JP7391649B2 - magenta toner - Google Patents

Description

The present invention relates to a magenta toner for developing electrostatic latent images in image forming methods such as electrophotography, electrostatic recording, and toner jet methods.

In recent years, there has been a demand for higher speeds and higher image quality in multifunction peripherals and printers, and there is a demand for improved toner performance.
In order to achieve high image quality at high speeds, it is necessary to improve the charging characteristics of toner. Patent Document 1 proposes a toner that includes a resin having a benzyloxysalicylic acid structure and has a good charging rise.
Furthermore, in order to achieve high image quality, it is desired to widen the color reproduction range, improve the coloring power of images, and form high quality and high quality color images. In particular, magenta toner is important in adding yellow toner to reproduce the red color to which humans are visually sensitive, and at the same time, it has excellent developability when reproducing the skin tones of people with complex tones, for example. is also required. In addition, cyan toner must be added to achieve secondary color reproduction of blue, which is frequently used as a business color.
To meet these demands, a highly saturated magenta toner is required. For this purpose, when using a pigment as a colorant, it is necessary to make the pigment sufficiently fine and uniformly disperse it in the toner. Therefore, Patent Document 2 proposes a toner that uses a polar resin that has a low adsorption rate with pigments and a pigment dispersant.

Japanese Patent Application Publication No. 2012-256044 Japanese Patent Application Publication No. 2016-157101

In the toner described in Patent Document 1, the adsorption rate between the charge control resin and the pigment was high, and there was room for improvement in pigment dispersion. The toner described in Patent Document 2 achieves both coloring power and durability by using a pigment dispersant and a polar resin that has a low adsorption rate for pigments. However, in Patent Document 2, there is a problem that the color tone changes due to the use of a pigment dispersant. Furthermore, since a pigment dispersant is used, material costs are high.
An object of the present invention is to provide a magenta toner with high chroma and excellent chargeability without using a pigment dispersant.

The present invention provides a toner having toner particles containing a binder resin, a pigment, and a polar resin,
The binder resin is a styrene acrylic resin,
The polar resin is a polyester resin having an acid value derived from a carboxyl group of 2.0 mgKOH/g or more and 20.0 mgKOH/g or less,
The adsorption rate of the polar resin to the pigment is 10% or less ,
The pigment contains a compound A represented by the below-mentioned formula (1) and a compound B shown by the below-mentioned formula (2),
The value of the ratio of the mass of the compound A to the mass of the compound B (the compound A/the compound B) is from 95/5 to 5/95 .
This invention relates to a magenta toner characterized by:

According to the present invention, a magenta toner with high chroma and excellent chargeability can be provided without using a pigment dispersant.

The present invention provides a toner having toner particles containing a binder resin, a pigment, and a polar resin, wherein the polar resin has an acid value derived from a carboxyl group of 2.0 mgKOH/g or more and 20.0 mgKOH/g or less. The magenta toner is characterized in that an adsorption rate of the polar resin to the pigment is 10% or less.

The toner having the above structure has excellent chargeability and can provide a magenta toner with high chroma without using a pigment dispersant.

When a polar resin is used to improve the chargeability of a toner, there is a problem in that the polar resin adsorbs to the pigment and causes the pigment to aggregate, making it difficult to maintain high chroma. Furthermore, there is a problem in that the pigment and the polar resin adsorb to each other, so that the pigment inhibits the charging performance of the polar resin. Conventionally, a solution to this problem has been to use a pigment dispersant that has a higher adsorption power to the pigment than a polar resin. However, as a result of intensive studies, the present inventors have found that this problem can be solved by suppressing the adsorption rate of the polar resin to the pigment to 10% or less.

The polar resin needs to have an acid value derived from a carboxy group of 2.0 mgKOH/g or more and 20.0 mgKOH/g or less. Having a carboxyl group makes it possible to suppress environmental differences in charging characteristics to a small level. Further, by setting the acid value to 2.0 mgKOH/g or more and 20.0 mgKOH/g or less, it is possible to achieve both fogging and charge-up suppression. More preferably, it is 4.0 mgKOH/g or more and 15.0 mgKOH/g or less.

Fog is a phenomenon in which toner remains on the photoreceptor when a white image is printed. This phenomenon is believed to be caused by the presence of charges of opposite polarity on the toner surface when the toner's chargeability is too low or when pigments are exposed on the toner surface. Furthermore, charge-up is a phenomenon caused when the toner has too high a chargeability, and the toner deteriorates as it is rubbed on the developing roller without being replaced, and the toner fuses to various parts, resulting in the image being imaged. I think there will be streaks on the top.

If the acid value is less than 2.0 mgKOH/g, there is a concern that fogging may occur. Moreover, if it exceeds 20.0 mgKOH/g, there is a concern that charge-up may occur.

Further, by setting the adsorption rate to the pigment to be 10% or less, both charging property and pigment dispersibility can be achieved, and a magenta toner with high chroma can be obtained. If the adsorption rate exceeds 10%, there is a concern that the pigment dispersibility will be insufficient and the saturation will decrease. More preferably, the polar group is only a carboxy group. By using only carboxy groups, charge-up can be suppressed more effectively.

In the present invention, the polar resin is not particularly limited as long as it satisfies the above conditions, and conventionally known polar resins can be used. Examples include polyester resin, styrene acrylic resin, polyamide resin, furan resin, epoxy resin, and silicone resin. Among them, polyester resin or styrene acrylic resin is preferable from the viewpoint of storage and use under high temperature and high humidity.

Magenta pigments that can be used in the present invention include quinacridone-based magenta pigments, thioindigo-based magenta pigments, xanthene-based magenta pigments, perylene-based magenta pigments, and monoazo-based magenta pigments, as long as the adsorption rate of the polar resin to the pigment is 10% or less. You can choose any. Among these, the magenta pigment used in the present invention is preferably a monoazo magenta pigment.

Among these, Compound C, which is a monoazo magenta pigment represented by the following formula (5), is preferred.

（式中、Ｒ₁は、メチル基、または炭素数３以上８以下のアルキル基の何れかを示す。Ｒ₂は、水素、または炭素数１以上４以下のアルキル基の何れかを示す。Ｒ₃は、炭素数１以上４以下のアルキル基または炭素数１以上４以下のアルコキシ基の何れかを示す。Ｒ₄は、炭素数１以上４以下のアルキル基、炭素数１以上４以下のアルコキシ基、フルオロ基、クロロ基、ブロモ基、シアノ基、ニトロ基の何れかを示す。）

(In the formula, R ₁ represents either a methyl group or an alkyl group having 3 to 8 carbon atoms. R ₂ represents hydrogen or an alkyl group having 1 to 4 carbon atoms. ₃ represents either an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. R ₄ represents an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. group, fluoro group, chloro group, bromo group, cyano group, or nitro group.)

As a method for producing the azo magenta pigment, a known method can be used, and for example, it can be produced by the following azo coupling method.

First, a compound D represented by the following formula (6) is reacted with a diazotizing agent such as sodium nitrite or nitrosyl sulfuric acid in a solvent such as methanol or water in the presence of an inorganic acid such as hydrochloric acid or sulfuric acid. A diazonium compound is produced. Furthermore, compound C can be produced by coupling this diazonium compound with compound E represented by the following formula (7).

Although this step can be carried out without a solvent, it is preferably carried out in the presence of a solvent to prevent rapid progress of the reaction. The solvent is not particularly limited as long as it does not inhibit the reaction, but examples include alcohols such as methanol, ethanol, and propanol, esters such as methyl acetate, ethyl acetate, and propyl acetate, and diethyl ether. , ethers such as tetrahydrofuran and dioxane, hydrocarbons such as benzene, toluene, xylene, hexane, and heptane, halogen-containing hydrocarbons such as dichloromethane, dichloroethane, and chloroform, N,N-dimethylformamide, N-methyl Examples include amides such as pyrrolidone, N, and N-dimethylimidazolidinone, nitriles such as acetonitrile and propionitrile, acids such as formic acid, acetic acid, and propionic acid, and water. Furthermore, two or more of the above solvents may be used in combination. The amount of the solvent to be used can be determined arbitrarily, but from the viewpoint of reaction rate, it is preferably in the range of 5.0 times or more and 50.0 times or less relative to compound D of formula (6). The azo coupling reaction is carried out at a temperature range of -5°C to 30°C.

After the synthesized compound C is washed with water and dried, it can be treated with a solvent for the purpose of controlling wettability with acetone. Depending on the desired acetone wettability, the following solvents can be selected. For example, ketone solvents such as acetone and MIBK, aromatic hydrocarbon solvents such as toluene and xylene, alcohol solvents such as isopropanol and isobutanol, and aliphatic hydrocarbon solvents such as hexane and heptane can be used. The temperature of the solvent treatment is preferably 10 to 50°C, and the treatment time is preferably 30 minutes to 24 hours.

（式中、Ｒ₅は、メチル基、または炭素数３以上８以下のアルキル基の何れかを示す。Ｒ₆は、水素、または炭素数１以上４以下のアルキル基の何れかを示す。Ｒ₇は、炭素数１以上４以下のアルキル基または炭素数１以上４以下のアルコキシ基の何れかを示す。）

(In the formula, R ₅ represents either a methyl group or an alkyl group having 3 to 8 carbon atoms. R ₆ represents hydrogen or an alkyl group having 1 to 4 carbon atoms. ₇ represents either an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.)

（式中、Ｒ₈は、炭素数１以上４以下のアルキル基、炭素数１以上４以下のアルコキシ基、フルオロ基、クロロ基、ブロモ基、シアノ基、ニトロ基の何れかを示す。）

(In the formula, R ₈ represents any one of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a fluoro group, a chloro group, a bromo group, a cyano group, and a nitro group.)

By using this pigment, it is possible to suppress the adsorption rate with polar resin to 10% or less. The monoazo magenta pigment of formula (5) has low polarity compared to other magenta pigments. Therefore, the interaction with the polar resin is reduced, and it is possible to suppress the adsorption rate to 10% or less. Although the details are not clear, when the pigment of formula (5) is made into particles, it is oriented so that the polar groups are present inside, and compared to other magenta pigments, the outermost surface of the pigment particles has a crystal structure with low polarity. I think this may be the case.

Among the monoazo magenta pigments of formula (5), it is preferable that the pigment contains compound A represented by formula (1) and compound B represented by formula (2). By containing Compound A and Compound B, a pigment having a smaller primary particle size than conventional magenta pigments can be obtained.

Furthermore, it is preferable that the mass ratio A/B of compound A and compound B is from 95/5 to 5/95. By setting A/B within the above range, a pigment with a smaller primary particle size can be obtained, and a toner with high chroma can be obtained. More preferably, A/B is from 80/20 to 60/40, or from 40/60 to 20/80.

It is preferable that the combined mass of the compound A1 and the compound A2 is 90% or more of the mass of the pigment in the toner particles. This is to keep the adsorption rate with the polar resin low.

Further, the content of the polar resin is preferably 1.0% by mass or more and 30.0% by mass or less based on the total mass of the binder resin. By setting it within the above range, it becomes possible to better control the charging performance of the toner. Specifically, by setting the content to 1.0% by mass or more, fogging can be suppressed. Further, by setting the content to 30.0% by mass or less, charge-up can be suppressed.

Furthermore, when the acid value obtained by measuring a dispersion obtained by dispersing toner particles in water by a titration method is defined as AVH (mgKOH/g), AVH is 0.20 mgKOH/g or more and 1.00 mgKOH/g or less. and AVH/AVE is 0.10 or more and 0.25 or less, where AVE (mgKOH/g) is the acid value obtained by measuring the dispersion obtained by dispersing the toner particles in ethanol by a titration method. It is preferable that

The chargeability of toner is strongly influenced by the state of the outermost surface of the toner. In the toner of the present invention, the polar resin exhibits its charge control function and is preferably present on the outermost surface of the toner. When toner particles are dispersed in water, the toner particles do not dissolve in water, so the obtained acid value AVH (mgKOH/g) is a measurement of the acid value of only the outermost surface of the toner particles. When the AVH is 0.20 mgKOH/g or more and 1.00 mgKOH/g or less, fogging and charge-up can be suppressed. On the other hand, when toner particles are dispersed in ethanol, although the toner particles do not dissolve, the vicinity of the surface swells due to the slight affinity for ethanol. The acid value measured in this state is the acid value near the surface, and represents how much polar resin exists near the surface. The presence of the polar resin near the surface can increase the durability of the toner. When AVH/AVE is 0.10 or more and 0.25 or less, a toner with good charging performance and durability can be obtained.

In addition, the pigment has an acetone concentration of 5.5% by volume or more and 10.0% by volume or less when the transmittance of light at a wavelength of 780 nm is 50% in a wettability test with an acetone/water mixed solvent, and The solubility parameter (SP value) of the binder resin is preferably 9.8 or more and 11.0 or less.

In the present invention, it is possible to obtain a good pigment dispersion state by controlling the adsorption rate of the polar resin and pigment to 10% or less. In order to suppress this adsorption rate to 10% or less, it is important to lower the polarity of the pigment. Pigments do not dissolve in solvents or toner constituents. Therefore, the pigment surface is responsible for adsorption. Therefore, it is important to control the polarity of the pigment surface, and a wettability test is a good means for evaluating polarity. In a wettability test for an acetone/water mixed solvent, the acetone concentration when the transmittance of light at a wavelength of 780 nm is 50% is preferably 5.5% by volume or more and 10.0% by volume or less. By setting it within this range, a toner with a low adsorption rate and good pigment dispersibility can be obtained. By setting the content to 5.5% by volume or more, the adsorption rate with the polar resin can be kept low. By setting the content to 10.0% by volume or less, affinity with the polar resin in the toner can be maintained to some extent, and pigment dispersibility becomes better. Furthermore, by maintaining the affinity between the pigment and the polar resin to some extent, the polar resin and the pigment repel each other during fixing, and it is possible to suppress a decrease in chroma due to aggregation.

Furthermore, in the present invention, it is preferable that the solubility parameter (SP value) of the binder resin determined by the Fedors equation is 9.8 or more and 11.0 or less. By setting it within this range, not only can the pigment dispersibility be maintained well, but also cracking of the toner can be suppressed. In the wettability test for an acetone/water mixed solvent, it is difficult to directly evaluate the affinity between the pigment and the polar resin, so it is performed to indirectly test the affinity between the pigment and the polar resin. The affinity between the pigment and the polar resin is simulated using acetone, and the actual affinity between acetone and the pigment is tested. The SP value of acetone is 10.0 (described in "Ecycle. Polym. Sci. chnol., 42, 76 (1965)"). It has been revealed that when a binder resin having an SP value close to that of acetone is used, the affinity balance between pigment/polar resin/binder resin can be maintained better and cracking of the toner can be suppressed. When the SP value of the binder resin is 9.8 or more and 11.0 or less, the effect of suppressing toner cracking is good. It is believed that this is because by setting it within this range, toner cracking caused by slight cracks at the interface between the binder resin and the pigment can be suppressed.

In order to maintain the above-described affinity balance between the pigment/polar resin/binder resin, the acid value of the binder resin is preferably lower than that of the polar resin.

Furthermore, when the acid value of the binder resin is AVB and the acid value of the polar resin is AVP, it is more preferable that AVB is 5.0 mgKOH/g or less and that formula (4) is satisfied.
Formula (4) AVB<AVP-2

By satisfying the condition of formula (4), the charging performance becomes better.

Further, in the present invention, in the XRD measurement of the pigment, it is preferable that the crystallite size D calculated at the peak having the maximum intensity within the range of 3°<2θ<60° satisfies the following formula (3).
Formula (3) 1.0nm≦D≦7.0nm

When the crystallite size is less than 1.0 nm, crystallinity decreases and light resistance deteriorates. Furthermore, when the crystallite size is larger than 7.0 nm, the scattered components increase and the saturation decreases. The crystallite size can be controlled by changing the structure of the pigment, by forming a solid solution using multiple types of pigment skeletons, by changing the temperature conditions in the pigmentation process, etc.

In the present invention, the amount of the polar resin is preferably 1.0 parts by mass or more and 15.0 parts by mass or less based on 100 parts by mass of the binder resin. Further, it is preferable that the amount of pigment is 1.0 parts by mass or more and 10.0 parts by mass or less based on 100 parts by mass of the binder resin. Further, it is preferable that the amount of pigment is 6.7 parts by mass or more and 1000 parts by mass or less based on 100 parts by mass of the polar resin. By setting the value within such a numerical range, pigment dispersibility and charging performance become better, and a toner with high chroma and high durability can be obtained.

As the binder resin of the present invention, known resins such as vinyl resins, maleic acid copolymers, polyester resins, and epoxy resins can be used. Among these, vinyl resins and polyester resins are preferred from the viewpoint of ease of manufacture. Further, from the viewpoint of storage and use under high temperature and high humidity conditions, styrene acrylic resin or polyester resin is more preferred.

Vinyl monomers that can be used in the production of vinyl resins include styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p - styrene derivatives such as methoxystyrene and p-phenylstyrene;
Methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate , n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, and 2-benzoyloxyethyl acrylate;
Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate , diethyl phosphate ethyl methacrylate, and methacrylic polymerizable monomers such as dibutyl phosphate ethyl methacrylate.

These can be used alone or in combination of two or more.

Polyhydric carboxylic acids and polyhydric alcohols can be used as polycondensation monomers that can be used in the polyester resin.

Examples of polyvalent carboxylic acids include oxalic acid, glutaric acid, succinic acid, maleic acid, adipic acid, β-methyladipic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, and fumaric acid. Acid, citraconic acid, diglycolic acid, cyclohexane-3,5-diene-1,2-dicarboxylic acid, hexahydroterephthalic acid, malonic acid, pimelic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid Acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylene diglycolic acid, p-phenylene diglycolic acid, o-phenylene diglycolic acid, diphenylacetic acid, diphenyl-p,p'-dicarboxylic acid , naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracenedicarboxylic acid, cyclohexanedicarboxylic acid, and the like. Examples of polycarboxylic acids other than dicarboxylic acids include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, and pyrenetetracarboxylic acid.

Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5 -Pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbitol, 1,2,3,6-hexanetetrol, 1, 4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4 -Butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, hydrogenated bisphenol A, hydrogenated bisphenol A ethylene Examples include oxide adducts, hydrogenated bisphenol A propylene oxide adducts, and the like.

The toner of the present invention may contain a release agent. As mold release agents, aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, and paraffin wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax; aliphatic hydrocarbon waxes; block copolymers of; waxes whose main component is fatty acid esters such as carnauba wax, Sasol wax, and montanic acid ester wax; and partially or fully deoxidized fatty acid esters such as deoxidized carnauba wax, and behenic acid. Partial esterification products of fatty acids and polyhydric alcohols such as monoglycerides; methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and fats can be mentioned.

As for the molecular weight distribution of the mold release agent, the main peak is preferably in a molecular weight range of 400 or more and 2400 or less, more preferably 430 or more and 2000 or less. This makes it possible to impart favorable thermal properties to the toner. The total amount of the release agent added is preferably 2.50 parts by mass or more and 40.0 parts by mass or less, and 3.00 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.

The method for manufacturing the toner of the present invention will be explained. The toner of the present invention can be manufactured by a conventionally known method. For example, a polymerizable monomer composition containing a polymerizable monomer, a pigment, a polar resin, and if necessary a mold release agent to obtain a binder resin is suspended and granulated in an aqueous medium, and the polymerizable monomer composition is Suspension polymerization method in which the polymerizable monomers in the monomer composition are polymerized; kneading in which various toner constituent materials such as binder resin, pigment, polar resin, and if necessary, release agent are kneaded, crushed, and classified. Grinding method: A dispersion obtained by emulsifying and dispersing a binder resin, a pigment dispersion, a dispersion obtained by emulsifying and dispersing a polar resin, and a dispersion such as a release agent as necessary are mixed, and aggregation, Emulsion aggregation method to obtain toner particles by heating and fusing; emulsion polymerization of polymerizable monomers constituting the binder resin, and polar resin dispersion in which the formed dispersion liquid, pigment dispersion liquid, and polar resin are emulsified and dispersed. emulsion polymerization aggregation method in which toner particles are obtained by mixing the liquid and a dispersion liquid such as a release agent as necessary, agglomerating and heating the mixture; Depending on the method, a dissolution/suspension method may be used in which an organic solvent dispersion containing a mold release agent and the like is suspended in an aqueous medium and granulated.

In the present invention, an external additive may be externally added to the toner particles in order to improve the image quality of the toner. As the external additive, inorganic fine powder such as fine silica powder, fine titanium oxide powder, or fine aluminum oxide powder is preferably used. These inorganic fine powders are preferably hydrophobized using a hydrophobizing agent such as a silane coupling agent, silicone oil, or a mixture thereof. Furthermore, in the toner of the present invention, external additives other than those mentioned above may be mixed into the toner particles, if necessary. The amount of the inorganic fine powder added is preferably 0.5 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of toner particles.

<Method for measuring adsorption rate of polar resin to pigment>
The adsorption rate is measured as follows.
Pigment 1.0g
Polar resin 0.15g
Styrene 16.0g
n-butyl acrylate 4.0g
Glass beads (diameter 0.8mm) 30.0g
Weigh the above materials into a 50 ml pressure bottle. Thereafter, it was shaken for 10 hours in a paint shaker (manufactured by Toyo Seiki Co., Ltd.).

The dispersion after shaking is separated using a centrifuge (Mini Spin Plus manufactured by Eppendorf, 14.5 krpm, 30 minutes), and the supernatant is taken.

The supernatant is filtered using Millex LH 0.45 μm (manufactured by Nippon Millipore), and the filtrate is analyzed by gel permeation chromatography (GPC). The peak area of the obtained chromatogram (vertical axis: concentration-dependent electrical intensity, horizontal axis: retention time) is defined as S1. Note that the vertical axis is not particularly limited as long as it is an index that depends on concentration.

Similarly, a solution containing the following materials is filtered through Millex, and the filtrate is analyzed by GPC.
Polar resin 0.15g
Styrene 16.0g
n-butyl acrylate 4.0g

The peak area of the obtained chromatogram is designated as S2. Note that since the area ratio between S1 and S2 is determined below, a chromatogram for determining the peak areas S1 and S2 is created using the vertical and horizontal axes of the same scale.

The adsorption rate of the pigment dispersant or amorphous resin to the pigment is calculated according to the following formula.
Adsorption rate (%) = (1-S1/S2) x 100

Note that GPC is analyzed 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, standard polystyrene resin (product name: "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, A molecular weight calibration curve prepared using "F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500" (manufactured by Tosoh Corporation) is used.

<Method for measuring resin acid value>
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 in the present invention is measured according to JIS K 0070-1992, and specifically, it is measured according to the following procedure.

Titration is performed using a 0.1 mol/L potassium hydroxide ethyl alcohol solution (manufactured by Kishida Chemical Co., Ltd.). The factor of the potassium hydroxide ethyl alcohol solution can be determined using a potentiometric titration device (potentiometric titration measurement device AT-510, manufactured by Kyoto Electronics Industry Co., Ltd.). 100 mL of 0.100 mol/L hydrochloric acid is placed in a 250 mL tall beaker, titrated with the potassium hydroxide ethyl alcohol solution, and determined from the amount of the potassium hydroxide ethyl alcohol solution required for neutralization. The 0.100 mol/L hydrochloric acid prepared according to JIS K 8001-1998 is used.

The measurement conditions for acid value measurement are shown below.
Titrator: Potentiometric titrator AT-510 (manufactured by Kyoto Electronics Industry Co., Ltd.)
Electrode: Composite glass electrode double junction type (manufactured by Kyoto Electronics Industry Co., Ltd.)
Control software for titrator: AT-WIN
Titration analysis software: Tview
The titration parameters and control parameters during titration are as follows.
Titration parameters Titration mode: Blank titration Titration format: Total volume titration Maximum titration volume: 20mL
Waiting time before titration: 30 seconds Titration direction: Automatic control parameter End point judgment potential: 30 dE
End point judgment potential value: 50 dE/dmL
End point detection judgment: Not set Control speed mode: Standard gain: 1
Data acquisition potential: 4mV
Data collection titration amount: 0.1mL

Main test;
0.100 g of the measurement sample was accurately weighed into a 250 mL tall beaker, 150 mL of a mixed solution of toluene/ethanol (3:1) was added, and the mixture was dissolved over 1 hour to obtain a measurement sample. Titration is carried out using the potentiometric titration apparatus and the potassium hydroxide ethyl alcohol solution.

Blank test;
Titration is performed in the same manner as above, except that no sample is used (that is, only a mixed solution of toluene/ethanol (3:1) is used).

The obtained results are substituted into the following formula to calculate the acid value.
A=[(CB)×f×5.611]/S
(In the formula, A: acid value (mgKOH/g), B: amount of potassium hydroxide ethyl alcohol solution added in the blank test (mL), C: amount added (mL) of potassium hydroxide ethyl alcohol solution in the main test, f: Factor of potassium hydroxide solution, S: Sample (g).)

<Measurement of number average particle diameter D1 of resin dispersion>
The particle size distribution of the resin dispersion is calculated using a dynamic light scattering type Microtrac particle size distribution analyzer [UPA-150] (Nikkiso Co., Ltd.). Measurement is performed while controlling the temperature of the cell so that the temperature of the aqueous medium used for measurement and the measurement cell are the same. Particle size measurements are carried out at a temperature of 25°C.
(1) After putting 3.0 g of RO water into the cell, perform a back ground check. Confirm that the sample loading is 0.0010 or less.
(2) After putting 3.0 g of RO water into the cell, perform Set Zero. Set Z
The ero condition is 60 seconds.
(3) Enter the following conditions.
Measurement time: 30s, number of measurements: 2 times Particle conditions: transparency, refractive index: 1.62, shape: non-spherical, density: 3.17
Solvent condition: WATER selected Refractive index: 1.333
Viscosity at high temperature: 0.797 (30℃), Viscosity at low temperature: 1.002 (20℃)
Display settings: Select standard Distribution display: Select volume (4) Put 3.0 g of aqueous medium containing emulsified particles into the measurement cell and start measurement.
(5) Analyze the measurement data using special software attached to the device and calculate the number average particle diameter (D1).

<Method for measuring pigment crystallite size>
The crystallite size of the pigment was measured by the following method using X-ray diffraction (XRD).

The pigment was measured using the following equipment and measurement conditions.
Measuring device: RINR-TTRII (manufactured by Rigaku Corporation)
Tube: Cu
Starting angle: 3°
End angle: 60°
Sampling width: 0.02°
Scan speed: 4.00°/min
Voltage: 50kV
Current: 300mA
Parallel beam optical system Divergent slit: Open divergent vertical slit: 10mm
Scattering slit: open Light receiving slit: open

The spectrum obtained under the above measurement conditions was subjected to waveform processing as follows, and a calculated spectrum was calculated.

Background processing was manually performed on the obtained spectrum. Thereafter, fitting was performed using a split-type pseudo-Voigt function, and if there was a discrepancy between the peak shape and the original spectrum, the calculated spectrum was manually adjusted.

Among the crystallite sizes of peaks within the Bragg angle range of 3° to 60° (3°<2θ<60°) in the calculated spectrum obtained by the above operation, the crystallite size at the peak with the maximum integrated intensity was defined as the crystallite size (D).

<How to measure AVH/AVE>
(Preparation of sample for AVH)
Weigh 0.500 g of toner particles into a 100 ml beaker, add 0.1 g of surfactant "Contaminon N" manufactured by Wako Pure Chemical Industries, Ltd. and 49.9 g of ion-exchanged water, and add 0.50 g of toner particles to a 100 ml beaker. 305HS) for 1 minute.

(AVE sample preparation)
Weigh 0.500 g of toner particles into a 100 ml beaker, add 50 g of ethanol, and stir for 30 minutes.

In the main test of the method for measuring the resin acid value described above, the acid value is measured in the same manner except that the measurement samples are changed to an AVH sample and an AVE sample.

<Method for isolating pigment from toner particles>
In measuring the crystallite size and acetone wettability of the present pigment, the pigment can be isolated from the toner and measured by the following method.

50 g of toner was placed in a 1 L beaker containing 500 g of THF, and stirred for 24 hours at a rotation speed of 100 rpm using a magnetic stirrer. The dispersion was allowed to stand for 24 hours to allow insoluble matter to settle. Next, the THF-soluble content (supernatant) containing the pigment dispersion was recovered by decantation. The collected supernatant liquid was centrifuged, and the precipitated pigment was collected. The collected pigment was washed three times with distilled water, dried, and the aggregated coarse particles were crushed in a mortar. If the amount of pigment required for measurement was not reached, the above operation was repeated.

<Method for measuring acetone wettability>
The acetone wettability W of the pigment was measured using a powder wettability tester in the following manner.
Measuring device: WET101P (manufactured by Resca Co., Ltd.)

50 mg of the pigment was weighed out and gently floated on a 200 ml tall beaker containing 70.0 ml of distilled water. While stirring the liquid with a stirrer, acetone was supplied to the aqueous phase at a rate of 0.5 ml/min, and the transmittance was measured using a semiconductor laser. The volume fraction of acetone in the water-acetone mixed solvent when the transmittance obtained in the measurement reached 50% was defined as acetone wettability.

<How to calculate SP value>
The SP value of the binder resin is determined as follows according to the calculation method proposed by Fedors.

For each polymerizable monomer, the evaporation energy (Δei) is determined for each atom or atomic group in the molecular structure from the table described in "polym.Eng.Sci., 14(2), 147-154 (1974)". (cal/mol) and molar volume (Δvi) (cm ³ /mol) are determined, and (ΣΔei/ΣΔvi) is set as the SP value (cal/cm ³ ).

The evaporation energy (Δei) and molar volume (Δvi) of the monomer unit derived from the polymerizable monomer constituting the polymer are determined for each monomer unit, and the product with the molar ratio (j) of each monomer unit is calculated. , is determined by dividing the total evaporation energy of each monomer unit by the total molar volume, and is calculated using the following formula (8).
SP value = {(Σj×ΣΔei)/(Σj×ΣΔvi)} ^0.5 (8)

<Measurement method of toner particles and toner weight average particle diameter (D4)>
The toner particles and the weight average particle diameter (D4) of the toner are measured using a precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter). Measurements are performed under the following conditions.
Effective measurement channels: 25,000 channels Total number of control motors: 50,000 Aperture: 100μm
Current: 1600μA
Gain; 2

The Kd value is measured using a value obtained using "Standard Particle 10.0 μm" (manufactured by Beckman Coulter). The measurement data is analyzed using special software attached to the device, and the weight average particle diameter (D4) is calculated. Note that when the graph/volume % is set in the dedicated software described above, the "average diameter" on the "analysis/volume statistics (arithmetic mean)" screen is the weight average particle diameter (D4).

The present invention will be specifically explained with reference to the following examples. However, this does not limit the invention in any way. Examples 5, 24, 31, 32 and 34 are reference examples. Unless otherwise specified, all "parts" in Examples and Comparative Examples are based on mass.

<Production example of polar resin 1>
A nitrogen inlet pipe, The mixture was placed in a 6-liter four-necked flask equipped with a dehydration tube, a stirrer, and a thermocouple, and reacted at 200° C. for 6 hours under a nitrogen atmosphere. Furthermore, trimellitic anhydride was added at 210°C, and the reaction was carried out under reduced pressure of 40 mmHg, and the reaction was continued until the weight average molecular weight (Mw) reached 12,000. The obtained polyester resin is referred to as Polar Resin 1. Further, the acid value of the obtained polar resin 1 was as shown in Table 1.

<Production examples of polar resins 2 to 6>
In the production example of polar resin 1, polar resins 2 to 6 were obtained in the same manner as in the production example of polar resin 1, except that the raw materials were mixed at the charging ratio shown in Table 1. The acid values of the obtained polar resins 2 to 6 are shown in Table 1.

<Production example of polar resin 7>
200 parts of xylene was charged into a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen inlet tube, and the mixture was refluxed under a nitrogen stream.
・2-acrylamido-2-methylpropanesulfonic acid 6.00 parts ・Styrene 78.0 parts ・2-ethylhexyl acrylate 16.0 parts ・Dimethyl-2,2'-azobis(2-methylpropionate) 5.00 The mixture was added dropwise to the reaction vessel with stirring and maintained for 10 hours. Thereafter, the solvent was distilled off and dried at 40° C. under reduced pressure to obtain polar resin 7. The acid value of the obtained polar resin 7 is shown in Table 1.

<Production example of polar resin 8>
300 parts of xylene is put into a flask, the inside of the container is sufficiently replaced with nitrogen while stirring, and then the temperature is raised to reflux.
- Styrene 92.53 parts - Methyl methacrylate 2.50 parts - 2-hydroxyethyl methacrylate 2.50 parts - Methacrylic acid 2.48 parts - Perbutyl D (manufactured by NOF) 2.00 parts The above mixed liquid was added. Thereafter, polymerization was carried out for 5 hours at a polymerization temperature of 175° C. and a pressure of 0.10 MPa. Thereafter, a solvent removal step was performed under reduced pressure for 3 hours to remove xylene, and the mixture was pulverized to obtain polar resin 8. The acid value of the obtained polar resin 8 is shown in Table 1.

<Production example of polar resin 9>
In the production example of polar resin 8, polar resin 9 was produced in the same manner as polar resin 8 except that the recipe was as follows and the pressure during polymerization was changed by 0.50 MPa. Table 1 shows the acid value of the obtained polar resin 9.
・Styrene 91.30 parts ・Methyl methacrylate 2.50 parts ・2-hydroxyethyl methacrylate 1.25 parts ・Methacrylic acid 4.95 parts ・Perbutyl D (manufactured by NOF) 2.00 parts

<Production example of polar resin 10>
(Step 1)
100 g of 2,5-dihydroxybenzoic acid and 1441 g of 80% sulfuric acid were heated and mixed at 50°C. 144 g of tert-butyl alcohol was added to this dispersion and stirred at 50° C. for 30 minutes. Thereafter, 144 g of tert-butyl alcohol was added to this dispersion and stirred for 30 minutes three times. The reaction solution was cooled to room temperature and slowly poured into 1 kg of ice water. The precipitate was filtered, washed with water, and then washed with hexane. This precipitate was dissolved in 200 mL of methanol and reprecipitated in 3.6 L of water. After filtration, 74.9 g of a salicylic acid intermediate represented by the following structural formula (9) was obtained by drying at 80°C.

(Step 2)
25.0 g of the obtained salicylic acid intermediate was dissolved in 150 mL of methanol, 36.9 g of potassium carbonate was added, and the mixture was heated to 65°C. A mixed solution of 18.7 g of 4-(chloromethyl)styrene and 100 mL of methanol was added dropwise to this reaction solution, and the mixture was reacted at 65° C. for 3 hours. After cooling the reaction solution, it was filtered, and the filtrate was concentrated to obtain a crude product. The crude product was dispersed in 1.5 L of water at pH=2 and extracted with ethyl acetate. Thereafter, it was washed with water, dried over magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain a precipitate. The precipitate was washed with hexane and purified by recrystallization from toluene and ethyl acetate to obtain 20.1 g of a polymerizable monomer represented by the following structural formula (10).

5.9 g of the polymerizable monomer shown in formula (10), 7.8 g of 2-ethylhexyl acrylate, and 56.4 g of styrene were dissolved in 42.0 ml of DMF, stirred for 1 hour while bubbling with nitrogen, and then heated to 110°C. did. A mixed solution of 2.1 g of tert-butylperoxyisopropyl monocarbonate (manufactured by NOF Corporation, trade name: Perbutyl I) and 42 ml of toluene was added dropwise to this reaction solution as an initiator. The reaction was further carried out at 110°C for 4 hours. Thereafter, the mixture was cooled and added dropwise to 1 L of methanol to obtain a precipitate. The obtained precipitate was dissolved in 120 ml of THF, and then added dropwise to 1.80 L of methanol to precipitate a white precipitate, filtered, and dried at 90° C. under reduced pressure to obtain 57.6 g of polar resin 10. Table 1 shows the acid value of the obtained polar resin 10.

<Production example of polar resin 11>
3 parts of polar resin 1 and 2 parts of polar resin 7 were placed in a reaction vessel equipped with a stirrer, and dissolved in 10 parts of xylene. After confirming that the mixture had been dissolved, the solvent was removed under reduced pressure to remove xylene, and the mixture was pulverized to obtain polar resin 11. Table 1 shows the acid value of the obtained polar resin 11.

<Production example of polar resin 12>
Polar resin 12 was obtained in the same manner as in the production example of polar resin 8 except that the formulation was changed as follows. Table 1 shows the acid value of the obtained polar resin 12.
・Styrene 94.25 parts ・Methyl methacrylate 2.42 parts ・Methacrylic acid 3.33 parts ・Perbutyl D (manufactured by NOF) 2.00 parts

<Production example of polar resin 13>
Polar resin 13 was obtained in the same manner as in the production example of polar resin 8 except that the recipe was changed as follows. Table 1 shows the acid value of the obtained polar resin 13.
・Styrene 92.87 parts ・Methyl methacrylate 2.46 parts ・2-hydroxyethyl methacrylate 4.35 parts ・Methacrylic acid 3.20 parts ・Perbutyl D (manufactured by NOF) 2.00 parts

表中のＴＰＡはテレフタル酸、ＩＰＡはイソフタル酸、ＴＭＡは無水トリメリット酸、ＢＰＡ（ＰＯ）はビスフェノールＡのプロピレンオキサイド２モル付加物、ＢＰＡ（ＥＯ）はビスフェノールＡのエチレンオキサイド２モル付加物、ＥＧはエチレングリコールを表す。

In the table, TPA is terephthalic acid, IPA is isophthalic acid, TMA is trimellitic anhydride, BPA (PO) is an adduct of 2 moles of propylene oxide of bisphenol A, BPA (EO) is an adduct of 2 moles of ethylene oxide of bisphenol A, EG represents ethylene glycol.

An example of manufacturing magenta pigment is shown.

<Production example of magenta pigment 1>

90 g (0.500 mol) of amine compound (D1) was dispersed in 1000 mL of distilled water, and the solution was stirred at 20°C. After the temperature was raised to 3° C., 140 mL of 12N hydrochloric acid (manufactured by Kishida Chemical Co., Ltd.) was added dropwise to obtain a hydrochloride. To this was added 90 g of a sodium nitrite aqueous solution (manufactured by Nissan Chemical Co., Ltd.), and the mixture was stirred at 10° C. for 20 minutes to obtain a diazo compound-containing solution.

<Preparation of coupling reaction aqueous solution>

Separately, 97 g (0.350 mol) of coupling compound (E1) and 47 g (0.150 mol) of coupling compound (E2) were dispersed in 1000 mL of distilled water and heated to 95°C, followed by 165 g of 33% aqueous sodium hydroxide solution. was added and stirred at 95°C for 2 minutes. Thereafter, the temperature was maintained at 70°C to obtain a coupling reaction aqueous solution.

(Production of magenta pigment by azo coupling reaction)
19 g of sodium acetate was added to the diazo compound-containing solution to adjust the pH to 4.5, and the solution was cooled to 10°C. Thereafter, the coupling reaction aqueous solution was added dropwise over a period of 1 hour, and the reaction solution was allowed to react while being cooled so as not to rise above 10°C. At that time, 12N hydrochloric acid (manufactured by Kishida Chemical Co., Ltd.) was added from time to time so that the pH was maintained at 4.9. Thereafter, the mixture was reacted at 20° C. for 4 hours. Thereafter, the solid content was filtered and washed with water, to obtain an untreated wet cake of magenta pigment 1 containing compound A and compound B at a ratio of 70:30.

(Adjustment of magenta pigment surface characteristics by solvent heat treatment)
200 parts of a wet cake of magenta pigment 1 was washed three times with acetone and then suspended in 1000 parts of acetone. After raising the liquid temperature to 60°C, the mixture was stirred for 24 hours while maintaining the temperature. After cooling to room temperature, it was filtered, washed with 100 parts of distilled water, and dried to obtain magenta pigment 1. Table 2 shows the physical properties of the obtained magenta pigment 1.

<Production examples of magenta pigments 2 to 8, 11, and 12>
Magenta pigment 1 was prepared in the same manner as magenta pigment 1, except that the amounts of amide compound (E1) and amide compound (E2) added and the solvent used to adjust the magenta pigment surface characteristics by solvent heat treatment were changed as shown in Table 2. Pigments 2-8, 11, and 12 were obtained. Table 2 shows the physical properties of the obtained magenta pigments 2 to 8, 11, and 12.

<Production example of magenta pigment 9>
(Adjustment of magenta pigment surface characteristics by rosin treatment)
- Distilled water 1000 parts - Magenta pigment 1 100 parts The above materials were stirred and mixed to suspend magenta pigment 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, 12N hydrochloric acid (manufactured by Kishida Chemical Co., Ltd.) was added to precipitate the resin. The precipitated composition was filtered, washed with distilled water, and then dried to obtain magenta pigment 9. Table 2 shows the physical properties of the obtained magenta pigment 9.

<Production example of magenta pigment 10>
Magenta pigment 10 was obtained in the same manner as in the production example of magenta pigment 9 except that the amount of tetrahydroabietic acid was changed to 5.0 parts and the amount of abietic acid was changed to 1.7 parts. Table 2 shows the physical properties of the obtained magenta pigment 10.

<Magenta pigment 13>
C.I. as magenta pigment 13. I. Pigment Red122 was used. The C. I. Table 2 shows the physical properties of Pigment Red122.

<Magenta pigment 14>
C.I. as magenta pigment 14. I. Pigment Red269 was used. The C. I. Table 2 shows the physical properties of Pigment Red269.

<Magenta pigment 15>
As magenta pigment 15, C.I. I. Pigment Red150 was used. The C. I. Table 2 shows the physical properties of Pigment Red150.

<Production example of magenta pigment 16>
In the production example of magenta pigment 9, magenta pigment 1 was prepared from C.I. I. Magenta pigment 16 was obtained in the same manner as in the production example of magenta pigment 9 except that Pigment Red 269 was used. Table 2 shows the physical properties of the obtained magenta pigment 16.

<Magenta pigment 17>
・Methanol 1000 parts ・Magenta pigment 8 100 parts ・C. I. Pigment Red 269 12 parts The above materials were stirred and mixed and suspended in methanol. After raising the liquid temperature to 60°C, the mixture was stirred for 24 hours while maintaining the temperature. After the temperature was lowered to room temperature, it was filtered, washed with 100 parts of distilled water, and dried to obtain magenta pigment 15. Table 2 shows the physical properties of the obtained magenta pigment 17.

<Magenta pigment 18>
In the production example of magenta pigment 17, C. I. Magenta pigment 18 was obtained in the same manner as in the production example of magenta pigment 17 except that Pigment Red 269 was changed to 10 parts. Table 2 shows the physical properties of the obtained magenta pigment 18.

An example of toner production will be shown.

<Production example of toner 1>
・Styrene 80.0 parts ・n-butyl acrylate 20.0 parts ・Divinylbenzene 0.25 parts ・Magenta pigment 1 5.0 parts ・Polar resin 1 5.0 parts ・Paraffin wax 10.0 parts (Nippon Seirosha) Manufactured by: HNP-51 Maximum heat peak: 74℃)
- A mixture consisting of 100.0 parts of toluene was prepared. The above mixture was put into an attritor (manufactured by Nippon Coke Co., Ltd.) and dispersed using zirconia beads with a diameter of 5 mm at 200 rpm for 2 hours to obtain a raw material dispersion.

Meanwhile, 735.0 parts of ion-exchanged water and 16.0 parts of trisodium phosphate (decahydrate) were added to a container equipped with a high-speed stirring device Homomixer (manufactured by Primix) and a thermometer, and the mixture was stirred at 12,000 rpm. At the same time, the temperature was raised to 60°C. A calcium chloride aqueous solution containing 9.0 parts of calcium chloride (dihydrate) dissolved in 65.0 parts of ion-exchanged water was added thereto, and the mixture was stirred at 12,000 rpm for 30 minutes while maintaining the temperature at 60°C. 10% hydrochloric acid was added thereto to adjust the pH to 5.5 to obtain an aqueous medium in which an inorganic dispersion stabilizer containing hydroxyapatite was dispersed in water.

Subsequently, the raw material dispersion was transferred to a container equipped with a stirring device and a thermometer, and the temperature was raised to 60° C. while stirring at 100 rpm. Thereto, 9.0 parts of a polymerization initiator (10 hour half-life temperature 54.6°C (manufactured by NOF) was added and stirred at 100 rpm for 5 minutes while maintaining the temperature at 60°C. The mixture was poured into an aqueous medium being stirred at 12,000 rpm. While maintaining the temperature at 60° C., stirring was continued for 20 minutes at 12,000 rpm using the high-speed stirring device described above to obtain a granulated liquid.

The above granulation liquid was transferred to a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen introduction tube, and the temperature was raised to 70° C. while stirring at 150 rpm under a nitrogen atmosphere. The polymerization reaction was carried out at 150 rpm for 10 hours while maintaining the temperature at 70°C. Next, 100.0 parts of ion-exchanged water was added, the reflux tube was removed, and a distillation apparatus was attached. Distillation was carried out at a temperature of 100° C. in the container for 5 hours. After the distillation was completed, the mixture was cooled to 30° C., diluted hydrochloric acid was added into the container to lower the pH to 1.5, and the dispersion stabilizer was dissolved. Further, the particles were filtered, washed, dried, and classified to obtain toner particles 1 having a weight average particle diameter (D4) of 6.5 μm.

To 100.0 parts of the obtained toner particles 1, silica fine particles (hydrophobic treatment with hexamethyldisilazane, number average particle diameter of primary particles: 10 nm, BET specific surface area: 170 m ² /g) were added as external additives. ) was added thereto and mixed for 15 minutes at 3000 rpm using a Henschel mixer (manufactured by Nippon Coke Co., Ltd.) to obtain Toner 1.

<Production examples of Toners 2 to 15, 18 to 30, and Comparative Toners 1 to 10>
Toners 2 to 15, 18 to 34, and comparative toners 1 to 10 were obtained in the same manner as in the production example of Toner 1, except that the types and amounts of various toner materials were changed as shown in Table 3. Ta.

Table 4 shows the physical properties of the obtained toners 1 to 15, 18 to 34, and comparative toners 1 to 10.

<Example of manufacturing toner 16>
(Manufacture of polyester resin 1)
After putting the monomers in the amount shown in Table 5 into a reaction tank equipped with a nitrogen introduction pipe, dehydration pipe, stirrer, and thermocouple, add 1.5 parts of dibutyltin as a catalyst to 100 parts of the total amount of monomers. did. Next, the temperature was quickly raised to 180° C. under normal pressure in a nitrogen atmosphere, and then water was distilled off while heating from 180° C. to 210° C. at a rate of 10° C./hour to perform polycondensation. After the temperature reached 210° C., the pressure inside the reaction tank was reduced to 5 kPa or less, and polycondensation was carried out under conditions of a temperature of 210° C. and 5 kPa or less to obtain polyester resin 1.

At that time, the polymerization time was adjusted so that the softening point of the resulting polyester resin B1 was 115°C.

ＴＰＡはテレフタル酸、ＢＰＡ－ＰＯはビスフェノールＡ－プロピレンオキサイド２ｍｏｌ付加物を表す。

TPA represents terephthalic acid, and BPA-PO represents a 2 mol bisphenol A-propylene oxide adduct.

・Polyester resin 1 90.0 parts ・Polar resin 1 10.0 parts ・Magenta pigment 1 7.0 parts ・Paraffin wax (DSC peak temperature: 80°C) 5.0 parts Mitsui Miike Kakoki Co., Ltd.) was used to mix the mixture, and then a twin-screw kneader (Ikegai Tekko Co., Ltd. PCM-30 model) was used at a rotation speed of 3.3 s ^-1 and a kneading temperature of 120°C. . 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, the obtained finely pulverized powder was classified using a multi-segment classifier utilizing the Coanda effect to obtain toner particles 16 having a weight average particle diameter of 7.0 μm.

To 100.0 parts of the obtained toner particles 16, silica fine particles (hydrophobized with hexamethyldisilazane, number average particle diameter of primary particles: 10 nm, BET specific surface area: 170 m ² /g) were added as external additives. ) and mixed for 15 minutes at 3000 rpm using a Henschel mixer (manufactured by Nippon Coke Co., Ltd.) to obtain Toner 16. Table 4 shows the physical properties of toner 16.

<Production example of toner 17>
(Production of dispersion liquid of binder resin fine particles)
60 g of ethylene vinyl acetate resin (Ultrasen 685, manufactured by Tosoh) was added to 200 g of toluene (manufactured by Wako Pure Chemical Industries, Ltd.), heated to 90° C., and then stirred for 3 hours to dissolve. To a toluene solution in which ethylene vinyl acetate resin was dissolved, 180 g of ion-exchanged water in which 6 g of an anionic surfactant (Neogen RK, manufactured by Daiichi Kogyo Seiyaku) and 3 g of an anionic surfactant (Nonsarl LN1, manufactured by NOF Corporation) were dissolved was added. . Then, ultra high speed stirring device T. K. The mixture was thoroughly stirred at 4000 rpm using Robomix (manufactured by Primix Co., Ltd.). Thereafter, the mixture was dispersed for about 1 hour using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo), and then toluene was removed using an evaporator to obtain a dispersion of fine binder resin particles.

(Manufacture of polar resin dispersion)
A dispersion of Polar Resin 1 was obtained in the same manner as in the production of the dispersion of binder resin particles, except that Polar Resin 1 was used instead of ethylene vinyl acetate resin.

(Manufacture of dispersion liquid of mold release agent fine particles)
- Mold release agent (HNP-51, melting point 78°C, manufactured by Nippon Seiro) 20.0 parts - Anionic surfactant (Daiichi Kogyo Seiyaku manufactured by Neogen RK) 1.0 parts - Ion exchange water 79.0 parts After putting the above recipe into a mixing container equipped with a stirring device, it was heated to 90°C and circulated to the Clearmix W Motion (manufactured by M Technique), where it was placed in a shear stirring section with a rotor outer diameter of 3 cm and a clearance of 0.3 mm. After stirring under the conditions of rotor rotation speed 19000 r/min and screen rotation speed 19000 r/min and dispersion treatment for 60 minutes, rotor rotation speed 1000 r/min, screen rotation speed 0 r/min, and cooling rate 10°C/min. By cooling to 40° C. under cooling treatment conditions, a dispersion liquid of release agent fine particles was obtained.

(Manufacture of pigment dispersion)
- Magenta pigment 1 10.0 parts - Ion exchange water 78.0 parts - Anionic surfactant (Daiichi Kogyo Seiyaku: Neogen RK) 2.0 parts The above materials were mixed. Thereafter, the mixture was dispersed for 1 hour using a high-pressure impact type dispersion device Nanomizer (manufactured by Yoshida Kikai Kogyo) to prepare a dispersion liquid of magenta pigment 1.

・Dispersion of fine binder resin particles (solid content 25%) 320.0 parts ・Dispersion of magenta pigment 1 (solid content 10%) 50.0 parts ・Dispersion of fine release agent particles (solid content 20%) 50 .0 parts Dispersion liquid of polar resin 1 (solid content 25%) 40.0 parts Each of the above materials was placed in a round stainless steel flask and mixed. An aqueous solution of 8 parts by mass of magnesium sulfate dissolved in 98 parts of ion-exchanged water was added thereto, and dispersed for 10 minutes at 5000 r/min using a homogenizer (Ultra Turrax T50, manufactured by IKA). Thereafter, the mixed solution was heated to 50° C. using a stirring blade in a heating water bath while appropriately controlling the rotation speed so that the mixed solution was stirred. After holding at 50° C. for 1 hour, the weight average particle diameter of the formed aggregated particles was measured. As a result, it was confirmed that aggregated particles having a weight average particle diameter of about 6.0 μm were formed.

An aqueous solution prepared by dissolving 40 parts of sodium ethylenediaminetetraacetate in 360 parts of ion-exchanged water was added to the resulting dispersion of aggregated particles, and further 2,800 parts of ion-exchanged water were added. The mixture was heated to 80° C. while stirring and kept in a closed state for 2 hours to obtain fully fused particles. Thereafter, after filtration and solid-liquid separation, the filtrate was sufficiently washed with ion-exchanged water and dried using a vacuum dryer to obtain toner particles 17 having a weight average particle diameter of 5.4 μm.

To 100.0 parts of the obtained toner particles 17, silica fine particles (hydrophobic treatment with hexamethyldisilazane, number average particle diameter of primary particles: 10 nm, BET specific surface area: 170 m ² /g) were added as external additives. ) and mixed for 15 minutes at 3000 rpm using a Henschel mixer (manufactured by Nippon Coke Co., Ltd.) to obtain Toner 17. Table 4 shows the physical properties of the obtained toner 17.

[Examples 1 to 34, Comparative Examples 1 to 10]
The following evaluations were performed on each of the above Toners 1 to 34 and Comparative Toners 1 to 10.

<Evaluation of image quality>
A color laser printer (HP Color LaserJet 3525dn, manufactured by HP) was prepared, and the fixing unit was made removable so that printing was possible only with the magenta station.

The toner filled in the magenta toner cartridge for this printer was removed, and the toner to be evaluated was filled instead. Next, using the filled toner, an unfixed toner image (0.40 mg/cm ² ) of 2.0 cm in length and 15.0 cm in width is placed on image receiving paper (GF-C081) at the upper end in the paper feeding direction. It was formed at a portion 1.0 cm from the base. Next, the removed fixing unit was modified so that the fixing temperature and process speed could be adjusted, and the process speed was set to 230 mm/s in a normal temperature and normal humidity environment (23° C., 60% RH), and the unfixed image was transferred to 100 mm/s. The unfixed image was fixed by changing the increments of 5°C from 180°C to 180°C. The chromaticity of the obtained fixed image in the L*a*b* color system was measured using a reflection densitometer SpectroLino (formerly manufactured by Gretag Macbeth). The values of chroma (C*) and hue angle (h) of the obtained results were read. Among the images measured at each fixing temperature, the image with the highest chroma (C*) was ranked according to the following criteria, and a C rank or higher was defined as an acceptable criterion in the present invention. If the hue angle (h) is outside the range of 300°≦h≦355°, it is ranked D regardless of the value of C*. The results are shown in Table 6.
[Evaluation criteria]
A: C* is 75.0 or more, 300°≦h≦355°
B: C* is 72.0 or more, 300°≦h≦355°
C: C* is 69.0 or more, 300°≦h≦355°
D: C* is less than 69.0

Using the printer used in the image quality evaluation and the cartridge filled with the evaluation toner, up to 3,000 images with a printing ratio of 1.0% were printed out, and the results were shown at the initial stage and at the time of outputting 3,000 sheets (after durability). Fog and durability were evaluated.

<Evaluation of fogging>
Solid white images were output at the initial stage and after printing 3,000 sheets, and the fogged toner on the photoreceptor was removed by taping with Mylar tape. Thereafter, the tape and the untaped tape were attached to a LETTER size XEROX 4200 paper (manufactured by XEROX, 75 g/m ² ). The reflectance (%) of each tape was measured using "REFLECTOMETER MODELTC-6DS" (manufactured by Tokyo Denshoku Co., Ltd.).

Evaluation was made using the numerical value (%) obtained by subtracting the reflectance (%) of the taped tape from the reflectance (%) of the untaped tape. The smaller the value, the more suppressed fogging is. The results are shown in Table 6. A rank of C or higher was judged to be a level that poses no practical problems.
(Evaluation criteria)
A: Difference in reflectance is less than 2.0% B: Difference in reflectance is 2.0% or more and less than 5.0% C: Difference in reflectance is 5.0% or more and less than 10.0% D: Reflectance The difference is 10.0% or more

<Durability evaluation>
The durability of the toner was evaluated based on the presence or absence of streak images. A streak image is a vertical streak of about 0.5 mm that occurs due to member contamination due to external additives or toner deterioration, and is an image defect that is easily observed when a full-scale halftone image is output.

As the evaluation paper, XEROX4200 paper (manufactured by XEROX, 75 g/m ² ) was used. After 3,000 prints, a full halftone image was output using the cartridge, and the presence or absence of streaks was observed. The following judgment criteria were used. The evaluation results are shown in Table 6.
[Evaluation criteria]
A: No streaks or toner lumps.
B: There are no speckled streaks, but there are 1 to 3 small toner lumps.
C: There are some spotty streaks at the edges, or there are 4 or 5 small toner lumps.
D: There are spot-like streaks on the entire surface, or there are small toner lumps or obvious toner lumps in 5 or more places.

In the evaluation, it was determined that the product had good durability if it was ranked C or higher.

<Evaluation of pigment dispersibility>
In order to evaluate the pigment dispersibility of the toner, ultrathin sections of the toner are prepared using a microtome and observed using a transmission electron microscope (TEM). If necessary, stain the sections with ruthenium oxide or osmic acid. The evaluation criteria were to observe whether the pigment was dispersed as a primary particle size, whether the pigment was segregated or exposed to the surface layer of the toner, and then ranked based on the following criteria. The results are shown in Table 6.
A: The pigment is dispersed in the primary particle size and is uniformly present throughout the toner.
B: Parts where the pigment aggregated are present, and the pigment is present non-uniformly.
C: Pigments are aggregated and many pigments are observed exposed on the toner surface.

<Evaluation of toner cracking>
0.10 g of toner and 10.0 g of 0.3 mm zirconia beads were placed in a 50 mL insulating plastic container and shaken at a rate of 200 times/min for 3 minutes. Thereafter, the shaken toner was placed on a carbon tape and observed using an SEM. The number of cracks (%) was calculated from 10 images magnified 2000 times using the following formula.
Number of cracks % = Number of toner particles with cracks or chips/Total number of toner particles x 100

Ranking was done based on the following criteria. It was determined that a C rank or higher is a level that poses no practical problems. The results are shown in Table 6.
A: The number of cracks (%) is less than 5%.
B: The number of cracks (%) is 5% or more and less than 10%.
C: The number of cracks (%) is 10% or more and less than 20%.
D: The number of cracks % is 20% or more.

Claims (9)

A toner having toner particles containing a binder resin, a pigment, and a polar resin,
The binder resin is a styrene acrylic resin,
The polar resin is a polyester resin having an acid value derived from a carboxyl group of 2.0 mgKOH/g or more and 20.0 mgKOH/g or less,
The adsorption rate of the polar resin to the pigment is 10% or less ,
The pigment contains a compound A represented by the following formula (1) and a compound B represented by the following formula (2),

The value of the ratio of the mass of the compound A to the mass of the compound B (the compound A/the compound B) is from 95/5 to 5/95 .
A magenta toner characterized by: The magenta toner according to claim 1 , wherein the combined mass of the compound A and the compound B in the toner particles is 90% or more of the mass of the pigment in the toner particles. The magenta toner according to claim 1 or 2 , wherein the content of the polar resin is 1.0% by mass or more and 30.0% by mass or less based on the total mass of the binder resin. The acid value obtained by measuring the dispersion obtained by dispersing the toner particles in water by a titration method is defined as AVH (mgKOH/g) , and the dispersion obtained by dispersing the toner particles in ethanol is measured by a titration method. When the acid value obtained by measurement is taken as AVE (mgKOH/g) ,
AVH is 0.20 mgKOH/g or more and 1.00 mgKOH/g or less,
AVH /AVE is 0.10 or more and 0.25 or less ,
The magenta toner according to any one of claims 1 to 3 . In the wettability test of the pigment with an acetone/water mixed solvent, the concentration of acetone when the transmittance of light at a wavelength of 780 nm is 50% is 5.5% by volume or more and 10.0% by volume or less,
The solubility parameter (SP value) of the binder resin is 9.8 or more and 11.0 or less ,
The magenta toner according to any one of claims 1 to 4 . In the XRD measurement of the pigment, the crystallite size D calculated at the peak having the maximum intensity within the range of 3° < 2θ < 60° satisfies the following formula (3) ,
Formula (3) 1.0nm≦D≦7.0nm
The magenta toner according to any one of claims 1 to 5 . The magenta toner according to any one of claims 1 to 6 , wherein the polar group of the polar resin is only a carboxy group. The content of the polar resin in the toner particles is 1.0 parts by mass or more and 15.0 parts by mass or less based on 100 parts by mass of the binder resin in the toner particles ,
The content of the pigment in the toner particles is 1.0 parts by mass or more and 10.0 parts by mass or less based on 100 parts by mass of the binder resin in the toner particles ,
The content of the pigment in the toner particles is 6.7 parts by mass or more and 1000 parts by mass or less based on 100 parts by mass of the polar resin in the toner particles .
The magenta toner according to any one of claims 1 to 7 . When the acid value of the binder resin is AVB and the acid value of the polar resin is AVP,
AVB is 5.0 mgKOH/g or less,
AVB and AVP satisfy the following formula (4) ,
Formula (4) AVB<AVP-2
The magenta toner according to any one of claims 1 to 8 .