JP6624853B2 - toner - Google Patents

Description

  The present invention relates to a toner used in an electrophotographic image forming method for developing an electrostatic image.

  2. Description of the Related Art In recent years, a copying machine or a printer has been required to be able to obtain a stable image under any environment in addition to miniaturization, high speed, and long life (a stable image can be obtained over a long period of time).

  In order to meet such a demand, a toner using a titanium oxide external additive having an action of reducing a charging environment difference has been proposed. For example, a toner using an external additive containing titanium oxide surface-treated with a silane compound or a coupling agent has been proposed (Patent Document 1). Further, for the purpose of further improving the chargeability under high temperature and high humidity, a toner using an external additive containing titanium oxide surface-treated with a fluorine atom-containing silane compound has been proposed (Patent Document 2). Among them, Patent Literature 2 describes that the use of an external additive containing titanium oxide surface-treated with a silane compound containing a fluorine atom, which is a high negative component, improves the rising property of charging. Further, it is described that the phenomenon that the density at the image front end in the initial solid image becomes lighter (hereinafter, referred to as lighter front end density) can be suppressed by improving the rising property of charging.

  However, in recent years, there has been an even greater demand for a toner having excellent charge stability and high durability, which has an excellent charge rising property from the beginning and can suppress an excessive increase in charge amount even in a low-temperature and low-humidity environment. I have.

Japanese Patent No. 3754909 Japanese Patent No. 4310146

  An object of the present invention is to provide a toner that can stably maintain a high charge amount even in a low-temperature and low-humidity environment, has excellent durability, and can maintain high image quality.

  The above problem can be solved by the following toner.

That is, the present invention provides a toner particle having a core containing a binder resin and a colorant, and a shell containing a polyester resin A present on the surface of the core,
External additive A,
A toner containing
The polyester resin A has a dielectric loss tangent at 25 ° C. and 10,000 Hz of 0.0070 or more and 0.0140 or less,
The toner contains 1.0 to 20.0 parts by mass of the polyester resin A with respect to 100.0 parts by mass of the binder resin,
The toner according to claim 1, wherein the external additive A is a titanium oxide surface-treated with a silane compound containing a fluorine atom.

  ADVANTAGE OF THE INVENTION According to this invention, the toner which can maintain high image quality in long-term use regardless of environment can be provided.

FIG. 4 is a schematic diagram of a low-end image density.

  In the present invention, by appropriately controlling the dielectric loss tangent of the polyester resin A present in the shell layer of the toner particles, the charge leakage property is improved, and the charge-up under low temperature and low humidity can be suppressed. This makes it possible to obtain excellent charge rising properties of the external additive A while suppressing charge-up.

[External additives]
The external additive A of the present invention is titanium oxide fine particles surface-treated with a silane compound containing a fluorine atom.

  Since the surface of the external additive of such titanium oxide fine particles is treated with a treating agent containing a fluorine atom having a strong negative component charge, the rising of charging is improved. As a result, the initial tip concentration can be reduced.

  On the other hand, the use of the external additive A also increases the absolute amount of charging. For this reason, adverse effects such as poor regulation due to charge-up are likely to occur, and this tendency becomes remarkable in a low-temperature and low-humidity environment when used as a one-component toner. The present inventor has found an effective means for solving this problem, and this means will be described in the section of toner particles.

  The treatment with the silane compound used in the external additive A of the present invention may be performed, for example, by reacting the silane compound with a hydroxyl group present on the surface of the untreated fine particles using the silane compound, and replacing the hydroxyl group with a siloxyl group or the like. Achieved. As a method, a dry process in which a vaporized silane compound is reacted with a cloud of fine particles by stirring or the like; a wet process in which the fine particles are dispersed in a solvent and a silane compound diluted with an appropriate solvent is added dropwise if necessary. Processing can be performed by a generally known method such as processing.

  Examples of the silane compound containing a fluorine atom for performing a surface treatment on the external additive A of the present invention include 3,3,3, -trifluoropropyltrimethoxysilane, trimethoxyfluorosilane, and the like. Further, it can be used in combination with a silane compound containing no fluorine atom or a coupling agent other than those described above. Examples include isobutyltrimethoxysilane, octyltrimethoxysilane, vinyltrimethoxysilane, dimethyldichlorosilane, trimethylchlorosilane, allyldimethylchlorosilane, hexamethyldisilazane, and the like.

  The treatment amount of the fluorine-containing silane compound is preferably 1 to 25%, more preferably 2 to 20%, based on the mass of the external additive A.

  The external additive A is preferably added in an amount of 0.01 to 2.00 parts by mass, more preferably 0.05 to 1.00 parts by mass, based on 100 parts by mass of the toner particles. It is.

  In the present invention, the degree of hydrophobicity of the external additive A is from 20 to 70%, preferably from 25 to 65%, from the viewpoint of obtaining a stable triboelectric charge.

  The degree of hydrophobicity in the present invention is defined by a “methanol titration test”.

  Specifically, 0.2 g of inorganic fine particles is added to 50 ml of water in a 250 ml Erlenmeyer flask. Methanol is titrated from the buret until the entire amount of inorganic fine particles is wetted. At this time, the solution in the flask is constantly stirred with a magnetic stirrer. The end point is observed by the suspension of the entire amount of the inorganic fine particles in the liquid, and the degree of hydrophobicity is expressed as the percentage of methanol in the liquid mixture of methanol and water when the end point is reached.

The external additive A of the present invention preferably has a specific surface area of from 5 to 70 m ² / g, more preferably from 20 to 55 m ² / g, from the viewpoint of obtaining sufficient adhesion to toner particles and spacer particles. .

  The titanium oxide fine particles, which are the base particles of the external additive A, are obtained by a sulfuric acid method, a chlorine method, and low-temperature oxidation (thermal decomposition, hydrolysis) of a volatile titanium compound (for example, titanium alkoxide, titanium halide, titanium acetylacetonate). Can be used. As the crystal system, any of anatase type, rutile type, a mixed crystal type thereof, and amorphous type can be used, but rutile type titanium oxide fine particles are preferable. This is because the rutile-type titanium oxide fine particles have high volume resistivity and can hold a stable charge. Further, since the rutile type titanium oxide fine particles are well dispersed on the toner and fluidity can be obtained, the rubbing with the member is suppressed, and it works advantageously on the durability and the charging stability.

An external additive other than the external additive A may be added to the toner of the present invention. Fluorinated resin powder such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; silica fine powder such as silica fine powder by a wet method, silica fine powder such as a silica fine powder by a dry method, a silane coupling agent, a titanium cup Examples include fine silica powder treated with a surface treating agent such as a ring agent and silicone oil; fine alumina powder, fine alumina oxide powder, and composite oxides thereof. The external additives other than the external additive A have a specific surface area of 30.0 m ² / g or more, preferably 50.0 m ² / g or more, as measured by the BET method using nitrogen adsorption. Further, the amount added to 100 parts by mass of the toner particles is preferably from 0.010 parts by mass to 8.0 parts by mass, and more preferably from 0.10 parts by mass to 4.0 parts by mass.

[Toner particles]
The toner particles are toner particles having a core containing a resin, a coloring agent and a wax, and a shell layer present on the surface of the core and containing a polyester resin A.

  As described above, the external additive A exerts an excellent effect of improving the charge rising property. On the other hand, it is considered that a fluorine-containing external additive tends to be easily charged up as a toner because fluorine has a strong negative property. In particular, in a low-temperature and low-humidity environment, when used under severe conditions such as printing a large number of sheets with a one-component developing device, charge-up is likely to occur, and as a result, there is a concern that image problems such as poor regulation may occur.

  In the present invention, by using the polyester resin A whose dielectric loss tangent is appropriately controlled as the shell of the toner particles, the charge is appropriately leaked, and the charge-up can be suppressed while controlling the charge reduction under high temperature and high humidity. . Further, the decrease in charge under high temperature and high humidity is also suppressed by the charge amount raised by the external additive A. As a result, it has been found that a toner which has a good charge rising property from the beginning, suppresses an excessive increase in charge amount even under low temperature and low humidity, and can stably maintain a high charge amount.

  Polyester resin A has a dielectric loss tangent at 25 ° C. and 10,000 Hz of 0.0070 or more and 0.0140 or less. When the dielectric loss tangent is in the above range, the shell layer on the surface of the toner has an appropriate charge leakage property, and good charge stability can be obtained without charge-up even under severe conditions. When it is less than 0.0070, sufficient charge leakage cannot be obtained, and when it is more than 0.0140, the charge leakage is too large, and the charge is reduced particularly under high temperature and high humidity.

  The dielectric loss tangent of the polyester resin A can be adjusted by appropriately adjusting the alcohol component and the acid component used in preparing the polyester, and the content thereof. Specifically, the dielectric tangent can be increased by adding a component having an ether structure such as an isosorbide unit represented by the formula (1) or ethylene glycol, and the dielectric tangent can be controlled by the content. it can.

  In the present invention, among others, it is preferable to adjust the content of the isosorbide unit so that the dielectric loss tangent is within the above range.

  It is presumed that the reason why it is preferable to adjust the content by the content of the isosorbide unit is as follows.

  Since the isosorbide unit has an ether bond in a cyclic structure, the isosorbide unit does not significantly affect the dielectric loss tangent per unit than a unit having an ether bond such as ethylene glycol, and is moderate. Therefore, it is presumed that this is because the polyester resin A can be given an appropriate dielectric tangent without partially increasing the dielectric tangent as the polyester resin.

  The content of the isosorbide unit is preferably from 0.10% by number to 20.00% by number based on the total number of all monomer units constituting the polyester resin A.

  When the content of the isosorbide unit is within the above range, it is easy to control the dielectric loss tangent of the polyester resin A within the range of the present invention. Further, since the glass transition temperature of the polyester resin A tends to increase as the content of the isosorbide unit increases, the above-mentioned range is preferable also from the viewpoint of minimizing a decrease in fixability due to the polyester resin A as the shell. More preferably, it is 1.00 number% or more and 15.00 number% or less.

  The toner of the present invention contains the polyester resin A in an amount of 1.0 to 20.0 parts by mass, preferably 1.5 to 10.0 parts by mass, based on 100.0 parts by mass of the binder resin. Part or less.

  When the amount of the polyester resin A is within the above range, a sufficient charge-up suppressing effect can be obtained. Further, when toner particles are produced by a suspension polymerization method, the solubility in a polymerizable monomer is reduced, so that the formation of a shell tends to be unstable.

  The acid value of the polyester resin A is preferably from 0.5 mgKOH / g to 25.0 mgKOH / g, more preferably from 0.5 mgKOH / g to 15.0 mgKOH / g. When the acid value of the polyester resin A is 0.5 mgKOH / g or more, the shell layer is more firmly formed, so that the effect of suppressing the charge-up by the polyester resin A is more effectively obtained. Further, when the acid value of the polyester resin A is 25.0 mgKOH / g or less, a sharper particle size distribution can be obtained when toner particles are produced by a suspension polymerization method, and image adverse effects such as fogging are less likely to occur. .

  In the polyester resin A of the present invention, it is preferable to use isosorbide as an alcohol component, but the following alcohol components can also be used in combination.

  Examples of the dihydric alcohol component include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane and 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 and 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, neopen Aliphatics such as glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene glycol Bisphenol A such as bisphenol A and hydrogenated bisphenol A.

  Examples of the trihydric or higher alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, and 1,2,4-butanetriol. , 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trihydroxymethylbenzene No.

  Further, examples of an acid component used for forming the polyester resin A include the following. For example, aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid; having 1 to 1 carbon atoms such as fumaric acid, maleic acid, adipic acid, succinic acid, dodecenylsuccinic acid, and octenylsuccinic acid. Aliphatic polycarboxylic acids of succinic acid substituted with 20 alkyl groups or alkenyl groups having 2 to 20 carbon atoms; anhydrides of these acids and alkyl (1 to 8 carbon) esters of these acids; .

  Among them, it is particularly preferable to use a polyester resin A obtained by condensation polymerization of a bisphenol derivative as an alcohol component, a divalent or higher carboxylic acid or an acid anhydride thereof, or a lower alkyl ester thereof as an acid component. it can.

  In the present invention, a conventionally known polyester resin may be used together with the polyester resin A.

  Next, the toner and the method for producing the toner of the present invention will be described in detail.

  The toner of the present invention preferably has a weight average particle size (D4) of 4.0 μm or more and 9.0 μm or less. More preferably, it is 5.0 μm or more and 7.5 μm or less.

  The toner particles can be manufactured by using a known pulverization method and polymerization method. Among them, production by a production method including a step of granulating in an aqueous medium such as a suspension polymerization method or a dissolution suspension polymerization method is preferable in that the core-shell structure can be easily formed and controlled. In particular, a suspension polymerization method that can easily reduce the particle size and easily obtain toner particles having a core-shell structure which is close to a true sphere and has few surface irregularities is preferable.

  Hereinafter, toner particles produced by a suspension polymerization method, which is a preferred method for producing the toner particles of the present invention, will be described in detail.

  When the toner particles are produced by the suspension polymerization method, for example, the particles are produced as follows. A polymerizable monomer composition is prepared by mixing a colorant, a polymerizable monomer, a wax, a polymerization initiator, and the like. Next, the polymerizable monomer composition is dispersed in an aqueous medium to granulate particles of the polymerizable monomer composition. Then, the polymerizable monomer in the particles of the polymerizable monomer composition is polymerized in an aqueous medium to obtain toner particles.

  As the polymerizable monomer, a vinyl polymerizable monomer capable of radical polymerization is used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used. Examples of the monofunctional polymerizable monomer include the following. Styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p-methylstyrene styrene derivatives such as n-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-phenylstyrene; methyl acrylate, Ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n- Acrylic polymerizable monomers such as nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, and 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, n -Propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl Phosphate ethyl methacrylate, dibutyl phosphate ethyl Methacrylic polymerizable monomers such as methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and vinyl formate; vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl Vinyl ethers such as ethers; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

  Examples of the polyfunctional polymerizable monomer include the following. Diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2 '-Bis (4- (acryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,3-butane Lenglycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2′-bis (4- (methacryloxydiethoxy) phenyl) propane, 2,2′-bis ( 4- (methacryloxypolyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethanetetramethacrylate, divinylbenzene, divinylnaphthalene, divinylether.

  The monofunctional polymerizable monomers are used alone or in combination of two or more, or in combination with a polyfunctional polymerizable monomer. Polyfunctional polymerizable monomers can also be used as crosslinking agents.

  The polymerizable monomer composition in the above step is prepared by mixing a dispersion in which the pigment composition is dispersed in a first polymerizable monomer with a second polymerizable monomer. Preferably, there is. That is, after the pigment composition is sufficiently dispersed in the first polymerizable monomer and then mixed with the second polymerizable monomer together with other toner materials, the pigment can be dispersed in a better dispersion state. Can be present in the toner particles.

  As the polymerization initiator used in the polymerization of the polymerizable monomer, an oil-soluble initiator and / or a water-soluble initiator are used. Examples of the oil-soluble initiator include the following. 2,2′-azobisisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis-4 Pigment dispersants such as -methoxy-2,4-dimethylvaleronitrile; acetylcyclohexylsulfonyl peroxide, diisopropyl peroxycarbonate, decanoyl peroxide, lauroyl peroxide, stearoyl peroxide, propionyl peroxide, acetyl peroxide, t- Butyl peroxy-2-ethylhexanoate, benzoyl peroxide, t-butyl peroxyisobutyrate, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, t-butyl hydroperoxide Kisaido, di -t- butyl peroxide, peroxide initiators such as cumene hydroperoxide.

  Examples of the water-soluble initiator include the following. Ammonium persulfate, potassium persulfate, 2,2'-azobis (N, N'-dimethyleneisobutyroamidine) hydrochloride, 2,2'-azobis (2-aminodinopropane) hydrochloride, azobis (isobutylamidine) Hydrochloride, sodium 2,2'-azobisisobutyronitrile sulfonate, ferrous sulfate or hydrogen peroxide.

  Further, in order to control the degree of polymerization of the polymerizable monomer, a chain transfer agent, a polymerization inhibitor and the like can be further added and used.

  The concentration of the polymerization initiator is preferably in the range of 0.1 to 20 parts by weight, more preferably in the range of 0.1 to 10 parts by weight, based on 100 parts by weight of the polymerizable monomer. is there. The kind of the polymerizable initiator slightly varies depending on the polymerization method, but is used alone or in combination with reference to the 10-hour half-life temperature.

  Further, in the present invention, a cross-linking agent can be used at the time of synthesizing the vinyl polymer in order to increase the stress resistance of the toner particles and to control the molecular weight of the particle constituting molecules.

  As the crosslinking agent, a compound having two or more polymerizable double bonds is used. Specifically, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; and divinyl compounds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, and 1,3-butanediol dimethacrylate. Carboxylic esters having two heavy bonds; divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide and divinyl sulfone; and compounds having three or more vinyl groups. These are used alone or as a mixture.

  These crosslinking agents are preferably used in an amount of 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the polymerizable monomer, in terms of toner fixability and offset resistance. It is preferable to use a part.

  The polymerizable monomer and the cross-linking agent are used singly or in an appropriate mixture of monomers so that the theoretical glass transition temperature (Tg) is in the range of 40 to 75 ° C. When the theoretical glass transition temperature is 40 ° C. or higher, it is difficult to cause problems in terms of storage stability and stress resistance of the toner. On the other hand, when the theoretical glass transition temperature is 75 ° C. or lower, transparency and low-temperature fixing in the case of toner full-color image formation. The property does not decrease.

  The aqueous medium used in the suspension polymerization method preferably contains a dispersion stabilizer. As the dispersion stabilizer, known inorganic and organic dispersion stabilizers can be used. Examples of the inorganic dispersion stabilizer include calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, and calcium sulfate. , Barium sulfate, bentonite, silica, alumina and the like.

  Examples of the organic dispersion stabilizer include polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salts of carboxymethylcellulose, starch and the like. It is also possible to use nonionic, anionic or cationic surfactants. Examples include sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate, and the like.

  In the present invention, among the above-mentioned dispersion stabilizers, it is preferable to use a poorly water-soluble inorganic dispersion stabilizer which is soluble in an acid. In addition, in the present invention, when a poorly water-soluble inorganic dispersion stabilizer is used to prepare an aqueous dispersion medium, these dispersion stabilizers are used in an amount of 0.2 to 2 based on 100 parts by mass of the polymerizable monomer. It is preferable to use them in such a ratio as to be in a range of 0.0 parts by mass. This is because the use of such a ratio in such a range improves the droplet stability of the polymerizable monomer composition in an aqueous medium. In the present invention, it is preferable to prepare an aqueous medium using water in the range of 300 to 3000 parts by mass with respect to 100 parts by mass of the polymerizable monomer composition.

  In the present invention, in the case of preparing an aqueous medium in which the poorly water-soluble inorganic dispersion stabilizer is dispersed, a commercially available dispersion stabilizer may be used as it is for dispersion. However, in order to obtain dispersion stabilizer particles having a fine and uniform particle size, it is preferable to prepare the poorly water-soluble inorganic dispersion stabilizer under high-speed stirring in water. For example, when calcium phosphate is used as a dispersion stabilizer, a preferable dispersion stabilizer can be obtained by mixing an aqueous solution of sodium phosphate and an aqueous solution of calcium chloride under high-speed stirring to form fine particles of calcium phosphate.

  In the suspension polymerization method, a polar resin is added to a polymerizable monomer composition to produce toner particles, so that a resin and a wax that mainly form a core are converted into a polar resin (shell) such as a polyester resin A by a polar resin (shell). A toner having a coated core-shell structure can be obtained.

  For this reason, the toners produced by these polymerization methods have good exposure of the wax to the toner, so that even if the toner contains a relatively large amount of wax, the toner is hardly exposed to the toner surface and the toner deterioration during continuous printing is suppressed. Can be.

  As the colorant of the toner of the present invention, the following black, yellow, magenta, and cyan pigments and, if necessary, dyes can be used.

  As the black colorant, a known black colorant can be used. For example, carbon black is mentioned as a black colorant. Further, there may be mentioned those in which the following yellow / magenta / cyan colorants are mixed and adjusted to black.

  Although there is no particular limitation on carbon black, for example, carbon black obtained by a production method such as a thermal method, an acetylene method, a channel method, a furnace method, and a lamp black method can be used. The above carbon blacks may be used alone or in combination of two or more. The average particle size of the primary particles of carbon black is not particularly limited, but is preferably from 14 to 80 nm, more preferably from 25 to 50 nm. The average particle size of the primary particles of carbon black can be measured by taking an enlarged photograph with a scanning electron microscope.

  As the yellow colorant, a known yellow colorant can be used.

  As the pigment-based yellow colorant, compounds represented by condensed polycyclic pigments, isoindolinone compounds, anthraquinone compounds, azo metal complex methine compounds, and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow 3, 7, 10, 12, 13, 14, 15, 17, 23, 24, 60, 62, 74, 75, 83, 93, 94, 95, 99, 100, 101, 104, 108, 109, 110,111,117,123,128,129,138,139,147,148,150,155,166,168,169,177,179,180,181,183,185,191: 1,191,192, 193, 199.

  Dye-based yellow colorants include C.I. I. solvent Yellow 33, 56, 79, 82, 93, 112, 162, 163, C.I. I. disperse Yellow 42, 64, 201, and 211.

  As the magenta colorant, a known magenta colorant can be used.

  As the magenta colorant, condensed polycyclic pigments, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specifically, 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 Violet 19.

  As the cyan colorant, a phthalocyanine compound and its derivative, an anthraquinone compound, and a basic dye lake compound are used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66.

  The coloring agents can be used alone or as a mixture or in the form of a solid solution. In the present invention, the colorant is selected in terms of hue angle, saturation, lightness, weather resistance, OHT transparency, and dispersibility in the toner. The amount of the colorant added is preferably from 1 part by weight to 20 parts by weight based on 100 parts by weight of the binder resin.

  The toner of the present invention preferably contains one or more waxes. The wax contained in the toner is preferably contained in a total amount of 2.5 parts by mass or more and 25.0 parts by mass or less, more preferably 4.0 parts by mass or more and 20 parts by mass with respect to 100 parts by mass of the binder resin. Or less, more preferably 6.0 to 18.0 parts by mass.

  Examples of the wax include the following. Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, Fischer-Tropsch wax, paraffin wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or block copolymers thereof A wax mainly containing a fatty acid ester such as carnauba wax and montanic acid ester wax, and a partially or entirely deoxidized fatty acid ester such as deoxidized carnauba wax; palmitic acid, stearic acid, montanic acid, etc. Unsaturated fatty acids such as brandinic acid, eleostearic acid, and parinaric acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, seryl alcohol, meryl Saturated alcohols such as alcohol; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide Fatty acid bisamides such as amide, hexamethylenebisstearic acid amide; unsaturated acids such as ethylenebisoleic amide, hexamethylenebisoleic amide, N, N 'dioleyl adipamide, N, N' dioleyl sebacic amide Fatty acid amides; aromatic bisamides such as m-xylene bisstearic acid amide and N, N 'distearyl isophthalic acid amide; calcium stearate, calcium laurate, zinc stearate, magnesium stearate and the like Aliphatic metal salts (commonly referred to as metallic soaps); waxes obtained by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid; fatty acids such as behenic acid monoglyceride and polyvalent Partial esterified products of alcohols; methyl ester compounds having a hydroxyl group obtained by hydrogenation of vegetable oils and the like.

  In the toner of the present invention, a charge control agent may be used in order to stably maintain the chargeability of the toner regardless of the environment.

  Examples of the negatively chargeable charge control agent include the following. Monoazo metal compound, acetylacetone metal compound, aromatic oxycarboxylic acid, aromatic dicarboxylic acid, oxycarboxylic acid and dicarboxylic acid-based metal compound, aromatic oxycarboxylic acid, aromatic mono- and polycarboxylic acids and metal salts thereof, Examples thereof include anhydrides, esters, phenol derivatives such as bisphenol, urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarenes, and resin charge control agents.

  The following are mentioned as a positive charge control agent. Modified nigrosine with nigrosine and fatty acid metal salts, etc .; guanidine compounds; imidazole compounds; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and analogs thereof Onium salts such as phosphonium salts, etc., and their lake pigments; triphenylmethane dyes and these lake pigments (phosphorotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic Acid, ferricyanide, ferrocyanide, etc.); metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borane DOO, dioctyl tin borate, such as diorganotin tin borate such dicyclohexyl tin borate; resin charge control agents.

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

  Among them, as the charge control agent other than the resin-based charge control agent, a metal-containing salicylic acid-based compound is preferable, and particularly, a metal whose aluminum or zirconium is used is preferable. Particularly preferred control agents are aluminum salicylate compounds.

  As the resin-based charge control agent, it is preferable to use a polymer or copolymer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group, a salicylic acid moiety, and a benzoic acid moiety.

  The preferable compounding amount of the charge control agent is 0.01 to 20.00 parts by mass, more preferably 0.05 to 10.00 parts by mass, based on 100.00 parts by mass of the polymerizable monomer. .

  The toner of the present invention may use a polar resin forming a shell layer in addition to the polyester resin A. Examples of the polar resin are given below, but other resins may be used.

  Examples of the polar resin used in the present invention include a polyester resin, a polycarbonate resin, a phenol resin, an epoxy resin, a polyamide resin, and a cellulose resin. More preferably, polyester resin is preferable from the viewpoint of variety of materials. The amount of the polar resin is preferably 20.0 parts by mass or less, more preferably 10.0 parts by mass or less per 100 parts by mass of the binder resin.

  The toner of the present invention may contain a crystalline polyester in the core for the purpose of improving the low-temperature fixability.

  Examples of the crystalline polyester include, for example, the following which is composed of a polycondensation resin of an aliphatic dicarboxylic acid and an aliphatic diol.

  Aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, glutaconic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecane Dicarboxylic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, isophthalic acid, terephthalic acid, n-dodecylsuccinic acid, n-dedenylsuccinic acid, cyclohexanedicarboxylic acid, anhydrides or lower alkyl esters of these acids, etc. Is mentioned.

  In the present invention, the carboxylic acid monomer as described above is used as a main component, but a trivalent or higher polyvalent carboxylic acid may be used in addition to the above components.

  Examples of the trivalent or higher polycarboxylic acid component include trimellitic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, pyromellitic acid, 1,2,4-butanetricarboxylic acid, Examples include 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, and derivatives thereof such as acid anhydrides and lower alkyl esters.

  As the aliphatic diol, specifically, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene Glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, neopentyl glycol, 1,4-butadiene glycol and the like. In the present invention, the alcohol monomer as described above is used as a main component. In addition to the above-mentioned components, polyoxyethylenated bisphenol A, polyoxypropylene bisphenol A, 1,4-cyclohexane dimethanol, and the like Dihydric alcohols, aromatic alcohols such as 1,3,5-trihydroxymethylbenzene, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, Trihydric alcohols such as glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, and trimethylolpropane may be used.

  Examples of the trivalent or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.

In particular, it is more preferable to be composed of a straight-chain dealiphatic dicarboxylic acid represented by the following formula (2) and a straight-chain aliphatic diol represented by the following formula (3).
HOOC- _(CH 2) m-COOH (2)
[Wherein, m represents an integer of 4 to 16]
HO- _(CH 2) n-OH (3)
[Wherein, n represents an integer of 4 to 16]

  When the resin is linear, the polyester resin has excellent crystallinity and an appropriate crystal melting point, and thus has excellent toner blocking resistance, image storability, and low-temperature fixability. Further, when the number of carbon atoms is 4 or more, the melting point (Tm) is appropriate, so that the toner blocking resistance, the image storability, and the low-temperature fixability are excellent. When the ratio is 16 or less, it is easy to obtain practical materials. The number of carbon atoms is more preferably 14 or less.

  The melting point Tm (C) of the crystalline polyester is preferably from 55 ° C to 90 ° C, more preferably from 60 ° C to 85 ° C. If the temperature is lower than 55 ° C., the toner tends to have toner blocking resistance, and the storability may be reduced. On the other hand, when the melting point is higher than 90 ° C., the solubility of the crystalline polyester in the polymerizable monomer tends to decrease, and the dispersibility of the toner constituent materials such as the pigment and the crystalline polyester deteriorates. Performance may be reduced.

  Tm (C) can be adjusted by the type of aliphatic dicarboxylic acid or aliphatic diol used, the degree of polymerization, and the like.

  Hereinafter, methods for measuring various physical properties according to the present invention will be described.

<Dielectric loss tangent measurement of polyester resin A>
The dielectric loss tangent of the polyester resin A in the present invention is determined by the following operation.

  The dielectric loss tangent (tan δ = ε ″ / ε ′) is calculated from the measured value of the complex permittivity at a frequency of 10000 KHz using a 4284A Precision LCR meter (manufactured by Hewlett-Packard Company).

0.3 to 0.7 g of the polyester resin coarsely ground in a mortar is weighed, and a load of 350 kgf / cm ² is molded over 2 minutes to obtain a disk-shaped measurement sample having a diameter of 25 mm and a thickness of 1 mm or less. This measurement sample was subjected to an ARES (manufactured by Rheometric Scientific F.E.) equipped with a dielectric constant measuring jig (electrode) having a diameter of 25 mm at 25 ° C. under a load of 350 g under a load of 350 g. It is obtained by measuring three times in a frequency range of 100,000 Hz and calculating an average value.

<Measurement of acid value of polyester A>
The acid value of the polyester resin A in the present invention is determined by the following operation.

  The acid value is the number of mg of potassium hydroxide required to neutralize the acid contained in 1 g of the sample. The acid value of the polar resin was measured according to JIS K0070-1992. Specifically, it measured according to the following procedures.

(1) Preparation of Reagent 1.0 g of phenolphthalein was dissolved in 90 ml of ethyl alcohol (95 vol%), and ion-exchanged water was added to make 100 ml to obtain a phenolphthalein solution.

  7 g of special grade potassium hydroxide was dissolved in 5 ml of water, and ethyl alcohol (95 vol%) was added to make 1 liter. After leaving the container in an alkali-resistant container for 3 days so as not to be exposed to carbon dioxide gas and the like, the mixture was filtered to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution was 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, and titration was performed with the potassium hydroxide solution. It was determined from the amount of the potassium solution. The 0.1 mol / l hydrochloric acid used was prepared according to JIS K 8001-1998.

(2) Operation (A) Main test A 2.0 g sample of the crushed polyester resin A was precisely weighed in a 200 ml Erlenmeyer flask, and 100 ml of a mixed solution of toluene: ethanol (2: 1) was added and dissolved for 5 hours. . Next, several drops of the phenolphthalein solution were added as an indicator, and titration was performed using the potassium hydroxide solution. The end point of the titration was defined as the time when the light red color of the indicator continued for about 30 seconds.

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

(3) The obtained result was substituted into the following equation to calculate the acid value.
A = [(CB) × f × 5.61] / S

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

<Weight average molecular weight of polyester resin A>
The weight average molecular weight of the polyester resin A is determined by the following operation.

  After dispersing 0.03 g of polyester resin in 10 ml of o-dichlorobenzene and dissolving it, the mixture was shaken at 135 ° C. for 24 hours with a shaker, filtered through a 0.2 μm filter, and the filtrate was used as a sample, under the following conditions. Analyze at.

[Analysis conditions]
Separation column: Shodex (TSK GMHHR-H HT20) x 2
Column temperature: 135 ° C
Mobile phase solvent: o-dichlorobenzene Mobile phase flow rate: 1.0 ml / min.
Sample concentration: about 0.3%
Injection volume: 300 μl
Detector: Differential refractive index detector Shodex RI-71

  In addition, in calculating the molecular weight of the sample, a standard polystyrene resin (TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-20, manufactured by Tosoh Corporation) was used. 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500).

<Method of Measuring Weight Average Particle Diameter (D4) of Toner>
The weight average particle diameter (D4) of the toner is calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) equipped with a 100 μm aperture tube by a pore electric resistance method is used. For setting of measurement conditions and analysis of measurement data, attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter) is used. The measurement is performed with 25,000 effective measurement channels. As the electrolytic aqueous solution used for the measurement, a solution prepared by dissolving a special grade sodium chloride in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter) can be used.

  Before performing the measurement and analysis, the dedicated software was set as follows. On the “Change standard measurement method (SOM)” screen of the dedicated software, set the total count number in the control mode to 50,000 particles, set the number of measurements to 1, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter Set the value obtained by using the following method. By pressing the “threshold / noise level measurement button”, the threshold and the noise level are automatically set. Also, the current is set to 1600 μA, the gain is set to 2, and the electrolytic solution is set to ISOTON II, and a check is made in “Flush aperture tube after measurement”. 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 from 2 μm to 60 μm.

The specific measuring method is as follows.
(1) Approximately 200 ml of the aqueous electrolytic solution is put into a 250 ml round bottom beaker made of glass exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 revolutions / second. Then, the dirt and air bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) About 30 ml of the electrolytic aqueous solution is put into a glass 100 ml flat bottom beaker. As a dispersant, "Contaminone N" (a 10% by mass aqueous solution of a neutral detergent for cleaning a precision measuring instrument at pH 7 comprising a nonionic surfactant, an anionic surfactant and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) ) Was diluted about 3 times by mass with ion-exchanged water, and about 0.3 ml of a diluent was added.
(3) An ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikkaki Bios Co., Ltd.) having two oscillators having an oscillation frequency of 50 kHz and having a phase shifted by 180 degrees and having an electrical output of 120 W is prepared. About 3.3 liters of ion-exchanged water is put into the water tank of the ultrasonic disperser, and about 2 ml of 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. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the aqueous electrolytic solution in the beaker is maximized.
(5) While irradiating ultrasonic waves to the electrolytic aqueous solution in the beaker of (4), about 10 mg of toner is added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion processing is continued for another 60 seconds. The ultrasonic dispersion is appropriately adjusted so that the temperature of the water in the water tank is 10 ° C. or more and 40 ° C. or less.
(6) The aqueous electrolyte solution of the above (5) in which the toner is dispersed is dropped using a pipette into the round bottom beaker of the above (1) installed in the sample stand, and adjusted so that the measured concentration becomes about 5%. . Then, measurement is performed until the number of particles to be measured reaches 50,000.
(7) Analyze the measured data with the dedicated software attached to the device, and calculate the weight average particle size (D4). The “average diameter” on the “analysis / volume statistical value (arithmetic average)” screen when the graph / volume% is set by the dedicated software is the weight average particle diameter (D4).

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

  As the measuring device, an “automatic specific surface area / pore distribution measuring device TriStar 3000 (manufactured by Shimadzu Corporation)” employing a gas adsorption method by a constant volume method as a measuring method is used. The setting of the measurement conditions and the analysis of the measurement data are performed using dedicated software “TriStar 3000 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 defined as the BET specific surface area in the present invention.

  Specifically, the measurement is performed according to the following procedure.

  The tare of a dedicated glass sample cell (3/8 inch in stem diameter, about 5 ml in volume) that has been sufficiently washed and dried is precisely weighed. Then, about 0.1 g of inorganic fine particles is put into this sample cell using a funnel.

  The sample cell containing the inorganic fine particles is set in "Pretreatment device VacuPrep 061 (manufactured by Shimadzu Corporation)" connected to a vacuum pump and a nitrogen gas pipe, and vacuum degassing is continued at 23 ° C. for about 10 hours. At the time of vacuum degassing, the gas is gradually degassed while adjusting the valve so that the inorganic fine particles are not sucked by the vacuum pump. The pressure in the cell gradually decreases with deaeration, and finally reaches about 0.4 Pa (about 3 mTorr). After completion of the vacuum deaeration, the inside of the sample cell is returned to the atmospheric pressure by gradually injecting nitrogen gas, 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 inorganic fine particles is calculated from the difference from the tare. At this time, the sample cell is covered with a rubber stopper during weighing so as to prevent the inorganic fine particles in the sample cell from being contaminated by moisture in the atmosphere or the like.

  Next, a dedicated “isothermal jacket” is attached to the stem of the sample cell containing the inorganic fine particles. Then, a special 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 tubular member whose inner surface is made of a porous material and whose outer surface is made of an impermeable material, which can suck up liquid nitrogen to a certain level by capillary action.

  Subsequently, the free space of the sample cell including the connection device is measured. Free space was measured at 23 ° C. using helium gas to measure the volume of the sample cell, followed by cooling the sample cell with liquid nitrogen and again measuring the volume of the sample cell 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 degassing in the sample cell, the sample cell is cooled with liquid nitrogen while continuing vacuum degassing. Then, nitrogen gas is introduced stepwise into the sample cell to cause the inorganic fine particles to adsorb nitrogen molecules. At this time, since the above-mentioned adsorption isotherm is obtained by measuring the equilibrium pressure P (Pa) as needed, this adsorption isotherm is converted into a BET plot. 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 squares method, and Vm is calculated from the slope and intercept of the straight line. Further, using the value of Vm, the BET specific surface area of the inorganic fine particles is calculated as described above.

  Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. In addition, "part" means "part by mass".

  Hereinafter, a method for producing a resin and a toner will be described.

<Production of polyester resin 1>
100 parts by mass of a mixture obtained by mixing the raw material monomers at the charging ratios shown in Table 1 and 0.55 parts by mass of tin di (2-ethylhexanoate) as a catalyst were equipped with a nitrogen introducing tube, a dehydrating tube, a stirrer, and a thermocouple. The mixture was placed in a liter four-necked flask and reacted at 200 ° C. for 6 hours under a nitrogen atmosphere. Further, trimellitic anhydride was added at 210 ° C., and the reaction was performed under a reduced pressure of 40 kPa, and the reaction was continued until the weight average molecular weight (Mw) became 12,000. The obtained polyester resin is designated as polyester resin 1.

  The composition of the polyester resin 1 was analyzed, and the ratio of units derived from the isosorbide monomer was determined. Table 1 shows the ratio of the isosorbide unit and the acid value in the polyester resin 1.

The composition analysis of the polyester resin 1 was performed by 1-NMR. The specific measuring method is as follows.
Measurement device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0 μs
Frequency range: 10500Hz
Number of integration: 64 times Measurement temperature: 30 ° C

  50 mg of a sample is placed in a sample tube having an inner diameter of 5 mm, deuterated chloroform (CDCl 3) is added as a solvent, and this is dissolved in a constant temperature bath at 40 ° C. to prepare a measurement sample. It measured on the said conditions using the said measurement sample.

<Production of polyester resins 2 to 13>
Polyester resins 2 to 13 were produced in the same manner as in the production of polyester resin 1, except that the charged amounts of the acid component and the alcohol component were changed as shown in Table 1. Table 1 shows the physical properties of the polyester resins 2 to 13.

TPA: Terephthalic acid TMA: Trimellitic acid BPA (PO2): Bisphenol A propylene oxide 2 mol adduct EG: Ethylene glycol

<Manufacture of charge control resin 1>
In a pressurizable reaction vessel equipped with a reflux tube, a stirrer, a thermometer, a nitrogen introduction tube, a dropping device, and a decompression device, 250 parts by mass of methanol, 150 parts by mass of 2-butanone, and 100 parts by mass of 2-propanol were used as solvents. Then, 77 parts by mass of styrene, 15 parts by mass of 2-ethylhexyl acrylate, and 8 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid were added as monomers, and the mixture was heated to reflux temperature with stirring. A solution obtained by diluting 1 part by mass of t-butylperoxy-2-ethylhexanoate as a polymerization initiator with 20 parts by mass of 2-butanone was added dropwise over 30 minutes, and stirring was continued for 5 hours. Further, a solution obtained by diluting 1 part by mass of t-butylperoxy-2-ethylhexanoate with 20 parts by mass of 2-butanone was added dropwise over 30 minutes, and the mixture was stirred for 5 hours to complete the polymerization. While maintaining the temperature, 500 parts by mass of deionized water was added, and the mixture was stirred at 80 to 100 rpm for 2 hours so that the interface between the organic layer and the aqueous layer was not disturbed. After standing for 30 minutes to separate the layers, the aqueous layer was discarded, and anhydrous sodium sulfate was added to the organic layer to dehydrate. Next, the polymer obtained after distilling off the polymerization solvent under reduced pressure was coarsely pulverized to 100 μm or less using a cutter mill equipped with a 150-mesh screen. The obtained charge control resin 1 having a sulfur atom had Tg = 58 ° C., Mp = 13,000, and Mw = 30,000.

<Production of Toner Particle 1>
With respect to 100 parts by mass of the styrene monomer, C.I. I. Pigment Blue 15: 3, 16.5 parts by mass, and 3.0 parts by mass of an aluminum compound of di-tert-butylsalicylic acid [Bontron E88 (manufactured by Orient Chemical Industries)]. These were introduced into an attritor (manufactured by Mitsui Miike Kakoki Co., Ltd.), and stirred for 180 minutes at 25 ° C. and 200 rpm using zirconia beads (140 parts by mass) with a radius of 1.25 mm to prepare master batch dispersion 1. Prepared.

On the other hand, 450 parts by mass of a 0.1 mol / l-Na ₃ PO ₄ aqueous solution was added to 710 parts by mass of ion-exchanged water, heated to 60 ° C., and then 67.7 parts by mass of a 1.0 mol / l-CaCl ₂ aqueous solution. Was gradually added to obtain an aqueous medium containing a calcium phosphate compound.
・ 40.0 parts by mass of master batch dispersion liquid ・ 49.5 parts by mass of styrene monomer ・ 16.5 parts by mass of n-butyl acrylate monomer ・ 9.0 parts by mass of hydrocarbon wax (Fischer-Tropsch wax, maximum (Endothermic peak temperature = 78 ° C., Mw = 750)
・ Charge control resin 1 0.3 parts by mass ・ Polyester resin 1 5.0 parts by mass

  The above material was heated to 65 ° C. K. Using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), the mixture was uniformly dissolved and dispersed at 5,000 rpm. Into this, 7.1 parts by mass of a 70% toluene solution of a polymerization initiator 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate was dissolved to prepare a polymerizable monomer composition.

Wherein the polymerizable monomer composition in an aqueous medium was charged, the temperature 65 ° C., under N ₂ atmosphere, T. K. The mixture was stirred at 12,000 rpm for 10 minutes with a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to granulate a polymerizable monomer composition. Thereafter, the temperature was raised to 67 ° C. while stirring with a paddle stirring blade, and when the polymerization conversion of the polymerizable vinyl monomer reached 90%, an aqueous 0.1 mol / liter sodium hydroxide solution was added. The pH of the aqueous dispersion medium was adjusted to 9. Further, the temperature was raised to 80 ° C. at a rate of 40 ° C./h, and the reaction was performed for 4 hours. After completion of the polymerization reaction, residual monomers in the toner particles were distilled off under reduced pressure. After cooling the aqueous medium, hydrochloric acid was added to adjust the pH to 1.4, and the mixture was stirred for 6 hours to dissolve the calcium phosphate salt. After the toner particles were separated by filtration and washed with water, they were dried at a temperature of 40 ° C. for 48 hours. The obtained dried product was strictly classified and removed simultaneously with a multi-segmentation classifier (Nippon Mining Co., Ltd. Elbow Jet Classifier) to obtain a cyan color having a weight average particle size (D4) of 6.3 μm. Was obtained.

<Production of toner particles 2 to 18>
Except that the kind of the polyester resin A to be used and the amount of the polyester resin A added were changed as shown in Table 2, toner particles 2 to 18 were obtained in the same manner as in the production example of the toner particles 1.
Table 2 shows the weight average particle size D4 of the obtained toner particles.

<External additive A>
Table 3 shows the external additives used in Examples and Comparative Examples.

<Production of Toner 1>
For 100 parts by mass of toner particles 1,
-Silica fine particles: RX300 (manufactured by Nippon Aerosil Co., Ltd.) 1.0 parts by mass-Titanium oxide fine particles: 0.2 mass parts of external additive 1 were used at 3600 rpm using a Mitsui FM mixer and FM10C (manufactured by Mitsui Mining Co., Ltd.). Then, dry mixing was performed for 12 minutes to obtain toner 1.

<Production of Toners 2 to 27>
In the production of Toner 1, Toners 2 to 27 were obtained in the same manner except that the type of toner particles and the type and amount of titanium oxide fine particles were changed as shown in Table 4.

<Example 1>
Using Toner 1 as a one-component developer, image evaluation was performed using A4 color laser copier paper (manufactured by Canon, 80 g / m ² ). A modified laser printer LBP-7700C (manufactured by Canon) was used as the image forming apparatus. The remodeling points of the evaluation machine (remodeling machine) are as follows.

  The process speed was increased 1.3 times by changing the gears and software of the evaluation machine. The cleaning blade was modified to have a contact line pressure of 0.3 N / cm and a contact angle of 23 degrees.

  A4 size plain paper was used as the evaluation paper. When cleaning a spherical suspension polymerization toner as manufactured in the present embodiment, it is general that the cleaning blade is brought into contact with a linear pressure of 1.0 N / cm or more. This is a severe condition for sex. The cartridge used for the evaluation was a cyan cartridge. That is, a product toner was extracted from a commercially available cyan cartridge, the inside was cleaned with an air blow, and 165 g of the toner according to the present invention was filled in for evaluation. It should be noted that each of the magenta, yellow, and black stations extracted the product toner, and inserted the magenta, yellow, and black cartridges for which the toner remaining amount detection mechanism was disabled, and evaluated the following. Table 5 shows the evaluation results.

<Evaluation of tip concentration>
In a low-temperature and low-humidity environment (15 ° C./10% Rh), a solid image is output, and the image density of one round of the D roller from the top of the solid image and the image density of the second and subsequent rounds are measured using a color reflection densitometer (X-Rite). 404A), and the image density difference at that time was evaluated as follows. The image density difference appears as shown in FIG.
A: The image density difference is 0.05 or less.
B: The image density difference is larger than 0.05 and 0.10 or less.
C: Image density difference is greater than 0.10.

<Evaluation of charging stability of toner>
In a high-temperature and high-humidity environment (temperature: 30 ° C., humidity: 80% RH), the developing device in which the cartridge was inserted was allowed to stand for 24 hours, and then the process speed was set to 200 mm / s in the cyan monochromatic mode. The "E" character (image printing rate 1%) was printed out 5000 sheets in the intermittent printing mode (stopped for 2 seconds every time two sheets were printed). Immediately after printing the first sheet (initial) and the next day after printing the 5000th sheet (after 5 k), the fog density on the image carrier was measured by the following method.

  A solid white image is printed out, the cartridge is pulled out at the time of transfer, a colorless and transparent tape is adhered to the image carrier before transfer, and the tape is adhered to paper (same type as transfer paper). The density D1 of the tape portion affixed on the paper is measured using a "white photometer TC-6DS" (manufactured by Tokyo Denshoku Co., Ltd.). On the other hand, a tape not adhered to the image carrier was directly adhered to paper, and the density D0 was measured under the same conditions. The density difference (D1-D0) was defined as the fog density. The filter used was an amber filter.

(Evaluation criteria)
A: Fog density is less than 1.0 B: Fog density is 1.0 or more and less than 2.0 C: Fog density is 2.0 or more and less than 3.0 D: Fog density is 3.0 or more

<Poor regulation>
Under a low-temperature and low-humidity environment (15 ° C./10% Rh), an endurance test was performed to output 10,000 images (10 k) at a printing ratio of 1%. The image was visually checked 100 sheets at a time, and the evaluation was made as follows based on the number of sheets until the toner regulation member and the toner carrier were poorly regulated and the toner was not regulated on the toner carrier until the image became uneven. did.

(Evaluation criteria)
A: No image unevenness up to 10,000 sheets.
B: Image unevenness occurs at 9,500 to 10,000 sheets.
C: Image unevenness occurs at 9000 sheets or more and less than 9500 sheets.
D: Image unevenness occurs on less than 9000 sheets.

<Examples 2 to 22, Comparative Examples 1 to 5>
The same evaluation as in Example 1 was performed using toners 2 to 27.

  The evaluation results are shown in Table 5 or Table 6.

Claims (3)

Toner particles having a core containing a binder resin and a colorant, and a shell containing a polyester resin A present on the surface of the core;
External additive A,
A toner containing
The polyester resin A has a dielectric loss tangent at 25 ° C. and 10,000 Hz of 0.0070 or more and 0.0140 or less,
The toner contains 1.0 to 20.0 parts by mass of the polyester resin A with respect to 100.0 parts by mass of the binder resin,
The external additive A is titanium oxide surface-treated with a silane compound containing a fluorine atom,
A toner characterized in that: The toner according to claim 1, wherein the toner contains 0.01 to 2.00 parts by mass of the external additive A based on 100 parts by mass of the toner particles. Hydrophobicity of the external additive A is from 20 to 70% toner according to claim 1 or 2.

Images