JP5984478B2 - Yellow toner - Google Patents

Description

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

  With the rapid spread of color copiers, the use of color copiers has expanded to a wide variety, and the demand for image quality has increased more than ever. For this reason, there is a demand for extending the color reproduction range of the output image as compared with the conventional case.

  Among cyan, magenta, and yellow generally used in color copying machines, particularly yellow has a smaller coloring power than other colors, and it is necessary to increase the amount of colorant added in order to widen the color reproduction range. However, when a large amount of a colorant is added, although the coloring power is increased, there is a problem that the color reproduction range becomes narrow due to aggregation of the pigment in the yellow toner and the color becomes cloudy. Therefore, it is necessary to improve the dispersion of the colorant in the yellow toner and improve the coloring power and saturation of the yellow toner.

  As a colorant for yellow toner having excellent coloring power and having light resistance and heat resistance equivalent to those of cyan pigments and magenta pigments used in toners, there are isoindoline yellow pigments. For example, Patent Document 1 uses Pigment Yellow 185, which is an isoindoline-based pigment, and is reported as a toner having excellent light resistance. However, the dispersion of Pigment Yellow 185 is not described and there is room for improvement. . Also, Patent Document 2 uses Pigment Yellow 185, which is an isoindoline pigment, and describes durability and color reproducibility, but there is only an example of color reproducibility with a small number of pigments added. However, there is still room for improvement in dispersibility of Pigment Yellow 185. Furthermore, since the number of durable sheets is as small as 10,000, there is still room for improvement in terms of durability. In addition, Patent Document 3 also has a known example of color reproducibility using Pigment Yellow 185. Patent Document 3 discusses light resistance in red, which is a secondary color of magenta toner and yellow toner, and discusses color variation to red due to light resistance. From the degree of variation to red during light irradiation in Patent Document 3, it can be seen that the dispersion of Pigment Yellow 185 is still insufficient. Therefore, the dispersibility of Pigment Yellow 185, which is an isoindoline pigment, still has room for improvement.

JP-A-6-118715 JP 2000-98661 A JP 2009-186664 A

  An object of the present invention is to provide a yellow toner that solves the above problems. Specifically, it is to provide a yellow toner having excellent coloring power and color stability and a wide color reproduction range. It is another object of the present invention to provide a yellow toner with less color variation by suppressing a change in frictional charge during durability.

  As a result of intensive studies, the present inventors have been able to provide a toner having excellent color strength and color stability and a wide color reproduction range by using the toner of the present invention. Furthermore, it is possible to provide a toner with less color variation by suppressing the change in frictional charge during durability.

That is, the present invention relates to a yellow toner having toner particles containing at least a binder resin, a yellow colorant and a hydrocarbon wax, and inorganic fine particles.
The binder resin contains at least a polyester resin,
The yellow colorant includes an isoindoline pigment (colorant A) and C.I. I. Solvent Yellow 162 at least, and the content of the colorant A with respect to 100 parts by mass of the binder resin is X parts by mass, and the C.I. I. When the content of Solvent Yellow 162 is Y parts by mass, X + Y is 3 parts by mass or more and 20 parts by mass or less, and Y / (X + Y) is 0.05 or more and 0.50 or less,
The toner particle relates to a yellow toner characterized by further containing a polymer having a structure in which a vinyl resin component having a nitrile group and a hydrocarbon compound are reacted.

  According to the present invention, it is possible to provide a yellow toner having excellent coloring power and color stability and a wide color reproduction range. Further, by suppressing the change in frictional charge during durability, it is possible to provide a yellow toner with little color variation.

  Hereinafter, the best mode for carrying out the present invention will be described in detail.

  The yellow toner of the present invention comprises an isoindoline pigment (colorant A) that does not contain an azo bond in the structure as a yellow colorant, and C.I. I. Solvent Yellow 162 (S.Y. 162) is contained, and the content of the coloring agent A is 100 parts by mass with respect to 100 parts by mass of the binder resin. Y. When the content of 162 is Y parts by mass, X + Y is 3 parts by mass or more and 20 parts by mass or less.

  When X + Y is less than 3 parts by mass, an output image having excellent saturation and lightness can be obtained. However, in order to obtain a desired density (for example, a reflection density of 1.45), the toner on paper is loaded. Since a large amount is required, it is not practical. When X + Y exceeds 20 parts by mass, the amount of toner on the paper required to produce a desired density (for example, reflection density 1.45) of the output image is reduced, but the pigment / dye is reduced. As a result of aggregation, the color becomes cloudy, so it is difficult to widen the range of color reproducibility.

  Further, in the toner of the present invention, the content of the colorant A is X parts by mass, the S.I. Y. When the content of 162 is Y parts by mass, Y / (X + Y) is 0.05 or more and 0.50 or less.

  In general, colorants used in color toners are roughly classified into dyes and pigments. Although pigments have high light resistance, they have problems in coloring power, transparency, and color gamut. On the other hand, dyes have high coloring power and transparency and a wide color gamut, but have a problem in light resistance.

  Among the pigments, isoindoline-based pigments have a strong coloring power of the pigment itself, but also a strong cohesion between the pigments. Therefore, it is difficult to disperse the pigment in a solid medium such as toner, and it is difficult to obtain high coloring power as the toner. However, as a result of investigations, it has become clear that the present inventors can improve the dispersion of an isoindoline pigment in the toner by adding another pigment or dye to the isoindoline pigment. Further, as pigments and dyes used in combination with isoindoline pigments, S.I. Y. 162 was able to improve the coloring power most and expand the color reproduction range.

  The reason is not clear, but the present inventors presume as follows.

  Unlike pigments, dyes are excellent in dispersibility because they are easily present as single molecules. Among the dyes, S.I. Y. As shown in the following formulas (1) and (2), 162 has a structure including a structural part containing many polar groups such as a cyano group and a hydroxyl group, and a structural part consisting of hydrocarbons.

  The isoindoline-based pigment has a structure (isoindoline skeleton) with relatively strong molecular rigidity as shown in the following formula (3). Examples of the pigment represented by the following formula (3) include C.I. I. Pigment Yellow 139, 185 and the like. Isoindoline pigments are difficult to disperse due to the strong rigidity of isoindoline, which is the basic skeleton, and strong interaction between isoindolines. However, isoindoline pigments and S.I. Y. 162 is used in combination with an isoindoline site that is a basic skeleton of an isoindoline-based pigment; Y. It is thought that the site | part containing many 162 polar groups interacts, the aggregation of isoindoline is suppressed, and the dispersion | distribution of an isoindoline pigment is improved. In addition, S. Y. 162 was the most effective because the isoindoline skeleton and S. cerevisiae. Y. The molecular size of the 162 polar site is relatively close, and the SP values, which are solubility parameters, are close to each other. Y. It is believed that 162 interactions are synergistic.

  S. Y. Since 162 has a wide color gamut and has high light resistance among dyes, it has been widely studied as a colorant for toner. However, compared to pigments, the light resistance is low and the color stability is poor.

  Therefore, in the present invention, S.I. Y. By setting the ratio 162 (Y / (X + Y)) to 0.05 or more and 0.50 or less, light resistance is ensured and color stability is maintained. Accordingly, in the toner of the present invention, it is possible to achieve a high coloring power and a wide color gamut by improving the dispersion of the isoindoline pigment while maintaining high light resistance.

  When Y / (X + Y) is less than 0.05, the light resistance is excellent. Y. The synergistic effect with 162 is not exhibited, and it is difficult to expand the high coloring power and the color reproducibility range. On the other hand, when Y / (X + Y) exceeds 0.50, the high coloring power and the color reproducibility range can be expanded, but the light resistance is deteriorated and it is difficult to satisfy the color stability.

  Furthermore, the toner particles of the present invention further include a polymer having a structure in which a vinyl resin component having a nitrile group and a hydrocarbon compound are reacted.

  The polymer having a structure in which a vinyl resin component and a hydrocarbon compound are reacted includes a graft polymer having a structure in which a polyolefin is grafted on a vinyl resin component or a vinyl resin component in which a vinyl monomer is graft-polymerized on a polyolefin. Graft polymers are particularly preferred.

  The following are mentioned as a vinyl-type monomer used for the said vinyl-type resin component.

  Styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethyl Styrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene Styrene monomers such as styrene and derivatives thereof.

  Amino group-containing α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; vinyl monomers containing N atoms such as acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide .

  Unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; unsaturated such as maleic acid anhydride, citraconic acid anhydride, itaconic acid anhydride, alkenyl succinic acid anhydride Dibasic acid anhydride: maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, alkenyl succinic acid Half-esters of unsaturated dibasic acids such as acid methyl half ester, fumaric acid methyl half ester and mesaconic acid methyl half ester; Unsaturated dibasic acid esters such as dimethylmaleic acid and dimethylfumaric acid; Acrylic acid, Methacrylic acid Α, β-unsaturated acids such as crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic acid anhydride, and anhydrous α and β-unsaturated acids and lower fatty acids. A vinyl monomer containing a carboxyl group such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides thereof, and monoesters thereof.

  Acrylic acid or methacrylic acid ester such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1-methyl) (Hexyl) Vinyl monomers containing hydroxyl groups such as styrene.

  Methyl acrylate, ethyl acrylate, acrylate-n-butyl, acrylate isobutyl, propyl acrylate, acrylate-n-octyl, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, acrylate-2- An ester unit comprising an acrylic ester such as chloroethyl and acrylic ester such as phenyl acrylate.

  Methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylate-n-butyl, methacrylate isobutyl, methacrylate-n-octyl, methacrylate-decyl, methacrylate-2-ethylhexyl, stearyl methacrylate, phenyl methacrylate, methacryl Ester units composed of methacrylic acid esters such as α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl acid and diethylaminoethyl methacrylate.

  The polyolefin is not particularly limited as long as it is a polymer or copolymer of an unsaturated hydrocarbon monomer having one double bond, and various polyolefins can be used. In particular, polyethylene and polypropylene are preferably used.

  The polymer having a structure in which a vinyl resin component and a hydrocarbon compound used in the present invention are reacted is the reaction between these vinyl monomers described above, the reaction between one polymer monomer and the other polymer, etc. Can be obtained by a known method.

  The present invention can provide a yellow toner having excellent coloring power by using together a polymer having a structure in which an isoindoline pigment, the vinyl resin component described above, and a hydrocarbon compound are reacted. is there.

  Although the mechanism is not clear, the present inventors presume as follows.

  Constituent materials of the toner are a binder resin, a release agent, and a colorant. The vinyl resin component of the polymer having a structure in which a vinyl resin component and a hydrocarbon compound are reacted has a structure that can be easily adapted to the binder resin, and the hydrocarbon portion has a structure that is easily adapted to the release agent. Furthermore, the vinyl-based resin component has a cyano group as a polar group and has a side chain that is relatively easily compatible with the pigment. When a polymer having a structure in which a vinyl resin component and a hydrocarbon compound are reacted is used, the release agent of the toner constituent material interacts with the hydrocarbon portion of the polymer, and the binder resin is contained in the binder resin. Highly dispersed. At that time, the side chain of the vinyl resin component having a strong resin affinity is adsorbed on the pigment surface, and the pigment is considered to be highly dispersed in the binder resin together with the release agent.

  The structural unit of the vinyl resin component of the polymer having a structure in which the vinyl resin component and the hydrocarbon compound used in the present invention are reacted includes a styrene unit, an ester unit, and further acrylonitrile or methacrylonitrile. Contains nitrile groups. Since the nitrile group is a functional group having a relatively high polarity, the nitrile group is familiar with the hetero five-membered ring having a highly polar isoindoline skeleton, and as a result, the pigment dispersion is considered to be improved. Further, in the case of pigments containing nitrile groups inside the pigment, such as Pigment Yellow 185, it is considered that further interaction between nitrile groups occurs, and pigment dispersion is further improved.

  The mass ratio of the hydrocarbon compound and the vinyl resin component in the polymer is preferably 1/99 to 75/25. If the mass ratio of the hydrocarbon compound and the vinyl resin component exceeds 75/25, the ratio of the vinyl resin component in the polymer having the binder resin and the release agent decreases, so Compatibility with coalesced decreases. For this reason, the function of dispersing the binder resin and the release agent is deteriorated, the dispersion of the release agent is deteriorated, and accordingly, the dispersion of the pigment becomes insufficient.

  On the other hand, if the mass ratio of the hydrocarbon compound to the vinyl resin component is less than 1/99, the hydrocarbon compound part in the polymer having the space between the binder resin and the release agent is reduced, and the resin is separated in the binder resin. There is a possibility that the function of dispersing the mold agent is lowered and the dispersion of the pigment becomes insufficient.

  The content of the polymer having a structure in which the vinyl resin component and the hydrocarbon compound are reacted is preferably 0.2 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the binder resin.

  The binder resin used in the present invention is characterized by containing at least a polyester resin. The polyester resin may be used by mixing a plurality of types of polyester resins having different molecular weight distributions.

  As a monomer structural unit of the polyester-based resin used in the present invention, a divalent or trivalent or higher alcohol and a carboxylic acid, or a divalent or trivalent or higher carboxylic acid component such as a carboxylic acid anhydride or a carboxylic acid ester is used. It is done.

  A dihydric alcohol is illustrated below. For example, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene ( 2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, poly Alkylene oxide adducts of bisphenol A such as oxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol 1,4-butanediol, neopentyl glycol, 1,4-butene All, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, propylene adduct of bisphenol A, bisphenol An ethylene adduct of A, hydrogenated bisphenol A, etc. are mentioned.

  Examples of the trivalent or higher alcohols include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1 , 2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. It is done. Among these alcohols, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane are Preferably used. These dihydric alcohol monomers and trihydric or higher polyhydric alcohol monomers can be used alone or in combination.

  The acid component is a carboxylic acid component and a divalent monomer such as maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, Sebacic acid, azelaic acid, malonic acid, n-dodecenyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, n-octyl succinic acid, isooctenyl succinic acid, isooctyl succinic acid Examples include acids, anhydrides of these acids, and lower alkyl esters. Of these divalent carboxylic acid components, maleic acid, fumaric acid, terephthalic acid, isododecenyl succinic acid, and anhydrides or lower alkyl esters of these acids are preferably used.

  Examples of the trivalent or higher carboxylic acid component include 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and 1,2,4-butanetricarboxylic acid. 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7 , 8-octanetetracarboxylic acid, pyromellitic acid, emporic trimer acid, their acid anhydrides, lower alkyl esters and the like. These divalent carboxylic acid monomers and trivalent or higher polyvalent carboxylic acid monomers can be used alone or in combination.

  Among these polyester resins, the mol% of propylene oxide with respect to the alcohol component in the polyester resin is 40 mol% or more, more specifically, the polycarboxylic acid and the bisphenol A-propylene oxide adduct are 40 mol% in the total alcohol component. It is preferable from the viewpoint of development stability that it is obtained by condensation polymerization with the alcohol component contained above.

  Furthermore, the acid value of the polyester resin is preferably 0 mgKOH / g or more and 10 mgKOH / g or less from the viewpoint of the stability of the triboelectric charge amount.

  Examples of the wax used in the toner of the present invention include the following. Low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymer, hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxide of hydrocarbon wax such as oxidized polyethylene wax or block copolymer thereof; Waxes mainly composed of fatty acid esters such as carnauba wax; those obtained by partially or fully deoxidizing fatty acid esters such as deoxidized carnauba wax.

  Furthermore, the following are mentioned. Saturated linear fatty acids such as palmitic acid, stearic acid and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid and valinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, seryl alcohol, Saturated alcohols such as sil alcohols; polyhydric alcohols such as sorbitol; fatty acids such as palmitic acid, stearic acid, behenic acid, montanic acid, and stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, seryl alcohol, Esters with alcohols such as sil alcohols; Fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; Methylene bis stearic acid amide, ethylene biscapric acid Saturated fatty acid bisamides such as amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide; Unsaturated fatty acid amides such as sebacic acid amides; aromatic bisamides such as m-xylene bis-stearic acid amide, N, N ′ distearyl isophthalic acid amide; calcium stearate, calcium laurate, zinc stearate, magnesium stearate Aliphatic metal salts such as those commonly referred to as metal soaps; waxes grafted to aliphatic hydrocarbon waxes using vinylic monomers such as styrene and acrylic acid; fatty acids such as behenic acid monoglycerides Price Partial esters of Lumpur; methyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable fats and oils.

  Among these waxes, hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax are preferable from the viewpoint of pigment dispersion because they have a high dispersion effect due to a polymer obtained by reacting a vinyl resin component and a hydrocarbon compound.

  In the present invention, the wax is preferably used in an amount of 0.5 to 20 parts by mass per 100 parts by mass of the binder resin.

  The peak temperature of the maximum endothermic peak of the wax is preferably 45 ° C. or higher and 140 ° C. or lower.

  The toner of the present invention may contain a charge control agent as necessary. As the charge control agent contained in the toner, known ones can be used. In particular, a metal compound of an aromatic carboxylic acid that is colorless, has a high toner charging speed, and can stably maintain a constant charge amount is preferable.

  Negative charge control agents include salicylic acid metal compounds, naphthoic acid metal compounds, dicarboxylic acid metal compounds, polymeric compounds having sulfonic acid or carboxylic acid in the side chain, sulfonates or sulfonated compounds in the side chain. Examples thereof include a polymer compound, a polymer compound having a carboxylate or a carboxylic acid ester in the side chain, a boron compound, a urea compound, a silicon compound, and calixarene. Examples of the positive charge control agent include a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, and an imidazole compound. The charge control agent may be added internally or externally to the toner particles. The addition amount of the charge control agent is preferably 0.2 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder resin.

  The toner of the present invention may contain inorganic fine particles as necessary. As the inorganic fine particles contained in the toner, known ones such as silica, titanium oxide, and aluminum oxide can be used. In particular, colorless inorganic fine particles are preferable because they have little influence on the coloring of the toner. The addition amount of the inorganic fine particles is preferably 9.9 parts by mass or less with respect to 100 parts by mass of the binder resin.

  It is preferable that an external additive is added to the toner of the present invention in order to improve fluidity and stabilize durability. As the external additive, inorganic fine powders such as silica, titanium oxide and aluminum oxide are preferable. The inorganic fine powder is preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil or a mixture thereof.

As an external additive for improving fluidity, an inorganic fine powder having a specific surface area of 50 m ² / g or more and 400 m ² / g or less is preferable. For stabilization of durability, the specific surface area is 10 m ² / g or more and 50 m or less. An inorganic fine powder of ² / g or less is preferable. In order to achieve both improvement in fluidity and stabilization of durability, inorganic fine particles having a specific surface area in the above range may be used in combination.

  The external additive is preferably used in an amount of 0.1 to 10.0 parts by mass with respect to 100 parts by mass of the toner particles. For mixing the toner particles and the external additive, a known mixer such as a Henschel mixer can be used.

  Further, regarding the addition amount of the inorganic fine particles, including the amount contained in the toner particles and the addition amount externally added to the toner particle surface, 5.0 parts by mass or more and 10.0 parts by mass with respect to 100 parts by mass of the toner particles. It is preferable from the viewpoint of stabilizing the triboelectric charge amount of the toner when the toner is durable.

  The toner of the present invention can also be used as a one-component developer, but in order to further improve dot reproducibility, it can be mixed with a magnetic carrier and used as a two-component developer. Is preferable in that it is obtained.

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

  When the toner of the present invention is mixed with a magnetic carrier and used as a two-component developer, the mixing ratio of the magnetic carrier is preferably 2% by mass or more and 15% by mass or less as the toner concentration in the developer. More preferable results are obtained when the content is more preferably 4% by mass or more and 13% by mass or less. If the toner concentration is less than 2% by mass, the image density tends to decrease, and if it exceeds 15% by mass, fogging or in-machine scattering tends to occur.

  As a method for producing toner particles, for example, a pulverization method in which a binder resin and a wax are melt-kneaded and the kneaded product is cooled and then pulverized and classified; a solution in which the binder resin and the wax are dissolved or dispersed in a solvent Suspension granulation method in which toner particles are obtained by introducing into a water-based medium and suspending granulation, and removing the solvent; a monomer composition in which a wax or the like is uniformly dissolved or dispersed in a monomer is contained in a dispersion stabilizer Suspension polymerization method in which toner particles are produced by dispersing in a continuous layer (for example, an aqueous phase) and carrying out a polymerization reaction; a monomer that is soluble in monomers but insoluble when a polymer is formed, and an aqueous organic solvent. A dispersion polymerization method that directly produces toner particles using an aqueous organic solvent that is soluble in the monomer that directly produces toner particles but is insoluble in the resulting polymer; it is polymerized directly in the presence of a water-soluble polar polymerization initiator. An emulsion polymerization method for producing particles; an emulsion aggregation method obtained by aggregating at least polymer fine particles and wax to form fine particle aggregates and an aging step for causing fusion between the fine particles in the fine particle aggregates; and so on.

  Hereinafter, a toner manufacturing procedure using the pulverization method will be described.

  In the raw material mixing step, as a material constituting the toner particles, for example, a predetermined amount of other components such as a binder resin and a wax and, if necessary, a colorant and a charge control agent are weighed and mixed. Examples of the mixing apparatus include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, and a mechano-hybrid (manufactured by Nippon Coke Industries, Ltd.).

  Next, the mixed material is melt-kneaded to disperse wax or the like in the binder resin. In the melt-kneading process, a batch kneader such as a pressure kneader or a Banbury mixer or a continuous kneader can be used, and a single-screw or twin-screw extruder has become the mainstream because of the advantage of continuous production. ing. For example, KTK type twin screw extruder (manufactured by Kobe Steel Co., Ltd.), TEM type twin screw extruder (manufactured by Toshiba Machine Co., Ltd.), PCM kneader (manufactured by Ikekai Tekko), twin screw extruder (manufactured by KC K ), Co-kneader (manufactured by Buss), kneedex (manufactured by Nippon Coke Industries Co., Ltd.) Furthermore, the resin composition obtained by melt-kneading may be rolled with two rolls or the like and cooled with water or the like in the cooling step.

  Next, the cooled product of the resin composition is pulverized to a desired particle size in the pulverization step. In the pulverization step, for example, after coarse pulverization with a pulverizer such as a crusher, a hammer mill, or a feather mill, for example, a kryptron system (manufactured by Kawasaki Heavy Industries), a super rotor (manufactured by Nisshin Engineering), a turbo mill Finely pulverize with a turbomill (made by Turbo Industries) or air jet type fine pulverizer.

  Then, if necessary, classification such as inertial class elbow jet (manufactured by Nippon Steel & Mining Co., Ltd.), centrifugal classification turboplex (manufactured by Hosokawa Micron), TSP separator (manufactured by Hosokawa Micron), Faculty (manufactured by Hosokawa Micron) The toner particles are obtained by classification using a machine or a sieving machine.

  In addition, if necessary, after pulverization, a hybridization system (manufactured by Nara Machinery Co., Ltd.), a mechano-fusion system (manufactured by Hosokawa Micron), a faculty (manufactured by Hosokawa Micron), or Meteole Inbo MR Type (manufactured by Nippon Pneumatic Co., Ltd.) is used. Thus, the toner particles can be subjected to a surface treatment such as a spheroidizing treatment.

  Further, as a method of externally adding the external additive, a predetermined amount of classified toner and various known external additives are blended, and a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, and a Nauta mixer are mixed. And a mixing device such as Mechano Hybrid (manufactured by Nippon Coke Kogyo Co., Ltd.), Nobilta (manufactured by Hosokawa Micron Co., Ltd.) or the like as an external additive.

  A method for measuring various physical properties of the toner and raw materials in the present invention will be described below.

<Measurement method of softening point of resin>
The softening point of the resin is measured by using a constant load extrusion type capillary rheometer “flow characteristic evaluation device Flow Tester CFT-500D” (manufactured by Shimadzu Corporation) according to the manual attached to the device. In this device, while applying a constant load from the top of the measurement sample with the piston, the measurement sample filled in the cylinder is heated and melted, and the melted measurement sample is pushed out from the die at the bottom of the cylinder, and the piston drop amount at this time A flow curve showing the relationship between temperature and temperature can be obtained.

  In the present invention, the “melting temperature in the 1/2 method” described in the manual attached to the “flow characteristic evaluation apparatus Flow Tester CFT-500D” is the softening point. The melting temperature in the 1/2 method is calculated as follows. First, ½ of the difference between the piston lowering amount Smax at the time when the outflow ends and the piston lowering amount Smin at the time when the outflow starts is obtained (this is X. X = (Smax−Smin) / 2). Then, the temperature of the flow curve when the piston descending amount is X in the flow curve is the melting temperature in the 1/2 method.

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

The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rising start temperature: 50 ° C
Achieving temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature increase rate: 4.0 ° C./min
Piston cross-sectional area: 1.000 cm ²
Test load (piston load): 10.0 kgf (0.9807 MPa)
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0mm

<Measurement of maximum endothermic peak of wax>
The peak temperature of the maximum endothermic peak of the wax is measured according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments). The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.

  Specifically, about 10 mg of wax is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference. Measurement is performed at ° C / min. In the measurement, the temperature is once raised to 200 ° C., subsequently lowered to 30 ° C., and then the temperature is raised again. The temperature showing the maximum endothermic peak of the DSC curve in the temperature range of 30 to 200 ° C. in the second temperature raising process is defined as the peak temperature of the maximum endothermic peak of the wax.

<Measurement of BET specific surface area of inorganic fine particles>
The BET specific surface area of the inorganic fine particles is measured according to JIS Z8830 (2001). A specific measurement method is as follows.

  As a measuring device, an “automatic specific surface area / pore distribution measuring device TriStar 3000 (manufactured by Shimadzu Corporation)” which employs a gas adsorption method by a constant volume method as a measuring method is used. Setting of measurement conditions and analysis of measurement data are performed using dedicated software “TriStar3000 Version 4.00” attached to the apparatus, and a vacuum pump, a nitrogen gas pipe, and a helium gas pipe are connected to the apparatus. The value calculated by the BET multipoint method using nitrogen gas as the adsorption gas is taken as the BET specific surface area of the inorganic fine particles in the present invention.

  The BET specific surface area is calculated as follows.

First, nitrogen gas is adsorbed onto the inorganic fine particles, and then the equilibrium pressure P (Pa) in the sample cell and the nitrogen adsorption amount Va (mol · g ⁻¹ ) of the external additive are measured. The relative pressure Pr, which is a value obtained by dividing the equilibrium pressure P (Pa) in the sample cell by the saturated vapor pressure Po (Pa) of nitrogen, is plotted on the horizontal axis, and the nitrogen adsorption amount Va (mol · g ⁻¹ ) is plotted on the vertical axis. The adsorption isotherm is obtained. Next, a monomolecular layer adsorption amount Vm (mol · g ⁻¹ ), which is an adsorption amount necessary for forming a monomolecular layer on the surface of the external additive, is determined by applying the following BET equation.
Pr / Va (1-Pr) = 1 / (Vm * C) + (C-1) * Pr / (Vm * C)
(Here, C is a BET parameter, which is a variable that varies depending on the measurement sample type, adsorbed gas type, and adsorption temperature.)

The BET equation is interpreted as a straight line with an inclination of (C-1) / (Vm × C) and an intercept of 1 / (Vm × C), where Pr is X axis and Pr / Va (1-Pr) is Y axis. Yes (this line is called a BET plot).
Straight line slope = (C-1) / (Vm × C)
Straight line intercept = 1 / (Vm × C)

  When the measured value of Pr and the measured value of Pr / Va (1-Pr) are plotted on a graph and a straight line is drawn by the least square method, the slope and intercept value of the straight line can be calculated. Vm and C can be calculated by solving the simultaneous equations of the slope of the straight line and the intercept using these values.

Furthermore, the BET specific surface area S (m ² / g) of the inorganic fine particles is calculated from the calculated Vm and the molecular occupation cross-sectional area (0.162 nm ² ) of the nitrogen molecule based on the following formula.
S = Vm × N × 0.162 × 10 ⁻¹⁸
(N is Avogadro's number (mole- ¹ ).)

  The measurement using this apparatus follows the “TriStar 3000 Instruction Manual V4.0” attached to the apparatus, and specifically, the measurement is performed according to the following procedure.

  Thoroughly weigh the tare of a dedicated glass sample cell (stem diameter 3/8 inch, volume about 5 ml) that has been thoroughly cleaned and dried. Then, about 0.1 g of an external additive is put into the sample cell using a funnel.

  The sample cell containing the inorganic fine particles is set in a “pretreatment device Bacrepprep 061 (manufactured by Shimadzu Corporation)” connected with a vacuum pump and a nitrogen gas pipe, and vacuum degassing is continued at 23 ° C. for about 10 hours. During vacuum deaeration, the inorganic fine particles are gradually deaerated while adjusting the valve so that the inorganic fine particles are not sucked into the vacuum pump. The pressure in the cell gradually decreases with deaeration and finally becomes about 0.4 Pa (about 3 mTorr). After completion of vacuum degassing, nitrogen gas is gradually injected to return the inside of the sample cell to atmospheric pressure, and the sample cell is removed from the pretreatment device. Then, the mass of the sample cell is precisely weighed, and the accurate mass of the external additive is calculated from the difference from the tare. At this time, the sample cell is covered with a rubber plug during weighing so that the external additive in the sample cell is not contaminated by moisture in the atmosphere.

  Next, a dedicated “isothermal jacket” is attached to the stem portion of the sample cell containing the inorganic fine particles. Then, a dedicated filler rod is inserted into the sample cell, and the sample cell is set in the analysis port of the apparatus. The isothermal jacket is a cylindrical member having an inner surface made of a porous material and an outer surface made of an impermeable material capable of sucking liquid nitrogen to a certain level by capillary action.

  Subsequently, the free space of the sample cell including the connection tool is measured. The free space is measured by measuring the volume of the sample cell using helium gas at 23 ° C., and then measuring the volume of the sample cell after cooling the sample cell with liquid nitrogen using helium gas. It is calculated by converting from the difference in volume. The saturated vapor pressure Po (Pa) of nitrogen is automatically measured separately using a Po tube built in the apparatus.

  Next, after performing vacuum deaeration in the sample cell, the sample cell is cooled with liquid nitrogen while continuing the vacuum deaeration. Thereafter, nitrogen gas is gradually introduced into the sample cell to adsorb nitrogen molecules to the toner. At this time, since the adsorption isotherm is obtained by measuring the equilibrium pressure P (Pa) as needed, the adsorption isotherm is converted into a BET plot. Note that the points of the relative pressure Pr for collecting data are set to a total of 6 points of 0.05, 0.10, 0.15, 0.20, 0.25, and 0.30. A straight line is drawn from the obtained measurement data by the least square method, and Vm is calculated from the slope and intercept of the straight line. Furthermore, using the value of Vm, the BET specific surface area of the inorganic fine particles is calculated as described above.

<Measurement of acid value of resin and toner>
The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample. The acid value of the binder resin is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.

(1) Preparation of Reagent 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.

  7 g of special grade potassium hydroxide is dissolved in 5 ml of water, and ethyl alcohol (95 vol%) is added to make 1 l. In order not to touch carbon dioxide, etc., put in an alkali-resistant container and let stand for 3 days, then filter to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was as follows: 25 ml of 0.1 mol / l hydrochloric acid was placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution were added, titrated with the potassium hydroxide solution, and the hydroxide required for neutralization. Determined from the amount of potassium solution. As the 0.1 mol / l hydrochloric acid, one prepared according to JIS K 8001-1998 is used.

(2) Operation (A) Main test 2.0 g of the sample (resin or toner) is precisely weighed into a 200 ml Erlenmeyer flask, and 100 ml of a mixed solution of toluene / ethanol (2: 1) is added and dissolved over 5 hours. Subsequently, several drops of the phenolphthalein solution is added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of titration is when the light red color of the indicator lasts 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) The acid value is calculated by substituting the obtained result into the following formula.
A = [(C−B) × f × 5.61] / S

  Here, A: acid value (mgKOH / g), B: addition amount (ml) of a potassium hydroxide solution in a blank test, C: addition amount (ml) of a potassium hydroxide solution in this test, f: potassium hydroxide Solution factor, S: sample (g).

<Method for Measuring Weight Average Particle Size (D4) of Toner Particles>
The weight average particle diameter (D4) of the toner particles is measured with a precision particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) equipped with a 100 μm aperture tube. Measured data with 25,000 effective measurement channels using the dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) for condition setting and measurement data analysis Analyze and calculate.

  As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, the dedicated software is set as follows.

  In the “Standard measurement method (SOM) change screen” of the dedicated software, set the total count in the control mode to 50000 particles, the number of measurements is 1 and the Kd value is “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash after measurement is checked.

  In the “pulse to particle size conversion setting screen” of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm or more and 60 μm or less.

The specific measurement method is as follows.
(1) About 200 ml of the electrolytic solution is placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.
(2) About 30 ml of the electrolytic aqueous solution is put in a glass 100 ml flat bottom beaker, and "Contaminone N" (nonionic surfactant, anionic surfactant, organic builder pH 7 precision measurement is used as a dispersant therein. About 0.3 ml of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for washing a vessel (made by Wako Pure Chemical Industries, Ltd.) 3 times with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and placed in a water tank of an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikkiki Bios Co., Ltd.) having an electrical output of 120 W. A predetermined amount of ion-exchanged water is put, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. The “average diameter” on the analysis / volume statistics (arithmetic average) screen when the graph / volume% is set with the dedicated software is the weight average particle diameter (D4).

<Measurement of true density of magnetic carrier>
The true density of the toner is measured by a dry automatic densimeter autopicometer (manufactured by Yuasa Ionics). The conditions are as follows.
Cell SM cell (10ml)
Sample amount about 2.0g

  This measurement method measures the true density of a solid / liquid based on a gas phase substitution method. Similar to the liquid phase replacement method, it is based on Archimedes' principle, but uses a gas (argon gas) as a replacement medium, and therefore has high accuracy for micropores.

<Primary particle size of conductive fine particles>
If the measurement range has a measurement range of submicron to several hundred microns, it can be measured using a dry or wet laser diffraction particle size distribution meter. Examples of the laser diffraction particle size distribution analyzer include laser diffraction particle size distribution analyzers SALD-3000, SALD-2200, and SALD-300V (manufactured by Shimadzu Corporation).

<Measurement of DBP oil absorption of carbon black>
Measured according to JIS 4656/1.

<Measurement method of 50% particle size (D50) based on volume distribution of magnetic substance and nonmagnetic inorganic compound used for carrier core>
The volume distribution standard 50% particle diameter (D50) of the magnetic material used for the carrier core of the resin-impregnated carrier can be measured according to the measurement of the carrier particles.

  On the other hand, the number average particle diameter of the magnetic substance contained in the carrier core of the magnetic substance-dispersed resin carrier is measured by the following procedure.

  The cross section of the carrier cut by the microtome is observed with a scanning electron microscope (50,000 times), and 300 or more particles having a particle size of 5 nm or more are extracted at random. The length of the major axis and minor axis of each extracted particle is measured with a digitizer. The average value of the measured lengths of the major axis and the minor axis is taken as the particle size, and the particle size distribution of 300 or more particles (column width is 5-15, 15-25, (unit: nm),. The particle diameter of the center value of the column that becomes the peak of the column is defined as the number average particle diameter.

  The number average particle diameter of the nonmagnetic inorganic compound used for the carrier core is also measured in the same manner as described above.

  In addition, the number average particle diameter of the magnetic substance or nonmagnetic inorganic compound is determined by measuring the raw material magnetic substance or nonmagnetic inorganic compound (in a state not contained in the resin) with a transmission electron microscope (TEM) (50,000 times). It can be observed and determined in the same manner as described above.

  Specific examples of the present invention will be described below, but the present invention is not limited to these examples. “Parts” in the following formulations are based on mass unless otherwise specified.

<Binder Resin Production Example 1>
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane. 51.1 parts (0.111 mol), polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane 30.0 parts (0.074 mol), terephthalic acid 25.0 parts ( 0.150 mol) and 0.5 part of titanium tetrabutoxide were placed in a glass 4-liter four-necked flask, and a thermometer, a stir bar, a condenser and a nitrogen inlet tube were attached and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 4 hours while stirring at a temperature of 200 ° C. (first reaction step). Thereafter, 1.2 parts (0.006 mol) of trimellitic anhydride was added and reacted at 180 ° C. for 1 hour (second reaction step), whereby a binder resin 1 was obtained.

  The binder resin 1 had an acid value of 6 mgKOH / g and a hydroxyl value of 65 mgKOH / g.

<Binder Resin Production Example 2>
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane. 51.1 parts (0.111 mol), polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane 30.0 parts (0.074 mol), terephthalic acid 24.1 parts ( 0.145 mol) and 0.6 parts of titanium tetrabutoxide were placed in a glass 4-liter four-necked flask, and a thermometer, a stir bar, a condenser and a nitrogen inlet tube were attached and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 2 hours while stirring at a temperature of 200 ° C. (first reaction step). Thereafter, 5.8 parts (0.030 mol%) of trimellitic anhydride was added and reacted at 170 ° C. for 12 hours (second reaction step), whereby a binder resin 2 was obtained.

  The binder resin 2 had an acid value of 10 mgKOH / g and a hydroxyl value of 12 mgKOH / g.

<Binder Resin Production Example 3>
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane. 51.1 parts (0.111 mol), polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane 30.0 parts (0.074 mol), terephthalic acid 20.0 parts ( 0.120 mol) and 0.6 part of titanium tetrabutoxide were placed in a glass 4-liter four-necked flask, and a thermometer, a stir bar, a condenser and a nitrogen inlet tube were attached and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 6 hours while stirring at a temperature of 200 ° C. (first reaction step). Thereafter, 1.0 part (0.005 mol) of trimellitic anhydride was added and reacted at 180 ° C. for 3 hours (second reaction step) to obtain a binder resin 3.

  The acid value of this binder resin 3 was 0 mgKOH / g, and the hydroxyl value was 82 mgKOH / g.

<Binder Resin Production Example 4>
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane. 51.1 parts (0.111 mol), polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane 30.0 parts (0.074 mol), terephthalic acid 24.1 parts ( 0.145 mol) and 0.6 parts of titanium tetrabutoxide were placed in a glass 4-liter four-necked flask, and a thermometer, a stir bar, a condenser and a nitrogen inlet tube were attached and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 2 hours while stirring at a temperature of 200 ° C. (first reaction step). Thereafter, 5.8 parts (0.030 mol%) of trimellitic anhydride was added and reacted at 170 ° C. for 12 hours (second reaction step), and then polyoxypropylene (2.2) -2,2- Bis (4-hydroxyphenyl) propane. 8.5 parts (0.067 mol) and 5.0 parts (0.013 mol) of polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane were added at 170 ° C. for 2 hours. The binder resin 4 was obtained by reacting (third reaction step).

  The binder resin 4 had an acid value of 0 mgKOH / g and a hydroxyl value of 94 mgKOH / g.

<Binder Resin Production Example 5>
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane. 51.1 parts (0.111 mol), polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane 30.0 parts (0.074 mol), terephthalic acid 26.5 parts ( 0.159 mol) and 0.6 parts of titanium tetrabutoxide were placed in a glass 4-liter four-necked flask, and a thermometer, a stir bar, a condenser and a nitrogen inlet tube were attached and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 4 hours while stirring at a temperature of 200 ° C. (first reaction step). Thereafter, 1.2 parts (0.006 mol) of trimellitic anhydride was added and reacted at 180 ° C. for 1 hour (second reaction step), whereby a binder resin 5 was obtained.

  The binder resin 5 had an acid value of 10 mgKOH / g and a hydroxyl value of 59 mgKOH / g.

<Binder Resin Production Example 6>
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane. 51.1 parts (0.111 mol), polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane 30.0 parts (0.074 mol), terephthalic acid 26.5 parts ( 0.159 mol) and 0.6 parts of titanium tetrabutoxide were placed in a glass 4-liter four-necked flask, and a thermometer, a stir bar, a condenser and a nitrogen inlet tube were attached and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 4 hours while stirring at a temperature of 200 ° C. (first reaction step). Thereafter, 1.4 parts (0.007 mol) of trimellitic anhydride was added and reacted at 180 ° C. for 1 hour (second reaction step), whereby a binder resin 6 was obtained.

  The binder resin 6 had an acid value of 14 mgKOH / g and a hydroxyl value of 57 mgKOH / g.

<Binder Resin Production Example 7>
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane. 77.1 parts (0.168 mol), polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane 7.5 parts (0.018 mol), terephthalic acid 26.5 parts ( 0.159 mol) and 0.6 parts of titanium tetrabutoxide were placed in a glass 4-liter four-necked flask, and a thermometer, a stir bar, a condenser and a nitrogen inlet tube were attached and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 4 hours while stirring at a temperature of 200 ° C. (first reaction step). Thereafter, 1.4 parts (0.007 mol) of trimellitic anhydride was added and reacted at 180 ° C. for 1 hour (second reaction step), whereby a binder resin 7 was obtained.

  The binder resin 7 had an acid value of 12 mgKOH / g and a hydroxyl value of 60 mgKOH / g.

<Binder Resin Production Example 8>
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane. 77.1 parts (0.168 mol), polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane 7.5 parts (0.018 mol), terephthalic acid 26.5 parts ( 0.159 mol) and 0.6 parts of titanium tetrabutoxide were placed in a glass 4-liter four-necked flask, and a thermometer, a stir bar, a condenser and a nitrogen inlet tube were attached and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 4 hours while stirring at a temperature of 200 ° C. (first reaction step). Thereafter, 1.4 parts (0.007 mol) of trimellitic anhydride was added and reacted at 180 ° C. for 10 hours (second reaction step), whereby a binder resin 8 was obtained.

  The binder resin 8 had an acid value of 12 mgKOH / g and a hydroxyl value of 78 mgKOH / g.

<Binder resin production example 9>
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane. 34.1 parts (0.074 mol), polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane 45.0 parts (0.112 mol), terephthalic acid 27.5 parts ( 0.165 mol) and 0.6 parts of titanium tetrabutoxide were placed in a glass 4-liter four-necked flask, and a thermometer, a stir bar, a condenser and a nitrogen inlet tube were attached and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 4 hours while stirring at a temperature of 200 ° C. (first reaction step). Thereafter, 1.4 parts (0.007 mol) of trimellitic anhydride was added and reacted at 180 ° C. for 1 hour (second reaction step), whereby a binder resin 9 was obtained.

  The binder resin 9 had an acid value of 12 mgKOH / g and a hydroxyl value of 59 mgKOH / g.

<Binder Resin Production Example 10>
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane. 34.1 parts (0.074 mol), polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane 45.0 parts (0.112 mol), terephthalic acid 27.5 parts ( 0.165 mol) and 0.7 parts of titanium tetrabutoxide were placed in a glass 4-liter four-necked flask, and a thermometer, a stir bar, a condenser and a nitrogen inlet tube were attached and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 4 hours while stirring at a temperature of 200 ° C. (first reaction step). Thereafter, 1.4 parts (0.007 mol) of trimellitic anhydride was added and reacted at 180 ° C. for 10 hours (second reaction step) to obtain a binder resin 10.

  The binder resin 10 had an acid value of 12 mgKOH / g and a hydroxyl value of 85 mgKOH / g.

<Production Example 11 of Binder Resin>
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane. 24.4 parts (0.053 mol), polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane 50.0 parts (0.124 mol), terephthalic acid 27.5 parts ( 0.165 mol) and 0.6 parts of titanium tetrabutoxide were placed in a glass 4-liter four-necked flask, and a thermometer, a stir bar, a condenser and a nitrogen inlet tube were attached and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 4 hours while stirring at a temperature of 200 ° C. (first reaction step). Thereafter, 1.4 parts (0.007 mol) of trimellitic anhydride was added and reacted at 180 ° C. for 1 hour (second reaction step) to obtain a binder resin 11.

  The binder resin 11 had an acid value of 12 mgKOH / g and a hydroxyl value of 60 mgKOH / g.

<Binder Resin Production Example 12>
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane. 24.4 parts (0.053 mol), polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane 50.0 parts (0.124 mol), terephthalic acid 27.5 parts ( 0.165 mol) and 0.7 parts of titanium tetrabutoxide were placed in a glass 4-liter four-necked flask, and a thermometer, a stir bar, a condenser and a nitrogen inlet tube were attached and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 4 hours while stirring at a temperature of 200 ° C. (first reaction step). Thereafter, 1.4 parts (0.007 mol) of trimellitic anhydride was added and reacted at 180 ° C. for 10 hours (second reaction step) to obtain a binder resin 12.

  The binder resin 12 had an acid value of 12 mgKOH / g and a hydroxyl value of 84 mgKOH / g.

<Production Example 1 of a polymer having a structure in which a vinyl resin component and a hydrocarbon compound are reacted>
・ 20 parts of low density polyethylene (Mw 1400, Mn 850, maximum endothermic peak by DSC is 100 ° C.)
Styrene 50.0 parts n-Butyl acrylate 10.0 parts Acrylonitrile 20.0 parts was charged into an autoclave, and kept in the system after N ₂ substitution, the 180 ° C. with stirring heating. In the system, 50 parts of a 2% by mass t-butyl hydroperoxide xylene solution was continuously dropped for 5 hours, and after cooling, the solvent was separated and removed, and the polymer 1 in which the vinyl resin component reacted with the low-density polyethylene. Got.

<Production Example 2 of a polymer having a structure in which a vinyl resin component and a hydrocarbon compound are reacted>
・ 20 parts of low density polyethylene (Mw 1400, Mn 850, maximum endothermic peak by DSC is 100 ° C.)
-60.0 parts of styrene-10.0 parts of n-butyl acrylate-10.0 parts of acrylonitrile were charged into an autoclave, and after replacing the system with N ₂ , the temperature was maintained at 180 ° C while stirring. Into the system, 50 parts of a 2% by mass t-butyl hydroperoxide xylene solution was continuously dropped for 5 hours, and after cooling, the solvent was separated and removed, and the polymer 2 in which the vinyl resin component reacted with the low-density polyethylene. Got.

<Production Example 3 of a polymer having a structure in which a vinyl resin component and a hydrocarbon compound are reacted>
・ 20 parts of low density polyethylene (Mw 1400, Mn 850, maximum endothermic peak by DSC is 100 ° C.)
-60.0 parts of styrene-10.0 parts of n-butyl acrylate-5.0 parts of acrylonitrile were charged into an autoclave, and after replacing the system with N ₂ , the mixture was kept at 180 ° C while stirring at elevated temperature. Into the system, 50 parts of a 2% by mass t-butyl hydroperoxide xylene solution was continuously dropped for 5 hours, and after cooling, the solvent was separated and removed, and the polymer 3 in which the vinyl resin component reacted with the low-density polyethylene. Got.

<Toner Production Example 1>
(First kneading step)
Binder resin 1 100 parts C.I. I. Pigment Yellow 185 (powder) 100 parts / distilled water 100 parts The above raw materials are first charged into a kneader-type mixer and heated while being mixed without pressure. When the maximum temperature (necessarily determined by the boiling point of the solvent in the paste. In this case, about 90 to 100 ° C.), the pigment in the aqueous phase is distributed or transferred to the molten resin phase to confirm this. After that, the mixture is further melted and kneaded for 30 minutes to sufficiently transfer the pigment in the paste. Then, once the mixer was stopped and the hot water was discharged, the temperature was further raised to 110 ° C., heated and melted and kneaded for about 30 minutes, the pigment was dispersed and the water was distilled off, and the process was completed. The kneaded product was taken out and cooled to obtain a first kneaded product.

(Second kneading step)
12.0 parts of the first kneaded product (pigment particle content 50% by mass) 65.0 parts of binder resin 1 35.0 parts of binder resin 2 5.0 parts of polymer 1 paraffin wax (Maximum endothermic peak 78 ° C.) 5.0 parts. 3,5-di-tert-butylsalicylic acid Al compound 1.0 part. C.I. I. Solvent Yellow 162 (powder) 2.0 parts Preliminarily mixed with a Henschel mixer with the above formulation, melt kneaded with a twin screw extruder kneader at a temperature of 150 ° C., and after cooling, about 1 using a hammer mill Coarsely pulverize to about 2 mm. Subsequently, it was finely pulverized to a particle size of 20 μm or less by an air jet type fine pulverizer. Further, the obtained finely pulverized product was classified to obtain yellow resin particles (classified product) having a weight average particle size distribution of 6.3 μm.

Thereafter, 0.7% by mass of titanium oxide fine particles having a primary average particle diameter of 50 nm and surface-treated with isobutyltrimethoxysilane was added as inorganic fine particles. Further, 100 parts of silica fine particles (BET specific surface area 200 m ² / g) produced by a dry method were treated with dimethyldichlorosilane and then with hexamethylene disilazane. Thereafter, 6.3 parts of hydrophobic silica treated with dimethyl silicone oil was added and externally added to obtain yellow toner 1.

<Toner Production Examples 2 to 28 >
Toners 2 to 28 were obtained in the same manner except that the toner formulation 1 was changed to the toner formulation shown in Table 1 below.

(Magnetic carrier production example 1)
For magnetite powder having a number average particle size of 0.30 μm and (magnetization intensity of 75 Am ² / kg under a magnetic field of 10,000 / 4π (kA / m)) and hematite powder having a number average particle size of 0.30 μm, respectively. 4.0% by mass of a silane coupling agent (3- (2-aminoethylaminopropyl) trimethoxysilane) was added and mixed and stirred at 100 ° C. or higher in a container to treat each fine particle.

・ Phenol 10 parts ・ Formaldehyde solution 6 parts (formaldehyde 40 mass%, methanol 10 mass%, water 50 mass%)
・ 75 parts of the above treated magnetite 9 parts of the above treated hematite 9 parts of the above material, 5 parts of 28% by weight ammonia water and 20 parts of water are placed in a flask and heated to 85 ° C. for 30 minutes while stirring and mixing. The resulting phenol resin was cured by a polymerization reaction for 3 hours. Thereafter, the cured phenol resin was cooled to 30 ° C., water was further added, the supernatant was removed, the precipitate was washed with water, and then air-dried. Subsequently, this was dried under reduced pressure (0.7 kPa or less) at a temperature of 60 ° C. to obtain a spherical magnetic substance-containing resin carrier core in which the magnetic substance was dispersed.

  As a coating material, a copolymer of methyl methacrylate and styrene (copolymerization ratio (mass% ratio) 80:20, weight average molecular weight 45,000) was used, and this was applied to 100 parts of the magnetic material-containing resin carrier core during coating. Thus, a carrier coat solution containing 10% by mass of a copolymer of methyl methacrylate and styrene was prepared using a mixed solvent of methyl ethyl ketone and toluene as a solvent. In addition, 0.5 parts of melamine resin (number average particle diameter 0.2 μm) and 1.0 part of carbon black (number average particle diameter 30 nm, DBP oil absorption 50 ml / 100 g) are well mixed with this carrier coat solution by a homogenizer. . Next, the magnetic material-containing resin carrier core is added to the mixed solution, and the solvent is volatilized at 70 ° C. while continuously applying a shear stress to the mixed solution. The copolymer of was coated.

The resin-coated magnetic material-dispersed resin core coated with the copolymer of methyl methacrylate and styrene is heat-treated by stirring at 100 ° C. for 2 hours, cooled and crushed, and classified with a 200-mesh sieve. A magnetic carrier 1 having an average particle diameter of 35 μm, a true density of 3.73 g / cm ³ , and a magnetization strength of 55 Am ² / kg was obtained.

The toner 1 and the magnetic carrier 1 are mixed with a V-type mixer (V-10 type: Tokuju Seisakusho Co., Ltd.) at 0.5 s ⁻¹ and a rotation time of 3 min so that the toner concentration is 8% by mass. Developer 1 was obtained.

[Evaluation method of toner coloring power]
Evaluation was performed by using a modified machine of imageRUNNER ADVANCE C5051 made by Canon as an image forming apparatus and introducing the two-component developer 1 into the developing unit of the magenta station.

The evaluation environment is a normal temperature and humidity environment (23 ° C., 50% RH), and the evaluation paper is copy paper CS-814 (A4, basis weight 81.4 g / m ² ) sold by Canon Marketing Japan Inc. It was.

  First, in the evaluation environment, the amount of toner on the paper was changed, and the relationship between the image density and the amount of applied toner on the paper was examined.

  Next, the image density of the FFH image (solid portion) was adjusted to 1.45, and the amount of applied toner when the image density became 1.45 was obtained.

  The FFH image is a value in which 256 gradations are displayed in hexadecimal, and 00H is the first gradation (white background), and FFH is the 256th gradation (solid part).

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

From the applied toner amount (mg / cm ² ), the coloring power of the toner was evaluated according to the following criteria.

(Evaluation criteria)
A: Less than 0.35 Excellent B: 0.35 or more and less than 0.50 Good C: 0.50 or more and less than 0.65 D: 0.65 or more, which is a level that is not a problem in the present invention Is not acceptable

  The evaluation results are shown in Table 3.

[Decrease rate after light resistance test]
Evaluation was performed using a two-component developer 1 using a remodeled imagerunner ADVANCE C5051 manufactured by Canon as a full-color copying machine manufactured by Canon. Copying paper CS-814 (A4, basis weight 81.4 g / m ² ) sold by Canon Marketing Japan Co., Ltd. as an evaluation paper in a normal temperature and humidity environment (23 ° C., 50% RH). The amount was changed to adjust the image density of the FFH image (solid portion) to 1.45, and an FFH image was output.

The output image was subjected to a light resistance test, and the concentration maintenance ratio before and after UV irradiation (after 100 hours) was calculated. Density was measured with a densitometer X-Rite500, and an average value of five points was taken as an image density. The initial image density was D1, and the image density maintenance ratio D100 / D1 when the image density after 100 hours of ultraviolet irradiation was D100 was determined.
Evaluation result D100 / D1 A: Image density maintenance ratio D100 / D1 is 0.95 or more B: Image density maintenance ratio D100 / D1 is 0.80 or more and less than 0.95 C: Image density maintenance ratio D100 / D1 is 0 .70 or more and less than 0.80 (acceptable level in the present invention)
D: Image density maintenance ratio D100 / D1 is less than 0.70 (not acceptable in the present invention)

  The evaluation results are shown in Table 3.

[Measurement of color fluctuation after light resistance test]
Canon Marketing Japan Co., Ltd., copy paper CS-814 (A4, basis weight 81.4 g / m ² ) as an evaluation paper under normal temperature and humidity conditions (23 ° C., 50% RH) using the same apparatus and developer 16-tone image was formed by changing the amount of toner on the paper. Images, SpectroScan Transmission (GretagMacbeth Co., Ltd.) (Measurement conditions: D ₅₀ viewing angle 2 °) with, L * of the image obtained, a *, was measured b *. In the measurement, L1 *, a1 *, and b1 * were each measured at a loading amount where C * = 85 on the L * -c * coordinate axis. The image was set in an ultraviolet fade meter set at 63 ° C. and 50% RH and irradiated with ultraviolet rays for 120 hours. Thereafter, L2 *, a2 *, and b2 * of the image irradiated with ultraviolet rays were measured, and ΔE was calculated.
ΔE = {(L ₁ ^* −L ₂ ^* ) ² + (a ₁ ^* −a ₂ ^* ) ² + (b ₁ ^* −b ₂ ^* ) ² } ^1/2
A: Less than 10.0 Good B: 10.0 or more and less than 15.0 C: 15.0 or more which is a level that is not a problem in the present invention Unacceptable in the present invention

  The evaluation results are shown in Table 4.

[Evaluation of color fluctuation after endurance test]
In an environment of 20 ° C. and 8% RH, a Canon full-color copier imageRUNNER ADVANCE C5051 remodeled machine is set with the two-component developer 1 in the developer, and the toner supply container in toner production example 1 is evaluated. Copy paper CS-814 (A4, basis weight 81.4 g / m ² ) sold by Canon Marketing Japan Co., Ltd. was used as the paper, and the toner loading amount on the paper was changed to form a 16 gradation image. Images, SpectroScan Transmission (GretagMacbeth Co., Ltd.) (Measurement conditions: D ₅₀ viewing angle 2 °) with, L * of the image obtained, a *, was measured b *. Measurement was performed for each of L1 *, a1 *, and b1 * at a riding amount where C * = 85 on the L * -c * coordinate axis.

  Next, the image density of the FFH image (solid portion) was adjusted to 1.45, the amount of applied toner when the image density reached 1.45 was obtained, and the development bias was adjusted.

  After adjusting the development bias, a fixed amount of toner was replenished with an image having a printing ratio of 1% so as to output 50,000 sheets (50k) of images.

After the end of the 50K endurance, the amount of toner on the paper was changed to form a 16 gradation image. Images, SpectroScan Transmission (GretagMacbeth Co., Ltd.) (Measurement conditions: D ₅₀ viewing angle 2 °) with, L * of the image obtained, a *, was measured b *. The measurement is performed by measuring L2 *, a2 *, b2 * at the riding amount where C * = 85 on the L * -c * coordinate axis, and the L *, a *, b * of the initial image and the image after 20K endurance. ΔE was calculated from the value.
ΔE = {(L ₁ ^* −L ₂ ^* ) ² + (a ₁ ^* −a ₂ ^* ) ² + (b ₁ ^* −b ₂ ^* ) ² } ^1/2
A: Less than 2.0 Excellent B: 2.0 or more and less than 3.5 Good C: 3.5 or more and less than 5.0 D: 5.0 or more, which is a level that is not a problem in the present invention. Is not acceptable

  The evaluation results are shown in Table 5.

<Examples 2 to 21 and Comparative Examples 1 to 7>
In Example 1, the evaluation was performed in the same manner except that the two-component developer used for evaluation was changed to the toner shown in Table 2. Tables 3 and 4 show the evaluation results.

Claims (4)

In a yellow toner having toner particles containing at least a binder resin, a yellow colorant and a hydrocarbon wax, and inorganic fine particles,
The binder resin contains at least a polyester resin,
The yellow colorant includes an isoindoline pigment (colorant A) and C.I. I. Solvent Yellow 162 at least, and the content of the colorant A with respect to 100 parts by mass of the binder resin is X parts by mass, and the C.I. I. When the content of Solvent Yellow 162 is Y parts by mass, X + Y is 3 parts by mass or more and 20 parts by mass or less, and Y / (X + Y) is 0.05 or more and 0.50 or less,
The yellow toner according to claim 1, wherein the toner particles further contain a polymer having a structure in which a vinyl resin component having a nitrile group and a hydrocarbon compound are reacted. The polyester resin, Ri Oh in condensation polymerization product of an alcohol component containing a polyvalent carboxylic acid, a bisphenol A- propylene oxide adduct,
2. The yellow toner according to claim 1, wherein the bisphenol A-propylene oxide adduct is contained in an amount of 40 mol% or more based on the total alcohol components .   The yellow toner according to claim 1 or 2, wherein the yellow toner has an acid value of 0 mgKOH / g or more and 10 mgKOH / g or less.   4. The yellow toner according to claim 1, wherein the content of the inorganic fine particles is 5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the toner particles.