JPH09274335A - Toner for developing electrostatic charge image - Google Patents
Toner for developing electrostatic charge imageInfo
- Publication number
- JPH09274335A JPH09274335A JP8502496A JP8502496A JPH09274335A JP H09274335 A JPH09274335 A JP H09274335A JP 8502496 A JP8502496 A JP 8502496A JP 8502496 A JP8502496 A JP 8502496A JP H09274335 A JPH09274335 A JP H09274335A
- Authority
- JP
- Japan
- Prior art keywords
- toner
- acid
- weight
- polyester resin
- lactic acid
- 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
Landscapes
- Developing Agents For Electrophotography (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、静電荷像現像用ト
ナーに関する。更に詳しくは、生分解性を有するバイン
ダー樹脂を主成分とする定着性（低温定着性、定着温
度、耐オフセット性）、耐ブロッキング性に優れた静電
荷像現像用トナーに関する。The present invention relates to a toner for developing an electrostatic image. More specifically, the present invention relates to a toner for developing an electrostatic charge image, which comprises a binder resin having biodegradability as a main component and is excellent in fixability (low-temperature fixability, fix temperature, offset resistance) and blocking resistance.
【０００２】[0002]
【従来の技術】近年、廃棄物処理、環境保全、およびリ
サイクル等の見地から、生分解性材料への期待が高まっ
ており、トナーについても例外ではない。従来のトナー
は、生分解性がないため、トナーまたはトナー樹脂を土
中に埋め立て処理をした場合に、土中に永久に残存する
という問題を抱えている。また近年、複写機やプリンタ
ーに使用される普通紙の使用量が飛躍的に増大してお
り、これらの普通紙を再生、再利用することが重要な技
術のひとつとなっているが、従来のスチレン系を中心と
するバインダー樹脂では、アルカリ加水分解による脱墨
が困難であり、普通紙をリサイクルする際の弊害のひと
つとなっている。2. Description of the Related Art In recent years, from the viewpoints of waste treatment, environmental protection, recycling and the like, expectations for biodegradable materials have increased, and toners are no exception. Since the conventional toner has no biodegradability, it has a problem that it remains permanently in the soil when the toner or the toner resin is buried in the soil. Also, in recent years, the amount of plain paper used in copiers and printers has increased dramatically, and recycling and reuse of these plain papers has become one of the important technologies. Sink-based binder resins are difficult to deink by alkaline hydrolysis, which is one of the harmful effects when recycling plain paper.
【０００３】[0003]
【発明が解決しようとする課題】このような観点から、
生分解性を有し、アルカリ加水分解において効率よく分
解され、紙のリサイクルにも有用であるとして、ポリヒ
ドロキシカルボン酸を中心とする脂肪族ポリエステルを
主成分とするトナーが提案されている。例えば特開平７
−１２０９７５号公報には乳酸ホモポリマーをトナー化
する方法が提案されており、その代表格として開環重合
法により得られたポリ乳酸があげられている。開環重合
法では、乳酸をいったん脱水反応によりオリゴマー化
し、これを解重合することにより環状二量体のラクチド
へと導き、さらにこれを開環重合するという手法がとら
れている。このような煩雑な工程をたどるため、得られ
たポリ乳酸をトナー用樹脂として使用するには非常に高
価なものとなる。またこの手法ではポリ乳酸の好ましい
変性の為に使用されるモノマー種が環状エステルに限ら
れ、実質的に３価以上の多官能成分を使用し、所望の架
橋構造をもたせることは非常に困難である。SUMMARY OF THE INVENTION From such a viewpoint,
A toner containing an aliphatic polyester mainly containing polyhydroxycarboxylic acid as a main component has been proposed as being biodegradable, efficiently decomposed by alkali hydrolysis, and useful for recycling paper. For example, JP-A-7
JP-A-120975 proposes a method of converting a lactic acid homopolymer into a toner, and a representative example thereof is polylactic acid obtained by a ring-opening polymerization method. In the ring-opening polymerization method, a method is employed in which lactic acid is once oligomerized by a dehydration reaction, depolymerized to lead to a lactide of a cyclic dimer, and then ring-opening polymerized. Since such a complicated process is followed, it is very expensive to use the obtained polylactic acid as a toner resin. Further, in this method, the monomer species used for the preferred modification of polylactic acid are limited to cyclic esters, and it is extremely difficult to use a polyfunctional component having a valence of 3 or more and to have a desired crosslinked structure. is there.
【０００４】一方、静電荷像現像用トナーは、速やかに
定着し、そしてトナーが定着ローラー表面に転移して、
以後定着工程を通過する転写材をローラー上のトナーに
よって汚す、所謂オフセット現像を発生しないことが必
要である。さらに、トナーは保存時あるいは運搬時等に
ブロッキングするような事があってはならない。このよ
うなトナーは、流動性、帯電性等が著しく劣化してお
り、もはや現像剤としての機能を果たすことが出来な
い。そこで、トナーの主要成分であるバインダー樹脂に
は微妙な硬度及び熱溶融特性が要求され、着色剤等が分
散されたバインダー樹脂を粉砕・分級して得られるトナ
ーは、現像器内の撹拌による機械的衝撃に対して微粉を
発生することなく、またトナー自体が凝集することなく
良好な流動性を示すことが必要であり、また定着時には
低温で速やかに溶融すること、そして溶融時に溶融トナ
ーが凝集性を示すことが必要である。On the other hand, the electrostatic image developing toner is rapidly fixed, and the toner is transferred to the surface of the fixing roller,
It is necessary not to cause so-called offset development, in which the transfer material that passes through the fixing step thereafter is soiled by the toner on the roller. Further, the toner should not block during storage or transportation. Such a toner is significantly deteriorated in fluidity, chargeability, etc., and can no longer function as a developer. Therefore, the binder resin, which is the main component of the toner, is required to have delicate hardness and heat melting characteristics, and the toner obtained by crushing and classifying the binder resin in which the colorant and the like are dispersed is mechanically agitated in the developing device. It is necessary for the toner to show good fluidity without the generation of fine powder against physical impact, and for the toner itself not to agglomerate. Also, the toner melts quickly at low temperature during fixing, and the molten toner agglomerates during melting. It is necessary to show sex.
【０００５】これらの性能を全て満足するバインダー樹
脂を設計することは極めて困難であり、特に定着性と耐
オフセット性・耐ブロッキング性は相反する性能である
為両者の性能を両立することは極めて難しい。そこで、
従来からバインダー樹脂として使用される重合体の分子
量及び分子量分布について多くの提案がなされている。
例えば、数平均分子量が１０００〜４０００の低温融
解、高流動性樹脂を５０〜９５重量％含有するトナーが
提案されているが（特公昭５９−１０７３６０号公
報）、耐オフセット性、耐ブロッキング性になお問題を
残している。It is extremely difficult to design a binder resin that satisfies all of these performances. Particularly, since fixing performance and offset resistance / blocking resistance are contradictory performances, it is extremely difficult to satisfy both performances. . Therefore,
Many proposals have heretofore been made regarding the molecular weight and molecular weight distribution of polymers used as binder resins.
For example, a toner containing a low-melting resin having a number average molecular weight of 1000 to 4000 and a high fluidity resin of 50 to 95% by weight has been proposed (Japanese Patent Publication No. 59-107360), but it has excellent offset resistance and blocking resistance. There is still a problem.
【０００６】また、特公昭６３−３２１８０号公報にお
いては分子量が１０3 〜８×１０4及び１０5 〜２×１
０6 の各々の領域に少なくとも１つの極大値をもつスチ
レン共重合体バインダー樹脂を使用することが提案され
ている。しかしながら、上記公報によるトナーは、転写
材への定着性特に定着強度と耐ブロッキング性の両立に
おいて未だ満足のいく結果が得られていない。すなわ
ち、該方法によると、定着性を良くする為には低分子量
成分の含有量を増やさなければならず、この為、耐ブロ
ッキング性に問題が生じる。一方、耐ブロッキング性を
良くする為には、高分子量成分の含有量を増やす必要が
あり、定着性に問題をきたす。In Japanese Patent Publication No. 63-32180, the molecular weight is 10 3 to 8 × 10 4 and 10 5 to 2 × 1.
It has been proposed to use a styrene copolymer binder resin having at least one local maximum in each region of 0 6 . However, the toner according to the above publication has not yet obtained satisfactory results in terms of fixing property to a transfer material, particularly fixing strength and blocking resistance. That is, according to this method, the content of the low molecular weight component must be increased in order to improve the fixing property, which causes a problem in blocking resistance. On the other hand, in order to improve the blocking resistance, it is necessary to increase the content of the high molecular weight component, which causes a problem in fixability.
【０００７】また、特開平６−３０８７６５号公報に
は、無水トリメリット酸、グリセリンまたはトリメチロ
ールプロパン等同種の官能基を有する架橋剤で架橋され
た乳酸ポリエステルを使用することが提案されている。
しかしながら、これらは、架橋性が悪く定着性特に耐オ
フセット性が充分でなく、熱ローラーがトナーによって
汚れやすいという欠点があった。Further, JP-A-6-308765 proposes to use a lactic acid polyester cross-linked with a cross-linking agent having the same functional group such as trimellitic anhydride, glycerin or trimethylolpropane.
However, these have the drawbacks that the crosslinkability is poor and the fixability, especially the offset resistance, is not sufficient, and the heat roller is easily soiled by the toner.
【０００８】[0008]
【課題を解決するための手段】本発明は、上記問題を解
決して、生分解性を有する脂肪族ポリエステルを含有す
る、定着性（低温定着性、定着温度、耐オフセット
性）、耐ブロッキング性に優れたトナーを提供すべく、
鋭意検討した結果、上記性能を満足するトナーを完成す
るに至ったものである。すなわち、本発明の要旨は、乳
酸および３官能以上のオキシカルボン酸を含有する組成
物を脱水重縮合して得られたポリエステル樹脂および着
色剤を含有することを特徴とする静電荷像現像用トナー
に存し、生分解性を有し、特に耐オフセット性に優れた
トナー樹脂を提供することにある。The present invention solves the above problems and contains an aliphatic polyester having biodegradability, fixing property (low temperature fixing property, fixing temperature, offset resistance), blocking resistance. To provide excellent toner,
As a result of intensive studies, a toner satisfying the above-mentioned performance has been completed. That is, the gist of the present invention is to provide a toner for developing an electrostatic charge image, which comprises a polyester resin obtained by dehydration polycondensation of a composition containing lactic acid and a trifunctional or higher functional oxycarboxylic acid, and a colorant. The present invention provides a toner resin having biodegradability and excellent in offset resistance.
【０００９】[0009]
【発明の実施の形態】本発明に用いられるトナーは乳酸
と３官能以上のオキシカルボン酸を脱水重縮合して得ら
れるポリエステル樹脂を含有するものであり、乳酸と３
官能以上のオキシカルボン酸の重量比（乳酸：３官能以
上のオキシカルボン酸）が８０：２０〜９９．９：０．
１であることが好ましい。このポリエステル樹脂は３官
能以上のオキシカルボン酸により、架橋されたゲル成分
を有し、ゲル成分量はテトラヒドロフラン不溶分を目安
として表される。BEST MODE FOR CARRYING OUT THE INVENTION The toner used in the present invention contains a polyester resin obtained by dehydration polycondensation of lactic acid and trifunctional or higher functional oxycarboxylic acid.
The weight ratio of the functional or higher oxycarboxylic acid (lactic acid: trifunctional or higher functional carboxylic acid) is 80:20 to 99.9: 0.
It is preferably 1. This polyester resin has a gel component cross-linked with a trifunctional or higher functional oxycarboxylic acid, and the amount of the gel component is expressed with tetrahydrofuran insoluble content as a guide.
【００１０】本発明に使用される乳酸には、Ｌ体、Ｄ
体、ＤＬ体、あるいはＤ体とＬ体の混合物が挙げられ、
特に限定されるものではない。ただし得られるポリ乳酸
に融点が現れると、トナーの定着性が悪化するため、融
点を有さないポリ乳酸が好ましい。このような非晶性の
ポリ乳酸を得るには、全乳酸単量体のうち、少なくとも
５モル％が、光学異性体で占められていることが好まし
く、２０モル％以上が光学異性体であることが好まし
い。Lactic acid used in the present invention includes L-form and D-form.
Body, DL body, or a mixture of D body and L body,
There is no particular limitation. However, when a melting point appears in the obtained polylactic acid, the fixing property of the toner is deteriorated, and therefore polylactic acid having no melting point is preferable. In order to obtain such amorphous polylactic acid, it is preferable that at least 5 mol% of all lactic acid monomers are occupied by optical isomers, and 20 mol% or more are optical isomers. It is preferable.
【００１１】本発明に使用される３官能以上のオキシカ
ルボン酸とは、１分子内に１個以上の水酸基及び１個以
上のカルボキシル基を有し、水酸基とカルボキシル基の
総和が３以上である化合物であって、芳香族のタイプと
脂肪族のタイプがあり、いずれも使用可能である。具体
的には、リンゴ酸、ジメチロールブタン酸、酒石酸、ク
エン酸等の脂肪族オキシカルボン酸類、２，５−ジヒド
ロキシテレフタル酸、２，５−ジヒドロキシ−１，４−
ベンゼンジアセチル酸等の芳香族オキシカルボン酸類な
どがある。生分解性という見地からすると脂肪族のもの
が好ましく、入手が容易であるという点から酒石酸、ク
エン酸等が特に好ましい。ただし使用するオキシカルボ
ン酸の種類によっては、反応系中にカルボキシル基ある
いは水酸基が過剰となってしまうため、所望のゲル成分
量が得られる以前に、反応が進まなくなる場合がある。
これを防止するためには、場合によっては２価のアルコ
ールあるいはジカルボン酸をさらに適当量添加するのが
好ましい。The trifunctional or higher functional oxycarboxylic acid used in the present invention has one or more hydroxyl groups and one or more carboxyl groups in one molecule, and the sum of the hydroxyl groups and the carboxyl groups is 3 or more. There are two types of compounds, an aromatic type and an aliphatic type, both of which can be used. Specifically, aliphatic oxycarboxylic acids such as malic acid, dimethylolbutanoic acid, tartaric acid, and citric acid, 2,5-dihydroxyterephthalic acid, 2,5-dihydroxy-1,4-
There are aromatic oxycarboxylic acids such as benzenediacetyl acid. Aliphatic ones are preferable from the viewpoint of biodegradability, and tartaric acid and citric acid are particularly preferable from the viewpoint of easy availability. However, depending on the type of the oxycarboxylic acid used, the carboxyl group or the hydroxyl group becomes excessive in the reaction system, so that the reaction may not proceed before the desired gel component amount is obtained.
In order to prevent this, in some cases, it is preferable to add an appropriate amount of dihydric alcohol or dicarboxylic acid.
【００１２】３官能以上のオキシカルボン酸成分の添加
によるゲル成分の生成は、樹脂の分子量分布を広げ、ガ
ラス転移温度を高める効果があると同時に、樹脂の溶融
時に弾性を付与することもできる。従って定着時の耐オ
フセット性を向上せしめることができる。しかし、多官
能化合物を大量に用いると、重合時、急激な架橋反応に
伴う粘度上昇が起こり、所望の分子量が得られる前に撹
拌が不良となり、均一な撹拌が出来なくなる。従って３
官能以上のオキシカルボン酸の添加量は、０．１〜２０
重量％、好ましくは１〜１５重量％、より好ましくは３
〜１０モル％である。また、得られた樹脂中のテトラヒ
ドロフラン（ＴＨＦ）不溶分は、通常１０〜８０重量
％、好ましくは１０〜７０重量％、より好ましくは１０
〜５０重量％である。なお、ＴＨＦ不溶分は、バインダ
ー樹脂１ｇを１００ｇのＴＨＦ中にスターラーで撹拌し
ながら２５℃で１０時間かけて溶解させ、濾過後の不溶
分を測定することにより求められる。The formation of a gel component by adding a trifunctional or higher functional oxycarboxylic acid component has the effects of broadening the molecular weight distribution of the resin and increasing the glass transition temperature, and at the same time, it is possible to impart elasticity when the resin is melted. Therefore, the offset resistance at the time of fixing can be improved. However, when a large amount of a polyfunctional compound is used, the viscosity increases due to a rapid crosslinking reaction during the polymerization, the stirring becomes poor before the desired molecular weight is obtained, and uniform stirring cannot be performed. Therefore 3
The addition amount of functional oxycarboxylic acid is 0.1 to 20.
% By weight, preferably 1 to 15% by weight, more preferably 3
10 to 10 mol%. The tetrahydrofuran (THF) insoluble matter in the obtained resin is usually 10 to 80% by weight, preferably 10 to 70% by weight, more preferably 10% by weight.
５０50% by weight. The THF insoluble matter is obtained by dissolving 1 g of the binder resin in 100 g of THF with stirring with a stirrer at 25 ° C. for 10 hours and measuring the insoluble matter after filtration.
【００１３】本発明における脱水重縮合とは、ラクチド
を原料とするいわゆる開環重合とは根本的に異なる製造
方法であり、開環重合が基本的に重付加であるのに対
し、本方法は重縮合である。本方法の脱水重縮合は、溶
媒を使用してもよいが、基本的にコスト増につながるた
め、好ましくは、溶媒を使用しない、溶融重縮合であ
る。さらに詳細に脱水重縮合について述べると、本方法
では例えば、触媒の存在下、常圧あるいは減圧下、乳酸
あるいは乳酸オリゴマーを加熱することにより、目的の
ポリマーを得ることが出来る。触媒としては特に限定さ
れないが、ゲルマニウム触媒あるいはチタン触媒が、所
望の分子量を有するポリマーが得られ易い点で好まし
い。具体的には、酸化ゲルマニウム、あるいはテトラエ
トキシゲルマニウム、テトラブトキシゲルマニウムなど
の有機アルコキシゲルマニウム、酸化チタン、あるいは
テトラブトキシチタン、テトラプロポキシチタンなどの
有機チタン化合物、さらにはこれらの混合物などが挙げ
られる。The dehydration polycondensation in the present invention is a production method which is fundamentally different from the so-called ring-opening polymerization using lactide as a raw material, and the ring-opening polymerization is basically a polyaddition, whereas this method is It is polycondensation. Although the dehydration polycondensation of the present method may use a solvent, it basically leads to an increase in cost. Therefore, it is preferably melt polycondensation without using a solvent. More specifically, the dehydration polycondensation will be described in detail. In this method, for example, the target polymer can be obtained by heating lactic acid or a lactic acid oligomer in the presence of a catalyst under normal pressure or reduced pressure. The catalyst is not particularly limited, but a germanium catalyst or a titanium catalyst is preferable because a polymer having a desired molecular weight can be easily obtained. Specific examples thereof include germanium oxide, organic alkoxy germanium such as tetraethoxygermanium and tetrabutoxygermanium, titanium oxide, organic titanium compounds such as tetrabutoxytitanium and tetrapropoxytitanium, and mixtures thereof.
【００１４】重縮合温度は通常は１４０〜２２０℃、乳
酸の環状２量化を抑制するという観点から好ましくは１
６０〜２１０℃、より好ましくは１８０〜２００℃であ
る。反応温度が２２０℃を超えると、ポリマーの熱分解
が起こり、乳酸の環状２量体であるラクチドが副生し、
好ましくない。反応温度が１４０℃以下だと、重合速度
が遅くなり、製造上好ましくない。The polycondensation temperature is usually 140 to 220 ° C., preferably 1 from the viewpoint of suppressing the cyclic dimerization of lactic acid.
The temperature is 60 to 210 ° C, more preferably 180 to 200 ° C. When the reaction temperature exceeds 220 ° C, thermal decomposition of the polymer occurs, and lactide, which is a cyclic dimer of lactic acid, is by-produced,
Not preferred. When the reaction temperature is 140 ° C. or lower, the polymerization rate becomes slow, which is not preferable in production.
【００１５】反応圧力は、通常は常圧〜２ｍｍＨｇ、最
終的には３０〜５ｍｍＨｇが好ましい。反応温度にもよ
るが、一般に２ｍｍＨｇ以下では、ラクチドが生成しや
すくなる。本発明のトナーに含有させる乳酸と３官能以
上のオキシカルボン酸からなる、架橋されたゲル成分を
含むポリエステル樹脂のガラス転移温度は３０〜８０℃
であることが好ましく、特に好ましくは４０〜８０℃、
更に好ましくは５０〜７０℃である。３０℃より低い値
では、ブロッキング性が悪くなり、また８０℃以上にな
ると定着性が悪くなる傾向にある。また、本発明におけ
るポリエステル樹脂の軟化点は、６０〜１７０℃が好ま
しい。特に好ましくは８０〜１４０℃である。６０℃以
下では耐オフセット性の悪化が見られ、１７０℃以上で
は定着温度が高くなる傾向にある。The reaction pressure is usually normal pressure to 2 mmHg, and finally 30 to 5 mmHg is preferable. Although it depends on the reaction temperature, generally, lactide is likely to be formed at 2 mmHg or less. The glass transition temperature of the polyester resin containing a cross-linked gel component, which is composed of lactic acid and trifunctional or more oxycarboxylic acid contained in the toner of the present invention, is 30 to 80 ° C.
Is preferable, and particularly preferably 40 to 80 ° C.,
More preferably, it is 50 to 70 ° C. If it is lower than 30 ° C, the blocking property tends to be poor, and if it is 80 ° C or higher, the fixing property tends to be poor. Further, the softening point of the polyester resin in the present invention is preferably 60 to 170 ° C. It is particularly preferably 80 to 140 ° C. When the temperature is 60 ° C or lower, the offset resistance is deteriorated, and when the temperature is 170 ° C or higher, the fixing temperature tends to be high.
【００１６】更に架橋度の目安となるテトラヒドロフラ
ン不溶分は、前述の如く通常１０〜８０重量％、好まし
くは１０〜７０重量％、より好ましくは１０〜５０重量
％である。本発明のポリエステル樹脂のＴＨＦ可溶分
は、数平均分子量が、好ましくは２０００以上、特に好
ましくは７０００〜１０万、更に好ましくは７０００〜
４万である。数平均分子量が低すぎると粉砕が極めて困
難であるので好ましくなく、また高すぎると粉砕性が悪
化する傾向にある。Further, the tetrahydrofuran insoluble content, which is a measure of the degree of crosslinking, is usually 10 to 80% by weight, preferably 10 to 70% by weight, and more preferably 10 to 50% by weight, as described above. The THF-soluble component of the polyester resin of the present invention has a number average molecular weight of preferably 2000 or more, particularly preferably 7,000 to 100,000, further preferably 7,000 to
It is 40,000. If the number average molecular weight is too low, the pulverization becomes extremely difficult, which is not preferable, and if it is too high, the pulverizability tends to deteriorate.
【００１７】これら所望の物性のポリエステル樹脂は、
上述の重縮合反応の条件を選択することによって得られ
る。例えば、重合時間を長くするか或いは減圧度を高め
れば数平均分子量の大きい樹脂が得られる。ガラス転移
温度、軟化点はポリエステル樹脂の分子量と相関関係を
有する。或いは、樹脂中のオリゴマー成分を除去すると
ガラス転移温度、軟化点を上げることが出来る。オリゴ
マーの除去は、例えば、溶媒抽出、再沈殿などの手段が
採られる。The polyester resin having these desired physical properties is
It is obtained by selecting the conditions of the above polycondensation reaction. For example, by increasing the polymerization time or increasing the degree of reduced pressure, a resin having a large number average molecular weight can be obtained. The glass transition temperature and the softening point have a correlation with the molecular weight of the polyester resin. Alternatively, the glass transition temperature and the softening point can be increased by removing the oligomer component in the resin. To remove the oligomer, for example, means such as solvent extraction and reprecipitation are adopted.
【００１８】ゲル成分（テトラヒドロフラン不溶分）の
量は、架橋剤の使用量及び反応条件の選択によって調節
できる。すなわち、ゲル成分量を大きくするには、架橋
剤の量を多くすれば良い。或いは架橋剤の使用量が同じ
でも、分子量を大きくする条件で重合すればゲル成分量
は大きくなる。本発明のトナーはバインダー樹脂の主成
分を上記のポリエステル樹脂とすることが好ましいが、
定着性向上のため、さらに、主として脂肪族ジオールと
脂肪族ジカルボン酸からなる、トナーの軟化点よりも低
い融点を有する脂肪族ポリエステルを添加することが出
来る。この主として脂肪族ジオールと脂肪族ジカルボン
酸からなる脂肪族ポリエステルは特に限定されないが、
ポリブチレンサクシナート、ポリブチレンアジペート、
ポリエチレンサクシナート、ポリエチレンアジペート、
あるいはこれらに脂肪族オキシカルボン酸が少量共重合
されたものであっても良い。The amount of the gel component (tetrahydrofuran insoluble matter) can be adjusted by selecting the amount of the crosslinking agent used and the reaction conditions. That is, in order to increase the amount of the gel component, the amount of the crosslinking agent should be increased. Alternatively, even if the amount of the cross-linking agent used is the same, if the polymerization is carried out under the condition of increasing the molecular weight, the amount of the gel component will increase. In the toner of the present invention, it is preferable that the main component of the binder resin is the above polyester resin,
In order to improve the fixing property, an aliphatic polyester mainly composed of an aliphatic diol and an aliphatic dicarboxylic acid and having a melting point lower than the softening point of the toner can be added. The aliphatic polyester mainly composed of the aliphatic diol and the aliphatic dicarboxylic acid is not particularly limited,
Polybutylene succinate, polybutylene adipate,
Polyethylene succinate, polyethylene adipate,
Alternatively, a small amount of an aliphatic oxycarboxylic acid may be copolymerized with these.
【００１９】本発明トナーはかかるポリエステル樹脂を
含有するバインダー樹脂以外に着色剤を含有する。更に
必要に応じて帯電制御剤等のトナーに使用される種々の
添加剤を含有する。着色剤としては、特に限定されるも
のではなく、例えば、カーボンブラック、ランプブラッ
ク、鉄黒、群青、ニグロシン染料、アニリンブルー、フ
タロシアニンブルー、フタロシアニングリーン、ハンザ
イエロー、クロムイエロー、ローズベンガル、トリアリ
ールメタン系染料、モノアゾ系、ジスアゾ系染顔料等を
挙げることができる。着色剤の量はバインダー樹脂１０
０重量部に対し３〜２０重量部程度である。The toner of the present invention contains a colorant in addition to the binder resin containing the polyester resin. Further, if necessary, various additives used for the toner such as a charge control agent are contained. The colorant is not particularly limited, and examples thereof include carbon black, lamp black, iron black, ultramarine blue, nigrosine dye, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa yellow, chrome yellow, rose bengal, triarylmethane. Examples thereof include dyes, monoazo dyes, and disazo dyes and pigments. The amount of colorant is 10
It is about 3 to 20 parts by weight with respect to 0 parts by weight.
【００２０】本発明トナーは、乾式１成分現像剤及び２
成分現像剤のいずれにも使用でき、１成分の現像剤に使
用する磁性体としては、フェライト、マグネタイト等を
はじめとする鉄、コバルト、ニッケル等の強磁性を示す
合金、或は化合物または強磁性元素を含まないが適当に
熱処理することによって強磁性を示すようになる合金、
例えば、マンガン−銅−アルミニウムあるいはマンガン
−銅−スズ等のマンガンと銅とを含むホイスラー合金と
呼ばれる種類の合金、または二酸化クロム等を挙げるこ
とが出来る。磁性体は、平均粒径０．３〜３０μｍの微
粉末の形でバインダー樹脂中に均一に分散される。磁性
体粒子の含有量は、バインダー１００重量部当り２０〜
７０重量部、好ましくは４０〜７０重量部が望ましい。The toner of the present invention comprises a dry one-component developer and a two-component developer.
It can be used in any of the component developers, and the magnetic substance used in the one-component developer is an alloy exhibiting ferromagnetism such as iron, cobalt and nickel including ferrite and magnetite, or a compound or ferromagnetism. An alloy that does not contain elements, but becomes ferromagnetic by proper heat treatment,
For example, an alloy of a type called Heusler alloy containing manganese and copper such as manganese-copper-aluminum or manganese-copper-tin, or chromium dioxide can be used. The magnetic substance is uniformly dispersed in the binder resin in the form of fine powder having an average particle size of 0.3 to 30 μm. The content of the magnetic particles is 20 to 100 parts by weight of the binder.
70 parts by weight, preferably 40 to 70 parts by weight is desirable.
【００２１】トナーの帯電制御は、バインダー樹脂、着
色剤自体で行っても良いが、必要に応じて帯電制御剤を
併用しても良い。正帯電制御剤として、４級アンモニウ
ム塩、塩基性・電子供与性の有機物質、負帯電制御剤と
して、金属キレート類、合金染料、酸性もしくは電子求
引性の有機物質等を用いることができる。帯電制御剤の
添加量はバインダー樹脂の帯電性、着色剤の添加量・分
散方法を含めた製造方法、その他の添加剤の帯電性等の
条件を考慮した上で決めることができるが、バインダー
樹脂１００重量部に対して０．１〜１０重量部が適当で
ある。この他、金属酸化物等の無機粒子や前記有機物質
で表面処理した無機物質を用いても良い。これら帯電制
御剤は、バインダー樹脂中に混合添加して用いても、ト
ナー粒子表面に付着させた形で用いても良い。The charge control of the toner may be performed by the binder resin and the colorant itself, but a charge control agent may be used in combination if necessary. As the positive charge control agent, a quaternary ammonium salt, a basic / electron-donating organic substance, and as the negative charge control agent, a metal chelate, an alloy dye, an acidic or electron-withdrawing organic substance, and the like can be used. The addition amount of the charge control agent can be determined in consideration of the chargeability of the binder resin, the manufacturing method including the addition amount / dispersion method of the colorant, and the chargeability of other additives. 0.1 to 10 parts by weight is suitable for 100 parts by weight. In addition, inorganic particles such as metal oxides or inorganic substances surface-treated with the organic substance may be used. These charge control agents may be mixed and added to the binder resin, or may be used in the form of being attached to the surface of the toner particles.
【００２２】さらにまた、固体電解質、高分子電解質、
電荷移動錯体、酸化スズ等の金属酸化物等の導電体、半
導体、あるいは強誘電体、磁性体等を添加しトナーの電
気的性質を制御することができる。この他、トナー中に
は熱特性・物理特性等を調整する目的で各種可塑剤・離
型剤等の助剤を添加することも可能である。この添加量
は、バインダー樹脂１００重量部に対し０．１〜１０重
量部が適当である。Furthermore, solid electrolytes, polymer electrolytes,
The electrical properties of the toner can be controlled by adding a charge transfer complex, a conductor such as a metal oxide such as tin oxide, a semiconductor, a ferroelectric substance, a magnetic substance, or the like. In addition, auxiliary agents such as various plasticizers and release agents can be added to the toner for the purpose of adjusting thermal characteristics, physical characteristics, and the like. The appropriate amount of addition is 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin.
【００２３】さらに、トナー粒子にたいして、Ｔｉ
Ｏ2 、Ａｌ2 Ｏ3 、ＳｉＯ2 等の微粉末を添加し、これ
らでトナー粒子表面を被覆せしめることによってトナー
の流動性・耐凝集性の向上を図ることができる。その添
加量は、バインダー樹脂１００重量部に対し０．１〜１
０重量部が好ましい。本発明のトナーの製造方法には、
従来から用いられている各種トナー製造法が適用できる
が、例えば一般的製造法として次の例が挙げられる。ま
ず、樹脂、着色剤（場合により帯電制御剤等）をボール
ミル、Ｖ型混合機、Ｓ型混合機、ヘンシェルミキサー等
で均一に分散する。次いで分散物を双腕ニーダー、加圧
ニーダー等で溶融混練する。該混合物をハンマーミル、
ジェットミル、ボールミル等の粉砕機で粉砕し、さらに
得られた粉体を風力分級機等で分級する。Further, for the toner particles, Ti
By adding fine powder such as O 2 , Al 2 O 3 , and SiO 2 and coating the surface of the toner particle with these, the fluidity and aggregation resistance of the toner can be improved. The addition amount is 0.1 to 1 with respect to 100 parts by weight of the binder resin.
0 parts by weight is preferred. The method for producing the toner of the present invention includes
Although various toner manufacturing methods that have been used conventionally can be applied, the following examples can be given as general manufacturing methods. First, a resin and a colorant (such as a charge control agent in some cases) are uniformly dispersed with a ball mill, a V-type mixer, an S-type mixer, a Henschel mixer, or the like. Next, the dispersion is melt-kneaded with a double-arm kneader, a pressure kneader or the like. Hammer mill the mixture,
It is crushed by a crusher such as a jet mill or a ball mill, and the obtained powder is classified by an air classifier or the like.
【００２４】得られたトナーは、キャリアと混合して電
子写真用現像剤を形成させ、従来から実施されている電
子写真法による複写に用いることができる。なお、キャ
リアは、公知の鉄粉系、フェライト系キャリア等の磁性
物質またはそれらの表面にコーティングを施したものを
トナー１部に対して１０部〜１００部用いることが好ま
しい。The obtained toner can be mixed with a carrier to form a developer for electrophotography, and can be used for copying by a conventional electrophotographic method. As the carrier, it is preferable to use 10 to 100 parts of a magnetic substance such as a known iron powder-based or ferrite-based carrier or a material coated on the surface thereof with respect to 1 part of the toner.
【００２５】[0025]
【実施例】以下に本発明の実施例を示すが、本発明はそ
の要旨を超えない限り以下に限定されるものではない。
なお、分子量、軟化点（Ｔｓ）、ガラス転移温度（Ｔ
ｇ）、ＴＨＦ不溶分の測定は次の測定方法により行なっ
た。EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto unless it exceeds the gist.
The molecular weight, softening point (Ts), glass transition temperature (T
g) and the THF insoluble content was measured by the following measuring method.
【００２６】（１）分子量 分子量の測定は、樹脂をＴＨＦに溶解し、不溶分を濾過
した後次の条件下にＧＰＣ測定を行ない得られた保持時
間を基にしてポリスチレンについて既知の保持時間と分
子量の関係から求めたポリスチレン換算分子量である。 分離カラム：以下の三種類のポリスチレン充填カラム
（東ソー（株）製）を順次に三本連結して使用した。 「ＴＳＫ ＧＥＬ Ｇ−１０００Ｈ」 「ＴＳＫ ＧＥＬ Ｇ−２０００Ｈ」 「ＴＳＫ ＧＥＬ Ｇ−４０００Ｈ」 流出液：テトラヒドロフラン 流出速度：１ｍｌ／分 流出温度：４０℃(1) Molecular weight The molecular weight was measured by dissolving the resin in THF, filtering the insolubles, and then performing GPC measurement under the following conditions to determine the retention time known for polystyrene based on the retention time obtained. It is a polystyrene-equivalent molecular weight determined from the relationship of molecular weight. Separation column: The following three types of polystyrene packed columns (manufactured by Tosoh Corp.) were used by sequentially connecting three columns. "TSK GEL G-1000H""TSK GEL G-2000H""TSK GEL G-4000H" Effluent: Tetrahydrofuran Outflow rate: 1 ml / min Outflow temperature: 40 ° C
【００２７】（２）軟化点（Ｔｓ） 軟化点の測定は、高架式フローテスター（島津フローテ
スターＣＦＴ−５００形）を用いて行なう。具体的に
は、重量１．０ｇの試料を昇温速度３℃／ｍｉｎでプラ
ンジャーにより３０ｋｇｆの荷重をかけ、直径１ｍｍ、
長さ１０ｍｍのノズルより押し出し、得られた流出曲線
より軟化点を求める。(2) Softening point (Ts) The softening point is measured by using an elevated flow tester (Shimadzu flow tester CFT-500 type). Specifically, a sample having a weight of 1.0 g is applied with a load of 30 kgf by a plunger at a temperature rising rate of 3 ° C./min, a diameter of 1 mm,
The softening point is determined from the outflow curve obtained by extruding from a nozzle having a length of 10 mm.
【００２８】（３）ガラス転移温度（Ｔｇ） ガラス転移温度の測定はＡＳＴＭ Ｄ３４１８−８２に
準じて行なう。測定装置は例えばＰＳＣ７０００ (真空
理工（株）製）を用いれば良い。 （４）ＴＨＦ不溶分 試験管に試料１ｇをとり、テトラヒドロフラン（ＴＨ
Ｆ）１００ｍｌに溶解させ、２５℃で、１０時間撹拌し
た。濾過にてＴＨＦ不溶分をとり、これを風乾後、５０
℃で５時間真空乾燥し、重量を求めた。(3) Glass transition temperature (Tg) The glass transition temperature is measured according to ASTM D3418-82. As the measuring device, for example, PSC7000 (manufactured by Vacuum Riko Co., Ltd.) may be used. (4) THF-insoluble matter 1 g of a sample was placed in a test tube, and tetrahydrofuran (TH
F) It was dissolved in 100 ml and stirred at 25 ° C. for 10 hours. The THF insoluble matter was removed by filtration, air-dried, and then 50
It was vacuum dried at ℃ for 5 hours, and the weight was obtained.
【００２９】実施例１ 撹拌装置、窒素導入管、加熱装置、温度計、助剤添加口
を備えた容量５００ｍｌの反応容器内に、９０％ＤＬ乳
酸水溶液３００ｇ、酒石酸１４ｇ、テトラブトキシゲル
マニウム４００μｌを仕込んだ。容器内反応物を撹拌
下、窒素ガスを導入し、窒素ガス雰囲気下、１８０℃で
２時間反応させた後、３０ｍｍＨｇの減圧下において３
時間重縮合反応を行なった。引続き反応温度を２００℃
に昇温したところ、２．５時間でゲル化し、撹拌不能と
なったので、反応を終了した。得られたポリマーはＭｎ
＝４０６０、Ｍｗ＝２４１７０、ＴＨＦ不溶分は３０重
量％、Ｔｇ＝３８℃、Ｔｓ＝１１６℃であった。Example 1 300 g of 90% DL lactic acid aqueous solution, 14 g of tartaric acid, and 400 μl of tetrabutoxygermanium were charged into a reaction vessel having a capacity of 500 ml equipped with a stirrer, a nitrogen inlet tube, a heating device, a thermometer, and an auxiliary agent addition port. It is. Nitrogen gas was introduced into the reaction vessel while stirring, and the reaction was performed at 180 ° C. for 2 hours in a nitrogen gas atmosphere.
A time polycondensation reaction was performed. Continued reaction temperature at 200 ℃
When the temperature was raised to 2, gelation occurred in 2.5 hours and stirring became impossible, so the reaction was terminated. The polymer obtained is Mn
= 4060, Mw = 24170, THF insoluble content was 30% by weight, Tg = 38 ° C., Ts = 116 ° C.
【００３０】上記方法で得られたポリマー１００重量部
に対して、カーボンブラック（三菱化学（株）製、＃３
０）６重量部、ポリアルキレンワックス（三洋化成
（株）製、ビスコール５５０Ｐ）３重量部、ニグロシン
染料（オリエント化学（株）製、ボントロンＮ−０４）
２重量部を分散混合した後、二軸押出機を用いて溶融混
練した。冷却後、ハンマーミルで粗粉砕し、次いで超音
速ジェットミル粉砕機にて微粉砕した。得られた粉体を
風力分級機で分級し、平均粒径１０．１μｍのトナーＡ
を得た。With respect to 100 parts by weight of the polymer obtained by the above method, carbon black (# 3 manufactured by Mitsubishi Chemical Co., Ltd.) was used.
0) 6 parts by weight, polyalkylene wax (manufactured by Sanyo Chemical Co., Ltd., Viscole 550P) 3 parts by weight, nigrosine dye (manufactured by Orient Chemical Co., Ltd., Bontron N-04)
After 2 parts by weight were dispersed and mixed, they were melt-kneaded using a twin-screw extruder. After cooling, it was roughly crushed with a hammer mill and then finely crushed with a supersonic jet mill crusher. The powder obtained is classified by an air classifier, and toner A having an average particle size of 10.1 μm is used.
I got
【００３１】実施例２ 撹拌装置、窒素導入管、加熱装置、温度計、助剤添加口
を備えた容量５００ｍｌの反応容器内に、９０％ＤＬ乳
酸水溶液３００ｇ、酒石酸１４ｇ、テトラブトキシチタ
ン２００μｌを仕込んだ。容器内反応物を撹拌下、窒素
ガスを導入し、窒素ガス雰囲気下、１８０℃で２時間反
応させた後、３０ｍｍＨｇの減圧下において３時間重縮
合反応を行なった。引続き反応温度を２００℃に昇温し
たところ、２．５時間でゲル化し、撹拌不能となったの
で、反応を終了した。得られたポリマーはＭｎ＝５１０
０、Ｍｗ＝２８２２０、ＴＨＦ不溶分は３５重量％、Ｔ
ｇ＝３９℃、Ｔｓ＝１１９℃であった。上記方法で得ら
れたポリマー１００重量部を用い実施例１と同様にして
混練、粉砕、分級を行い、平均粒径１０．１μｍのトナ
ーＢを得た。Example 2 300 g of 90% DL lactic acid aqueous solution, 14 g of tartaric acid, and 200 μl of tetrabutoxytitanium were charged into a reaction vessel having a capacity of 500 ml equipped with a stirrer, a nitrogen introduction tube, a heating device, a thermometer, and an auxiliary agent addition port. It is. Nitrogen gas was introduced to the reaction product in the vessel with stirring, and the reaction was performed at 180 ° C. for 2 hours in a nitrogen gas atmosphere, and then a polycondensation reaction was performed for 3 hours under reduced pressure of 30 mmHg. When the reaction temperature was subsequently raised to 200 ° C., gelation occurred in 2.5 hours and stirring became impossible, so the reaction was terminated. The polymer obtained has Mn = 510
0, Mw = 28220, THF insoluble content 35% by weight, T
g = 39 ° C. and Ts = 119 ° C. Using 100 parts by weight of the polymer obtained by the above method, kneading, pulverization and classification were carried out in the same manner as in Example 1 to obtain a toner B having an average particle size of 10.1 μm.
【００３２】実施例３ 撹拌装置、窒素導入管、加熱装置、温度計、助剤添加口
を備えた容量５００ｍｌの反応容器内に、９０％ＤＬ乳
酸水溶液３００ｇ、２，５−ジヒドロキシテレフタル酸
２０ｇ、テトラブトキシゲルマニウム４００μｌを仕込
んだ。容器内反応物を撹拌下、窒素ガスを導入し、窒素
ガス雰囲気下、１８０℃で２時間反応させた後、３０ｍ
ｍＨｇの減圧下において３時間重縮合反応を行なった。
引続き反応温度を２００℃に昇温したところ、３．０時
間でゲル化し、撹拌不能となったので、反応を終了し
た。得られたポリマーはＭｎ＝６０００、Ｍｗ＝３１２
２０、ＴＨＦ不溶分は４０重量％、Ｔｇ＝４０℃、Ｔｓ
＝１２３℃であった。上記ポリマー１００重量部を用い
て、実施例１と同様にして混練、粉砕、分級を行い、平
均粒径１０．１μｍのトナーＣを得た。Example 3 300 g of 90% DL lactic acid aqueous solution, 20 g of 2,5-dihydroxyterephthalic acid were placed in a reaction vessel having a capacity of 500 ml equipped with a stirrer, a nitrogen inlet tube, a heating device, a thermometer, and an auxiliary agent addition port. 400 μl of tetrabutoxy germanium was charged. Nitrogen gas was introduced while stirring the reaction product in the vessel, and the reaction was performed at 180 ° C. for 2 hours in a nitrogen gas atmosphere, then 30 m
The polycondensation reaction was performed for 3 hours under reduced pressure of mHg.
When the reaction temperature was subsequently raised to 200 ° C., gelation occurred in 3.0 hours and stirring became impossible, so the reaction was terminated. The polymer obtained had Mn = 6000 and Mw = 312.
20, THF insoluble content is 40% by weight, Tg = 40 ° C., Ts
= 123 ° C. Using 100 parts by weight of the above polymer, kneading, pulverization and classification were carried out in the same manner as in Example 1 to obtain a toner C having an average particle size of 10.1 μm.
【００３３】実施例４ 撹拌装置、窒素導入管、加熱装置、温度計、助剤添加口
を備えた容量５００ｍｌの反応容器内に、９０％ＤＬ乳
酸水溶液３００ｇ、リンゴ酸６．７ｇ、エチレングリコ
ール１．６ｇ、テトラブトキシゲルマニウム４００μｌ
を仕込んだ。容器内反応物を撹拌下、窒素ガスを導入
し、窒素ガス雰囲気下、１８０℃で２時間反応させた
後、３０ｍｍＨｇの減圧下において３時間重縮合反応を
行なった。引続き反応温度を２００℃に昇温したとこ
ろ、３．０時間でゲル化し、撹拌不能となったので、反
応を終了した。得られたポリマーはＭｎ＝４１００、Ｍ
ｗ＝２５２００、ＴＨＦ不溶分は２０重量％、Ｔｇ＝３
８℃、Ｔｓ＝１２０℃であった。Example 4 300 g of 90% DL lactic acid aqueous solution, 6.7 g of malic acid and 1 part of ethylene glycol were placed in a reaction vessel having a capacity of 500 ml equipped with a stirrer, a nitrogen introducing tube, a heating device, a thermometer and an auxiliary agent addition port. 0.6 g, tetrabutoxy germanium 400 μl
Was charged. Nitrogen gas was introduced to the reaction product in the vessel with stirring, and the reaction was performed at 180 ° C. for 2 hours in a nitrogen gas atmosphere, and then a polycondensation reaction was performed for 3 hours under reduced pressure of 30 mmHg. When the reaction temperature was subsequently raised to 200 ° C., gelation occurred in 3.0 hours and stirring became impossible, so the reaction was terminated. The polymer obtained has Mn = 4100, M
w = 25200, THF insoluble content 20% by weight, Tg = 3
It was 8 ° C. and Ts = 120 ° C.
【００３４】上記ポリマー１００重量部を用いて、実施
例１と同様にして混練、粉砕、分級を行い、平均粒径１
０．１μｍのトナーＤを得た。トナーＡ、Ｂ、Ｃ、Ｄを
用いて、以下の試験を行なった。 定着テスト：未定着のトナーを４００ｍｍ／ｓｅｃの定
着ローラーに通紙し、定着する下限温度とホットオフセ
ットが発生する温度を調べた。 耐ブロッキングテスト：トナーに一定荷重を加え、放置
した後のブロッキング性の良否を判定した。 こすり残存率テスト：種々の付着量を有する未定着トナ
ーを１５０℃、４００ｍｍ／ｓｅｃの定着ローラーに通
紙後、こすり試験を行った。こすり残存率を下式より求
め、その最小値を最低こすり残存率と定義した。Using 100 parts by weight of the above polymer, kneading, pulverization and classification were carried out in the same manner as in Example 1 to obtain an average particle size of 1
Toner D of 0.1 μm was obtained. The following tests were conducted using Toners A, B, C and D. Fixing test: Unfixed toner was passed through a fixing roller of 400 mm / sec, and the lower limit temperature for fixing and the temperature at which hot offset occurred were examined. Blocking resistance test: A constant load was applied to the toner, and the blocking property after standing was judged. Rubbing residual rate test: Unfixed toner having various amounts of adhesion was passed through a fixing roller at 150 ° C. and 400 mm / sec, and then a rubbing test was performed. The rubbing residual rate was obtained from the following formula, and the minimum value was defined as the minimum rubbing residual rate.
【００３５】[0035]
【数１】 [Equation 1]
【００３６】結果を表−１に示す。The results are shown in Table 1.
【００３７】[0037]
【表１】 [Table 1]
【００３８】[0038]
【発明の効果】本発明により、定着性、定着強度、耐オ
フセット性、および耐ブロッキング性に優れた生分解性
を有するトナーを得ることができる。According to the present invention, a toner having excellent biodegradability, which is excellent in fixing property, fixing strength, offset resistance and blocking resistance, can be obtained.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山岡 弘明 神奈川県横浜市青葉区鴨志田町1000番地 三菱化学株式会社横浜総合研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroaki Yamaoka 1000 Kamoshida-cho, Aoba-ku, Yokohama-shi, Kanagawa Mitsubishi Chemical Corporation Yokohama Research Institute
Claims (5)
酸を含有する組成物を脱水重縮合して得られたポリエス
テル樹脂および着色剤を含有することを特徴とする静電
荷像現像用トナー。1. A toner for developing an electrostatic charge image, which comprises a polyester resin obtained by dehydration polycondensation of a composition containing lactic acid and a trifunctional or higher functional oxycarboxylic acid, and a colorant.
重量比（乳酸：３官能以上のオキシカルボン酸）が８
０：２０〜９９．９：０．１であることを特徴とする請
求項１に記載の静電荷像現像用トナー。2. The weight ratio of lactic acid to trifunctional or higher functional oxycarboxylic acid (lactic acid: trifunctional or higher functional oxycarboxylic acid) is 8.
The toner for developing an electrostatic charge image according to claim 1, which is 0:20 to 99.9: 0.1.
００以上であることを特徴とする請求項１または２に記
載の静電荷像現像用トナー。3. A polyester resin having a number average molecular weight of 20.
The toner for developing an electrostatic charge image according to claim 1 or 2, wherein the toner is at least 00.
不溶分が１０〜８０重量％であることを特徴とする請求
項１乃至３に記載の静電荷像現像用トナー。4. The toner for developing an electrostatic charge image according to claim 1, wherein the tetrahydrofuran insoluble matter of the polyester resin is 10 to 80% by weight.
〜８０℃であり、軟化点が６０〜１７０℃であることを
特徴とする請求項１乃至４に記載の静電荷像現像用トナ
ー。5. The glass transition point of the polyester resin is 30.
The toner for developing an electrostatic charge image according to any one of claims 1 to 4, wherein the toner has a softening point of 60 to 170 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8502496A JPH09274335A (en) | 1996-04-08 | 1996-04-08 | Toner for developing electrostatic charge image |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8502496A JPH09274335A (en) | 1996-04-08 | 1996-04-08 | Toner for developing electrostatic charge image |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09274335A true JPH09274335A (en) | 1997-10-21 |
Family
ID=13847166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8502496A Pending JPH09274335A (en) | 1996-04-08 | 1996-04-08 | Toner for developing electrostatic charge image |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09274335A (en) |
Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6777153B2 (en) | 2001-03-27 | 2004-08-17 | Canon Kabushiki Kaisha | Polyhydroxyalkanoate containing unit with thienyl structure in the side chain, process for its production, charge control agent, toner binder and toner which contain this polyhydroxyalkanoate, and image-forming method and image-forming apparatus which make use of the toner |
| US6808854B2 (en) | 2001-04-27 | 2004-10-26 | Canon Kabushiki Kaisha | Polyhydroxyalkanoates having in its side chain phenylsulfinyl structure and/or phenyl sulfonyl structure and production process therefor; charge control agent, toner binder and toner containing same; and image forming method and image forming apparatus using the toner |
| US6828074B2 (en) | 2001-04-27 | 2004-12-07 | Canon Kabushiki Kaisha | Binder resin containing polyhydroxyalkanoate, toner containing the binder resin, and image-forming method and image-forming apparatus which make use of the toner |
| US6855472B2 (en) | 2001-04-27 | 2005-02-15 | Canon Kabushiki Kaisha | Polyhydroxyalkanoate, producing method therefor, charge control agent containing such polyhydroxyalkanoate, toner containing such control agent and image forming method and image forming apparatus utilizing such toner |
| US6858367B2 (en) | 2001-04-27 | 2005-02-22 | Canon Kabushiki Kaisha | Binder resin containing novel polyhydroxyalkanoate, toner containing the binder resin, and image-forming method and image-forming apparatus which make use of the toner |
| WO2005038531A1 (en) * | 2003-10-16 | 2005-04-28 | Mitsui Chemicals, Inc. | Resin microparticle as raw material for toner, dispersion system thereof and toner |
| US6908721B2 (en) | 2002-02-15 | 2005-06-21 | Canon Kabushiki Kaisha | Polyhydroxyalkanoate having amide group and sulfonic group, method of producing the same, charge controlling agent containing novel polyhydroxyalaknaote, toner binder, toner, and image forming apparatus using the toner |
| US6911520B2 (en) | 2002-02-28 | 2005-06-28 | Canon Kabushiki Kaisha | Polyhydroxyalkanoate, method of producing the same, charge controlling agent containing polyhydroxyalkanoate, toner binder and toner, and image formation method and image forming apparatus using toner |
| JP2006284614A (en) * | 2005-03-31 | 2006-10-19 | Ricoh Co Ltd | Toner for electrostatic image development, developer, image forming method and image forming apparatus |
| EP1744222A2 (en) | 2005-07-15 | 2007-01-17 | Ricoh Company, Ltd. | Toner, developer, image forming method, and toner container |
| US7351786B2 (en) | 2002-10-24 | 2008-04-01 | Canon Kabushiki Kaisha | Polyhydroxyalkanoate containing unit having cyclohexyl structure at side chain, production process therefor, and binder resin containing polyhydroxyalkanoate |
| US7452960B2 (en) | 2002-10-24 | 2008-11-18 | Canon Kabushiki Kaisha | Polyhydroxyalkanoate copolymer, resin composition, molded product, toner, image forming method and image forming apparatus |
| US7459517B2 (en) | 2002-10-24 | 2008-12-02 | Canon Kabushiki Kaisha | Polyhydroxyalkanoate, process for preparing the same, and resin composition containing the polyhydroxyalkanoate |
| JP2010169764A (en) * | 2009-01-20 | 2010-08-05 | Casio Electronics Co Ltd | Electrophotographic toner |
| JP2010266839A (en) * | 2009-01-22 | 2010-11-25 | Ricoh Co Ltd | Toner |
| JP2010271583A (en) * | 2009-05-22 | 2010-12-02 | Casio Electronics Co Ltd | Electrophotographic toner |
| EP2270603A1 (en) | 2009-06-30 | 2011-01-05 | Ricoh Company, Ltd. | Electrostatic image developing toner, developer and image forming apparatus |
| JP2012037585A (en) * | 2010-08-03 | 2012-02-23 | Casio Electronics Co Ltd | Electrophotographic toner using bioplastic |
| JP2012108181A (en) * | 2010-11-15 | 2012-06-07 | Casio Electronics Co Ltd | Electrophotographic toner using bioplastic |
| JP2012141542A (en) * | 2011-01-06 | 2012-07-26 | Ricoh Co Ltd | Toner for image formation, two-component developer, image forming method, image forming apparatus, and process cartridge |
| DE112010003903T5 (en) | 2009-10-01 | 2012-11-15 | Kao Corp. | Polyester for toner |
| US8383307B2 (en) | 2008-10-23 | 2013-02-26 | Ricoh Company, Limited | Toner, developer, and image forming method and apparatus using the toner |
| JP2013515060A (en) * | 2009-12-21 | 2013-05-02 | エボニック デグサ コーポレイション | Process for preparing cyclic esters containing unsaturated functional groups and polyesters prepared therefrom |
| US8603713B2 (en) | 2009-02-26 | 2013-12-10 | Ricoh Company, Limited | Toner, and developer, toner cartridge, image forming apparatus, process cartridge and image forming method using the same |
| US8623580B2 (en) | 2009-08-03 | 2014-01-07 | Ricoh Company, Ltd. | Toner, developer, image forming method and image forming apparatus |
| US8741520B2 (en) | 2008-07-01 | 2014-06-03 | Ricoh Company, Ltd. | Image forming toner, image forming apparatus, image forming method, and process cartridge |
| US8877415B2 (en) | 2012-03-14 | 2014-11-04 | Ricoh Company, Ltd. | Toner, method of manufacturing toner, developer, toner container, image forming method, and process cartridge |
| US8883386B2 (en) | 2010-01-08 | 2014-11-11 | Sk Chemicals Co., Ltd. | Polyester resin and toner including same |
-
1996
- 1996-04-08 JP JP8502496A patent/JPH09274335A/en active Pending
Cited By (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6777153B2 (en) | 2001-03-27 | 2004-08-17 | Canon Kabushiki Kaisha | Polyhydroxyalkanoate containing unit with thienyl structure in the side chain, process for its production, charge control agent, toner binder and toner which contain this polyhydroxyalkanoate, and image-forming method and image-forming apparatus which make use of the toner |
| US6808854B2 (en) | 2001-04-27 | 2004-10-26 | Canon Kabushiki Kaisha | Polyhydroxyalkanoates having in its side chain phenylsulfinyl structure and/or phenyl sulfonyl structure and production process therefor; charge control agent, toner binder and toner containing same; and image forming method and image forming apparatus using the toner |
| US6828074B2 (en) | 2001-04-27 | 2004-12-07 | Canon Kabushiki Kaisha | Binder resin containing polyhydroxyalkanoate, toner containing the binder resin, and image-forming method and image-forming apparatus which make use of the toner |
| US6855472B2 (en) | 2001-04-27 | 2005-02-15 | Canon Kabushiki Kaisha | Polyhydroxyalkanoate, producing method therefor, charge control agent containing such polyhydroxyalkanoate, toner containing such control agent and image forming method and image forming apparatus utilizing such toner |
| US6858367B2 (en) | 2001-04-27 | 2005-02-22 | Canon Kabushiki Kaisha | Binder resin containing novel polyhydroxyalkanoate, toner containing the binder resin, and image-forming method and image-forming apparatus which make use of the toner |
| US6908721B2 (en) | 2002-02-15 | 2005-06-21 | Canon Kabushiki Kaisha | Polyhydroxyalkanoate having amide group and sulfonic group, method of producing the same, charge controlling agent containing novel polyhydroxyalaknaote, toner binder, toner, and image forming apparatus using the toner |
| US6911520B2 (en) | 2002-02-28 | 2005-06-28 | Canon Kabushiki Kaisha | Polyhydroxyalkanoate, method of producing the same, charge controlling agent containing polyhydroxyalkanoate, toner binder and toner, and image formation method and image forming apparatus using toner |
| US7351786B2 (en) | 2002-10-24 | 2008-04-01 | Canon Kabushiki Kaisha | Polyhydroxyalkanoate containing unit having cyclohexyl structure at side chain, production process therefor, and binder resin containing polyhydroxyalkanoate |
| US7459517B2 (en) | 2002-10-24 | 2008-12-02 | Canon Kabushiki Kaisha | Polyhydroxyalkanoate, process for preparing the same, and resin composition containing the polyhydroxyalkanoate |
| US7452960B2 (en) | 2002-10-24 | 2008-11-18 | Canon Kabushiki Kaisha | Polyhydroxyalkanoate copolymer, resin composition, molded product, toner, image forming method and image forming apparatus |
| KR100767855B1 (en) * | 2003-10-16 | 2007-10-17 | 미쓰이 가가쿠 가부시키가이샤 | Resin microparticle as raw material for toner, dispersion system thereof and toner |
| JPWO2005038531A1 (en) * | 2003-10-16 | 2007-11-22 | 三井化学株式会社 | Resin fine particles for toner raw material, aqueous dispersion thereof, and toner |
| US8247153B2 (en) | 2003-10-16 | 2012-08-21 | Mitsui Chemicals, Inc. | Process for producing resin microparticles for a toner raw material |
| WO2005038531A1 (en) * | 2003-10-16 | 2005-04-28 | Mitsui Chemicals, Inc. | Resin microparticle as raw material for toner, dispersion system thereof and toner |
| JP4624925B2 (en) * | 2003-10-16 | 2011-02-02 | 三井化学株式会社 | Resin fine particles for toner raw material, aqueous dispersion thereof, and toner |
| JP2006284614A (en) * | 2005-03-31 | 2006-10-19 | Ricoh Co Ltd | Toner for electrostatic image development, developer, image forming method and image forming apparatus |
| EP1744222A2 (en) | 2005-07-15 | 2007-01-17 | Ricoh Company, Ltd. | Toner, developer, image forming method, and toner container |
| US8741520B2 (en) | 2008-07-01 | 2014-06-03 | Ricoh Company, Ltd. | Image forming toner, image forming apparatus, image forming method, and process cartridge |
| US8383307B2 (en) | 2008-10-23 | 2013-02-26 | Ricoh Company, Limited | Toner, developer, and image forming method and apparatus using the toner |
| JP2010169764A (en) * | 2009-01-20 | 2010-08-05 | Casio Electronics Co Ltd | Electrophotographic toner |
| JP2010266839A (en) * | 2009-01-22 | 2010-11-25 | Ricoh Co Ltd | Toner |
| US8632932B2 (en) | 2009-01-22 | 2014-01-21 | Ricoh Company, Limited | Toner, color toner set, developer, process cartridge, and image forming method |
| US8603713B2 (en) | 2009-02-26 | 2013-12-10 | Ricoh Company, Limited | Toner, and developer, toner cartridge, image forming apparatus, process cartridge and image forming method using the same |
| JP2010271583A (en) * | 2009-05-22 | 2010-12-02 | Casio Electronics Co Ltd | Electrophotographic toner |
| US8691486B2 (en) | 2009-06-30 | 2014-04-08 | Ricoh Company, Ltd. | Electrostatic image developing toner, developer, image forming apparatus, image forming method, and process cartridge |
| EP2270603A1 (en) | 2009-06-30 | 2011-01-05 | Ricoh Company, Ltd. | Electrostatic image developing toner, developer and image forming apparatus |
| US8623580B2 (en) | 2009-08-03 | 2014-01-07 | Ricoh Company, Ltd. | Toner, developer, image forming method and image forming apparatus |
| DE112010003903T5 (en) | 2009-10-01 | 2012-11-15 | Kao Corp. | Polyester for toner |
| US8835087B2 (en) | 2009-10-01 | 2014-09-16 | Kao Corporation | Polyester for toner |
| JP2013515060A (en) * | 2009-12-21 | 2013-05-02 | エボニック デグサ コーポレイション | Process for preparing cyclic esters containing unsaturated functional groups and polyesters prepared therefrom |
| US8883386B2 (en) | 2010-01-08 | 2014-11-11 | Sk Chemicals Co., Ltd. | Polyester resin and toner including same |
| JP2012037585A (en) * | 2010-08-03 | 2012-02-23 | Casio Electronics Co Ltd | Electrophotographic toner using bioplastic |
| JP2012108181A (en) * | 2010-11-15 | 2012-06-07 | Casio Electronics Co Ltd | Electrophotographic toner using bioplastic |
| JP2012141542A (en) * | 2011-01-06 | 2012-07-26 | Ricoh Co Ltd | Toner for image formation, two-component developer, image forming method, image forming apparatus, and process cartridge |
| US8877415B2 (en) | 2012-03-14 | 2014-11-04 | Ricoh Company, Ltd. | Toner, method of manufacturing toner, developer, toner container, image forming method, and process cartridge |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH09274335A (en) | Toner for developing electrostatic charge image | |
| JPH09281746A (en) | Electrostatic charge image developing toner | |
| US6383705B2 (en) | Toner for electrophotography | |
| JP6547976B2 (en) | Binder resin composition for toner | |
| JP4830631B2 (en) | Resin particle dispersion for electrostatic image developing toner and method for producing the same, electrostatic image developing toner and method for producing the same, electrostatic image developer and image forming method | |
| US20070092822A1 (en) | Method of producing toner for developing electrostatic charge image, toner for developing electrostatic charge image, developer for electrostatic charge image and method for forming image | |
| JP2004226569A (en) | Crystalline polyester | |
| WO2003001302A1 (en) | Polyester resin for toner, process for producing polyester resin for toner, and toner containing the same | |
| JP2785176B2 (en) | Electrophotographic toner and method for producing the same | |
| JP2003057875A (en) | Electrophotographic toner | |
| KR100609344B1 (en) | Binder resin for toner and toner | |
| JP3075696B2 (en) | Polyester resin for toner, method for producing the same, and toner for electrophotography using the same | |
| JPH11106494A (en) | Polyester resin, its production and use | |
| JP3133015B2 (en) | Polyester resin for toner, method for producing the same, and toner for electrophotography using the same | |
| JP2017146593A (en) | Electrophotographic toner | |
| JP5912819B2 (en) | Binder resin for toner | |
| JP3065994B2 (en) | Electrophotographic toner binder | |
| KR101250887B1 (en) | Polyester resin and toner including the same | |
| JP3521505B2 (en) | Polyester resin and toner for toner | |
| JPS62276565A (en) | Electrostatic image developing toner | |
| JPS6368853A (en) | Electrophotographic developer composition | |
| JPH10123756A (en) | Polyester resin for toner, its production and electrophotographic toner using the same | |
| JPH09152743A (en) | Polyester resin for toner binder, its production and toner using the polyester resin | |
| JP4776112B2 (en) | Crystalline polyester | |
| JP4035704B2 (en) | Resin composition for toner, method for producing the same, toner, and image forming method |