JP7077124B2 - Yellow toner - Google Patents

Description

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

In recent years, with the development of color image forming technology by electrophotographic method, the demand for higher image quality is increasing more and more.

In order to achieve high image quality, it is important to improve the dispersibility of the pigment in the toner particles and maximize the coloring ability of the pigment in the toner particles.

In general, organic pigments are excellent in color development and light resistance, but are less likely to be dispersed in toner particles than inorganic pigments. Therefore, studies have been conducted to increase the primary particle size of the pigment in order to improve the dispersibility of the organic pigment, but if the primary particle size of the pigment is increased, it is difficult to fully demonstrate the coloring ability of the pigment. Met.

In particular, Pigment Yellow 74, which is a yellow pigment, has a large distortion in its crystal structure when it receives a strong share in the toner manufacturing process, and is prone to color variation and reaggregation, making it difficult to exhibit sufficient coloring ability. Met. Further, in recent years, studies have been made to increase the number of organic pigments in order to reduce the amount of toner used, and it is difficult to uniformly disperse the organic pigment while maintaining a more desired crystal structure.

In addition, if the number of openings of the organic pigment is increased, the area where the functional groups serving as charging sites in the organic pigment are exposed on the toner surface increases, and the charging property of the toner, especially the charging property under high temperature and high humidity, decreases, resulting in fog. There is also the issue of occurring.

Therefore, it is necessary to develop a toner that is dispersed in the binder resin while maintaining a desired crystalline state even if a large amount of Pigment Yellow 74 is added, and that can improve the chargeability under high temperature and high humidity. Has been done.

Patent Document 1 proposes a technique for uniformly dispersing Pigment Yellow 74 in a binder resin by impregnating it with water when creating a master batch containing Pigment Yellow 74 and a binder resin.

In Patent Document 2, a technique for improving chargeability and color characteristics by creating a masterbatch using a polyester containing Pigment Yellow 74 and an amide bond structure having a weight average molecular weight (Mw) of 5,000 or more and 50,000 or less. Has been proposed.

However, in the toner containing Pigment Yellow 74, the color of Pigment Yellow 74 is fully utilized, and there is still room for improvement in improving environmental stability.

Japanese Unexamined Patent Publication No. 2005-157342 Japanese Unexamined Patent Publication No. 2011-203704

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 having excellent color and little change in chargeability due to environmental change.

As a result of diligent studies, the present inventors have improved the dispersibility of the pigment in the toner particles, improved the color of the toner, and improved the environmental stability of the toner by using the configuration of the present invention. It became possible. The present invention is as follows.

Amorphous polyester and C.I. I. A yellow toner having toner particles containing Pigment Yellow 74.
The C.I. I. Pigment Yellow 74 is contained in the toner particles in a crystalline state, and is contained in the toner particles.
The C.I. in the toner particles. I. Pigment Yellow 74 is used for X-ray diffraction with CuKα rays.
(I) It has a diffraction peak with a half width of 0.37 to 0.41 ° in the range of 26.00 to 27.00 ° at the diffraction angle (2θ ± 0.2 °).
(Ii) The diffraction intensity of the diffraction peak at 26.60 ° at the diffraction angle (2θ ± 0.2 °) was set to I _{26.60 °} , and the diffraction intensity of the diffraction peak at 11.70 ° was set to I _{11.70 °} . When, the ratio (I _{26.60 °} / I _{11.70 °} ) is 0.66 or more and 0.84 or less.
C.I. in the toner particles. I. A yellow toner characterized in that the content of Pigment Yellow 74 is 3 to 20 parts by mass with respect to 100 parts by mass of the amorphous polyester.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a toner having excellent color and having a small change in chargeability due to environmental changes.

The toner of the present invention is
Amorphous polyester and C.I. I. A yellow toner having toner particles containing Pigment Yellow 74 (hereinafter, also referred to as “PY74”).
The C.I. I. Pigment Yellow 74 is contained in the toner particles in a crystalline state, and is contained in the toner particles.
The C.I. in the toner particles. I. Pigment Yellow 74 is used for X-ray diffraction with CuKα rays.
(I) It has a diffraction peak with a half width of 0.37 to 0.41 ° in the range of 26.00 to 27.00 ° at the diffraction angle (2θ ± 0.2 °).
(Ii) The diffraction intensity of the diffraction peak at 26.60 ° at the diffraction angle (2θ ± 0.2 °) was set to I _{26.60 °} , and the diffraction intensity of the diffraction peak at 11.70 ° was set to I _{11.70 °} . When, the ratio (I _{26.60 °} / I _{11.70 °} ) is 0.66 or more and 0.84 or less.
C.I. in the toner particles. I. The content of Pigment Yellow 74 is 3 to 20 parts by mass with respect to 100 parts by mass of the amorphous polyester.

It is believed that the X-ray diffraction peak of PY74 in the toner particles can be controlled by controlling the crystallite diameter (representing the size of the smallest microcrystal unit) and the distortion of the crystal structure of the crystals of PY74 in the toner particles. ..

The half width of the main peak derived from the crystal of PY74 obtained in the X-ray diffraction analysis is considered to reflect the crystallite diameter, and the more the crystallite grows, the sharper the X-ray diffraction peak becomes. The half width becomes smaller.

The half width of the diffraction peak of the present invention is 0.37 to 0.41 °. More preferably, it is 0.38 to 0.40 °. If the half width of the diffraction peak is within the above range, the growth of the crystallites of PY74 is appropriate, so that both dispersibility and color development are achieved, and both environmental stability and good color are achieved. It will be possible.

Further, in the X-ray diffraction analysis, the ratio (I ₂₆ ) when the diffraction intensity of the diffraction peak at 26.60 ° is I _{26.60 °} and the diffraction intensity of the diffraction peak at 11.70 ° is I _{11.70 °. .60 °} / I _{11.70 °} ) is considered to reflect the distortion of the crystal structure, and the smaller the distortion of the crystal structure, the closer the ratio becomes to 1.00.

The ratio of the present invention (I _{26.60 °} / I _{11.70 °} ) is 0.66 or more and 0.84 or less. When the ratio is within the above range, the distortion of the crystal structure becomes appropriate, the variation and aggregation of the color can be suppressed, and both environmental stability and good color can be achieved.

As a method for controlling the crystal structure of PY74 in the toner particles, there is a method of adding a compound acting on the crystal structure of PY74 when preparing a masterbatch using PY74 and a binder resin.

In the conventional masterbatch step, since the reaggregation property of PY74 is strong, the crystal structure of the PY74 compound is easily distorted, and it is difficult to reduce the amount of pigment exposed on the surface of the toner particles when the toner particles are formed.

However, in the masterbatch step, by adding a compound having a crystallinity different from that of PY74, for example, a crystalline polyester resin, an interaction between PY74 and the crystalline polyester resin is caused, and the reaggregation property of PY74 is generated. Can be weakened.

[Bundling resin]
The toner of the present invention contains an amorphous polyester as the binder resin.

The amorphous polyester does not have a heat absorption peak in the measurement of the amount of heat absorption, and has a divalent or higher alcohol monomer component, a divalent or higher carboxylic acid, a divalent or higher carboxylic acid anhydride, and a divalent or higher valent. It is obtained by shrink-polymerizing an acid monomer component such as a carboxylic acid ester of the above.

For example, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane and polyoxypropylene (3.3) -2,2-bis (4-) as divalent or higher alcohol monomer components. Hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis (4-Hydroxyphenyl) Propylene, Polyoxypropylene (6) -2,2-Bis (4-hydroxyphenyl) Propylene and other bisphenol A alkylene oxide adducts, ethylene glycol, diethylene glycol, triethylene glycol, 1,2- Polypropylene 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, sorbit, 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-tri Examples thereof include hydroxymethylbenzene.

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

On the other hand, as the acid monomer component such as a divalent or higher carboxylic acid, a divalent or higher carboxylic acid anhydride and a divalent or higher carboxylic acid ester, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrous thereof. Substances; Alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or their anhydrides; succinic acid or an anhydride thereof substituted with an alkyl group or an alkenyl group having 6 to 18 carbon atoms; fumaric acid, maleic acid. And unsaturated dicarboxylic acids such as citraconic acid or anhydrides thereof;

Among these, the acid monomer component preferably used is a polyvalent carboxylic acid such as terephthalic acid, succinic acid, adipic acid, fumaric acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and its anhydride.

The acid value of polyester is preferably 20 mgKOH / g or less from the viewpoint of environmental stability. Further, it is more preferably 15 mgKOH / g or less. When the acid value exceeds 20 mgKOH / g, the amount of water absorption increases in a high humidity environment, and the environmental stability of the toner decreases.

The acid value can be set in the above range by adjusting the type and blending amount of the monomer used in the resin. Specifically, it can be controlled by adjusting the alcohol monomer component ratio / acid monomer component ratio and the molecular weight at the time of resin production. Further, after the ester polycondensation polymerization, it is possible to control the reaction of the terminal alcohol with a polyhydric acid monomer (for example, trimellitic acid).

In addition to the amorphous polyester, other resins can also be used as the toner. For example, homopolymers of styrene such as polystyrene, poly-p-chlorstyrene, polyvinyltoluene and its substitution products; styrene-p-chlorstyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalin copolymer. , Styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chlormethylmethacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinylmethyl ether copolymer, styrene-vinyl Stylized copolymers such as ethyl ether copolymers, styrene-vinylmethylketone copolymers, styrene-acrylonitrile-inden copolymers; polyvinyl chlorides, phenolic resins, naturally modified phenolic resins, natural resin modified maleic acid resins, Acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyurethane, polyamide, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, kumaron-inden resin, petroleum resin and the like can be used.

[Crystalline polyester]
The toner preferably contains crystalline polyester.
From the viewpoint of improving environmental stability, the content of the crystalline polyester is preferably 5 parts by mass or more and 30 parts by mass or less, and 10 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin. Is more preferable.

In the present invention, the crystalline resin is a resin in which an endothermic peak is observed in differential scanning calorimetry (DSC).

The crystalline polyester can be obtained by reacting a polyvalent carboxylic acid having a divalent value or higher with a diol. Among them, a condensed polymer of an aliphatic diol and an aliphatic dicarboxylic acid is preferable because it has a high crystallinity and easily interacts with PY74. Further, in the present invention, only one kind of crystalline polyester may be used, or a plurality of kinds may be used in combination.

The crystalline polyester contains an alcohol component containing an aliphatic diol having 2 to 22 carbon atoms and at least one compound selected from the group consisting of derivatives thereof, an aliphatic dicarboxylic acid having 2 to 22 carbon atoms, and the like. It is preferable that the resin is obtained by shrink-polymerizing a carboxylic acid component containing at least one compound selected from the group consisting of these derivatives. Among them, crystalline polyester has an alcohol component containing at least one compound selected from the group consisting of an aliphatic diol having 6 to 12 carbon atoms and a derivative thereof, and an aliphatic diol having 6 to 12 carbon atoms. A crystalline polyester obtained by shrink-polymerizing a carboxylic acid component containing at least one compound selected from the group consisting of a dicarboxylic acid and a derivative thereof is more preferable from the viewpoint of improving environmental stability.

The larger the molecular weight of the aliphatic dicarboxylic acid of the crystalline polyester, the stronger the crystallinity of the crystalline polyester, and therefore, the stronger the interaction with PY74 is exhibited. Therefore, it becomes easy to control the crystallinity of PY74.

The aliphatic diol having 2 or more and 22 or less carbon atoms (preferably 6 or more and 12 or less carbon atoms) is not particularly limited, but a chain-like (preferably linear) aliphatic diol is used to stabilize the environment of the toner. Optimal from the viewpoint of improving sex.

For example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-butadiene glycol, 1,5-pentanediol, Neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanezil, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12 -Dodecanediol can be mentioned.

Among these, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12 -Linear aliphatic α, ω-diol such as dodecanediol is preferably exemplified.

In the present invention, the derivative is not particularly limited as long as the same resin structure can be obtained by the above polycondensation. For example, a derivative obtained by esterifying the above diol can be mentioned.

In the alcohol component constituting the crystalline polyester, at least one compound selected from the group consisting of the above-mentioned aliphatic diols having 2 or more and 22 or less carbon atoms (preferably 6 or more and 12 or less carbon atoms) and derivatives thereof is all. It is preferably 50% by mass or more, more preferably 70% by mass or more, based on the alcohol component.

Polyhydric alcohols other than the above aliphatic diols can also be used.

Among the polyhydric alcohols, examples of diols other than the above aliphatic diols include aromatic alcohols such as polyoxyethylene glycol A and polyoxypropylene glycol A; 1,4-cyclohexanedimethanol and the like.

Among the polyhydric alcohols, the trihydric or higher polyhydric alcohols include aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-. Examples thereof include aliphatic alcohols such as butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, and trimethylolpropane. ..

Further, a monohydric alcohol may be used to the extent that the characteristics of the crystalline polyester are not impaired. Examples of the monohydric alcohol include n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, 2-ethylhexanol, cyclohexanol, and benzyl alcohol.

On the other hand, the aliphatic dicarboxylic acid having 2 or more and 22 or less carbon atoms (preferably 6 or more and 12 or less carbon atoms) is not particularly limited, but may be a chain (preferably linear) aliphatic dicarboxylic acid. ..

For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, glutaconic acid, azelaic acid, sebacic acid, nonandicarboxylic acid, decandicarboxylic acid, undecandicarboxylic acid, dodecandicarboxylic acid, maleic acid. , Fumaric acid, mesaconic acid, citraconic acid, itaconic acid and the like.

Hydrolyzed acid anhydrides or lower alkyl esters are also included.

In the present invention, the derivative is not particularly limited as long as a similar resin structure can be obtained by polycondensation. For example, an acid anhydride of a dicarboxylic acid component, a derivative obtained by methyl esterifying, ethyl esterifying, or acid chlorideizing a dicarboxylic acid component can be mentioned.

Among the carboxylic acid components constituting the crystalline polyester, at least one compound selected from the group consisting of aliphatic dicarboxylic acids having 2 or more and 22 or less carbon atoms (preferably 6 or more and 12 or less carbon atoms) and derivatives thereof is used. It is preferably 50% by mass or more, more preferably 70% by mass or more, based on the total carboxylic acid component.

Polyvalent carboxylic acids other than aliphatic dicarboxylic acids can also be used. Among the polyvalent carboxylic acids, the divalent carboxylic acids other than the aliphatic dicarboxylic acid include aromatic carboxylic acids such as isophthalic acid and terephthalic acid; and aliphatic carboxylic acids such as n-dodecylsuccinic acid and n-dodecenylsuccinic acid; Examples thereof include alicyclic carboxylic acids such as cyclohexanedicarboxylic acid, and these acid anhydrides or lower alkyl esters are also included.

Among other polyvalent carboxylic acids, the trivalent or higher polyvalent carboxylic acids include 1,2,4-benzenetricarboxylic acid (trimeritic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2, Aromatic carboxylic acids such as 4-naphthalentricarboxylic acid and pyromellitic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2- Examples thereof include aliphatic carboxylic acids such as methylenecarboxypropane, and derivatives such as acid anhydrides or lower alkyl esters thereof are also included.

Further, a monovalent carboxylic acid may be used to the extent that the characteristics of the crystalline polyester are not impaired. Examples of the monovalent carboxylic acid include benzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenylcarboxylic acid, acetic acid, propionic acid, butyric acid and octanoic acid.

The crystalline polyester can be produced according to a conventional polyester synthesis method. For example, a crystalline polyester can be obtained by subjecting a carboxylic acid component and an alcohol component to an esterification reaction or a transesterification reaction, and then subjecting them to a shrink polymerization reaction under reduced pressure or by introducing nitrogen gas according to a conventional method.

The esterification or transesterification reaction is carried out using a conventional esterification catalyst or transesterification catalyst such as sulfuric acid, titanium butoxide, tin 2-ethylhexanoate, dibutyltin oxide, manganese acetate, and magnesium acetate, if necessary. be able to.

Further, the polymerization reaction is carried out by using a usual polymerization catalyst, for example, known catalysts such as titanium butoxide, tin 2-ethylhexanoate, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, and germanium dioxide. Can be done using. The polymerization temperature and the amount of catalyst are not particularly limited and may be appropriately determined.

In the esterification or transesterification reaction, or the polycondensation reaction, all the monomers are charged in a batch to increase the strength of the obtained crystalline polyester resin, or the divalent monomer is first reacted to reduce the low molecular weight components. After that, a method such as adding a monomer having a valence of 3 or more and causing the reaction may be used.

[wax]
If necessary, the toner may contain wax. Hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystallin wax, paraffin wax, Fishertropush wax; oxides of hydrocarbon waxes such as polyethylene oxide wax or block copolymers thereof; Waxes whose main component is a fatty acid ester such as carnauba wax; deoxidized A part or all of a fatty acid ester such as carnauba wax is deoxidized. In addition, the following can be mentioned. Saturated linear fatty acids such as palmitic acid, stearic acid and montanoic acid; unsaturated fatty acids such as brushzic acid, eleostearic acid and valinaphosphate; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubil alcohol, ceryl alcohol, meli Saturated alcohols such as sill alcohols; polyhydric alcohols such as sorbitol; fatty acids such as palmitic acid, stearic acid, behenic acid and montanic acid, and stearyl alcohols, aralkyl alcohols, behenyl alcohols, carnaubil alcohols, ceryl alcohols and meli. Esters with alcohols such as sill alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, hexamethylene bissteer Saturated fatty acid bisamides such as acid amides; unsaturated fatty acid amides such as ethylene bisoleic acid amides, hexamethylene bisoleic acid amides, N, N'diorail adipic acid amides, N, N'diorail sebasic acid amides; m -Aromatic bisamides such as xylene bisstearic acid amide, N, N'distearyl isophthalic acid amide; aliphatic metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate (generally referred to as metal soap). ); Waxes grafted with an aliphatic hydrocarbon wax using a vinyl monomer such as styrene or acrylic acid; a partial esterified product of a fatty acid such as behenic acid monoglyceride and a polyhydric alcohol; hydrogen of vegetable fats and oils A methyl ester compound having a hydroxyl group obtained by addition.

Among these waxes, Fischer-Tropsch wax is preferable from the viewpoint of improving environmental stability.

The wax content is preferably 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin. Further, it is more preferably 3.0 parts by mass or more and 12 parts by mass or less. Further, from the viewpoint of improving the environmental stability of the toner, the peak temperature of the maximum endothermic peak existing in the temperature range of 30 ° C. or higher and 200 ° C. or lower in the endothermic curve at the time of temperature rise measured by the differential scanning calorimetry device (DSC). However, it is preferably 50 ° C. or higher and 110 ° C. or lower. Further, it is more preferably 70 ° C. or higher and 100 ° C. or lower.

[Colorant]
As the colorant, C.I. I. Pigment Yellow 74 (PY74) is used. The amount of PY74 used is 1 to 25 parts by mass, preferably 3 to 20 parts by mass with respect to 100 parts by mass of the amorphous polyester.

A known yellow colorant other than PY74 may be used in combination.

[Charge control agent]
The toner may also contain a charge control agent, if necessary. As the charge control agent contained in the toner, known ones can be used, but in particular, a metal compound of an aromatic carboxylic acid which is colorless, has a high charge speed of the toner, and can stably maintain a constant charge amount is preferable.

Negative charge control agents include salicylate metal compounds, naphthoic acid metal compounds, dicarboxylic acid metal compounds, polymer compounds having sulfonic acid or carboxylic acid in the side chain, sulfonates or sulfonic acid esterified products in the side chain. Examples thereof include a high molecular weight compound, a high molecular weight compound having a carboxylate or a carboxylic acid esterified product in a side chain, a boron compound, a urea compound, a silicon compound, and a calix array. 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.

[External agent]
An external additive may be further added to the toner in order to improve the fluidity and adjust the triboelectric charge amount.

As the external additive, inorganic fine particles such as silica, titanium oxide, aluminum oxide, and strontium titanate are preferable. The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil or a mixture thereof.

As the specific surface area of the external additive, 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 the embedding of the external additive.

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

A known mixer such as a Henschel mixer can be used for mixing the toner particles and the external additive, but the mixing is not particularly limited as long as the toner particles can be mixed.

[Two-component developer]
The toner of the present invention is preferably mixed with a magnetic carrier and used as a two-component developer.

Examples of the magnetic carrier include iron powder whose surface is oxidized, unoxidized iron powder, metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, and rare earth, and alloys thereof. A known material such as a magnetic material such as particles, oxide particles, ferrite, or a magnetic material-dispersed resin carrier (so-called resin carrier) containing the magnetic material and a binder resin that holds the magnetic material in a dispersed state is used. can.

[Production method]
In the present invention, the method for producing the toner particles is not particularly limited, but it is preferable to use the melt-kneading method from the viewpoint of controlling the crystallinity of the PY74 compound in the toner particles and improving the dispersibility.

Hereinafter, a procedure for manufacturing toner particles using the melt-kneading method will be described.

In the raw material mixing step, as materials constituting the toner particles, for example, a binder resin and wax containing amorphous polyester, and if necessary, other components such as a colorant and a charge control agent are weighed in a predetermined amount. Mix and mix. 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 Nauter mixer, a mechano hybrid (manufactured by Nippon Coke Industries, Ltd.) and the like.

Next, the mixed materials are melt-kneaded to disperse the colorant and the like in the binder resin. In the melt-kneading process, a batch-type kneader such as a pressurized kneader or a Bambary mixer or a continuous-type kneader can be used, and a single-screw or twin-screw extruder has become the mainstream because of its superiority in continuous production. There is. For example, KTK type twin-screw extruder (manufactured by Kobe Steel), TEM type twin-screw extruder (manufactured by Toshiba Machinery Co., Ltd.), PCM kneader (manufactured by Ikekai Iron Works), twin-screw extruder (manufactured by KCC). ), Co-kneader (manufactured by Bus), Kneedex (manufactured by Nippon Coke Industries Co., Ltd.), etc. Further, the kneaded product obtained by melt-kneading may be rolled with two rolls or the like and cooled with water or the like in the cooling step.

In the melt-kneading step, it is preferable to knead a part of the binder resin and the colorant to produce a masterbatch, and then knead the masterbatch and the remaining binder resin. In particular, when obtaining a masterbatch, it is preferable to add water to form a water-containing masterbatch.

Specifically, a part of the binder resin (first amorphous polyester), crystalline polyester, and PY74 are heated and mixed in the presence of water, and the water content is 5% by mass or more and 25% by mass or less. It is preferable to obtain a water-containing master batch, and then melt-knead the water-containing master batch and the remaining binder resin (second amorphous polyester) to obtain a kneaded product.

Then, the cooled product of the kneaded product is pulverized to a desired particle size in the pulverization step. In the crushing process, after coarse crushing with a crusher such as a crusher, a hammer mill, or a feather mill, further, for example, a cryptron system (manufactured by Kawasaki Heavy Industries), a super rotor (manufactured by Nisshin Engineering Co., Ltd.), a turbo mill. (Made by Turbo Industry) or an air jet type crusher to pulverize.

After that, if necessary, classification such as inertial classification type elbow jet (manufactured by Nittetsu Mining Co., Ltd.), centrifugal force classification method turboplex (manufactured by Hosokawa Micron), TSP separator (manufactured by Hosokawa Micron), faculty (manufactured by Hosokawa Micron) Classify using a machine or a sieving machine to obtain toner particles.

Then, by adding an external additive such as an inorganic fine powder or resin particles selected as necessary and mixing (externally adding), for example, fluidity is imparted, environmental stability is improved, and a toner is obtained. The mixing device is performed by a mixing device having a rotating body having a stirring member and a main body casing provided with a gap between the stirring member.

As an example of such a mixing device, Henshell mixer (manufactured by Mitsui Mining Co., Ltd.); Super mixer (manufactured by Kawata Co., Ltd.); Ribocorn (manufactured by Okawara Seisakusho Co., Ltd.); Nowter mixer, Turbulizer, Cyclomix (manufactured by Hosokawa Micron Co., Ltd.) Spiral pin mixer (manufactured by Pacific Kiko Co., Ltd.); Ladyge mixer (manufactured by Matsubo Co., Ltd.), Nobilta (manufactured by Hosokawa Micron Co., Ltd.) and the like. In particular, a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) is preferably used for uniformly mixing and loosening silica aggregates.

The mixing device conditions include the amount of processing, the number of rotations of the stirring shaft, the stirring time, the shape of the stirring blade, the temperature inside the tank, and the like. It is selected as appropriate in consideration of the type of the above, and is not particularly limited.

Further, for example, when the coarse agglomerates of the additive are freely present in the obtained toner, a sieving machine or the like may be used if necessary.

[Measurement method of each physical property]
Next, a method for measuring various physical properties of the toner and raw materials in the present invention will be described below.
[Plastic peak molecular weight (Mp), number average molecular weight (Mn), weight average molecular weight (Mw)]
The peak molecular weight (Mp), the number average molecular weight (Mn), and the weight average molecular weight (Mw) are measured by gel permeation chromatography (GPC) as follows.

First, the sample (resin) is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. Then, the obtained solution is filtered with a solvent-resistant membrane filter "Maeshori Disc" (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. This sample solution is used for measurement under the following conditions.
Equipment: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: 7 stations of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow velocity: 1.0 mL / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 mL

In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade names "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 Toso Co., Ltd.) is used.

[Plastic softening point]
The softening point of the resin is measured by using a constant load extrusion type thin tube rheometer "Flow Tester CFT-500D" (manufactured by Shimadzu Corporation) and following the manual attached to the device. In this device, while applying a constant load from the top of the measurement sample with a piston, the temperature of the measurement sample filled in the cylinder is raised and melted, and the melted measurement sample is pushed out from the die at the bottom of the cylinder. A flow curve showing the relationship between and temperature can be obtained.

In the present invention, the softening point is the "melting temperature in the 1/2 method" described in the manual attached to the "flow characteristic evaluation device flow tester CFT-500D". The melting temperature in the 1/2 method is calculated as follows. First, 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 when the outflow starts is obtained (this is defined 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.

As a measurement sample, about 1.0 g of resin was compression-molded in an environment of 25 ° C. using a tablet molding compressor (for example, NT-100H, manufactured by NPA System Co., Ltd.) at about 10 MPa for about 60 seconds. Use a columnar one with a diameter of about 8 mm.

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

[Acid value of resin]
The acid value of the binder resin is measured according to JIS K 0070-1992, but specifically, it is measured according to the following procedure.

(1) Preparation of Reagents 1.0 g of phenolphthalein is dissolved in 90 mL of ethyl alcohol (95 vol%), and ion-exchanged water is added 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 vol%) to make 1 L. Put it in an alkali-resistant container so as not to touch carbon dioxide gas, leave it for 3 days, and then filter it to obtain a potassium hydroxide solution. The resulting potassium hydroxide solution is stored in an alkali resistant container. As for the factor of the potassium hydroxide solution, take 25 mL of 0.1 mol / L hydrochloric acid in a triangular flask, add a few drops of the phenolphthalein solution, titrate with the potassium hydroxide solution, and the hydroxylation required for neutralization. Obtained from the amount of potassium solution. As the 0.1 mol / L hydrochloric acid, those prepared according to JIS K 8001-1998 are used.

(2) Operation (A) 2.0 g of this test sample is precisely weighed in a 200 mL Erlenmeyer flask, 100 mL of a mixed solution of toluene / ethanol (2: 1) is added, and the mixture is dissolved over 5 hours. Then, a few drops of the phenolphthalein solution are added as an indicator, and titration is performed 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 Titration is performed 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 result into the following formula to calculate the acid value.
A = [(CB) x f x 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount of potassium hydroxide solution in blank test (mL), C: addition amount of potassium hydroxide solution in this test (mL), f: potassium hydroxide Solution factor, S: sample (g).

[Hydroxyl group value of resin]
The hydroxyl value of the binder resin is measured according to JIS K 0070-1992, but specifically, it is measured according to the following procedure.

(1) Preparation of reagent Put 25 g of special grade acetic anhydride in a 100 mL volumetric flask, add pyridine to make the total volume 100 mL, and shake well to obtain an acetylation reagent. The obtained acetylation reagent is stored in a brown bottle so as not to come into contact with moisture, carbon dioxide, or the like.

Dissolve 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95 vol%) and add ion-exchanged 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 vol%) to make 1 L. Put it in an alkali-resistant container so as not to touch carbon dioxide gas, leave it for 3 days, and then filter it to obtain a potassium hydroxide solution. The resulting potassium hydroxide solution is stored in an alkali resistant container. As for the factor of potassium hydroxide solution, take 25 mL of 0.5 mol / L hydrochloric acid in a triangular flask, add a few drops of phenolphthaline solution, titrate with potassium hydroxide solution, and the amount of potassium hydroxide solution required for neutralization. Ask from. As 0.5 mol / L hydrochloric acid, the one prepared according to JIS K 8001-1998 is used.

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

Place a small funnel on the mouth of the flask and immerse the bottom of the flask about 1 cm in a glycerin bath at about 97 ° C. to heat it. 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 thick paper having a round hole.

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

Add a few drops of phenolphthalein solution as an indicator and titrate with 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 the same titration as the above operation except that the binder resin sample is not used.

(3) Substitute the obtained result into the following formula to calculate the hydroxyl value.
A = [{(BC) x 28.05 x f} / S] + D
Here, A: hydroxyl value (mgKOH / g), B: addition amount of potassium hydroxide solution in blank test (mL), C: addition amount of potassium hydroxide solution in this test (mL), f: potassium hydroxide Solution factor, S: sample (g), D: acid value of binder resin (mgKOH / g).

[Weight average particle size of toner particles (D4)]
The weight average particle size (D4) of the toner particles is measured with a precision particle size distribution measuring device "Colter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter) equipped with a 100 μm aperture tube by the pore electric resistance method. Measurement data is measured with 25,000 effective measurement channels using the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter) for setting conditions and analyzing measurement data. Is analyzed and calculated.

As the electrolytic aqueous solution used for the measurement, one in which special grade sodium chloride is dissolved in ion-exchanged water so that the concentration becomes about 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter) can be used.

Before performing measurement and analysis, set the dedicated software as follows.

On the "Change standard measurement method (SOM) screen" of the dedicated software, set the total count number of the control mode to 50,000 particles, measure once, and set the Kd value to "Standard particles 10.0 μm" (Beckman Coulter). Set the value obtained using (manufactured by the company). By pressing the threshold / noise level measurement button, the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, and the electrolyte to ISOTON II, and check the flash of the aperture tube after measurement.

On the "Pulse to particle size conversion setting screen" of the dedicated software, set the bin spacing to the logarithmic particle size, the particle size bin to the 256 particle size bin, and the particle size range to 2 μm or more and 60 μm or less.

The specific measurement method is as follows.

(1) Put about 200 mL of the electrolytic aqueous solution in a glass 250 mL round bottom beaker dedicated to Multisizer 3, set it on a sample stand, and stir the stirrer rod counterclockwise at 24 rpm. Then, the dirt and air bubbles in the aperture tube are removed by the "aperture flash" function of the analysis software.

(2) Place about 30 mL of the electrolytic aqueous solution in a 100 mL flat-bottomed beaker made of glass, and use "Contaminone N" as a dispersant (nonionic surfactant, anionic surfactant, and organic builder for precise measurement of pH 7). Add about 0.3 mL of a diluted solution of a 10% by mass aqueous solution of a neutral detergent for cleaning the vessel, manufactured by Wako Pure Chemical Industries, Ltd.) diluted 3 times by mass with ion-exchanged water.

(3) Two oscillators with an oscillation frequency of 50 kHz are built in with the phase shifted by 180 degrees, and are installed in the water tank of the ultrasonic disperser "Ultrasonic Dispension System Tetora 150" (manufactured by Nikkaki Bios) with an electrical output of 120 W. A predetermined amount of ion-exchanged water is added, and about 2 mL of the Contaminone N is added into the water tank.

(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic solution in the beaker is maximized.

(5) With the electrolytic aqueous solution in the beaker of (4) being irradiated with ultrasonic waves, about 10 mg of toner is added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion processing is continued for another 60 seconds. For ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10 ° C. or higher and 40 ° C. or lower.

(6) Using a pipette, drop the aqueous electrolyte solution of (5) in which toner is dispersed into the round-bottomed beaker of (1) installed in the sample stand, and adjust the measured concentration to about 5%. .. Then, the measurement is performed until the number of measured particles reaches 50,000.

(7) The measurement data is analyzed by the dedicated software attached to the device, and the weight average particle size (D4) is calculated. The "average diameter" of the analysis / volume statistical value (arithmetic mean) screen when the graph / volume% is set by the dedicated software is the weight average particle diameter (D4).

[Maximum endothermic peak of wax and crystalline polyester resin]
The peak temperature of the maximum endothermic peak of wax is measured according to ASTM D3418-82 using a differential scanning calorimetry device "Q1000" (manufactured by TA Instruments). The melting point of indium and zinc is used for temperature correction of the device detector, and the heat of fusion of indium is used for the correction of calorific value.

Specifically, about 5 mg of a sample is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference, and the temperature rise rate is 10 in the measurement temperature range of 30 to 200 ° C. Measure at ° C / min. In the measurement, the temperature is raised to 200 ° C., then lowered to 30 ° C., and then raised again. The temperature showing the maximum endothermic peak of the DSC curve in the temperature range of 30 to 200 ° C. in the second temperature raising process is defined as the peak temperature of the maximum endothermic peak of the wax.
[X-ray diffraction]
The X-ray diffraction measurement uses the measuring device "RINT-TTRII" (manufactured by Rigaku Co., Ltd.) and the control software and analysis software attached to the device. The measurement conditions are as follows.

X-ray: Cu / 50kV / 300mA
Goniometer: Rotor horizontal goniometer (TTR-2)
Attachment: Standard sample holder Divergence slit: Open Divergence vertical limiting slit: 10.00 mm
Scattering slit: Open Light receiving slit: Open Counter: Scintillation counter Scan mode: Continuous Scan speed: 4.0000 ° / min
Sampling width: 0.0200 °
Scanning axis: 2θ / θ
Scanning range: 10.000 to 40.000 °

Then, the toner is set on the sample plate and the measurement is started. Measurement was performed on the CuKα characteristic X-ray with a Bragg angle (2θ ± 0.20deg) in the range of 3deg to 35deg, and from the obtained spectrum, 2θ was the half-value width of the spectrum at 26.00 to 27.00deg and 26.60 ±. The value of the ratio of the diffraction intensity of the diffraction peak of 0.20 deg to the diffraction intensity of the diffraction peak of 11.70 ± 0.20 deg is determined by C.I. I. It was used as an index of distortion of the crystal structure of Pigment Yellow 74.

Hereinafter, the present invention will be specifically described based on Examples. However, the present invention is not limited thereto.

[Production Example 1 of Amorphous Polyester]
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 76.9 parts by mass (0.167 mol parts), terephthalic acid 24.1 parts by mass (0.145 mol parts), adipine Place 8.0 parts by mass (0.054 mol parts) of acid and 0.5 parts by mass of titanium tetrabutoxide in a 4-liter glass four-necked flask, and attach a thermometer, stirring rod, condenser and nitrogen introduction tube to the mantle heater. I was inside. Next, the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 4 hours while stirring at a temperature of 200 ° C.

(First reaction step)
Then, 1.2 parts by mass (0.006 mol part) of anhydrous trimellitic acid was added and reacted at 180 ° C. for 1 hour (second reaction step) to obtain a binder resin 1.

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

[Production Example 2 of Amorphous Polyester]
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 71.3 parts by mass (0.155 parts by mass), terephthalic acid 24.1 parts by mass (0.145 parts by mass), and 0.6 parts by mass of titanium tetrabutoxide was placed in a 4-liter glass 4-necked flask, and a thermometer, a stirring rod, a condenser and a nitrogen introduction tube were attached and placed in a mantle heater. Next, the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 2 hours while stirring at a temperature of 200 ° C. (First reaction step)
Then, 5.8 parts by mass (0.030 mol part) 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 the binder resin 2 is 15 mgKOH / g, and the hydroxyl value is 7 mgKOH / g. The molecular weight by GPC was 200,000 by weight average molecular weight (Mw), 5,000 by number average molecular weight (Mn), and 10,000 by peak molecular weight (Mp), and the softening point was 130 ° C.

[Production Example 1 of Crystalline Polyester]
33.9 parts of 1,6-hexanediol (0.29 mol parts; 100.0 mol% of the total number of moles of polyhydric alcohol)
66.1 parts of dodecanedioic acid (0.29 mol parts; 100.0 mol% with respect to the total number of moles of polyvalent carboxylic acid)
The above materials were weighed and placed in a condenser, a stirrer, a nitrogen introduction tube and a flask with a thermocouple.

Next, after replacing the inside of the flask with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 3 hours while stirring at a temperature of 140 ° C. Then, 0.5 part of tin 2-ethylhexanoate was added, the pressure in the flask was lowered to 8.3 kPa, and the reaction was carried out for 4 hours while maintaining the temperature at 200 ° C. Then, the inside of the flask was reduced to 5 kPa or less and reacted at 200 ° C. for 3 hours to obtain crystalline polyester 1. In the crystalline polyester 1, an endothermic peak derived from the crystal structure was observed.

[Production Examples 2 to 5 of Crystalline Polyester]
Crystalline polyesters 2 to 5 were obtained in the same manner as in Production Example 1 of the crystalline polyester except that the aliphatic diol and the aliphatic dicarboxylic acid were changed as shown in Table 1. In the crystalline polyesters 2 to 5, an endothermic peak derived from the crystal structure was observed.

[Manufacturing example of masterbatch 1]
-Atypical polyester 1 (corresponding to the first amorphous polyester) 35.0 parts by mass-Crystalular polyester 1 35.0 parts by mass-Solid obtained by removing water from a pigment slurry containing Pigment Yellow 74 30% by mass of paste-like pigment (the remaining 70% by mass is water) (average diameter of primary particles 139 nm, obtained after synthesis without any drying step) 100.0 parts by mass

(First kneading process)
The above raw materials were first charged into a kneader type mixer, and the temperature was raised under non-pressurization while mixing. It was heated to the maximum temperature (which is inevitably determined by the boiling point of the solvent in the paste. In this case, about 80 to 100 ° C.), and was heated, melted and kneaded at 90 to 100 ° C. for 15 minutes. In this step, the pigment in the aqueous phase (pigment slurry) is distributed or transferred to the molten resin phase. Then, the mixer was stopped once, hot water was discharged, and the mixture was mixed for 10 minutes without heating to distill off the water, and then cooled. Further, it was pulverized to about 1 mm by pin mill pulverization to obtain a master batch 1. The water content of the masterbatch 1 was 15.0% by mass, the pigment content was 30.0% by mass, and the resin content was 55.0% by mass.

[Manufacturing examples 2 to 6 of masterbatch]
Masterbatches 2 to 6 were obtained in the same manner except that the types of raw materials and the ratio of each component in the masterbatch were changed to the values shown in Table 2 in Production Example 1 of the masterbatch.

[Manufacturing example of masterbatch 7]
・ Amorphous polyester 1 (corresponding to the first amorphous polyester) 54.0 parts by mass ・ Crystalline polyester 3 16.0 parts by mass ・ Powder pigment yellow 74 30.0 parts by mass is charged into a kneader type mixer. The temperature was raised under non-pressurization while mixing, and the mixture was heated, melted and kneaded at 90 to 110 ° C. for 30 minutes to sufficiently disperse the pigment in the resin. After cooling, it was pulverized to about 1 mm by pin mill pulverization to obtain a yellow masterbatch 7.

[Manufacturing examples 8 to 10 of masterbatch]
Masterbatches 8 to 10 were obtained in the same manner except that the types of raw materials and the ratio of each component in the masterbatch were changed to the values shown in Table 3 in Production Example 7 of the masterbatch.

[Manufacturing example of masterbatch 11]
In Production Example 1 of the masterbatch, the masterbatch 11 was obtained in the same manner except that the resin of the raw material was only 70 parts by mass of the amorphous polyester 1.

[Manufacturing example of masterbatch 12]
In Production Example 7 of the masterbatch, the masterbatch 12 was obtained in the same manner except that the resin of the raw material was only 70 parts by mass of the amorphous polyester 1.

[Toner manufacturing example 1]
・ Aspherical polyester 1 61.7 parts by mass ・ Aspherical polyester 2 30.0 parts by mass ・ Fisher tropschwax (peak temperature of maximum heat absorption peak 90 ° C) 5.0 parts by mass ・ Master batch 1 30.0 parts by mass The above raw materials were mixed using a Henshell mixer (FM-75 type, manufactured by Mitsui Mine Co., Ltd.) at a rotation speed of 20s ^-1 and a rotation time of 5 min. Then, the mixture was kneaded with a twin-screw kneader (PCM-70 type, manufactured by Ikegai Corp.) set at a temperature of 120 ° C. The two types of amorphous polyester mixed with the masterbatch correspond to the "second amorphous polyester". The obtained kneaded product was cooled and coarsely pulverized with a hammer mill to 1 mm or less to obtain a coarsely crushed product. The obtained coarse crushed product was finely pulverized with a mechanical crusher (T-250, manufactured by Turbo Industries, Ltd.). Further, classification was performed using a rotary classifier (200TSP, manufactured by Hosokawa Micron Co., Ltd.) to obtain toner particles. The operating conditions of the rotary classifier (200TSP, manufactured by Hosokawa Micron Co., Ltd.) were that the classifier rotor speed was classified at 50.0 s ^-1 . The obtained toner particles had a weight average particle diameter (D4) of 6.5 μm.

To 100 parts by mass of the obtained toner particles, 0.8 parts by mass of hydrophobic silica fine particles (surface treated with 20% by mass of hexamethyldisilazane) having an average particle size of 10 nm of primary particles were added, and a Henshell mixer ( The toner 1 was obtained by mixing with FM-75 type, manufactured by Mitsui Mine Co., Ltd. at a rotation speed of 30s ^-1 for 10 minutes.

When the peak of X-ray diffraction was measured using toner 1, C.I. I. Pigment Yellow 74 had a peak in the range of 26.00 to 27.00 °, and the half width of the peak was 0.39. The ratio (I _{26.60 °} / I _{11.70 °} ) was 0.75.

[Toner manufacturing examples 2 to 12, 14 to 18]
In Toner Production Example 1, toners 2 to 12 and 14 to 18 were obtained in the same manner except that the types and addition amounts of the raw materials were changed as shown in Table 4.

The half-value widths of the peaks shown in Table 4 are all half-value widths of the peaks appearing in the range of 26.00 to 27.00 °.

[Toner Production Example 13]
(Preparation of Amorphous Polyester Dispersion Liquid 1)
Amorphous polyester 1 and ion-exchanged water were mixed at a ratio of 2: 8 (based on mass). Then, the pH of the mixed solution was adjusted to 8.5 using ammonia, and the Cavitron was operated under heating conditions of 150 ° C. to obtain a dispersion liquid of amorphous polyester 1 (solid content: 20%).

(Preparation of Amorphous Polyester Dispersion Liquid 2)
A dispersion liquid (solid content: 20%) of the amorphous polyester 2 was obtained in the same manner as in the preparation of the amorphous polyester dispersion liquid 1 except that the amorphous polyester 2 was used.

(Preparation of colorant dispersion)
-Masterbatch 1 1000 parts-Anionic surfactant 150 parts-Ion-exchanged water 9000 parts After mixing the above raw materials, they were dispersed using a high-pressure impact disperser.

The volume-based 50% diameter (D50) of the colorant particles in the obtained colorant dispersion was 0.16 μm, and the colorant concentration was 6.9%.

(Preparation of wax dispersion)
-Fischer-Tropsch wax 45 parts (peak temperature of maximum endothermic peak 90 ° C)
-5 parts of anionic surfactant-150 parts of ion-exchanged water After mixing the above raw materials, the mixture was heated to 95 ° C. and dispersed using a homogenizer. Then, the dispersion treatment was carried out with a pressure discharge type golin homogenizer to prepare a wax dispersion liquid (wax concentration: 20%) in which wax particles having a volume-based 50% diameter (D50) of 0.21 μm were dispersed.

(Preparation of toner)
・ Aspherical polyester dispersion 1 309.0 parts ・ Aspherical polyester dispersion 2 150.0 parts ・ Colorant dispersion 130.0 parts ・ Wax dispersion 25.0 parts ・ 1.5 mass% magnesium sulfate aqueous solution 50.0 parts The above material was dispersed using a homogenizer (manufactured by IKA: Ultratalax T50). Subsequently, the pH was adjusted to 8.1 with a 0.1 mol / L sodium hydroxide aqueous solution.

Then, it was heated to 45 ° C. in a heating water bath while stirring with a stirring blade. After holding at 45 ° C. for 1 hour and observing with an optical microscope, it was confirmed that aggregated particles having a number average particle size of about 5.5 μm were formed.

After adding 40.0 parts of a 5 mass% trisodium citrate aqueous solution, the temperature was raised to 85 ° C. while stirring and held for 120 minutes to fuse the resin particles.

Then, while continuing stirring, water was put into the water bath and cooled to 25 ° C. Further, when the particle size of the resin particles was measured by a particle size distribution analyzer (Coulter Multisizer III: manufactured by Coulter) by the Coulter method, the volume-based median diameter was 5.5 μm.

Then, after filtration and solid-liquid separation, 800.0 parts of ion-exchanged water whose pH was adjusted to 8.0 with the above sodium hydroxide was added to the solid content, and the mixture was stirred and washed for 30 minutes.

After that, filtration and solid-liquid separation were performed again. Subsequently, 800.0 parts of ion-exchanged water was added to the solid content, and the mixture was stirred and washed for 30 minutes. Then, filtration and solid-liquid separation were performed again, and this was repeated 5 times.

Next, the obtained solid content was dried to obtain toner particles.

To 100.0 parts of the obtained toner particles, 0.8 part of hydrophobic silica fine particles (surface treated with 20% by mass of hexamethyldisilazane) having an average particle size of 10 nm of primary particles was added, and a Henshell mixer (Henshell mixer () Using FM-75 type, manufactured by Mitsui Mine Co., Ltd., mixing was performed at a rotation speed of 30s ^-1 for 10 minutes to obtain toner 13.

In the DSC measurement of the obtained toner 13, an endothermic peak derived from the crystalline resin was observed.

[Manufacturing of carriers]
(Production example of magnetic core particle 1)
-Step 1 (Weighing / mixing step):
Fe ₂ O ₃ 62.7 parts by mass MnCO ₃ 29.5 parts by mass Mg (OH) ₂ 6.8 parts by mass SrCO ₃ 1.0 part by mass Weighing the above materials, stainless beads with a diameter of 1/8 inch were used. It was crushed and mixed with a dry vibration mill for 5 hours.

-Step 2 (temporary firing step):
The obtained pulverized product was made into pellets of about 1 mm square by a roller compactor. Coarse powder was removed from the pellets with a vibrating sieve having an opening of 3 mm, and then fine powder was removed with a vibrating sieve having an opening of 0.5 mm. Then, using a burner type firing furnace, the calcined ferrite was prepared by firing in a nitrogen atmosphere (oxygen concentration 0.01% by volume) at a temperature of 1000 ° C. for 4 hours. The composition of the obtained calcined ferrite is as follows.

(MnO) _a (MgO) _b (SrO) _c (Fe ₂ O ₃ ) _d
In the above formula, a = 0.257, b = 0.117, c = 0.007, d = 0.393.
-Step 3 (crushing step):
After crushing the calcined ferrite to about 0.3 mm with a crusher, 30 parts by mass of water was added to 100 parts by mass of the calcined ferrite using zirconia beads having a diameter of 1/8 inch, and the mixture was pulverized with a wet ball mill for 1 hour. The slurry was pulverized with a wet ball mill using alumina beads having a diameter of 1/16 inch for 4 hours to obtain a ferrite slurry (a finely pulverized product of calcined ferrite).

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

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

・ Process 6 (sorting process):
After crushing the agglomerated particles, low magnetic force products are cut by magnetic force beneficiation, sieved with a sieve having a mesh size of 250 μm to remove coarse particles, and a magnetic core having a volume-based 50% diameter (D50) of 37.0 μm. Obtained particles.

(Preparation of coating resin)
・ Cyclohexylmethacrylate 26.8% by mass
・ Methyl methacrylate 0.2% by mass
-Methyl methacrylate macromonomer 8.4% by mass
(Macrmonomer having a methacryloyl group at one end and having a weight average molecular weight of 5000)
・ 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-port separable flask equipped with a reflux condenser, a thermometer, a nitrogen introduction tube, and a stirrer. Nitrogen gas was introduced into the separable flask to give 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 and precipitate a copolymer, and the precipitate was filtered off and then vacuum dried to obtain a coated resin. The obtained coating resin was dissolved in 30 parts by mass, 40 parts by mass of toluene, and 30 parts by mass of methyl ethyl ketone to obtain a polymer solution (solid content: 30% by mass).

(Preparation of coated resin solution)
-The above polymer solution (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)
The above material was put into a paint shaker together with zirconia beads having a diameter of 0.5 mm and dispersed for 1 hour. The obtained dispersion was filtered through a 5.0 μm membrane filter to obtain a coated resin solution.

(Resin coating process)
The coating resin solution was added to a vacuum degassing type kneader maintained at room temperature so as to be 2.5 parts by mass as a resin component with respect to 100 parts by mass of the magnetic core particles. After the addition, the mixture was stirred at a rotation speed of 30 rpm for 15 minutes, the solvent was volatilized above a certain level (80% by mass), the temperature was raised to 80 ° C. while mixing under reduced pressure, toluene was distilled off over 2 hours, and then the mixture was cooled. The obtained magnetic particles were separated into low magnetic force products by magnetic dressing. Further, after passing through a sieve having an opening of 70 μm, classification was performed with a wind power classifier to obtain a magnetic carrier having a 50% diameter (D50) of 38.2 μm based on the volume.

[Examples 1 to 13, Comparative Examples 1 to 5]
Using toner 1 and a magnetic carrier, mix with a V-type mixer (V-10 type: Tokuju Seisakusho Co., Ltd.) at 0.5 s ^-1 and a rotation time of 5 min so that the toner concentration becomes 9% by mass, and two components are used. The developer 1 was obtained. Further, the toner was changed as shown in Table 5 to obtain two-component developing agents 2 to 21.

Then, using the obtained two-component developing agents 1 to 21, the evaluation shown below was performed. The evaluation results are shown in Table 6.

<Evaluation method of toner coloring power>
As an image forming apparatus, a modified machine of Canon's full-color copying machine imageRUNNER ADVANCE C5255 was used, and a two-component developer was put into a developer of a magenta station for evaluation.

The evaluation environment is normal temperature and humidity (temperature 23 ° C, relative humidity 50%), and the evaluation paper is plain paper for copying CS-680 (A4 paper, basis weight: 68 g / m ² , Canon Marketing Japan Co., Ltd.) Sold from) was used.

First, the image was output with the development bias constant, and the image density of the output image was examined.

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

From the results of the X-Rite color reflection densitometer, the tinting strength of the toner was evaluated according to the following criteria. The evaluation results are shown in Table 6.

(Evaluation criteria)
A: 1.30 or higher (very good)
B: 1.25 or more and less than 1.30 (good)
C: 1.20 or more and less than 1.25 (a level that does not cause any problem in the present invention)
D: Less than 1.20 (not acceptable in the present invention)

<Evaluation method of toner brightness / saturation>
As an image forming apparatus, a modified machine of Canon's full-color copying machine imageRUNNER ADVANCE C5255 was used, and a two-component developer was put into a developer of a magenta station for evaluation.

The evaluation environment is a normal temperature and humidity environment (23 ° C, 50% RH), and the evaluation paper is plain paper for copying CS-680 (A4 paper, basis weight: 68 g / m ² , sold by Canon Marketing Japan Co., Ltd.). ) Was used.

First, the relationship between the image density and the amount of toner on the paper was investigated by changing the amount of toner on the paper. Next, the toner loading amount was adjusted so that the image density of the FFH image (solid portion) was 1.40, and the solid image was output. L ^* , a ^* , and b ^* of solid images were measured using SpectroScan Transition (manufactured by Gretag Macbeth) (measurement conditions: _D50 viewing angle 2 °).
The larger the L ^* , the higher the brightness, and the evaluation was performed according to the following criteria. The evaluation results are shown in Table 6.

(Evaluation criteria)
A: L ^* is 86 or more (very excellent)
B: L ^* is 84 or more and less than 86 (good)
C: L ^* is 82 or more and less than 84 (a level that does not cause any problem in the present invention)
D: L ^* is less than 82 (not acceptable in the present invention)
In addition, C ^* was calculated from the following formula.
C ^* = {(a ^* ) ² + (b ^* ) ² } ^0.5
The larger the C ^* , the higher the saturation, and the evaluation was performed according to the following criteria. The evaluation results are shown in Table 6.

(Evaluation criteria)
A: C ^* is 90 or more (very excellent)
B: C ^* is 85 or more and less than 90 (good)
C: C ^* is 80 or more and less than 85 (a level that does not cause any problem in the present invention)
D: C ^* is less than 80 (not acceptable in the present invention)

<Environmental stability>
In a high temperature and high humidity environment (30 ° C./80%), after continuously outputting 50,000 sheets under the condition of an image printing ratio of 40%, a solid image (solid white image) of 00 hours was printed on the entire surface of A3 paper. Using the obtained solid image, the judgment was made according to the following criteria. The reflectance of the non-printing paper and the non-printing paper was measured at 6 points each by a reflect meter (“REFLECTOMETER MODEL TC-6DS” manufactured by Tokyo Denshoku Co., Ltd.). The fog ratio (%) was calculated from the following formula using the average reflectance Dr (%) of 6 points of the non-printed paper and the average reflectance Ds (%) of 6 points of the printed paper.
Fog rate (%) = Dr (%) -Ds (%)
(Evaluation criteria)
A: Fog rate is less than 0.5% (very excellent)
B: Fog rate is 0.5% or more and less than 1.0% (good)
C: Fog rate is 1.0% or more and less than 3.0% (level that does not cause any problem in the present invention)
D: Fog rate is 3.0% or more (a level that is unacceptable for the present invention)

Claims (4)

Amorphous polyester and C.I. I. A yellow toner having toner particles containing Pigment Yellow 74.
The C.I. I. Pigment Yellow 74 is contained in the toner particles in a crystalline state, and is contained in the toner particles.
The C.I. in the toner particles. I. Pigment Yellow 74 is used for X-ray diffraction with CuKα rays.
(I) It has a diffraction peak with a half width of 0.37 to 0.41 ° in the range of 26.00 to 27.00 ° at the diffraction angle (2θ ± 0.2 °).
(Ii) The diffraction intensity of the diffraction peak at 26.60 ° at the diffraction angle (2θ ± 0.2 °) was set to I _{26.60 °} , and the diffraction intensity of the diffraction peak at 11.70 ° was set to I _{11.70 °} . When, the ratio (I _{26.60 °} / I _{11.70 °} ) is 0.66 or more and 0.84 or less.
C.I. in the toner particles. I. A yellow toner characterized in that the content of Pigment Yellow 74 is 3 to 20 parts by mass with respect to 100 parts by mass of the amorphous polyester. The yellow toner according to claim 1, wherein the toner particles further contain crystalline polyester. The yellow toner according to claim 2, wherein the crystalline polyester is a condensed polymer of an aliphatic diol having 6 or more and 12 or less carbon atoms and an aliphatic dicarboxylic acid having 6 or more and 12 or less carbon atoms. The method for producing yellow toner according to any one of claims 1 to 3.
The first amorphous polyester, crystalline polyester, and C.I. I. A step of heating and mixing Pigment Yellow 74 in the presence of water to obtain a water-containing masterbatch having a water content of 5% by mass or more and 25% by mass or less.
A step of melt-kneading the hydrous masterbatch and a second amorphous polyester to obtain a kneaded product, and a step of crushing the kneaded product to obtain toner particles.
A method for producing yellow toner, which comprises.