JP5818609B2 - toner - Google Patents

Description

  The present invention relates to a toner used in an electrophotographic system, an electrostatic recording system, an electrostatic printing system, and a toner jet system.

In recent years, with the widespread use of electrophotographic color image forming apparatuses, their applications have been diversified and demands for image quality have become stricter. When copying images such as general photographs, catalogs, and maps, it is required to reproduce very fine and faithfully even down to the finest parts. Accordingly, the demand for color vividness is increasing. It is desired to extend the reproduction range. In particular, with the recent advancement to the printing field, high-definition, high-definition, graininess, etc. that are equal to or higher than the printing quality are also required in the electrophotographic system.
In particular, in the case of a full-color image, color reproduction is performed with three chromatic toners, which are the three primary colors of the color material, yellow toner, magenta toner, and cyan toner, or four color toners including black toner. Therefore, in order to obtain an image having a target color tone, balance with other colors is important. Therefore, for the purpose of slightly changing the color tone of the toner, the combined use with the same color pigment / dye, the combined use with other color pigment / dye, and the like have been proposed.
Patent Documents 1 and 2 propose a toner having high image quality, high durability, and light resistance by using a yellow dye as a colorant for yellow toner.
However, the conventionally known colorant for yellow toner has many problems. For example, although dye-based colorants generally have excellent coloring power, they are inferior in light resistance and have problems with image storage stability, and pigment-based colorants improve in light resistance, but coloring power is poor. Many are inferior.

JP-A-4-243267 JP-A-6-250440

  The present invention provides a toner that solves the above problems. Specifically, the present invention provides a toner that is particularly excellent in light resistance and has a small image density fluctuation during durable use.

As a result of intensive studies, the present inventors have found that the light resistance of the colorant can be remarkably improved by blending a specific dye and a pigment in a specific ratio, and that the toner is triboelectrically charged during durable use. The inventors have found that the change in the amount is small and that the density fluctuation of the image can be reduced as much as possible.
That is, the present invention is as follows.
A toner having toner particles containing a binder resin, a yellow colorant and a wax,
The yellow colorant contains colorant A and colorant B,
The colorant A is C.I. I. Solvent Yellow 98,
The colorant B is C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 180, C.I. I. One or more pigments selected from the group consisting of Pigment Yellow 185,
The content of the colorant A with respect to 100 parts by mass of the binder resin is YA (parts by mass), and the binder resin 1
The present invention relates to a toner characterized in that YA / (YA + YB) is 0.05 or more and 0.30 or less when the content of the colorant B with respect to 00 parts by mass is YB (parts by mass).

  According to the present invention, it is possible to provide a toner that is particularly excellent in light resistance and has a small image density fluctuation during durable use.

Hereinafter, embodiments for carrying out the present invention will be described in detail.
The toner of the present invention is a toner having toner particles containing a binder resin, a yellow colorant and a wax,
The yellow colorant contains colorant A and colorant B,
The colorant A is C.I. I. Solvent Yellow 98,
The colorant B is C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 180, C.I. I. One or more pigments selected from the group consisting of Pigment Yellow 185,
When the content of the colorant A with respect to 100 parts by mass of the binder resin is YA (parts by mass) and the content of the colorant B with respect to 100 parts by mass of the binder resin is YB (parts by mass), YA / ( YA + YB) is 0.05 or more and 0.30 or less.
The toner of the present invention includes C.I. I. Solvent Yellow 98 (dye) and C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 180, C.I. I. By containing one or more pigments selected from the group consisting of Pigment Yellow 185 at a specific ratio, the light resistance of the colorant can be remarkably enhanced, and the change in the triboelectric charge amount of the toner during durable use is small. Thus, it is possible to reduce the density fluctuation of the image as much as possible.
Although conventional dyes are excellent in coloring power, they are inferior in light resistance, so that there is a large variation in color tone of the image and there is a problem in storage stability. On the other hand, when a pigment-based colorant is used, the light resistance is improved to some extent, but it is not sufficient and the coloring power is inferior in many cases.
The inventors of the present invention can significantly improve the light resistance of the colorant by using a combination of the above-mentioned dye and pigment as a colorant in a specific ratio, and change the triboelectric charge amount of the toner during durable use. Has been found to be small and to reduce the density fluctuation of the image as much as possible.
First, C.I. I. Solvent Yellow 98 (hereinafter also referred to as SY98) has high affinity with the wax that is a material constituting the toner, and is presumed to be because it promotes the dispersibility of the wax. It is considered that the dispersibility of the wax is improved, and as a result, the change in the triboelectric charge amount of the toner during durable use is reduced.
This is because C.I. I. It is thought that it originates in the hydrocarbon chain which exists in the molecular structure of Solvent Yellow 98.
If the dispersibility of the wax is poor, the wax may exist in domains on the toner surface. Deterioration of toner that occurs during durable use often occurs due to structural changes on the toner surface, and is likely to occur in wax portions with low hardness. Therefore, it is considered that when the wax is uniformly dispersed, the hardness distribution on the toner surface becomes uniform, so that the change in the triboelectric charge amount of the toner during durable use is reduced.

In the toner of the present invention, when the content of the colorant A with respect to 100 parts by mass of the binder resin is YA (parts by mass) and the content of the colorant B with respect to 100 parts by mass of the binder resin is YB (parts by mass). , YA / (YA + YB) is 0.05 or more and 0.30 or less. Preferably, they are 0.07 or more and 0.25 or less, More preferably, they are 0.08 or more and 0.20 or less.
When [YA / (YA + YB)] is within the above range, the light resistance of the colorant is remarkably enhanced, the change in the triboelectric charge amount of the toner during durable use is small, and the density fluctuation of the image is suppressed as much as possible. .
When [YA / (YA + YB)] is less than 0.05, C.I. I. The effect of Solvent Yellow 98 is less likely to be exhibited, the change in the triboelectric charge amount of the toner during endurance use becomes extremely large, the effect of improving the light resistance of the colorant is lowered, and the color variation of the image is increased.
When [YA / (YA + YB)] exceeds 0.30, the effect of improving the light resistance of the colorant is significantly deteriorated.
The reason why the light resistance of the colorant can be remarkably enhanced by adjusting [YA / (YA + YB)] is as follows. As described above, C.I. I. Solvent Yellow 98 (hereinafter also referred to as SY98) has a high affinity with the wax that is a material constituting the toner, and is considered to promote the dispersibility of the wax. And it seems that the state where the wax exists around SY98 and the coloring agent B (pigment) is created. As a result, it is considered that the presence of wax reduces damage to SY98 and colorant B (pigment) due to ultraviolet rays.

In the present invention, (YA + YB) is preferably 3 parts by mass or more and 20 parts by mass or less. More preferably, they are 4 mass parts or more and 15 mass parts or less, Especially preferably, they are 5 mass parts or more and 10 mass parts or less.
This is because the coloring power as a toner is low when (YA + YB) is less than 3 parts by mass, and therefore the image density is increased by increasing the amount of toner loaded. However, in this case, the toner consumption increases more than necessary.
On the other hand, if it exceeds 20 parts by mass, tends to dispersibility of the colorant in the toner is reduced, the same chroma (C ^*) lightness in (L ^*) is lowered, it may become dull color is there.

Although it does not specifically limit as a wax used for the toner of this invention, The following are mentioned. Low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymer, hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxide of hydrocarbon wax such as oxidized polyethylene wax or block copolymer thereof; Waxes mainly composed of fatty acid esters such as carnauba wax; those obtained by partially or fully deoxidizing fatty acid esters such as deoxidized carnauba wax. Furthermore, the following are mentioned. 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, carnauvyl alcohol, seryl alcohol, Saturated alcohols such as sil alcohols; polyhydric alcohols such as sorbitol; fatty acids such as palmitic acid, stearic acid, behenic acid, montanic acid, and stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, seryl alcohol, Esters with alcohols such as sil alcohols; Fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; Methylene bis stearic acid amide, ethylene biscapric acid Saturated fatty acid bisamides such as amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide; ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N 'dioleyl adipic acid amide, N, N' dioleyl Unsaturated fatty acid amides such as sebacic acid amides; aromatic bisamides such as m-xylene bis-stearic acid amide, N, N ′ distearyl isophthalic acid amide; calcium stearate, calcium laurate, zinc stearate, magnesium stearate Aliphatic metal salts such as those commonly referred to as metal soaps; waxes grafted to aliphatic hydrocarbon waxes using vinylic monomers such as styrene and acrylic acid; fatty acids such as behenic acid monoglycerides Alcohol Partial ester; methyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable fats and oils.
Among these waxes, C.I. I. From the viewpoint of high affinity with Solvent Yellow 98, hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax are preferred.
The content of the wax is preferably 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin. Further, from the viewpoint of achieving both storage stability and high-temperature offset property, the maximum endotherm existing in the temperature range of 30 ° C. to 200 ° C. in the endothermic curve at the time of temperature rise measured by a differential scanning calorimeter (DSC). The peak temperature is preferably 50 ° C. or higher and 110 ° C. or lower.

The toner of the present invention preferably further contains in the toner particles a polymer having a structure in which a vinyl resin component and a hydrocarbon compound are reacted.
As the polymer having a structure in which the vinyl resin component and the hydrocarbon compound are reacted, a graft polymer obtained by graft polymerization of a polyolefin to a vinyl resin component or a graft polymer obtained by graft polymerization of a vinyl monomer to a polyolefin is particularly preferable.
The polymer having a structure in which the vinyl resin component and the hydrocarbon compound react with each other acts as a surfactant for the binder resin and wax melted in the kneading step at the time of toner production. Therefore, the polymer is preferable because the average primary dispersed particle diameter of the wax in the toner particles can be controlled.
A polymer having a structure in which the vinyl resin component and a hydrocarbon compound are reacted is C.I. I. High affinity with Solvent Yellow 98, more C.I. I. Since it is possible to improve the dispersibility of Solvent Yellow 98 in toner particles, it is preferable.
Regarding the graft polymer obtained by graft polymerization of polyolefin on the vinyl resin component or the graft polymer obtained by graft polymerization of vinyl monomer on polyolefin, the polyolefin is a polymer or copolymer of unsaturated hydrocarbon monomers having one double bond. If it is a coalescence, it will not specifically limit, Various polyolefin can be used. In particular, polyethylene and polypropylene are preferably used.
On the other hand, the following are mentioned as a vinyl-type monomer.
Styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethyl Styrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene Styrene monomers such as styrene and derivatives thereof.
Amino group-containing α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; vinyl monomers containing nitrogen atoms such as acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.
Unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; unsaturated such as maleic acid anhydride, citraconic acid anhydride, itaconic acid anhydride, alkenyl succinic acid anhydride Dibasic acid anhydride: maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, alkenyl succinic acid Half-esters of unsaturated dibasic acids such as acid methyl half ester, fumaric acid methyl half ester and mesaconic acid methyl half ester; Unsaturated dibasic acid esters such as dimethylmaleic acid and dimethylfumaric acid; Acrylic acid, Methacrylic acid Α, β-unsaturated acids such as crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic acid anhydride, and anhydrous α and β-unsaturated acids and lower fatty acids. A vinyl monomer containing a carboxyl group such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides thereof, and monoesters thereof.
Acrylic acid or methacrylic acid ester such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1-methyl) (Hexyl) Vinyl monomers containing hydroxyl groups such as styrene.
Methyl acrylate, ethyl acrylate, acrylate-n-butyl, acrylate isobutyl, propyl acrylate, acrylate-n-octyl, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, acrylate-2- An ester unit comprising an acrylic ester such as chloroethyl and acrylic ester such as phenyl acrylate.
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylate-n-butyl, methacrylate isobutyl, methacrylate-n-octyl, methacrylate-decyl, methacrylate-2-ethylhexyl, stearyl methacrylate, phenyl methacrylate, methacryl Ester units composed of methacrylic acid esters such as α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl acid and diethylaminoethyl methacrylate.
A polymer having a structure in which a vinyl resin component and a hydrocarbon compound are reacted is obtained by a known method such as a reaction between these monomers described above or a reaction between a monomer of one polymer and the other polymer. Can do.
The constituent unit of the vinyl resin component preferably includes a styrene unit, and further acrylonitrile or methacrylonitrile.
The mass ratio of the hydrocarbon compound and the vinyl resin component in the polymer is preferably 1/99 to 75/25. The use of a hydrocarbon compound and a vinyl-based resin component in the above-mentioned range includes C.I. I. It is preferable for improving dispersibility of Solvent Yellow 98 in toner particles.
The content of the polymer having a structure in which the vinyl resin component and the hydrocarbon compound are reacted is preferably 0.2 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin.
The use of the polymer in the above range is C.I. I. It is preferable for improving dispersibility of Solvent Yellow 98 in toner particles.

The binder resin used in the toner of the present invention is not particularly limited, and the following polymers or resins can be used.
For example, homopolymers of styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene, and substituted products thereof; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer , Styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl Styrenic copolymers such as ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-acrylonitrile-indene copolymer; polyvinyl chloride, phenol resin, natural modified phenol resin, natural resin modified maleic acid resin, Acrylic resin, meta Lil resins, polyvinyl acetate, silicone resins, polyester resins, polyurethane, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, coumarone - indene resins, and petroleum resins.
Among these, it is preferable to use a polyester resin from the viewpoint of low-temperature fixability and chargeability control.
The polyester resin preferably used in the present invention is a resin having a “polyester unit” in the binder resin chain. Specifically, the component constituting the polyester unit is a dihydric or higher alcohol. And monomer components and acid monomer components such as divalent or higher carboxylic acids, divalent or higher carboxylic acid anhydrides, and divalent or higher carboxylic acid esters.
For example, polyoxypropylene (2.2) is used as the dihydric or higher alcohol monomer component.
) -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-bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2 -Alkylene oxide adducts of bisphenol A such as bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neo Pentyl glycol, 1,4-butenediol, 1,5-pentanediol, , 6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbit, 1,2,3,6-hexanetetrol, 1,4-sorbitan, penta Erythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, tri Examples include methylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene and the like.
Of these, the alcohol monomer component preferably used is an aromatic diol. In the alcohol monomer component constituting the polyester resin, the aromatic diol is preferably contained in a proportion of 80 mol% or more.
On the other hand, the acid monomer component such as the divalent or higher carboxylic acid, the divalent or higher carboxylic acid anhydride, and the divalent or higher carboxylic acid ester includes aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or the like. Anhydrides; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; succinic acid substituted with alkyl groups or alkenyl groups having 6 to 18 carbon atoms or anhydrides thereof; fumaric acid, maleic acid Unsaturated dicarboxylic acids such as acids and citraconic acid or anhydrides thereof.
Of these, the acid monomer component preferably used is a polyvalent carboxylic acid such as terephthalic acid, succinic acid, adipic acid, fumaric acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, or an anhydride thereof.
The acid value of the polyester resin is preferably 1 mgKOH / g or more and 20 mgKOH / g or less from the viewpoint of the stability of the triboelectric charge amount.
In addition, this acid value can be made the said range by adjusting the kind and compounding quantity of the monomer used for resin. Specifically, it can be controlled by adjusting the alcohol monomer component ratio / acid monomer component ratio and molecular weight during resin production. Moreover, it can control to make terminal alcohol react with a polyvalent acid monomer (for example, trimellitic acid) after ester condensation polymerization.

The toner of the present invention may contain a charge control agent as necessary. As the charge control agent contained in the toner, known ones can be used. In particular, a metal compound of an aromatic carboxylic acid that is colorless, has a high toner charging speed, and can stably maintain a constant charge amount is preferable.
Negative charge control agents include salicylic acid metal compounds, naphthoic acid metal compounds, dicarboxylic acid metal compounds, polymeric compounds having sulfonic acid or carboxylic acid in the side chain, sulfonates or sulfonated compounds in the side chain. Examples thereof include a polymer compound, a polymer compound having a carboxylate or a carboxylic acid ester in the side chain, a boron compound, a urea compound, a silicon compound, and calixarene. Examples of the positive charge control agent include a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, and an imidazole compound. The charge control agent may be added internally or externally to the toner particles. The addition amount of the charge control agent is preferably 0.2 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder resin.

An external additive may be added to the toner of the present invention as necessary to improve fluidity and adjust the triboelectric charge amount.
As the external additive, inorganic fine particles such as silica, titanium oxide, aluminum oxide, and strontium titanate are preferable. The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.
The specific surface area of the external additive used is preferably 10 m ² / g or more and 50 m ² / g or less from the viewpoint of suppressing embedding of the external additive.
The addition of the external additive is preferably 0.1 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the toner particles.
The mixing of the toner particles and the external additive is not particularly limited, but a known mixer such as a Henschel mixer can be used.

The toner of the present invention can also be used as a one-component developer. However, in order to further improve dot reproducibility and to obtain a stable image over a long period of time, it is mixed with a magnetic carrier as a two-component developer. It is preferable to use it.
Examples of the magnetic carrier include iron powder with oxidized surface or non-oxidized iron powder; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, rare earth, and alloy particles thereof. Commonly known materials such as magnetic particles such as oxide particles; ferrite; and a magnetic material-dispersed resin carrier (so-called resin carrier) containing a magnetic material and a binder resin that holds the magnetic material in a dispersed state are used. it can.
When the toner of the present invention is mixed with a magnetic carrier and used as a two-component developer, the mixing ratio of the magnetic carrier is preferably 2% by mass or more and 15% by mass or less as the toner concentration in the developer. More preferably, when the content is 4% by mass or more and 13% by mass or less, usually good results are obtained. If the toner concentration is less than 2% by mass, the image density tends to decrease, and if it exceeds 15% by mass, fogging or in-machine scattering tends to occur.

The method for producing the toner of the present invention is not particularly limited, and a known production method can be used. Here, a toner manufacturing method using a pulverization method will be described as an example.
In the raw material mixing step, a predetermined amount of other components such as a binder resin, a yellow colorant and a wax, and, if necessary, a charge control agent are weighed and mixed as materials constituting the toner particles and mixed. Examples of the mixing apparatus include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a nauter mixer, and a mechano hybrid (manufactured by Nippon Coke Industries, Ltd.).
Next, the mixed material is melt-kneaded to disperse the yellow colorant and wax in the binder resin. In the melt-kneading step, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. Due to the advantage of continuous production, single-screw or twin-screw extruders are the mainstream. For example, KTK type twin screw extruder (manufactured by Kobe Steel Co., Ltd.), TEM type twin screw extruder (manufactured by Toshiba Machine Co., Ltd.), PCM kneader (manufactured by Ikekai Tekko), twin screw extruder (manufactured by K.C.K. ), Co-kneader (manufactured by Buss), kneedex (manufactured by Nippon Coke Industries Co., Ltd.) Furthermore, the resin composition obtained by melt-kneading may be rolled with two rolls or the like and cooled with water or the like in the cooling step.
Next, the cooled product of the resin composition is pulverized to a desired particle size in the pulverization step. In the pulverization step, for example, after coarse pulverization with a pulverizer such as a crusher, a hammer mill, or a feather mill, for example, a kryptron system (manufactured by Kawasaki Heavy Industries), a super rotor (manufactured by Nisshin Engineering), a turbo mill Finely pulverize with a turbomill (made by Turbo Industries) or air jet type fine pulverizer.
Then, if necessary, classification such as inertial class elbow jet (manufactured by Nippon Steel & Mining Co., Ltd.), centrifugal classification turboplex (manufactured by Hosokawa Micron), TSP separator (manufactured by Hosokawa Micron), Faculty (manufactured by Hosokawa Micron) The toner particles are obtained by classification using a machine or a sieving machine.
In addition, if necessary, after pulverization, a hybridization system (manufactured by Nara Machinery Co., Ltd.), a mechano-fusion system (manufactured by Hosokawa Micron), a faculty (manufactured by Hosokawa Micron), or Meteole Inbo MR Type (manufactured by Nippon Pneumatic Co., Ltd.) is used. Thus, the toner particles can be subjected to a surface treatment such as a spheroidizing treatment.

A method for measuring various physical properties of the toner and raw materials in the present invention will be described below.
<Measurement Method of Resin Peak Molecular Weight (Mp), Number Average Molecular Weight (Mn), and Weight Average Molecular Weight (Mw)>
The peak molecular weight (Mp), number average molecular weight (Mn), and weight average molecular weight (Mw) are measured using gel permeation chromatography (GPC) as follows.
First, a sample (resin) is dissolved in tetrahydrofuran (THF) at room temperature over 24 hours. The obtained solution is filtered through a solvent-resistant membrane filter “Maescho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Shodex KF-801, 802, 803, 804, 805,
7 series of 806, 807 (made by Showa Denko)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml
In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F— 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) are used.

<Measurement method of softening point of resin>
The softening point of the resin is measured by using a constant load extrusion type capillary rheometer “flow characteristic evaluation device Flow Tester CFT-500D” (manufactured by Shimadzu Corporation) according to the manual attached to the device. In this device, while applying a constant load from the top of the measurement sample with the piston, the measurement sample filled in the cylinder is heated and melted, and the melted measurement sample is pushed out from the die at the bottom of the cylinder, and the piston drop amount at this time A flow curve showing the relationship between temperature and temperature can be obtained.
In the present invention, the “melting temperature in the 1/2 method” described in the manual attached to the “flow characteristic evaluation apparatus Flow Tester CFT-500D” is the softening point. The melting temperature in the 1/2 method is calculated as follows. First, ½ of the difference between the piston lowering amount Smax at the time when the outflow ends and the piston lowering amount Smin at the time when the outflow starts is obtained (this is X. X = (Smax−Smin) / 2). Then, the temperature of the flow curve when the piston descending amount is X in the flow curve is the melting temperature in the 1/2 method.
As a measurement sample, about 1.0 g of resin is compression-molded at about 10 MPa using a tablet molding compressor (for example, NT-100H, manufactured by NPA System Co., Ltd.) in an environment of 25 ° C. for about 60 seconds. A cylindrical shape having a diameter of about 8 mm is used.
The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rising start temperature: 50 ° C
Achieving temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature increase rate: 4.0 ° C./min
Piston cross-sectional area: 1.000 cm ²
Test load (piston load): 10.0 kgf (0.9807 MPa)
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0mm

<Measurement method of peak temperature of maximum endothermic peak of wax>
The peak temperature of the maximum endothermic peak of the wax is measured according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments). The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.
Specifically, about 10 mg of wax is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference. Measurement is performed at ° C / min. In the measurement, the temperature is once raised to 200 ° C., subsequently lowered to 30 ° C., and then the temperature is raised again. The temperature showing the maximum endothermic peak of the DSC curve in the temperature range of 30 to 200 ° C. in the second temperature raising process is defined as the peak temperature of the maximum endothermic peak of the wax.

<Method for measuring BET specific surface area of inorganic fine particles>
The BET specific surface area of the inorganic fine particles is measured according to JIS Z8830 (2001). A specific measurement method is as follows.
As a measuring device, an “automatic specific surface area / pore distribution measuring device TriStar 3000 (manufactured by Shimadzu Corporation)” which employs a gas adsorption method by a constant volume method as a measuring method is used. Setting of measurement conditions and analysis of measurement data are performed using dedicated software “TriStar3000 Version 4.00” attached to the apparatus, and a vacuum pump, a nitrogen gas pipe, and a helium gas pipe are connected to the apparatus. The value calculated by the BET multipoint method using nitrogen gas as the adsorption gas is taken as the BET specific surface area of the inorganic fine particles in the present invention.
The BET specific surface area is calculated as follows.
First, nitrogen gas is adsorbed onto the inorganic fine particles, and the equilibrium pressure P (Pa) in the sample cell and the nitrogen adsorption amount Va (mol · g ⁻¹ ) of the inorganic fine particles at that time are measured. The relative pressure Pr, which is a value obtained by dividing the equilibrium pressure P (Pa) in the sample cell by the saturated vapor pressure Po (Pa) of nitrogen, is plotted on the horizontal axis, and the nitrogen adsorption amount Va (mol · g ⁻¹ ) is plotted on the vertical axis. The adsorption isotherm is obtained. Next, a monomolecular layer adsorption amount Vm (mol · g ⁻¹ ), which is an adsorption amount necessary for forming a monomolecular layer on the surface of the inorganic fine particles, is obtained by applying the following BET equation.
Pr / Va (1-Pr) = 1 / (Vm * C) + (C-1) * Pr / (Vm * C)
(Here, C is a BET parameter, which is a variable that varies depending on the measurement sample type, adsorbed gas type, and adsorption temperature.)
The BET equation is interpreted as a straight line with an inclination of (C-1) / (Vm × C) and an intercept of 1 / (Vm × C), where Pr is X axis and Pr / Va (1-Pr) is Y axis. Yes (this line is called a BET plot).
Straight line slope = (C-1) / (Vm × C)
Straight line intercept = 1 / (Vm × C)
When the measured value of Pr and the measured value of Pr / Va (1-Pr) are plotted on a graph and a straight line is drawn by the least square method, the slope and intercept value of the straight line can be calculated. Vm and C can be calculated by solving the simultaneous equations of the slope and intercept using these values.
Furthermore, the BET specific surface area S (m ² / g) of the inorganic fine particles is calculated from the calculated Vm and the molecular occupation cross-sectional area of the nitrogen molecule (0.162 nm ² ) based on the following formula.
S = Vm × N × 0.162 × 10 ⁻¹⁸
(N is Avogadro's number (mol- ¹ ).)
The measurement using this apparatus is carried out by referring to “TriStar3000 Instruction Manual V4.0” attached to the apparatus.
Specifically, the measurement is performed according to the following procedure.
Thoroughly weigh the tare of a dedicated glass sample cell (stem diameter 3/8 inch, volume about 5 ml) that has been thoroughly cleaned and dried. Then, about 0.1 g of inorganic fine particles are put into this sample cell using a funnel.
The sample cell containing the inorganic fine particles is set in a “pretreatment device Bacrepprep 061 (manufactured by Shimadzu Corporation)” connected with a vacuum pump and a nitrogen gas pipe, and vacuum degassing is continued at 23 ° C. for about 10 hours. During vacuum deaeration, the inorganic fine particles are gradually deaerated while adjusting the valve so that the inorganic fine particles are not sucked into the vacuum pump. The pressure in the cell gradually decreases with deaeration and finally becomes about 0.4 Pa (about 3 mTorr). After completion of vacuum degassing, nitrogen gas is gradually injected to return the inside of the sample cell to atmospheric pressure, and the sample cell is removed from the pretreatment device. Then, the mass of the sample cell is precisely weighed, and the accurate mass of the inorganic fine particles is calculated from the difference from the tare. At this time, the sample cell is covered with a rubber plug during weighing so that the inorganic fine particles in the sample cell are not contaminated by moisture in the atmosphere.
Next, a dedicated “isothermal jacket” is attached to the stem portion of the sample cell containing the inorganic fine particles. Then, a dedicated filler rod is inserted into the sample cell, and the sample cell is set in the analysis port of the apparatus. The isothermal jacket is a cylindrical member having an inner surface made of a porous material and an outer surface made of an impermeable material capable of sucking liquid nitrogen to a certain level by capillary action.
Subsequently, the free space of the sample cell including the connection tool is measured. The free space is measured by measuring the volume of the sample cell using helium gas at 23 ° C., and then measuring the volume of the sample cell after cooling the sample cell with liquid nitrogen using helium gas. It is calculated by converting from the difference in volume. Further, the saturated vapor pressure Po (Pa) of nitrogen is automatically measured separately using a Po tube built in the apparatus.
Next, after performing vacuum deaeration in the sample cell, the sample cell is cooled with liquid nitrogen while continuing the vacuum deaeration. Thereafter, nitrogen gas is gradually introduced into the sample cell to adsorb nitrogen molecules on the inorganic fine particles. At this time, since the adsorption isotherm is obtained by measuring the equilibrium pressure P (Pa) as needed, the adsorption isotherm is converted into a BET plot. Note that the points of the relative pressure Pr for collecting data are set to a total of 6 points of 0.05, 0.10, 0.15, 0.20, 0.25, and 0.30. A straight line is drawn from the obtained measurement data by the least square method, and Vm is calculated from the slope and intercept of the straight line. Furthermore, using the value of Vm, the BET specific surface area of the inorganic fine particles is calculated as described above.

<Method for Measuring Weight Average Particle Size (D4) of Toner Particles>
The weight average particle diameter (D4) of the toner particles is measured with a precision particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) equipped with a 100 μm aperture tube. Measured data with 25,000 effective measurement channels using the dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) for condition setting and measurement data analysis Analyze and calculate.
As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.
Prior to measurement and analysis, the dedicated software is set as follows.
In the “Standard measurement method (SOM) change screen” of the dedicated software, set the total count in the control mode to 50000 particles, the number of measurements is 1 and the Kd value is “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash after measurement is checked.
In the special software "Pulse to particle size conversion setting screen", bin interval is changed to logarithmic particle size.
The particle size bin is set to 256 particle size bins, and the particle size range is set to 2 μm or more and 60 μm or less.
The specific measurement method is as follows.
(1) About 200 ml of the electrolytic solution is placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.
(2) About 30 ml of the electrolytic aqueous solution is put in a glass 100 ml flat bottom beaker, and "Contaminone N" (nonionic surfactant, anionic surfactant, organic builder pH 7 precision measurement is used as a dispersant therein. About 0.3 ml of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for washing a vessel (made by Wako Pure Chemical Industries, Ltd.) 3 times with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and is placed in a water tank of an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) with an electrical output of 120 W. A predetermined amount of ion-exchanged water is put, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. The “average diameter” on the analysis / volume statistics (arithmetic average) screen when the graph / volume% is set with the dedicated software is the weight average particle diameter (D4).

Specific examples of the present invention will be described below, but the present invention is not limited to these examples. Note that “parts” and “%” in the following formulations are based on mass unless otherwise specified.
<Binder Resin Production Example 1>
76.9 parts by mass (0.167 mol) of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 24.1 parts by mass (0.145 mol) of terephthalic acid, and titanium tetra 0.5 parts by mass of butoxide was placed in a 4-liter 4-neck flask made of glass, and a thermometer, a stir bar, a condenser and a nitrogen inlet tube were attached and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 4 hours while stirring at a temperature of 200 ° C. (first reaction step). Thereafter, 2.0 parts by mass (0.010 mol) of trimellitic anhydride was added and reacted at 180 ° C. for 1 hour (second reaction step), whereby a binder resin 1 was obtained.
The binder resin 1 had an acid value of 10 mgKOH / g and a hydroxyl value of 65 mgKOH / g. Moreover, the molecular weight by GPC was a weight average molecular weight (Mw) 8,000, a number average molecular weight (Mn) 3,500, a peak molecular weight (Mp) 5,700, and the softening point was 90 degreeC.

<Binder Resin Production Example 2>
71.3 parts by mass (0.155 mol) of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 24.1 parts by mass (0.145 mol) of terephthalic acid, and titanium tetra 0.6 parts by mass of butoxide was put into a 4-liter 4-neck flask made of glass, and a thermometer, a stirring rod, a condenser and a nitrogen introducing tube were attached and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 2 hours while stirring at a temperature of 200 ° C. (first reaction step). Thereafter, 5.8 parts by mass (0.030 mol%) of trimellitic anhydride was added and reacted at 180 ° C. for 10 hours (second reaction step), whereby a binder resin 2 was obtained.
The binder resin 2 has an acid value of 15 mgKOH / g and a hydroxyl value of 7 mgKOH / g. Moreover, the molecular weight by GPC was the weight average molecular weight (Mw) 200,000, the number average molecular weight (Mn) 5,000, the peak molecular weight (Mp) 10,000, and the softening point was 130 degreeC.

<Production Example 1 of a polymer having a structure in which a vinyl resin component and a hydrocarbon compound are reacted>
・ 20.0 parts by mass of low density polyethylene (Mw 1400, Mn 850, DSC has a maximum endothermic peak of 100 ° C.)
Styrene 64.0 parts by mass n-butyl acrylate 13.5 parts by mass Acrylonitrile 2.5 parts by mass were charged into an autoclave, and the system was replaced with N ₂ and maintained at 180 ° C while stirring at elevated temperature. In the system, 50 parts by mass of a 2% by mass t-butyl hydroperoxide xylene solution was continuously added dropwise for 5 hours. After cooling, the solvent was separated and removed, and the vinyl resin component was graft polymerized onto the low-density polyethylene. Combined A was obtained. When the molecular weight of the polymer A was measured, it was weight average molecular weight (Mw) 7000 and number average molecular weight (Mn) 3000.

<Toner Production Example 1>
(First kneading step)
-Binder resin 1 50 parts by mass-C.I. I. Pigment Yellow 180 (powder) 50 parts by mass / distilled water 50 parts by mass The above raw materials are first charged in a kneader-type mixer and heated without pressure while being mixed. When the maximum temperature (necessarily determined by the boiling point of the solvent in the paste. In this case, about 90 to 100 ° C.), the pigment in the aqueous phase is distributed or transferred to the molten resin phase to confirm this. After that, the mixture is further melted and kneaded for 30 minutes to sufficiently transfer the pigment in the paste. Then, once the mixer was stopped and the hot water was discharged, the temperature was further raised to 110 ° C., heated and melted and kneaded for about 30 minutes, the pigment was dispersed and the water was distilled off, and the process was completed. The mixture was cooled and the kneaded product was taken out to obtain a first kneaded product.
(Second kneading step)
-1st kneaded material (content of pigment particles 50 mass%) 14.0 parts by mass-Binder resin 1 53.0 parts by mass-Binder resin 2 40.0 parts by mass-Polymer A 5.0 masses Part ・ C. I. Solvent Yellow 98 (powder) 1.0 part by mass, paraffin wax (maximum endothermic peak temperature: 78 ° C.) 5.0 part by mass, 3,5-di-tert-butylsalicylic acid Al compound 1.0 part by mass Preliminary mixing is sufficiently performed with a Henschel mixer, and the mixture is melt-kneaded with a twin-screw extruder kneader at a temperature of 150 ° C. After cooling, coarsely pulverized to about 1 to 2 mm using a hammer mill. Subsequently, it was finely pulverized to a particle size of 20 μm or less by an air jet type fine pulverizer. Further, the obtained finely pulverized product was classified to obtain yellow resin particles (classified product) having a weight average particle size distribution of 6.2 μm.
Thereafter, titanium oxide fine particles having an average primary particle diameter of 50 nm that are surface-treated with isobutyltrimethoxysilane (treatment amount: 10 parts by mass per 100 parts by mass of titanium oxide fine particles) as inorganic fine particles with respect to 100 parts by mass of the yellow resin particles. 0.8 parts by mass and 0.6 parts by mass of the following hydrophobic silica were added and externally added to obtain yellow toner 1.
Hydrophobic silica was prepared by treating silica fine particles (BET specific surface area 200 m ² / g) produced by a dry method with hexamethylene disilazane (treatment amount: 10 parts by mass per 100 parts by mass of silica fine particles). Thereafter, dimethyl silicone oil treatment (treatment amount: 16 parts by mass per 100 parts by mass of silica fine particles) was further performed.

<Toner Production Examples 2 to 24>
Toners 2 to 24 were obtained in the same manner except that the toner formulation 1 was changed to the toner formulation shown in Table 1 below.

<Production example 1 of magnetic core particles>
Process 1 (weighing / mixing process):
・ Fe ₂ O ₃ 60.2 mass%
· MnCO ₃ 33.9% by weight
Mg (OH) ₂ 4.8% by mass
・ SrCO ₃ 1.1 mass%
The ferrite raw material was weighed so as to achieve the above composition ratio. Thereafter, the mixture was pulverized and mixed for 2 hours in a dry ball mill using zirconia balls having a diameter of 10 mm.
Step 2 (temporary firing step):
After pulverization and mixing, firing was performed at a temperature of 950 ° C. for 2 hours in the air using a burner-type firing furnace to prepare calcined ferrite. The composition of the ferrite was as follows.
(MnO) _0.387 (MgO) _0.108 (SrO) _0.010 (Fe ₂ O ₃ ) _0.495
Step 3 (grinding step):
After pulverizing to about 0.5 mm with a crusher, 30 parts by mass of water was added to 100 parts by mass of calcined ferrite using a ball of stainless steel having a diameter of 10 mm, and pulverized with a wet ball mill for 6 hours.
The slurry was pulverized for 3 hours by a wet bead mill using zirconia beads having a diameter of 1.0 mm to obtain a ferrite slurry.
Process 4 (granulation process):
To the ferrite slurry, 2.0 parts by mass of polyvinyl alcohol was added as a binder with respect to 100 parts by mass of calcined ferrite, and granulated into spherical particles of about 36 μm with a spray dryer (manufacturer: Okawahara Chemical).
Process 5 (main baking process):
In order to control the firing atmosphere, firing was performed in an electric furnace in a nitrogen atmosphere (oxygen concentration of 0.01% by volume or less) at a temperature of 1300 ° C. for 4 hours.
Process 6 (screening process):
After the aggregated particles were crushed, coarse particles were removed by sieving with a sieve having an opening of 250 μm to obtain magnetic core particles 1.

<Manufacture example 1 of a magnetic carrier>
・ Straight silicone resin (SR2411 Toray Dow Corning) 20.0% by mass
(Kinematic viscosity in 20% by weight toluene solution 1.1 × 10 ⁻⁴ m ² / sec)
・ Γ-aminopropyltriethoxysilane 0.5% by mass
・ Toluene 79.0% by mass
The said material was mixed so that it might become the said composition ratio, and the resin liquid 1 was obtained.
With respect to 100 parts by mass of the magnetic core particles 1, the resin liquid 1 was added to a Nauter mixer so as to be 1.0 part by mass as a resin component. It heated at 70 degreeC under pressure reduction, mixed by 1.7S < ^-1 > (100 rpm), and solvent removal and application | coating operation were performed over 4 hours. Thereafter, the obtained sample was transferred to a Julia mixer, heat-treated for 2 hours at a temperature of 200 ° C. in a nitrogen atmosphere, and then classified with a sieve having an opening of 70 μm to obtain a magnetic carrier 1. The obtained magnetic carrier 1 had a volume distribution standard 50% particle size (D50) of 36.5 μm.

[Example 1]
<Preparation of two-component developer>
The toner 1 and the magnetic carrier 1 are mixed with a V-type mixer (V-10 type: Tokuju Seisakusho Co., Ltd.) at 0.5 s ⁻¹ and a rotation time of 5 min so that the toner concentration becomes 8% by mass, and a two-component system. Developer 1 was obtained. The following evaluation was carried out using the two-component developer 1.

<Developability evaluation>
As an image forming apparatus, a Canon full-color copier imageRUNNER ADVANCE C5051 modified machine was used for evaluation. The modified part of the modified machine is that the development conditions and transfer conditions can be adjusted to arbitrary values by an external power source.
Image evaluation (A4 horizontal, 10% printing ratio, 1,000 sheets continuously passed) was performed in a normal temperature and humidity environment (23 ° C., 50% RH).
During the continuous sheet passing time of 1000 sheets, the sheet was passed under the same development conditions and transfer conditions (no calibration) as the first sheet. As the evaluation paper, copy paper CS-814 (A4, basis weight 81.4 g / m ² ) sold by Canon Marketing Japan Inc. was used. In the evaluation environment, the image density of the FFH image (solid portion) on the paper was adjusted to 1.50. The FFH image is a value in which 256 gradations are displayed in hexadecimal, and 00H is the first gradation (white background), and FFH is the 256th gradation (solid part).
The image density (FFH image portion; solid portion) at the initial stage (first sheet) and at the time of continuous 1,000 sheets was measured. For measurement of image density, an X-Rite color reflection densitometer (500 series: manufactured by X-Rite) was used.
The difference in image density between the initial (first image) and the 1,000th FFH image portion (solid portion) was evaluated according to the following criteria. The evaluation results are shown in Table 3.
(Evaluation criteria)
A: Less than 0.05 Very excellent B: 0.05 or more and less than 0.10 Good C: 0.10 or more and less than 0.20 It is a level that is not a problem in the present invention D: 0.20 or more In the present invention Is not acceptable

<Evaluation of chromaticity (lightness, saturation) and tint variation after light resistance test>
As an image forming apparatus, a Canon full-color copier imageRUNNER ADVANCE C5051 modified machine was used for evaluation. Under a normal temperature and humidity environment (23 ° C., 50% RH), a toner gradation amount (mg / cm ² ) on the paper was changed to form a 16-gradation image. Images, SpectroScan Transmission (GretagMacbeth Co., Ltd.) (Measurement _{conditions: D 50} viewing angle 2 °) with, ^L * of the image ^obtained, a *, was measured ^{b *.} In the measurement, L ₁ ^* , a ₁ ^* , and b ₁ ^* were respectively measured at the riding amount where C ^* = 90 on the L ^* -C ^* coordinate axis. In the light resistance test, L ₂ ^* , a ₂ ^* , and b ₂ ^* before and after ultraviolet irradiation (after 120 hours) were measured, and ΔE was calculated. The evaluation results are shown in Table 4.
ΔE = {(L ₁ ^* −L ₂ ^* ) ² + (a ₁ ^* −a ₂ ^* ) ² + (b ₁ ^* −b ₂ ^* ) ² } ^1/2 (Evaluation Criteria)
A: Less than 2.00 Excellent B: 2.00 or more and less than 3.50 Good C: 3.50 or more and less than 5.00 D: 5.00 or more In the present invention Is not acceptable

<Examples 2 to 20 and Comparative Examples 1 to 4>
In Example 1, the evaluation was performed in the same manner except that the two-component developer used for evaluation was changed to the combination shown in Table 2. The evaluation results are shown in Tables 3 and 4.

Claims (4)

A toner having toner particles containing a binder resin, a yellow colorant and a wax,
The yellow colorant contains colorant A and colorant B,
The colorant A is C.I. I. Solvent Yellow 98,
The colorant B is C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 180, C.I. I. One or more pigments selected from the group consisting of Pigment Yellow 185,
When the content of the colorant A with respect to 100 parts by mass of the binder resin is YA (parts by mass) and the content of the colorant B with respect to 100 parts by mass of the binder resin is YB (parts by mass), YA / ( YA + YB) is 0.05 to 0.30.   The toner according to claim 1, wherein (YA + YB) is 3 parts by mass or more and 20 parts by mass or less.   The toner according to claim 1, wherein the toner particles further contain a polymer having a structure in which a vinyl resin component and a hydrocarbon compound are reacted.   The toner according to claim 1, wherein the wax is a hydrocarbon wax.