JP2537503B2 - Toner for electrostatic image development - Google Patents
Toner for electrostatic image developmentInfo
- Publication number
- JP2537503B2 JP2537503B2 JP62017378A JP1737887A JP2537503B2 JP 2537503 B2 JP2537503 B2 JP 2537503B2 JP 62017378 A JP62017378 A JP 62017378A JP 1737887 A JP1737887 A JP 1737887A JP 2537503 B2 JP2537503 B2 JP 2537503B2
- Authority
- JP
- Japan
- Prior art keywords
- toner
- polar group
- particles
- polymer
- examples
- 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.)
- Expired - Lifetime
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/0825—Developers with toner particles characterised by their structure; characterised by non-homogenuous distribution of components
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/0802—Preparation methods
- G03G9/0804—Preparation methods whereby the components are brought together in a liquid dispersing medium
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、電子写真、静電記録、静電印刷などにおけ
る静電荷像を現像するためのトナー及びその製法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing and the like, and a method for producing the toner.
従来技術 従来、一般に広く用いられて来たトナーは懸濁重合に
より得られるスチレン／アクリレート系共重合体粉末に
カーボンブラツクのような着色剤、随意帯電制御剤及び
／又は磁性体をドライブレンドして後押出し機等で溶融
混練し、次いで粉砕・分級することによって製造されて
来た（特開昭51−23354号参照）。2. Description of the Related Art Conventionally widely used toners are obtained by dry blending a styrene / acrylate copolymer powder obtained by suspension polymerization with a colorant such as carbon black, an optional charge control agent and / or a magnetic material. It has been produced by melt-kneading with a post-extruder or the like, and then crushing and classifying (see Japanese Patent Laid-Open No. 51-23354).
しかし、上記のような溶融混練−粉砕法で得られる従
来のトナーは、トナーの粒径の制御に限界があり、実質
的に10μ以下、特に８μ以下、殊に５μ以下の平均粒径
のトナーを歩留りよく製造することが困難である許り
か、現像剤にした場合解像度が低く且つかぶりが発生す
るという欠点を避けることが困難であった。However, the conventional toner obtained by the melt-kneading-pulverization method as described above has a limitation in controlling the particle size of the toner, and a toner having an average particle size of substantially 10 μm or less, particularly 8 μm or less, and particularly 5 μm or less. Although it is difficult to manufacture the toner with high yield, it is difficult to avoid the drawbacks that the resolution is low and fog occurs when it is used as a developer.
本発明の目的 本発明は従来一般に広く用いられて来たトナーの有し
た上記の欠点を大巾に改善し、しかも新規な製法を用い
ることによって従来法のトナーよりも安価なトナーを提
供することを目的とするものである。OBJECT OF THE INVENTION The present invention greatly improves the above-mentioned drawbacks of the toners that have been widely used in the past, and provides a toner which is cheaper than the toners of the conventional methods by using a novel manufacturing method. The purpose is.
本発明の特徴 本発明の静電荷像現像用トナーは、酸性極性基又は塩
基性極性基を有する重合体（以下「極性基を有する重合
体」という）、好ましくは酸性極性基を有する重合体の
一次粒子及び着色剤粒子並びに随意帯電制御剤を含有し
てなる二次粒子の会合粒子であることを特徴とする静電
荷像現像用トナーである。Features of the present invention The toner for developing an electrostatic image of the present invention comprises a polymer having an acidic polar group or a basic polar group (hereinafter referred to as "polymer having a polar group"), preferably a polymer having an acidic polar group. A toner for developing an electrostatic charge image, comprising associated particles of secondary particles containing primary particles, colorant particles, and an optional charge control agent.
本発明で用いられる極性基を有する重合体の一次粒子
は0.05〜0.5μ、好ましくは0.1〜0.3μの平均粒径を有
する熱可塑性重合体の粒子であって、一般に乳化重合法
によって好適に得られる。本発明のトナーである上記会
合粒子を構成する二次粒子は、0.01〜0.5、好ましくは
0.03〜0.1μの平均粒径をもつ着色剤粒子と極性基を有
する重合体の一次粒子とがイオン性結合、水素結合、金
属配位結合、弱酸−弱基結合、或いはフアンデアワール
ス力等の結合力によって凝集している粒子であって、一
般に0.5〜５μ、好ましくは１μ〜４μの平均粒径をも
っている。第１図は本発明のトナー製造工程において生
成した二次粒子の一例を示す倍率1,000倍の走査電子顕
微鏡写真である。The primary particles of the polymer having a polar group used in the present invention are particles of a thermoplastic polymer having an average particle diameter of 0.05 to 0.5μ, preferably 0.1 to 0.3μ, and are generally suitably obtained by an emulsion polymerization method. To be The secondary particles constituting the above-mentioned associated particles, which are the toner of the present invention, are 0.01 to 0.5, preferably
The colorant particles having an average particle diameter of 0.03 to 0.1μ and the primary particles of the polymer having a polar group have ionic bonds, hydrogen bonds, metal coordination bonds, weak acid-weak group bonds, or van der Waals forces, etc. The particles are aggregated by the binding force and generally have an average particle size of 0.5 to 5μ, preferably 1 to 4μ. FIG. 1 is a scanning electron microscope photograph at a magnification of 1,000 times showing an example of secondary particles produced in the toner manufacturing process of the present invention.
本発明の会合粒子は上記二次粒子が凝集して生成した
不定形の粒子であって、その平均粒径は一般に３〜25
μ、好ましくは５〜15μ、最もしくは５〜13μである。
第２図は本発明のトナーである会合粒子の一例を示す倍
率1,000倍の走査電子顕微鏡写真である。The associated particles of the present invention are indefinite particles produced by agglomeration of the above secondary particles, and the average particle size thereof is generally 3 to 25.
μ, preferably 5 to 15 μ, and most preferably 5 to 13 μ.
FIG. 2 is a scanning electron micrograph at a magnification of 1,000 times showing an example of associated particles which are the toner of the present invention.
本発明の好適な態様では、上記会合粒子を構成する二
次粒子間の接触部分の少くとも一部、好ましくは二次粒
子間の接触部分の大半、が造膜融着している会合粒子が
用いられる。第３図は本発明の二次粒子間の接触部分の
少くとも一部が造膜融着した会合粒子の倍率1,000倍の
走査形電子顕微鏡写真である。In a preferred embodiment of the present invention, at least a part of the contact portion between the secondary particles constituting the above-mentioned associated particles, preferably the majority of the contact portion between the secondary particles, the associated particles are film-fused. Used. FIG. 3 is a scanning electron micrograph (magnification: 1000) of the associated particles in which at least a part of the contact portion between the secondary particles of the present invention is film-fused.
本発明のトナーである会合粒子は、極性基を有する重
合体と着色剤の合計当り、極性基を有する重合体を20〜
99.9重量％、好ましくは30〜98重量％、最も好ましくは
40〜95重量％及び着色剤を80〜0.1重量％、好ましくは7
0〜２重量％、最も好ましくは60〜５重量％含有してな
るものである。The associated particles, which are the toner of the present invention, have a polar group-containing polymer in an amount of 20 to 20 per the total amount of the polymer having a polar group and the colorant.
99.9% by weight, preferably 30-98% by weight, most preferably
40-95% by weight and 80-0.1% by weight of colorant, preferably 7
The content is 0 to 2% by weight, most preferably 60 to 5% by weight.
本発明で用いられる極性基を有する重合体の好ましい
例はスチレン類、アルキル（メタ）アクリレート及び酸
性極性基又は塩基性極性基を有するコモノマー（以下
「極性基を有するコモノマー」という）の共重合体であ
る。Preferred examples of the polymer having a polar group used in the present invention are copolymers of styrenes, alkyl (meth) acrylates and comonomers having an acidic polar group or a basic polar group (hereinafter referred to as "comonomer having a polar group"). Is.
このような共重合体の好ましい例は、 （イ）、（イ）及び（ロ）の合計に基づいてスチレン類
90〜20重量％、好ましくは70〜30重量％、 （ロ）、（イ）及び（ロ）の合計に基づいてアルキル
（メタ）アクリレート10〜80重量％、好ましくは30〜70
重量％及び （ハ）、（イ）及び（ロ）の合計を100重量部とした場
合極性基を有するコモノマー0.05〜30重量部、好ましく
は１〜20重量部 を含有してなる共重合体である。また、上記共重合体
は、（イ）、（ロ）及び（ハ）のモノマー以外に、本発
明のトナーの性能を損じない程度に共重合し得る他のコ
モノマーを随意含有していてもよい。Preferred examples of such copolymers include styrenes based on the sum of (a), (a) and (b).
90 to 20% by weight, preferably 70 to 30% by weight, 10 to 80% by weight, preferably 30 to 70% by weight of alkyl (meth) acrylate based on the sum of (b), (a) and (b)
%, And a copolymer containing 0.05 to 30 parts by weight, preferably 1 to 20 parts by weight of a comonomer having a polar group, when the total of (c), (a) and (b) is 100 parts by weight. is there. In addition to the monomers (a), (b) and (c), the above copolymer may optionally contain other comonomers that can be copolymerized to the extent that the performance of the toner of the present invention is not impaired. .
上記（イ）のスチレン類の例としては、スチレン、ｏ
−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルス
チレン、α−メチルスチレン、ｐ−エチルスチレン、2,
4−ジメチルスチレン、ｐ−ｎ−ブチルスチレン、ｐ−t
ert−ブチルスチレン、ｐ−ｎ−ヘキシルスチレン、ｐ
−ｎ−オクチルスチレン、ｐ−ｎ−ノニルスチレン、ｐ
−ｎ−デシルスチレン、ｐ−ｎ−ドデシルスチレン、ｐ
−メトキシスチレン、ｐ−フエニルスチレン、ｐ−クロ
ルスチレン、3,4−ジクロルスチレン、ｐ−クロロメチ
ルスチレンなどを挙げることができ、スチレンが特に好
ましい。Examples of (a) styrenes include styrene and o
-Methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,
4-dimethylstyrene, pn-butylstyrene, pt
ert-butyl styrene, pn-hexyl styrene, p
-N-octyl styrene, pn-nonyl styrene, p
-N-decyl styrene, pn-dodecyl styrene, p
-Methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-chloromethylstyrene and the like can be mentioned, with styrene being particularly preferred.
上記（ロ）のアルキル（メタ）アクリレートの例とし
てはアクリル酸メチル、アクリル酸エチル、アクリル酸
ｎ−ブチル、アクリル酸イソブチル、アクリル酸プロピ
ル、アクリル酸ｎ−オクチル、アクリル酸ドデシル、ア
クリル酸ラウリル、アクリル酸２−エチルヘキシル、ア
クリル酸ステアリル、アクリル酸２−クロルエチル、α
−クロルアクリル酸メチル、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ｎ−ブチル、メタアクリル酸イソブチル、メタ
アクリル酸ｎ−オクチル、メタアクリル酸ドデシル、メ
タアクリル酸ラウリル、メタアクリル酸２−エチルヘキ
シル、メタアクリル酸ステアリルを挙げることができる
が、中でも炭素原子数１〜12、好ましくは３〜８、特に
好ましくは４の脂肪族アルコールの（メタ）アクリル酸
エステルが用いられる。Examples of the (b) alkyl (meth) acrylate include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, α
-Methyl chloroacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate, Examples thereof include 2-ethylhexyl methacrylate and stearyl methacrylate. Among them, (meth) acrylic acid ester of aliphatic alcohol having 1 to 12 carbon atoms, preferably 3 to 8 carbon atoms, and particularly preferably 4 is used. .
上記（ハ）の酸性極性基を有するモノマーとしては、
（ｉ）カルボキシル基（−COOH）を有するα、β−エチ
レン性不飽和化合物及び（ii）スルホン基（−SO3H）を
有するα，β−エチレン性不飽和化合物を挙げることが
できる。As the monomer having an acidic polar group of (c) above,
Examples include (i) an α, β-ethylenically unsaturated compound having a carboxyl group (—COOH) and (ii) an α, β-ethylenically unsaturated compound having a sulfone group (—SO 3 H).
（ｉ）の−COO基を有するα，β−エチレン性不飽和
化合物の例としては、アクリル酸、メタアクリル酸、フ
マール酸、マレイン酸、イタコン酸、ケイ皮酸、マレイ
ン酸モノブチルエステル、マレイン酸モノオクチルエス
テル、およびこれらのNaZn等の金属塩類等を挙げること
ができる。Examples of the α, β-ethylenically unsaturated compound having a —COO group (i) include acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, cinnamic acid, maleic acid monobutyl ester, and maleic acid. Examples thereof include acid monooctyl ester and metal salts thereof such as NaZn.
（ii）の−SO3H基を有するα，β−エチレン性不飽和
化合物の例としてはスルホン化スチレン、そのNa塩、ア
リルスルホコハク酸、アリルスルホコハク酸オクチル、
そのNa塩等を挙げることができる。Examples of the α, β-ethylenically unsaturated compound having a —SO 3 H group in (ii) include sulfonated styrene, its Na salt, allylsulfosuccinic acid, octyl allylsulfosuccinate,
The Na salt etc. can be mentioned.
また、上記（ハ）の塩基性極性基を有するコモノマー
としては、（ｉ）アミン基あるいは４級アンモニウム基
を有する炭素原子数１〜12、好ましくは２〜８、特に好
ましくは２の脂肪族アルコールの（メタ）アクリル酸エ
ステル、（ii）（メタ）アクリル酸アミドあるいは随意
Ｎ上で炭素原子数１〜18のアルキル基でモノ−又はジー
置換された（メタ）アクリル酸アミド、（iii）Ｎを環
員として有する複素環基で置換されたビニール化合物及
び（iv）N,N−ジアリル−アルキルアミンあるいはその
四級アンモニウム塩を例示することができる。中でも、
（ｉ）のアミン基あるいは四級アンモニウム基を有する
脂肪族アルコールの（メタ）アクリル酸エステルが塩基
性基を有するコモノマーとして好ましい。Further, as the comonomer having a basic polar group of (C), (i) an aliphatic alcohol having an amine group or a quaternary ammonium group and having 1 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and particularly preferably 2 (Meth) acrylic acid ester, (ii) (meth) acrylic acid amide or (meth) acrylic acid amide mono- or di-substituted with an alkyl group having 1 to 18 carbon atoms on N, (iii) N Examples thereof include a vinyl compound substituted with a heterocyclic group having as a ring member and (iv) N, N-diallyl-alkylamine or a quaternary ammonium salt thereof. Above all,
The (meth) acrylic acid ester of an aliphatic alcohol having an amine group or a quaternary ammonium group of (i) is preferable as a comonomer having a basic group.
（ｉ）のアミン基あるいは四級アンモニウム基を有す
る脂肪族アルコールの（メタ）アクリル酸エステルの例
としては、ジメチルアミノエチルアクリレート、ジメチ
ルアミノエチルメタクリレート、ジエチルアミノエチル
アクリレート、ジエチルアミノエチルメタクリレート、
上記４化合物の四級アンモニウム塩３−ジメチルアミノ
フエニルアクリレート、２−ヒドロキシ−３−メタクリ
ルオキシプロピルトリメチルアンモニウム塩等を挙げる
ことができる。Examples of (meth) acrylic acid esters of aliphatic alcohols having an amine group or a quaternary ammonium group of (i) include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate,
Examples thereof include quaternary ammonium salts of the above-mentioned 4 compounds, 3-dimethylaminophenyl acrylate, and 2-hydroxy-3-methacryloxypropyl trimethylammonium salt.
（ii）の（メタ）アクリル酸アミドあるいはＮ上で随
意モノ−又はジ−アルキル置換された（メタ）アクリル
酸アミドとしては、アクリルアミド、Ｎ−ブチルアクリ
ルアミド、N,N−ジブチルアクリルアミド、ピペリジル
アクリルアミド、メタクリルアミド、Ｎ−ブチルメタク
リルアミド、N,N−ジメチルアクリルアミド、Ｎ−オク
タデシルアクリルアミド等を挙げることができる。(Ii) (Meth) acrylic amide or (meth) acrylic amide optionally mono- or di-alkyl substituted on N includes acrylamide, N-butyl acrylamide, N, N-dibutyl acrylamide, piperidyl acrylamide, Methacrylamide, N-butylmethacrylamide, N, N-dimethylacrylamide, N-octadecylacrylamide and the like can be mentioned.
（iii）のＮを環員として有する複素環基で置換され
たビニール化合物としては、ビニールピリジン、ビニー
ルピロリドン、ビニルＮ−メチルピリジニウムクロリ
ド、ビニルＮ−エチルピリジニウムクロリド等を挙げる
ことができる。Examples of the vinyl compound (iii) substituted with a heterocyclic group having N as a ring member include vinyl pyridine, vinyl pyrrolidone, vinyl N-methylpyridinium chloride, vinyl N-ethylpyridinium chloride and the like.
（iv）のN,N−ジアリルアルキルアミンの例として
は、N,N−ジアリルメチルアンモニウムクロリド、N,N−
ジアリルエチルアンモニウムクロリド等を挙げることが
できる。Examples of N, N-diallylalkylamine of (iv) include N, N-diallylmethylammonium chloride, N, N-
Examples include diallylethylammonium chloride.
本発明で用いられる極性基を有する重合体のガラス転
移点は−90〜100℃、好ましくは、−30〜80℃、最も好
ましくは、−10〜60℃であり、またそのゲル化度は、ア
セトン還流下ソツクスレー抽出時の不溶分で表わして0.
0〜99.9重量％、好ましくは１〜30重量％である。ガラ
ス転移点が100℃を越えて高過ぎては、低温定着性が悪
くなる傾向があって好ましくなく、また−90℃未満と低
すぎては、トナーの粉体流動性が低下する傾向があるの
で好ましくない。一方、ゲル化度が50重量％を越えて高
すぎては低温定着性が悪くなる傾向があるので好ましく
ない。The glass transition point of the polymer having a polar group used in the present invention is −90 to 100 ° C., preferably −30 to 80 ° C., most preferably −10 to 60 ° C., and its gelation degree is Represented by insoluble matter during Soxhlet extraction under acetone reflux.
It is 0 to 99.9% by weight, preferably 1 to 30% by weight. If the glass transition point is higher than 100 ° C and is too high, the low-temperature fixability tends to be poor, which is not preferable, and if it is lower than -90 ° C, the powder fluidity of the toner tends to be low. It is not preferable. On the other hand, if the degree of gelation exceeds 50% by weight and is too high, the low temperature fixability tends to deteriorate, which is not preferable.
本明細書で「着色剤」の語は、静電荷像現像剤として
必要な色彩を該現像剤に与える着色性の添加剤と言う意
味で用いられるもので、マグネタイトのような磁性体や
ニグロシン染料のような帯電制御剤のように磁性又は帯
電制御性のような着色剤以外の性能を現像剤に賦与する
添加剤も現像剤に所期の着色性を与えるならば「着色
剤」に含まれるものである。In the present specification, the term "colorant" is used to mean a coloring additive that gives the developer a color required for an electrostatic image developer, and a magnetic substance such as magnetite or a nigrosine dye. An additive that imparts a property other than a colorant such as a magnetic property or a charge controllability to the developer, such as a charge control agent, is included in the “colorant” if it imparts the desired colorability to the developer. It is a thing.
本発明で用いられる着色剤としては、無機顔料又は、
有機顔料及び有機染料、好ましくは、無機顔料又は、有
機顔料が用いられるが、一種、又は二種以上の顔料又は
／及び一種又は二種以上の染料を必要に応じて組合せて
用いてもよい。このような無機顔料としては、 （イ）金属粉系顔料、 （ロ）金属酸化物系顔料、 （ハ）カーボン系顔料、 （ニ）硫化物系顔料、 （ホ）クロム酸塩系顔料、 （ヘ）フエロシアン化塩系顔料 等が好適である。The colorant used in the present invention, an inorganic pigment or,
Organic pigments and organic dyes, preferably inorganic pigments or organic pigments are used, but one or more pigments or / and one or more dyes may be used in combination as required. Examples of such inorganic pigments include (a) metal powder pigments, (b) metal oxide pigments, (c) carbon pigments, (d) sulfide pigments, (e) chromate pigments, (F) Preference is given to ferrocyanide salt pigments and the like.
このような（イ）金属粉系顔料の例としては、亜鉛
粉、鉄粉、銅粉等が挙げられる。Examples of such (a) metal powder pigments include zinc powder, iron powder, and copper powder.
（ロ）金属酸化物系顔料の例としてはマグネタイト、フ
エライト、ベンガラ、酸化チタン、亜鉛華、シリカ、酸
化クロム、ウルトラマリーン、コバルト青、セルリアン
ブルー、ミネラルバイオレツト、四酸化三鉛、などが挙
げられる。(B) Examples of metal oxide pigments include magnetite, ferrite, red iron oxide, titanium oxide, zinc white, silica, chromium oxide, ultramarine, cobalt blue, cerulean blue, mineral violet, trilead tetraoxide, and the like. To be
（ハ）カーボン系顔料としてはカーボンブラツク、サー
マトミツクカーボン、ランプブラツク、フアーネスブラ
ツク、などが挙げられる。(C) Examples of carbon-based pigments include carbon black, thermatomic carbon, lamp black, and fannes black.
（ニ）硫化物系顔料としては硫化亜鉛、カドミウムレツ
ド、セレンレツド、硫化水銀、カドミウムイエロー、な
どが挙げられる。(D) Examples of sulfide pigments include zinc sulfide, cadmium red, selenium red, mercury sulfide, and cadmium yellow.
（ホ）クロム酸塩系顔料としてはモリブデンレツド、バ
リウムイエロー、ストロンチウムイエロー、クロムイエ
ロー、などが挙げられる。(E) Examples of chromate pigments include molybdenum red, barium yellow, strontium yellow, and chrome yellow.
（ヘ）フエロシアン化化合物系顔料としてはミロリブル
ーなどが挙げられる。(F) Examples of ferrocyanide compound-based pigments include miloli blue.
また前記の有機顔料としては、下記のものを例示でき
る。Moreover, the following can be illustrated as said organic pigment.
（イ）アゾ系顔料： ハンザイエローＧ、ベンジジンイエロー、ベンジジン
オレンジ、パーマネントレツド4R、ピラゾロンレツド、
リソールレツド、ブリリアントスカーレツトＧ、ボンマ
ルーンライト、など−。(A) Azo pigments: Hansa Yellow G, Benzidine Yellow, Benzidine Orange, Permanent Red 4R, Pyrazolone Red,
Resol red, brilliant scarlet G, bon maroon light, etc.
（ロ）酸性染料系顔料及び 塩基性染料系顔料、 オレンジII、アシツトオレンジＲ、エオキシン、キノ
リンイエロー、タートラジンイエロー、アシツドグリー
ン、ピーコツクブルー、アルカリブルー等の染料を沈殿
剤により沈殿したもの。ローダミン、マゼンタ、マラカ
イトグリーン、メチルバイオレツト、ビクトリアブルー
等の染料をタンニン酸、吐酒石、PTA、PMA、PTMAなどで
沈殿したものなど−。(B) Acid dyes and basic dyes, orange II, acid orange R, eoxin, quinoline yellow, tartrazine yellow, acid green, pekotsk blue, alkali blue and other dyes were precipitated with a precipitant. thing. Rhodamine, magenta, malachite green, methyl violet, Victoria blue and other dyes precipitated with tannic acid, tartar, PTA, PMA, PTMA, etc.
（ハ）媒染染料系顔料 ヒドロキシアンスラキノン類の金属塩類、アリザリン
マーダーレーキなど−。(C) Mordant dye-based pigments Metal salts of hydroxyanthraquinones, alizarin murder lake, etc.
（ニ）フタロシアニン系顔料 フタロシアニンブルー、スルホン化銅フタロシアニン
など−。(D) Phthalocyanine pigments such as phthalocyanine blue and sulfonated copper phthalocyanine.
（ホ）キナクリドン系顔料及びジオキサン系顔料 キナクリドンレツド、キナクリドンバイオレツト、カ
ルバゾールジオキサジンバイオレツトなど−。(E) Quinacridone pigments and dioxane pigments Quinacridone red, quinacridone violet, carbazole dioxazine violet, and the like.
（ニ）その他 有機蛍光顔料、アニリンブラツクなど−。(D) Other organic fluorescent pigments, aniline black, etc.
また、前記の有機染料としては、ニグロシン染料、ア
ニリン染料が用いられる。Further, as the organic dye, a nigrosine dye or an aniline dye is used.
本発明のトナーは、前記のように、必要に応じ、帯電
制御剤や磁性体等を含有するものである。このような帯
電制御剤としては、プラス用としてニグロシン系の電子
供与性染料、その他ナフテン酸または高級脂肪酸の金属
塩、アルコキシル化アミン、四級アンモニウム塩、アル
キルアミド、キレート、顔料、フツ素処理活性剤など、
マイナス用として電子受容性の有機錯体、その他塩素化
パラフイン、塩素化ポリエステル、酸基過剰のポリエス
テル、銅フタロシアニンのスルホニルアミンなどが例示
できる。As described above, the toner of the present invention contains a charge control agent, a magnetic material and the like, if necessary. Examples of such a charge control agent include nigrosine-based electron-donating dyes for positive use, other metal salts of naphthenic acid or higher fatty acids, alkoxylated amines, quaternary ammonium salts, alkylamides, chelates, pigments, and fluorine treatment activity. Agents,
For minus, electron-accepting organic complexes, other chlorinated paraffins, chlorinated polyesters, polyesters having excess acid groups, sulfonylamines of copper phthalocyanine and the like can be exemplified.
また、本発明のトナーは、必要により流動化剤等の添
加剤と共に用いることができ、そのような流動化剤とし
ては疎水性シリカ、酸化チタン、酸化アルミニウム等の
微粉末を例示でき、トナー100重量部当り0.01〜５重量
部、好ましくは0.1〜１重量部用いられる。Further, the toner of the present invention can be used together with an additive such as a fluidizing agent if necessary, and as such fluidizing agent, fine powder of hydrophobic silica, titanium oxide, aluminum oxide or the like can be exemplified, and toner 100 The amount is 0.01 to 5 parts by weight, preferably 0.1 to 1 part by weight.
本発明のトナーの好適な製法を例示すれば、以下の通
りである。乳化重合により得られた酸性極性基又は塩基
性極性基を有する重合体のエマルジヨンに所要量の着色
剤粉末並びに随意帯電制御剤を添加混合して均一に分散
させ0.5〜４時間、好ましくは１〜３時間攪拌を続ける
と極性基を有する重合体の一次粒子と着色剤粒子は次第
に凝集して第１図の写真に示したような0.5〜５μの平
均粒径をもった二次粒子に生長する。このような分散体
を更にそのまま0.5〜３時間、好適には１〜２時間攪拌
を続けると二次粒子が更に凝集して第２図の写真に示し
たような５〜25μの平均粒径をもった会合粒子に生長す
る。本発明のトナーの最も好適な製法では、このように
して生成した分散液を、更に、極性基を有する重合体の
ガラス転移点〜ガラス転移点より20℃高い温度に１〜６
時間、好適には２〜４時間攪拌を続けると第３図の写真
に示したように、二次粒子間の接触部分の少くとも一部
が造膜融着した会合粒子が生成する。このような会合粒
子は、二次粒子間が造膜融着しているので、貯蔵、輸
送、現像剤製造時等に殆んど崩壊することが無いので静
電荷像現像用現像剤としては特に好適である。The preferred method for producing the toner of the present invention is as follows. Emulsion of a polymer having an acidic polar group or a basic polar group obtained by emulsion polymerization is added and mixed with a required amount of a colorant powder and an optional charge control agent to uniformly disperse it for 0.5 to 4 hours, preferably 1 to When stirring is continued for 3 hours, the primary particles of the polymer having a polar group and the colorant particles gradually aggregate to grow into secondary particles having an average particle size of 0.5 to 5 μ as shown in the photograph of FIG. . When such a dispersion is further stirred as it is for 0.5 to 3 hours, preferably 1 to 2 hours, the secondary particles are further aggregated to give an average particle diameter of 5 to 25 μ as shown in the photograph of FIG. Propagate to the associated particles. In the most preferable method for producing the toner of the present invention, the dispersion liquid thus produced is further added to a glass transition point of the polymer having a polar group to a temperature 20 ° C. higher than the glass transition point by 1 to 6 ° C.
When stirring is continued for a time, preferably 2 to 4 hours, as shown in the photograph of FIG. 3, associated particles in which at least a part of the contact portion between the secondary particles are film-fused are formed. Since such associated particles have a film-forming fusion between the secondary particles, they are hardly disintegrated during storage, transportation, production of the developer, etc., and thus are particularly suitable as a developer for developing an electrostatic image. It is suitable.
本発明のトナーは、鉄、ガラスビース等のキヤリアと
混合されて現像剤とされるが、トナー自体がフエライト
等を既に着色剤として含有するような場合には、フエラ
イト等はキヤリアの働きもするので、その場合にはトナ
ーはそのまま現像剤として用い得る。なお、上記キヤリ
アーとしては、樹脂被覆、好ましくは弗素系樹脂被覆に
より負の摩擦帯電特性を有する鉄粉が殊に好適である。The toner of the present invention is mixed with carriers such as iron and glass beads to be a developer, but when the toner itself already contains ferrite or the like as a colorant, the ferrite or the like also functions as the carrier. Therefore, in that case, the toner can be used as a developer as it is. As the carrier, iron powder having a negative triboelectrification characteristic by resin coating, preferably fluorine resin coating, is particularly suitable.
本発明の効果 本発明のトナーは、粒度分布が比較的狭く且つ平均粒
径が比較的小さいので、静電荷像現像剤にした場合、従
来品に較べ解像度が著しく向上し且つかぶりの発生が殆
んど無いといった優れた効果を奏し、更に粉砕分級を要
しない等製法が従来法に較べて簡略化され且つ必要なト
ナー粒分の収率も高いので経済性においても優れている
といった効果を奏するものである。EFFECTS OF THE INVENTION The toner of the present invention has a relatively narrow particle size distribution and a relatively small average particle size. Therefore, when it is used as an electrostatic image developer, the resolution is remarkably improved and the occurrence of fogging is almost eliminated. It has an excellent effect that it does not exist, and further that the manufacturing method that does not require pulverization classification is simpler than the conventional method and the yield of necessary toner particles is high, so that it is also excellent in economic efficiency It is a thing.
以下に実施例により本発明を具体的に説明する。な
お、特記しない限り数量は重量によって表示した。The present invention will be specifically described below with reference to examples. In addition, unless otherwise specified, the quantities are indicated by weight.
実施例１ 酸性極性基含有重合樹脂の調整 スチレンモノマー（ST） 60部 アクリル酸ブチル（BA） 40部 アクリル酸（AA） ８部 以上のモノマー混合物を 水 100部 ノニオン乳化剤 １部 （エマルゲン950） アニオン乳化剤 1.5部 （ネオゲンＲ） 過硫酸カリウム 0.5部 の水溶液混合物に添加し、攪拌下70℃で８時間重合させ
て固形分50％の酸性極性基含有樹脂エマルジヨンを得
た。Example 1 Preparation of acidic polar group-containing polymerized resin Styrene monomer (ST) 60 parts Butyl acrylate (BA) 40 parts Acrylic acid (AA) 8 parts Water of the above monomer mixture 100 parts Nonionic emulsifier 1 part (Emulgen 950) anion 1.5 parts of emulsifier (Neogen R) 0.5 part of potassium persulfate was added to an aqueous solution mixture, and the mixture was polymerized at 70 ° C. for 8 hours with stirring to obtain an emulsion containing acidic polar group having a solid content of 50%.
トナーの調整（１） 酸性極性基含有樹脂エマルジヨン 120部 マグネタイト 40部 ニグロシン染料 ５部 （ボントロンＮ−04） カーボンブラツク ５部 （ダイヤブラツク♯100） 水 380部 以上の混合物をスラツシヤーで分散攪拌しながら約30℃
に２時間保持した。その後、さらに攪拌しながら70℃に
加温して３時間保持した。この間顕微鏡で観察して、樹
脂粒子とマグネタイト粒子とのコンプレツクスが約10μ
に生長するのが確認された。冷却して、得られた液状分
散物をブフナーロ過、水洗し、50℃真空乾燥10時間させ
た。Preparation of toner (1) Resin containing acidic polar group Emulsion 120 parts Magnetite 40 parts Nigrosine dye 5 parts (Bontron N-04) Carbon black 5 parts (diamond # 100) water 380 parts While stirring with stirring the above mixture. About 30 ℃
Hold for 2 hours. Then, the mixture was further heated to 70 ° C. with stirring and held for 3 hours. During this time, observing with a microscope, the complex between the resin particles and the magnetite particles was about 10μ.
Was confirmed to grow. After cooling, the obtained liquid dispersion was filtered with a Buchner filter, washed with water, and vacuum dried at 50 ° C. for 10 hours.
この得られたトナー100重量部に流動化剤としてシリ
カ（日本アエロジル社製アエロジルR972）を0.5重量部
を添加混合し、試験用現像剤とした。To 100 parts by weight of the toner thus obtained, 0.5 parts by weight of silica (Aerosil R972 manufactured by Nippon Aerosil Co., Ltd.) as a fluidizing agent was added and mixed to prepare a test developer.
このトナーで用いた上記重合体のTgは45℃、ゲル化度
は５％、軟化点は148℃、トナーの平均粒径は、12μで
あった。The Tg of the above polymer used in this toner was 45 ° C., the degree of gelation was 5%, the softening point was 148 ° C., and the average particle size of the toner was 12 μ.
上記現像剤を市販の複写機（キヤノン製NP−270Z）に
入れ複写を行ったところ、濃度の高い、かぶりの少ない
複写画が得られた。結果を表−２に示した。When the above developer was put into a commercially available copying machine (NP-270Z manufactured by Canon Inc.) and copying was performed, a copy image having high density and less fog was obtained. The results are shown in Table-2.
実施例２〜７ 表−１に示したモノマー組成を用い実施例１と同様の
操作を繰り返した。結果を表−２に示す。なお、表−１
で用いた略記号の意味を以下に示す。Examples 2 to 7 The same operation as in Example 1 was repeated using the monomer composition shown in Table 1. Table 2 shows the results. Table-1
The meanings of the abbreviations used in Step 1 are shown below.
2EHA;アクリル酸２エチルヘキシル MAA;メタクリル酸 MBM;マレイン酸モノブチル BQA;2−ヒドロキシプロピル−N,N,N−トリメチルアンモ
ニウムクロライドアクリレート DMAA;アクリル酸ジメチルアミノエチル LMA;メタクリル酸ラウリル VP;ビニルピリジン DMPC;N,N−ジアリルメチルアンモニウムクロライド 実施例８ 実施例１と同様の酸性極性基含有樹脂エマルジヨンを
調整した後、トナー調整時に以下の操作を行った。2EHA; 2-ethylhexyl acrylate MAA; methacrylic acid MBM; monobutyl maleate BQA; 2-hydroxypropyl-N, N, N-trimethylammonium chloride acrylate DMAA; dimethylaminoethyl acrylate LMA; lauryl methacrylate VP; vinylpyridine DMPC; N, N-Diallylmethylammonium chloride Example 8 After preparing an acidic polar group-containing resin emulsion similar to that in Example 1, the following operations were performed during toner preparation.
トナーの調整（２） 実施例１の酸性極性基含有樹脂 エマルジヨン 184部 クロム染料（ボントロンＥ−81） １部 カーボンブラツク（リーガル330R） ７部 水 307部 以上の混合物を実施例１と同様の操作を行って、試験用
トナーを調整した。得られた重合体のTgは、43℃、ゲル
化度590、軟化点147℃、トナーの平均粒径は、10.5μｍ
であった。このトナーを市販の複写機（東芝製レオドラ
イBD−4140）に入れ、複写を行ったところ、濃度の高
い、かぶりの少ない複写画が得られた。結果を表−２に
示す。Preparation of Toner (2) Acid Polar Group-Containing Resin of Example 1 184 parts Chromium dye (Bontron E-81) 1 part Carbon black (Regal 330R) 7 parts Water 307 parts The above mixture was treated in the same manner as in Example 1. Then, the test toner was prepared. The polymer obtained has a Tg of 43 ° C., a gelation degree of 590, a softening point of 147 ° C., and an average particle diameter of the toner is 10.5 μm.
Met. When this toner was put in a commercially available copying machine (Toshiba made Rhodry BD-4140) and copying was performed, a copy image having high density and less fog was obtained. Table 2 shows the results.
実施例９〜11 表−１に示すモノマー組成を用い実施例８と同様の操
作を繰り返した。結果を表−２に示す。Examples 9 to 11 The same operation as in Example 8 was repeated using the monomer composition shown in Table 1. Table 2 shows the results.
実施例12 実施例１における会合粒子形成反応時、70℃、２時間
保持の代りに60℃加温２時間に保持したところ、粒子成
長が制御され収率60％で平均粒径５μｍのトナーが得ら
れた。このトナーにより複写試験を行ったところ、非常
に解像度の良好で、濃度が高く、かぶりの少ない画像が
えられた。Example 12 During the association particle formation reaction in Example 1, when the temperature was kept at 70 ° C. for 2 hours instead of 70 ° C. for 2 hours, particle growth was controlled and a toner having an average particle size of 5 μm was obtained at a yield of 60%. Was obtained. When a copying test was carried out using this toner, an image having very good resolution, high density and little fog was obtained.
比較例１ 表−１に示すように、実施例１の樹脂モノマー組成中
酸性素極性基モノマーであるAAを添加せず重合した樹脂
エマルジヨンを用いたところ、会合粒子の成長がなく、
試験用トナーがえられなかった。Comparative Example 1 As shown in Table 1, when a resin emulsion prepared by polymerizing without adding AA which is an acidic elementary polar group monomer in the resin monomer composition of Example 1 was used, there was no growth of associated particles,
No test toner was obtained.
比較例２ 実施例１における樹脂エマルジヨンをスプレードライ
ヤー（アシザワニロアトマイザー製、モービルマイナ
ー）で入口温度120℃、出口温度90℃、供給量1.5l/mi
n、アトマイザー３×104rpmの運転条件にて乾燥させ、
樹脂を得た。この樹脂60部、マグネタイト40部、ニグロ
シン染料（ボントロンＮ−04）５部、カーボンブラツク
（ダイヤブラツク♯100）５部を溶融混練、粉砕して平
均粒径５μｍのトナーを得た。この時の収率は、35％で
あった。Comparative Example 2 The resin emulsion obtained in Example 1 was sprayed with a spray drier (manufactured by Ashiza Vanillo atomizer, Mobile Miner) at an inlet temperature of 120 ° C., an outlet temperature of 90 ° C., and a supply amount of 1.5 l / mi.
n, dried under the operating conditions of atomizer 3 × 10 4 rpm,
A resin was obtained. 60 parts of this resin, 40 parts of magnetite, 5 parts of nigrosine dye (Bontron N-04) and 5 parts of carbon black (diamond black # 100) were melt-kneaded and pulverized to obtain a toner having an average particle size of 5 μm. The yield at this time was 35%.
この得られたトナー100重量部に流動化剤としてシリ
カ（日本アエロジル社製Ｒ−972）を0.5重量部を添加混
合し、試験用現像剤とした。To 100 parts by weight of the obtained toner, 0.5 parts by weight of silica (R-972 manufactured by Nippon Aerosil Co., Ltd.) was added and mixed as a fluidizing agent to prepare a test developer.
この現像剤は、非常に流動性の悪いものであった。こ
の現像剤を用いて、実施例１と同様の複写試験を行った
ところ、非常にかぶりの多い画像がえられた。This developer had very poor fluidity. When a copying test similar to that in Example 1 was conducted using this developer, an image with very large fog was obtained.
比較例３ 比較例２と同様の操作を行い表−１に示すような樹脂
組成を得て、比較例２と同様の配合で溶融混練、粉砕し
て収率55％で平均粒径12.0μｍのトナーを得た。このト
ナーを用いて、同様の複写試験を行った。結果を表−２
に示す。Comparative Example 3 The same operation as in Comparative Example 2 was carried out to obtain a resin composition as shown in Table 1. Melt kneading and pulverization were carried out in the same composition as in Comparative Example 2 to obtain a yield of 55% and an average particle size of 12.0 μm. Toner was obtained. A similar copying test was conducted using this toner. The results are shown in Table-2.
Shown in
複写画解像度評価方法 データクウエスト社テストパターンAR−４を複写し、
1mmあたりのライン数を目視確認して、解像度の評価と
した。本評価方法において、表−１の樹脂組成では、解
像度6.3以上で良好、3.6以下で不良と判断できる。Duplicate image resolution evaluation method Duplicate the data quat company test pattern AR-4,
The number of lines per 1 mm was visually confirmed to evaluate the resolution. In this evaluation method, with the resin composition of Table-1, it can be judged that the resolution of 6.3 or more is good, and the resolution of 3.6 or less is bad.
複写画かぶり評価法： 村上カラーラボラトリー社製CM−53Pの反射率計を用
いて、光角45°にて複写前の白紙の反射率と複写後の非
文字部分の反射率を比較し、反射率比にてかぶり濃度
（％）とした。かぶり濃度0.7以下でかぶり良好、1.0以
上で不良と判断できる。Copy image fogging evaluation method: Using a CM-53P reflectometer made by Murakami Color Laboratory Co., Ltd., the reflectance of the blank paper before copying and the reflectance of the non-character portion after copying were compared at an optical angle of 45 °, and the reflectance was compared. The fog density (%) was defined as a ratio. It can be judged that the fog density is 0.7 or less and the fog is good, and that the fog density is 1.0 or more is bad.
第１図は本発明のトナー製造時の二次粒子の粒子構造を
示す電子顕微鏡写真の図面代用写真、第２図は本発明ト
ナーの会合粒子の粒子構造を示す電子顕微鏡写真の図面
代用写真、第３図は二次粒子間の接触部分の少くとも一
部が造膜融着した会合粒子の粒子構造を示す電子顕微鏡
写真の図面代用写真である。FIG. 1 is a drawing substitute photograph of an electron microscope photograph showing a particle structure of secondary particles at the time of producing the toner of the present invention, and FIG. 2 is a drawing substitute photograph of an electron microscope photograph showing a particle structure of associated particles of the toner of the present invention. FIG. 3 is a drawing-substituting photograph of an electron micrograph showing the particle structure of associated particles in which at least a part of the contact portion between secondary particles is film-fused.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭63−33753（ＪＰ，Ａ) 特開 昭61−210368（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-63-33753 (JP, A) JP-A-61-210368 (JP, A)
Claims (4)
合体の一次粒子及び着色剤粒子並びに随意帯電制御剤を
含有してなる二次粒子の会合粒子であることを特徴とす
る静電荷像現像用トナー。1. An electrostatic charge image which is an association particle of primary particles and a colorant particle of a polymer having an acidic polar group or a basic polar group, and secondary particles containing an optional charge control agent. Toner for development.
造膜融着している特許請求の範囲第１項記載のトナー。2. The toner according to claim 1, wherein at least a part of the contact portion between the secondary particles is film-fused.
電制御剤を添加し、20〜45℃で１〜３時間攪拌下加熱
し、次いで重合体のガラス転移点〜ガラス転移点より20
℃高い温度に１〜３時間攪拌下加熱して生成した会合粒
子を、随意過し、乾燥することを特徴とする、酸性極
性基又は塩基性極性基を有する重合体の一次粒子及び着
色剤粒子並びに随意帯電制御剤を含有してなる二次粒子
の会合粒子である静電荷像現像用トナーの製法。3. A coloring agent and an optional charge control agent are added to a polymer emulsion, the mixture is heated at 20 to 45 ° C. for 1 to 3 hours with stirring, and then the glass transition point to the glass transition point of the polymer is 20.
The primary particles and the colorant particles of a polymer having an acidic polar group or a basic polar group, characterized in that the associated particles produced by heating to a high temperature of 1 ° C for 1 to 3 hours with stirring are optionally dried. And a method for producing a toner for developing an electrostatic charge image, which is an associated particle of secondary particles containing an optional charge control agent.
る重合体の一次粒子及び着色剤粒子並びに帯電制御剤を
含有してなる二次粒子の会合粒子である静電荷像現像用
トナー及び （２）キヤリヤー を含有してなる静電荷像現像用現像剤。4. A toner for developing an electrostatic charge image, which is (1) an associated particle of primary particles and a colorant particle of a polymer having an acidic polar group or a basic polar group, and secondary particles containing a charge control agent. And (2) a developer for developing an electrostatic charge image, which comprises a carrier.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62017378A JP2537503B2 (en) | 1987-01-29 | 1987-01-29 | Toner for electrostatic image development |
| US07/261,829 US4996127A (en) | 1987-01-29 | 1988-01-29 | Toner for developing an electrostatically charged image |
| DE3855939T DE3855939T2 (en) | 1987-01-29 | 1988-01-29 | TONER FOR DEVELOPING ELECTROSTATICALLY CHARGED IMAGES |
| PCT/JP1988/000073 WO1988005930A1 (en) | 1987-01-29 | 1988-01-29 | Toner for developing electrostatically charged image |
| EP88901304A EP0302939B1 (en) | 1987-01-29 | 1988-01-29 | Toner for developing electrostatically charged image |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62017378A JP2537503B2 (en) | 1987-01-29 | 1987-01-29 | Toner for electrostatic image development |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63186253A JPS63186253A (en) | 1988-08-01 |
| JP2537503B2 true JP2537503B2 (en) | 1996-09-25 |
Family
ID=11942348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62017378A Expired - Lifetime JP2537503B2 (en) | 1987-01-29 | 1987-01-29 | Toner for electrostatic image development |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2537503B2 (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7018766B2 (en) | 2002-11-08 | 2006-03-28 | Seiko Epson Corporation | Toner and production process thereof |
| US7258959B2 (en) | 2003-03-26 | 2007-08-21 | Ricoh Company, Ltd. | Toner for electrophotography and image forming apparatus |
| US7261989B2 (en) | 2003-10-10 | 2007-08-28 | Ricoh Company, Ltd. | Toner for developing electrostatic images, developer, image forming method, and image forming apparatus |
| EP1835352A1 (en) | 2006-03-17 | 2007-09-19 | Ricoh Company, Ltd. | Toner, process cartridge, and image forming method |
| US7374851B2 (en) | 2003-09-18 | 2008-05-20 | Ricoh Company, Ltd. | Toner, and, developer, toner container, process cartridge, image forming apparatus and image forming method |
| US7435521B2 (en) | 2002-06-28 | 2008-10-14 | Ricoh Company, Ltd. | Toner for developing electrostatic image |
| US7449273B2 (en) | 2004-08-27 | 2008-11-11 | Ricoh Company, Limited | Toner containing unsaturated polyester in binder resin, method for preparing the toner, and developer including the toner |
| US7455942B2 (en) | 2004-09-17 | 2008-11-25 | Ricoh Company, Ltd. | Toner, developer, toner container, process cartridge, image forming apparatus, and image forming method using the same |
| US7504188B2 (en) | 2005-05-10 | 2009-03-17 | Ricoh Company, Ltd. | Toner and developer, toner container, process cartridge, image forming apparatus, and image forming method using the same |
| US7824835B2 (en) | 2006-09-15 | 2010-11-02 | Ricoh Company, Ltd. | Toner, production method thereof, developer, toner container, process cartridge, image forming method, and image forming apparatus |
| EP2348362A2 (en) | 2010-01-20 | 2011-07-27 | Ricoh Company, Ltd | Toner, method for producing the same, and developer |
| US8163455B2 (en) | 2008-03-14 | 2012-04-24 | Ricoh Company, Ltd. | Toner for image formation, method for producing toner, container containing toner, two-component developer, process cartridge, and image forming method |
| US8178268B2 (en) | 2008-09-26 | 2012-05-15 | Ricoh Company, Limited | Magenta toner and developer |
| US8501379B2 (en) | 2007-06-19 | 2013-08-06 | Ricoh Company, Ltd. | Toner and method for producing the same and developer |
| US8580476B2 (en) | 2010-03-25 | 2013-11-12 | Ricoh Company, Ltd. | Method for preparing particulate release agent, toner using the particulate release agent, and method for preparing the toner |
| US8771914B2 (en) | 2007-03-23 | 2014-07-08 | Ricoh Company, Ltd. | Toner for developing latent electrostatic image, two-component developer, image forming method and image forming apparatus |
| US9625848B2 (en) | 2011-09-08 | 2017-04-18 | Ricoh Company, Ltd. | Toner and method for producing toner |
Families Citing this family (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2748419B2 (en) * | 1988-08-12 | 1998-05-06 | 三菱化学株式会社 | Polymerized toner and method for producing the same |
| JPH0778644B2 (en) * | 1989-11-30 | 1995-08-23 | 株式会社巴川製紙所 | Dry toner for electrophotography |
| EP0609443B1 (en) * | 1991-10-22 | 1999-01-27 | Nippon Carbide Kogyo Kabushiki Kaisha | Colored toner for developing electrostatic image |
| JP2880356B2 (en) * | 1991-10-30 | 1999-04-05 | 沖電気工業株式会社 | Image forming apparatus and image forming method |
| JP3212195B2 (en) * | 1992-08-24 | 2001-09-25 | 株式会社東芝 | Electrophotographic developer and manufacturing method thereof |
| JPH07244422A (en) * | 1994-03-02 | 1995-09-19 | Fujitsu Ltd | Image forming device and photoreceptor |
| JP2735096B2 (en) * | 1994-06-03 | 1998-04-02 | 富士通株式会社 | Image forming method and apparatus |
| JP3225175B2 (en) * | 1995-03-22 | 2001-11-05 | 株式会社東芝 | Manufacturing method of developer |
| CA2176444C (en) * | 1995-05-15 | 1999-10-12 | Kengo Hayase | Toner for developing electrostatic image, apparatus unit and image forming method |
| US6002903A (en) * | 1995-05-15 | 1999-12-14 | Canon Kabushiki Kaisha | Toner for developing electrostatic image, apparatus unit and image forming method |
| DE69614605T2 (en) * | 1995-05-22 | 2002-07-04 | Canon Kk | Toner for developing electrostatic images |
| JP3576374B2 (en) * | 1998-03-18 | 2004-10-13 | 日本カーバイド工業株式会社 | Method for producing toner for developing electrostatic images |
| US6717602B2 (en) | 1999-07-02 | 2004-04-06 | Konica Corporation | Image forming method and image forming apparatus, and electrostatic latent image developing toner used by the same |
| EP1176474B1 (en) | 2000-07-28 | 2005-11-23 | Canon Kabushiki Kaisha | Toner, toner production process and image forming method |
| US6617091B2 (en) | 2000-08-03 | 2003-09-09 | Konica Corporation | Production method of toner |
| DE60223778T3 (en) | 2001-11-02 | 2015-08-06 | Ricoh Co., Ltd. | Toner for the development of electrostatic images, developers, and development processes |
| JP4030907B2 (en) | 2003-03-19 | 2008-01-09 | 株式会社リコー | Toner for electrostatic image development |
| US7348117B2 (en) | 2003-08-07 | 2008-03-25 | Ricoh Company Limited | Toner, method for manufacturing the toner, developer including the toner, toner container containing the toner, and image forming method, image forming apparatus and process cartridge using the toner |
| US7250241B2 (en) | 2003-12-05 | 2007-07-31 | Canon Kabushiki Kaisha | Toner and process for producing toner |
| JP4474211B2 (en) | 2004-06-15 | 2010-06-02 | 株式会社リコー | Method for producing toner for developing electrostatic image |
| CN101107279B (en) | 2005-03-29 | 2011-06-01 | 佳能株式会社 | Charge control resin and toner |
| US7741001B2 (en) | 2005-04-04 | 2010-06-22 | Sharp Kabushiki Kaisha | Toner for electrostatic image development and process for preparing the same |
| JP4628269B2 (en) | 2005-09-05 | 2011-02-09 | 株式会社リコー | Yellow toner for image formation and developer for developing electrostatic latent image using the same |
| CN101379441A (en) | 2005-11-11 | 2009-03-04 | 佳能株式会社 | Resin for toner and toner |
| JP4717671B2 (en) * | 2006-03-17 | 2011-07-06 | キヤノン株式会社 | toner |
| WO2008044427A1 (en) | 2006-10-06 | 2008-04-17 | Canon Kabushiki Kaisha | Developing roller, developing apparatus using the same and image forming apparatus |
| CN101776854A (en) | 2010-01-06 | 2010-07-14 | 湖北鼎龙化学股份有限公司 | Method for manufacturing carbon power for developing electrostatic charge image |
| CN102193354B (en) | 2011-05-17 | 2012-08-22 | 湖北鼎龙化学股份有限公司 | Bicomponent developer |
| KR101497264B1 (en) | 2011-05-18 | 2015-02-27 | 캐논 가부시끼가이샤 | Toner |
| JP6351296B2 (en) | 2014-02-24 | 2018-07-04 | キヤノン株式会社 | toner |
| EP3798731A4 (en) | 2018-05-22 | 2022-01-26 | Sanyo Chemical Industries, Ltd. | Toner binder |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0629989B2 (en) * | 1984-04-23 | 1994-04-20 | 日立化成工業株式会社 | Method of manufacturing electrophotographic toner |
| JPS6193603A (en) * | 1984-10-15 | 1986-05-12 | Japan Synthetic Rubber Co Ltd | Manufacture of magnetic particle |
-
1987
- 1987-01-29 JP JP62017378A patent/JP2537503B2/en not_active Expired - Lifetime
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7435521B2 (en) | 2002-06-28 | 2008-10-14 | Ricoh Company, Ltd. | Toner for developing electrostatic image |
| US7018766B2 (en) | 2002-11-08 | 2006-03-28 | Seiko Epson Corporation | Toner and production process thereof |
| US7258959B2 (en) | 2003-03-26 | 2007-08-21 | Ricoh Company, Ltd. | Toner for electrophotography and image forming apparatus |
| US7521164B2 (en) | 2003-09-18 | 2009-04-21 | Ricoh Company, Ltd. | Toner, and, developer, toner container, process cartridge, image forming apparatus and image forming method |
| EP2423755A1 (en) | 2003-09-18 | 2012-02-29 | Ricoh Company, Ltd. | Toner, developer,image forming apparatus and image forming method |
| US7374851B2 (en) | 2003-09-18 | 2008-05-20 | Ricoh Company, Ltd. | Toner, and, developer, toner container, process cartridge, image forming apparatus and image forming method |
| US7261989B2 (en) | 2003-10-10 | 2007-08-28 | Ricoh Company, Ltd. | Toner for developing electrostatic images, developer, image forming method, and image forming apparatus |
| US7449273B2 (en) | 2004-08-27 | 2008-11-11 | Ricoh Company, Limited | Toner containing unsaturated polyester in binder resin, method for preparing the toner, and developer including the toner |
| US7455942B2 (en) | 2004-09-17 | 2008-11-25 | Ricoh Company, Ltd. | Toner, developer, toner container, process cartridge, image forming apparatus, and image forming method using the same |
| US7695883B2 (en) | 2005-05-10 | 2010-04-13 | Ricoh Company, Ltd. | Toner and developer, toner container, process cartridge, image forming apparatus, and image forming method using the same |
| US7504188B2 (en) | 2005-05-10 | 2009-03-17 | Ricoh Company, Ltd. | Toner and developer, toner container, process cartridge, image forming apparatus, and image forming method using the same |
| US7820350B2 (en) | 2006-03-17 | 2010-10-26 | Ricoh Company, Ltd. | Toner, developer, toner container, process cartridge, image forming apparatus, and image forming method |
| EP1835352A1 (en) | 2006-03-17 | 2007-09-19 | Ricoh Company, Ltd. | Toner, process cartridge, and image forming method |
| US7824835B2 (en) | 2006-09-15 | 2010-11-02 | Ricoh Company, Ltd. | Toner, production method thereof, developer, toner container, process cartridge, image forming method, and image forming apparatus |
| US8771914B2 (en) | 2007-03-23 | 2014-07-08 | Ricoh Company, Ltd. | Toner for developing latent electrostatic image, two-component developer, image forming method and image forming apparatus |
| US8501379B2 (en) | 2007-06-19 | 2013-08-06 | Ricoh Company, Ltd. | Toner and method for producing the same and developer |
| US8163455B2 (en) | 2008-03-14 | 2012-04-24 | Ricoh Company, Ltd. | Toner for image formation, method for producing toner, container containing toner, two-component developer, process cartridge, and image forming method |
| US8178268B2 (en) | 2008-09-26 | 2012-05-15 | Ricoh Company, Limited | Magenta toner and developer |
| EP2348362A2 (en) | 2010-01-20 | 2011-07-27 | Ricoh Company, Ltd | Toner, method for producing the same, and developer |
| US8580476B2 (en) | 2010-03-25 | 2013-11-12 | Ricoh Company, Ltd. | Method for preparing particulate release agent, toner using the particulate release agent, and method for preparing the toner |
| US9625848B2 (en) | 2011-09-08 | 2017-04-18 | Ricoh Company, Ltd. | Toner and method for producing toner |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63186253A (en) | 1988-08-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2537503B2 (en) | Toner for electrostatic image development | |
| JP2547016B2 (en) | Toner for electrostatic image development | |
| EP0302939B1 (en) | Toner for developing electrostatically charged image | |
| EP0594126B1 (en) | Toner for use in electrostatic development | |
| JP4434967B2 (en) | Magnetic toner | |
| JP2547014B2 (en) | Toner for electrostatic image development | |
| JPH08292599A (en) | Toner for electrostatic charge development and its production | |
| US6251556B1 (en) | Toner for developing electrostatic images | |
| JP3238720B2 (en) | toner | |
| US5591556A (en) | Toners for developing electrostatic image | |
| JP3114295B2 (en) | Toner for electrostatic image development | |
| JP2829880B2 (en) | Toner for developing electrostatic images | |
| JP2557646B2 (en) | Toner for electrostatic image development | |
| JPH04188156A (en) | Manufacture of polymerized toner | |
| JPH06102699A (en) | Picture forming method | |
| JP2547011B2 (en) | Toner for electrostatic image development | |
| JP2537503C (en) | ||
| JP2974169B2 (en) | Toner for developing electrostatic images | |
| JP2547013B2 (en) | Toner for electrostatic image development | |
| JP2547015B2 (en) | Toner for electrostatic image development | |
| JP2991312B2 (en) | Toner for electrostatic image development | |
| JP3584407B2 (en) | Amorphous polymer particles, their production method and application to electrophotographic toner and carrier for supporting bioactive substances | |
| JP3026526B2 (en) | Toner for electrostatic image development | |
| JPH07114201A (en) | Electrostatic charge image developing toner, its production, and developer | |
| JPH04284461A (en) | Electrostatic charge image developing toner |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |