JP2006065015A - Method for manufacturing toner for electrostatic image development - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for efficiently manufacturing a toner excellent in low-temperature fixability, offset resistance and durability, a toner, a toner vessel, an image forming method and a process cartridge. <P>SOLUTION: The method for manufacturing the toner for electrostatic image development containing at least a colorant and a binder resin, wherein at least part of the binder resin is a crystalline polyester resin, has a step of storing an intermediate product or a final product in the toner manufacturing process at 45-65°C. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a toner for developing an electrostatic image for developing an electrostatic latent image on an image carrier used in an electrophotographic apparatus, an electrostatic recording apparatus or the like, a toner, a toner container, and an image forming method. The present invention relates to an apparatus and a process cartridge.

In recent years, in order to save energy by fixing the toner at a low temperature, the thermal energy given to the toner during fixing tends to be small. The 1999 International Energy Agency (IEA) DSM (Demand-side Management) program includes a technology procurement project for next-generation copiers, the requirements for which were published, and for copiers of 30 cpm and above, It is required to achieve dramatic energy saving compared to conventional copying machines so that the standby time is within 10 seconds and the standby power consumption is 10 to 30 watts or less (differs depending on the copying speed). In order to save such energy, it is required to reduce the standby time and power consumption during standby by reducing the heat capacity of the fixing device, and to reduce the heating temperature by fixing the toner at a low temperature.
In terms of the low-temperature fixing of toner, an attempt has been made to use a polyester resin having excellent low-temperature fixability and relatively good heat-resistant storage, in place of styrene-acrylic resins that have been frequently used. However, for further low-temperature fixing, it is necessary to control the thermal characteristics of the resin itself. However, if the glass transition temperature (Tg) is lowered too much, the heat-resistant storage stability is deteriorated or the molecular weight is decreased. If the softening temperature [T (F _1/2 )] of the resin is lowered too much, there are problems such as lowering the hot offset occurrence temperature. For this reason, even a polyester resin excellent in low-temperature fixability has not yet obtained a toner having excellent low-temperature fixability and high hot offset occurrence temperature by controlling the thermal characteristics of the resin itself.

  In order to solve this problem, an attempt is made to add a specific non-olefinic crystalline polymer having a sharp melt property in which the melt viscosity rapidly decreases from the solid state to the liquid state at the glass transition temperature in the binder resin ( Patent Document 1) and attempts to use crystalline polyester (Patent Document 2, Patent Document 3, and Patent Document 4) are available. However, in toners using crystalline resins, crystalline resins and binder resins other than crystalline resins are used. Optimization in terms of manufacturability such as fine dispersion mixing with components and improvement in grindability by melt kneading-pulverization method is insufficient. Regarding the fine dispersion mixing of the crystalline resin and the binder resin component other than the crystalline resin, the crystalline resin is finely mixed in the binder resin component other than the crystalline resin by using the finely divided crystalline resin as a raw material. Attempts to disperse (Patent Document 5) are also conceivable, however, investigations to thermally and finely disperse a crystalline resin having crystallinity and an amorphous binder resin, grindability by melt-kneading-pulverization classification method It is essential to consider improvement in the future.

JP 62-63940 A JP 2003-167384 A Japanese Patent No. 2931899 JP 2001-222138 A JP 2004-221740 A

  An object of the present invention is to provide an efficient toner production method, toner, toner container, image forming method, and process cartridge excellent in low-temperature fixability, offset resistance and durability.

It is solved by (1) to (22) of the present invention.
(1) “A method for producing an electrostatic charge image developing toner comprising at least a colorant and a binder resin, wherein at least one of the binder resins is a polyester resin (A) having crystallinity, A process for producing a toner for developing an electrostatic charge image, comprising a step of storing an intermediate product or a final product at a temperature of 45 ° C. to 65 ° C. ”
(2) The electrostatic charge according to item (1), wherein the storage time of the step of storing the intermediate product or the final product of the toner manufacturing process at a temperature of 45 ° C. to 65 ° C. is 6 hours or more. Toner manufacturing method for image development. "
(3) “The storage time of the step of storing the intermediate product or the final product of the toner production process at a temperature of 45 ° C. to 65 ° C. is 6 hours to 7 days,” Toner production method for electrostatic image development. "
(4) “The storage time of the step of storing the intermediate product or the final product of the toner manufacturing process at a temperature of 45 ° C. to 65 ° C. is 6 hours to 24 hours,” Toner production method for electrostatic image development. "
(5) “The step of producing the toner includes at least an external additive mixing step, and the step of storing the intermediate product of the toner production step at a temperature of 45 ° C. to 65 ° C. is performed before the external additive mixing step. The method for producing a toner for developing an electrostatic charge image according to any one of the above items (1) to (4), characterized in that it is carried out in the step (1).
(6) “The toner production process includes at least a classification process, and the step of storing the intermediate product of the toner production process at a temperature of 45 ° C. to 65 ° C. is performed in a process prior to the classification process. The method for producing a toner for developing an electrostatic charge image according to any one of the above items (1) to (4).
(7) “The process for producing the toner includes at least a pulverization process, and the step of storing the intermediate product in the toner production process at a temperature of 45 ° C. to 65 ° C. is performed in a process prior to the pulverization process. The method for producing a toner for developing an electrostatic charge image according to any one of the above items (1) to (4).
(8) The above (1) to (7), wherein the relative humidity in the step of storing the intermediate product or the final product of the toner manufacturing process at a temperature of 45 ° C. to 65 ° C. is 80% or less. The method for producing a toner for developing an electrostatic image according to any one of the items.
(9) “The polyester resin (A) has the following general formula (1) in its molecular main chain.

（式中、Ｒは炭素数２〜２０の直鎖状不飽和脂肪族基を示し、ｎは２〜２０の整数を示す）
で表わされるエステル結合を少なくとも６０モル％含有する結晶性ポリエステル樹脂（Ａ）であることを特徴とする前記第（１）項乃至第（８）項のいずれかに記載の静電荷像現像用トナー製造方法。」
（１０）「該ポリエステル樹脂（Ａ）の軟化温度〔Ｔ（Ｆ_１／２）〕が８０〜１３０℃の範囲にあり、そのガラス転移温度（Ｔｇ）が８０〜１３０℃の範囲にあることを特徴とする前記第（１）項乃至第（９）項のいずれかに記載の静電荷像現像用トナー製造方法。」
（１１）「該ポリエステル樹脂（Ａ）の粉末Ｘ線回折パターンにおいて、少なくとも２θ＝２０〜２５°の位置に回折ピークが存在することを特徴とする前記第（１）項乃至第（１０）項のいずれかに記載の静電荷像現像用トナー製造方法。」
（１２）「該結着樹脂における該ポリエステル樹脂（Ａ）の含有率が１〜５０重量％であることを特徴とする前記第（１）項乃至第（１１）項のいずれかに記載の静電荷像現像用トナー製造方法。」
（１３）「該ポリエステル樹脂（Ａ）を構成するアルコール成分が１，４−ブタンジオールおよび１，６−ヘキサンジオールの中から選ばれる少なくとも１つからなり、一方、該ポリエステル樹脂（Ａ）を構成する酸成分がマレイン酸およびフマル酸の中から選ばれる少なくとも１つからなることを特徴とする前記第（１）項乃至第（１２）項のいずれかに記載の静電荷像現像用トナー製造方法。」
（１４）「該結着樹脂が、少なくともガラス転移温度（Ｔｇ）が４０〜７０℃であり、その軟化温度〔Ｔ（Ｆ_１／２）〕が１２０〜１６０℃である非結晶性ポリエステル樹脂（Ｂ）を含有することを特徴とする前記第（１）項乃至第（１３）項のいずれかに記載の静電荷像現像用トナー製造方法。」
（１５）「該トナーが離型剤を含有する静電荷像現像用トナーであって、該離型剤が７０〜９０℃のガラス転移温度（Ｔｇ）を有するものであることを特徴とする前記第（１）項乃至第（１４）項のいずれかに記載の静電荷像現像用トナー製造方法。」
（１６）「該離型剤が脱遊離脂肪酸型カルナウバワックス、モンタンワックスおよび酸化ライスワックスから選ばれた１種または２種以上であることを特徴とする前記第（１）項乃至第（１５）項のいずれかに記載の画像形成用トナー製造方法。」
（１７）「該ポリエステル樹脂（Ａ）の粉末Ｘ線回折パターンにおいて、その２θが（ｉ）１９°〜２０°、（ii）２１°〜２２°、（iii）２３°〜２５°および（iv）２９°〜３１°の位置に回折ピークが現れることを特徴とする前記第（１）項乃至第（１６）項のいずれかに記載の静電荷像現像用トナー製造方法。」
（１８）「前記第（１）項乃至第（１７）項のいずれかに記載のトナー製造方法により製造された静電荷像現像用トナー。」
（１９）「前記第（１８）項に記載の静電荷像現像用トナーが充填されたトナー容器。」
（２０）「像担持体上に形成した静電潜像をトナーで現像する画像形成方法において、該トナーとして前記第（１８）項に記載の静電荷像現像用トナーを用いることを特徴とする画像形成方法。」
（２１）「少なくとも、感光体と、該感光体の表面を帯電させる帯電手段と、該感光体の表面に形成される静電潜像を静電潜像現像剤で現像する現像手段と、前記感光体の表面に残存する現像剤を払拭するクリーニング手段とを有し、該現像手段が前記第（１８）項に記載のトナーを用いるものであることを特徴とする画像形成装置。」
（２２）「現像手段と、帯電手段、クリーニング手段より選ばれる少なくとも１つの手段とを一体に支持し、画像形成装置本体に着脱自在なプロセスカートリッジであって、該現像手段が前記第（１８）項に記載の静電荷像現像用トナーを用いるものであることを特徴とするプロセスカートリッジ。」

(In the formula, R represents a linear unsaturated aliphatic group having 2 to 20 carbon atoms, and n represents an integer of 2 to 20)
The toner for developing an electrostatic charge image according to any one of (1) to (8) above, which is a crystalline polyester resin (A) containing at least 60 mol% of an ester bond represented by the formula: Production method. "
(10) “The softening temperature [T (F _1/2 )] of the polyester resin (A) is in the range of 80 to 130 ° C., and the glass transition temperature (Tg) is in the range of 80 to 130 ° C. 10. The method for producing a toner for developing an electrostatic charge image according to any one of the above items (1) to (9).
(11) In the powder X-ray diffraction pattern of the polyester resin (A), a diffraction peak exists at least at a position of 2θ = 20 to 25 °, wherein the items (1) to (10) are characterized. Or a method for producing a toner for developing an electrostatic image according to any one of the above.
(12) The static according to any one of (1) to (11), wherein the content of the polyester resin (A) in the binder resin is 1 to 50% by weight. Toner manufacturing method for charge image development. "
(13) “The alcohol component constituting the polyester resin (A) comprises at least one selected from 1,4-butanediol and 1,6-hexanediol, while constituting the polyester resin (A) The method for producing a toner for developing an electrostatic charge image according to any one of (1) to (12), wherein the acid component to be formed comprises at least one selected from maleic acid and fumaric acid . "
(14) “A non-crystalline polyester resin in which the binder resin has a glass transition temperature (Tg) of 40 to 70 ° C. and a softening temperature [T (F _1/2 )] of 120 to 160 ° C. ( The method for producing a toner for developing an electrostatic charge image according to any one of the items (1) to (13), comprising B). "
(15) “The toner is an electrostatic charge image developing toner containing a releasing agent, and the releasing agent has a glass transition temperature (Tg) of 70 to 90 ° C. The method for producing a toner for developing an electrostatic charge image according to any one of items (1) to (14). "
(16) The above-mentioned items (1) to (15), wherein the release agent is one or more selected from a liberated fatty acid type carnauba wax, a montan wax and an oxidized rice wax. The method for producing an image forming toner according to any one of the items).
(17) “In the powder X-ray diffraction pattern of the polyester resin (A), 2θ is (i) 19 ° to 20 °, (ii) 21 ° to 22 °, (iii) 23 ° to 25 ° and (iv The method for producing a toner for developing an electrostatic charge image according to any one of items (1) to (16), wherein a diffraction peak appears at a position of 29 ° to 31 °.
(18) “An electrostatic charge image developing toner produced by the toner production method according to any one of (1) to (17)”.
(19) “A toner container filled with the electrostatic image developing toner according to item (18)”.
(20) “In an image forming method for developing an electrostatic latent image formed on an image bearing member with toner, the toner for developing an electrostatic image according to the item (18)” is used as the toner. Image forming method. "
(21) “At least a photosensitive member, a charging unit for charging the surface of the photosensitive member, a developing unit for developing an electrostatic latent image formed on the surface of the photosensitive member with an electrostatic latent image developer, An image forming apparatus comprising: a cleaning unit that wipes off the developer remaining on the surface of the photosensitive member, wherein the developing unit uses the toner described in item (18).
(22) “A process cartridge which integrally supports a developing unit and at least one unit selected from a charging unit and a cleaning unit, and is detachable from an image forming apparatus main body. A process cartridge using the toner for developing an electrostatic charge image according to the item. "

  According to the present invention, a high-quality image having excellent crushability, low-temperature fixability, excellent offset resistance (high-temperature offset resistance, low-temperature offset resistance), excellent durability, good resolution, and no background stains. Image forming toner, an efficient manufacturing method thereof, an image forming method and apparatus using the same, and a process cartridge are provided.

  Hereinafter, the present invention will be described in detail.

(Manufacturing method, manufacturing process)
The toner of the present invention is obtained by melting and kneading toner constituent materials and then pulverizing and classifying, and is generally used as a conventional method, but is not limited to this method, and various methods including a polymerization method are possible. It is.
The polymerization method is different from other polymerization methods such as suspension polymerization method, emulsion polymerization method and dispersion polymerization method, but extension reaction method and the like can be used in addition to dissolution suspension method and polymer suspension method.

  In order to thermally and finely disperse and mix the crystalline polyester (A) and the amorphous polyester resin (B) in the toner in the present invention, the intermediate product of the toner manufacturing process is 45 ° C. to 45 ° C. It is necessary to provide a process of storing at a temperature of 65 ° C. for 6 hours or more. This treatment also achieves improvement in grindability in the melt-kneading-pulverization method. By storing the intermediate product of the toner production process at a temperature of 45 ° C. to 65 ° C. for 6 hours or more, at the domain interface between the crystalline polyester (A) and the amorphous polyester resin (B) in the intermediate product of the toner production process, A component derived from the crystalline polyester (A) that is compatible with the partially amorphous polyester resin (B) and is not crystallized is annealed (crystallized). As a result, in the non-crystalline state, the component derived from the crystalline polyester (A) having a low melting point and a low glass transition temperature is crystallized, whereby the glass transition temperature of this component is increased and the heat resistant storage stability of the toner is improved. To do. In addition, the domain interface between the crystalline polyester (A) and the non-crystalline polyester resin (B) is phase-separated, whereby a pulverized interface is easily formed, and the pulverization property is improved.

The storage temperature needs to be in the temperature range of 45 ° C. to 65 ° C., and the temperature of the toner resin component does not change at a temperature lower than 45 ° C., and the component derived from the crystalline polyester (A) at a temperature higher than 65 ° C. Other waxes and binder resins also undergo thermal changes, which may impair toner properties such as blocking.
The storage time is preferably long, and specifically needs to be in the range of 6 hours to 7 days. The higher the storage temperature is, the faster the crystallization speed of the component derived from the crystalline polyester (A) is, so that it can be stored for a short time. Since storage at 65 ° C. for 6 hours almost completes the crystallization of the component derived from the crystalline polyester (A), it may be stored for 6 hours or more. On the other hand, in storage at 45 ° C., the crystallization of the component derived from the crystalline polyester (A) is almost completed in 24 hours to 7 days. Therefore, when the amount of the crystalline polyester (A) is small, that is, less than 10% by weight. In some cases, when the amount of the crystalline polyester (A) is large, that is, when it is 10% by weight or more, crystallization of the component derived from the crystalline polyester (A) is almost completed by storing for 7 days. Therefore, storage for 24 hours to 7 days may be performed.

In addition, as the order of performing the process of storing at a temperature of 45 ° C. to 65 ° C., the process after the raw materials constituting the toner are mixed, that is, [1] before the external additive mixing process, [2] before the classification process, [ 3] It is effective to carry out in three ways before the grinding step. After mixing the external additive, the apparent volume of the intermediate product in the toner production process becomes large, so it is necessary to increase the storage space, and the external additive is stored in the middle of the toner production process by storing at a temperature of 45 ° C. to 65 ° C. Since it may be buried from the outer surface of the product to the inside, it is preferably performed in the step before mixing the external additive. In particular, when [3] is performed before the pulverization step, it is possible to obtain both the effects of improving heat storage stability and improving pulverization.
In the step of storing the toner at a temperature of 45 ° C. to 65 ° C., the relative humidity needs to be 80% or less. Under high humidity conditions where the relative humidity is 80% or higher, the intermediate product in the toner production process is likely to be blocked by a phenomenon such as moisture adsorbing on the surface of the intermediate product in the toner production process and increasing the cohesive force between particles in the toner production process intermediate product.

(Crystalline polyester (A))
In the toner of the present invention, the crystalline polyester resin (A) undergoes a crystal transition at the glass transition temperature (Tg), and at the same time the melt viscosity suddenly decreases from the solid state, and has a fixing function to a recording medium such as paper. To express.
Here, “Tg” means an endothermic point in DSC. In the process of increasing the temperature of the resin at a constant rate, the glass transition temperature (Tg) as an endothermic point (heat generation when releasing the temperature = release of internal latent heat) and the exothermic state (endothermic in the temperature lowering mode) flow out. Melting temperature (Tm) is not the same, the former is said to be absolute temperature and about 2/3 of the latter, but in actual differential thermal analysis, glass transition and melting coexist at different sites in the same sample. As a result of the measurement, whichever is dominant appears significantly, and therefore “Tg” in the present invention also means the endothermic point as a result.
On the other hand, the amorphous resin gradually decreases in melt viscosity from Tg, and it takes time until the fixing function is exhibited. Therefore, in this case, it is necessary to lower the melt viscosity at a low temperature by lowering Tg or lowering the molecular weight, but storage stability and hot offset resistance tend to be insufficient. However, by including a polyester resin having crystallinity, it is possible to achieve a decrease in melt viscosity without deteriorating storage stability and hot offset resistance, which was not possible with an amorphous resin alone.

In addition, the polyester resin having crystallinity is excellent in thermal stability because the melt viscosity is drastically decreased at Tg, so that it is not necessary to lower Tg as the amorphous resin. Therefore, the toner of the present invention in which the polyester resin having crystallinity is present on the toner surface is a toner having excellent heat storage stability. Therefore, the Tg of the amorphous resin can be further reduced, and a toner having a lower temperature fixability can be obtained.
The content of the polyester resin fine particles having crystallinity in the present invention needs to be 1 part by weight or more when the total of the binder resin is 100 parts by weight in order to express the effect on the low-temperature fixability. The amount is desirably 5 parts by weight or more. If this amount is large, the effect on fixing at low temperature is great, but if it is too large, the resin having crystallinity deteriorates the hot offset resistance. Therefore, it is preferably at most 50% by weight. More preferably, it is 30% by weight or less.

(Toner structure)
Since the resin having crystallinity rapidly decreases in melt viscosity, it is possible to control the minimum fixing temperature not only by the content but also by Tg and T (F _1/2 ). In this invention, it is preferable that it is low in the range which does not deteriorate heat-resistant storage stability, Tg of the polyester resin which has crystallinity is the range of 80-130 degreeC, and T (F1 _{/ 2} ) is in the range of 80-130 degreeC. It is preferable. When Tg and T (F _1/2 ) are lower than the above ranges, it is difficult to synthesize a crystalline polyester that has sharp melt properties and easily exhibits an effect on low-temperature fixability. Since the minimum fixing temperature becomes high, the low temperature fixability cannot be obtained.

On the other hand, in order to obtain a toner satisfying the hot offset resistance without hindering the effect of the crystalline resin on fixing at low temperature, it is preferable to use a non-crystalline resin together, and the Tg of the non-crystalline resin is 40. It is preferable that -70 degreeC and T (F1 _{/ 2} ) are 120-160 degreeC. When Tg is less than 40 ° C., the heat-resistant storage stability of the toner is remarkably deteriorated and blocking occurs. On the other hand, when the temperature exceeds 70 ° C., the low-temperature fixability of the toner deteriorates. When the T (F _1/2 ) temperature is less than 120 ° C., the resistance to hot offset deteriorates, and when it exceeds 160 ° C., the elasticity tends to be high, and the share when the toner constituent materials are dispersed becomes high, and the dispersion becomes high. The trouble that it is difficult occurs. Also, the low-temperature fixability deteriorates. In the present invention, “crystallinity” means a ratio of a softening point to a maximum peak temperature of heat of fusion by DSC (softening point / peak temperature) of 0.9 or more and less than 1.1, preferably 0.98 to 1. .05, and “amorphous” means that the ratio of the softening point to the maximum peak temperature of the heat of fusion (softening point / peak temperature) is 1.1 to 4.0, preferably 1.5 to It means 3.0.

The Tg of the release agent used in the toner of the present invention (the endothermic point in DSC analysis as described above) is preferably 70 to 90 ° C. If it is less than 70 ° C., the heat-resistant storage stability of the toner is deteriorated, and if it exceeds 90 ° C., the releasability at a low temperature is not expressed, the cold offset resistance is deteriorated, and the paper is wound around the fixing machine.
The toner of the present invention contains a crystalline polyester resin (A) and an amorphous resin (B) that are substantially incompatible with each other in the toner, and both of them are in an incompatible phase-separated state. Therefore, it has excellent hot offset resistance and low-temperature fixability. That is, in the toner of the present invention, the crystalline polyester resin (A) and the amorphous resin (B) exist in a phase-separated state, and therefore the crystalline polyester resin (A) and the amorphous resin (B) ) Expresses each unique characteristic. That is, the amorphous resin (B) having a high T (F _1/2 ) increases the elasticity of the toner and improves the hot offset resistance, while the crystalline polyester having a low T (F _1/2 ) ( A) improves the low-temperature fixability.

In the toner, whether or not the polyester resin (A) and the resin (B) are present in a phase-separated state can be confirmed by any of the following methods.
[1] Whether or not a phase separation structure is formed can be confirmed by measuring an endothermic peak due to the first temperature increase of the DSC of the toner. In the DSC endothermic peak measurement, there are at least three endothermic peaks <A>, <B>, <C> attributed to the resin (B), the release agent and the polyester resin (A), respectively. The endothermic peak <A> attributed has a peak top in the range of 40 to 70 ° C., and the endothermic peak <B> attributed to the release agent has a peak top in the range of 70 to 90 ° C. The endothermic peak <C> attributed to the polyester resin (A) has a peak top in the range of 80 to 130 ° C.
[2] The presence or absence of the formation of a phase separation structure can be confirmed by measuring an X-ray diffraction pattern with a powder X-ray diffractometer of toner. This is because, in the case of the toner of the present invention, the polyester resin (A) having crystallinity is present in the toner in a state of being phase-separated from the amorphous polyester resin (B) while maintaining crystallinity. A diffraction peak attributed to the polyester resin (A) exists at a position of at least 2θ = 20 ° to 25 °. When the phase separation structure is not formed, the crystal structure of the polyester resin (A) is not maintained, and the diffraction peak attributed to the polyester resin (A) is present in order to be compatible with the amorphous polyester resin (B). It does not appear.

The glass transition temperature (Tg) and melting point shown in the present specification are measured using a thermal analyzer DSC-60 manufactured by Shimadzu Corporation at a temperature range of 20 ° C. to 150 ° C. and a heating rate of 10 ° C./min. It is a thing. When performing the second temperature increase, the temperature was decreased to the measurement start temperature at a temperature decrease rate of 10 ° C./min without a holding time after the first temperature increase. Tg was determined by the tangent method when the temperature was raised twice.
The softening temperature [T (F _1/2 )] is 1 cm 3 under the conditions of using an elevated flow tester CF-500 manufactured by Shimadzu Corporation, a die diameter of 1 mm, a pressure of 10 kgf / cm ² , and a temperature rising rate of 3 ° C./min. This is the temperature at which the stroke when the sample is melted and flowed out becomes ½ of the stroke change amount from the outflow start point to the outflow end point.

(Crystalline polyester A)
The crystalline polyester resin (A) used in the present invention comprises a crystalline aliphatic polyester resin containing at least 60 mol% of an ester bond represented by the following general formula (1) in its molecular main chain. And

前記一般式（１）中、Ｒは直鎖状不飽和脂肪族２価カルボン酸残基を示し、炭素数２〜２０、好ましくは２〜４の直鎖状不飽和脂肪族基である。ｎは２〜２０、好ましくは２〜６の整数である。
一般式（１）の構造の存在は固体Ｃ１３ＮＭＲにより確認することができる。
前記直鎖状不飽和脂肪族基の具体例としては、マレイン酸、フマル酸、１，３−ｎ−プロペンジカルボン酸、１，４−ｎ−ブテンジカルボン酸等の直鎖状不飽和２価カルボン酸由来の直鎖状不飽和脂肪族基を挙げることができる。

In the general formula (1), R represents a linear unsaturated aliphatic divalent carboxylic acid residue, and is a linear unsaturated aliphatic group having 2 to 20 carbon atoms, preferably 2 to 4 carbon atoms. n is an integer of 2 to 20, preferably 2 to 6.
The presence of the structure of the general formula (1) can be confirmed by solid C13 NMR.
Specific examples of the linear unsaturated aliphatic group include linear unsaturated divalent carboxylic acids such as maleic acid, fumaric acid, 1,3-n-propene dicarboxylic acid, and 1,4-n-butene dicarboxylic acid. Mention may be made of linear unsaturated aliphatic groups derived from acids.

In the general formula (1), (CH ₂ ) n represents a linear aliphatic dihydric alcohol residue. Specific examples of the linear aliphatic dihydric alcohol residue in this case include linear aliphatic 2 such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, and 1,6-hexanediol. Those derived from dihydric alcohols can be indicated. Since the polyester resin (A) uses a linear unsaturated aliphatic dicarboxylic acid as the acid component, the polyester resin (A) exhibits an effect that a crystal structure is easily formed as compared with the case where an aromatic dicarboxylic acid is used.

  The polyester resin (A) is a polyvalent carboxylic acid comprising (i) a linear unsaturated aliphatic divalent carboxylic acid or a reactive derivative thereof (an acid anhydride, a lower alkyl ester having 1 to 4 carbon atoms, an acid halide, etc.). It can be produced by subjecting an acid component and (ii) a polyhydric alcohol component composed of a linear aliphatic diol to a polycondensation reaction by a conventional method. In this case, a small amount of other polyvalent carboxylic acid can be added to the polyvalent carboxylic acid component as necessary. The polyvalent carboxylic acid in this case includes (i) a saturated aliphatic divalent carboxylic acid having a branched chain, (ii) a saturated aliphatic divalent carboxylic acid, a saturated aliphatic trivalent carboxylic acid, and the like. In addition to polyvalent carboxylic acids, (iii) aromatic polyvalent carboxylic acids such as aromatic divalent carboxylic acids and aromatic trivalent carboxylic acids are included. The addition amount of these polyvalent carboxylic acids is usually 30 mol% or less, preferably 10 mol% or less, based on the total carboxylic acid, and is appropriately added within the range where the resulting polyester has crystallinity.

Specific examples of polyvalent carboxylic acids that can be added as needed include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, etc. A divalent carboxylic acid of: trimetic anhydride, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, And trivalent or higher polyvalent carboxylic acids such as 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxypropane, 1,2,7,8-octanetetracarboxylic acid, etc. it can.
A trivalent or higher polyhydric alcohol can be added to the polyhydric alcohol component, if necessary, in addition to a small amount of an aliphatic branched dihydric alcohol or cyclic dihydric alcohol. The addition amount is 30 mol% or less, preferably 10 mol% or less, based on the total alcohol, and is appropriately added within the range in which the resulting polyester has crystallinity.
Examples of polyhydric alcohol added as needed include 1,4-bis (hydroxymethyl) cyclohexane, polyethylene glycol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, glycerin and the like.

In the polyester resin (A), the molecular weight distribution is preferably sharp from the viewpoint of low-temperature fixability, and the molecular weight is preferably a relatively low molecular weight. As for the molecular weight of the polyester resin (A), the weight average molecular weight (Mw) is 5500-6500, the number average molecular weight (Mn) is 1300-1500 and The Mw / Mn ratio is preferably 2-5.
The molecular weight distribution of the polyester resin (A) is based on a molecular weight distribution diagram in which the horizontal axis is log (M: molecular weight) and the vertical axis is weight%. In the case of the polyester resin (A) used in the present invention, in this molecular weight distribution diagram, it is preferable to have a molecular weight peak in the range of 3.5 to 4.0 (wt%), and the half width of the peak is 1. 5 or less is preferable.
In the polyester resin (A), the glass transition temperature (Tg) and the softening temperature [T (F _1/2 )] are desirably low so long as the heat-resistant storage stability of the toner is not deteriorated. Tg is 80 to 130 ° C., preferably 80 to 125 ° C., and T (F _1/2 ) is 80 to 130 ° C., preferably 80 to 125 ° C. When Tg and T (F _1/2 ) are higher than the above ranges, the lower limit fixing temperature of the toner is increased, so that the low temperature fixing property of the toner is deteriorated.

Whether or not the resin fine particles in the present invention have crystallinity can be confirmed by whether or not a peak exists in the X-ray diffraction pattern by the powder X-ray diffractometer. The polyester resin (A) having crystallinity used in the present invention has a diffraction pattern in which at least one diffraction peak exists at a position where 2θ is 20 ° to 25 °, and preferably 2θ is at least (i It is characterized in that diffraction peaks are present at positions of 19 ° to 20 °, (ii) 21 ° to 22 °, (iii) 23 ° to 25 °, and (iv) 29 ° to 31 °.
The powder X-ray diffraction measurement was performed using a Rigaku Electric RINT1100, using a wide-angle goniometer under the conditions of a tube bulb with Cu and a tube voltage-current of 50 kV-30 mA.

(Polyester resin B)
The binder resin (B) used in combination with the crystalline polyester resin (A) is an amorphous (non-crystalline) resin, and conventionally known resins can be used for this. For example, styrene, α-methylstyrene, chlorostyrene, styrene-propylene copolymer, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene-maleic acid copolymer, Styrene resins such as styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-acrylonitrile-acrylic acid ester copolymer, polyester resin, vinyl chloride resin, rosin modified maleic acid resin, phenol resin, There are epoxy resins, polyethylene resins, polypropylene resins, ionomer resins, polyurethane resins, silicone resins, ketone resins, xylene resins, petroleum resins, hydrogenated petroleum resins, and the like. Of these, styrene resins and polyester resins containing an aromatic compound as a component are preferred. Particularly preferred are polyester resins.
The amorphous polyester resin (B) is synthesized from a polyhydric alcohol and a polyvalent carboxylic acid. As the polyhydric alcohol and polycarboxylic acid, the components used in the crystalline polyester resin (A) can be used. Besides this, alkylene oxide adducts of bisphenol A, isophthalic acid, terephthalic acid and derivatives thereof are also available. is there. These resins are not limited to single use but can be used in combination of two or more.

The molecular weight of the polyester resin (B) used in the present invention is such that its weight average molecular weight (Mw) is 3000 to 100,000, its number average molecular weight (Mn) is 1500 to 4000, and The Mw / Mn ratio is preferably 2-50.
The molecular weight distribution of the polyester resin (B) is based on a molecular weight distribution chart in which the horizontal axis is log (M: molecular weight) and the vertical axis is weight%. In the case of the polyester resin (B) used in the present invention, in this molecular weight distribution diagram, it is preferable to have a molecular weight peak in the range of 2.5 to 4.5 (% by weight).
In the polyester resin (B), the glass transition temperature (Tg) and the softening temperature [T (F _1/2 )] are desirably low as long as the heat-resistant storage stability of the toner is not deteriorated. Tg is 40 to 70 ° C., preferably 45 to 65 ° C., and T (F _1/2 ) thereof is 120 to 160 ° C., preferably 130 to 150 ° C. When Tg and T (F _1/2 ) are higher than the above ranges, the lower limit fixing temperature of the toner is increased, so that the low temperature fixing property of the toner is deteriorated.

(Release agent)
As the release agent used for the toner in the present invention, known ones can be used, and in particular, a free fatty acid type carnauba wax, a montan wax and an oxidized rice wax can be used alone or in combination. The carnauba wax is preferably a microcrystalline one, having an acid value of 5 or less and a particle size of 1 μm or less when dispersed in a toner binder. The montan wax generally refers to a montan wax refined from minerals, and like a carnauba wax, it is microcrystalline and preferably has an acid value of 5 to 14. The oxidized rice wax is obtained by air-oxidizing rice bran wax, and the acid value is preferably 10-30.
As other mold release agents, any conventionally known mold release agents such as solid silicone varnish, higher fatty acid higher alcohol, montan ester wax, and low molecular weight polypropylene wax can be mixed and used.
The amount of these release agents used is 1 to 20 parts by weight, preferably 3 to 10 parts by weight, based on the toner resin component.

(Coloring agent)
Examples of the colorant include carbon black, lamp black, iron black, blackened low-magnetization metal oxides (compounds of elements selected from Fe, Mn, Ti, Cu, Si, C, or their Oxides, or mixtures thereof), aniline blue, phthalocyanine blue, phthalocyanine green, Hansa Yellow G, rhodamine 6C lake, calco oil blue, chrome yellow, quinacridone, benzidine yellow, rose bengal, triallylmethane dyes, etc. Any conventionally known dyes and pigments can be used alone or in combination, and can be used as a black toner or a full color toner. The amount of these colorants to be used is usually 1 to 30% by weight, preferably 3 to 20% by weight, based on the toner resin component.

  Furthermore, the toner of the present invention can be used as a magnetic toner containing a magnetic substance. Examples of magnetic materials contained in the toner include iron oxides such as magnetite, hematite, and ferrite, metals such as iron, cobalt, and nickel, These metals include alloys of metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof. Magnetite is particularly preferable from the viewpoint of magnetic properties.

(Charge control agent)
The toner of the present invention can be blended with a charge control agent as required. As the charge control agent, any conventionally known polarity control agent such as a nigrosine dye, a metal complex dye, or a quaternary ammonium salt can be used alone or in combination. The amount of these charge control agents used is 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on the toner resin component. These ferromagnetic materials preferably have an average particle size of about 0.1 to 2 μm. The amount of the ferromagnetic material to be contained in the toner is about 15 to 200 parts by weight, particularly preferably 100 parts by weight of the resin component, with respect to 100 parts by weight of the resin component. 20 to 100 parts by weight per part.
In the production of the base particles of the present invention, those obtained by melting and kneading the base particle constituent materials and then pulverizing and classifying are generally used as conventional methods. Is possible.

(External additive)
If necessary, a fluidity improver can be added to the toner of the present invention. As the fluidity improver, any conventionally known fluidity improver such as hydrophobic silica, titanium oxide, silicon carbide, aluminum oxide, and barium titanate can be used alone or in combination. Titanium is excellent in terms of improving fluidity, stabilizing charging and stabilizing image quality. More preferably, when a combination of hydrophobic silica and titanium oxide is used, a good toner with stable fluidity and chargeability can be obtained. The amount of these fluidity improvers used is 0.1 to 5 parts by weight, preferably 0.5 to 2 parts by weight, based on the toner weight. Addition of the fluidity improver is carried out by stirring and mixing using a mixer, in the same manner as external addition of fine particles having crystallinity. This step may be performed after the external addition of the crystalline polyester resin fine particles, or may be performed simultaneously.

(Career)
The toner of the present invention can be used as a one-component developer or a two-component developer combined with a carrier. When the toner of the present invention is used as either a one-component developer or a two-component developer, the toner is filled in a container, and the container filled with the toner (toner container) is distributed separately from the image forming apparatus. In general, a user attaches to an image forming apparatus to form an image.

(cartridge)
What is used as the container is not limited, and is not limited to the conventional bottle type or cartridge type.

(apparatus)
The image forming apparatus is not limited as long as it is an apparatus for forming an image by electrophotography, and includes, for example, a copying machine or a printer.

Another example of the image forming apparatus of the present invention (for example, still another mode for carrying out the image forming method of the present invention using the image forming apparatus and cartridge shown in FIGS. 2, 3 and 4 will be described with reference to the drawings.
FIG. 2 shows an example of an image forming apparatus in which a container filled with toner of the present invention is mounted. The developing unit (131) mounted in the main body of the image forming apparatus and the developing unit ( 131) is a partial cross-sectional view showing the toner container (132) filled with the toner of the present invention to be replenished in 131) and the developer flow means (133) connecting the two.

  In FIG. 2, the developing section (131) includes a developing housing (134) filled with a developer using the toner (D) of the present invention and first and second stirring screws for stirring and mixing the developer (D). (135), (136) and a developing roller (137), and the developing roller (137) is arranged to face the photosensitive member (138) of the latent image carrier. The photoreceptor (138) is rotationally driven in the direction indicated by the arrow, and an electrostatic latent image is formed on the surface thereof. In the drawing, reference numeral (126) denotes a cap fitted on the connecting member (124) with or without the filter (125). Around the photoconductor (138), other known units such as a charging unit, an exposure unit, a transfer unit, a charge eliminating unit, and a cleaning unit (not shown) are arranged.

  As the first and second agitating screws (135) and (136) rotate, the toner (D) in the developing housing (134) is agitated, and the toner is triboelectrically charged with the opposite polarities. The toner developer (D) is supplied to the peripheral surface of the developing roller (137) that is rotationally driven in the direction of the arrow, and the supplied toner is carried on the peripheral surface of the developing roller (137). 137) is conveyed in the rotation direction. Next, the amount of the conveyed toner is regulated by the doctor blade (139), and the regulated toner is conveyed to the developing area between the photoconductor (138) and the developing roller (137), where the toner is However, the electrostatic latent image is electrostatically transferred to the surface of the photosensitive member, and the electrostatic latent image is visualized as a toner image.

The tandem image forming apparatus (120) shown in FIG. 3 is a tandem color image forming apparatus. The tandem image forming apparatus (120) includes a copying apparatus main body (150), a paper feed table (200), a scanner (300), and an automatic document feeder (ADF) (400). The copying machine main body (150) is provided with an endless belt-like intermediate transfer member (50) at the center. The intermediate transfer member (50) is stretched around the support rollers (14), (15) and (16), and can rotate clockwise in FIG. An intermediate transfer body cleaning device (17) for removing residual image forming particles on the intermediate transfer body (50) is disposed in the vicinity of the support roller (15). The intermediate transfer member (50) stretched between the support roller (14) and the support roller (15) has four image forming units (18) of yellow, cyan, magenta, and black along the conveyance direction. A tandem developing means (120) arranged opposite to each other is arranged. An exposure means (21) is disposed in the vicinity of the tandem developing means (120). A secondary transfer unit (22) is disposed on the side of the intermediate transfer member (50) opposite to the side on which the tandem type developing unit (120) is disposed. In the secondary transfer means (22), a secondary transfer belt (24), which is an endless belt, is stretched between a pair of rollers (23), and a transfer sheet conveyed on the secondary transfer belt (24); The intermediate transfer member (50) can contact each other. A fixing means (25) is disposed in the vicinity of the secondary transfer means (22). The fixing means (25) includes a fixing belt (26) that is an endless belt, and a pressure roller (27) that is pressed against the fixing belt (26).
In the tandem image forming apparatus (120), a sheet reversal is performed in the vicinity of the secondary transfer unit (22) and the fixing unit (25) for reversing the transfer paper in order to form an image on both sides of the transfer paper. A device (28) is arranged.

  Next, full color image formation (color copying) using the tandem developing means (120) will be described. That is, first, a document is set on the document table (130) of the automatic document feeder (ADF) (400) or the automatic document feeder (400) is opened and the contact glass (32) of the scanner (300) is opened. A document is set on the document and the automatic document feeder (400) is closed.

  When a start switch (not shown) is pressed, when a document is set on the automatic document feeder (400), the document is transported and moved onto the contact glass (32). ) Immediately after the document is set on the scanner (300), the first traveling body (33) and the second traveling body (34) travel. At this time, light from the light source is irradiated by the first traveling body (33) and reflected light from the document surface is reflected by the mirror in the second traveling body (34), and is read through the imaging lens (35). The color original (color image) is read at (36), and is read as black, yellow, magenta and cyan image information.

  Each image information of black, yellow, magenta and cyan is stored in each image forming means (18) (black image forming means, yellow image forming means, magenta image forming means and cyan) in the tandem developing means (120). Image forming means), and image forming particle images of black, yellow, magenta and cyan are formed in each image forming means. That is, each image forming means (18) (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem developing means (120) is a photosensitive member (10). ) (A black photoconductor (10K), a yellow photoconductor (10Y), a magenta photoconductor (10M) and a cyan photoconductor (10C)), and charging means (not shown) for uniformly charging the photoconductor ), An exposure unit that exposes the photoconductor corresponding to each color image based on each color image information, and forms an electrostatic latent image corresponding to each color image on the photoconductor, and the electrostatic latent image Developing means (not shown) for developing an image using each color developer (black developer, yellow developer, magenta developer and cyan developer) of the present invention to form a toner image with each color developer; A transfer charger (62) for transferring the developed toner image onto the intermediate transfer member (50), a photosensitive member cleaning means (not shown), and a static eliminator (not shown) are provided. Each single color image (black image, yellow image, magenta image, and cyan image) can be formed based on the color image information. The black image, the yellow image, the magenta image, and the cyan image formed in this way are respectively transferred onto the intermediate transfer member (50) that is rotationally moved by the support rollers (14), (15), and (16). Black image formed on the photoconductor (10K), yellow image formed on the yellow photoconductor (10Y), magenta image formed on the magenta photoconductor (10M), and cyan photoconductor (10C). ) The cyan image formed thereon is sequentially transferred (primary transfer). Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member (50) to form a composite color image (color transfer image).

On the other hand, in the paper feed table (200), one of the paper feed rollers (142) is selectively rotated so that the sheet (recording paper) is fed from one of the paper feed cassettes (144) provided in the paper bank (143). ), Separated one by one by the separation roller (145), sent to the paper feed path (146), and conveyed by the conveyance roller (147) to the paper feed path (148) in the copier body (150). Guide and stop against the registration roller (49). Alternatively, the sheet feed roller (142) is rotated to feed out the sheets (recording paper) on the manual feed tray (54), separated one by one by the separation roller (52), and put into the manual feed path (53). Stop against the registration roller (49). The registration roller (49) is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet.
Then, the registration roller (49) is rotated in synchronism with the synthesized color image (color transfer image) in which the respective toners are synthesized on the intermediate transfer member (50), and the intermediate transfer member (50) and the secondary transfer means ( 22), a sheet (recording paper) is sent to the sheet (recording paper), and the composite color image (color transfer image) is transferred (secondary transfer) onto the sheet (recording paper) by the secondary transfer means (22). A color image is transferred and formed on the sheet (recording paper). The residual toner on the intermediate transfer member (50) after the image transfer is cleaned by the intermediate transfer member cleaning device (17).

  The sheet (recording paper) on which the color image has been transferred is transported by the secondary transfer means (22) and sent to the fixing means (25). The fixing means (25) generates heat and pressure. The composite color image (color transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by the switching claw (55) and discharged by the discharge roller (56) and stacked on the discharge tray (57), or switched by the switching claw (55) and the sheet is reversed. The image is reversed by the device (28) and guided again to the transfer position, and an image is recorded also on the back surface. Then, the image is discharged by the discharge roller (56) and stacked on the discharge tray (57).

FIG. 4 specifically shows a schematic view of an image forming apparatus equipped with the process cartridge of the present invention. The process cartridge of the present invention comprises at least one selected from a developing means using a developer using the toner of the present invention, an electrostatic latent image carrying means (typically a photoreceptor), a charging means, and a cleaning means. It is a process cartridge that integrally supports the means and is detachable from the main body of the image forming apparatus.
In the figure, (101) indicates the entire process cartridge, (10) indicates a photosensitive member, (20) indicates a charging unit, (40) indicates a developing unit, and (60) indicates a cleaning unit.
In the present invention, a plurality of components such as the photosensitive member (10), the charging unit (20), the developing unit (40), and the cleaning unit (60) are integrally combined as a process cartridge. The process cartridge is configured to be detachable from an image forming apparatus main body such as a copying machine or a printer.

  In the image forming apparatus having the process cartridge of the present invention, the photosensitive member is rotationally driven at a predetermined peripheral speed. In the rotation process, the photosensitive member is uniformly charged with a positive or negative predetermined potential on its peripheral surface by the charging unit, and then receives image exposure light from an image exposing unit such as slit exposure or laser beam scanning exposure. An electrostatic latent image is sequentially formed on the peripheral surface of the body, and the formed electrostatic latent image is then developed with toner by a developing unit, and the developed toner image is transferred between the photosensitive member and the transfer unit from the paper feeding unit. Then, the image is sequentially transferred to the transfer material fed in synchronization with the rotation of the photosensitive member by the transfer means. The transfer material that has received the image transfer is separated from the surface of the photosensitive member, introduced into the image fixing means, and fixed on the image, and printed out as a copy (copy). The surface of the photoconductor after the image transfer is cleaned by removing toner remaining after transfer by a cleaning unit, and after being further neutralized, it is repeatedly used for image formation.

Hereinafter, the present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto. All parts are parts by weight.
<Toner Production Example 1>
Crystalline polyester resin A1 15 parts Amorphous polyester resin B1 85 parts Desorbed fatty acid type carnauba wax (Tg: 83 ° C.) 5 parts Carbon black (Mitsubishi Chemical # 44) 10 parts The above toner constituent materials in a Henschel mixer After sufficiently stirring and mixing, the mixture was melt-kneaded with a twin-screw extruder, and after cooling, the kneaded product was stored for 6 hours under conditions of a relative humidity of 60% and a temperature of 45 ° C. Next, pulverized and classified to obtain a toner base having a weight average particle diameter of 6.5 μm. To the obtained toner base, 0.5% by weight of hydrophobic silica and 0.3% by weight of titanium oxide were added and mixed. Toner was used. FIG. 5 shows a DSC chart of the crystalline polyester resin A1, and FIG. 6 shows a DSC chart of the non-crystalline polyester resin B1.

<Toner Production Example 2>
A toner was prepared in the same manner as in Toner Preparation Example 1 except that the storage conditions of the kneaded product after melt-kneading and cooling in Toner Production Example 1 were changed to 24 hours under the conditions of 60% relative humidity and 45 ° C.

<Toner Production Example 3>
A toner was prepared in the same manner as in Toner Preparation Example 1 except that the storage conditions of the kneaded product after melt-kneading and cooling were changed to 7 days under the conditions of 60% relative humidity and 45 ° C. in Toner Production Example 1.

<Toner Production Example 4>
A toner was prepared in the same manner as in Toner Production Example 1 except that the storage conditions of the kneaded product after melt-kneading and cooling in Toner Production Example 1 were changed to 6 hours under the conditions of a relative humidity of 60% and a temperature of 65 ° C.

<Toner Production Example 5>
A toner was prepared in the same manner as in Toner Production Example 1 except that the storage conditions of the kneaded product after melt-kneading and cooling in Toner Production Example 1 were changed to 24 hours under the conditions of a relative humidity of 60% and a temperature of 65 ° C.

<Toner Production Example 6>
A toner was prepared in the same manner as in Toner Preparation Example 1 except that the storage conditions of the kneaded product after melt-kneading and cooling were changed to 7 days under the conditions of 60% relative humidity and 65 ° C. in Toner Production Example 1.

<Toner Production Example 7>
A toner was prepared in the same manner as in Toner Production Example 1 except that the storage conditions of the kneaded product after melt-kneading and cooling were changed to 6 hours under the conditions of 60% relative humidity and 40 ° C. in Toner Production Example 1.

<Toner Production Example 8>
In Example 1 of the toner, except that the kneaded product after melt kneading and cooling was not immediately stored and classified by pulverization, and then the absorbent product was stored for 6 hours at 60% relative humidity and 70 ° C. temperature. Prepared a toner in the same manner as in Toner Production Example 1.

<Toner Production Example 9>
In the toner production example 1, except that the kneaded product after melting and kneading and cooling was not immediately stored and then subjected to pulverization and classification, and then the absorbent product was stored for 6 hours at a relative humidity of 90% and a temperature of 65 ° C. Prepared a toner in the same manner as in Toner Production Example 1.

<Toner Production Example 10>
A toner was prepared in the same manner as in Toner Production Example 1 except that the kneaded product after melt kneading and cooling was not stored in Toner Production Example 1 but immediately pulverized and classified.

<Toner Production Example 11>
A toner was prepared in the same manner as in Toner Production Example 6 except that the polyester A1 was changed to the non-crystalline polyester A2 in Toner Production Example 6.

<Toner Production Example 12>
A toner was prepared in the same manner as in Toner Production Example 6 except that the polyester A1 was changed to the crystalline polyester A3 in Toner Production Example 6.

<Toner Production Example 13>
A toner was prepared in the same manner as in Toner Preparation Example 6 except that the polyester A1 was changed to the crystalline polyester A4 in Toner Preparation Example 6.

<Toner Production Example 14>
A toner was prepared in the same manner as in Toner Production Example 6 except that the formulation was changed to the following.
Polyester resin A1 60 parts Polyester resin B1 40 parts Desorbed fatty acid type carnauba wax (Tg: 83 ° C) 5 parts Carbon black (Mitsubishi Chemical # 44) 10 parts

<Toner Production Example 15>
A toner was prepared in the same manner as in Toner Production Example 6 except that the formulation was changed to the following.
Polyester resin A1 0.5 part Polyester resin B1 90.5 part Desorbed fatty acid type carnauba wax (Tg: 83 ° C) 5 parts Carbon black (Mitsubishi Chemical # 44) 10 parts

<Toner Production Example 16>
A toner was prepared in the same manner as in Toner Preparation Example 6 except that the polyester B1 was changed to the non-crystalline polyester B2 in Toner Preparation Example 6.

<Toner Production Example 17>
A toner was prepared in the same manner as in Toner Preparation Example 6 except that the polyester B1 was changed to the non-crystalline polyester B3 in Toner Preparation Example 6.

<Toner Production Example 18>
A toner was obtained in the same manner as in Toner Production Example 6 except that the de-free fatty acid type carnauba wax in Toner Production Example 6 was changed to polyethylene wax (Tg 110 ° C.).

<Toner Production Example 19>
A toner was obtained in the same manner as in Toner Production Example 3 except that the de-free fatty acid type carnauba wax in Toner Production Example 3 was changed to polyethylene wax (Tg 58 ° C.).

<Manufacture of polyester A>
Polyesters A1 to A4 were prepared by putting 4000 g of the composition shown in Table 1 and 4 g of hydroquinone into a 5 L four-necked round bottom flask equipped with a thermometer, stirrer, condenser and nitrogen gas inlet tube. Set in a heater, introduce nitrogen gas from the nitrogen gas inlet tube, raise the temperature in a state where the flask is kept in an inert atmosphere, and maintain at 160 ° C. for 5 hours, and then react at 200 ° C. for 1 hour. Each polyester was obtained by reaction at 8.3 kPa for 1 hour.

Table 1 shows components of each polyester A1 to A4, and Table 2 shows physical property values of each polyester A1 to A4.
BPA / EO shown in Table 1 represents an ethylene oxide adduct of bisphenol A (2.2 mol adduct), and BPA / PO represents a propylene oxide adduct of bisphenol A (2.2 mol adduct). Indicates.

(注)ポリエステルＡ２のみ酸成分、アルコール成分ともに重量比

(Note) Only polyester A2 has a weight ratio for both acid and alcohol components.

なお、結晶性の有りのものとは、粉末Ｘ線回折装置によるＸ線回折パターンにおいて、少なくとも２θ＝１９〜２０°、２１〜２２°、２３〜２５°、２９〜３１°の位置に回折ピークが現れたものである。推定分子式有りのものとは固体Ｃ１３ＮＭＲにより一般式（１）の分子構造の存在が確認されたものである。

In addition, the thing with crystallinity is a diffraction peak in the position of at least 2 (theta) = 19-20 degrees, 21-22 degrees, 23-25 degrees, 29-31 degrees in the X-ray-diffraction pattern by a powder X-ray-diffraction apparatus. Appears. Those having an estimated molecular formula are those in which the presence of the molecular structure of the general formula (1) has been confirmed by solid-state C13 NMR.

<Manufacture of polyester B>
For polyesters B1 to B3, 4000 g of the composition shown in Table 3 was placed in a 5 L four-necked round bottom flask equipped with a thermometer, a stirrer, and a condenser. The flask was set in a mantle heater, and 4 g of dibutyltin. The temperature was raised by adding an oxide, and the reaction was carried out for 8 hours while maintaining the temperature at 220 ° C., and then the reaction was carried out at 8.3 kPa until a predetermined softening point was reached, thereby obtaining each polyester.
Table 3 shows components of the respective polyesters B1 to B3, and Table 4 shows physical property values of the respective polyesters B1 to B3.
BPA / EO shown in Table 3 represents an ethylene oxide adduct of bisphenol A (2.2 mol adduct), and BPA / PO represents a propylene oxide adduct of bisphenol A (2.2 mol adduct). Indicates.

<Example of carrier production>
(I) Core material: Cu—Zn ferrite particles (volume average diameter: 45 μm) 5000 parts (ii) Coating material 450 parts of toluene Silicone resin SR2400
(Toray Dow Corning Silicone, 50% nonvolatile content) 450 parts Aminosilane SH6020
(Toray / Dow Corning / Silicone) 10 parts Carbon black 10 parts The above coating material is dispersed with a stirrer for 10 minutes to prepare a coating liquid, and this coating liquid and core material are placed in a fluidized bed. The coating liquid was applied to the core material, and the coating liquid was applied on the core material.
Next, the obtained carrier was baked in an electric furnace at 250 ° C. for 2 hours, and the carrier particles of the production example (saturation magnetization 65 emu / g when 3 kOe was applied, residual magnetization 0 emu / g when 3 kOe was applied, specific resistance 3.2). × 108 Ω · cm, volume average diameter 45 μm).

<Examples of developer production>
A developer (1) corresponding to each toner corresponding to Toner Production Examples 1 to 19 is prepared by mixing 2.5 parts of the toner of Production Examples 1 to 19 and 97.5 parts of the carrier of the Production Examples with a tumbler mixer. To (19).

A method for evaluating the characteristics of the developers 1 to 19 used in each example will be described.
○ Fixability evaluation The Ricoh copier IMAGEIO NEO350 was modified so that the original fixing device can be removed and another fixing device can be attached, so that the set temperature of the fixing device can be changed. The toner, developer, fixing device, and Ricoh type 6200 paper shown in the examples were set on this, and a copy test was conducted.
The fixing device used for the evaluation is the heat roller fixing device shown in FIG. 1 and has the following configuration.
The metal cylinder of the fixing roller is SUS and has a thickness of 3.0mm
The offset prevention layer of the fixing roller is made of PTFE and has a thickness of 20μm.
The metal cylinder of the pressure roller is 2mm thick with SUS
An anti-offset layer of the pressure roller is formed on a 4 μm thick silicon rubber and a 50 μm thick PFA.
Surface pressure 2.5 × 105Pa
Line speed 180mm / sec

The cold offset generation temperature and the hot offset generation temperature were obtained by changing the fixing temperature. The evaluation conditions for the offset resistance were set such that the linear speed of paper feed was 50 mm / sec, which was strict against the occurrence of offset.
The criteria for each characteristic evaluation are as follows.
[1] Low temperature fixability (five-level evaluation)
◎; Less than 130 ° C ○; 130-140 ° C
□; 140-150 ° C
Δ: 150-160 ° C
×: 160 ° C. or higher [2] Hot offset property (five-level evaluation)
◎; 201 ° C or higher ○; 200-191 ° C
□; 190-181 ° C
Δ: 180-171 ° C.
×: 170 ° C. or less

○ Evaluation of heat preservability Fill a glass container with toner and leave it in a constant temperature bath at 60 ° C. for 24 hours. The toner is cooled to 24 ° C., and the penetration is measured by a penetration test (JIS K2235-1991). A toner having a larger value has better storage stability against heat. When this value is 5 mm or less, there is a high possibility of problems in use.
Judgment criteria for thermal storage stability based on the penetration is as follows.
○… 25mm or more □… 15-25mm
Δ: 5-15mm
×: Less than 5mm

Evaluation of pulverization The ease of pulverization was determined from the throughput per unit time when the kneaded material crushed to an average particle size of 3 mm or less was pulverized with an IDS type pulverizer manufactured by Nippon Pneumatic. The larger the processing amount per unit time, the easier the pulverization and the better the toner productivity.
The criteria for determining the ease of grinding based on the throughput per unit time are as follows.
◎; 1.5 kg / H or more ○; 0.8 to 1.5 kg / H
□; 0.5-0.8kg / H
Δ: 0.2 to 0.5 kg / H
×: Less than 0.2 kg / H

○ Measuring method of toner particle size Examples of a measuring device for measuring the particle size distribution of toner particles by the Coulter counter method include Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). The measurement method is described below.
First, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using first grade sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as an aperture. Volume distribution and number distribution are calculated. From the obtained distribution, the weight average particle diameter and the number average particle diameter of the toner can be obtained. As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 .35 to less than 8.00 μm; 8.00 to less than 10.08 μm; 10.08 to less than 12.70 μm; 12.70 to less than 16.00 μm; 16.00 to less than 20.20 μm; Uses 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm.

○ Measurement of molecular weight by GPC [1] Measurement of molecular weight by GPC of polyesters B1 to B3 and polyester A2 A column is stabilized in a heat chamber at 40 ° C., and THF is used as a solvent at a flow rate of 1 ml / min. Pour, and measure by injecting 50-200 μl of a THF sample solution of the resin. The THF sample solution of the resin was prepared by stirring a THF solution having a resin concentration of 0.5% by weight with a ball mill at room temperature for 24 hours, and then filtering with a 0.2 μm hole diameter membrane filter manufactured by Toyo Filter Paper Co., Ltd. is there. Waters GPC-150C can be used as a measuring device, and Shodex KF801-807 can be used as a column. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Alternatively, the molecular weights manufactured by Toyo Soda Industry Co., Ltd. are 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9. It is appropriate to use x10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

[2] Measurement of molecular weight by GPC of polyesters A1 and A3 to A4 GPC (gel permeation chromatography) is measured as follows.
The column was stabilized in a heat chamber at 145 ° C., and o-dichlorobenzene containing 0.3% BHT as an eluent was allowed to flow through the column at this temperature at a flow rate of 1 ml / min to a sample concentration of 0.3% by weight. Measurement is performed by injecting 50 to 200 μl of 140 ° C. o-dichlorobenzene solution of the prepared resin. Waters 150CV type can be used as a measuring instrument, and Shodex AT-G + AT-806MS (two) can be used as a column.

Molecular structure of resin Using solid C13-NMR (FT-NMR SYSTEM JNM-α400 manufactured by JEOL Ltd.), observation nucleus C13, reference material adamantane, accumulated number 8192 times, pulse series CPMAS. IRMOD: IRLEV, observation frequency 100.4 MHz, OBSET: 134500 Hz, POINT: 4096, PD: 7.0 sec, SPIN 6088 Hz, and molecular structure estimation is performed by Chem Draw Pro Ver. 4.5.
The following two measurements were used in combination to confirm the results of molecular structure analysis by solid C13-NMR.
(A) A sample is measured by a Fourier transform infrared spectrophotometry (FT-IR) transmission method, and a structure is estimated from standard spectrum comparison.
Measuring machine: Nicolet Magna 850
Measurement range: 4000 to 400 cm-1
Standard sample: KBr
(B) Structure estimation of pyrolyzable organisms using pyrolysis gas chromatogram mass spectrometer Measuring instrument: Shimadzu Corporation GC-17A, Shimadzu CR-4A
Thermal decomposition temperature: Nippon Analytical Industry JHB-3S
Thermal decomposition temperature: sample heating temperature × time is 590 ° C. × 4 seconds Column: DB-5 (J and W Co.) L = 30 m, I.V. D = 0.2
5mm, Film = 0.25mm
Column temperature: raised from 50 ° C. (holding time 1 minute) to 300 ° C. at 10 ° C./min. Injection temperature: 320 ° C.
Carrier gas pressure: From 90 kPa (holding time 2 minutes) to 2 kPa / min, 150
Boost to kPa Detector: FID

  Table 5 shows the evaluation results of the toner and developer in each example.

1 is a diagram illustrating an example of a fixing device used in the present invention. FIG. 3 is a diagram illustrating an example of a toner storage container and an image forming apparatus according to the present invention. It is a figure which shows another example of the image forming apparatus of this invention. It is a figure which shows one example of the process cartridge of this invention. It is a figure which shows the DSC chart of crystalline polyester resin A1 in this invention. It is a figure which shows the DSC chart of non-crystalline polyester resin B1 in this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Fixing roller 2 Pressure roller 3 Metal cylinder 4 Offset prevention layer 5 Heating lamp 6 Metal cylinder 7 Offset prevention layer 8 Heating lamp D Toner T Toner image S Adhering support 10 Photoconductor 10K Black photoconductor 10Y Yellow photoconductor 10M Magenta Photoconductor 10C Cyan Photoconductor 14 Support Roller 15 Support Roller 16 Support Roller 17 Intermediate Transfer Body Cleaning Device 18 Image Forming Unit 20 Charging Unit 21 Exposure Unit 22 Secondary Transfer Unit 23 Roller 24 Secondary Transfer Belt 25 Fixing Unit 26 Fixing belt 27 Pressure roller 28 Sheet reversing device 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 36 Reading sensor 40 Developing means 49 Registration roller 50 Intermediate transfer body 55 Switching claw 56 Discharging roller 57 Discharging roller 59 Charging means 60 Cleaning means 61 Developing means 62 Transfer charger 63 Photoconductor cleaning means 64 Charger 101 Process cartridge 120 Image forming apparatus 130 Document table 131 Developing unit 132 Toner storage container 133 Developer feeding means 134 Developing housing 135 First 1 stirring screw 136 second stirring screw 137 developing roller 138 photoconductor 124 connecting member 125 filter 126 cap 139 doctor blade 142 paper feeding roller 143 paper bank 144 paper feeding cassette 145 separation roller 146 paper feeding path 147 transport roller 148 paper feeding path 150 Copier body 200 Paper feed table 300 Scanner 400 Automatic document feeder (ADF)

Claims (22)

  A method for producing a toner for developing an electrostatic image, comprising at least a colorant and a binder resin, wherein at least one of the binder resins is a polyester resin (A) having crystallinity, wherein the toner production process intermediate product Alternatively, the method for producing a toner for developing an electrostatic charge image, comprising a step of storing the final product at a temperature of 45 ° C. to 65 ° C.   The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the storage time of the step of storing the intermediate product or the final product of the toner production process at a temperature of 45 ° C to 65 ° C is 6 hours or more.   2. The toner production for electrostatic image development according to claim 1, wherein the storage time of the step of storing the intermediate product or the final product of the toner production process at a temperature of 45 ° C. to 65 ° C. is 6 hours to 7 days. Method.   2. The toner production for electrostatic image development according to claim 1, wherein the storage time of the step of storing the intermediate product or the final product of the toner production process at a temperature of 45 ° C. to 65 ° C. is 6 hours to 24 hours. Method.   The toner manufacturing process includes at least an external additive mixing process, and the step of storing the intermediate product of the toner manufacturing process at a temperature of 45 ° C. to 65 ° C. is performed before the external additive mixing process. The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 4.   The toner production process includes at least a classification process, and the step of storing the intermediate product of the toner production process at a temperature of 45 ° C. to 65 ° C. is performed before the classification process. Item 5. The method for producing a toner for developing an electrostatic charge image according to any one of Items 1 to 4.   The toner production process includes at least a pulverization process, and the step of storing the intermediate product of the toner production process at a temperature of 45 ° C. to 65 ° C. is performed before the pulverization process. Item 5. The method for producing a toner for developing an electrostatic charge image according to any one of Items 1 to 4.   8. The electrostatic charge image development according to claim 1, wherein the relative humidity in the step of storing the intermediate product or the final product of the toner manufacturing process at a temperature of 45 ° C. to 65 ° C. is 80% or less. Toner manufacturing method. The polyester resin (A) has the following general formula (1) in its molecular main chain.

(In the formula, R represents a linear unsaturated aliphatic group having 2 to 20 carbon atoms, and n represents an integer of 2 to 20)
The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 8, which is a crystalline polyester resin (A) containing at least 60 mol% of an ester bond represented by the formula: The softening temperature [T (F _1/2 )] of the polyester resin (A) is in the range of 80 to 130 ° C, and the glass transition temperature (Tg) thereof is in the range of 80 to 130 ° C. Item 10. The method for producing a toner for developing an electrostatic charge image according to any one of Items 1 to 9.   11. The electrostatic charge image developing according to claim 1, wherein a diffraction peak exists at least at a position of 2θ = 20 to 25 ° in the powder X-ray diffraction pattern of the polyester resin (A). Toner manufacturing method.   The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 11, wherein the content of the polyester resin (A) in the binder resin is 1 to 50% by weight.   The alcohol component constituting the polyester resin (A) comprises at least one selected from 1,4-butanediol and 1,6-hexanediol, while the acid component constituting the polyester resin (A) comprises 13. The method for producing a toner for developing an electrostatic charge image according to claim 1, comprising at least one selected from maleic acid and fumaric acid. The binder resin contains an amorphous polyester resin (B) having at least a glass transition temperature (Tg) of 40 to 70 ° C. and a softening temperature [T (F _1/2 )] of 120 to 160 ° C. The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 13.   15. The electrostatic image developing toner containing a release agent, wherein the release agent has a glass transition temperature (Tg) of 70 to 90 ° C. The method for producing a toner for developing an electrostatic image according to any one of the above.   The image forming agent according to any one of claims 1 to 15, wherein the releasing agent is one or more selected from a liberated fatty acid type carnauba wax, a montan wax and an oxidized rice wax. Toner manufacturing method.   In the powder X-ray diffraction pattern of the polyester resin (A), the 2θ is (i) 19 ° to 20 °, (ii) 21 ° to 22 °, (iii) 23 ° to 25 °, and (iv) 29 ° to The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 16, wherein a diffraction peak appears at a position of 31 °.   An electrostatic image developing toner produced by the toner production method according to claim 1.   A toner container filled with the electrostatic image developing toner according to claim 18.   19. An image forming method for developing an electrostatic latent image formed on an image carrier with toner, wherein the toner for developing an electrostatic charge image according to claim 18 is used as the toner.   At least a photosensitive member, charging means for charging the surface of the photosensitive member, developing means for developing an electrostatic latent image formed on the surface of the photosensitive member with an electrostatic latent image developer, and the surface of the photosensitive member An image forming apparatus comprising: a cleaning unit that wipes away the developer remaining in the toner, wherein the developing unit uses the toner according to claim 18. 19. A process cartridge that integrally supports a developing unit and at least one unit selected from a charging unit and a cleaning unit and is detachable from an image forming apparatus main body, wherein the developing unit is an electrostatic charge image according to claim 18. A process cartridge using a developing toner.

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