JP5482478B2 - Toner production method for electrostatic charge development, toner for electrostatic charge development - Google Patents

Description

  The present invention relates to an electrostatic charge developing toner manufacturing method and an electrostatic charge developing toner.

  In general, in the electrophotographic image forming method, when transferring from a photoreceptor to a transfer material, it is necessary to clean the toner remaining on the photoreceptor without transferring to the transfer material from the photoreceptor. As a method for cleaning the toner remaining on the photoconductor, a method of bringing the edge of a cleaning blade made of an elastic material such as urethane rubber into contact with the surface of the photoconductor is widely used. At this time, the cleaning blade is generally used with one edge thereof being pressed against the running direction of the photosensitive member in the counter direction.

  If the toner has a small particle size and a wide particle size distribution, and the toner contains fine toner, the fine toner will pass through the cleaning blade if it is used as described above, and cleaning is very difficult. Things are known.

  Therefore, as a method for producing a toner having a narrow particle size distribution, a pigment dispersion containing a pigment, a cationic surfactant, and an arbitrary charge control agent is manufactured, and this is used as a resin, an anionic surfactant, and a nonionic surfactant. A technique is disclosed for shearing with a latex comprising a surfactant and heating the shear blend at a temperature below the resin Tg to form an agglomerate and then heating it at a temperature above the resin Tg. (For example, refer to Patent Document 1).

  Also, a dispersion of resin fine particles in which resin fine particles are dispersed, a dispersion of a colorant, a dispersion of a release agent, and a dispersion of inorganic fine particles are mixed and heteroaggregated to prepare an aggregated particle dispersion, Techniques for producing toner by heating to a temperature equal to or higher than the glass transition point of the resin fine particles to fuse and coalesce are disclosed (for example, see Patent Document 2).

JP-A-7-146487 JP 2001-228647 A

  In the method for producing an electrostatic charge developing toner in which an aqueous dispersion containing resin particles and colorant particles is agglomerated and fused, in order to suppress further agglomeration before the agglomeration is finished and the temperature is increased to proceed to the fusing step. Further addition of surfactant and pH adjustment are performed.

  However, if a surfactant is added or the pH is adjusted, the cohesive force is weakened and the heteroaggregates are unraveled, so that fine aggregates are mixed into the aggregates. There was a problem that became wide.

  With the technology disclosed above, it is not sufficient to sharpen the toner particle size distribution, and the toner is not transferred to a transfer material by a high-speed image forming apparatus (for example, 65 sheets per minute A4 size lateral feed). When the remaining toner is cleaned with a cleaning blade, a cleaning failure occurs, and when a large number of sheets are printed, fogging or in-machine contamination occurs.

  The present invention does not transfer to a transfer material with a high-speed image forming apparatus (for example, 65 sheets / minute A4 size lateral feed), and does not cause poor cleaning when the toner remaining on the photoreceptor is cleaned with a cleaning blade. It is an object of the present invention to provide a method for producing an electrostatic charge developing toner that does not cause fogging and does not generate stains even after printing a large number of sheets, and an electrostatic charge developing toner (hereinafter also simply referred to as toner).

    The object of the present invention is achieved by the following configurations.

1. Producing an aqueous dispersion containing at least resin particles and a colorant;
In the method for producing a toner for electrostatic charge development, comprising the step of aggregating and fusing the resin particles and the colorant to produce a heteroaggregate,
In the step of preparing the aqueous dispersion of the resin particles or the aqueous dispersion of the colorant particles, at least an anionic sulfate ester type surfactant is used,
In the step of producing the heteroaggregate, before heating and aggregating and fusing the resin particles and the colorant particles, at least one inorganic salt of sulfate or hydrogen sulfate is added ,
The electrostatic charge development characterized in that the amount of the inorganic salt of at least one of the sulfate and hydrogen sulfate is 10 times to 150 times (molar ratio) of the anionic sulfate ester surfactant. Of manufacturing toner.

  2. 2. The method for producing a toner for electrostatic charge development according to 1 above, wherein the anionic sulfate type surfactant is a surfactant having a structure containing an alkyl sulfate ester salt.

3 . 3. An electrostatic charge developing toner obtained by the method for producing an electrostatic charge developing toner according to 1 or 2 above.

  The method for producing an electrostatic charge developer toner of the present invention and the electrostatic charge developer toner are not transferred onto a transfer material by a high-speed image forming apparatus (for example, 65 sheets / 1 minute, A4 size lateral feed) and remain on the photoreceptor. When the toner is cleaned with a cleaning blade, there is no cleaning failure, and there is an excellent effect that no fogging occurs and no in-machine contamination occurs even when a large number of sheets are printed.

1 is a schematic cross-sectional view showing an example of a color image forming apparatus using toner according to the present invention.

  When the toner remaining on the photoreceptor is cleaned with a cleaning blade without being transferred to a transfer material with a high-speed image forming apparatus (for example, 65 sheets / minute, A4 size lateral feed), the toner particle size distribution is broad and If the toner is mixed with fine toner, the cleaning performance of the cleaning blade deteriorates, and when a large number of prints are made, the surface of the photoconductor is toner filmed by the fine toner in the toner, and fog occurs. There was a problem of scattering.

  The inventors of the present invention have also studied a method for producing a toner that can produce a toner having a sharp particle size distribution even when a toner is produced from a resin particle and a colorant particle through a heteroaggregate.

  When an anionic sulfate ester type surfactant is used, the surface active function is lowered when heated to a temperature required for fusion of the heteroaggregates (for example, 60 ° C. or higher). This is considered to be due to the hydrolysis of the anionic sulfate ester type surfactant by heating.

  If sulfate is added, hydrolysis of the anionic sulfate ester surfactant is suppressed even when heated during aggregation and fusion, and the surface active function can be kept constant during aggregation and fusion. It was.

  As a result of various studies, a step of producing an aqueous dispersion of resin particles and an aqueous dispersion of colorant particles, and a step of producing heteroaggregates by aggregating and fusing the resin particles and colorant particles in the aqueous dispersion In the method for producing an electrostatic charge developing toner in this order, a surfactant for preparing an aqueous dispersion of the resin particles and the colorant particles is used as an anionic sulfate ester type dispersion in either the resin particles or the colorant particles. Decomposition of an anionic sulfate ester type surfactant by adding an inorganic salt of at least one of sulfate and hydrogen sulfate before starting heating and fusing when producing the heteroaggregate using a surfactant. It was found that a toner having a sharp particle size distribution can be obtained by preparing a heteroaggregate while preventing the above.

  In the present invention, in order to prevent hydrolysis of the anionic sulfate ester type surfactant, at least one inorganic salt of sulfate or hydrogen sulfate is added, and the sulfate is hydrolyzed to form hydrogen sulfate. By replenishing the hydrogen salt, the anionic sulfate ester type surfactant is prevented from being hydrolyzed.

  As a result, the function of the anionic sulfate ester type surfactant can be kept constant during agglomeration and fusion, so no additional surfactants or pH adjustments are required, preventing the heteroaggregates from unraveling, Heteroaggregates having a sharp particle size distribution can be obtained. By using this heteroaggregate having a narrow particle size distribution, a toner having a sharp particle size distribution can be produced.

  The reaction scheme in which sulfate is hydrolyzed to hydrogen sulfate and the decomposed alkyl sulfate surfactant is returned to the original alkyl sulfate surfactant (sodium alkyl sulfate) is shown below.

  The toner production method of the present invention includes at least a step of producing an aqueous dispersion of resin particles and an aqueous dispersion of colorant particles, and agglomerating and fusing the resin particles and colorant particles to produce a heteroaggregate. A method for producing a toner for developing an electrostatic charge having a process.

  If the anionic sulfate-type surfactant that keeps the particle aggregation conditions constant is hydrolyzed, even if the aggregation is finished and the temperature is raised and the process proceeds to the fusing step, further aggregation proceeds. If a surfactant or pH adjustment is performed in order to suppress further aggregation, the cohesive force is weakened and the heteroaggregation is released, and fine aggregates are mixed in the aggregate. Fine toner particles are mixed in, and the particle size distribution becomes broad.

  In the step of preparing an aqueous dispersion of resin particles and an aqueous dispersion of colorant particles, at least an alkyl sulfate ester type surfactant is used when preparing an aqueous dispersion of resin particles or an aqueous dispersion of colorant particles.

  In the present invention, in order to prevent the anionic sulfate ester type surfactant from being hydrolyzed during the aggregation of the resin particles and the colorant particles, the sulfate is contained in the aqueous dispersion of resin particles or the aqueous dispersion of colorant particles. Alternatively, at least any inorganic salt of hydrogen sulfate is added.

  In the step of preparing an aqueous dispersion of resin particles and an aqueous dispersion of colorant particles, at least an alkyl sulfate ester type surfactant is used when preparing an aqueous dispersion of resin particles or an aqueous dispersion of colorant particles.

  Specifically, when an alkyl sulfate ester surfactant is used when preparing an aqueous dispersion of resin particles, an amphoteric surfactant or a cationic surfactant is used to prepare an aqueous dispersion of colorant particles. When an amphoteric surfactant or a cationic surfactant was used in the preparation of an aqueous dispersion of the above, an alkyl sulfate ester surfactant was used for the preparation of an aqueous dispersion of colorant particles, and an aqueous dispersion of resin particles was prepared. And surfactants of different polarities are used to prepare an aqueous dispersion of colorant particles.

  In the step of agglomerating and fusing the resin particles and the colorant particles to produce a heteroaggregate, the addition of at least one inorganic salt of sulfate or hydrogen sulfate (hereinafter also simply referred to as inorganic salt) is performed by heating. Is performed before the function of the alkyl sulfate surfactant is lowered (hydrolyzed).

  Specifically, before heating and fusing the resin particles and the colorant particles, a sulfate or hydrogen sulfate is added and heated in a state in which decomposition of the alkyl sulfate surfactant is suppressed, The fusion is advanced to obtain heteroaggregates.

  In this step, after mixing the aqueous dispersion of resin particles and the aqueous dispersion of colorant particles, the aqueous dispersion is adjusted to be acidic, so that when the amphoteric surfactant is used, the amphoteric surfactant is added. It is preferable that the resin particles and the colorant particles are agglomerated by cationization.

  The amount of sulfate or hydrogen sulfate added in the step of producing the heteroaggregate is 10 times to 150 times (molar ratio) of the alkyl sulfate ester surfactant contained in the aqueous dispersion. The amount is preferably 20 times or more and 100 times or less (molar ratio).

  Even when heated by adding an amount of 10 times (molar ratio) or more of the alkyl sulfate surfactant contained in the aqueous dispersion, decomposition of the alkyl sulfate surfactant can be suppressed, and the aqueous dispersion By adding 150 times or less (molar ratio) of the alkyl sulfate ester surfactant contained therein, the toner base particles can be easily cleaned.

  When the above-mentioned amount of sulfate or hydrogen sulfate is added to the aqueous dispersion, decomposition of the alkyl sulfate surfactant can be prevented (suppressed) even when heated.

  In the present invention, the heteroaggregate refers to an aggregate containing at least resin particles and a colorant.

  The toner according to the present invention may have a structure composed only of heteroaggregates, or a core-shell type structure in which heteroaggregates are core particles and a shell layer is provided on the surface thereof.

  Next, the surfactant and sulfate or hydrogen sulfate used in the present invention will be described.

<Anionic sulfate ester surfactant>
As the anionic sulfate type surfactant, an anionic surfactant having a structure containing an alkyl sulfate is preferably used.

What is a surfactant having a structure containing an alkyl sulfate ester?
It is a surfactant having an R—O—SO ₃ X structure.

(Wherein R represents an alkyl group, and X represents an alkali metal)
Examples of preferred compounds include sulfates (sodium dodecylbenzene sulfate, polyoxyethylene-2-dodecyl ether sulfate sodium), sulfate esters (sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, etc.). it can.

《Sulfate》
The sulfate used in the present invention is a compound that is hydrolyzed in an aqueous dispersion to form a hydrogen sulfate.

  Preferred examples of the sulfate include potassium sulfate, sodium sulfate, and ammonium sulfate.

<< hydrogen sulfate >>
Preferred examples of the sulfate include potassium hydrogen sulfate, sodium hydrogen sulfate, and ammonium hydrogen sulfate.

  Next, an example of the toner manufacturing method of the present invention will be described.

(1) The polymerizable monomer solution is converted into oil droplets in an aqueous medium containing either an alkyl sulfate ester surfactant, an amphoteric surfactant or a cationic surfactant, and the polymerizable monomer in the oil droplets A process for preparing an aqueous dispersion of resin particles having a particle size of 100 to 200 nm by polymerizing the body, and a surfactant having a polarity different from that of the surfactant used when preparing the aqueous dispersion of resin particles for the colorant particles (2) Resin particles and coloration step of dispersing in an aqueous solution containing an agent (either alkyl sulfate surfactant, amphoteric surfactant or cationic surfactant) to prepare an aqueous dispersion of colorant particles After the aqueous dispersion of the agent particles is acidified, the inorganic salt is added in an amount of 10 to 150 times (molar ratio) of the alkyl sulfate ester surfactant, and then heated to cause heteroaggregation of the heteroaggregate. Aggregation step for producing aqueous dispersion (3) Aging step for producing aqueous dispersion of toner base particles by adjusting the particle size and shape by aging the aqueous dispersion of heteroaggregates with thermal energy (4) Toner Cooling step for cooling the aqueous dispersion of base particles (5) Filtration and washing for solid-liquid separation of the toner base particles from the cooled aqueous dispersion of toner base particles and removing the surfactant from the toner base particles Step (6) Drying Step for Drying Washed Toner Base Particles (7) The step includes adding an external additive to the dried toner base particles to produce a toner.

  Details will be described below.

(1) a step of preparing an aqueous dispersion of resin particles and an aqueous dispersion of colorant particles;
An aqueous dispersion of resin particles is obtained by adding a polymerizable monomer solution to an aqueous medium containing either an alkyl sulfate ester surfactant, an amphoteric surfactant, or a cationic surfactant to increase mechanical energy. In addition, oil droplets can be formed, and then a polymerization reaction can be performed in the oil droplets by radicals from a water-soluble radical polymerization initiator.

  In this polymerization step, an aqueous dispersion of resin particles containing a binder resin and a release agent added as necessary is obtained.

  Here, the “aqueous medium” means that the main component (50% by mass or more) is made of water. Examples of components other than water include organic solvents that dissolve in water, such as methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, and tetrahydrofuran. Among these, alcohol-based organic solvents such as methanol, ethanol, isopropanol, and butanol, which are organic solvents that do not dissolve the resin, are particularly preferable.

  The method for producing oil droplets by dispersing the polymerizable monomer solution in an aqueous medium is not particularly limited, but a method of dispersing by mechanical energy is preferred. Examples of the disperser that forms oil droplets by mechanical energy include CLEARMIX, ultrasonic disperser, mechanical homogenizer, Manton Gorin, and pressure homogenizer. As a particle size of an oil droplet, 10-1000 nm is preferable and 30-300 nm is more preferable.

  The aqueous dispersion of colorant particles is a surfactant having a different polarity from the surfactant used when preparing the aqueous dispersion of resin particles (for example, an alkyl sulfate ester when preparing an aqueous dispersion of resin particles). When a surfactant is used, it can be prepared by dispersing colorant particles in an aqueous medium containing either an amphoteric surfactant or a cationic surfactant having different polarities.

  The disperser used for the dispersion treatment of the colorant particles is not particularly limited, but preferably an ultrasonic disperser, a mechanical homogenizer, a pressure disperser such as a manton gourin or a pressure homogenizer, a sand grinder, a Getzmann mill or a diamond fine mill. Media type dispersers.

(2) agglomeration step;
In the aggregation step, an aqueous dispersion of colorant particles containing a surfactant having a polarity different from the surfactant used when the aqueous dispersion of resin particles was prepared in the aqueous dispersion of resin particles, The resin particles and the colorant particles are aggregated. In the middle of the aggregation process, binder resin particles having different resin compositions can be added to obtain aggregated particles.

  Further, in the aggregation step, aggregated particles containing internal additive particles such as a release agent and a charge control agent can be obtained together with the binder resin particles and the colorant particles.

  In the present invention, particle growth is performed by mixing resin particles and colorant particles having electrically different polarities. Add an inorganic salt after acidifying the aqueous dispersion of resin particles and colorant particles, or add an inorganic salt to the aqueous dispersion of resin particles and colorant particles to acidify the aqueous dispersion, and then heat. Then, the mixture is heteroaggregated and, if necessary, heating for controlling the particle size is continued.

  The inorganic salt is added at a stage before heating the aqueous dispersion of resin particles and colorant particles.

  In this aggregation step, it is necessary to quickly raise the temperature by heating, and the rate of temperature rise is preferably 1 ° C./min or more. The upper limit of the temperature rising rate is not particularly limited, but is preferably 15 ° C./min or less from the viewpoint of suppressing the generation of coarse particles due to rapid aggregation and progress of fusion.

  Furthermore, after the aqueous dispersion reaches a temperature equal to or higher than the glass transition temperature of the resin particles, it is important to continue aggregation by maintaining the temperature of the aqueous dispersion for a certain period of time. As a result, the aggregation of the resin particles and the colorant particles and the fusion (disappearance of the interface between the particles) can be effectively advanced to produce a heteroaggregate, and the durability of the finally obtained toner Can be improved.

(3) Aging process;
This aging step is a step of aging the hetero-aggregate with thermal energy until a desired particle size and shape are obtained to produce an aqueous dispersion of toner base particles.

(4) Cooling step;
This cooling step is a step of cooling the aqueous dispersion of the toner base particles. The cooling rate in the cooling treatment is preferably 1 to 20 ° C./min. The cooling treatment method is not particularly limited, and examples thereof include a method of cooling by introducing a refrigerant from the outside of the reaction vessel, and a method of cooling by directly introducing cold water into the reaction system.

(5) Filtration and washing process;
In this filtration / washing step, the toner base particles are solid-liquid separated from the aqueous dispersion of the toner base particles cooled to a predetermined temperature in the above-described step and filtered, and the toner base particles ( And a cleaning treatment for removing deposits such as surfactants from the cake-like aggregate).

  Here, the washing treatment is performed by washing with water until the electric conductivity of the filtrate reaches 10 μS / cm. Examples of the filtration method include a centrifugal separation method, a vacuum filtration method using Nutsche, and a filtration method using a filter press, and are not particularly limited.

(6) drying step;
This step is a step of drying the washed cake-like aggregate to obtain dried toner base particles. Examples of dryers used in this process include spray dryers, vacuum freeze dryers, vacuum dryers, etc., stationary shelf dryers, mobile shelf dryers, fluidized bed dryers, rotary dryers It is preferable to use a stirring dryer or the like. The moisture content of the dried toner base particles is preferably 5% by mass or less, and more preferably 2% by mass or less. In addition, when the toner base particles subjected to the drying treatment are aggregated due to weak interparticle attraction, the aggregate may be crushed. Here, as the crushing treatment apparatus, a mechanical crushing apparatus such as a jet mill, a Henschel mixer, a coffee mill, or a food processor can be used.

(7) External additive treatment process;
This step is a step of adding an external additive to the dried toner base particles. As a mixing device used for adding the external additive, a mechanical mixing device such as a Henschel mixer or a coffee mill can be used.

  Next, substances used in the toner production method of the present invention will be described.

<Resin particles>
Examples of the polymerizable monomer for obtaining resin particles constituting the toner include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-chlorostyrene, and 3,4-dichloro. Styrene, p-phenyl styrene, p-ethyl styrene, 2,4-dimethyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn -Styrene or styrene styrene derivatives such as decylstyrene, pn-dodecylstyrene; methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n- methacrylate Octyl, 2-ethylhexyl methacrylate, meta Methacrylic acid ester derivatives such as stearyl laurate, lauryl methacrylate, phenyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-acrylate -Acrylic ester derivatives such as butyl, isobutyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, lauryl acrylate, phenyl acrylate; olefins such as ethylene, propylene, isobutylene; vinyl chloride, Vinyl halides such as vinylidene chloride, vinyl bromide, vinyl fluoride, vinylidene fluoride; vinyl esters such as vinyl propionate, vinyl acetate, vinyl benzoate; vinyl methyl Vinyl ethers such as ether and vinyl ethyl ether; vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl hexyl ketone; N-vinyl compounds such as N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; vinyl naphthalene And vinyl compounds such as vinylpyridine; vinyl polymerizable monomers such as acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide. These vinyl polymerizable monomers can be used alone or in combination of two or more.

  Moreover, it is preferable to use combining what has an ionic dissociation group as a polymerizable monomer. The polymerizable monomer having an ionic dissociation group has, for example, a substituent such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group as a constituent group, preferably acrylic acid, methacrylic acid, maleic acid, Itaconic acid, cinnamic acid, fumaric acid, maleic acid monoalkyl ester, itaconic acid monoalkyl ester, styrenesulfonic acid, allylsulfosuccinic acid, 2-acrylamido-2-methylpropanesulfonic acid, acid phosphooxyethyl methacrylate, 3 -Chloro-2-acid phosphooxypropyl methacrylate and the like.

  Furthermore, as a polymerizable monomer, divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl A binder resin having a crosslinked structure can also be obtained using a polyfunctional vinyl such as glycol diacrylate.

<Polymerization initiator>
The resin particles constituting the toner can be prepared by polymerizing a polymerizable monomer in the presence of a radical polymerization initiator.

  In the case of using the suspension polymerization method, an oil-soluble radical polymerization initiator can be used. As the oil-soluble polymerization initiator, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2 ′ -Azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile, etc. Azo or diazo polymerization initiator, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, 2,4- Dichlorobenzoyl peroxide, lauroyl peroxide, 2 Peroxide polymerization initiators such as 2-bis- (4,4-t-butylperoxycyclohexyl) propane and tris- (t-butylperoxy) triazine, polymer initiators having a peroxide in the side chain, etc. Can be mentioned.

  In the case of using the miniemulsion polymerization aggregation method or the emulsion polymerization aggregation method, a water-soluble radical polymerization initiator can be used, and the water-soluble radical polymerization initiator includes persulfates such as potassium persulfate and ammonium persulfate. Azobisaminodipropane acetate, azobiscyanovaleric acid and its salts, hydrogen peroxide, and the like.

《Chain transfer agent》
When the resin particles constituting the toner are produced by suspension polymerization, miniemulsion polymerization aggregation or emulsion polymerization aggregation, a commonly used chain transfer agent is used for the purpose of adjusting the molecular weight of the resin. Can do.

  The chain transfer agent is not particularly limited. For example, mercaptans such as n-octyl mercaptan, n-decyl mercaptan, tert-dodecyl mercaptan, n-octyl-3-mercaptopropionate, terpinolene, carbon tetrabromide And α-methylstyrene dimer and the like are used.

"Release agent"
The toner particles preferably contain a release agent that contributes to the suppression of the offset phenomenon. This release agent may be contained in the resin particles, or may be added during aggregation to be taken into the toner particles. The release agent is not particularly limited, and examples thereof include low molecular weight polyethylene wax, low molecular weight oxidized polyethylene wax, low molecular weight polypropylene wax, low molecular weight oxidized polypropylene wax, Fischer-Tropsch wax, microcrystalline wax, and paraffin wax. Hydrocarbon wax such as carnauba wax, sazol wax, rice wax, candelilla wax, jojoba oil wax, beeswax wax and other natural product wax, pentaerythritol behenate ester, pentaerythritol stearate ester And synthetic ester waxes such as behenyl behenate and stearyl stearate.

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

  The content ratio of the release agent in the toner particles is usually 0.5 to 5 parts by mass, preferably 1 to 3 parts by mass with respect to 100 parts by mass of the resin forming the toner particles. When the content ratio of the offset inhibitor is less than 0.5 parts by mass with respect to 100 parts by mass of the resin forming the toner particles, it is difficult to obtain a sufficient offset prevention effect. On the other hand, if it is larger than 5 parts by mass, the obtained toner may have low translucency and color reproducibility.

<Colorant particles>
As the colorant particles used in the present invention, known inorganic or organic colorant particles can be used. In the following, preferred colorant particles are shown.

  Examples of black colorant particles include carbon black such as furnace black, channel black, acetylene black, thermal black, and lamp black, and magnetic powder such as magnetite and ferrite.

  Examples of colorant particles for magenta or red include C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 48; 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 139, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. And CI Pigment Red 222.

  Examples of the colorant particles for orange or yellow include C.I. I. Pigment orange 31, C.I. I. Pigment orange 43, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 138, and the like.

  Examples of the colorant particles for green or cyan include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15; 2, C.I. I. Pigment blue 15; 3, C.I. I. Pigment blue 15; 4, C.I. I. Pigment blue 16, C.I. I. Pigment blue 60, C.I. I. Pigment blue 62, C.I. I. Pigment blue 66, C.I. I. And CI Pigment Green 7.

  The above colorant particles can be used alone or in combination of two or more.

  Further, the addition amount of the colorant particles is preferably 1 to 30% by mass and more preferably 2 to 20% by mass with respect to the total mass of the toner.

<Amphoteric surfactant>
Examples of amphoteric surfactants used when preparing polymerizable monomer particles or when preparing a dispersion of colorant particles include N-ethylnitrilotriacetic acid, N-ethyldimethyl N oxide, and α-trimethyl. Ammonio fatty acid, N-ethyl-β-aminopropionate, N-ethyl-β-iminopropionate, N-ethyl-oxymethyl-N, N-diethyl N oxide, N-ethyl-N, N-diamino Examples thereof include ethyl glycine hydrochloride, 2-ethyl imidazoline derivative, aminoethyl imidazoline organic acid salt, N-ethylsulfo N oxide, N-ethyl taurine salt, lauric acid amidopropyl betaine, lauryl dimethylaminoacetic acid betaine.

<Cationic surfactant>
Cationic surfactants used when preparing polymerizable monomer particles or when preparing a dispersion of colorant particles include laurylamine hydrochloride, stearylamine hydrochloride, oleylamine acetate, stearylamine acetate. Amine salts such as stearylaminopropylamine acetate; lauryltrimethylammonium chloride, dilauryldimethylammonium chloride, distearylammonium chloride, distearyldimethylammonium chloride, lauryldihydroxyethylmethylammonium chloride, oleylbispolyoxyethylenemethylammonium chloride, Lauroylaminopropyldimethylethylammonium etosulphate, lauroylaminopropyldimethylhydroxyethylammonium par Loreto, can be ethylbenzene dimethyl ammonium chloride, quaternary ammonium salts such as trimethylammonium chloride and the exemplified.

<External additive>
It is preferable to add a so-called external additive to the toner according to the present invention for the purpose of improving fluidity, charging property and cleaning property. These external additives are not particularly limited, and various inorganic fine particles, organic fine particles and lubricants can be used.

  As the inorganic fine particles, it is preferable to use inorganic oxide particles such as silica, titania and alumina, and these inorganic fine particles are preferably hydrophobized with a silane coupling agent or a titanium coupling agent. . As the organic fine particles, spherical particles having a number average primary particle size of about 10 to 2000 nm can be used. As the organic fine particles, polymers such as polystyrene, polymethyl methacrylate, and styrene-methyl methacrylate copolymer can be used.

  The addition ratio of these external additives is preferably 0.1 to 5.0% by mass, and more preferably 0.5 to 4.0% by mass with respect to the total mass of the toner. In addition, various external additives may be used in combination.

<Characteristics of toner>
Next, the characteristics of the toner according to the present invention will be described.

(Toner particle size)
The toner according to the present invention preferably has a volume-based median diameter (D ₅₀ ) of 3.0 to 8.0 μm, more preferably 3.0 to 7.0 μm.

The median diameter (D ₅₀ ) on the volume basis is 3.0 to 8.0 μm, so that dot reproducibility and color printing with high image quality can be achieved, and toner consumption is large. It can be reduced compared to the case where it was.

  In the toner production method described above, the particle size and particle size distribution of the toner are determined using an anionic sulfate ester type surfactant in the step of preparing an aqueous dispersion, and an anionic sulfate type in the step of preparing the heteroaggregate. It can be controlled by adding an inorganic salt that prevents hydrolysis of the surfactant.

(Toner particle size distribution (coefficient of variation))
The particle size distribution of the toner according to the present invention is represented by a coefficient of variation (CV value) in the volume-based particle size distribution. The coefficient of variation (CV value) in the volume-based particle size distribution is preferably 2% or more and 21% or less, particularly preferably 5% or more and 15% or less.

  By setting the CV value within the above range, toner sizes are uniform, and a clear image can be formed.

(Average circularity of toner)
The toner according to the present invention preferably has an average circularity of 0.916 to 0.955.

(Measuring method)
A method for measuring the particle size, particle size distribution (coefficient of variation) and average circularity of the toner will be described.

The volume-based median diameter (D ₅₀ ) representing the particle diameter of the toner corresponds to a count number (cumulative value) corresponding to 50% of the total particle number when a certain volume of toner is counted in order of increasing or decreasing particle diameter. The toner has a particle size.

  The coefficient of variation in the volume-based particle size distribution of the toner is a value calculated from the following equation.

Coefficient of variation (CV value) (%) = (S2 / Dn) × 100
(In the formula, S2 represents the standard deviation in the particle size distribution based on volume, and Dn represents the median diameter (D ₅₀ ) (μm) based on volume).
For median diameter (D ₅₀ ) and coefficient of variation (CV value) of toner based on volume, connect a computer system for data processing (Beckman Coulter) to “Coulter Multisizer 3 (Beckman Coulter)” It can be measured and calculated using the apparatus.

  As a measurement procedure, 0.02 g of toner is blended with 20 ml of a surfactant solution (for example, a surfactant solution obtained by diluting a neutral detergent containing a surfactant component 10 times with pure water for the purpose of dispersing the toner). After that, ultrasonic dispersion is performed for 1 minute to prepare a toner dispersion. Pipet this toner dispersion into a beaker containing the electrolyte “ISOTONII” (manufactured by Beckman Coulter) in the sample stand until the measured concentration reaches 8%, and set the measuring machine count to 2500. To measure. The aperture diameter of “Coulter Multisizer 3” is 50 μm.

  The average circularity of the toner is calculated from the following equation.

Circularity = (perimeter of a circle having the same projection area as the particle image) / (perimeter of the particle projection image)
The average circularity is a value calculated by dividing the sum of the circularity of individual toner particles by the total number of particles.

  As an apparatus for measuring the circularity of the toner, for example, “FPIA-2100 (manufactured by Sysmex)” can be mentioned. In the measurement using FPIA-2100, the toner is blended with an aqueous solution containing a surfactant, and after ultrasonic dispersion treatment is performed for 1 minute to disperse the toner, the measurement is performed using FPIA-2100. Measurement conditions are set to the HPF (high magnification imaging) mode and the number of HPF detections is set to an appropriate density of 3000 to 10,000.

  In the present invention, the toner is an aggregate of toner particles.

<Developer>
The toner according to the present invention is not particularly limited as long as it is a dry developer, and can be used for a known two-component developer using a carrier, a magnetic one-component developer, and a non-magnetic one-component developer.

<Image forming apparatus>
The toner according to the present invention can be preferably used in a known electrophotographic image forming apparatus having a dry development, a heat fixing unit, and a cleaning unit using a cleaning blade.

  Hereinafter, a color image forming method and an image forming apparatus in which the toner according to the present invention is preferably used will be described.

  FIG. 1 is a schematic cross-sectional view showing an example of a color image forming apparatus using toner according to the present invention.

  First, an outline of an image forming apparatus for color electrophotography equipped with a detection sensor and a secondary transfer device will be described.

  The image forming apparatus GS is called a tandem type color image forming apparatus, and arranges image forming units that form yellow, magenta, cyan, and black color toner images along the moving direction of the intermediate transfer material. The color toner image formed on the image carrier of the image forming unit is transferred onto the intermediate transfer material by multiple transfer, and then transferred onto the transfer material at a time.

  In FIG. 1, a document image placed on an image reading device SC disposed at a position occupying the upper portion of the image forming device GS is scanned and exposed by an optical system, read into a line image sensor CCD, and line image sensor CCD. The analog signal photoelectrically converted by the above is subjected to analog processing, A / D conversion, shading correction, image compression processing, and the like in the image processing section, and then sent to the exposure optical system 3 as image writing means. .

  The intermediate transfer material includes a drum type and an endless belt type, both of which have the same function. However, in the following description, the intermediate transfer material refers to an endless belt-like intermediate transfer 6. I will decide.

  In FIG. 1, four sets of process units 100 are formed on the peripheral edge of the intermediate transfer material 6 for image formation for each color of yellow (Y), magenta (M), cyan (C) and black (K). Is provided. The process unit 100 is arranged in a vertical column along the intermediate transfer material 6 as a color toner image forming unit along the intermediate transfer material 6 with respect to the rotation direction of the vertical intermediate transfer material 6 indicated by arrows in the drawing. , K in this order.

  Each of the four sets of process units 100 has a common structure, and each includes a photosensitive drum 1, a charger 2 as a charging unit, an exposure optical system 3 as an image writing unit, a developing device 4, and an image. It comprises a photoconductor cleaning device 190 as a carrier cleaning means.

  In the photosensitive drum 1, a photosensitive layer having a layer thickness (film thickness) of about 20 to 40 μm is formed on the outer periphery of a cylindrical substrate formed of a metallic member such as aluminum having an outer diameter of about 40 to 100 mm. Is. The photosensitive drum 1 is rotated in the direction of the arrow in a state where the substrate is grounded by power from a driving source (not shown), for example, at a linear velocity of about 80 to 280 mm / s, preferably 220 mm / s.

  Around the photosensitive drum 1, an image forming unit including a charger 2 as a charging unit, an exposure optical system 3 as an image writing unit, and a developing device 4 is set as a photosensitive drum indicated by an arrow in the figure. 1 with respect to the rotation direction.

  The charger 2 as a charging unit is attached in close proximity to the photosensitive drum 1 in a direction parallel to the rotation axis of the photosensitive drum 1. The charger 2 includes a discharge wire as a corona discharge electrode that applies a predetermined potential to the photosensitive layer of the photosensitive drum 1, and performs a charging action (negative charging in the present embodiment) by corona discharge having the same polarity as the toner. A uniform potential is applied to the photosensitive drum 1.

  An exposure optical system 3 serving as an image writing means rotationally scans laser light emitted from a semiconductor laser (LD) light source (not shown) in a main scanning direction by a rotating polygon mirror (no symbol), and an fθ lens (no symbol). ), A reflection mirror (without a symbol), etc., the photosensitive drum 1 is exposed to an electrical signal corresponding to an image signal (image writing), and an electrostatic latent image corresponding to a document image is formed on the photosensitive layer of the photosensitive drum 1. Form an image.

  The developing device 4 as a developing unit is configured to supply a two-component developer of each color of yellow (Y), magenta (M), cyan (C), and black (K) charged to the same polarity as the charging polarity of the photosensitive drum 1. A developing roller 4a, which is a developer carrier formed of a cylindrical nonmagnetic stainless steel or aluminum material having a thickness of 0.5 to 1 mm and an outer diameter of 15 to 25 mm, for example, is provided. The developing roller 4a is kept in contact with the photosensitive drum 1 with a predetermined gap (for example, 100 to 1000 μm) by an abutting roller (not shown), and rotates in the same direction as the rotational direction of the photosensitive drum 1. At the time of development, a photoconductor drum is applied by applying to the developing roller 4a a DC voltage having the same polarity as the toner (negative polarity in the present embodiment) or a developing bias voltage that superimposes an AC voltage on the DC voltage. The reversal development is performed on the upper exposed portion.

The intermediate transfer material 6 has a volume resistivity of about 1.0 × 10 ^{7 to} 1.0 × 10 ⁹ Ω · cm and a surface resistivity of about 1.0 × 10 ^{10 to} 1.0 × 10 ¹² Ω / □. A semiconductive endless (seamless) resin belt is used. As the resin belt, a semiconductive material having a thickness of 0.05 to 0.5 mm in which a conductive material is dispersed in engineering plastics such as modified polyimide, thermosetting polyimide, ethylene tetrafluoroethylene copolymer, polyvinylidene fluoride, and nylon alloy. A resin film can be used. In addition to this, a semiconductive rubber belt having a thickness of 0.5 to 2.0 mm in which a conductive material is dispersed in silicone rubber, urethane rubber or the like can also be used as the intermediate transfer material 6. The intermediate transfer material 6 is wound around a plurality of roller members including a tension roller 6a and a backup roller 6B facing the secondary transfer member, and is supported so as to be rotatable in the vertical direction.

  The primary transfer roller 7 as the first transfer unit for each color is made of a roller-like conductive member using foamed rubber such as silicone or urethane, for example, and the photosensitive drum 1 for each color with the intermediate transfer material 6 interposed therebetween. The transfer area is formed between the photosensitive drum 1 and the back surface of the intermediate transfer material 6 by pressing the back surface thereof. A DC constant current having a polarity opposite to that of the toner (positive polarity in the present embodiment) is applied to the primary transfer roller 7 by constant current control, and a toner image on the photosensitive drum 1 is formed by a transfer electric field formed in the transfer area. Transferred onto the intermediate transfer material 6.

  The toner image transferred onto the intermediate transfer material 6 is transferred to the transfer material P. A detection sensor 8 for measuring the density of the patch image toner is provided on the periphery of the intermediate transfer material 6.

  In order to clean the residual toner on the intermediate transfer material 6, a cleaning device 190A is provided.

  Further, a secondary transfer device 70 is provided for cleaning the patch image toner on the secondary transfer member 7A.

  Next, an image forming process (image forming process) will be described.

  When the image recording is started, the photosensitive drum drive motor (not shown) is rotated to rotate the Y photosensitive drum 1 in the direction indicated by the arrow in the figure, and a potential is applied to the Y photosensitive drum 1 by the Y charger 2. . After the Y photosensitive drum 1 is applied with a potential, the Y exposure optical system 3 performs exposure (image writing) with an electrical signal corresponding to the first color signal, that is, the Y image data. An electrostatic latent image corresponding to a yellow (Y) image is formed on the body drum 1. The latent image is reversely developed by the Y developing device 4 to form a toner image made of yellow (Y) toner on the Y photosensitive drum 1. The Y toner image formed on the Y photosensitive drum 1 is transferred onto the intermediate transfer material 6 by a primary transfer roller 7 as a primary transfer means.

  Next, a potential is applied to the M photosensitive drum 1 by the M charger 2. After the potential is applied to the M photoconductor drum 1, the M exposure optical system 3 performs exposure (image writing) with an electrical signal corresponding to the first color signal, that is, the M image data, and the M photosensitivity. An electrostatic latent image corresponding to a magenta (M) image is formed on the body drum 1. The latent image is reversely developed by the M developing device 4 to form a toner image made of magenta (M) toner on the M photoconductor drum 1. The M toner image formed on the M photoconductor drum 1 is transferred onto the intermediate transfer material 6 by being superimposed on the Y toner image by a primary transfer roller 7 as a primary transfer unit.

  By a similar process, a toner image made of cyan (C) toner formed on the C photoconductive drum 1 and a toner image made of black (K) toner formed on the K photoconductive drum 1 are obtained. The toner images are sequentially superimposed on the intermediate transfer material 6, and a superimposed color toner image composed of Y, M, C, and K toners is formed on the peripheral surface of the intermediate transfer material 6.

  The toner remaining on the peripheral surface of each photoreceptor drum 1 after the transfer is cleaned by the photoreceptor cleaning device 190.

  On the other hand, the transfer material P as recording paper accommodated in the paper feed cassettes 20A, 20B, and 20C is fed by the feed roller 21 and the paper feed roller 22A provided in the paper feed cassettes 20A, 20B, and 20C, respectively, and conveyed. A secondary transfer member serving as a secondary transfer unit that is transported on the path 22 by transport rollers 22B, 22C, and 22D and to which a voltage having a polarity opposite to that of the toner (plus polarity in the present embodiment) is applied via the registration roller 23. The superimposed color toner images (color images) formed on the intermediate transfer material 6 are transferred onto the transfer material P in a lump in the transfer area of the secondary transfer member 7A.

  The transfer material P onto which the color image has been transferred is heated and pressed at the fixing nip NA formed by the heating member 17a and the pressure roller 17b of the fixing device 17, and is fixed by the paper discharge roller 24. It is placed on the outer paper discharge tray 25.

  The above describes the state in which image formation is performed on the first surface, which is one side of the transfer material P. In the case of duplex copying, the sheet discharge switching member 26 is switched, the sheet guide portion 26A is opened, and the transfer is performed. The material P is conveyed in the direction of a broken line arrow.

  Further, the transfer material P is transported to the lower transport path 27B by the transport mechanism 27A, switched back by the sheet reversing portion 27C, and the transport path is switched by the branching portion 27D. And is conveyed into the duplex copying paper feed unit 130.

  The transfer material P moves in the paper feeding direction through a conveyance guide 131 provided in the duplex copying paper supply unit 130, and the transfer material P is re-fed by the paper supply roller 132 and guided to the conveyance path 22.

  Then, as described above, the transfer material P is conveyed in the direction of the secondary transfer member 7A, the toner image is transferred to the second surface which is the back surface of the transfer material P, fixed by the fixing device 17, and then the paper discharge tray. 25 is discharged.

  Further, after the color image is transferred onto the transfer material P by the secondary transfer member 7A as the secondary transfer means, the residual toner on the intermediate transfer material 6 which has separated the curvature of the transfer material P becomes the intermediate transfer material cleaning device 190A. Is removed.

  Further, the patch image toner on the secondary transfer member 7 </ b> A is cleaned by the cleaning blade 71 of the secondary transfer device 70.

  As a material for the cleaning blade, urethane rubber, silicone rubber, fluorine rubber, chloroprene rubber, butadiene rubber, or the like can be used. Among these, urethane rubber is preferable in terms of excellent wear characteristics. The shape and material of the cleaning blade are appropriately selected according to various conditions such as thickness, toner characteristics, characteristics of the photosensitive member, intermediate transfer belt and secondary transfer member, cleaning blade contact angle and contact pressure. The

<Transfer material>
The transfer material on which the toner image according to the present invention is formed is a support for holding the toner image, and is preferably coated with plain paper, fine paper, art paper or coated paper from thin paper to thick paper. Various types of printing paper, commercially available Japanese paper, postcard paper, OHP plastic film, cloth, and the like can be used, but the invention is not limited to these.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, the aspect of this invention is not limited to this.

<Production of toner>
A toner was prepared as follows.

<Preparation of aqueous dispersion 1 of resin particles>
A reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introducing device was charged with a solution prepared by dissolving 7 parts by mass of sodium polyoxyethylene-2-dodecyl ether sulfate in 800 parts by mass of ion-exchanged water, and the temperature was 90 ° C. After heating, 241 parts by mass of styrene, 89 parts by mass of n-butyl acrylate, 2 parts by mass of n-dodecyl mercaptan, 180 parts by mass of paraffin wax dissolved at 90 ° C. (melting point: 68 ° C.) are added and have a circulation path. An aqueous dispersion containing emulsified particles (oil droplets) was prepared by mixing and dispersing for 1 hour using a mechanical disperser “CREARMIX” (manufactured by M Technique).

  Next, an initiator solution in which 6 parts by mass of potassium persulfate (manufactured by Kanto Kagaku Co., Ltd .: special grade) is dissolved in 200 parts by mass of ion-exchanged water is added to the aqueous dispersion, and the system is added at 82 ° C. for 3 hours. Polymerization was carried out by heating and stirring over time to prepare “Aqueous dispersion 1 of resin particles”. When the particle diameter of the resin particles in this aqueous dispersion was measured using an electrophoretic light scattering photometer “ELS-800” (manufactured by Otsuka Electronics Co., Ltd.), the median diameter on a volume basis was 120 nm. The glass transition point was 40 ° C.

<Preparation of aqueous dispersion 2 of resin particles>
A reaction vessel equipped with a stirrer, a temperature sensor, a condenser, and a nitrogen introducing device was charged with a solution prepared by dissolving 7 parts by mass of lauryldimethylaminoacetate betaine in 800 parts by mass of ion-exchanged water, heated to 90 ° C., and then styrene 241. Mass part, 89 parts by mass of n-butyl acrylate, 2 parts by mass of n-dodecyl mercaptan, 180 parts by mass of paraffin wax (melting point 68 ° C.) are dissolved at 90 ° C., and a polymerizable monomer solution is added to have a circulation route. An aqueous dispersion containing emulsified particles (oil droplets) was prepared by mixing and dispersing for 1 hour using a mechanical disperser “CREARMIX” (manufactured by M Technique).

  Next, an initiator solution in which 6 parts by mass of potassium persulfate (manufactured by Kanto Kagaku Co., Ltd .: special grade) is dissolved in 200 parts by mass of ion-exchanged water is added to the aqueous dispersion, and the system is added at 82 ° C. for 3 hours. Polymerization was carried out by heating and stirring over time to prepare “Aqueous dispersion 2 of resin particles”. When the particle diameter of the resin particles in this aqueous dispersion was measured using an electrophoretic light scattering photometer “ELS-800” (manufactured by Otsuka Electronics Co., Ltd.), the median diameter on a volume basis was 120 nm. The glass transition point was 40 ° C.

<Preparation of aqueous dispersion 1 of colorant particles>
While stirring a solution prepared by dissolving 10 parts by mass of lauryldimethylaminoacetic acid betaine in 160 parts by mass of ion-exchanged water, 36 parts by mass of carbon black “Mogal L” (manufactured by Cabot) was gradually added, and then mechanical dispersion was performed. An aqueous dispersion of colorant particles was prepared by dispersing using a machine “CREARMIX” (M Technique Co., Ltd.). When the particle diameter of the colorant particles in the aqueous dispersion of the colorant particles was measured using an electrophoretic light scattering photometer “ELS-800” (manufactured by Otsuka Electronics Co., Ltd.), the median diameter on a volume basis was 110 nm. there were.

<Preparation of aqueous dispersion 2 of colorant particles>
While stirring a solution prepared by dissolving 10 parts by mass of sodium polyoxyethylene-2-dodecyl ether sulfate in 160 parts by mass of ion-exchanged water, 36 parts by mass of carbon black “Mogal L” (manufactured by Cabot) was gradually added. Next, an aqueous dispersion of colorant particles was prepared by performing a dispersion treatment using a mechanical disperser “CREARMIX” (manufactured by M Technique Co., Ltd.). When the particle diameter of the colorant particles in the aqueous dispersion of the colorant particles was measured using an electrophoretic light scattering photometer “ELS-800” (manufactured by Otsuka Electronics Co., Ltd.), the median diameter on a volume basis was 110 nm. there were.

<Preparation of aqueous dispersion 3 of colorant particles>
While stirring a solution prepared by dissolving 10 parts by mass of lauryltrimethylammonium chloride in 160 parts by mass of ion-exchanged water, 36 parts by mass of carbon black “Mogal L” (manufactured by Cabot) was gradually added, and then a mechanical disperser An aqueous dispersion of colorant particles was prepared by dispersing using “CREARMIX” (manufactured by M Technique). When the particle diameter of the colorant particles in the aqueous dispersion of the colorant particles was measured using an electrophoretic light scattering photometer “ELS-800” (manufactured by Otsuka Electronics Co., Ltd.), the median diameter on a volume basis was 110 nm. It was.

<Preparation of Toner 1>
(Aggregation / fusion process)
(Preparation of heteroaggregate 1)
In a reaction vessel equipped with a stirrer, a temperature sensor, and a cooling pipe, 200 parts by mass (in terms of solids) of “aqueous dispersion 1 of resin particles 1” (using an anionic sulfate ester type surfactant) having a solid content of 30% by mass, 500 parts by mass of ion-exchanged water was added, and the pH was adjusted to 10 by adding a 5 mol / liter aqueous sodium hydroxide solution. Thereafter, 50 parts by weight (in terms of solid content) of “colorant particle aqueous dispersion 1” was added, and a 5 mol / liter hydrochloric acid aqueous solution was added to adjust to the acidic side of pH 2 to 3. Thereto was added 98 times the amount of “sodium sulfate” relative to the anionic sulfate ester type surfactant brought in by the dispersion of resin particles. Then, aggregation reaction was performed by heating up to 60 degreeC. The particle size of the aggregated particles was measured using “Coulter Multisizer 3”, and it was confirmed that the particle size was 5.8 μm.

(Shape control process)
Furthermore, the particle shape was controlled by heating and stirring at a liquid temperature of 90 ° C. This shape was measured by “FPIA-2100” with an average shape factor, and when the shape factor of the particle became 0.940, it was cooled to 25 ° C. to obtain an “aqueous dispersion of heteroaggregates”. .

(Cooling process)
The shape was monitored, and after the average shape factor reached 0.96, the liquid temperature was cooled to 30 ° C. and stirring was stopped to obtain “aqueous dispersion of toner base particles 1”.

(Washing / drying process)
The “toner base particles” in the aqueous dispersion of the toner base particles 1 obtained in the above process are solid-liquid separated with a basket type centrifuge “MARK III model number 60 × 40” (manufactured by Matsumoto Kikai Co., Ltd.). Then, a wet cake of toner base particles is formed, and this wet cake is washed with ion exchange water at 45 ° C. until the electric conductivity of the filtrate reaches 10 μS / cm by the basket type centrifuge, and then “flash jet” is used. The product was transferred to a “dryer” (manufactured by Seishin Enterprise Co., Ltd.) and dried until the water content became 0.5 mass% to obtain “toner base particle 1”.

(External additive mixing process)
1% by mass of hydrophobic silica (number average primary particle size = 12 nm) and 0.3% by mass of hydrophobic titania (number average primary particle size = 20 nm) are added to the toner base particles 1 obtained above. Then, “Toner 1” was prepared by mixing with a Henschel mixer.

<Preparation of Toner 2>
“Toner 2” was prepared in the same manner except that the aggregation / fusion process was changed as follows in preparation of toner 1.

(Aggregation / fusion process)
In a reaction vessel equipped with a stirrer, a temperature sensor, and a cooling pipe, 200 parts by mass (in terms of solids) of “aqueous dispersion 1 of resin particles 1” (using an anionic sulfate ester type surfactant) having a solid content of 30% by mass, 500 parts by mass of ion-exchanged water was added, and the pH was adjusted to 10 by adding a 5 mol / liter aqueous sodium hydroxide solution.

  Thereafter, 50 parts by weight (in terms of solid content) of “colorant particle aqueous dispersion 1” was added, and a 5 mol / liter hydrochloric acid aqueous solution was added to adjust to the acidic side of pH 2 to 3.

  Thereto was added 98 times the amount of “sodium sulfate” relative to the anionic sulfate ester type surfactant brought in by the dispersion of resin particles.

  Thereafter, the resin particles and the colored particles were aggregated by raising the temperature to 60 ° C. When the particle diameter of the aggregated particles was measured using “Coulter Multisizer 3”, it was 5.9 μm.

<Preparation of Toner 3>
“Toner 3” was prepared in the same manner except that the amount of “sodium sulfate” used in preparation of toner 1 was changed from 98 times to 150 times. When the particle diameter of the aggregated particles was measured using “Coulter Multisizer 3”, it was 5.4 μm.

<Preparation of Toner 4>
“Toner 4” was prepared in the same manner except that the amount of “sodium sulfate” used in preparation of toner 1 was changed from 98 times to 10 times. When the particle size of the aggregated particles was measured using “Coulter Multisizer 3”, it was 7.6 μm.

<Preparation of Toner 5>
“Toner 5” was prepared in the same manner except that the amount of “sodium sulfate” used in preparation of toner 1 was changed from 98 times to 50 times. The particle diameter of the aggregated particles was measured using “Coulter Multisizer 3” to be 6.6 μm.

<Preparation of Toner 6>
“Toner 6” was prepared in the same manner except that “sodium sulfate” used in preparation of toner 1 was changed to “potassium sulfate”. When the particle diameter of the aggregated particles was measured using “Coulter Multisizer 3”, it was 6.5 μm.

<Preparation of Toner 7>
“Toner 7” was prepared in the same manner except that “sodium sulfate” used in preparation of toner 1 was changed to “sodium hydrogen sulfate”. When the particle diameter of the aggregated particles was measured using “Coulter Multisizer 3”, it was 6.9 μm.

<Preparation of Toner 8>
“Toner 8” was prepared in the same manner except that the amount of “sodium sulfate” used in preparation of toner 1 was changed from 98 times to 6 times. The particle diameter of the aggregated particles was measured using “Coulter Multisizer 3” and found to be 8.0 μm.

<Preparation of Toner 9>
“Toner 9” was prepared in the same manner except that the amount of “sodium sulfate” used in preparation of toner 1 was changed from 98 times to 156 times. When the particle size of the aggregated particles was measured using “Coulter Multisizer 3”, it was 5.3 μm.

<Preparation of Toner 10>
200 parts by weight (in terms of solid content) of “resin particle aqueous dispersion 1” (using an anionic sulfate ester type surfactant) used in preparation of the toner 1 is 200 parts by weight (solid content). 50 parts by weight of “colorant particle aqueous dispersion 1” (solid content conversion) is 50 parts by weight of “colorant particle aqueous dispersion 2” (using an anionic sulfate ester type surfactant). The amount of added “sodium sulfate” is from 98 times the number of moles of the anionic sulfate ester-type surfactant brought into “resin particle aqueous dispersion 1”. “Toner 10” was prepared in the same manner except that the amount of the anionic sulfate ester surfactant brought in “2” was changed to 98 times the number of moles. When the particle diameter of the aggregated particles was measured using “Coulter Multisizer 3”, it was 5.8 μm.

<Preparation of Toner 11>
The same procedure except that 50 parts by weight (in terms of solid content) of “colorant particle aqueous dispersion 1” used in preparation of toner 1 was changed to 50 parts by weight (in terms of solid content) of “colorant particle aqueous dispersion 3”. Thus, “Toner 11” was produced. The particle diameter of the aggregated particles was measured using “Coulter Multisizer 3” to be 6.6 μm.

<Preparation of Toner 12>
50 parts by weight (in terms of solid content) of “colorant particle aqueous dispersion 1” used in preparation of toner 1 is 50 parts by weight of “colorant particle aqueous dispersion 2” (using an anionic sulfate ester type surfactant). Preparation of “Toner 12” was tried in the same manner except that the solid content was changed. However, aggregation did not progress and a toner could not be obtained.

<Preparation of Toner 13>
200 parts by weight (in terms of solid content) of “resin particle aqueous dispersion 1” (using an anionic sulfate ester type surfactant) used in preparation of the toner 1 is 200 parts by weight (solid content). The production of “Toner 13” was attempted in the same manner except that the amount was changed to “minute conversion”. However, aggregation did not progress and a toner could not be obtained.

<Preparation of Toner 14>
“Toner 14” was prepared in the same manner except that the aggregation / fusion process was changed as follows in preparation of toner 1. When the particle size of the agglomerated particles was measured using “Coulter Multisizer 3”, the particle size was too large and could not be measured because it was out of the measurement range.

(Aggregation / fusion process)
In a reaction vessel equipped with a stirrer, a temperature sensor, and a cooling pipe, 200 parts by mass (in terms of solids) of “aqueous dispersion 1 of resin particles 1” (using an anionic sulfate ester type surfactant) having a solid content of 30% by mass, 500 parts by mass of ion-exchanged water was added, and the pH was adjusted to 10 by adding a 5 mol / liter aqueous sodium hydroxide solution. Thereafter, 50 parts by weight (in terms of solid content) of “colorant particle aqueous dispersion 1” was added, and a 5 mol / liter hydrochloric acid aqueous solution was added to adjust to the acidic side of pH 2 to 3. After raising the temperature to 75 ° C., 98 times the amount of “sodium sulfate” was added, and then an aggregation reaction was performed.

<Preparation of Toner 15>
In the production of the toner 1, the aggregated particles were measured using “Coulter Multisizer 3” without adding sodium sulfate, and when the toner particle size reached 6.6 μm, the polyoxyethylene which is a nonionic surfactant “Toner 15” was prepared in the same manner except that 50 parts by mass of distyrenated phenyl ether was added. When the particle diameter of the aggregated particles was measured using “Coulter Multisizer 3”, it was 6.4 μm.

  Table 1 shows the dispersion used in the preparation of the toner, the inorganic salt used, the addition timing and amount of the inorganic salt, and the particle size and particle size distribution of the toner.

  The particle diameter and particle size distribution of the toner are values obtained by measurement using the above method.

<Evaluation>
As an image forming apparatus for evaluation, a commercially available image forming apparatus “bizhub C6500” (manufactured by Konica Minolta Business Technologies Co., Ltd.) (65 sheets / 1 minute, A4 size lateral feed) was prepared.

<Cleaning failure>
The poor cleaning was evaluated by the fog caused by passing through the cleaning blade.

  Specifically, using the above image forming apparatus, after printing 500,000 character images with a printing rate of 5% in a printing environment of 20 ° C. and 50% RH, printing a solid image, passing a blank sheet, The observation was performed visually. ◎ and ○ are acceptable.

Evaluation criteria A: No fogging caused by slipping through the cleaning blade ○: Fog caused by slipping through the cleaning blade is slight, but there is no problem in practical use ×: Fog caused by slipping through the cleaning blade is serious and problematic in practical use

(Cover)
The fog was evaluated by the fog caused by the surface of the photoreceptor being contaminated with toner (toner filming).

  Specifically, using the above-described image forming apparatus, after printing 500,000 character images with a printing rate of 5% in a printing environment of 20 ° C. and 50% RH, white paper was printed and evaluated by the white paper density of the transfer material. The white paper density of the transfer material is measured at 20 points of A4 size, and the average value is defined as the white paper density. Density measurement was performed using a reflection densitometer “RD-918” (manufactured by Macbeth). ◎ and ○ are acceptable.

Evaluation criteria A: The fog density is less than 0.003 B: The fog density is 0.003 or more and less than 0.010, and there is no practical problem. ×: The fog density is 0.010 or more and the problem is practical. .

<Toner scattering>
Toner scattering was evaluated by visually observing the state of contamination inside the machine due to toner scattering around the developing device after the completion of printing 500,000 sheets using the image forming apparatus.

Evaluation criteria A: No in-machine contamination due to toner scattering ○: In-machine contamination due to slight toner scattering, but a level that does not require a vacuum cleaner during maintenance and is practically no problem ×: In-machine contamination due to toner scattering is severe, maintenance At times, it is necessary to clean your hands with a dirt cleaner, which is a practical problem.

  Table 2 shows the evaluation results.

  As shown in Table 2, it can be seen that the “toners 1 to 11” of Examples 1 to 11 achieve the object or effect of the present invention. On the other hand, it can be seen that “toners 14 and 15” of Comparative Examples 3 and 4 have a problem in any of the evaluation items and the purpose or effect is not achieved.

DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Charger 3 Exposure optical system 4 Developing device 6 Intermediate transfer material 7 Primary transfer roller 7A Secondary transfer roller 8 Optical sensor 17 Fixing device 190 Photoconductor cleaning device 190A Intermediate transfer material cleaning device 70 Secondary transfer member cleaning apparatus

Claims (3)

Producing an aqueous dispersion containing at least resin particles and a colorant;
In the method for producing a toner for electrostatic charge development, comprising the step of aggregating and fusing the resin particles and the colorant to produce a heteroaggregate,
In the step of preparing the aqueous dispersion of the resin particles or the aqueous dispersion of the colorant particles, at least an anionic sulfate ester type surfactant is used,
In the step of producing the heteroaggregate, before heating and aggregating and fusing the resin particles and the colorant particles, at least one inorganic salt of sulfate or hydrogen sulfate is added ,
The electrostatic charge development characterized in that the amount of the inorganic salt of at least one of the sulfate and hydrogen sulfate is 10 times to 150 times (molar ratio) of the anionic sulfate ester surfactant. Of manufacturing toner.   2. The method for producing a toner for developing an electrostatic charge according to claim 1, wherein the anionic sulfate type surfactant is a surfactant having a structure containing an alkyl sulfate ester salt. An electrostatic charge developing toner obtained by the method for producing an electrostatic charge developing toner according to claim 1.

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