JPS59226358A - Electrostatic charge image developing color toner - Google Patents
Electrostatic charge image developing color tonerInfo
- Publication number
- JPS59226358A JPS59226358A JP58101539A JP10153983A JPS59226358A JP S59226358 A JPS59226358 A JP S59226358A JP 58101539 A JP58101539 A JP 58101539A JP 10153983 A JP10153983 A JP 10153983A JP S59226358 A JPS59226358 A JP S59226358A
- Authority
- JP
- Japan
- Prior art keywords
- toner
- resin
- vinyl
- mol
- manufactured
- 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.)
- Pending
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
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Developing Agents For Electrophotography (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はファンクショナルカラーコピー用に適した静電
荷像現像用カラートナーに関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a color toner for developing electrostatic images suitable for functional color copying.
静電記録法による着色画像の記録には三色分解目元と減
色法3原色(或いは黒を含む4色)のカラートナーの組
合せKよって原色の色再現をはかる方式のカラーコピー
が行われているが\これとは別に通常用いられる黒色の
外、1種若しくはそれ以上の黒以外の色を用いて画面中
の特許の文字・図形等を色分は表示したりするいわゆる
ファンクシHすに;h5−の手法が用いられる。ファン
クシ叢ナルカラー用のカラートナーには色による識別、
強調を主目的とす仝ため、他の色の画像、着色物等の上
に重ね刷りされた場合にも下地の色の影響を受けること
なく鮮明な画像を形成するよう高い隠ぺい性と鮮かな呈
色性をもっことが要求される。When recording colored images using the electrostatic recording method, color copying is performed using a combination K of color toners of three color separations and three primary colors (or four colors including black) using a subtractive color method to reproduce the primary colors. However, apart from this, so-called funksi H5 is used to display patent characters, figures, etc. on the screen using one or more colors other than black, which is usually used. − method is used. The color toner for funksicolor is distinguished by color,
Since the main purpose is to emphasize the image, it has high opacity and vividness so that even if it is overprinted on other colored images or colored objects, it will form a clear image without being affected by the underlying color. High color development is required.
通常用いられるファンクシ5ナルカラー用トナーは主と
して結着用樹脂と高隠ぺい性の有色顔料から成っており
、その大部分をなす結着用樹脂は紙等の転写材に転写後
、熱足着されることにより溶融し定着後固化して均−且
つ強固な樹脂層を形成し着色剤を転写材上に結着する役
割を有している。トナー像の定着は熱ローラ等の加熱さ
れた部材をトナー像に接触させ結着樹脂を溶融させる接
触加熱足着法が一般に用いられているが、接触加熱定着
用トナーに使用される結着猫脂には下記のような特性を
もつことが必要とされる。The commonly used funxional color toner mainly consists of a binder resin and a highly opaque colored pigment.The binder resin, which makes up the majority of the toner, is transferred to a transfer material such as paper and then thermally adhered to it. After being melted and fixed, it solidifies to form a uniform and strong resin layer, which serves to bind the colorant onto the transfer material. To fix the toner image, a contact heating method is generally used in which a heated member such as a heat roller is brought into contact with the toner image to melt the binder resin. Fats are required to have the following properties:
(1)溶融したトナーが熱定着ローラに転写し、次に来
る転写材を汚損するいわゆるオフセント現象を起さない
こと。オフセント現象は熱ローラ温度が高まると発生す
る傾向があり・その発生開始温度が高いほど好ましいト
ナーと言える。(1) The so-called offset phenomenon, in which molten toner is transferred to a heat fixing roller and stains the next transfer material, should not occur. The off-cent phenomenon tends to occur as the temperature of the heat roller increases, and it can be said that the higher the temperature at which the off-cent phenomenon begins to occur, the more preferable the toner is.
(2) 転写材のローラ巻付の原因となる熱定着ロー
ラへの転写及び対向ローラへの再転写によるローラ汚れ
を起さないこと。(2) Avoid staining the roller due to transfer to the heat fixing roller and retransfer to the opposing roller, which causes the transfer material to wrap around the roller.
(3) 溶融したトナーが適度の流動性を有し・定着
後均−緻密な適度の厚みの層を形成すること。(3) The molten toner should have appropriate fluidity and form a uniform, dense layer with an appropriate thickness after fixing.
特にカラートナーにおいては黒色トナーの場合にくらべ
顔料の隠ぺい率が低いため充分な色濃度、隠ぺい性を得
るためにはある程度の層厚を必要とするため上記(2)
項にのべた溶融樹脂の流動性は耐脂選択上の重要なポイ
ントとなる。溶融樹脂の粘度が高すぎると不均一分散の
トナーが出来易く1また定着温度を高めることが必要と
なり、低すぎる場合には定着時トナ一層が拡がって層厚
が下がり必要な隠ぺい性が得られない。In particular, in color toners, the hiding rate of the pigment is lower than in the case of black toners, so a certain layer thickness is required to obtain sufficient color density and hiding properties, so (2)
The fluidity of the molten resin mentioned above is an important point in selecting a grease-resistant material. If the viscosity of the molten resin is too high, non-uniformly dispersed toner is likely to be produced (1) It is also necessary to raise the fixing temperature, and if it is too low, the toner layer will spread during fixing and the layer thickness will decrease, making it difficult to obtain the necessary hiding power. do not have.
(4)定着可能温度が低いこと。(4) Low fixing temperature.
機器の設計、使用時の取扱い、エネルギー節減等の点か
ら定着温度はできるだけ低いことが望ましい。It is desirable that the fixing temperature be as low as possible from the viewpoints of equipment design, handling during use, energy saving, etc.
一般に定着温度の低いトナーは低い温度でのオフセット
現象を起しやすく、低い定着温度と高いオフセント発生
温度の二つはトナーの性能として両立し難いものであっ
た。In general, toners with a low fixing temperature tend to cause an offset phenomenon at low temperatures, and it has been difficult to achieve both a low fixing temperature and a high offset generation temperature in terms of toner performance.
従来すぐれたトナー結着用樹脂として
1)不飽和ポリエステル痔の熱架橋性樹脂2)ポリエス
テル樹脂とビニル系重合体の混合物
3)3価のアルコール及び(又は)3価のカルボン酸を
単量体の一部として用いた三次元構造をもつポリエステ
ル樹脂
等が提案されているが、1)は流動性が低いため実用が
邦しく・2)は両種の樹脂の相溶性が悪くトナーの帯電
量分布が広がり画像にカブリを生じやすい、3)はオフ
セント防止効果が低い等の欠点があり満足すべきものと
は言えILかった。Conventionally, excellent toner binding resins include 1) thermally crosslinkable unsaturated polyester resins, 2) mixtures of polyester resins and vinyl polymers, and 3) trivalent alcohols and/or trivalent carboxylic acids as monomers. Polyester resins with a three-dimensional structure have been proposed, but 1) is difficult to put into practical use due to low fluidity, and 2) has poor compatibility between the two types of resins, resulting in toner charge distribution. 3) tends to spread and cause fog in the image, and 3) has drawbacks such as low offset prevention effect, and although it is satisfactory, the IL was poor.
またビニール系重合体も使用されているがオフセット現
象を生じ易い欠点があった。Vinyl polymers have also been used, but they have the drawback of being prone to offset phenomena.
本発明の目的は定着可能温度が低く、オフセント裏面汚
れ、巻付き等の現象を起こさず隠ぺい性にすぐれ、且つ
帯″重分布の狭いファンクショナルカラーコピーに適し
たカラートナーを提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a color toner that has a low fixing temperature, does not cause phenomena such as off-center backside staining or wrapping, and has excellent hiding properties, and is suitable for functional color copying with a narrow band weight distribution. .
上記の目的は結着樹脂としてゲルバーミエイション乎ク
ロマトグラフィーで測定した分子量分布が分子量103
乃至5XIO’及びio”乃至106の二つの領域内に
それぞれ少くとも一つの極大を有する、ビニール糸単量
体の重合体若しくは共重合体を用いたカラートナーによ
って達成された。The above purpose is to use a binder resin with a molecular weight distribution of 103 as measured by gel permeation and chromatography.
This was achieved with a color toner using a polymer or copolymer of vinyl thread monomers, each having at least one maximum in two regions, 5XIO' to 5XIO' and io'' to 106.
上記分子量の測定は下記のようにして行われる。The above molecular weight is measured as follows.
「ウォーターズ200型GPC(Water/s 20
0 Type GPC)副足器」 (ウォーターズ社製
)を用い、温度25°Cで溶媒(テトラハイドロフラン
)を毎分1mtの流速で流下せしめながら、濃度0.2
g/1ill!のテトラハイドロフラン試料溶液を、試
料型組にして4■の量カラム内に注入して測定する。こ
こで使用するカラムとしては、10’ −1,0’ −
10’ −104の組合せを用いる。“Water/s 200 GPC (Water/s 20
0 Type GPC) (manufactured by Waters), the solvent (tetrahydrofuran) was allowed to flow down at a flow rate of 1 mt/min at a temperature of 25°C, and the concentration was 0.2.
g/1ill! The sample solution of tetrahydrofuran is made into a sample mold and injected into the column in an amount of 4 cm for measurement. The column used here is 10'-1,0'-
A combination of 10'-104 is used.
検量線を設定するための単分散ポリスチレン標準試料は
、プレッシャーケミカル社製ポリスチレンであって、分
子量が、1.800,000.860,000゜411
.000.160.000.98,200 、51,0
00 。The monodisperse polystyrene standard sample for setting the calibration curve is polystyrene manufactured by Pressure Chemical Co., Ltd., and has a molecular weight of 1.800,000.860,000°411.
.. 000.160.000.98,200, 51,0
00.
19.800.10,000.4,000のものを使用
する。19.800.10,000.4,000 is used.
本発明によるカラートナーに用いられる重合体を与える
ビニール単量体としては例えば、スチレン、0−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 −te
rt−プチルスチレン4こニム」 ・
−−シし毛十÷、p−n−へキシルスチレン、p−n
−オクpn−7ニルスチレン、p−れ
−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−7エニルスチレン、p−クロルス
チレン、3.4−ジクロルスチレン等のスチレン単量体
を好ましいものとして挙げることができる。このほか、
例えばエチレン・プロピレン1ブチレン、インブチレン
等のエチレン不飽和モノオレフィンi;LJX化ビニル
、塩化ビニリデン、臭化ビニル、弗化ビニル等のハロゲ
ン化ビニル類;酢酸ビニル、プロピオン酸ビニル、ベン
ジェ酸ビニル、酪酸ビニル等のビニルエステル類ニアク
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1アクリル酸
ステアリル\アク’)km2−10ルエチル、アクリル
酸フェニル、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、メタアクリル醪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、メタ
アクリル酸フェニル・メタアクリル酸ジメチルアミノエ
チル、メタアクリル酸ジエチルアミンエチル等のα−メ
チレン脂肪族モノカルボン厳エステル類;アクリロニト
リル)メタアクリロニトリル、アクリルアミド等のアク
リル酸もしくはメタアクリル酸誘導体;ビニルメチルエ
ーテル、ビニルエチルエーテル、ビニルイソブチルエー
テル等のビニルエーテル類;ビニルメチルケトン、ビニ
ルへキシルケトン、メチルイソプロペニルケトン等のビ
ニルケトン類:N−ビニルピロール、N−ビニルカルバ
ゾール、N−ビニルインドール、N−ビニルピロリドン
等のN−ビニル化合物;ビニルナフタレン類、ソの他を
挙げることができる。Vinyl monomers providing the polymer used in the color toner of the present invention include, for example, styrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene,
α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-te
rt-butylstyrene 4-konym" ・
--Shishigeju÷, p-n-hexylstyrene, p-n
-Styrene monomers such as pn-7nylstyrene, p-redecylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-7enylstyrene, p-chlorostyrene, and 3,4-dichlorostyrene can be mentioned as preferred. other than this,
For example, ethylenically unsaturated monoolefins such as ethylene/propylene 1-butylene and imbutylene; vinyl halides such as LJX vinyl, vinylidene chloride, vinyl bromide, and vinyl fluoride; vinyl acetate, vinyl propionate, vinyl benzoate, Vinyl esters such as vinyl butyrate, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate/propyl acrylate\n-octyl acrylate, dodecyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate 1 acrylic Acid stearyl\ac') km2-10 ethyl, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate-ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacrylate α-methylene such as n-octyl acrylic, dodecyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate/dimethylaminoethyl methacrylate, diethylamine ethyl methacrylate, etc. Aliphatic monocarboxylic esters; Acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl ether; Vinyl methyl ketone, vinyl hexyl ketone, and methyl iso Vinyl ketones such as propenyl ketone; N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, and N-vinylpyrrolidone; vinylnaphthalenes, and others.
斯かる単量体により得られるもののうち、特にスチレン
−アクリル系共重合体が好ましい。Among those obtained using such monomers, styrene-acrylic copolymers are particularly preferred.
上記のIP量体を用いて本発明に用いられる分子量分布
に2つもしくはそれ以上の極大をもつ重合物若しくは共
重合物は、得ようとする重合体の種類に応じて選んだ1
種若しくはそれ以上の上記単量体と過酸化ベンゾイル等
の重合開始剤を混合し一定の反応条件下で重合せしめ、
得られた重合物を新たな単量体、重合開始剤と混合し更
に重合反応を行なう、等の方法によって得ることができ
る本発明によるトナーに用いられる有彩色着色剤として
は各種の有機無機顔料、或いは各種の染料があるが、色
彩の鮮明な・耐光性・隠ぺい性の高い有機顔料が好まし
く、例えば下記のごときものが挙げられる。(顔料はカ
ラーインデックス 第3版 1971同増補1975に
記載のC,1,名称番号、及びそれに該当する商品名の
1例で示した。JC,1,ピグメントレッド48:1
(スミカプリントレッドC1、住方化学■製)C,1,
ピグメントレッド53:1
(クロモフクールマゼンタG、\チバ嘩ガイギー社製)
C,1,ピグメントレッド 123
(カヤセットレッドE−B、日本化薬■製)C,1,ピ
グメントレッド 139
(カヤセットレッドE −GR,日本化薬■製)C,1
,ピグメントレッド 144
(クロモフタールレッドBRN、チバ・ガイキー社製)
C,1,ピグメントレッド 149
(PV ファストレッドB1ベキスト・ジャパン社製)
C,1,ビグメントレンド 166
(クロモフタールスカーレノトR・チパ・ガイキー社製
)C,1,ピグメントレッド 177
(クロモフクールレッドA3B 、チバ働ガイギー社製
)C,1,ピグメントレッド 178
(カヤセットレッドE−GG・日本化薬■製)C,1,
ピグメントオレンジ 31
(クロモアタールオレンジ4R,チバ・ガイキー社製)
C,1,ピグメントイエロー 17
()7ストイエローGBFN 、住友化学社製〕C,1
,ピグメントイエロー 93
Cクロモフクールイエロー3G、チバ・ガイキー社製)
C,1,ピグメントイエロー 94
(クロセフクールイエロー6G、千バ・ガイキー社製)
c、1.ピグメントグリーン 7
(クロモフタールグリーンGF、チバ・ガイキー社i1
C,1,ピグメントブルー15:3
(カーマインブルーGNR−0、住方化学社製)C,1
,ピグメントブルー 60
(クロモフタールブルーA3R、チバ・ガイギー社りこ
れら有色着色剤のトナーにおける使用量ハ\該トナーを
構成する結着樹脂100重量部に対し3乃至20重量部
であることが好ましい。The polymer or copolymer having two or more maxima in the molecular weight distribution used in the present invention using the above IP polymer is one selected depending on the type of polymer to be obtained.
A species or more of the above monomers and a polymerization initiator such as benzoyl peroxide are mixed and polymerized under certain reaction conditions,
The chromatic colorant used in the toner of the present invention, which can be obtained by a method such as mixing the obtained polymer with a new monomer and a polymerization initiator and further performing a polymerization reaction, includes various organic and inorganic pigments. Alternatively, there are various dyes, but organic pigments with vivid colors, high light resistance, and high hiding properties are preferable, and examples include the following. (Pigments are shown as C,1, name number and an example of the corresponding product name listed in Color Index 3rd edition 1971 1975 supplement.JC,1, Pigment Red 48:1 (Sumika Print Red C1, Manufactured by Sumikata Chemical Co., Ltd.) C, 1,
Pigment Red 53:1 (Chromov Cool Magenta G, manufactured by Ciba Geigy)
C, 1, Pigment Red 123 (Kaya Set Red E-B, manufactured by Nippon Kayaku ■) C, 1, Pigment Red 139 (Kaya Set Red E-GR, manufactured by Nippon Kayaku ■) C, 1
, Pigment Red 144 (Chromophthal Red BRN, manufactured by Ciba Gaikie)
C, 1, Pigment Red 149 (PV Fast Red B1 Manufactured by Vext Japan Co., Ltd.)
C, 1, Big Men Trend 166 (Chromophthal Scarlenoto R, manufactured by Chipa Geiki) C, 1, Pigment Red 177 (Chromophthal Red A3B, manufactured by Ciba Geigy) C, 1, Pigment Red 178 (Kayaset Red E-GG, manufactured by Nippon Kayaku) C, 1,
Pigment Orange 31 (Chromatar Orange 4R, manufactured by Ciba Gaikie)
C,1, Pigment Yellow 17 ()7 St Yellow GBFN, manufactured by Sumitomo Chemical Co., Ltd.] C,1
, Pigment Yellow 93C Chromof Cool Yellow 3G, manufactured by Ciba Gaikie)
C, 1, Pigment Yellow 94 (Kurosef Cool Yellow 6G, manufactured by Senba Gaiki Co.)
c.1. Pigment Green 7 (Chromophthal Green GF, Ciba Geikie i1
C,1, Pigment Blue 15:3 (Carmine Blue GNR-0, manufactured by Sumikata Chemical Co., Ltd.) C,1
, Pigment Blue 60 (Chromophthal Blue A3R, manufactured by Ciba Geigy) The amount of these colored colorants used in the toner is preferably 3 to 20 parts by weight per 100 parts by weight of the binder resin constituting the toner. .
本発明のトナーには上記のビニール系樹脂及び有彩色着
色剤の外各種々の荷電制御剤、或いはトナーの流動性、
クリーニング性を向上させるための疎水性シリカ、脂肪
酸金属塩等の各種添加剤を加えることができ、更にトナ
ーのオフセットを防止するため低分子のポリプロピレン
、ポリエチレン或いはワックス等の1lIIC型剤を加
えることも出来る0
ポリプロピレンのような陰型剤の添加三は・ トナーを
構成する結着樹脂100重貝部に対し1乃至10重置部
であることが好ましい。In addition to the above-mentioned vinyl resin and chromatic colorant, the toner of the present invention may contain various charge control agents, or fluidity of the toner.
Various additives such as hydrophobic silica and fatty acid metal salts can be added to improve cleaning performance, and 1lIIC type agents such as low-molecular polypropylene, polyethylene or wax can also be added to prevent toner offset. The addition of a negative agent such as polypropylene is preferably 1 to 10 parts per 100 parts of the binder resin constituting the toner.
本発明によるカラートナーを製造するには・前記ビニー
ル系重合体、前記有色着色剤及び離型剤等の各種添加剤
をボールミル等でよく混和し、更にエクストルーダ中で
充分に溶融、線混して冷却・微粉砕して分級し所定の粒
径のトナーを得ればよい。得られたトナーは下記の測定
による隠ぺい性が30%以上であることが望ましい。上
記隠ぺい性が30%以下のトナーは重ね刷りし、た場合
下地の影響を受は画像の呈度が鮮明さを欠く傾向を示す
。To produce the color toner according to the present invention: - The vinyl polymer, the colored colorant, and various additives such as a release agent are thoroughly mixed in a ball mill or the like, and then thoroughly melted and wire-mixed in an extruder. It is sufficient to obtain toner of a predetermined particle size by cooling, pulverizing, and classifying. It is desirable that the obtained toner has a hiding power of 30% or more as measured below. Toners with the above-mentioned opacity of 30% or less are overprinted, and when they are affected by the undercoating, the image appearance tends to lack sharpness.
(隠ぺい性の測定)
被検トナー25gをメチルエチルケトン150mjに溶
解分散し、厚み100μmのポリエスタ−フィルム上に
ワイヤーバーを用い乾燥膜厚約lOμmとなるように塗
布し乾燥する。得られた試料を白紙(明度約85)、及
び黒紙(明度約5)に密接させ試料側よりCMS −1
0008型高速分元色彩計(村上色彩研究新製)でそれ
ぞれの明度を測定する。(Measurement of Concealability) 25 g of the toner to be tested is dissolved and dispersed in 150 mj of methyl ethyl ketone, applied onto a 100 μm thick polyester film using a wire bar to a dry film thickness of about 10 μm, and dried. The obtained sample was brought into close contact with white paper (lightness approximately 85) and black paper (lightness approximately 5) and CMS-1 was applied from the sample side.
The brightness of each color was measured using a 0008 model high-speed fractional colorimeter (manufactured by Murakami Color Research Co., Ltd.).
隠ぺい性を次の弐によって表示する。Concealability is indicated by the following 2.
YB:黒紙上の明度
Yw:白紙上の明度
トナ一層の隠ぺい性が低く裏に置かれた黒紙が透視され
れば試料の見掛の明度は低下し上記の値は低下する。YB: Brightness on black paper Yw: Brightness on white paper If the toner has a lower hiding power and the black paper placed on the back is seen through, the apparent brightness of the sample decreases and the above value decreases.
上記のように本発明によるカラートナーは、高分子領域
と低分子量域の二つの領域に極大のある分子量分布をも
つ結着樹脂で構成されているため、定着温度が低いと言
う比較的低分子の樹脂の特徴とオフセクト現象発生温度
が高くオフセットを起しにくい比較的高分子の樹脂の特
徴を併有する、熱定着用トナーとして極めて好ましい性
質を有するものとなる。また上記の樹脂は最初より一体
の樹脂として合成されるため2種の樹脂を単に混合した
場合のよ5に荷1!景分布が広がってカブリを生ずるよ
うな欠点が現われることもない。As mentioned above, the color toner according to the present invention is composed of a binder resin that has a molecular weight distribution with a maximum in two regions, a high molecular weight region and a low molecular weight region, and therefore has a relatively low molecular weight that has a low fixing temperature. The toner has extremely desirable properties as a heat fixing toner, which has both the characteristics of a resin and the characteristics of a relatively high-molecular resin that has a high offset phenomenon occurrence temperature and is difficult to cause offset. In addition, since the above resins are synthesized as a single resin from the beginning, the load is 5 to 1 compared to simply mixing two types of resin. Defects such as the spread of the landscape and the occurrence of fog do not appear.
以下実施例によって本発明の詳細な説明する。The present invention will be explained in detail below with reference to Examples.
C本発明による樹脂の合成)
容ff1lJのセパラブルフラスコにポリビニルアルコ
ール部分ケン化物「ゴーセノールGH−17J(日本合
成工業社製)0.1.9を入れ純水100mtを加えて
溶解し、その中にスチレン3ON・アクリル酸n−ブチ
ル15 F及び過酸化ベンゾイル0.1#よりなる混合
物を加えて懸濁分散し、気相を窒素ガスで置換した後間
℃に保って重合を行なった0冷却後脱水及び水洗を繰返
した後乾燥して重合物を得た。C) Synthesis of resin according to the present invention) In a separable flask with a volume of ff1lJ, partially saponified polyvinyl alcohol "Gohsenol GH-17J (manufactured by Nippon Gosei Kogyo Co., Ltd.) 0.1.9" was placed, and 100 mt of pure water was added to dissolve it. A mixture of 3ON styrene, 15F n-butyl acrylate, and 0.1 # of benzoyl peroxide was added to the solution, suspended and dispersed, and after the gas phase was replaced with nitrogen gas, polymerization was carried out by keeping the temperature at ℃. Post-dehydration and water washing were repeated, followed by drying to obtain a polymer.
得られた重合物4019をスチレン70I!−アクリル
酸30.9よりなるモノマー混合物に溶解し更に過酸化
ベンゾイル5gを加えた溶液を調製した。容filJの
セパラブルフラスコ純水200mをとり「ゴーセノール
GH−17J 0.2I!を入れて溶解し、更に前記重
合体のモノマー溶液を加えて懸濁分散し気相を窒素ガス
で置換した後(資)℃に保って再び重合を行った。その
後冷却、水洗を行ない乾燥して樹脂■を得た。The obtained polymer 4019 was converted into styrene 70I! - A solution was prepared by dissolving 30.9 g of benzoyl peroxide in a monomer mixture consisting of 30.9 g of acrylic acid. Take 200 m of pure water in a separable flask with a volume of filJ, add Gohsenol GH-17J 0.2I!, dissolve it, add the monomer solution of the polymer, suspend and disperse, and replace the gas phase with nitrogen gas. (Note) Polymerization was carried out again while maintaining the temperature at ℃.Then, the resin was cooled, washed with water, and dried to obtain a resin (①).
得られた樹脂は前記のゲル≠バーミエイシ厘ンiクロマ
トグラフィ測定器に掛は分子量分布を求めたところ分子
ffi 13,000と220,000にそれぞれ極大
を有するものであった〇
(対比猫脂の合成)
樹脂lの場合と同じく、ス°チレン30I!、アクリル
酸ブチル15g及び過酸化ベンゾイル0.1.9の混合
液を「ゴー七ノールG)t −17J O,119を溶
かした純水1001nt中に懸濁し、窒素ガス気相中で
(資)℃保って重合を行った。冷却後脱水1水洗・乾燥
して樹脂■を得た。The molecular weight distribution of the obtained resin was determined using the gel ≠ vermiacetic chromatography analyzer, and it was found that the molecular weight distribution had maximums at molecular ffi of 13,000 and 220,000, respectively (compared to the synthesis of cat fat). ) As in the case of resin l, styrene 30I! A mixed solution of 15 g of butyl acrylate and 0.1.9 g of benzoyl peroxide was suspended in 1001 nt of pure water in which 119 of "Go-7Nol G) t-17J O,119 was dissolved, and the mixture was suspended in a nitrogen gas phase. Polymerization was carried out while maintaining the temperature at ℃.After cooling, the resin was dehydrated, washed with water, and dried to obtain resin (■).
ゲルパーミェーションクロマトグラフィーにより測った
結果によれば樹脂■の分子量分布は60.000附近に
一つの極大をもつものであった。また猫脂■と同一処方
で重合時間を延長し樹脂■を得た。樹脂■の分子量分布
は350,000附近に一つの極大をもつものであった
。According to the results measured by gel permeation chromatography, the molecular weight distribution of resin (1) had one maximum around 60,000. Resin ■ was also obtained by extending the polymerization time using the same formulation as cat fat ■. The molecular weight distribution of resin (1) had one maximum around 350,000.
(トナーの調製及び試!lり
上記の樹脂Iiooim部をとり赤色顔料pvソファト
レッドB(ヘキスト・ジャパン社i)5重量部及び離型
剤としてポリプロピレン「ビスフール660PJ (
三洋化成社製)2重社部を加えヘキシエルミキサーで予
備混合の上エクス)A/−タテ溶融、混練し、冷却後微
粉砕、分級して平均粒径約12.5μm の赤色トナー
■を得た。得られたトナー21に磁性キャリヤDIP
−135(平均粒径100μm ・同和鉄粉社製)1k
gを混合攪拌して現像剤を調製し、特に定着器の熱ロー
ラ温度を自由に変更\設定できるように改造した電子複
写機rU−BIX 3000 J (小西六写真工秦
礼製)に装填して上記熱ローラ温度を変化して実写試験
を行ないオフセット現象が発生しはじめる熱ローラの最
低温度T、及び定着可能の最低温度T、を求めた。(Preparation and testing of toner!) Take part of the above resin, add 5 parts by weight of red pigment PV Sofa Tread B (Hoechst Japan Co., Ltd.), and use polypropylene "Bisful 660PJ" as a release agent.
Sanyo Kasei Co., Ltd.) 2-jusha part was added and pre-mixed with a hexyl mixer, then Ex) A/- was melted vertically, kneaded, cooled, pulverized and classified to produce red toner ■ with an average particle size of approximately 12.5 μm. Obtained. Magnetic carrier DIP is applied to the obtained toner 21.
-135 (average particle size 100 μm, manufactured by Dowa Iron Powder Co., Ltd.) 1k
Prepare a developer by mixing and stirring g, and load it into an electronic copying machine rU-BIX 3000 J (manufactured by Konishiroku Photography Hata Rei), which has been modified so that the temperature of the heat roller of the fixing device can be freely changed/set. A photocopying test was conducted while changing the temperature of the heat roller, and the minimum temperature T of the heat roller at which the offset phenomenon began to occur and the minimum temperature T at which fixing was possible were determined.
また上記樹脂■、或いは■を用い上記トナーIと同一の
方法によってトナーn、IIIを調製し、それぞれキャ
リヤと混合してトナーIの場合と同条件で試験を行ない
T1、T、を求めた。Further, toners n and III were prepared using the resins (1) and (2) in the same manner as toner I, mixed with a carrier, and tested under the same conditions as for toner I to determine T1 and T.
尚上記の試験に用いた定着器は、加熱ローラの表層がテ
フロン(デュポン社製)、対向ローラの表層がシリコン
ゴム「KE−130OR,T、V−J (信越化学工
業社製)より成るものであった。In the fuser used in the above test, the surface layer of the heating roller was made of Teflon (manufactured by DuPont), and the surface layer of the opposing roller was made of silicone rubber KE-130OR, T, V-J (manufactured by Shin-Etsu Chemical Co., Ltd.). Met.
また上3種のトナーの隠ぺい性はいずれも35%前後で
あり、この点では実用上充分な性質を有するものであっ
た。試験の結果得られた各トナーのT1、T2は第1表
の通りであった。Furthermore, the hiding properties of the above three types of toners were all around 35%, and in this respect, they had practically sufficient properties. T1 and T2 of each toner obtained as a result of the test were as shown in Table 1.
第 1 表
ト す − A T1
721230℃以上 160°G
■190℃ 160℃
■230℃以上 200℃
本発明によるトナーIげ・定着可能温度Ttが低いにも
拘らずオフセクト発生111K ’r、が高く、実用・
止すぐれた足着峙性を示すのに対し、対比試料であるト
ナー■はT、が低い反面T1も低くオフセントが起りや
すい欠点を有し、トナー■はオフセンF開始温度は高い
ものの定着に必要な温度が高く満足すべきものでtri
なかった。Table 1 - A T1
721230°C or higher 160°G ■190°C 160°C ■230°C or higher 200°C Despite the low toner I/fixing temperature Tt of the present invention, the offset occurrence 111K'r is high, making it suitable for practical use.
On the other hand, toner ■, which is a comparison sample, has a low T, but also has a low T1, which tends to cause off-cent, and although toner ■ has a high offset F starting temperature, it is necessary for fixing. Try something with a high and satisfying temperature.
There wasn't.
トナー■を用いて、また得られた画像はカブリのない鮮
明なもので荷量分布のひろがりによるカブリの発生等も
全く認められなかったO上記の実施例が示す通り、本発
明によるカラートナーは比較的低温での定着が可能であ
り・且つオフセット現象も発せし難いすぐれた熱定着適
性を有することが立証されTこ。Using the toner ■, the images obtained were clear with no fog, and no fog was observed due to the spread of the load distribution.OAs shown in the above examples, the color toner according to the present invention was It has been proven that it can be fixed at a relatively low temperature and has excellent heat fixing suitability with no offset phenomenon.
代理人 桑 原 5 美Agent Kuwa Hara 5 Mi
Claims (1)
電荷像現像用カラートナーにおいて、上記結着樹脂が、
ゲルパーミエイション≠クロマトグラフィーで測定した
分子量分布が分子量108乃至5XIO’、及びio5
乃至106の二つの領域内にそれぞれ少くとも一つの極
大を有する・ビニ■ル糸単量体の重合物若しくは共重合
体であることを特徴とする静電荷像現像用カラートナー
。(1) In a color toner for developing electrostatic images mainly consisting of a binder resin and a chromatic colorant, the binder resin is
Gel permeation ≠ Molecular weight distribution measured by chromatography is molecular weight 108 to 5XIO' and io5
A color toner for developing electrostatic images, characterized in that it is a polymer or copolymer of vinyl thread monomers having at least one maximum in each of the two regions of 1 to 106.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58101539A JPS59226358A (en) | 1983-06-06 | 1983-06-06 | Electrostatic charge image developing color toner |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58101539A JPS59226358A (en) | 1983-06-06 | 1983-06-06 | Electrostatic charge image developing color toner |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS59226358A true JPS59226358A (en) | 1984-12-19 |
Family
ID=14303238
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP58101539A Pending JPS59226358A (en) | 1983-06-06 | 1983-06-06 | Electrostatic charge image developing color toner |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS59226358A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62191858A (en) * | 1986-02-18 | 1987-08-22 | Mitsui Toatsu Chem Inc | Electrophotographic toner composition |
JPH0266560A (en) * | 1988-08-31 | 1990-03-06 | Sekisui Chem Co Ltd | Resin composition for toner and toner containing the composition |
JPH02176668A (en) * | 1988-12-28 | 1990-07-09 | Mita Ind Co Ltd | Toner for electrophotography and its production |
JPH0377962A (en) * | 1989-08-21 | 1991-04-03 | Mita Ind Co Ltd | Electrophotographic toner |
US5102761A (en) * | 1989-05-02 | 1992-04-07 | Canon Kabushiki Kaisha | Color toner for electrophotography containing a phenolic compound |
US5418102A (en) * | 1990-11-29 | 1995-05-23 | Canon Kabushiki Kaisha | Developer for developing electrostatic image, image forming method, toner imager fixing method and image forming apparatus |
-
1983
- 1983-06-06 JP JP58101539A patent/JPS59226358A/en active Pending
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62191858A (en) * | 1986-02-18 | 1987-08-22 | Mitsui Toatsu Chem Inc | Electrophotographic toner composition |
JPH0266560A (en) * | 1988-08-31 | 1990-03-06 | Sekisui Chem Co Ltd | Resin composition for toner and toner containing the composition |
JPH02176668A (en) * | 1988-12-28 | 1990-07-09 | Mita Ind Co Ltd | Toner for electrophotography and its production |
US5102761A (en) * | 1989-05-02 | 1992-04-07 | Canon Kabushiki Kaisha | Color toner for electrophotography containing a phenolic compound |
JPH0377962A (en) * | 1989-08-21 | 1991-04-03 | Mita Ind Co Ltd | Electrophotographic toner |
US5418102A (en) * | 1990-11-29 | 1995-05-23 | Canon Kabushiki Kaisha | Developer for developing electrostatic image, image forming method, toner imager fixing method and image forming apparatus |
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