JP2004191970A - Toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To bring out the potential of a toner containing a release agent to the maximum extent and to provide a toner excellent in developing performance, transferability and fixability, nearly independent of the environment, and having good durability. <P>SOLUTION: The toner comprises at least toner particles comprising at least a binder resin, a colorant and a release agent and silica particles. On a heat absorption curve of the toner measured with a differential scanning calorimeter (DSC), the peak temperature of the highest heat absorption peak in the temperature range of 30-200°C is within the range of 60-100°C, the silica particles contain elementary titanium, and in X-ray diffraction, the silica particles satisfy the expressions: 0.7≤(Ia<SB>1</SB>/Ib<SB>1</SB>)≤2.0 and 0.7≤(Ia<SB>2</SB>/Ib<SB>2</SB>)≤2.0, wherein Ia<SB>1</SB>represents maximum intensity at 2θ=25.3; Ib<SB>1</SB>represents the mean value of intensity at 2θ=25.3±2.0 deg; Ia<SB>2</SB>represents maximum intensity at 2θ=27.5; and Ib<SB>2</SB>represents the average value of intensity at 2θ=27.5±2.0 deg. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention relates to a toner that can be used for electrostatic charge development in an image forming method such as electrophotography, electrostatic recording, and electrostatic printing, or a toner that can be used for image formation in a toner jet system, and does not use oil for preventing high-temperature offset. Also, the present invention relates to a color toner that exhibits high definition and high image quality even when a fixing unit using a small amount of oil is used.

  2. Description of the Related Art In recent years, electrophotographic apparatuses have been required to have specifications such as small size, light weight, and low power consumption while achieving colorization, high definition, and high image quality with simpler elements.

  As described above, demands for higher definition and higher image quality of electrophotography are increasing in the market, and attempts to achieve high image quality and full color are being made in the technical field. In the case of full-color electrophotography, an image is formed by superimposing three or four color toners. If the color toners of the respective colors are not developed and transferred in the same manner, color reproduction is poor or color unevenness occurs. Will occur. However, these colorings are performed by pigments and dyes, and they greatly affect development and transfer. Further, in a full-color image, the fixing property, color mixing property, and offset resistance at the time of fixing are important, and a binder resin suitable for these performances is selected, but the effect of the binder resin on the developability and transferability is selected. Is also big. One of the effects is the influence of temperature and humidity on the charge amount, and there is an urgent need to develop a color toner having a stable charge amount even in a wide range of environments.

  One of means for solving such problems is a method of adding various external additives to the toner. In particular, for the purpose of improving various image characteristics such as resolution, uniformity of density, fog, etc., external addition of various fine particles has been widely performed to improve the chargeability and transferability of the toner. I have.

  Commonly used inorganic fine particles include (i) inorganic fine particles surface-treated with silicone oil, silicone varnish and silane compound, or (ii) titania surface-treated or aminosilane-treated. Are preferably used (Patent Documents 1 to 16).

  Further, (iii) those containing two types of inorganic fine particles are preferably used (Patent Documents 17 to 30).

  However, in these proposals, although the electrophotographic properties are certainly improved, the uniformity of the hydrophobicity is insufficient, and a sufficient amount of triboelectricity cannot be obtained due to high humidity or long-term storage, and the image density is reduced. And fogging. Alternatively, the amount of triboelectric charge may become excessive under low humidity, causing image density unevenness and fog. Insufficient releasability of the toner from the developer carrying member (photosensitive drum) may not be obtained, resulting in insufficient transferability, which may cause a decrease in transfer efficiency and omission during transfer. There was no solution. Furthermore, when applied to a full-color toner, it was not particularly satisfactorily satisfactory.

Further, in Patent Document 2, low bulk density having an amino group and a hydrophobic group on the particle surface, having a specific surface area of at least 50 m ² / g, in which the -OH group is blocked, and having a positive or zero charged surface. It has been proposed for metal oxide powders. However, since the chargeability of the surface of the metal oxide fine powder is controlled by the treatment agent, it is not preferable because the micro charge amount distribution on the silica particle surface is broad or the toner charge amount distribution is broad.

  Further, Patent Documents 31 and 32 propose a toner containing a high-temperature vapor phase oxide of a silicon halide and a halogen compound of a specific metal. However, since this silica is oxidized in a vapor phase at a high temperature, it is presumed that titanium exhibits crystallinity and contains a large amount of a halogen component, and thus has an adverse effect. Also, since the purpose is only to adjust the charge of silica, the content of the titanium compound is high, and further, the transferability of toner having excellent low-temperature fixability and oil-less fixability is sufficiently considered. There were problems that had to be improved.

  Patent Document 33 discloses that the surface of silica is coated with a hydroxide or oxide of titanium, zirconium, tin, or aluminum in an aqueous system and then subjected to a surface treatment with an alkoxysilane in an aqueous system. A method for controlling gender has been proposed. However, even if an attempt is made to coat the silica surface with a hydroxide or oxide of titanium, zirconium, tin or aluminum in an aqueous system, it is difficult to obtain sufficient reactivity and adhesion. Further, even if the surface treatment is successfully performed, it is considered that the characteristics of the dissimilar metals existing near the surface of the silica particles strongly affect the toner. In the case of the above-mentioned metals, the charging polarity and the surface electric resistance greatly change, which is presumed to adversely affect the chargeability and the charge amount distribution of the toner.

  As described above, there is no satisfactory toner that sufficiently controls and suppresses the negative charging property of the silica particles, is not easily affected by temperature and humidity, and has good charging property, transferability, fixing property, and durability. is the current situation.

JP-B-53-22447 Japanese Patent Publication No. 1-34422 JP-A-58-216252 JP-A-59-201063 JP-A-64-88554 Japanese Patent Publication No. 3-39307 JP-A-4-204750 JP-A-4-214568 JP-A-4-340558 JP-A-5-19528 JP-A-5-61224 JP-A-5-94037 JP-A-5-119517 JP-A-5-139748 JP-A-6-11886 JP-A-6-11887 Japanese Patent Publication No. 2-27664 JP-A-60-238847 JP-A-61-188546 JP-A-61-18847 JP-A-62-174772 JP-A-2-151872 JP-A-2-222966 JP-A-2-291565 JP-A-4-204751 JP-A-4-280255 JP-A-4-345168 JP-A-4-345169 JP-A-4-348354 JP-A-5-113688 JP-A-11-174721 JP-A-11-174726 JP 2002-029730 A

  An object of the present invention is to provide a toner that solves the above-mentioned problems.

  SUMMARY OF THE INVENTION An object of the present invention is to provide a toner having excellent developing properties, transfer properties and fixing properties, being less affected by the environment, and having good durability, by maximizing the potential of a toner having a release agent. is there.

  SUMMARY OF THE INVENTION An object of the present invention is to provide a toner which can form a clear image without fogging, has a high image density, is excellent in fine line reproducibility, has excellent gradation in a highlight portion, and has excellent durability stability. .

  An object of the present invention is to provide a toner having excellent fluidity and excellent resolution and transferability.

  SUMMARY OF THE INVENTION An object of the present invention is to provide a toner capable of polishing and removing deposits on the surface of a photoreceptor generated by long-term use or suppressing the occurrence of the deposits and obtaining a stable image without image defects for a long period of time. To provide.

  A further object of the present invention is to provide a toner which is hardly influenced by the environment such as temperature and humidity and has stable triboelectric charging characteristics.

  An object of the present invention is to provide a suitable color toner for forming a full-color image or a multi-color image.

  An object of the present invention is to provide a color toner having good transparency in OHP, and excellent in low-temperature fixing property and high-temperature offset resistance.

  An object of the present invention is to provide a color toner having excellent storage stability, heat resistance and blocking resistance.

The present invention provides at least a binder resin, a toner having a colorant and a release agent, and a toner having at least silica particles.
An endothermic curve of the toner measured by a differential scanning calorimeter (DSC) shows that the maximum endothermic peak temperature in the temperature range of 30 to 200 ° C. is in the range of 60 to 100 ° C.
The silica particles contain a titanium element,
The silica particles satisfy the following formulas in X-ray diffraction: 0.7 ≦ (Ia ₁ / Ib ₁ ) ≦ 2.0 and 0.7 ≦ (Ia ₂ / Ib ₂ ) ≦ 2.0. Related to toner.
(Ia ₁ indicates the maximum intensity at 2θ = 25.3, Ib ₁ indicates the average intensity at 2θ = 25.3 ± 2.0 deg, Ia ₂ indicates the maximum intensity at 2θ = 27.5, Ib ₂ indicates the average value of the intensity at 2θ = 27.5 ± 2.0 deg.)

  The present inventors do not use oil to prevent high-temperature offset, or even in a fixing means using a small amount of oil, while achieving excellent low-temperature fixability, color mixing, high-temperature offset resistance. In order to obtain a toner that achieves excellent developability, transferability, fixability, and durability in all environments, and further achieves long-term storage in a high-temperature environment, as a result of intensive studies, a binder resin, It has been found that a toner having at least a colorant, a release agent and silica containing a titanium compound is extremely effective.

  Even in the fixing means that does not use oil to prevent high-temperature offset or uses less oil, it achieves excellent low-temperature fixing property, color mixing property, and high-temperature offset resistance, and is excellent in all environments. As a result, a toner having excellent developability, transferability, fixability and durability was obtained.

  In the X-ray diffraction of the silica particles containing the titanium element according to the present invention, the ratio of the intensity Ia at 2θ = 25.3 and 27.5 deg to the intensity Ib which is the average value of the intensity at 2θ + 2.0 deg and 2θ−2.0 deg. (Ia / Ib) is a physical property value related to the crystal form of titanium oxide contained in the silica particles.

More specifically, the silica particles of the present invention are titanium compound-containing silica particles containing a titanium element (hereinafter referred to as “titanium compound-containing silica particles”), and have a maximum intensity Ia _{1 at} 2θ = 25.3 in X-ray diffraction. The ratio (Ia ₁ / Ib ₁ ) of the intensity Ib ₁ , which is the average value of the intensity at 2θ + 2.0 deg and 2θ−2.0 deg, is 0.7 ≦ Ia ₁ / Ib ₁ ≦ 2.0, and 27. The ratio (Ia ₂ / Ib ₂ ) of the maximum intensity Ia ₂ at 5 deg to the intensity Ib ₂ , which is the average value of the intensity at 2θ + 2.0 deg and 2θ−2.0 deg, is 0.7 ≦ Ia ₂ / Ib ₂ ≦ 2.0. It is characterized by being.

  Satisfying the above-mentioned relational expression means that the titanium compound contained in the titanium compound-containing silica particles does not have crystallinity.

  Generally, in X-ray diffraction, titanium oxide is known to have several peaks. It is known that the crystal system has a characteristic and large peak at around 2θ = 25.3 when the crystal system is an anatase type, and at around 2θ = 27.5 when the crystal system is a rutile type.

  Further, in X-ray diffraction, amorphous silica has no peak, and the intensity tends to increase gradually from around 2θ = 10 deg to around 2θ = 21 deg, and the intensity gradually decreases from around 2θ = 22 deg to around 2θ = 40 deg. Show a tendency to become

  That is, in the X-ray diffraction, it clearly defines that the titanium compound does not have a crystal unique to titanium oxide in the titanium compound-containing silica particles according to the present invention satisfying the above relational expression.

  The present inventors have intensively studied the chargeability and transferability of the silica particles on the toner having excellent low-temperature fixability and oil-less fixability. By controlling the chargeability of silica, which is known as a strong negative material, from weak negative chargeability (weak negative property) to weak positive chargeability (weak positive property), more ideal characteristics for the toner are obtained. Has been found to be able to be provided. At that time, they have found that a great effect can be obtained by disposing a titanium compound which is a weakly positive material in the silica particles. The inventor has found that by setting the titanium compound to have no crystal system, it is possible to control the chargeability of the silica particles without adversely affecting the titanium compound.

  When the titanium compound in the silica particles has the crystallinity of titanium oxide, the characteristics of the titanium compound become remarkable, the positive chargeability (positive property) increases, and the adhesion between the titanium compound exposed on the surface and the surface treating agent is increased. However, it is not preferable because the particle size distribution becomes difficult to control and the adverse effect on the toner characteristics is large.

  The raw materials and the production method of the titanium compound-containing silica particles of the present invention are not particularly limited, but production examples are shown below.

  The titanium compound-containing silica particles used in the present invention can be obtained by heating and firing a mixture of a halogen-free siloxane and a volatile titanium compound in a gas phase.

  Here, examples of the siloxane include a linear organosiloxane cyclic organosiloxane and a mixture thereof, and those containing no halogen are preferable.

  Examples of the organosiloxane include hexamethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane. These siloxanes preferably do not contain halogen such as chlorine and are obtained by purification. These can be used alone or in combination of two or more.

  The volatile titanium compound is not particularly limited, and may be a compound having volatility such as chloride, alkoxide and acetylacetonate of titanium and thermally decomposing or hydrolyzing in a gas phase. These can be used alone or in combination of two or more.

  Specifically, the volatile titanium compound used in the present invention includes titanium alkoxides such as titanium tetramethoxide, titanium tetraethoxide, titanium tetrapropoxide, titanium tetrabutoxide, and diethoxy titanium oxide; titanium tetrachloride, tetraodor Volatile titanium compounds such as tetrahalogenated titanium such as titanium halide; titanium halide alkoxide such as trihalogenated monoalkoxytitanium, dihalogenated dialkoxytitanium, and monohalogenated trialkoxytitanium can be used.

  A mixture of the siloxane and the volatile titanium compound is introduced into the burner in a liquid state, sprayed by a nozzle attached to the tip of the burner and burned, or the mixture of the siloxane and the volatile titanium compound is heated, The steam may be introduced into a burner and burned.

  The titanium compound-containing silica particles thus obtained are used in the present invention because the titanium compound is uniformly dispersed, so that the chargeability is good and the uniform reactivity with the surface treatment agent is excellent. Is preferred.

  On the other hand, by firing a mixture of a silicon halide and a titanium halide in a gas phase at a high temperature, silica containing a titanium compound can be obtained. No titanium compound-containing silica can be obtained. Further, since a large amount of a halogen compound is used as a starting material, the generated silica particles contain halogen (chlorine) as an impurity. The impurity halogen (chlorine) has a large adverse effect on the chargeability of the toner. In particular, in a toner containing a release agent, the adverse effect is remarkable, and scattering and fogging of the toner under a high temperature and high humidity environment become a problem. Therefore, in the present invention, it can be said that it is not preferable to use a large amount of a halogen compound as a starting material.

  Furthermore, the silica particles of the present invention can also be obtained by mixing silica fine particles and amorphous titanium oxide fine particles and baking them at about 800 ° C. at a low temperature. However, since silica fine particles and amorphous titanium oxide fine particles are used as raw materials, it is difficult to obtain a uniform dispersion state, and the charge amount distribution tends to be broad.

  When the calcination temperature is higher than 800 ° C., the crystal growth of the amorphous titanium oxide fine particles remarkably progresses, so that the titanium compound-containing silica particles having no crystallinity as in the present invention cannot be obtained.

  The content of the titanium compound contained in the titanium compound-containing silica particles is preferably 0.1 to 20 parts by mass (per 100 parts by mass of the titanium compound-containing silica particles). When the content of the titanium compound is more than 20 parts by mass, the negative chargeability (negativeness) of the silica particles is extremely reduced, and the charge amount distribution of the toner becomes broad, or an appropriate charge amount cannot be maintained. Absent. On the other hand, if the content of the titanium compound is less than 0.1 part by mass, the negative chargeability (negativeness) of the silica particles is remarkably exhibited, and the charge amount of the toner in a low humidity environment becomes extremely high, which is not preferable. .

  Examples of the surface treatment agent for the titanium compound-containing silica particles of the present invention include known coupling agents such as silane coupling agents, titanate coupling agents, aluminum coupling agents, and zircoaluminate coupling agents, silicone oils, and silicone varnishes. Can be used.

  For example, alkylalkoxysilanes such as dimethyldimethoxysilane, trimethylethoxysilane, butyltrimethoxysilane, etc., dimethyldichlorosilane, trimethylchlorosilane, allyldimethylchlorosilane, hexamethyldisilazane, allylphenyldichlorosilane, benzyldimethyl Silane coupling agents such as chlorosilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, divinylchlorosilane, and dimethylvinylchlorosilane can be used.

  As the surface treatment agent for the titanium compound-containing silica particles of the present invention, it is particularly preferable to treat with a silazane compound or a silazane compound and silicone oil, and it is preferable to treat with hexamethyldisilazane and dimethyl silicone oil to obtain good chargeability. This is preferable in that transferability can be obtained.

  The amount of the treatment agent is preferably 1 to 30 parts by mass, more preferably 1 to 30 parts by mass, based on 100 parts by mass of the titanium compound-containing silica particles, in order to prevent aggregation of the silica particles and maximize the properties of the treatment agent. 3 to 20 parts by mass is good.

  In the present invention, the surface treatment of the titanium compound-containing silica particles is performed by a wet method, a dry method, or the like, but the present invention is not particularly limited to these methods.

  In the present invention, the number average primary particle diameter of the titanium compound-containing silica particles is preferably 10 to 400 nm.

  The number average particle diameter is preferably from 1 to 400 nm from the viewpoints of imparting fluidity to the toner and polishing. When the number average particle diameter is smaller than 1 nm, the toner is easily embedded in the surface of the toner particles, so that the toner is likely to deteriorate at an early stage, the durability is reduced, and the polishing property is low.

  On the other hand, when the average particle diameter is larger than 400 nm, the toner fluidity is reduced, so that the charging is likely to be non-uniform. In addition, the surface of the photoreceptor is easily damaged and image defects are likely to occur, and a cleaning member such as a cleaning blade is likely to be deformed or damaged.

  With respect to polishing and removal of the surface of the photoconductor and its attached matter, when the toner is cleaned from the surface of the photoconductor, the toner temporarily stays at the pressure contact portion of a cleaning member such as a cleaning blade. The titanium compound-containing silica particles present on the surface of the staying toner particles function to polish and remove the surface of the photoreceptor and its adhered matter. However, it is preferable that the titanium compound-containing silica particles are not embedded in the surface of the toner particles, are dispersed in the toner in a state close to the primary particle size without agglomerates, and exist uniformly on the surface of the toner particles. In order for the titanium compound-containing silica particles to have suitable polishing properties, the number average particle diameter is from 1 to 400 nm, and the specified intensity ratio in the X-ray diffraction of the titanium compound-containing silica particles indicates the value of the present invention. Is very effective.

BET of the titanium compound-containing silica particles of the present invention is preferably 5 to 300 m ² / g. If the BET specific surface area of the titanium compound-containing silica particles is less than 5 m ² / g, it indicates that the particles have a large particle size and that aggregates or coarse particles are present. Problems such as scratching and deformation or damage of a cleaning means such as a cleaning blade are likely to occur. In addition, when the particle diameter of the titanium compound-containing silica particles is large, the silica particles are easily released from the toner particles, and the released titanium compound-containing silica particles are left in a large amount in the developing machine or adhere to various devices in the image forming apparatus main body. It is not preferable because it has an adverse effect.

When the BET specific surface area of the titanium compound-containing silica particles is larger than 300 m ² / g, the amount of water adsorbed on the titanium compound-containing silica particles increases, which may adversely affect the charging characteristics of the toner. In particular, the amount of triboelectric charge of the toner decreases in a high humidity environment, and toner scattering, fogging, and image quality deterioration are likely to occur.

  The titanium compound-containing silica particles of the present invention are preferably added in an amount of 0.1 to 5 parts by mass based on 100 parts by mass of the toner particles. When the addition amount is less than 0.1 part by mass, the effect of improving the chargeability and transferability is small. On the other hand, when the amount exceeds 5 parts by mass, the fluidity of the toner is greatly reduced, so that uniform charging is hindered.

  The toner of the present invention may have one or more types of inorganic fine particles in addition to the titanium compound-containing silica particles, if necessary. Known inorganic fine particles can be used. For example, metal oxide fine particles such as silica fine particles, alumina fine particles, titanium oxide fine particles, zirconium oxide fine particles, magnesium oxide fine particles, and zinc oxide; nitrides such as boron nitride fine particles, aluminum nitride fine particles, and carbon nitride fine particles; Examples thereof include calcium titanate, strontium titanate, barium titanate, and magnesium titanate. In particular, inorganic fine particles having an average primary particle diameter of 1 to 200 nm are preferably used. The inorganic fine particles are preferably subjected to a surface treatment in order to obtain necessary characteristics. At that time, as the surface treatment agent, the above-mentioned known agents can be used.

  As the binder resin used for the toner particles, various material resins conventionally known as toner binder resins are used.

  For example, styrene-based copolymers such as polystyrene, styrene-butadiene copolymer and styrene-acrylic copolymer; ethylene-based copolymers such as polyethylene, ethylene-vinyl acetate copolymer and ethylene-vinyl alcohol copolymer Phenolic resins, epoxy resins, acrylic phthalate resins, polyamide resins, polyester resins, maleic acid resins, and the like. These resins may be used alone or as a mixture of two or more resins.

  Among these resins, (a) a polyester resin having a particularly high negative chargeability, (b) a hybrid resin having a polyester unit and a vinyl copolymer unit, or (c) a mixture thereof is used. Is preferred, and when a hybrid resin is used, the effect of the present invention is increased. These resins, particularly when combined with a release agent, can effectively function as a release agent at the time of fixing, and therefore have extremely excellent fixability, and have good color mixing properties, heat resistance, and blocking resistance. Although it is suitable for color toners, it has a strong negative charging ability and tends to be excessively charged. However, by using the silica particles containing titanium used in the present invention, the adverse effects can be improved and an excellent toner can be obtained. . Here, that the binder resin of the toner is a polyester resin means that the main component of the binder resin is a polyester resin.

  The toner of the present invention contains one or more release agents.

  Known release agents can be used as the release agent used in the present invention. In the present invention, an aliphatic hydrocarbon-based release agent is particularly preferably used. For example, a low molecular weight alkylene polymer obtained by radical polymerization of alkylene under high pressure or a Ziegler catalyst under low pressure; an alkylene polymer obtained by thermally decomposing a high molecular weight alkylene polymer; Synthetic hydrocarbon release agents obtained from hydrocarbon distillation residues obtained by the process or by hydrogenating them are preferred. Further, those obtained by separating a hydrocarbon release agent by use of a press sweating method, a solvent method, vacuum distillation or a separation crystallization method are more preferably used. Hydrocarbons as a base are synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide-based catalyst (often a multi-component system) [for example, the Zintol method, the Hydrochol method (fluidized catalyst beds). Compound); hydrocarbons having a carbon number of up to about several hundreds obtained by the Aggé method (using an identified catalyst bed) that can obtain a large amount of release agent-like hydrocarbons; The hydrocarbon polymerized by the catalyst is preferable because it is a straight-chain hydrocarbon having a small number of branches and a small saturation and a long saturation. In particular, a release agent synthesized by a method not based on the polymerization of alkylene is preferable from the viewpoint of its molecular weight distribution.

  Regarding the molecular weight distribution of the release agent, the main peak is preferably in a region having a molecular weight of 400 to 2400, and more preferably in a region of 430 to 2000. By providing such a molecular weight distribution, it is possible to impart favorable thermal characteristics to the toner.

  In order to function more effectively at the time of fixing the toner, the melting point of the release agent is preferably from 60 to 100C, more preferably from 65 to 90C. The endothermic peak temperature of the toner of the present invention refers to a temperature at which a maximum endothermic peak of a main peak of an endothermic curve is obtained in a differential scanning calorimeter (DSC) measurement of the toner containing the release agent. It is. The endothermic peak temperature is a physical property value derived from the melting point of the release agent.

  The release agent is used in an amount of 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, per 100 parts by mass of the binder resin.

  The method for adding the release agent is not particularly limited. The resin is added to the toner by a method in which the resin is dissolved in a solvent, the temperature of the resin solution is raised, and a release agent is added and mixed while stirring, or a method in which the resin and the release agent are mixed and then melt-kneaded.

  Known dyes and / or pigments are used as the colorant of the present invention.

  Coloring pigments for magenta toner include C.I. 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, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, C. 90, 112, 114, 122, 123, 155, 163, 202, 206, 207.209; I. Pigment Violet 19; I. Butt Red 1, 2, 10, 13, 15, 15, 23, 29, 35 and the like.

  The pigment alone may be used, but it is more preferable to improve the sharpness by using the dye and the pigment in combination from the viewpoint of the image quality of a full-color image.

  Magenta toner dyes include C.I. C. I Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; I. Disperse Red 9; I. Solvent violet 8, 13, 14, 21, 27; C.I. I. Oil-soluble dyes such as Disper 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; I. And basic dyes such as Basic Violet 1,3,7,10,14,15,21,25,26,27,28.

  Examples of the coloring pigment for cyan toner include C.I. I. Pigment Blue 2, 3, 15, 16, 17; I. Bat blue 6; I. Acid Blue 45 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on a phthalocyanine skeleton having a structure represented by the following formula.

〔式中、ｎは１〜５の整数を示す。〕

[In formula, n shows the integer of 1-5. ]

  Examples of yellow color pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 65, 73, 74, 83, 97, 155, 180; I. Bat Yellow 1, 3, 20 and the like.

  In addition, C.I. I. Direct Green 6, C.I. I. Basic Green 4, C.I. I. Dyes such as Basic Green 6 and Solvent Yellow 162 can also be used.

  As the black colorant used in the present invention, carbon black, a magnetic material, and those toned to black using the above-described yellow / magenta / cyan colorants can be used.

  The amount of the colorant to be used is preferably 0.1 to 15 parts by mass, more preferably 0.5 to 12 parts by mass, and most preferably 2 to 10 parts by mass with respect to 100 parts by mass of the binder resin.

  As a method for producing the toner particles used in the present invention, a method of kneading the constituent materials well by a heat kneader such as a hot roll, a kneader, and an extruder, pulverizing mechanically, and classifying the pulverized powder to obtain toner particles. A method in which a material such as a colorant is dispersed in a binder resin solution and then spray-dried to obtain toner particles; a method in which a predetermined material is mixed with a polymerizable monomer to constitute the binder resin; A toner production method by suspension polymerization in which a composition is obtained and toner particles are obtained by polymerizing an emulsion suspension of the composition can be applied.

  In the present invention, an organometallic compound can be contained in the toner. As the organometallic compound used in the present invention, a compound of an aromatic carboxylic acid and a divalent or higher valent metal is preferable.

  Examples of the aromatic carboxylic acid include the following three compounds.

〔式中、Ｒ₁乃至Ｒ₇は同一又は異なる基を示し、水素原子、炭素数１〜１２のアルキル基、炭素数２〜１２のアルケニル基、−ＯＨ，−ＮＨ₂，−ＮＨ（ＣＨ₃），−Ｎ（ＣＨ₃）₂，−ＯＣＨ₃，−Ｏ（Ｃ₂Ｈ₅），−ＣＯＯＨ又は−ＣＯＮＨ₂を示す。〕

[Wherein, R _{1 to} R ₇ represent the same or different groups, and represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, —OH, —NH ₂ , —NH (CH _{3 ), - N (CH 3)} 2, -OCH 3, -O (C 2 H 5), - shows a COOH or -CONH _2. ]

Preferred R ₁ includes a hydroxyl group, an amino group and a methoxy group, and among them, a hydroxyl group is preferred. As the aromatic carboxylic acid, dialkyl salicylic acid such as di-tert-butyl salicylic acid is particularly preferred.

  In the present invention, when the toner is made to be negatively chargeable, an organic metal complex and a chelate compound are effective as a charge control agent having negative chargeability, and a monoazo metal complex, an acetylacetone metal complex, an aromatic hydroxycarboxylic acid And aromatic dicarboxylic acid-based metal complexes. In addition, aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, or phenol derivatives such as bisphenol can be added.

The metal forming the organometallic 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 the divalent metal, Zn ²⁺ , Ca ²⁺ , Mg ²⁺ , and Sr ²⁺ are preferable. Examples of the metal having three or more valences include Al ³⁺ , Cr ³⁺ , Fe ³⁺ , and Ni ³⁺ . Of these metals, preferred are Al ³⁺ , Fe ³⁺ , Cr ³⁺ , Zn ²⁺ , and particularly preferred is Al ³⁺ .

  In the present invention, the organometallic compound is preferably an aluminum compound of di-tert-butylsalicylic acid or a zinc compound of di-tert-butylsalicylic acid.

  As the metal compound of the aromatic carboxylic acid, for example, an aromatic carboxylic acid is dissolved in an aqueous solution of sodium hydroxide, an aqueous solution in which divalent or higher valent metal atoms are melted is added dropwise to the aqueous solution of sodium hydroxide, and heated and stirred. After adjusting the pH of the aqueous solution, cooling to room temperature, and washing with filtered water, a metal compound of an aromatic carboxylic acid can be synthesized. However, the present invention is not limited to the above synthesis method.

  The organic metal compound is used in an amount of 0.1 to 10 parts by mass (more preferably, 0.2 to 5 parts by mass) per 100 parts by mass of the binder resin in terms of adjusting the viscoelastic properties and triboelectric charging properties of the toner. preferable.

  In the toner of the present invention, a compound other than the above-mentioned organometallic compound can be used as a charge control agent, if necessary, in order to further stabilize the chargeability. Examples of the charge control agent include nigrosine and imidazole compounds. The charge control agent is used in an amount of 0.1 to 10 parts by mass, preferably 0.1 to 7 parts by mass, per 100 parts by mass of the binder resin.

  In the present invention, when the toner is made positively chargeable, it is preferable to add nigrosine, a triphenylmethane-based compound, a rhodamine-based dye, polyvinyl pyridine, or the like as a charge control agent having a positive charge.

  When producing a color toner, it is preferable to use a colorless or light-colored positive charge control agent that does not affect the color tone of the toner.

  Next, the particle size of the toner used in the present invention will be described.

  As a result of intensive studies on image density, highlight reproducibility (halftone reproducibility), and fine line reproducibility, the toner to which titanium compound-containing silica particles are externally added preferably has a weight average particle diameter of 3 to 9 μm.

  When the weight-average particle diameter of the toner is larger than 9 μm, there are basically few toner particles that can contribute to high image quality, and it is difficult to adhere faithfully on a fine electrostatic image on the photosensitive drum, and the highlight reproducibility is low. Poor and low resolution. There is a tendency that the toner excessively rides on the electrostatic charge image more than necessary, which tends to increase the toner consumption.

  On the other hand, when the weight average particle diameter of the toner is smaller than 3 μm, the charge amount per unit mass of the toner tends to be high, and the density is low, particularly, the image density is low under low temperature and low humidity. Particularly, it is not suitable for developing an image having a high image area ratio such as a graphic image.

  Further, when the weight average particle diameter of the toner is smaller than 3 μm, the specific surface area of the toner becomes large, and the amount of the release agent near the toner surface becomes extremely large, so that the contact charging with the carrier is not performed smoothly. The amount of toner that cannot be sufficiently charged increases, scatters to non-image areas, and fog becomes noticeable. 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, in the case of a toner having a weight average diameter of less than 3 μm, self-aggregation of the toner is likely to occur, and uniform mixing with the carrier is achieved in a short time. However, in continuous toner replenishment durability, fogging tends to occur.

  The toner of the present invention can be used in any of non-magnetic one-component toner development and two-component development.

  When the toner of the present invention is used in a two-component developer, the carrier used in combination is, for example, iron such as surface oxidized or unoxidized, nickel, copper, zinc, cobalt, manganese, chromium, and rare earth metals and the like. Alloys or oxides and ferrites can be used.

  Particularly, magnetic ferrite particles of three elements of Mn-Mg-Fe formed mainly of manganese, magnesium and iron are preferable in that good charging characteristics can be obtained. The magnetic ferrite particles preferably contain 0.001 to 1 part by mass (more preferably 0.005 to 0.5 parts by mass) of silicon element per 100 parts by mass of the magnetic ferrite particles. It is particularly preferable when a resin is used.

  The magnetic carrier particles are preferably coated with a resin, and the resin is preferably a silicone resin. In particular, when a nitrogen-containing silicone resin or a modified silicone resin produced by a reaction between a nitrogen-containing silane coupling agent and a silicone resin is used as a color toner, a negative triboelectric charge on the color toner is obtained. This is preferred in terms of imparting properties, environmental stability, and suppressing contamination of the carrier surface.

  The magnetic carrier preferably has an average particle size of 15 to 60 μm (more preferably, 25 to 50 μm) in relation to the weight average particle size of the color toner.

  In order to obtain stable charging characteristics in any environment, it is preferable to coat the surface of the carrier particles with a resin.

  As a method of coating the surface of the carrier particles with a resin, a conventionally known method such as a method in which a resin is dissolved or suspended in a solvent and applied, and a method in which the resin is attached to the carrier particles, a method in which the resin is simply mixed with a powder, or the like can be applied. .

  The fixing substance on the carrier particle surface varies depending on the toner, for example, polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resin, polyester resin, styrene resin, acrylic resin, polyamide, polyvinyl butyral, It is appropriate to use an amino acrylate resin alone or in combination.

  In particular, a silicone resin is preferable from the viewpoints of charge imparting property, toner spent resistance and the like.

  The coating resin is preferably 0.1 to 30 parts by mass (preferably 0.2 to 15 parts by mass) per 100 parts by mass of the carrier.

  When the two-component developer is prepared by mixing with the toner of the present invention, the mixing ratio is 2 to 15% by mass, preferably 3 to 13% by mass, more preferably 4 to 10% by mass as the toner concentration in the developer. Usually, good results are obtained when the content is in the range of mass%. If the toner concentration is less than 2% by mass, the image density tends to be low, and if a toner containing a release agent as in the present invention is used, the deterioration of the developer tends to occur, which is not preferable. If the amount is more than 15% by mass, the charge amount distribution of the toner becomes wide and fog and scattering in the apparatus are undesirably generated.

  Hereinafter, a method for measuring each physical property value used in the present invention will be described.

Method for Measuring Ia and Ib of Silica of the Present Invention The X-ray diffraction measurement of the silica of the present invention was carried out using CuKα radiation and using the silica powder as a sample under the following conditions.

Measuring machine used / Mc Science Co., Ltd., fully automatic X-ray diffractometer MXP18
X-ray tube / Cu
Tube voltage / 50KV
Tube current / 300mA
Scan method / 2θ / θ scan Scan speed / 4deg. / Min
Sampling interval / 0.020 deg.
Start angle (2θ) / 3 deg.
Stop angle (2θ) / 60 deg.
Divergence slit / 0.5 deg.
Scattering slit / 0.5 deg.
Receiving slit / 0.3mm.
Using curved monochromator

Method for Measuring the Titanium Compound Content of Silica of the Present Invention In the method for measuring the titanium compound content of silica, a calibration curve is first prepared using a calibration curve sample, and the amount of the sample added is calculated from the calibration curve.

(1) Preparation of Calibration Curve Titanium oxide fine powder was 0%, 0.5%, 1.0%, 3.0%, 5.0%, and 10% of silica (X) using a coffee mill. Mix each at a ratio of 0% and 15.0% (mass%) to prepare a calibration curve sample.

  Using a sample press molding machine (MAEKAWA Testing machine (manufactured by MFG Co., LTD)), press-mold the above 7 samples, and determine the Kα peak angle (a) of the Ti element from the 2θ table. The sample for the calibration curve is put into (manufactured by Rigaku Denki Kogyo Co., Ltd.), the sample chamber is decompressed and evacuated, and the X-ray intensity of each sample is determined under the following conditions to prepare a calibration curve. X-ray analysis is performed in accordance with JIS K0119 general rules for fluorescent X-ray analysis.

〔Measurement condition〕
Measurement potential, voltage: 50kV-50mA
2θ angle: a
Crystal plate: LiF
Measurement time: 60 seconds

(2) Determination of titanium compound in silica particles After molding a measurement sample in the same manner as in (1) above, the X-ray intensity was determined under the same measurement conditions, and the amount of the titanium compound in the silica particles was determined from the calibration curve. Is calculated.

Method for measuring the primary average particle diameter of the silica and inorganic fine particles of the present invention The primary particle diameter is the number average particle diameter by observing the silica and inorganic fine particles of the present invention with a transmission electron microscope, measuring the major diameter of 100 particles, Ask. The particle diameter on the toner particles is observed with a scanning electron microscope, and the long diameter of 100 particles is measured to determine the number average particle diameter.

  The magnification at the time of measurement is 40,000 to 60,000 times, and targets particles of 0.5 nm or more.

Method for measuring BET specific surface area of silica of the present invention The BET specific surface area of the silica and inorganic fine particles of the present invention is measured as follows.

  The BET specific surface area is determined by, for example, a BET multipoint method using a fully automatic gas adsorption amount measuring device (Auto Soap 1) manufactured by Yuasa Ionics Co., Ltd., using nitrogen as the adsorbed gas. As pretreatment of the sample, deaeration is performed at 50 ° C. for 10 hours.

Differential scanning calorimeter (DSC) measurement of the toner The toner is measured using a differential scanning calorimeter (DSC measuring apparatus), DSC-7 (manufactured by PerkinElmer) in accordance with ASTM D3418-82.

  A measurement sample is accurately weighed in an amount of 2 to 10 mg, preferably 5 mg. This is put in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rising rate of 10 ° C./min under normal temperature and normal humidity within a measurement temperature range of 30 to 200 ° C. In this heating process, an endothermic peak of the main peak of the DSC curve in the temperature range of 30 to 200 ° C. is obtained. The endothermic peak temperature is a temperature at which a maximum value is shown.

A Coulter Counter TA-II or a Coulter Multisizer II (manufactured by Beckman Coulter, Inc.) is used as the measuring device for measuring the particle size of the toner of the present invention . As the electrolyte, about 1% NaCl aqueous solution is prepared using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter Scientific Japan KK) can be used. As a measuring method, 0.1 to 5 ml of a surfactant (preferably an alkylbenzene sulfonate) 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 was suspended was subjected to dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and the volume and number of toner particles were measured for each channel by the measurement device using a 100 μm aperture as an aperture. Then, the volume distribution and the number distribution of the toner are calculated. Then, the weight-average particle diameter (D4) of the toner based on the weight obtained from the volume distribution of the toner particles (the median value of each channel is set as a representative value for each channel) is obtained.

  As channels, 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. 8.0 μm 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 32.00 to 40.30 μm are used.

  Hereinafter, Production Examples and Examples relating to the present invention will be described, but the present invention is not limited thereto.

<Production of silica particles containing titanium compound>
(Example 1 of producing silica particles containing a titanium compound)
92 parts by mass of hexamethyldisiloxane and 8 parts by mass of titanium tetrapropoxide are sufficiently mixed at room temperature. This mixture was sprayed into fine droplets, introduced into the burner together with oxygen, air, and propane, and flame-hydrolyzed at a flame temperature of 2300 ° C. to obtain untreated titanium compound-containing silica particles.

  Next, surface treatment of the titanium compound-containing silica particles is performed. 100 parts by mass of the above-mentioned titanium compound-containing silica particles were put into a stirrer, and a mixed solution of 10 parts by mass of hexamethyldisilazane and 10 parts by mass of hexane was sprayed with stirring, followed by stirring. Next, 5 parts by mass of dimethyl silicone oil and 10 parts by mass of hexane were sprayed and stirred. Thereafter, the obtained fine powder was heated to 120 ° C. and stirred, and the solvent was dried to obtain titanium compound-containing silica particles 1.

  The presence of the titanium compound in the silica particles was confirmed by EDAX (non-dispersive X-ray diffraction analyzer).

  Table 1 shows production examples of the titanium compound-containing silica particles.

(Production example 2 of silica particles containing titanium compound)
Titanium compound-containing silica particles 2 were obtained in the same manner as in the preparation of titanium compound-containing silica particles 1 except that the reaction temperature was 2500 ° C. and no dimethyl silicone oil was used.

(Titanium compound-containing silica particle production example 3)
Titanium compound-containing silica particles 3 were obtained in the same manner as in the preparation of titanium compound-containing silica particles 2 except that 1.5 parts by mass of titanium tetraisopropoxide was used and the amount of dimethyl silicone oil added was 10 parts by mass. Was.

(Production example 4 of silica particles containing titanium compound)
Titanium compound-containing silica particles 4 were obtained in the same manner as in the preparation of titanium compound-containing silica particles 3 except that 13 parts by mass of titanium tetraisopropoxide was used.

(Production example 5 of titanium compound-containing silica particles)
Titanium compound-containing silica particles 5 were obtained in the same manner as in the preparation of titanium compound-containing silica particles 3 except that 23 parts by mass of titanium tetraisopropoxide was used.

(Example 6 of producing titanium compound-containing silica particles)
Except that 28 parts by mass of titanium tetraisopropoxide is used and that the reaction temperature is set to 2000 ° C. by controlling the amount of propane supplied, the titanium compound-containing silica particles 6 are prepared in the same manner as in the preparation of titanium compound-containing silica particles 3. Obtained.

(Example 7 of producing silica particles containing a titanium compound)
Production of silica particles containing titanium compound except that the reaction temperature is controlled to 4200 ° C. by controlling the amount of propane supplied, 7 parts by mass of dimethyldichlorosilane is added instead of hexamethyldisilazane, and dimethylsilicone oil is not used. In the same manner as in Example 4, titanium compound-containing silica particles 7 were obtained.

(Production example 8 of silica particles containing titanium compound)
Except that the reaction temperature was controlled to 1400 ° C. by controlling the amount of propane supplied, that 20 parts by mass of dimethyldichlorosilane was added, and that no dimethylsilicone oil was used, the same procedure as in Preparation Example 7 of titanium compound-containing silica particles was carried out. Titanium compound-containing silica particles 8 were obtained.

(Example 9 of producing silica particles containing a titanium compound)
Titanium compound-containing silica particles 9 were obtained in the same manner as in the preparation of titanium compound-containing silica particles 4 except that hexamethyldisiloxane and titanium tetrachloride were used as raw materials.

(Titanium compound-containing silica particle production example 10)
Using silicon tetrachloride and titanium tetraisopropoxide as raw materials, baking at 1000 ° C. by controlling the propane supply amount, except that dimethyl silicone oil is not used, in the same manner as in the titanium compound-containing silica particle production example 4, Titanium compound-containing silica particles 10 were obtained.

(Production example 11 of silica particles containing titanium compound)
Except that silicon tetrachloride and titanium tetrachloride are used as raw materials, baking is performed at 1000 ° C. while controlling the amount of propane supplied, and dimethyl silicone oil is not used, a titanium compound is prepared in the same manner as in the titanium compound-containing silica particle production example 4. Containing silica particles 11 were obtained.

(Titanium compound-containing silica particle production example 12)
After thoroughly mixing 90 parts by mass of a silica sol having a BET specific surface area of 120 m ² / g and 10 parts by mass of a titania sol having a BET specific surface area of 200 m ² / g, dehydration and drying are performed, followed by baking at 300 ° C. for 3 hours. Thus, a mixed oxide was obtained. After that, the titanium compound-containing silica particles 12 were obtained by performing the surface treatment in the same manner as in the preparation example 2 of the titanium compound-containing silica particles.

(Titanium compound-containing silica particle production example 13)
BET specific surface area amorphous silica 90 parts by weight and the BET specific surface area of 120 m ² / g using the amorphous titanium oxide 200m ² / g, except that calcination at 1000 ° C., similarly to the titanium compound-containing silica particles prepared Example 12 Thus, silica particles 13 containing a titanium compound were obtained.

(Production example 14 of titanium compound-containing silica particles)
Titanium compound-containing silica particles 14 were obtained in the same manner as in the preparation of titanium compound-containing silica particles 13 except that anatase-type titanium oxide having a BET specific surface area of 180 m ² / g was used.

(Production example 15 of silica particles containing titanium compound)
Titanium compound-containing silica particles 15 were obtained in the same manner as in Titanium compound-containing silica particle production example 14 except that firing was performed at 300 ° C.

(Production example 16 of titanium compound-containing silica particles)
Titanium compound-containing silica particles 16 were obtained in the same manner as in the preparation of titanium compound-containing silica particles 13 except that a rutile type titanium oxide having a BET specific surface area of 150 m ² / g was used.

<Production of external additives other than titanium compound-containing silica particles>
Production example 1 of hydrophobic alumina fine particles
100 parts by mass of amorphous alumina (BET specific surface area: 190 m ² / g) was put into a stirrer, and a mixed solution of 20 parts by mass of i-butyltrimethoxysilane and 20 parts by mass of hexane was sprayed with stirring, followed by stirring. The resulting fine powder was heated to 120 ° C. and stirred, and the solvent was dried to obtain hydrophobic alumina fine particles A (BET specific surface area: 130 m ² / g).

Production example 1 of hydrophobic titanium oxide fine particles
100 parts by mass of anatase type titanium oxide fine powder (BET specific surface area: 180 m ² / g) synthesized by a sulfuric acid method is put into a stirrer, and a mixed solution of 20 parts by mass of i-butyltrimethoxysilane and 20 parts by mass of hexane is stirred. Was sprayed and stirred. The resulting fine powder was heated to 120 ° C. and stirred, and the solvent was dried to obtain hydrophobic titanium oxide fine particles A (BET specific surface area: 120 m ² / g).

Production example 2 of hydrophobic titanium oxide fine particles
100 parts by mass of fine powder of anatase type titanium oxide (BET specific surface area: 100 m ² / g) synthesized by the sulfuric acid method are put into a stirrer, and a mixed solution of 10 parts by mass of hexamethyldisilazane and 10 parts by mass of hexane is sprayed while stirring. Then, the mixture was stirred. The obtained fine powder was heated to 120 ° C. and stirred, and the solvent was dried to obtain hydrophobic titanium oxide fine particles B (BET specific surface area: 75 m ² / g).

Silica fine particle production example 1
100 parts by mass of silica fine powder (BET specific surface area: 100 m ² / g) synthesized by a dry method is put into a stirrer, and a mixed solution of 10 parts by mass of hexamethyldisilazane and 10 parts by mass of hexane is sprayed with stirring, and stirred. Processed. The obtained fine powder was heated to 120 ° C. and stirred, and the solvent was dried to obtain silica fine particles A (BET specific surface area: 75 m ² / g).

Production example 1 of positive silica fine particles
100 parts by mass of silica fine powder (BET specific surface area: 100 m ² / g) synthesized by a dry method is put into a stirrer, and a mixed solution of 10 parts by mass of γ-aminopropyltriethoxysilane and 10 parts by mass of hexane is sprayed with stirring. Then, the mixture was stirred. The resulting fine powder was heated to 120 ° C. and stirred, and the solvent was dried to obtain positive silica fine particles A (BET specific surface area: 75 m ² / g).

<Manufacture of binder resin>
(Hybrid resin production example 1)
As a vinyl copolymer, 1.9 mol of styrene, 0.21 mol of 2-ethylhexyl acrylate, 0.15 mol of fumaric acid, 0.03 mol of a dimer of α-methylstyrene, and 0.05 mol of dicumyl peroxide are put into a dropping funnel. . In addition, 7.0 mol of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 3. 0 mol, 3.0 mol of succinic 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 glass four-necked flask, and a thermometer, a stirring rod, a condenser and nitrogen are added. An inlet tube was attached and placed in the mantle heater. Next, after the inside of the flask is replaced with nitrogen gas, the temperature is gradually increased while stirring, and while stirring at a temperature of 145 ° C., the vinyl-based resin monomer, the crosslinking agent, and the polymerization initiator are added from the preceding dropping funnel. It was added dropwise over 4 hours. Then, the temperature was raised to 200 ° C., and the mixture was reacted for 4 hours to obtain a hybrid resin (1). Table 2 shows the results of the molecular weight measurement by GPC.

(Production example 1 of polyester resin)
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 glass 4-liter four-necked flask, and a thermometer, a stirring rod, a condenser and a nitrogen inlet tube are used. And placed in the mantle heater. The reaction was performed at 215 ° C. for 5 hours under a nitrogen atmosphere to obtain a polyester resin (1). Table 2 shows the results of the molecular weight measurement by GPC.

(Production example 1 of vinyl resin)
1000 ml of a toluene solvent and 2.4 mol of styrene, 0.26 mol of n-butyl acrylate, 0.09 mol of monobutyl maleate and 0.11 mol of di-t-butyl peroxide as a vinyl copolymer were stirred with a thermometer and stainless steel. Put into a 3 liter four-necked flask equipped with a rod, a falling condenser and a nitrogen inlet tube, and react with stirring in a mantle heater at a temperature of 120 ° C. in a nitrogen atmosphere at a temperature of 120 ° C. while refluxing toluene. (1) was obtained. Table 2 shows the results of the molecular weight measurement by GPC.

Release Agent Production Examples Table 3 shows the release agents used in the present invention.

(Wax A)
Normal paraffin wax: wax (A) (melting point: 74.3 ° C.) obtained by purifying a hydrocarbon synthesized by the Age method by a press sweating method was used.

(Wax B)
After dissolving and stirring benzene, a long-chain alkyl carboxylic acid component, a long-chain alkyl alcohol component, and p-toluenesulfonic acid, azeotropic distillation is performed. The product was sufficiently washed with sodium hydrogen carbonate, dried, recrystallized, washed and purified, and an ester wax: wax (B) (melting point: 72.7 ° C.) was used.

(Wax C)
Normal paraffin wax: wax (C) (melting point: 51.0 ° C.) obtained without sufficiently purifying hydrocarbons synthesized by the Age method was used.

(Wax D)
A polyethylene wax obtained by polymerizing at a low pressure with a Ziegler catalyst: wax (D) (melting point: 95.7 ° C) was used.

(Wax E)
An alcohol-modified polyethylene wax having a high melting point: wax (E) (melting point: 108.9 ° C.) was used.

[Example 1]
Hybrid resin A 100 parts by mass Phthalocyanine pigment (cyan colorant) 4 parts by mass Aluminum complex of di-tert-butylsalicylic acid (negative charge control agent)
3 parts by mass Wax A 4 parts by mass The above compound is sufficiently premixed by a Henschel mixer, melt-kneaded by a twin-screw extruder, cooled, coarsely ground to about 1 to 2 mm using a hammer mill, and then air-cooled. It was pulverized with a jet pulverizer. The obtained finely pulverized product was classified to obtain negatively triboelectrically non-magnetic cyan toner particles having a weight average particle diameter of 6.0 μm.

  100 parts by mass of the cyan toner particles, 1: 1.0 parts by mass of titanium compound-containing silica particles, and 0.5 parts by mass of hydrophobic alumina fine particles A were mixed with a Henschel mixer to obtain a nonmagnetic cyan toner. The obtained cyan toner has a weight average particle diameter of 6.0 μm (21.5 number% when the particle diameter is 4.0 μm or less, 48.1 number% when the particle diameter is 5.04 μm or less, and 6 when the particle diameter is 8.0 μm or more). 0.3% by volume, and 0.6% by volume for a particle size of 10.08 μm or more).

The above-mentioned cyan toner and a carrier obtained by coating Mn-Mg ferrite particles with a silicon resin (carrier particle size: 45 μm, resin coating amount: 0.6 parts by mass with respect to 100 parts by mass of carrier core particles) A two-component developer was prepared by mixing at a density of 6%, and an image was output using a color copier CLC-800 (manufactured by Canon, single color mode A4 size 28 sheets / min). At that time, the fixing unit of the color copying machine used was a modified fixing machine without an oil application mechanism, and the photosensitive drum used was a photosensitive drum having a surface roughness Rz of 1.3 μm whose surface layer was polished with a # 500 abrasive sheet. Was. Then, using an original document having an image area ratio of 25% under a high temperature and high humidity environment (35 ° C./90%), and using an original document having an image area ratio of 5% under a normal temperature and low humidity environment (23 ° C./5 %), The amount of applied toner per unit area was set to 0.6 mg / cm ^2, and a printing durability test of 10,000 sheets was performed in the monocolor mode.

  As a result, the change in image density was stable irrespective of the environment, a high-quality image with no missing lines was stably obtained, and the temperature range in which the image could be fixed was wide and good results were obtained.

  Table 4 shows the results of Examples and Comparative Examples.

[Example 2]
A printing durability test was performed in the same manner as in Example 1 except that the titanium compound-containing silica particles 2 were used.

[Example 3]
A printing durability test was performed in the same manner as in Example 1 except that the titanium compound-containing silica particles 3 were not used and hydrophobic alumina was not used.

[Example 4]
A printing durability test was performed in the same manner as in Example 1 except that the titanium compound-containing silica particles 4 were used.

[Example 5]
A printing durability test was performed in the same manner as in Example 1 except that the titanium compound-containing silica particles 5 were used.

[Example 6]
Except that the weight average particle diameter of the toner was 4.0 μm by changing the operating conditions in the fine pulverization by the air jet method in the toner production example and by changing the operating conditions when classifying the finely pulverized product. A printing durability test was performed in the same manner as in Example 1.

[Example 7]
Except that the weight average particle diameter of the toner is changed to 9.0 μm by changing the operating conditions in the fine pulverization by the air jet method in the toner production example and by changing the operating conditions in classifying the finely pulverized material. A printing durability test was performed in the same manner as in Example 1.

Example 8
C. instead of phthalocyanine pigment I. A printing durability test was performed in the same manner as in Example 1, except that 6 parts by mass of C.I. Pigment Red-155 (magenta colorant) was used and that the titanium compound-containing silica particles 6 were used.

[Example 9]
C. instead of phthalocyanine pigment I. A printing durability test was performed in the same manner as in Example 1, except that 8 parts by mass of CI Pigment Yellow-74 (yellow colorant) was used and the silica particles 7 containing the titanium compound were used.

[Example 10]
A printing durability test was performed in the same manner as in Example 1 except that carbon black was used instead of the phthalocyanine pigment and that silica particles 8 containing a titanium compound were used. Next, the output of a full-color image was examined using the four color toners used in Example 1 and Examples 8 to 10. It was possible to obtain a high-definition, high-quality image with excellent color mixing properties.

[Example 11]
Same as Example 1 except that the polyester resin 1 is used instead of the hybrid resin 1, the titanium compound-containing silica particles 9 are used, and the hydrophobic titanium oxide fine particles A are used instead of the hydrophobic alumina fine particles A. And a printing durability test was performed.

[Example 12]
A printing durability test was performed in the same manner as in Example 1, except that 80 parts by mass of the polyester resin 1 and 20 parts by mass of the vinyl resin 1 were used instead of the hybrid resin 1 and that the silica particles 10 containing the titanium compound were used. Was.

Example 13
A printing durability test was performed in the same manner as in Example 1 except that the vinyl resin 1 was used instead of the hybrid resin 1 and the silica particles 11 containing the titanium compound were used.

[Example 14]
A printing durability test was performed in the same manner as in Example 1, except that wax B was used instead of wax A and that silica particles 12 containing the titanium compound were used.

[Example 15]
A printing durability test was performed in the same manner as in Example 1 except that wax D was used instead of wax A and that silica particles 12 containing a titanium compound were used.

[Comparative Example 1]
A printing durability test was performed in the same manner as in Example 1 except that the titanium compound-containing silica particles 13 were used.

[Comparative Example 2]
A printing durability test was performed in the same manner as in Example 1 except that the titanium compound-containing silica particles 14 were used.

[Comparative Example 3]
A printing durability test was performed in the same manner as in Example 1 except that the titanium compound-containing silica particles 15 were used.

[Comparative Example 4]
A printing durability test was performed in the same manner as in Example 1 except that the titanium compound-containing silica particles 16 were used.

[Comparative Example 5]
A printing durability test was performed in the same manner as in Example 1, except that 0.8 parts by mass of silica fine particles A and 0.2 parts by mass of titanium oxide fine particles B were used instead of the titanium compound-containing silica particles 1.

[Comparative Example 6]
A printing durability test was performed in the same manner as in Example 1 except that the positive silica fine particles A were used instead of the titanium compound-containing silica particles 1.

[Comparative Example 7]
A printing durability test was performed in the same manner as in Example 1 except that wax E was used instead of wax A.

[Comparative Example 8]
A printing durability test was performed in the same manner as in Example 1 except that wax C was used instead of wax A.

Claims (13)

At least, in a toner having at least a binder resin, a toner particle having a colorant and a release agent and a silica particle,
An endothermic curve of the toner measured by a differential scanning calorimeter (DSC) shows that the maximum endothermic peak temperature in the temperature range of 30 to 200 ° C. is in the range of 60 to 100 ° C.
The silica particles contain a titanium element,
The silica particles satisfy the following formulas in X-ray diffraction: 0.7 ≦ (Ia ₁ / Ib ₁ ) ≦ 2.0 and 0.7 ≦ (Ia ₂ / Ib ₂ ) ≦ 2.0. Toner.
(Ia ₁ indicates the maximum intensity at 2θ = 25.3, Ib ₁ indicates the average intensity at 2θ = 25.3 ± 2.0 deg, Ia ₂ indicates the maximum intensity at 2θ = 27.5, Ib ₂ indicates the average value of the intensity at 2θ = 27.5 ± 2.0 deg.)   The silica particles are titanium compound-containing silica particles containing a titanium element, and contain 0.1 to 20 parts by mass of a titanium compound with respect to 100 parts by mass of the titanium compound-containing silica particles. The toner as described in the above.   The toner according to claim 1, wherein the silica particles are fired in a gas phase.   4. The toner according to claim 1, wherein the silica particles have been subjected to a hydrophobic treatment with at least a silazane compound.   The toner according to any one of claims 1 to 4, wherein the silica particles have an average particle diameter of 10 to 400 nm. The toner according to claim 1, wherein the silica particles have a BET of 5 to 300 m ² / g.   The toner according to any one of claims 1 to 6, wherein the silica particles are prepared by baking a mixture containing a main halogen-free siloxane and a volatile titanium compound.   The binder resin is (a) a polyester resin, (b) a hybrid resin having a polyester unit and a vinyl copolymer unit, or (c) a mixture of a polyester resin and a hybrid resin. The toner according to any one of claims 1 to 7, wherein:   9. The toner according to claim 1, wherein the binder resin is a hybrid resin containing a polyester unit.   The toner according to any one of claims 1 to 9, wherein the toner contains inorganic fine particles in addition to the silica.   11. The toner according to claim 1, wherein the toner has a weight average particle diameter of 3 to 9 [mu] m.   The toner according to claim 1, wherein the toner contains a negative charge control agent. The toner according to any one of claims 1 to 12, wherein the toner contains an aluminum complex of di-tert-butylsalicylic acid.