JP4806335B2 - Method for producing polyester resin for toner - Google Patents
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- JP4806335B2 JP4806335B2 JP2006322114A JP2006322114A JP4806335B2 JP 4806335 B2 JP4806335 B2 JP 4806335B2 JP 2006322114 A JP2006322114 A JP 2006322114A JP 2006322114 A JP2006322114 A JP 2006322114A JP 4806335 B2 JP4806335 B2 JP 4806335B2
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本発明は、トナー用ポリエステル樹脂の製造方法に関する。 The present invention relates to a method for producing a polyester resin for toner.
ポリエステル樹脂の製造工程においては、重合反応を行った後、不活性ガスで重合釜内を加圧してポリエステル樹脂を吐出させ、冷却装置によって冷却固化した後、粉砕機にて粉砕することが行われている。 In the production process of the polyester resin, after the polymerization reaction is performed, the inside of the polymerization kettle is pressurized with an inert gas, the polyester resin is discharged, cooled and solidified by a cooling device, and then pulverized by a pulverizer. ing.
この場合、ポリエステル樹脂を重合釜内から吐出させる際に、吐出時間に対応するポリエステル樹脂の重合釜内での滞在時間の差によって、吐出されるポリエステル樹脂の粘度、溶融弾性等の樹脂物性が変化し、結果として得られるポリエステル樹脂は、吐出時の経過時間に対応した異なる樹脂物性を有するものの混合物となることが知られている。このような異なる樹脂物性を有するポリエステル樹脂の混合物では、樹脂物性の均一性が低いために、これをトナー用バインダー樹脂として用いた場合、トナーの紙への定着不良あるいは感光体汚染が発生するという問題があった。特に、ポリエステル樹脂の平均の軟化温度に対してプラス１０℃程度の樹脂成分が混入していると、これを用いたトナーの物性に影響を及ぼし、定着不良等が発生しやすくなる。一方、平均の軟化温度に対してマイナス１０℃程度の樹脂成分が混入していると、これを用いたトナーの物性に影響を及ぼし、感光体汚染や定着ロールへの付着、いわゆるオフセット現象が発生しやすいことが知られている。 In this case, when the polyester resin is discharged from the polymerization vessel, the resin properties such as viscosity and melt elasticity of the discharged polyester resin change depending on the difference in the residence time of the polyester resin corresponding to the discharge time in the polymerization vessel. The resulting polyester resin is known to be a mixture of different resin properties corresponding to the elapsed time during ejection. In such a mixture of polyester resins having different resin physical properties, since the uniformity of the resin physical properties is low, when this is used as a binder resin for toner, poor fixing of toner to paper or photoreceptor contamination occurs. There was a problem. In particular, if a resin component of about + 10 ° C. with respect to the average softening temperature of the polyester resin is mixed, it affects the physical properties of the toner using the polyester resin, and fixing defects are likely to occur. On the other hand, if a resin component of about minus 10 ° C. is mixed with respect to the average softening temperature, it affects the physical properties of the toner using this, causing the photoreceptor contamination and adhesion to the fixing roll, so-called offset phenomenon. It is known to be easy to do.
この吐出経時変化に対応する樹脂物性の不均一性を改良するために、特許文献１には、反応温度より樹脂吐出温度を低く設定し、かつ、吐出開始時の樹脂粘度と吐出終了時の樹脂粘度との差を特定の範囲とする方法が提案されている。この方法で得られるポリエステル樹脂は、釜からの吐出中の樹脂粘度、溶融弾性等の樹脂物性の経時変化が大きく、軟化温度範囲の上下限値の差が３０℃以上あるため、十分な樹脂物性を得るためには、吐出された樹脂粉砕物を混合機によりさらに混合する必要があり、より煩雑な工程が必要となるという問題があった。 In order to improve the non-uniformity of the resin physical properties corresponding to the change with time of the discharge, Patent Document 1 discloses that the resin discharge temperature is set lower than the reaction temperature, and the resin viscosity at the start of discharge and the resin at the end of discharge. A method has been proposed in which the difference from the viscosity is in a specific range. The polyester resin obtained by this method has a large change with time in resin properties such as resin viscosity and melt elasticity during discharge from the kettle, and the difference between the upper and lower limits of the softening temperature range is 30 ° C. In order to obtain the above, it is necessary to further mix the discharged resin pulverized product with a mixer, and there is a problem that a more complicated process is required.
本発明の目的は、吐出時の経時変化による樹脂物性の不均一化を抑制し、混合機等を使用しなくても均一な樹脂物性を有するトナー用ポリエステル樹脂を製造することのできる方法を提供することにある。 An object of the present invention is to provide a method capable of producing a polyester resin for a toner having a uniform resin physical property without suppressing a non-uniform resin physical property due to a change with time during discharge. There is to do.
本発明は、上記課題を解決するため、下記の（Ａ）工程、（Ｂ）工程及び（Ｃ）工程を経た後、吐出中の樹脂の軟化温度が吐出開始時の樹脂の軟化温度より低下した時点で吐出を一旦中止し、再度（Ｂ）工程及び（Ｃ）工程を行うことを特徴とするトナー用ポリエステル樹脂の製造方法を提供する。
（Ａ）２価以上の酸成分と２価以上のアルコール成分を反応させるエステル化反応又はエステル交換反応工程
（Ｂ）減圧下で行う重縮合反応工程
（Ｃ）ポリエステル樹脂を吐出する工程
In order to solve the above-mentioned problems, the present invention has undergone the following steps (A), (B) and (C), and the softening temperature of the resin during discharge is lower than the softening temperature of the resin at the start of discharge. Disclosed is a method for producing a polyester resin for toner , wherein the discharge is temporarily stopped at the time, and the steps (B) and (C) are performed again .
(A) Esterification reaction or transesterification reaction step in which a divalent or higher valent acid component and a divalent or higher alcohol component are reacted (B) A polycondensation reaction step performed under reduced pressure (C) A step of discharging a polyester resin
また、本発明は、重合釜中の反応物を混合しながら吐出させることを特徴とする上記トナー用ポリエステル樹脂の製造方法を提供する。 The present invention also provides a method for producing a polyester resin for toner, wherein the reactants in the polymerization vessel are discharged while being mixed.
本発明のトナー用ポリエステル樹脂の製造方法を用いることにより、吐出時の経時変化による樹脂物性の不均一化を抑制させるとともに、混合機等を使用しなくても均一な樹脂物性を有するトナー用ポリエステル樹脂を提供することができる。 By using the method for producing a polyester resin for toner according to the present invention, it is possible to suppress non-uniform resin physical properties due to changes over time during ejection, and to have uniform resin physical properties without using a mixer or the like. A resin can be provided.
以下、本発明の好ましい態様について説明するが、本発明はこれらの態様のみに限定されるものではなく、その精神と実施の範囲内において様々な変更が可能であることを理解されたい。 Hereinafter, preferred embodiments of the present invention will be described. However, it should be understood that the present invention is not limited to these embodiments, and that various modifications can be made within the spirit and scope of implementation.
本発明の製造方法で製造するトナー用ポリエステル樹脂は、２価以上の酸成分と２価以上のアルコール成分とを基本構成成分とするものである。
２価以上の酸成分としては、テレフタル酸、イソフタル酸等の芳香族ジカルボン酸、フタル酸、セバシン酸、イソデシル琥珀酸、マレイン酸、フマル酸、アジピン酸等の脂肪族ジカルボン酸、及びそれらの低級アルキルエステル又は酸無水物等が挙げられる。これらのジカルボン酸の低級アルキルエステルとしては、例えば、モノメチルエステル、モノエチルエステル、ジメチルエステル、ジエチルエステル等が挙げられる。また、３価以上の多価カルボン酸成分を使用することもでき、かかる多価カルボン酸成分としては、例えば、トリメリット酸、ピロメリット酸、１，２，４−シクロヘキサントリカルボン酸、２，５，７−ナフタレントリカルボン酸、１，２，４−ナフタレントリカルボン酸、１，２，５−ヘキサントリカルボン酸、１，２，７，８−オクタンテトラカルボン酸及びそれらの低級アルキルエステル又は酸無水物を挙げることができる。
The polyester resin for toner produced by the production method of the present invention comprises a divalent or higher acid component and a divalent or higher alcohol component as basic constituent components.
The divalent or higher acid component includes aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, aliphatic dicarboxylic acids such as phthalic acid, sebacic acid, isodecyl succinic acid, maleic acid, fumaric acid and adipic acid, and lower Examples include alkyl esters and acid anhydrides. Examples of lower alkyl esters of these dicarboxylic acids include monomethyl esters, monoethyl esters, dimethyl esters, diethyl esters and the like. Trivalent or higher polyvalent carboxylic acid components can also be used. Examples of such polyvalent carboxylic acid components include trimellitic acid, pyromellitic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5. , 7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,2,7,8-octanetetracarboxylic acid and their lower alkyl esters or acid anhydrides Can be mentioned.
２価以上のアルコール成分としては、例えば、エチレングリコール、ネオペンチルグリコール、１，２−プロパンジオール、１，３−プロパンジオール、１，３−ブタンジオール、１，４−ブタンジオール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、１，４−シクロヘキサンジメタノール等のジオール類、ビスフェノールＡ、水添ビスフェノールＡ、ポリオキシエチレン−（２．０）−２，２−ビス（４−ヒドロキシフェニル）プロパン、ポリオキシプロピレン−（２．０）−２，２−ビス（４−ヒドロキシフェニル）プロパン、ポリオキシプロピレン−（２．２）−ポリオキシエチレン−（２．０）−２，２−ビス（４−ヒドロキシフェニル）プロパン、ポリオキシプロピレン−（６．０）−２，２−ビス（４−ヒドロキシフェニル）プロパン、ポリオキシプロピレン−（２．２）−２，２−ビス（４−ヒドロキシフェニル）プロパン、ポリオキシプロピレン−（２．４）−２，２−ビス（４−ヒドロキシフェニル）プロパン、ポリオキシプロピレン−（３．３）−２，２−ビス（４−ヒドロキシフェニル）プロパン等のビスフェノールＡアルキレンオキシド付加物などの２価のアルコールを挙げることができる。また、３価以上の多価アルコール成分として、例えば、ソルビトール、１，２，３，６−ヘキサテトラロール、１，４−ソルビタン、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、１，２，４−ブタントリオール、１，２，５−ペンタトリオール、グリセロール、２−メチルプロパントリオール、２−メチル−１，２，４ブタントリオール、トリメチロールプロパン、１，３，５−トリヒドロキシメチルベンゼンなどを使用することもできる。これらの酸成分及びアルコール成分は、それぞれ単独で使用してもよく、２種以上を併用してもよい。 Examples of the dihydric or higher alcohol component include ethylene glycol, neopentyl glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, diethylene glycol, and triethylene. Diols such as glycol, polyethylene glycol, 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxy Propylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.2) -polyoxyethylene- (2.0) -2,2-bis (4-hydroxy) Phenyl) propane, polyoxypropylene- (6.0) -2,2-bi (4-hydroxyphenyl) propane, polyoxypropylene- (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.4) -2,2-bis (4-hydroxy) And dihydric alcohols such as bisphenol A alkylene oxide adducts such as phenyl) propane and polyoxypropylene- (3.3) -2,2-bis (4-hydroxyphenyl) propane. Examples of the trihydric or higher polyhydric alcohol component include sorbitol, 1,2,3,6-hexatetralol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4. -Uses butanetriol, 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4butanetriol, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. You can also These acid components and alcohol components may be used alone or in combination of two or more.
本発明の（Ａ）工程について述べる。
２価の酸成分及び２価のアルコール成分、さらに所望によりこれらに加えて３価以上の多価カルボン酸成分及び／又は３価以上の多価アルコール成分を反応容器に投入し、加熱昇温して、エステル化反応又はエステル交換反応を行う。エステル化反応又はエステル交換反応の温度は、１５０〜３００℃であることが好ましい。エステル化反応又はエステル交換反応の温度が１５０℃以上である場合に、反応率を十分上げることができる傾向にあり、３００℃以下である場合には分解反応を抑制することができる傾向にある。この反応温度の下限値は１８０℃以上がより好ましく、２００℃以上がさらに好ましく、２２０℃以上が特に好ましく、２４０℃以上が最も好ましい。また、上限値は２９０℃以下がより好ましく、２８０℃以下が特に好ましい。
次いで、常法に従って反応で生じた水またはアルコールを除去する。
The step (A) of the present invention will be described.
A divalent acid component and a divalent alcohol component, and if desired, in addition to these, a trivalent or higher polyvalent carboxylic acid component and / or a trivalent or higher polyhydric alcohol component are added to the reaction vessel, and the temperature is raised. Then, esterification reaction or transesterification reaction is performed. The temperature of the esterification reaction or transesterification reaction is preferably 150 to 300 ° C. When the temperature of the esterification reaction or transesterification reaction is 150 ° C. or higher, the reaction rate tends to be sufficiently increased, and when it is 300 ° C. or lower, the decomposition reaction tends to be suppressed. The lower limit of the reaction temperature is more preferably 180 ° C. or higher, further preferably 200 ° C. or higher, particularly preferably 220 ° C. or higher, and most preferably 240 ° C. or higher. The upper limit is more preferably 290 ° C. or less, and particularly preferably 280 ° C. or less.
Next, water or alcohol generated by the reaction is removed according to a conventional method.
本発明の（Ｂ）工程について述べる。
その後引き続き重合反応を実施するが、このとき、好ましくは１５０ｍｍＨｇ（２０ｋＰａ）以下の、減圧下でアルコール成分を留出除去させながら重縮合を行う。重縮合反応の温度は、１５０〜３００℃であることが好ましい。重縮合反応の温度が１５０℃以上である場合に反応率を十分上げることができる傾向にあり、３００℃以下である場合に分解反応を抑制することができる傾向にある。この反応温度の下限値は１８０℃以上がより好ましく、２００℃以上がさらに好ましく、２２０℃以上が特に好ましい。また、上限値は２９０℃以下がより好ましく、２８０℃以下がさらに好ましく、２６０℃以下が特に好ましい。また、真空度は１００ｍｍＨｇ（１３．３ｋＰａ）以下がより好ましく、５０ｍｍＨｇ（６．７ｋＰａ）以下が特に好ましい。また、重合釜内を減圧する方法としては、エゼクターを使用して減圧する方法や、真空ポンプを使用して減圧する方法等が挙げられるが、工業的な設備の簡素化、減圧操作の容易さの観点から、エゼクターを使用して減圧する方法が好ましい。この減圧方法を用いると、作業性が良く、また重合釜から反応物を吐出する際に、重合釜内の樹脂の増粘や樹脂物性の吐出経時に対する変化をより効果的に抑制することができる。また、重合釜内の攪拌翼の形状としては、十字型、パドル型、ディスクタービン型、ダブルヘリカル型、マックスブレンド、アンカー型、ファウドラー型、フルゾーン型、リボン型等があるが、釜内の樹脂温度の均一化や、重縮合反応による樹脂粘度上昇等から、マックスブレンドが好ましい。
The step (B) of the present invention will be described.
Subsequently, the polymerization reaction is carried out. At this time, polycondensation is preferably carried out while distilling off the alcohol component under reduced pressure, preferably 150 mmHg (20 kPa) or less. The temperature of the polycondensation reaction is preferably 150 to 300 ° C. When the temperature of the polycondensation reaction is 150 ° C. or higher, the reaction rate tends to be sufficiently increased, and when it is 300 ° C. or lower, the decomposition reaction tends to be suppressed. The lower limit of the reaction temperature is more preferably 180 ° C. or higher, further preferably 200 ° C. or higher, and particularly preferably 220 ° C. or higher. The upper limit is more preferably 290 ° C. or less, further preferably 280 ° C. or less, and particularly preferably 260 ° C. or less. The degree of vacuum is more preferably 100 mmHg (13.3 kPa) or less, and particularly preferably 50 mmHg (6.7 kPa) or less. In addition, examples of a method for reducing the pressure in the polymerization kettle include a method for reducing the pressure using an ejector, a method for reducing the pressure using a vacuum pump, and the like. From this point of view, a method of reducing the pressure using an ejector is preferable. When this pressure reduction method is used, workability is good, and when the reactant is discharged from the polymerization kettle, the thickening of the resin in the polymerization kettle and the change in the physical properties of the resin over time can be more effectively suppressed. . The shape of the stirring blade in the polymerization kettle includes a cross, paddle, disc turbine, double helical, max blend, anchor, fouller, full zone, ribbon, etc. Max blend is preferable from the viewpoint of uniform temperature and increased resin viscosity due to polycondensation reaction.
また、エステル化反応、エステル交換反応、重縮合時に用いる触媒としては、チタンブトキサイド、ジブチルスズオキサイド、酢酸スズ、酢酸亜鉛、二硫化スズ、三酸化アンチモン、二酸化ゲルマニウム等の公知の触媒を挙げることができる。 Examples of catalysts used for esterification, transesterification, and polycondensation include known catalysts such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, and germanium dioxide. Can do.
また、架橋構造を有するポリエステル樹脂を製造する場合には、高真空下でアルコール成分を留出除去させながら重縮合を進めてゆく過程で、ゲル化反応が生じ反応系内の粘度が急激に上昇するので、この粘度上昇に対応しながら、反応系内の真空度を調整してゲル化反応を制御するのが好ましい。 In addition, when producing a polyester resin having a cross-linked structure, a gelling reaction occurs and the viscosity in the reaction system rapidly increases in the process of polycondensation while distilling off alcohol components under high vacuum. Therefore, it is preferable to control the gelation reaction by adjusting the degree of vacuum in the reaction system while coping with this increase in viscosity.
本発明の（Ｃ）工程について述べる。
（Ｂ）工程終了後、反応系内の圧力を常圧に戻し、窒素により加圧して重合釜より樹脂を吐出することが好ましい。また、重合釜の樹脂の吐出先としては、冷却ベルト、ピンクラッシャーを有するベルトクーラーやドラムクーラー、自然放冷をさせるバット出し等の方法があるが、工業的作業性からベルトクーラーに吐出させる方法が好ましい。ベルトクーラーを用いると、作業性が良く、樹脂が冷却されるため、樹脂温度の均一化をはかることができる。さらに、吐出中の樹脂温度は、軟化温度に対して３０℃以上高いほうが好ましい。この温度を保つことにより、吐出する際に閉塞なく吐出することができる。
The step (C) of the present invention will be described.
(B) After completion of the step, it is preferable to return the pressure in the reaction system to normal pressure, pressurize with nitrogen and discharge the resin from the polymerization kettle. In addition, as a discharge destination of the resin in the polymerization kettle, there are a cooling belt, a belt cooler having a pink lasher, a drum cooler, a method of discharging a bat for natural cooling, etc., but a method of discharging the belt cooler from industrial workability Is preferred. When a belt cooler is used, workability is good and the resin is cooled, so that the resin temperature can be made uniform. Furthermore, the resin temperature during discharge is preferably higher by 30 ° C. than the softening temperature. By maintaining this temperature, it is possible to discharge without blocking when discharging.
本発明の製造方法の特徴は、（Ａ）工程、（Ｂ）工程及び（Ｃ）工程を経た後、反応釜からのポリエステル樹脂の吐出を途中で一旦中止し、減圧下での重縮合反応を再度行った後、吐出工程を再開する方法である。本発明の方法において、減圧下での重縮合反応を再度行う際の真空度としては、７５ｍｍＨｇ（１０ｋｐａ）以下が好ましい。７５ｍｍＨｇ（１０ｋｐａ）以下で減圧した場合、重合釜から吐出した反応物の樹脂粘度、溶融弾性等の樹脂物性の吐出経時に対する変化を抑制することができ、この真空度は６８ｍｍＨｇ（９ｋｐａ）以下がより好ましく、５３ｍｍＨｇ（７ｋｐａ）以下がさらに好ましく、４０ｍｍＨｇ（５ｋｐａ）以下が特に好ましい。また、（Ｂ）工程を再度開始するタイミングとしては、吐出中の樹脂の軟化温度が吐出開始時の樹脂の軟化温度から１０℃以下の範囲で低下した場合に行うことが好ましい。吐出開始時の樹脂の軟化温度から１０℃以下の範囲で低下した場合に（Ｂ）工程を再度行うことにより、反応物の樹脂粘度、溶融弾性等の樹脂物性の吐出経時に対する変化を抑制することができる。この（Ｂ）工程を再度開始するタイミングは、吐出中の樹脂の軟化温度が吐出開始時の樹脂の軟化温度から５℃以下の範囲で低下した場合がより好ましく、２℃以下の範囲で低下した場合が特に好ましい。また、再度行った（Ｂ）工程を終了し、（Ｃ）工程を再度開始するタイミングとしては、吐出中の樹脂の軟化温度が吐出開始時の樹脂の軟化温度から１０℃以下の範囲で上昇した場合に行うことが好ましい。吐出開始時の樹脂の軟化温度から１０℃以下の範囲で上昇した場合に（Ｃ）工程を再度行うことにより、反応物の樹脂粘度、溶融弾性等の樹脂物性の吐出経時に対する変化を抑制することができるとともに、トナーの品質安定化を図ることができる。この（Ｃ）工程を再度開始するタイミングは、吐出中の樹脂の軟化温度が吐出開始時の樹脂の軟化温度から５℃以下の範囲で上昇した場合がより好ましく、２℃以下の範囲で上昇した場合が特に好ましい。
ここで、（Ｂ）工程と（Ｃ）工程を繰り返す回数には特に制限はない。
The feature of the production method of the present invention is that after passing through the steps (A), (B) and (C), the discharge of the polyester resin from the reaction kettle is temporarily stopped halfway, and the polycondensation reaction under reduced pressure is performed. This is a method of restarting the discharge process after performing again. In the method of the present invention, the degree of vacuum when the polycondensation reaction under reduced pressure is performed again is preferably 75 mmHg (10 kpa) or less. When the pressure is reduced to 75 mmHg (10 kpa) or less, changes in the resin physical properties such as the resin viscosity and melt elasticity of the reaction product discharged from the polymerization kettle can be suppressed, and the degree of vacuum is 68 mmHg (9 kpa) or less. Preferably, 53 mmHg (7 kpa) or less is more preferable, and 40 mmHg (5 kpa) or less is particularly preferable. Moreover, it is preferable to perform the timing at which the step (B) is started again when the softening temperature of the resin being discharged falls within a range of 10 ° C. or less from the softening temperature of the resin at the start of discharging. When the temperature decreases within 10 ° C. or less from the softening temperature of the resin at the start of discharge, the change in the resin physical properties such as resin viscosity and melt elasticity of the reaction product over time is suppressed by performing step (B) again. Can do. The timing at which the step (B) is started again is more preferably when the softening temperature of the resin being discharged falls within a range of 5 ° C. or less from the softening temperature of the resin at the start of discharging, and falls within a range of 2 ° C. or less. The case is particularly preferred. In addition, as the timing to finish the step (B) performed again and start the step (C) again, the softening temperature of the resin being discharged rose within a range of 10 ° C. or less from the softening temperature of the resin at the start of discharging. It is preferable to carry out in some cases. When the temperature rises within a range of 10 ° C. or less from the softening temperature of the resin at the start of discharge, the change in the resin physical properties such as resin viscosity and melt elasticity of the reaction product over time is suppressed by performing step (C) again. In addition, the toner quality can be stabilized. The timing at which the step (C) is started again is more preferably when the softening temperature of the resin during discharge rises within a range of 5 ° C. or less from the softening temperature of the resin at the start of discharge, and rises within a range of 2 ° C. or less. The case is particularly preferred.
Here, there is no restriction | limiting in particular in the frequency | count of repeating a (B) process and a (C) process.
重合釜のスケールには特に制限はないが、吐出時間や重合釜冷却速度、攪拌翼の攪拌スピード等から５０ｔ／釜以下のスケールが好ましい。 The scale of the polymerization kettle is not particularly limited, but a scale of 50 t / kettle or less is preferable from the viewpoint of discharge time, polymerization kettle cooling speed, stirring blade stirring speed and the like.
また、本発明の製造方法により効果が最もよく達成されるトナー用ポリエステル樹脂としては、酸成分１００モル部に対し、３価以上の多価カルボン酸及び／又は３価以上の多価アルコール成分が５〜５０モル部であるポリエステル樹脂が好ましい。３価以上の多価カルボン酸および／または３価以上の多価アルコール成分が５モル部以上である場合には（Ｃ）工程時における吐出経時に対する反応釜中のポリエステル樹脂の樹脂粘度、溶融弾性等の変化が大きくなる傾向にあり、本発明の（Ｂ）工程及び（Ｃ）工程を繰り返す製造方法が、樹脂の品質安定化により大きな効果を及ぼすからである。一方、３価以上の多価カルボン酸及び／又は３価以上の多価アルコール成分が５０モル部を超えた場合には本発明の（Ｂ）工程及び（Ｃ）工程を繰り返す製造方法を用いても、樹脂粘度及び溶融弾性等の変化を抑制しにくくなる傾向がある。この３価以上の多価カルボン酸及び／又は３価以上の多価アルコール成分の量の下限値は７モル部以上がより好ましく、８モル部以上がさらに好ましく、９モル部以上が特に好ましい。また、上限値は４０モル部以下がより好ましく、３５モル部以下がさらに好ましく、３０モル部以下が特に好ましい。また、製造されるポリエステル樹脂の軟化温度範囲は１００〜１５０℃であることが好ましい。軟化温度が１００℃以上である場合には樹脂物性の吐出経時に対する変化をより効果的に抑制することができ、また１５０℃以下である場合には（Ｃ）工程をより容易に行うことができる。この軟化温度範囲の下限値は１１０℃以上がより好ましく、１２０℃以上がさらに好ましく、１３０℃以上が特に好ましい。また、上限値は１４５℃以下が特に好ましい。また、重合釜中の反応物を混合しながら吐出する方法としては、攪拌翼による攪拌混合やヘラなどを使用しての手動混合等の方法があるが、工業的作業性から、攪拌翼による攪拌を行って反応物を混合しながら吐出する方法が好ましい。この混合方法を用いると、作業性が良く、また釜内の樹脂温度にムラがなくなり、樹脂温度の均一化をはかることができ、反応物の樹脂粘度、溶融弾性等の樹脂物性の吐出経時に対する変化をより効果的に抑制することができる。 In addition, the polyester resin for toner that is most effectively achieved by the production method of the present invention includes a trivalent or higher polyvalent carboxylic acid and / or a trivalent or higher polyhydric alcohol component with respect to 100 mol parts of the acid component. The polyester resin which is 5-50 mol part is preferable. When the trivalent or higher polyvalent carboxylic acid and / or the trihydric or higher polyhydric alcohol component is 5 mol parts or more, the resin viscosity and melt elasticity of the polyester resin in the reaction kettle with respect to discharge time during the step (C) This is because the manufacturing method in which the steps (B) and (C) of the present invention are repeated has a great effect on stabilizing the quality of the resin. On the other hand, when the trivalent or higher polyvalent carboxylic acid and / or the trivalent or higher polyhydric alcohol component exceeds 50 mol parts, the production method of repeating the steps (B) and (C) of the present invention is used. However, it tends to be difficult to suppress changes in resin viscosity and melt elasticity. The lower limit of the amount of the trivalent or higher polyvalent carboxylic acid and / or trivalent or higher polyhydric alcohol component is more preferably 7 mol parts or more, further preferably 8 mol parts or more, and particularly preferably 9 mol parts or more. The upper limit is more preferably 40 parts by mole or less, still more preferably 35 parts by mole or less, and particularly preferably 30 parts by mole or less. Moreover, it is preferable that the softening temperature range of the polyester resin manufactured is 100-150 degreeC. When the softening temperature is 100 ° C. or higher, the change in the physical properties of the resin with respect to discharge time can be more effectively suppressed, and when it is 150 ° C. or lower, the step (C) can be performed more easily. . The lower limit of the softening temperature range is more preferably 110 ° C. or higher, further preferably 120 ° C. or higher, and particularly preferably 130 ° C. or higher. The upper limit is particularly preferably 145 ° C. or lower. In addition, as a method of discharging while mixing the reactants in the polymerization kettle, there are methods such as stirring and mixing with a stirring blade or manual mixing using a spatula. A method of discharging while mixing the reactants is preferable. When this mixing method is used, the workability is good, the resin temperature in the kettle is not uneven, the resin temperature can be made uniform, and the resin properties such as the resin viscosity of the reaction product and the melt elasticity against the discharge time. The change can be suppressed more effectively.
以下に実施例及び比較例を挙げて本発明をさらに具体的に説明するが、本発明はこれらの例により何らの限定もされるものではない。なお、実施例および比較例における性能評価は以下の方法を用いて行った。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples. In addition, the performance evaluation in an Example and a comparative example was performed using the following method.
樹脂の評価方法
（１）軟化温度（℃）
島津製作所（株）製フローテスターＣＦＴ−５００を用いて１ｍｍφ×１０ｍｍのノズル、荷重２９４Ｎ（３０ｋｇｆ）、昇温速度３℃／分の等速昇温下で測定した時、サンプル１．０ｇ中の１／２が流出した時の温度を軟化温度とした。
Resin evaluation method (1) Softening temperature (° C)
When using a flow tester CFT-500 manufactured by Shimadzu Corporation with a nozzle of 1 mmφ × 10 mm, a load of 294 N (30 kgf), and a temperature increase rate of 3 ° C./min, a sample of 1.0 g The temperature at which 1/2 flowed out was defined as the softening temperature.
（２）経時変化
吐出開始から終了までの間において、１時間毎に樹脂サンプリングし、軟化温度を測定して、以下の基準で判断した。
○（良好）：軟化温度の差が３℃未満
△（可）：軟化温度の差が３℃以上５℃未満
×（不良）：軟化温度の差が５℃以上
(2) Temporal change Resin sampling was performed every hour during the period from the start to the end of discharge, and the softening temperature was measured.
○ (Good): Difference in softening temperature is less than 3 ° C △ (possible): Difference in softening temperature is 3 ° C or more and less than 5 ° C × (Poor): Difference in softening temperature is 5 ° C or more
（３）トナー評価
ポリエステル樹脂を９３質量部、キナクリドン顔料（クラリアント社製Ｅ０２）３質量部、カルナバワックス（東洋ペトロライド社製）３質量部、負帯電性の荷電制御剤（オリエント化学社製Ｅ−８４）１質量部を使用し、ヘンシェルミキサーで３０分間混合した。次いで、得られた混合物を２軸混練機により１５０〜２００℃の範囲内の温度で溶融混練した。混練後、冷却してトナー塊を得、ジェットミル微粉砕機で微粉砕し、分級機でトナーの粒径を整えて、粒径を５μｍとした。得られた微粉末１００質量部に対して、０．２５質量部のシリカ（日本アエロジル社製Ｒ−９７２）を加え、ヘンシェルミキサーで混合して付着させ、最終的にトナーを得た。このトナーを用い、０．５ｍｇ／ｃｍ２のトナー濃度にて４．５ｃｍ×１５ｃｍのベタ画像を紙上に印刷した。このベタ画像紙をシリコーンオイルが塗布されていない定着ローラーを有し、ローラー速度１００ｍｍ／秒、温度１７０℃に設定したプリンター（カシオ計算機（株）製 ＳＰＥＥＤＩＡ Ｎ４−６１４）にて定着させ、以下の基準で判断した。
○（良好）：ホットオフセット（ＨＯＳ）、コールドオフセット（ＣＯＳ）ともに発生しない
×（劣る）：ホットオフセット（ＨＯＳ）及び／又はコールドオフセット（ＣＯＳ）が発生する
(3) Toner Evaluation 93 parts by weight of polyester resin, 3 parts by weight of quinacridone pigment (E02 manufactured by Clariant), 3 parts by weight of carnauba wax (manufactured by Toyo Petroride), negative charge control agent (E-, manufactured by Orient Chemical Co., Ltd.) 84) One part by mass was mixed with a Henschel mixer for 30 minutes. Subsequently, the obtained mixture was melt-kneaded at a temperature in the range of 150 to 200 ° C. by a biaxial kneader. After kneading, the mixture was cooled to obtain a toner lump, finely pulverized with a jet mill fine pulverizer, and the particle size of the toner was adjusted with a classifier to make the particle size 5 μm. To 100 parts by mass of the fine powder obtained, 0.25 part by mass of silica (R-972 manufactured by Nippon Aerosil Co., Ltd.) was added, mixed and adhered with a Henschel mixer, and finally a toner was obtained. Using this toner, a solid image of 4.5 cm × 15 cm was printed on paper at a toner concentration of 0.5 mg / cm 2 . This solid image paper was fixed with a printer (SPEDIA N4-614, manufactured by Casio Computer Co., Ltd.) having a fixing roller not coated with silicone oil, a roller speed of 100 mm / second, and a temperature of 170 ° C. Judged by criteria.
○ (Good): Neither hot offset (HOS) nor cold offset (COS) occurs × (Inferior): Hot offset (HOS) and / or cold offset (COS) occurs
実施例１
攪拌翼、蒸留塔、釜内温度検出端、温度計、窒素ガス導入管、コンデンサー、真空装置、真空計、トルク計、吐出口、熱交換器を備えた容積４ｍ３の重合釜に、表１に示す仕込み組成にて、モノマー成分を２０００ｋｇ仕込んだ。さらに、重合触媒として１０００ｐｐｍの三酸化アンチモンを添加した。次いで、重合釜中の攪拌翼の回転数を１２０ｒｐｍに保ち、熱媒ジャケットにより昇温を開始し、反応系内の温度を２６５℃になるように加熱し、この温度を保持した。反応系から水が留出し、エステル化反応が開始してから約７時間後、水の留出がなくなり、反応を終了した。次いで、反応系内の温度を２３０℃まで下げ、重合釜内を約１時間かけて７ｍｍＨｇ（１ｋＰａ）まで減圧し、反応系からジオール成分を留出させながら重縮合反応を行った。減圧開始から約２時間後に反応とともに反応系の粘度が上昇してきたため、真空度を７５ｍｍＨｇ（１０ｋＰａ）まで下げて反応を続けた。減圧開始から４時間経過後、反応系を常圧に戻した。次いで、攪拌翼の回転数６ｒｐｍで攪拌を行い、吐出速度４００ｋｇ／ｈにて、窒素により加圧して吐出口より釜内樹脂の吐出を開始した。吐出開始から１時間毎にサンプリングを行い、その都度フローテスターにて樹脂の軟化温度を測定したところ、吐出開始から２時間後に軟化温度の低下が始まったため、一旦吐出を中止し、７５ｍｍＨｇ（１０ｋｐａ）まで再度減圧を行った。１５分間減圧後、反応系を常圧に戻し、再度吐出を開始した。吐出しながら冷却ベルトにて樹脂を挟み、ピンクラッシャーで粉砕を行った。粉砕した樹脂をサンプリングし、それぞれの吐出経時の樹脂の軟化温度測定と、この樹脂を用いたトナー評価を行った。また、すべての吐出樹脂をヘンシェルミキサーを用いて混合し、この混合物についてトナー評価を行った。結果を表１に示す。
Example 1
Table 1 shows a 4 m 3 polymerization kettle equipped with a stirring blade, distillation tower, temperature detection end in the kettle, thermometer, nitrogen gas introduction pipe, condenser, vacuum device, vacuum gauge, torque meter, discharge port, and heat exchanger. The monomer composition was charged in an amount of 2000 kg. Further, 1000 ppm of antimony trioxide was added as a polymerization catalyst. Next, the number of revolutions of the stirring blade in the polymerization kettle was kept at 120 rpm, the temperature was raised by the heat medium jacket, and the temperature in the reaction system was heated to 265 ° C., and this temperature was maintained. Water was distilled from the reaction system, and about 7 hours after the start of the esterification reaction, the water was not distilled and the reaction was completed. Next, the temperature in the reaction system was lowered to 230 ° C., the pressure in the polymerization vessel was reduced to 7 mmHg (1 kPa) over about 1 hour, and a polycondensation reaction was performed while distilling the diol component from the reaction system. About 2 hours after the start of decompression, the viscosity of the reaction system increased with the reaction, so the degree of vacuum was lowered to 75 mmHg (10 kPa) and the reaction was continued. After 4 hours from the start of decompression, the reaction system was returned to normal pressure. Next, stirring was carried out at a rotation speed of 6 rpm of the stirring blade, and at a discharge speed of 400 kg / h, pressurization with nitrogen was started to start discharging the resin in the kettle from the discharge port. Sampling was performed every hour from the start of discharge, and the softening temperature of the resin was measured with a flow tester each time. As the softening temperature began to decrease 2 hours after the start of discharge, the discharge was temporarily stopped and 75 mmHg (10 kpa) The pressure was reduced again. After reducing the pressure for 15 minutes, the reaction system was returned to normal pressure, and discharging was started again. While discharging, the resin was sandwiched between cooling belts and pulverized with a pink lasher. The pulverized resin was sampled, and the softening temperature of the resin during each discharge was measured, and toner evaluation using this resin was performed. Further, all the discharged resins were mixed using a Henschel mixer, and the toner was evaluated for this mixture. The results are shown in Table 1.
実施例２
ポリエステル樹脂の製造に用いる無水トリメリット酸の仕込み組成を１８モルに変更した以外は実施例１の操作を繰り返した。評価結果を表１に示す。
Example 2
The procedure of Example 1 was repeated except that the trimellitic anhydride charge composition used for the production of the polyester resin was changed to 18 mol. The evaluation results are shown in Table 1.
実施例３
ポリエステル樹脂の製造に用いる無水トリメリット酸の仕込み組成を２５モルに変更した以外は実施例１の操作を繰り返した。評価結果を表１に示す。
Example 3
The procedure of Example 1 was repeated except that the trimellitic anhydride charge composition used for the production of the polyester resin was changed to 25 mol. The evaluation results are shown in Table 1.
実施例４
吐出時に攪拌を行わなかった以外は実施例１の操作を繰り返した。評価結果を表１に示す。
Example 4
The operation of Example 1 was repeated except that stirring was not performed during discharge. The evaluation results are shown in Table 1.
比較例１
実施例１と同様にエステル化反応および重縮合反応を行った後、反応系を常圧に戻し、窒素により加圧して吐出口より釜内樹脂の吐出を開始した。吐出開始から１時間毎にサンプリングを行い、その都度フローテスターにて樹脂の軟化温度を測定したところ、吐出開始から２時間後に軟化温度の低下が始まったが、再度減圧にする操作を行わず、そのまま吐出した。評価結果を表２に示す。
Comparative Example 1
After the esterification reaction and the polycondensation reaction were performed in the same manner as in Example 1, the reaction system was returned to normal pressure, pressurized with nitrogen, and the discharge of the resin in the kettle from the discharge port was started. Sampling was performed every hour from the start of discharge, and each time the softening temperature of the resin was measured with a flow tester, the softening temperature began to decrease after 2 hours from the start of discharge. It was discharged as it was. The evaluation results are shown in Table 2.
上記の実施例及び比較例の結果から、以下のことが判る。
１）実施例１〜３のように、再度減圧を実施し、反応物を重合釜から吐出させて製造したポリエステル樹脂は、いずれも吐出経時に対する樹脂の軟化温度の変化が小さく、また得られたポリエステル樹脂を含むトナーは良好な定着特性を示す。
２）吐出中に攪拌を行った実施例１で得られたポリエステル樹脂は、攪拌を行わなかった実施例４で得られたポリエステル樹脂に比べて、特に吐出経時に対する樹脂の軟化温度の変化が小さい。
The following can be seen from the results of the above-mentioned Examples and Comparative Examples.
1) As in Examples 1 to 3, the polyester resin produced by reducing the pressure again and discharging the reaction product from the polymerization kettle had a small change in the softening temperature of the resin with the passage of time and was obtained. A toner containing a polyester resin exhibits good fixing properties.
2) The polyester resin obtained in Example 1 that was agitated during discharge had a smaller change in the softening temperature of the resin particularly with respect to discharge time than the polyester resin obtained in Example 4 that was not agitated. .
３）架橋性成分である無水トリメリット酸の仕込み組成を１２モル％および１８モル％とした実施例１および２で得られた樹脂では、特に吐出経時に対する樹脂の軟化温度の変化が小さい。 3) In the resins obtained in Examples 1 and 2 in which the charge composition of trimellitic anhydride, which is a crosslinkable component, was 12 mol% and 18 mol%, the change in the softening temperature of the resin particularly with respect to discharge time was small.
４）吐出途中で再度減圧を行わなかった比較例１で得られたポリエステル樹脂では、吐出経時に対する樹脂の軟化温度の変化が大きく、特に吐出開始から３時間経過以降に吐出回収された樹脂は、これを含むトナー評価において、ホットオフセット（ＨＯＳ）が発生した。また、吐出された全部の樹脂の混合物を用いたトナー評価においても、ホットオフセットが発生した。このように、樹脂製造過程で樹脂物性の経時変化が大きい場合は、これをトナー用バインダー樹脂として用いた際に必要となる定着特性が得られないため工業的利用価値が低い。 4) In the polyester resin obtained in Comparative Example 1 in which decompression was not performed again in the middle of discharge, the change in the softening temperature of the resin with respect to discharge time was large. Particularly, the resin recovered and discharged after 3 hours from the start of discharge In the toner evaluation including this, hot offset (HOS) occurred. In addition, hot offset occurred in toner evaluation using a mixture of all discharged resins. As described above, when the change in physical properties of the resin during the resin production process is large, the fixing characteristics required when this resin is used as a binder resin for toner cannot be obtained, and thus the industrial utility value is low.
本発明は、吐出時の経時変化による樹脂物性の不均一化を抑制させるとともに、混合機等を使用しなくても均一な樹脂物性を有するトナー用ポリエステル樹脂を提供することができるので、産業上極めて有用である。 INDUSTRIAL APPLICABILITY Since the present invention can provide a polyester resin for a toner that suppresses non-uniform resin physical properties due to changes over time during ejection and has uniform resin physical properties without using a mixer or the like. Very useful.
Claims (2)
（Ａ）２価以上の酸成分と２価以上のアルコール成分を反応させるエステル化反応又はエステル交換反応工程
（Ｂ）減圧下で行う重縮合反応工程
（Ｃ）ポリエステル樹脂を吐出する工程 After the following steps (A), (B) and (C) , the discharge is temporarily stopped when the softening temperature of the resin being discharged is lower than the softening temperature of the resin at the start of discharge, and again (B ) Step and (C) step, a method for producing a polyester resin for toner.
(A) Esterification reaction or transesterification reaction step in which a divalent or higher valent acid component and a divalent or higher alcohol component are reacted (B) A polycondensation reaction step performed under reduced pressure (C) A step of discharging a polyester resin
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| JPH064696B2 (en) * | 1986-01-24 | 1994-01-19 | ダイセル化学工業株式会社 | Process for producing fluidity-modified polycarbonate |
| JP2567614B2 (en) * | 1987-07-20 | 1996-12-25 | 三菱レイヨン株式会社 | Method for producing crosslinked polyester resin |
| JPH02989A (en) * | 1988-03-17 | 1990-01-05 | Mitsubishi Rayon Co Ltd | Crosslinked polyester for toner |
| JPH0354574A (en) * | 1989-07-21 | 1991-03-08 | Mitsubishi Rayon Co Ltd | Polyester resin for toner and production thereof |
| JPH0920087A (en) * | 1995-05-02 | 1997-01-21 | Toray Ind Inc | Film for high definition thermal stencil printing base paper |
| JPH11236493A (en) * | 1998-02-20 | 1999-08-31 | Kuraray Co Ltd | Polyester resin composition and its production |
| JP3828872B2 (en) * | 2003-03-13 | 2006-10-04 | 三菱レイヨン株式会社 | Linear polyester resin for toner, toner, and method for producing linear polyester resin for toner |
| JP2005107182A (en) * | 2003-09-30 | 2005-04-21 | Mitsubishi Rayon Co Ltd | Polyester resin for toner and toner |
| JP2005157074A (en) * | 2003-11-27 | 2005-06-16 | Toyo Ink Mfg Co Ltd | Method for producing polyester resin for toner |
| JP2005275390A (en) * | 2004-02-26 | 2005-10-06 | Mitsubishi Rayon Co Ltd | Polyester resin for toner, its manufacturing method and toner |
| JP2006131752A (en) * | 2004-11-05 | 2006-05-25 | Toyobo Co Ltd | Method for producing polyester resin |
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