JP7387392B2 - Toner and toner manufacturing method - Google Patents

Description

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

2. Description of the Related Art In recent years, as electrophotographic color image forming apparatuses have rapidly become popular, their uses have expanded to a wide variety of uses, and demands for image quality have become higher than ever. For example, as computer equipment for personal users becomes cheaper, full-color video communication is becoming more widespread. Image forming devices such as printers and copying machines, which are one of the output means for this purpose, are also required to faithfully reproduce even the smallest details.
Along with this, demands for color vividness are increasing, and an expansion of the color reproduction range is required.
Furthermore, in recent years, there has been a remarkable expansion into the printing field, and electrophotographic output images are required to have improved printing speed and image quality such as high definition, high definition, and graininess that are equivalent to or higher than printing quality. It is becoming more and more common. At the same time, improvements in print speed, reduction in running costs, and stability of image quality regardless of the usage environment are required, and there is a need for toners that satisfy these various required characteristics.
In general, electrophotography involves forming an electrical latent image on a photoreceptor, then developing the latent image with toner, transferring the toner image to a medium such as paper, and then applying heat and/or pressure using a fixing means. It is used to fix the image and obtain an image. In the case of a full-color image, color reproduction is performed using four color toners, including three primary colors of chromatic toner: yellow toner, magenta toner, and cyan toner, and black toner.
Among color toners, yellow toner is particularly sensitive to changes in its hue angle, and changes in chromaticity of transmitted light are easily felt. Furthermore, the charging properties are considerably higher than those of cyan toners and magenta toners, and improvements such as reducing the amount of yellow colorant added to the toner as much as possible are required. Therefore, in order to solve these problems, it is desirable to use monoazo yellow pigments in color toners because they have excellent reflected color and coloring power, but when dried or heated after synthesis, It has not been fully utilized in toners because it tends to cause crystal growth of the primary particles of the pigment and problems with transparency tend to occur. Therefore, the problem has been how to suppress the aggregation of pigments and the growth of primary particles and how to disperse the pigments in toner while keeping the pigment particle size small.
To solve this problem of pigment dispersion, generally, after pigment synthesis, it is not necessary to turn it into powder, but it is heated and mixed with a resin in a water-containing state (paste pigment), and then dried into pellets, or the powdered pigment is heated and mixed with water and resin, and then mixed with a resin. Techniques have been proposed to improve pigment dispersibility by drying and pelletizing.
In Patent Document 1 and Patent Document 2, C. I. A method for producing a water-containing masterbatch of Pigment Yellow 74 is described, and an example of producing a toner with good tinting power and chargeability is given. Furthermore, in Patent Document 3, C.I. I. There is an example of a yellow toner containing Pigment Yellow 74.

Japanese Patent Application Publication No. 2005-157342 JP2009-271545A JP 2017-62402 Publication

However, according to the studies of the present inventors, the method of using the pigment in the form of a paste as described above, the method of adding water when kneading the resin and the pigment, or the method of using an additive when kneading the resin and the pigment, The growth of primary pigment particles could not be sufficiently suppressed, and there was still room for improvement in terms of transparency and hue. In addition, the charging start-up was slow, and the charging properties could not be controlled to match those of other colors. In addition, methods of mixing different types of raw materials (additives) with pigments to improve dispersibility improve dispersibility, but may change the color of the pigment itself or cause filming on the photosensitive drum. There were issues such as:
In particular, since many pigments have poor dispersibility, the dispersed particles tend to scatter light, which tends to reduce the transparency, color reproducibility, saturation, and image density of fixed images. In addition, if the dispersibility of the pigment is poor, the chargeability of the toner is also affected, which may cause fogging.
An object of the present invention is to provide a toner that solves the above problems. Specifically, it is an object of the present invention to provide a toner with excellent color reproducibility, saturation, coloring power, and chargeability of fixed images.

The above problem can be solved by a toner having the following configuration.
The present invention provides a toner comprising toner particles containing a binder resin and a colorant, and inorganic fine particles,
The toner particles contain silica particles or strontium titanate particles,
The binder resin is a polyester resin,
The colorant contains the following compound (1),

該トナー粒子は、カルシウム元素とマグネシウム元素を含有し、該トナー粒子中の化合物（１）の質量を基準とし、該カルシウム元素の含有量をＡ（ｐｐｍ）、該マグネシウム元素の含有量をＢ（ｐｐｍ）とするとき、以下の式を満たすことを特徴とするトナーである。
Ａ＋Ｂ≦３００．０
４．０≦Ａ≦１８０．０
４．０≦Ｂ≦１８０．０
また、本発明は、トナーの製造方法であって、
結着樹脂と上記化合物（１）と塩化カルシウム、及び塩化マグネシウムとを水の存在下で加熱混合して、含水率が５質量％以上２５質量％以下の含水着色剤マスターバッチを得る工程と、該含水着色剤マスターバッチと該結着樹脂とを溶融混練し、混練物を得る工程と、該混練物を粉砕してトナー粒子を得る工程を有し、
得られるトナーが、結着樹脂、着色剤を含有するトナー粒子と無機微粒子とを有し、
該結着樹脂はポリエステル樹脂であり、
該着色剤は上記化合物（１）を含有し、
該トナー粒子は、カルシウム元素とマグネシウム元素を含有し、該トナー粒子中の化合 物（１）の質量を基準とし、該カルシウム元素の含有量をＡ（ｐｐｍ）、該マグネシウム元素の含有量をＢ（ｐｐｍ）とするとき、以下の式：
Ａ＋Ｂ≦３００．０
４．０≦Ａ≦１８０．０
４．０≦Ｂ≦１８０．０
を満たすことを特徴とするトナーの製造方法である。

The toner particles contain a calcium element and a magnesium element, and based on the mass of compound (1) in the toner particles, the content of the calcium element is A (ppm), and the content of the magnesium element is B ( ppm), the toner is characterized by satisfying the following formula.
A+B≦300.0
4.0≦A≦180.0
4.0≦B≦180.0
The present invention also provides a method for producing a toner, comprising:
A step of heating and mixing a binder resin, the above compound (1), calcium chloride, and magnesium chloride in the presence of water to obtain a water-containing colorant masterbatch having a water content of 5% by mass or more and 25% by mass or less; A step of melt-kneading the water-containing colorant masterbatch and the binder resin to obtain a kneaded product, and a step of pulverizing the kneaded product to obtain toner particles,
The obtained toner has toner particles containing a binder resin and a colorant, and inorganic fine particles,
The binder resin is a polyester resin,
The colorant contains the above compound (1),
The toner particles contain a calcium element and a magnesium element, and the content of the calcium element is A (ppm), and the content of the magnesium element is B, based on the mass of the compound (1) in the toner particle. (ppm), the following formula:
A+B≦300.0
4.0≦A≦180.0
4.0≦B≦180.0
This is a toner manufacturing method characterized by satisfying the following.

According to the present invention, it is possible to provide a toner with excellent color reproducibility, saturation, coloring power, and chargeability of a fixed image.

The present inventors consider the effects of using the toner of the present invention as follows.

The toner of the present invention contains the compound (1), a polyester resin, a calcium element, and a magnesium element, and the interaction between the compound (1) and the calcium element and the magnesium element in the polyester resin is We believe that this will occur.

[Colorant]
Due to these interactions, the toner of the present invention has excellent image color reproducibility, saturation, and coloring power because the pigment containing the compound (1) as a main component in the toner is finely dispersed during fixing. They estimate that. Organic pigment surfaces generally have low polarity. Some pigments have polar groups in their molecular structure, but when pigments crystallize, the molecules often overlap, centering on interactions between polar groups, so they are exposed on the particle surface. This is because the number of polar groups decreases. Therefore, since the surface of a low-energy pigment with few polar groups has little ability to adsorb polar groups in the dispersion medium, it is difficult to maintain a stable dispersion state. Therefore, it is necessary to improve the dispersibility by generating electrical repulsion on the surface of the compound (1) by containing the calcium element and the magnesium element as in the present case.

Examples of pigments to be combined with compound (1) include the following. C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; C. I. Bat yellow 1, 3, 20. As a dye, C. I. There is Solvent Yellow 162.

Other compounds to be combined with compound (1) include C. I. Solvent Yellow 162 is preferred. When used in combination with compound (1), the dispersibility of the pigment increases during fixing, and the color reproducibility, saturation, and coloring power of the fixed image improve.

The content of compound (1) in the toner of the present invention is preferably 0.5 parts by mass or more and 20.0 parts by mass or less, and 1.0 parts by mass or more and 3.0 parts by mass or less, based on 100 parts by mass of the binder resin. More preferably, it is 0 part by mass or less. When the content of compound (1) is 0.5 parts by mass or more, an effect of improving hot offset resistance during fixing can be expected. Further, when the amount is 20.0 parts by mass or less, the pigment does not aggregate and exist in the toner, so there is no color turbidity, and it is possible to widen the range of color reproducibility.

The content of the colorant in the toner of the present invention is preferably 3.0 parts by mass or more and 20.0 parts by mass or less, and 5.0 parts by mass or more and 15.0 parts by mass or less based on 100 parts by mass of the binder resin. It is more preferable that there be. When the content of the colorant is 3.0 parts by mass or more, the amount of toner applied on the paper becomes appropriate in order to produce an output image with a desired density. Further, when the amount is 20.0 parts by mass or less, the pigment becomes difficult to aggregate, the color becomes difficult to become cloudy, and the range of color reproducibility is likely to be widened.

In the present invention, it is preferable to include the coloring agent after preparing the master badge, and the details will be described later.

[Calcium element/Magnesium element]
In the present invention, when the content of calcium element is A (ppm) and the content of magnesium element is B (ppm) based on the mass of compound (1) in the toner particles, the following formula is satisfied. is necessary.
A+B≦300.0
4.0≦A≦180.0
4.0≦B≦180.0

That is, the content of calcium element in the toner of the present invention is 4.0 ppm or more and 180.0 ppm or less. Preferably it is 10.0 ppm or more and 150.0 ppm or less, and more preferably 10.0 ppm or more and 100.0 ppm or less. If the content of calcium element is less than 4.0 ppm, the dispersion effect of compound (1) cannot be obtained. If the content of calcium element exceeds 180.0 ppm, the chargeability of the toner deteriorates.

Further, the content of magnesium element in the toner of the present invention is 4.0 ppm or more and 180.0 ppm or less. Preferably it is 10.0 ppm or more and 150.0 ppm or less, and more preferably 10.0 ppm or more and 100.0 ppm or less. If the content of magnesium element is less than 4.0 ppm, the dispersion effect of compound (1) cannot be obtained. When the content of the magnesium element exceeds 180.0 ppm, the charging property of the toner deteriorates.

In the toner of the present invention, the total (A+B) of the calcium element content (A) and the magnesium element content (B) is 300.0 ppm or less. When it exceeds 300.0 ppm, the dispersibility of compound (1) deteriorates, and the tinting strength, color reproducibility, and chargeability deteriorate.

In the toner of the present invention, the ratio (A/B) between the calcium element content (A) and the magnesium element content (B) is preferably 1.5 or more and 10.0 or less. Within the above range, the dispersibility of compound (1) is further improved, and the coloring power, color reproducibility, and chargeability of the toner are further improved.

In the toner of the present invention, the calcium element and the magnesium element may be contained in any form in the toner, but they are contained in the toner particles in order to further strengthen the interaction with the compound (1). It is preferable. A known method can be used to incorporate the toner particles into the toner particles. For example, it may be contained in the toner particles in the form of fine particles such as calcium carbonate fine particles or magnesium carbonate fine particles, or it may be contained in the toner particles in the form of a water-soluble inorganic salt such as calcium metasilicate or calcium sulfate. good. Further, inorganic compounds such as calcium hydroxide and magnesium hydroxide may be contained in the toner particles.

[Binder resin]
In the present invention, the binder resin contains a polyester resin from the viewpoints of pigment dispersibility, fixing properties, and development stability. The content of the polyester resin in the total binder resin is 50% by mass or more and 100% by mass or less, preferably 70% by mass or more and 100% by mass or less.

The polyester resin used in the present invention is a resin having a polyester unit in a binder resin chain, and the components constituting the polyester unit include an alcohol monomer component having a valence of 2 or more. , 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, as the dihydric or higher alcohol monomer component, polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene (3.3)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene (3.3)-2,2-bis(4-hydroxyphenyl) -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-bis(4-hydroxyphenyl)propane and other alkylene oxide adducts of bisphenol A, ethylene glycol, diethylene glycol, triethylene glycol, 1,2 -Propanediol, 1,3-propanediol, 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, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2 , 4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5- Examples include trihydroxymethylbenzene.

Among these, the alcohol monomer component preferably used is an aromatic diol, and in the alcohol monomer component constituting the polyester resin, the aromatic diol is preferably contained in a proportion of 80 mol% or more and 100 mol% or less. .

On the other hand, the acid monomer components such as divalent or higher carboxylic acids, divalent or higher carboxylic acid anhydrides, and divalent or higher carboxylic acid esters include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid; Anhydrides thereof; Alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid, or anhydrides thereof; succinic acids substituted with alkyl or alkenyl groups having 6 to 18 carbon atoms; fumaric acid; acid, unsaturated dicarboxylic acids such as maleic acid and citraconic acid, or anhydrides thereof;

Among these, preferred acid monomer components are polyhydric carboxylic acids such as terephthalic acid, succinic acid, adipic acid, fumaric acid, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and its anhydride.

Further, the acid value of the polyester resin is preferably 20 mgKOH/g or less from the viewpoint of pigment dispersibility and development stability. More preferably, it is 15 mgKOH/g or less. The lower limit is not particularly limited and is 0 mgKOH/g or more, preferably 1 mgKOH/g or more, more preferably 3 mgKOH/g or more. When the acid value is 20 mgKOH/g or less, the dispersibility of the pigment will be good, and the fixability and developability will be improved.

The acid value can be adjusted within the above range by adjusting the type and amount of monomers used in the 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 be controlled by reacting the terminal alcohol with a polyhydric acid monomer (for example, trimellitic acid) after ester condensation polymerization.

[Resin composition having a structure in which a vinyl resin component and a hydrocarbon compound have reacted]
The toner particles according to the present invention may contain a resin composition having a structure in which a vinyl resin component and a hydrocarbon compound have reacted, if necessary. By containing the resin composition, the pigment and wax in the toner can be more uniformly and finely dispersed.

The resin composition having a structure in which the vinyl resin component and a hydrocarbon compound have reacted may be a graft polymer having a structure in which a polyolefin is grafted to a vinyl resin component, or a vinyl resin component in which a vinyl monomer is graft-polymerized to a polyolefin. Graft polymers having the following are particularly preferred.

The resin composition having a structure in which the vinyl resin component and the hydrocarbon compound have reacted acts like a surfactant for the melted binder resin and wax during the kneading process and surface smoothing process during toner production. Therefore, the resin composition is preferable because it allows control of the primary average dispersed particle size of the wax in the toner particles and, if necessary, the transfer rate of the wax to the toner surface when surface treatment is performed with hot air.

Regarding the graft polymer having a structure in which a polyolefin is grafted to a vinyl resin component or the graft polymer having a vinyl resin component in which a vinyl monomer is grafted to a polyolefin, the polyolefin is an unsaturated hydrocarbon having one double bond. Various polyolefins can be used without particular limitation as long as they are polymers or copolymers of monomers. In particular, polyethylene and polypropylene are preferably used.

On the other hand, examples of vinyl monomers include the following.
Styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethyl Styrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene Styrenic monomers such as styrene and its derivatives.
Amino group-containing α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; vinyl-based esters containing nitrogen atoms such as acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide monomer.
Unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenylsuccinic acid, fumaric acid, mesaconic acid; such as maleic anhydride, citraconic anhydride, itaconic anhydride, alkenylsuccinic anhydride. Unsaturated dibasic acid anhydride; methyl maleate half ester, ethyl maleate half ester, butyl maleate half ester, methyl citraconate half ester, ethyl citraconate half ester, butyl citraconate half ester, methyl itaconate half ester, Half esters of unsaturated dibasic acids such as methyl alkenylsuccinate half ester, methyl fumarate half ester, methyl mesaconate half ester; unsaturated dibasic acid esters such as dimethylmaleic acid, dimethyl fumaric acid; acrylic acid, α,β-unsaturated acids such as methacrylic acid, crotonic acid, and cinnamic acid; α,β-unsaturated acid anhydrides such as crotonic anhydride and cinnamic acid; Anhydrides with lower fatty acids; vinyl monomers containing carboxyl groups such as alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid, these acid anhydrides, and these monoesters.
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-methyl) Vinyl monomers containing hydroxyl groups such as (hexyl) styrene.
Methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-acrylate An ester unit consisting of acrylic esters such as acrylic esters such as chloroethyl and phenyl acrylate.
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, methacrylate An ester unit consisting of a methacrylic acid ester such as α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl acid and diethylaminoethyl methacrylate.

A resin composition having a structure in which a vinyl resin component and a hydrocarbon compound have reacted can be obtained by known methods such as the reaction of these monomers with each other or the reaction of the monomer of one polymer with the other polymer. be able to.

It is preferable that the vinyl resin component contains a styrene unit, and further acrylonitrile or methacrylonitrile.

The mass ratio of the hydrocarbon compound to the vinyl resin component (hydrocarbon compound/vinyl resin component) in the resin composition is preferably 1/99 to 75/25. It is preferable to use the hydrocarbon compound and the vinyl resin component within the above ranges in order to disperse the pigment into the toner particles.

The content of the resin composition having a structure in which the vinyl resin component and the hydrocarbon compound have reacted is preferably 0.2 parts by mass or more and 20 parts by mass or less, based on 100 parts by mass of the binder resin, and 3 parts by mass or less. More preferably, the amount is .0 parts by mass or more and 10 parts by mass or less. It is preferable to use the resin composition within the above range in order to disperse the pigment into the toner particles.

Further, the weight average molecular weight (Mw) of the resin composition is preferably 6,000 or more and 8,000 or less, and the number average molecular weight (Mn) is preferably 1,500 or more and 5,000 or less.

[wax]
The toner of the present invention can also contain wax, if necessary. The wax contained in the toner is preferably a hydrocarbon wax.

Hydrocarbon waxes include, but are not particularly limited to, the following: Hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxides of hydrocarbon waxes such as oxidized polyethylene wax, or block copolymers thereof Products: Waxes whose main component is fatty acid esters such as carnauba wax; Partially or fully deoxidized fatty acid esters such as deoxidized carnauba wax.

Additionally, the following may be mentioned: Saturated straight chain fatty acids such as palmitic acid, stearic acid, montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, parinaric acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubil alcohol, seryl alcohol , saturated alcohols such as mericyl alcohol; polyhydric alcohols such as sorbitol; fatty acids such as palmitic acid, stearic acid, behenic acid, montanic acid, and stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubil alcohol. esters with alcohols such as , ceryl alcohol, and mericyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylene bisstearic acid amide, ethylene biscapric acid amide, and ethylene bislauric acid amide. acid amide, saturated fatty acid bisamides such as hexamethylene bis-stearamide; ethylene bis-oleic acid amide, hexamethylene bis-oleic acid amide, N,N' dioleyl adipate amide, N, N' dioleyl sebacic acid amide; unsaturated fatty acid amides such as m-xylene bisstearamide, aromatic bisamides such as N,N' distearyl isophthalic acid amide; calcium stearate, calcium laurate, zinc stearate, magnesium stearate Aliphatic metal salts (generally called metal soaps); Waxes made by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid; Fatty acids such as behenic acid monoglyceride Partial esterification product of polyhydric alcohol; methyl ester compound having a hydroxyl group obtained by hydrogenating vegetable oil.

Among these waxes, paraffin wax and Fischer-Tropsch wax are preferred from the viewpoint of improving color reproducibility.

The content of the wax is preferably 0.5 parts by mass or more and 20.0 parts by mass or less, more preferably 3.0 parts by mass or more and 12.0 parts by mass or less, based on 100 parts by mass of the binder resin. In addition, from the perspective of achieving both toner storage stability and high-temperature offset properties, in the endothermic curve during temperature rise measured with a differential scanning calorimeter (DSC), the maximum endotherm that exists in the temperature range of 30°C or more and 200°C or less It is preferable that the peak temperature is 50°C or more and 110°C or less. Furthermore, it is more preferable that the temperature is 70°C or more and 100°C or less.

[Charge control agent]
The toner of the present invention can also contain a charge control agent, if necessary. As the charge control agent contained in the toner, any known charge control agent can be used, but a metal compound of an aromatic carboxylic acid is particularly preferable because it is colorless, has a high charging speed of the toner, and can stably maintain a constant charge amount.

Examples of negative charge control agents include salicylic acid metal compounds, naphthoic acid metal compounds, dicarboxylic acid metal compounds, polymer-type compounds with sulfonic acid or carboxylic acid in the side chain, and sulfonate or sulfonic acid ester compounds in the side chain. Examples include polymeric compounds, polymeric compounds having carboxylates or carboxylic acid esters in their side chains, boron compounds, urea compounds, silicon compounds, and calixarene. The charge control agent may be added internally or externally to the toner particles. The amount of the charge control agent added 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.

[Inorganic fine particles]
The toner particles of the present invention may contain strontium titanate particles, if necessary. Strontium titanate particles have relatively low resistance and high dielectric constant, and are preferable from the viewpoint of charging stability of the toner. Among the strontium titanate particles, strontium titanate particles having a cubic or rectangular parallelepiped particle shape and a perovskite crystal structure are preferable from the viewpoint of charging stability of the toner.

When the volume resistivity of the strontium titanate particles used in the present invention is in the range of 2.0×10 ⁹ Ω·cm to 2.0×10 ¹² Ω·cm, the amount of charge can be reduced while suppressing charge injection by the transfer bias. This is more preferable because the distribution is sharpened.

The number average particle diameter of the strontium titanate particles used in the present invention is preferably 20 nm or more and 300 nm or less, more preferably 30 nm or more and 100 nm or less, and even more preferably 20 nm or more and 60 nm or less. Moreover, in those particle size distributions, it is preferable that the peak top of the number frequency is within the above particle size range. When the number average particle diameter is within the above range, the effect of improving charging stability after low printing durability in a high temperature and high humidity environment is likely to occur, and the repulsive force with the surface of compound (1) is likely to work. This is preferable because the dispersion effect of compound (1) is enhanced.

The strontium titanate particles used in the present invention preferably have their surfaces hydrophobicized using a surface treatment agent. As the surface treatment agent, fatty acids or metal salts thereof, disilylamine compounds, halogenated silane compounds, silicone oils, silane coupling agents, titanium coupling agents, and the like are preferable because they can improve the charging stability of the toner. Among these, n-octylethoxysilane treatment and 3,3,3-trifluoropropyltrimethoxysilane treatment are preferred from the standpoint of further enhancing the dispersion effect of compound (1).

The content of strontium titanate particles in the toner particles is preferably 0.1 parts by mass or more and 30.0 parts by mass or less, based on 100 parts by mass of the toner particles. When the amount is 0.1 parts by mass or more, the dispersion effect of compound (1) is easily exhibited, and when it is 30.0 parts by mass or less, there is no decrease in charging property. From the viewpoint of dispersibility and chargeability of compound (1), it is more preferably 0.5 parts by mass or more and 10 parts by mass or less, and even more preferably 1.0 parts by mass or more and 6.0 parts by mass or less.

Strontium titanate particles as an example of inorganic fine particles used in the present invention can be obtained by a normal pressure heating reaction method. At this time, it is preferable to use a mineral acid peptized product of a hydrolyzate of a titanium compound as the titanium oxide source, and to use a water-soluble acidic strontium compound as the strontium oxide source. It can be produced by a method in which a mixture thereof is reacted with an aqueous alkali solution at 60° C. or higher, and then treated with an acid.

(Normal pressure heating reaction method)
As a titanium oxide source, a mineral acid peptized product of a hydrolyzate of a titanium compound can be used. Preferably, metatitanic acid having an SO ₃ content of 1.0% by mass or less, preferably 0.5% by mass or less obtained by the sulfuric acid method is adjusted to a pH of 0.8 or more and 1.5 or less with hydrochloric acid. A peptized one can be used.

As the strontium oxide source, metal nitrates, hydrochlorides, etc. can be used, and for example, strontium nitrate and strontium chloride can be used.

As the alkaline aqueous solution, a caustic alkali can be used, and among them, a sodium hydroxide aqueous solution is preferable.

In the method for producing strontium titanate particles, factors that affect the particle size include the mixing ratio of the titanium oxide source and the strontium oxide source during the reaction, the titanium oxide source concentration at the initial stage of the reaction, and the temperature when adding the alkaline aqueous solution. and addition rate. These can be adjusted as appropriate to obtain the desired particle size and particle size distribution. In addition, in order to prevent the formation of carbonate during the reaction process, it is preferable to prevent the contamination of carbon dioxide gas, such as by conducting the reaction in a nitrogen gas atmosphere.

In the method for producing the resulting strontium titanate particles, factors that affect the dielectric constant include conditions/operations that disrupt particle crystallinity. In particular, in order to obtain strontium titanate particles with a low dielectric constant, it is preferable to carry out an operation in which energy is applied to disrupt crystal growth while the concentration of the reaction solution is increased. A specific method includes, for example, adding microbubbling with nitrogen to the crystal growth process. Further, the content of cubic and rectangular parallelepiped particles can also be controlled by the flow rate of this nitrogen microbubbling.

The mixing ratio of the titanium oxide source and the strontium oxide source during the reaction is preferably 0.9 or more and 1.4 or less, and more preferably 1.05 or more and 1.20 or less, as a molar ratio of SrO/TiO ₂ . Within the above range, unreacted titanium oxide is unlikely to remain. The concentration of the titanium oxide source at the initial stage of the reaction is preferably 0.05 mol/L or more and 1.3 mol/L or less, more preferably 0.08 mol/L or more and 1.0 mol/L or less in terms of TiO ₂ .

The temperature when adding the alkaline aqueous solution is preferably 60°C or higher and 100°C or lower. Furthermore, regarding the addition rate of the alkaline aqueous solution, the slower the addition rate, the larger the particle size of strontium titanate particles can be obtained, and the faster the addition rate, the smaller the particle size of the strontium titanate particles. The rate of addition of the alkaline aqueous solution is preferably 0.001 equivalent/h or more and 1.2 equivalent/h or less, more preferably 0.002 equivalent/h or more and 1.1 equivalent/h or less, based on the raw material to be prepared. It can be adjusted as appropriate depending on the desired particle size.

(acid treatment)
It is preferable that the strontium titanate particles obtained by the normal pressure heating reaction are further treated with an acid. When performing a normal pressure heating reaction to synthesize strontium titanate particles, if the mixing ratio of the titanium oxide source and the strontium oxide source exceeds 1.0 in the molar ratio of SrO/TiO ₂ , residual particles remain after the reaction is completed. Unreacted metal sources other than titanium may react with carbon dioxide gas in the air, producing impurities such as metal carbonates. If impurities such as metal carbonates remain on the surface, it is not possible to uniformly coat the surface with the organic surface treatment agent due to the influence of the impurities when performing organic surface treatment to impart hydrophobicity. Therefore, after adding the alkaline aqueous solution, it is preferable to perform acid treatment to remove unreacted metal sources.

In the acid treatment, it is preferable to use hydrochloric acid to adjust the pH to 2.5 or more and 7.0 or less, more preferably pH 4.5 or more and 6.0 or less. As the acid, in addition to hydrochloric acid, nitric acid, acetic acid, etc. can be used for the acid treatment.

[Silica particles]
The toner particles of the present invention can contain silica particles, if necessary. The silica particles may be produced by a known production method such as a combustion method or hydrothermal synthesis, but amorphous silica particles produced by the combustion method are preferred because they are less susceptible to the influence of moisture in the air. Furthermore, the surface of the silica particles is hydrophobized with a fatty acid or a metal salt thereof, silicone oil, a silane coupling agent, a titanium coupling agent, etc. to enhance the dispersion effect of the compound (1). It is preferable from the viewpoint of charging property, and among them, silane coupling agents such as hexamethyldisiloxane (HMDS), octyltriethoxysilane, and dichlorosilane are more preferable.

The content of silica particles in the toner particles of the present invention is preferably 0.1 parts by mass or more and 20.0 parts by mass or less, based on 100 parts by mass of the toner particles. When the amount is 0.1 parts by mass or more, the dispersion effect of compound (1) is easily exhibited, and when it is 20.0 parts by mass or less, there is no decrease in charging property. From the viewpoint of dispersibility and chargeability of compound (1), it is more preferably 0.5 parts by mass or more and 8.0 parts by mass or less, and even more preferably 1.0 parts by mass or more and 5.0 parts by mass or less.

[External additive]
In the present invention, external additives may be further added to improve fluidity and adjust the amount of triboelectric charge, if necessary.

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 using a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.

As the external additive used, inorganic fine particles having a specific surface area of 10 m ² /g or more and 50 m ² /g or less are preferable from the viewpoint of suppressing embedding of the external additive.

Further, the external additive is preferably used in an amount of 0.1 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of toner particles.

A known mixer such as a Henschel mixer can be used to mix the toner particles and the external additive, but the device is not particularly limited as long as it is capable of mixing.

[Magnetic carrier]
The toner of the present invention is preferably mixed with a magnetic carrier and used as a two-component developer, since a stable image can be obtained over a long period of time.

Examples of magnetic carriers include iron powder with an oxidized surface, unoxidized iron powder, metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, and rare earth metals. Generally known materials such as magnetic materials such as alloy particles, oxide particles, and ferrite, and magnetic material-dispersed resin carriers (so-called resin carriers) containing magnetic materials and a binder resin that holds the magnetic materials in a dispersed state. can be used.

[Hydrous colorant master badge]
The toner of the present invention preferably contains a colorant masterbatch in which the colorant is diluted with a binder resin or the like in advance from the viewpoint of pigment dispersibility. In order to manufacture a colorant masterbatch, for example, the following manufacturing method can be mentioned.

When preparing a colorant masterbatch, a paste colorant is used or water is added, and the resin and colorant are heated and mixed in the presence of water to disperse the colorant in the resin. After that, the colorant masterbatch would normally be dried by evaporating the water, but by applying only the minimum amount of heat necessary, the water in the colorant masterbatch is dried without completely evaporating it. It is left as is and used in the next step (usually the melt-kneading step). By applying as little heat as possible to the yellow colorant, the growth of the colorant can be suppressed and minute colorants can be dispersed in the toner particles.

The water content of a water-containing colorant masterbatch (water-containing colorant masterbatch) also has a great effect on toner quality. The water content of the desired colorant masterbatch in the present invention is 5% by mass or more and 25% by mass or less, preferably 8% by mass or more and 20% by mass or less. If the water content is reduced to less than 5% by mass, excess heat will be applied to the colorant, which may result in particle growth. On the other hand, if the water content is more than 25% by mass, deposits on the equipment wall or uneven agglomerates may occur when toner raw materials are mixed, and the stability of feeding into the kneading machine may decrease. Therefore, it becomes difficult to disperse the colorant into the toner particles well, and color uniformity and charging uniformity tend to deteriorate.

That is, in the present invention, the step of heating and mixing the colorant and a part of the binder resin in the presence of water to obtain a water-containing colorant masterbatch having a water content of 5% by mass or more and 25% by mass or less; It is preferable to produce a toner through a melt-kneading step of melt-kneading the water-containing colorant masterbatch and the remaining binder resin to obtain a kneaded product, and a pulverizing step of pulverizing the kneaded product to obtain a toner.

[Production method]
The method for manufacturing the toner of the present invention is not particularly limited, and any known manufacturing 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, predetermined amounts of materials constituting the toner particles, such as a binder resin, a colorant, a wax, and, if necessary, other components such as a charge control agent, are weighed out, blended, and mixed. Examples of the mixing device include a double con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, a mechano hybrid (manufactured by Nippon Coke Industry Co., Ltd.), and the like.

Next, the mixed materials are melt-kneaded to disperse the colorant, wax, etc. in the binder resin. In the melt-kneading process, batch-type kneaders such as pressure kneaders and Banbury mixers, as well as continuous-type kneaders can be used, and single-screw or twin-screw extruders have become mainstream due to their advantage in continuous production. ing. For example, KTK type twin screw extruder (manufactured by Kobe Steel, Ltd.), TEM type twin screw extruder (manufactured by Toshiba Machinery Co., Ltd.), PCM kneader (manufactured by Ikegai Iron Works), twin screw extruder (manufactured by K.C.K.) ), Co-Kneader (manufactured by Busu Co., Ltd.), and Kneedex (manufactured by Nippon Coke Industry Co., Ltd.). Further, the resin composition obtained by melt-kneading may be rolled with two rolls or the like, and cooled with water or the like in a cooling step.

Next, the cooled resin composition is pulverized to a desired particle size in a pulverization step. In the pulverization process, after coarse pulverization is performed using a pulverizer such as a crusher, hammer mill, or feather mill, the grinding process is performed using a crusher such as a Kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), a super rotor (manufactured by Nissin Engineering Co., Ltd.), or a turbo rotor. Finely pulverize using a mill (manufactured by Turbo Industries) or an air jet type pulverizer.

After that, if necessary, use an inertial classification type elbow jet (manufactured by Nippon Steel Mining Co., Ltd.), a centrifugal force classification type Turboplex (manufactured by Hosokawa Micron Company), a TSP separator (manufactured by Hosokawa Micron Company), or a faculty member (manufactured by Hosokawa Micron Company). Classify using a classifier or sieve to obtain toner particles.

Thereafter, by adding and mixing (external addition) external additives such as inorganic fine powder or resin particles selected as necessary, fluidity is imparted, charging stability is improved, and a toner is obtained. The mixing device is a mixing device having a rotating body having a stirring member and a main body casing provided with a gap from the stirring member.

Examples of such mixing devices include Henschel Mixer (manufactured by Mitsui Mining Co., Ltd.); Super Mixer (manufactured by Kawata Co., Ltd.); Ribocorn (manufactured by Okawara Seisakusho Co., Ltd.); Nauta Mixer, Turbulizer, and Cyclomix (manufactured by Hosokawa Micron Co., Ltd.). Spiral pin mixer (manufactured by Taiheiyo Kiko Co., Ltd.); Loedige mixer (manufactured by Matsubo Co., Ltd.), Nobilta (manufactured by Hosokawa Micron Co., Ltd.), and the like. In particular, in order to mix uniformly and loosen silica aggregates, a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) is preferably used.

Mixing equipment conditions include throughput, stirring shaft rotation speed, stirring time, stirring blade shape, tank temperature, etc., but in order to achieve the desired toner performance, physical properties of heat-treated toner particles and additives must be adjusted. It is selected as appropriate in consideration of the type, etc., and is not particularly limited. Furthermore, if, for example, coarse aggregates of the additive are present freely in the obtained toner, a sieve or the like may be used as necessary.

Next, methods for measuring various physical properties of toner and raw materials in the present invention will be described below.

[Method for measuring peak molecular weight (Mp), number average molecular weight (Mn), and weight average molecular weight (Mw) of resin]
The peak molecular weight (Mp), number average molecular weight (Mn), and weight average molecular weight (Mw) are measured by gel permeation chromatography (GPC) as follows.

First, a sample (resin) is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. Then, the obtained solution is filtered through a solvent-resistant membrane filter "Maeshori Disk" (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. Note that the sample solution is adjusted so that the concentration of components soluble in THF is approximately 0.8% by mass. Using this sample solution, measurements are performed under the following conditions.
Equipment: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: 7 series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0ml/min
Oven temperature: 40.0℃
Sample injection amount: 0.10ml

When calculating the molecular weight of the sample, use 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).

[Method for measuring the softening point of resin]
The softening point of the resin is measured 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, a constant load is applied from the top of the measurement sample by a piston, the temperature of the measurement sample filled in the cylinder is raised and melted, and the molten measurement sample is pushed out from the die at the bottom of the cylinder. A flow curve can be obtained that shows the relationship between temperature and temperature.

In the present invention, the "melting temperature in the 1/2 method" described in the manual attached to the "Flow Tester CFT-500D" is defined as the softening point. The melting temperature in the 1/2 method is calculated as follows. First, find 1/2 of the difference between the piston descent amount Smax at the time when the outflow ends and the piston descent amount Smin at the time the outflow starts (this is set as X. X = (Smax - Smin) / 2). The temperature of the flow curve when the amount of descent of the piston becomes X in the flow curve is the melting temperature in the 1/2 method.

The measurement sample was obtained by compression molding about 1.0 g of resin at about 10 MPa for about 60 seconds using a tablet molding and compression machine (for example, NT-100H, manufactured by NP Systems, Inc.) in an environment of 25 ° C. A cylinder with a diameter of about 8 mm is used.

The measurement conditions of CFT-500D are as follows.
Test mode: Heating method Starting temperature: 40℃
Achieved temperature: 200℃
Measurement interval: 1.0℃
Temperature increase rate: 4.0℃/min
Piston cross-sectional area: 1.000cm ²
Test load (piston load): 10.0kgf (0.9807MPa)
Preheating time: 300 seconds Die hole diameter: 1.0mm
Die length: 1.0mm

[Method for measuring acid value of resin]
The acid value is the number of mg of potassium hydroxide required to neutralize the acid contained in 1 g of sample. The acid value of the binder resin is measured according to JIS K 0070-1992, and specifically, it is measured according to the following procedure.

(1) Preparation of reagents Dissolve 1.0 g of phenolphthalein in 90 ml of ethyl alcohol (95% by volume) and add ion-exchanged water to make 100 ml to obtain a phenolphthalein solution.

Dissolve 7 g of special grade potassium hydroxide in 5 ml of water, and add ethyl alcohol (95% by volume) to make 1 L. After leaving it in an alkali-resistant container for 3 days to avoid contact with carbon dioxide gas, filter it to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was determined by placing 25 ml of 0.1 mol/l hydrochloric acid in an Erlenmeyer flask, adding a few drops of the phenolphthalein solution, and titrating with the potassium hydroxide solution. Determine from the amount of potassium solution. The 0.1 mol/l hydrochloric acid prepared according to JIS K 8001-1998 is used.

(2) Operation (A) Main test 2.0 g of the sample was accurately weighed into a 200 ml Erlenmeyer flask, 100 ml of a mixed solution of toluene/ethanol (2:1) was added, and the sample was dissolved over 5 hours. Next, several drops of the phenolphthalein solution are added as an indicator, and titration is carried out using the potassium hydroxide solution. The end point of the titration is when the light red color of the indicator continues for about 30 seconds.

(B) Blank test Perform titration in the same manner as above, except that no sample is used (that is, only a mixed solution of toluene/ethanol (2:1) is used).

(3) Substitute the obtained results into the following formula to calculate the acid value.
A=[(CB)×f×5.61]/S
Here, A: acid value (mgKOH/g), B: amount of potassium hydroxide solution added in blank test (ml), C: amount of potassium hydroxide solution added in main test (ml), f: potassium hydroxide Solution factor, S: sample (g).

[Method for measuring hydroxyl value of resin]
The hydroxyl value is the number of mg of potassium hydroxide required to neutralize acetic acid bonded to hydroxyl groups when 1 g of a sample is acetylated. The hydroxyl value of the resin is measured according to JIS K 0070-1992, and specifically, it is measured according to the following procedure.

(1) Preparation of reagent Place 25 g of special grade acetic anhydride in a 100 ml volumetric flask, add pyridine to bring the total volume to 100 ml, and shake thoroughly to obtain an acetylation reagent. The obtained acetylation reagent is stored in an amber bottle to prevent it from coming into contact with moisture, carbon dioxide, etc.

Dissolve 1.0 g of phenolphthalein in 90 ml of ethyl alcohol (95% by volume) and add ion exchange water to make 100 ml to obtain a phenolphthalein solution.

Dissolve 35 g of special grade potassium hydroxide in 20 ml of water, and add ethyl alcohol (95% by volume) to make 1 L. After leaving it in an alkali-resistant container for 3 days to avoid contact with carbon dioxide gas, filter it to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was determined by placing 25 ml of 0.5 mol/l hydrochloric acid in an Erlenmeyer flask, adding a few drops of the phenolphthalein solution, and titrating with the potassium hydroxide solution. Determine from the amount of potassium solution. The 0.5 mol/l hydrochloric acid prepared according to JIS K 8001-1998 is used.

(2) Operation (A) Main test 1.0 g of the pulverized resin sample is accurately weighed into a 200 ml round bottom flask, and 5.0 ml of the acetylation reagent described above is accurately added thereto using a whole pipette. At this time, if the sample is difficult to dissolve in the acetylation reagent, add a small amount of special grade toluene to dissolve it.

Place a small funnel on the mouth of the flask, and heat the flask by immersing the bottom of the flask about 1 cm into a glycerin bath at about 97°C. At this time, in order to prevent the temperature of the neck of the flask from rising due to the heat of the bath, it is preferable to cover the base of the neck of the flask with cardboard with round holes.

After 1 hour, remove the flask from the glycerin bath and allow to cool. After cooling, add 1 ml of water from the funnel and shake to hydrolyze acetic anhydride. For more complete hydrolysis, the flask is heated again in the glycerin bath for 10 minutes. After cooling, wash the funnel and flask walls with 5 ml of ethyl alcohol.

Add several drops of the phenolphthalein solution as an indicator, and titrate with the potassium hydroxide solution. The end point of the titration is when the light red color of the indicator continues for about 30 seconds.

(B) Blank test Perform titration in the same manner as above, except that no resin sample is used.

(3) Substitute the obtained results into the following formula to calculate the hydroxyl value.
A=[{(B-C)×28.05×f}/S]+D
Here, A: hydroxyl value (mgKOH/g), B: amount of potassium hydroxide solution added in blank test (ml), C: amount of potassium hydroxide solution added in main test (ml), f: potassium hydroxide Solution factor, S: sample (g), D: acid value of resin (mgKOH/g).

[Measurement 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 part uses the melting points of indium and zinc, and the heat of fusion of indium is used to correct the amount of heat.

Specifically, approximately 10 mg of wax was accurately weighed, placed in an aluminum pan, and using an empty aluminum pan as a reference, the temperature was increased at a heating rate of 10 within the measurement temperature range of 30 to 200°C. Measurements are carried out at °C/min. In addition, in the measurement, the temperature is raised once to 200°C, then the temperature is 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. during this second temperature raising process is defined as the peak temperature of the maximum endothermic peak of the wax.

[Measurement of content of compound (1) in toner]
To measure the content of compound (1) in the toner, for example, a measuring device "RINT-TTRII" (manufactured by Rigaku Co., Ltd.) as an X-ray diffraction device and control software and analysis software attached to the device can be used. Can be done.

The measurement conditions are as follows.
X-ray: Cu/50kV/300mA
Goniometer: Rotor horizontal goniometer (TTR-2)
Attachment: Standard sample holder Divergent slit: Open divergent vertical restriction slit: 10.00mm
Scattering slit: Open light receiving slit: Open Counter: Scintillation counter Scanning mode: Continuous scan speed: 4.0000°/min.
Sampling width: 0.0200°
Scanning axis: 2θ/θ
Scanning range: 10.0000~40.0000°

Set the target toner on the sample plate and start measurement. In the CuKα characteristic X-ray, measurement is performed in the Bragg angle (2θ ± 0.20deg) range of 3deg to 35deg, and from the obtained spectrum, the integrated intensity of the spectrum at 2θ of 4.0deg to 5.0deg is calculated in advance from the compound (1 ) to determine the content of compound (1) in the toner.

[Measurement of acid value of polyester resin from toner]
The following method can be used to measure the acid value of the polyester resin from the toner. Separate the polyester resin from the toner using the following method and measure the acid value.

The toner is dissolved in tetrahydrofuran (THF), and the solvent is distilled off from the resulting soluble component under reduced pressure to obtain a tetrahydrofuran (THF)-soluble component of the toner. The tetrahydrofuran (THF) soluble component of the obtained toner is dissolved in chloroform to prepare a sample solution with a concentration of 25 mg/ml.

3.5 ml of the obtained sample solution is injected into the apparatus described below, and resin components having a molecular weight of 2000 or more are fractionated under the following conditions.
Preparative GPC device: Japan Analytical Industry Co., Ltd. Preparative HPLC LC-980 type Preparative column: JAIGEL 3H, JAIGEL 5H (Japan Analytical Industry Co., Ltd.)
Eluent: Chloroform Flow rate: 3.5ml/min

After separating the high molecular weight component derived from the resin, the solvent is distilled off under reduced pressure, and the sample is further dried under reduced pressure in an atmosphere of 90° C. for 24 hours. The above operation is repeated until about 2.0 g of the resin component is obtained. Using the obtained sample, measure the acid value according to the above procedure.

[Measurement of calcium element and magnesium element content in toner]
When measuring the content of the above elements in a toner containing external additives, place the toner in a solvent that does not dissolve the toner, such as isopropanol, and wash the toner by applying vibrations for 10 minutes with an ultrasonic cleaner. , Measurement is performed after removing external additives. If toner particles are available, pretreatment as described above is not necessary.

In the Examples described later, the content of each metal element was measured using fluorescent X-ray analysis. The measurement of fluorescent X-rays of each element is in accordance with JIS K 0119-1969, and specifically as follows.

(1) Measuring device The measuring device is a wavelength dispersive X-ray fluorescence analyzer “Axios” (manufactured by PANalytical) and the attached dedicated software “SuperQ ver. 4.0F” for setting measurement conditions and analyzing measurement data. ” (manufactured by PANalytical) is used. Note that Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 27 mm, and the measurement time is 10 seconds. Further, when measuring light elements, a proportional counter (PC) is used, and when measuring heavy elements, a scintillation counter (SC) is used.

As a measurement sample, approximately 4 g of toner was placed in a special press aluminum ring, flattened, and then compressed at 20 MPa and 60 Pellets are used which are pressurized for seconds and molded to a thickness of about 2 mm and a diameter of about 39 mm.

Measurement is performed under the above conditions, the element is identified based on the peak position of the obtained X-rays, and its concentration is calculated from the counting rate (unit: cps), which is the number of X-ray photons per unit time.

(2) Regarding creation of a calibration curve A complex compound for quantitative purposes is added to 100 parts by mass of toner particles in an amount of 0.001 parts by mass, and thoroughly mixed using a coffee mill. Similarly, the composite compound for quantitative purposes was mixed with toner particles in amounts of 0.01 parts by mass, 0.10 parts by mass, 0.50 parts by mass, and 1.0 parts by mass, respectively, and these were mixed with the toner particles for the calibration curve. Use as a sample. The above sample is press-molded using a sample press-molding machine. The [M]Kα peak angle (a) in the complex compound is determined from the 2θ table. Place the calibration curve sample into the fluorescent X-ray analyzer, and reduce the pressure in the sample chamber to create a vacuum. The X-ray intensity of each sample is determined under the following conditions and a calibration curve (mass ratio: expressed in ppm) is created.

(3) Regarding measurement conditions Measurement potential and voltage: 50kV, 50 to 70mA
2θ angle: a
Crystal plate: LiF
Measurement time: 60 seconds

(4) Quantification of the above elements in toner particles After forming a sample in the same manner as the above calibration curve, the X-ray intensity is determined under the same measurement conditions, and the content is calculated from the calibration curve.

The basic configuration and features of the present invention have been described above, and the present invention will be specifically described below based on Examples. However, the present invention is not limited to this in any way. Note that parts in the examples are based on mass unless otherwise specified.

[Production example of binder resin 1]
Polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane 76.9 parts (0.167 mol), terephthalic acid 25 parts (0.145 mol), adipic acid 8.0 parts ( 0.054 mol) and 0.5 part of titanium tetrabutoxide were placed in a 4-liter glass four-necked flask, equipped with a thermometer, stirring rod, condenser, and nitrogen inlet tube, and placed in a heating mantle. Next, after purging the inside of the flask with nitrogen gas, the temperature was gradually raised while stirring, and reaction was carried out for 4 hours while stirring at a temperature of 200°C. (First reaction step) Thereafter, 1.2 parts (0.006 mol) of trimellitic anhydride was added and reacted at 180° C. for 1 hour (second reaction step) to obtain Binder Resin 1.

The acid value of this binder resin 1 was 5 mgKOH/g, and the hydroxyl value was 65 mgKOH/g. Further, the molecular weight determined by GPC was a weight average molecular weight (Mw) of 8,000, a number average molecular weight (Mn) of 3,500, a peak molecular weight (Mp) of 5,700, and a softening point of 90°C.

[Example of manufacturing binder resin 2]
Polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane 71.3 parts by mass (0.155 mol), terephthalic acid 24.1 parts (0.145 mol), and titanium tetrabutoxide 0.6 part was placed in a 4-liter glass four-necked flask, which was equipped with a thermometer, stirring rod, condenser, and nitrogen inlet tube, and placed in a heating mantle. Next, after purging the inside of the flask with nitrogen gas, the temperature was gradually raised while stirring, and the mixture was reacted for 2 hours while stirring at a temperature of 200° C. (first reaction step). Thereafter, 5.8 parts (0.030 mol %) of trimellitic anhydride was added and reacted at 180° C. for 10 hours (second reaction step) to obtain a binder resin 2.

The acid value of this binder resin 2 is 15 mgKOH/g, and the hydroxyl value is 7 mgKOH/g. The molecular weight determined by GPC was a weight average molecular weight (Mw) of 200,000, a number average molecular weight (Mn) of 5,000, a peak molecular weight (Mp) of 10,000, and a softening point of 130°C.

[Example of manufacturing binder resin 3]
Polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane 76.9 parts (0.167 mol), terephthalic acid 20.0 parts (0.120 mol), acrylic acid 4.3 (0.060 mol) and 0.5 part of titanium tetrabutoxide were placed in a 4-liter glass four-necked flask, equipped with a thermometer, stirring rod, condenser, and nitrogen inlet tube, and placed in a heating mantle. Next, after purging the inside of the flask 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, 1.0 part (0.005 mol) of trimellitic anhydride was added and reacted at 180° C. for 1 hour (second reaction step) to obtain a binder resin 3.

The acid value of this binder resin 3 was 0 mgKOH/g, and the hydroxyl value was 82 mgKOH/g. Further, the molecular weight determined by GPC was a weight average molecular weight (Mw) of 8,000, a number average molecular weight (Mn) of 3,500, a peak molecular weight (Mp) of 5,700, and a softening point of 92°C.

[Production example of binder resins 4 to 6]
Same as Binder Resin 3 except that the amounts of terephthalic acid (TPA) and trimellitic anhydride (TMA) were changed as shown in Table 1 in order to adjust the acid value of the resulting binder resin. Then, binder resins 4 to 6 were obtained. Table 1 shows the acid value and hydroxyl value of Binder Resins 4 to 6.

[Production example of compound (1)]
After uniformly dispersing 50 parts of 3-hydroxy-4-methoxybenzanilide in 1000 parts of water, add ice to bring the temperature to 0 to 5°C, and then slowly dropwise add 60 parts of a 35% HCl aqueous solution while stirring at high speed. After that, strong stirring was continued for 20 minutes. Thereafter, 50 parts of a 30% sodium nitrite aqueous solution was added, and after stirring for 60 minutes, 2 parts of sulfamic acid was added to eliminate the nitrous acid. Furthermore, 50 parts of sodium acetate and 75 parts of 90% acetic acid were added to prepare a diazonium salt solution.

Separately, 50 parts of N-phenyl-2-naphthalenecarboxamide was dissolved with 1000 parts of water and 25 parts of sodium hydroxide at 80° C. or below, and 3 parts of sodium alkylbenzenesulfonate were added to prepare a coupler solution.

While maintaining the coupler solution at 10° C. or lower, the above diazonium salt solution was added all at once under strong stirring. After the addition, gentle stirring was continued until the coupling reaction was completed, and then the mixture was heated to 120°C and filtered to obtain compound (1).

[Production example of colorant 1]
- 1500 parts of ion-exchanged water - 100.0 parts of compound (1) The above materials were stirred and mixed to suspend compound (1) in water. Thereafter, 15.0 parts of tetrahydroabietic acid, 5.0 parts of abietic acid and 30 parts of a 33% strength aqueous sodium hydroxide solution were added. After raising the liquid temperature to 98°C, the mixture was stirred for 1 hour while maintaining the temperature. After the temperature was lowered to 65°C, about 60 parts of 31% hydrochloric acid was added to precipitate the resin. The precipitated composition was filtered, washed with ion-exchanged water, and then dried to obtain Colorant 1.

[Production example of colorant masterbatch 1]
- Binder resin 1 70 parts - Colorant 1 30 parts - Water 10 parts - Calcium chloride aqueous solution 5.0 parts - Magnesium chloride aqueous solution 2.5 parts The temperature was raised with Heat and melt-knead at 90 to 100°C for another 15 minutes, then stop the mixer, drain the hot water, mix for 10 minutes without heating, distill off water, cool, and grind with a pin mill to about 1 mm. Colorant masterbatch 1 was obtained by pulverization. The water content of Colorant Masterbatch 1 was 10% by mass. Based on the mass of compound (1), the amount of calcium element in the colorant masterbatch was 15,000 ppm, and the amount of magnesium element was 4,500 ppm.

[Production example of colorant masterbatch 2]
- Binder resin 1 70 parts - Colorant 1 30 parts - Water 10 parts - Calcium chloride aqueous solution 4.0 parts - Magnesium chloride aqueous solution 2.5 parts The temperature was raised with Heat and melt-knead at 90 to 100°C for another 15 minutes, then stop the mixer, drain the hot water, mix for 10 minutes without heating, distill off water, cool, and grind with a pin mill to about 1 mm. Colorant masterbatch 2 was obtained by pulverization. The water content of Colorant Masterbatch 2 was 10% by mass. Based on the mass of compound (1), the amount of calcium element in the colorant masterbatch was 8500 ppm, and the amount of magnesium element was 4500 ppm.

[Production example of resin composition 1]
- 18 parts of low-density polyethylene (Mw 1400, Mn 850, maximum endothermic peak measured by DSC at 100°C) - 66 parts of styrene - 13.5 parts of n-butyl acrylate - 2.5 parts of acrylonitrile were charged into an autoclave, and the system was replaced with _N2. Thereafter, the temperature was raised and maintained at 180°C while stirring. 50 parts by mass of a xylene solution of 2% by mass of t-butyl hydroperoxide was continuously dropped into the system for 5 hours, and after cooling, the solvent was separated and removed to obtain a resin composition in which the vinyl resin component reacted with the above-mentioned low-density polyethylene. I got item 1. When the molecular weight of Resin Composition 1 was measured, it was found that the weight average molecular weight (Mw) was 7,100 and the number average molecular weight (Mn) was 3,000. Further, the transmittance at a wavelength of 600 nm measured at a temperature of 25° C. in a dispersion in a 45% by volume methanol aqueous solution was 69%.

[Production example of resin composition 2]
・Low density polyethylene 20.0 parts (Mw 1300, Mn 800, maximum endothermic peak by DSC is 95°C)
- 65.0 parts of o-methylstyrene, 11.0 parts of n-butyl acrylate, and 4.0 parts of methacrylonitrile were charged into an autoclave, and after replacing the inside of the system with _N2 , the temperature was raised and maintained at 170°C with stirring. 50 parts of a 2% by mass xylene solution of t-butyl hydroperoxide was continuously dropped into the system for 5 hours, and after cooling, the solvent was separated and removed to create a resin composition in which the vinyl resin component reacted with the low density polyethylene. I got 2. When the molecular weight of resin composition 2 was measured, it was found that the weight average molecular weight (Mw) was 6,900 and the number average molecular weight (Mn) was 2,900. Furthermore, the transmittance at a wavelength of 600 nm measured at a temperature of 25° C. in a dispersion in a 45% by volume methanol aqueous solution was 63%.

[Example of manufacturing styrene acrylic resin]
・70 parts of styrene ・25 parts of n-butyl acrylate ・5 parts of monobutyl maleate ・1 part of di-t-butyl peroxide The mixture was purged with nitrogen and the temperature was raised to 120°C, followed by dropwise addition over 3.0 hours. Polymerization was further completed under reflux of xylene, and the solvent was distilled off under reduced pressure to obtain a styrene acrylic resin.

[Production example of toner 1]
・Binder resin 1 70.0 parts ・Binder resin 2 30.0 parts ・Colorant masterbatch 1 1.0 parts ・Fischer-Tropsch wax (peak temperature of maximum endothermic peak 78°C) 5.0 parts ・3.5 parts - Di-t-butylsalicylic acid aluminum compound 0.5 parts, resin composition 1 5.0 parts, silica particles 1.0 parts, strontium titanate particles 1.0 parts. 75 model, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 20 s ^-1 and a rotation time of 5 minutes, the mixture was transferred to a twin-screw kneader (PCM-30 model, manufactured by Ikegai Co., Ltd.) set at a temperature of 125°C. and kneaded. The obtained kneaded product was cooled and coarsely ground to 1 mm or less using a hammer mill to obtain a coarsely ground product. The obtained coarse material was pulverized using a mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.). Further, classification was performed using a rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) to obtain toner particles. The operating conditions of the rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) were such that classification was performed at a classification rotor rotation speed of 50.0 s ^-1 . The obtained toner particles had a weight average particle diameter (D4) of 5.9 μm.

To 100 parts of the obtained treated toner particles, 0.8 parts of hydrophobic silica fine particles having a number average particle diameter of 10 nm as primary particles whose surface was treated with 20% by mass of hexamethyldisilazane and 16% by mass of isobutyltrimethoxysilane were added to the surface. 0.2 parts of titanium oxide fine particles having a number average particle diameter of 30 nm as treated primary particles were added, and mixed with a Henschel mixer (FM-75 model, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 30 s ^-1 and a rotation time of 10 min. As a result, Toner 1 was obtained.

[Production example of toners 2 to 5]
As shown in Table 2, Toners 2 to 5 were prepared in the same manner as in Toner 1, except that the types of binder resin, wax, resin composition, and colorant masterbatch and the number of each added were changed. Obtained.

[Example of manufacturing toner 6]
・Binder resin 1 70.0 parts ・Binder resin 2 30.0 parts ・Compound (1) 0.3 parts ・Fischer-Tropsch wax (peak temperature of maximum endothermic peak 78°C) 5.0 parts ・3,5- Di-t-butylsalicylic acid aluminum compound 0.5 parts, resin composition 1 5.0 parts, calcium carbonate particles 0.5 parts, magnesium carbonate particles 0.2 parts, silica particles 1.0 parts, strontium titanate particles 1 .0 part The raw materials shown in the above recipe were mixed using a Henschel mixer (FM-75 model, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 20 s ^-1 and a rotation time of 5 min, and then mixed at a temperature of 125°C. The mixture was kneaded using a shaft kneader (PCM-30 model, manufactured by Ikegai Co., Ltd.). The obtained kneaded product was cooled and coarsely ground to 1 mm or less using a hammer mill to obtain a coarsely ground product. The obtained coarse material was pulverized using a mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.). Further, classification was performed using a rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) to obtain toner particles. The operating conditions of the rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) were such that classification was performed at a classification rotor rotation speed of 50.0 s ^-1 . The obtained toner particles had a weight average particle diameter (D4) of 5.9 μm.

To 100 parts of the obtained treated toner particles, 0.8 parts of hydrophobic silica fine particles having a number average particle diameter of 10 nm as primary particles whose surface was treated with 20% by mass of hexamethyldisilazane and 16% by mass of isobutyltrimethoxysilane were added to the surface. 0.2 parts of titanium oxide fine particles having a number average particle diameter of 30 nm as treated primary particles were added, and mixed with a Henschel mixer (FM-75 model, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 30 s ^-1 and a rotation time of 10 min. As a result, Toner 6 was obtained.

[Production example of toners 7 to 20]
As shown in Table 2, except for changing the types and amounts of the binder resin, wax, resin composition, magnesium carbonate particles, silica particles, and strontium titanate particles. Toners 7 to 20 were obtained.

[Example of manufacturing toner 21]
470 parts of ion-exchanged water and 3.3 parts of Na ₃ PO ₄ were put into a 2-liter four-necked flask equipped with a high-speed stirring device Clearmix (manufactured by M Techniques), and the rotation speed of the high-speed stirring device was set to 10. ,000 rpm and heated to 65°C. A CaCl ₂ aqueous solution was added thereto to prepare an aqueous dispersion medium containing a minute slightly water-soluble dispersant Ca ₃ (PO ₄ ) ₂ . On the other hand, as a dispersoid,
・Styrene 66.0 parts・n-butyl acrylate 34.0 parts・Divinylbenzene 0.2 parts・Ester wax (peak temperature of maximum endothermic peak 80°C) 5.0 parts・Colorant masterbatch 1 15.0 parts・A mixture consisting of 0.5 part of aluminum 3,5-di-t-butylsalicylate compound was dispersed for 3 hours using an attritor (manufactured by Mitsui Kinzoku Co., Ltd.), and then 2,2'-azobis(2, 3 parts of 4-dimethylvaleronitrile) were added and stirred for 1 minute to prepare a polymerizable monomer composition.

After preparing the polymerizable monomer composition, the polymerizable monomer composition was poured into the aqueous dispersion medium in which the rotational speed of a high-speed stirring device was increased to 15,000 rpm, and the mixture was stirred under an N ₂ atmosphere at an internal temperature of 60°C. The mixture was stirred for 3 minutes to granulate the polymerizable monomer composition. After that, the stirring device was changed to one equipped with a paddle stirring blade, and the temperature was maintained while stirring at 200 rpm, and the first reaction step was terminated when the polymerization conversion rate of the polymerizable vinyl monomer reached 90%. did. The reaction temperature was further raised to 80° C., and when the polymerization conversion rate reached approximately 100%, the second reaction step was terminated, and the polymerization step was completed. After the polymerization was completed and the mixture was cooled, dilute hydrochloric acid was added to dissolve the poorly water-soluble dispersant. Furthermore, after repeating water washing several times using a pressure filter, drying treatment was performed to obtain polymer particles. This polymer particle had a weight average particle diameter of 7.2 μm.

To 100 parts of the obtained polymer particles, 0.8 parts of hydrophobic silica fine particles whose primary particles have a number average particle size of 10 nm were surface-treated with 20% by mass of hexamethyldisilazane, and the surface was treated with 16% by mass of isobutyltrimethoxysilane. 0.2 parts of titanium oxide fine particles having a number average particle diameter of 30 nm as treated primary particles were added, and mixed with a Henschel mixer (FM-75 model, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 30 s ^-1 and a rotation time of 10 min. As a result, Toner 21 was obtained. The amount of calcium element in toner 21 was 106 ppm, and the amount of magnesium element was 65 ppm.

[Example of manufacturing cyan toner]
・Binder resin 1 70.0 parts ・Binder resin 2 30.0 parts ・C. I. Pigment Blue 15:3 0.5 parts Colorant Masterbatch 1 1.0 parts Fischer-Tropsch wax (peak temperature of maximum endothermic peak 78°C) 5.0 parts 3,5-di-t-butylsalicylic acid aluminum compound 0.5 parts/Resin composition 1 5.0 parts A cyan toner was obtained in the same manner as in the production example of toner 1 except that the raw materials were changed to the above formulation.

[Example of manufacturing carrier]
(Production example of magnetic core particle 1)
・Process 1 (weighing/mixing process):
Fe ₂ O ₃ 62.7 parts MnCO ₃ 29.5 parts Mg(OH) ₂ 6.8 parts SrCO ₃ 1.0 parts The ferrite raw materials were weighed so that the above materials had the above composition ratios. Thereafter, the mixture was ground and mixed for 5 hours using a dry vibration mill using stainless steel beads with a diameter of 1/8 inch.

・Process 2 (temporary firing process):
The obtained pulverized material was made into pellets of approximately 1 mm square using a roller compactor. Coarse powder was removed from the pellets using a vibrating sieve with an opening of 3 mm, then fine powder was removed using a vibrating sieve with an opening of 0.5 mm, and then the pellets were heated in a nitrogen atmosphere (oxygen concentration 0. 01% by volume) at a temperature of 1000° C. for 4 hours to produce calcined ferrite. The composition of the obtained calcined ferrite is as follows.
(MnO)a(MgO)b(SrO)c(Fe2O3)d
In the above formula, a=0.257, b=0.117, c=0.007, d=0.393

・Process 3 (pulverization process):
After crushing to about 0.3 mm with a crusher, 30 parts of water was added to 100 parts of calcined ferrite using zirconia beads having a diameter of 1/8 inch, and the mixture was crushed with a wet ball mill for 1 hour. The slurry was ground for 4 hours in a wet ball mill using alumina beads with a diameter of 1/16 inch to obtain a ferrite slurry (finely ground product of calcined ferrite).

・Process 4 (granulation process):
To the ferrite slurry, 1.0 parts of ammonium polycarboxylate as a dispersant and 2.0 parts of polyvinyl alcohol as a binder were added to 100 parts of calcined ferrite, and the mixture was made into spherical particles using a spray dryer (manufacturer: Okawara Kakoki). Granulated. After adjusting the particle size of the obtained particles, they were heated at 650° C. for 2 hours using a rotary kiln to remove the organic components of the dispersant and binder.

・Process 5 (firing process):
In order to control the firing atmosphere, the temperature was raised from room temperature to 1300°C in 2 hours in an electric furnace under a nitrogen atmosphere (oxygen concentration 1.00% by volume), and then fired at a temperature of 1150°C for 4 hours. Thereafter, the temperature was lowered to 60° C. over a period of 4 hours, the temperature was returned to the atmosphere from the nitrogen atmosphere, and the sample was taken out at a temperature of 40° C. or lower.

・Process 6 (sorting process):
After crushing the agglomerated particles, the low-magnetic particles are cut by magnetic separation, and coarse particles are removed by sieving with a sieve with an opening of 250 μm. Magnetic core particles 1 were obtained.

(Preparation of coating resin 1)
Cyclohexyl methacrylate monomer 26.8% by mass
Methyl methacrylate monomer 0.2% by mass
Methyl methacrylate macromonomer 8.4% by mass
(Macromonomer with a weight average molecular weight of 5000 having a methacryloyl group at one end)
Toluene 31.3% by mass
Methyl ethyl ketone 31.3% by mass
Azobisisobutyronitrile 2.0% by mass
Of the above materials, cyclohexyl methacrylate, methyl methacrylate, methyl methacrylate macromonomer, toluene, and methyl ethyl ketone were added to a four-neck separable flask equipped with a reflux condenser, thermometer, nitrogen inlet tube, and stirring device, and nitrogen gas was added. was introduced to create a sufficient nitrogen atmosphere, the mixture was heated to 80° C., azobisisobutyronitrile was added, and the mixture was refluxed for 5 hours for polymerization. Hexane was injected into the obtained reaction product to precipitate the copolymer, and the precipitate was filtered off and dried under vacuum to obtain coated resin 1. The obtained coating resin 1 was dissolved in 30 parts of toluene, 40 parts of toluene, and 30 parts of methyl ethyl ketone to obtain a polymer solution 1 (solid content 30% by mass).

(Preparation of coating resin solution 1)
Polymer solution 1 (resin solid content concentration 30%) 33.3% by mass
Toluene 66.4% by mass
Carbon black (Regal330; manufactured by Cabot) 0.3% by mass
(Primary particle size 25 nm, nitrogen adsorption specific surface area 94 m ² /g, DBP oil absorption 75 ml/100 g)
was dispersed in a paint shaker for 1 hour using zirconia beads with a diameter of 0.5 mm. The obtained dispersion liquid was filtered through a 5.0 μm membrane filter to obtain coating resin solution 1.

[Manufacturing example of magnetic carrier 1]
(Resin coating process):
The coating resin solution 1 was put into a vacuum degassing type kneader maintained at room temperature in an amount of 2.5 parts as a resin component based on 100 parts of the filled core particles 1. After the addition, the mixture was stirred at a rotational speed of 30 rpm for 15 minutes, and after a certain amount of the solvent (80% by mass) had evaporated, the temperature was raised to 80° C. while mixing under reduced pressure, and the toluene was distilled off over 2 hours, followed by cooling. The obtained magnetic carrier was separated into low-magnetic products by magnetic separation, passed through a sieve with an opening of 70 μm, and then classified with an air classifier to obtain a magnetic carrier with a 50% particle size (D50) of 38.2 μm based on volume distribution. I got 1.

[Example of manufacturing two-component developer 1]
8.0 parts of Toner 1 was added to 92.0 parts of Magnetic Carrier 1 and mixed using a V-type mixer (V-20, manufactured by Seishin Enterprises) to obtain Two-Component Developer 1.

[Production examples of two-component developers 2 to 21]
Two-component developers 2 to 21 were produced in the same manner as in the production example of two-component developer 1, except that the toner was changed as shown in Table 3.

[Example of manufacturing two-component developer C]
Two-component developer C was obtained by changing the toner to be combined from the manufacturing example of two-component developer 1 to cyan toner.

(Evaluation method of toner coloring power)
As an image forming apparatus, a modified Canon full-color copying machine imageRUNNER ADVANCE C5255 was used, and two-component developer 1 was put into the developing device of the yellow station for evaluation.

The evaluation environment was a normal temperature and humidity environment (23°C, 50% RH), and the evaluation paper was plain copy paper GFC-081 (A4, basis weight 81.4 g/m ² sold by Canon Marketing Japan Inc.). Using.

First, in this evaluation environment, the relationship between image density and the amount of toner on paper was investigated by varying the amount of toner on paper. Next, the image density of the FFH image (solid area) was adjusted to 1.40, and the amount of toner applied when the image density became 1.40 was determined. The FFH image is a value in which 256 gradations are expressed in hexadecimal notation, with 00H being the 1st gradation (white area) and FFH being the 256th gradation (solid area).

Image density was measured using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite).

The coloring power of the toner was evaluated based on the applied toner amount (mg/cm ² ) according to the following criteria. The evaluation results are shown in Table 4.

(Evaluation criteria)
A: Less than 0.25 B: 0.25 or more and less than 0.30 C: 0.30 or more and less than 0.40 D: 0.40 or more and less than 0.50 E: 0.50 or more

(Evaluation of toner color reproducibility)
As an image forming apparatus, a modified Canon full-color copying machine imageRUNNER ADVANCE C5255 was used, and two-component developer 1 was put into the developing device of the yellow station, and two-component developer C was put into the developing device of the cyan station. We conducted an evaluation. The evaluation environment was a normal temperature and humidity environment (23°C, 50% RH), and the evaluation paper was plain copy paper GFC-081 (A4, basis weight 81.4 g/m ² sold by Canon Marketing Japan Inc.) was used.

Two-component developer 1 and two-component developer C were used to form a green image, which is a secondary color. At this time, images were formed divided into 16 gradations from 00H (solid white) to FFH image (solid portion). In the secondary color image formation, the applied amount of the FFH image (solid portion) of the two-component developer 1 was set to the applied amount such that the image density in a single color was 1.40. Regarding the two-component developer C, the amount of the FFH image (solid area) applied was adjusted to 0.40 mg/cm ² . The applied amount of 0.40 mg/cm ² is the applied amount such that the monochromatic image density of the two-component developer C is 1.40. Regarding the obtained 16-gradation secondary color (green) image, L ^* , a ^* , b ^* of each gradation image was measured using SpectroScan Transmission (manufactured by GretagMacbeth) (measurement conditions: D ₅₀ viewing angle 2°). was measured, and C ^* of each gradation was determined from the following formula.
C ^* = {(a ^* ) ² + (b ^* ) ² } ^0.5

The C ^* of each gradation was compared, and the largest C ^* (C ^* max) was determined and used as an index for evaluation of green reproducibility. The larger the C ^* max, the better the green reproducibility, and the evaluation was made based on the following criteria. The evaluation results are shown in Table 4.

(Evaluation criteria)
A: 75 or more B: 70 or more and less than 75 C: 65 or more and less than 70 D: 55 or more and less than 65 E: Less than 55

(Evaluation method for fog in non-image area (white background area))
As an image forming apparatus, a modified Canon full-color copying machine imageRUNNER ADVANCE C5255 was used, and two-component developer 1 was put into the developing device of the yellow station for evaluation.

The evaluation environment was a normal temperature and humidity environment (23°C, 50% RH), and the evaluation paper was plain copy paper GFC-081 (A4, basis weight 81.4 g/m ² sold by Canon Marketing Japan Inc.). Using.

Fog on the white background was measured before and after durability in each environment.

The average reflectance Dr (%) of the evaluation paper before image formation was measured with a reflectometer ("REFLECTOMETER MODEL TC-6DS" manufactured by Tokyo Denshoku Co., Ltd.). The reflectance Ds (%) of the 00H image area (white background area) was measured at the initial stage (1st sheet) and after durability (50,000th sheet). Fog (%) was calculated from the obtained Dr and Ds (initial and after durability) using the following formula. The resulting fog was evaluated according to the following evaluation criteria. The evaluation results are shown in Table 4.
Fog (%) = Dr (%) - Ds (%)

(Evaluation criteria)
A: Less than 0.5% B: 0.5% or more and less than 1.0% C: 1.0% or more and less than 2.0% D: 2.0% or more

Claims (5)

A toner comprising toner particles containing a binder resin and a colorant, and inorganic fine particles,
The toner particles contain silica particles or strontium titanate particles,
The binder resin is a polyester resin,
The colorant contains the following compound (1),

The toner particles contain a calcium element and a magnesium element, and based on the mass of compound (1) in the toner particles, the content of the calcium element is A (ppm), and the content of the magnesium element is B ( ppm), a toner that satisfies the following formula.
A+B≦300.0
4.0≦A≦180.0
4.0≦B≦180.0 The toner according to claim 1, wherein the content (A) of the calcium element and the content (B) of the magnesium element satisfy 1.5≦A/B≦10.0. The toner according to claim 1 or 2, wherein the polyester resin has an acid value of 0 mgKOH/g or more and 20 mgKOH/g or less. A method for producing toner, the method comprising:
A step of heating and mixing a binder resin, the following compound (1), calcium chloride, and magnesium chloride in the presence of water to obtain a water-containing colorant masterbatch having a water content of 5% by mass or more and 25% by mass or less; A step of melt-kneading the water-containing colorant masterbatch and the binder resin to obtain a kneaded product, and a step of pulverizing the kneaded product to obtain toner particles ,
The obtained toner has toner particles containing a binder resin and a colorant, and inorganic fine particles,
The binder resin is a polyester resin,
The colorant contains the following compound (1),

The toner particles contain a calcium element and a magnesium element, and based on the mass of compound (1) in the toner particles, the content of the calcium element is A (ppm), and the content of the magnesium element is B ( ppm), the following formula:
A+B≦300.0
4.0≦A≦180.0
4.0≦B≦180.0
A method for producing a toner characterized by satisfying the following. 5. The method for producing a toner according to claim 4, wherein the toner particles contain silica particles or strontium titanate particles.