JP3118341B2 - Electrophotographic toner and method for producing the same - Google Patents
Electrophotographic toner and method for producing the sameInfo
- Publication number
- JP3118341B2 JP3118341B2 JP05008979A JP897993A JP3118341B2 JP 3118341 B2 JP3118341 B2 JP 3118341B2 JP 05008979 A JP05008979 A JP 05008979A JP 897993 A JP897993 A JP 897993A JP 3118341 B2 JP3118341 B2 JP 3118341B2
- Authority
- JP
- Japan
- Prior art keywords
- toner
- molecular weight
- vinyl resin
- cooh
- average molecular
- 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
Landscapes
- Developing Agents For Electrophotography (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は電子写真、静電記録、静
電印刷などに於ける、静電荷像を現像するための電子写
真用トナーに関する。さらに詳しくは高速機に対応で
き、しかも定着オフセット性のバランスが良く且つ粉砕
性に優れた電子写真用トナーに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic toner for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, and the like. More specifically, the present invention relates to an electrophotographic toner that can be used in a high-speed machine, has a good balance of fixing offset property, and has excellent pulverizability.
【０００２】[0002]
【従来の技術】一般に、ＰＰＣ複写機やプリンターに於
ける電子写真用法は、光感光体上に静電気的潜像を形成
し、ついで該潜像をトナーを用いて現像し、紙等の被定
着シート上にトナー画像を転写した後、熱ロールで加熱
圧着する方法が行われている。この方法は、加熱加圧下
で定着を行うので迅速でしかも熱効率が極めて良好であ
り、従って定着効率が非常に良い。しかしながら、この
熱ロール方式に於いては熱効率が良い反面、熱ロール表
面とトナーが溶融状態で接触するため、トナーが熱ロー
ル表面に付着転移し、次の被着シートにこれが再転移し
て汚す（オフセット現象）という問題がある。2. Description of the Related Art In general, an electrophotographic method in a PPC copier or a printer is to form an electrostatic latent image on a photoreceptor, develop the latent image using toner, and fix the latent image on paper or the like. After a toner image is transferred onto a sheet, a method of heat-pressing with a hot roll is used. In this method, fixing is performed under heating and pressing, so that the method is quick and the heat efficiency is very good, and therefore, the fixing efficiency is very good. However, in this hot roll system, although the thermal efficiency is good, the toner is in contact with the surface of the hot roll in a molten state, so that the toner adheres and transfers to the hot roll surface, and re-transfers to the next adhered sheet and becomes dirty. (Offset phenomenon).
【０００３】一方、複写機は、高速化の方向を指向して
おり、必然的に定着ロールのスピードも速くなり、短時
間の加熱で定着出来るトナーが要求されている。また、
省エネ、或いは安全性の面からもなるだけ低い温度で定
着できるトナーが熱望されている。低い温度で定着させ
るためには、できるだけ低温で融け、かつ溶融時の流動
性が優れていることが必要である。このような低温で溶
融し、流動性の良いトナーをえる為には、用いる樹脂の
分子量を小さくすれば良いが、分子量の低下により樹脂
の凝集力が不足し、オフセット現象が発生しやすくな
り、好ましくない。この為通常、流動性はある程度犠牲
にするが、高分子量のものと混合使用して、高分子量の
ものが有する凝集力により性能を補っている。このよう
な例として、例えば、特公昭55- 6895号公報、特公昭63
-32180号公報、USP 4,921,771 等に係る技術が提案され
ている。しかし、高速化に対しては、いまだ充分ではな
く、機械の改良等で対応策を講じている場合が多々あ
る。即ち、熱ロールの表面に布や紙でシリコンオイルを
塗布してオフセットを防止する方法である。この場合、
機械の設備が複雑になるため、機械の補修、管理が複雑
になり、コストアップに繋がり、好ましくない。したが
って高速機用トナーで、且つシリコンオイル等のオイル
の使用を必要としない定着用トナー（オイルレス定着方
式）の開発が望まれている。On the other hand, the copier is oriented to increase the speed, the speed of the fixing roll is inevitably increased, and a toner that can be fixed by heating for a short time is required. Also,
There is a strong demand for a toner that can be fixed at a temperature as low as possible from the viewpoint of energy saving and safety. In order to fix at a low temperature, it is necessary to melt at as low a temperature as possible and to have excellent fluidity at the time of melting. In order to obtain a toner with good fluidity, which is melted at such a low temperature, the molecular weight of the resin used may be reduced, but the cohesion of the resin is insufficient due to the decrease in the molecular weight, and the offset phenomenon is likely to occur, Not preferred. For this reason, the fluidity is usually sacrificed to some extent, but the performance is supplemented by the cohesive force of the high molecular weight compound by mixing and using the high molecular weight compound. For example, Japanese Patent Publication No. 55-6895, Japanese Patent Publication No. 63
-32180, US Pat. No. 4,921,771 and the like have been proposed. However, speeding up is not yet sufficient, and there are many cases where countermeasures are taken by improving the machine. That is, a method of applying silicone oil to the surface of the heat roll with a cloth or paper to prevent offset. in this case,
Since the equipment of the machine is complicated, the repair and management of the machine are complicated, which leads to an increase in cost, which is not preferable. Therefore, development of a fixing toner (oil-less fixing method) which is a toner for a high-speed machine and does not require the use of oil such as silicone oil is desired.
【０００４】[0004]
【発明が解決しようとする課題】オイルレス定着方式用
トナーの開発に於けるオフセット防止方法としては架橋
ポリマーを用いたトナーも数多く提案されている。例え
ば特公昭60-36582号公報等には、乳化重合法で製造され
た架橋ポリマーを用いる方法が開示されている。この場
合、用いられる架橋ポリマーはゲル分を50〜99％含有し
ており、このゲル分は多くなると、耐オフセット性を改
良させるが粉砕性を悪化させる。また他方架橋ポリマー
分が少なくなると粉砕性はよくなるが耐オフセット性は
良くならず、耐オフセット性と粉砕性の両者を満足する
ことは極めて困難であった。また、この方法では架橋ポ
リマー製造時に分散剤や分散助剤を併用させる必要があ
る。これら分散剤は吸湿し易いため電気特性、特にチャ
ージ安定性に悪影響を及ぼす為、架橋ポリマー製造後、
できるだけこれらを取り除く必要性がある。しかし、こ
れらを洗浄して完全に取り除くには多大の労力が必要で
あり、また、排水量も多くなりその処理も大変である。
また、USP 4,966,829号公報には、ゲル成分が０．１〜
６０重量パーセント含み且つテトラヒドロフラン可溶分
に於いてメインピークの分子量が1,000〜25,000、且
つ、サブピーク又はショルダーの分子量が3,000〜150,0
00が少なくとも一つ有するビニル系重合体を含有するト
ナーが良い旨開示されている。しかし、これを製造する
方法はサスペンション法であり、この場合も乳化重合と
全く同じ問題があった。この為、本発明者等は定着性の
良いトナー用樹脂として、溶液重合法による樹脂(USP
4,963,456) を開発してきた。A number of toners using a crosslinked polymer have been proposed as an offset prevention method in the development of an oilless fixing type toner. For example, Japanese Patent Publication No. 60-36582 discloses a method using a crosslinked polymer produced by an emulsion polymerization method. In this case, the crosslinked polymer used contains 50 to 99% of a gel component, and when this gel component is increased, the offset resistance is improved but the pulverizability is deteriorated. On the other hand, when the crosslinked polymer content is reduced, the pulverizability is improved but the offset resistance is not improved, and it is extremely difficult to satisfy both the offset resistance and the pulverizability. In addition, in this method, it is necessary to use a dispersant and a dispersing aid together during the production of the crosslinked polymer. Since these dispersants easily absorb moisture, they adversely affect electrical properties, especially charge stability.
It is necessary to remove these as much as possible. However, a great deal of effort is required to completely remove these by washing, and the amount of wastewater is increased, and the treatment thereof is also difficult.
Also, USP 4,966,829 discloses that the gel component is 0.1 to
It contains 60% by weight and has a main peak molecular weight of 1,000-25,000 and a sub-peak or shoulder molecular weight of 3,000-150,0
No. 00 discloses that a toner containing a vinyl polymer having at least one is preferable. However, the method for producing the suspension is a suspension method, and in this case, there is exactly the same problem as in emulsion polymerization. For this reason, the present inventors have developed a resin (USP) prepared by a solution polymerization method as a toner resin having good fixability.
4,963,456).
【０００５】溶液重合法による樹脂は、重合終了後溶剤
を除去するが、この時、未反応の残存モノマーや開始剤
の分解物等低揮発成分は全て留去出来るので、非常に不
純物の少ない電気的には安定な均質な樹脂が得られ、ト
ナー用には最適のものが得られるものと考えられる。し
かしながら、溶液重合法による架橋ポリマーの製造は、
ワイゼンベルグ効果( 攪拌棒に樹脂が巻きつく）が発生
し製造出来なくなるという問題があった。したがって、
本発明者等は、さらにバルク等で出来るだけ高分子化す
る方法(USP 5,084,368) を開発した、しかし製造できる
高分子量のものには限界があり、オフセット性を完全に
克服するところまでは至っていなかった。また、特公昭
60ー38700には、グリシジル基含有単量体を３〜４０％有
する共重合体（Ａ）と架橋性化合物（Ｂ）とを加熱混合
して製造したトナーバインダーが良い旨開示されている
が、このトナーに於いてはエポキシ基が多量残っている
ため長期のテストで逆チヤージのトナーが発生し、耐久
性に問題を生じており、必ずしも満足するようなトナー
は開発されていなかった。[0005] The resin obtained by the solution polymerization method removes the solvent after completion of the polymerization. At this time, since all the low-volatile components such as unreacted residual monomers and decomposition products of the initiator can be distilled off, there is very little impurity in the resin. It is considered that a stable and homogeneous resin is obtained, and an optimum resin is obtained for toner. However, the production of crosslinked polymers by the solution polymerization method,
There was a problem that the Weissenberg effect (resin wrapped around the stirring rod) occurred and production became impossible. Therefore,
The present inventors have further developed a method of polymerizing as much as possible in bulk or the like (USP 5,084,368), but there is a limit to the high molecular weight that can be produced, and it has reached the point where the offset property is completely overcome. Did not. In addition,
60-38700 discloses that a toner binder produced by heating and mixing a copolymer (A) having 3 to 40% of a glycidyl group-containing monomer and a crosslinkable compound (B) is preferable. Since a large amount of epoxy groups remain in this toner, a reverse-charging toner is generated in a long-term test, causing a problem in durability, and a toner that is not always satisfactory has not been developed.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、これらの
要求を満足すべく鋭意検討した結果、溶液重合法にて製
造した特定の樹脂とグリシジル基を有する化合物を用い
て溶融混練させ、ＣＯＯＨ基とグリシジル基との反応を
充分に行わせ、特定の比率で架橋させることにより、高
速機に対応でき、且つ定着・オフセット性・ブロッキン
グ性のバランスが良い且つ粉砕性の良いトナーを得る技
術を開発したものである。Means for Solving the Problems The present inventors have conducted intensive studies to satisfy these requirements, and as a result, melt kneading using a specific resin produced by a solution polymerization method and a compound having a glycidyl group , Reaction between COOH group and glycidyl group
The technology has been developed to obtain a toner capable of coping with a high-speed machine, having a good balance of fixing / offset properties / blocking properties and having good pulverizability by sufficiently performing the crosslinking at a specific ratio.
【０００７】即ち、本発明は、少なくとも着色剤と結着
剤と荷電調整剤からなる電子写真用トナーにおいて、該
結着剤が数平均分子量（Ｍｎ）1,000 〜20,000、重量平
均分子量（Ｍｗ）50,000〜1,000,000 、酸価1.0 〜10で
あり、かつＴｇ点が４０〜７５℃であるＣＯＯＨ含有ビ
ニル樹脂（Ａ）と該ＣＯＯＨ含有ビニル樹脂（Ａ）中の
ＣＯＯＨ基１当量当りグリシジル基として0.05〜1.0 当
量を有するグリシジル化合物（Ｂ）より構成されている
ことを特徴とする電子写真用トナーである。さらには、
着色剤、荷電調整剤及び結着剤として数平均分子量1,00
0 〜20,000、重量平均分子量50,000〜1,000,000 、Ｍｗ
／Ｍｎが３．５以上で、酸価1.0〜10であり、かつＴｇ
点が４０〜７５℃であるＣＯＯＨ含有ビニル樹脂（Ａ）
と該ＣＯＯＨ含有ビニル樹脂（Ａ）中のＣＯＯＨ基１当
量当りグリシジル基として0.05〜1.0 当量を有するグリ
シジル化合物（Ｂ）を用いた組成物を溶融混練し、得ら
れた混練物を微粉砕することを特徴とする電子写真用ト
ナーの製造法でもある。That is, the present invention relates to an electrophotographic toner comprising at least a colorant, a binder and a charge controlling agent, wherein the binder has a number average molecular weight (Mn) of 1,000 to 20,000 and a weight average molecular weight (Mw) of 50,000. A COOH-containing vinyl resin (A) having an acid value of 1.0 to 10 and an acid value of 1.0 to 10 and a Tg point of 40 to 75 ° C., and 0.05 to 1.0 as a glycidyl group per equivalent of COOH group in the COOH-containing vinyl resin (A). An electrophotographic toner comprising an equivalent amount of a glycidyl compound (B). Furthermore,
Number average molecular weight 1,00 as colorant, charge control agent and binder
0 to 20,000, weight average molecular weight 50,000 to 1,000,000, Mw
/ Mn is 3.5 or more, acid value is 1.0 to 10 and Tg
COOH-containing vinyl resin having a point of 40 to 75 ° C (A)
And melt-kneading a composition using a glycidyl compound (B) having 0.05 to 1.0 equivalent as a glycidyl group per equivalent of COOH group in the COOH-containing vinyl resin (A), and finely pulverizing the obtained kneaded product. And a method for producing an electrophotographic toner.
【０００８】本発明に於いて結着剤に使用されるＣＯＯ
Ｈ含有ビニル樹脂（Ａ）の製造に用いられるＣＯＯＨ含
有ビニル単量体としては、アクリル酸、メタクリル酸、
無水マレイン酸、マレイン酸、フマール酸、ケイヒ酸、
フマール酸メチル、フマール酸エチル、フマール酸プロ
ピル、フマール酸ブチル、フマール酸オクチル、マレイ
ン酸メチル、マレイン酸エチル、マレイン酸プロピル、
マレイン酸ブチル、マレイン酸オクチル等の不飽和二塩
基酸のモノエステル類等から選ばれた少なくとも一種が
用いられる。[0008] COO used as a binder in the present invention
Examples of the COOH-containing vinyl monomer used for producing the H-containing vinyl resin (A) include acrylic acid, methacrylic acid,
Maleic anhydride, maleic acid, fumaric acid, cinnamic acid,
Methyl fumarate, ethyl fumarate, propyl fumarate, butyl fumarate, octyl fumarate, methyl maleate, ethyl maleate, propyl maleate,
At least one selected from monoesters of unsaturated dibasic acids such as butyl maleate and octyl maleate is used.
【０００９】また、ＣＯＯＨ含有ビニル単量体と共重合
しうるビニル単量体としてはスチレン、P-メチルスチレ
ン、αメチルスチレン、ビニルトルエン等のスチレン
類、アクリル酸メチル、アクリル酸エチル、アクリル酸
プロピル、アクリル酸ブチル、アクリル酸オクチル、ア
クリル酸シクロヘキシル、アクリル酸ステアリル、アク
リル酸ベンジル、アクリル酸フルフリル、アクリル酸ヒ
ドロキシエチル、アクリル酸ヒドロキシブチル、アクリ
ル酸ジメチルアミノメチル、アクリル酸ジメチルアミノ
エチル等のアクリル酸エステル類、メタアクリル酸メチ
ル、メタアクリル酸エチル、メタアクリル酸プロピル、
メタアクリル酸ブチル、メタアクリル酸オクチル、メタ
アクリル酸シクロヘキシル、メタアクリル酸ステアリ
ル、メタアクリル酸ベンジル、メタアクリル酸フルフリ
ル、メタアクリル酸ヒドロキシエチル、メタアクリル酸
ヒドロキシブチル、メタアクリル酸ジメチルアミノメチ
ル、メタアクリル酸ジメチルアミノエチル等のメタアク
リル酸エステル類、フマール酸ジメチル、フマール酸ジ
ブチル、フマール酸ジオクチル、マレイン酸ジメチル、
マレイン酸ジブチル、マレイン酸ジオクチル等の不飽和
二塩基酸のジエステル類、アクリロニトリル、メタアク
リロニトリル、アクリル酸、メタアクリル酸、ケイヒ酸
等の不飽和カルボン酸類、アクリルアミド、メタアクリ
ルアミド、、Ｎ置換アクリルアミド、Ｎ置換メタアクリ
ルアミド、アクリルアミドプロパンスルフォン酸等があ
り、これらの単量体の少なくとも１種が用いられる。
これらの中で特に好ましいビニル単量体はスチレン類、
アクリル酸エステル類、メタアクリル酸エステル類、フ
マール酸ジアルキルエステル類、アクリロニトリル、ア
クリルアミド、メタクリルアミド等である。Further, vinyl monomers copolymerizable with the COOH-containing vinyl monomer include styrenes such as styrene, P-methylstyrene, α-methylstyrene, vinyltoluene, methyl acrylate, ethyl acrylate, and acrylic acid. Acrylics such as propyl, butyl acrylate, octyl acrylate, cyclohexyl acrylate, stearyl acrylate, benzyl acrylate, furfuryl acrylate, hydroxyethyl acrylate, hydroxybutyl acrylate, dimethylaminomethyl acrylate, and dimethylaminoethyl acrylate Acid esters, methyl methacrylate, ethyl methacrylate, propyl methacrylate,
Butyl methacrylate, octyl methacrylate, cyclohexyl methacrylate, stearyl methacrylate, benzyl methacrylate, furfuryl methacrylate, hydroxyethyl methacrylate, hydroxybutyl methacrylate, dimethylaminomethyl methacrylate, methacrylate Methacrylates such as dimethylaminoethyl acrylate, dimethyl fumarate, dibutyl fumarate, dioctyl fumarate, dimethyl maleate,
Diesters of unsaturated dibasic acids such as dibutyl maleate and dioctyl maleate; unsaturated carboxylic acids such as acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, cinnamic acid, acrylamide, methacrylamide, N-substituted acrylamide, N There are substituted methacrylamide, acrylamidopropanesulfonic acid and the like, and at least one of these monomers is used.
Particularly preferred vinyl monomers among these are styrenes,
Acrylic esters, methacrylic esters, dialkyl fumaric esters, acrylonitrile, acrylamide, methacrylamide and the like.
【００１０】ＣＯＯＨ含有ビニル樹脂（Ａ）は、数平均
分子量1,000 〜20,000、重量平均分子量（Ｍｗ）50,000
〜1,000,000 、Ｍｗ／Ｍｎが３．５以上である分子量分
布の広い樹脂で、かつＴｇ点が４０〜７５℃である樹脂
が好ましい。数平均分子量が1,000 以下では、Ｔｇ点が
４０℃以下になりブロッキングを起こし好ましくなく、
数平均分子量が20,000以上では、流動性が悪くなり定着
性が悪化する。また、重量平均分子量が50,000以下では
オフセットを良くするためには多量の架橋を必要とし、
架橋を増加すると全体の分子量があがってしまい定着性
が悪化する。1,000,000 以上でも逆に少量の架橋でゲル
化を起こし定着性が悪化する。特に、Ｍｗ／Ｍｎが３．
５以下の場合は定着ーオフセットのバランスがとり難
く、オフセットを良くすると、どうしても定着性が悪く
なる。また、Ｔｇ点が７５℃以上になると軟化点が上昇
し、定着性が悪化して本目的のトナーが得られない。ま
たＣＯＯＨ含有ビニル樹脂（Ａ）中のＣＯＯＨ含有量
は、酸価として1.0 〜10 KOHmg/gが好ましい。1.0 以下
では本発明の効果が発現出来ず、逆に10 KOHmg/g以上で
は、少量の架橋でゲル化を起こし且つ樹脂中で分離析出
するので増粘せずオフセット性が良くならない。The COOH-containing vinyl resin (A) has a number average molecular weight of 1,000 to 20,000 and a weight average molecular weight (Mw) of 50,000.
A resin having a wide molecular weight distribution of あ る 1,000,000 and Mw / Mn of 3.5 or more, and a resin having a Tg point of 40 to 75 ° C. is preferable. When the number average molecular weight is 1,000 or less, the Tg point becomes 40 ° C or less, causing blocking, which is not preferable.
If the number average molecular weight is 20,000 or more, the fluidity becomes poor and the fixability becomes poor. Also, if the weight average molecular weight is 50,000 or less, a large amount of crosslinking is required to improve the offset,
When the crosslinking is increased, the overall molecular weight increases, and the fixability deteriorates. Conversely, even if the amount is 1,000,000 or more, a small amount of crosslinking causes gelation, and the fixability deteriorates. In particular, Mw / Mn is 3.
In the case of 5 or less, it is difficult to balance the fixing and the offset, and if the offset is improved, the fixing property is inevitably deteriorated. On the other hand, if the Tg point is 75 ° C. or higher, the softening point increases, and the fixability deteriorates, so that the intended toner cannot be obtained. The COOH content in the COOH-containing vinyl resin (A) is preferably from 1.0 to 10 KOH mg / g as an acid value. If it is less than 1.0, the effect of the present invention cannot be exhibited. Conversely, if it is more than 10 KOHmg / g, a small amount of crosslinking causes gelation and separates and precipitates in the resin, so that the viscosity does not increase and the offset property is not improved.
【００１１】本発明に於けるグリシジル化合物（Ｂ）と
しては、重量平均分子量が3,000 〜10,000で且つエポキ
シ価が0.01〜0.3Eq/100gであるグリシジルエステル含有
ビニル樹脂が好ましい。グリシジルエステル含有ビニル
樹脂は、グリシジル基を含有するビニル単量体、例えば
アクリル酸グリシジル、アクリル酸βメチルグリシジ
ル、メタアクリル酸グリシジル、メタアクリル酸βメチ
ルグリシジル等のビニル単量体の少なくとも一種と他の
ビニル単量体との共重合して得られた樹脂である。重量
平均分子量が3,000 以下では、架橋しても殆ど増粘せ
ず、耐オフセット性を改良する事はできない。逆に10,0
00以上でも、架橋途中で架橋体の相溶性が悪化し樹脂中
にその架橋体が分離析出するので増粘せずオフセット性
が良くならない。また、エポキシ価は0.01〜0.3Eq/100g
の範囲のものが好ましい。0.01Eq/100g 以下にあっては
増粘が殆ど起こらずオフセット性の改良は出来ない。0.
3 Eq/100g 以上では、架橋体の相溶性が悪化し樹脂中に
その架橋体が分離析出するのでゲルは生成するが増粘せ
ずオフセット性も良くならない。As the glycidyl compound (B) in the present invention, a glycidyl ester-containing vinyl resin having a weight average molecular weight of 3,000 to 10,000 and an epoxy value of 0.01 to 0.3 Eq / 100 g is preferable. The glycidyl ester-containing vinyl resin is a vinyl monomer containing a glycidyl group, such as at least one vinyl monomer such as glycidyl acrylate, β-methyl glycidyl acrylate, glycidyl methacrylate, and β-methyl glycidyl methacrylate. Is a resin obtained by copolymerization with a vinyl monomer. If the weight average molecular weight is 3,000 or less, the viscosity hardly increases even when crosslinked, and the offset resistance cannot be improved. Conversely 10,0
Even with a value of 00 or more, the compatibility of the crosslinked body deteriorates during the crosslinking, and the crosslinked body separates and precipitates in the resin, so that the viscosity does not increase and the offset property is not improved. In addition, the epoxy value is 0.01~ 0.3 Eq / 100g
Are preferred. If it is less than 0.01Eq / 100g, thickening hardly occurs and the offset property cannot be improved. 0.
Above 3 Eq / 100 g, the compatibility of the crosslinked product deteriorates and the crosslinked product separates and precipitates in the resin, so that a gel is formed but the viscosity does not increase and the offset property does not improve.
【００１２】またＣＯＯＨ含有ビニル樹脂（Ａ）の製造
方法としては、溶液重合が好ましく、さらに上述の様な
分子量分布の広い樹脂を造るには低分子量のものと高分
子量のものの混合が好ましく、下記に一例を説明する。
即ち、ベンゼン、トルエン、エチルベンゼン、キシレ
ン、キュメン等の芳香族炭化水素、ソルベッソ#100,#15
0(エッソ化学製商品名) 等の中から一つ以上の溶剤とビ
ニル単量体と重合開始剤とを均一に溶解混合せしめた溶
液を、予め溶剤で満液に仕込んだ耐圧容器に、温度と内
圧を一定に保ちつつ連続的に供給して重合を行う。定常
状態になった時よりタンクに貯液し、低分子量重合液を
得る。別に、バルク溶液重合で高分子量重合液を得て、
低分子量のものと高分子量のものとを充分に混合溶解
後、連続的に約0 〜200 mmHgの真空系にフラッシュして
溶剤等を留去してビニル樹脂と溶剤とを分離して、固形
のＣＯＯＨ含有ビニル樹脂（Ａ）を得る。As a method for producing the COOH-containing vinyl resin (A), solution polymerization is preferable, and in order to produce a resin having a wide molecular weight distribution as described above, mixing of a low molecular weight resin and a high molecular weight resin is preferable. An example will be described below.
That is, aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene and cumene, Solvesso # 100, # 15
0 (trade name, manufactured by Esso Chemical Co., Ltd.), etc., into a pressure vessel, which is prepared by uniformly dissolving and mixing at least one solvent, a vinyl monomer, and a polymerization initiator with a solvent in advance. The polymerization is carried out by continuously supplying the pressure while keeping the internal pressure constant. The liquid is stored in a tank from a time when the steady state is reached, and a low molecular weight polymerization liquid is obtained. Separately, a high molecular weight polymerization solution is obtained by bulk solution polymerization,
After sufficiently mixing and dissolving the low-molecular-weight and high-molecular-weight ones, it is continuously flashed to a vacuum system of about 0 to 200 mmHg to distill off the solvent and the like, and the vinyl resin and the solvent are separated. To obtain a COOH-containing vinyl resin (A).
【００１３】本発明の特徴とする結着剤、ＣＯＯＨ含有
ビニル樹脂（Ａ）及びグリシジル化合物（Ｂ）を用いる
態様については次に示す種々の方法をとりうる。 (1) ＣＯＯＨ含有ビニル樹脂（Ａ）にグリシジル化合物
（Ｂ）をヘンシェルミキサーで混合後、２軸混練機等を
用いて160 〜220 ℃の温度で溶融混練させ、ＣＯＯＨ基
とグリシジル基との反応を充分に行わせた後に、着色剤
や荷電調整剤等のトナーに必要な充填剤を添加してトナ
ーにする方法。The following various methods can be employed for the embodiment using the binder, the COOH-containing vinyl resin (A) and the glycidyl compound (B), which are characteristic of the present invention. (1) The glycidyl compound (B) is mixed with the COOH-containing vinyl resin (A) using a Henschel mixer, and then melt-kneaded at a temperature of 160 to 220 ° C. using a twin-screw kneader or the like, thereby reacting the COOH group with the glycidyl group. And then adding a necessary filler to the toner, such as a colorant and a charge adjusting agent, to obtain a toner.
【００１４】(2) ＣＯＯＨ含有ビニル樹脂（Ａ）とグリ
シジル化合物（Ｂ）を未反応状態のまま、着色剤や荷電
調整剤等のトナーに必要な充填剤と一緒に充分混合後、
２軸混練機等を用いて160 〜220 ℃の温度で溶融混練さ
せるトナー化工程時に反応させる方法。(2) After the COOH-containing vinyl resin (A) and the glycidyl compound (B) are mixed in an unreacted state together with a filler such as a colorant and a charge controlling agent, which is necessary for the toner,
A method of reacting at the time of a toner forming step of melting and kneading at a temperature of 160 to 220 ° C. using a biaxial kneader or the like.
【００１５】(3) ＣＯＯＨ含有ビニル樹脂（Ａ）とグリ
シジル化合物（Ｂ）を未反応状態のまま、着色剤や荷電
調整剤等のトナーに必要な充填剤と一緒に充分混合後、
２軸混練機等を用いて110 〜140 ℃の温度で溶融混練さ
せ、この溶融混練時には殆ど反応させず、複写機の定着
時に熱ロールの温度を160 〜220 ℃にして反応させる方
法等があり、いずれの方法で行っても良いが、トナー化
工程時に於ける溶融混練時に同時に行うのが最も効率的
である。(3) After the COOH-containing vinyl resin (A) and the glycidyl compound (B) are mixed in an unreacted state together with a filler such as a colorant and a charge controlling agent, which is necessary for the toner,
There is a method in which the mixture is melt-kneaded at a temperature of 110 to 140 ° C. using a twin-screw kneader or the like, the reaction hardly occurs during the melt kneading, and the reaction is performed by setting the temperature of the hot roll to 160 to 220 ° C. when fixing the copying machine. Any of these methods may be used, but it is most efficient to perform the method simultaneously with the melt-kneading in the toner-forming step.
【００１６】本発明に於いて、使用される着色剤として
は、一般に用いられている周知の染顔料が使用出来る。
例えば、カーボンブラック、アセチレンブラック、ラン
プブラック、マグネタイト等の黒色顔料、黄鉛、黄色酸
化鉄、ハイザイエローＧ、キノリンイエローレーキ、パ
ーマネントイエローＮＣＧ、モリブデンオレンジ、バル
カンオレンジ、インダンスレン、ブリリアントオレンジ
ＧＫ、ベンガラ、ブリリアントカーミン６Ｂ、ブリザリ
ンレーキ、メチルバイオレットレーキ、ファストバイオ
レットＢ、コバルトブルー、アルカリブルーレーキ、フ
タロシアニンブルー、ファストスカイブルーネピグメン
トグリーンＢ、マラカイトグリーンレーキ、酸化チタ
ン、亜鉛華、マグネタイトやソフトフェライト等の磁性
粉等が挙げられる。使用量は通常用いられる0.1 〜20重
量部である。In the present invention, well-known dyes and pigments that are generally used can be used as the coloring agent.
For example, carbon black, acetylene black, lamp black, black pigments such as magnetite, graphite, yellow iron oxide, Heiza Yellow G, quinoline yellow lake, permanent yellow NCG, molybdenum orange, Vulcan orange, indanthrene, brilliant orange GK, Bengala, Brilliant Carmine 6B, Brizarin Lake, Methyl Violet Lake, Fast Violet B, Cobalt Blue, Alkaline Blue Lake, Phthalocyanine Blue, Fast Sky Blue Nepigment Green B, Malachite Green Lake, Titanium Oxide, Zinc White, Magnetite and Soft Ferrite And the like. The amount used is usually 0.1 to 20 parts by weight.
【００１７】本発明に於いて、本発明の目的を阻害しな
い範囲に於いて、他の樹脂、例えばポリエステル樹脂・
ポリアミド樹脂・塩ビ樹脂・ポリビニールブチラール樹
脂・スチレンーブタジエン樹脂・クマロンーインデン樹
脂・メラミン樹脂・ポリオレフィン樹脂等を一部混合使
用出来る。また、ニグロシン、４級アンモニュウム塩や
含金属アゾ染料を初めとする公知の荷電調整剤を適宜選
択して使用出来、使用量は通常用いられる０．１〜１０
重量部である。本発明に於いて、トナーを作る方法とし
ては、従来公知のいかなる方法も採用出来る。例えば、
樹脂・着色剤・荷電調整剤・ワックス等を予めプレミッ
クスし、ついで２軸混練機で加熱溶融混練後冷却粉砕し
分級して約10ミクロンの微粒子にする。本発明における
数平均分子量や重量平均分子量はＧＰＣ法により求めた
もので、単分散標準ポリスチレンで検量線を作成した換
算分子量である。測定条件は下記の通り。 ＧＰＣ装置； JASCO TWINCLE HPLC DETECTOR ； SHODEX RI SE-31 COLUMN ； SHODEX GPCA-80M*2+KF-802 溶 媒 ； TETRAHYDROFURAN 流 速 ； 1.2ml ／min.In the present invention, other resins such as polyester resin,
Polyamide resin, PVC resin, polyvinyl butyral resin, styrene butadiene resin, coumarone-indene resin, melamine resin, polyolefin resin, etc. can be partially used. Also, known charge regulators such as nigrosine, quaternary ammonium salts and metal-containing azo dyes can be appropriately selected and used, and the amount used is usually 0.1 to 10
Parts by weight. In the present invention, as a method for producing a toner, any conventionally known method can be adopted. For example,
A resin, a coloring agent, a charge adjusting agent, a wax, etc. are premixed in advance, then heated and melted and kneaded by a twin-screw kneader, then cooled and pulverized to classify into fine particles of about 10 microns. In the present invention, the number average molecular weight and the weight average molecular weight are determined by GPC method, and are converted molecular weights obtained by preparing a calibration curve with monodisperse standard polystyrene. The measurement conditions are as follows. GPC system; JASCO TWINCLE HPLC DETECTOR; SHODEX RI SE-31 COLUMN; SHODEX GPCA-80M * 2 + KF-802 solvent; TETRAHYDROFURAN flow rate: 1.2 ml / min.
【００１８】[0018]
製造例１ スチレン69.3部、メタアクリル酸0.7 部とキシレン溶媒
30部からなる溶液にスチレン100 部当たり0.5 部のジ-t
- ブチルパーオキサイドを均一に溶解したものを、内温
200 ℃内圧 6kg/cm2に保持した５ｌの反応器に750cc/hr
で連続的に供給して重合し低分子量重合液を得た。別
に、ビニル単量体として、スチレン66部、メタアクリル
酸n-ブチル33部、メタアクリル酸 1部を窒素置換したフ
ラスコに仕込み、内温120 ℃に昇温後、同温度に保ち、
バルク重合を10時間おこなった。この時の重合率は51%
であった。ついで、キシレン50部を加え、予め混合溶解
しておいたジブチルパーオキサイドの0.1 部キシレン50
部を130 ℃に保ちながら8 時間かけて連続添加し、更に
2 時間残モノマー重合して、重合を完結し、高分子量重
合液を得た。ついで、上記低分子量重合液100 部と高分
子量重合液140 部とを混合したのち、これを160 ℃10mm
Hgのベッセル中にフラッシュして溶剤等を留去した。得
られたビニル樹脂の数平均分子量は3800であり、重量平
均分子量は210,000 であり、Tgは63℃であった、酸価は
6.2 であった。Production Example 1 69.3 parts of styrene, 0.7 parts of methacrylic acid and xylene solvent
0.5 part di-t per 100 parts styrene in a 30 part solution
-Dissolve butyl peroxide uniformly in
750 cc / hr in a 5 l reactor maintained at 200 ° C and an internal pressure of 6 kg / cm 2
To continuously polymerize to obtain a low molecular weight polymerization solution. Separately, as a vinyl monomer, 66 parts of styrene, 33 parts of n-butyl methacrylate, and 1 part of methacrylic acid were charged into a flask purged with nitrogen, heated to an internal temperature of 120 ° C, and maintained at the same temperature.
Bulk polymerization was performed for 10 hours. The polymerization rate at this time is 51%
Met. Then, 50 parts of xylene was added and 0.1 part of xylene 50 of dibutyl peroxide mixed and dissolved in advance was added.
Over 8 hours while maintaining the temperature at 130 ° C.
The remaining monomer was polymerized for 2 hours to complete the polymerization to obtain a high molecular weight polymerization solution. Then, after mixing 100 parts of the low molecular weight polymerization solution and 140 parts of the high molecular weight polymerization solution, the mixture was heated at 160 ° C. for 10 mm.
The mixture was flushed into an Hg vessel to distill off the solvent and the like. The number average molecular weight of the obtained vinyl resin was 3800, the weight average molecular weight was 210,000, the Tg was 63 ° C., and the acid value was
6.2.
【００１９】製造例２，３ 製造例１に於いて低分子量重合液を製造する際に重合温
度200 ℃を180 ℃および220 ℃とした以外は全く製造例
１と同様にしてビニル樹脂を得た。重合温度が180 ℃の
ものを製造例２、重合温度が220 ℃のものを製造例３と
し、得られた物性値を表−１に示した。Production Examples 2 and 3 A vinyl resin was obtained in exactly the same manner as in Production Example 1 except that the polymerization temperature was changed from 200 ° C. to 180 ° C. and 220 ° C. when producing a low molecular weight polymerization solution. . The polymer having a polymerization temperature of 180 ° C. was referred to as Production Example 2, and the polymer having a polymerization temperature of 220 ° C. was referred to as Production Example 3, and the obtained physical properties are shown in Table 1.
【００２０】製造例４ 製造例１に於いて低分子量重合液を製造する際に重合温
度200 ℃を160 ℃とした以外は全く製造例１と同様にし
てビニル樹脂を得た。得られたものの物性値を表−１に
示した。Production Example 4 A vinyl resin was obtained in exactly the same manner as in Production Example 1 except that the polymerization temperature was changed from 200 ° C. to 160 ° C. when producing a low molecular weight polymerization solution. Table 1 shows the physical property values of the obtained product.
【００２１】製造例５，６, 12 製造例１に於いて低分子量重合液と高分子量重合液との
比率100/140 を100/70と100/14と100/420 とした以外は
製造例１と全く同様にしてビニル樹脂を得た。比率100/
70のものを製造例５、比率100/14のものを製造例６、比
率100/420 のものを製造例12とし、各物性値を表−１に
示した。Production Examples 5, 6, and 12 Production Example 1 was the same as Production Example 1 except that the ratio of the low-molecular-weight polymerization solution to the high-molecular-weight polymerization solution was 100/140, 100/70, 100/14, and 100/420. A vinyl resin was obtained in exactly the same manner as described above. Ratio 100 /
The physical properties were shown in Table 1 with 70 being Production Example 5, 100/14 in Production Example 6, and 100/420 in Production Example 12.
【００２２】製造例７ 製造例１に於いて低分子量重合液を製造する際にビニル
単量体としてスチレン69.3部、メタアクリル酸0.7 部を
スチレン65.1部、アクリル酸n-ブチル4.2 部、メタアク
リル酸0.7 部とした以外は全く製造例１と同様にしてビ
ニル樹脂を得た。得られたものの物性値を表−１に示し
た。Production Example 7 In the production of the low-molecular-weight polymerization solution in Production Example 1, 69.3 parts of styrene, 0.7 parts of methacrylic acid were used in 65.1 parts of styrene, 4.2 parts of n-butyl acrylate and 4.2 parts of methacrylic acid were used as vinyl monomers. A vinyl resin was obtained in exactly the same manner as in Production Example 1 except that the acid content was changed to 0.7 part. Table 1 shows the physical property values of the obtained product.
【００２３】製造例８ 製造例１に於いて高分子量重合液を製造する際にビニル
単量体としてスチレン66部、メタアクリル酸n-ブチル33
部、メタアクリル酸1 部をスチレン79部、フマール酸オ
クチル20部、メタアクリル酸1 部とした以外は全く製造
例１と同様にしてビニル樹脂を得た。得られたものの物
性値を表−１に示した。Production Example 8 When producing a high molecular weight polymerization solution in Production Example 1, 66 parts of styrene and n-butyl methacrylate 33 were used as vinyl monomers.
A vinyl resin was obtained in exactly the same manner as in Production Example 1 except that 79 parts of styrene, 79 parts of octyl fumarate and 1 part of methacrylic acid were used. Table 1 shows the physical property values of the obtained product.
【００２４】製造例９ 製造例１に於いて高分子量重合液を製造する際にビニル
単量体としてスチレン66部、メタアクリル酸n-ブチル33
部、メタアクリル酸1 部をスチレン69部、メタアクリル
酸n-ブチル30部、マレイン酸モノブチル1 部とした以外
は全く製造例１と同様にしてビニル樹脂を得た。得られ
たものの物性値を表−１に示した。Production Example 9 When producing a high molecular weight polymerization solution in Production Example 1, 66 parts of styrene and n-butyl methacrylate 33 were used as vinyl monomers.
A vinyl resin was obtained in exactly the same manner as in Production Example 1, except that 69 parts of styrene, 1 part of methacrylic acid was changed to 69 parts of styrene, 30 parts of n-butyl methacrylate, and 1 part of monobutyl maleate were used. Table 1 shows the physical property values of the obtained product.
【００２５】製造例10 製造例１に於いて低分子量重合液を製造する際にビニル
単量体としてスチレン69.3部、メタアクリル酸0.7 部を
スチレン60.9部、アクリル酸n-ブチル6.3 部、メタアク
リル酸2.8 部とした以外は全く製造例１と同様にしてビ
ニル樹脂を得た。得られたものの物性値を表−１に示し
た。Production Example 10 When producing a low molecular weight polymerization solution in Production Example 1, 69.3 parts of styrene as a vinyl monomer, 60.9 parts of styrene, 60.9 parts of methacrylic acid, 6.3 parts of n-butyl acrylate, methacrylic acid A vinyl resin was obtained in the same manner as in Production Example 1 except that 2.8 parts of the acid was used. Table 1 shows the physical property values of the obtained product.
【００２６】製造例11 製造例１に於いて重合液を製造する際にメタアクリル酸
をスチレンに置き換えた以外は全く製造例１と同様にし
てビニル樹脂を得た。得られたものの物性値を表−１に
示した。Production Example 11 A vinyl resin was obtained in the same manner as in Production Example 1 except that methacrylic acid was replaced with styrene when producing the polymerization solution. Table 1 shows the physical property values of the obtained product.
【００２７】実施例１ 製造例１で得られたビニル樹脂86部、PD6300（グリシジ
ル基を含有したスチレンーアクリル系樹脂で、エポキシ
価0.19eq/100g,重量平均分子量＝8,000,Tg＝52℃, 三井
東圧化学製) 2.5 部をヘンシェルミキサーにて混合後、
２軸混練機(PCM-30 型、池貝鉄工製) にて200 ℃で混練
反応させた。冷却・粉砕後、カーボンブラックＭＡ100
(三菱化成製）8 部、ポリプロピレンワックス( ビスコ
ール550P)5 部、荷電調整剤としてアイゼンスピロンブ
ラックTRH 1 部添加し、再度ヘンシェルミキサーにて混
合後、２軸混練機(PCM-30 型、池貝鉄工製) にて150 ℃
で混練させた。ついで冷却・粉砕・分級して約10ミクロ
ンのトナーを得た。このトナー3 部とキャリヤ97部とを
混合して現像剤とし、市販の高速複写機を改造して、画
像を書かせて評価し結果を表−１に示す。Example 1 86 parts of the vinyl resin obtained in Production Example 1, PD6300 (a styrene-acrylic resin containing a glycidyl group, epoxy value 0.19 eq / 100 g, weight average molecular weight = 8,000, Tg = 52 ° C., After mixing 2.5 parts with a Henschel mixer,
The kneading reaction was carried out at 200 ° C. using a twin-screw kneader (PCM-30, manufactured by Ikegai Iron Works). After cooling and grinding, carbon black MA100
(Mitsubishi Chemical) 8 parts, polypropylene wax (Viscol 550P) 5 parts, Aizen Spiron Black TRH 1 part as a charge control agent was added and mixed again with a Henschel mixer, and then a twin-screw kneader (PCM-30, Ikegai) 150 ° C)
And kneaded. Then, it was cooled, pulverized and classified to obtain a toner of about 10 microns. A mixture of 3 parts of the toner and 97 parts of the carrier was used as a developer. A commercially available high-speed copying machine was modified, an image was written and evaluated. The results are shown in Table 1.
【００２８】実施例２ 製造例１で得られたビニル樹脂を製造例２で得られたビ
ニル樹脂に替えた他は実施例１と全く同様にしてトナー
を得、実施例１と全く同様にして画像評価し結果を表−
１に示す。Example 2 A toner was obtained in exactly the same manner as in Example 1, except that the vinyl resin obtained in Production Example 1 was replaced with the vinyl resin obtained in Production Example 2. Image evaluation and table
It is shown in FIG.
【００２９】実施例３ 製造例１で得られたビニル樹脂を製造例３で得られたビ
ニル樹脂に替えた他は実施例１と全く同様にしてトナー
を得、実施例１と全く同様にして画像評価し結果を表−
１に示す。Example 3 A toner was obtained in exactly the same manner as in Example 1, except that the vinyl resin obtained in Production Example 1 was replaced with the vinyl resin obtained in Production Example 3. Image evaluation and table
It is shown in FIG.
【００３０】実施例４ 製造例１で得られたビニル樹脂を製造例５で得られたビ
ニル樹脂に替えた他は実施例１と全く同様にしてトナー
を得、実施例１と全く同様にして画像評価し結果を表−
１に示す。Example 4 A toner was obtained in exactly the same manner as in Example 1 except that the vinyl resin obtained in Production Example 1 was replaced with the vinyl resin obtained in Production Example 5. Image evaluation and table
It is shown in FIG.
【００３１】実施例５ 実施例１に於いて、PD6300 2.5部を1.25部にした以外は
実施例１と全く同様にしてトナーを得、実施例１と全く
同様にして画像評価し結果を表−１に示す。Example 5 A toner was obtained in the same manner as in Example 1 except that 2.5 parts of PD6300 was changed to 1.25 parts, and an image was evaluated in the same manner as in Example 1. It is shown in FIG.
【００３２】実施例６ 実施例１に於いて、PD6300をPD6100（グリシジル基を含
有したスチレンーアクリル系樹脂で、エポキシ価0.10eq
/100g,重量平均分子量＝8,000,Tg＝56℃, 三井東圧化学
製) にした以外は実施例１と全く同様にしてトナーを
得、実施例１と全く同様にして画像評価し結果を表−１
に示す。Example 6 In Example 1, PD6300 was replaced with PD6100 (a styrene-acrylic resin containing a glycidyl group and an epoxy value of 0.10 eq).
/ 100 g, weight average molecular weight = 8,000, Tg = 56 ° C, manufactured by Mitsui Toatsu Chemicals, Inc.), and a toner was obtained in the same manner as in Example 1. -1
Shown in
【００３３】実施例７ 製造例１で得られたビニル樹脂を製造例７で得られたビ
ニル樹脂に替えた他は実施例１と全く同様にしてトナー
を得、実施例１と全く同様にして画像評価し結果を表−
１に示す。Example 7 A toner was obtained in exactly the same manner as in Example 1 except that the vinyl resin obtained in Production Example 1 was replaced with the vinyl resin obtained in Production Example 7. Image evaluation and table
It is shown in FIG.
【００３４】実施例８ 製造例１で得られたビニル樹脂を製造例８で得られたビ
ニル樹脂に替えた他は実施例１と全く同様にしてトナー
を得、実施例１と全く同様にして画像評価し結果を表−
１に示す。Example 8 A toner was obtained in exactly the same manner as in Example 1 except that the vinyl resin obtained in Production Example 1 was replaced with the vinyl resin obtained in Production Example 8. Image evaluation and table
It is shown in FIG.
【００３５】実施例９ 製造例１で得られたビニル樹脂を製造例９で得られたビ
ニル樹脂に替えた他は実施例１と全く同様にしてトナー
を得、実施例１と全く同様にして画像評価し結果を表−
１に示す。Example 9 A toner was obtained in exactly the same manner as in Example 1, except that the vinyl resin obtained in Production Example 1 was replaced with the vinyl resin obtained in Production Example 9. Image evaluation and table
It is shown in FIG.
【００３６】実施例10，11 製造例１で得られたビニル樹脂86部、PD6300（三井東圧
化学製) 2.5 部、カーボンブラックＭＡ100(三菱化成
製）8 部、ポリプロピレンワックス( ビスコール550P)
5 部、荷電調整剤としてアイゼンスピロンブラックTRH
1 部添加し、ヘンシェルミキサーにて混合後、２軸混練
機(PCM-30 型、池貝鉄工製) にて130 ℃及び170 ℃で混
練させた。他は実施例１と全く同様にしてトナーを得、
実施例１と全く同様にして画像評価し結果を表−１に示
す。Examples 10 and 11 86 parts of the vinyl resin obtained in Production Example 1, 2.5 parts of PD6300 (manufactured by Mitsui Toatsu Chemicals), 8 parts of carbon black MA100 (manufactured by Mitsubishi Kasei), polypropylene wax (Viscol 550P)
5 parts, Aizenspiron Black TRH as charge control agent
One part was added, mixed with a Henschel mixer, and kneaded at 130 ° C and 170 ° C with a twin-screw kneader (PCM-30, manufactured by Ikegai Iron Works). Others were the same as in Example 1 to obtain a toner.
The image was evaluated exactly in the same manner as in Example 1, and the results are shown in Table 1.
【００３７】実施例12 製造例１で得られたビニル樹脂86部、PD6300 2.5部、カ
ーボンブラックＭＡ100(三菱化成製）8 部、ポリプロピ
レンワックス( ビスコール550P) 5 部、荷電調整剤とし
てセチルトリメチルアンモニウムブロマイド２部をヘン
シェルミキサーにて混合後、２軸混練機(PCM-30 型、池
貝鉄工製) にて150 ℃で混練させた。ついで冷却・粉砕
・分級して約10ミクロンのトナーを得た。このトナー３
部とキャリャ97部とを混合して現像剤とし、＋チャージ
トナーを用いる市販の高速複写機を改良して、画像を書
かせて実施例１と同様にして評価し結果を表ー１に示
す。Example 12 86 parts of the vinyl resin obtained in Production Example 1, 2.5 parts of PD6300, 8 parts of carbon black MA100 (manufactured by Mitsubishi Kasei), 5 parts of polypropylene wax (Biscol 550P), and cetyltrimethylammonium bromide as a charge control agent The two parts were mixed with a Henschel mixer and then kneaded at 150 ° C. with a twin-screw kneader (PCM-30, manufactured by Ikegai Iron Works). Then, it was cooled, pulverized and classified to obtain a toner of about 10 microns. This toner 3
And 97 parts of Carrier were used as a developer, and a commercial high-speed copying machine using + charged toner was improved. An image was written and evaluated in the same manner as in Example 1. The results are shown in Table 1. .
【００３８】[0038]
【表１】 [Table 1]
【００３９】比較例１ 製造例１で得られたビニル樹脂を用い、グリシジル化合
物を用いない他は実施例１と全く同様にしてトナーを
得、実施例１と全く同様にして画像評価し結果を表−２
に示す。Comparative Example 1 A toner was obtained in exactly the same manner as in Example 1 except that the glycidyl compound was not used, except that the vinyl resin obtained in Production Example 1 was not used. Table-2
Shown in
【００４０】比較例２ 製造例１で得られたビニル樹脂を製造例４で得られたビ
ニル樹脂に替えた他は実施例１と全く同様にしてトナー
を得、実施例１と全く同様にして画像評価し結果を表−
２に示す。Comparative Example 2 A toner was obtained in exactly the same manner as in Example 1, except that the vinyl resin obtained in Production Example 1 was replaced with the vinyl resin obtained in Production Example 4. Image evaluation and table
It is shown in FIG.
【００４１】比較例３ 製造例１で得られたビニル樹脂を製造例６で得られたビ
ニル樹脂に替えた他は実施例１と全く同様にしてトナー
を得、実施例１と全く同様にして画像評価し結果を表−
２に示す。Comparative Example 3 A toner was obtained in exactly the same manner as in Example 1, except that the vinyl resin obtained in Production Example 1 was replaced with the vinyl resin obtained in Production Example 6. Image evaluation and table
It is shown in FIG.
【００４２】比較例４ 製造例１で得られたビニル樹脂を製造例10で得られたビ
ニル樹脂に替えた他は実施例１と全く同様にしてトナー
を得、実施例１と全く同様にして画像評価し結果を表−
２に示す。Comparative Example 4 A toner was obtained in exactly the same manner as in Example 1, except that the vinyl resin obtained in Production Example 1 was replaced with the vinyl resin obtained in Production Example 10. Image evaluation and table
It is shown in FIG.
【００４３】比較例５ 製造例１で得られたビニル樹脂を製造例11で得られたビ
ニル樹脂に替えた他は実施例１と全く同様にしてトナー
を得、実施例１と全く同様にして画像評価し結果を表−
２に示す。Comparative Example 5 A toner was obtained in exactly the same manner as in Example 1, except that the vinyl resin obtained in Production Example 1 was replaced with the vinyl resin obtained in Production Example 11. Image evaluation and table
It is shown in FIG.
【００４４】比較例６ 製造例１で得られたビニル樹脂を製造例12で得られたビ
ニル樹脂に替え、且つグリシジル化合物を用いない他は
実施例１と全く同様にしてトナーを得、実施例１と全く
同様にして画像評価し結果を表−２に示す。Comparative Example 6 A toner was obtained in the same manner as in Example 1 except that the vinyl resin obtained in Production Example 1 was replaced with the vinyl resin obtained in Production Example 12, and no glycidyl compound was used. Image evaluation was performed in exactly the same manner as in Example 1, and the results are shown in Table 2.
【００４５】[0045]
【表２】 [Table 2]
【００４６】〔トナーの評価方法〕 1)定着性;10℃刻みで定着ロールの温度を替えてコピー
し、このコピーしたベタ黒部分と白地の間を消しゴム
(トンボ鉛筆社製プラスチック消しゴム”ＭＯＮＯ”)
により、一定の力で100 回往復させ、ベタ黒部分の黒度
をインキ濃度計で測定し、トナーの脱落の程度を濃度比
で表した。80％以上残っている最低温度を示した。 2)オフセット性;コピーした場合のオフセット発生した
温度をそのまま表示した。 3)ブロッキング性;重合トナーを温度50℃、相対湿度50
％の環境下に１週間放置した後の粉体の凝集の程度を目
視にて以下の様に測定した。 ◎；全く凝集していない ○；わずかに凝集しているが、容器を軽く振るとほぐれ
る △；容器を良く振ってもほぐれない凝集物がある ×；完全に団塊化している 4)高速耐久性;市販の高速複写機(72 枚／分のコピース
ピード）10,000枚連続テストを実施、パターンをコピー
し再現性をチェックした。連続テスト前後で画質の違い
をチェックした。 ○；前後で、殆ど差がないもの。 △；連続テスト後IDが大きくダウン。 ×；カブリが発生し、画質が大きく乱れた。 5)粉砕性;トナー製造時、２軸混練後冷却したものを一
部採取して粉砕し、10メッシュアンダー16メッシュオン
の粒度に揃えてジェットミルにて粉砕した。コールター
カウンターにて粒度分布を測定、5 〜20μの粒度の割合
を求める。 ◎；85% 以上 ○；70〜85% △；50〜70% ×；50% 以下[Evaluation Method of Toner] 1) Fixing property: Copying by changing the temperature of the fixing roll in steps of 10 ° C., and erasing between the copied solid black portion and white background.
(Plastic eraser "MONO" manufactured by Dragonfly Pencil)
Was reciprocated 100 times with a constant force, the blackness of the solid black portion was measured with an ink densitometer, and the degree of toner falling off was expressed as a density ratio. It showed the lowest temperature remaining above 80%. 2) Offset property: The temperature at which offset occurred when copying was displayed as it is. 3) Blocking property; polymerized toner at a temperature of 50 ° C and a relative humidity of 50
%, And the degree of aggregation of the powder after being left for one week in an environment was visually measured as follows. ◎: Not aggregated at all ○: Slightly aggregated, but loosened when the container was shaken lightly △: Some aggregates could not be loosened even if the container was shaken well ×: Completely aggregated 4) High-speed durability A continuous test of 10,000 high-speed copiers (copy speed of 72 sheets / min) on the market was performed, and patterns were copied to check reproducibility. The difference in image quality was checked before and after the continuous test. ；: Little difference between before and after. Δ: ID dropped greatly after continuous test. X: Fog occurred and image quality was greatly disturbed. 5) Pulverizability: During the production of the toner, a part obtained by cooling after biaxial kneading was partially collected and pulverized, and then pulverized with a jet mill to a particle size of 10 mesh under 16 mesh on. The particle size distribution is measured with a Coulter counter, and the ratio of the particle size of 5 to 20 μ is determined. ◎; 85% or more ○; 70-85% △; 50-70% ×; 50% or less
【００４７】[0047]
【発明の効果】表−１に示した如く、本発明の方法によ
り、より簡単にオフセット性を強化出来ることが分かっ
た。また、定着・ブロッキング性のバランスも良く、粉
砕性・高速耐久性も良好で、実用上優れた性能を有して
いる。As shown in Table 1, it was found that the offset property can be more easily enhanced by the method of the present invention. Further, it has a good balance between fixing and blocking properties, good pulverizability and high-speed durability, and has practically excellent performance.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平３−63662（ＪＰ，Ａ) 特開 平３−209265（ＪＰ，Ａ) 特開 平６−63661（ＪＰ，Ａ) 特開 昭61−179458（ＪＰ，Ａ) 特開 昭58−82254（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) G03G 9/087 ──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-3-63662 (JP, A) JP-A-3-209265 (JP, A) JP-A-6-63661 (JP, A) JP-A-61- 179458 (JP, A) JP-A-58-82254 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) G03G 9/087
Claims (4)
からなる電子写真用トナーにおいて、該結着剤が数平均
分子量（Ｍｎ）1,000 〜20,000、重量平均分子量（Ｍ
ｗ）50,000〜1,000,000 、Ｍｗ／Ｍｎが３．５以上で、
酸価1.0 〜10であり、かつＴｇ点が４０〜７５℃である
ＣＯＯＨ含有ビニル樹脂（Ａ）と該ＣＯＯＨ含有ビニル
樹脂（Ａ）中のＣＯＯＨ基１当量当りグリシジル基とし
て0.05〜1.0 当量を有する重量平均分子量3,000 〜10,0
00で且つエポキシ価0.01〜0.3Eq/100gであるグリシジル
化合物（Ｂ）とを溶融混練させた結着剤であることを特
徴とする電子写真用トナー。1. An electrophotographic toner comprising at least a colorant, a binder and a charge control agent, wherein the binder has a number average molecular weight (Mn) of 1,000 to 20,000 and a weight average molecular weight (M).
w) 50,000-1,000,000, Mw / Mn is 3.5 or more,
COOH-containing vinyl resin (A) having an acid value of 1.0 to 10 and a Tg point of 40 to 75 ° C. and 0.05 to 1.0 equivalent as glycidyl group per equivalent of COOH group in the COOH-containing vinyl resin (A). Weight average molecular weight 3,000-10,0
An electrophotographic toner, which is a binder obtained by melt-kneading a glycidyl compound (B) having a value of 00 and an epoxy value of 0.01 to 0.3 Eq / 100 g.
ニル単量体とアクリル酸、メタクリル酸、無水マレイン
酸、マレイン酸、フマール酸、ケイヒ酸、不飽和二塩基
酸のモノエステル類から選ばれた少なくとも一種を共重
合して得られたものである請求項１記載の電子写真用ト
ナー。2. The COOH-containing vinyl resin (A) is selected from a vinyl monomer and monoesters of acrylic acid, methacrylic acid, maleic anhydride, maleic acid, fumaric acid, cinnamic acid, and unsaturated dibasic acid. 2. The electrophotographic toner according to claim 1, wherein the toner is obtained by copolymerizing at least one of the above.
酸エステル類、メタアクリル酸エステル類、フマール酸
ジアルキルエステル類、アクリロニトリル、アクリルア
ミド、メタクリルアミドから選ばれたものである請求項
２記載の電子写真用トナー。3. The electron according to claim 2, wherein the vinyl monomer is selected from styrenes, acrylates, methacrylates, dialkyl fumarate, acrylonitrile, acrylamide, and methacrylamide. Photo toner.
平均分子量（Ｍｎ）1,000 〜20,000、重量平均分子量
（Ｍｗ）50,000〜1,000,000 、Ｍｗ／Ｍｎが３．５以上
で、酸価1.0 〜10であり、かつＴｇ点が４０〜７５℃で
あるＣＯＯＨ含有ビニル樹脂（Ａ）と該ＣＯＯＨ含有ビ
ニル樹脂（Ａ）中のＣＯＯＨ基１当量当りグリシジル基
として0.05〜1.0 当量を有する重量平均分子量3,000 〜
10,000で、かつエポキシ価0.01〜0.3Eq/100gであるグリ
シジル化合物（Ｂ）を用いた組成物を溶融混練し、得ら
れた混練物を微粉砕することを特徴とする電子写真用ト
ナーの製造法。4. A number average molecular weight (Mn) of 1,000 to 20,000 as a colorant, a charge control agent and a binder, and a weight average molecular weight.
(Mw) COOH-containing vinyl resin (A) having 50,000 to 1,000,000, Mw / Mn of 3.5 or more, acid value of 1.0 to 10, and Tg point of 40 to 75 ° C .; ) Having a weight-average molecular weight of 3,000 to 0.05 to 1.0 equivalent as glycidyl group per equivalent of COOH group in
A method for producing an electrophotographic toner, comprising: melt-kneading a composition using a glycidyl compound (B) having an epoxy value of 0.01 to 0.3 Eq / 100 g and pulverizing the obtained kneaded product. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05008979A JP3118341B2 (en) | 1992-01-31 | 1993-01-22 | Electrophotographic toner and method for producing the same |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1587792 | 1992-01-31 | ||
| JP10751092 | 1992-04-27 | ||
| JP4-15877 | 1992-04-27 | ||
| JP4-107510 | 1992-04-27 | ||
| JP05008979A JP3118341B2 (en) | 1992-01-31 | 1993-01-22 | Electrophotographic toner and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0611890A JPH0611890A (en) | 1994-01-21 |
| JP3118341B2 true JP3118341B2 (en) | 2000-12-18 |
Family
ID=27278275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05008979A Expired - Lifetime JP3118341B2 (en) | 1992-01-31 | 1993-01-22 | Electrophotographic toner and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3118341B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7351509B2 (en) | 2004-02-20 | 2008-04-01 | Canon Kabushiki Kaisha | Toner |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3363856B2 (en) | 1998-12-17 | 2003-01-08 | キヤノン株式会社 | Positively chargeable toner, image forming method and image forming apparatus |
| US6670087B2 (en) | 2000-11-07 | 2003-12-30 | Canon Kabushiki Kaisha | Toner, image-forming apparatus, process cartridge and image forming method |
| EP1462860B1 (en) | 2003-03-27 | 2006-08-30 | Canon Kabushiki Kaisha | Toner |
| JPWO2004107058A1 (en) * | 2003-05-29 | 2006-07-20 | 三井化学株式会社 | Binder resin for toner and toner for electrophotography |
| EP1505449B1 (en) | 2003-08-01 | 2009-09-16 | Canon Kabushiki Kaisha | Toner |
| US7306889B2 (en) | 2004-02-20 | 2007-12-11 | Canon Kabushiki Kaisha | Process for producing toner, and toner |
-
1993
- 1993-01-22 JP JP05008979A patent/JP3118341B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7351509B2 (en) | 2004-02-20 | 2008-04-01 | Canon Kabushiki Kaisha | Toner |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0611890A (en) | 1994-01-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3794762B2 (en) | Toner for electrophotography | |
| EP0555022B1 (en) | Electrophotographic toner and process for producing it | |
| US6497983B2 (en) | Toner binder for electrophotography and toner for electrophotography | |
| JP4043475B2 (en) | Binder resin and toner for toner | |
| JP3118341B2 (en) | Electrophotographic toner and method for producing the same | |
| JPH08320593A (en) | Bonding resin and toner for developing electrostatic charge image containing same | |
| JP3701691B2 (en) | Toner for electrophotography | |
| JP3761330B2 (en) | Resin composition for toner and toner | |
| JP2006171364A (en) | Binder resin for toner, and electrophotographic toner | |
| JP3929272B2 (en) | Electrophotographic toner binder and electrophotographic toner | |
| JP3891610B2 (en) | Toner for electrophotography | |
| JP3532033B2 (en) | Electrophotographic toner | |
| KR20220120775A (en) | Toner for high speed machinery and its effects | |
| JPH07113786B2 (en) | Toner | |
| JP3638963B2 (en) | Toner for electrophotography | |
| JP2981362B2 (en) | Resin composition for electrophotographic toner | |
| JP2001305792A (en) | Toner | |
| JP3128897B2 (en) | Method for producing polymerized toner | |
| JP2938567B2 (en) | Electrophotographic toner | |
| JPH05341564A (en) | Toner for heat roller fixation | |
| JP2590332B2 (en) | Positive charging toner | |
| JPH07287419A (en) | Production of binder resin for electrophotographic toner | |
| JP4017548B2 (en) | Binder resin for toner and toner for electrophotography | |
| JP4368511B2 (en) | Toner for electrophotography | |
| JPH06313983A (en) | Electrophotographic toner |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081006 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091006 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101006 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101006 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111006 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121006 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121006 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131006 Year of fee payment: 13 |
|
| EXPY | Cancellation because of completion of term | ||
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131006 Year of fee payment: 13 |