JPH09281746A - Electrostatic charge image developing toner - Google Patents
Electrostatic charge image developing tonerInfo
- Publication number
- JPH09281746A JPH09281746A JP9092796A JP9092796A JPH09281746A JP H09281746 A JPH09281746 A JP H09281746A JP 9092796 A JP9092796 A JP 9092796A JP 9092796 A JP9092796 A JP 9092796A JP H09281746 A JPH09281746 A JP H09281746A
- Authority
- JP
- Japan
- Prior art keywords
- toner
- polylactic acid
- electrostatic charge
- charge image
- weight
- 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、定着強
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, it 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 strength, 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】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号明
細中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。しかしポリ乳酸をそのまま
トナー化した場合、トナーの保存性、耐オフセット性に
問題があり、未だ実用化には到っていない。From this point of view, since it has biodegradability, is efficiently decomposed in alkaline hydrolysis, and is useful for paper recycling, it is mainly composed of an aliphatic polyester mainly containing polyhydroxycarboxylic acid. Toners have been proposed. For example, Japanese Patent Application Laid-Open No. 7-120975 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. However, when polylactic acid is used as a toner as it is, there is a problem in the storage stability and offset resistance of the toner, and it has not yet been put to practical use.
【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号公報中に
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さ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 crosslinked with trimellitic anhydride, glycerin or trimethylolpropane. However, these have the drawbacks that the crosslinkability is poor, the fixability, particularly the offset resistance is not sufficient, and the heat roller is easily soiled by the toner.
【０００８】[0008]
【発明が解決しようとする課題】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。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems and provides a fixability (low-temperature fixability, fix temperature, offset resistance) and resistance which is mainly composed of an aliphatic polyester having biodegradability. As a result of intensive studies to provide a toner excellent in blocking property, a toner satisfying the above-mentioned performance has been completed.
【０００９】[0009]
【課題を解決するための手段】すなわち、本発明の要旨
は、ポリ乳酸を３官能以上の多価イソシアナートにより
架橋して得られるウレタン化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
に存する。Means for Solving the Problems That is, the gist of the present invention is that it contains a urethanated polyester resin obtained by crosslinking polylactic acid with a polyfunctional isocyanate having a functionality of 3 or more and a colorant. It exists in the toner for charge image development.
【００１０】[0010]
【発明の実施の形態】本発明に用いられるトナーは、脱
水縮合あるいは開環反応により得られたポリ乳酸、好ま
しくは脱水縮合により得られたポリ乳酸に、３官能以上
の多価イソシアナートを反応せしめることにより得られ
るウレタン化ポリエステル樹脂を含有する（好ましくは
バインダー樹脂の主成分として含有する）ものである。
このウレタン化ポリエステル樹脂は３官能以上の多価イ
ソシアナートにより、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（ＴＨＦ）不溶分を目安と
して表される。BEST MODE FOR CARRYING OUT THE INVENTION In the toner used in the present invention, polylactic acid obtained by dehydration condensation or ring-opening reaction, preferably polylactic acid obtained by dehydration condensation is reacted with trifunctional or higher functional polyisocyanate. It contains a urethanized polyester resin obtained by hardening (preferably as a main component of a binder resin).
This urethanized polyester resin has a gel component crosslinked with a polyfunctional isocyanate having a functionality of 3 or more, and the amount of the gel component is represented by using tetrahydrofuran (THF) insoluble matter as a guide.
【００１１】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更に好ま
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. More preferably.
【００１２】本発明に使用される３官能以上の多価イソ
シアナートとしては、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が、生分解性であると
いう見地からすれば、脂肪族のタイプのものが好まし
い。具体的には、リジントリイソシアナート、ヘキサメ
チレンジイソシアナートの環状３量体などが入手が容易
であるという点から好ましい。The tri- or higher functional polyvalent isocyanate used in the present invention includes an aromatic type and an aliphatic type, both of which can be used, but from the viewpoint of being biodegradable. The aliphatic type is preferable. Specifically, lysine triisocyanate, hexamethylene diisocyanate cyclic trimer and the like are preferable because they are easily available.
【００１３】３官能以上の多価イソシアナート成分の添
加によるゲル成分の存在は、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、撹拌が不良となり、均一な撹
拌が出来ない。従って３官能以上の多価イソシアナート
の添加量は、通常０．１〜５０重量％、好ましくは１〜
３０重量％、より好ましくは３〜２０重量％である。ま
たテトラヒドロフラン不溶分は、通常１０〜８０重量
％、好ましくは２０〜７０重量％、より好ましくは３０
〜６０重量％である。ＴＨＦ不溶分の測定は、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℃、１０時間で溶解させ、濾過後の不溶分
の重量を測定することにより求めた。The presence of the gel component due to the addition of the trifunctional or higher polyvalent isocyanate component broadens the molecular weight distribution of the resin,
At the same time as having the effect of increasing the glass transition temperature, elasticity can be imparted 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 at the time of polymerization, stirring becomes poor, and uniform stirring cannot be performed. Therefore, the amount of trifunctional or higher polyvalent isocyanate added is usually 0.1 to 50% by weight, preferably 1 to
It is 30% by weight, more preferably 3 to 20% by weight. The tetrahydrofuran insoluble content is usually 10 to 80% by weight, preferably 20 to 70% by weight, more preferably 30% by weight.
６０60% by weight. The THF-insoluble matter was measured 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 weight of the insoluble matter after filtration.
【００１４】本発明における３官能以上の多価イソシア
ナートで架橋させたポリ乳酸を含有するバインダー樹脂
の製造法は、乳酸の脱水重縮合法またはラクチドの開環
反応により得られたポリ乳酸に、３官能以上の多価イソ
シアナートを重付加により反応せしめるものである。こ
こで言うラクチドの開環反応とは、精製した乳酸の環状
二量体（ラクチド）を原料とし、スズ系化合物等の触媒
存在下で加熱反応（１４０〜２００℃）することにより
得られる。また、ここで言う乳酸の脱水重縮合法とは、
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。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、さらにはこれらの混合物などが挙げられる。The method for producing a binder resin containing polylactic acid crosslinked with a trifunctional or higher functional polyisocyanate in the present invention is a polylactic acid obtained by a dehydration polycondensation method of lactic acid or a ring-opening reaction of lactide. A polyfunctional isocyanate having a functionality of 3 or more is reacted by polyaddition. The ring-opening reaction of lactide referred to herein is obtained by using a purified cyclic dimer of lactic acid (lactide) as a raw material and performing a heating reaction (140 to 200 ° C.) in the presence of a catalyst such as a tin compound. Further, the dehydration polycondensation method of lactic acid referred to here is
This is a radically different production method from the so-called ring-opening polymerization using lactide as a raw material. The ring-opening polymerization is basically polyaddition, whereas this method is polycondensation. A solvent may be used for the dehydration polycondensation, but since it basically leads to an increase in cost, 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 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 tetraethoxy germanium and tetrabutoxy germanium, and a mixture thereof.
【００１５】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。減圧度は、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。ポリ乳酸の数平均分子量
は２０００以上であることが好ましい。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. The degree of reduced pressure is usually normal pressure to 2 mmHg, and finally 30 to 5 mmHg is preferable. Although it depends on the reaction temperature, in general, at 2 mmHg or less,
Lactide is easily generated. The number average molecular weight of polylactic acid is preferably 2000 or more.
【００１６】ウレタン化ポリエステルの製造におけるウ
レタン化反応は、上記の方法で得られた溶融状態のポリ
乳酸に３官能以上の多価イソシアナートを添加すること
により行われる。反応温度は１００〜２２０℃、好まし
くは１２０〜２００℃、さらに好ましくは１４０〜１８
０℃で、常圧〜２ｍｍＨｇの圧力下で行われる。２２０
℃を超えると、ポリマーの熱分解が起こり、好ましくな
い。ウレタン化ポリエステル樹脂中の乳酸成分は５０〜
９９．９重量％であることが好ましい。The urethanization reaction in the production of the urethanized polyester is carried out by adding a polyfunctional isocyanate having a functionality of 3 or more to the polylactic acid in a molten state obtained by the above method. The reaction temperature is 100 to 220 ° C, preferably 120 to 200 ° C, more preferably 140 to 18 ° C.
It is carried out at 0 ° C. under normal pressure to a pressure of 2 mmHg. 220
If the temperature exceeds ℃, thermal decomposition of the polymer occurs, which is not preferable. The lactic acid component in the urethanized polyester resin is 50-
It is preferably 99.9% by weight.
【００１７】本発明のトナーに使用されるウレタン化ポ
リエステル樹脂のガラス転移温度は３０〜８０℃、好ま
しくは４０〜７０℃、さらに好ましくは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高くなる。また本
発明におけるウレタン化ポリエステル樹脂の軟化点は、
好ましくは６０〜１７０℃、さらに好ましくは８０〜１
４０℃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。The glass transition temperature of the urethanized polyester resin used in the toner of the present invention is 30 to 80 ° C, preferably 40 to 70 ° C, more preferably 50 to 70 ° C. If the value is lower than 30 ° C, the blocking property will be poor, and if it is 80 ° C or higher, the fixing property will be high. The softening point of the urethanized polyester resin in the present invention is
Preferably 60 to 170 ° C., more preferably 80 to 1
40 ° 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 is high.
【００１８】本発明のウレタン化ポリエステル樹脂は、
重量平均分子量Ｍｗが好ましくは５０００〜３０万であ
り、数平均分子量Ｍｎが好ましくは２０００〜１０万、
特に好ましくは７０００〜５万である。重量平均分子量
Ｍｗが、５０００未満ではガラス転移温度が著しく低下
し、耐ブロッキング性が悪くなり、また３０万を超える
と溶融時における粘度が高くなり、低温定着性が悪化す
る。数平均分子量Ｍｎについても同じことが言える。The urethanized polyester resin of the present invention is
The weight average molecular weight Mw is preferably 5,000 to 300,000, and the number average molecular weight Mn is preferably 2,000 to 100,000.
Particularly preferably, it is 7,000 to 50,000. When the weight average molecular weight Mw is less than 5,000, the glass transition temperature is remarkably lowered and the blocking resistance is deteriorated, and when it exceeds 300,000, the viscosity at the time of melting is increased and the low temperature fixing property is deteriorated. The same applies to the number average molecular weight Mn.
【００１９】所望の物性のウレタン化ポリエステル樹脂
は、ポリ乳酸の製造条件、架橋剤の使用量及び反応条件
を適宜選択することにより得られる。例えば、分子量を
上げるには重合時間を長くする、あるいは減圧度を高め
る等の手段が採られ、ガラス転移温度、軟化点を上げる
には樹脂の分子量を上げるか、または樹脂中のオリゴマ
ー成分を除去する等の手段が採られる。The urethane-modified polyester resin having desired physical properties can be obtained by appropriately selecting the production conditions of polylactic acid, the amount of the crosslinking agent used, and the reaction conditions. For example, in order to increase the molecular weight, a means such as increasing the polymerization time or increasing the degree of reduced pressure is adopted. To increase the glass transition temperature and softening point, the molecular weight of the resin is increased or the oligomer component in the resin is removed. Means such as
【００２０】本発明のトナーは、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。To improve the fixing property, the toner of the present invention may further contain 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. The aliphatic polyester mainly composed of an aliphatic diol and an aliphatic dicarboxylic acid is not particularly limited, but polybutylene succinate, polybutylene adipate, polyethylene succinate, polyethylene adipate, or a small amount of aliphatic oxycarboxylic acid copolymerized therewith. It may be something.
【００２１】本発明トナーは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、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１００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. Further, if necessary, various additives used in 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 the colorant is about 3 to 20 parts by weight with respect to 100 parts by weight of the binder resin.
【００２２】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、或い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
とができる。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.
As the magnetic substance which can be used in any of the component developers and which is used in the one-component developer, an alloy showing ferromagnetism such as iron, cobalt, nickel and the like such as ferrite and magnetite, or a compound or a ferromagnetic element is used. An alloy that does not contain, but becomes ferromagnetic by proper heat treatment,
Examples thereof include manganese-copper-aluminum, manganese-copper-tin, and other types of alloys called Heusler alloys containing manganese and copper, or chromium dioxide. 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.
【００２３】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、含金染料、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。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, a metal-containing dye, an acidic or electron-withdrawing organic substance, and the like can be used. .
【００２４】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 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 of the binder resin. 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.
【００２５】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誘電体、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。その添加量
は、バインダー樹脂１００重量部に対して、０．１〜１
０重量部が適当である。さらに、トナー粒子に対して、
ＴｉＯ2 、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重量部に対して０．
１〜１０重量部が好ましい。Furthermore, a solid electrolyte, a polymer electrolyte,
The electrical properties of the toner can be controlled by adding a charge transfer complex, a dielectric such as a metal oxide such as tin oxide, a semiconductor, or a ferroelectric or a magnetic material. 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 addition amount is 0.1 to 1 with respect to 100 parts by weight of the binder resin.
0 parts by weight is suitable. Furthermore, for toner particles,
Add fine powder such as TiO 2 , Al 2 O 3 and SiO 2 ,
By coating the surface of the toner particles with these, the fluidity and aggregation resistance of the toner can be improved. The amount of addition is 0.1% with respect to 100 parts by weight of the binder resin.
1 to 10 parts by weight is preferred.
【００２６】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
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。Various conventionally used toner production methods can be applied to the toner production method of the present invention. For example, the following examples can be given as general production methods. First of all, a resin, a colorant (in some cases, a charge control agent, etc.), a ball mill
Disperse uniformly with a V-type mixer, S-type mixer, Henschel mixer, or the like. Then, the dispersion is melt-kneaded with a double-arm kneader, a pressure kneader or the like. The mixture is crushed by a crusher such as a hammer mill, a jet mill or a ball mill, and the obtained powder is classified by an air classifier or the like.
【００２７】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、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, a ferrite carrier or the like or a material having a coating on the surface thereof for 1 part of the toner.
【００２８】[0028]
【実施例】以下、本発明の具体的実施例について説明す
るが、本発明はこれらの実施例に限定されるものではな
い。なお、分子量、軟化点（Ｔｓ）、架橋度の目安とし
てのＴＨＦ不溶分の測定は次の測定方法により行った。EXAMPLES Hereinafter, specific examples of the present invention will be described, but the present invention is not limited to these examples. The THF-insoluble matter as a measure of the molecular weight, the softening point (Ts) and the degree of crosslinking was measured by the following measuring method.
【００２９】（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 and filtering the insoluble matter, and then performing GPC measurement under the following conditions. Based on the obtained retention time, the known retention time for polystyrene was determined. 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
【００３０】（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、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, pushed from a nozzle having a diameter of 1 mm and a length of 10 mm, and the softening point is obtained from the obtained outflow curve.
【００３１】（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ＤＳＣ７０００（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２５０℃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.
Perform according to. As the measuring device, for example, DSC7000 (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 250 ° C. for 10 hours. The THF insoluble matter was removed by filtration, air-dried, and then 50
It was vacuum dried at 5 ° C. for 5 hours and the weight was determined.
【００３２】実施例１ 撹拌装置、窒素道入管、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３００ｇ、テトラブトキシゲルマニウム２４０μｌを
仕込んだ。容器内容物を撹拌下、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、２時間反応させた。引き続いて温度を
２２０℃とし、２０ｍｍＨｇの減圧下において８時間重
縮合を行ったところ、Ｍｎ＝４６６０、Ｍｗ＝８７９０
の透明なポリ乳酸が得られた。このポリ乳酸樹脂２００
ｇにヘキサメチレンジイソシアナートの環状３量体３２
ｇを添加し、１４０℃で反応させて、Ｍｎ＝９８００、
Ｍｗ＝２９６３０、ＴＨＦ不溶分４５重量％、Ｔｇ＝３
９℃、Ｔｓ＝１１８℃のウレタン化ポリ乳酸を得た。Example 1 300 g of 90% DL lactic acid and 240 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. Nitrogen gas was introduced with stirring the contents of the container, and after reacting for 2 hours at 180 ° C. in a nitrogen gas atmosphere, 30 m
The reaction was performed for 2 hours under reduced pressure of mHg. Subsequently, when the temperature was set to 220 ° C. and polycondensation was performed for 8 hours under a reduced pressure of 20 mmHg, Mn = 4660 and Mw = 8790.
As a result, transparent polylactic acid was obtained. This polylactic acid resin 200
hexamethylene diisocyanate cyclic trimer 32
g, and reacted at 140 ° C., Mn = 9800,
Mw = 29630, THF insoluble matter 45% by weight, Tg = 3
A urethanized polylactic acid having 9 ° C. and Ts = 118 ° C. was obtained.
【００３３】上記の方法で得られたウレタン化ポリ乳酸
樹脂（トナー用樹脂）１００重量部に対してカーボンブ
ラック（三菱化学（株）製、＃３０）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５５
０Ｐ）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。6 parts by weight of carbon black (# 30 manufactured by Mitsubishi Chemical Co., Ltd.), polyalkylene wax (Sanyo Chemical ( Co., Ltd., Viscole 55
3 parts by weight of 0P) and 2 parts by weight of nigrosine dye (Bontron N-04 manufactured by Orient Chemical Co., Ltd.) were dispersed and mixed, and then 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 obtained powder is classified with an air classifier,
Toner A having an average particle size of 10.1 μm was obtained.
【００３４】実施例２ 撹拌装置、窒素道入管、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３００ｇ、テトラブトキシゲルマニウム２４０μｌを
仕込んだ。容器内容物を撹拌下、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、２時間反応させた。引き続いて温度を
２２０℃とし、２０ｍｍＨｇの減圧下において１０時間
重縮合を行ったところ、Ｍｎ＝８２６０、Ｍｗ＝２３５
２０の透明なポリ乳酸が得られた。このポリ乳酸樹脂２
００ｇにリジントリイソシアナート３量体２０ｇを添加
し、１４０℃で反応させて、Ｍｎ＝１３２００、Ｍｗ＝
３１０２０、ＴＨＦ不溶分３０重量％、Ｔｇ＝４１℃、
Ｔｓ＝１２４℃のウレタン化ポリ乳酸を得た。上記の方
法で得られたウレタン化ポリ乳酸樹脂（トナー用樹脂）
１００重量部を用い実施例１と同様にして混練・粉砕・
分級を行ない、平均粒径１０．１μｍのトナーＢを得
た。Example 2 300 g of 90% DL lactic acid and 240 μl of tetrabutoxygermanium 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. Nitrogen gas was introduced with stirring the contents of the container, and after reacting for 2 hours at 180 ° C. in a nitrogen gas atmosphere, 30 m
The reaction was performed for 2 hours under reduced pressure of mHg. Subsequently, when the temperature was set to 220 ° C. and polycondensation was performed for 10 hours under a reduced pressure of 20 mmHg, Mn = 8260, Mw = 235.
20 transparent polylactic acids were obtained. This polylactic acid resin 2
20 g of lysine triisocyanate trimer was added to 00 g and reacted at 140 ° C., Mn = 13200, Mw =
31020, THF insoluble content 30% by weight, Tg = 41 ° C.,
Urethane polylactic acid with Ts = 124 ° C. was obtained. Urethane-modified polylactic acid resin (resin for toner) obtained by the above method
Using 100 parts by weight, kneading, crushing,
After classification, a toner B having an average particle size of 10.1 μm was obtained.
【００３５】実施例３ 撹拌装置、窒素道入管、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、ＤＬ−ラクチ
ド３００ｇ、ラウリルアルコール０．１５ｇ、オクチル
酸錫０．６ｇを仕込んだ。容器内容物を撹拌下、窒素ガ
スを導入し、窒素ガス雰囲気下、１９０℃、１００ｍｍ
Ｈｇの減圧下において２時間反応を行ったところ、Ｍｎ
＝５５５００、Ｍｗ＝１１８０００の透明なポリ乳酸が
得られた。このポリ乳酸樹脂２００ｇにリジントリイソ
シアナート３量体２５ｇを添加し、１４０℃で反応させ
て、Ｍｎ＝７８０００、Ｍｗ＝２２６０２０、ＴＨＦ不
溶分４０％、Ｔｇ＝５０℃、Ｔｓ＝１３１℃のウレタン
化ポリ乳酸を得た。上記の方法で得られたウレタン化ポ
リ乳酸樹脂（トナー用樹脂）１００重量部を用い実施例
１と同様にして混練・粉砕・分級を行ない平均粒径１
０．３μｍのトナーＣを得た。Example 3 DL-lactide (300 g), lauryl alcohol (0.15 g) and tin octylate (0.10 g) 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. Charged 6g. Nitrogen gas was introduced while stirring the contents of the container, and under nitrogen gas atmosphere, 190 ° C, 100 mm
When the reaction was performed for 2 hours under a reduced pressure of Hg, Mn
= 55500, Mw = 118000, transparent polylactic acid was obtained. To 200 g of this polylactic acid resin, 25 g of lysine triisocyanate trimer was added and reacted at 140 ° C., and Mn = 78000, Mw = 226020, THF insoluble matter 40%, Tg = 50 ° C., Ts = 131 ° C. urethane. The modified polylactic acid was obtained. Using 100 parts by weight of the urethanized polylactic acid resin (resin for toner) obtained by the above method, kneading, pulverizing and classifying were carried out in the same manner as in Example 1 to obtain an average particle size of 1
Toner C of 0.3 μm was obtained.
【００３６】以上、トナーＡ〜Ｃを用いて以下の試験を
行った。 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。The following tests were carried out using the toners A to C. 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.
【００３７】[0037]
【数１】 [Equation 1]
【００３８】結果を表１に示す。The results are shown in Table 1.
【００３９】[0039]
【表１】 [Table 1]
【００４０】[0040]
【発明の効果】本発明により、低温定着性、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
性トナーを得ることができる。According to the present invention, low temperature fixability, fix strength,
It is possible to obtain a biodegradable toner having excellent offset resistance and blocking resistance.
───────────────────────────────────────────────────── 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 (7)
ートにより架橋して得られるウレタン化ポリエステル樹
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, comprising a urethanated polyester resin obtained by crosslinking polylactic acid with a polyfunctional isocyanate having a functionality of 3 or more and a colorant.
上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 toner for developing an electrostatic charge image according to claim 1, wherein the polylactic acid has a number average molecular weight of 2000 or more.
分を５０〜９９．９重量％、３官能以上の多価イソシア
ナート成分を０．１〜５０重量％含有することを特徴と
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. The urethane-containing polyester resin contains 50 to 99.9% by weight of a lactic acid component and 0.1 to 50% by weight of a trifunctional or higher polyvalent isocyanate component. 2. The toner for developing an electrostatic charge image according to item 2.
ヒドロフラン不溶分が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 urethanized polyester resin has a tetrahydrofuran insoluble content of 10 to 80% by weight.
転移温度が３０〜８０℃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 urethane transition polyester resin has a glass transition temperature of 30 to 80 ° C. and a softening point of 60 to 170.
The toner for developing an electrostatic charge image according to any one of claims 1 to 4, which has a temperature of ° C.
られたものであることを特徴とする請求項１乃至５に記
載の静電荷像現像用トナー。6. The toner for developing an electrostatic charge image according to claim 1, wherein the polylactic acid is obtained by dehydration polycondensation of lactic acid.
得られたものであることを特徴とする請求項１乃至５に
記載の静電荷像現像用トナー。7. The toner for developing an electrostatic charge image according to claim 1, wherein the polylactic acid is obtained by a ring-opening reaction of lactide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9092796A JPH09281746A (en) | 1996-04-12 | 1996-04-12 | Electrostatic charge image developing toner |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9092796A JPH09281746A (en) | 1996-04-12 | 1996-04-12 | Electrostatic charge image developing toner |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09281746A true JPH09281746A (en) | 1997-10-31 |
Family
ID=14012078
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9092796A Pending JPH09281746A (en) | 1996-04-12 | 1996-04-12 | Electrostatic charge image developing toner |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09281746A (en) |
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-
1996
- 1996-04-12 JP JP9092796A patent/JPH09281746A/en active Pending
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