JP4594036B2 - Yellow toner and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve OHT transparency and to further improve fixing performance so as to attain compatibility with the transparency. <P>SOLUTION: In yellow toner containing at least a binder resin, a colorant and a wax, C.I. Pigment Yellow 74 and C.I. Solvent Yellow 162 are contained, and when a content of the C.I. Pigment Yellow 74 based on 100 parts by mass of the binder resin is represented by X (parts by mass) and a content of the C.I. Solvent Yellow 162 by Y (parts by mass), X is in the range of 1-10, Y is in the range of 0.5-8 and the sum of X and Y is in the range of 2-13, and lightness L<SP>*</SP>in the powder state satisfies L<SP>*</SP>&gt;83 and chromaticity b<SP>*</SP>satisfies 100&lt;b<SP>*</SP>&lt;120. <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

  The present invention relates to a yellow toner used in an image forming method such as an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and a toner jet method, and an image forming method for forming an image on a recording medium using the yellow toner. It is.

  In full-color copying machines and printers, cyan toner, magenta toner, yellow toner, black toner, etc. are used and developed by superimposing the toners of each color using the subtractive color mixing action, and each color toner image formed by development Is transferred onto a transfer material such as plain paper or overhead projector sheet (OHT), and the toner image superimposed on the transfer material is fixed on the transfer material to form a desired color image. ing.

  In recent electrophotography, miniaturization and energy saving have been increasingly demanded. Among them, by incorporating a release agent into the toner, it has contributed to downsizing of the apparatus by removing the oil application mechanism of the fixing device. In recent years, from the viewpoint of energy saving, a heat fixing method in which a heating member is brought into close contact with a heating body through a film can be cited as one effective means. In the heating method through a film, fixing is performed by allowing the toner image surface of a fixing sheet to pass through the surface of a film having a surface formed of a material having releasability with respect to toner while being in contact therewith. However, with this method, due to the kinking and durability of the film, it cannot be fixed by applying pressure as much as heat roller fixing. Furthermore, since the heat capacity of the fixing film is extremely smaller than that of the roller, the fixing temperature is greatly lowered when thick paper or the like is continuously fed. In particular, in a color image, the toner layer becomes thick in order to overlap the toner, and the overlapped toner layer must be melted and mixed. Therefore, it is required for the toner that the upper toner layer has transparency that does not interfere with the color of the lower toner layer when the toner is mixed, and that the toner layer is made thinner by increasing the coloring power. . Among the color toners, especially the yellow toner has a smaller coloring power than other colors, and it is necessary to increase the amount of the coloring agent to obtain the same coloring power as the other colors. It is necessary to improve.

  Many proposals have been made as colorants for yellow toner. Among them, monoazo yellow pigments are used because of their excellent reflection color and coloring power (see, for example, Patent Document 1). Furthermore, it has been proposed to use two types of pigments together (for example, see Patent Document 2). However, although pigment yellow 74, which is a monoazo pigment, is excellent in the color and coloring power of the reflected color, primary particles of the pigment tend to grow when dried or heated after synthesis. For this reason, in the conventional method, a fixing system having a light pressure and a small heat capacity is likely to have a problem in OHT transparency, so that it has not been sufficiently utilized for toner. Further, proposals have been made to improve the OHT transparency by increasing the coloring power by using a pigment and a dye together, and making the toner layer thinner (see, for example, Patent Documents 3 and 4). However, in the study by the present inventors, although the OHT transparency is improved by making the toner layer thinner, more heat than necessary is applied to the toner. Therefore, the fixability is deteriorated when the toner is excessively melted. In such a fixing method with a small heat capacity, it is difficult to achieve both transparency improvement and fixing property by thinning the toner layer by simply adding a large amount of colorant.

  Furthermore, as a method for improving the dispersibility of the colorant, it is necessary to reduce the average particle diameter of the colorant in the toner. When the average particle diameter of the colorant is large, the light transmittance of the obtained color image is poor, and it becomes difficult to obtain a desired color when forming the color image. In general, when a pigment is used, primary particles tend to aggregate when dried or heated after synthesis, and problems with transparency tend to occur. Based on this idea, for example, a method of preventing agglomeration by using the paste in a water-containing paste state without drying it, or a different raw material having a polar group introduced when the pigment is synthesized by a coupling reaction. A method for improving the transparency of a pigment by mixing a small amount has been proposed (see, for example, Patent Documents 5, 6 and 7). However, it is not possible to completely prevent the pigment from aggregating only by using the pigment in the paste state, and the method of mixing different raw materials into which polar groups are introduced improves the dispersion, but the color of the pigment itself is improved. There is a problem because will change.

Japanese Patent Laid-Open No. 2-136865 JP 2001-109197 A JP 2000-347459 A JP 2000-347458 A JP-A-6-161154 Japanese Patent Laid-Open No. 8-234489 JP 2000-63694 A

  In the present invention, the OHT transparency is insufficient in the prior art, particularly in a light pressure fixing system. Therefore, it is an object of the first invention to improve the OHT transparency.

  Furthermore, in the prior art, the compatibility between the transparency and the fixing property was insufficient. Therefore, it is an object of the second invention to improve the fixing performance and achieve the compatibility with the transparency.

  Furthermore, in the prior art, the dispersibility of the colorant was insufficient. Therefore, it is an object of the third invention to improve the dispersibility and to improve the chargeability and durability stability.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on the toner colorant and dispersibility and the viscoelasticity of the toner. As a result, excellent transparency and fixing can be achieved by using a specific colorant. It was possible to find a yellow toner and an image forming method that have sufficient color and coloring power, stable charging properties, and can sufficiently cope with simplification and downsizing of the configuration of the image forming apparatus.

That is, the present invention is as follows.
(1) In a yellow toner containing at least a binder resin, a colorant and a wax, C.I. I. Pigment Yellow 74 and C.I. I. Solvent Yellow 162, and C.I. with respect to 100 parts by mass of the binder resin. I. Pigment Yellow 74 is contained in an amount of X parts by mass, C.I. I. When the content of Solvent Yellow 162 is Y parts by mass, X is in the range of 1-10, Y is in the range of 0.5-8, and the sum of X and Y is in the range of 2-13. A yellow toner having a lightness L ^* in a powder state satisfying L ^* > 83 and a chromaticity b ^* satisfying 100 <b ^* <120.
(2) In the viscoelastic characteristics of the yellow toner, the storage elastic modulus (G′80) at a temperature of 160 ° C. in the range of the storage elastic modulus (G′80) at a temperature of 80 ° C. of 1 × 10 ⁵ to 1 × 10 ⁸ (Pa). (160) is in the range of 1 × 10 ¹ to 1 × 10 ⁴ (Pa), the yellow toner according to (1).
(3) In the viscoelastic property of the yellow toner, the ratio of the storage elastic modulus (G ′) to the loss elastic modulus (G ″) at a temperature of 120 to 150 ° C. (G ″ / G ′ = tan δ) is 0. The yellow toner according to (1) or (2), wherein the yellow toner is 5 to 5.
(4) A mixture containing at least the first binder resin, the colorant and water is heat-kneaded to obtain a colorant masterbatch which is the first kneaded product, and the second binder resin and the colorant masterbatch are obtained. (1) to (2) including a second melt-kneading step for melt-kneading at least the toner raw material mixture contained therein to obtain a second kneaded product, and a pulverizing step for pulverizing the second kneaded product. 3) One of the yellow toners.
(5) A first melt-kneading step of obtaining a water-containing colorant master batch by adjusting and removing the water content so that the water content is 2 to 25% by mass is provided (4) ) Yellow toner.
(6) A heating and fixing apparatus that sandwiches and conveys a heated member between the heating member and the pressure member. The heated member is a film, and the pressure member is pressed against the heated member via a recording material. In the image forming method of forming a fixed image on the recording material by heating and pressing and fixing the toner image on the recording material, a yellow toner containing at least a binder resin, a colorant and a wax is used as the toner. The toner is C.I. I. Pigment Yellow 74 and C.I. I. Solvent Yellow 162, and C.I. with respect to 100 parts by mass of the binder resin. I. Pigment Yellow 74 is contained in an amount of X parts by mass, C.I. I. When the content of Solvent Yellow 162 is Y parts by mass, X is in the range of 1-10, Y is in the range of 0.5-8, and the sum of X and Y is in the range of 2-13. An image forming method, wherein the lightness L ^* in the powder state satisfies L ^* > 83, and the chromaticity b ^* satisfies 100 <b ^* <120.

  According to the present invention, a color toner capable of stably forming an image satisfying high definition can be provided. More specifically, a yellow toner and an image forming method that have excellent transparency, fixing property, coloring power, stable charging property, and can sufficiently cope with simplification and downsizing of the configuration of the image forming apparatus. Can be provided.

  Hereinafter, the present invention will be described in detail.

  The yellow toner of the present invention contains at least a binder resin, a colorant and a wax. I. Pigment Yellow 74, C.I. I. Solvent Yellow 162.

  In the toner of the present invention, C.I. per 100 parts by mass of the binder resin contained in the toner. I. Pigment Yellow 74 is contained in an amount of X parts by mass, C.I. I. When the content of Solvent Yellow 162 is Y parts by mass, X is in the range of 1 to 10, Y is in the range of 0.5 to 8, and the sum of X and Y is in the range of 2 to 13. It is a feature.

Furthermore, the toner of the present invention is characterized in that the lightness L ^* in the powder state satisfies L ^* > 83, and the chromaticity b ^* satisfies 100 <b ^* <120.

  C. I. Pigment Yellow 74 and C.I. I. When both Solvent Yellow 162 are contained in the toner, C.I. I. Pigment Yellow 74 contained in the toner alone and good color tone and C.I. I. High coloring power of Solvent Yellow 162 is obtained.

In the powder state, by identifying a range of L ^* and b ^* of 83 <L ^* and 100 <b ^* <120, it is possible to obtain a yellow toner having coloring power and good transparency. The L ^* and b ^* represent colors in numerical form.

There is an L ^* a ^* b ^* color system in the color space. This L ^* a ^* b ^* color system is composed of lightness L ^* and a ^* and b ^* indicating chromaticity, where a ^* indicates the chromaticity in the red direction and b ^* indicates the chromaticity in the yellow direction. Important items regarding yellow toner are L ^* and b ^* . That is, in yellow toner, L ^* is a parameter related to transparency, and b ^* can be used as a parameter related to coloring power.

If 83 ≧ L ^* , the transparency is insufficient, so that the color mixing when colors are superimposed is inferior and the color reproduction range is narrowed. If it is too high such as b ^* ≧ 120, the coloring power is high, and in order to obtain a constant density, the yellow toner layer becomes thin, so the balance of the color mixture with other color toners becomes worse and color unevenness occurs. Will occur. On the other hand, if b ^* ≦ 100, the tinting strength is too low, and in order to obtain a constant density, it is necessary to make the toner layer thick, and the transparency of the image deteriorates.

In order to further exhibit the effects of the present invention, the lightness L * is preferably 85 <L ^* , more preferably 87 <L ^* , and the chromaticity b ^* is preferably 103 <b ^* <120, more Preferably 106 <b ^* <120.

  When X is less than 1, Y is less than 0.5, or the sum of X and Y is less than 2, the coloring power is insufficient, so it is necessary to increase the amount of toner on the transfer paper in order to obtain the density. In a light pressure fixing device, fixing failure may occur. When X is greater than 10, Y is greater than 8, or X + Y is greater than 15, there may be a case where an image having a clear color tone and transparency is not obtained even if the image density is sufficient.

  More preferably, X is in the range of 2-9, Y is in the range of 0.5-6, and the sum of X and Y is in the range of 3-12. More preferably, X is in the range of 3-8, Y is in the range of 0.5-4, and the sum of X and Y is in the range of 5-12.

  By satisfying the above items, a high-definition image can be obtained even in a fixing system with a light pressure and a small heat capacity, and further excellent transparency can be obtained. The reason is not clear, but C.I. I. Pigment Yellow 74 and C.I. I. Since Solvent Yellow 162 coexists, even when heated during kneading, these pigments inhibit each other's crystal growth, and the dispersion of pigment particles is highly maintained. As a result, the present inventors believe that a yellow toner having high coloring power, clear color and good color mixing properties, and excellent transparency can be obtained.

  C. I. When Pigment Yellow 74 is used alone, the pigment crystal grows easily due to the heating during dispersion when it is converted into a toner, the pigment particle diameter is enlarged, and agglomerates are easily formed, and the color and transparency are deteriorated. C. I. When Solvent Yellow 162 is used alone, the light resistance deteriorates.

  The toner of the present invention includes C.I. I. Pigment Yellow 74 and C.I. I. Yellow colorants other than Solvent Yellow 162 can be included. Examples of yellow colorants that can be used include various compounds such as condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and compounds represented by allylamide compounds. Specifically, C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 15, C.I. I. Pigment Yellow 17, C.I. I. Pigment Yellow 62, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 94, C.I. I. Pigment Yellow 95, C.I. I. Pigment Yellow 97, C.I. I. Pigment Yellow 109, C.I. I. Pigment Yellow 110, C.I. I. Pigment Yellow 111, C.I. I. Pigment Yellow 120, C.I. I. Pigment Yellow 127, C.I. I. Pigment Yellow 128, C.I. I. Pigment Yellow 129, C.I. I. Pigment Yellow 147, C.I. I. Pigment Yellow 151, C.I. I. Pigment Yellow 154, C.I. I. Pigment Yellow 154, C.I. I. Pigment Yellow 168, C.I. I. Pigment Yellow 174, C.I. I. Pigment Yellow 175, C.I. I. Pigment Yellow 176, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 181, C.I. I. Pigment Yellow 191, C.I. I. Pigment Yellow 194, C.I. I. Vat Yellow 1, 3, 20, Mineral Fast Yellow, Navel Yellow, Naphthol Yellow S, Hansa Yellow G, Permanent Yellow NCG, C.I. I. Solvent Yellow 9, C.I. I. Solvent Yellow 17, C.I. I. Solvent Yellow 24, C.I. I. Solvent Yellow 31, C.I. I. Solvent Yellow 35, C.I. I. Solvent Yellow 58, C.I. I. Solvent Yellow 93, C.I. I. Solvent Yellow 100, C.I. I. Solvent Yellow 102, C.I. I. Solvent Yellow 103, C.I. I. Solvent Yellow 105, C.I. I. Solvent Yellow 112, C.I. I. Solvent Yellow 163 etc. can be used suitably.

In the yellow toner of the present invention, the storage elastic modulus (G′160) at a temperature of 160 ° C. is in the range of the storage elastic modulus (G′80) at a temperature of 80 ° C. of 1 × 10 ⁵ to 1 × 10 ⁸ (Pa). Is preferably in the range of 1 × 10 ¹ to 1 × 10 ⁴ (Pa). According to the present inventors, in addition to the interaction between the pigments described above, the color dispersion in which the pigment dispersion in the toner is optimally controlled by controlling the interaction between the pigment and the binder resin, and color mixing is necessary. Even if the toner layer is thinned, it is possible to obtain a fixing performance that can be applied to a good light pressure fixing system corresponding to various materials.

When (G′80) is smaller than 1 × 10 ⁵ (Pa), the high-temperature offset resistance deteriorates and fixing unevenness occurs. When (G′80) is larger than 1 × 10 ⁸ (Pa), the low-temperature fixability and the color mixing property deteriorate. When (G′160) is smaller than 1 × 10 ¹ (Pa), the high temperature offset resistance is insufficient and fixing unevenness occurs. When (G′160) is greater than 1 × 10 ⁴ (Pa), low-temperature fixability and color mixing are achieved.

  The storage elastic modulus G ′ is an index representing elasticity in a polymer, that is, a reversible property with respect to stress. In the fixing scene, when the toner passes through the fixing roller, heat and pressure are applied to the toner, and this represents the force to restore the original state when the toner is deformed. In other words, it indicates whether the molecule forming the toner has a spring-like property. In particular, in a fixing method using a film, since the heat capacity is small and pressure during fixing may not be applied, unevenness in the amount of heat at the time of fusing and fixing the toner tends to occur. However, by regulating the elasticity at the temperature at which the toner becomes a rubber region (80 ° C.) and the elasticity at the temperature at which the toner becomes a flow region (160 ° C.), the effect of suppressing image unevenness during fixing is exhibited.

Further, the storage elastic modulus (G′80) at a temperature of 80 ° C. is in the range of 1 × 10 ⁵ to 1 × 10 ⁷ (Pa), and the storage elastic modulus (G′160) at a temperature of 160 ° C. is 1 × 10 ² to 1 A range of × 10 ⁴ (Pa) is more preferable.

  Further, it is preferable that the ratio of the storage elastic modulus (G ′) and the loss elastic modulus (G ″) at a temperature of 120 to 150 ° C. (G ″ / G ′ = tan δ) is 0.5 to 5. Fixability and toner storage stability can be obtained. The loss elastic modulus G ″ is an index representing the irreversible property with respect to the viscosity, ie, stress, in the polymer, and represents the ease of deformation with respect to the pressure when passing through the fixing roller in the fixing scene. Therefore, the ratio of loss elastic modulus to storage elastic modulus (G ″ / G ′ = tan δ) defined in the present invention is an index representing the balance between the two, and tan δ at a temperature of 120 to 150 ° C. is smaller than 0.5. In this case, since the toner is difficult to be thermally deformed, the fixing method using a film impairs the fixing property on the high temperature side. Further, when tan δ at a temperature of 120 to 150 ° C. is greater than 5, the storage stability of the toner is deteriorated and fixing unevenness may occur.

  The ratio of the storage elastic modulus (G ′) to the loss elastic modulus (G ″) at a temperature of 120 to 150 ° C. (G ″ / G ′ = tan δ) is 1 to 4 in consideration of fixing properties. And more preferred.

  As a method for producing the yellow toner of the present invention, a mixture containing at least a first binder resin, a colorant and water is heat-kneaded to obtain a colorant masterbatch which is a first kneaded product, and a second binder is obtained. A toner raw material mixture containing at least a resin and the colorant master batch is melt-kneaded to obtain a second melt-kneaded product, and a pulverizing step of pulverizing the second kneaded product. preferable.

  According to the study by the present inventors, the pigment in the toner is in an optimal state, and superior developability is manifested by stabilizing the chargeability of the toner compared to the conventionally known yellow toner. Further, the fogging of the image background portion, which is likely to occur due to non-uniform charging, is very small, and the image density becomes stable even when a large number of images are output in a low temperature and low humidity environment.

  As described above, by the method of making a colorant master batch as an intermediate of toner, C.I. I. Pigment Yellow 74 and C.I. I. Dispersibility with Solvent Yellow 162 can be more reliably performed. Accordingly, it is considered that the colorant crystals can be prevented from being enlarged in the toner, and the durability stability of the toner can be obtained by minimizing the influence of the colorant on the chargeability of the toner. As a specific method of making this colorant master batch, after flushing treatment, that is, after colorant synthesis, it is heated and mixed with resin in a water-containing state (paste colorant) without powdering, and then dried pelletized, or powder coloring Although it is possible to improve the dispersibility of the colorant by heating and mixing the agent, water, and resin, and then drying the pellet, the present invention is not limited to these methods.

  More preferably, the colorant masterbatch that is the first kneaded product is adjusted and removed so that the water content is 2 to 25% by mass to obtain a water content colorant masterbatch (hereinafter referred to as “water content MB”). The method is good. Preferably it is 3-20 mass%, More preferably, it is 5-18 mass%.

  In the first melt-kneading process, for example, the method for producing the water-containing MB is obtained as follows. A mixture containing at least a first binder resin, a colorant and water is charged into a kneader or a mixer, heated and kneaded while mixing under non-pressure or under pressure, and the first binder resin is melted and heated. The first binder resin, that is, the molten resin phase is distributed or transferred to obtain a first kneaded product, the phase-separated water is removed by decantation, and the first binder resin and the colorant are further removed. A colorant master batch is obtained by melt-kneading and evaporating and removing moisture. In addition, about the removal method of the water | moisture content from the 1st kneaded material, although the method by the decantation and the evaporation removal of a water | moisture content was illustrated above, this invention is not limited to it.

  The water-containing MB is obtained, for example, by the above-described manufacturing method. Unlike the conventional colorant master batch, the water-containing MB is not removed more than necessary, and the water-containing MB has a water content of 2 to 25% by mass. The colorant can be uniformly and finely dispersed therein. The reason for this is not clear, but is estimated as follows.

  First, in the step of melt-kneading the toner raw material mixture containing at least the second binder resin and the water-containing MB to obtain the second kneaded product (second melt-kneading step), a large amount of moisture is contained in the water-containing MB. Therefore, the presence of water between the colorant particles prevents aggregation of the colorant particles. Furthermore, the water that permeates the aggregates of the colorant particles that are partly present expands due to the heat in the second kneading and kneading step, breaks the aggregates, and makes a good dispersion.

  Secondly, the second kneaded material becomes high in temperature when the toner raw material mixture has a strong share during the second melt-kneading and the water-containing MB self-heats, and if necessary, is heated from the outside. However, when water evaporates, heat is removed as heat of vaporization, so that strong adhesion / aggregation due to heat between the colorant particles can be prevented.

  Third, water vapor is generated during the second melt-kneading and the second kneaded product expands, increasing the pressure in the kneader to increase the shear, generating a stronger shearing force, It is very effective for dispersing all components contained in the kneaded material including the colorant particles.

  In the present invention, when the water content of the water-containing MB exceeds 25% by mass, the water content is too much, so the adhesive force of the water-containing MB is too strong, and it is fused to a manufacturing apparatus such as a Henschel mixer or the fluidity is reduced. Large aggregates may be generated in the toner raw material mixture, which is not preferable. In addition, when the water content is less than 2% by mass, the minute amount of water remaining in the master batch is removed, and in the heating / drying step under normal pressure or reduced pressure, the dispersed colorant particles are strongly aggregated. In some cases, it may be difficult to disperse the colorant well again in the subsequent kneading step of toner production. As a result, the colorant is difficult to uniformly disperse, resulting in poor dispersion, and good color uniformity and charging uniformity may not be obtained.

  In addition, as a state of the colorant in the present invention, a paste colorant containing moisture in which the colorant particles are not subjected to a drying process in the colorant particle production process may be used. That is, in the case of a paste-like colorant, since heat is not applied in the drying process after the colorant is produced, crystal growth of the colorant is suppressed. Therefore, it is preferable because the colorant exists in the state of primary particles.

  The yellow toner of the present invention contains at least a binder resin.

  The binder resin contained in the yellow toner of the present invention is not particularly limited as it is a conventional resin that has been conventionally used in toners. However, a hybrid resin having a polyester unit and a vinyl copolymer unit, or a polyester resin. Or more preferably a mixture of a vinyl copolymer and these resins, and 50% by mass or more, more preferably 70% by mass or more of the total binder resin is a resin having a polyester unit. Further preferred. By making the resin having the polyester unit 50% by mass or more of the total binder resin, high coloring power, clear color and good color mixing property, and excellent transparency can be expressed more remarkably, and further better Improvements in pigment dispersibility, wax dispersibility, low-temperature fixability, and high-temperature offset resistance can be expected.

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

  In the present invention, “hybrid resin” means a resin in which a vinyl copolymer unit and a polyester unit are chemically bonded. Specifically, for example, a vinyl copolymer unit obtained by polymerizing a monomer having a carboxylic ester group such as (meth) acrylic acid ester and a polyester unit are formed by a transesterification reaction. A graft copolymer (or block copolymer) in which the copolymer is a trunk polymer and the polyester unit is a branch polymer is formed.

  When a hybrid resin having a polyester resin or a polyester unit is used as the binder resin contained in the yellow toner of the present invention, a polyhydric alcohol and a polyester monomer for producing a polyester unit of the polyester resin or the hybrid resin are used. A polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, a polyvalent 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 -Bisphenol A alkylene oxide adducts such as bis (4-hydroxyphenyl) propane and 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 Neopentyl 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 trihydric or higher alcohol components 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 divalent carboxylic acid component include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof; alkyldicarboxylic acids such as succinic acid, dodecenyl succinic acid, adipic acid, sebacic acid and azelaic acid, or anhydrides thereof. And succinic acid substituted with an alkyl group having 6 to 12 carbon atoms or an anhydride thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, and citraconic acid, or anhydrides thereof.

  Examples of the trivalent or higher carboxylic acid component include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 2,5,7- Naphthalenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, and anhydrides and ester compounds thereof are mentioned. The amount of the trivalent or higher polyvalent carboxylic acid component is preferably 0.1 to 1.9 mol% based on the total monomer.

  Among the above, in particular, a bisphenol derivative represented by the following general formula (1) as a diol component, a carboxylic acid component (for example, a divalent or higher carboxylic acid or acid anhydride thereof, or a lower alkyl ester thereof) , Fumaric acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.) as an acid component, and polyester resins obtained by condensation polymerization of these are particularly preferable. The polyester resin having this composition has good charging characteristics.

  When a vinyl resin or a hybrid resin having a vinyl copolymer unit is used as the binder resin contained in the toner of the present invention, a vinyl copolymer or a vinyl copolymer unit of the hybrid resin is generated. The following can be used as the vinyl monomer for the purpose. 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 its derivatives 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, vinylidene chloride, vinyl bromide, vinyl Vinyl halides such as vinyl halide; 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, acrylic acid Ethyl, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, acrylic acid 2 Acrylic esters such as chloroethyl 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-vinylcarbazole, N-vinylindole and N-vinylpyrrolidone; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.

  Further, 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, Unsaturated dibasic acid half esters such as alkenyl succinic acid methyl half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester; dimethyl maleic acid, dimethyl fumaric acid and the like; 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.

  When a hybrid resin having a vinyl copolymer or a vinyl copolymer unit is used as the binder resin to be included in the yellow toner of the present invention, these resins are crosslinked with a crosslinking agent having two or more vinyl groups. It may be what was done. The following are mentioned as a crosslinking agent used in this case. 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 acrylates of the above compounds replaced with methacrylate; linked by alkyl chains containing ether linkages. Examples of the diacrylate compounds include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, and polyethylene glycol # 400 diacrylate. Acrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate and those in which the acrylate of the above compound is replaced by methacrylate; examples of diacrylate compounds linked by a chain containing an aromatic group and an ether bond , Polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate and acrylates of the above compounds Is replaced with methacrylate. Other polyfunctional crosslinking agents include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds replaced with methacrylate; Examples include allyl cyanurate and triallyl trimellitate.

  When a binder resin containing a vinyl copolymer unit or a polyester unit is contained in the toner of the present invention, the vinyl copolymer unit or the polyester unit contains a monomer component that can react with both resin components. It is preferable to include. Examples of the monomer constituting the polyester unit that can react with the vinyl copolymer unit include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Among the monomers constituting the vinyl copolymer unit, those capable of reacting with the polyester unit include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

  As a method for obtaining a reaction product of a vinyl copolymer unit and a polyester unit, a polymer containing a monomer component capable of reacting with each of the vinyl copolymer unit and the polyester unit described above exists. A method obtained by polymerizing one or both of the resins is preferred.

  Examples of radical polymerization initiators used for producing a vinyl resin or a hybrid resin having a vinyl copolymer unit include 2,2′-azobisisobutyronitrile and 2,2′-azobis. (4-methoxy-2,4-dimethylvaleronitrile), 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 Ketone peroxides such as oxide, acetylacetone peroxide, cyclohexanone peroxide, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3- Tetramethylbutyl hydroperoxide, 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-methoxy Butyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxyneodecanoate, t-butylperoxy-2-ethylhexanoate, t-butyl peroxylaurate, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, di-t-butyl peroxyisophthalate, t-butyl peroxyallyl carbonate, t-amyl peroxy 2 Ethylhexanoate, di -t- butyl peroxy hexahydro terephthalate, di -t- butyl peroxy azelate and the like.

  Examples of the method for producing a hybrid resin that can be contained in the yellow toner of the present invention include the following production methods (1) to (6).

  (1) A method in which a vinyl copolymer, a polyester resin and a hybrid resin component are blended after production, and the blend is produced by dissolving and swelling in an organic solvent (for example, xylene) and then distilling the organic solvent. . The hybrid resin component is prepared by separately producing a vinyl copolymer 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. Synthesized ester compounds can be used.

  (2) A method of producing a polyester unit and a hybrid resin component in the presence of a vinyl copolymer unit in the presence of the vinyl copolymer unit. The hybrid resin component is produced by a reaction between a vinyl copolymer 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 of producing a vinyl copolymer unit and a hybrid resin component in the presence of the polyester unit after the production thereof. 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 copolymer unit.

  (4) After producing the vinyl copolymer unit and the polyester unit, a 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, a vinyl monomer unit and / or a polyester monomer (alcohol, carboxylic acid) are added to perform addition polymerization and / or polycondensation reaction, whereby a vinyl copolymer unit and a polyester unit are obtained. Manufactured. 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 copolymer 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 an addition polymerization and a condensation polymerization reaction. . Furthermore, an organic solvent can be used as appropriate.

  In the production methods of (1) to (6) above, a vinyl copolymer unit and / or a polyester unit can use a plurality of polymer units having different molecular weights and cross-linking degrees.

  The yellow toner of the present invention preferably has a peak molecular weight (Mp) of the resin component contained in the toner in the range of 4000 to 20000 in the molecular weight distribution in gel permeation chromatography (GPC) measurement, and the weight average molecular weight The ratio (Mw / Mn) between (Mw) and the number average molecular weight (Mn) is preferably 100 or more. If the peak molecular weight of the resin component contained in the toner is less than 4000, there will be problems in storage stability of the toner, high temperature offset resistance will be insufficient, and fusion and filming to the photoreceptor will occur. May be easier to do. On the other hand, when the peak molecular weight exceeds 20000, the low-temperature fixability may be insufficient, the image gloss may be too low, or a problem may occur in color mixing. Moreover, when Mw / Mn is less than 100, a problem may occur in high temperature offset resistance.

  The yellow toner of the present invention contains at least a wax.

  Examples of the wax that can be contained in the yellow toner of the present invention include the following. Oxides of aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight olefin copolymer wax, microcrystalline wax, Fischer-Tropsch wax and paraffin wax, and aliphatic hydrocarbon waxes such as oxidized polyethylene wax Or block copolymers thereof; waxes mainly composed of fatty acid esters such as carnauba wax and montanic acid ester wax; esters that are a synthetic reaction product of higher fatty acids such as behenyl behenate and behenyl stearate and higher alcohols Examples thereof include waxes and fatty acid esters such as deoxidized carnauba wax which are partially or fully deoxidized.

  In addition, saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and valinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, and seryl alcohol , Saturated alcohols such as melyl alcohol; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bis stearic acid amide, ethylene biscapric acid amide, ethylene bis laurin Saturated fatty acid bisamides such as acid amides and hexamethylene bis stearic acid amides; ethylene bis oleic acid amides, hexamethylene bis oleic acid amides, N, N ′ dioleyl adipic acid amides, N, N ′ diacids Unsaturated fatty acid amides such as rail sebacic acid amides; Aromatic bisamides such as m-xylene bisstearic acid amide and N, N ′ distearyl isophthalic acid amides; Calcium stearate, calcium laurate, zinc stearate, magnesium stearate Aliphatic metal salts such as those commonly referred to as metal soaps; waxes grafted with aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; fatty acids such as behenic acid monoglycerides and the like Examples include partially esterified products of polyhydric alcohols; methyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable oils and the like.

  In the present invention, the wax preferably used includes aliphatic hydrocarbon waxes, more preferably low molecular weight polyethylene wax, Fischer-Tropsch wax, paraffin wax, and particularly preferably paraffin wax. When aliphatic hydrocarbon waxes are used, it is easy to optimize the dispersion state of the wax and not only has excellent low-temperature fixability, but also exhibits high coloring power, clear color and color mixing properties, developability, transferability and durability. It is easy to obtain a toner having an excellent balance of various properties such as properties.

  In order to achieve excellent low-temperature fixability, high coloring power, clear color and color mixing, and excellent environmental stability and durability, in the endothermic curve in the differential thermal analysis (DSC) measurement of the wax, The peak temperature of the maximum endothermic peak is preferably in the range of 50 to 105 ° C, more preferably in the range of 60 to 90 ° C. When the temperature is lower than 50 ° C., for example, the storage stability of the toner may be inferior, and when the temperature exceeds 105 ° C., it may be difficult to perform low-temperature fixing desired from the viewpoint of energy saving.

  The wax is used in an amount of 1 to 10 parts by weight, preferably 2 to 7 parts by weight, per 100 parts by weight of the binder resin. When the amount is less than 1 part by mass, there is no effect on the low-temperature fixability, and when it exceeds 10 parts by mass, there may be a problem in storage stability and developability of the toner.

  The yellow toner of the present invention has one or a plurality of endothermic peaks in the temperature range of 30 to 200 ° C. in the endothermic curve in differential thermal analysis (DSC) measurement, and the peak temperature of the maximum endothermic peak in the endothermic peak is It is preferably in the range of 50 to 105 ° C, particularly preferably in the range of 60 to 90 ° C. If the peak temperature of the maximum endothermic peak is within this range, the balance between excellent low-temperature fixability and developability will be good. When the peak temperature of the maximum endothermic peak is less than 50 ° C., the storage stability of the toner may be inferior, and when it exceeds 105 ° C., it may be difficult to perform low-temperature fixing desired from the viewpoint of energy saving. The peak temperature of the maximum endothermic peak can be set to 50 to 105 ° C. by adding the wax having the maximum endothermic peak peak temperature of 50 to 105 ° C. described above to the toner.

Further, the yellow toner of the present invention may further contain an organometallic compound. The inclusion of an organometallic compound is more preferable in that the charge level can be adjusted, the rising of charge can be improved, and the thermal melting characteristics of the toner can be improved. The organometallic compound contained in the yellow toner of the present invention is preferably an aromatic carboxylic acid derivative selected from an aromatic oxycarboxylic acid and an aromatic alkoxycarboxylic acid, a metal compound of the aromatic carboxylic acid derivative, The metal is preferably a divalent or higher valent metal. An aromatic carboxylic acid metal compound is prepared by, for example, dropping an aqueous solution in which a divalent or higher-valent metal ion is dissolved into an aqueous sodium hydroxide solution in which an aromatic carboxylic acid is dissolved, heating and stirring, and then adjusting the pH of the aqueous solution. Although it can synthesize | combine by adjusting and cooling to normal temperature and washing with filtered water, it is not limited only to said synthesis | combining method. Examples of the divalent metal include Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Zn ²⁺ and Cu ²⁺ . Of these, Ca ²⁺ , Mg ²⁺ and Sr ²⁺ are preferred. Examples of the trivalent or higher metal include Al ³⁺ , Cr ³⁺ , Fe ³⁺ , Ni ³⁺ and Zr ⁴⁺ . Among these trivalent or higher metals, Al ³⁺ , Cr ³⁺ and Zr ⁴⁺ are preferable, and Al ³⁺ and Zr ⁴⁺ are particularly preferable.

  When the yellow toner of the present invention contains an organometallic compound, the organometallic compound is preferably contained in an amount of 0.1 to 5 parts by mass per 100 parts by mass of the binder resin. Therefore, it is easy to obtain an absolute charge amount necessary for development, and the heat melting characteristics of the toner can be improved.

The yellow toner of the present invention preferably has a fluidity improver added externally (hereinafter referred to as external addition). Here, the fluidity improver has a function of increasing fluidity by being externally added to the toner particles, and is added from the viewpoint of improving the image quality. For example, fluorine resin powder such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; silica fine powder such as silica fine powder by wet process, silica fine powder by dry process, silica fine powder such as silane compound, titanium cup A treated silica fine powder subjected to a surface treatment with a treating agent such as a ring agent or silicone oil; a titanium oxide fine powder; an alumina fine powder, a treated titanium oxide fine powder, or a treated alumina oxide fine powder is used. Such a fluidity improver gives a good result when the specific surface area by nitrogen adsorption measured by the BET method is 30 m ² / g or more, preferably 50 m ² / g or more.

  The fluidity improver is used in an amount of 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the toner particles.

  Next, a method for producing the yellow toner of the present invention will be described.

  The yellow toner of the present invention obtains a second kneaded material by melting and kneading the raw materials mixed in the raw material mixing step of mixing toner raw materials (internal additives), and dispersing the colorant and the like. Preferably manufactured by a manufacturing method including a second melt-kneading step, a cooling step for cooling the obtained second kneaded product, and a pulverizing step for pulverizing the cooled second kneaded product to a predetermined particle size. it can.

  First, in the raw material mixing step, a predetermined amount of a toner internal additive containing at least a binder resin, a colorant, and a wax is weighed, mixed, 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, by melting and kneading the toner raw materials mixed in the raw material mixing step, the resins are melted, and the colorant master batch and the like are dispersed therein. In the second 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. At this time, as described above, in order to suppress the particle growth of the colorant and to improve the dispersion state of the colorant in the toner, the second kneading resin temperature Tmix is set to [softening point temperature of the binder resin]. Tm + 20 ° C.] or less is preferable. By controlling the temperature of the second kneading resin as described above, a minimum amount of heat necessary for dispersing the colorant can be added, and crystal growth of the colorant can be suppressed. Furthermore, the second kneaded product obtained by melt-kneading the toner raw material is rolled by a two-roll roll after the second melt-kneading and cooled through a cooling step of cooling by water cooling or the like.

  Next, the second kneaded product obtained in the cooling step is generally pulverized to a desired particle size in the pulverization step. In the pulverization step, first, coarse pulverization is performed by a crusher, a hammer mill, a feather mill or the like, and further pulverization is performed by a kryptron system manufactured by Kawasaki Heavy Industries, Ltd., a super rotor manufactured by Nissin 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 Gives a classified product of 3 to 11 μm. When the weight average particle size is less than 3 μm, for example, the adhesion force to the surface of the photosensitive drum is increased, which tends to cause uneven image unevenness due to transfer defects. Further, the charge amount per unit mass of the toner becomes high, and the image density may be lowered in a low temperature and low humidity environment, for example. Furthermore, due to a decrease in fluidity and an increase in adhesion to a member, for example, frictional charging with a carrier is difficult to be performed smoothly, toner that cannot be sufficiently charged increases, and fogging of non-image areas becomes conspicuous. . On the other hand, if the weight average particle size exceeds 11 μm, it means that there are few fine particles that can contribute to high image quality, and there is a merit that the fluidity of the toner is excellent, but on the fine electrostatic charge image on the photosensitive drum. It may be difficult to adhere faithfully, the reproducibility of the highlight portion may be lowered, and the gradation may be further lowered. In addition, fusion to a member such as the surface of the photosensitive drum is likely to occur. At this time, if necessary, a classified product may be obtained by performing a surface modification, that is, a spheronization treatment in a surface modification step. Examples of the apparatus used for such surface modification include a hybridization system manufactured by Nara Machinery Co., Ltd. and a mechano-fusion system manufactured by Hosokawa Micron Corporation. Further, if necessary, a sieving machine such as a wind-type sieve high voltor (manufactured by Shin Tokyo Machine Co., Ltd.) may be used.

  The obtained pulverized product or classified product, that is, toner particles, is mixed with a known external additive as necessary to obtain the yellow toner of the present invention. As a method for externally adding the external additive to the toner particles, a predetermined amount of an external additive such as silica or titanium oxide is blended into the pulverized or classified toner particles, and a powder such as a Henschel mixer or a super mixer is used. A toner can be obtained by stirring and mixing using a high-speed stirrer that gives a shearing force as an external additive.

  The toner of the present invention can be used as a one-component developer or a two-component developer. However, when used as a two-component developer, a clear full-color image can be easily obtained over a long period of time, which is preferable.

  When the toner of the present invention is used as a two-component developer, the toner of the present invention and a magnetic carrier may be mixed to form a two-component developer. As the carrier, for example, surface-oxidized or non-oxidized iron, nickel, copper, zinc, cobalt, manganese, chromium, calcium, magnesium, rare earth and other metals and their alloys or oxides and magnetic ferrite can be used.

  Moreover, the resin coat carrier which coat | covered the surface of the said carrier with resin etc. is used suitably in this invention. As a method for producing a resin-coated carrier, a conventionally known method can be adopted and is not particularly limited.For example, a method of forming a coat film on the surface of a carrier by spraying a resin solution while causing the carrier to float and flow, Examples include a spray drying method, a method in which a coating material such as resin is dissolved or suspended in a solvent and mixed with a carrier, and the solvent is gradually volatilized while applying a shear stress, or a method in which powder and a carrier are simply mixed. .

  Examples of carrier coating materials include resins with low surface energy, such as silicone resins and fluororesins, which are considered useful for preventing toner fusion and the like from being spent on the carrier. Resins, acrylic resins, polyamides, polyvinyl butyral, amino acrylate resins and the like are exemplified, and these are used alone or in combination.

  Moreover, in order to improve the adhesiveness with respect to a carrier, it is preferable to use various additives together and to improve the toughness of a film. In particular, when coating a silicone resin, the durability and charging characteristics of the resulting coated carrier are further improved by adding water to the coating resin dilution solvent to be used. This is because the crosslinking point of the curable silicone resin and the hydrolysis of the silane coupling agent are accelerated, the curing reaction proceeds further, and the surface energy of the silicone resin increases for a short time, and the adhesion to the carrier. This is due to the improvement.

  The coating amount of the coating resin with respect to the carrier is such that the resin solid content is 0.05 mass% to 10 mass%, preferably 0.1 mass% to 5 mass%.

  Moreover, it is preferable that the volume average diameter of a carrier has 25-80 micrometers, More preferably, it has 30-65 micrometers. The measurement can be performed using a SRA type of a Microtrac particle size analyzer (Nikkiso Co., Ltd.) with a range setting of 0.7 to 125 μm. When the weight average diameter of the carrier is smaller than 25 μm, mixing with the toner becomes difficult. On the other hand, when the weight average diameter exceeds 80 μm, the specific surface area of the carrier is small, so that the charging ability at the time of toner replenishment is inferior, which may cause fogging and toner scattering.

  When the two-component developer is prepared by mixing the toner of the present invention and the carrier of the above-mentioned form, the mixing ratio is 2 to 15% by mass, preferably 4 to 13% by mass, as the toner concentration in the developer. Then usually good results are obtained. If the toner concentration is less than 2% by mass, the image density tends to decrease. If the toner concentration exceeds 15% by mass, fogging or in-machine scattering tends to occur, and the useful life of the developer tends to decrease.

  The yellow toner of the present invention can be used in a conventionally known image forming apparatus such as an electrophotographic apparatus, and is not particularly limited. However, a heating fixing apparatus that sandwiches and conveys a heated member between a heating member and a pressure member. The heated member is a film, and the toner image on the recording material is heated and pressed and fixed while the pressing member is pressed against the heated member via the recording material, and the fixed image is formed on the recording material. It is preferably formed using the yellow toner of the present invention.

  More preferably, the member to be heated has a release layer and an elastic layer in consideration of uneven gloss and durability.

  For the release layer, a material having good release properties and heat resistance such as fluororesin, silicone resin, fluorosilicone rubber, fluororubber, silicone rubber, PFA, PTFE, and FEP can be selected. The thickness of the release layer is preferably 1 to 100 μm. When the thickness of the release layer is less than 1 μm, there arises a problem that a part having poor releasability is formed due to coating unevenness of the coating film or durability is insufficient. Moreover, when a release layer exceeds 100 micrometers, the problem that heat conduction deteriorates generate | occur | produces.

  The elastic layer 2 is a material having good heat resistance and good thermal conductivity, such as silicone rubber, fluorine rubber, fluorosilicone rubber, and the like.

  Further, the thickness of the elastic layer is preferably 10 to 500 μm in order to prevent uneven glossiness due to the fact that the heating surface (release layer) cannot follow the unevenness of the recording material or the unevenness of the toner layer when printing an image.

  Further, since the yellow toner of the present invention is a color toner, it can be suitably used in a full-color image forming apparatus together with magenta, cyan, and, if necessary, black toner. Here, the full-color image forming apparatus has a unit including a latent image carrier, a charging unit, a latent image forming unit, and a developing unit for each color toner, and a toner image of each color is placed on each color latent image carrier. A so-called tandem system may be used in which a full-color image is obtained by forming the image and transferring and fixing the image on a transfer material. In addition, using a plurality of developing means corresponding to the number of toners used for one latent image carrier, toner images of each color are created on the latent image carrier, and these images are sequentially superimposed on the intermediate transfer member and transferred. In addition, a full color image may be obtained by transferring the toner image transferred onto the intermediate transfer member onto a transfer material. Needless to say, the toner may be used together with toners of colors other than those described above.

  Hereinafter, various physical property measuring methods used in the present invention will be described.

<Measurement of weight average particle size and particle size distribution of toner>
The weight average particle size and particle size distribution of the color toner can be measured by various methods such as Coulter Counter TA-II type or Coulter Multisizer (manufactured by Coulter). In the present invention, a Coulter Multisizer is used to connect a number distribution and volume distribution interface (manufactured by Nikka Kisha Co., Ltd.) and a personal computer, and the electrolyte is adjusted to a 1% NaCl aqueous solution using first-grade sodium chloride. To do. For example, ISOTON R-II (manufactured by Coulter Scientific Japan) can be used. As a measuring method, a surfactant, preferably alkylbenzene sulfonate 0.1 to 0.3 cm ³ is added as a dispersant to 100 to 150 cm ^{3 of the} electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolyte solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the volume and number of toner particles of 2 μm or more are measured with the Coulter Multisizer using a 100 μm aperture. Calculate the distribution.

  Then, the weight average particle diameter obtained from the volume distribution according to the present invention (D4: the median value of each channel is the representative value of the channel) can be obtained.

<Differential thermal analysis measurement>
It measures according to ASTM D3418-82 using a differential scanning calorimeter (DSC measuring device), DSC-7 (manufactured by PerkinElmer) or DSC2920 (manufactured by TA Instruments Japan). The measurement sample is precisely 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 within a measurement temperature range of 30 to 200 ° C. In the measurement, the temperature is increased and then the temperature is decreased once, and then the temperature is increased again. The maximum endothermic peak of the DSC curve in the temperature range of 30 to 200 ° C. Let it be the endothermic peak in the invention.

<Measurement of molecular weight distribution>
The measurement of the molecular weight distribution of the resin component by gel permeation chromatography (GPC) may be performed as follows.

  A solution obtained by allowing a binder resin or toner to stand in tetrahydrofuran (THF) for 24 hours at room temperature and dissolving the solution is a solvent resistant membrane filter having a pore diameter of 0.45 μm (for example, trade name “Maeshori Disc” manufactured by Tosoh Corporation). The sample solution is filtered through and measured under the following conditions. In addition, sample preparation adjusts the quantity of THF so that the density | concentration of the component soluble in THF may be 0.4-0.6 mass%.

Equipment: High-speed GPC HLC8120 GPC (manufactured by Tosoh Corporation)
Column: Shodex KF-801, 802, 803, 804, 805, 8
7 series of 06, 807 (made by Showa Denko)
Eluent: Tetrahydrofuran Flow rate: 1.0 cm ³ / min
Oven temperature: 40.0 ° C
Sample injection amount: 0.10 cm ³

  In calculating the molecular weight of the sample, standard polystyrene resin (TSO standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F- manufactured by Tosoh Corporation) was used. 10, F-4, F-2, F-1, A-5000, A-5.000, A-1000, A-500).

<Measurement of viscoelasticity of toner>
The storage elastic modulus G ′ and loss elastic modulus G ″ of the toner were measured by the following methods and conditions.
・ Equipment: Rheometer RDA-II type manufactured by Rheometrics ・ Measurement jig: Parallel plate with a diameter of 8 mm ・ Measurement sample: Toner is molded into a disk-shaped sample with a diameter of about 8 mm and a height of about 3 mm. Conditions: 40 to 190 ° C. at a rate of 2 ° C./min. Measurement frequency: 6.28 rad / sec
-Measurement strain setting: Automatic measurement mode (initial value set to 0.1%)
・ Sample extension correction: Automatic measurement mode

<Measurement of moisture content of hydrous MB>
In the present invention, “moisture content” refers to the mass-based moisture content based on the Karl Fischer method, that is, the ratio of the moisture mass to the total mass of the hydrous MB, and the sample was prepared by leaving it at 23 ° C. and 60% RH for 24 hours. Based on the Karl Fischer method (JIS K-0068 moisture vaporization method), the gas at 125 ° C. heating is measured.

<Measurement of L ^* and b ^* in powder state>
L ^* and b ^* in the yellow toner in the powder state are measured using a spectroscopic color difference meter “SE-2000” (manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS Z-8722, and the light source is measured in a C light source with a double field of view. To do. The measurement is performed according to the attached instruction manual. For standardization of the standard version, it is preferable to perform the measurement through a glass of 2 mm thickness and φ30 mm in an optional powder measurement cell. More specifically, the measurement is performed in a state in which a cell filled with the sample powder is placed on the sample table (attachment) for the powder sample of the spectroscopic color difference meter. Before placing the cell on the sample table for powder sample, fill the powder sample with 80% or more with respect to the internal volume of the cell, and apply vibration once per second for 30 seconds on the vibration table. Then, L ^* and b ^* are measured.

  Specific examples of the present invention will be described below, but the present invention is not limited to these examples.

<Example of production of hybrid resin 1>
In a reaction vessel equipped with a thermometer, a stirrer, a condenser and a nitrogen introduction tube, 49.5 parts by mass of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane (PO-BPA), 19.6 parts by mass of polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane (EO-BPA), 19.8 parts by mass of terephthalic acid, 8.4 parts by mass of trimellitic anhydride, 2.7 parts by mass of fumaric acid and 0.30 part by mass of dibutyltin oxide were added, and the inside of the reaction vessel was replaced with nitrogen gas, and then the temperature was gradually raised while stirring and stirred at a temperature of 130 ° C. On the other hand, 7.4 parts by mass of styrene, 1.7 parts by mass of 2-ethylhexyl acrylate, 0.9 parts by mass of fumaric acid, 0.12 parts by mass of dimer of α-methylstyrene, 0.20 parts by mass of dicumyl peroxide. The parts were mixed well at room temperature and added dropwise to the previous reaction vessel over 5 hours. Thereafter, the reaction solution was heated to 200 ° C. and reacted for 6 hours to obtain a hybrid resin 1. Table 1 shows the results of molecular weight measurement by GPC.

<Example of production of hybrid resin 2>
A hybrid resin 2 was obtained in the same manner as the hybrid resin 1 except that the components of the polyester unit were changed. Table 1 shows the results of molecular weight measurement by GPC.

<Example of production of polyester resin 3>
In a reaction vessel equipped with a thermometer, a stirrer, a condenser and a nitrogen introduction tube, 49.5 parts by mass of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane (PO-BPA), 19.6 parts by mass of polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane (EO-BPA), 19.8 parts by mass of terephthalic acid, 8.4 parts by mass of trimellitic anhydride, 2.7 parts by mass of fumaric acid and 0.30 part by mass of dibutyltin oxide were added, the inside of the reaction vessel was replaced with nitrogen gas, the temperature was gradually increased while stirring, and a condensation reaction was carried out at 215 ° C. for 4 hours to obtain a polyester resin E was obtained. Table 1 shows the results of molecular weight measurement by GPC.

<Production example of vinyl copolymer 4>
Into a reaction vessel equipped with a thermometer, a stirrer, a condenser, and a nitrogen introduction tube, 200 parts by mass of xylene was charged, and the inside of the vessel was sufficiently replaced with nitrogen while stirring to raise the temperature to 120 ° C. A mixture obtained by thoroughly mixing the following components at room temperature was dropped over 5 hours to perform radical polymerization. Further, the temperature was raised, radical polymerization was completed under reflux of xylene, and the solvent was distilled off under reduced pressure to obtain a vinyl copolymer F. Table 1 shows the results of molecular weight measurement by GPC.
-Styrene 75 parts by mass-2-ethylhexyl acrylate 20 parts by mass-Monobutyl maleate 5 parts by mass-Di-t-butyl peroxide 1 part by mass

<Preparation of colorant master batch>
(Preparation of Colorant Masterbatch 1: First Melt-Kneading Step to MB Preparation)
The 1st melt-kneading process was performed with the following method, and the coloring agent masterbatch 1 was produced.
Hybrid resin 1 100.0 parts by mass Pigment Yellow 74 45.5 parts by mass Solvent Yellow 162 18.2 parts by mass Distilled water 80.0 parts by mass The temperature is raised under pressure. When the maximum temperature (in this case, about 80 to 100 ° C.) is reached, the pigment is distributed or transferred to the molten resin phase, and after confirming this, the mixture is further melted and kneaded at 90 to 100 ° C. for 15 minutes. The first pigment is sufficiently transferred to obtain a first kneaded product. Thereafter, the mixer was once stopped, the hot water was discharged, the water was distilled off by mixing for 5 minutes without heating, the mixture was cooled, and pulverized to about 1 mm by pin mill pulverization to obtain a colorant master batch 1. . The water content of this colorant master batch 1 was 10% by mass. Table 3 shows the blending amounts of the raw materials of the colorant master batch 1.

(Preparation of colorant master batches 2 and 3)
The same as the colorant masterbatch 1 except that the addition amount of the colorants 1 and 2 and the amount of added water are changed, and the time for heating and melt-kneading is changed to 10 minutes while visually confirming the dispersion state of the pigment. Colorant masterbatches 2 and 3 were obtained by this method. Table 3 shows the blending amounts of the raw materials of the colorant master batches 2 and 3.

(Preparation of colorant master batch 4)
A colorant masterbatch 4 was obtained in the same manner as the colorant masterbatch 1 except that the addition amount of Pigment Yellow 74 and the amount of added water were changed without adding Solvent Yellow 162. Table 3 shows the amounts of the raw materials of the colorant master batch 4.

(Preparation of colorant master batch 5)
Pigment Yellow 74 is not added, the addition amount of Solvent Yellow 162 and the amount of added water are changed, and the colorant is changed to 30 minutes while heating and kneading while visually confirming the dispersion state of the pigment. Colorant masterbatch 5 was obtained in the same manner as masterbatch 1. Table 3 shows the amounts of the raw materials of the colorant master batch 4.

(Preparation of colorant master batch 6)
Pigment Yellow 93 is added as a colorant, the amount added and the amount of water added are changed, and the colorant masterbatch is changed to 30 minutes while heating and kneading while visually confirming the dispersion state of the pigment. A colorant master batch 6 was obtained in the same manner as in Example 1. Table 3 shows the blending amounts of the raw materials of the colorant master batch 6.

(Preparation of colorant master batch 7)
The first melt-kneading step was performed by the following method, and a master batch 7 was prepared using a paste pigment containing moisture as a colorant.
・ Hybrid resin 1 100.0 mass parts ・ Pigment Yellow 74
(Solid content 50% by mass, moisture 50% by mass) 140.0 parts by mass The above raw materials are first charged into a kneader-type mixer and heated while being mixed with no pressure. After reaching the maximum temperature (necessarily determined by the boiling point of the solvent in the paste, in this case, about 80 to 100 ° C.), the pigment is distributed or transferred to the molten resin phase, and after confirming this, Further, the mixture is heated and melted and kneaded at 90 to 100 ° C. for 15 minutes to sufficiently transfer the pigment in the paste to obtain a first kneaded product. Thereafter, the mixer was once stopped, the hot water was discharged, the water was distilled off by mixing for 5 minutes without heating, and the mixture was cooled, and then pulverized to about 1 mm by pin mill pulverization to obtain a colorant master batch 7. . Table 3 shows the blending amounts of the raw materials of the colorant master batch 7.

(Preparation of colorant master batch 8)
The first melt-kneading step was performed by the following method, and a master pigment 8 was prepared using a paste pigment containing moisture as a colorant.
・ Hybrid resin 1 100.0 parts by mass ・ Solvent Yellow 162
(Solid content 50% by mass, moisture 50% by mass) 140.0 parts by mass The above raw materials are first charged into a kneader-type mixer and heated while being mixed with no pressure. After reaching the maximum temperature (necessarily determined by the boiling point of the solvent in the paste, in this case, about 80 to 100 ° C.), the pigment is distributed or transferred to the molten resin phase, and after confirming this, Further, the mixture is heated and melted and kneaded at 90 to 100 ° C. for 15 minutes to sufficiently transfer the pigment in the paste to obtain a first kneaded product. Thereafter, the mixer was once stopped, the hot water was discharged, the water was distilled off by mixing for 5 minutes without heating, the mixture was cooled, and pulverized to about 1 mm by pin mill pulverization to obtain a colorant master batch 8. . Table 3 shows the blending amounts of the raw materials of the colorant master batch 8.

<Example 1>
<Toner Production Example 1>
(Second kneading step-preparation of toner)
The second kneading step was performed by the following method to prepare toner 1.
Hybrid resin 1 89.0 parts by mass Wax A (purified normal paraffin (1), melting point 76 ° C.) 4.0 parts by mass Organic metal compound (1,4-di-t-butylsalicylic acid aluminum compound) 3.0 Part by mass / Colorant master batch 1 20.0 parts by mass The above materials are sufficiently premixed by a Henschel mixer, melt-kneaded at a set temperature of a biaxial extrusion kneader of 120 ° C. (kneaded product temperature: 126 ° C.), A second kneaded product was obtained, and after cooling, coarsely pulverized to about 1-2 mm using a hammer mill, and then finely pulverized to a particle size of 20 μm or less with an air jet type pulverizer. Further, the obtained finely pulverized product was classified using a classifier (elbow jet classifier) to obtain a yellow toner (classified product). Table 4 shows the composition of the toner.

With respect to 100 parts by mass of the yellow toner, 1.0 part by mass of acicular titanium oxide fine powder (MT-100T: manufactured by Teika, BET = 62 m ² / g, treated with 10% by mass of isobutyltrimethoxysilane) was added to a Henschel mixer. A yellow toner 1 was obtained by external addition.

  Further, the weight average diameter of the yellow toner 1 was 7.0 μm. Further, toner 1 and magnetic ferrite carrier particles (average particle diameter 45 μm: Mn—Mg ferrite) surface-coated with a silicone resin were mixed so that the toner concentration would be 7.0% by mass to obtain a two-component developer 1. .

  Table 3 shows toner constituent materials, and Table 4 shows toner physical properties and developer evaluation results.

  The coloring power was high and the light resistance was also good. In addition, the coloring power is high and the OHT transparency is good. Further, since the coloring power is high, the low-temperature fixability and the high-temperature offset resistance are good even when the toner loading is lowered. In addition, since the pigment was well dispersed, the charge was uniform, fog did not occur, and developability was also good.

  In addition, the measuring method used by evaluation of the Example in this invention is as follows.

1) Coloring power With a color laser printer LBP2510 (manufactured by Canon), the fixing unit was used at a process speed of 110 mm / sec by using a fixing machine modified so that the fixing temperature can be manually set. The image is 0.1 mg / cm ² to 0.7 mg / cm on A4 paper (TKCLA4, which is CLC recommended paper) in a single color mode at room temperature and normal humidity (23 ° C./60%) in CLC5000 with the fixing unit removed. Several solid unfixed images having a width of 100 mm and a length of 280 mm with different toner loading amounts are produced on the transfer paper in the range of ² . The temperature control of the fixing device is set to 180 ° C. (In the following examples, those not fixed at 180 ° C. were performed as <(maximum temperature that can be fixed) −5 ° C.>) A4 longitudinal direction Fixed to. These image densities are measured using an X-Rite color reflection densitometer (color reflection density X-Rite 404A), and the relationship between the toner amount on the transfer paper and the image density is graphed. The image density when the applied amount of toner was 0.5 mg / cm ² was read from the graph, and the coloring power was relatively evaluated as follows.
A: Very good (above 1.45)
B: Good (1.35 or more and less than 1.45)
C: Normal (1.25 or more, less than 1.35)
D: Practical level (1.15 or more, less than 1.25)
E: Impractical level (less than 1.15)

2) Fixing evaluation method A fixing test is performed with a fixing unit of a color laser printer LBP2510 (manufactured by Canon Inc.) modified so that the fixing temperature can be manually set. The image is CLC5000 with the fixing unit removed, in a single color mode in a normal temperature and humidity environment (23 ° C./60%), when the color strength is evaluated as 1.0 (0.3 mg / cm 2 in Example 1). The development contrast is adjusted in accordance with the amount of applied toner on the paper to create an unfixed image. At this time, a solid image having a front end margin of 5 mm, a width of 100 mm, and a length of 280 mm was used on A4 paper (TKCLA4 which is a CLC recommended paper). The fixing test was conducted by increasing the temperature in the A4 vertical direction by 5 ° C. in order from 150 ° C. in a normal temperature and normal humidity environment (23 ° C./60%). After fixing, a new A4 paper (TKCLA4 which is a CLC recommended paper) was similarly passed through the fixing device.

2) -1 fixing start temperature 5 cm from the rear end of the fixed image was rubbed 5 times with a soft thin paper (for example, “Dasper”, manufactured by Ozu Sangyo Co., Ltd.) while applying a load of 4.9 KPa, The image density before and after rubbing was measured, respectively, and the reduction rate ΔD (%) of the image density was calculated by the following equation. The image density was measured with an X-Rite color reflection densitometer (Color reflection densitometer X-Rite 404A).
ΔD (%) = (Image density before rubbing−Image density after rubbing) × 100 / Image density before rubbing

  The temperature at which ΔD (%) was less than 1% was determined as the fixing start temperature.

2) -2 Fixing temperature range width After fixing the unfixed image, the worst value Da of the whiteness of the paper passed through the fixing device and the worst value Db of the whiteness of the same unused paper are respectively measured. The difference in whiteness was calculated. And about the difference of this whiteness, the high temperature offset resistance was evaluated on the following references | standards. In addition, the whiteness was measured by a reflectometer (“REFLECTOMETER MODEL TC-6DS” manufactured by Tokyo Denshoku Co., Ltd.) equipped with a blue filter.
(High temperature offset resistance) [%] = Da [%] − Db [%]

  The fixing temperature range was set to a temperature at which the difference in whiteness at this time was less than 0.5%.

3) Light resistance evaluation Using a fixed image used in the fixing evaluation and using a UV auto fade meter “FAL-AU” (manufactured by Suga Test Instruments Co., Ltd.) with a carbon arc lamp as a light source, conforming to “JIS K 7102” And evaluated. The maximum irradiation time was set to 80 hours, and the image density before and after the light irradiation was measured with an X-Rite color reflection densitometer (Color reflection densitometer X-Rite 404A) to calculate the maintenance ratio, and the light resistance of the image was evaluated. The closer the image density maintenance rate (%) is to 100%, the better the image light resistance.
(Maintenance rate) = image density after irradiation / initial image density × 100
A: Excellent at 90% or more B: 75% or more, good at less than 90% C: 60% or more, less than 75%, normal D: 45% or more, less than 60%, practically level E: 45% Less than practically impossible level

4) Measuring method of OHP transmittance Using a color copying machine CLC-5000 (manufactured by Canon) with the fixing unit removed, an unfixed image of A4 half-sided solid image was created on an OHP sheet, and a color laser printer LBP2510 (manufactured by Canon) ) And a process speed of 30 mm / sec. At that time, an image is created by adjusting the development contrast so that the solid portion of the OHP fixed image has an image density satisfying the following expression.
D (on solid paper) −D (on REF paper) = 1.0
(In the above formula, D (on solid paper): OHP was placed on plain paper and the reflection density of the solid image portion was measured. D (on REF paper): OHP was placed on plain paper and the reflection density of the solid white portion was measured. )

  For reflection density measurement, X-rite 504 was used, and image density was measured.

  The OHP transmittance was evaluated using the above-mentioned OHP image, using a transmission light measurement mode of JASCO (JASCO Corporation) V-570 UV / vis / NIR Spectrophotometer, and a yellow image: 578 nm.

Evaluation criteria for OHP permeability are as follows.
A: Good at 80% or more B: 70% or more, good at less than 80% C: 60% or more, less than 70%, no practical problem D: 50% or more, less than 60%, practically level E: 50 Less than%

5) Development evaluation method Image area ratio in a single-color mode under normal temperature and low humidity (23 ° C / 5% RH) using a remodeling machine from which the oil application mechanism of the fixing unit of the color copier CLC-5000 (manufactured by Canon) is removed. The printing durability test of 10,000 sheets was evaluated using a 5% original document.

5) -1 Charging stability A schematic diagram of an apparatus for measuring the triboelectric charge quantity is shown in FIG. About 0.5 to 1.5 g of two-component developer collected from the developing sleeve of a copying machine or printer is placed in a metal measuring container 52 having a screen 53 having a 500 mesh (25 μm opening) at the bottom. Cover 54. The total weight of the measurement container 52 at this time is weighed and is defined as W1 (g). Next, in the suction device 51 (at least the insulator is in contact with the measurement container 52), the pressure of the vacuum gauge 55 is set to 4 kPa by suctioning from the suction port 57 and adjusting the air volume control valve 56. In this state, the toner is removed by suction for 2 minutes. The potential of the electrometer 59 at this time is set to V (volt). Here, 58 is a capacitor, and the capacity is C (mF). 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 this sample is calculated as follows.
Sample triboelectric charge (mC / kg) = C × V / (W1-W2)
(However, the measurement conditions are 23 ° C. and 60% RH)

The following is the change in charging with a durability of 10,000 sheets from the start.
A: Good at less than 2 mC / kg B: Good at 2 mC / kg and less than 4 mC / kg C: No problem in practical use at 4 mC / kg and less than 6 mC / kg D: Practical at 6 mC / kg and less than 8 mC / kg Upper limit level E: practically impossible at 8 mC / kg or more

5) -2 Fog As a method for measuring the fog in the durability test, in the case of a yellow image, the reflectivity meter (Tokyo Denshoku Co., Ltd.) equipped with a blue filter is used to calculate the average reflectance Dr (%) of plain paper before image printing. “REFLECTOMETER MODEL TC-6DS”) On the other hand, a solid white image was drawn on plain paper, and then the reflectance Ds (%) of the solid white image was measured. The fog (Fog [%]) is represented by the following formula: Fog [%] = Dr [%] − Ds [%]
Calculated from

A: Good with less than 0.7% B: Good with 0.7 or more and less than 1.2% C: Good with 1.2 or more and less than 1.5% No practical problem D: 1.5 or more and 2.0 Less than%, practically level E: 2.0% or more practically impossible level

6) Preservability About 10 g of toner is put in a 100 ml plastic cup, left at 50 ° C. for 7 days, and then visually evaluated.
-Anti-blocking crank A: No aggregates are seen.
B: Aggregates are slightly seen but easily collapse.
C: Aggregates are seen but easily collapse.
D: Agglomerates are seen, but collapse if shaken. Practical level E: Aggregates can be grasped and do not collapse easily. Impractical level

7) Color unevenness (Cyan developer preparation method)
The cyan developer used was prepared as follows. 70 parts by mass of hybrid resin; B. (Pigment Blue) A pigment-like slurry containing 15: 3 to some extent water was removed, and a paste-like pigment having a solid content of 30% by mass (the remaining 70% by mass was water) obtained without any drying process 100 A water-containing colorant master batch was prepared using parts by mass.

First, the above raw materials were charged into a kneader type mixer, and the temperature was raised under no pressure while mixing. When the temperature reaches about 80 to 100 ° C., the pigment in the aqueous phase is distributed or transferred to the molten resin phase. After confirming this, the mixture is heated and melt-kneaded for 15 minutes at 90 to 100 ° C. To the molten resin phase. Then, once the mixer was stopped and the hot water was discharged, the water was removed by heating and mixing at 120 ° C. for 15 minutes, and the dried cyan master batch (water content 0) was pulverized to about 1 mm by pin milling. 0.7% by mass).
Hybrid resin 1 89.0 parts by mass Wax A (purified normal paraffin (1), melting point 76 ° C.) 4.0 parts by mass Organic metal compound (aluminum 1,4-di-t-butylsalicylate compound) 3.0 Part by mass / Dry masterbatch 20.0 parts by mass A cyan toner and a cyan developer were obtained by the same method as the production method of the toner 1 except that the above formulation was used.

Using the cyan developer and the yellow developer for evaluation, a color copier CLC-5000 (manufactured by Canon Inc.) with the fixing unit removed is used to create an unfixed image in which yellow and cyan images are superimposed on A4 paper. At that time, an unfixed image was created by overlapping the amount of toner on paper of each color by 0.3 mg / cm ² and used at a process speed of 110 mm / sec using a fixing device of a color laser printer LBP2510 (manufactured by Canon). The fixed green image was evaluated as follows.
A: Uniform green and excellent B: Almost no color tone of cyan, good C: Partially cyan and green tone, but no problem in practical use D: Practicable cyan and green tone on the entire surface, practical use Top problem E: Cyan and green gradations are clearly seen on the entire surface, which is bad

<Examples 2-3>
Developers 2 to 3 were obtained in the same manner as in Example 1 except that the type of the colorant master batch and the addition amount of the hybrid resin 1 were changed.

  Table 3 shows toner constituent materials, and Table 4 shows toner physical properties and developer evaluation results.

  Although the fog was slightly inferior, the coloring power was high, the light resistance was good, and the fixability was satisfactory.

<Examples 4 to 5>
Developers 4 to 5 were obtained in the same manner as in Example 1 except that the colorant master batch 3 was used and the addition amount thereof and the addition amount of the hybrid resin 1 were changed.

  Table 3 shows toner constituent materials, and Table 4 shows toner physical properties and developer evaluation results.

  Although there was a tendency to charge up and fogging to deteriorate, the coloring power was high, the light resistance was good, and the fixing property was satisfactory.

<Examples 6 to 7>
Developers 6 to 7 were obtained in the same manner as in Example 1 except that the colorant master batch 2 was used and the addition amount thereof and the addition amount of the hybrid resin 1 were changed.

  Table 3 shows toner constituent materials, and Table 4 shows toner physical properties and developer evaluation results.

  Although the developer 6 was slightly inferior in fog, the coloring power was high, the light resistance was good, and the fixability was satisfactory.

  Since the developer 7 has poor coloring power, the amount of applied toner necessary to obtain the image density is increased, the low-temperature fixability tends to be slightly deteriorated, and the OHT transparency tends to be deteriorated. there were.

<Examples 8 to 11>
Except that the polyester resin 3 and the vinyl copolymer 4 are used in combination as the binder resin and the addition amount thereof, and that the colorant master batches 4 and 5 are used in combination and the addition amount thereof are changed, the same as in Example 1. Thus, developers 8 to 11 were obtained.

  Table 3 shows toner constituent materials, and Table 4 shows toner physical properties and developer evaluation results.

  Since developer 8 has inferior coloring power, the amount of applied toner necessary for obtaining image density is increased and OHT transparency is deteriorated.

  Developer 9 had high coloring power, good light fastness, and good fixability. However, the effect of Solvent Yellow 162 on the growth of Pigment Yellow 74 was small, and the OHT transparency was slightly deteriorated. However, there was no problem in practical use.

  Although the developer 10 has high coloring power, the amount of applied toner necessary for obtaining the image density is reduced, and the high-temperature offset resistance and the light resistance are deteriorated.

  The developer 11 was deteriorated in light resistance, and the amount of Solvent Yellow 162 added was too large, so that a charge-up tendency was observed and fogging was deteriorated.

<Example 12>
Developer 12 in the same manner as in Example 1 except that the hybrid resin 2 and the vinyl copolymer 4 are used in combination and the addition amount thereof, and the colorant master batches 4 and 5 are used in combination and the addition amount thereof are changed. Got.

  Table 3 shows toner constituent materials, and Table 4 shows toner physical properties and developer evaluation results.

  Developer 12 has poor coloring power and low tan δ of viscoelastic properties, so that the high-temperature offset resistance and the OHT transparency are deteriorated.

<Example 13>
A developer 13 was obtained in the same manner as in Example 1 except that the polyester resin 3 was used alone and the addition amount thereof, and the colorant master batches 4 and 5 were used in combination and the addition amount thereof was changed.

  Table 3 shows toner constituent materials, and Table 4 shows toner physical properties and developer evaluation results.

  The developer 13 has a low level of viscoelasticity (G′80) and a high level of (G′160), which deteriorates the high-temperature offset property, but has a practically no problem level.

<Example 14>
A developer 14 was obtained in the same manner as in Example 1 except that the hybrid resin 2 was used alone and the addition amount thereof, and the colorant master batches 4 and 5 were used together and the addition amount thereof were changed.

  Table 3 shows toner constituent materials, and Table 4 shows toner physical properties and developer evaluation results.

  Developer 14 has high (G'80) and low (G'160) viscoelastic properties, and thus low-temperature fixability and OTH transparency are deteriorated.

<Example 15>
The developer 15 is used in the same manner as in Example 1 except that the polyester resin 3 is used alone and its addition amount, and Pigment Yellow 74 and Solvent Yellow 162 are added as they are during toner production and the addition amount thereof is changed. Obtained.

  Table 3 shows toner constituent materials, and Table 4 shows toner physical properties and developer evaluation results.

  The crystal growth suppression effect of Solvent Yellow 162 with respect to Pigment Yellow 74 was small, the OHT transparency was deteriorated, and the fixability was also deteriorated.

<Comparative Example 1>
A developer 16 was obtained in the same manner as in Example 1 except that the polyester resin 3 was used alone and its addition amount, and the colorant master batch 4 was used and its addition amount was changed.

  Table 3 shows toner constituent materials, and Table 4 shows toner physical properties and developer evaluation results.

  Pigment Yellow 74 alone has low coloring power, crystal growth occurs in addition to it, and the OHT transparency is very poor and not at a practical level. Further, the fixability and developability were also deteriorated.

<Comparative example 2>
A developer 17 was obtained in the same manner as in Example 1 except that the polyester resin 3 was used alone and its addition amount, and the colorant master batch 5 was used and its addition amount was changed.

  Table 3 shows toner constituent materials, and Table 4 shows toner physical properties and developer evaluation results.

  Solvent Yellow 162 alone was not at a practical level because the light resistance deteriorated. In addition, the charge-up also occurred very much, and the background fogging occurred, resulting in an image defect.

<Comparative Example 3>
A developer 18 was obtained in the same manner as in Example 1 except that the polyester resin 3 was used alone and the addition amount thereof, the colorant master batches 6 and 5 were used in combination, and the addition amount thereof was changed.

  Table 3 shows toner constituent materials, and Table 4 shows toner physical properties and developer evaluation results.

  When Pigment Yellow 74 and Solvent Yellow 162 were used in combination, the coloring power was lowered, and the OHT transparency was not practical. Further, the developability also deteriorated and fogging occurred, making it impractical.

<Example 16>
Except that the polyester resin 3 and the vinyl copolymer 4 are used in combination as the binder resin and the amount thereof added, and that the colorant master batches 7 and 8 are used in combination and the amount thereof is changed, the same as in Example 1. Thus, developer 19 was obtained.

  Table 3 shows toner constituent materials, and Table 4 shows toner physical properties and developer evaluation results.

  By using a pigment containing water (hydrous paste pigment), transparency was better than that of a dry pigment.

<Comparative Examples 4-5>
Developers 20 to 21 were obtained in the same manner as in Example 1 except that the addition amount of the colorant master batch was changed.

  Table 3 shows toner constituent materials, and Table 4 shows toner physical properties and developer evaluation results.

  Since developer 20 has too much colorant, transparency and developability deteriorated, making it impractical. Further, since the developer 21 has a small amount of colorant, it has a low coloring power and is not practical. Further, since the amount of toner necessary for producing a predetermined density is large, the toner was not fixed.

It is explanatory drawing of the apparatus which measures the tribo charge amount of the toner used in the Example of this invention.

Explanation of symbols

1 Suction Machine 2 Measuring Device 3 Screen 4 Lid 5 Vacuum Gauge 6 Air Volume Control Valve 7 Suction Port 8 Capacitor 9 Electrometer

Claims (6)

In a yellow toner containing at least a binder resin, a colorant and a wax, C.I. I. Pigment Yellow 74 and C.I. I. Solvent Yellow 162, and C.I. with respect to 100 parts by mass of the binder resin. I. Pigment Yellow 74 is contained in an amount of X parts by mass, C.I. I. When the content of Solvent Yellow 162 is Y parts by mass, X is in the range of 1-10, Y is in the range of 0.5-8, and the sum of X and Y is in the range of 2-13. A yellow toner having a lightness L ^* in a powder state satisfying L ^* > 83 and a chromaticity b ^* satisfying 100 <b ^* <120. In the viscoelastic properties of the yellow toner, the storage elastic modulus (G′160) at a temperature of 160 ° C. is in the range of the storage elastic modulus (G′80) at a temperature of 80 ° C. of 1 × 10 ⁵ to 1 × 10 ⁸ (Pa). The yellow toner according to claim 1, wherein is in the range of 1 × 10 ¹ to 1 × 10 ⁴ (Pa).   In the viscoelastic characteristics of the yellow toner, the ratio of the storage elastic modulus (G ′) to the loss elastic modulus (G ″) at a temperature of 120 to 150 ° C. (G ″ / G ′ = tan δ) is 0.5 to 5. The yellow toner according to claim 1, wherein the toner is a yellow toner.   A mixture containing at least a first binder resin, a colorant, and water is heat-kneaded to obtain a colorant masterbatch that is a first kneaded product, and contains at least a second binder resin and the colorant masterbatch. 4. The method according to claim 1, further comprising: a second melt-kneading step for melt-kneading the toner raw material mixture to obtain a second kneaded product; and a pulverizing step for pulverizing the second kneaded product. The yellow toner described in 1.   5. The method according to claim 4, further comprising a first melt-kneading step of obtaining a water-containing colorant master batch by adjusting and removing the water content so that the water content is 2 to 25% by mass. Yellow toner. A heating and fixing apparatus that sandwiches and conveys a heated member between a heating member and a pressure member. The heated member is a film, and the recording is performed while pressing the pressure member against the heated member via a recording material. In an image forming method in which a toner image on a material is heated and pressed to form a fixed image on the recording material, a yellow toner containing at least a binder resin, a colorant and a wax is used as the toner, and the toner is C . I. Pigment Yellow 74 and C.I. I. Solvent Yellow 162, and C.I. with respect to 100 parts by mass of the binder resin. I. Pigment Yellow 74 is contained in an amount of X parts by mass, C.I. I. When the content of Solvent Yellow 162 is Y parts by mass, X is in the range of 1-10, Y is in the range of 0.5-8, and the sum of X and Y is in the range of 2-13. An image forming method, wherein the lightness L ^* in the powder state satisfies L ^* > 83, and the chromaticity b ^* satisfies 100 <b ^* <120.

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