプリンターの高画質
化、フルカラー化、省エネルギー化等トナー自体の多機
能化が要求されている。例えば、高画質化にともない高
解像度・デジタル方式に対応するトナー粒子の微小粒径
化、フルカラー化にともなうＯＨＰ画像の透明性の向
上、省エネルギー化にともなう低温定着化に対応するた
めトナー中に低軟化点物質の含有、転写材への転写効率
の向上に有効であるトナー粒子の形状化等が要求されて
おり、これらの要求を実現する手段として重合法による
トナーが挙げられる。Further, in recent years, the multifunction of the toner itself has been demanded, such as high image quality, full color, and energy saving of copying machines and printers. For example, to reduce toner particle size to support high resolution and digital system with higher image quality, to improve transparency of OHP image due to full colorization, and to reduce toner concentration to support low temperature fixing due to energy saving. It is required to contain a softening point substance and to shape toner particles which are effective for improving transfer efficiency to a transfer material. As a means for achieving these demands, there is a toner by a polymerization method.
【０００８】フルカラー画像用のトナーに用いる荷電制
御剤としては、カルボキシル基を含有する化合物が良
く、重合トナーの場合、重合性単量体中に分散させて用
いられる。色の影響を考慮すると、無色または、白色ま
たは淡色の結晶状態のものが好ましく、特に、アルキル
サリチル酸の金属錯体または、錯塩または、錯体と錯塩
の混合物がカラートナー用に好ましく用いられる。As a charge control agent used for a toner for a full-color image, a compound containing a carboxyl group is preferable, and in the case of a polymerized toner, it is used by dispersing it in a polymerizable monomer. Taking into account the effect of color, a colorless, white or light-colored crystalline state is preferable, and a metal complex or a complex salt of an alkylsalicylic acid or a mixture of a complex and a complex salt is particularly preferably used for a color toner.
【０００９】しかしながら、重合法においては、水中で
の造粒・重合工程が必要となり、その際、重合性単量体
中に分散あるいは溶解した物質が水に対して溶解性を有
する場合、あるいは不安定な場合には、その物質が水中
に溶解し、溶解した分解不純物がトナー表面に付着する
ため、製造工程、特に重合終了後の洗浄工程の条件によ
り、トナーの帯電特性や、環境特性に変化を起こすこと
が明らかになった。However, in the polymerization method, a granulation / polymerization step in water is required. At this time, when the substance dispersed or dissolved in the polymerizable monomer has solubility in water, When stable, the substance dissolves in water, and the dissolved decomposition impurities adhere to the toner surface.Therefore, the charging characteristics and environmental characteristics of the toner change depending on the conditions of the manufacturing process, especially the washing process after polymerization is completed. It became clear that it would cause.
【００１０】一般に工業的に用いられる水は、蒸留法、
イオン交換法、逆浸透法、ろ過法などによって、不純物
が取り除かれた水が挙げられ、トナー合成における水洗
浄工程で用いる水も同様である。[0010] Generally, water used industrially is obtained by distillation,
Examples of the water include water from which impurities have been removed by an ion exchange method, a reverse osmosis method, a filtration method, and the like. The same applies to water used in a water washing step in toner synthesis.
【００１１】しかし、本発明者が、検討を行った結果、
Ｎａ+，Ｋ+，Ｍｇ2+及びＣａ2+の総含有量が５ｍｇ／リ
ットル未満の水で洗浄した場合の乾燥後のトナーは、高
温高湿環境下に放置すると、帯電性が低下する現象が明
らかになった。However, as a result of the study by the present inventor,
A phenomenon in which the toner after drying when washed with water having a total content of Na + , K + , Mg 2+, and Ca 2+ of less than 5 mg / liter, has a reduced chargeability when left in a high-temperature, high-humidity environment. Was revealed.
【００１２】一方、Ｎａ+，Ｋ+，Ｍｇ2+及びＣａ2+の総
含有量が１０ｍｇ／リットル以上の水のみで洗浄した場
合には、乾燥後のトナー表面に残存するアルキルサリチ
ル酸の金属錯体または、錯塩または、錯体と錯塩の混合
物から起因する化合物の量が低減し、初期より、トナー
の帯電性が低下する現象が明らかになった。また、この
場合、イオンの含有量や水温によって、乾燥後のトナー
表面に残存するアルキルサリチル酸の金属錯体または、
錯塩または、錯体と錯塩の混合物から起因する化合物の
量の低減度合が変動することがわかった。On the other hand, when washing is carried out only with water having a total content of Na + , K + , Mg 2+ and Ca 2+ of 10 mg / l or more, the metal complex of alkyl salicylic acid remaining on the dried toner surface Alternatively, the amount of the compound derived from the complex salt or the mixture of the complex and the complex salt was reduced, and the phenomenon that the chargeability of the toner was reduced from the beginning was clarified. Further, in this case, depending on the ion content and the water temperature, a metal complex of alkyl salicylic acid remaining on the toner surface after drying or
It has been found that the degree of reduction in the amount of the compound resulting from the complex salt or the mixture of the complex and the complex salt varies.
【００１３】[0013]
【発明が解決しようとする課題】本発明の目的は、上述
のごとき問題点を解決したトナーの製造方法を提供する
ことにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a toner which has solved the above-mentioned problems.
【００１４】詳しくは、本発明の目的は、懸濁重合法に
よるトナーの製造において、荷電制御剤などの添加剤に
起因する水中への溶解物の乾燥後のトナー表面への存在
状態を制御し、帯電性に優れたトナーの製造方法を提供
することにある。More specifically, an object of the present invention is to control the presence state of a dissolved substance in water due to additives such as a charge control agent on the toner surface after drying in the production of a toner by a suspension polymerization method. Another object of the present invention is to provide a method for producing a toner having excellent chargeability.
【００１５】[0015]
【課題を解決するための手段】そこで本発明者は、鋭意
検討を行った結果、重合終了後の酸洗浄工程後の洗浄工
程において、その水に含有されるイオン成分に着目し、
酸洗浄工程後の水洗浄工程を、金属陽イオンの総含有量
が５ｍｇ／リットル未満の水で洗浄し、洗浄排水中に分
散安定剤由来の金属陽イオンの総含有量が５ｍｇ／リッ
トル未満になった後に、一定量のアルカリ金属及びアル
カリ土類金属イオン（Ｎａ+，Ｋ+，Ｍｇ 2+及びＣａ2+）
を含有する水で行うことにより、荷電制御剤であるアル
キルサリチル酸の金属錯体または、錯塩または、錯体と
錯塩の混合物の分解生成物や他の添加剤の水中への溶解
物の乾燥後のトナー表面への存在状態を制御した、帯電
性に優れたトナーの製造方法を提供することを見出し、
本発明に達した。Means for Solving the Problems Accordingly, the present inventor has earnestly studied.
As a result of the study, the cleaning process after the acid cleaning process
In the process, focusing on the ionic components contained in the water,
The water washing step after the acid washing step is performed according to the total content of metal cations.
Is washed with less than 5 mg / liter of water, and
The total content of metal cations derived from the dispersion stabilizer is 5 mg / liter.
After the pressure drops to less than
Potassium earth metal ion (Na+, K+, Mg 2+And Ca2+)
By using water containing
With a metal complex or complex salt or complex of kirsalicylic acid
Dissolution of decomposition products of complex salts and other additives in water
Control the state of presence of toner on the toner surface after drying
To provide a method for producing a toner having excellent properties,
The present invention has been reached.
【００１６】即ち、本発明は、少なくとも重合性単量体
と着色剤とを含有する重合性単量体組成物を、水系分散
安定剤中で懸濁させて重合を行い、着色重合体粒子を生
成した後、酸洗浄を行い、脱水後、金属陽イオンの総含
有量が５ｍｇ／リットル未満の水で洗浄し、洗浄排水中
に分散安定剤由来の金属陽イオンの総含有量が５ｍｇ／
リットル未満になった後に、Ｎａ+，Ｋ+，Ｍｇ2+及びＣ
ａ2+の総含有量が１０乃至１５０ｍｇ／リットルの水を
注水し、脱水し、得られた湿潤着色重合体粒子を乾燥す
ることを特徴とするトナーの製造方法である。That is, according to the present invention, a polymerizable monomer composition containing at least a polymerizable monomer and a colorant is suspended in an aqueous dispersion stabilizer and polymerized to form a colored polymer particle. After the formation, acid washing is performed, and after dehydration, washing is performed with water having a total content of metal cations of less than 5 mg / l, and the total content of metal cations derived from the dispersion stabilizer in the washing wastewater is 5 mg / liter.
After being less than 1 liter, Na + , K + , Mg 2+ and C
This is a method for producing a toner, characterized by injecting water having a total content of a 2+ of 10 to 150 mg / liter, dehydrating, and drying the obtained wet colored polymer particles.
【００１７】[0017]
【発明の実施の形態】以下、本発明のトナーの製造方法
の好ましい形態を挙げて、本発明を詳細に説明する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to preferred embodiments of a method for producing a toner of the present invention.
【００１８】本発明のトナー製造方法においては、以下
の如き製造方法によって具体的にトナーを製造すること
が可能である。In the toner manufacturing method of the present invention, a toner can be specifically manufactured by the following manufacturing method.
【００１９】即ち、重合性単量体中に低軟化点物質から
なる離型剤，着色剤，荷電制御剤，重合開始剤その他の
添加剤を加え、ホモジナイザー，超音波分散機等によっ
て均一に溶解又は分散せしめた単量体系を、分散安定剤
を含有する水相中に通常の撹拌機またはクリアミキサ
ー，ホモミキサー，ホモジナイザー等により分散せしめ
る。好ましくは単量体液滴が所望のトナー粒子のサイズ
を有するように撹拌速度，時間を調整し、造粒する。そ
の後は分散安定剤の作用により、粒子状態が維持され、
且つ粒子の沈降が防止される程度の撹拌を行えば良い。
重合温度は４０℃以上、一般的には５０〜９０℃の温度
に設定して重合を行うのが良い。また、重合反応後半に
昇温しても良く、更に、トナー定着時の臭いの原因等と
なる未反応の重合性単量体、副生成物等を除去するため
に反応後半、又は、反応終了後に一部水系媒体を留去し
ても良い。懸濁重合法においては、通常単量体系１００
質量部に対して水３００〜３０００質量部を分散媒とし
て使用するのが好ましい。That is, a release agent, a colorant, a charge control agent, a polymerization initiator and other additives comprising a low softening point substance are added to the polymerizable monomer, and the mixture is uniformly dissolved by a homogenizer, an ultrasonic disperser or the like. Alternatively, the dispersed monomer system is dispersed in an aqueous phase containing a dispersion stabilizer using a conventional stirrer, a clear mixer, a homomixer, a homogenizer, or the like. Preferably, the agitation speed and time are adjusted so that the monomer droplets have the desired size of the toner particles, and granulation is performed. After that, due to the action of the dispersion stabilizer, the particle state is maintained,
In addition, stirring may be performed to such an extent that settling of particles is prevented.
The polymerization is preferably performed at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. Further, the temperature may be raised in the latter half of the polymerization reaction, and further, in order to remove unreacted polymerizable monomers and by-products which cause odor at the time of fixing the toner, the second half of the reaction, or the end of the reaction. Later, a part of the aqueous medium may be distilled off. In the suspension polymerization method, the monomer system 100
It is preferable to use 300 to 3000 parts by weight of water with respect to parts by weight as a dispersion medium.
【００２０】本発明に係る重合トナーにおいて、特に分
散安定剤を用いた懸濁重合を利用する場合用いる分散安
定剤としては、リン酸三カルシウム，リン酸マグネシウ
ム，リン酸アルミニウム，リン酸亜鉛，炭酸カルシウ
ム，炭酸マグネシウム，水酸化カルシウム，水酸化マグ
ネシウム，水酸化アルミニウム，メタケイ酸カルシウ
ム，硫酸カルシウム，硫酸バリウム，ベントナイト，シ
リカ，アルミナ等の無機化合物が挙げられる。これらの
分散安定剤は、重合性単量体１００質量部に対して０．
２〜２０質量部を使用することが好ましい。In the polymerized toner according to the present invention, particularly when using suspension polymerization using a dispersion stabilizer, dispersion stabilizers used include tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, and carbonate. Examples include inorganic compounds such as calcium, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, and alumina. These dispersion stabilizers are used in an amount of 0.1 to 100 parts by mass of the polymerizable monomer.
It is preferable to use 2 to 20 parts by mass.
【００２１】これらの無機化合物の分散安定剤を用いる
場合、市販のものをそのまま用いても良いが、細かい粒
子を得るために、分散媒中にて該無機化合物を生成させ
ても良い。例えば、リン酸三カルシウムの場合、高撹拌
下において、リン酸ナトリウム水溶液と塩化カルシウム
水溶液を混合すると良い。When using these inorganic compound dispersion stabilizers, commercially available ones may be used as they are, but in order to obtain fine particles, the inorganic compounds may be formed in a dispersion medium. For example, in the case of tricalcium phosphate, an aqueous sodium phosphate solution and an aqueous calcium chloride solution may be mixed under high stirring.
【００２２】また、これら分散安定剤の微細な分散の為
に、０．００１〜０．１質量部の界面活性剤を使用して
もよい。これは上記分散安定剤の初期の作用を促進する
為のものであり、その具体例としては、ドデシルベンゼ
ン硫酸ナトリウム，テトラデシル硫酸ナトリウム，ぺン
タデシル硫酸ナトリウム，オクチル硫酸ナトリウム，オ
レイン酸ナトリウム，ラウリル酸ナトリウム，ステアリ
ン酸カリウム，オレイン酸カルシウム等が挙げられる。For fine dispersion of these dispersion stabilizers, 0.001 to 0.1 parts by mass of a surfactant may be used. This is to promote the initial action of the above-mentioned dispersion stabilizer, and specific examples thereof include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, and sodium laurate. , Potassium stearate, calcium oleate and the like.
【００２３】本発明においては、重合が終了し、冷却し
た着色重合体粒子スラリーに酸を加え、撹拌し、無機化
合物の分散安定剤を溶解させた後、固液分離することに
より、無機化合物の分散安定剤を除去する。In the present invention, after the polymerization is completed, an acid is added to the cooled colored polymer particle slurry, the mixture is stirred, and the dispersion stabilizer of the inorganic compound is dissolved. Remove the dispersion stabilizer.
【００２４】用いる酸としては、塩酸、硫酸、硝酸、臭
化水素酸、クロム酸、ヨウ化水素酸、亜硫酸、クエン
酸、酢酸、ホウ酸、炭酸、フッ酸、リン酸、亜硝酸等が
挙げられる、塩酸、硫酸、硝酸等が価格や取扱いの点で
好ましい。Examples of the acid used include hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid, chromic acid, hydroiodic acid, sulfurous acid, citric acid, acetic acid, boric acid, carbonic acid, hydrofluoric acid, phosphoric acid, and nitrous acid. Hydrochloric acid, sulfuric acid, nitric acid, etc. are preferred in terms of price and handling.
【００２５】また、酸添加後のｐＨは、３以下、より好
ましくは２以下が無機化合物の分散安定剤の除去効果が
高く、好ましい。The pH after addition of the acid is preferably 3 or less, more preferably 2 or less, because the effect of removing the inorganic compound dispersion stabilizer is high.
【００２６】酸洗浄の時間は、数１０分から３時間が好
ましく、１０分以下では、無機化合物の分散安定剤の除
去効果が低く、３時間以上行っても、それ以上の除去効
果は得られない。The acid washing time is preferably several tens of minutes to 3 hours, and if it is 10 minutes or less, the effect of removing the inorganic compound dispersion stabilizer is low, and even if it is carried out for 3 hours or more, no further effect can be obtained. .
【００２７】固液分離は、市販の固液分離装置で行える
が、後工程の洗浄をケーキヘの注水で行うことができ、
乾燥装置へ供給できるケーキを排出することが容易な、
加圧ろ過方式の装置、例えば、ＳＰフィルター（（株）
ニッセン製）や、ＫＦフィルター（三進製作所製）、フ
ィルタープレス（各社）等が好ましく用いられる。The solid-liquid separation can be performed with a commercially available solid-liquid separation device, but the post-process washing can be performed by pouring water into the cake.
It is easy to discharge the cake that can be supplied to the drying device,
Apparatus of pressure filtration system, for example, SP filter (Ltd.)
Nissen), KF filters (manufactured by Sanshin Seisakusho), filter presses (manufacturers) and the like are preferably used.
【００２８】さらに、固液分離装置中に残った着色重合
体粒子ケーキに、金属陽イオンの総含有量が５ｍｇ／リ
ットル未満の水を注水して洗浄し、洗浄排水中に分散安
定剤由来の金属陽イオンの総含有量が５ｍｇ／リットル
未満になった後に、アルカリ金属及びアルカリ土類金属
イオン（Ｎａ+，Ｋ+，Ｍｇ2+及びＣａ2+）の総含有量が
２０乃至１５０ｍｇ／リットルの水を注水する。このよ
うな注水・洗浄によって、着色重合体粒子ケーキに付着
した無機化合物の分散安定剤を除去すると同時に、荷電
制御剤であるアルキルサリチル酸の金属錯体または、錯
塩または、錯体と錯塩の混合物に起因する水中への溶解
物の乾燥後のトナー表面への存在状態を制御する。Further, the colored polymer particle cake remaining in the solid-liquid separation device is washed by pouring water having a total content of metal cations of less than 5 mg / liter, and the water derived from the dispersion stabilizer is contained in the washing wastewater. After the total content of metal cations is less than 5 mg / l, the total content of alkali metal and alkaline earth metal ions (Na + , K + , Mg 2+ and Ca 2+ ) is 20-150 mg / l Pour water. By such water injection and washing, the dispersion stabilizer of the inorganic compound attached to the colored polymer particle cake is removed, and at the same time, the metal complex or the complex salt or the mixture of the complex and the complex salt of the alkylsalicylic acid as the charge control agent is caused. The presence state of the dissolved matter in water on the toner surface after drying is controlled.
【００２９】なお、着色重合体粒子ケーキに水を加え、
撹拌し、リスラリーした後に、再度固液分離装置で固液
分離をすれば、除去効果は高いが、工程が煩雑になりコ
スト上の問題から、固液分離装置中に残った着色重合体
粒子ケーキに、水を注水し、脱水することが望ましい。Water is added to the colored polymer particle cake,
If the solid-liquid separation is performed again by the solid-liquid separation device after stirring and reslurry, the removal effect is high, but the process becomes complicated and cost problems cause the colored polymer particle cake remaining in the solid-liquid separation device. It is desirable to pour water and dehydrate.
【００３０】洗浄水量は、乾燥後のトナー中に分散安定
剤由来の金属イオンが１００ｍｇ／ｋｇ以下の存在にな
るまで必要であり、初期に注水洗浄する金属陽イオンの
総含有量が５ｍｇ／リットル未満の水の量は、洗浄排水
中に分散安定剤由来の金属陽イオンの総含有量が５ｍｇ
／リットル未満になるまで必要であり、固液分離をした
スラリー１質量部に対して１乃至５質量部に相当する。The amount of washing water is required until 100 mg / kg or less of metal ions derived from the dispersion stabilizer is present in the dried toner, and the total content of metal cations to be initially washed with water is 5 mg / liter. The amount of water less than the total content of metal cations derived from the dispersion stabilizer in the washing wastewater is 5 mg.
Per liter / liter, which corresponds to 1 to 5 parts by mass with respect to 1 part by mass of the slurry subjected to solid-liquid separation.
【００３１】さらに、追加して洗浄を行う、Ｎａ+，
Ｋ+，Ｍｇ2+及びＣａ2+の総含有量が２０乃至１５０ｍ
ｇ／リットル（より好ましくは７０乃至１２０ｍｇ／リ
ットル）の水の量は、固液分離をしたスラリー１質量部
に対して０．１乃至１．０質量部が好ましい。[0031] In addition, to add to the wash, Na +,
The total content of K + , Mg 2+ and Ca 2+ is 20 to 150 m
The amount of water of g / liter (more preferably 70 to 120 mg / liter) is preferably 0.1 to 1.0 part by mass per 1 part by mass of the slurry subjected to solid-liquid separation.
【００３２】０．１質量部より少ない場合には、追加洗
浄の効果が現われにくく、また、１．０質量部より多い
場合には、再度、荷電制御剤であるアルキルサリチル酸
の金属錯体または、錯塩または、錯体と錯塩の混合物の
分解生成物や他の添加剤の水中への溶解物を取り除いて
しまうことになり、過剰に減少してしまうため、トナー
として帯電性が悪くなる。When the amount is less than 0.1 part by mass, the effect of additional washing is hardly exhibited, and when the amount is more than 1.0 part by mass, a metal complex or a complex salt of an alkylsalicylic acid as a charge controlling agent is again used. Alternatively, the decomposition product of the mixture of the complex and the complex salt and the dissolved matter of other additives in water are removed, and the amount is excessively reduced, so that the chargeability of the toner is deteriorated.
【００３３】本発明によるトナーは、高画質化のためよ
り微小な潜像ドットを忠実に現像するために、トナーも
より微小粒径の、具体的にはコールターカウンターによ
り測定された重量平均径が４〜１０μｍで個数変動係数
が３５％以下のトナーが最も好ましい。重量平均径が４
μｍ未満のトナーにおいては、転写効率の悪さから感光
体や中間転写体上に転写残トナーが多く発生し、カブ
リ，転写不良に基づく画像の不均一ムラの原因となり好
ましくない。また、トナーの重量平均径が１０μｍを超
える場合には、部材への融着が起きやすく、トナーの個
数変動係数が３５％を超えると更にその傾向が強まり問
題となる。In order to faithfully develop finer latent image dots for higher image quality, the toner according to the present invention also has a finer particle diameter, specifically, a weight average diameter measured by a Coulter counter. The toner having a number variation coefficient of 4 to 10 μm and a number variation coefficient of 35% or less is most preferable. Weight average diameter of 4
In the case of a toner having a particle diameter of less than μm, a large amount of untransferred toner is generated on a photoreceptor or an intermediate transfer member due to poor transfer efficiency, which causes ununiform unevenness of an image due to fogging or poor transfer. Further, when the weight average diameter of the toner exceeds 10 μm, fusion to a member is likely to occur, and when the coefficient of variation of the number of toners exceeds 35%, the tendency is further increased, which causes a problem.
【００３４】本発明に係るトナーに用いられる低軟化点
物質としては、ＡＳＴＭ Ｄ３４１８−８に準拠し測定
された主体極大ピーク値が、４０〜９０℃を示す化合物
が好ましい。極大ピークが４０℃未満であると低軟化点
物質の自己凝集力が弱くなり、結果として耐高温オフセ
ット性が弱くなりフルカラートナーには好ましくない。
一方極大ピークが９０℃を超えると定着温度が高くな
り、定着画像表面を適度に平滑化せしめることが困難と
なり混色性の点から好ましくない。更に直接重合方法に
よりトナーを得る場合においては、水系で造粒，重合を
行うため極大ピーク値の温度が高いと、主に造粒中に低
軟化点物質が析出してきて懸濁系を阻害するため好まし
くない。As the low softening point substance used in the toner according to the present invention, a compound having a main maximum peak value of 40 to 90 ° C. measured according to ASTM D3418-8 is preferable. If the maximum peak is less than 40 ° C., the self-cohesive force of the low softening point substance becomes weak, and as a result, the hot offset resistance becomes weak, which is not preferable for a full color toner.
On the other hand, if the maximum peak exceeds 90 ° C., the fixing temperature becomes high, and it is difficult to appropriately smooth the surface of the fixed image, which is not preferable from the viewpoint of color mixing. Further, in the case of obtaining a toner by a direct polymerization method, when the temperature of the maximum peak value is high due to granulation and polymerization in an aqueous system, a substance having a low softening point is mainly deposited during granulation, and the suspension system is hindered. Therefore, it is not preferable.
【００３５】上記の極大ピーク値の温度の測定には、例
えばパーキンエルマー社製ＤＳＣ−７を用いる。装置検
出部の温度補正はインジウムと亜鉛の融点を用い、熱量
の補正についてはインジウムの融解熱を用いる。サンプ
ルは、アルミニウム製パンを用い対照用に空パンをセッ
トし、昇温速度１０℃／分で測定を行う。For the measurement of the temperature of the maximum peak value, for example, DSC-7 manufactured by Perkin Elmer Co., Ltd. is used. The temperature correction of the device detection unit uses the melting points of indium and zinc, and the heat quantity correction uses the heat of fusion of indium. For the sample, an aluminum pan is used, an empty pan is set as a control, and measurement is performed at a heating rate of 10 ° C./min.
【００３６】具体的にはパラフィンワックス，ポリオレ
フィンワックス，フィッシャートロピッシュワックス，
アミドワックス，高級脂肪酸，エステルワックス及びこ
れらの誘導体又はこれらのグラフト／ブロック化合物等
が利用できる。好ましくは下記一般構造式で示す炭素数
が１０以上の長鎖エステル部分を１個以上有するエステ
ルワックスが、ＯＨＰの透明性を阻害せずに耐高温オフ
セット性に効果を有するので本発明においては特に好ま
しい。本発明に好ましい具体的なエステルワックスの代
表的化合物の構造式を以下に一般構造式，一般構造式
及び一般構造式として示す。Specifically, paraffin wax, polyolefin wax, Fischer-Tropsch wax,
Amide waxes, higher fatty acids, ester waxes and their derivatives or their graft / block compounds can be used. In the present invention, an ester wax having at least one long-chain ester moiety having 10 or more carbon atoms represented by the following general structural formula preferably has an effect on high-temperature offset resistance without inhibiting the transparency of OHP. preferable. The structural formulas of representative compounds of the specific ester wax preferred in the present invention are shown below as a general structural formula, a general structural formula and a general structural formula.
【００３７】[0037]
【化１】 （式中、ａ及びｂは０〜４の整数を示し、ａ＋ｂは４で
あり、Ｒ1及びＲ2は炭素数が１〜４０の有機基を示し、
且つＲ1とＲ2との炭素数差が１０以上である基を示し、
ｎ及びｍは０〜１５の整数を示し、ｎとｍが同時に０に
なることはない。）Embedded image (Where a and b represent an integer of 0 to 4, a + b is 4, R 1 and R 2 represent an organic group having 1 to 40 carbon atoms,
And a group in which the carbon number difference between R 1 and R 2 is 10 or more,
n and m each represent an integer of 0 to 15, and n and m do not become 0 at the same time. )
【００３８】[0038]
【化２】 （式中、ａ及びｂは０〜４の整数を示し、ａ＋ｂは４で
あり、Ｒ1は炭素数が１〜４０の有機基を示し、ｎ及び
ｍは０〜１５の整数を示し、ｎとｍが同時に０になるこ
とはない。）Embedded image (Where a and b represent an integer of 0 to 4, a + b is 4, R 1 represents an organic group having 1 to 40 carbon atoms, n and m each represent an integer of 0 to 15, n And m do not become 0 at the same time.)
【００３９】[0039]
【化３】 （式中、ａ及びｂは０〜３の整数を示し、ａ＋ｂは３以
下であり、Ｒ1及びＲ2は炭素数が１〜４０の有機基を示
し、且つＲ1とＲ2との炭素数差が１０以上である基を示
し、Ｒ3は炭素数が１以上の有機基を示し、ｎ及びｍは
０〜１５の整数を示し、ｎとｍが同時に０になることは
ない。）Embedded image (Wherein a and b each represent an integer of 0 to 3, a + b is 3 or less, R 1 and R 2 each represent an organic group having 1 to 40 carbon atoms, and carbon atoms of R 1 and R 2 A number difference is 10 or more, R 3 represents an organic group having 1 or more carbon atoms, n and m each represent an integer of 0 to 15, and n and m do not become 0 at the same time.)
【００４０】本発明で好ましく用いられるエステルワッ
クスは、硬度０．５〜５．０を有するものが好ましい。
エステルワックスの硬度は、直径２０ｍｍφで厚さが５
ｍｍの円筒形状のサンプルを作製した後、例えば島津製
作所製ダイナミック超微小硬度計（ＤＵＨ−２００）を
用いビッカース硬度を測定した値である。測定条件は、
０．５ｇの荷重で負荷速度が９．６７ｍｍ／秒の条件で
１０μｍ変位させた後１５秒間保持し、得られた打痕形
状を測定しビッカース硬度を求める。硬度が０．５未満
の低軟化点物質では定着器の圧力依存性及びプロセスス
ピード依存性が大きくなり、耐高温オフセット効果の発
現が不十分となりやすく、他方５．０を超える場合では
トナーの保存安定性に乏しく、離型剤自身の自己凝集力
も小さいため同様に耐高温オフセットが不十分となりや
すい。具体的化合物としては、下記化合物が挙げられ
る。The ester wax preferably used in the present invention preferably has a hardness of 0.5 to 5.0.
The hardness of the ester wax is 5mm in diameter and 5mm in thickness.
This is a value obtained by measuring a Vickers hardness using a dynamic ultra-fine hardness tester (DUH-200) manufactured by Shimadzu Corporation after preparing a cylindrical sample having a diameter of mm. The measurement conditions are
After displacing 10 μm under the condition of a load speed of 9.67 mm / sec with a load of 0.5 g and holding it for 15 seconds, the resulting dent shape is measured to determine Vickers hardness. A low softening point substance having a hardness of less than 0.5 has a large dependence on the pressure and process speed of the fixing device, and tends to exhibit insufficient high-temperature offset resistance. Since the stability is poor and the self-cohesive force of the release agent itself is small, similarly, the high-temperature offset resistance tends to be insufficient. Specific compounds include the following compounds.
【００４１】[0041]
【化４】 Embedded image
【００４２】近年フルカラー両面画像の必要性も増して
きており、両面画像を形成せしめる際においては、最初
に表面に形成された転写紙上のトナー像が次に裏面に画
像を形成する時にも定着器の加熱部を再度通過する可能
性があり、よりトナーの耐高温オフセット性を十分に考
慮する必要がある。その為に本発明においては、多量の
低軟化点物質の添加が望ましい。具体的には、低軟化点
物質をトナー中に５〜４０質量％添加することが好まし
い。５質量％未満の添加では、十分な耐高温オフセット
性を示さず、更に両面画像の定着時において裏面の画像
がオフセット現象を示す傾向がある。また４０質量％を
超える場合は、造粒時にトナー粒子同士の合一が起きや
すく、粒度分布の広いものが生成しやすく、本発明には
不適当であった。In recent years, the necessity of full-color double-sided images has been increasing. When forming a double-sided image, the toner image formed on the transfer paper first on the front surface is also used for forming the image on the rear surface. Therefore, it is necessary to sufficiently consider the high-temperature offset resistance of the toner. Therefore, in the present invention, it is desirable to add a large amount of a low softening point substance. Specifically, it is preferable to add a low softening point substance to the toner in an amount of 5 to 40% by mass. When added in an amount of less than 5% by mass, sufficient high-temperature offset resistance is not exhibited, and the image on the back surface tends to exhibit an offset phenomenon when a double-sided image is fixed. On the other hand, when it exceeds 40% by mass, coalescence of toner particles tends to occur at the time of granulation, and a toner having a wide particle size distribution is easily generated, which is not suitable for the present invention.
【００４３】本発明のトナー粒子を製造する方法として
は、特公昭３６−１０２３１号公報、特開昭５９−５３
８５６号公報、特開昭５９−６１８４２号公報に述べら
れている懸濁重合方法を用いて直接トナーを生成する方
法を用いトナーを製造することが可能である。The method for producing the toner particles of the present invention is described in JP-B-36-10231 and JP-A-59-53.
No. 856 and JP-A-59-61842 can be used to produce a toner by using a method of directly producing a toner using the suspension polymerization method.
【００４４】本発明においては、一旦得られた重合粒子
に更に単量体を吸着せしめた後、重合開始剤を用い重合
せしめる所謂シード重合方法も本発明に好適に利用する
ことができる。In the present invention, a so-called seed polymerization method in which a monomer is further adsorbed on the polymer particles once obtained and then polymerized using a polymerization initiator can also be suitably used in the present invention.
【００４５】また、本発明において、定着性の観点から
多量の低軟化点物質をトナーに含有せしめることを考え
ると、必然的に低軟化点物質を外殻樹脂中に内包化せし
める必要がある。低軟化点物質を内包化せしめる具体的
方法としては、水系媒体中での材料の極性を主要単量体
より低軟化点物質の方を小さく設定し、更に少量の極性
の大きな樹脂又は単量体を添加せしめることで低軟化点
物質を外殻樹脂で被覆した所謂コア−シェル構造を有す
るトナーを得ることができる。トナーの粒度分布制御や
粒径の制御は、難水溶性の無機塩や保護コロイド作用を
する分散安定剤の種類や添加量を変える方法や機械的装
置条件、例えばローターの周速，パス回数，撹拌羽根形
状等の撹拌条件や容器形状又は、水溶液中での固形分濃
度等を制御することにより所定の本発明のトナーを得る
ことができる。Further, in the present invention, considering that a large amount of a low softening point substance is contained in a toner from the viewpoint of fixability, it is necessary to enclose the low softening point substance in the outer shell resin. As a specific method for encapsulating the low softening point substance, the polarity of the material in the aqueous medium is set to be smaller for the low softening point substance than for the main monomer, and a small amount of a large polar resin or monomer is used. Is added, a toner having a so-called core-shell structure in which a low softening point substance is coated with an outer shell resin can be obtained. The particle size distribution and the particle size of the toner can be controlled by changing the type or amount of the hardly water-soluble inorganic salt or dispersion stabilizer acting as a protective colloid, or by mechanical device conditions such as the peripheral speed of the rotor, the number of passes, The predetermined toner of the present invention can be obtained by controlling the stirring conditions such as the shape of the stirring blade, the shape of the container, or the solid content concentration in the aqueous solution.
【００４６】本発明においてトナーの断層面を測定する
具体的方法としては、常温硬化性のエポキシ樹脂中にト
ナーを十分分散させた後、温度４０℃の雰囲気中で２日
間硬化させ、得られた硬化物を四三酸化ルテニウム、必
要により四三酸化オスミウムを併用し染色を施した後、
ダイヤモンド歯を備えたミクロトームを用い薄片状のサ
ンプルを切り出し透過電子顕微鏡（ＴＥＭ）を用いトナ
ーの断層形態を測定した。本発明においては、用いる低
軟化点物質と外殻を構成する樹脂との若干の結晶化度の
違いを利用して材料間のコントラストを付けるため、四
三酸化ルテニウム染色法を用いることが好ましい。In the present invention, as a specific method for measuring the tomographic plane of the toner, the toner is obtained by sufficiently dispersing the toner in a room temperature curable epoxy resin and then curing it in an atmosphere at a temperature of 40 ° C. for 2 days. After dyeing the cured product with ruthenium tetroxide, osmium tetroxide, if necessary,
A flaky sample was cut out using a microtome provided with diamond teeth, and the tomographic morphology of the toner was measured using a transmission electron microscope (TEM). In the present invention, it is preferable to use a ruthenium tetroxide dyeing method in order to give a contrast between materials by utilizing a slight difference in crystallinity between the low softening point substance used and the resin constituting the outer shell.
【００４７】上記重合トナーに使用できる重合性単量体
としては、スチレン，ｏ（ｍ−，ｐ−）−メチルスチレ
ン，ｍ（ｐ−）−エチルスチレン等のスチレン系単量
体；（メタ）アクリル酸メチル，（メタ）アクリル酸エ
チル，（メタ）アクリル酸プロピル，（メタ）アクリル
酸ブチル，（メタ）アクリル酸オクチル，（メタ）アク
リル酸ドデシル，（メタ）アクリル酸ステアリル，（メ
タ）アクリル酸ベヘニル，（メタ）アクリル酸２−エチ
ルヘキシル，（メタ）アクリル酸ジメチルアミノエチ
ル，（メタ）アクリル酸ジエチルアミノエチル等の（メ
タ）アクリル酸エステル系単量体；ブタジエン，イソプ
レン，シクロヘキセン，（メタ）アクリロニトリル，ア
クリル酸アミド等のビニル系単量体が好ましく用いられ
る。これらは、単独または一般的には出版物ポリマーハ
ンドブック第２版ＩＩＩ−Ｐ１３９〜１９２（Ｊｏｈｎ
Ｗｉｌｅｙ＆Ｓｏｎｓ社製）に記載の理論ガラス転移
温度（Ｔｇ）が、４０〜７５℃を示すように単量体を適
宜混合し用いられる。理論ガラス転移温度が４０℃未満
の場合には、トナーの保存安定性や現像剤の耐久安定性
の面から問題が生じ、一方７５℃を超える場合は定着点
の上昇をもたらし、特にフルカラートナーの場合におい
ては各色トナーの混色が不十分となり色再現性に乏し
く、更にＯＨＰ画像の透明性を著しく低下させ高画質の
面から好ましくない。The polymerizable monomers usable in the above-mentioned polymerized toner include styrene-based monomers such as styrene, o (m-, p-)-methylstyrene and m (p-)-ethylstyrene; Methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, (meth) acryl (Meth) acrylate monomers such as behenyl acrylate, 2-ethylhexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and diethylaminoethyl (meth) acrylate; butadiene, isoprene, cyclohexene, (meth) Vinyl monomers such as acrylonitrile and acrylamide are preferably used. These can be used alone or generally in the published Polymer Handbook, 2nd edition III-P 139-192 (John
The monomers are appropriately mixed and used so that the theoretical glass transition temperature (Tg) described in (Wiley & Sons) indicates 40 to 75 ° C. If the theoretical glass transition temperature is lower than 40 ° C., problems arise in terms of the storage stability of the toner and the durability stability of the developer. In this case, the color mixture of each color toner is insufficient and the color reproducibility is poor, and the transparency of the OHP image is remarkably reduced, which is not preferable from the viewpoint of high image quality.
【００４８】本発明において、外殻樹脂中に低軟化点物
質を内包化せしめる場合、外殻樹脂の他に更に極性樹脂
を添加せしめることが特に好ましい。本発明に用いられ
る極性樹脂としては、スチレンと（メタ）アクリル酸の
共重合体，マレイン酸共重合体，飽和ポリエステル樹
脂，エポキシ樹脂が好ましく用いられる。該極性樹脂
は、外殻樹脂又は単量体と反応しうる不飽和基を分子中
に含まないものが特に好ましい。不飽和基を有する極性
樹脂を含む場合においては、外殻樹脂層を形成する単量
体と架橋反応が起きフルカラー用トナーとしては、極め
て高分子量になり四色トナーの混色には不利となり好ま
しくない。In the present invention, when a low softening point substance is included in the outer shell resin, it is particularly preferable to add a polar resin in addition to the outer shell resin. As the polar resin used in the present invention, a copolymer of styrene and (meth) acrylic acid, a maleic acid copolymer, a saturated polyester resin, and an epoxy resin are preferably used. It is particularly preferable that the polar resin does not contain an unsaturated group capable of reacting with a shell resin or a monomer in the molecule. When a polar resin having an unsaturated group is contained, a cross-linking reaction occurs with the monomer forming the outer shell resin layer, and as a full-color toner, it becomes extremely high in molecular weight and disadvantageous for color mixing of four-color toner, which is not preferable. .
【００４９】本発明に用いられる着色剤は、黒色着色剤
としてカーボンブラック，磁性体，以下に示すイエロー
／マゼンタ／シアン着色剤を用い黒色に調色されたもの
が利用される。As the colorant used in the present invention, a black colorant which is prepared by using carbon black, a magnetic substance, and a yellow / magenta / cyan colorant shown below as a black colorant is used.
【００５０】イエロー着色剤としては、縮合アゾ化合
物，イソインドリノン化合物，アンスラキノン化合物，
アゾ金属錯体，メチン化合物，アリルアミド化合物に代
表される化合物が用いられる。具体的には、Ｃ．Ｉ．ピ
グメントイエロー１２、１３、１４、１５、１７、６
２、７４、８３、９３、９４、９５、１０９、１１０、
１１１、１２８、１２９、１４７、１６８等が好適に用
いられる。Examples of the yellow colorant include condensed azo compounds, isoindolinone compounds, anthraquinone compounds,
Compounds represented by azo metal complexes, methine compounds and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 6
2, 74, 83, 93, 94, 95, 109, 110,
111, 128, 129, 147, 168 and the like are preferably used.
【００５１】マゼンタ着色剤としては、縮合アゾ化合
物，ジケトピロロピロール化合物，アンスラキノン，キ
ナクリドン化合物，塩基染料レーキ化合物，ナフトール
化合物，ベンズイミダゾロン化合物，チオインジゴ化合
物，ペリレン化合物が用いられる。具体的には、Ｃ．
Ｉ．ピグメントレッド２、３、５、６、７、２３、４
８：２、４８：３、４８：４、５７：１、８１：１、１
２２、１４４、１４６、１６６、１６９、１７７、１８
４、１８５、２０２、２０６、２２０、２２１、２５４
が特に好ましい。As the magenta coloring agent, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds and perylene compounds are used. Specifically, C.I.
I. Pigment Red 2, 3, 5, 6, 7, 23, 4
8: 2, 48: 3, 48: 4, 57: 1, 81: 1, 1
22, 144, 146, 166, 169, 177, 18
4, 185, 202, 206, 220, 221, 254
Is particularly preferred.
【００５２】シアン着色剤としては、銅フタロシアニン
化合物及びその誘導体，アンスラキノン化合物，塩基染
料レーキ化合物等が利用できる。具体的には、Ｃ．Ｉ．
ピグメントブルー１、７、１５、１５：１、１５：２、
１５：３、１５：４、６０、６２、６６等が特に好適に
利用できる。As the cyan coloring agent, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds and the like can be used. Specifically, C.I. I.
Pigment Blue 1, 7, 15, 15: 1, 15: 2,
15: 3, 15: 4, 60, 62, 66, etc. can be particularly preferably used.
【００５３】これらの着色剤は、単独又は混合し更には
固溶体の状態で用いることができる。本発明の着色剤
は、色相角，彩度，明度，耐候性，ＯＨＰ透明性，トナ
ー中への分散性の点から選択される。該着色剤の添加量
は、樹脂１００質量部に対し１〜２０質量部添加して用
いられる。These colorants can be used alone or as a mixture or in the form of a solid solution. The colorant of the present invention is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in toner. The colorant is used in an amount of 1 to 20 parts by mass per 100 parts by mass of the resin.
【００５４】黒色着色剤として磁性体を用いた場合に
は、他の着色剤と異なり、樹脂１００質量部に対し４０
〜１５０質量部添加して用いられる。When a magnetic material is used as a black colorant, unlike other colorants, 40 parts by mass with respect to 100 parts by mass of resin.
１５０150 parts by mass are used.
【００５５】本発明に用いられる荷電制御剤としては、
公知のものが利用できるが、フルカラー画像用のトナー
に用いる荷電制御剤としては、カルボキシル基を含有す
る化合物が良く、重合トナーの場合、重合性単量体中に
分散させて用いられる。色の影響を考慮すると、無色ま
たは、白色または淡色の結晶状態のものが好ましく、特
に、アルキルサリチル酸の金属化合物がカラートナー用
として好ましく、金属化合物としては、金属錯体また
は、金属錯塩または、金属錯体と金属錯塩の混合物が挙
げられ、低結晶性又は非結晶性のものが好ましく用いら
れる。The charge control agents used in the present invention include:
Known compounds can be used, but as the charge control agent used for the toner for full-color images, a compound containing a carboxyl group is preferable. In the case of a polymerized toner, the compound is used by dispersing it in a polymerizable monomer. In consideration of the effect of color, a colorless or white or light-colored crystalline state is preferable, and a metal compound of alkyl salicylic acid is particularly preferable for a color toner. As the metal compound, a metal complex or a metal complex salt or a metal complex And low-crystalline or non-crystalline ones are preferably used.
【００５６】本発明に係る重合トナーに使用できる重合
開始剤としては、例えば、２，２’−アゾビス−（２，
４−ジメチルバレロニトリル）、２，２’−アゾビスイ
ソブチロニトリル、１，１’−アゾビス（シクロヘキサ
ン−１−カルボニトリル）、２，２’−アゾビス−４−
メトキシ−２，４−ジメチルバレロニトリル、アゾビス
イソブチロニトリル等のアゾ系又はジアゾ系重合開始
剤；ベンゾイルペルオキシド、メチルエチルケトンペル
オキシド、ジイソプロピルペルオキシカーボネート、ク
メンヒドロペルオキシド、２，４−ジクロロベンゾイル
ペルオキシド、ラウロイルペルオキシド等の過酸化物系
重合開始剤が用いられる。該重合開始剤の添加量は、目
的とする重合度により変化するが一般的には単量体に対
し０．５〜２０質量％添加され用いられる。重合開始剤
の種類は、重合方法により若干異なるが、１０時間半減
期温度を参考に、単独又は混合し利用される。Examples of the polymerization initiator that can be used in the polymerization toner according to the present invention include, for example, 2,2′-azobis- (2,2
4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-
Azo or diazo polymerization initiators such as methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl A peroxide-based polymerization initiator such as peroxide is used. The amount of the polymerization initiator varies depending on the desired degree of polymerization, but is generally used in an amount of 0.5 to 20% by mass based on the monomer. The type of the polymerization initiator varies slightly depending on the polymerization method, but is used alone or in combination with reference to the 10-hour half-life temperature.
【００５７】重合度を制御するため公知の架橋剤，連鎖
移動剤，重合禁止剤等を更に添加し用いることも可能で
ある。In order to control the degree of polymerization, a known crosslinking agent, chain transfer agent, polymerization inhibitor or the like may be further added and used.
【００５８】また、外添剤が添加され、乾燥されたトナ
ー粒子は、更に機械的衝撃力を付与し、トナー粒子への
外添剤の付着状態を調整することが好ましい。即ち、ヘ
ンシェルミキサーの如き乾式混合機により、機械的衝撃
力を付与してトナー粒子への外添剤の付着状態を調整す
ることが好ましい。より具体的には、ヘンシェルミキサ
ーの高速回転羽根の周速及び処理時間を調整して、トナ
ー粒子への外添剤の付着状態を調整する。It is preferable that the toner particles to which an external additive is added and dried are further provided with a mechanical impact force to adjust the state of attachment of the external additive to the toner particles. That is, it is preferable to adjust the state of attachment of the external additive to the toner particles by applying a mechanical impact force using a dry mixer such as a Henschel mixer. More specifically, the peripheral speed of the high-speed rotating blades of the Henschel mixer and the processing time are adjusted to adjust the state of attachment of the external additive to the toner particles.
【００５９】またこのとき、必要に応じ、帯電性付与
剤、研磨剤等の他の外添剤を加え、同時に処理すること
が好ましい。At this time, it is preferable to add another external additive such as a charge-imparting agent and an abrasive, if necessary, and carry out the treatment simultaneously.
【００６０】[0060]
【実施例】以下、本発明の実施例及び比較例を挙げて本
発明を更に具体的に説明する。The present invention will be described more specifically below with reference to examples and comparative examples of the present invention.
【００６１】用いた各水のアルカリ金属及びアルカリ土
類金属イオン（Ｎａ+，Ｋ+，Ｍｇ2+及びＣａ2+）含有量
を表１に示す。Table 1 shows the contents of alkali metal and alkaline earth metal ions (Na + , K + , Mg 2+ and Ca 2+ ) of each water used.
【００６２】[0062]
【表１】 [Table 1]
【００６３】＜実施例１＞まず、イオン交換水（水Ａ）
７１０質量部に０．１モル／リットル−Ｎａ3ＰＯ4（米
山化学社製）水溶液４５０質量部を投入し６０℃に加温
した後、クリアミキサー（エム・テクニック社製）を用
いて３，５００回転／分にて撹拌した。これに１．０モ
ル／リットル−ＣａＣｌ2水溶液６８質量部を添加し、
Ｃａ3（ＰＯ4）2を含むｐＨ６．０のりん酸とカルシウ
ムの化合物の水系媒体を得た。Example 1 First, ion-exchanged water (water A)
450 parts by mass of an aqueous solution of 0.1 mol / l-Na 3 PO 4 (manufactured by Yoneyama Chemical Co., Ltd.) were added to 710 parts by mass, and the mixture was heated to 60 ° C., and then mixed with a clear mixer (manufactured by M Technique Co., Ltd.). Stirring was performed at 500 rpm. 68 parts by mass of 1.0 mol / liter-CaCl 2 aqueous solution was added thereto,
An aqueous medium containing a compound of phosphoric acid and calcium having a pH of 6.0 and containing Ca 3 (PO 4 ) 2 was obtained.
【００６４】一方、分散質としては、まず、下記処方の
うち、Ｃ．Ｉ．ピグメントブルー１５：３、ジアルキル
サリチル酸アルミニウム化合物とスチレン単量体１００
質量部をアトライター（三井三池化工機製）を用い３時
間分散し、着色剤分散液を得た。次に、着色剤分散液に
下記処方の残りすべてを添加し、６０℃に加温し３０分
間溶解混合した。これに、重合開始剤である２，２’−
アゾビス（２，４−ジメチルバレロニトリル）８質量部
を溶解し、重合性単量体組成物を調製した。 ・スチレン単量体 １６５質量部 ・ｎ−ブチルアクリレート ３５質量部 ・Ｃ．Ｉ．ピグメントブルー１５：３ １０質量部 ・飽和ポリエステル １０質量部 ・ジアルキルサリチル酸アルミニウム化合物 ２質量部 ・化合物（１）のワックス ２５質量部 （ＤＳＣにおけるピーク温度５９．４℃，ビッカース硬度１．５）On the other hand, as the dispersoid, C.I. I. Pigment Blue 15: 3, aluminum dialkylsalicylate compound and styrene monomer 100
The mass parts were dispersed for 3 hours using an attritor (manufactured by Mitsui Miike Kakoki Co., Ltd.) to obtain a colorant dispersion. Next, all the remaining ingredients of the following formulation were added to the colorant dispersion, and the mixture was heated to 60 ° C. and dissolved and mixed for 30 minutes. In addition, 2,2′-
8 parts by mass of azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition. Styrene monomer 165 parts by mass n-butyl acrylate 35 parts by mass C.I. I. Pigment Blue 15: 3 10 parts by mass-Saturated polyester 10 parts by mass-Aluminum dialkylsalicylate compound 2 parts by mass-Compound (1) wax 25 parts by mass (DSC peak temperature 59.4 ° C, Vickers hardness 1.5)
【００６５】上記重合性単量体組成物を前記水系分散媒
中に投入し、回転数を維持しつつ１５分間造粒した。そ
の後、高速撹拌機からプロペラ撹拌羽根に撹拌機を変
え、内温を６０℃に昇温させ５０回転／分で重合を５時
間継続させた後、内温を８０℃に昇温させ８時間重合を
継続させた。重合終了後、スラリーを３０℃まで冷却し
た。The polymerizable monomer composition was charged into the aqueous dispersion medium and granulated for 15 minutes while maintaining the rotation speed. Then, the stirrer was changed from a high-speed stirrer to a propeller stirring blade, the internal temperature was raised to 60 ° C, polymerization was continued at 50 rpm for 5 hours, and then the internal temperature was raised to 80 ° C for 8 hours. Was continued. After the completion of the polymerization, the slurry was cooled to 30 ° C.
【００６６】着色重合体粒子スラリーを洗浄容器に移
し、撹拌しながら、酸洗浄のために希塩酸を添加し、ｐ
Ｈ１．５で２時間撹拌し、Ｃａ3（ＰＯ4）2を含むりん
酸とカルシウムの化合物を溶解させた後、加圧ろ過方式
の装置ＫＦフィルター（三進製作所製）で固液分離を行
った。The colored polymer particle slurry was transferred to a washing vessel, and while stirring, dilute hydrochloric acid was added for acid washing, and p
The mixture was stirred at H1.5 for 2 hours to dissolve a compound of phosphoric acid and calcium containing Ca 3 (PO 4 ) 2 , and then subjected to solid-liquid separation with a pressure filtration system KF filter (manufactured by Sanshin Seisakusho). Was.
【００６７】次に、ＫＦフィルター中に残った着色重合
体粒子ケーキに、水Ｂを、導入したスラリー量の４倍量
注水した。この時点での排水中の分散安定剤由来の金属
イオンの濃度は、０．１ｍｇ／リットル未満であった
（Ｎａ+＝１．５ｍｇ／リットル…水Ｂ中の濃度、Ｃａ
2+＝０．０ｍｇ／リットル）。その後、水Ｃを、導入し
たスラリー量の０．２倍量注水した。さらに脱水した
後、解砕し、乾燥を行った。Next, water B was injected into the colored polymer particle cake remaining in the KF filter in an amount 4 times the amount of the introduced slurry. At this time, the concentration of the metal ion derived from the dispersion stabilizer in the wastewater was less than 0.1 mg / liter (Na + = 1.5 mg / liter ... concentration in water B, Ca
2 + = 0.0 mg / liter). Thereafter, water C was injected in an amount 0.2 times the amount of the introduced slurry. After further dehydration, it was crushed and dried.
【００６８】乾燥後の着色重合体粒子表面に付着残存し
ている荷電制御剤の不純物及び分解物の濃度を以下のよ
うにして求めた。着色重合体粒子１．０ｇを０．１規定
の水酸化ナトリウム水溶液５０ｇ中に投入し、３時間撹
拌させた後、ろ過によって得られた濾液を吸光度測定法
により所定の検量線を用い測定した。その結果、１５０
０ｐｐｍであった。The concentration of impurities and decomposed products of the charge control agent remaining on the surface of the dried colored polymer particles was determined as follows. 1.0 g of the colored polymer particles was put into 50 g of a 0.1 N aqueous solution of sodium hydroxide, and the mixture was stirred for 3 hours. Then, the filtrate obtained by filtration was measured by an absorbance measurement method using a predetermined calibration curve. As a result, 150
It was 0 ppm.
【００６９】また、着色重合体粒子の重量平均粒径は
６．９μｍであった。The weight average particle size of the colored polymer particles was 6.9 μm.
【００７０】得られた着色重合体粒子１００質量部に対
し、平均粒径０．０３μｍの疎水性シリカ０．７質量部
と平均粒径０．０５μｍの酸化チタン０．７質量部を添
加してヘンシェルミキサーで混合しトナーとした。To 100 parts by mass of the obtained colored polymer particles, 0.7 parts by mass of hydrophobic silica having an average particle size of 0.03 μm and 0.7 parts by mass of titanium oxide having an average particle size of 0.05 μm were added. The mixture was mixed with a Henschel mixer to obtain a toner.
【００７１】また、他に、得られた着色重合体粒子を３
０℃／８０％ＲＨの環境下に２日間放置した後、上記と
同様に、平均粒径０．０３μｍの疎水性シリカと平均粒
径０．０５μｍの酸化チタンを添加してヘンシェルミキ
サーで混合しトナーとした。In addition, the obtained colored polymer particles were
After leaving for 2 days in an environment of 0 ° C./80% RH, hydrophobic silica having an average particle size of 0.03 μm and titanium oxide having an average particle size of 0.05 μm were added and mixed with a Henschel mixer in the same manner as described above. The toner was used.
【００７２】これらいずれのトナーに、トナー５質量部
に対し、磁性体分散型樹脂キャリア９５質量部を混合
し、現像剤とした。Each of these toners was mixed with 5 parts by mass of the toner and 95 parts by mass of a magnetic material-dispersed resin carrier to prepare a developer.
【００７３】これらの現像剤を用いて、キヤノン製カラ
ー複写機ＣＬＣ５００改造機を用いて２３℃／６５％Ｒ
Ｈの環境下で画出し試験を行ったところ、いずれも、１
万枚耐久においても、初期と耐久後の画像濃度に変化が
なく、中抜けのない高画質の画が得られた。また、有機
半導体である感光体に、トナー融着やメモリーゴースト
のような問題を生じなかった。さらに両面画像を形成さ
せたが、転写材の表裏面共にオフセットの発生は認めら
れなかった。Using these developers, a modified color copying machine CLC500 manufactured by Canon Inc. was used at 23 ° C./65% R.
When the image extraction test was performed in the environment of H,
Even in the endurance of 10,000 sheets, there was no change in the image density at the initial stage and after the endurance, and a high-quality image with no hollow was obtained. In addition, problems such as toner fusion and memory ghost did not occur on the photoconductor made of an organic semiconductor. Further, a double-sided image was formed, but no offset was observed on both the front and back surfaces of the transfer material.
【００７４】また、下記の方法により求めた転写効率
は、いずれも９８％であった。The transfer efficiencies obtained by the following methods were all 98%.
【００７５】［転写効率］１０ｃｍ2のベタ画像を感光
体上に形成し、感光体上のトナーの量（Ｗ１）と、転写
後の紙上のトナーの量（Ｗ２）を用い、両者の比：Ｗ２
／Ｗ１×１００（％）より算出した。[Transfer Efficiency] A solid image of 10 cm 2 is formed on a photoreceptor, and the amount of toner on the photoreceptor (W1) and the amount of toner on the paper after transfer (W2) are used. W2
/ W1 × 100 (%).
【００７６】また、３０℃／８０％ＲＨの環境下で同様
な画出し試験を行ったところ、同様な結果が得られた。A similar image-drawing test was conducted in an environment of 30 ° C./80% RH, and similar results were obtained.
【００７７】＜実施例２＞酸洗浄後、ＫＦフィルター中
に残った着色重合体粒子ケーキに、水Ｂを、導入したス
ラリー量の４倍量注水した後、水Ｄを、導入したスラリ
ー量の０．３倍量注水した以外は実施例１と同様に行っ
た。乾燥後の着色重合体粒子表面に付着残存している荷
電制御剤の不純物及び分解物の濃度は１５５０ｐｐｍで
あった。Example 2 After the acid washing, water B was poured into the colored polymer particle cake remaining in the KF filter four times the amount of the introduced slurry, and then water D was added to the amount of the introduced slurry. The same operation as in Example 1 was performed except that a 0.3-fold amount of water was injected. The concentration of impurities and decomposed products of the charge control agent remaining on the surface of the dried colored polymer particles was 1550 ppm.
【００７８】実施例１と同様に、得られた着色重合体粒
子、及び、３０℃／８０％ＲＨの環境下に２日間放置し
た後の前記着色重合体粒子を、それぞれ１００質量部に
対し、平均粒径０．０３μｍの疎水性シリカ０．７質量
部と平均粒径０．０５μｍの酸化チタン０．７質量部を
添加してヘンシェルミキサーで混合しトナーとした。In the same manner as in Example 1, the obtained colored polymer particles and the colored polymer particles left to stand in an environment of 30 ° C./80% RH for 2 days were added to 100 parts by mass of each. 0.7 parts by mass of hydrophobic silica having an average particle size of 0.03 μm and 0.7 parts by mass of titanium oxide having an average particle size of 0.05 μm were added and mixed with a Henschel mixer to obtain a toner.
【００７９】これらのトナー５質量部に対し、磁性体分
散型樹脂キャリア９５質量部を混合し、現像剤とした。
さらに、この現像剤を用いて、実施例１と同様の画出し
評価を行ったところ、実施例１と同様に良好な画像が得
られた。To 5 parts by mass of the toner, 95 parts by mass of a magnetic material-dispersed resin carrier were mixed to prepare a developer.
Further, using this developer, image evaluation was performed in the same manner as in Example 1. As a result, a good image was obtained as in Example 1.
【００８０】＜比較例１＞酸洗浄後、ＫＦフィルター中
に残った着色重合体粒子ケーキに、水Ｂを、導入したス
ラリー量の４．５倍量注水した以外は実施例１と同様に
行った。乾燥後の着色重合体粒子表面に付着残存してい
る荷電制御剤の不純物及び分解物の濃度は、１５００ｐ
ｐｍであった。<Comparative Example 1> The same procedure as in Example 1 was carried out except that 4.5 parts of water B was introduced into the colored polymer particle cake remaining in the KF filter after the acid washing. Was. The concentration of impurities and decomposition products of the charge control agent remaining on the surface of the dried colored polymer particles is 1500 p.
pm.
【００８１】実施例１と同様に、得られた着色重合体粒
子、及び、３０℃／８０％ＲＨの環境下に２日間放置し
た後の前記着色重合体粒子を、それぞれ１００質量部に
対し、平均粒径０．０３μｍの疎水性シリカ０．７質量
部と平均粒径０．０５μｍの酸化チタン０．７質量部を
添加してヘンシェルミキサーで混合しトナーとした。In the same manner as in Example 1, the obtained colored polymer particles and the colored polymer particles after being left for 2 days in an environment of 30 ° C./80% RH were added to 100 parts by mass of each. 0.7 parts by mass of hydrophobic silica having an average particle size of 0.03 μm and 0.7 parts by mass of titanium oxide having an average particle size of 0.05 μm were added and mixed with a Henschel mixer to obtain a toner.
【００８２】これらのトナー５質量部に対し、磁性体分
散型樹脂キャリア９５質量部を混合し、現像剤とした。
さらに、この現像剤を用いて、実施例１と同様の画出し
評価を行ったところ、２３℃／６５％ＲＨの環境下で
は、実施例１と同様に良好な画像が得られたが、３０℃
／８０％ＲＨの環境下では、次第に画像濃度が低くな
り、カブリが顕著になった。また、３０℃／８０％ＲＨ
の環境下に２日間放置した後に、トナーとしたものは、
初期より画像濃度が低く、カブリがみられた。A developer was prepared by mixing 95 parts by mass of a magnetic material-dispersed resin carrier with 5 parts by mass of these toners.
Further, image evaluation was performed in the same manner as in Example 1 using this developer. Under an environment of 23 ° C./65% RH, a good image was obtained as in Example 1. 30 ° C
Under the environment of / 80% RH, the image density gradually decreased and fog became remarkable. 30 ° C / 80% RH
After leaving for 2 days in the environment of
The image density was low from the beginning, and fog was observed.
【００８３】＜比較例２＞酸洗浄後、ＫＦフィルター中
に残った着色重合体粒子ケーキに、水Ｃを、導入したス
ラリー量の４倍量注水した以外は実施例１と同様に行っ
た。乾燥後の着色重合体粒子表面に付着残存している荷
電制御剤の不純物及び分解物の濃度は、７００ｐｐｍで
あった。<Comparative Example 2> The procedure of Example 1 was repeated, except that water C was injected into the colored polymer particle cake remaining in the KF filter after washing with the acid, in an amount 4 times the amount of the introduced slurry. The concentration of impurities and decomposition products of the charge control agent remaining on the surface of the dried colored polymer particles was 700 ppm.
【００８４】実施例１と同様に、得られた着色重合体粒
子、及び、３０℃／８０％ＲＨの環境下に２日間放置し
た後の前記着色重合体粒子を、それぞれ１００質量部に
対し、平均粒径０．０３μｍの疎水性シリカ０．７質量
部と平均粒径０．０５μｍの酸化チタン０．７質量部を
添加してヘンシェルミキサーで混合しトナーとした。In the same manner as in Example 1, the obtained colored polymer particles and the colored polymer particles left to stand in an environment of 30 ° C./80% RH for 2 days were added to 100 parts by mass of each. 0.7 parts by mass of hydrophobic silica having an average particle size of 0.03 μm and 0.7 parts by mass of titanium oxide having an average particle size of 0.05 μm were added and mixed with a Henschel mixer to obtain a toner.
【００８５】これらのトナー５質量部に対し、磁性体分
散型樹脂キャリア９５質量部を混合し、現像剤とした。To 5 parts by mass of the toner, 95 parts by mass of a magnetic material-dispersed resin carrier were mixed to prepare a developer.
【００８６】さらに、この現像剤を用いて、実施例１と
同様の画出し評価を行ったところ、実施例１と同様な画
像濃度の画像は得られたが、初期より、カブリが多く、
また現像器からの現像剤の飛散が激しい。Further, using this developer, image formation evaluation was performed in the same manner as in Example 1. As a result, an image having the same image density as in Example 1 was obtained.
Further, the scattering of the developer from the developing device is severe.
【００８７】＜実施例３＞酸洗浄後の固液分離をフィル
タープレス（則武鉄工所製）で行い、フィルタープレス
中に残った着色重合体粒子ケーキに、水Ｂを、導入した
スラリー量の３倍量注水した（この時点での排水中の分
散安定剤由来の金属イオンの濃度は、０．１ｍｇ／リッ
トル未満であった（Ｎａ+＝１．５ｍｇ／リットル…水
Ｂ中の濃度、Ｃａ2+＝０．０ｍｇ／リットル））後、水
Ｄを、導入したスラリー量の０．２倍量注水した以外は
実施例１と同様に行った。乾燥後の着色重合体粒子表面
に付着残存している荷電制御剤の不純物及び分解物の濃
度は、１８００ｐｐｍであった。Example 3 Solid-liquid separation after acid washing was carried out by a filter press (manufactured by Noritake Iron Works), and water B was introduced into the colored polymer particle cake remaining in the filter press by the amount of 3 (The concentration of the metal ion derived from the dispersion stabilizer in the waste water at this point was less than 0.1 mg / liter (Na + = 1.5 mg / liter ... concentration in water B, Ca 2 + = 0.0 mg / liter)), and the same procedure as in Example 1 was carried out except that water D was injected in an amount 0.2 times the amount of the introduced slurry. The concentration of impurities and decomposition products of the charge control agent remaining on the surface of the dried colored polymer particles was 1800 ppm.
【００８８】実施例１と同様に、得られた着色重合体粒
子１００質量部に対し、平均粒径０．０３μｍの疎水性
シリカ０．７質量部と平均粒径０．０５μｍの酸化チタ
ン０．７質量部を添加してヘンシェルミキサーで混合し
トナーとした。As in Example 1, 0.7 parts by mass of hydrophobic silica having an average particle size of 0.03 μm and 0.1 parts by mass of titanium oxide having an average particle size of 0.05 μm were added to 100 parts by mass of the obtained colored polymer particles. 7 parts by mass were added and mixed with a Henschel mixer to obtain a toner.
【００８９】このトナー５質量部に対し、磁性体分散型
樹脂キャリア９５質量部を混合し、現像剤とした。さら
に、この現像剤を用いて、実施例１と同様の画出し評価
を行ったところ、実施例１と同様に良好な画像が得られ
た。To 5 parts by mass of this toner, 95 parts by mass of a magnetic material-dispersed resin carrier were mixed to prepare a developer. Further, using this developer, image evaluation was performed in the same manner as in Example 1. As a result, a good image was obtained as in Example 1.
【００９０】＜実施例４＞酸洗浄後の固液分離をフィル
タープレス（則武鉄工所製）で行い、フィルタープレス
中に残った着色重合体粒子ケーキに、水Ｂを、導入した
スラリー量の３倍量注水した後、水Ｅを、導入したスラ
リー量の０．３倍量注水した以外は実施例１と同様に行
った。乾燥後の着色重合体粒子表面に付着残存している
荷電制御剤の不純物及び、分解物の濃度は、１７８０ｐ
ｐｍであった。Example 4 Solid-liquid separation after acid washing was carried out by a filter press (manufactured by Noritake Iron Works), and water B was introduced into the colored polymer particle cake remaining in the filter press by the amount of 3 After the double injection, the same procedure as in Example 1 was carried out except that water E was injected 0.3 times the amount of the introduced slurry. The concentration of impurities and decomposition products of the charge control agent remaining on the surface of the dried colored polymer particles is 1780 p.
pm.
【００９１】実施例１と同様に、得られた着色重合体粒
子１００質量部に対し、平均粒径０．０３μｍの疎水性
シリカ０．７質量部と平均粒径０．０５μｍの酸化チタ
ン０．７質量部を添加してヘンシェルミキサーで混合し
トナーとした。As in Example 1, 0.7 parts by mass of hydrophobic silica having an average particle size of 0.03 μm and 0.1 parts by mass of titanium oxide having an average particle size of 0.05 μm were added to 100 parts by mass of the obtained colored polymer particles. 7 parts by mass were added and mixed with a Henschel mixer to obtain a toner.
【００９２】このトナー５質量部に対し、磁性体分散型
樹脂キャリア９５質量部を混合し、現像剤とした。さら
に、この現像剤を用いて、実施例１と同様の画出し評価
を行ったところ、実施例１と同様に良好な画像が得られ
た。To 5 parts by mass of this toner, 95 parts by mass of a magnetic material-dispersed resin carrier were mixed to prepare a developer. Further, using this developer, image evaluation was performed in the same manner as in Example 1. As a result, a good image was obtained as in Example 1.
【００９３】＜実施例５＞酸洗浄後の固液分離をフィル
タープレス（則武鉄工所製）で行い、フィルタープレス
中に残った着色重合体粒子ケーキに、水Ｂを、導入した
スラリー量の３倍量注水した後、水Ｆを、導入したスラ
リー量の１．０倍量注水した以外は実施例１と同様に行
った。乾燥後の着色重合体粒子表面に付着残存している
荷電制御剤の不純物及び分解物の濃度は、１８１０ｐｐ
ｍであった。Example 5 Solid-liquid separation after acid washing was carried out by a filter press (manufactured by Noritake Iron Works), and water B was introduced into the colored polymer particle cake remaining in the filter press by the amount of 3 After the double injection, the same procedure as in Example 1 was carried out except that water F was injected 1.0 times the amount of the introduced slurry. The concentration of impurities and decomposition products of the charge control agent remaining on the surface of the colored polymer particles after drying was 1810 pp
m.
【００９４】実施例１と同様に、得られた着色重合体粒
子１００質量部に対し、平均粒径０．０３μｍの疎水性
シリカ０．７質量部と平均粒径０．０５μｍの酸化チタ
ン０．７質量部を添加してヘンシェルミキサーで混合し
トナーとした。As in Example 1, 0.7 parts by mass of hydrophobic silica having an average particle size of 0.03 μm and 0.1 parts by mass of titanium oxide having an average particle size of 0.05 μm were added to 100 parts by mass of the obtained colored polymer particles. 7 parts by mass were added and mixed with a Henschel mixer to obtain a toner.
【００９５】このトナー５質量部に対し、磁性体分散型
樹脂キャリア９５質量部を混合し、現像剤とした。さら
に、この現像剤を用いて、実施例１と同様の画出し評価
を行ったところ、３０℃／８０％ＲＨの環境下に２日間
放置した後にトナーとしたものは、若干カブリがあるも
のの、実施例１と同様に良好な画像が得られた。To 5 parts by mass of this toner, 95 parts by mass of a magnetic material-dispersed resin carrier were mixed to prepare a developer. Further, using this developer, the same image formation evaluation as in Example 1 was performed. As a result, the toner which was left for two days in an environment of 30 ° C./80% RH was slightly fogged. A good image was obtained in the same manner as in Example 1.
【００９６】＜実施例６＞酸洗浄後の固液分離をフィル
タープレス（則武鉄工所製）で行い、フィルタープレス
中に残った着色重合体粒子ケーキに、水Ｂを、導入した
スラリー量の３倍量注水した後、水Ｇを、導入したスラ
リー量の１．０倍量注水した以外は実施例１と同様に行
った。乾燥後の着色重合体粒子表面に付着残存している
荷電制御剤の不純物及び分解物の濃度は、１８２０ｐｐ
ｍであった。<Example 6> Solid-liquid separation after acid washing was carried out with a filter press (manufactured by Noritake Iron Works), and water B was introduced into the colored polymer particle cake remaining in the filter press at a slurry amount of 3%. After the double injection, the same procedure as in Example 1 was carried out except that water G was injected 1.0 times the amount of the introduced slurry. The concentration of impurities and decomposition products of the charge control agent remaining on the surface of the colored polymer particles after drying was 1820 pp.
m.
【００９７】実施例１と同様に、得られた着色重合体粒
子１００質量部に対し、平均粒径０．０３μｍの疎水性
シリカ０．７質量部と平均粒径０．０５μｍの酸化チタ
ン０．７質量部を添加してヘンシェルミキサーで混合し
トナーとした。As in Example 1, 0.7 parts by mass of hydrophobic silica having an average particle size of 0.03 μm and 0.1 parts by mass of titanium oxide having an average particle size of 0.05 μm were added to 100 parts by mass of the obtained colored polymer particles. 7 parts by mass were added and mixed with a Henschel mixer to obtain a toner.
【００９８】このトナー５質量部に対し、磁性体分散型
樹脂キャリア９５質量部を混合し、現像剤とした。さら
に、この現像剤を用いて、実施例１と同様の画出し評価
を行ったところ、３０℃／８０％ＲＨの環境下に２日間
放置した後にトナーとしたものは、若干のカブリがあ
り、現像器からの現像剤の飛散がわずかにみられるもの
の、実施例１と同様に良好な画像が得られた。To 5 parts by mass of this toner, 95 parts by mass of a magnetic material-dispersed resin carrier were mixed to prepare a developer. Further, the same image formation evaluation as in Example 1 was carried out using this developer. As a result, the toner obtained after being left in an environment of 30 ° C./80% RH for 2 days had some fog. Although a small amount of the developer was scattered from the developing device, a good image was obtained as in Example 1.
【００９９】＜比較例３＞酸洗浄後の固液分離をフィル
タープレス（則武鉄鋼所製）で行い、フィルタープレス
中に残った着色重合体粒子ケーキに、水Ａを、導入した
スラリー量の５倍量注水した以外は実施例１と同様に行
った。乾燥後の着色重合体粒子表面に付着残存している
荷電制御剤の不純物及び分解物の濃度は、１８００ｐｐ
ｍであった。<Comparative Example 3> Solid-liquid separation after acid washing was carried out with a filter press (manufactured by Noritake Iron & Steel Works), and water A was introduced into the colored polymer particle cake remaining in the filter press by the amount of 5%. The procedure was performed in the same manner as in Example 1 except that a double amount of water was injected. The concentration of impurities and decomposed products of the charge control agent remaining on the surface of the dried colored polymer particles is 1800 pp.
m.
【０１００】実施例１と同様に、得られた着色重合体粒
子１００質量部に対し、平均粒径０．０３μｍの疎水性
シリカ０．８質量部と平均粒径０．０５μｍの酸化チタ
ン０．３質量部を添加してヘンシェルミキサーで混合し
トナーとした。In the same manner as in Example 1, 0.8 parts by mass of hydrophobic silica having an average particle size of 0.03 μm and 0.1 parts by mass of titanium oxide having an average particle size of 0.05 μm were added to 100 parts by mass of the obtained colored polymer particles. 3 parts by mass were added and mixed with a Henschel mixer to obtain a toner.
【０１０１】このトナー５質量部に対し、磁性体分散型
樹脂キャリア９５質量部を混合し、現像剤とした。さら
に、この現像剤を用いて、実施例１と同様の画出し評価
を行ったところ、２３℃／６５％ＲＨの環境下では、実
施例１と同様に良好な画像が得られたが、３０℃／８０
％ＲＨの環境下では、次第に画像濃度が低くなり、カブ
リが顕著になった。また、３０℃／８０％ＲＨの環境下
に２日間放置した後に、トナーとしたものは、初期より
画像濃度が低く、カブリがみられた。To 5 parts by mass of this toner, 95 parts by mass of a magnetic material-dispersed resin carrier were mixed to prepare a developer. Further, image evaluation was performed in the same manner as in Example 1 using this developer. Under an environment of 23 ° C./65% RH, a good image was obtained as in Example 1. 30 ° C / 80
Under the environment of% RH, the image density gradually decreased, and fog became remarkable. In addition, after being left in an environment of 30 ° C./80% RH for 2 days, the toner used as the toner had a lower image density than the initial stage and fogging was observed.
【０１０２】＜比較例４＞酸洗浄後の固液分離を加圧ろ
過方式の装置ＫＦフィルターで行い、フィルタープレス
中に残った着色重合体粒子ケーキに、水Ｄを、導入した
スラリー量の５倍量注水した以外は実施例１と同様に行
った。乾燥後の着色重合体粒子表面に付着残存している
荷電制御剤の不純物及び分解物の濃度は、１２００ｐｐ
ｍであった。<Comparative Example 4> Solid-liquid separation after acid washing was carried out with a pressure filtration system KF filter, and water D was introduced into the colored polymer particle cake remaining in the filter press by the amount of 5% of the slurry. The procedure was performed in the same manner as in Example 1 except that a double amount of water was injected. The concentration of impurities and decomposed products of the charge control agent adhering and remaining on the surface of the dried colored polymer particles was 1200 pp.
m.
【０１０３】実施例１と同様に、得られた着色重合体粒
子１００質量部に対し、平均粒径０．０３μｍの疎水性
シリカ０．８質量部と平均粒径０．０５μｍの酸化チタ
ン０．３質量部を添加してヘンシェルミキサーで混合し
トナーとした。As in Example 1, 0.8 parts by mass of hydrophobic silica having an average particle size of 0.03 μm and 0.1 parts by mass of titanium oxide having an average particle size of 0.05 μm were added to 100 parts by mass of the obtained colored polymer particles. 3 parts by mass were added and mixed with a Henschel mixer to obtain a toner.
【０１０４】このトナー５質量部に対し、磁性体分散型
樹脂キャリア９５質量部を混合し、現像剤とした。さら
に、この現像剤を用いて、実施例１と同様の画出し評価
を行ったところ、実施例１と同様な画像濃度の画像は得
られたが、初期より、カブリが多く、また現像器からの
現像剤の飛散が激しい。To 5 parts by mass of this toner, 95 parts by mass of a magnetic material-dispersed resin carrier were mixed to prepare a developer. Further, the same image density evaluation as in Example 1 was obtained using this developer, and an image having the same image density as in Example 1 was obtained. The developer scatters sharply.
【０１０５】＜比較例５＞酸洗浄後の固液分離をフィル
タープレス（則武鉄工所製）で行い、フィルタープレス
中に残った着色重合体粒子ケーキに、水Ｂを、導入した
スラリー量の３倍量注水した後、水Ｄを、導入したスラ
リー量の３倍量注水した以外は実施例１と同様に行っ
た。乾燥後の着色重合体粒子表面に付着残存している荷
電制御剤の不純物及び分解物の濃度は、１４５０ｐｐｍ
であった。<Comparative Example 5> Solid-liquid separation after acid washing was carried out with a filter press (manufactured by Noritake Iron Works), and water B was introduced into the colored polymer particle cake remaining in the filter press at a slurry amount of 3%. After the double injection, the same procedure as in Example 1 was carried out except that water D was injected three times the amount of the introduced slurry. The concentration of impurities and decomposition products of the charge control agent remaining on the surface of the dried colored polymer particles was 1450 ppm.
Met.
【０１０６】実施例１と同様に、得られた着色重合体粒
子１００質量部に対し、平均粒径０．０３μｍの疎水性
シリカ０．８質量部と平均粒径０．０５μｍの酸化チタ
ン０．３質量部を添加してヘンシェルミキサーで混合し
トナーとした。In the same manner as in Example 1, 0.8 parts by mass of hydrophobic silica having an average particle size of 0.03 μm and 0.1 parts by mass of titanium oxide having an average particle size of 0.05 μm were added to 100 parts by mass of the obtained colored polymer particles. 3 parts by mass were added and mixed with a Henschel mixer to obtain a toner.
【０１０７】このトナー５質量部に対し、磁性体分散型
樹脂キャリア９５質量部を混合し、現像剤とした。さら
に、この現像剤を用いて、実施例１と同様の画出し評価
を行ったところ、初期は実施例１と同様な画像が得られ
たが、次第にカブリが多くなり、また現像器からの現像
剤の飛散が目立つようになった。To 5 parts by mass of the toner, 95 parts by mass of a magnetic material-dispersed resin carrier were mixed to prepare a developer. Further, the same image evaluation as in Example 1 was performed using this developer. As a result, an image similar to that of Example 1 was obtained at the initial stage. The scattering of the developer became noticeable.
【０１０８】上記実施例１〜６並びに比較例１〜５の結
果を表２にまとめて示す。The results of Examples 1 to 6 and Comparative Examples 1 to 5 are summarized in Table 2.
【０１０９】[0109]
【表２】 [Table 2]
【０１１０】＜実施例７＞まず、イオン交換水（水Ａ）
７１０質量部に０．１モル／リットル−Ｎａ3ＰＯ4（ラ
サ工業社製）水溶液４５０質量部を投入し６０℃に加温
した後、クリアミキサーを用いて３，５００回転／分に
て撹拌した。これに１．０モル／リットル−ＣａＣｌ2
水溶液６８質量部を添加し、Ｃａ3（ＰＯ4）2を含むｐ
Ｈ５．８のりん酸とカルシウムの化合物の水系媒体を得
た。Example 7 First, ion-exchanged water (water A)
450 parts by mass of an aqueous solution of 0.1 mol / l-Na 3 PO 4 (manufactured by Rasa Kogyo Co., Ltd.) was added to 710 parts by mass, heated to 60 ° C., and then stirred at 3,500 rpm using a clear mixer. did. 1.0 mol / l-CaCl 2
68 parts by mass of an aqueous solution is added, and p 3 containing Ca 3 (PO 4 ) 2 is added.
An aqueous medium of a compound of H5.8 phosphoric acid and calcium was obtained.
【０１１１】一方、分散質としては、まず、下記処方の
うち、ピグメントレッド顔料、ジアルキルサリチル酸ア
ルミニウム化合物とスチレン単量体１００質量部をアト
ライター（三井三池化工機製）を用い３時間分散し、着
色剤分散液を得た。次に、着色剤分散液に下記処方の残
りすべてを添加し、６０℃に加温し３０分間溶解混合し
た。これに、重合開始剤である２，２’−アゾビス
（２，４−ジメチルバレロニトリル）８質量部を溶解
し、重合性単量体組成物を調製した。 ・スチレン単量体 １６５質量部 ・ｎ−ブチルアクリレート ３５質量部 ・ピグメントレッド１２２ ２０質量部 ・飽和ポリエステル ２０質量部 ・ジアルキルサリチル酸アルミニウム化合物 ２質量部 ・化合物（１）のワックス ２５質量部 （ＤＳＣにおけるピーク温度５９．４℃，ビッカース硬度１．５）On the other hand, as a dispersoid, pigment red pigment, aluminum dialkyl salicylate compound and 100 parts by mass of styrene monomer in the following formulation were dispersed for 3 hours using an attritor (manufactured by Mitsui Miike Kakoki) and colored. An agent dispersion was obtained. Next, all the remaining ingredients of the following formulation were added to the colorant dispersion, and the mixture was heated to 60 ° C. and dissolved for 30 minutes. In this, 8 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was dissolved to prepare a polymerizable monomer composition. -Styrene monomer 165 parts by mass-n-butyl acrylate 35 parts by mass-Pigment Red 122 20 parts by mass-Saturated polyester 20 parts by mass-Aluminum dialkylsalicylate compound 2 parts by mass-Compound (1) wax 25 parts by mass (in DSC) Peak temperature 59.4 ° C, Vickers hardness 1.5)
【０１１２】上記重合性単量体組成物を前記水系分散媒
中に投入し、回転数を維持しつつ１５分間造粒した。そ
の後、高速撹拌機からプロペラ撹拌羽根に撹拌機を変
え、内温を６０℃に昇温させ５０回転／分で重合を５時
間継続させた後、内温を８０℃に昇温させ１０時間重合
を継続させた。重合終了後、スラリーを３０℃まで冷却
した。The polymerizable monomer composition was charged into the aqueous dispersion medium and granulated for 15 minutes while maintaining the rotation speed. Then, the stirrer was changed from a high-speed stirrer to a propeller stirring blade, the internal temperature was raised to 60 ° C, polymerization was continued at 50 rpm for 5 hours, and then the internal temperature was raised to 80 ° C and polymerization was performed for 10 hours. Was continued. After the completion of the polymerization, the slurry was cooled to 30 ° C.
【０１１３】着色重合体粒子スラリーを洗浄容器に移
し、撹拌しながら、酸洗浄のために希塩酸を添加し、ｐ
Ｈ１．８で、２時間撹拌し、Ｃａ3（ＰＯ4）2を含むり
ん酸とカルシウムの化合物を溶解させた後、加圧ろ過方
式の装置ＫＦフィルター（三進製作所製）で固液分離を
行った。The colored polymer particle slurry was transferred to a washing vessel, and while stirring, dilute hydrochloric acid was added for acid washing, and p
After stirring for 2 hours at H1.8 to dissolve the compound of phosphoric acid and calcium containing Ca 3 (PO 4 ) 2 , solid-liquid separation was performed using a KF filter (manufactured by Sanshin Seisakusho) of a pressure filtration system. went.
【０１１４】次に、ＫＦフィルター中に残った着色重合
体粒子ケーキに、水Ｂを、導入したスラリー量の３倍量
注水した。この時点での排水中の分散安定剤由来の金属
イオンの濃度は、０．１ｍｇ／リットル未満であった
（Ｎａ+＝１．５ｍｇ／リットル…水Ｂ中の濃度、Ｃａ
2+＝０．０ｍｇ／リットル）。その後、水Ｈを、導入し
たスラリー量の０．４倍量注水した。さらに脱水した
後、解砕し、乾燥を行った。Next, water B was poured into the colored polymer particle cake remaining in the KF filter in an amount three times the amount of the introduced slurry. At this time, the concentration of the metal ion derived from the dispersion stabilizer in the wastewater was less than 0.1 mg / liter (Na + = 1.5 mg / liter ... concentration in water B, Ca
2 + = 0.0 mg / liter). Thereafter, water H was injected 0.4 times the amount of the introduced slurry. After further dehydration, it was crushed and dried.
【０１１５】乾燥後の着色重合体粒子表面に付着残存し
ている荷電制御剤の不純物及び分解物の濃度は、１７２
０ｐｐｍであった。The concentration of impurities and decomposition products of the charge control agent remaining on the surface of the dried colored polymer particles was 172.
It was 0 ppm.
【０１１６】実施例１と同様に、得られた着色重合体粒
子、及び、３０℃／８０％ＲＨの環境下に２日間放置し
た後の前記着色重合体粒子を、それぞれ１００質量部に
対し、平均粒径０．０３μｍの疎水性シリカ０．７質量
部と平均粒径０．０５μｍの酸化チタン０．７質量部を
添加してヘンシェルミキサーで混合しトナーとした。In the same manner as in Example 1, the obtained colored polymer particles and the colored polymer particles left to stand in an environment of 30 ° C./80% RH for 2 days were added to 100 parts by mass of each. 0.7 parts by mass of hydrophobic silica having an average particle size of 0.03 μm and 0.7 parts by mass of titanium oxide having an average particle size of 0.05 μm were added and mixed with a Henschel mixer to obtain a toner.
【０１１７】これらのトナー５質量部に対し、磁性体分
散型樹脂キャリア９５質量部を混合し、現像剤とした。
さらに、この現像剤を用いて、実施例１と同様の画出し
評価を行ったところ、実施例１と同様に良好な画像が得
られた。To 5 parts by mass of these toners, 95 parts by mass of a magnetic material-dispersed resin carrier were mixed to prepare a developer.
Further, using this developer, image evaluation was performed in the same manner as in Example 1. As a result, a good image was obtained as in Example 1.
【０１１８】＜実施例８＞酸洗浄後、ＫＦフィルター中
に残った着色重合体粒子ケーキに、水Ｂを、導入したス
ラリー量の３倍量注水した後、水Ｉを、導入したスラリ
ー量の０．４倍量注水した以外は実施例７と同様に行っ
た。乾燥後の着色重合体粒子表面に付着残存している荷
電制御剤の不純物及び分解物の濃度は１６７０ｐｐｍで
あった。Example 8 After the acid washing, water B was poured into the colored polymer particle cake remaining in the KF filter three times the amount of the introduced slurry, and water I was added to the amount of the introduced slurry. The same operation as in Example 7 was performed except that a 0.4-fold amount of water was injected. The concentration of impurities and decomposed products of the charge controlling agent remaining on the surface of the dried colored polymer particles was 1670 ppm.
【０１１９】実施例１と同様に、得られた着色重合体粒
子、及び、３０℃／８０％ＲＨの環境下に２日間放置し
た後の前記着色重合体粒子を、それぞれ１００質量部に
対し、平均粒径０．０３μｍの疎水性シリカ０．７質量
部と平均粒径０．０５μｍの酸化チタン０．７質量部を
添加してヘンシェルミキサーで混合しトナーとした。In the same manner as in Example 1, the obtained colored polymer particles and the colored polymer particles left to stand in an environment of 30 ° C./80% RH for 2 days were added to 100 parts by mass of each. 0.7 parts by mass of hydrophobic silica having an average particle size of 0.03 μm and 0.7 parts by mass of titanium oxide having an average particle size of 0.05 μm were added and mixed with a Henschel mixer to obtain a toner.
【０１２０】これらのトナー５質量部に対し、磁性体分
散型樹脂キャリア９５質量部を混合し、現像剤とした。
さらに、この現像剤を用いて、実施例１と同様の画出し
評価を行ったところ、実施例７と同様に良好な画像が得
られた。To 5 parts by mass of the toner, 95 parts by mass of a magnetic material-dispersed resin carrier were mixed to prepare a developer.
Further, image evaluation was performed using this developer in the same manner as in Example 1, and a good image was obtained as in Example 7.
【０１２１】＜実施例９＞酸洗浄後、ＫＦフィルター中
に残った着色重合体粒子ケーキに、水Ｂを、導入したス
ラリー量の３倍量注水した後、水Ｊを、導入したスラリ
ー量の１．０倍量注水した以外は実施例７と同様に行っ
た。乾燥後の着色重合体粒子表面に付着残存している荷
電制御剤の不純物及び分解物の濃度は１７４０ｐｐｍで
あった。Example 9 After the acid washing, water B was poured into the colored polymer particle cake remaining in the KF filter three times the amount of the introduced slurry, and then water J was added to the amount of the introduced slurry. The same operation as in Example 7 was carried out except that a 1.0-fold amount of water was injected. The concentration of impurities and decomposed products of the charge control agent remaining on the surface of the dried colored polymer particles was 1740 ppm.
【０１２２】実施例１と同様に、得られた着色重合体粒
子、及び、３０℃／８０％ＲＨの環境下に２日間放置し
た後の前記着色重合体粒子を、それぞれ１００質量部に
対し、平均粒径０．０３μｍの疎水性シリカ０．７質量
部と平均粒径０．０５μｍの酸化チタン０．７質量部を
添加してヘンシェルミキサーで混合しトナーとした。In the same manner as in Example 1, the obtained colored polymer particles and the colored polymer particles after being left for 2 days in an environment of 30 ° C./80% RH were added to 100 parts by mass of each. 0.7 parts by mass of hydrophobic silica having an average particle size of 0.03 μm and 0.7 parts by mass of titanium oxide having an average particle size of 0.05 μm were added and mixed with a Henschel mixer to obtain a toner.
【０１２３】これらのトナー５質量部に対し、磁性体分
散型樹脂キャリア９５質量部を混合し、現像剤とした。
さらに、この現像剤を用いて、実施例１と同様の画出し
評価を行ったところ、３０℃／８０％ＲＨの環境下に２
日間放置した後にトナーとしたものは、若干カブリがあ
り、若干現像器からの現像剤の飛散があるものの、実施
例７と同様な画像が得られた。A developer was prepared by mixing 95 parts by mass of a magnetic material-dispersed resin carrier with 5 parts by mass of these toners.
Further, using this developer, the same image formation evaluation as in Example 1 was performed.
An image similar to that of Example 7 was obtained when the toner was left as it was after being left for a few days, with some fog and slight scattering of the developer from the developing device.
【０１２４】＜比較例６＞酸洗浄後、ＫＦフィルター中
に残った着色重合体粒子ケーキに、水Ｂを、導入したス
ラリー量の３倍量注水した後、水Ｋを、導入したスラリ
ー量の０．４倍量注水した以外は実施例７と同様に行っ
た。乾燥後の着色重合体粒子表面に付着残存している荷
電制御剤の不純物及び分解物の濃度は、１５３０ｐｐｍ
であった。<Comparative Example 6> Water B was poured into the colored polymer particle cake remaining in the KF filter after the acid washing in an amount three times the amount of the introduced slurry, and then water K was added to the amount of the introduced slurry. The same operation as in Example 7 was performed except that a 0.4-fold amount of water was injected. The concentration of impurities and decomposed products of the charge control agent remaining on the surface of the dried colored polymer particles was 1530 ppm.
Met.
【０１２５】実施例１と同様に、得られた着色重合体粒
子１００質量部に対し、平均粒径０．０３μｍの疎水性
シリカ０．８質量部と平均粒径０．０５μｍの酸化チタ
ン０．３質量部を添加してヘンシェルミキサーで混合し
トナーとした。As in Example 1, 0.8 parts by mass of hydrophobic silica having an average particle size of 0.03 μm and 0.1 parts by mass of titanium oxide having an average particle size of 0.05 μm were added to 100 parts by mass of the obtained colored polymer particles. 3 parts by mass were added and mixed with a Henschel mixer to obtain a toner.
【０１２６】このトナー５質量部に対し、磁性体分散型
樹脂キャリア９５質量部を混合し、現像剤とした。さら
に、この現像剤を用いて、実施例１と同様の画出し評価
を行ったところ、初期は、実施例７と同様な画像が得ら
れたが、次第にカブリが多くなり、また現像器からの現
像剤の飛散が目立つようになった。A developer was prepared by mixing 95 parts by mass of a magnetic material-dispersed resin carrier with 5 parts by mass of the toner. Further, when the same image evaluation as that of Example 1 was performed using this developer, an image similar to that of Example 7 was obtained at the initial stage. Of the developer became noticeable.
【０１２７】＜比較例７＞酸洗浄後、ＫＦフィルター中
に残った着色重合体粒子ケーキに、水Ｂを、導入したス
ラリー量の３倍量注水した後、水Ｌを、導入したスラリ
ー量の０．４倍量注水した以外は実施例７と同様に行っ
た。乾燥後の着色重合体粒子表面に付着残存している荷
電制御剤の不純物及び分解物の濃度は、１０２０ｐｐｍ
であった。<Comparative Example 7> After washing with acid, water B was poured into the colored polymer particle cake remaining in the KF filter three times the amount of the introduced slurry, and then water L was added to the amount of the introduced slurry. The same operation as in Example 7 was performed except that a 0.4-fold amount of water was injected. The concentration of impurities and decomposed products of the charge control agent remaining on the surface of the colored polymer particles after drying is 1020 ppm.
Met.
【０１２８】実施例１と同様に、得られた着色重合体粒
子１００質量部に対し、平均粒径０．０３μｍの疎水性
シリカ０．８質量部と平均粒径０．０５μｍの酸化チタ
ン０．３質量部を添加してヘンシェルミキサーで混合し
トナーとした。In the same manner as in Example 1, 0.8 parts by mass of hydrophobic silica having an average particle size of 0.03 μm and 0.1 parts by mass of titanium oxide having an average particle size of 0.05 μm were added to 100 parts by mass of the obtained colored polymer particles. 3 parts by mass were added and mixed with a Henschel mixer to obtain a toner.
【０１２９】このトナー５質量部に対し、磁性体分散型
樹脂キャリア９５質量部を混合し、現像剤とした。さら
に、この現像剤を用いて、実施例１と同様の画出し評価
を行ったところ、カブリが多く、また現像器からの現像
剤の飛散が目立った。To 5 parts by mass of the toner, 95 parts by mass of a magnetic material-dispersed resin carrier were mixed to prepare a developer. Further, the same image formation evaluation as in Example 1 was performed using this developer. As a result, fog was large and the developer scattered from the developing device was conspicuous.
【０１３０】上記実施例７〜９並びに比較例６〜７の結
果を表３にまとめて示す。The results of Examples 7 to 9 and Comparative Examples 6 to 7 are summarized in Table 3.
【０１３１】[0131]
【表３】 [Table 3]
【０１３２】＜実施例１０＞まず、イオン交換水（水
Ａ）７１０質量部に０．１モル／リットル−Ｎａ3ＰＯ4
（ラサ工業社製）水溶液４５０質量部を投入し６０℃に
加温した後、クリアミキサーを用いて３，５００回転／
分にて撹拌した。これに１．０モル／リットル−ＣａＣ
ｌ2水溶液６８質量部を添加し、Ｃａ3（ＰＯ4）2を含む
ｐＨ１０．５のりん酸とカルシウムの化合物の水系媒体
を得た。Example 10 First, 0.1 mol / l-Na 3 PO 4 was added to 710 parts by mass of ion-exchanged water (water A).
After 450 parts by mass of an aqueous solution (manufactured by Lhasa Industry Co., Ltd.) was added and heated to 60 ° C., 3,500 revolutions /
For 2 minutes. 1.0 mol / l-CaC
68 parts by mass of an aqueous solution of l 2 were added to obtain an aqueous medium of a compound of phosphoric acid and calcium having a pH of 10.5 and containing Ca 3 (PO 4 ) 2 .
【０１３３】一方、分散質としては、まず、下記処方の
うち、ピグメントイエロー顔料、結晶性ジアルキルサリ
チル酸の亜鉛錯体とスチレン単量体１００質量部をアト
ライター（三井三池化工機製）を用い３時間分散し、着
色剤分散液を得た。次に、着色剤分散液に下記処方の残
りすべてを添加し、６０℃に加温し３０分間溶解混合し
た。これに、重合開始剤である２，２’−アゾビス
（２，４−ジメチルバレロニトリル）８質量部を溶解
し、重合性単量体組成物を調製した。 ・スチレン単量体 １６０質量部 ・ｎ−ブチルアクリレート ４０質量部 ・ピグメントイエロー９３ １５質量部 ・飽和ポリエステル ２０質量部 ・結晶性ジアルキルサリチル酸の亜鉛錯体 ３質量部 ・化合物（１）のワックス ２５質量部 （ＤＳＣにおけるピーク温度５９．４℃，ビッカース硬度１．５）On the other hand, as a dispersoid, first, a pigment yellow pigment, a zinc complex of crystalline dialkylsalicylic acid and 100 parts by mass of a styrene monomer were dispersed in an attritor (manufactured by Mitsui Miike Kakoki) for 3 hours. Thus, a colorant dispersion was obtained. Next, all the remaining ingredients of the following formulation were added to the colorant dispersion, and the mixture was heated to 60 ° C. and dissolved and mixed for 30 minutes. In this, 8 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was dissolved to prepare a polymerizable monomer composition. 160 parts by mass of styrene monomer 40 parts by mass of n-butyl acrylate 15 parts by mass of Pigment Yellow 93 20 parts by mass of saturated polyester 3 parts by mass of zinc complex of crystalline dialkylsalicylic acid 25 parts by mass of wax of compound (1) (DSC peak temperature 59.4 ° C, Vickers hardness 1.5)
【０１３４】上記重合性単量体組成物を前記水系分散媒
中に投入し、回転数を維持しつつ１５分間造粒した。そ
の後、高速撹拌機からプロペラ撹拌羽根に撹拌機を変
え、内温を６０℃に昇温させ５０回転／分で重合を５時
間継続させた後、内温を８０℃に昇温させ８時間重合を
継続させた。重合終了後、スラリーを３０℃まで冷却し
た。The polymerizable monomer composition was charged into the aqueous dispersion medium and granulated for 15 minutes while maintaining the rotation speed. Then, the stirrer was changed from a high-speed stirrer to a propeller stirring blade, the internal temperature was raised to 60 ° C, polymerization was continued at 50 rpm for 5 hours, and then the internal temperature was raised to 80 ° C for 8 hours. Was continued. After the completion of the polymerization, the slurry was cooled to 30 ° C.
【０１３５】着色重合体粒子スラリーを洗浄容器に移
し、撹拌しながら、酸洗浄のために希塩酸を添加し、ｐ
Ｈ１．６で、２時間撹拌し、Ｃａ3（ＰＯ4）2を含むり
ん酸とカルシウムの化合物を溶解させた後、加圧ろ過方
式の装置ＫＦフィルター（三進製作所製）で固液分離を
行った。The colored polymer particle slurry was transferred to a washing vessel, and while stirring, dilute hydrochloric acid was added for acid washing, and p
After stirring at H1.6 for 2 hours to dissolve the compound of phosphoric acid and calcium containing Ca 3 (PO 4 ) 2 , solid-liquid separation was performed using a KF filter (manufactured by Sanshin Seisakusho) of a pressure filtration system. went.
【０１３６】次に、ＫＦフィルター中に残った着色重合
体粒子ケーキに、水Ｂを、導入したスラリー量の４倍量
注水した。この時点での排水中の分散安定剤由来の金属
イオンの濃度は、０．１ｍｇ／リットル未満であった
（Ｎａ+＝１．５ｍｇ／リットル…水Ｂ中の濃度、Ｃａ
2+＝０．０ｍｇ／リットル）。その後、水Ｄを、導入し
たスラリー量の０．２倍量注水した。さらに脱水した
後、解砕し、乾燥を行った。Next, water B was poured into the colored polymer particle cake remaining in the KF filter in an amount 4 times the amount of the introduced slurry. At this time, the concentration of the metal ion derived from the dispersion stabilizer in the wastewater was less than 0.1 mg / liter (Na + = 1.5 mg / liter ... concentration in water B, Ca
2 + = 0.0 mg / liter). Thereafter, water D was injected in an amount of 0.2 times the amount of the introduced slurry. After further dehydration, it was crushed and dried.
【０１３７】乾燥後の着色重合体粒子表面に付着残存し
ている荷電制御剤の不純物及び分解物の濃度は、１６３
０ｐｐｍであった。The concentration of impurities and decomposition products of the charge control agent remaining on the surface of the dried colored polymer particles was 163.
It was 0 ppm.
【０１３８】得られた着色重合体粒子、及び、３０℃／
８０％ＲＨの環境下に２日間放置した後の前記着色重合
体粒子を、それぞれ１００質量部に対し、平均粒径０．
００５μｍの疎水性シリカ１．５質量部を添加してヘン
シェルミキサーで混合しトナーとした。The obtained colored polymer particles and 30 ° C. /
Each of the colored polymer particles left to stand in an environment of 80% RH for 2 days was mixed with 100 parts by mass of each having an average particle diameter of 0.1 part by mass.
1.5 parts by mass of 005 μm hydrophobic silica was added and mixed with a Henschel mixer to obtain a toner.
【０１３９】このトナーを用いて、中間転写体を備えた
キヤノン製カラーレーザージェットプリンターカラーレ
ーザーショット−２０３０改造機を用いて２３℃／６５
％ＲＨの環境下で画出し試験を行ったところ、５，００
０枚耐久においても、初期と耐久後の画像濃度に変化が
なく、中抜けのない高画質の画像が得られた。Using this toner, at 23 ° C./65 using a modified Canon Color Laser Jet Printer Color Laser Shot-2030 equipped with an intermediate transfer member.
% RH.
In the zero-sheet durability, there was no change in the image density between the initial stage and the endurance stage, and a high-quality image with no voids was obtained.
【０１４０】また、３０℃／８０％ＲＨの環境下で同様
な画出し試験を行ったところ、同様な結果が得られた。A similar image-drawing test was conducted in an environment of 30 ° C./80% RH, and similar results were obtained.
【０１４１】＜比較例８＞酸洗浄後、ＫＦフィルター中
に残った着色重合体粒子ケーキに、水Ｂを、導入したス
ラリー量の４．５倍量注水した以外は実施例１０と同様
に行った。乾燥後の着色重合体粒子表面に付着残存して
いる荷電制御剤の不純物及び分解物の濃度は、１５００
ｐｐｍであった。<Comparative Example 8> The same procedure as in Example 10 was carried out except that water B was injected into the colored polymer particle cake remaining in the KF filter after the acid washing, by 4.5 times the amount of the introduced slurry. Was. The concentration of impurities and decomposition products of the charge control agent remaining on the surface of the dried colored polymer particles was 1500
ppm.
【０１４２】実施例１０と同様に、得られた着色重合体
粒子、及び、３０℃／８０％ＲＨの環境下に２日間放置
した後の前記着色重合体粒子を、それぞれ１００質量部
に対し、平均粒径０．００５μｍの疎水性シリカ１．５
質量部を添加してヘンシェルミキサーで混合しトナーと
した。In the same manner as in Example 10, the obtained colored polymer particles and the colored polymer particles after being left for 2 days in an environment of 30 ° C./80% RH were added to 100 parts by mass of each. Hydrophobic silica 1.5 with an average particle size of 0.005 μm
A part by weight was added and mixed with a Henschel mixer to obtain a toner.
【０１４３】さらに、この現像剤を用いて、実施例１０
と同様の画出し評価を行ったところ、２３℃／６５％Ｒ
Ｈの環境下では、実施例１０と同様に良好な画像が得ら
れたが、３０℃／８０％ＲＨの環境下では、次第に画像
濃度が低くなり、カブリが顕著になった。また、３０℃
／８０％ＲＨの環境下に２日間放置した後に、トナーと
したものは、初期より画像濃度が低く、カブリがみら
れ、また、現像器からのトナーの飛散が発生した。Further, in Example 10 using this developer,
23 ° C / 65% R
Under the environment of H, a good image was obtained in the same manner as in Example 10. However, under the environment of 30 ° C./80% RH, the image density gradually decreased, and fog became remarkable. 30 ° C
After leaving for 2 days in an environment of / 80% RH, the toner used had a lower image density than the initial stage, fogging was observed, and toner scattered from the developing device.
【０１４４】[0144]
【発明の効果】上述したように本発明によれば、懸濁重
合法によって得られた着色重合体粒子から、無機化合物
の安定化剤を効率良く除去を行い、荷電制御剤であるア
ルキルサリチル酸の金属錯体または、錯塩または、錯体
と錯塩の混合物の分解生成物や他の添加剤の水中への溶
解物に起因する水中への溶解物の乾燥後のトナー表面へ
の存在状態を制御し、帯電性の環境安定性が良く、画像
濃度変化及びカブリのないトナー得るトナーの製造方法
を提供することができる。As described above, according to the present invention, the stabilizer for the inorganic compound is efficiently removed from the colored polymer particles obtained by the suspension polymerization method, and the alkylsalicylic acid as the charge control agent is removed. Controls the state of presence of dissolved substances in water due to the decomposition products of metal complexes or complex salts, or mixtures of complexes and complex salts, and other additives dissolved in water on the toner surface after drying, and charging The present invention can provide a method for producing a toner having good environmental stability and a toner free from image density change and fog.
Claims (6)
有する重合性単量体組成物を、水系分散安定剤中で懸濁
させて重合を行い、着色重合体粒子を生成した後、酸洗
浄を行い、脱水後、金属陽イオンの総含有量が５ｍｇ／
リットル未満の水で洗浄し、洗浄排水中に分散安定剤由
来の金属陽イオンの総含有量が５ｍｇ／リットル未満に
なった後に、Ｎａ+，Ｋ+，Ｍｇ2+及びＣａ2+の総含有量
が１０乃至１５０ｍｇ／リットルの水を注水し、脱水
し、得られた湿潤着色重合体粒子を乾燥することを特徴
とするトナーの製造方法。Claims 1. A polymerizable monomer composition containing at least a polymerizable monomer and a colorant is suspended in an aqueous dispersion stabilizer and polymerized to produce colored polymer particles. After acid washing and dehydration, the total content of metal cations was 5 mg /
After washing with less than 1 liter of water and the total content of metal cations derived from the dispersion stabilizer in the washing wastewater is less than 5 mg / liter, the total content of Na + , K + , Mg 2+ and Ca 2+ A method for producing a toner, which comprises injecting water in an amount of 10 to 150 mg / liter, dehydrating, and drying the obtained wet-colored polymer particles.
量が７０乃至１２０ｍｇ／リットルの水を注水し、脱水
し、得られた湿潤着色重合体粒子を乾燥することを特徴
とする請求項１に記載のトナーの製造方法。2. The method according to claim 1, wherein water having a total content of Na.sup. + , K.sup. + , Mg.sup.2 + and Ca.sup.2 + of 70 to 120 mg / l is injected, dehydrated, and the obtained wet colored polymer particles are dried. The method for producing a toner according to claim 1, wherein:
量が７０乃至１２０ｍｇ／リットルの水の注水量が、被
洗浄懸濁液量１質量部に対して０．１乃至１．０質量部
であることを特徴とする請求項２に記載のトナーの製造
方法。3. The injection amount of water having a total content of Na.sup. + , K.sup. + , Mg.sup.2 + and Ca.sup.2 + of 70 to 120 mg / l is 0.1 to 1 part by mass of the suspension to be washed. 3. The method according to claim 2, wherein the amount is from 1.0 to 1.0 part by mass.
チル酸の金属化合物を含有することを特徴とする請求項
１乃至３のいずれかに記載のトナーの製造方法。4. The method according to claim 1, wherein the polymerizable monomer composition contains a metal compound of alkyl salicylic acid.
低結晶性または非結晶性のアルキルサリチル酸の金属錯
塩、または金属錯体、または金属錯塩と金属錯体の混合
物であることを特徴とする請求項４に記載のトナーの製
造方法。5. The metal compound of the alkyl salicylic acid,
The method for producing a toner according to claim 4, wherein the toner is a metal complex salt of a low crystalline or non-crystalline alkyl salicylic acid, a metal complex, or a mixture of a metal complex salt and a metal complex.
によって行われることを特徴とする請求項１乃至５のい
ずれかに記載のトナーの製造方法。6. The method according to claim 1, wherein the washing after the acid washing is performed by pouring water into the dewatered cake.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000073280A JP3748505B2 (en) | 2000-03-16 | 2000-03-16 | Toner production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000073280A JP3748505B2 (en) | 2000-03-16 | 2000-03-16 | Toner production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001265059A true JP2001265059A (en) | 2001-09-28 |
| JP3748505B2 JP3748505B2 (en) | 2006-02-22 |
Family
ID=18591541
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000073280A Expired - Fee Related JP3748505B2 (en) | 2000-03-16 | 2000-03-16 | Toner production method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3748505B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003215841A (en) * | 2002-01-28 | 2003-07-30 | Nippon Zeon Co Ltd | Method for manufacturing toner |
| JP2009230104A (en) * | 2008-02-29 | 2009-10-08 | Ricoh Co Ltd | Toner for developing electrostatic image and image forming device, toner container and process cartridge using same |
| JP2010204434A (en) * | 2009-03-04 | 2010-09-16 | Konica Minolta Business Technologies Inc | Method of manufacturing electrostatic charge image developing toner |
-
2000
- 2000-03-16 JP JP2000073280A patent/JP3748505B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003215841A (en) * | 2002-01-28 | 2003-07-30 | Nippon Zeon Co Ltd | Method for manufacturing toner |
| JP2009230104A (en) * | 2008-02-29 | 2009-10-08 | Ricoh Co Ltd | Toner for developing electrostatic image and image forming device, toner container and process cartridge using same |
| JP2010204434A (en) * | 2009-03-04 | 2010-09-16 | Konica Minolta Business Technologies Inc | Method of manufacturing electrostatic charge image developing toner |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3748505B2 (en) | 2006-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3466872B2 (en) | Method for producing toner for developing electrostatic images | |
| JP4521953B2 (en) | Toner production method | |
| JP3748505B2 (en) | Toner production method | |
| JPH0844111A (en) | Production of toner for developing electrostatic charge image | |
| JPH0566613A (en) | Production of toner | |
| JP2005055734A (en) | Toner and method for manufacturing toner | |
| US6953648B2 (en) | Process for producing toner particles | |
| JP2000010341A (en) | Production of polymerized toner grain | |
| JP4422885B2 (en) | Method for producing polymerization toner | |
| JP2000310887A (en) | Manufacture of toner | |
| JP2002091073A (en) | Method for producing toner | |
| JP4137126B2 (en) | Toner production method | |
| JP4387520B2 (en) | Method for producing polymerized toner | |
| JP4478276B2 (en) | Toner production method | |
| JP3437433B2 (en) | Method for producing toner for developing electrostatic images | |
| JP4508408B2 (en) | Method for producing toner particles | |
| JP3984755B2 (en) | Toner production method | |
| JP3870094B2 (en) | Toner production method | |
| JP3576801B2 (en) | Manufacturing method of toner | |
| JP2000081725A (en) | Production of toner | |
| JP3943866B2 (en) | Method for producing polymerization toner | |
| JP4378032B2 (en) | Toner production method and electrostatic image developing toner | |
| JPH08234485A (en) | Production of electrostatic charge image developing toner | |
| JP2007155860A (en) | Method for manufacturing electrostatic charge image developing toner | |
| JP4429324B2 (en) | Method for producing polymerization toner |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20040603 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20050823 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20051021 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20051122 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20051128 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081209 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091209 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091209 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101209 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111209 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121209 Year of fee payment: 7 |
|
| LAPS | Cancellation because of no payment of annual fees |