JPS58100859A - Toner for developing electrostatic charge image - Google Patents
Toner for developing electrostatic charge imageInfo
- Publication number
- JPS58100859A JPS58100859A JP56199473A JP19947381A JPS58100859A JP S58100859 A JPS58100859 A JP S58100859A JP 56199473 A JP56199473 A JP 56199473A JP 19947381 A JP19947381 A JP 19947381A JP S58100859 A JPS58100859 A JP S58100859A
- Authority
- JP
- Japan
- Prior art keywords
- toner
- polymer
- copolymer
- styrene
- polymerization
- 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
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
- G03G9/087—Binders for toner particles
- G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
- G03G9/08786—Graft polymers
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Developing Agents For Electrophotography (AREA)
- Graft Or Block Polymers (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は電子写真、静電印刷や靜電配鍮などにおける静
電荷像を現像するための新規なトナーに関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new toner for developing electrostatic images in electrophotography, electrostatic printing, electrostatic distribution, and the like.
本発明の静電荷儂現儂用の新規なトナーは、所謂乾式現
像方式に用いられる微粉末現儂剤であ抄、カスケード法
、毛ツラツシ法、磁気プラッタ法、イングレツシ■ン法
、ノ#9メー゛クラウド法等の乾式現像方式に用いるこ
とが出来る本ので、α、/−不飽和エチレン性単量体を
主な構成単位として含有しかつMw/Mmが41!−1
00の重合体を主要樹脂成分として含有することt−特
徴とする。The novel toner for electrostatic charge development of the present invention is a fine powder developer used in the so-called dry development method, and can be used in the shaving method, cascade method, combing method, magnetic platter method, ingress printing method, etc. This book can be used in a dry development method such as the May cloud method, so it contains α,/-unsaturated ethylenic monomer as the main structural unit and has an Mw/Mm of 41! -1
00 polymer as the main resin component.
周知のように、一般に静電荷像現像用トナーは樹脂成分
、#l科もしくは染料からなる着色剤成分および可塑剤
、電荷制御剤等の添加成分によって構成されており、樹
脂成分としては天然ま九は合成at脂が単独或いは適宜
混廿して使用されている。As is well known, toners for developing electrostatic images are generally composed of a resin component, a colorant component consisting of #1 family or dye, and additive components such as a plasticizer and a charge control agent. Synthetic AT fats are used alone or in appropriate combinations.
近年急速に技術開発が進められ友軒式現儂方式に適した
トナーに対して4七の樹脂成分に関し多くの改IL技術
が提案されている。特に高速雇複写を目的とする電子写
真複写機において#′i、加熱ローラ一定着法が採用さ
れ、静電記録体(感光ドラム)上に現像によって得られ
たトナー像を一旦紙などの転写シートに転写した後、該
転写シートを加熱圧着を行う定着ローラーに通してトナ
ーgItシートに融着させて定着が行なわれる。しかし
ながら、定着ロールの表面とトナー像が加熱溶融状−で
圧接触する定め導を形成するトナーの一部が定着ロール
に付着移転し、次の被定着シート上(これが再移転され
て所謂“オフセット現象”を生じ、被定着シートに汚れ
全発生させる。そのため高速度複写においても定着ロー
ラー表面に対してトナーが付着せず、しかも定着が十分
行なわれる樹脂成分が待望された。Technological development has progressed rapidly in recent years, and many improved IL technologies have been proposed regarding 47 resin components for toners suitable for the Yuken-style Genmei method. Particularly, in electrophotographic copying machines aimed at high-speed copying, a heated roller constant deposition method is adopted, and the toner image obtained by development is transferred onto an electrostatic recording medium (photosensitive drum) onto a transfer sheet such as paper. After the transfer sheet is transferred to the toner gIt sheet, the transfer sheet is passed through a fixing roller that performs heat and pressure bonding to fuse it to the toner gIt sheet, thereby performing fixing. However, some of the toner that forms a pressure contact between the surface of the fixing roll and the toner image in a heated molten state adheres to the fixing roll and is transferred onto the next sheet to be fixed (this is transferred again to the so-called "offset"). Therefore, there has been a long-awaited resin component that prevents toner from adhering to the surface of the fixing roller even in high-speed copying, and which can perform sufficient fixing.
特公昭5113354号は、このようなオフセット現象
の生じない所謂“耐オフセット性”に優れたトナー用樹
脂成分としてモノマーに対してa6es−zoffil
l−の架橋剤を含有する樹脂成分の使用が提案されてい
る。tた特公昭55−6895号は、重量平均分子1t
(以下Mwという)/数平均分子量(以下M%という)
が15〜40の4リスチレン系樹脂を主要樹脂成分とし
て使用し、定着性及び耐オフセット性に優れた静電荷像
現像用トナーが得られることを開示している。Japanese Patent Publication No. 5113354 discloses that a6es-zoffil is used as a resin component for toners with excellent so-called "offset resistance" that does not cause such an offset phenomenon.
The use of resin components containing l-crosslinking agents has been proposed. Tokuko No. 55-6895 has a weight average molecular weight of 1t.
(hereinafter referred to as Mw)/number average molecular weight (hereinafter referred to as M%)
It is disclosed that a toner for developing electrostatic images having excellent fixing properties and anti-offset properties can be obtained by using a 4-styrene resin having a polystyrene of 15 to 40 as the main resin component.
しかしながら、近年複写速[が益々高速化し、しかも鮮
明で安定した複写が望まれる傾向が著しくなるにつれ、
上記の従来技術以上に更に喪好な定着性及び耐オフセッ
ト性を待ったトナーが強く要望されるようになり交1本
発明者は、この様なlN!望に沿い得るトナー用樹Sa
分について鋭意研究を重ねて来几結果、順〈本発明によ
って従来技術よりも一段と優れた定着性及び耐オフセッ
ト性を有するトナーの発明を完成するに至った。However, in recent years, as copying speeds have become increasingly faster, and there has been a growing desire for clear and stable copies,
There has been a strong demand for toners with even better fixing properties and anti-offset properties than those of the prior art described above, and the inventors of the present invention have developed such lN! Toner tree Sa that can meet your wishes
As a result of extensive research on the topic, we have completed the invention of a toner that has better fixing properties and anti-offset properties than those of the prior art.
本発明の静電荷像現像用トナーは、α、β−不飽卯性エ
チレン系本量体を主な構成巣位として含有し、かりM、
7M%が45〜tooの重合体を主要**成分として含
有する−のである0本明細書で主な構成単位の「主な」
とは、#α、β−不飽和性エチレン系単量体會該重合体
当りS・重量−以上好ましくFl@@重量係以上含有す
ることを意味する。tた本明細書で扛Mw%M%F1%
rル÷
・)々−イユレーシン・クロi)グラフィ(l[Fa、
p、cという)で、THF=2溶媒に用いて分離したも
のt1示差屈折率計(SHODEX 5M−11)の方
法で、検出し標準分子1i11Jスナレン(ウォーター
スポリスチレンスタン〆−ド)換算値として夫々表わさ
れる重量平均分子量及び数平均分子量を意味する。一方
、本明細書で「主要樹脂成分」とは、静電荷像現像用ト
ナーに配合されている樹脂成分の中食〈と−フO重量S
會占める樹脂成分を表すものである。The toner for developing electrostatic images of the present invention contains an α,β-unsaturated ethylene-based polymer as a main constituent site, and
7M% contains 45 to too much polymer as a main component - 0 As used herein, the term "main" for main structural units refers to
This means that #α,β-unsaturated ethylenic monomers are contained in an amount of S·weight or more per polymer, preferably at least Fl@@weight ratio. In this specification, Mw%M%F1%
rru ÷ ・) - Iuresin Kuro i) Graph (l[Fa,
p, c), separated using THF=2 solvent, detected by the method of t1 differential refractometer (SHODEX 5M-11), and converted to standard molecule 1i11J Sunalene (waters polystyrene stand). It means the weight average molecular weight and number average molecular weight respectively expressed. On the other hand, in this specification, the term "main resin component" refers to a resin component mixed in an electrostatic image developing toner.
It represents the resin components present.
斯くて、本発明による静電荷儂現偉用トナーは、従来の
トナーに較べて定着性、耐オフセット性に優れ、更に優
れた耐ツロツ午ンダ性及び被粉砕性を併せ有する卓越し
た玄車性能を有する−のである。この様な優れた性能を
併せ有するには、主要**成分をなす重合体のU、/M
、が45−1・O好ましくはso−ms%罠に好ましく
は60−口・の−のが使用される。M、/MIBが4S
未満と小さすぎては本発明の優れたオフセット性が得ら
れず、一方toe(越えて大きすぎては定着性及び被粉
砕性が劣るので好筐しくない。Therefore, the electrostatically charged toner according to the present invention has excellent fixing properties and anti-offset properties compared to conventional toners, and also has excellent anti-slip properties and shattering properties, and has outstanding vehicle performance. It has -. In order to have such excellent performance, the U, /M of the polymer that forms the main component
, is preferably 45-1.O, preferably so-ms%, and preferably 60-mouth.O- is used in the trap. M, /MIB is 4S
If it is too small (less than toe), the excellent offset properties of the present invention cannot be obtained, while if it is too large than toe (toe), the fixing property and pulverizability will be poor, which is not desirable.
従来耐オフセット性の向上をめざして檀々の工夫がなさ
れている(たとえは特公昭1it−11854号〕架橋
4リマー1特公FM4m m −m JI I s号の
Mw/M、16〜40の一すマー)が、今−歩不足で加
熱ロー9にシリコーンオイルt−塗布fるとか、トナー
(ワックス、オレフィン等の非粘着性物質を添加する等
の手段が加えられてようヤ(満足すべき耐オフセツト性
能が付与されているのが現状であるが、複写機内部にオ
イル塗布装置を内蔵するために装置全体が大型化せざる
を得ない問題、あるいは時としてオイルの安定供給が行
なわれない友め、オフセット現象を起こし機械故障の原
因となっている。しかしワックス、オレフィン等を添加
するとトナーを流動摩擦帯電させる時流動性能が悪くな
るので帯電が一様に行なわれず1ili儂の鮮明ざが得
られない問題点を有している。In the past, various efforts have been made to improve the offset resistance (for example, in Japanese Patent Publication No. 11854). However, due to insufficient steps, measures such as applying silicone oil to the heating roller 9 and adding non-adhesive substances such as toner (wax, olefin, etc.) have been added (I am satisfied). Currently, copying machines have the necessary offset resistance, but since the oil applicator is built into the copying machine, the overall size of the equipment has to be increased, or sometimes it is difficult to maintain a stable supply of oil. Dear friend, this causes an offset phenomenon and causes machine failure. However, when wax, olefin, etc. are added, the flow performance deteriorates when the toner is charged by fluid friction, so the charging is not done uniformly and the sharpness of the 1ilii is reduced. The problem is that it cannot be obtained.
本発明のトナーは加−熱ローラーにオイルを塗布する必
要がなく、ま危ワックス、オレフィン等の非粘着性物質
を添加することなく卓越した耐オフセット性能Yt有す
る。The toner of the present invention does not require oil to be applied to a heating roller, and has excellent anti-offset performance Yt without adding any non-adhesive substances such as hazardous wax or olefin.
また、本発明の静電荷像現像用トナーは、驚くべき耐プ
ロツキンダ性能を有する。従来定着性性能の向上を計る
ためトナーを形成する/者インメー樹脂の熱溶融IJi
ll可能のかぎり低く設計して来たが、溶融湯[を、下
げると、貯蔵時あるいは流動摩擦帯電時にケーキ状Kp
集しトナーとしての性能t−はたさなくなる。この下限
の熱熔融温度表示する方法として一般にガラス転移温度
1y)が有効に利用されている。従来のトナーでFiパ
イングー樹脂のTlが5s℃以下ではブロッキン!現象
を起こし、使用されなかったが1本発明のトナーではI
I’C以下において一゛耐プロッキンダ性能を有するの
で熱熔融温ft従来のトナーよりも低く設計することが
可能である。このため定着性能が良好でかり耐ツロツ中
ンダ性の優秀なトナーが得られることとなり九。Further, the toner for developing electrostatic images of the present invention has surprising anti-blocking performance. Conventionally, heat-melting IJi resin is used to form toner in order to improve fixing performance.
Although we have designed the molten metal to be as low as possible, lowering the molten metal will result in a cake-like Kp during storage or flow friction charging.
The performance as a collected toner is degraded. Generally, the glass transition temperature 1y) is effectively used as a method of indicating the lower limit of the thermal melting temperature. With conventional toners, if the Tl of the Fi-Pain Goo resin is below 5s℃, it will block! However, with the toner of the present invention, I
Since the toner has a high resistance to blockade at temperatures below I'C, it is possible to design a thermal melting temperature ft lower than that of conventional toners. Therefore, it is possible to obtain a toner with good fixing performance and excellent stain resistance.
さらに本願発明の峙電荷像用トナーに、上記の優れた諸
性質に併せて優れた被粉砕性會有する。Furthermore, the toner for counter-charge images of the present invention has excellent pulverizability in addition to the above-mentioned excellent properties.
こ\で、被粉砕性とは、主要樹脂成分に後記の添加剤を
添加して粉砕するさい、所望の粒度分布(効率よく粉砕
される性質をいう。これによって、優れた性質を有する
トナーを経済的に有利に工業的規模で製造し得ることが
可能となつt。In this case, pulverizability refers to the ability to obtain a desired particle size distribution (the property of being efficiently pulverized) when adding the additives described below to the main resin component and pulverizing it. It becomes possible to manufacture it economically and advantageously on an industrial scale.
本発明の主要樹脂成分の主な構成単位でめるα、β−不
飽和エチレン系単量体としては、例えばスチレン、O−
%賜−s’l’−メチルスチレン、p−エチルスチレン
、p−t−エチルスチレン等のスチレン類、ビニルナフ
タレン1111エチレン、!ロビレン、ブチレン、イソ
ブチレン等のエチレン系不飽和モノオレフィン類、塩化
ビニル、弗化Vニル、酢酸ビニル、酪酸ビニル郷のビニ
ルエステル類、アクリル酸メチル、アクリル酸エチル、
アクリル酸界ブチル、アクリル酸イソツチル、アクリル
酸鴨オクチル、アクリル酸エチルヘキシル、アクリル酸
クロルエチル、メタクリル酸メチル。Examples of the α,β-unsaturated ethylenic monomer which is the main structural unit of the main resin component of the present invention include styrene, O-
Styrenes such as %-s'l'-methylstyrene, p-ethylstyrene, and pt-ethylstyrene, vinylnaphthalene 1111 ethylene,! Ethylenically unsaturated monoolefins such as robylene, butylene, isobutylene, vinyl chloride, vinyl fluoride, vinyl acetate, vinyl esters of vinyl butyrate, methyl acrylate, ethyl acrylate,
Butyl acrylate, isotutyl acrylate, octyl acrylate, ethylhexyl acrylate, chloroethyl acrylate, methyl methacrylate.
メタクリル酸エチル、メタクリル酸舊ブチル、メタクリ
ル酸イソブチル、メタクリル酸算−オクチル、メタクリ
ル酸ドデシル、メタクリル酸ステ了すル等のエチレン性
モノカルがン酸およびそのエステル、アクリ脚ニトリル
、メタアクリロニトリル、アクリルアミド、メタアフリ
ロア2ド等のエチレン性モノカルがン酸誘導体、ビニル
メチルエーテル、ビニルエチルエーテル、ビニルイ)f
チルエーテル等のビニルエーテル類、マレイン酸vメチ
ル、iレインlit/エチル、マレイン酸Vツチル等の
エチレン性ジカルがン酸およびその誘導体、ビニルメチ
ルケトン、ビニルへ中シルケトン等のビニルケトン類、
ビニリデンクロリド、ピニリデンクロルフルオリド等の
、ビニリデンハロダン化物、N−ビニルピロール、N−
ビニルカルI4ソール、N−ビニルインドール%N−ビ
ニルピロリドン等のN−ビニル化会物類等かめる。Ethylenic monocarboxylic acids and their esters, such as ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, octyl methacrylate, dodecyl methacrylate, and sterol methacrylate, acrylic nitrile, methacrylonitrile, acrylamide, Ethylenic monocarboxylic acid derivatives such as metaafrylor 2, vinyl methyl ether, vinyl ethyl ether, vinyl) f
Vinyl ethers such as thyl ether, ethylenic dicarnic acid and its derivatives such as v-methyl maleate, i-rein lit/ethyl maleate, v-tutyl maleate, vinyl ketones such as vinyl methyl ketone, vinyl silketone,
Vinylidene halodides such as vinylidene chloride and pinylidene chloride, N-vinylpyrrole, N-
N-vinylated compounds such as vinylcal I4 sole, N-vinylindole% N-vinylpyrrolidone, etc.
ま九本−発明の靜電祷像現像用トナーの主要樹脂成分t
なす電合体の構成単位である非共軛性二1結合t−2備
以上有する化合物としては、洞見はジビニルベンゼン、
ゾピニルナフタレン等の芳香族ジビニル化合物、エチレ
ングリコール・ジメタアクリレート、テトラエチレング
リコール・ジメタクリレート、1.Sブタンノオール・
ジメタクリレート、アリール譬メタクリレート、等のジ
エチレン性カルがン酸エステル、N、N/ビニルアニリ
ン、ジビニルエーテル、ジビニルスルフィY等がある。Makuhon - Main resin component of toner for developing the Seiden Sei image of the invention
As compounds having more than 21 non-conjunctive bonds t-2, which are the constituent units of the electrocombinant, Horami uses divinylbenzene,
Aromatic divinyl compounds such as zopinylnaphthalene, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1. S-butanol・
Examples include diethylene carboxylic acid esters such as dimethacrylate and aryl methacrylate, N,N/vinylaniline, divinyl ether, and divinylsulfy Y.
ジビニルベンゼン、エチレングリコールジメタアクリレ
ートが好適rc使用される。Divinylbenzene, ethylene glycol dimethacrylate are preferably used.
本発明の静電荷像現1象用トナーの主要樹脂成分をなす
重合体の一つの好適な態様は、スチレン1・〜eo[4
1%(メタ)了クリル酸アルキルエステルt’ o〜7
0重V%、非共軛性2重−結合を!回以上有する化合物
α05〜2重量−含有する共重合体であり、好ましくは
、スチレンi0〜80重量−1(メタ)アクリル酸アル
中ルエステルR〇−io重普−1及び非共明性8重結合
t!個以上含有する化合物11〜〜1重普暢含有する共
重合体である。スチレンが30重量−未満と少なすぎて
は適切な被粉砕性が得られないので好ましくなく、90
重普96t−超えて多すぎては定着温匿が高くなるので
好ま・しくない、ま危非共軛性st結合t−1個以上有
する化合物が(LO505重量満と少なすぎてイ「/「
が4s以上にならないので好ましくなく、まへ量−
を超して多すぎては不溶性となるので本発明の共重合体
が得られない。この様な電メタ)アクリル酸アル中ルエ
ステルトシては、ガえはアクリル酸エチル、アクリル酸
エチル。One preferred embodiment of the polymer constituting the main resin component of the toner for electrostatic image development of the present invention is styrene 1.~eo[4
1% (meth)acrylic acid alkyl ester t'o~7
0 fold V%, non-mutual double bond! A copolymer containing a compound α05 to 2 times by weight, preferably styrene i0 to 80 times by weight, (meth)acrylic acid alkyl ester R〇-io double bond T! It is a copolymer containing 11 to 1 compound containing at least one compound. If the amount of styrene is too small (less than 30% by weight), appropriate crushability cannot be obtained, which is undesirable;
If the amount exceeds 96 t-, it is not preferable or undesirable because the fixation temperature becomes high.
is not preferable because it does not exceed 4s, and the amount of
If the amount exceeds too much, the copolymer of the present invention cannot be obtained because the copolymer becomes insoluble. In this case, acrylic acid ester in alcohol is used as ethyl acrylate or ethyl acrylate.
アクリル#諮−ツチル、アクリル酸イソエチル、アクリ
ル酸エチルへ中シル、メタアクリル酸メチル、メタクリ
ル酸エチル、メタクリル酸鴇ブチル、メタクリル酸イソ
エチル、メタクリル酸ラウリル、メタクリル酸ラウリル
等があり、%にアクリル酸エチル、アクリル酸エチル^
キシル、メタクリル酸算−プチル、メタクリル酸ラウリ
ルが好ましい、非共軛性意重結会t l +m以上有す
る化合物としては、ジビニルベンゼン、エチレングリコ
ール・ジメタ了クリレート等があるが、特vcyビニル
ベンゼンが好ましい。There are acrylic compounds such as acrylic salt, isoethyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isoethyl methacrylate, lauryl methacrylate, lauryl methacrylate, etc., and % acrylic acid. Ethyl, ethyl acrylate
Preferred are xyl, abutyl methacrylate, and lauryl methacrylate. Compounds having a non-mutual association of t l +m or more include divinylbenzene, ethylene glycol dimethacrylate, and especially vinylbenzene. preferable.
コノヨうす重合体t)Mwn、i、ooo−210,0
00の−のが好ましいが、%VC@00G−1&・O・
のものが好適に使用される0M%がLooo未満と小さ
すぎてはトナーの貯蔵時及び摩擦帯電時の耐凝集性が悪
くなるので好ましくなく、iたSへooo2超えて夫°
きすぎては定着性及び被粉砕性が悪くなるので好ましく
ない。Konoyo thin polymer t) Mwn, i, ooo-210,0
00- is preferable, but %VC@00G-1&・O・
If the 0M% is preferably used, it is less than Looo, which is undesirable because the agglomeration resistance of the toner during storage and frictional charging will deteriorate;
If it is too thick, the fixability and pulverizability will deteriorate, which is not preferable.
本発明の静電荷視像用トナーの主要樹脂成分【なす重合
体のもう一つの好適な態様は、ゴム弾性重合体に前記の
α、β−不飽和性エチレン系単普体をダラフト重合させ
て得られる共重合体である。The main resin component of the toner for electrostatically charged visual images of the present invention [Another preferred embodiment of the polymer is obtained by subjecting the rubber elastic polymer to the above-mentioned α,β-unsaturated ethylene monomer by raft polymerization. This is the copolymer obtained.
本明細書でいう「ゴム弾性重合体」とFi、共軛二重結
合を有する化合物を構成単位として含有する所請ツエン
系エラストマー及び容易に脱水素反応等を受けて架橋可
能となる所謂非ジエン系エラスト1−t−いう。前者と
しては、例えばツタジエンゴム、スチレン−ツタジエン
ゴム、ニトリルジム、天然ゴム、合成イソグレンゴム、
タロロデレンゾム等があり、後者としては、例えばエチ
レン・プロピレンゴム・エチルがム、アクリルゴム、エ
チレンー酢ビ♂ム、クロロスルホン化ポリエチレン、塩
素化ポリエチレン、4リイソプチレン、ポリエステルジ
ム、エビクロルヒドリンシム、塩素化プ9− ルf五等
があるが、スチレン・フタジエンゴム、フタジエンゴム
、ニトリルジム、エチレンーグロピレンノムが好筐しく
、#にスチレン・ブタシンがムが好適VcgII用され
る。The "rubber elastic polymer" referred to in this specification refers to Fi, a tene-based elastomer containing a compound having conjoint double bonds as a constituent unit, and a so-called non-diene that can be easily crosslinked by undergoing a dehydrogenation reaction, etc. Type elast 1-t-. Examples of the former include tutadiene rubber, styrene-tutadiene rubber, nitrile gym, natural rubber, synthetic isogrene rubber,
The latter include, for example, ethylene/propylene rubber/ethyl gum, acrylic rubber, ethylene-acetate vinyl, chlorosulfonated polyethylene, chlorinated polyethylene, 4-lisoptylene, polyester gym, shrimp chlorohydrin shim, and chlorine. Among them, styrene-phtadiene rubber, phtadiene rubber, nitrile dimium, and ethylene-glopyrene rubber are preferred, and styrene-butacine rubber is preferably used as VcgII.
これらのシム弾性重合体は重合度Mwで80へ000以
下好ましくFisoへOS・以下のものか好IIlに使
用される0重合質が10Q、Go。These shim elastic polymers have a degree of polymerization Mw of 80 to 000 or less, preferably Fiso to OS or less, or preferably 10 to 10Q, Go.
を超えて大きすぎては、ダラフト共重合体が不溶性とな
るので好筐しくない。If it is too large, the duraft copolymer becomes insoluble, which is not desirable.
一方fム弾性重合体にダラフト重合されるα。On the other hand, α is draft-polymerized into an elastomeric polymer.
β−共重合性エチレン系単量体、一般に前記のスチレン
m、エチレン系不飽和モノオレフィン類、ビニルエステ
ル類、エチレン性モノカルーン酸類、そのエステル頌、
エチレン性モノカルーン酸−導体類、Vニールエーテル
類、エチレン性ジカルがン酸類、その−導体類、ビニル
ケトン類、ビニリデンハログン化合物類、及びN−ビニ
ル化合物類等があるが、好ましくはスチレン及び(メタ
)アクリル酸了ルΦルエステル%に好ましくはスチレン
、アクリル酸メチル、アクリル酸エチル、アクリル酸算
−プチル、アクリル酸イソッチル、アクリル酸エチルヘ
キシル、メタアクリル酸メチル、メタクリル酸エチル、
メタクリル酸鴨ブチル、メタクリル酸イソブチル、メタ
クリル酸ラウリル、メタクリル酸ステアリル、最も好ま
しくはスチレン、アクリル酸鴨ブチル、アクリル酸エチ
ルへ中シル、メタクリル酸乳−ブチル、メタクリル酸ラ
ウリルが用いられる。β-copolymerizable ethylene monomers, generally the above-mentioned styrene m, ethylenically unsaturated monoolefins, vinyl esters, ethylenic monocaronic acids, esters thereof,
Examples include ethylenic monocaronic acid conductors, V-niyl ethers, ethylenic dicaronic acids, their conductors, vinyl ketones, vinylidene halogen compounds, and N-vinyl compounds, but styrene and ( Preferably styrene, methyl acrylate, ethyl acrylate, butyl acrylate, isotyl acrylate, ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate,
Duck butyl methacrylate, isobutyl methacrylate, lauryl methacrylate, stearyl methacrylate, most preferably styrene, duck butyl acrylate, ethyl acrylate, lact-butyl methacrylate, lauryl methacrylate are used.
本発明の静電荷像現儂用トナーの主要樹脂成分をなすこ
の様なダラフト共重合体の好適な1様は、ゴム弾性重合
体al−冨oatg、スチレン10〜−011m5.(
メタ)アクリル酸アル中ルエステル10〜マo*t−1
含有する共重合体であり、好ましくはプム弾性重合体+
lL5〜S重量−、スチレンsO〜8oy普−1(メタ
)アクリル酸アルキル・エステルgo−8011[普慢
の4のが用いられる。ゴム弾性重合体がαtS未満と少
なすぎてはνw/Mnが4暴以上とならずで好ましくな
く、また震6重tit超えて多すぎてはダラフト共重酋
体が不溶性となるので好ましくない、またスチレンがI
O電量−未満と少なすぎては、適切な粉砕性が得られな
いので好1しなく、901jl置−を超えて多すぎては
定着温度が高くなるので好ましない。Suitable examples of such a duraft copolymer constituting the main resin component of the toner for developing electrostatic images of the present invention include rubber elastic polymer al-tomi oatg, styrene 10 to -011m5. (
meth)acrylic acid ester in alkali 10-mao*t-1
A copolymer containing, preferably Pum elastomeric polymer +
lL5~Swt-, styrene sO~8oy 1 (meth)acrylic acid alkyl ester go-8011 [Permanent 4 is used. If the amount of the rubber elastic polymer is too small, less than αtS, νw/Mn will not be 4 or more, which is undesirable, and if it is too large, exceeding 6 tits, the dart copolymer will become insoluble, which is not preferable. Also, styrene is I
If the amount of electricity is too small, less than 0, it is not preferable because appropriate pulverization properties cannot be obtained, and if it is too large, it is not preferable because the fixing temperature becomes high.
本発明のトナーの主要m脂成分となす重合体は、次のよ
うな製法により好適に製造される。The polymer constituting the main fat component of the toner of the present invention is suitably produced by the following method.
重合体が構成巣位として非共軛性怠重結合を1個以上含
有する化付物(以下架橋性単量体という)【有する場合
Ktj、ラジカル重合法重合剤され、ラジカル重合開始
剤が下記の式
で示される関係を満足する量で使用されることが好まし
い、この様な条件の下に塊状重合、溶液重合、乳化重合
、懸濁重合等の重合法等が採用されるが、乳化重合、M
漏電合法が好ましい、また、シム弾性重合体を含有する
場合[4,、ラジカル重合法が採用され、ラジカル重合
開始剤が下記の式で示される関係を満足する曽て使用さ
れることが好ましい、fム弾性重曾体が容易に脱水素反
応等を受けて架橋可能となる所絹非ジエン系エラヌトマ
−の場合vcは、一般的に水素引抜き反応といわれる条
件を選んで共有合反応が行われる。この様な条件の下に
塊状重合、溶液重付、乳化重合及び懸濁重゛会法等が採
用されるが、乳化重合及び懸濁重合法が好筐しい。If the polymer contains one or more non-coterminous lazy bonds as constituent sites (hereinafter referred to as crosslinkable monomer), Ktj is used as a polymerization agent by radical polymerization method, and the radical polymerization initiator is It is preferable to use the amount that satisfies the relationship shown by the formula. Under such conditions, polymerization methods such as bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, etc. are employed, but emulsion polymerization ,M
The electric leakage method is preferable, and when the shim contains an elastic polymer [4. In the case of silk non-diene elanuttomers, where the elastomeric elastomer can easily undergo dehydrogenation and crosslinking, a covalent reaction is generally carried out under conditions known as a hydrogen abstraction reaction. . Under such conditions, bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, etc. are employed, but emulsion polymerization and suspension polymerization are preferred.
本発明に係る静電荷像現像用トナーは上記の如き樹li
1′に王!!樹脂成分とする4のであるが、この様な主
I!樹脂成分の外に必gIに応じて他の重合体【1%佇
して使用することが出来る。この様に混合して使用され
る他の重合体としては、フェノールホルムアルデヒド樹
脂類、工Iキシ樹脂類、ぼりウレタン樹脂拳、セルロー
ズ系樹脂類、ポリエーテル債[i#I、キシレン系41
111類等がある。The toner for developing an electrostatic image according to the present invention has the above-mentioned tree li.
King on 1'! ! 4, which is a resin component, is the main I! In addition to the resin component, other polymers (1%) can be used depending on the required gI. Other polymers that can be mixed and used in this way include phenol formaldehyde resins, 1-oxylic resins, polyurethane resins, cellulose resins, polyether bonds [i#I, xylene-based 41
There are 111 classes, etc.
また、本発明に係る静電#像現澹用トナーには1歯な顔
料またに染料が着色剤として配合される。Further, the toner for electrostatic image development according to the present invention contains a pigment or a dye as a coloring agent.
そのような顔料又は染料のガとしては、力−−ンプ2ツ
ク、セルラオイル1ルー、デ:L1f!ンオイルレッド
、フタロシアニンツルー、アニリンブルー、エダロシン
染料、ウルトラマリンブルー、中ノリンイエロー、マラ
カイトグリーンオクサレート、ローXベンガルや之等の
混合物があり、トナーの着色に必要な量が配合される。Examples of such pigments or dyes include: 2 ml of power, 1 ml of cellular oil, and 1 ml of cellulose oil. There are mixtures of oil red, phthalocyanine true, aniline blue, edarosine dye, ultramarine blue, Chunolin yellow, malachite green oxalate, Rho-X Bengal, etc., and are blended in the amount necessary for coloring the toner.
更に本発明に係る静電荷像現像用トナーは、必要に応じ
て離型剤tll!に配合してもよい。そのような化合物
としては例えばステアリン酸のCd。Furthermore, the toner for developing an electrostatic image according to the present invention may contain a release agent tll!, if necessary. It may be added to. Such compounds include, for example, Cd of stearic acid.
Ba、Ni、Co、 St、 Cm、Kg、Ca塩、オ
レイン酸)jl n、Mn%Fa、Co、Cm、Ph、
M(1塩、A#電チン酸toZv*、 =Co、 Cs
、 Kg、81.Cm塩、リノール酸の2%、00%C
a塩、リシノール酸のZ謡、xFiCd塩、カグリル酸
のPh塩、力lロン酸のph塩等高級脂肪酸の金属塩や
天然及び台底の/#テラフィン類び脂肪酸エステル類又
はその部分鹸化物類、アルキレンビス脂肪酸アマイド類
等があり゛、これ等化合物の1種或いは鴬種以上を適宜
組合せて本願発明のトナーに配合して屯よい。Ba, Ni, Co, St, Cm, Kg, Ca salt, oleic acid) jl n, Mn%Fa, Co, Cm, Ph,
M(1 salt, A#electrotinic acid toZv*, =Co, Cs
, Kg, 81. Cm salt, 2% of linoleic acid, 00% C
Metal salts of higher fatty acids such as a-salt, ricinoleic acid Z-salt, xFiCd salt, ph-salt of cargyrylic acid, ph-salt of chloric acid, natural and natural terrafins and fatty acid esters, or partially saponified products thereof. and alkylene bis fatty acid amides, etc., and one or more of these compounds may be mixed as appropriate in the toner of the present invention.
tた、本発明に係る静電荷像現像用トナーには、更に必
’IIKEじて電荷制御剤、可塑剤などの他の種類のト
ナー株加剤を配合せしめることができる。In addition, the toner for developing electrostatic images according to the present invention may further contain other types of toner additives such as charge control agents and plasticizers, if necessary.
斯くて、本発明に係る静電#偉現像用トナーFi、高速
の電子写真複写において優れ次定着性と優れ次耐オフセ
ット性を有し、更に優れ危耐ツロツ會ンダ性を併ぜ有す
るものであるが、本発明は篤くべきことにトナー製造時
の優れ九被粉砕性を有するという全く意外な効果tも有
することが判つ九。Therefore, the toner Fi for electrostatic development according to the present invention has excellent subsequent fixing properties and excellent next offset resistance in high-speed electrophotographic copying, and also has excellent damage resistance. However, it has been found that the present invention also has the completely unexpected effect of having excellent pulverizability during toner production.
トナーは、主要w脂成分に上記添加剤を配合して均一(
混合溶融し、溶融混合物を冷却後必gIvc応じ粗砕し
た上ジェットミル等で微粉砕することにより、蝋終!1
11In+とされるのであるが、平均粒径が10〜1m
1mの所望粒度分布の最終製品(トナー)を効率よく得
ることは従来必し一容易ではなかったが、本発明によっ
て、所望粒度の最終製品に効率よく工業的vc徽粉砕す
ることが可能となった。The toner is made by blending the above-mentioned additives with the main fat component (
After mixing and melting, the molten mixture is crushed according to gIvc after cooling, and then finely pulverized with a jet mill, etc., and the wax is finished! 1
11In+, but the average particle size is 10 to 1 m.
In the past, it has not always been easy to efficiently obtain a final product (toner) with a desired particle size distribution of 1 m, but the present invention has made it possible to efficiently perform industrial VC crushing into a final product with a desired particle size. Ta.
以下に本発明を実施例に二快詳細に説明する。The present invention will be explained in detail below using examples.
参 考 I’ll 1(樹脂、4(0811m1)I
SOtの重合機にスチレン8に#、アクリルill1w
s−プチル!匂、ノビニルベンゼン(Mf!1811)
60f1過酸化ベンゾイルs o o tt−仕込み%
混合8%させt後ポリビニルアルコール(ゴー七ノール
Aff−19)left”溶解させた脱イオン水の水溶
液10Ktt加え皮、続いて重合機内部會eo’ctで
加熱して攪拌下[1!時間保つた後SO−の苛性ソーダ
水溶液1180ft−加え重合機内部を加熱して加圧下
l!O℃で6時間保ち重合反応を完結させた。得られた
重合体のスラIJ−を冷却して脱水、洗浄をくり返し乾
燥処理を行りたところC−ズ状の樹脂afLS−が得ら
れた。祷らありた。Reference I'll 1 (resin, 4 (0811m1) I
Styrene 8, #, acrylic ill 1w in SOt polymerization machine
S-Putyl! Odor, novinylbenzene (Mf!1811)
60f1 benzoyl peroxide so o tt-Preparation%
After mixing to 8% polyvinyl alcohol (Go-7Nol Aff-19), add 10Ktt of an aqueous solution of deionized water dissolved in it, then heat it inside the polymerizer and keep it under stirring for 1 hour. After that, 1,180 ft of aqueous sodium hydroxide solution of SO- was added, and the inside of the polymerization machine was heated and kept under pressure at 1!O ℃ for 6 hours to complete the polymerization reaction.The obtained polymer slug IJ- was cooled, dehydrated, and washed. When the drying process was repeated, a C-shaped resin afLS- was obtained.
参 考 例 ff1(樹脂HのAllり参考1Fltr
cおいてVビニルベンゼンの量t11Ofと変更した以
外はまり九〈同様に重合反応を行ないM が4800.
Mw / unが72の樹脂路
B會得た。Reference example ff1 (All reference 1 Fltr of resin H
The following is the same except that the amount of V-vinylbenzene was changed to t11Of in c. The polymerization reaction was carried out in the same manner, and M was 4800.
A resin road B with Mw/un of 72 was obtained.
参考例畠(樹脂Cの調製1
参考飼lにおいてアクリル酸笥−プチル!−tメタクリ
ル酸ラウリル!−に変更し、Vぜニルベンゼンの1li
t’l!OFK質更し定以外はまった〈同様に重合反応
を行ない、M%が&I06.&、/Mn1)E9BF)
@脂Cf得た。Reference Example Hatake (Preparation of Resin C 1) In the reference feed 1, acrylic acid butyl!-t was changed to methacrylic acid lauryl!-, and Vzenylbenzene was
t'l! Except for OFK refining, the polymerization reaction was carried out in the same manner, and M% was &I06. &, /Mn1)E9BF)
@ Fat Cf was obtained.
参 考 例 4(樹@DのII4襄)
情酸三ナトリウム(l意水塩)4f、炭酸水翼ナトリ9
ム4t、過硫酸カリクム8f1アニオン乳化剤(DOW
fas−1AI ) II f、ノニオン乳化41 (
=zd−ルPEfi m ) 82 ft*410 f
VCp11鱗させ3tの耐圧ガラスフラスコに仕込みm
素を吹き込み系内の酸素含率を0.2%とした。Reference Example 4 (Tsuki @ D's II 4) Trisodium hydroxide 4f, sodium carbonate 9
4t, potassium persulfate 8f1 anionic emulsifier (DOW
fas-1AI) II f, nonionic emulsification 41 (
=zd-lePEfi m) 82 ft*410 f
Scale VCp11 and prepare it in a 3t pressure glass flask.
The oxygen content in the system was set to 0.2%.
続いて窒素雰囲気で計量混合したスチレントlf、fタ
ジエン160f、s−ラウリルメルカプタンIfの混合
溶液を上記フラスコに肩先フラスコ内部を加熱して@O
℃とし攪拌下tCS時間保つ皮、冷却後、樹脂の乳化液
2stのメチルアルコールに再沈して分離し、乾gI後
フレーク状の樹脂180ft−得た。上記樹脂のM%は
6λo o (1゜Mw/M% Fi4.0 ’T”h
りft−@参考f%IIにおいて、ジビニルベンゼン5
att上記樹@*ootvr:、変更した以外Fiまっ
たく同じ重合反応を行ないMn 4 !106.A(v
/ Ar4が−8の樹@0%た。Subsequently, a mixed solution of styrene lf, f-tadiene 160f, and s-lauryl mercaptan If, which were weighed and mixed in a nitrogen atmosphere, was added to the above flask by heating the inside of the shoulder flask and adding @O.
After cooling, the skin was kept under stirring for tCS hours, and then reprecipitated in 2 parts of methyl alcohol to separate the resin emulsion. After drying, 180 ft of flaky resin was obtained. M% of the above resin is 6λo (1゜Mw/M% Fi4.0 'T”h
ft-@reference f%II, divinylbenzene 5
att above tree @*ootvr:, Fi performs the exact same polymerization reaction except for the change, and Mn 4 ! 106. A(v
/ Tree with Ar4 of -8 @0%.
参 考 f171Ji(樹脂1t:vf14製)hot
の重合機にスチレン1L4−、アクリル酸部−ツチル1
.114. 冨メルカ1トエタノール1.1flfY
t仕込み、内径!〜の吹込み管よりmt/m11で空気
ft送りながら重合機内部を加熱して90℃とし10時
間重合反応を行った。Reference f171Ji (1 ton of resin: made by vf14) hot
In the polymerization machine, styrene 1L4-, acrylic acid part-Tutyl 1
.. 114. Tommerka 1 ton ethanol 1.1 flfY
T preparation, inner diameter! The interior of the polymerization machine was heated to 90° C. while supplying ft of air at a rate of mt/m11 from the blowing pipe of ~ to conduct a polymerization reaction for 10 hours.
続いてスチレン111Kf、アクリル酸界−ブチル40
0 f、ジビニルペンey6t (純[5816i −
過酸化ベンゾイル100Fの混合溶液を上記反応生成物
に7JI、tた後、ブーセノールKH,1丁10ftl
ll解させ几脱イオン水の水溶液!0Kfi加えて重合
機内部を攪拌下10’C[11時間保ち、1合反応を完
結させ友1重合体スラリーを水と分離し、乾燥して得ら
れ几樹@ E (D W港へ500、MSl、7M%は
41でありt。Next, styrene 111Kf, acrylic acid world-butyl 40
0 f, divinyl pen ey6t (pure [5816i -
After adding 7JI of a mixed solution of benzoyl peroxide 100F to the above reaction product, add 100ftl of Bousenol KH.
An aqueous solution of deionized water! 0 Kfi was added and the inside of the polymerization machine was kept at 10'C for 11 hours under stirring to complete the 1-polymer reaction, and the polymer slurry was separated from water and dried. MSl, 7M% is 41 and t.
参考ガロ(樹V#IFの調製)
sOtの重合機にスチレン!L!1す、メタタリル酸メ
チルlO@f、!−メルカプトエタノールB ! Of
’を仕込み、内径2%の吹込み管より!t/misで9
気を送砂ながら重合機内部を90℃とし10時間重合反
応【行りた。。Reference Gallo (Preparation of Tree V#IF) Styrene in the sOt polymerization machine! L! 1. Methyl metatallylate lO@f,! -Mercaptoethanol B! Of
' from a blowing pipe with an inner diameter of 2%! 9 in t/mis
The interior of the polymerization machine was heated to 90°C while blowing air and sand, and the polymerization reaction was carried out for 10 hours. .
続いてスチレン181i1.メタクリル酸メチル27〜
、アクリル酸旙−エチルIIKF%過酸化ラウリルIR
fの混合溶液を上記反応生成物に加えた後ゴーセノール
KIi”−1710tk溶解させち脱イオン水の水溶液
ionを加えて重合機内部を攪拌下66℃に20時間保
ち重合反応管完結させた1重合体スラIJ−を水と分離
し、乾燥して得であった。Next, styrene 181i1. Methyl methacrylate 27~
, ethyl acrylate IIKF% lauryl peroxide IR
After adding the mixed solution of f to the above reaction product, dissolve Gohsenol KIi''-1710tk, add an aqueous solution of deionized water, and keep the inside of the polymerization machine at 66°C for 20 hours with stirring to complete the polymerization reaction tube. The combined slurry IJ- was separated from water and dried.
参 考 例 丁(樹@Gの調製)
50tの重合機にスチレン?Kt、メタクリル酸亀−ブ
チル3−、エチレンダリコールジメタクリレー) 98
F、詐−ラウリルメルカプタン91 F。Reference Example Ding (Preparation of Tree @G) Styrene in a 50t polymerization machine? Kt, tortoise-butyl 3-methacrylate, ethylene dalycol dimethacrylate) 98
F. Frau-lauryl mercaptan 91 F.
アゾビスイソブチロニトリルxoott−仕込み混合溶
液させた後が一セノールKM−1〒 10ft溶解させ
た脱イオン水の水溶液10Kft−加え重合機内部を攪
拌下80’Cにli1時間保ち1重合反応を行つ几6重
合体スラリー會水と分離し、乾燥して得られた樹脂Gは
THFVc不溶であり、分子量の#1走は不能であった
。After making the azobisisobutyronitrile xooott mixed solution, add 10 Kft of an aqueous solution of deionized water dissolved in 10 Kft of monocenol KM-1 and keep the inside of the polymerization machine at 80'C with stirring for 1 hour to carry out a polymerization reaction. Resin G obtained by separating the hexapolymer slurry from the water and drying it was insoluble in THFVc and was unable to run at #1 molecular weight.
参 考 fl g(樹脂H及Ig)―製)satの電
会機にトルエンgoV42仕込み110℃に加熱した後
、過酸化2パル酸t−エチル400 F、過酸化ベンゾ
イル400ft混合溶解させtスチレン溶液lαl11
t4時間で重合機内に添加し皮、さらに同装置て1時間
電合反応r続は曳後、!io’cまで冷却して得られた
重合体溶液Vr160J!のメタノールの中に再沈させ
、フレーク状の樹Ill Ht−分−離し友。このもの
のM、は8、500.Mw 7M%は表sであり友。Reference Flg (resin H and Ig) - After charging toluene goV42 in a SAT electric machine and heating it to 110℃, mix and dissolve 400 F of t-ethyl peroxide and 400 ft of benzoyl peroxide, and add t-styrene solution. lαl11
After 4 hours, it was added to the polymerization machine, and then the polymerization reaction was continued for 1 hour in the same machine. Polymer solution Vr160J obtained by cooling to io'c! The mixture was reprecipitated into methanol to form flakes. The M of this item is 8,500. Mw 7M% is table s and friend.
別に、上記スチレン溶液のかわりにスチレン& 2 i
4、メタクリル酸詐−ツチルL8す、過酸化ピ/譬ル酸
t−ブチル400 F、過酸化ベンゾイル4GOfの混
合溶液IQIりを用いた他はまったく同様の重合操作及
び後処理操作を行ってMIlが&10o、fw/Usが
表3の樹脂It得た。Separately, instead of the above styrene solution, styrene & 2 i
4. Exactly the same polymerization and post-treatment operations were carried out to obtain MIl, except that IQI was used as a mixed solution of tutyl methacrylate L8, t-butyl peroxide/t-butyl monoxide, and benzoyl peroxide 4GOf. Resin It was obtained with &10o and fw/Us shown in Table 3.
実施例1
参考例1で製造した樹脂4100部とカーIンブラック
(ダイヤブラック5H)io部tS合した後140℃の
熱ロールで20分間よく混練した。Example 1 4100 parts of the resin produced in Reference Example 1 and io parts tS of Carne Black (Diablack 5H) were combined and then thoroughly kneaded for 20 minutes using heated rolls at 140°C.
冷却後粗砕して約300μの粉体としVエラ)fル1l
Ds−ft型)で空気圧sKe/−供給普瓢SKg /
Hrで微粉砕し、平均粒径is声の微粉体を得、これ
をトナーとした。このトナーts s℃の恒温室vc1
時間貯蔵したところまったくツロツ中行ったところ画像
の定着は110℃から可能になり、290℃においても
熱ロールへのトナーのオフセットによる汚れはなく2へ
006枚の複写後も汚れのない鮮明な画像が得られた。After cooling, crush it into a powder of about 300 μm (1 liter)
Ds-ft type) with air pressure sKe/-supply SKg/
The powder was finely pulverized with Hr to obtain a fine powder having an average particle size of 100 ml, which was used as a toner. This toner ts s℃ constant temperature room VC1
After storing it for a while, the image could be fixed from 110 degrees Celsius, and even at 290 degrees Celsius, there was no stain due to toner offset to the heat roll, and even after copying 006 sheets to 2, the image remained clean and clear. was gotten.
実施湾2〜4
参考IP12〜4で製造した樹!11t−用いて実施I
pH1と同じ方法でトナー化しt複写試験を行つ九とこ
ろの結果を第1讃に示した。Implementation Bay 2-4 Trees manufactured with reference IP12-4! 11t - Performed using I
The results of 9 cases where a toner was made using the same method as pH 1 and a t-copying test were shown in the first review.
比較例1−3
参iIJ例5〜丁で製造した樹脂を用いて実施例1と同
じ方法でトナー化し、複写試験全行ったところの結果を
第1表に示した。冑、比較例1は特公昭51−1111
4号実施例1の追試に当る。Comparative Examples 1-3 The resins prepared in Examples 5 to 1 were made into toners in the same manner as in Example 1, and all copying tests were conducted. The results are shown in Table 1. Comparative example 1 is the special public helmet Sho 51-1111.
This corresponds to a supplementary test of No. 4 Example 1.
比 411!fN4(特公昭5!−6815号実施例8
の追試)
参考例Sで製造した#M脂HおよびIfそれぞれgo部
ずつ混合して使用したほかはまった〈実施9111と同
じ方法でトナー化し、複写v:、*に行つ皮ところの結
’It−@1表に示した。Ratio 411! fN4 (Special Publication No. 5!-6815 Example 8
Supplementary test) #M fats H and If produced in Reference Example S were mixed and used, except that go parts were used. It-@1 Table shows.
5656
Claims (1)
して含有しかつM 7M が48−100W
% 1 該重合体が、非共軛性!菖結合t2個以上有する化
合物も構成巣位として含有する共重合体である特許請求
の範囲第1項記載のトナー。 亀 非共梶性2重結合t−1個以上有する化合物が、α
、β−不飽和エチレン系鵬緻体当e)a65〜意重普−
である特許請求の範囲第g墳記載のトナー。 也 該電合体が、がム弾性重合体にα、β−不飽和エチ
レン系率賃体全グラフト重会させて得られる共重合体で
ある特許請求の範囲第1項記載のトナー。 翫 プ五弾性重合体が該共重合体当り(Ll〜ll01
′?#−である特許請求の範囲第1項記載のトナー。[Scope of Claims] Contains L α,β-unsaturated ethylenic monomer as a main structural unit and has M 7M of 48-100W
% 1 The polymer is non-coherent! 2. The toner according to claim 1, which is a copolymer which also contains a compound having two or more irises bonds as constituent sites. Tortoise A compound having t-1 or more non-covalent double bonds, α
, β-unsaturated ethylenic compound e) a65 ~ yichupu -
The toner according to claim g. 2. The toner according to claim 1, wherein the electropolymer is a copolymer obtained by total grafting an α,β-unsaturated ethylenic polymer onto an elastic polymer. Five elastic polymers per copolymer (Ll~ll01
′? The toner according to claim 1, which is #-.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP56199473A JPS58100859A (en) | 1981-12-12 | 1981-12-12 | Toner for developing electrostatic charge image |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP56199473A JPS58100859A (en) | 1981-12-12 | 1981-12-12 | Toner for developing electrostatic charge image |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1217581A Division JPH0277066A (en) | 1989-08-25 | 1989-08-25 | Electrostatic charge image developing toner |
JP3236805A Division JP2553787B2 (en) | 1991-08-26 | 1991-08-26 | New copolymer resin |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS58100859A true JPS58100859A (en) | 1983-06-15 |
JPH0241747B2 JPH0241747B2 (en) | 1990-09-19 |
Family
ID=16408377
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP56199473A Granted JPS58100859A (en) | 1981-12-12 | 1981-12-12 | Toner for developing electrostatic charge image |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS58100859A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS603644A (en) * | 1983-06-22 | 1985-01-10 | Fuji Xerox Co Ltd | Toner composition |
US4591900A (en) * | 1983-03-14 | 1986-05-27 | Rca Corporation | Encoding pattern for single chip CCD camera processing scheme |
JPS61176603A (en) * | 1985-01-31 | 1986-08-08 | Mitsubishi Rayon Co Ltd | Production of resin for toner |
JPH01214873A (en) * | 1988-02-23 | 1989-08-29 | Sanyo Chem Ind Ltd | Binder for toner |
WO1991009347A1 (en) * | 1989-12-12 | 1991-06-27 | Mitsui Toatsu Chemicals, Incorporated | Electrophotographic toner composition |
JPH04190244A (en) * | 1990-11-23 | 1992-07-08 | Sanyo Chem Ind Ltd | Toner binder for electronic photography |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE215665C (en) * | ||||
JPS50134652A (en) * | 1974-04-10 | 1975-10-24 | ||
JPS55147638A (en) * | 1979-05-08 | 1980-11-17 | Canon Inc | Magnetic toner |
JPS55151647A (en) * | 1979-05-16 | 1980-11-26 | Denki Kagaku Kogyo Kk | Toner for electrostatic development |
JPS55166651A (en) * | 1979-06-15 | 1980-12-25 | Dainippon Ink & Chem Inc | Toner for static charge developer |
JPS56158340A (en) * | 1980-05-13 | 1981-12-07 | Konishiroku Photo Ind Co Ltd | Toner for developing electrostatic charge image |
-
1981
- 1981-12-12 JP JP56199473A patent/JPS58100859A/en active Granted
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE215665C (en) * | ||||
JPS50134652A (en) * | 1974-04-10 | 1975-10-24 | ||
DE2515665A1 (en) * | 1974-04-10 | 1975-10-30 | Konishiroku Photo Ind | TONER FOR DEVELOPING LATENT ELECTROSTATIC IMAGES |
JPS55147638A (en) * | 1979-05-08 | 1980-11-17 | Canon Inc | Magnetic toner |
JPS55151647A (en) * | 1979-05-16 | 1980-11-26 | Denki Kagaku Kogyo Kk | Toner for electrostatic development |
JPS55166651A (en) * | 1979-06-15 | 1980-12-25 | Dainippon Ink & Chem Inc | Toner for static charge developer |
JPS56158340A (en) * | 1980-05-13 | 1981-12-07 | Konishiroku Photo Ind Co Ltd | Toner for developing electrostatic charge image |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4591900A (en) * | 1983-03-14 | 1986-05-27 | Rca Corporation | Encoding pattern for single chip CCD camera processing scheme |
JPS603644A (en) * | 1983-06-22 | 1985-01-10 | Fuji Xerox Co Ltd | Toner composition |
JPH0259986B2 (en) * | 1983-06-22 | 1990-12-14 | Fuji Xerox Co Ltd | |
JPS61176603A (en) * | 1985-01-31 | 1986-08-08 | Mitsubishi Rayon Co Ltd | Production of resin for toner |
JPH0473442B2 (en) * | 1985-01-31 | 1992-11-20 | Mitsubishi Rayon Co | |
JPH01214873A (en) * | 1988-02-23 | 1989-08-29 | Sanyo Chem Ind Ltd | Binder for toner |
JPH0447310B2 (en) * | 1988-02-23 | 1992-08-03 | Sanyo Chemical Ind Ltd | |
WO1991009347A1 (en) * | 1989-12-12 | 1991-06-27 | Mitsui Toatsu Chemicals, Incorporated | Electrophotographic toner composition |
JPH04190244A (en) * | 1990-11-23 | 1992-07-08 | Sanyo Chem Ind Ltd | Toner binder for electronic photography |
Also Published As
Publication number | Publication date |
---|---|
JPH0241747B2 (en) | 1990-09-19 |
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