JP3633137B2 - Toner for developing electrostatic image and fixing method of toner for developing electrostatic image - Google Patents

Description

を加え２００℃にて反応させポリエステル樹脂（Ｂ４）を得た。詳細を表２に示す。以下同様にしてポリエステル樹脂（Ｂ５）、（Ｂ６）を得た。
【００９２】
なお表１、表２中の略号は次の通りである。
【００９３】
ＮＤＣ ナフタレンジカルボン酸
ＴＰＡ テレフタル酸
ＩＰＡ イソフタル酸
ＯＰＡ オルソフタル酸
１４ＣＨＤＡ １，４−シクロヘキサンジカルボン酸
１２ＣＨＤＡ １，２−シクロヘキサンジカルボン酸
ＤＳＡ ドデセニルコハク酸
ＭＡ マレイン酸
ＴＭＡ トリメリット酸
ＳＩＰ ５−ナトリウムスルホイソフタル酸
ＥＧ エチレングリコール
ＰＧ プロピレングリコール
ＮＰＧ ネオペンチルグリコール
ＣＨＤＭ シクロヘキサンジメタノール
ＢＰＡ−ＥＯ ビスフェノールＡのエチレンオキサイド付加物（平均分子量３５０）
ＢＰＡ−ＰＯ ビスフェノールＡのプロピレンオキサイド付加物（平均分子量４００）
ＤＡＯＨ 水添ダイマージオール
ＰＰＧ ポリプロピレングリコール（平均分子量１５００）
である。
【００９４】
（実施例１〜１１、比較例１〜８）
ポリエステル樹脂の前記重合例にて得られたポリエステル樹脂（Ａ１）９５重量部をチョッパーミルにて粗粉砕し、銅フタロシアニン系シアン色顔料ヘリオゲンブルーＳ７０８４［ＢＡＳＦ社］５重量部とボールミルにて予備混合した後、熱ロールミルにて混練し冷却後、再び粗粉砕し、次いでジェットミルにて微粉砕の後分級し、さらにヘンシェルミキサーにて疎水性シリカ微粉末アエロジルによる表面処理を行い、平均粒子径８．５μｍのシアン色トナー（Ｔ１）を得た。得られたトナー５重量部をフェライト系キャリアＦ−１００［パウダーテック社製］９５重量部と共にボールミルに仕込み、約１５分間攪拌し現像剤とした。
【００９５】
得られた現像剤を市販の乾式電子写真方式の複写機の定着器を取り外した試験機に仕込み、ＰＰＣ用紙に静電像を形成し現像した。
【００９６】
得られた未定着の画像を図１に示す定着装置にて定着した。サーマルヘッドの表面温度は８０℃〜３００℃の間で可変とした。耐熱フィルムにはトナーとの接触面に導電性フィラーを分散させた低抵抗のＰＴＦＥコーティングを行った２５μｍ厚のポリイミドフィルムを用いた。耐熱フィルムのコーティング処理面の表面エネルギーは１２．５ｄｙｎ／ｃｍであった。
【００９７】
サーマルヘッドの温度を８０℃から５℃づつ上げて画像定着を行い、定着状態及びオフセット発生状態を観察した。定着性はトナー厚みが５μｍ程度以上となっている画像部分にセロハンテープを一定圧力にて張り付け、一定速度にて引き剥がしてセロハンテープにトナーが付着しているか否かを評価し、付着しなくなる温度を「定着開始温度」とした。さらに昇温し、オフセットが発生する温度を「オフセット発生温度」とした。記録紙の送り速度はＡ４縦方向毎分１０枚程度とした。定着開始温度＋１０℃の温度にヒートロール温度を設定し透明ポリエステルフィルム上に画像出し及び定着を行い、オーバーヘッドプロジェクタにて投影観察し、「投影画像評価」をした。結果を表３に示す。
【００９８】
以下同様にポリエステル樹脂（Ａ２）〜（Ａ１１）から実施例トナー（Ｔ２）〜（Ｔ１１）、ポリエステル樹脂（Ｂ１）〜（Ｂ８）から比較例トナー（Ｔ１２）〜（Ｔ１９）を作製し、同様に評価した。結果を表３に示す。
【００９９】
（実施例１２〜１５）
ポリエステル樹脂（Ａ８）１００重量部、メチルエチルケトン５０重量部、テトラヒドロフラン２５重量部、紫外線吸収剤シーソーブ７０６［シプロ化成社製］３重量部、マゼンタ染料Ｃ．Ｉ．ディスパースレッド６０コンクケーキ［三井東圧化学社製］５重量部をセパラブルフラスコに仕込み、約８０℃にて溶解した。次いで温度を７０℃に下げ、６８℃の水２５０部を添加し、転相自己乳化法にて粒子径約０．１μｍのポリエステル樹脂の水系分散体を得た。
【０１００】
さらに得られたポリエステル水系ミクロ分散体を蒸留用フラスコに入れ、留分温度が１０３℃に達するまで蒸留し、冷却後に水を加え固形分濃度を２５％とした。温度計、コンデンサー、攪拌羽根を備えた四つ口の１リットルセパラブルフラスコに、得られたポリエステル水系分散体４００重量部を仕込み、７０℃に加熱した。
【０１０１】
次いで、ジメチルアミノエチルメタクリレート１５．８重量部を溶解した水１００重量部を入れ、８時間攪拌を続けた。その結果、ポリエステル水系ミクロ分散体に存在したサブミクロンオーダーの粒子径の共重合体は合体粒子成長し、平均粒直径６．５μｍ、平均粒子直径をＤとした場合に０．５Ｄ〜２Ｄの範囲の粒径を有する粒子の占有率９５ｗｔ％、平均球形度０．９８、球形度０．７以上の粒子占有率９７％のほぼ球形のポリエステル樹脂粒子を得た。得られたポリエステル樹脂粒子を吸引漏斗を用いて脱水洗浄し、流動乾燥機にて乾燥させ、マゼンタトナー（Ｔ２０）を得た。
【０１０２】
以下同様に染料をネオペン・イエロー０７５［ＢＡＳＦ社製］５重量部に換えイエロートナー（Ｔ２１）を得た。同様に染料をネオペン・シアンＦＦ４２３８［ＢＡＳＦ社製］８重量部に換え、シアントナー（Ｔ２２）を得た。さらに染料をオイルブラック８６０［オリエント化学社製］１０重量部及びＴ−７７［保土ヶ谷化学社製］５重量部に換え、以下同様に操作してブラックトナー（Ｔ２３）を得た。以下同様に評価した。結果を表３に示す。
【０１０３】
（カラー画像形成試験）
カラー印刷用に、色分解され１７５線にて網点交換されたＹＭＣＫ４色のポジ画像（風景写真）を原稿とし、前記４色のトナーを用い、前述の試験機により、定着温度を４色の定着開始温度の平均値とオフセット発生温度の平均値の中間値に設定し、まずイエロー画像出しを行い、得られた画像上にマゼンタ画像、次いでシアン、ブラックの順に色重ねを行いフルカラー画像を形成した。得られた画像は多少の位置ズレは生じたが鮮明な色彩を示し、色の異なるトナーが重なり合った部分においてもオフセットを生じること無く良好な定着性を示し、また２次色の発色も好ましいものであった。同様に透明フィルム上にフルカラー画像を形成しオーバーヘッドプロジェクタにて観察した結果、鮮明な投影画像を得ていることを確認した。
【０１０４】
（実施例１６〜１９）
ポリエステル樹脂（Ａ９）１００重量部、メチルエチルケトン５０重量部、テトラヒドロフラン２５重量部、紫外線吸収剤シーソーブ７０６［シプロ化成社製］３重量部、マゼンタ染料Ｃ．Ｉ．ディスパースレッド６０コンクケーキ［三井東圧化学社製］５重量部をセパラブルフラスコに仕込み、約８０℃にて溶解した。次いで温度を７０℃に下げ、トリエタノールアミン３重量部を添加し、次いで６８℃の水２５０部を添加し、転相自己乳化法にて粒子径約０．１μｍのポリエステル樹脂の水分散体を得た。さらに得られた水系ミクロ分散体を蒸留用フラスコに入れ、留分温度が１０３℃に達するまで蒸留し、冷却後に水を加え固形分濃度を２５％とした。以下実施例１２〜１５と同様に操作しマゼンタトナー（Ｔ２４）、イエロートナー（Ｔ２５）、シアントナー（Ｔ２６）、ブラックトナー（Ｔ２７）を得た。得られたトナーの平均粒子径Ｄは５．８μｍ、０．５Ｄ〜２．０Ｄの占有率９８％、真球度０．７以上の粒子の占有率８５％であった。以下同様に評価した。結果を表３に示す。
【０１０５】
（カラー画像形成試験）
カラー印刷用に、色分解され１７５線にて網点交換されたＹＭＣＫ４色のポジ画像（風景写真）を原稿とし、上記４色のトナーを用い、以下実施例１２〜１５と同様に操作しフルカラー画像を形成した。得られた画像は多少の位置ズレは生じたが鮮明な色彩を示し、色の異なるトナーが重なり合った部分においてもオフセットを生じること無く良好な定着性を示し、また２次色の発色も好ましいものであった。同様に透明フィルム上にフルカラー画像を形成しオーバーヘッドプロジェクタにて観察した結果、鮮明な投影画像を得ていることを確認した。
【０１０６】
（実施例２０〜２２）
ポリエステル樹脂（Ａ１）を用い、顔料をマゼンタ顔料ホスタパーム・ピンクＥ０２（トナーグレード）［ヘキスト社製］５重量部、イエロー顔料としてノヴァパーム・イエローＰ−ＨＧＶＰ２０６６［ヘキスト社製］５重量部、ブラック顔料としてプリンテックス１５０Ｔ［デグサ社製］５重量部に代え、以下実施例と同様にしてトナー（Ｔ２８）（Ｔ２９）（Ｔ３０）を得た。以下実施例と同様に評価した結果を表３に示す。
【０１０７】
（カラー画像形成試験）
カラー印刷用に、色分解され１７５線にて網点交換されたＹＭＣＫ４色のポジ画像（風景写真）を原稿とし、上記３色のトナーとシアントナー（Ｔ１）を用い、以下実施例１２〜１５と同様に操作しフルカラー画像を形成した。得られた画像が多少の位置ズレは生じたが鮮明な色彩を示し、色の異なるトナーが重なり合った部分においてもオフセットを生じること無く良好な定着性を示し、また２次色の発色も好ましいものであった。同様に透明フィルム上にフルカラー画像を形成しオーバーヘッドプロジェクタにて観察した結果、鮮明な投影画像を得ていることを確認した。
【０１０８】
（比較例９）
ポリエステル樹脂の重合例にて得られたポリエステル樹脂（Ｂ１）９５重量部をチョッパーミルにて粗粉砕し、銅フタロシアニン系シアン色顔料ヘリオゲンブルーＳ７０８４［ＢＡＳＦ社］５重量部、軟化点１１０℃のエチレン／プロピレン共重合ワックス２重量部、ステアリルケテンダイマー３重量部とをボールミルにて予備混合した後、熱ロールミルにて混練し冷却後、再び粗粉砕し、次いでジェットミルにて微粉砕の後分級し平均粒子径８．３μｍのシアン色トナー（Ｔ３１）を得た。以下実施例と同様に評価した。オフセット発生温度は上昇し、ある程度平滑な表面を有する画像を得ることができるようになったが、投影画像は不鮮明なものであった。
【０１０９】
【表１】

【０１１０】
【表２】

【０１１１】
【表３】

【０１１２】
【発明の効果】
請求項１に記載した静電荷像現像用トナーは、定着開始温度とオフセット発生温度との間隔が広く、定着性が良好で、省電力、クイックスタートが可能な耐熱フィルムとサーマルヘッドを組み合わせた定着装置においても優れた定着画像が得られ、カラー画像の再現性もよく、特に、高温の加熱定着装置において定着性に優れている。
【０１１４】
請求項２に記載した静電荷像現像用トナーは、特に良好な定着性と優れた耐オフセット性を実現することができる。
【０１１５】
請求項３に記載した静電荷像現像用トナーは、特に良好な定着性と優れた耐オフセット性を実現することができる。
【０１１６】
請求項４に記載した静電荷像現像用トナーは、トナーの帯電が安定し、また、トナーの耐湿性が良好で、環境変化によりトナーの帯電量が変動して画像形成に支障を来すようなことがない。
【０１１７】
請求項５に記載した静電荷像現像用トナーは、特に安定して静電荷像を現像することができる。
【０１１８】
請求項６に記載した静電荷像現像用トナーの定着方法は、定着開始温度とオフセット発生温度との間隔が広く、定着性が良好で、省電力、クイックスタートが可能な耐熱フィルムとサーマルヘッドを組み合わせた定着装置においても優れた定着画像を得ることができ、また、カラー画像の再現性もよい。
【図面の簡単な説明】
【図１】評価に用いる、複写機にとりつける定着装置の説明図である。
【符号の説明】
１ サーマルヘッド
２ 耐熱フィルム
３ 駆動ロール
４ 従動ロール
５ 記録紙
６ 加圧ロール[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a recording apparatus with thermal fixing, mainly an electrophotographic printer such as a copying machine, a laser printer, and an LED printer, a printer using an electrostatic recording system such as ion flow, ion injection, and discharge recording, or a ferroelectric substance. The present invention relates to a toner for developing an electrostatic charge image used for developing a latent image due to an electrostatic charge and a fixing method for the toner for developing an electrostatic charge image in a printer using an electrostatic latent image formed by spontaneous polarization. More specifically, it is excellent in color image recording quality, and is preferably used for a fixing method that combines a thermal head and a thermal head, which are increasingly demanded by recent printer miniaturization, price reduction, quick start, and power saving. The present invention relates to a toner for developing an electrostatic charge image and a fixing method for the toner for developing an electrostatic charge image.
[0002]
[Prior art]
A powder that develops an electrostatic latent image in an electrophotographic system, an electrostatic recording system, or the like and is finally transferred to a recording paper or a substrate such as a film to form an image is referred to as toner. As the toner for developing an electrostatic charge image, a so-called pulverization in which a colorant, a charge control agent, and the like are added to a binder and then kneaded and then pulverized and further classified, and a fluidity modifier is externally added as necessary. Particles produced by the method are used. As the binder, styrene / acrylic copolymer resins have been mainly used, but in recent years, polyester resins that are excellent in low-temperature fixability and image surface gloss tend to be used with higher speed and colorization. The polyester resin mainly used is an unsaturated polyester resin obtained mainly by condensation polymerization of aliphatic unsaturated carboxylic acids such as fumaric acid and maleic acid and diols having a bisphenol structure.
[0003]
Recently, the present invention relates to a saturated polyester resin comprising an aromatic polycarboxylic acid such as terephthalic acid or isophthalic acid, an aliphatic diol such as ethylene glycol, an alicyclic diol such as cyclohexanedimethanol, or the aromatic diol having the bisphenol structure described above. Many patent proposals have been made. The polyester resin is excellent in gloss on the surface of the image after fixing, so that the color is good and a wide color reproduction range is realized. In particular, when an image is recorded on a transparent film such as an overhead projector, the light transmittance is high and the quality of the projected image is high.
[0004]
In general, toner obtained by developing an electrostatic latent image on a recording paper is heat-fixed in a dry electrophotographic system or an electrostatic recording system. As a heating method, a heat roll is generally used. As the material of the heat roll, silicone rubber, fluorine rubber, etc. having high releasability and elasticity are used. However, since such a rubber roll has a large heat capacity, preheating is necessary in advance, and it cannot be used for a while after the device is turned on. For the same reason, since it is necessary to always pass an electric current to keep the heater warm, there is a great problem in terms of power saving.
[0005]
In order to cope with this problem, a method of heating with a thermal head or the like via a heat-resistant film or the like has been proposed and put into practical use in some models.
[0006]
By contacting the heat source, the toner particles are melted and fixed on the recording paper. However, the melted toner resin partially adheres not only to the recording paper but also to the heat source side and contaminates the surface of the heat source. This phenomenon is referred to as an offset phenomenon, and when the fixing process is further continued using a contaminated heat source, the contamination is transferred to the subsequent recording paper and the quality of the recorded image is remarkably lowered. Such an offset phenomenon is particularly remarkable in the fixing method in which the heat-resistant film and the thermal head described above are combined.
[0007]
In order to prevent such an offset phenomenon, the toner binder has been improved. It is known that the offset phenomenon can be reduced by broadening the molecular weight distribution of the binder, partially crosslinking or gelling, and many patent proposals have been made. However, these measures alone have not completely prevented the offset phenomenon.
[0008]
Many proposals have also been made regarding improvements in toner constituents. A toner is produced by kneading and dispersing a colorant, a charge control agent, and in some cases magnetic powder, etc. in a binder, and externally adding a fluidizing agent after pulverization and classification with a jet mill or the like. Further, it has been proposed to reduce the offset phenomenon by blending specific waxes. For example, Japanese Patent Application Laid-Open Nos. 59-164560 and 59-228661 propose that an amide wax, a ketone wax, a specific alkyl ketene dimer, and the like are blended as an anti-offset agent. However, this method cannot completely prevent the offset phenomenon, and the quality of the color image is remarkably lowered. In particular, an overhead projector or the like can obtain only a projected image having a dark and turbid tone.
[0009]
Japanese Patent Laid-Open No. 63-121059 proposes that the fixing characteristics can be improved by introducing dimer acid as a copolymer component of a polyester resin as an acid component. Although the fixing characteristics are somewhat improved by such means, increasing the copolymerization amount of the dimer acid to a region where a sufficient effect can be obtained lowers the glass transition point of the resin and lowers the storage stability of the toner.
[0010]
For example, JP-A-59-164560, JP-A-61-105562, JP-A-59-29257, JP-A-59-29258, JP-A-59-198469, JP-A-59-223456, JP-A-60-4947. No. 61-176948, No. 61-240248, JP-A-3-155563, JP-A-3-122664, etc. also use alkyl or alkenyl-substituted succinic acid as a copolymer component of a polyester resin. A proposal has been made that the introduction can improve the fixing characteristics. In particular, Japanese Patent Application Laid-Open Nos. 3-155563 and 3-122664 are proposed mainly for improvement of fixing characteristics in a fixing method in which a heat-resistant film and a thermal head are combined. Although the fixing properties are somewhat improved by such means, the glass transition point is remarkably lowered as in the case of dimer acid copolymerization. Further, there arises a problem that odor is generated during toner fixing.
[0011]
JP-A-56-1952 and 58-17452 disclose cyclohexene dicarboxylic acid (cyclohexylene dicarboxylic acid) anhydride or cyclohexane dicarboxylic acid anhydride as a polyvalent carboxylic acid component, and a polyhydric alcohol having a bisphenol structure. Have proposed a toner composition for electrophotography using a polyester resin obtained by an atmospheric pressure polymerization method. Such a proposal is based on the glass transition point of an unsaturated polyester resin obtained by condensation polymerization of aliphatic unsaturated carboxylic acids such as fumaric acid and maleic acid and diols having a bisphenol structure, which are mainly used as a polyester resin for toner. It is considered that the main purpose is to improve the storage stability of the toner. It is possible to increase the glass transition point by introducing such an alicyclic polyvalent carboxylic acid into a copolymer component, but conversely, when an alicyclic polyvalent carboxylic acid is used, it is particularly a normal pressure polymerization method. In this case, it is difficult to increase the molecular weight, and only a low-molecular weight resin can be obtained. On the other hand, the storage stability may be impaired. Furthermore, the monomer having a bisphenol structure used in the diol component has recently been regarded as a problem from the viewpoint of safety, and considering not only the working environment but also the thermal decomposition of the resin in the thermal fixing process, There is a concern that special consideration will be required even under the actual toner usage environment.
[0012]
Japanese Patent Application Laid-Open No. 7-209906 proposes a toner having good fixing characteristics obtained by defining the surface energy of a polyester resin and the particle size of a secondary aggregate of a colorant as a toner raw material. However, when discussing the surface energy with respect to the fixing characteristics, it is necessary to define the relationship between the surface energy of the toner resin and the surface energy of the fixing member, but the proposal has not studied the surface energy on the fixing member side. Furthermore, the relationship between the monomer used and the surface energy is not clear. Further, the colorant specifically shown is only carbon black, and no investigation has been made on the toner for color image reproduction which is the main subject of the present invention.
[0013]
[Problems to be solved by the invention]
As described above, in the conventional image recording technique in which the toner for electrostatic image development is used and heat fixing is performed, a binder composition that solves the problem particularly in heat fixing has not been obtained. The actual situation is that the problem is solved on the surface by comprehensive engineering such as formulation and various devices on the fixing device side. In particular, it is satisfactory when the fixing device is limited for the purpose of downsizing the device, quick start, energy saving, etc. (for example, heat fixing with a thermal head through a heat-resistant film). No toner binder having characteristics has been obtained.
[0014]
In view of such circumstances, the present invention avoids an offset phenomenon at the time of thermal fixing in an image recording apparatus accompanied by thermal fixing, and can obtain a high-quality image, particularly a toner for developing an electrostatic image, particularly a heat-resistant film or the like. It is an object of the present invention to provide a toner capable of avoiding an offset phenomenon and realizing higher image quality even in a system in which heat is fixed by a thermal head or the like via a toner.
[0015]
[Means for Solving the Problems]
In order to achieve the above object, the toner for developing an electrostatic charge image of the present invention comprises a polyvalent carboxylic acid containing 5% or more of cyclohexanedicarboxylic acid and an aromatic polyhydric alcohol mainly composed of an aliphatic diol or an alicyclic diol. A polyester resin having a glass transition point of 50 ° C. or higher obtained by polycondensation with a polyhydric alcohol having a content of 5 mol% or less is a main component.In the electrostatic image developing toner containing the binder, the polyester resin is
・ 10 to 70 mol% of cyclohexanedicarboxylic acid
-30-90 mol% of asymmetric aromatic dicarboxylic acid
A polyvalent carboxylic acid,
-10 to 80 mol% of ethylene glycol
-10-80 mol% of propylene glycol
-0-10 mol% of dimer diol
-Polypropylene glycol (converted to the number of glycol residues) is 0 to 20 mol%
-0-5 mol% of diol derived from bisphenol A
With polyhydric alcohols
It is a polyester resin obtained by polycondensationIt is characterized by that.
[0016]
The toner for developing an electrostatic charge image having the above-described configuration has a wide interval between the fixing start temperature and the offset generation temperature, a good fixing property, a power-saving and quick start heat-resistant film and a thermal head combined with a fixing device. Can obtain excellent fixed images,AlsoAnd color image reproducibilityIn addition, it exhibits good fixability in a high-temperature heat fixing device.
[0019]
In this case, the polyester resin is
The temperature at which the melt viscosity of the polyester resin becomes 10,000 poise is T_a, The value of the intrinsic viscosity of the polyester resin is η_{sp / c}When
T_a≦ 160 × η_{sp / c}+75
It is preferable to satisfy.
[0020]
The electrostatic image developing toner having the above-described configuration can realize particularly good fixability and excellent offset resistance.
[0021]
In this case, the surface energy of the polyester resin is preferably 45 dyn / cm or less.
[0022]
The electrostatic image developing toner having the above-described configuration can realize particularly good fixability and excellent offset resistance.
[0023]
In this case, the polyester resin is 20 to 2000 eq. It is preferable to contain an ionic group of / ton.
[0024]
The toner for developing an electrostatic charge image having the above-described structure is stable in charging of the toner, and has good moisture resistance, and the charge amount of the toner fluctuates due to an environmental change, thereby hindering image formation. There is nothing.
[0025]
In this case, the average particle diameter D of the toner is preferably 2 to 10 μm, and particles having a sphericity of 0.7 or more are preferably substantially spherical particles occupying 70% or more of the whole.
[0026]
The electrostatic image developing toner having the above-described configuration can develop an electrostatic image particularly stably.
[0027]
The electrostatic charge image developing toner fixing method of the present invention is such that the surface energy of the surface of the electrostatic charge image developing toner of the present invention that is in direct contact with the toner is 50 dyn / cm or less, and the surface temperature during fixing is 60 to 200. It is characterized by being fixed by a fixing member in the range of ° C.
[0028]
The fixing method of the electrostatic image developing toner of the present invention having the above-described structure is a heat-resistant film and a thermal film that have a wide interval between the fixing start temperature and the offset generation temperature, good fixability, power saving, and quick start. Even in a fixing device combined with a head, an excellent fixed image can be obtained, and color image reproducibility is also good.
[0029]
DETAILED DESCRIPTION OF THE INVENTION
Details of the embodiment of the present invention will be described below.
[0030]
The polyester resin used in the present invention is obtained mainly by condensation polymerization of polyvalent carboxylic acids and polyhydric alcohols.
[0031]
Examples of the polyvalent carboxylic acids used in the production of the polyester resin used in the present invention include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and diphenic acid. Aromatic dicarboxylic acids, p-oxybenzoic acids, aromatic oxycarboxylic acids such as p- (hydroxyethoxy) benzoic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid Aliphatic dicarboxylic acids such as fumaric acid, maleic acid, itaconic acid, mesaconic acid, citraconic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, trimer acid, hydrogenated dimer acid, cyclohexanedicarboxylic acid, cyclohexene dicarboxylic acid, etc. Unsaturated aliphatic and cycloaliphatic di The carboxylic acid or the like, also can be used other trimellitic acid as a polycarboxylic acid, trimesic acid, and the like trivalent or higher polyvalent carboxylic acids such as pyromellitic acid.
[0032]
Examples of the polyhydric alcohol used in the production of the polyester resin include aliphatic polyhydric alcohols, alicyclic polyhydric alcohols, aromatic polyhydric alcohols and the like.
[0033]
Aliphatic polyhydric alcohols include ethylene glycol, propylene glycol, 1,3-propanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, Ring opening of lactones such as neopentyl glycol, diethylene glycol, dipropylene glycol, dimethylol heptane, 2,2,4-trimethyl-1,3-pentanediol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ε-caprolactone Examples include aliphatic diols such as lactone-based polyester polyols obtained by polymerization, triols such as trimethylolethane, trimethylolpropane, glycerin, and pentaerythritol, and tetraols.
[0034]
Alicyclic polyhydric alcohols include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, spiroglycol, hydrogenated bisphenol A, ethylene oxide adduct and propylene oxide adduct of hydrogenated bisphenol A, tricyclodecane Examples include diol, tricyclodecane dimethanol, dimer diol, hydrogenated dimer diol and the like.
[0035]
As aromatic polyhydric alcohols, para-xylene glycol, meta-xylene glycol, ortho-xylene glycol, 1,4-phenylene glycol, ethylene oxide adduct of 1,4-phenylene glycol, bisphenol A, ethylene oxide adduct of bisphenol A and Examples thereof include propylene oxide adducts.
[0036]
A monofunctional monomer may be introduced into the polyester resin for the purpose of blocking the polar group at the end of the polyester resin and improving the environmental stability of toner charging characteristics. Monofunctional monomers include benzoic acid, chlorobenzoic acid, bromobenzoic acid, parahydroxybenzoic acid, sulfobenzoic acid monoammonium salt, sulfobenzoic acid monosodium salt, cyclohexylaminocarbonylbenzoic acid, n-dodecylaminocarbonylbenzoic acid Acid, tertiary butylbenzoic acid, naphthalenecarboxylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, salicylic acid, thiosalicylic acid, phenylacetic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, octanecarboxylic acid, lauric acid, stearyl Monocarboxylic acids such as acids and lower alkyl esters thereof, or monoalcohols such as aliphatic alcohols, aromatic alcohols, and alicyclic alcohols can be used.
[0037]
In the present invention, it is essential to use polyvalent carboxylic acids containing 5 mol% or more of cyclohexanedicarboxylic acid, and the amount of cyclohexanedicarboxylic acid used is preferably 10 to 70 mol% in the polyvalent carboxylic acid, preferably 15 to 50 More preferred is mol%, and still more preferred is 20 to 40 mol%. As the cyclohexanedicarboxylic acid, one or more of 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,2-cyclohexanedicarboxylic acid can be used. Moreover, you may combine what substituted some hydrogen of the cyclohexane ring by the alkyl group etc. If the content of cyclohexanedicarboxylic acid is less than this range, the fixing characteristics cannot be exhibited. If the content is too large, the unit price of the resin increases, resulting in a problem in cost.
[0038]
In the present invention, it is preferable to use an aromatic polyvalent carboxylic acid as the polyvalent carboxylic acid other than the cyclohexanedicarboxylic acid, and it is more preferable to use an asymmetric aromatic polyvalent carboxylic acid. As the asymmetric aromatic polycarboxylic acid, use of isophthalic acid or orthophthalic acid is preferable.
[0039]
The polyhydric alcohol used in the present invention is mainly composed of an aliphatic or alicyclic diol, and it is essential that the content of the aromatic polyhydric alcohol is 5 mol% or less. Furthermore, polyhydric alcohols
10-80 mol% ethylene glycol
10-80 mol% propylene glycol
0-10 mol% dimer diol
0-20 mol% polypropylene glycol
(In terms of propylene glycol residue)
Preferably it consists of. It is preferable not to use an aromatic polyhydric alcohol typified by an ethylene oxide adduct of bisphenol A or a propylene oxide adduct, and even when used, the amount used is 5 mol% or less, more preferably 3 mol%. In the following, it is most preferably limited to 1 mol% or less and not used at all.
[0040]
Here, dimer diol is generally derived from dimer acid. The dimer acid is a generic term for dimers mainly composed of unsaturated fatty acids having 10 to 24 carbon atoms, preferably around 18 carbon atoms, and includes a slight amount of monomeric acid and trimer acid. Industrially, purified vegetable fatty acids obtained from oleic acid, elaidic acid, their mixture of tall oil fatty acids, linoleic acid, etc., drying oils, semi-drying oils, etc. are used for the existence of catalysts such as montmorillonite clays. Those obtained by thermal polymerization are known. Hydrogenated dimer acids in which unsaturated double bonds are saturated by hydrogenation are also known. The dimer diol may also contain some monomers and trimers like the dimer acid. Also known are those in which unsaturated bonds such as cyclohexene ring remain and those saturated by hydrogenation. In the present invention, either unsaturated or saturated may be used, but it is preferable to use a saturated hydrogenated dimer diol.
[0041]
Examples of preferred polyester resins in the present invention
(A) Cyclohexanedicarboxylic acid 20-50 mol%
Isophthalic acid 10-70 mol%
Orthophthalic acid 10-70 mol%
However, isophthalic acid + orthophthalic acid 50-80 mol%
A polycarboxylic acid consisting of
10-50 mol% ethylene glycol
Propylene glycol 50-90 mol%
A polyester resin obtained from a polyhydric alcohol consisting of
(B) Cyclohexanedicarboxylic acid 20-50 mol%
Isophthalic acid 10-70 mol%
Orthophthalic acid 10-70 mol%
However, isophthalic acid + orthophthalic acid 50-80 mol%
A polycarboxylic acid consisting of
10-50 mol% ethylene glycol
Propylene glycol 50-90 mol%
Dimer diol 5-10 mol%
Polyester resin obtained from polyhydric alcohols comprising
(C) Cyclohexanedicarboxylic acid 20-50 mol%
Isophthalic acid 10-70 mol%
Orthophthalic acid 10-70 mol%
However, isophthalic acid + orthophthalic acid 50-80 mol%
A polycarboxylic acid consisting of
10-50 mol% ethylene glycol
Propylene glycol 50-90 mol%
Polypropylene glycol (converted to propylene glycol residue) 5-10 mol%
The polyester resin obtained from the polyhydric alcohol which consists of can be illustrated.
[0042]
The glass transition point of the polyester resin used in the present invention is essential to be 50 ° C. or higher, more preferably 55 ° C. or higher, further 60 ° C. or higher, and still more preferably 65 ° C. or higher. When the glass transition point is lower than this, there is a tendency to aggregate during handling or storage, which may cause a problem in storage stability.
[0043]
Moreover, it is preferable that the softening point of resin used for this invention is the range of 80-150 degreeC. In a toner in which the softening temperature of the resin is kept lower than this, there is a tendency to agglomerate during handling or storage, and the fluidity may be greatly deteriorated particularly during long-time storage. If the softening point is higher than this, the fixing property is hindered. Further, since it is necessary to heat the fixing roll to a high temperature, the material of the fixing roll and the material of the base material to be copied are limited.
[0044]
In the present invention, the polyester resin is
The temperature at which the melt viscosity of the polyester resin becomes 10,000 poise is T_a, The intrinsic viscosity of the polyester resin is η_{sp / c}When
T_a≦ 160 × η_{sp / c}+75 (Formula 1)
It is preferable to satisfy. More preferably
T_a≦ 160 × η_{sp / c}+72 (Formula 2)
It is preferable to satisfy. Even more preferably
T_a≦ 160 × η_{sp / c}+70 (Formula 3)
It is preferable to satisfy.
[0045]
The surface energy of the polyester resin is preferably 45 dyn / cm or less, more preferably 42 dyn / cm or less, still more preferably 40 dyn / cm or less, and even more preferably less than 30 dyn / cm. . Such surface energy can be obtained by introducing an alkyl group having 2 or more carbon atoms, preferably 4 or more, and more preferably 6 or more into the side chain of the polyester resin. More specifically, it is obtained by copolymerizing 1 to 20 mol% of alkyl-substituted succinic acid, dimer acid, trimer acid, tetramer acid, dimer diol, dimethylol heptane, dimethylol octane, dimethylol decane, dimethylol dodecane and the like. be able to. When such a component having a long-chain alkyl group is introduced into a polyhydric alcohol component instead of a polyhydric carboxylic acid component, a preferable result can be obtained with a relatively low decrease in the glass transition point.
[0046]
Furthermore, such surface energy can also be realized by introducing polyalkylene glycol units. As the polyalkylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, polyethylene / propylene glycol and the like can be used. Polyalkylene glycol having a molecular weight of 300 to 30,000 can be used, and those having a molecular weight of about 3 to 1,000 can be used in terms of alkylene glycol units. The amount of copolymerization with respect to the polyester resin is preferably about 1 to 20 mol% in terms of alkylene glycol units.
[0047]
Furthermore, in this invention, the said polyester resin is 20-2000 eq. It is preferable that it contains an ionic group of / ton. Examples of the ionic group contained in the polyester resin include a carboxyl group, a sulfonic acid group, a sulfuric acid group, a phosphoric acid group, or an anionic group such as an alkali metal salt, an ammonium salt, an alkyl ammonium salt, an alkanol ammonium salt, or the like. A cationic group such as a primary to tertiary amine group, preferably a carboxyl group, a carboxylate group, a sulfonic acid group, or a sulfonic acid alkali metal salt group.
[0048]
The sulfonic acid group and the sulfonic acid alkali metal salt group can be obtained using a compound containing a sulfonic acid group or a sulfonic acid metal salt copolymerizable with the polyester resin. Specific examples include alkali metal salts such as sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and 5 [4-sulfophenoxy] isophthalic acid. . In particular, when an ionic group is introduced at the molecular end, sulfobenzoic acid or the like can be used. Examples of the metal salt include salts of Li, Na, K, Mg, Ca, Ba, Ni, Cu, Fe and the like, and particularly preferable is a Na salt. Among these, 5-sodium sulfoisophthalic acid or sodium sulfobenzoic acid is preferably used.
[0049]
As the carboxyl group, a carboxyl group remaining at the polyester terminal can be used. Furthermore, it is also possible to introduce an acid anhydride such as trimellitic anhydride or phthalic anhydride at the end of polymerization to add a carboxyl group to the terminal. The carboxyl group thus obtained can be neutralized with alkali metal hydroxides or carbon salts, ammonia, alkylamines, alkanolamines, cyclic amines, etc. to obtain carboxylate groups. .
[0050]
The content of ionic groups is 20 to 2000 eq. / Ton range is preferred, 30-1000 eq. / Ton, more preferably 50 to 500 eq. / Ton is still preferable, and 80 to 300 eq. Even more preferred is / ton.
[0051]
When the content of the ionic group is below this range, the charging of the toner becomes unstable, and the toner forming method using water dispersion described later cannot be applied. On the other hand, if the ionic group content exceeds this range, the toner absorptance increases and the toner charge amount fluctuates due to environmental changes, which may hinder image formation.
[0052]
The above is the polyester resin as a binder that characterizes the toner for developing an electrostatic charge image of the present invention. In the present invention, it is essential to use such a polyester resin as a main component of the entire binder. The present polyester resin is used by blending 50 wt% or more of the binder, preferably 70 wt% or more, more preferably 80 wt% or more.
[0053]
The colorant, the charge control agent, the fluidity modifier and the like to be blended in the electrostatic image developer of the present invention are not particularly limited, and known ones can be used as necessary.
[0054]
As the colorant, a dye, a pigment, carbon black, or the like may be used. These dyes, pigments, carbon black and the like may be used alone or in combination as necessary. In particular, it is preferable to use a dye from the viewpoint of spectral transmission characteristics.
[0055]
When pigments are used for coloring, benzidine, azo and isocindrine pigments are used for yellow coloring, and azo lake, rhodamine rake, quinacridone, naphthol and diketopyrrolopyrrole pigments are cyan for magenta coloring. For these, phthalocyanine pigments and indanthrene pigments are preferably used. When black toner is obtained, carbon black or the like can be used. As the carbon black, thermal black, acetylene black, channel black, furnace black, lamp black and the like can be used.
[0056]
When dyes are used for coloring, azo, nitro, quinoline, quinophthalone, and methine dyes are used for yellow coloring, anthraquinone, azo, and xanthene dyes are used for magenta coloring, and anthraquinone is used for cyan coloring. , Phthalocyanine and indoaniline dyes are preferably used.
[0057]
The method for producing the toner for developing an electrostatic charge image in the present invention is not particularly limited, and a colorant, a charge control agent, etc. are mixed with the binder and then pulverized with a jet mill or the like, and a fluidity modifier is externally added. A so-called pulverization method can be used. When the content of cyclohexanedicarboxylic acid is relatively high, the pulverizability of the resin is lowered, and therefore it may be preferable to perform pulverization by cooling the inside of the pulverization system.
[0058]
As another method, a toner process using a wet process in which a colorant, a charge control agent, etc. are mixed and dispersed in a solution consisting of a solvent and a binder, then the solution is introduced into an aqueous system, suspended or coarsely emulsified, and classified and dried. Can be used.
[0059]
In the present invention, particularly when the polyester resin contains an ionic group, the polyester resin exhibits water dispersibility (self-emulsifying property). In this case, a method can be exemplified in which a polyester resin is emulsified and dispersed in an aqueous system, and polyester resin fine particles contained in the obtained dispersion are slowly agglomerated to coalesce and grow to a size suitable for the toner to obtain a toner.
[0060]
When the content of cyclohexanedicarboxylic acid is relatively high, the pulverizability of the resin is lowered, and therefore it may be preferable to use a method other than the exemplified pulverization method.
[0061]
An aqueous dispersion of a polyester resin can be obtained by dissolving the polyester resin in a water-soluble solvent such as ketones, alcohols, tetrahydrofuran, cellosolves, dioxane, etc., then adding water and removing the solvent by azeotropy. it can. Slow agglomeration is possible by appropriate addition of electrolyte into the water dispersion system and temperature operation. In particular, a method in which an amino group-containing ester composed of amino alcohols and carboxylic acids is added and the ester is hydrolyzed in the system by raising the temperature, operating the pH, or the like to produce an amine salt of carboxylic acid leads to a slow aggregation region. Preferred as a method. If water-dispersed fine particles such as pigment and carbon black coexist in the slow aggregation region, particles containing pigment (carbon black) can be produced. It is also possible to obtain toner particles colored with a dye by allowing the dye to coexist at the time of emulsification, and it is also possible to post-color the colorless particles obtained by a high-temperature dispersion dyeing method.
[0062]
By this method, it is possible to obtain a toner for developing an electrostatic charge image comprising substantially spherical particles having an average particle diameter D of 2 to 10 μm and particles having a sphericity of 0.7 or more occupying 70% or more of the whole. Since it is substantially spherical, it is highly suitable for the non-magnetic one-component development method.
[0063]
In addition, the surface energy of the fixing member directly contacting the toner of the present invention electrostatically adhering to the recording paper is 50 dyn / cm or less, and the surface temperature of the fixing member at the time of fixing is in the range of 60 to 200 ° C. It can be fixed by a fixing device.
[0064]
The surface energy of the fixing member used in the present invention is essential to be 50 dyn / cm or less, preferably 40 dyn / cm or less, more preferably 30 dyn / cm or less, and 3 to 20 dyn / cm. The range is more preferable, and the range of 5 to 15 dyn / cm is more preferable. Further, the surface temperature at the time of fixing of the fixing member must be in the range of 60 to 200 ° C, preferably in the range of 80 to 180 ° C, and more preferably in the range of 100 to 160 ° C.
[0065]
Although the material of the fixing member is not particularly limited here, it is preferably a member mainly used in a fixing method by a combination of a heat-resistant film and a thermal head, and the base material is a heat-resistant film such as polyimide, polyamide, polyamideimide or the like. It is a heat-resistant film obtained by surface-treating fluorine resin, silicone resin or the like. Similarly, the present invention can be applied to a member used in a fixing device using an elastic roll that has been widely used conventionally.
[0066]
In the present invention, a better fixing result can be obtained by using a fixing device having a fixing member that satisfies such conditions.
[0067]
The present invention provides a polyester resin for toner,
The temperature at which the melt viscosity of the polyester resin becomes 10,000 poise is T_a, The intrinsic viscosity of the polyester resin is η_{sp / c}When
T_a≦ 160 × η_{sp / c}+75 (Formula 1)
And, more preferably, when the surface energy of the polyester resin is satisfied to be 45 dyn / cm or less, it has been found that good fixing characteristics can be realized.
[0068]
The outline of the fixing process is as follows.
[0069]
1. The heated fixing member comes into contact with the toner particles electrostatically adhering to the recording paper,
The toner particles are heated by heat conduction.
[0070]
2. Pressure is simultaneously applied to the toner layer that has reached the molten state, and the toner layer is fixed to the recording paper.
[0071]
3. The fixing member is separated from the toner layer.
[0072]
The inventors of the present invention have first found that the melt viscosity of the polyester resin needs to be lowered to about 10,000 poises in order to fix the toner on the recording paper at a normal pressure. The temperature to reach such melt viscosity is T_aIs defined. The melt viscosity generally has a positive correlation with the molecular weight of the resin. On the other hand, in the fixing operation, it is important that no offset phenomenon occurs when the fixing member is separated from the toner resin layer. In this offset phenomenon, the relationship between the surface energy of the polyester resin layer of the toner and the surface energy of the fixing member should of course be defined, but at the same time, the viscoelastic characteristics of the polyester resin layer of the melted toner are also defined. It should be. Here, the viscoelastic property is qualitatively understood as the cohesive force of the molten resin. It is known that the viscoelastic properties of the resin largely depend on the copolymer composition of the resin, the molecular weight, and the presence or absence of branching, but the present inventors preferably use the intrinsic viscosity of the resin as its representative value. The right side of (Equation 1) derived from_aIt has been found that good offset resistance is exhibited when the value is larger. In other words, good fixability and offset resistance are considered to be compatible only when a low enough viscosity to be fixed on the recording paper is realized with a molecular weight of a predetermined value or more.
[0073]
Polyester resins obtained from cyclohexanedicarboxylic acid, preferably polyvalent carboxylic acids containing asymmetric aromatic dicarboxylic acid, and polyhydric alcohols not containing aromatics, realize the above-mentioned fixing properties and other requirements for toner Satisfies a wide range of characteristics.
[0074]
Of particular importance in the present invention is that the use of aromatic polyhydric alcohols is limited to 5 mol% or less for polyhydric alcohols combined with cyclohexanedicarboxylic acid and preferably polycarboxylic acids containing asymmetric aromatic dicarboxylic acids. Preferably, an aromatic polyhydric alcohol is not used. Aromatic polyhydric alcohols, especially alkylene oxide adducts of bisphenol A, are mainly used to increase the glass transition point of polyester resins, and are almost universally used in practical polyester color toners. However, such aromatic polyhydric alcohols increase the affinity for the heat-resistant film and, on the contrary, lack the affinity for the recording paper in the fixing method combining the heat-resistant film and the thermal head as the main subject of the present invention. It does not show good fixing properties. Further, the durability of the obtained image, particularly the affinity with a plasticizer contained in a vinyl chloride sheet, poppy rubber or the like is high, and the image may be damaged by long-time contact with an object containing these plasticizers.
[0075]
In addition, the ionic group is necessary when a substantially spherical toner is produced in the wet process. Spherical toners are considered to be highly suitable for recent non-magnetic one-component development systems and the like, and in the present invention, which is mainly intended to be compatible with small color machines, the non-magnetic one is a powerful developing mechanism in small color machines. A toner composition suitable for component development is considered to be particularly important for enhancing the value of the invention.
[0076]
【Example】
[0077]
Hereinafter, although the manufacture example of a polyester resin and an Example are shown and this invention is demonstrated further in detail, this invention is not a thing limited to this at all.
[0078]
The characteristic values were measured as follows.
[0079]
(1) Dispersion ratio (weight average molecular weight / number average molecular weight)
According to GPC analysis.
[0080]
(2) Specific gravity
According to the floating method.
[0081]
(3) Temperature at which the melt viscosity reaches 10,000 poise
A value obtained from a plot in which the melt viscosity of the resin was measured in increments of 5 ° C. using a flow tester CFT-500C manufactured by Shimadzu Corporation, and the logarithm of the melt viscosity was plotted on the vertical axis and the temperature was plotted on the horizontal axis.
[0082]
(4) Intrinsic viscosity
The value calculated | required using the 60/1/40 weight ratio liquid mixture of a phenol / 1,1,2,2, -tetrachloroethane for a solvent.
[0083]
(5) Surface energy
Value calculated from contact angle between water and methylene iodide.
[0084]
(6) Acid value
By titration method.
[0085]
(7) SO₃Na group equivalent
Value converted from S (sulfur) element content determined by fluorescent X-ray analysis.
[0086]
(8) Average particle size, particle size distribution
According to the Coulter counter method.
[0087]
(9) Sphericality
A value obtained by image processing (500 or more measured particles) using an image analyzer V10 (manufactured by Toyobo Co., Ltd.) of SEM photographs of particles.
[0088]
(Polyester resin polymerization example 1) (vacuum polymerization method)
In an autoclave equipped with a thermometer and a stirrer,
58 parts by weight of dimethyl terephthalate
58 parts by weight of dimethyl isophthalate
102 parts by weight of ethylene glycol
79 parts by weight of cyclohexanedimethanol
0.07 parts by weight of tetrabutoxy titanate
Was transesterified by heating at 170-220 ° C. for 180 minutes. Next, the temperature of the reaction system is lowered to 160 ° C.
34 parts by weight of 1,4-cyclohexanedicarboxylic acid
1,2-cyclohexanedicarboxylic anhydride 30 parts by weight
As a result of raising the temperature of the reaction system to 240 ° C. and conducting an esterification reaction for 100 minutes, and further continuing the reaction at 240 ° C. under a system pressure of 1 to 10 mmHg for 60 minutes, a polyester resin (A1) was obtained. The intrinsic viscosity of the polyester resin (A1) was 0.285, and the glass transition point was 51 ° C. The copolymer composition ratio by NMR analysis is
Terephthalic acid 30 mol%
Isophthalic acid 30 mol%
1,4-cyclohexanedicarboxylic acid 20 mol%
1,2-cyclohexanedicarboxylic acid 20 mol%
Against alcohol components
Ethylene glycol 75 mol%
Cyclohexanedimethanol 25 mol%
Met. Other characteristic values are shown in Table 1.
[0089]
Thereafter, polymerization was carried out in the same manner to obtain polyester resins (A2) to (A8), (A10), (A11), (B1) to (B3), (B7) and (B8) shown in Tables 1 and 2.
[0090]
(Polyester resin polymerization example 2) (vacuum polymerization method, carboxyl group terminal addition)
In an autoclave equipped with a thermometer and a stirrer,
58 parts by weight of dimethyl isophthalate
68 parts by weight of ethylene glycol
81 parts by weight of propylene glycol
0.07 parts by weight of tetrabutoxy titanate
Was transesterified by heating at 170-220 ° C. for 180 minutes. Next, the temperature of the reaction system is lowered to 160 ° C.
45 parts by weight of phthalic anhydride
53 parts by weight of 1,2-cyclohexanedicarboxylic anhydride
The reaction system was heated to 240 ° C. and esterified for 100 minutes, and the reaction was continued at 240 ° C. under a system pressure of 1 to 10 mmHg for 60 minutes. Thereafter, the inside of the autoclave is replaced with nitrogen gas, the pressure is changed to atmospheric pressure, the temperature is maintained at 190 ° C,
Trimellitic anhydride 10 parts by weight
As a result of continuing the reaction for 30 minutes, a polyester resin (A9) was obtained. Details are shown in Table 1.
[0091]
(Polyester resin polymerization example 3) (atmospheric pressure polymerization method)
In an autoclave equipped with a thermometer and a stirrer,

And reacted at 200 ° C. to obtain a polyester resin (B4). Details are shown in Table 2. Thereafter, polyester resins (B5) and (B6) were obtained in the same manner.
[0092]
The abbreviations in Tables 1 and 2 are as follows.
[0093]
NDC naphthalene dicarboxylic acid
TPA terephthalic acid
IPA Isophthalic acid
OPA orthophthalic acid
14CHDA 1,4-cyclohexanedicarboxylic acid
12CHDA 1,2-cyclohexanedicarboxylic acid
DSA dodecenyl succinic acid
MA maleic acid
TMA trimellitic acid
SIP 5-sodium sulfoisophthalic acid
EG ethylene glycol
PG propylene glycol
NPG Neopentyl glycol
CHDM cyclohexanedimethanol
BPA-EO Bisphenol A ethylene oxide adduct (average molecular weight 350)
Propylene oxide adduct of BPA-PO bisphenol A (average molecular weight 400)
DAOH hydrogenated dimer diol
PPG polypropylene glycol (average molecular weight 1500)
It is.
[0094]
(Examples 1-11, Comparative Examples 1-8)
95 parts by weight of the polyester resin (A1) obtained in the above polymerization example of the polyester resin is coarsely pulverized with a chopper mill, and 5 parts by weight of copper phthalocyanine-based cyan pigment heliogen blue S7084 [BASF Corp.] is preliminarily prepared with a ball mill. After mixing, knead in a hot roll mill, cool, then coarsely pulverize again, then finely pulverize in a jet mill, and then classify, further surface treatment with a hydrophobic silica fine powder Aerosil in a Henschel mixer, average particle size An 8.5 μm cyan toner (T1) was obtained. 5 parts by weight of the obtained toner was charged into a ball mill together with 95 parts by weight of a ferrite carrier F-100 [manufactured by Powdertech Co., Ltd.] and stirred for about 15 minutes to obtain a developer.
[0095]
The obtained developer was loaded into a test machine from which a fixing device of a commercially available dry electrophotographic copying machine was removed, and an electrostatic image was formed on PPC paper and developed.
[0096]
The obtained unfixed image was fixed by the fixing device shown in FIG. The surface temperature of the thermal head was variable between 80 ° C and 300 ° C. As the heat-resistant film, a 25 μm-thick polyimide film having a low resistance PTFE coating in which a conductive filler is dispersed on the contact surface with the toner was used. The surface energy of the coating surface of the heat resistant film was 12.5 dyn / cm.
[0097]
The temperature of the thermal head was increased from 80 ° C. by 5 ° C., and the image was fixed, and the fixing state and the offset occurrence state were observed. As for the fixability, the cellophane tape is attached to the image portion where the toner thickness is about 5 μm or more at a constant pressure, and peeled off at a constant speed to evaluate whether the toner adheres to the cellophane tape. The temperature was defined as “fixing start temperature”. Further, the temperature was raised and the temperature at which the offset occurred was defined as the “offset generation temperature”. The recording paper feed speed was about 10 sheets per minute in the A4 vertical direction. The heat roll temperature was set to a temperature of fixing start temperature + 10 ° C., an image was printed and fixed on a transparent polyester film, projected and observed with an overhead projector, and “projected image evaluation” was performed. The results are shown in Table 3.
[0098]
In the same manner, Example toners (T2) to (T11) are produced from the polyester resins (A2) to (A11), and Comparative toners (T12) to (T19) are produced from the polyester resins (B1) to (B8). evaluated. The results are shown in Table 3.
[0099]
(Examples 12 to 15)
100 parts by weight of polyester resin (A8), 50 parts by weight of methyl ethyl ketone, 25 parts by weight of tetrahydrofuran, 3 parts by weight of UV absorber Seesorb 706 [manufactured by Cypro Kasei Co., Ltd.], magenta dye C.I. I. Disperse Red 60 Conc Cake (Mitsui Toatsu Chemical Co., Ltd.) 5 parts by weight was charged into a separable flask and dissolved at about 80 ° C. Next, the temperature was lowered to 70 ° C., 250 parts of water at 68 ° C. was added, and an aqueous dispersion of a polyester resin having a particle size of about 0.1 μm was obtained by a phase inversion emulsification method.
[0100]
Further, the obtained polyester aqueous micro-dispersion was put in a distillation flask and distilled until the fraction temperature reached 103 ° C., and after cooling, water was added to make the solid content concentration 25%. In a four-necked 1 liter separable flask equipped with a thermometer, a condenser, and a stirring blade, 400 parts by weight of the obtained polyester aqueous dispersion was charged and heated to 70 ° C.
[0101]
Next, 100 parts by weight of water in which 15.8 parts by weight of dimethylaminoethyl methacrylate was dissolved was added, and stirring was continued for 8 hours. As a result, the copolymer having a particle size of submicron order existing in the polyester water-based micro-dispersion grows coalesced particles, and when the average particle diameter is 6.5 μm and the average particle diameter is D, the range is 0.5D to 2D. A substantially spherical polyester resin particle having a particle occupancy of 95 wt%, an average sphericity of 0.98, and a particle occupancy of 97% with a sphericity of 0.7 or more was obtained. The obtained polyester resin particles were dehydrated and washed using a suction funnel and dried with a fluid dryer to obtain a magenta toner (T20).
[0102]
In the same manner, yellow toner (T21) was obtained by changing the dye to 5 parts by weight of Neopen Yellow 075 (manufactured by BASF). Similarly, the dye was changed to 8 parts by weight of Neopen / Cyan FF4238 (manufactured by BASF) to obtain cyan toner (T22). Further, the dye was changed to 10 parts by weight of oil black 860 [manufactured by Orient Chemical Co., Ltd.] and 5 parts by weight of T-77 [manufactured by Hodogaya Chemical Co., Ltd.], and the same operation was carried out to obtain a black toner (T23). The same evaluation was made hereinafter. The results are shown in Table 3.
[0103]
(Color image formation test)
For color printing, a positive image (landscape photograph) of YMCK, which is color-separated and dot-exchanged at 175 lines, is used as a document, and the fixing temperature is set to 4 colors by using the above-mentioned 4 color toners. Set to an intermediate value between the average value of the fixing start temperature and the average value of the offset generation temperature, first a yellow image is produced, and a full color image is formed on the obtained image by superimposing colors in the order of magenta image, then cyan and black. did. The obtained image shows a clear color with some misalignment, shows good fixability without causing an offset even in a portion where toners of different colors overlap, and develops secondary colors as well. Met. Similarly, as a result of forming a full-color image on a transparent film and observing with an overhead projector, it was confirmed that a clear projected image was obtained.
[0104]
(Examples 16 to 19)
100 parts by weight of polyester resin (A9), 50 parts by weight of methyl ethyl ketone, 25 parts by weight of tetrahydrofuran, 3 parts by weight of UV absorber Seesorb 706 [manufactured by Cypro Kasei Co., Ltd.], magenta dye C.I. I. Disperse Red 60 Conc Cake (Mitsui Toatsu Chemical Co., Ltd.) 5 parts by weight was charged into a separable flask and dissolved at about 80 ° C. Next, the temperature is lowered to 70 ° C., 3 parts by weight of triethanolamine is added, and then 250 parts of water at 68 ° C. is added. Obtained. Further, the obtained aqueous micro-dispersion was placed in a distillation flask and distilled until the fraction temperature reached 103 ° C. After cooling, water was added to make the solid content concentration 25%. Thereafter, operations were carried out in the same manner as in Examples 12 to 15 to obtain magenta toner (T24), yellow toner (T25), cyan toner (T26) and black toner (T27). The obtained toner had an average particle diameter D of 5.8 μm, an occupation ratio of 0.5D to 2.0D of 98%, and an occupation ratio of particles having a sphericity of 0.7 or more of 85%. The same evaluation was made hereinafter. The results are shown in Table 3.
[0105]
(Color image formation test)
For color printing, a YMCK four-color positive image (landscape photograph), which is color-separated and dot-exchanged at 175 lines, is used as a document, and the same operation as in Examples 12 to 15 below is performed using the above-mentioned four colors of toner. An image was formed. The obtained image shows a clear color with some misalignment, shows good fixability without causing an offset even in a portion where toners of different colors overlap, and develops secondary colors as well. Met. Similarly, as a result of forming a full-color image on a transparent film and observing with an overhead projector, it was confirmed that a clear projected image was obtained.
[0106]
(Examples 20 to 22)
Using polyester resin (A1), the pigment is 5 parts by weight of magenta pigment Hosta Palm Pink E02 (toner grade) [manufactured by Hoechst], 5 parts by weight of Nova Palm Yellow P-HGVP2066 [manufactured by Hoechst] as a yellow pigment, black pigment As a substitute for 5 parts by weight of Printex 150T (Degussa), toners (T28), (T29) and (T30) were obtained in the same manner as in the following examples. Table 3 shows the results evaluated in the same manner as in the following examples.
[0107]
(Color image formation test)
For color printing, a YMCK four-color positive image (landscape photograph) that was color-separated and dot-exchanged at line 175 was used as a document, and the above three-color toner and cyan toner (T1) were used. A full color image was formed by operating in the same manner as described above. The obtained image has a slight misalignment but shows a clear color, shows good fixability without causing an offset even in a portion where toners of different colors overlap, and has a favorable secondary color development Met. Similarly, as a result of forming a full-color image on a transparent film and observing with an overhead projector, it was confirmed that a clear projected image was obtained.
[0108]
(Comparative Example 9)
95 parts by weight of the polyester resin (B1) obtained in the polymerization example of the polyester resin is roughly pulverized by a chopper mill, and 5 parts by weight of a copper phthalocyanine-based cyan pigment heliogen blue S7084 [BASF Corp.] having a softening point of 110 ° C. 2 parts by weight of ethylene / propylene copolymer wax and 3 parts by weight of stearyl ketene dimer are premixed in a ball mill, kneaded in a hot roll mill, cooled, coarsely ground again, and then finely ground in a jet mill and classified. As a result, a cyan toner (T31) having an average particle diameter of 8.3 μm was obtained. Evaluation was performed in the same manner as in the following examples. The offset generation temperature increased, and an image having a somewhat smooth surface could be obtained, but the projected image was unclear.
[0109]
[Table 1]

[0110]
[Table 2]

[0111]
[Table 3]

[0112]
【The invention's effect】
The toner for developing an electrostatic charge image according to claim 1 has a wide interval between a fixing start temperature and an offset generation temperature, a good fixing property, a combination of a heat resistant film capable of saving power and quick start, and a thermal head. Excellent fixed images can be obtained with the equipment, and color image reproducibility is also good.In particular, the fixing property is excellent in a high-temperature heat fixing device.
[0114]
Claim 2The toner for developing an electrostatic charge image described in 1 can realize particularly good fixability and excellent offset resistance.
[0115]
Claim 3The toner for developing an electrostatic charge image described in 1 can realize particularly good fixability and excellent offset resistance.
[0116]
Claim 4The electrostatic charge image developing toner described in 1) has a stable toner charge, good toner moisture resistance, and the amount of charge of the toner fluctuates due to environmental changes, which may hinder image formation. Absent.
[0117]
Claim 5The electrostatic image developing toner described in 1) can develop an electrostatic image particularly stably.
[0118]
Claim 6The electrostatic charge image developing toner fixing method described in 1) has a wide interval between the fixing start temperature and the offset generation temperature, good fixability, power saving, and a combination of a heat resistant film capable of quick start and a thermal head. An excellent fixed image can be obtained also in the apparatus, and color image reproducibility is also good.
[Brief description of the drawings]
FIG. 1 is an explanatory diagram of a fixing device attached to a copying machine used for evaluation.
[Explanation of symbols]
1 Thermal head
2 heat resistant film
3 Drive roll
4 Followed roll
5 Recording paper
6 Pressure roll

Claims (6)

By polycondensation of a polycarboxylic acid containing 5% or more of cyclohexanedicarboxylic acid and a polyhydric alcohol mainly composed of an aliphatic diol or an alicyclic diol and having an aromatic polyhydric alcohol content of 5 mol% or less. In the obtained toner for developing an electrostatic charge image containing a binder mainly composed of a polyester resin having a glass transition point of 50 ° C. or higher, the polyester resin comprises:
・ 10 to 70 mol% of cyclohexanedicarboxylic acid
-30-90 mol% of asymmetric aromatic dicarboxylic acid
A polyvalent carboxylic acid,
-10 to 80 mol% of ethylene glycol
-10-80 mol% of propylene glycol
-0-10 mol% of dimer diol
-Polypropylene glycol (converted to the number of glycol residues) is 0 to 20 mol%
-0-5 mol% of diol derived from bisphenol A
With polyhydric alcohols
A toner for developing an electrostatic image, which is a polyester resin obtained by polycondensation . Polyester resin
T _a ≦ 160 × η _{sp / c} +75 where T _{a is} the temperature at which the melt viscosity of the polyester resin is 10,000 poises and η _{sp / c} is the value of the intrinsic viscosity of the polyester resin.
The toner for developing an electrostatic charge image according to claim 1, wherein: 3. The electrostatic image developing toner according to claim 1 , wherein the surface energy of the polyester resin is 45 dyn / cm or less. The polyester resin is 20 to 2000 eq. The toner for developing an electrostatic charge image according to claim 1, 2 or 3 , which contains an ionic group of / ton. The average particle diameter D of toner is is 2 to 10 [mu] m, according to claim 1, 2, 3 or 4, wherein the sphericity of 0.7 or more of the particles are particles of substantially spherical account for more than 70% of the total Toner for developing electrostatic images. 6. The toner for developing an electrostatic charge image according to claim 1, wherein the surface energy of the surface in direct contact with the toner is 50 dyn / cm or less, and the surface temperature at the time of fixing is in the range of 60 to 200 ° C. fixing process of the toner for electrostatic image development, which comprises fixing by some fixing member.

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