JP2005148421A - Toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner with which images maintaining high sharpness and more particularly high transferability can be obtained even in use for a long time. <P>SOLUTION: The toner containing at least coloring particles having a binder resin and a colorant, and inorganic particulates (A) is characterized in that (i) the binder resin contains at least a polyester unit, (ii) the mean circularity is 0.915 to 0.960 in the toner particles of ≥2 μm in the diameter of the equivalent circle, and (iii) the particulates (A) are 1.0 to <1.5 in the aspect ratio (major axis/minor axis ratio) on the toner surface and 0.06 to 0.30 μm in the number average grain size on the toner surface. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a toner used in electrophotography, electrostatic recording, electrostatic printing, toner jet recording, and magnetic recording.

  In recent years, copying machines and printers are required to be smaller, lighter, faster, and more reliable due to demands for space saving and energy saving. As a result, the hardware configuration is configured with simple elements in various respects, and conversely, the performance required for the toner is becoming higher. Therefore, excellent hardware cannot be provided unless the toner performance can be improved. In particular, a toner having good transferability is required. By improving this transfer, it is possible to obtain merits such as reduction of toner consumption, higher image quality, and simplification of the toner collection system.

  Therefore, in recent years, as one of the techniques for increasing the transfer efficiency, the toner shape has been made closer to a spherical shape. For example, polymerized toner such as suspension polymerization or emulsion polymerization, pulverized toner spheroidized in a solvent (for example, see Patent Document 1), spheroidized with hot air (for example, see Patent Document 2), machine For example, a method of spheroidizing with a static impact force (for example, see Patent Document 3). These techniques are effective techniques for improving transfer efficiency. However, in the case of polymerized toner, a release agent is inevitably included, so that it is difficult for the release agent to come out on the toner surface when pressure cannot be applied so much during fixing. Therefore, the fixing property is inferior. Patent Document 1 discloses a toner that has excellent developability and transferability, good offset resistance in an oilless fixing system, and excellent OHP permeability. The toner used was made into a sphere by using a linear or non-linear polyester resin, dispersing a colorant and a release agent in an organic solvent in which the resin is dissolved, and taking out the toner after granulation. It is a toner, has very high transferability, and is excellent in high temperature offset resistance. However, it is difficult to adjust the particle size, particularly 5 μm or less, and the fine dispersion and dispersibility of the release agent are controlled, but the requirements for low temperature fixability for further speedup are still not fully satisfied.

  Further, Patent Document 3 discloses a method in which a toner containing a colorant and a release agent is spheroidized with a mechanical impact force to increase transfer efficiency. As a device that spheroidizes by a mechanical impact force, a hybridization system manufactured by Nara Machinery Co., Ltd., a mechano-fusion system manufactured by Hosokawa Micron, a kryptron system manufactured by Kawasaki Heavy Industries, Ltd., and the like are disclosed. However, these systems give mechanical impact force while crushing although there is a difference in the degree of crushing, and the release of the release agent tends to occur due to the new surface coming out at the same time as the spheroidization, and the developability deteriorates. May be invited. In particular, bleeding of the release agent becomes remarkable when the release agent is poorly dispersed.

  From the above circumstances, for example, Patent Document 4 and Patent Document 5 define the aspect ratio of inorganic fine particles because of the necessity of manipulating the shape or composition of inorganic fine particles in order to make full use of toner with improved sphericity. In this way, the degree of adhesion of the inorganic fine particles to the toner particles is manipulated to control transferability and charging ability. However, in any of these, it is possible to obtain a toner having a reduced diameter in which the powder properties of the toner, the transferability and the chargeability of the toner, the scattering of the toner, and the color developability by the transmitted light of the OHP image are improved in a balanced manner. Was difficult.

  Recently, there is a high demand for colorization, especially on-demand printing, and a method of forming a multicolor image on a transfer belt to support high-speed copying, transferring the multicolor image to an image fixing material at a time, and fixing it. Has been reported. If the process of transferring from the photoconductor to the transfer belt is the primary transfer, and the process of transferring from the transfer belt to the transfer body is the secondary transfer, the transfer is repeated twice, and a technique for improving the transfer efficiency becomes more and more important. In particular, in the case of secondary transfer, a multicolor image is transferred at a time, and the transfer material (for example, in the case of paper, its thickness, surface property, etc.) changes variously. Therefore, it is necessary to control the transfer property extremely high.

  In view of the above, there has been a demand for a toner that obtains excellent transferability, durability, and charging characteristics by improving inorganic fine particles while improving the degree of spheroidization.

Japanese Patent Laid-Open No. 11-44969 JP 2000-029241 A Japanese Patent Application Laid-Open No. 07-181732 JP-A-6-332232 JP 2000-267346 A

  SUMMARY An advantage of some aspects of the invention is to provide a toner that solves the above-described problems. That is, it is an object of the present invention to provide a toner capable of obtaining an image maintaining high image quality, particularly high transferability, even when used for a long time. Furthermore, it is an object of the present invention to provide a toner having excellent transferability and durability and having stable charging characteristics with respect to the environment.

  As a result of intensive studies, the present inventors have found that the above problems can be solved by focusing on the circularity of the toner and the size and shape of the inorganic fine particles contained in the toner, and making them specific. Was completed. That is, the present invention is characterized by the following configuration.

(1) In a toner containing at least a binder resin and a colored particle having a colorant and inorganic fine particles (A), (i) the binder resin includes at least a polyester unit, and (ii) the equivalent circle diameter of 2 μm or more. The toner particles have an average circularity of 0.915 to 0.960, and (iii) the inorganic fine particles (A) have an aspect ratio (major axis / minor axis ratio) on the toner surface of 1.0 to 1. A toner having a number average particle size of 0.06 to 0.30 μm on the toner surface of less than 5.
(2) The inorganic fine particles (A) and the inorganic fine particles (B) are further contained, and the inorganic fine particles (B) are particles having a number average particle diameter of 0.01 to less than 0.06 μm on the toner surface. The toner according to (1).
(3) In the viscoelastic properties of the toner, the storage elastic modulus (G′80) at a temperature of 80 ° C. is in the range of 1 × 10 ^{5 to} 1 × 10 ⁸ (Pa), and the storage elastic modulus at a temperature of 160 ° C. (G The toner according to (1) or (2), wherein '160) is in the range of 1 × 10 ^{1 to} 1 × 10 ⁴ (Pa).

  According to the present invention, a toner having excellent transfer performance, durability stability, and environmental stability can be provided.

  Hereinafter, the present invention will be described in detail. The toner of the present invention contains at least colored particles having a binder resin and a colorant and inorganic fine particles (A), the binder resin has a polyester unit, and the average circularity of the toner having an equivalent circle diameter of 2 μm or more. 0.915 to 0.960, the inorganic fine particles (A) have an aspect ratio (major axis / minor axis ratio) of 1.0 to 1.5 on the toner surface, and a number average particle diameter of 0.06. A toner containing inorganic fine particles having a particle size of 0.30 μm.

  By improving the circularity of the toner particles to a specific range, that is, by positively controlling the surface shape, the transferability can be improved without impairing the fixing ability. Further, by containing the inorganic fine particles (A) having a specific size and shape, the adhesion with the photosensitive drum and the transfer belt can be reduced, and the transferability can be further improved. Compared to toner particles whose surface shape is not controlled, the toner of the present invention has less irregularities on the surface of the toner particles, and the added inorganic fine particles do not enter the concave portions. Can be made. In other words, the additive effect of inorganic fine particles is maximized by the synergistic effect obtained only by externally adding inorganic fine particles to the toner particles whose surface shape is controlled, and the toner particles become inorganic fine particles even after long-term use. It is possible to obtain a toner that is less deteriorated due to embedding and desorption of the toner and less deteriorated due to transfer to the carrier, that is, maintains high transferability and charging stability. In other words, by adjusting the circularity of the toner, the size and shape of the inorganic fine particles contained in the toner to the above ranges, it has excellent transferability and charging characteristics, and high image quality even in long-term durable use. An image can be formed.

  The toner of the present invention has an average circularity of 0.915 to 0.960 for particles having an equivalent circle diameter of 2 μm or more. The average circularity is preferably 0.918 to 0.948, and more preferably 0.918 to 0.942. If the average circularity of the toner is less than 0.915, the contact area between the toners, between the toner carriers, and further with the photosensitive drum and the intermediate transfer member is increased, and the toner separation is inhibited, leading to deterioration of transferability. On the other hand, if the average circularity is larger than 0.960, the shape approaches a spherical shape, and the transferability is deteriorated. As a result, defective cleaning such as transfer residual toner slipping through the cleaning blade occurs, and frictional charging between the toners or between the toner and the carrier becomes difficult, resulting in an unclear image with much fog and scattering on the non-image area.

  The toner of the present invention has an inorganic fine powder (A) having an aspect ratio (major axis / minor axis ratio) of 1.0 to 1.5 and a number average particle diameter of 0.06 to 0.30 μm on the toner surface. ). The aspect ratio and number average particle diameter on the toner surface of the inorganic fine powder (A) are determined from an electron micrograph, and the number average particle diameter of the inorganic fine powder (A) is 0.06 to 0.30 μm. The thickness is preferably from 0.07 to 0.20 μm, more preferably from 0.08 to 0.15 μm. If it is smaller than 0.06 μm, the function as a spacer is weak, and the contribution to the improvement of transferability becomes small. On the other hand, when it is larger than 0.3 μm, the toner is easily detached from the toner, and it is difficult to stably adhere to the surface of the toner base particles, and the transfer efficiency is lowered. In addition, the toner is detached from the toner during development and contaminates the surroundings of the developing device, or the detached fine powder adheres to the photosensitive drum, the carrier, and the like, resulting in deterioration of charging performance.

  In the toner of the present invention, the inorganic fine particles (B) have a number average particle diameter on the toner surface of 0.01 to less than 0.06 μm. More preferably, it is 0.01-0.05 micrometer. The inorganic fine particles (B) may be surface-treated with a silane compound or a coupling agent. If it is smaller than 0.01 μm, the inorganic fine particles (B) are likely to be embedded in the toner surface due to long-term use, the physical adhesion of the toner increases, and transferability may be impaired. On the other hand, if it is larger than 0.06 μm, the effect of imparting fluidity tends to be small, and the charging characteristics tend to become unstable.

  It is preferable to use the inorganic fine particles (B) together with the inorganic fine particles (A) from the viewpoint of improving the fluidity and chargeability. Due to the fluidity imparting effect of the inorganic fine particles (B), the toner is sufficiently charged by stirring in the developing device. This is effective against fogging and toner scattering, and the effect becomes more conspicuous particularly in a high temperature and high humidity (H / H) environment. In general, if the toner is left in an H / H environment, the absolute charge amount decreases, and a necessary image density may not be obtained when the toner is started up after being left, but this also has an effect of suppressing this problem.

  Further, by controlling the average circularity of the toner to 0.915 to 0.960, it is possible to obtain a toner with few concave portions. Therefore, the spacer effect can be sufficiently exhibited without the inorganic fine particles added externally to the toner entering the recesses. In addition, by adding the inorganic fine particles (B), the inorganic fine particles (A) adhere uniformly to the toner surface, and evenly adhere to the toner surface without being localized even after long-term use. I found a synergistic effect that I could continue. In fact, a toner obtained by adding the fine particles (A) and (B) to a toner having an average circularity of 0.915 to 0.960 has a stable charge and a small fluctuation in transfer efficiency even under long-term use. .

  The inorganic fine particles (A) have a spherical shape to a substantially spherical shape, have a small contact area with the toner base, and move over the toner surface by long-term use, and localize to a site where friction is expected to be large. This is confirmed from a later toner electron microscopic image. However, in order to maintain stable transferability, it is desirable that the inorganic fine particles (A) are uniformly attached on the surface of the toner and remain in the initial position even under long-term use. By adhering the inorganic fine particles (B) to the surface of the toner, the inorganic fine particles (B) become minute irregularities on the toner surface, and receive moderate friction against particles having a size as large as the inorganic fine particles (A). This is considered to be the effect of preventing the localization of (A).

Further, in the present invention, the storage elastic modulus (G′80) of the toner at 80 ° C. is 1 × 10 ^{5 to} 1 × 10 ⁸ (Pa), and the storage elastic modulus (G′160) at a temperature of 160 ° C. When it is in the range of 1 × 10 ^{1 to} 1 × 10 ⁴ (Pa), it is possible to provide a toner having fixability at low temperature and storage resistance, heat resistance, blocking resistance, and offset resistance. In the viscoelastic characteristics of the toner, when the storage elastic modulus G′80 at a temperature of 80 ° C. of the toner is smaller than 1 × 10 ^5, the storage stability, heat resistance, and blocking resistance in a high temperature environment are inferior. The toner particles may be combined to form a large toner aggregate. In addition, when used for a long period of time, the inorganic fine particles are driven deeply into the toner base particles, making it difficult to exhibit the spacer effect. When G′80 at a temperature of 80 ° C. of the toner is greater than 1 × 10 ⁸ (Pa), the toner has storage stability, heat resistance, and blocking resistance, but low temperature fixability is difficult to obtain. When the storage elastic modulus G′160 at a temperature of 160 ° C. is smaller than 1 × 10 ¹ , the offset resistance may be deteriorated. Further, when G′160 is larger than 1 × 10 ⁴ (Pa), it is difficult to obtain a fixing property at a low temperature.

  In addition, the inorganic fine particles (A) or the inorganic fine particles (A) and (B) are contained, and the viscoelastic properties of the toner are within the above range, so that the inorganic fine particles bite into the toner base particles appropriately and can be used for a long time. In other words, the toner is not embedded more deeply than necessary, and therefore, it has been found that a toner that exhibits excellent charging stability and transferability over a long period of time and forms a good image can be provided. Due to the recent increase in output speed of copying machines and printers and the miniaturization of the main body, the temperature inside the main body tends to increase. Therefore, it is required to have sufficient storage stability, heat resistance, and anti-blocking property in a high temperature environment. In addition, from the viewpoint of environmental friendliness, toner that can be fixed at a lower temperature and reduction of consumption are required. By setting the storage elastic modulus G ′ within the above range and controlling the circularity and the shape of the inorganic fine particles. It has been found that it is possible to achieve a high level of storage stability, heat resistance, blocking resistance, low-temperature fixability, high transferability and durability stability.

  In the present invention, the inorganic fine powder (A) has an aspect ratio (major axis / minor axis ratio) of 1.0 to 1.5 on the toner surface and a number average particle size of 0.06 to 0.00. If it is 30 micrometers, the composition will not specifically limit, such as a silica, an alumina, a titanium oxide. For example, in the case of silica, those produced by a conventionally known technique obtained by any method such as a gas phase decomposition method, a combustion method, and a deflagration method can be used. In particular, the number produced by a known sol-gel method in which the solvent is removed from the silica sol suspension obtained by hydrolyzing and condensing the alkoxysilane with a catalyst in an organic solvent in which water is present, and then dried to form particles. Particles having an average particle size of 0.06 to 0.30 μm are preferred. Further, the silica surface of the sol-gel method may be used after being hydrophobized. As the hydrophobizing agent, a silane compound is preferably used, monochlorosilane such as hexamethyldisilazane, trimethylchlorosilane, triethylchlorosilane, trimethylmethoxysilane, trimethyl. Examples thereof include monoalkoxysilanes such as ethoxysilane, monoaminosilanes such as trimethylsilyldimethylamine and trimethylsilyldiethylamine, and monoacyloxysilanes such as trimethylacetoxysilane. In the toner of the present invention, the amount of the inorganic fine powder (A) added is 0.3 to 5.0 parts by mass, more preferably 0.5 to 3.0 parts by mass with respect to 100 parts by mass of the toner base particles. is there.

  In the present invention, the inorganic fine powder (B) specifically includes various metal compounds (aluminum oxide, titanium oxide, strontium titanate, cerium oxide, magnesium oxide, chromium oxide, tin oxide, zinc oxide, etc.) / Nitriding Products (silicon nitride, etc.), carbides (silicon carbide, etc.), metal salts (calcium sulfate, barium sulfate, calcium carbonate, etc.), fatty acid metal salts (zinc stearate, calcium stearate, etc.), carbon black, silica, etc. Preferably, they are hydrophobic titanium oxide fine particles and / or hydrophobic silica fine particles. The addition of the hydrophobic titanium oxide fine particles brings about stabilization of the charge, and the addition of the hydrophobic silica fine particles makes it possible to provide a toner having an appropriate charge amount for imparting fluidity and high negative chargeability. The amount of the inorganic fine powder (B) added is 0.1 to 5.0 parts by mass, and more preferably 0.1 to 1.5 parts by mass with respect to 100 parts by mass of the toner base particles.

  Regarding the major axis diameter, minor axis diameter and number average particle diameter of the inorganic fine particles (A) used in the present invention, and the number average particle diameter of the inorganic fine particles (B), observation of the toner surface by FE-SEM and photographic images thereof are used. It can be obtained by image analysis. The aspect ratio is the maximum diameter (major axis diameter) of the particle and the diameter perpendicular to the maximum diameter (minor axis diameter), and is measured from the FE-SEM photograph image. The ratio (aspect ratio) of the major axis diameter / minor axis diameter of each particle is calculated, and the calculated average value is defined as the aspect ratio of the inorganic fine particles (A). 50 to 100 samples of inorganic fine particles having a long axis diameter / short axis diameter ratio (aspect ratio) of 1.0 to 1.5 are randomly extracted from an electron micrograph, and the diameter of the spherical particles and the elliptical spherical particles are extracted. The length of one direction was taken as the particle size of the particle, the average value was obtained, and the number average particle size was calculated. As for the inorganic fine particles (B), 50 to 100 samples are extracted from particles having a number average particle diameter of 0.01 to less than 0.06 μm and aggregated particles having a grain boundary from a photographic image under the same conditions. The diameter of spherical particles and the length of one direction in the case of elliptical spherical particles were used as the particle diameter of the particles, and the average value was obtained as the number average particle diameter.

  In addition, as a method of evaluating the characteristics of the fine particles along with the particle diameter, measurement of specific surface area (BET) is also common, but irregularities, wrinkles, holes, etc. on the particle surface are assumed to be processed to the same raw material. However, it has been confirmed that the specific surface area varies depending on the type of treatment agent, the amount of treatment agent, and the like.

In the present invention, the relationship of the particle size of the fine particles on the actual toner surface greatly affects the effect and action. In the present invention, the specific surface area is not evaluated, but the inorganic fine particles (B) are preferably 50 to 350 m ² / g, more preferably 50 to 300 m ² / g. When the specific surface area of the inorganic fine particles (B) is less than 50 m ² / g, the particle size becomes large and the effect as a fluidity imparting agent is lost. On the other hand, if it exceeds 350 m ² / g, the particle size is too small, embedding in the toner occurs, and the fluidity is deteriorated. The specific surface area is measured according to the BET method by using a specific surface area measuring device Autosorb 1 (manufactured by Yuasa Ionics) to adsorb nitrogen gas on the sample surface and using the BET multipoint method.

  The average circularity in the present invention is used as a simple method for quantitatively expressing the shape of the particles. In the present invention, the average circularity is measured using a flow type particle image analyzer FPIA-2100 manufactured by Sysmex Corporation. .

  In the toner of the present invention, the toner base particles (colored particles) are not particularly limited, and contain at least a binder resin having a polyester unit, a colorant, and other components as necessary.

  The binder resin used in the toner of the present invention includes (a) a polyester resin, (b) a hybrid resin having a polyester unit and a vinyl polymer unit, or (c) a hybrid resin and a vinyl polymer. Or (d) a mixture of a polyester resin and a vinyl polymer, and / or (e) a mixture of a hybrid resin and a polyester resin, and (f) a mixture of a polyester unit, a hybrid resin, and a vinyl polymer. It is a resin selected from either.

  In the present invention, “polyester unit” refers to a portion derived from polyester, and “vinyl polymer unit” refers to a portion derived from a vinyl polymer. The polyester monomer constituting the polyester unit is a polyvalent carboxylic acid component and a polyhydric alcohol component, and the vinyl polymer unit is a monomer component having a vinyl group. A monomer having a vinyl group or a monomer having a polyhydric alcohol component and a vinyl group is defined as a “polyester unit” component.

  The binder resin used in the toner of the present invention has a molecular weight distribution measured by gel permeation chromatography (GPC) of the resin component, and has a main peak in a region having a molecular weight of 3500 to 30000, preferably, The molecular weight is in the range of 5000 to 20000, and Mw / Mn is preferably 5.0 or more.

  When the main peak is less than 3500, the high temperature offset resistance of the toner is insufficient. On the other hand, if the main peak exceeds the molecular weight of 30000, sufficient low-temperature fixability cannot be obtained, and application on a high-speed machine becomes difficult. Moreover, when Mw / Mn is less than 5.0, it becomes sharp melt and high gloss is easily obtained, but high-temperature offset resistance cannot be obtained.

  When a polyester resin is used as the binder resin, alcohol and carboxylic acid, carboxylic acid anhydride, carboxylic acid ester, or the like can be used as a raw material monomer. Specifically, for example, as the dihydric alcohol component, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis ( 4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2 -Alkylene oxide adducts of bisphenol A such as bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, Opentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A And hydrogenated bisphenol A.

  Examples of the trivalent or higher alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. Can be mentioned.

  Examples of the acid component include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; Succinic acid substituted with an alkyl group or an anhydride thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof;

  Among these, in particular, a bisphenol derivative represented by the following general formula (1) is used as a diol component, and a carboxylic acid component (for example, fumaric acid) composed of a divalent or higher carboxylic acid or an acid anhydride thereof or a lower alkyl ester thereof. A polyester resin obtained by polycondensation using acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.) as an acid component is preferable because it has good charging characteristics as a color toner. .

〔式中、Ｒはエチレン、プロピレン基であり、ｘ，ｙはそれぞれ１以上の整数であり、かつｘ＋ｙの平均値は２〜１０である。〕

[Wherein, R is an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10. ]

  Examples of the trivalent or higher polyvalent carboxylic acid component for forming the non-linear polyester resin include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4, and the like. -Naphthalene tricarboxylic acid, 2,5,7-naphthalene tricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, and anhydrides and ester compounds thereof. The amount of the trivalent or higher polyvalent carboxylic acid component is preferably 0.1 to 1.9 mol% based on the total monomer.

  Further, when a hybrid resin having a polyester unit and a vinyl polymer unit is used as the binder resin, further improved release agent dispersibility, low-temperature fixability, and offset resistance can be expected. The “hybrid resin component” used in the present invention means a resin in which a vinyl polymer unit and a polyester unit are chemically bonded. Specifically, a polyester unit and a vinyl polymer unit obtained by polymerizing a monomer having a carboxylic acid ester group such as (meth) acrylic acid ester are formed by a transesterification reaction, preferably a vinyl polymer. Is used to form a graft copolymer (or block copolymer) having a backbone polymer and a polyester unit as a branch polymer.

  The following are mentioned as a vinyl-type monomer for producing | generating a vinyl-type polymer. Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert- Butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-chloro styrene, 3, Styrene and derivatives thereof such as 4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene; styrene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated such as butadiene and isoprene Polyenes; vinyl chloride, vinyl chloride, vinyl bromide, fluoride Vinyl halides such as vinyl; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-methacrylate Α-methylene aliphatic monocarboxylic acid esters such as octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate Propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-acrylate Acrylic esters such as lorethyl and phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole; N-vinyl compounds such as N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.

  In addition, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride, etc. Unsaturated dibasic acid anhydride; maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, Alkenyl succinic acid half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester unsaturated dibasic acid half ester; dimethylmaleic acid, dimethyl fumaric acid unsaturated dibasic acid ester; acrylic acid, meta Α, β-unsaturated acids such as rillic acid, crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic acid anhydride, the α, β-unsaturated acid and lower fatty acids And monomers having a carboxyl group such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof.

  Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1) -Methylhexyl) Monomers having a hydroxy group such as styrene.

  In the toner of the present invention, the vinyl polymer unit of the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. In this case, the crosslinking agent used is Examples of aromatic divinyl compounds include divinylbenzene and divinylnaphthalene; examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, and 1,4-butanediol di Examples include acrylate, 1,5-pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate, and the above compounds in which acrylate is replaced by methacrylate; linked by an alkyl chain containing an ether bond. As diacrylate compounds For example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate and those obtained by replacing acrylates of the above compounds with methacrylate Examples of diacrylate compounds linked by a chain containing an aromatic group and an ether bond include polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4 ) -2,2-bis (4-hydroxyphenyl) propane diacrylate and those obtained by replacing the acrylate of the above compound with methacrylate.

  Polyfunctional cross-linking agents include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds replaced with methacrylate; triallylcia Examples include nurate and triallyl trimellitate.

  In the present invention, it is preferable that a monomer component capable of reacting with both resin components is contained in the vinyl polymer component and / or the polyester resin component. Examples of the monomer constituting the polyester resin component that can react with the vinyl polymer include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Among the monomers constituting the vinyl polymer component, those capable of reacting with the polyester resin component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

  As a method of obtaining a reaction product of a vinyl polymer and a polyester resin, either a polymer containing a monomer component capable of reacting with each of the vinyl polymer and the polyester resin listed above is present, or either A method obtained by polymerizing both resins is preferred.

  Examples of the polymerization initiator used for producing the vinyl polymer of the present invention include 2,2′-azobisisobutyronitrile and 2,2′-azobis (4-methoxy-2,4-dimethyl). Valeronitrile), 2,2′-azobis (-2,4-dimethylvaleronitrile), 2,2′-azobis (-2methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate, 1 , 1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl -4-methoxyvaleronitrile, 2,2'-azobis (2-methyl-propane), methyl ethyl ketone peroxide, acetylacetone peroxide, cyclo Ketone peroxides such as xanone peroxide, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroper Oxide, di-t-butyl peroxide, t-butylcumyl peroxide, di-cumyl peroxide, α, α'-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl Peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-trioyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate Di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxylaurate, t-butyl peroxy Oxybenzoate, t-butyl peroxyisopropyl carbonate, di-t-butyl peroxyisophthalate, t-butyl peroxyallyl carbonate, t-amyl peroxy 2-ethylhexanoate, di-t-butyl peroxyhex Hydro terephthalate, di -t- butyl peroxy azelate and the like.

  Examples of the production method capable of preparing the hybrid resin used in the toner of the present invention include the following production methods (1) to (6).

  (1) A method in which a vinyl polymer, a polyester resin, and a hybrid resin component are blended after production. The blend is produced by dissolving and swelling in an organic solvent (for example, xylene) and then distilling off the organic solvent. The hybrid resin component is synthesized by separately producing a vinyl polymer and a polyester resin, dissolving and swelling in a small amount of an organic solvent, adding an esterification catalyst and an alcohol, and performing a transesterification reaction by heating. The ester compound used can be used.

  (2) A method of producing a polyester unit and a hybrid resin component in the presence of a vinyl polymer unit in the presence of the vinyl polymer unit. The hybrid resin component is produced by a reaction between a vinyl polymer unit (a vinyl monomer can be added if necessary) and a polyester monomer (alcohol, carboxylic acid) and / or polyester. Also in this case, an organic solvent can be appropriately used.

  (3) A method for producing a vinyl polymer unit and a hybrid resin component in the presence of the polyester unit after the production. The hybrid resin component is produced by a reaction between a polyester unit (a polyester monomer can be added if necessary) and a vinyl monomer and / or vinyl polymer unit.

  (4) After the production of the vinyl polymer unit and the polyester unit, the hybrid resin component is produced by adding a vinyl monomer and / or a polyester monomer (alcohol, carboxylic acid) in the presence of these polymer units. Also in this case, an organic solvent can be appropriately used.

  (5) After producing the hybrid resin component, vinyl polymer units and / or polyester units (alcohol, carboxylic acid) are added to carry out addition polymerization and / or polycondensation reaction to produce vinyl polymer units and polyester units. Is done. In this case, as the hybrid resin component, those produced by the production methods (2) to (4) can be used, and those produced by a known production method can be used as necessary. Furthermore, an organic solvent can be used as appropriate.

  (6) A vinyl polymer unit, a polyester unit, and a hybrid resin component are produced by mixing a vinyl monomer and a polyester monomer (alcohol, carboxylic acid, etc.) and continuously performing addition polymerization and condensation polymerization reaction. Furthermore, an organic solvent can be used as appropriate.

  In the production methods (1) to (5), the vinyl polymer unit and / or the polyester unit can use a plurality of polymer units having different molecular weights and crosslinking degrees.

  The binder resin contained in the toner of the present invention may be a mixture of the polyester resin and the hybrid resin.

  As the binder resin contained in the toner of the present invention, a mixture of the polyester resin and vinyl polymer may be used.

  As the binder resin contained in the toner of the present invention, a mixture of the above hybrid resin and vinyl polymer may be used.

  The glass transition temperature of the binder resin contained in the toner of the present invention is preferably 40 to 90 ° C, more preferably 45 to 85 ° C. The acid value of the resin is preferably 1 to 40 mgKOH / g.

  A known pigment or dye can be used as the colorant contained in the toner of the present invention, and is not particularly limited. Examples of the pigment include the following. As a colorant suitable for the magenta color, a pigment or a dye can be used. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48; 2, 48; 3, 48; 4, 49, 50, 51, 52, 53, 54, 55, 57, 57; 1, 58, 60, 63, 64, 68, 81, 81; 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 144, 146, 150, 163, 166, 169, 177, 184, 185, 202, 206, 207, 209, 220, 221, 238, 254, etc., C.I. I. Pigment violet 19; C.I. I. Examples of magenta dyes such as Vat Red 1, 2, 10, 13, 15, 23, 29, and 35 include C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 52, 58, 63, 81, 82, 83, 84, 100, 109, 111, 121, 122, etc. I. Disper thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27 etc., C.I. I. Oil-soluble dyes such as disperse violet 1, C.I. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, etc. I. Basic violet 1,3,7,10,14,15,21,25,26,27,28, etc. may be mentioned, and such a pigment may be used alone. It is more preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using in combination, and these are used alone or in combination of two or more.

  As other color pigments, as colorants suitable for cyan, pigments or dyes can be used. I. Pigment Blue 1, 7, 15, 15; 1, 15; 2, 15; 3, 15; 4, 16, 17, 60, 62, 66, etc., C.I. I. Bat Blue 6, C.I. I. Acid Blue 45 and the dye include C.I. I. Solvent Blue 25, 36, 60, 70, 93, 95 etc. are mentioned, These are used alone or in combination of two or more.

  As the colorant suitable for the yellow color, a pigment or a dye can be used. Specifically, examples of the pigment include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 17, 23, 62, 65, 73, 74, 81, 83, 93, 94, 95, 97, 98, 109, 110, 111, 117, 120, 127, 128, 129, 137, 138, 139, 147, 151, 154, 167, 168, 173, 174, 176, 180, 181, 183, 191, C. I. Vat yellow 1, 3, 20 etc. I. Solvent yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162 etc. are mentioned, These are used alone or in combination of two or more.

  As the black colorant, for example, carbon black such as furnace black, channel black, acetylene black, thermal black, and lamp black is used, and iron oxide such as magnetite and ferrite, or yellow / magenta / cyan / black as shown above. The thing adjusted to black using the coloring agent can be utilized.

  The amount of the colorant used is preferably 0.1 to 60 parts by mass, more preferably 0.5 to 50 parts by mass with respect to 100 parts by mass of the binder resin.

  It is preferable to add a release agent to the toner base particles as other components. Next, the release agent that can be used in the present invention will be described. Examples of the release agent that can be used in the present invention include the following. Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, polyolefin copolymers, polyolefin wax, microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax; Alternatively, block copolymers thereof; waxes mainly composed of fatty acid esters such as carnauba wax, behenyl behenate, and montanic acid ester wax; partially or entirely deoxidized fatty acid esters such as deoxidized carnauba wax. Things. Further, saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or long-chain alkyl carboxylic acids having a long-chain alkyl group; unsaturated fatty acids such as brandic acid, eleostearic acid, and valinal acid Saturated alcohols such as stearic alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, seryl alcohol, melyl alcohol, or long-chain alkyl alcohols having a long-chain alkyl group; polyhydric alcohols such as sorbitol; linol Fatty acid amides such as acid amide, oleic acid amide, lauric acid amide; saturated fatty acids such as methylene bis stearic acid amide, ethylene biscapric acid amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide Unsaturated fatty acid amides such as samides, ethylenebisoleic acid amide, hexamethylenebisoleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide; Aromatic bisamides such as stearamide, N, N'-distearylisophthalamide; fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate (generally referred to as metal soap) Waxes grafted to aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; partially esterified products of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; by hydrogenation of vegetable oils and fats, etc. The resulting hydroxyl group And methyl ester compounds are exemplified.

  The toner of the present invention preferably contains one or more waxes. Furthermore, the toner of the present invention has one or more endothermic peaks in a temperature range of 30 to 200 ° C. in an endothermic curve in differential thermal analysis (DSC) measurement from the viewpoint of achieving both low-temperature fixability and blocking resistance. The peak temperature of the maximum endothermic peak in the endothermic peak is preferably in the range of 60 to 110 ° C. More preferably, the maximum peak of the endothermic curve is in the range of 65 to 100 ° C. When the peak temperature of the maximum endothermic peak is less than 60 ° C., the blocking resistance of the toner may deteriorate, and conversely, when the peak temperature of the maximum endothermic peak exceeds 110 ° C., the fixability is deteriorated.

  The release agent is used in an amount of 0.5 to 10 parts by weight, preferably 2 to 8 parts by weight, per 100 parts by weight of the binder resin.

  If necessary, a charge control agent can be added to the toner base particles as other components. Known charge control agents can be used, and examples thereof include aromatic carboxylic acid derivatives and aromatic carboxylic acid metal compounds. For example, the metal of the aromatic carboxylic acid metal compound is preferably a divalent or higher valent metal atom.

Examples of the divalent metal include Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Pb ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Zn ²⁺ and Cu ²⁺ . As such a divalent metal, Zn ²⁺ , Ca ²⁺ , Mg ²⁺ and Sr ²⁺ are preferable. Examples of the trivalent or higher metal include Al ³⁺ , Cr ³⁺ , Fe ³⁺ , Ni ³⁺ , Ti ⁴⁺ , Zr ⁴⁺ and Si ⁴⁺ . Among these metals, Al ³⁺ and Cr ³⁺ are preferable, and Al ³⁺ is particularly preferable. In the present invention, an aluminum compound of di-tert-butylsalicylic acid is particularly preferably used as the charge control agent.

  When the charge control agent is used in an amount of 0.1 to 10% by mass based on the mass of the toner, the initial fluctuation of the toner charge amount is small, and an absolute charge amount necessary for development can be easily obtained. This is preferable since there is no decrease in image quality such as density reduction.

  Further, in addition to the inorganic particles (A) and, if necessary, (B), the toner particles of the present invention are further added with inorganic or organic fine particles as fluidity imparting / charging control / abrasive / cleaning aid. It can also be used. Particles used include fluororesin powders such as vinylidene fluoride fine powder and tetrafluoroethylene fine powder, titanium oxide fine powder, alumina fine powder, wet process silica, fine process silica such as dry process silica, and silane Examples thereof include treated silica whose surface is treated with a compound or an organic silicon compound, a titanium coupling agent, silicone oil, or the like.

  The addition amount of the fine particles for the purpose of fluidity is 0.3 to 4.0 parts by mass, and more preferably 0.5 to 3.0 parts by mass with respect to 100 parts by mass of the toner particles.

  Next, a method for producing the toner of the present invention will be described. First, in the raw material mixing step, at least a binder resin and a colorant and, if necessary, other components are weighed and mixed as a toner internal additive constituting the toner particles, and mixed. Examples of the mixing apparatus include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, and a Nauter mixer.

  Next, the blended and mixed toner particle raw materials are melt-kneaded to melt the resins and disperse the colorant and the like therein. In the melt-kneading step, for example, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. In recent years, single-screw or twin-screw extruders have become mainstream due to the advantage of being capable of continuous production. For example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type twin screw extruder manufactured by Toshiba Machine Co., Ltd. In general, a twin-screw extruder manufactured by Kay Sea Kay, a co-kneader manufactured by Buss, or the like is used. Further, the colored resin composition obtained by melt-kneading the toner particle raw material is rolled by a two-roll or the like after being melt-kneaded, and then cooled through a cooling step of cooling by water cooling or the like.

  In general, the cooled colored resin composition obtained above is then pulverized to a desired particle size in a pulverization step. In the pulverization step, first, coarse pulverization is performed with a crusher, a hammer mill, a feather mill or the like, and further, pulverization is performed with a kryptron system manufactured by Kawasaki Heavy Industries, Ltd., a super rotor manufactured by Nisshin Engineering Co., Ltd. or the like. After that, if necessary, classification is performed using a classifier such as an inertia class elbow jet (manufactured by Nippon Steel & Mining Co., Ltd.) or a centrifugal class turbo turbo (manufactured by Hosokawa Micron Co., Ltd.), and the weight average particle diameter Is obtained as toner particles.

  In the present invention, after pulverizing with an air jet pulverizer without using mechanical pulverization in the pulverization step, classification and surface modification treatment using mechanical impact force as shown in FIGS. A classified product having a weight average particle diameter of 3 to 11 μm is obtained using an apparatus that is simultaneously used. Further, if necessary, a sieving machine such as a wind-type sieve high voltor (manufactured by Shin Tokyo Machine Co., Ltd.) may be used.

  Next, inorganic fine particles and, if necessary, other external additives are externally added to the obtained toner particles. As a method of external addition, classified toner particles, the above-mentioned inorganic fine particles (A), and inorganic fine particles (B) and other known external additives as required are blended in predetermined amounts, and a Henschel mixer, a super The toner of the present invention can be obtained by stirring and mixing using a high-speed stirrer that applies shearing force to the powder, such as a mixer, as an external additive.

  The apparatus used for producing the toner of the present invention will be described in detail below. As described above, in order to adjust the circularity of the toner within the above range, a surface modification process such as a pulverization process and / or a spheroidization process of toner particles is performed while discharging fine powder generated during the process to the outside of the system. It is preferable to carry out the treatment. FIG. 1 is a schematic cross-sectional view showing a process of an example of a surface modification apparatus preferably used for producing the toner of the present invention, and FIG. 2 is a schematic plan view showing the configuration of the dispersion rotor of FIG. 1 includes a casing 30, a jacket (not shown) through which cooling water or antifreeze liquid can be passed, a square disk or cylindrical pin 40 attached to the central rotating shaft in the casing 30. The rotor is a disk-like rotating body that rotates at a high speed, and the surface of the dispersion rotor 36 is arranged on the outer periphery of the dispersion rotor 36 at a constant interval. Liner 34 (which does not have to have a groove on the liner surface), a classification rotor 31 which is a means for classifying the surface-modified raw material into a predetermined particle size, and cold air for introducing cold air Inlet port 35, raw material supply port 33 for introducing the raw material to be treated, discharge valve 38 installed so as to be openable and closable so that the surface modification time can be freely adjusted, and discharged powder after treatment You The powder discharge port 37, the space between the classification rotor 31 and the dispersion rotor 36-liner 34, the first space 41 before being introduced into the classification rotor 31 and the fine powder are classified and removed by the classification means. It is composed of a cylindrical guide ring 39 which is a guide means for partitioning the particles into a second space 42 for introducing the particles into the surface treatment means. A gap portion between the dispersion rotor 36 and the liner 34 is a surface modification zone, and the classification rotor 31 and its peripheral portion are classification zones.

  In the surface reforming apparatus configured as described above, when a finely pulverized product is introduced from the raw material supply port 33 with the discharge valve 38 closed, the introduced finely pulverized product is first sucked by a blower (not shown). And classified by the classification rotor 31. At that time, the classified fine powder having a predetermined particle diameter or less is continuously discharged and removed out of the apparatus, and the coarse powder having a predetermined particle diameter or more passes along the inner periphery (second space 42) of the guide ring 39 by centrifugal force. The circulating flow generated by the dispersion rotor 36 is guided to the surface modification zone.

  The raw material guided to the surface modification zone is subjected to a surface modification treatment by receiving a mechanical impact force between the dispersion rotor 36 and the liner 34. The surface-modified particles having undergone surface modification are guided to the classification zone along the outer periphery (first space 41) of the guide ring 39 on the cold air passing through the machine. The fine powder generated at this time is again discharged out of the machine by the classification rotor 31, and the coarse powder is returned to the surface reforming zone again through the circulating flow and repeatedly undergoes the surface reforming action. After a certain period of time, the discharge valve 38 is opened and the surface modified particles are recovered from the discharge port 37.

  As a result of investigations by the present inventors, in the surface modification step using the surface modification device, the time (cycle time) from the introduction of the finely pulverized product from the raw material supply port 33 to the release valve opening and the rotation of the dispersion rotor The number has been found to be important in controlling the sphericity of the toner and the amount of release agent on the toner particle surface (ie, toner transmittance).

To increase the sphericity, it is effective to increase the cycle time or increase the peripheral speed of the dispersion rotor. In order to keep the amount of the release agent on the toner particle surface low, it is effective to shorten the cycle time or lower the peripheral speed. In particular, the toner cannot be efficiently spheroidized unless the peripheral speed of the dispersion rotor exceeds a certain level. Therefore, the cycle time must be increased to spheroidize, and the amount of surface release agent must be increased more than necessary. It may end up. In order to improve the circularity of the toner while keeping the amount of the release agent on the surface of the toner particles below a predetermined value, and to make the circularity and transmittance of the toner within the above ranges, the peripheral speed of the dispersion roller is set to 1.2 × 10. It is effective to set the cycle time to 15 to 60 seconds at ⁵ mm / sec.

  In addition, the weight average particle diameter of the toner of the present invention is preferably 4 to 10 μm, and more preferably 5 to 9 μm. The toner of the present invention has a number average particle size of 3.5 to 9.5 μm, 5 to 50% by number of particles having a particle size of 4 μm or less in the toner number distribution, and a particle size in the toner volume distribution. It is preferable that the particle | grains of 12.70 micrometers or more are 5 volume% or less.

  When the weight average particle diameter of the toner is larger than 10 μm, it means that there are few fine particles that can contribute to high image quality, and it is easy to obtain a high image density and has the advantages of excellent toner fluidity. It is difficult to adhere faithfully on the fine electrostatic image above, and the reproducibility of the highlight portion is lowered, and the resolution is also lowered. In addition, the toner tends to overload the electrostatic charge image more than necessary, and the toner consumption tends to increase.

  On the other hand, when the weight average particle diameter of the toner is smaller than 4 μm, the charge amount per unit mass of the toner becomes high, and the decrease in image density, particularly the decrease in image density under low temperature and low humidity becomes remarkable. This is not particularly suitable for applications with a high image area ratio such as graphic images.

  When the thickness is smaller than 4 μm, contact charging with a charging member such as a carrier is difficult to be performed smoothly, toner that cannot be sufficiently charged increases, and fogging due to scattering to a non-image portion becomes conspicuous. In order to cope with this, it is conceivable to reduce the diameter of the carrier in order to increase the specific surface area of the carrier. However, with toner having a weight average diameter of less than 4 μm, toner self-aggregation easily occurs, and uniform mixing with the carrier can be achieved in a short time. In the continuous toner replenishment durability, fogging tends to occur.

  In the toner of the present invention, toner particles having a particle diameter of 4 μm or less are preferably 5 to 50% by number, and preferably 5 to 25% by number of the total number of particles. If the number of toner particles having a particle diameter of 4 μm or less is less than 5% by number, it means that there are few fine toner particles that are essential components for high image quality. As the toner is continuously used, the effective toner particle component decreases, the balance of the toner particle size distribution shown in the present invention is deteriorated, and the image quality gradually decreases.

  Further, when the number of toner particles having a particle size of 4 μm or less exceeds 50% by number, the toner particles are likely to be agglomerated with each other and often behave as a toner lump having a particle size larger than the original particle size. An image is likely to be formed, the resolution is deteriorated, or the density difference between the edge portion and the inside of the electrostatic charge image is increased, and the image tends to be hollow. Furthermore, it is preferable for improving the image quality that the particle size is 12.70 μm or more is 7% by volume or less.

  The toner of the present invention can be applied to both a one-component developer composed only of toner (not including a carrier) and a two-component developer composed of a toner and a carrier. When the toner is used as a two-component developer, the toner is mixed with a magnetic carrier. Examples of the magnetic carrier include surface oxidized or unoxidized iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, rare earth metal particles, alloy particles thereof, oxide particles, ferrite and the like. Can be used. The coated carrier obtained by coating the surface of the magnetic carrier particles with a resin is particularly preferable in a developing method in which an AC bias is applied to the developing sleeve. As a coating method, a method in which a coating solution prepared by dissolving or suspending a coating material such as a resin in a solvent is adhered to the surface of the magnetic carrier core particle, and a method in which the magnetic carrier core particle and the coating material are mixed with powder. A conventionally known method can be applied. Examples of the coating material on the surface of the magnetic carrier core particle include silicone resin, polyester resin, styrene resin, acrylic resin, polyamide, polyvinyl butyral, and aminoacrylate resin. These are used alone or in plural. The treatment amount of the coating material is preferably 0.1 to 30% by mass (preferably 0.5 to 20% by mass) with respect to the carrier core particles. These carriers have an average particle diameter of 10 to 100 μm, preferably 20 to 70 μm. When a two-component developer is prepared by mixing the toner of the present invention and a magnetic carrier, the mixing ratio is usually 2 to 15% by mass, preferably 4 to 13% by mass, as the toner concentration in the developer. Good results are obtained. If the toner concentration is less than 2% by mass, the image density tends to decrease, and if it exceeds 15% by mass, fogging and scattering in the apparatus are likely to occur.

  In particular, Mn-Mg-Fe three-element magnetic ferrite particles formed mainly of manganese, magnesium and iron components are preferred as carriers. Such a magnetic carrier is preferably coated with a resin, and a silicone resin is preferable as the resin. In particular, the nitrogen-containing silicone resin or the modified silicone resin produced by the reaction of the nitrogen-containing silane coupling agent and the silicone resin is capable of imparting negative triboelectric charge to the toner of the present invention, environmental stability, and the surface of the carrier. This is preferable in terms of suppression of contamination.

  The number average particle diameter of the magnetic carrier is preferably 15 to 60 μm (more preferably 25 to 50 μm) in relation to the weight average particle diameter of the toner. As a method for preparing the magnetic particles constituting the magnetic carrier so as to have the above-mentioned number average particle diameter, for example, classification can be performed by using a sieve. In particular, in order to classify with high accuracy, it is preferable to repeat a plurality of times using a sieve having an appropriate opening. It is also an effective means to use a mesh opening whose shape is controlled by plating or the like.

  Next, the measurement method used in the present invention will be described.

<Measurement of average toner circularity>
The average circularity of the toner is measured using a flow type particle image measuring device “FPIA-2100 type” (manufactured by Sysmex Corporation), and is calculated using the following equation.

  Here, the “particle projected area” is the area of the binarized toner particle image, and the “peripheral length of the particle projected image” is the length of the contour line obtained by connecting the edge points of the toner particle image. Define. The measurement uses the perimeter of the particle image when image processing is performed at an image processing resolution of 512 × 512 (pixels of 0.3 μm × 0.3 μm).

  In the present invention, the circularity is an index indicating the degree of unevenness of the toner particles, and is 1.000 when the toner particles are completely spherical. The more complicated the surface shape, the smaller the circularity.

  The average circularity C, which means the average value of the circularity frequency distribution, is calculated from the following equation, where ci is the circularity (center value) at the dividing point i of the particle size distribution and m is the number of measured particles.

  In addition, “FPIA-2100”, which is a measuring apparatus used in the present invention, calculates the circularity of each particle, and then calculates the average circularity and the circularity standard deviation. The degree 0.4 to 1.0 is divided into classes equally divided every 0.01, and the average circularity and the circularity standard deviation are calculated using the center value of the division points and the number of measured particles.

  As a specific measuring method, 10 ml of ion-exchanged water from which impure solids have been removed in advance is prepared in a container, and a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant therein, followed by further measurement. Add 0.02 g of sample and disperse uniformly. As a means for dispersion, an ultrasonic disperser “Tetora 150 type” (manufactured by Nikka Ki Bios Co., Ltd.) is used, and dispersion treatment is performed for 2 minutes to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of this dispersion may not be 40 degreeC or more. In order to suppress variation in circularity, the installation environment of the apparatus is controlled at 23 ° C. ± 0.5 ° C. so that the temperature inside the flow type particle image analyzer FPIA-2100 is 26 to 27 ° C. Preferably, autofocus is performed using 2 μm latex particles every 2 hours.

  To measure the circularity of the toner particles, the flow type particle image measuring device is used, and the concentration of the dispersion is readjusted so that the toner particle concentration at the time of measurement is 3000 to 10,000 particles / μl. Measure more than one. After the measurement, using this data, data having an equivalent circle diameter of less than 2 μm is cut to determine the average circularity of the toner particles.

  Furthermore, “FPIA-2100”, which is a measuring apparatus used in the present invention, has a thinner sheath flow (7 μm) than “FPIA-1000” that has been used to calculate the shape of the toner. (To 4 μm) and the processing particle image magnification, and the processing resolution of the captured image is improved (256 × 256 → 512 × 512), so that the accuracy of toner shape measurement is improved, thereby making sure the fine particles are more reliable. A device that has achieved supplementation. Therefore, when it is necessary to measure the shape more accurately as in the present invention, the FPIA 2100 that can obtain information on the shape more accurately is more useful.

(Number average particle diameter and aspect ratio measurement method of inorganic fine particles)
The measurement is performed using a scanning electron microscope S-4700 (manufactured by Hitachi, Ltd.). The shooting magnification is 50,000 times, and after the photographed photograph is doubled, the aspect ratio is the maximum diameter (major axis diameter) of the particles and the diameter that is perpendicular to the maximum diameter (minor axis diameter). -Measure from the SEM photograph image. The ratio of the major axis diameter / minor axis diameter (aspect ratio) of individual particles is calculated, and the average value of these is defined as the aspect ratio of the inorganic fine particles (A). 50 to 100 samples of inorganic fine particles having a minor axis diameter ratio (aspect ratio) of 1.0 to 1.5 are randomly extracted. The diameter of the spherical particles and the length of the elliptical spherical particles in one direction were taken as the particle diameter of the particles, and the average value was obtained to calculate the number average particle diameter. As for the inorganic fine particles (B), 50 to 100 samples of particles having a number average particle diameter of 0.01 to less than 0.06 μm and aggregated particles having a grain boundary are extracted from a photographic image under the same conditions. The diameter of spherical particles and the length of one direction in the case of elliptical spherical particles were used as the particle diameter of the particles, and the average value was obtained as the number average particle diameter.

(Measurement method of viscoelasticity of toner)
The toner is pressure-molded into a disk-shaped sample having a diameter of 8 mm and a thickness of 2 to 3 mm. Next, it is set on a barrel plate and gradually heated within a temperature range of 50 to 200 ° C. to measure temperature dispersion. The heating rate is 2 ° C./min, the angular frequency (ω) is fixed at 6.28 rad / sec, and the distortion rate is automatic. The temperature is taken on the horizontal axis, and the storage elastic modulus (G ′) is taken on the vertical axis, and the value at each temperature is read. For the measurement, RDA-II (manufactured by Rheometrics) was used.

(Measurement of toner particle or toner particle size distribution)
As a measuring device, Coulter Counter TA-II or Coulter Multisizer II (manufactured by Coulter Inc.) is used. About 1% NcCl aqueous solution is prepared using 1st grade sodium chloride as electrolyte solution. For example, ISOTON (registered trademark) -II (manufactured by Coulter Scientific Japan) can be used. As a measurement method, 0.1 to 5 ml of a surfactant (preferably alkylbenzenesulfone hydrochloric acid) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion process for about 1 to 3 minutes with an ultrasonic disperser, and the volume and the number of toners of 2.00 μm or more are measured by using the 100 μm aperture as the aperture by the measuring device. Distribution and number distribution were calculated. Then, a weight-based weight average particle diameter (D4) obtained from the volume distribution according to the present invention (the median value of each channel is a representative value for each channel) was obtained.

  Channels are 2.00 to 2.52 μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm; 4.00 to 5.04 μm; 5.04 to 6.35 μm; 6.35 to 8. 00μm; 8.00 to 10.08 μm; 10.08 to 12.70 μm; 12.70 to 16.00 μm; 16.00 to 20.20 μm; 20.20 to 25.40 μm; 25.40 to 32.00 μm; 13 channels of 32 to 40.30 μm are used.

(Measurement of molecular weight by GPC (toner binder resin)
The molecular weight of the chromatogram by gel permeation chromatograph (GPC) is measured under the following conditions.

Resin prepared by stabilizing the column in a heat chamber at 40 ° C., and flowing tetrahydrofuran (THF) as a solvent at a flow rate of 1 ml / min to the column at this temperature to adjust the sample concentration to 0.05 to 0.6% by mass. Measurement is performed by injecting 50 to 200 μl of a THF sample solution. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Manufactured by Toyo Soda Kogyo Co., Ltd. and having molecular weights of 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3 .9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ are used, and it is appropriate to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

As the column, in order to accurately measure a molecular weight region of 10 ^{3 to} 2 × 10 ⁶ , it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, μ-styragel 500, 103, 104, manufactured by Waters A combination of 105 and a combination of shodex KA-801, 802, 803, 804, 805, 806, and 807 manufactured by Showa Denko are preferable.

(Measurement of maximum endothermic peak of wax and toner, measurement of glass transition temperature of resin)
The glass transition temperature (Tg) of the resin is measured according to ASTM D3418-82 using a differential scanning calorimeter (DSC measuring device), DCS-7 (manufactured by PerkinElmer), DSC2920 (manufactured by TA Instruments Japan), and the like. To do. The sample to be measured is precisely weighed 5 to 20 mg, preferably 10 mg. The sample is put in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rise rate of 10 ° C./min at room temperature and humidity in a measurement range of 30 to 200 ° C.

  In this temperature raising process, a specific heat change is obtained in the temperature range of 40 ° C to 100 ° C. At this time, the intersection of the intermediate point line of the baseline before and after the change in specific heat and the differential heat curve is defined as the glass transition temperature Tg of the resin of the present invention.

  Moreover, the endothermic peak of the main peak in the temperature range of 30-200 degreeC is obtained in this temperature rising process. The maximum endothermic peak is, of course, the temperature at which the maximum value is exhibited. When there are a plurality of peaks, the highest endothermic peak is the one having the highest height from the baseline in the region above the endothermic peak due to the resin.

(Measurement of acid value (JIS acid value))
2-10 g of sample is weighed into a 200-300 ml Erlenmeyer flask, and about 50 ml of a mixed solvent of methanol: toluene = 30: 70 is added to dissolve the resin. If solubility is poor, a small amount of acetone may be added. Using a mixed indicator of 0.1% bromthymol blue and phenol red, titration with a pre-standardized N / 10 potassium potash-alcohol solution, and the acid value is determined from the consumption of the alcohol potash solution by the following calculation.
Acid value = KOH (ml) × f × 56.1 / sample weight (where f is a factor of N / 10 KOH)

  Examples of embodiments of the present invention are listed below.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited only to these examples.

(Example of hybrid resin production)
As a vinyl polymer, 1.9 mol of styrene, 0.21 mol of 2-ethylhexyl acrylate, 0.15 mol of fumaric acid, 0.03 mol of α-methylstyrene dimer, and 0.05 mol of dicumyl peroxide were placed in a dropping funnel. . In addition, 7.0 mol of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane; 0 mol, 3.0 mol of terephthalic acid, 2.0 mol of trimellitic anhydride, 5.0 mol of fumaric acid and 0.2 g of dibutyltin oxide are placed in a 4-liter four-necked flask made of glass, a thermometer, a stirring rod, a condenser and nitrogen The introduction tube was installed and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually increased while stirring, and while stirring at a temperature of 145 ° C., the monomer of the vinyl resin, the crosslinking agent and the polymerization initiator were added from the previous dropping funnel. It was dripped over 4 hours. Next, the temperature was raised to 200 ° C. and reacted for 4 hours to obtain a hybrid resin. Table 1 shows the results of molecular weight measurement by GPC (gel permeation chromatography). In Table 1, Mw is a weight average molecular weight, Mn is a number average molecular weight, and Mp is a peak molecular weight.

(Example of polyester resin production)
3.6 mol of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 1.6 mol of polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 1.7 mol of terephthalic acid, 1.1 mol of trimellitic anhydride, 2.4 mol of fumaric acid and 0.1 g of dibutyltin oxide are placed in a 4-liter 4-neck flask made of glass, a thermometer, a stirring rod, a condenser and a nitrogen inlet tube Was installed in a mantle heater. Under a nitrogen atmosphere, reaction was performed at 215 ° C. for 5 hours to obtain a polyester resin.

(Example of styrene-acrylic resin production)
-70 parts by mass of styrene-24 parts by mass of n-butyl acrylate-6 parts by mass of monobutyl maleate-1 part by mass of di-t-butyl peroxide Stir the above components in 200 parts by mass of xylene in a four-necked flask. Then, the inside of the container was sufficiently replaced with nitrogen, and the temperature was raised to 120 ° C., followed by dropwise addition over 3.5 hours. Further, the polymerization was completed under reflux of xylene, and the solvent was distilled off under reduced pressure to obtain a styrene-acrylic resin. The results of molecular weight measurement by GPC are shown in Table 1.

<Example 1>
Cyan toner 1 was prepared by the following method.

・ Hybrid resin 100 parts by mass I. Pigment Blue 15: 3 5 parts by mass / normal paraffin wax (maximum thermal peak: 78 ° C.) 5 parts by mass / aluminum compound of di-tert-butylsalicylic acid (charge control agent) 2.0 parts by mass The mixture was sufficiently premixed and melt-kneaded at an arbitrary barrel temperature with a twin-screw extrusion kneader. After cooling, it was coarsely pulverized to about 1 to 2 mm using a hammer mill, and then finely pulverized to a particle size of 20 μm or less with an air jet fine pulverizer. Further, the obtained finely pulverized product is classified and spheroidized by an apparatus that simultaneously performs classification and surface modification treatment using mechanical impact force, and cyan resin particles (colored particles having a volume average particle size distribution of 5.5 μm in the particle size distribution ( Classification product) was obtained.

  The inorganic fine particles (A) used in the examples are shown in Table 2, and the inorganic fine particles (B) are shown in Table 3, respectively. Inorganic fine particles A-1 shown in Table 2 were externally added and mixed with 100 parts by mass of the cyan resin particles to obtain cyan toner 1 having an average circularity of 0.935 for particles of 2 μm or more.

  Further, cyan toner 1 and magnetic ferrite carrier particles (number average particle size 50 μm) surface-coated with a silicone resin were mixed so that the toner concentration was 7% by mass, and this was used as cyan developer 1.

(1) Durability Charge Stability Evaluation With this cyan developer 1, using a remodeled machine from which the oil application mechanism of the fixing unit of the full color copier CLC-1000 (manufactured by Canon Inc.) has been removed, in a single color mode in a high temperature and high humidity environment (30 ° C / 80%), normal temperature and humidity environment (23 ° C / 5%), normal temperature and humidity environment (23 ° C / 50%), using an original with an image area ratio of 7% A printing test was conducted, and charging stability was evaluated on the basis of the following evaluation criteria for the triboelectric charge amount value (mC / kg) on the sleeve after each and the endurance of 50,000 sheets. The evaluation results are shown in Table 5.

  A method for measuring the triboelectric charge value on the sleeve will be described in detail with reference to the drawings.

FIG. 3 is an explanatory diagram of an apparatus for measuring the triboelectric charge amount of the two-component toner. First, in a metal measuring container 2 having a screen 1 having a mesh opening of 30 μm on the bottom, 0.5 to 1.5 g of the two-component developer collected from the sleeve is put and a metal lid 3 is placed. The total weight of the measurement container 2 at this time is weighed and is defined as W1 (g). Next, in the suction machine 4 (at least the part in contact with the measurement container 2) is suctioned from the suction port 5 and the air volume control valve 6 is adjusted to set the pressure of the vacuum gauge 7 to 4 KPa. In this state, suction is sufficiently performed, preferably for about 2 minutes, and the toner is removed by suction. The potential of the electrometer 8 at this time is set to V (volt). Here, 9 is a capacitor, and the capacity is C (μF). Moreover, the weight of the whole measurement container after suction is weighed and is defined as W2 (g). The triboelectric charge amount (mC / kg) of the toner is calculated as follows:
Friction charge amount of two-component toner (mC / kg) = C × V / (W1-W2)

(Evaluation criteria)
A: The difference between the initial and endurance of 50,000 sheets is within Δ5.
B: The tribo difference between the initial stage and the endurance of 50,000 sheets is Δ5 to 10 or less.
C: The difference in tribo between the initial stage and the endurance of 50,000 sheets is within Δ10 to 15
D: There is a problem in charging stability when the tribo difference after the endurance of 50,000 sheets is Δ15 or more.

(2) Transfer efficiency Transfer efficiency was evaluated based on the following evaluation method and evaluation criteria after printing 50,000 sheets in a normal temperature and low humidity environment (23 ° C / 5%).

Using a color copier CLC-1000 (manufactured by Canon Inc.), adjusting the potential contrast of the photoconductor so that the developer loading is 0.6 mg / cm ² on the photoconductor, and transferring the image onto the transfer paper Then, the image density of the untransferred image on the photoconductor was measured using a densitometer (X-rite 500Series, manufactured by X-rite). In the measurement, the developer on the image on the transfer paper and the image remaining on the photoconductor was collected by taping, and the image density of the tape stuck on the paper was measured. From the obtained image density, the loading amount of the developer on the transfer paper and the photosensitive member was converted to obtain the transfer efficiency onto the transfer paper. The transfer current used was adjusted to maximize transfer efficiency. The image density obtained by taping the remaining transfer portion of the photoreceptor and pasting it on the paper is D1, and the image density obtained by taping on the developer transferred onto the paper and sticking it on the paper is D2. Efficiency was calculated.
Transfer efficiency (%) = D2 / (D1 + D2) × 100

  The obtained transfer efficiency was evaluated based on the following evaluation criteria.

(Evaluation criteria)
A: The transfer efficiency after printing for 50,000 sheets is 92% or more.
B: Transfer efficiency after printing 50,000 sheets is 87 to 92%.
C: Transfer efficiency after printing 50,000 sheets is 80 to 87%. Within the allowable range in actual use.
D: Transfer efficiency after 50,000 sheet printing is less than 80%.

(3) Fixing temperature region In the fixing temperature region, the oil application mechanism of the color copier CLC1000 (manufactured by Canon) was removed, and the fixing test was performed by modifying the fixing device so that the fixing temperature could be freely set. Adjust the development contrast so that the amount of toner on the paper is 1.2 mg / cm ² under normal temperature and humidity conditions (23 ° C / 60%) in single color mode, and on A4 paper (SK80, which is recommended by CLC) An unfixed image was created with an image area ratio of 25%. The unfixed image was fixed by increasing the fixing temperature in increments of 10 ° C. in order from 120 ° C., and the temperature range where no offset or wrapping occurred was defined as the fixable region.

  The developer of Example 1 secured a wide fixable area, was excellent in transferability, and had good charge durability stability. Tables 4 and 5 show the physical property measurement results and evaluation results such as average circularity and toner particle size.

<Example 2>
In Example 1, except that the finely pulverized product was subjected to a surface reforming process using classification and mechanical impact force at the same time, and the processing cycle time was extended, and the pulverized product was manufactured under conditions that make it easier to spheroidize than Example 1. A cyan toner 2 was prepared in substantially the same manner as in Example 1 above. The average circularity of particles larger than 2 μm of the cyan toner 2 was 0.956, and it was confirmed that the toner toner was more spherical than the first example. The cyan developer 2 was obtained by mixing the carrier in the same manner as in Example 1, and various evaluations were made in the same manner as in Example 1. As shown in Table 5, the transfer efficiency was extremely high at the initial stage of durability. However, it decreased with the progress of endurance. In the end, the transfer efficiency was less than 90%, but it was within a practically acceptable range.

<Example 3>
In Example 1, in the apparatus which performs the surface modification process using classification and mechanical impact force at the same time for the finely pulverized product, the processing cycle time was shortened, and the pulverized product was manufactured under milder spheroidization conditions than in Example 1. A cyan toner 3 was produced in substantially the same manner as in Example 1 above. The average circularity of the cyan toner 3 with particles larger than 2 μm was 0.916. The cyan developer 3 was obtained by mixing the carrier in the same manner as in Example 1 and various evaluations were performed in the same manner as in Example 1. As a result, the transfer efficiency tended to decrease, but there was no problem in practical use. The results were almost the same as those in Example 1.

<Example 4>
In Example 1, except that the inorganic fine particles A-2 were used as the inorganic fine particles (A), the cyan toner 4 was prepared in substantially the same manner as in Example 1, and the carrier was mixed in the same manner as in Example 1. Cyan developer 4 was obtained. When various evaluations were performed in the same manner as in Example 1, the transfer efficiency tended to decrease, but there was no problem in practical use. As shown in Table 5, good results almost equivalent to those in Example 1 were obtained. Got. Although it was confirmed that the periphery of the developing machine was slightly whitish, it was within a practically acceptable range.

<Example 5>
In Example 1, except that inorganic fine particles A-3 were used as the inorganic fine particles (A), cyan toner 7 was prepared in substantially the same manner as in Example 1, and the carrier was mixed in the same manner as in Example 1. Cyan developer 7 was obtained. When various evaluations were performed in the same manner as in Example 1, as shown in Tables 4 and 5, the results were almost the same as in Example 1 and the durability variation was within the allowable range in actual use.

<Example 6>
After adding 1.5 parts by mass of inorganic fine particles B-1 shown in Table 2 as inorganic fine particles (B) to 100 parts by mass of the cyan resin particles, 1.0 mass of inorganic fine particles A-1 is further added. Cyan toner 6 having an average circularity of 0.935 with particles of 2 μm or more was obtained by external addition. A cyan developer 6 was obtained by mixing carriers in the same manner as in Example 1. When various evaluations were performed in the same manner as in Example 1, as shown in Table 5, while ensuring a wide fixable region, the transfer efficiency was excellent within a transfer property of Δ2% or less, and the inorganic fine particles B The charging stabilization effect by addition was added, charging stability before and after durability was improved in each environment, and extremely good durability stability was exhibited.

<Example 7>
In Example 6, except that inorganic fine particle B-2 was used as the inorganic fine particle (B), cyan toner 7 was prepared in substantially the same manner as in Example 1, and the carrier was mixed in the same manner as in Example 1. Cyan developer 7 was obtained. When various evaluations were performed in the same manner as in Example 1, the amount of change in transfer efficiency before and after endurance was larger than that in Example 6, but it showed high endurance stability. A result almost equivalent to Example 6 was obtained.

<Example 8>
In Example 6, except that inorganic fine particles B-3 were used as the inorganic fine particles (B), cyan toner 8 was prepared in substantially the same manner as in Example 1, and the carrier was mixed in the same manner as in Example 1. Cyan developer 8 was obtained. When various evaluations were performed in the same manner as in Example 1, the amount of change in transfer efficiency before and after endurance increased with respect to Example 6, but high durability stability was exhibited, as shown in Tables 4 and 5. In addition, almost the same results as in Example 6 were obtained.

<Example 9>
In Example 6, except that the inorganic fine particles B-4 were used as the inorganic fine particles (B), a cyan toner 9 was prepared in substantially the same manner as in Example 1, and the carrier was mixed in the same manner as in Example 1. Cyan developer 9 was obtained. When various evaluations were performed in the same manner as in Example 1, the amount of change in transfer efficiency before and after endurance increased with respect to Example 6, but high durability stability was exhibited, as shown in Tables 4 and 5. In addition, almost the same results as in Example 6 were obtained.

<Example 10>
In Example 6, except that inorganic fine particles B-5 were used as the inorganic fine particles (B), a cyan toner 10 was prepared in substantially the same manner as in Example 1, and the carrier was mixed in the same manner as in Example 1. Cyan developer 10 was obtained. When various evaluations were performed in the same manner as in Example 1, the transfer efficiency showed a tendency to decrease before and after durability although it was at a level where there was no problem in actual use.

<Example 11>
In Example 1, C.I. I. Pigment Blue 15: 3 instead of C.I. I. Pig. Except for adding 6 parts by mass of Yellow 74, after obtaining yellow resin particles (classified product) in the same manner as in Example 1, yellow toner 1 was prepared in substantially the same manner as in Example 6 above. A yellow developer 1 was obtained by mixing a carrier with the toner. Various evaluations were performed in the same manner as in Example 1. As shown in Table 5, extremely good results equivalent to those in Example 6 were obtained.

<Example 12>
In Example 1, C.I. I. Pigment Blue 15: 3 instead of C.I. I. Pig. 4 parts by weight of Red122, C.I. I. Pig. Magenta resin particles (classified product) were obtained in the same manner as in Example 1 except that 4 parts by mass of Red57 was used. Magenta toner 1 was prepared in substantially the same manner as in Example 6 above, and a magenta developer 1 was obtained by mixing the carrier in the same manner as in Example 1. Various evaluations were performed in the same manner as in Example 1. As shown in Table 5, extremely good results equivalent to those in Example 6 were obtained.

<Example 13>
In Example 1, C.I. I. Black toner 1 was prepared in substantially the same manner as in Example 6 except that carbon black (BET: 50 m ² / g): 6 parts by mass was used instead of Pigment Blue 15: 3. Black developer 1 was obtained by mixing the carrier. Various evaluations were performed in the same manner as in Example 1. As shown in Table 5, extremely good results equivalent to those in Example 6 were obtained.

<Example 14>
In Example 1, cyan resin fine particles (classified product) were obtained in substantially the same manner as in Example 1 except that a polyester resin was used as the binder resin. A cyan toner 11 was prepared in the same manner as in Example 6, and a cyan developer 11 was obtained by mixing the carrier in the same manner as in Example 1. When various evaluations were performed in the same manner as in Example 1, the fixing temperature range was narrowed as shown in Table 5, but good results were obtained.

<Comparative example 1>
In Example 1, the finely pulverized product is not classified and spheroidized by an apparatus that simultaneously performs classification and surface modification treatment using mechanical impact force, and the obtained finely pulverized product is classified using a multi-division classifier. Cyan-based resin fine particles were obtained in the same manner as in Example 1 except that the treatment was performed. In the same manner as in Example 6, cyan toner 12 having an average circularity of 0.910 was prepared, and a cyan developer 12 was obtained by mixing carriers. A test was conducted in the same manner as in Example 1 using this developer. The effect of adding inorganic fine particles was not fully exhibited, transfer efficiency was poor from the beginning, charging stability deteriorated according to durability, and transferability was at a level unbearable for actual use.

<Comparative example 2>
In Example 1, a finely pulverized product is not classified and spheroidized by an apparatus that simultaneously performs classification and surface modification treatment using mechanical impact force, and a surfing system (Japan) is used as a classification process using a multi-division classifier. Except for using Pneumatic), cyan resin fine particles were obtained in the same manner as in Example 1 above. A cyan toner 13 having an average circularity of 0.970 was produced in the same manner as in Example 6, and a cyan developer 13 was obtained by mixing the carrier in the same manner as in Example 1. A test was conducted in the same manner as in Example 1 using this developer. The initial transferability was very high and the low-temperature fixability was excellent, but the toner spent on the carrier was severe, the change in developability occurred at an early stage of durability, and the developing sleeve was also contaminated. Deterioration of transferability due to durability was also observed.

<Comparative Example 3>
A cyan toner 14 was produced in substantially the same manner as in Example 6 except that the inorganic fine particles (A) were not added, and a cyan developer 14 was obtained by mixing the carrier in the same manner as in Example 1. Various evaluations were performed in the same manner as in Example 1. As a result, the transfer efficiency was not able to withstand actual use from the beginning.

<Comparative example 4>
In Example 6, except that inorganic fine particles A-4 were used as the inorganic fine particles (A), cyan toner 15 was prepared in substantially the same manner, and the cyan developer 15 was prepared by mixing the carrier in the same manner as in Example 1. Obtained. Various evaluations were performed in the same manner as in Example 1. As the durability test progressed, the transfer efficiency deteriorated and the charging characteristics also deteriorated. In addition, it was confirmed that contamination of the developing device was confirmed, and detachment from the toner base particles was progressing.

<Comparative Example 5>
In Example 1, cyan fine particles were obtained in substantially the same manner except that styrene-acrylic resin was used instead of hybrid resin. A cyan toner 16 was prepared in substantially the same manner as in Example 1 except that the inorganic fine particles A-5 were used as the inorganic fine particles (A), and a carrier was mixed in the same manner as in Example 1 to obtain the cyan developer 16. Obtained. When various evaluations were performed in the same manner as in Example 1, the transfer efficiency deteriorated with the progress of the durability test, and it was in a state where it could not withstand actual use.

It is a schematic sectional drawing of the surface modification apparatus of an example used in the surface modification process of this invention. It is the schematic which shows an example of the top view of the dispersion | distribution rotor shown in FIG. FIG. 6 is an explanatory diagram of an apparatus for measuring the triboelectric charge amount of toner.

Explanation of symbols

31 Classification rotor 32 Fine powder collection port 33 Raw material supply port 34 Liner 35 Cold air introduction port 36 Dispersion rotor 37 Product discharge port 38 Discharge valve 39 Guide ring 40 Square disk 41 First space 42 Second space

Claims (3)

In a toner containing colored particles having at least a binder resin and a colorant and inorganic fine particles (A),
The binder resin includes at least a polyester unit;
The toner particles having an equivalent circle diameter of 2 μm or more have an average circularity of 0.915 to 0.960,
The inorganic fine particles (A) have an aspect ratio (major axis / minor axis ratio) of 1.0 to 1.5 on the toner surface, and a number average particle diameter on the toner surface of 0.06 to 0.30 μm. Toner characterized by being.   The inorganic fine particles (A) and inorganic fine particles (B) are contained, and the inorganic fine particles (B) have a number average particle diameter on the toner surface of 0.01 to less than 0.06 μm. The toner according to 1. In the viscoelastic properties of the toner, the storage elastic modulus (G′80) at a temperature of 80 ° C. is in the range of 1 × 10 ^{5 to} 1 × 10 ⁸ (Pa), and the storage elastic modulus (G′160) at a temperature of 160 ° C. The toner according to claim 1, wherein the toner is in a range of 1 × 10 ^{1 to} 1 × 10 ⁴ (Pa).

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