JP2017040772A - Toner and method for manufacturing toner, and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner which causes little contamination in a machine in the vicinity of a fixing device, and is excellent in developability after left under high temperature and high humidity environment.SOLUTION: There is provided a toner having toner particles obtained by forming particles of a polymerizable monomer composition containing a polymerizable monomer, ester wax and a polyester resin in an aqueous medium, and polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition, where the polymerizable monomer contains styrene, a number average molecular weight (Mn) of a soluble content of an o-dichlorobenzene of the ester wax measured by high temperature gel permeation chromatography (GPC) is 700 or more, and when interfacial tension of a solution obtained by dissolving the polyester resin in styrene with water by a pendant drop method is represented by Xp(mN/m), and interfacial tension of a solution obtained by dissolving the ester wax in the styrene with water by a pendant drop method is represented by Xw(mN/m), a relationship of (1): 20≤Xw-Xp holds.SELECTED DRAWING: None

Description

  The present invention relates to a toner that reveals an electrostatic latent image, a method for producing the toner, and an image forming method using the toner.

In recent years, with the development of computers and multimedia, there has been a demand for toners that have good fixability to print on plain paper in high-speed processes in a wide range of fields from offices to homes. On the other hand, for output to thick paper such as gloss paper performed in a low-speed process, a toner that exhibits uniform and high gloss is desired. For this reason, the toner has been improved in order to form a good image even under various conditions. However, when high-speed printing or output to cardboard is repeatedly performed, there is a new problem that the internal contamination of the image forming apparatus occurs due to the wax contained in the toner. Therefore, there is a need for a toner that can prevent in-machine contamination (particularly in the vicinity of the fixing device) even during long-term use in high-speed printing and cardboard output.
Also, when transporting toner bottles and cartridges to the world by ship, etc., they are exposed to severer high-temperature and high-humidity environments, blooming from the inside of the toner occurs, and the triboelectric chargeability and fluidity of the toner gradually decrease. Come on. It has been found that the toner in such a state causes a problem in the image due to a decrease in charge amount, non-uniform charge distribution, and further, toner physical properties represented by toner transportability are further reduced in the developing device. ing.

In Patent Document 1, a toner composed of a polyfunctional ester compound in which each functional group of a trifunctional or higher polyhydric alcohol and a carboxylic acid having 10 to 30 carbon atoms are reacted to form an ester bond, respectively. By using a mold release agent, a toner having a low fixing temperature and a uniform melting property, excellent storage stability (blocking resistance), and is less likely to cause fogging and a decrease in printing density. Possible toner technology is disclosed.
Patent Document 2 discloses a technique for obtaining a toner excellent in low-temperature fixability, storage stability, and printing durability by using a fatty acid ester of a polyhydric alcohol and a fatty acid ester of a monohydric alcohol in combination at a specific ratio. ing.

Japanese Patent Laid-Open No. 2001-272813 JP 2009-133922 A

Certainly, the development durability of the toner containing the ester wax described in Patent Document 1 and Patent Document 2 is improved. However, as a result of intensive studies by the present inventors, it is possible to say that any of the disclosed technologies has sufficient developability after being left in a more severe high-temperature and high-humidity environment considering transportation to ships around the world. There wasn't. Therefore, there is still room for improvement in various characteristics in order to satisfy the quality required in the market.
An object of the present invention is to provide a toner capable of solving the above problems. Specifically, the present invention is to provide a toner which has little in-machine contamination and has excellent developability even after being left in a high temperature and high humidity environment, and an image forming method using the toner.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by the following toner.
In the present invention, particles of a polymerizable monomer composition containing a polymerizable monomer, an ester wax and a polyester resin are formed in an aqueous medium, and the particles contained in the particles of the polymerizable monomer composition are contained in the particles. A toner having toner particles obtained by polymerizing a polymerizable monomer,
The polymerizable monomer includes styrene,
The number average molecular weight (Mn) of the o-dichlorobenzene soluble matter of the ester wax measured by high temperature gel permeation chromatography (GPC) is 700 or more,
Xp (mN / m) is the interfacial tension of the solution obtained by dissolving the polyester resin in styrene with water by the hanging drop method, and the interfacial tension with water by the hanging drop method of the solution obtained by dissolving the ester wax in styrene. And Xw (mN / m), the toner satisfies the relationship of the following formula (1).
20.0 ≦ Xw−Xp (1)
The present invention also relates to a method for producing the toner and an image forming method using the toner.

  According to the present invention, it is possible to provide a toner that has little in-machine contamination and has excellent developability even after being left in a high temperature and high humidity environment, and an image forming method using the toner.

Schematic of an image forming apparatus that can be used in the present invention Schematic of a process cartridge that can be used in the present invention

Hereinafter, the present invention will be described in detail.
In the present invention, particles of a polymerizable monomer composition containing a polymerizable monomer, an ester wax and a polyester resin are formed in an aqueous medium, and the particles contained in the particles of the polymerizable monomer composition are contained in the particles. A toner having toner particles obtained by polymerizing a polymerizable monomer,
The polymerizable monomer includes styrene,
The number average molecular weight (Mn) of the o-dichlorobenzene soluble matter of the ester wax measured by high temperature gel permeation chromatography (GPC) is 700 or more,
Xp (mN / m) is the interfacial tension of the solution obtained by dissolving the polyester resin in styrene with water by the hanging drop method, and the interfacial tension with water by the hanging drop method of the solution obtained by dissolving the ester wax in styrene. And Xw (mN / m), the toner satisfies the relationship of the following formula (1).
20.0 ≦ Xw−Xp (1)

In the present invention, by using a toner that satisfies the above conditions, it is possible to obtain a toner with less in-machine contamination and excellent developability after being left in a high temperature and high humidity environment.
Although the reason why the effect of the present invention can be obtained by satisfying the above conditions is not clear, the present inventors consider as follows.

The toner of the present invention is formed by forming particles of a polymerizable monomer composition containing a polymerizable monomer, an ester wax, a polyester resin, and, if necessary, a colorant in an aqueous medium. A toner having toner particles obtained by polymerizing the polymerizable monomer contained in the particles of the body composition. By granulating the polymerizable monomer composition in an aqueous medium, the polyester resin can be selectively present on the toner surface, and the ester wax can be easily contained inside the toner. Further, the precipitation of the shell containing the polyester resin continuously proceeds in the polymerization step, so that the polyester resin can be selectively distributed unevenly on the toner surface. Therefore, the inclusion of the ester wax inside the toner is further promoted.

Further, from the viewpoint of the above-mentioned internal contamination (especially in the vicinity of the fixing device), it is preferable that the wax is not easily volatilized when the toner is fixed. Therefore, when the molecular weight of the wax is increased, volatilization due to heat is reduced and internal contamination is suppressed. On the other hand, when the molecular weight of the wax is small, the volatilization due to heat is large and internal contamination is likely to occur.
From such a viewpoint, it is essential that the ester wax used in the present invention has a Mn content of o-dichlorobenzene solubles of 700 or more as measured by high temperature GPC. When the Mn of the ester wax is 700 or more, volatilization due to heat is reduced, and in-machine contamination is suppressed. The Mn is preferably 800 or more and 3000 or less. The Mn can be controlled by the ester wax synthesis conditions and the kind and amount of raw material monomers.
On the other hand, from the viewpoint of developability after standing in the high temperature and high humidity environment described above, it is preferable that the blooming of the wax from the inside of the toner is sufficiently small after standing in the high temperature and high humidity environment. When blooming is large, the toner becomes an agglomerate, and streak-like image defects, so-called “development streaks” tend to occur. Also, the blooming of the wax reduces the chargeability of the toner, the desired toner amount cannot be placed on the image, and the image density decreases. Hereinafter, in the present invention, developability is evaluated from the viewpoint of development streak and image density.

  Therefore, in granulating toner particles in an aqueous medium, it is important to form a shell with a polyester resin to enclose the wax inside the toner. That is, it is essential that the difference in interfacial tension with water when the polyester resin forming the shell and the ester wax are dissolved in styrene is large. By increasing the difference in interfacial tension, the ester wax is more easily included in the toner in the step of granulating in an aqueous medium. As described above, blooming of the ester wax from the inside of the toner after being left in a high temperature and high humidity environment is suppressed.

The toner of the present invention is a toner in which the above-described Xp and Xw satisfy the relationship of the following formula (1).
20.0 ≦ Xw−Xp (1)
When the above formula (1) is satisfied, the difference in interfacial tension between the polyester resin and the ester wax becomes appropriate. That is, when the above formula (1) is satisfied, the inclusion of the ester wax becomes better, so that blooming of the ester wax is suppressed and the developability of the toner becomes better. On the other hand, when the above formula (1) is not satisfied, ester wax is insufficiently encapsulated, blooming from the inside of the toner occurs, and the developability of the toner decreases. Xw-Xp is preferably 20 or more and 60 or less, and more preferably 30 or more and 50 or less. The Xw can be controlled by the kind and amount of the monomer for the synthesis condition of the ester wax. The Xp can be controlled by the polymerization conditions and monomer composition of the polyester resin.

Hereinafter, further preferred embodiments of the toner of the present invention will be described.
The ester wax used in the present invention is a divalent to hexavalent (more preferably trivalent to hexavalent) alcohol and aliphatic monocarboxylic acid ester, or a divalent to hexavalent (more preferably trivalent or more) ester. Hexavalent or less) carboxylic acid and aliphatic monoalcohol ester are preferred.
The above ester wax not only suppresses in-machine contamination by the toner, but also has a higher interfacial tension than monohydric alcohol and carboxylic acid esters, or monohydric carboxylic acid and aliphatic alcohol esters, It is easy to encapsulate inside the toner. Therefore, blooming of the ester wax from the inside of the toner is suppressed even after being left in a high temperature and high humidity environment, and the developability is improved.
The toner of the present invention preferably contains 1.0 to 20.0 parts by mass of ester wax with respect to 100.0 parts by mass of the polymerizable monomer. More preferably, it is 2.0 parts by mass or more and 15 parts by mass or less. When the content of the ester wax is in the above range, not only the developability of the toner is improved but also the low-temperature fixability is improved. This is because at 1.0 parts by mass or more, the plastic effect of the binder resin by the ester wax is good. On the other hand, when the amount is 20.0 parts by mass or less, the amount of the ester wax contained in the toner becomes an appropriate amount, so that sufficient embedding by the polyester resin is expressed, so that the developability of the toner is good. It will be a thing.

  The polyester resin preferably contains 0.10 mol% or more and 20.00 mol% or less of an isosorbide unit represented by the following structural formula (2) based on all monomer units used in the polyester resin. More preferably, the content is 15.0 mol% or less. The isosorbide unit has high hydrophilicity, and when it is in the above range, the interfacial tension of the polyester resin is lowered depending on the content. Developability is improved. The “monomer unit” refers to a reacted form of a monomer substance in a polymer.

The materials used for the toner of the present invention will be described below.
The polyester resin used in the present invention preferably uses isosorbide as an alcohol component, but the following can also be used as other alcohol components.
Examples of the dihydric alcohol component include 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) -Alkylene oxide adducts of bisphenol A such as hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane; ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene Glycol, 1,3-propylene glycol, 1,4-butanediol, neope Fats such as til glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol Group-based diols; bisphenol A such as bisphenol A and hydrogenated bisphenol A.

  Examples of the trivalent or higher alcohol component 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. Is mentioned.

Moreover, the following are mentioned as an acid component used in order to form a polyester resin.
Aromatic polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid and pyromellitic acid; 1 to 20 carbon atoms such as fumaric acid, maleic acid, adipic acid, succinic acid, dodecenyl succinic acid, octenyl succinic acid Aliphatic carboxylic acids of succinic acid substituted with an alkyl group of the above or an alkenyl group having 2 to 20 carbon atoms; anhydrides of these acids and alkyl (carbon number of 1 to 8) esters of these acids.
In the present invention, a conventionally known polyester resin may be used in combination with the polyester resin. In the toner of the present invention, the content of the polyester resin is preferably 1.0 part by mass or more and 30.0 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer.

The acid value of the polyester resin used in the present invention is preferably 0.5 mgKOH / g or more and 25.0 mgKOH / g or less. If the acid value is within the above range, good development durability and good chargeability can be easily obtained. It is considered that the optimum range as described above exists due to the balance between the wax encapsulation with the polyester resin and the chargeability due to the hygroscopic property.
In particular, in the present invention, the added polyester resin forms a shell on the surface of the toner particles. By making the acid value of a polyester resin into the said range, the effect of this invention becomes easy to express more and is preferable.

  Moreover, it is preferable that the interfacial tension Xp with water by the hanging drop method of a solution obtained by dissolving the polyester resin in styrene is 30.0 or more and 80.0 or less. If Xp is within the above range, good development durability is easily obtained. The above range is preferable because a polyester resin is formed on the toner surface in an aqueous medium and the wax is easily included.

Moreover, it is preferable that the weight average molecular weight (Mw) of the THF soluble part of the polyester resin measured by GPC is 5000 or more and 30000 or less. If Mw is within the above range, good development durability and good low-temperature fixability can be easily obtained. It is considered that the optimum range as described above exists with an appropriate molecular weight that does not hinder the encapsulation and fixing of the wax with the polyester resin.
In particular, in the present invention, the added polyester resin forms a shell on the surface of the toner particles. It is considered that by increasing the molecular weight of the polyester resin appropriately within a range that does not impair the fixability, it is possible to precipitate the wax moderately quickly in the course of the polymerization reaction and to facilitate the encapsulation of the wax.

The ester wax used in the present invention is preferably a divalent to hexavalent alcohol and aliphatic monocarboxylic acid ester, or a divalent to hexavalent carboxylic acid and aliphatic monoalcohol ester. The aliphatic monocarboxylic acid is a carboxylic acid having 16 to 25 carbon atoms, the aliphatic monoalcohol is preferably an alcohol having 16 to 25 carbon atoms, and the aliphatic monocarboxylic acid has 18 or more carbon atoms. It is a carboxylic acid having 22 or less, and the aliphatic monoalcohol is more preferably an alcohol having 18 to 22 carbon atoms.
Examples of the carboxylic acid include myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, mellicic acid, oleic acid, vaccenic acid, linoleic acid, and linolenic acid. It is done.
Examples of the divalent carboxylic acid include butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid), octanedioic acid (suberic acid), Nonanedioic acid (azelaic acid), decanedioic acid (sebacic acid), dodecanedioic acid, phthalic acid, isophthalic acid, terephthalic acid and the like can be mentioned.
Further, examples of the trivalent or higher carboxylic acid include trimellitic acid and pyromellitic acid.

Examples of the aliphatic monoalcohol include myristyl alcohol, cetanol, stearyl alcohol, aralkyl alcohol, behenyl alcohol, tetracosanol, hexacosanol, octacosanol, triacontanol and the like.
Examples of the divalent alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,10-decane. Diol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol, 1,20-eicosanediol, 1,30-triacontanediol, diethylene glycol, Dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, spiroglycol, 1,4-phenylene glycol, bisphenol A, hydrogenated bisphenol A, etc. Can be mentioned.
Furthermore, examples of trihydric or higher alcohols include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, diglycerin, and triglycerin.

  Examples of the carboxylic acid having 16 to 25 carbon atoms include stearic acid, oleic acid, vaccenic acid, linoleic acid, linolenic acid, eleostearic acid, tuberculostearic acid, arachidic acid, arachidonic acid, behenic acid, lignoserine. An acid, nervonic acid, etc. are mentioned. Examples of the alcohol having 16 to 25 carbon atoms include cetanol, 1-heptadecanol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, linoleyl alcohol, elide linoleyl alcohol, linolenyl alcohol, and eleido alcohol. Examples include norenyl alcohol, nonadecyl alcohol, arachidyl alcohol, heneicosanol, behenyl alcohol, lignoceryl alcohol, and the like.

The method for producing the toner of the present invention will be described below. It is essential that the toner of the present invention is produced by a suspension polymerization method. In this suspension polymerization method,
(1) Polymerizable monomer (2) Wax (3) Polyester resin Further, a polymerizable monomer composition is prepared by uniformly dissolving or dispersing a colorant, a crosslinking agent, a charge control agent and other additives as necessary. Prepare the product. This polymerizable monomer composition is preferably dispersed in an aqueous medium containing a dispersion stabilizer by using an appropriate stirrer to form particles of the polymerizable monomer composition in the aqueous medium. Then, preferably, a polymerization initiator is used to polymerize the polymerizable monomer contained in the particles of the polymerizable monomer composition to obtain toner particles having a desired particle size. . After completion of the polymerization, the toner of the present invention can be obtained by performing filtration, washing and drying by a known method, mixing a fluidity improver if necessary, and adhering it to the surface of the toner particles.

  When toner particles are produced by the suspension polymerization method, since the shape of each toner particle is almost spherical, the charge amount distribution is uniform. In addition, since the polymerizable monomer is suspended and polymerized in an aqueous medium, the respective materials are arranged in order of increasing polarity from the surface layer of the toner particles according to the polarity. Accordingly, the ester wax can be included by selectively allowing the polyester resin having a high polarity to be selectively present on the surface layer of the toner particles.

In the present invention, a vinyl monomer capable of radical polymerization is used as the polymerizable monomer used in producing the toner particles. As the vinyl monomer, a monofunctional monomer or a polyfunctional monomer can be used.
Monofunctional monomers include styrene; styrene derivatives such as α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene; methyl acrylate, ethyl Acrylic polymerizable monomers such as acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate Body; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n Methacrylic polymerizable monomers such as amyl methacrylate and n-hexyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate; And vinyl ethers such as ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone. The polymerizable monomer used in the present invention contains styrene. In addition to styrene, it preferably contains a styrene derivative or an acrylic polymerizable monomer.
In the present invention, the content of styrene in the polymerizable monomer is preferably 60% by mass or more and 90% by mass or less.

As polyfunctional monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, 2,2′-bis (4- (acryloxy-diethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene Glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentylglyco Dimethacrylate, 2,2'-bis (4- (methacryloxy-diethoxy) phenyl) propane, 2,2'-bis (4- (methacryloxy-polyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethanetetra Methacrylate, divinylbenzene, divinylnaphthalene, divinyl ether and the like can be mentioned.
In the present invention, in addition to styrene, the aforementioned monofunctional monomers can be used alone or in combination of two or more, or the aforementioned monofunctional monomers and polyfunctional monomers can be used in combination.

Examples of the polymerization initiator used for producing the toner of the present invention include an oil-soluble initiator and / or a water-soluble initiator, and the half-life at the reaction temperature during the polymerization reaction is 0.5 hours or more and 30 hours or less. Are preferably used. Further, when the polymerization reaction is carried out at an addition amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer, a polymer having a maximum between usually 10,000 and 100,000 is obtained. And toner particles having appropriate strength and melting characteristics can be obtained.
As polymerization initiators, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), Azo or diazo polymerization initiators such as 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; benzoyl peroxide, t-butylperoxy 2-ethylhexano Ate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoylper Peroxide polymerization initiators such as oxide and lauroyl peroxide Can be illustrated.
In the present invention, in order to control the degree of polymerization of the polymerizable monomer, a known chain transfer agent, polymerization inhibitor or the like can be further added and used.

Examples of the colorant used in the present invention include a black colorant, a yellow colorant, a magenta colorant, and a cyan colorant.
An example of the black colorant is carbon black.
Examples of the yellow colorant include compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, the following C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 128, 129, 138, 147, 150, 151, 154, Examples include 155, 168, 180, 185, 214 and the like.

Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, the following C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. Pigment Bio Red 19 and the like can be exemplified.
Examples of cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like. Specifically, C.I. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66, and the like.
These colorants can be used alone or in combination and further in the form of a solid solution. The colorant is selected from the viewpoints of hue angle, saturation, lightness, light resistance, OHP transparency, and dispersibility in toner particles. These colorants are preferably used in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

Further, the toner of the present invention can use a magnetic material as a black colorant. Examples of the magnetic material include magnetite, hematite, and ferrite. When a magnetic material is used as the black colorant, it is preferable to use a magnetic material whose surface has been subjected to a hydrophobic treatment. Examples of the hydrophobizing agent used at this time include a silane coupling agent and a titanium coupling agent.
The magnetic material preferably has a number average particle diameter of 2 μm or less, more preferably 0.1 μm or more and 0.5 μm or less. These magnetic materials are preferably used in an amount of 40 to 150 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

The toner of the present invention may contain a charge control agent in order to stabilize charging characteristics. As the charge control agent, known ones can be used, in particular, the charging speed is fast and a constant charge amount can be stably maintained, the polymerization inhibition property is low, and the solubilized product in the aqueous dispersion medium is substantially reduced. No charge control agent is preferred. Specific compounds include, as negative charge control agents, metal compounds of aromatic carboxylic acids such as salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid, metal salts or metal complexes of azo dyes or azo pigments, boron Compound, silicon compound, calixarene and the like can be mentioned. 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, a nigrosine compound, and an imidazole compound.
These charge control agents are used in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

A dispersion stabilizer is added to the aqueous medium. Examples of inorganic compounds used as a dispersion stabilizer include calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, Examples thereof include barium sulfate, bentonite, silica, and alumina. Examples of the organic compound include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, carboxymethyl cellulose sodium salt, polyacrylic acid and its salt, starch and the like. These dispersion stabilizers are preferably used in an amount of 0.2 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer.
When an inorganic compound is used as the dispersion stabilizer, a commercially available product may be used as it is. However, in order to obtain finer particles, the above inorganic compound may be generated and used in an aqueous medium.
For example, in the case of calcium phosphate, fine calcium phosphate can be produced by adding an aqueous sodium phosphate solution and an aqueous calcium chloride solution to an aqueous medium under high stirring.

Furthermore, in the toner of the present invention, a fluidity improver may be added to the toner particles for the purpose of improving the fluidity of the toner particles. Flowability improvers include: vinylidene fluoride fine powder, fluorine-based resin powder such as polytetrafluoroethylene fine powder; fatty acid metal salts such as zinc stearate, calcium stearate and lead stearate; titanium oxide powder, aluminum oxide Powder, metal oxide such as zinc oxide powder, or powder obtained by hydrophobizing the above metal oxide; and silica fine particles such as wet-process silica and dry-process silica, or silane coupling agents and titanium couplings on these silicas Examples thereof include surface-treated silica fine particles that have been surface-treated with a treating agent such as an agent and silicone oil.
The fluidity improver is preferably added in an amount of 0.01 parts by weight to 5.0 parts by weight with respect to 100 parts by weight of the toner particles. If the addition amount is within the above range, a sufficient fluidity improving effect can be obtained while suppressing a decrease in fixing property. The fluidity improver preferably has a number average particle diameter (D1) of primary particles of 4 nm or more and 120 nm or less.

The image forming method of the present invention is an image forming method having a developing step of developing the electrostatic latent image formed on the electrostatic latent image carrier using toner with a developing device to form a toner image,
The developing device
A developing chamber having a toner carrier, and a toner supply member arranged to form a contact portion with the toner carrier;
A toner storage chamber,
The rotation directions of the toner carrier and the toner supply member are the same in the respective contact portions on the respective surfaces,
The amount of penetration of the toner supply member into the toner carrier at the contact portion is 0.3 mm or more and 1.5 mm or less,
The peripheral speed of the toner supply member at the contact portion is 110% or more and 250% or less with respect to the peripheral speed of the toner carrier,
An image forming method using the toner as the toner.

Hereinafter, an example of an image forming apparatus to which the image forming method of the present invention is applied will be described in more detail, but this does not limit the present invention.
FIG. 1 is a schematic cross-sectional view of an image forming apparatus 100 to which the image forming method of the present invention can be applied. The image forming apparatus 100 is a full-color laser printer that employs an inline method or an intermediate transfer method, and can form a full-color image on a recording material in accordance with image information.
The image forming apparatus 100 includes, as a plurality of image forming units, first, second, and third images for forming yellow (Y), magenta (M), cyan (C), and black (K) images, respectively. And fourth image forming units SY, SM, SC, and SK. In the present embodiment, the first to fourth image forming units SY, SM, SC, and SK are arranged in a line in a direction that intersects the vertical direction.
In the following example, the configurations and operations of the first to fourth image forming units SY, SM, SC, and SK are substantially the same except that the colors of the images to be formed are different. Therefore, in the following, unless there is a particular distinction, the subscripts Y, M, C, and K given to the reference numerals to indicate that they are elements provided for any color are omitted, and generally explain.

The image forming apparatus 100 includes, as a plurality of image carriers, four drum-type electrophotographic photoreceptors, that is, the photoreceptor drums 1 arranged in parallel in a direction intersecting the vertical direction. The photosensitive drum 1 is rotationally driven by a driving means (drive source) (not shown) in the direction indicated by an arrow A (clockwise). Around the photosensitive drum 1, a charging roller 2 as a charging means for uniformly charging the surface of the photosensitive drum 1, a laser is irradiated based on image information, and an electrostatic image (electrostatic) is formed on the photosensitive drum 1. A scanner unit (exposure device) 3 is disposed as exposure means for forming a (latent image). Further, around the photosensitive drum 1, a developing unit (developing device) 4 as developing means for developing an electrostatic image as a toner image, toner remaining on the surface of the photosensitive drum 1 after transfer (transfer residual toner) A cleaning member 6 is disposed as a cleaning means for removing water. Further, an intermediate transfer belt 5 as an intermediate transfer body for transferring the toner image on the photosensitive drum 1 to the recording material 12 is disposed opposite to the four photosensitive drums 1.
The developing unit 4 uses toner of a non-magnetic one-component developer as a developer, and performs reverse development by bringing a developing roller (described later) as a developer carrying member into contact with the photosensitive drum 1. That is, the developing unit 4 is a portion (image portion, exposure portion) in which the charge is attenuated by exposure on the photosensitive drum 1 with toner charged to the same polarity (negative polarity in this embodiment) as the charging polarity of the photosensitive drum 1. ) To develop the electrostatic image.

Next, the overall configuration of the process cartridge 7 attached to the image forming apparatus 100 will be described. In the present invention, it is preferable to use a process cartridge 7 having substantially the same configuration and operation except for the type (color) of toner contained therein.
FIG. 2 is a schematic cross-sectional view (main cross-sectional view) of the process cartridge 7 as viewed along the longitudinal direction (rotational axis direction) of the photosensitive drum 1. The posture of the process cartridge 7 in FIG. 2 is a posture in a state where the process cartridge 7 is mounted on the image forming apparatus main body. When the positional relationship and direction of each member of the process cartridge are described below, the positional relationship and direction in this posture are described below. Etc.
The process cartridge 7 is configured by integrating a photosensitive unit 13 including the photosensitive drum 1 and the developing unit 4 including a developing roller 17 and the like.

In the photoconductor unit 13, a cleaning member 6 and a charging roller 2 are disposed so as to contact the circumferential surface of the photoconductor drum 1. The transfer residual toner removed from the surface of the photosensitive drum 1 by the cleaning member 6 falls and is stored in the cleaning frame 14.
The charging roller 2 as charging means is driven to rotate by bringing the roller portion of conductive rubber into pressure contact with the photosensitive drum 1.
Here, as a charging process, a predetermined DC voltage is applied to the core of the charging roller 2 with respect to the photosensitive drum 1, whereby a uniform dark portion potential (Vd) is applied to the surface of the photosensitive drum 1. Is formed. The spot pattern of the laser beam emitted in accordance with the image data by the laser beam from the scanner unit 3 described above exposes the photosensitive drum 1, and the exposed portion is charged on the surface by the carrier from the carrier generation layer. Disappears and the potential drops. As a result, an electrostatic latent image is formed on the photosensitive drum 1 with a predetermined light portion potential (Vl) at an exposed portion and a predetermined dark portion potential (Vd) at an unexposed portion.

On the other hand, the developing unit 4 has a developing chamber in which a developing roller 17 as a toner carrying member for carrying toner 80 and a toner supply roller 20 as a supply member for supplying toner to the developing roller 17 are arranged. Yes.
A stirring and conveying member 22 is provided in the toner storage chamber 18. The agitating and conveying member 22
In addition to stirring the toner stored in the toner storage chamber 18, the toner is transported toward the upper portion of the toner supply roller 20 in the direction of arrow G in the figure.

The developing blade 21 is disposed below the developing roller 17 and is in contact with the developing roller at a counter, and regulates the coating amount of toner supplied by the toner supply roller 20 and applies a charge. The developing blade 21 uses, for example, a thin plate made of SUS having a thickness of 0.1 mm, forms contact pressure by utilizing the spring elasticity of the thin plate, and its surface contacts the toner and the developing roller 17. Is done.
The toner is triboelectrically charged by rubbing between the developing blade 21 and the developing roller 17 to be charged, and at the same time the layer thickness is regulated. A predetermined voltage was applied to the developing blade 21 from a blade bias power source (not shown). By applying this voltage, the toner coat layer is stabilized.
The developing roller 17 and the photosensitive drum 1 rotate so that the surfaces of the developing roller 17 and the photosensitive drum 1 move in the same direction (the direction from bottom to top in FIG. 2). The toner charged negatively by frictional charging with respect to a predetermined DC bias applied to the developing roller 17 is transferred only to the bright portion potential portion from the potential difference in the developing portion contacting the photosensitive drum 1 and statically. Visualize the electrostatic latent image.

The surfaces of the toner supply roller 20 and the developing roller 17 are rotated in the same direction at the contact portion N. In FIG. 2, the toner supply roller 20 rotates in the direction of the arrow E (clockwise) and the developing roller 17 rotates in the direction of the arrow D (counterclockwise). As a result, the load on the toner can be reduced, and high image quality can be maintained even during long-term use. The toner supply roller 20 is, for example, an elastic sponge roller in which a foam layer is formed on the outer periphery of a conductive metal core. The toner supply roller 20 and the developing roller 17 are in contact with each other with a predetermined intrusion amount, that is, the indentation amount ΔE in which the toner supply roller 20 is recessed by the developing roller 17. The intrusion amount is set to 0.3 mm or more and 1.5 mm or less from the balance between the peelability of the development residual toner and the load on the toner.
The toner supply roller 20 and the developing roller 17 are rotated with a peripheral speed difference in the same direction at the abutting portion N. With this operation, the toner supply roller 20 and the toner supply to the developing roller 17 are separated from each other. Is going. At this time, the toner supply amount to the developing roller can be adjusted by adjusting the potential difference between the toner supply roller and the developing roller. The peripheral speed of the supply roller (supply member) at the contact portion is 110% to 250% with respect to the peripheral speed of the developing roller (toner carrier), and a DC bias is applied to the toner supply roller. .

Hereinafter, details of the toner supply roller suitably used in the image forming method of the present invention will be described.
The toner supply roller 20 in FIG. 2 includes, for example, a conductive support and a foam layer supported by the conductive support. Specifically, a foamed urethane layer 20b is provided as a foam layer composed of a cored bar electrode 20a as a conductive support and an open cell body (open cell) in which bubbles are connected to the periphery thereof, It rotates in the direction of E in the figure. A large amount of toner can enter the inside of the toner supply roller 20 by using urethane on the surface layer as an open cell body. The surface cell diameter of the toner supply roller 20 is preferably 50 μm or more and 1000 μm or less.

Here, the cell diameter means the average diameter of the foamed cells having an arbitrary cross section. First, the area of the foamed cell that is the maximum is measured from the enlarged image of the arbitrary cross section, and the maximum cell diameter is converted from this area by converting the equivalent circle diameter. Get. And after deleting the foam cell which is 1/2 or less of this maximum cell diameter as noise, it points out the average value of each cell diameter converted similarly from the remaining individual cell area.
As described above, the image forming method of the present invention can reduce the load on the toner by rotating the toner supply roller and the developing roller in the same direction, and can maintain high image quality even during long-term use. it can.
According to the image forming apparatus to which the image forming method of the present invention is applied, since the physical load on the toner is reduced, the generation of toner agglomerates is suppressed and development streaks are less likely to occur.

The measurement method will be described below.
<Measurement of number average molecular weight (Mn) of ester wax>
The molecular weight of the ester wax can be measured by high temperature gel permeation chromatography (GPC).
As a specific method, 0.03 g of ester wax was added to o-dichlorobenzene for gel chromatography, and special grade 2,6-di-t-butyl-4-methylphenol (BHT) was added at a concentration of 0.10 wt / vol%. And dissolve at room temperature. The wax and o-dichlorobenzene to which the above BHT is added are put into a sample bottle and heated on a hot plate set at 150 ° C. to dissolve the wax. Once the wax has melted, place it in a preheated filter unit and place it on the body. The sample that has passed through the filter unit is used as a GPC sample. The sample solution is adjusted so that the concentration is about 0.15% by mass. Using this sample solution, measurement is performed under the following conditions.
[Analysis conditions]
Apparatus: HLC-8121GPC / HT (manufactured by Tosoh Corporation)
Detector: RI for high temperature
Column: TSKgel GMHHR-H HT 2 series (manufactured by Tosoh Corporation)
Temperature: 135.0 ° C
Solvent: o-dichlorobenzene for gel chromatography (BHT added at 0.10 wt / vol%)
Flow rate: 1.0 ml / min
Injection volume: 0.4ml
In calculating the molecular weight of the wax, a standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F— 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation), and a molecular weight calibration curve is used.

<Measurement of interfacial tension of polyester resin and ester wax with water by the hanging drop method>
The interfacial tension was measured by the hanging drop method described below. Specifically, using a FACE solid-liquid interface analyzer Drop Master 700 manufactured by Kyowa Interface Science Co., Ltd. under an environment of a temperature of 60 ° C., measurement was performed with WIDE 1 as a field of view of the lens portion. First, styrene or a sample styrene solution from which the tip portion of a narrow tube with an inner diameter of 0.4 mm in the vertical direction using a forward needle is degassed is added.
Next, the thin tube is connected to the syringe part. Ion exchange water is put into the syringe part. In the measurement method of the present invention, the sample concentration dissolved in styrene was 4.76% by mass. Next, the syringe part is connected to AUTO DISPENSER AD-31 manufactured by Kyowa Interface Science Co., Ltd., and ion-exchanged water is pushed out of the capillary tube to create a droplet at the tip of the capillary tube in styrene or a sample styrene solution. it can. Then, the interfacial tension with water is calculated from the shape of the droplet. The control and calculation method for creating droplets was performed using a measurement analysis system manufactured by Kyowa Interface Science Co., Ltd. The measurement method was interfacial tension measurement (hanging drop method), and the analysis method was ds / de method. The density difference between water and the styrene solution necessary for the calculation was set to 0.1 g / cm ³ , which is the density difference between water and styrene. The final measurement result of the interfacial tension was the average value of 10 measurements.

<Structural analysis of polyester resin>
The structure of the polyester resin can be determined using a nuclear magnetic resonance apparatus ( ¹ H-NMR, ¹³ C-NMR) and an FT-IR spectrum. The apparatus used below will be described.
The measurement sample may be collected by analyzing from the toner and analyzed.
(I) ¹ H-NMR, ¹³ C-NMR
FT-NMR JNM-EX400 manufactured by JEOL (solvent: heavy chloroform)
(Ii) FT-IR spectrum Thermo Fisher Scientific Inc. Made AVATAR360FT-IR

<Method of measuring acid value of polyester resin>
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 polyester 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% by volume), 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% by volume) 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 pulverized polyester resin sample 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).

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

  The present invention will be specifically described with reference to the following examples. In this embodiment, all are based on mass unless otherwise specified.

<Ester wax>
As the ester wax, those shown in Table 1 below were prepared.

<Manufacture of amorphous polyester resin P1>
In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, a dehydration tube, and a decompression device, 100.0 parts by mass of raw material monomers shown in Table 2 other than trimellitic anhydride were mixed and stirred while stirring. Heated to ° C. Thereafter, 0.52 parts by mass of di (2-ethylhexanoic acid) tin was added as an esterification catalyst, the temperature was raised to 200 ° C., and polycondensation was performed over 6 hours. Furthermore, trimellitic anhydride was added at a molar ratio shown in Table 2, and a condensation reaction was performed under a reduced pressure of 40 kPa until Mw became 16000 to obtain amorphous polyester resin P1. Table 2 shows the physical properties of the obtained amorphous polyester resin P1.

<Production of amorphous polyester resins P2 to P7>
Amorphous polyester resins P2 to P7 were produced in the same manner as in the production of the amorphous polyester resin P1, except that the molar ratio of the raw material monomers was changed to the ratio shown in Table 2.

In addition, the isosorbide in a table | surface is a compound represented by the structure of following formula (3).

  In the table, TPA is terephthalic acid, IPA is isophthalic acid, TMA is trimellitic anhydride, BPA (PO) is bisphenol A propylene oxide 2 mol adduct, and BPA (EO) is bisphenol A ethylene oxide 2 mol adduct. The product, EG, represents ethylene glycol. Moreover, the isosorbide unit in a table | surface is a structure shown by the said Formula (2).

<Toner Production Example 1>
(Dispersion medium)
To 1000 parts by mass of ion-exchanged water in the reaction vessel, 14 parts by mass of sodium phosphate and 4.5 parts by mass of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), while stirring at 12000 rpm, an aqueous solution of calcium chloride in which 8 parts by mass of calcium chloride is dissolved in 10 parts by mass of ion-exchanged water is added and dispersed. An aqueous medium containing a stabilizer was prepared. The pH of the adjusted aqueous medium was 5.5.

(Polymerizable monomer composition)
-Styrene 60.0 parts by mass-Pigment Blue 15: 3 6.0 parts by mass-Charge control agent (Orient: Bontron E-88) 0.5 parts by mass Attritor (Mitsui Miike Chemical Co., Ltd.) Was further dispersed at 220 rpm for 5 hours using zirconia particles having a diameter of 1.7 mm.
To this dispersion, 15.0 parts by mass of styrene, 25.0 parts by mass of n-butyl acrylate, 5.0 parts by mass of ester wax E1 (dibehenyl sebacate), 6.0 parts by mass of amorphous polyester resin P1 were added. A polymerizable monomer composition was obtained.
The above polymerizable monomer composition was kept at 65 ° C. in a separate container, and uniformly dissolved and dispersed at 500 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). In this, 11.0 mass parts of polymerization initiator perhexyl PV (made by NOF Corporation) was melt | dissolved, and it injected into the said aqueous medium. The mixture was stirred at 10000 rpm for 5 minutes with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) under a N ₂ purge at 65 ° C. and granulated at pH 5.5. Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 65 ° C. for 6 hours, further to 90 ° C., and reacted for 6 hours.
After completion of the polymerization reaction, the suspension was cooled to room temperature, and the dispersion stabilizer was dissolved while stirring for 2 hours in a state of adding pH 2 to 10% hydrochloric acid. Thereafter, the suspension was filtered under pressure and further washed with 2000 parts by mass of ion-exchanged water. The obtained cake was returned to 1000 parts by mass of ion-exchanged water and stirred for 2 hours with 10% hydrochloric acid added to a pH of 1 or less. The suspension was filtered under pressure in the same manner as described above, further washed with 2000 parts by mass of ion exchange water, and sufficiently ventilated. Then, it dried in a 40 degreeC hot-air dryer. Further, air classification was performed to remove fine powder and coarse powder, and toner particles 1 having a weight average particle diameter (D4) of 7.0 μm were obtained.
Hydrophobic silica fine particles (primary particle number average diameter (D1): 7 nm, surface-treated with 20% by mass of dimethyl silicone oil based on 10% by mass of toner particles based on 100.0 parts by mass of the toner particles) 1.5 parts by mass and hydrophobic titanium oxide fine particles (number average diameter (D1) of primary particles: 50 nm, surface-treated with 15.0% by mass of isobutyltrimethoxysilane) 0.3 part by mass Added. These were mixed for 15 minutes at a stirring speed of 3000 rpm using a Mitsui Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.) to obtain toner 1.

<Toner Production Examples 2 to 4>
C. of Toner Production Example 1 I. Pigment Blue 15: 3, C.I. I. Pigment yellow 93, C.I. I. Toners 2 to 4 were obtained in the same manner except that they were changed to CI Pigment Red 269 or Carbon Black.

<Toner Production Examples 5 to 17>
As shown in Table 3, toners 5 to 17 were obtained in the same manner as in the toner 1 production method, except that the type of ester wax, the amount of ester wax added, and the type of polyester resin were changed.

<Example 1>
Toner 1 was evaluated for the following items.

<In-flight contamination>
Using a commercially available laser beam printer HP LaserJet Pro 400 Color M451dn (manufactured by HP) modified as described below, a durability test of 200,000 sheets was performed. As conditions for remodeling the printer, the process speed in the plain paper mode was changed to 360 mm / sec, the process speed in the thick paper mode was changed to 90 mm / sec, and the fixing temperature control was set to 200 ° C. The durability evaluation chart is an original chart with a color printing rate of 5% (full color printing rate of 20%). Each time the yellow, magenta, cyan and black stations are loaded with cartridges refilled with toner 1, each time the toner runs out The cartridge was replaced and printing continued.
Durability test conditions are normal under high temperature and high humidity environment (30 ° C, 80% RH), normal temperature and normal humidity environment (23 ° C, 50% RH), and low temperature and low humidity environment (15 ° C, 10% RH). Repeat the pattern of passing 8,000 sheets of paper with a basis weight of 68 g / m ² (A4 size) in the paper mode and 2,000 sheets of paper with a basis weight of 220 g / m ² (LETTER size) in the thick paper mode. A total of 200,000 print tests were conducted.
The state of contamination around the fixing device after endurance was visually evaluated according to the following criteria.
The evaluation results are shown in Table 4.
A: There is no noticeable contamination around the fixing device.
B: A small amount of contamination is observed around the fixing device.
C: The spread of contamination is clearly observed in the fixing guide portion.

The toner was evaluated by modifying a commercially available laser printer LBP-7700C (manufactured by Canon) and a toner cartridge 323 (cyan) (manufactured by Canon) as a process cartridge and conducting a durability test. The process speed was 240 mm / sec.
This modified cartridge was modified so that each surface of the toner supply roller moved in the same direction at the contact portion with the developing roller by changing / adding the gear inside the cartridge. The amount of penetration of the toner supply roller into the developing roller was 1.1 mm, and the toner supply roller was adjusted so that the peripheral speed based on the developing roller was 160%. The product toner was extracted from the inside of the cartridge, cleaned by air blow, and then filled with 160 g of toner 1 of the present invention. Then, by evaluating the image density and development streaks after being left in a high-temperature and high-humidity environment by the following method, the developability was evaluated.
A cartridge filled with the toner 1 of the present invention, which was left in a high temperature and high humidity environment (40 ° C., 90% RH) for 72 hours, was mounted on the LBP-7700C in a normal temperature and normal humidity environment (23 ° C., 60% RH). Three solid images were output on paper (trade name: “GF-C081”, 81.4 g / m ² , manufactured by Canon Inc.). In addition, one halftone image was output. Thereafter, 20000 images with a printing rate of 1% were output. Further, a solid image and a halftone image were output in the same manner as described above. Image density and development streak were evaluated according to the following criteria for all solid images and halftone images obtained at the initial stage and after outputting 20000 sheets. The evaluation results are shown in Table 4.

(Image density)
Evaluation was made based on the image density of the solid portion. For measurement of the image density, a “Macbeth reflection densitometer RD918” (manufactured by Macbeth) was used to measure a relative density with respect to a printout image of a white background portion having a document density of 0.00.
A: 1.40 or more B: 1.30 or more and less than 1.40 C: 1.20 or more and less than 1.30 D: 1.15 or more and less than 1.20 E: less than 1.15

(Development stripe)
Evaluation was made based on the number of development lines appearing on the halftone image.
A: Not generated B: 1 or more and 3 or less C: 4 or more and 6 or less D: 7 or more or streaks with a width of 0.5 mm or more

<Preservation test>
In order to evaluate stability during storage, blocking resistance was evaluated. About 5 g of toner 1 was put in a 100 ml polycup and allowed to stand for 3 days at 55 ° C. in a 5% RH environment. The degree of aggregation of the toner was measured as follows and evaluated according to the following criteria.
As the measuring apparatus, a “powder tester” (manufactured by Hosokawa Micron Co., Ltd.) having a vibration table side surface portion connected with a digital display vibrometer “Digivibro MODEL 1332A” (manufactured by Showa Keiki Co., Ltd.) was used. Then, a sieve having a mesh size of 38 μm (400 mesh), a sieve having a mesh size of 75 μm (200 mesh), and a sieve having a mesh size of 150 μm (100 mesh) were stacked in this order on the vibrating table of the powder tester. The measurement was performed as follows in an environment of 23 ° C. and 60% RH.
(1) The vibration width of the vibration table was adjusted in advance so that the displacement value of the digital display vibrometer was 0.60 mm (peak-to-peak).
(2) After the toner left for 3 days as described above is left to stand for 24 hours in an environment of 23 ° C. and 60% RH in advance, 5.0 g is precisely weighed and gently placed on a sieve having an opening of 150 μm. I put it.
(3) After vibrating the sieve for 15 seconds, the mass of toner remaining on each sieve was measured, and the degree of aggregation was calculated based on the following equation.
Aggregation degree (%) =
{(Sample mass (g) on a sieve having an opening of 150 μm) /5.0 (g)} × 100
+ {(Sample mass (g) on a sieve having an opening of 75 μm) /5.0 (g)} × 100 × 0.6
+ {(Sample mass (g) on a sieve having an opening of 38 μm) /5.0 (g)} × 100 × 0.2
The evaluation criteria are as follows.
A: Aggregation degree is less than 20% (heat resistance is particularly excellent)
B: Aggregation degree is 20% or more and less than 30% (excellent heat resistance)
C: Aggregation degree is 30% or more and less than 40% (no problem in use in heat resistance)
D: Aggregation degree is 40% or more (inferior in heat resistance and problematic in use)

<Fixability test>
A commercially available laser printer LBP-7700C (manufactured by Canon) and a process cartridge toner cartridge 323 (cyan) (manufactured by Canon) were modified for fixing property evaluation, and a fixing rubbing test was performed.
A 10 mm × 10 mm 3 dot 3 space (600 dpi) image for density measurement, adjusted to 0.6 mg / cm ² toner mass per unit area on A4 copier plain paper (105 g / m ² ). The fixed image thus obtained was rubbed five times with sylbon paper applied with a weight of 50 g / cm ² , and the reduction rate of the image density after the rub was evaluated based on the following. When outputting the image, the gear and software of the evaluator main body were changed so that the process speed was 330 mm / sec, and the fixing temperature was set to 160 ° C.
The image density is measured using a Macbeth reflection densitometer (manufactured by Macbeth Co., Ltd.). The relative density with respect to the printout image of the white background portion where the document density is 0.00 is measured, and the reduction rate of the image density after rubbing Was calculated.
A: Less than 2.0% B: 2.0% or more and less than 5.0% C: 5.0% or more and less than 10.0% D: 10.0% or more

<Examples 2-15, Comparative Examples 1-2>
In the same manner as in Example 1, toners 2 to 17 were evaluated. The evaluation results are shown in Table 4.

1: photosensitive drum, 2: charging roller, 3: scanner unit, 4: developing unit, 5: intermediate transfer belt, 6: cleaning member, 7: process cartridge, 8: primary transfer roller, 9: secondary transfer roller, 10: fixing device, 11: intermediate transfer belt cleaning device, 12: recording material, 13: photoconductor unit, 14: cleaning frame,
15: development chamber, 17: development roller (toner carrier), 18: toner storage chamber, 20: toner supply roller (toner supply member), 20a: cored bar electrode, 20b: foamed urethane layer, 21: development blade, 22 : Stirring transport member, 30a-b: development opening, 51: drive roller, 52: secondary transfer counter roller, 53: driven roller, 80: toner, 100: image forming apparatus, 100A: image forming apparatus main body

Claims (6)

Particles of a polymerizable monomer composition containing a polymerizable monomer, an ester wax and a polyester resin are formed in an aqueous medium, and the polymerizable monomer contained in the particles of the polymerizable monomer composition A toner having toner particles obtained by polymerizing a body,
The polymerizable monomer includes styrene,
The number average molecular weight (Mn) of the o-dichlorobenzene soluble matter of the ester wax measured by high temperature gel permeation chromatography (GPC) is 700 or more,
Xp (mN / m) is the interfacial tension of the solution obtained by dissolving the polyester resin in styrene with water by the hanging drop method, and the interfacial tension with water by the hanging drop method of the solution obtained by dissolving the ester wax in styrene. Is a toner satisfying the relationship of the following formula (1), where Xw (mN / m).
20 ≦ Xw−Xp (1)   The toner according to claim 1, wherein the ester wax is an ester of a divalent to hexavalent alcohol and an aliphatic monocarboxylic acid, or a divalent to hexavalent carboxylic acid and an aliphatic monoalcohol ester.   The toner according to claim 1, wherein a content of the ester wax is 1.0 part by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer. The polyester resin contains 0.10 mol% or more and 20.00 mol% or less of an isosorbide unit represented by the following structural formula (2) based on all monomer units used in the polyester resin. The toner according to item.

In an image forming method including a developing step of developing an electrostatic latent image formed on an electrostatic latent image carrier using toner with a developing device,
The developing device
A developing chamber having a toner carrier and a toner supply member arranged to form a contact portion with the toner carrier;
A toner storage chamber,
The rotation directions of the toner carrier and the toner supply member are the same in the respective contact portions on the respective surfaces,
The amount of penetration of the toner supply member into the toner carrier at the contact portion is 0.3 mm or more and 1.5 mm or less,
The peripheral speed of the toner supply member at the contact portion is 110% or more and 250% or less with respect to the peripheral speed of the toner carrier,
An image forming method, wherein the toner is the toner according to claim 1. A step of preparing a polymerizable monomer composition containing a polymerizable monomer, an ester wax and a polyester resin;
Forming the particles of the polymerizable monomer composition in an aqueous medium, and polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition;
A method for producing a toner comprising:
The polymerizable monomer includes styrene,
The number average molecular weight (Mn) of the o-dichlorobenzene soluble matter of the ester wax measured by high temperature gel permeation chromatography (GPC) is 700 or more,
Xp (mN / m) is the interfacial tension of the solution obtained by dissolving the polyester resin in styrene with water by the hanging drop method, and the interfacial tension with water by the hanging drop method of the solution obtained by dissolving the ester wax in styrene. Wherein Xw (mN / m) satisfies the relationship of the following formula (1).
20 ≦ Xw−Xp (1)

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