JP2006201691A - Toner and developer for electrostatic image development, image forming apparatus, process cartridge using the same and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner and a developer which are stable even after outputting several ten thousand images, do not cause such problems as surface stain, toner flying-off and toner spattering, and ensure little change in charging ability even after performing output of several ten thousand images, and also to provide a toner and a developer which ensure little weakly charged or reversely charged toner and a sharp charge amount distribution and can form visible images having good sharpness and color reproducibility over a prolonged period of time. <P>SOLUTION: The toner for electrostatic image development comprises at least a resin binder, inorganic fine particles, a colorant and a wax, wherein the toner satisfies a relationship represented by the expression (1), has a D50 of 3-8 μm, and includes aggregates of ≥25 μm in an amount of ≤0.5% to the weight of the toner. In the expression, D10, D50 and D90 denote particle diameters at which, when the toner is integrated from the smaller particle diameter side, volume percentages to all particles become 10%, 50% and 90%, respectively. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an electrostatic charge image developing toner and developer, an image forming apparatus and an image forming method, and a process cartridge using the same.

  In electrophotographic devices and electrostatic recording devices, toner is attached to an electrostatic latent image formed on a photoreceptor, transferred to a transfer material, and then fixed to the transfer material by heat to form a toner image. is doing. Also, full-color image formation is generally performed by using four color toners of black, yellow, magenta, and cyan. Each toner is developed and each toner layer is superimposed on a transfer material. To obtain a full-color image.

  However, for users who are familiar with printing in general, images on full-color copiers are not yet satisfactory, and there is a demand for higher image quality that satisfies photography, high-definition, and high resolution. It is known to use a toner having a small particle size and a narrow particle size distribution to improve the image quality.

  Conventionally, an electrical or magnetic latent image has been visualized with toner. Toner used for electrostatic image development is generally colored particles in which a binder, a colorant, a charge control agent, and other additives are contained in a binder resin. There is a polymerization method. In the pulverization method, a colorant, a charge control agent, an offset preventive agent, and the like are melt-mixed and uniformly dispersed in a thermoplastic resin, and the resulting composition is pulverized and classified to produce a toner.

  According to the pulverization method, a toner having some excellent characteristics can be produced, but there is a limitation in the selection of the toner material. For example, the composition obtained by melt mixing must be capable of being pulverized and classified by economically usable equipment. From this requirement, the melt-mixed composition must be made sufficiently brittle. This is because the composition cannot be pulverized until the target particle size is reached unless it is a brittle composition. For this reason, when the above composition is actually pulverized into particles, a high-range particle size distribution is likely to be formed, and when attempting to obtain a copy image with good resolution and gradation, for example, the particle size There is a disadvantage that the fine powder of 5 μm or less and the coarse powder of 20 μm or more must be removed by classification and the yield becomes very low. Further, in the pulverization method, it is difficult to uniformly disperse the colorant, the charge control agent, and the like in the thermoplastic resin. The uneven dispersion of the compounding agent adversely affects the fluidity, developability, durability, image quality and the like of the toner.

In recent years, in order to overcome these problems in the pulverization method, for example, as described in Patent Document 1, toner particles are obtained by a suspension polymerization method. However, although the toner particles obtained by the suspension polymerization method are spherical, there is a disadvantage that the cleaning property is inferior. Development and transfer with a low image area ratio results in a small amount of residual toner, and poor cleaning does not become a problem. Toner may be generated on the photosensitive member as untransferred toner, and accumulation will cause image smudges. In addition, the charging roller that contacts and charges the photosensitive member is contaminated, and the original charging ability cannot be exhibited. Also, the low temperature fixability is not sufficient, and a large amount of energy required for fixing is required, which is a problem.
On the other hand, Patent Document 2 discloses a method of obtaining irregular toner particles by associating resin fine particles obtained by an emulsion polymerization method. However, in the toner particles obtained by the emulsion polymerization method, a large amount of the surfactant remains not only on the surface but also inside the particles even after the water washing step, and the environmental stability of the toner charging is impaired. The amount distribution is widened, and the background stain of the obtained image becomes poor. In addition, the remaining surfactant contaminates the photoreceptor, the charging roller, the developing roller, and the like, and the original charging ability cannot be exhibited.

  On the other hand, in a fixing process by a contact heating method performed using a heating member such as a heat roller, the toner particles are required to release from the heating member (hereinafter referred to as “offset resistance”). Here, the offset resistance can be improved by the presence of a release agent on the toner particle surface. On the other hand, Patent Documents 3 and 4 disclose a method for improving offset resistance not only by containing resin fine particles in toner particles but also by unevenly distributing the resin fine particles on the surface of the toner particles. Yes. However, there is a problem that the lower limit fixing temperature is increased and the low temperature fixing property, that is, the energy saving fixing property is not sufficient.

  In addition, the following problems occur in the method of obtaining irregularly shaped toner particles by associating resin fine particles obtained by an emulsion polymerization method. That is, when the release agent fine particles are associated with each other in order to improve the offset resistance, the release agent fine particles are taken into the toner particles, and as a result, the offset resistance can be sufficiently improved. Can not. Resin fine particles, release agent fine particles, colorant fine particles, etc. are randomly fused to constitute toner particles, so there is a variation in composition (content ratio of constituent components) and molecular weight of constituent resins among the obtained toner particles. As a result, the toner particles have different surface characteristics, and a stable image cannot be formed over a long period of time. Further, in a low-temperature fixing system that requires low-temperature fixing, there is a problem that fixing temperature range cannot be secured because fixing inhibition occurs due to resin fine particles unevenly distributed on the toner surface.

On the other hand, Patent Document 5 has recently proposed a new production method called dissolution suspension method (EA; Emulsion-Aggregation method). This method is a method of granulating toner base particles from a polymer dissolved in an organic solvent, etc., while suspension polymerization forms particles from monomers, and expands the range of resin selection and polarity controllability. And so on. In addition, although the advantage that the structure control of the toner particles (core / shell structure control) is possible is given, the shell structure is a resin-only layer intended to reduce the exposure to the surface of the pigment or wax, The surface state is not devised, nor is such a structure (see Non-Patent Document 1). Therefore, although the shell structure is used, the surface of the toner is a normal resin and is not particularly devised. When aiming at fixing at a lower temperature, it is not sufficient in terms of heat-resistant storage stability and environmental charge stability.
In addition, the suspension polymerization method, the emulsion polymerization method, and the dissolution suspension method generally use a styrene / acrylic resin, and the polyester resin has difficulty in particle formation, and the particle size, particle size distribution, and shape control. It was difficult. In addition, there was a limit to fixability when aiming at lower temperature fixing.

  On the other hand, it is also known to use polyester modified with a urea bond for the purpose of heat-resistant storage and low-temperature fixing (see Patent Document 6). The problem was not sufficient in terms of strict environmental charge stability.

Japanese Patent Laid-Open No. 9-43909 Japanese Patent No. 2537503 JP 2000-292773 A JP 2000-292978 A Japanese Patent No. 3141784 Japanese Patent Laid-Open No. 11-133667 4th Joint Imaging Symposium (2002.2.79)

  The object of the present invention is stable even after outputting tens of thousands of images, and (1) the problem of background smearing, toner scattering, and toner dust does not occur. (2) Toner and developer capable of forming a visible image with a small amount of weakly charged and reversely charged toner, sharp charge amount distribution, sharpness and good color reproducibility over a long period of time It is to provide an agent.

The inventors of the present invention have studied the above problems and have arrived at the present invention.
That is, the above-mentioned problem is (1) of the present invention, “in an electrostatic charge image developing toner containing at least a resin binder, inorganic fine particles, a colorant, and a wax, the toner satisfies the relationship represented by the following formula (1): And an electrostatic charge image developing toner, wherein D50 is 3 to 8 μm, and the amount of aggregates of 25 μm or more present in the toner is 0.5% or less based on the toner weight.

（Ｄ１０、Ｄ５０、Ｄ９０はトナーを小粒径側から積算した時に全粒子に対する体積百分率が１０％、５０％、９０％となる粒径を示す。）」；
（２）「少なくとも官能基含有ポリエステル系樹脂が溶解されている有機溶媒相と、活性水素含有化合物と、着色剤とを、樹脂微粒子が分散されている水系媒体相中に分散させて、前記官能基含有ポリエステル系樹脂と前記活性水素含有化合物との伸長反応および／または架橋反応を起こさせ、これにより得られた分散液から粒子を形成し、この分散液の溶媒を除去、洗浄して得られたものであることを特徴とする請求項１に記載の静電荷像現像用トナー」；
（３）「前記有機溶媒相中に、前記官能基含有ポリエステル樹脂とともに、更に、非反応性ポリエステルが溶解されており、前記官能基含有ポリエステル系樹脂と前記非反応性ポリエステルとの重量比が５／９５〜７５／２５であることを特徴とする請求項１又は２に記載の静電荷像現像用トナー」；
（４）「トナー粒子の円形度が０．９４〜０．９８であることを特徴とする請求項１乃至３のいずれかに記載の静電荷像現像用トナー」；
（５）「前記無機微粒子が少なくとも２種類の無機微粒子からなることを特徴とする請求項１乃至４のいずれかに記載の静電荷像現像用トナー」；
（６）「前記無機微粒子が疎水性シリカ及びチタンであることを特徴とする請求項１乃至５のいずれかに記載の静電荷像現像用トナー」；
（７）「前記ワックスがカルナバワックスを含有することを特徴とする請求項１乃至６のいずれかに記載の静電荷像現像用トナー」；
（８）「前記ワックスのトナー粒子内部の含有量が５重量％以上であることを特徴とする請求項１乃至７のいずれかに記載の静電荷像現像用トナー」；
（９）「請求項１乃至８のいずれかに記載の静電荷像現像用トナーと磁性粒子からなるキャリアを含むことを特徴とする２成分系静電荷像現像用現像剤」；
（１０）「感光体上に形成された静電潜像をトナーを含む現像剤で現像し、感光体上に形成されたトナー画像を画像支持体上に転写し、該トナー画像を加熱部材を内包した加熱ローラと、対向配設された加圧ローラとからなる定着装置により定着し、該加圧ローラをクリーニングするクリーニング部材を用いる画像形成装置であって、請求項１乃至８のいずれかに記載の静電荷像現像用トナー又は請求項９に記載の現像剤を用い、該クリーニング部材に回収された該トナーが再び溶け出さないことを特徴とする画像形成装置」；
（１１）「静電荷像担持体と帯電手段と露光手段と現像手段と接触転写手段と定着手段とクリーニング手段と除電手段を有し、前記現像手段が請求項１乃至８のいずれかに記載の静電荷像現像用トナーを使用するものであることを特徴とする画像形成装置」；
（１２）「前記帯電手段は、静電荷像担持体に帯電部材を接触させ、当該帯電部材に電圧を印加することによって帯電を行なう帯電手段であることを特徴とする請求項１１記載の画像形成装置」；
（１３）「前記静電荷像担持体がアモルファスシリコン静電荷像担持体であることを特徴とする請求項１１又は１２に記載の画像形成装置」；
（１４）「前記定着手段が、発熱体を具備する加熱体と、前記加熱体と接触するフィルムと、該フィルムを介して前記加熱体と圧接する加圧部材とを有し、前記フィルムと前記加圧部材の間に未定着トナー画像を形成させた被記録材を通過させて加熱定着する定着装置であることを特徴とする請求項１１乃至１３のいずれかに記載の画像形成装置」；
（１５）「感光体と現像手段を有し、かつ帯電手段、クリーニング手段より選ばれる少なくとも一つの手段を一体に支持していてもよく、画像形成装置本体に着脱自在であるプロセスカートリッジにおいて、前記現像手段は、トナーを擁し、該トナーは、少なくとも無機微粒子、着色剤、ワックスを含む静電荷像現像用トナーであって、該トナーが下記式（１）で表わされる関係を満足し、かつＤ５０が３〜８μｍであり、かつトナー中に存在する２５μｍ以上の凝集体量がトナー重量に対して０．５％以下であることを特徴とする請求項１乃至８のいずれか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プロセスカートリッジ。

(D10, D50, and D90 indicate the particle diameters at which the volume percentage with respect to all the particles becomes 10%, 50%, and 90% when the toner is accumulated from the small particle diameter side.);
(2) “At least the organic solvent phase in which the functional group-containing polyester resin is dissolved, the active hydrogen-containing compound, and the colorant are dispersed in an aqueous medium phase in which resin fine particles are dispersed, It is obtained by causing elongation reaction and / or cross-linking reaction between the group-containing polyester resin and the active hydrogen-containing compound, forming particles from the resulting dispersion, and removing and washing the solvent of this dispersion. The toner for developing an electrostatic charge image according to claim 1, wherein
(3) “A non-reactive polyester is further dissolved in the organic solvent phase together with the functional group-containing polyester resin, and the weight ratio of the functional group-containing polyester resin to the non-reactive polyester is 5”. The toner for developing an electrostatic charge image according to claim 1, wherein the toner is / 95 to 75/25;
(4) "The toner for developing an electrostatic image according to any one of claims 1 to 3, wherein the toner particles have a circularity of 0.94 to 0.98";
(5) "The toner for developing an electrostatic charge image according to any one of claims 1 to 4, wherein the inorganic fine particles are composed of at least two types of inorganic fine particles";
(6) "The toner for developing an electrostatic charge image according to any one of claims 1 to 5, wherein the inorganic fine particles are hydrophobic silica and titanium";
(7) "The toner for developing electrostatic image according to any one of claims 1 to 6, wherein the wax contains carnauba wax";
(8) "The toner for developing an electrostatic charge image according to any one of claims 1 to 7, wherein the content of the wax in the toner particles is 5% by weight or more";
(9) “A two-component electrostatic image developing developer comprising the electrostatic image developing toner according to any one of claims 1 to 8 and a carrier comprising magnetic particles”;
(10) “The electrostatic latent image formed on the photoreceptor is developed with a developer containing toner, the toner image formed on the photoreceptor is transferred onto the image support, and the toner image is transferred to the heating member. 9. An image forming apparatus using a cleaning member that fixes and cleans the pressure roller by a fixing device comprising an encapsulated heating roller and a pressure roller disposed oppositely. An image forming apparatus using the toner for developing an electrostatic charge image according to claim 9 or the developer according to claim 9, wherein the toner collected on the cleaning member does not melt again;
(11) “An electrostatic charge image carrier, a charging unit, an exposure unit, a developing unit, a contact transfer unit, a fixing unit, a cleaning unit, and a charge eliminating unit, wherein the developing unit is described in any one of claims 1 to 8. An image forming apparatus using toner for developing an electrostatic charge image ”;
(12) The image forming apparatus according to (11), wherein the charging unit is a charging unit that performs charging by bringing a charging member into contact with an electrostatic charge image carrier and applying a voltage to the charging member. apparatus";
(13) “The image forming apparatus according to claim 11 or 12, wherein the electrostatic image carrier is an amorphous silicon electrostatic image carrier”;
(14) "The fixing means includes a heating body provided with a heating element, a film in contact with the heating body, and a pressure member in pressure contact with the heating body through the film, 14. An image forming apparatus according to claim 11, wherein the image forming apparatus is a fixing device that heats and fixes a recording material on which an unfixed toner image is formed between pressure members.
(15) In the process cartridge having a photosensitive member and a developing unit, and may integrally support at least one unit selected from a charging unit and a cleaning unit, and is detachable from the main body of the image forming apparatus, The developing means includes a toner, and the toner is an electrostatic image developing toner containing at least inorganic fine particles, a colorant, and a wax, and the toner satisfies the relationship represented by the following formula (1), and D50 The electrostatic charge according to any one of claims 1 to 8, wherein the amount of the aggregate of 25 µm or more present in the toner is 0.5% or less with respect to the toner weight. A process cartridge using an image developing toner.

（Ｄ１０、Ｄ５０、Ｄ９０はトナーを小粒径側から積算した時に全粒子に対する体積百分率が１０％、５０％、９０％となる粒径を示す。）」；
（１６）「発熱体を具備する加熱体と、前記加熱体と接触するフィルムと、前記フィルムを介して前記加熱体と圧接する加圧部材とを有し、前記フィルムと前記加圧部材の間に未定着トナー画像を形成させた被記録材を通過させて加熱定着する定着装置を用いる画像形成方法であって、前記トナー画像の形成に用いるトナーが請求項１乃至８のいずれかに記載の静電荷像現像用トナーであることを特徴とする画像形成方法」により解決される。

(D10, D50, and D90 indicate the particle diameters at which the volume percentage with respect to all the particles becomes 10%, 50%, and 90% when the toner is accumulated from the small particle diameter side.);
(16) “A heating element including a heating element, a film that contacts the heating element, and a pressure member that press-contacts the heating element via the film, between the film and the pressure member An image forming method using a fixing device that heats and fixes a recording material on which an unfixed toner image is formed, wherein the toner used for forming the toner image is according to any one of claims 1 to 8. This is solved by an “image forming method characterized by being an electrostatic charge image developing toner”.

  According to the present invention, even after outputting tens of thousands of images, the following effects can be obtained. (1) Problems such as dirt, toner scattering, and toner dust do not occur, and tens of thousands of images are output. Can provide a toner and a developer with little change in charging ability, and (2) form a visible image with a long period of weakly charged and reversely charged toner, a sharp charge amount distribution, excellent sharpness and color reproducibility. The excellent effect of providing a toner and a developer that can be provided is exhibited at the same time.

  Hereinafter, the present invention will be described in detail. Here, as for the toner, the manufacturing method and material of the developer used in the present invention, and the overall system relating to the electrophotographic process, known ones can be used if the conditions are satisfied.

（Ｄ１０、Ｄ５０、Ｄ９０はトナーを小粒径側から積算した時に全粒子に対する体積百分率が１０％、５０％、９０％となる粒径を示す。） In the present invention, it is important to satisfy the relationship represented by the following formula (1).

(D10, D50, and D90 indicate particle diameters at which the volume percentage with respect to all particles becomes 10%, 50%, and 90% when the toner is accumulated from the small particle diameter side.)

  If the relationship of D90 / D10 ≦ 1.90−0.05 × D50 cannot be satisfied, the particle size distribution spreads and the image quality deteriorates. In addition, since the charge amount is non-uniform, image problems such as fogging and toner scattering occur. If 1.60−0.05 × D50 ≦ D90 / D10 is not satisfied, problems such as a decrease in yield during toner production and an increase in production cost occur. It is also important that D50 is 3 to 8 μm. When D50 exceeds 8 μm, the image quality deteriorates, and even if the particle size distribution satisfies the above equation (1), good image quality is not obtained. Further, when D50 is less than 3 μm, problems such as poor cleaning and toner scattering occur, which is not preferable.

  When the toner of the present invention is produced, the toner particles may be fused by heat or the like to generate aggregates. These aggregates are likely to be generated in the polymerized toner, but in the case of particles of about several tens of μm, many particles are present in the toner through the sieve. However, in the present invention, it is very important to control the amount of aggregates of 25 μm or more present in these toners to 0.5% or less with respect to the toner weight. When these agglomerates are present in large numbers, problems such as toner scattering, fogging, toner dust, and toner clogging during replenishment are caused. Further, when the amount of aggregate is large, problems such as toner scattering occur even if the above formula (1) is satisfied, and therefore it is necessary to satisfy all these conditions.

Measurement of D10, D50, and D90 was used by connecting to a Coulter Counter TAII manufactured by Coulter Electronics, USA, an interface (manufactured by Nikkiki) that outputs number distribution and volume distribution, and a PC9801 personal computer (manufactured by NEC). The electrolyte was adjusted to a 1% NaCl aqueous solution using primary sodium chloride.
As a measuring method, 0.1 to 5 ml of a surfactant, preferably alkylbenzenesulfonate is added as a dispersant to 50 to 100 ml of the electrolytic solution, and 1 to 10 mg of a sample is added. This is subjected to a dispersion treatment for 1 minute with an ultrasonic disperser, and 100 to 200 ml of an electrolytic aqueous solution is put into another beaker, and the sample dispersion is added to a predetermined concentration therein, and the Coulter Counter TA- Based on type II, 30000 particle size distributions of 2 to 40 μm particles are measured using a 100 μm aperture as an aperture, and the volume distribution and number distribution of 2 to 40 μm particles are calculated. D10, D50, and D90 were obtained from the calculated volume distribution.

  The amount of aggregates of 25 μm or more is measured by sieving a test sample having a known weight, and mesh No. This is done by calibrating the residue on a sieve having 60 openings.

The dry toner of the present invention can be produced by the following method, but is not limited thereto.
In the production of the toner of the present invention, an oil phase composed of a binder containing a modified polyester, a colorant, a wax and a pigment and an aqueous phase composed of resin fine particles, a solvent and the like are first emulsified in a pipeline homomixer. Thereafter, after condensing and solvent removal, rough separation is performed using a centrifuge or a filter press. Finally, cleaning is performed and then drying is performed to complete the toner production.

  As the modified polyester used in the present invention, there can be used those in which a bonding group other than an ester bond is present in the polyester resin, or different resin components are bonded to the polyester resin by a covalent bond, an ionic bond or the like. For example, a polyester end is reacted with something other than an ester bond, specifically, a functional group such as an acid group or an isocyanate group that reacts with a hydroxyl group is introduced at the end, and further reacted with an active hydrogen compound to terminate the end. Examples thereof include modified ones. Of these, polyesters modified with urea bonds are particularly preferred.

  Examples of the urea-modified polyester include a reaction product of a polyester prepolymer (A) having an isocyanate group and amines (B). The polyester prepolymer (A) having an isocyanate group is a polycondensate of a polyol (1) and a polycarboxylic acid (2), and a polyester obtained by further reacting a polyester having an active hydrogen group with a polyisocyanate (3). Etc. Examples of the active hydrogen group include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like, and alcoholic hydroxyl groups are preferred.

  Examples of the polyol (1) include a diol (1-1) and a trihydric or higher polyol (1-2). (1-1) alone or (1-1) and a small amount of (1-2) Mixtures are preferred. Examples of the diol (1-1) include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol) , Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol) F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; Alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts. Of these, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is combined use with. The trihydric or higher polyol (1-2) includes 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (Trisphenol PA, phenol novolak, cresol novolak, etc.); and alkylene oxide adducts of the above trivalent or higher polyphenols.

  Examples of polycarboxylic acid (2) include dicarboxylic acid (2-1) and trivalent or higher polycarboxylic acid (2-2). (2-1) alone and (2-1) with a small amount of ( The mixture of 2-2) is preferred. Dicarboxylic acid (2-1) includes alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid) , Naphthalenedicarboxylic acid, etc.). Among these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). In addition, you may make it react with a polyol (1) using the acid anhydride or lower alkyl ester (Methyl ester, ethyl ester, isopropyl ester, etc.) of said thing as polycarboxylic acid (2).

The ratio of the polyol (1) to the polycarboxylic acid (2) is usually 2/1 to 1/1, preferably 1 as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 0.5 / 1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.
Examples of the polyisocyanate (3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; polyisocyanates such as phenol derivatives, oximes, caprolactams, etc. And a combination of two or more of these.

  The ratio of the polyisocyanate (3) is usually 5/1 to 1/1, preferably 4 /, as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] is greater than 5, the low-temperature fixability of the toner is deteriorated. On the other hand, when [NCO] / [OH] is less than 1, the urea content in the modified polyester is decreased, and hot offset resistance is reduced. This is not preferable because the properties deteriorate.

  The content of the polyisocyanate (3) component in the prepolymer (A) having an isocyanate group at the terminal is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight. It is. If the content of the polyisocyanate (3) component is less than 0.5% by weight, the hot offset resistance of the toner deteriorates and it becomes difficult to achieve both heat-resistant storage stability and low-temperature fixability. If the amount is large, the low-temperature fixability deteriorates, which is not preferable. The number of isocyanate groups per molecule in the prepolymer (A) is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. When the number of isocyanate groups per molecule is less than 1, it is not preferable because the molecular weight of the urea-modified polyester is lowered and the hot offset resistance is deteriorated.

  The elongation and / or crosslinking reaction time varies depending on the reactivity of the isocyanate group structure of the prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. The reaction temperature is usually 0 to 150 ° C., preferably 40 to 98 ° C. If necessary, a conventionally known catalyst such as dibutyltin laurate or dioctyltin laurate can be used. If necessary, the molecular weight of the urea-modified polyester can be adjusted using an elongation terminator. Examples of the elongation terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).

  Moreover, in this invention, what contains a urethane bond in the polyester modified | denatured by the urea bond as a modified polyester can also be used preferably. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance of the toner is deteriorated, which is not preferable.

  The urea-modified polyester used in the present invention can be produced by a one-shot method or a prepolymer method. The weight average molecular weight of the urea-modified polyester is usually 10,000 or more, preferably 20,000 to 10,000,000, more preferably 30,000 to 1,000,000. The peak molecular weight at this time is 2500 to 10000, and if the peak molecular weight is less than 2500, the extension reaction is difficult to proceed, so the elasticity of the toner is lowered and the hot offset resistance is deteriorated. On the other hand, if it is more than 10,000, the fixability is lowered and it is not preferable because it becomes difficult to form particles or finely pulverize.

  The number average molecular weight of the urea-modified polyester is usually 20000 or less, preferably 1000 to 10000, more preferably 2000 to 8000. When the number average molecular weight is larger than 20000, the low-temperature fixability of the obtained toner is deteriorated, and the glossiness when used in a full-color apparatus is not preferable.

  In the present invention, it is preferable to use urea-modified polyester and unmodified polyester in combination as a binder. By using the unmodified polyester in combination, the low-temperature fixability of the toner is improved as compared with the case where the urea-modified polyester is used alone, and the glossiness when used in a full-color device is improved. In addition, when using polyester which is not modified | denatured, the number average molecular weight of urea modified polyester is not restrict | limited in particular, What is necessary is just the number average molecular weight from which the said weight average molecular weight is obtained.

  Examples of the unmodified polyester include polycondensates of the above-mentioned urea-modified polyester component and the same kind of polyol (1) and polycarboxylic acid (2), and the preferred is the same as the urea-modified polyester. By making the modified polyester and the unmodified polyester have a similar composition, at least a part of both is compatible and the low-temperature fixability and hot offset resistance are improved. The polyester may be modified with a chemical bond other than a urea bond, such as a urethane bond, as well as an unmodified polyester.

  When the urea-modified polyester and the unmodified polyester are used in combination, the weight ratio between the two is usually 5/95 to 80/20, preferably 5/95 to 30/70, more preferably 5/95 to 25/75. More preferably, it is 7/93 to 20/80. When the weight ratio of the urea-modified polyester is less than 5%, the hot offset resistance of the toner is deteriorated, and the heat resistant storage stability and the low temperature fixability are deteriorated.

  The peak molecular weight of the unmodified polyester is usually 2500 to 10,000, preferably 3500 to 8000, and more preferably 3500 to 5000. When the peak molecular weight is less than 2500, the heat resistant storage stability of the toner is deteriorated. On the other hand, when it is more than 10,000, the low temperature fixability is deteriorated, which is not preferable.

  The hydroxyl value of the unmodified polyester is usually 5 or more, preferably 10 to 120, more preferably 20 to 80. A hydroxyl value of less than 5 is not preferable because the heat resistant storage stability and low-temperature fixability of the toner deteriorate. Moreover, an acid value is 1-5 normally, Preferably it is 2-4. Since a high acid value wax is used for the wax, the binder is preferably a low acid value binder. Chargeability and high volume resistance are obtained, which is suitable for a two-component toner.

  The glass transition point (Tg) of a binder is 40-65 degreeC normally, Preferably it is 45-60 degreeC. When Tg is lower than 40 ° C., the heat-resistant storage stability of the toner is deteriorated, while when it is higher than 65 ° C., the low-temperature fixability is deteriorated. By using urea-modified polyester as a binder, the heat-resistant storage stability of the toner is improved even when the glass transition point is low as compared with conventionally known polyester-based toners.

  The colorant can also be used as a master batch combined with a resin. The binder resin used in the production of the masterbatch or kneaded with the masterbatch includes, in addition to the above-mentioned modified and non-modified polyester, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, etc. Copolymer: Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Polymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene- α-chloromethyl methacrylate copolymer, Tylene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-malein Styrene copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, poly Acrylic resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like can be mentioned, and these can be used alone or in combination.

  The masterbatch can be obtained by mixing and kneading a masterbatch resin and a colorant with a high shear force. At this time, an organic solvent can also be used to enhance the interaction between the colorant and the resin. In addition, a method (flushing method) in which an aqueous paste containing a colorant is mixed and kneaded with a resin and an organic solvent, the colorant is transferred to the resin side, and moisture and the organic solvent component are removed (flushing method) is also used. Since it can be used without drying, it is preferably used. For mixing and kneading the colorant and the resin, a high shear dispersion device such as a three roll mill is preferably used.

  Further, a wax may be contained together with the toner binder and the colorant. Known waxes can be used as the wax of the present invention, and examples thereof include polyolefin waxes (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbons (paraffin wax, sazol wax, etc.); carbonyl group-containing waxes. Of these, carbonyl group-containing waxes are preferred. Carbonyl group-containing waxes include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18 -Octadecanediol distearate, etc.); polyalkanol esters (trimellitic acid tristearyl, distearyl maleate, etc.); polyalkanoic acid amides (ethylenediamine dibehenyl amide, etc.); polyalkylamides (trimellitic acid tristearyl amide, etc.) And dialkyl ketones (such as distearyl ketone). Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred. The melting point of the wax of the present invention is usually 40 to 160 ° C, preferably 50 to 120 ° C, more preferably 60 to 90 ° C. A wax having a melting point of less than 40 ° C. has an adverse effect on heat resistant storage stability, and a wax having a melting point of more than 160 ° C. tends to cause a cold offset when fixing at a low temperature. Further, the melt viscosity of the wax is preferably 5 to 1000 cps, more preferably 10 to 100 cps as a measured value at a temperature 20 ° C. higher than the melting point. Waxes exceeding 1000 cps have poor effects for improving hot offset resistance and low-temperature fixability. The content of the wax in the toner is usually 0 to 40% by weight, preferably 3 to 30% by weight.

  As the wax used in the present invention, it is very preferable to use carnauba wax as a wax component. Carnauba wax is a natural wax obtained from the leaves of carnabay palm, but a low acid value type from which free fatty acids are eliminated is particularly preferable because it can be uniformly dispersed in the binder resin. In addition, a low acid value type carnauba wax from which free fatty acids are eliminated is particularly preferable because it has a small amount of volatile components and therefore has little filming on the photoconductor and little spent on the charging member.

  In the present invention, the content of the wax inside the toner is particularly preferably 5% by weight or more in terms of weight. If it is less than 5%, not only is the image quality deteriorated and the gloss is lowered, but also hot offset is likely to occur, which is not preferable.

  The toner of the present invention may contain a charge control agent as necessary. As the charge control agent, conventionally known ones can be used without any particular limitation. For example, nigrosine dye, triphenylmethane dye, chromium-containing metal complex dye, molybdate chelate pigment, rhodamine dye, alkoxy amine, quaternary ammonium Salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, metal salts of salicylic acid derivatives, and the like. Specifically, Bontron 03 of nigrosine dye, Bontron P-51 of quaternary ammonium salt, Bontron S-34 of metal-containing azo dye, E-82 of oxynaphthoic acid metal complex, E of salicylic acid metal complex -84, phenolic condensate E-89 (above, Orient Chemical Industries), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Co., Ltd.), quaternary Copy charge PSY VP2038 of ammonium salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (above, manufactured by Hoechst), LRA-901, LR- which is a boron complex 147 (Nippon Carlit), copper phthalocyanine, perylene, quinacrid And azo pigments, and other polymer compounds having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts.

  The amount of charge control agent used is determined by the type of binder resin, the presence or absence of additives used as needed, and the toner production method including the dispersion method. The amount is usually 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight. If the amount used is more than 10 parts by weight, the chargeability of the toner becomes too high, the effect of the main charge control agent is reduced, and the electrostatic attraction force with the developing roller is increased. This is not preferable because the image density is lowered. The above colorant and charge control agent can be melt-kneaded together with the master batch and resin, or can be added when dissolved and dispersed in an organic solvent.

  Although it does not restrict | limit especially as a manufacturing method of the binder (binder) used for this invention, For example, the following method can be used. First, a polyol (1) and a polycarboxylic acid (2) are produced by heating to 150 to 280 ° C. in the presence of a conventionally known esterification catalyst such as tetrabutoxy titanate and dibutyltin oxide, and if necessary, reducing the pressure. Water is distilled off to obtain a polyester having a hydroxyl group. Subsequently, after cooling this to 40-140 degreeC, polyisocyanate (3) is made to react and the prepolymer (A) which has an isocyanate group is obtained. Further, the amine (B) is reacted with the prepolymer (A) at 0 to 140 ° C. to obtain a polyester modified with a urea bond. In the case of using unmodified polyester together, a non-modified polyester is produced in the same manner as the above polyester having a hydroxyl group, and this is dissolved and mixed in the urea-modified polyester solution after completion of the reaction. .

  When the polyisocyanate (3) is reacted and when the prepolymer (A) and the amines (B) are reacted, a solvent can be used as necessary. Usable solvents include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.) and ethers Inerts with respect to (3), such as a class (tetrahydrofuran, etc.).

  As a method of stably forming toner base particles having a D50 of 3 to 8 μm and a narrow particle size distribution as described above in an aqueous medium, a toner raw material containing urea-modified polyester or prepolymer (A) in the aqueous medium is used. A method of adding the composition and dispersing it by shearing force can be used. The prepolymer (A) and other toner components such as a colorant, a colorant masterbatch, a wax, a fluidizing agent, a charge control agent, an unmodified polyester (hereinafter referred to as toner raw material) are dispersed in an aqueous medium. It is preferable to mix the prepolymer (A) and the toner raw material in advance, and then add and disperse the resulting mixture in an aqueous medium. The toner raw materials are not necessarily mixed when forming particles in an aqueous medium, and may be added individually after the particles are formed. For example, after forming particles that do not contain a colorant, a colorant can be added using a conventionally known dyeing method.

  As a method for producing the base particles in the above aqueous medium, for example, the following method can be used. As an aqueous medium to be used, water alone may be used, or a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohols (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), and the like. The toner particles may be formed by reacting a dispersion composed of a prepolymer (A) having an isocyanate group with an amine (B) in an aqueous medium, or using a urea-modified polyester prepared in advance. May also be formed.

  The method for dispersing the toner raw material composition in the aqueous medium is not particularly limited, and conventionally known methods such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be used. It is preferable to use a high-speed shearing method in order to make the particle size of 2 to 20 μm. When a high-speed shearing disperser is used, the rotation speed is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm, and more preferably 6000 to 18000 rpm in order to reliably control the particle size distribution in the narrow range as described above. . The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. Moreover, the temperature of the aqueous medium at the time of dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C. By increasing the temperature of the aqueous medium, the viscosity of the dispersion is lowered and the dispersion becomes easy.

  The amount of the aqueous medium used is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight, based on 100 parts of the toner raw material composition. When the amount used is less than 50 parts by weight, the dispersion state of the toner raw material composition is deteriorated and toner particles having a desired particle diameter cannot be obtained. .

  In the aqueous medium, a dispersant can be used as necessary in order to sharpen the particle size distribution of the toner particles and stabilize the dispersibility. Examples of the dispersant for emulsifying and dispersing the oily phase in which the toner raw material composition is dispersed in an aqueous medium include anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates and phosphate esters, alkyls Amine salt type such as amine salt, amino alcohol fatty acid derivative, polyamine fatty acid derivative, imidazoline, alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride, etc. Quaternary ammonium salt type cationic surfactants, nonionic surfactants such as fatty acid amide derivatives and polyhydric alcohol derivatives such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl -N, - amphoteric surfactants such as downy dimethylammonium tines can be used.

  A surfactant containing a fluoroalkyl group is economical because it exhibits a dispersion effect even in a very small amount. Examples of the anionic surfactant containing a fluoroalkyl group include C2-C10 fluoroalkylcarboxylic acids and metal salts thereof, disodium perfluorooctanesulfonylglutamate, 3- [omega-fluoroalkyl (C6-C11) oxy. ] 1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carboxylic acid and Metal salt, perfluoroalkyl carboxylic acid (C7 to C13) and its metal salt, perfluoroalkyl (C4 to C12) sulfonic acid and its metal salt, perfluorooctane sulfonic acid diethanolamide, N-propyl-N- (2 hydroxy Ethyl) perfluoroocta Sulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. can be used. . Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (Daikin Kogyo Co., Ltd.), Mega-Fac F-l0, F-l20, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF-102 , 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fgentent F-100, F150 (manufactured by Neos).

  In addition, as the cationic surfactant, aliphatic quaternary ammonium salts such as aliphatic primary, secondary or tertiary amine acids containing perfluoroalkyl groups, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts, etc. , Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (manufactured by Asahi Glass), Florard FC-135 (manufactured by Sumitomo 3M), Unidyne DS-202 (Daikin Industries) Smoke), MegaFuck F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products), Footage F-300 (Neos), etc. can be used.

  Furthermore, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like can also be used as an inorganic compound dispersant that is hardly soluble in water.

  Further, the dispersed droplets may be stabilized by a polymer protective colloid. Examples of polymeric protective colloids include acids such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride, or hydroxyl groups (Meth) acrylic monomers such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-methacrylate Hydroxypropyl, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol Monomethacrylic acid ester, N-methylolacrylamide, N-methylolmethacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or vinyl alcohol and carboxyl group Esters of the compounds contained, such as vinyl acetate, vinyl propionate, vinyl butyrate, etc., acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl Homopolymers or copolymers such as those having a nitrogen atom such as pyrrolidone, vinylimidazole, ethyleneimine, or a heterocyclic ring thereof, polyoxyethylene, polyoxypropylene , Polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxy Polyoxyethylenes such as ethylene nonylphenyl ester, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

  When a dispersant is used, it is not particularly limited. However, in order to improve the charging property of the toner, it is preferable to remove it after the elongation and / or crosslinking reaction. In addition, when an acid or alkali-soluble material such as calcium phosphate salt is used as the dispersant, the calcium phosphate salt is removed from the fine particles by a method such as washing with water after dissolving the calcium phosphate salt with an acid such as hydrochloric acid. Further, the calcium phosphate salt may be removed by an operation such as enzymatic degradation.

  Further, although not particularly limited, in order to lower the viscosity of the toner raw material composition and sharpen the particle size distribution of the toner particles, a solvent in which the urea-modified polyester or the prepolymer (A) is soluble can be used. As the solvent, it is particularly preferable to use a volatile solvent having a boiling point of less than 100 ° C. in order to facilitate removal and control the amount of aggregates of 25 μm or more to 0.5% or less with respect to the toner weight. For example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl A ketone etc. can be used individually or in combination of 2 or more types. In particular, it is preferable to use an aromatic solvent such as toluene or xylene, or a halogenated hydrocarbon such as methylene chloride, 1,2-dichloroethane, chloroform, or carbon tetrachloride. The amount of the solvent used is usually 300 parts or less, preferably 100 parts or less, more preferably 25 to 70 parts, per 100 parts of the urea-modified polyester or prepolymer (A). In addition, when using a solvent, it is removed by heating under normal pressure or reduced pressure after the elongation and / or crosslinking reaction.

  As a method for removing the organic solvent from the obtained emulsified dispersion, a method of gradually elevating the temperature of the entire system and completely evaporating and removing the organic solvent in the droplets can be used. It is also possible to spray the emulsified dispersion in a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and to evaporate and remove the aqueous dispersant together. The dry atmosphere for spraying the emulsified dispersion is generally a gas heated from air, nitrogen, carbon dioxide, combustion gas, etc., and various air streams heated to a temperature higher than the boiling point of the highest boiling solvent used are used. it can. Toner particles with satisfactory quality can be obtained by short-time treatment using a spray dryer, belt dryer, rotary kiln or the like.

  When the particle size distribution at the time of emulsification dispersion becomes wide, toner particles having a desired particle size distribution can be obtained by performing a classification operation using the following method after washing and drying. In the classification operation, the fine particle portion is removed in the liquid using a cyclone, a decanter, a centrifugal separator or the like. Although classification may be performed as a powder after drying, it is preferably performed in a liquid from the viewpoint of production efficiency. The obtained fine particles or coarse particles can be returned to the kneading step and used for forming particles. At that time, the fine particles or coarse particles may be wet. The used dispersant is preferably removed from the dispersion as much as possible simultaneously with the classification operation.

  The toner powder and inorganic fine particles after drying are mixed with different types of particles such as wax, charge control agent, fluidizing agent, colorant, etc., and mechanical impact force is applied to the mixed powder to fix and fuse on the surface. In order to control the amount of aggregates of 25 μm or more to 0.5% or less with respect to the toner weight, it is preferable to prevent the dissociation of foreign particles from the surface of the composite particles obtained. Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting the mixture into a high-speed air stream and accelerating, and causing particles or composite particles to collide with an appropriate collision plate, etc. Can be used. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) to reduce pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.) Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.

  When preparing the developer, external additives such as the above inorganic fine particles may be further added and mixed in order to improve the fluidity, storage stability, developability, and transferability of the developer. The method of mixing the external additive is not particularly limited, and a conventionally known powder mixer can be used, but it is preferable to adjust the internal temperature by providing a jacket or the like. In order to change the load history applied to the external additive, the external additive may be added in the middle of the mixing or gradually, and the rotational speed, rolling speed, time, temperature, etc. of the mixer may be changed. A strong load at the beginning of mixing and then a relatively weak load may be applied, and vice versa. As the mixer, a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, a Henschel mixer, or the like can be used.

  Examples of the inorganic fine particles added to the toner of the present invention include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, and silica sand. , Clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, etc. .

  Further, in the present invention, it is desirable that the average primary particle diameters of the two kinds of inorganic fine particles are different. These additives are known to be gradually embedded in the toner due to a load in the development process, but when the two types of particle sizes are different, the inorganic fine particles having the larger particle size are separated from the toner surface. It plays the role of a spacer in contact with the photoreceptor or the carrier surface, and has a role of preventing the inorganic fine particles having a smaller particle diameter from being embedded in the toner surface. Therefore, the toner surface covering state of the additive in the initial state is maintained for a long time, and the filming suppressing effect in the present invention can be further maintained.

  Furthermore, in the present invention, it is desirable that the amount of inorganic fine particles having a small average primary particle diameter of the two types of inorganic fine particles is larger than the amount of inorganic fine particles having a large average primary particle diameter. The smaller the additive amount in the larger particle size and the larger the additive amount in the smaller particle size, the smaller the change in toner characteristics over time. This is considered to be because the embedding proceeds first from the toner having a large particle diameter.

  Furthermore, it is preferable that at least one inorganic fine particle used in the present invention has an average primary particle size of 0.03 μm or less from the viewpoint of imparting fluidity. When the average primary particle size is 0.03 μm or less, necessary fluidity is obtained, toner charging becomes uniform, and toner scattering and background smearing are improved.

  The inorganic fine particles used in the present invention are required to have an average primary particle diameter of 80 to 500 nm for at least one silica from the viewpoint of cleaning residual toner on the photoreceptor. By setting the average primary particle diameter to 80 to 500 nm, silica adheres to the cleaning blade and the photosensitive member contact portion, and the cleaning is improved by the dam effect.

  In addition, since at least one of the inorganic fine particles used in the present invention is a hydrophobic inorganic fine particle treated with an organic silane compound, it achieves high image quality with excellent environmental stability and fewer image defects such as missing characters. More preferred. Of course, both of the two inorganic fine particles used in the present invention may be hydrophobized.

Examples of the hydrophobizing agent include dimethyldichlorosilane, trimethylchlorosilane, methyltrichlorosilane, allyldimethyldichlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane. P-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, chloromethyltrichlorosilane, p-chlorophenyltrichlorosilane, 3-chloropropyltrichlorosilane, 3-chloropropyltrimethoxysilane, vinyltriethoxysilane, vinylmethoxysilane, Vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, divinyldichlorosilane, dimethylbi Luchlorosilane, octyltrichlorosilane, decyltrichlorosilane, nonyltrichlorosilane, (4-t-propylphenyl) trichlorosilane, (4-t-butylphenyl) trichlorosilane, dipentyldichlorosilane, dihexyldichlorosilane, dioctyldichlorosilane , Dinonyl dichlorosilane, didecyl dichlorosilane, didodecyl dichlorosilane, dihexadecyl dichlorosilane, (4-t-butylphenyl) octyl dichlorosilane, dioctyl dichlorosilane, didecenyl dichlorosilane, Dinonenyldichlorosilane, di-2-ethylhexyldichlorosilane, di-3,3-dimethylpentyldichlorosilane, trihexylchlorosilane, trioctylchlorosilane, tridecylchlorosilane, dioctylmethyl Lorsilane, octyldimethylchlorosilane, (4-t-propylphenyl) diethylchlorosilane, isobutyltrimethoxysilane, methyltrimethoxysilane, octyltrimethoxysilane, trimethoxy (3,3,3-trifluoropropyl) silane, hexamethyl Organic silane compounds such as disilazane, hexaethyldisilazane, diethyltetratyldisilazane, hexaphenyldisilazane, hexatolyldisilazane, dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, Alkyl modified silicone oil, fluorine modified silicone oil, polyether modified silicone oil, alcohol modified silicone oil, amino modified silicone oil, epoxy Silicone oil such as xy-modified silicone oil, epoxy-polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, acrylic, methacryl-modified silicone oil, α-methylstyrene-modified silicone oil, and other silylation Agents, silane coupling agents having a fluoroalkyl group, organic titanate coupling agents, aluminum coupling agents, and the like. Of these, organic silane compounds are preferred.
By treating these hydrophobizing agents with the inorganic fine particles, the hydrophobic inorganic fine particles used in the present invention are produced.

  The trade names of hydrophobized silica fine particles include HDKH 2050EP, HVK21 (above Hoechst), R972, R974, RX200, RY200, R202, R805, R812 (above Nippon Aerosil), TS530, TS720 (above Cabot). .

  As specific trade names of surface-treated titanium oxide fine particles, anatase-type or rutile-type crystalline or non-crystalline ones can be used, such as T-805 (Nippon Aerosil) or rutile. Examples of the mold include STT-30A (Titanium Industry), STT-30A-FS (Titanium Industry), and the like.

  The particle size of the inorganic fine particles used in the present invention can be measured by a particle size distribution measuring apparatus using dynamic light scattering, for example, DLS-700 manufactured by Otsuka Electronics Co., Ltd. or Coulter N4 manufactured by Coulter Electronics. It is. However, since it is difficult to dissociate the secondary aggregation of the particles after the treatment with the organic silane compound, it is preferable to directly determine the particle diameter from a photograph obtained by a scanning electron microscope or a transmission electron microscope. In this case, at least 100 or more inorganic fine particles are observed, and the average value of the major axis is obtained.

  The toner according to the present invention is more effective when it has a specific shape. The toner shape is charged by contact with a carrier, and the chargeability of the toner sandwiched between the developing roll and the toner layer regulating member or the supply roller. And almost uniform thin layer properties. In an irregular shape that is too far from the spherical shape, the toner thin layer is too thin, and a sufficient development amount cannot be obtained. Further, in order to provide a clearer, better color reproducibility and high quality image, it is desirable that the toner has a uniform spherical shape. Therefore, in the present invention, it is preferable that the toner has a specific shape in order to form a high-definition image having a reproducibility with an appropriate density. In the present invention, the circularity is 0.94 to 0.00. It is preferable to regulate to 98.

  A flow type particle image analyzer FPIA-2100 (manufactured by Sysmex Corporation) is used for measurement of the ultrafine toner and the circularity. As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably alkylbenzene sulfonate is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance, and further measurement is performed. Add about 0.1-0.5g of sample. The suspension in which the sample is dispersed is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the concentration of the dispersion is set to 3000 to 10,000 / μl, and the ultrafine powder is measured with the apparatus.

  When toner particles are used for a two-component developer, the toner particles may be mixed with a magnetic carrier. The carrier to toner content ratio in the developer is 1 to 10 parts by weight of toner with respect to 100 parts by weight of carrier. As the magnetic carrier, iron powder, ferrite powder, magnetite powder, magnetic resin carrier, glass beads, etc. having a particle diameter of about 20 to 200 μm, and various conventionally known ones such as those treated with a resin or the like can be used. .

Examples of the resin powder that can be coated on the carrier in the present invention include a styrene-acrylic copolymer, a silicone resin, a maleic acid resin, a fluorine resin, a polyester resin, and an epoxy resin. In the case of a styrene-acrylic copolymer, those having a styrene content of 30 to 90% by weight are preferred. In this case, if the styrene content is less than 30% by weight, the development characteristics are low, and if it exceeds 90% by weight, the coating film becomes hard and easily peeled, and the life of the carrier is shortened.
Moreover, the resin coating of the carrier in the present invention may contain an adhesion-imparting agent, a curing agent, a lubricant, a conductive agent, a charge control agent and the like in addition to the resin.

[Process cartridge]
The process cartridge of the present invention uses the toner of the present invention, may have a photosensitive member and a developing unit, and may integrally support at least one unit selected from a charging unit and a cleaning unit. The process cartridge is detachable.
FIG. 1 shows a schematic configuration of an image forming apparatus having a process cartridge of the present invention.
In the figure, (10) shows the entire process cartridge, (11) shows a photoconductor, (12) shows charging means, (13) shows developing means, and (14) shows cleaning means.
In the present invention, a plurality of components such as the above-described photoreceptor (11), charging means (12), developing means (13), and cleaning means (14) 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.

The image forming apparatus of the present invention uses the toner of the present invention, and the fixing means is a heating body provided with a heating element, a film in contact with the heating body, and a pressure contact with the heating body through the film. An image forming apparatus comprising: a pressure member; and a fixing unit that heats and fixes a recording material on which an unfixed image is formed between the film and the pressure member.
As shown in FIG. 2, the fixing means of the present invention is a so-called surf fixing device that rotates and fixes a fixing film. In detail, the fixing film is an endless belt-like heat-resistant film, and is fixed and supported by a driving roller, a driven roller, and a heater support provided below the rollers, which are support rotating members of the film. It is stretched around the heating element.
The driven roller also serves as a tension roller for the fixing film, and the fixing film is rotated in the clockwise direction by the rotational driving of the driving roller in the clockwise direction in the drawing. The rotational driving speed is adjusted to a speed at which the transfer material and the fixing film have the same speed in the fixing nip region L where the pressure roller and the fixing film are in contact with each other.
Here, the pressure roller is a roller having a rubber elastic layer having good releasability such as silicon rubber, and a contact pressure of a total pressure of 4 to 10 kg against the fixing nip region L while rotating counterclockwise. With pressure contact.
The fixing film preferably has excellent heat resistance, releasability and durability, and a thin film having a total thickness of 100 μm or less, preferably 40 μm or less is used. For example, at least an image of a single layer film of a heat-resistant resin such as polyimide, polyetherimide, PES (polyether sulfide), PFA (tetrafluoroethylene perfluoroalkyl vinyl ether copolymer resin), or a composite layer film, for example, a 20 μm thick film The contact surface is coated with a release coating layer of PTFE (tetrafluoroethylene resin), PFA or other fluororesin added with a conductive material to a thickness of 10 μm, or an elastic layer such as fluororubber or silicon rubber. It is a thing.

In FIG. 2, the heating body of the present embodiment is composed of a flat substrate and a fixing heater, and the flat substrate is made of a material having high thermal conductivity and high electrical resistivity such as alumina and is in contact with the fixing film. A fixing heater composed of a resistance heating element is provided on the surface in the longitudinal direction. Such a fixing heater is formed by coating an electric resistance material such as Ag / Pd or Ta ₂ N in a linear or belt shape by screen printing or the like. In addition, electrodes (not shown) are formed at both ends of the fixing heater, and the resistance heating element generates heat when energized between the electrodes. Furthermore, a fixing temperature sensor constituted by a thermistor is provided on the surface of the substrate opposite to the surface provided with the fixing heater.
The temperature information of the substrate detected by the fixing temperature sensor is sent to a control means (not shown), and the amount of electric power supplied to the fixing heater is controlled by the control means, and the heating body is controlled to a predetermined temperature.

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Hereinafter, “part” means part by weight, and “%” means weight%.
(Manufacture of toner)
Production Example 1
~ Example of production of inorganic fine particles ~
Blowing liquid SiCl ₄ ingredients core at a flow rate of Ar gas as a carrier gas using a liquid material supply system 300 SCCM (min standard volume flow (CC)), the SiCl ₄ vapor flow rate 250 SCCM, _{H 2} gas 20 SLM (per Minute standard volume flow rate (L)) and O ₂ gas 20SLM were sent to a core burner for flame hydrolysis and fusion to produce SiO ₂ fine particles. The fine particles were grown to a predetermined primary particle size, and the obtained fine particles were hydrophobized with hexamethyldisilazane to obtain [Inorganic fine particles 1] having an average primary particle size of 5 nm.

Production Example 2
~ Synthesis of organic fine particle emulsion ~
In a reaction vessel in which a stir bar and a thermometer were set, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 80 parts of styrene, 83 parts of methacrylic acid, When 110 parts of butyl acrylate, 12 parts of butyl thioglycolate, and 1 part of ammonium persulfate were added and stirred for 15 minutes at 400 rpm, a white emulsion was obtained. The system was heated to raise the temperature in the system to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion was obtained. This is designated as [fine particle dispersion 1]. The volume average particle diameter of the [fine particle dispersion 1] measured by a laser diffraction particle size distribution analyzer (LA-920, manufactured by Shimadzu Corp.) was 120 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The Tg of the resin was 42 ° C., and the weight average molecular weight was 30,000.

Production Example 3
~ Preparation of aqueous phase ~
990 parts of water, 65 parts of [fine particle dispersion 1], 37 parts of a 48.5% aqueous solution of sodium dodecyldiphenyl ether disulfonate (ELEMINOL MON-7, Sanyo Chemical Industries) and 90 parts of ethyl acetate were mixed and stirred to give a milky white color Obtained liquid. This is designated as [Aqueous Phase 1].

Production Example 4
~ Synthesis of low molecular weight polyester ~
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl Add 2 parts of tin oxide, react for 8 hours at 230 ° C. under normal pressure, and further react for 5 hours under reduced pressure of 10-15 mmHg, then put 44 parts of trimellitic anhydride into the reaction vessel, and at 180 ° C. under normal pressure. The mixture was reacted for 2 hours to obtain [Low molecular weight polyester 1]. [Low molecular polyester 1] had a number average molecular weight of 2500, a weight average molecular weight of 6700, a Tg of 43 ° C., and an acid value of 25.

Production Example 5
~ Synthesis of intermediate polyester ~
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. for 8 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, Tg of 55 ° C., an acid value of 0.5, and a hydroxyl value of 51.

Production Example 6
-Synthesis of a modified polyester resin (referred to as prepolymer 1) capable of reacting with a compound having at least an active hydrogen group-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 410 parts of the above [intermediate polyester 1], 125 parts of isophorone diisocyanate, and 500 parts of ethyl acetate were added and reacted at 100 ° C. for 5 hours. ] Was obtained. The average number of isocyanate groups contained per molecule of [Prepolymer 1] was 2.15.

Production Example 7
~ Synthesis of ketimine ~
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 418.

Production Example 8
~ Master batch synthesis ~
1200 parts water, 40 parts carbon black (manufactured by Cabot, Regal 400R), 60 parts polyester resin (manufactured by Sanyo Kasei, RS801), 30 parts water, and mixed with a Henschel mixer (manufactured by Mitsui Mining) The mixture was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1].

Production Example 9
-Production of oil phase, that is, toner composition containing inorganic fine particles, colorant, and wax-
In a container equipped with a stir bar and a thermometer, 400 parts of [Low molecular weight polyester 1], 110 parts of carnauba wax and 947 parts of ethyl acetate were charged, heated to 80 ° C. with stirring, and maintained at 80 ° C. for 5 hours. Thereafter, it was cooled to 30 ° C. at 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were placed in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw material solution 1] 1324 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feed speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. The wax was dispersed under the conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] and 34 parts of [inorganic fine particles 1] were added, followed by one pass using a bead mill under the above conditions to obtain [Pigment / Wax Dispersion 1]. The solid content concentration of [Pigment / Wax Dispersion 1] (130 ° C., 30 minutes) was 50%.

Production Example 10
~ Emulsification ~
[Pigment / Wax Dispersion 1] 648 parts, [Prepolymer 1] 154 parts, [Ketimine Compound 1] 8.5 parts in a container, and TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 1 minute After mixing, 1200 parts of [Aqueous Phase 1] was added to the container and mixed with a TK homomixer at a rotation speed of 10,000 rpm for 20 minutes to obtain [Emulsion Slurry 1].
That is, it is dispersed in an aqueous medium containing resin fine particles and an elongation reaction is performed.

Production Example 11
~ Solvent removal ~
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain [Dispersion slurry 1].

Production Example 12
~ Washing and drying ~
[Dispersion Slurry 1] After 100 parts under reduced pressure,
(I): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(Ii): 100 parts of a 10% sodium hydroxide aqueous solution was added to the filter cake of (i), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(Iii): 100 parts of 10% hydrochloric acid was added to the filter cake of (ii), mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(Iv): 300 parts of ion-exchanged water was added to the filter cake of (iii), mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered twice to obtain a cake. . This is designated as [Filter cake 1].
[Filter cake 1] was dried with a circulating dryer at 45 ° C. for 48 hours to obtain toner base particles. This is designated as [toner base particle 1].

Example 1
[Toner base particle 1] is sieved with a 75 μm mesh, fine powder and coarse powder are then cut by classification operation, silica fine particles have a silica addition amount of 2.0 parts by weight of the toner amount, and titanium fine particles have a titanium addition amount of The toner was blended so as to have a toner amount of 0.75 part by weight, and stirred and mixed with a Henschel mixer to be used as an electrophotographic toner.

Example 2
[Toner base particle 1] is sieved with a 45 μm mesh, fine powder and coarse powder are then cut by classification operation, silica fine particles have a silica addition amount of 2.0 parts by weight of the toner amount, and titanium fine particles have a titanium addition amount of The toner was blended so as to have a toner amount of 0.75 part by weight, and stirred and mixed with a Henschel mixer to be used as an electrophotographic toner.

Comparative Example 1
[Toner base particle 1] is sieved with a 75 μm mesh, and then only fine powder is cut by classification operation. Silica fine particles have a silica addition amount of 2.0 parts by weight of the toner amount, and titanium fine particles have a titanium addition amount of the toner amount. The mixture was blended so as to be 0.75 part by weight, and stirred and mixed with a Henschel mixer to be used as an electrophotographic toner.

Comparative Example 2
[Toner base particle 1] is sieved with a 75 μm mesh, and then only coarse powder is cut by classification operation. Silica fine particles have a silica addition amount of 2.0 parts by weight of the toner amount, and titanium fine particles have a titanium addition amount of the toner. The amount was mixed to 0.75 part by weight, and the mixture was stirred and mixed with a Henschel mixer and used as an electrophotographic toner.

Comparative Example 3
Fine powder and coarse powder are cut by classification operation without sieving [Mother toner particles 1] with a mesh. Silica fine particles have a silica addition amount of 2.0 parts by weight of the toner amount, and titanium fine particles have a titanium addition amount. Was mixed so as to be 0.75 part by weight of the toner amount, and stirred and mixed by a Henschel mixer to be used as an electrophotographic toner.

Comparative Example 4
[Toner base particle 1] is sieved with a 150 μm mesh, fine powder and coarse powder are then cut by classification operation, silica fine particles have a silica addition amount of 2.0 parts by weight, and titanium fine particles have a titanium addition amount. The toner was blended so as to have a toner amount of 0.75 part by weight, and stirred and mixed with a Henschel mixer to be used as an electrophotographic toner.

Comparative Example 5
Cartonava wax used in Production Example 8 was changed to ester wax to produce [Mother toner particles 1]. [Toner base particle 1] is sieved with a 75 μm mesh, fine powder and coarse powder are then cut by classification operation, silica fine particles have a silica addition amount of 2.0 parts by weight of the toner amount, and titanium fine particles have a titanium addition amount of The toner was blended so as to have a toner amount of 0.75 part by weight, and stirred and mixed with a Henschel mixer to be used as an electrophotographic toner.

Comparative Example 6
<First step>
-Preparation of dispersion (1) Styrene 370g
n-butyl acrylate 30g
Acrylic acid 8g
24g dodecanethiol
Carbon tetrabromide 4g
After mixing and dissolving the above, 6 g of nonionic surfactant (Sanyo Kasei Co., Ltd .: Nonipol 400) and 10 g of anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) were ionized. Dispersed in 550 g of exchange water, dispersed in a flask, emulsified, and slowly mixed for 10 minutes, charged with 50 g of ion exchange water in which 4 g of ammonium persulfate was dissolved, and after nitrogen replacement, While stirring in the flask, the contents were heated in an oil bath until the content reached 70 ° C., and emulsion polymerization was continued for 5 hours. As a result, a dispersion (1) was prepared by dispersing resin particles having an average particle size of 155 nm, a glass transition point of 59 ° C., and a weight average molecular weight (Mw) of 12,000.
-Preparation of dispersion (2) 280 g of styrene
n-butyl acrylate 120g
Acrylic acid 8g
The above mixture was dissolved, and 6 g of a nonionic surfactant (Sanyo Kasei Co., Ltd .: Nonipol 400) and 12 g of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) were ionized. Dispersed in 550 g of exchange water, dispersed in a flask, emulsified, and slowly mixed for 10 minutes, charged with 50 g of ion exchange water in which 3 g of ammonium persulfate was dissolved, and after substituting with nitrogen, While stirring in the flask, the contents were heated in an oil bath until the content reached 70 ° C., and emulsion polymerization was continued for 5 hours. The average particle size was 105 nm, the glass transition point was 53 ° C., and the weight average molecular weight (Mw) was 550. A dispersion liquid (2) was prepared by dispersing resin particles having a molecular weight of 1,000.
-Preparation of colorant dispersion (1) Carbon black 50g
(Cabot Corporation: Mogal L)
Nonionic surfactant 5g
(Sanyo Kasei Co., Ltd .: Nonipol 400)
200g of ion exchange water
The above is mixed, dissolved, and dispersed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T50) to disperse a colorant (carbon black) having an average particle size of 250 nm (carbon black) 1) was prepared.
-Preparation of release agent dispersion (1) Paraffin wax 50g
(Nippon Seiwa Co., Ltd .: HNP0190, melting point 85 ° C.)
Cationic surfactant 7g
(Manufactured by Kao Corporation: Sanizol B50)
200g of ion exchange water
The above was heated to 95 ° C. and dispersed using a homogenizer (manufactured by IKA: Ultra Turrax T50), and then dispersed with a pressure discharge homogenizer to disperse a release agent having an average particle size of 550 nm. A release agent dispersion (1) was prepared.
-Preparation of agglomerated particles Dispersion (1) 120g
Dispersion (2) 80g
Colorant dispersion (1) 30g
Release agent dispersion (1) 40 g
Cationic surfactant 1.5g
(Manufactured by Kao Corporation: Sanizol B50)
The above was mixed and dispersed in a round stainless steel flask using a homogenizer (manufactured by IKA: Ultra Turrax T50), and then heated to 48 ° C. while stirring the inside of the flask in an oil bath for heating. After maintaining at 48 ° C. for 30 minutes, observation with an optical microscope confirmed that aggregated particles (volume: 95 cm 3) having an average particle diameter of about 5 μm were formed.
<Second step>
-Preparation of adhered particles 60 g of dispersion (1) as a resin-containing fine particle dispersion was gradually added. In addition, the volume of the resin particle contained in the dispersion liquid (1) is 25 cm ³ . And the temperature of the heating oil bath was raised to 50 degreeC, and was hold | maintained for 1 hour.
<Third step>
Then, after adding 3 g of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC), the stainless steel flask was sealed, and stirring was continued using a magnetic seal up to 105 ° C. Heated and held for 3 hours. Then, after cooling, the reaction product was filtered, thoroughly washed with ion exchange water, and then dried to obtain a toner base.
The toner base is sieved with a 75 μm mesh, and then fine powder and coarse powder are cut by classification operation. Silica fine particles have a silica addition amount of 2.0 parts by weight of the toner amount and titanium fine particles have a titanium addition amount of the toner amount. The mixture was blended so as to be 0.75 part by weight, and stirred and mixed with a Henschel mixer to be used as an electrophotographic toner.

[Evaluation methods]
(Evaluation item)
(1) Measurement of D10, D50, and D90 The particle size of the toner was measured using a particle size measuring device “Coulter Counter TAII” manufactured by Coulter Electronics Co., Ltd., with an aperture diameter of 100 μm. D10, D50, and D90 were calculated based on the volume distribution.
(2) Aggregate amount of 25 μm or more The toner 100 g was uniformly placed on a sieve having an opening of 25 μm, and vibration was applied for 5 minutes using a vibration sieve. Thereafter, the weight of the toner remaining on the mesh was measured, and the amount of aggregates of 25 μm or more was calculated.
(3) Average circularity The average circularity can be measured by a flow particle image analyzer FPIA-2100 (manufactured by Toa Medical Electronics Co., Ltd.). As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably alkylbenzene sulfonate is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance, and further measurement is performed. Add about 0.1-0.5g of sample. The suspension in which the sample is dispersed is obtained by performing dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser and measuring the shape and distribution of the toner with the above apparatus at a dispersion concentration of 3000 to 10,000 / μl. .
(4) Image graininess and sharpness Using an evaluation machine that was tuned by remodeling Ricoh's IPSiO Color 8100 to an oilless fixing system, a photographic image was output in a single color, and the degree of graininess and sharpness was visually evaluated. did. Evaluations were made from GOOD, ◎, ○, Δ, and ×.並 is equivalent to offset printing, ◯ is slightly worse than offset printing, Δ is much worse than offset printing, and × is very bad compared to conventional electrophotographic images.
(5) Charging stability Using an evaluation machine in which Ricoh's IPSiO Color 8100 was modified and tuned to an oil-less fixing system, an image area ratio 7% chart continuous 100,000 sheet output durability test was conducted using each toner. The change in the charge amount was evaluated. 1 g of developer was weighed and the change in charge amount was determined by the blow-off method. When the change in the charge amount was 5 μc / g or less, it was evaluated as ◯, when it was 10 μc / g or less, Δ when it exceeded 10 μc / g.
(6) Stain on the background Using an evaluation machine that has been tuned by remodeling Ricoh's IPSiO Color 8100 into an oil-less fixing system, a blank image is being developed after running 30,000 image charts of 50% image area in monochrome mode The developer on the photoconductor after development was transferred to tape, and the difference from the image density of the untransferred tape was measured with a 938 spectrocytometer (manufactured by X-Rite). The smaller the difference in image density, the better the background dirt. ◎ indicates ΔID of less than 0.01, ◯ indicates ΔID is 0.01 to 0.02, Δ indicates ΔID is 0.02 to 0.05, and X indicates ΔID is 0.05 or more.
(7) Toner scattering Using an evaluation machine remodeled from Ricoh's IPSiO Color 8100 to an oil-less fixing system, using each toner, image area ratio 5%, chart continuous 50,000-sheet output durability test, and copying with toner ◎ If there is no contamination inside the machine, ◎, a level that is slightly present but no problem in practical use, △ a level that has a large amount of scattering but no problem on the image, △, a large amount of scattering, and even a problem on the image The level at which is generated is indicated by x.
(8) Toner fluidity A powder tester (PT-N type, manufactured by Hosokawa Micron Co., Ltd.) is loaded with meshes of 75 μm, 45 μm, and 22 μm openings in order from the top, and 2 g of toner base is put on the uppermost 75 μm mesh. Then, a vibration of 1 mm in the vertical direction was applied for 10 seconds, and the fluidity (cohesion degree) of the toner base was calculated from the residual amount of toner on each mesh.
Aggregation degree (%) = (5 × (remaining toner amount (g) on 75 μm mesh))
+ 3 × (residual toner amount on 45 μm mesh (g))
+ (Residual toner amount on 22 μm mesh (g))) × 10
When the degree of aggregation was 8% or less, ◎, when it was 8 to 16%, ◯, when it was 16 to 25%, Δ, and when it was 25% or more, ×.
(9) Cleanability Using an evaluation machine that has been tuned by remodeling Ricoh's IPSiO Color 8100 into an oilless fixing system, the transfer residual toner on the photosensitive member that has passed the cleaning process after outputting 100 sheets is scotch tape (Sumitomo 3M Limited). )) And then measured with a Macbeth reflection densitometer RD 514 type, ◎ if the difference from the blank is less than 0.005, ◯ 0.005-0.010, 0.011, Evaluation was made with Δ for 0.02 and Δ for over 0.02.
(10) Filming In an environment of a temperature of 35 ° C. and a humidity of 95%, an image area ratio 7% chart continuous 100000 using each toner using an evaluation machine that was tuned by remodeling Ricoh IPSiO Color 8100 into an oilless fixing system. When the sheet output durability test was performed, the case where filming appeared in the middle was marked with x, and the case where filming did not appear was marked with ◯.
The physical properties of the obtained toner are shown in Table 1, and the evaluation results are shown in Table 2.

1 is a diagram showing a schematic configuration of an image forming apparatus having a process cartridge of the present invention. It is a figure which shows the fixing means of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Process cartridge 11 Photoconductor 12 Charging means 13 Developing means 14 Cleaning means

Claims (16)

In an electrostatic charge image developing toner containing at least a resin binder, inorganic fine particles, a colorant, and wax, the toner satisfies the relationship represented by the following formula (1), D50 is 3 to 8 μm, and the toner An electrostatic charge image developing toner, wherein the amount of aggregates of 25 μm or more present in the toner is 0.5% or less based on the toner weight.

(D10, D50, and D90 indicate particle diameters at which the volume percentage with respect to all particles becomes 10%, 50%, and 90% when the toner is accumulated from the small particle diameter side.) An organic solvent phase in which at least a functional group-containing polyester resin is dissolved, an active hydrogen-containing compound, and a colorant are dispersed in an aqueous medium phase in which resin fine particles are dispersed, and the functional group-containing polyester system is dispersed. It is obtained by causing an elongation reaction and / or a crosslinking reaction between the resin and the active hydrogen-containing compound, forming particles from the resulting dispersion, and removing and washing the solvent of the dispersion. The electrostatic image developing toner according to claim 1, wherein In addition to the functional group-containing polyester resin, a non-reactive polyester is further dissolved in the organic solvent phase, and the weight ratio of the functional group-containing polyester resin to the non-reactive polyester is 5/95 to 75. The electrostatic charge image developing toner according to claim 1, wherein the toner is / 25. 4. The electrostatic image developing toner according to claim 1, wherein the toner particles have a circularity of 0.94 to 0.98. The electrostatic image developing toner according to claim 1, wherein the inorganic fine particles comprise at least two kinds of inorganic fine particles. 6. The electrostatic image developing toner according to claim 1, wherein the inorganic fine particles are hydrophobic silica and titanium. The electrostatic image developing toner according to claim 1, wherein the wax contains carnauba wax. The toner for developing an electrostatic charge image according to any one of claims 1 to 7, wherein the content of the wax inside the toner particles is 5% by weight or more. 9. A two-component electrostatic charge image developing developer comprising the electrostatic charge image developing toner according to claim 1 and a carrier comprising magnetic particles. The electrostatic latent image formed on the photoconductor is developed with a developer containing toner, the toner image formed on the photoconductor is transferred onto the image support, and the heating roller enclosing the toner image in a heating member An electrostatic charge apparatus according to any one of claims 1 to 8, wherein the image forming apparatus uses a cleaning member that is fixed by a fixing device including a pressure roller disposed opposite to the pressure roller and that cleans the pressure roller. An image forming apparatus using the image developing toner or the developer according to claim 9, wherein the toner collected on the cleaning member does not melt again. 9. An electrostatic charge image developing device according to claim 1, further comprising: an electrostatic charge image carrier, a charging device, an exposure device, a developing device, a contact transfer device, a fixing device, a cleaning device, and a charge removing device. An image forming apparatus characterized by using a toner. 12. The image forming apparatus according to claim 11, wherein the charging unit is a charging unit that performs charging by bringing a charging member into contact with an electrostatic charge image carrier and applying a voltage to the charging member. The image forming apparatus according to claim 11, wherein the electrostatic charge image carrier is an amorphous silicon electrostatic charge image carrier. The fixing unit includes a heating body provided with a heating element, a film in contact with the heating body, and a pressure member in pressure contact with the heating body through the film, and the film and the pressure member The image forming apparatus according to claim 11, wherein the image forming apparatus is a fixing device that heats and fixes a recording material on which an unfixed toner image is formed. In a process cartridge that includes a photosensitive member and a developing unit, and that integrally supports at least one unit selected from a charging unit and a cleaning unit, and is detachable from the main body of the image forming apparatus, the developing unit includes: A toner for developing an electrostatic charge image containing at least inorganic fine particles, a colorant and a wax, the toner satisfying a relationship represented by the following formula (1), and D50 of 3 to 8 μm: The toner for developing an electrostatic charge image according to any one of claims 1 to 8, wherein the amount of aggregates of 25 µm or more present in the toner is 0.5% or less with respect to the toner weight. Process cartridge characterized by using.

(D10, D50, and D90 indicate particle diameters at which the volume percentage with respect to all particles becomes 10%, 50%, and 90% when the toner is accumulated from the small particle diameter side.) An unfixed toner having a heating body including a heating element, a film in contact with the heating body, and a pressure member in pressure contact with the heating body through the film. 9. An electrostatic image development method according to claim 1, wherein the image forming method uses a fixing device that heats and fixes a recording material on which an image is formed, and the toner used to form the toner image is formed. An image forming method, wherein the toner is a toner.

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