JP4747873B2 - Toner for developing electrostatic image and method for producing toner for developing electrostatic image - Google Patents

Description

The present invention particularly relates to an electrostatic charge image developing toner (hereinafter also simply referred to as toner) used for electrophotographic image formation, such as a printer or a copying machine, and a toner manufacturing method .

  The need for color image formation by electrophotographic image forming apparatuses represented by laser printers, MFPs (multifunctional peripherals) and the like is expected to expand further in the future. In order to achieve further spread, compactness and maintainability are also required. As a color image forming apparatus that satisfies these needs, a non-magnetic one-component developer capable of forming an image without using a carrier is used. The ones used are increasing. An image forming method using a non-magnetic one-component developer includes, for example, a non-magnetic material comprising a toner that is transported and supplied by a developer carrier such as a developing roller for a latent image formed on an electrostatic latent image carrier. A method of developing with a one-component developer, transferring a formed toner image to a transfer material, and thermally fixing the toner image on the transfer material is mainly used.

  In recent years, rapid full-color image formation has been required in the market, such as creation of documents in offices, output of digital cameras, and creation of light prints. When high-speed printing is performed with a compact color printer, the toner is required to have a quick and stable charge rising performance. As a technique corresponding to this need, for example, there is a technique that realizes a rapid charge rise using a pulverized toner containing a polyester resin, a colorant, a charge control agent, and the like (see, for example, Patent Document 1).

  However, the toners disclosed in the above-mentioned patent documents are not necessarily perfect because there is a tendency for image density reduction due to charge-up to gradually appear when continuous printing is performed in a low-temperature and low-humidity environment. In addition, since the shape, particle size, and charge amount distribution are non-uniform, the reproducibility of high-definition images such as fine lines is difficult.

  By the way, looking at recent technological trends in toner, it is remarkable to increase and improve the so-called polymerized toner produced through a process of aggregating resin particles in an aqueous medium. The polymerized toner is suitable for producing a toner having a small particle size and a uniform shape and particle size distribution in the manufacturing process, and can provide an optimum toner for pictorial image formation (for example, patents). Reference 2).

  By the way, along with the downsizing of the image forming apparatus, the developing apparatus used in the apparatus is smaller than the conventional one, and toner filming on the surface of the developing roller becomes a problem. As a technique for solving this problem, for example, there is a technique for producing a toner in which an average value of a softening point, a particle hardness, and a circularity coefficient is specified through particle formation in an aqueous medium (see, for example, Patent Document 2). ).

Therefore, as a technique for preventing a decrease in density due to continuous printing using a polymerized toner, for example, by producing a polymerized toner by combining a positive charge control resin and a negative charge control resin, a single amount is obtained in an aqueous suspension medium. There is a technique for stabilizing a droplet of a body composition so as to obtain a small-diameter toner having a sharp particle size distribution (see, for example, Patent Document 3).
JP 2000-235280 A JP 2000-214629 A JP 2000-347445 A

  However, the reliability and stability demanded by users are increasing year by year. One of them is that good image quality can be obtained under any humidity environment and use conditions. Specifically, the image density is lowered when printing is performed in a low temperature and low humidity (for example, 10 ° C., 20% RH) environment. Furthermore, it is to extend the service life and life of the developing roller, and to reduce the trouble of replacing the developing roller. Or, the fixing strength on special paper (paper coated with a large amount of white pigment such as calcium carbonate in order to increase whiteness).

  That is, when image formation is performed by applying the technology disclosed in the above-mentioned patent document to a non-magnetic one-component developer, it is difficult to obtain sufficient fixing strength in a toner image formed on paper with high whiteness. Was pointed out. In particular, when an image is formed on a “high whiteness cardboard” that is often used in greetings, thank you letters, etc., when the paper surface is rubbed, the fixed toner is peeled off and the white background is contaminated. Caused it to occur. In particular, when laminating the paper, there is a problem that the toner and the laminate are lifted from the paper.

  In addition, it has been confirmed that it is difficult for an image forming apparatus using a non-magnetic one-component developer to exhibit sufficient charging start-up performance depending on the installation environment. In particular, continuous printing is performed in a low-temperature and low-humidity environment. When this was done, a significant decrease in density appeared.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and manufacture of a toner for developing an electrostatic charge image and a toner capable of forming a toner image having a sufficient fixing strength even when paper having high whiteness is used. It aims to provide a method . Another object of the present invention is to provide a toner for developing an electrostatic image and a method for producing the toner, which can quickly develop the charge rising performance without being affected by the installation environment of the image forming apparatus.

1.
An electrostatic charge image developing toner comprising at least a resin and a colorant,
In the step of aggregating the resin particles at the time of producing the electrostatic image developing toner,
The resin particles contain a vinyl polymer,
Tricarboxylic acid or a salt thereof having a hydroxyl group, or by adding tricarboxylic acid or its salt shown below,
Tricarboxylic acid or a salt thereof having a hydroxyl group in the electrostatic toner for electrostatic image development, or electrostatic image, characterized in that the tricarboxylic acid or its salt is obtained by incorporating 20ppm or 264ppm below Developing toner.

2.
Toner for developing an electrostatic image, the toner for developing an electrostatic charge image according to the 1, characterized in that to 1ppm sodium element 134 ppm, the divalent or trivalent metal elements are those containing 6 00Ppm to 1800ppm .

3.
3. The electrostatic image developing toner according to 1 or 2, wherein the electrostatic image developing toner is used in a non-magnetic one-component image forming method.
4).
A method for producing an electrostatic image developing toner comprising at least a resin and a colorant,
In the step of aggregating the resin particles at the time of producing the electrostatic image developing toner,
The resin particles contain a vinyl polymer,
When the diameter of the resin particles reaches the diameter of the electrostatic image developing toner,
Tricarboxylic acid or a salt thereof having a hydroxyl group, or by adding tricarboxylic acid or its salt shown below,
Tricarboxylic acid or a salt thereof having a hydroxyl group in the electrostatic toner for electrostatic image development, or electrostatic image, characterized in that the tricarboxylic acid or its salt is obtained by incorporating 20ppm or 264ppm below A method for producing a developing toner.

  According to the present invention, in toner image formation using a non-magnetic one-component developer, a toner image having sufficient strength can be formed on a sheet having high whiteness. In particular, when a cardboard-like paper with high whiteness such as a greeting card or a thank-you letter is used, it has become possible to provide a print with a good finish free from white background contamination due to insufficient fixing. Even when images were laminated, the problem of the laminate floating with the toner image disappeared.

  In addition, according to the present invention, rapid toner charge rising is realized, and a toner having a stable charge amount is supplied onto the image carrier, so that a high-quality toner image can be formed quickly and reliably. It became like. As a result, continuous printing can be performed without causing a change in density even in an environment where there is a concern about a decrease in density, such as continuous printing in a low temperature and low humidity environment. In addition, in an image forming apparatus using a non-magnetic one-component developer that performs rapid print creation via a compact development device, a full-color print can be created quickly and reliably. Reliability has been greatly improved.

In the present invention, to 1ppm a sodium element 134 ppm, 2 divalent or trivalent toner to 6 00Ppm to be contained 1800ppm metal element, quick charge rise is significantly demonstrated, the non-magnetic one-component developer Can be used to quickly form high-quality color images.

  Furthermore, according to the present invention, it is possible to reduce the load on the developing device, such as reducing the filming amount of the developing roller accompanying the image formation, thereby extending the service life. It became possible to create things stably over a long period of time.

  The present invention relates to a toner containing a specific amount of tricarboxylic acid or a salt thereof.

  In the present invention, it is possible to form a toner image having a sufficient fixing strength on a sheet having high whiteness. In this way, the reason why the fixing strength of the toner can be improved is probably because the adhesion of the toner to the paper surface is improved by the action of the tricarboxylic acid contained in the toner. Is done. Specifically, a strong ionic bond or coordination to ions occurs between the tricarboxylic acid contained in the toner and calcium carbonate added as a white pigment in the paper, and the toner is held on the paper surface. This is presumed to be due to the formation of a structure that is difficult to desorb. This means that the effect is prominent when image formation is performed on imported paper specified by some foreign companies (calcium carbonate content is said to be about 5 times that of domestic paper). It is guessed from.

  According to the present invention, the toner can be quickly charged and image formation with toner having a stable charge amount can be performed. The reason is not clear, but it is probably because the imino group or carboxyl group in the tricarboxylic acid contained in the toner is ionized, and the generated ammonium ion or carboxyl ion stabilizes the charge generated on the toner surface. Guessed. Further, it is presumed that the tricarboxylic acid itself prevents an increase in charge on the toner particle surface due to a residue of a polymerization initiator such as sulfate ion. As a result, it is possible to perform stable image formation without causing a decrease in density even in an environment where the charge on the toner surface is likely to rise, such as when performing continuous printing in a low-temperature and low-humidity environment along with the rapid charge rise of the toner. Guessed.

  Furthermore, according to the present invention, it is possible to extend the life of the developing device, such as reducing the load applied to the developing device during image formation and reducing the filming of the developing roller. The reason is probably that the tricarboxylic acid contained in the toner forms a strong hydrogen bond in the binding resin of the toner, and the toner particles do not crush even when subjected to a strong impact. Is estimated to have decreased. The effect of tricarboxylic acid was remarkable in the carboxylic acid compound.

  Hereinafter, the present invention will be described in detail.

  The toner according to the present invention contains 20 ppm to 264 ppm of tricarboxylic acid or a salt thereof in the toner. The tricarboxylic acid referred to in the present invention is an organic compound containing three carboxyl groups in the molecular structure, and has three acid ionization indices pKa.

  In the present invention, it is also possible to use a metal salt formed by binding a metal ion to a carboxyl group of tricarboxylic acid. As what forms the metal salt of tricarboxylic acid, the monovalent metal called alkali metals, such as sodium, potassium, lithium, is preferable, for example.

  In addition, what was substituted by the metal atom mentioned above instead of the carboxyl group in a tricarboxylic acid or the H atom in a hydroxyl group is equivalent to the salt of the tricarboxylic acid which concerns on this invention. Among the tricarboxylic acids, preferred are tricarboxylic acid compounds having a hydroxyl group.

  Below, the specific example of the tricarboxylic acid compound which can be used for this invention is illustrated.

Among the above exemplified compounds, examples of the compound preferably used in the present invention include ( 6-1 ), ( 6-2 ), and ( 7-7 ).

  The amount of tricarboxylic acid or its salt contained in the toner can be measured by the following measuring method.

  1. The extraction operation (1-1) to (1-2) is performed for the toner to be measured.

  (1-1) Add 10 ml of a methanol solution containing 1N hydrochloric acid to 500 mg of toner, and apply it to an ultrasonic disperser for 15 minutes.

  (1-2) This is filtered through a chromatographic disk having an opening of 0.2 μm, and the filtrate is diluted 10-fold with ultrapure water.

  2. The aqueous solution obtained in the above (1-2) is analyzed by ion chromatography under the following conditions (2-1). The structure of the obtained peak is determined by a conventional method after fractionation. Specifically, it is performed by mass spectrometry (mass spectrometry) or nuclear magnetic resonance analysis (NMR). Once the structure is determined, a calibration curve is created using a standard sample of the same structure by ion chromatography. Further, from the comparison of peak areas, the amount of tricarboxylic acid contained in the toner is determined by conversion from the concentration of the extracted liquid obtained from the toner. When a plurality of tricarboxylic acids are contained, the sum is taken as the amount of tricarboxylic acids contained in the toner.

(2-1) Ion chromatography apparatus conditions Detection: UV 210 nm
Column: Tosoh ODS-80TM4.6 × 250mm
+ Tosoh ODS-80TM 4.6 x 150mm
Flow rate: 0.5 ml / min
Mobile phase: 5 mM ammonium dihydrogen phosphate (pH = 2.4)
Column temperature: 25 ° C
Analytical volume: 20 μl
Analysis time: 45 minutes As for the mobile phase, 1.15 g of ammonium dihydrogen phosphate (special grade) was dissolved in 1980 g of ion-exchanged water, adjusted to pH 2.40 with 85% by mass normal phosphoric acid, and ion-exchanged water was further added. It was prepared by stirring well to 2000 g.

  The toner of the present invention preferably contains 1 ppm to 134 ppm of sodium element in the toner.

The toner of the present invention, a divalent or trivalent metallic element in the toner, arbitrary preferred to contain 6 00Ppm to 1800 ppm. Examples of the divalent metal element include calcium, magnesium, manganese, copper and the like. Examples of the trivalent metal element include aluminum and iron.

  The amount of metal element contained in the toner is measured with an inductively coupled plasma spectrometer (ICP).

  The metal element contained in the toner can be quantified by the following procedure.

  First, 0.1 g of toner is weighed, 1.5 ml of sulfuric acid is added thereto, and carbonization is performed using a microwave. Next, 0.5 ml of nitric acid and 1.5 ml of hydrogen peroxide are added to the carbonized one, and decomposition treatment is performed using a microwave. Distilled water is added to the decomposed product to dissolve it, and the solution is accurately measured in a 50 ml volumetric flask.

  By measuring the aqueous solution in the volumetric flask with an inductively coupled plasma spectrometer, the content of sodium, divalent or trivalent metal element in the toner is quantified.

  Examples of inductively coupled plasma spectrometers include ICP emission spectrometers “SPS7800 series, SPS3100 series, SPS5100 series” (manufactured by Seiko Instruments Inc. (SII Nanotechnology)), and ICP emission analyzers “CIROS”. Mark II "(manufactured by Rigaku Corporation) and the like.

  Next, physical properties of the toner of the present invention will be described.

(Median diameter based on volume (D ₅₀ ))
The median diameter (D ₅₀ ) on the volume basis of the toner of the present invention is preferably 3 to 9 μm.

For the volume-based median diameter (D ₅₀ ) and the coefficient of variation in the volume-based particle size distribution, a computer system for data processing (Beckman Coulter) is connected to Coulter Multisizer III (Beckman Coulter). Measurement and calculation can be performed by using the apparatus.

  As a measurement procedure, 0.02 g of toner was mixed 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). Then, ultrasonic dispersion is performed for 1 minute to prepare a toner dispersion. This toner dispersion is poured into a beaker containing ISOTON II (manufactured by Beckman Coulter, Inc.) in a sample stand with a pipette until a measurement concentration of 8% by mass, and the measuring machine count is set to 2500 and measured. . The aperture diameter of the Coulter Multisizer is 50 μm.

(Coefficient of variation in volume-based particle size distribution)
The coefficient of variation in the volume-based particle size distribution of the toner of the present invention is preferably 8 to 21%, more preferably 10 to 19%.

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

Coefficient of variation (%) in volume-based particle size distribution = (S2 / Dn) × 100
(In the formula, S2 represents the standard deviation in the volume-based particle size distribution, and Dn represents the median diameter (D ₅₀ ) based on the volume.)
(Average circularity)
The average circularity of the toner of the present invention is preferably 0.951 to 0.990.

  The circularity of the toner is defined by the following formula.

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 each particle by the total number of particles.

  The circularity of the toner is a value measured using “FPIA-2100” (manufactured by Sysmex). Specifically, the toner is blended with an aqueous solution containing a surfactant, subjected to ultrasonic dispersion treatment for 1 minute to disperse the toner, and then measured 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.

(Toner production method)
The production method of the toner according to the present invention is not particularly limited, but a production method in which the toner is produced through the steps of forming resin particles by an emulsion polymerization method and aggregating the resin particles is preferable.

  An example of a toner production method for producing toner through a process of aggregating resin particles will be described in detail. The step of adding the tricarboxylic acid is not limited, but it is preferably added in the step (2) below. However, since there is a part that flows out in the step (4), it is preferable to determine the amount of the tricarboxylic acid compound added to the toner by a preliminary experiment.

The toner manufacturing method according to the present invention is manufactured through the following steps.
(1) Polymerization step for preparing a resin particle dispersion by polymerizing polymerizable monomers (2) A toner base material is obtained by aggregating toner particle constituent materials such as resin particles and colorant particles in an aqueous medium. Aggregation step for forming toner particle intermediate (hereinafter referred to as a step of aggregating resin particles)
(3) Shape control step of controlling the shape while completing the fusion of the materials constituting the toner particle intermediate by heating and stirring following the step of aggregating the resin particles (4) The generated toner particle intermediate is water-based Solid-liquid separation from the medium and solid-liquid separation and washing step for cleaning the surface of the toner particle intermediate (5) Drying step (6) for drying the toner particle intermediate subjected to the solid-liquid separation and washing step ) It has an external additive processing step for making a toner usable for image formation by adding an external additive to the dried toner particle intermediate.

  Hereinafter, each step will be specifically described.

[Polymerization process]
In a preferred example of the polymerization step, a radically polymerizable monomer solution is added to an aqueous medium containing a surfactant, mechanical energy is applied to form droplets, and then water-soluble radical polymerization is initiated. The polymerization reaction proceeds in the droplets by radicals from the agent. In addition, you may add the resin particle as a core particle in the said aqueous medium.

  In the polymerization, it is preferable to control the molecular weight distribution in several stages by changing the amount of the chain transfer agent. By this polymerization step, resin particles are obtained.

  Such resin particles may contain a release agent (wax) or may contain a colorant. The colored resin particles can be obtained by polymerizing a monomer composition containing a colorant.

Further, when using uncolored resin particles, in the aggregation step described later, the toner particles are aggregated by adding the colorant particle dispersion to the resin particle dispersion and aggregating the resin particles and the colorant particles. It can be an intermediate (toner base).
[Step of aggregating resin particles]
This step corresponds to the “step of agglomerating resin particles in an aqueous medium to grow the particles” in the present invention. In the present invention, it is preferable to add at least one of tricarboxylic acid or a salt thereof to the aqueous medium in this step, that is, in a state where the aggregation of the resin particles is proceeding. In this step, the resin particles produced in the polymerization step are aggregated with toner particle constituent materials such as colorant particles, whereby a toner particle intermediate (before a function as a toner is imparted by a final treatment such as an external additive treatment). Particles, also referred to as toner matrix and colored particles). In this step, agglomeration (fusion) is also performed in which the aggregated particles are firmly bonded together by an action such as heat.

  It is preferable that the fusion or fusion of the resin particles and the colorant proceed together with the aggregation. In addition, after the aggregation is completed, it may be fused at a stretch by means such as heating.

  Specifically, by adding a divalent or trivalent salt into the aqueous medium, the electrostatic repulsion between the particles such as the resin particles and the colorant particles is alleviated. These particles aggregate and grow to form a toner particle intermediate. The agglomerated particles are fused by being bonded by receiving an action such as heat. In this way, the toner particle intermediate is formed and grown.

  In this step, the amount of tricarboxylic acid or a salt thereof added is preferably 0.8 to 2.8 parts by mass with respect to 100 parts by mass of the aqueous medium. By setting it as the said addition amount, it is possible to express the effect of this invention more reliably.

  The step of aggregating the resin particles will be further described. In the step of aggregating the resin particles, as described above, the resin particles and colorant particles generated in the polymerization step are agglomerated and the particles are fused in a temperature environment equal to or higher than the glass transition temperature of the resin particles. is there.

  Particle agglomeration is performed by mixing a resin particle dispersion or a colorant particle dispersion below the glass transition temperature of the resin particles, and simultaneously fusing the agglomerated particles by fusing the particles while aggregating the particles. There is a method of aggregating particles. According to this method, since the fusion can proceed while growing the particles, there is an advantage that the particle shape and the particle size distribution can be easily controlled.

  From this point of view, in the step of aggregating the resin particles, agglomeration and fusion (fusion) are advanced in parallel to grow to the desired particle size and heating is continued to control the particle shape as necessary. It is preferable to use a so-called “salting out / fusion method”.

  The “aqueous medium” in the present invention refers to a material whose main component (50% by mass or more) is water. Examples of components other than water include water-soluble organic solvents such as methanol, ethanol, isopropanol, butanol, and acetone.

  Aggregation of particles is promoted by adding a metal salt such as a divalent salt. Examples of the metal salt that promotes aggregation include monovalent alkali metal salts such as sodium, potassium, and lithium, divalent metal salts such as calcium, magnesium, manganese, and copper, and trivalent metal salts such as aluminum and iron. Etc. Specific examples include sodium chloride, potassium chloride, lithium chloride, calcium chloride, magnesium chloride, zinc chloride, copper sulfate, magnesium sulfate, and manganese sulfate. These salts may be used alone or in combination of two or more.

  Among these metal salts, a divalent metal salt is particularly preferable because aggregation can be advanced with a small addition amount.

  The addition amount of these metal salts is preferably added so that the concentration of the metal salt is equal to or higher than the critical aggregation concentration in the aqueous medium, specifically, 1.2 times the critical aggregation concentration or more, preferably It is preferable to add 1.5 times or more. Here, the “critical aggregation concentration” is an index relating to the stability of the aqueous dispersion. The critical aggregation concentration can be calculated in detail, for example, by the technique described in Seizo Okamura et al., “Polymer Chemistry, Vol 17, 601 (1960) (edited by the Society of Polymer Science)”. Also, a desired salt is added to the target dispersion for aggregation at different concentrations, the ζ (zeta) potential of the dispersion for aggregation is measured, and the salt concentration at which this value changes is calculated as the critical aggregation concentration. It is also possible.

  In the step of aggregating the resin particles, it is possible to agglomerate toner particle constituent materials such as wax, fixing aid, charge control agent and the like together with the resin particles and the colorant particles.

[Shape control process]
In the toner manufacturing method according to the present invention, after adding the tricarboxylic acid or a salt thereof in the step of aggregating the resin particles, the shape of the toner particle intermediate (toner base) is controlled by continuing the heating and stirring. is doing. That is, by increasing the heating and stirring time, it is possible to control the shape of the toner particle intermediate (toner base) to be nearly spherical.

[Solid-liquid separation and washing process]
In the solid-liquid separation / washing step, a solid-liquid separation process in which the toner particle intermediate (toner base) is solid-liquid separated from the dispersion of the toner-particle intermediate (toner base) cooled to a predetermined temperature in the above step; And a cleaning process for removing unnecessary substances such as surfactants and salting-out agents from the solid-liquid separated toner cake (a lump obtained by agglomerating a toner particle intermediate (toner base material) in a wet state). Applied.

  In the washing treatment, the filtrate is washed with water until the electric conductivity of the filtrate reaches 10 μS / cm.

  Here, the solid-liquid separation and washing methods are not particularly limited, such as a centrifugal separation method, a vacuum filtration method using Nutsche or the like, a method using a filter press or the like.

[Drying process]
The drying step is a step of drying the cleaned toner particle intermediate. In the drying process, the drying process is usually performed in the state of a toner cake. 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 water content of the dried toner particle intermediate is preferably 5% by mass or less, and more preferably 2% by mass or less. In the case where toner particle intermediates (toner base materials) that have been dried are agglomerated weakly due to the attractive force between the particles, the agglomerates 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.

[External process]
In this step, an external additive is mixed with the dried toner particle intermediate (toner base) to produce a toner that can be used for image formation.

  As an external additive mixing device, a mechanical mixing device such as a Henschel mixer or a coffee mill can be used.

  Next, materials (raw materials) used in the present invention will be described.

(Binder resin)
The binder resin constituting the resin particles preferably contains a vinyl polymer, and can be prepared by polymerizing a polymerizable monomer. Examples of the polymerizable monomer used for polymerization include a polymerizable monomer having a carboxyl group and a polymerizable monomer used in combination with the polymerizable monomer having a carboxyl group.

  Specifically, as a polymerizable monomer having a carboxyl group, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, Methacrylic acid ester derivatives such as 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, phenyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate, methyl acrylate, ethyl acrylate, isopropyl acrylate, acrylic acid n -Butyl, t-butyl acrylate, isobutyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, lauryl acrylate, phenyl acrylate, etc. Le ester derivatives, acrylonitrile, methacrylonitrile, acrylic acid or methacrylic acid derivatives such as acrylamide.

  Moreover, as a polymerizable monomer used in combination with a polymerizable monomer having a carboxyl group, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p -Ethyl styrene, 2,4-dimethyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn- Styrene or styrene derivatives such as dodecylstyrene, olefins such as ethylene, propylene and isobutylene, vinyl esters such as vinyl propionate, vinyl acetate and vinyl benzoate, vinyl ethers such as vinyl methyl ether and vinyl ethyl ether, vinyl methyl Ketone, vinyl ethyl ketone, vinyl hex Vinyl ketones such as ketones, N- vinylcarbazole, N- vinyl indole, N- vinyl compounds such as N- vinylpyrrolidone, vinyl naphthalene, and vinyl compounds such as vinyl pyridine.

  Further, it is more preferable to use a combination of monomers having an ionic dissociation group as the polymerizable monomer constituting the resin. For example, it has a substituent such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group as a constituent group of the monomer. Specifically, acrylic acid, methacrylic acid, maleic acid, itaconic acid, cinnamic acid, fumar Examples include acid, maleic acid monoalkyl ester, itaconic acid monoalkyl ester, styrene sulfonic acid, allyl sulfosuccinic acid, 2-acrylamido-2-methylpropane sulfonic acid, and acid phosphooxyethyl methacrylate.

  Furthermore, polyfunctionality such as divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, etc. It is also possible to use a crosslinkable resin by using a functional vinyl.

  Moreover, when using an emulsion association method, it is preferable to use a water-soluble radical polymerization initiator. Examples of the water-soluble polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, azobisaminodipropane acetate, azobiscyanovaleric acid and its salts, hydrogen peroxide and the like.

  The resin constituting the toner of the present invention preferably has a number average molecular weight (Mn) of 1,000 to 100,000 and a weight average molecular weight (Mw) of 2,000 to 1,000,000. The molecular weight of the resin constituting the toner can be calculated by, for example, gel permeation chromatography or gel permeation chromatography.

  Here, molecular weight measurement by gel permeation chromatography (hereinafter also referred to as GPC) will be described.

  Specifically, the following procedure is performed. First, 1 ml of tetrahydrofuran solvent is added to 1 mg of the measurement resin, and the mixture is stirred at room temperature using a magnetic stirrer, etc., and the resin is sufficiently dissolved and filtered through a membrane filter having a pore size of 0.45 to 0.50 μm. To prepare a sample for GPC measurement. Next, after the GPC measurement column is heated and stabilized at 40 ° C., tetrahydrofuran is flowed at a rate of 1 ml per minute, and 100 μl of a measurement sample having a concentration of 1 mg / ml is injected and measured. The measurement column is preferably used in combination with a commercially available polystyrene gel column. For example, combinations of Shodex GPC KF-801, 802, 803, 804, 806, and 807 manufactured by Showa Denko KK and TSK gel G1000H, G2000H, G3000H, G4000H, G5000H, G6000H, G7000H, and TSK guard column manufactured by Tosoh Corporation Etc. As a detector, a refractive index detector (IR detector) or a UV detector may be used.

  The number average molecular weight and weight average molecular weight of the tetrahydrofuran-dissolved component in the resin particles are expressed in terms of styrene resin equivalent molecular weight. The molecular weight in terms of styrene resin is determined from a styrene calibration curve. A styrene calibration curve may be prepared by measuring about 10 monodisperse polystyrene standard resins.

(Coloring agent)
As the colorant used in the present invention, a known inorganic or organic colorant can be used. Specific colorants are shown below.

  Examples of the black colorant 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 the colorant 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 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. And CI Pigment Yellow 138.

  Examples of the colorant 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.

  These colorants may be used alone or in combination of two or more as required. The addition amount of the colorant is set in the range of 1 to 30% by mass, preferably 2 to 20% by mass with respect to the whole toner.

(Chain transfer agent)
In order to adjust the molecular weight of the resin, a commonly used chain transfer agent can be used. The chain transfer agent used is not particularly limited. For example, mercaptans such as n-octyl mercaptan, n-decyl mercaptan, tert-dodecyl mercaptan, and mercaptopropionate esters such as n-octyl-3-mercaptopropionate. , Terpinolene and α-methylstyrene dimer are used.

(wax)
A known compound can be used for the wax used in the present invention.

  As such, for example, polyolefin wax such as polyethylene wax and polypropylene wax, long chain hydrocarbon wax such as paraffin wax and sazol wax, dialkyl ketone wax such as distearyl ketone, carnauba wax, montan wax, Trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol tetrastearate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18-octadecanediol distearate, tristearyl trimellitic acid , Ester waxes such as distearyl maleate, amide waxes such as ethylenediamine behenyl amide, trimellitic acid tristearyl amide, etc. It is.

  The amount of wax contained in the toner is preferably 1 to 20% by mass, and more preferably 3 to 15% by mass with respect to the total toner.

(Charge control agent)
A charge control agent can be added to the toner of the present invention as necessary. A known compound can be used as the charge control agent.

(External additive)
Examples of inorganic particles that can be used as an external additive include conventionally known particles. Specifically, silica fine particles, titania fine particles, alumina fine particles, and complex oxides thereof can be preferably used. These inorganic particles are preferably hydrophobic.

  Examples of the organic fine particles that can be used as the external additive include spherical fine particles having a number average primary particle diameter of about 10 to 2000 nm. Examples of the constituent material of the organic fine particles include polystyrene, polymethyl methacrylate, styrene-methyl methacrylate copolymer and the like.

  The toner of the present invention can be used as a one-component developer or a two-component developer.

  When used as a one-component developer, a non-magnetic one-component developer or a magnetic one-component developer containing about 0.1 μm to 0.5 μm of magnetic particles in the toner can be used. be able to.

  Further, it can be mixed with a carrier and used as a two-component developer. As the carrier, conventionally known magnetic particles such as metals such as iron, ferrite, and magnetite, and alloys of these metals with metals such as aluminum and lead can be used. Ferrite particles are particularly preferable. The particle diameter of the carrier is preferably 20 to 100 μm, and more preferably 25 to 80 μm.

  The toner of the present invention is preferably used as a non-magnetic one-component developer from the viewpoints of downsizing the developing device and low price.

  Next, an image forming apparatus that forms a toner image using the toner of the present invention will be described.

  An example of a developing method using the toner of the present invention as a non-magnetic one-component developer will be described below, but is not necessarily limited thereto.

  FIG. 1 is a schematic cross-sectional view showing an example of a developing device for a non-magnetic one-component developer.

  In FIG. 1, reference numeral 14 denotes a developing unit for a non-magnetic one-component developer, and reference numeral 10 denotes a latent image holding member (photosensitive drum). The latent image is formed by electrophotographic process means or electrostatic recording means (not shown). A developing roller 14a is made of a nonmagnetic sleeve made of aluminum or stainless steel.

  The developing roller may be an aluminum or stainless steel rough tube as it is, but preferably the surface of the developing roller is uniformly roughened by blowing glass beads or the like, mirror-finished, or coated with a resin or the like. .

  The toner T is stored in the hopper 3 and is supplied onto the toner carrier by the supply roller 4. The supply roller is made of a foam material such as polyurethane foam, and rotates with a relative speed in the forward or reverse direction with respect to the toner carrier, and with toner supply, the toner on the toner carrier after development (undeveloped toner) I'm also stripping off. The toner supplied onto the toner carrier is uniformly and thinly applied by a toner regulating blade 5 which is a kind of toner thinning regulating member.

  The contact pressure between the toner regulating blade and the toner carrier is 3 to 250 N / m, preferably 5 to 12 N / m, as the linear pressure in the sleeve bus direction. When the contact pressure is less than 3 N / m, it is difficult to uniformly apply the toner, and the toner charge amount distribution becomes broad, which may cause fogging or scattering. On the other hand, if the contact pressure exceeds 250 N / m, a large pressure is applied to the toner and the toner deteriorates, which is not preferable because toner aggregation occurs. Further, it is not preferable because a large torque is required to drive the toner carrier. That is, by adjusting the contact pressure to 3 to 250 N / m, it is possible to effectively loosen the aggregation of the toner of the present invention, and it is possible to instantaneously raise the charge amount of the toner.

  As the toner thinning regulating member, it is preferable to use a material of a frictional charging series suitable for charging the toner to a desired polarity with an elastic blade, an elastic roller or the like.

  In the present invention, silicone rubber, urethane rubber, styrene-butadiene rubber and the like are suitable. Furthermore, an organic resin layer such as polyamide, polyimide, nylon, melamine, melamine cross-linked nylon, phenol resin, fluorine resin, silicone resin, polyester resin, urethane resin, styrene resin may be provided. In addition, conductive rubber, conductive resin, etc. are used, or fillers such as metal oxide, carbon black, inorganic whisker, inorganic fiber, and charge control agent are dispersed in the blade rubber and resin. It is preferable because it imparts charge imparting properties and can charge the toner appropriately.

  In the system in which the toner is thinly coated on the developing roller with a blade, in order to obtain a sufficient image density, the thickness of the toner layer on the developing roller is larger than the opposing gap length between the developing roller and the photosensitive drum. It is preferable to reduce the size and apply an alternating electric field to this gap. That is, the bias power source 7 shown in FIG. 1 applies an alternating electric field or a developing bias in which a DC electric field is superimposed on the alternating electric field between the developing roller 14 a and the photosensitive drum 10, so that the developing roller is transferred onto the photosensitive drum. Therefore, it is possible to easily move the toner and to obtain a higher quality image.

  The toner of the present invention is suitably used in an image forming method including a step of fixing a transfer material on which a toner image is formed between a heating roller and a pressure roller constituting a fixing device.

  FIG. 2 is a cross-sectional view illustrating an example of a full-color image forming apparatus that forms an image using the toner of the present invention.

  The full-color image forming apparatus shown in FIG. 2 includes units 10Y, 10M, 10C, and 10Bk, a belt-shaped intermediate transfer body 16, transfer rollers 17Y, 17M, 17C, and 17Bk, a transfer material conveyance roller 18, and a fixing device 2. And. In the present invention, the belt-shaped intermediate transfer member 16 includes the belt-shaped intermediate transfer member according to the present invention as a belt material. In the present invention, a polyimide resin is used as a belt material for the intermediate transfer member 16 and an endless belt of the fixing device 2 described later.

  The units 10Y, 10M, 10C, and 10Bk are respectively provided with photosensitive drums 11Y, 11M, 11C, and 11Bk so as to be rotatable at a predetermined peripheral speed (process speed) in the clockwise direction of an arrow. Around the photosensitive drums 11Y, 11M, 11C, and 11Bk, corotron chargers 12Y, 12M, 12C, and 12Bk, exposure units 13Y, 13M, 13C, and 13Bk, and color developing units (yellow developing unit 14Y and magenta developing unit) 14M, cyan developing device 14C, black developing device 14Bk), and photoreceptor cleaners 15Y, 15M, 15C, 15Bk, respectively.

  Four units 10Y, 10M, 10C, and 10Bk are arranged in parallel to the intermediate transfer belt 16, but an appropriate order is set according to the image forming method, such as the order of the units 10Bk, 10Y, 10C, and 10M. can do.

  The intermediate transfer belt 16 can be rotated by the backup roller 30 and the support rollers 31, 32, and 33 in the counterclockwise direction indicated by the arrow at the same peripheral speed as the photosensitive drums 11 </ b> Y, 11 </ b> M, 11 </ b> C, and 11 </ b> Bk. , 33 is disposed so that a part thereof is in contact with the photosensitive drums 11Y, 11M, 11C, and 11Bk. The intermediate transfer belt 16 is provided with a belt cleaning device 34. The support roller 31 plays the role of a tension roller and is arranged to be movable in the direction of the surface of the intermediate transfer belt 16, and can adjust the tension of the intermediate transfer belt 16.

  The transfer rollers 17Y, 17M, 17C, and 17Bk are disposed inside the intermediate transfer belt 16 and at positions facing the portions where the intermediate transfer belt 16 and the photosensitive drums 11Y, 11M, 11C, and 11Bk are in contact with each other. The photosensitive drums 11Y, 11M, 11C, and 11Bk and a primary transfer portion (nip portion) for transferring the toner image to the intermediate transfer belt 16 are formed.

  The bias roller 35 is disposed on the surface side of the intermediate transfer belt 16 on which the toner image is carried so as to face the backup roller 30 with the intermediate transfer belt 16 interposed therebetween. The bias roller 35 and the backup roller 30 via the intermediate transfer belt 16 form a secondary transfer portion (nip portion). In addition, the backup roller 30 includes an electrode roller 26 that rotates in pressure contact with the backup roller 30.

  The fixing device 2 is arranged so that the transfer material P can be conveyed after passing through the secondary transfer portion.

  In the unit 10Y of the image forming apparatus shown in FIG. 2, the photosensitive drum 11Y is rotationally driven. In conjunction with this, the corotron charger 12Y is driven to uniformly charge the surface of the photosensitive drum 11Y to a predetermined polarity and potential. The photosensitive drum 11Y having a uniformly charged surface is then exposed imagewise by the exposure device 13Y, and an electrostatic latent image is formed on the surface.

  Subsequently, when the electrostatic latent image is developed by the yellow developing device 14Y, a toner image is formed on the surface of the photosensitive drum 11Y.

  This toner image passes through the primary transfer portion (nip portion) between the photosensitive drum 11Y and the intermediate transfer belt 16, and at the same time, the toner image is generated by the electric field formed by the transfer bias applied from the transfer roller 17Y. The primary transfer is sequentially performed on the outer peripheral surface.

  Thereafter, the toner remaining on the photoreceptor drum 11Y is cleaned and removed by the photoreceptor cleaner 15Y. Then, the photosensitive drum 11Y is subjected to the next transfer cycle.

  The above transfer cycle is similarly performed in the units 10M, 10C, and 10Bk, and a second color toner image, a third color toner image, and a fourth color toner image are sequentially formed and superimposed on the intermediate transfer belt 16. As a result, a full-color toner image is formed.

  The full-color toner image transferred to the intermediate transfer belt 16 reaches the secondary transfer portion (nip portion) where the bias roller 35 is installed by the rotation of the transfer belt 16.

  The transfer material P is fed at a predetermined timing between the intermediate transfer belt 16 and the bias roller 35 in the secondary transfer portion. The toner image carried on the intermediate transfer belt 16 is transferred onto the transfer material P by the pressure conveyance by the bias roller 35 and the backup roller 30 and the rotation of the intermediate transfer belt 16.

  The transfer material P onto which the toner image has been transferred is conveyed to the fixing device 2 and fixes the toner image by pressure / heating treatment. After the transfer, the intermediate transfer belt 16 is subjected to removal of residual toner by a belt cleaning device 34 provided downstream of the secondary transfer portion, and prepared for the next transfer.

  Polyimide resin is preferably used as a belt material for the intermediate transfer belt of the image forming apparatus and the endless belt of the fixing apparatus according to the present invention.

(Transfer material)
The transfer material used in the present invention is a support for holding a toner image and is usually called an image support, a transfer material or a transfer paper. Specifically, various transfer materials such as plain paper and fine paper from thin paper to thick paper, coated printing paper such as art paper and coated paper, commercially available Japanese paper and postcard paper, plastic film for OHP, cloth, etc. However, it is not limited to these.

  As the transfer material, a material containing a large amount of calcium carbonate (about 5 times that of Japan) for the purpose of increasing whiteness is also used.

  The embodiments of the present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

<Preparation of resin particle dispersion 1>
In a separable flask equipped with a stirrer, a temperature sensor, a cooling pipe, a nitrogen introducing device, and a stirrer, 97.0 parts by mass of sodium dodecyl sulfate aqueous solution (2.6 parts by mass of active ingredient) is 1510 parts by mass of ion-exchanged water. Then, an “aqueous medium 1” was prepared by dissolving the mixture in the aqueous solution, and a mixed liquid composed of the following components was added to the “aqueous medium 1”.

Styrene 213 parts by mass n-butyl acrylate 62 parts by mass Acrylic acid 7 parts by mass Pentaerythritol tetrastearate 154 parts by mass In the above-mentioned “aqueous medium 1”, an initiator solution having the following constitution was added and the temperature was adjusted to 82.5. After raising the temperature to 0 ° C., the polymerization reaction was carried out over 2 hours.

Hydrogen peroxide aqueous solution (active ingredient 2.5 parts by mass) 42 parts by mass Sodium erythorbate aqueous solution (active ingredient 6.5 parts by mass) 42 parts by mass n-octyl mercaptan 0.6 parts by mass
Styrene 542 parts by weight n-butyl acrylate 157 parts by weight A monomer mixture consisting of 18 parts by weight of acrylic acid was added, followed by
Hydrogen peroxide aqueous solution (active ingredient 9 parts by mass) 145 parts by mass Sodium erythorbate aqueous solution (active ingredient 23.5 parts by mass) 153 parts by mass An initiator solution consisting of n-octyl mercaptan 8.2 parts by mass was added. Further, 48 parts by mass of an aqueous sodium dodecyl sulfate solution (4.8 parts by mass of active ingredient) was added, the temperature was raised to 90 ° C., and the polymerization reaction was carried out with stirring for 1 hour to prepare a resin particle dispersion. This was designated as “resin particle dispersion 1”.

<Preparation of colorant particle dispersion>
The colorant particle dispersion is a C.I. I. Pigment Red 122 was dispersed in ion-exchanged water to a solid content concentration of 12.5% by mass to prepare an aqueous dispersion. This was designated as “colorant particle dispersion”.

<Production of toner>
<Preparation of Toner 1>
"Resin particle dispersion 1" 1700 parts by mass (in terms of solid content), ion exchange water 2100 parts by mass, "colorant particle dispersion" 250 parts by mass, thermometer, cooling tube, nitrogen introducing device, and stirring device It poured into the provided separable flask. Further, a sodium hydroxide aqueous solution (25% by mass) was added while maintaining the temperature in the system at 30 ° C., and the pH was adjusted to 10.

Next, an aqueous solution in which 54.3 parts by mass of magnesium chloride hexahydrate is dissolved in 104.3 parts by mass of ion-exchanged water is added, and then the temperature in the system is raised to 75 ° C. to obtain resin particles. And the aggregation reaction of the colorant particles was started. After starting the agglutination reaction, sampling is performed periodically, and the particle size distribution measuring device “Coulter Multisizer III” (manufactured by Beckman Coulter, Inc.) is used to set the median diameter (D ₅₀ ) on the volume basis of the particles to 5.8 μm. When it became, 26.4 mass parts of exemplary compound (6-1) was added, and also stirring was continued.

When the circularity of the particles reached 0.976, the temperature in the system was cooled to 30 ° C. to complete the aggregation reaction, and a dispersion of “colored particles 1” was produced. The produced “colored particles 1” had a volume-based median diameter (D ₅₀ ) of 5.8 μm and a coefficient of variation in the volume-based particle size distribution of 18.8.

  Next, the dispersion of “colored particles 1” is subjected to solid-liquid separation with a basket-type centrifuge “MARK III type” (model number 60 × 40) (manufactured by Matsumoto Opportunity Manufacturing Co., Ltd.). A cake was formed. Thereafter, washing and solid-liquid separation of “colored particles 1” were repeated until the electric conductivity of the filtrate reached 15 μS / cm or less.

  The final wet cake was transferred to an air-flow dryer “flash jet dryer” (manufactured by Seishin Enterprise Co., Ltd.), and “colored particles 1” were dried until the water content became 0.5 mass%. The drying process was performed by blowing an air current of 40 ° C. and 20% RH.

  Using “Henschel Mixer” (Mitsui Miike Chemical Co., Ltd.) to “Colored Particle 1” after drying treatment, 1 mass of hydrophobic silica having a number average primary particle size of 12 nm and a hydrophobization degree of 68 is used. %, And a number average primary particle diameter of 80 nm and a hydrophobicity of 63 hydrophobic titanium oxide were added so as to be 1% by mass to prepare “Toner 1”.

The volume-based median diameter (D ₅₀ ) of the obtained “Toner 1” and the variation coefficient in the volume-based particle size distribution were the same as the above-mentioned measured values.

<Preparation of Toner 2>
In the preparation of “Toner 1”, 108.6 parts by mass of magnesium chloride hexahydrate was used instead of an aqueous solution in which 54.3 parts by mass of magnesium chloride hexahydrate was dissolved in 104.3 parts by mass of ion-exchanged water. An aqueous solution in which 160.8 parts by mass of ion-exchanged water was dissolved was used. In addition, when the median diameter (D ₅₀ ) on the volume basis of the particles becomes 3.1 μm after the aggregation reaction between the resin particles and the colorant particles is started, the sodium salt of the exemplary compound (6-1) is 52.9. Part of mass was added. Other than that, “Toner 2” was prepared in the same procedure.

<Preparation of Toner 3>
In the preparation of “Toner 1”, instead of an aqueous solution in which 54.3 parts by mass of magnesium chloride hexahydrate was dissolved in 104.3 parts by mass of ion-exchanged water, 162.9 parts by mass of magnesium chloride hexahydrate was prepared. Was used in an aqueous solution in which 198.0 parts by mass of ion-exchanged water was dissolved. Further, after the start of the aggregation reaction between the resin particles and the colorant particles, when the median diameter (D ₅₀ ) on the volume basis of the particles becomes 8.9 μm, the sodium salt of the exemplified compound (6-1) is changed to 70.5. Part by weight was added. Other than that, “Toner 3” was prepared in the same procedure.

<Preparation of Toner 4>
In the production of “Toner 1”, 45.7 parts by mass of aluminum sulfate was used in place of an aqueous solution in which 54.3 parts by mass of magnesium chloride hexahydrate was dissolved in 104.3 parts by mass of ion-exchanged water. An aqueous solution dissolved in 3 parts by mass was used. Moreover, 26.4 mass parts of exemplary compound (6-1) was changed into 26.4 mass parts of exemplary compound (6-2). Other than that, “Toner 4” was prepared in the same procedure.

<Preparation of Toner 5>
In the preparation of “Toner 4”, 91.4 parts by weight of aluminum sulfate was changed to 160.8 parts by weight of ion-exchanged water instead of an aqueous solution in which 45.7 parts by weight of aluminum sulfate was dissolved in 104.3 parts by weight of ion-exchanged water. A dissolved aqueous solution was used. Moreover, when the median diameter (D ₅₀ ) on the volume basis of the particles becomes 7.5 μm after the aggregation reaction between the resin particles and the colorant particles is started, the sodium salt of the exemplified compound (6-2) is 26.7 masses. Parts were added. Other than that, “Toner 5” was prepared in the same procedure.

<Preparation of Toner 6>
In the production of “Toner 4”, instead of the aqueous solution in which 45.7 parts by mass of aluminum sulfate was dissolved in 104.3 parts by mass of ion-exchanged water, 137.1 parts by mass of aluminum sulfate was changed to 201.3 parts by mass of ion-exchanged water. A dissolved aqueous solution was used. In addition, when the median diameter (D ₅₀ ) on the volume basis of the particles becomes 4.0 μm after starting the aggregation reaction between the resin particles and the colorant particles, 70.5 mass of the sodium salt of the exemplary compound (6-2) Parts were added. Other than that, “Toner 6” was prepared in the same procedure.

<Preparation of Toner 7>
In the production of “Toner 1”, 26.4 parts by mass of the exemplified compound (6-1) was changed to 26.4 parts by mass of the exemplified compound (7-7). Other than that, “Toner 7” was prepared in the same procedure.

<Preparation of Toner 8>
In the production of “Toner 7”, 26.4 parts by mass of the exemplified compound (7-7) was changed to 52.9 parts by mass of the sodium salt of the exemplified compound (7-7). Other than that, “Toner 8” was prepared in the same procedure.

<Preparation of Toner 9>
In the production of “Toner 7”, 26.4 parts by mass of the exemplified compound (7-7) was changed to 70.5 parts by mass of the sodium salt of the exemplified compound (7-7). Other than that, “Toner 9” was prepared in the same procedure.

<Preparation of Toner 10>
“Toner 10” was prepared in the same manner as in “Toner 1” except that the amount of Example Compound (6-1) added was changed to 19.8 parts by mass.

<Preparation of Toner 11>
“Toner 11” was prepared in the same manner as in “Toner 4” except that the amount of Example Compound (6-2) added was changed to 19.8 parts by mass.

<Preparation of Toner 12>
“Toner 12” was prepared in the same manner as in “Toner 7” except that the amount of the exemplified compound (7-7) added was changed to 19.8 parts by mass.

<Preparation of Toner 13>
“Toner 13” was prepared in the same manner as in “Toner 2” except that the amount of sodium salt of Exemplified Compound (6-1) was changed to 73.4 parts by mass.

<Preparation of Toner 14>
“Toner 14” was prepared in the same manner as in “Toner 5” except that the amount of sodium salt of Exemplified Compound (6-2) was changed to 73.4 parts by mass.

<Preparation of Toner 15>
“Toner 15” was prepared in the same manner as in “Toner 8” except that the amount of the sodium salt of Exemplified Compound (7-7) was changed to 73.4 parts by mass.

<Preparation of Toner 16>
In the production of “Toner 1”, when the median diameter (D ₅₀ ) on the volume basis of the particles becomes 5.8 μm after starting the aggregation reaction of the resin particles and the colorant particles, the exemplified compound (6-1) 26 “Toner 16” was prepared in the same manner except that 4 parts by mass was changed to 41.8 parts by mass of the exemplified compound (A) having the following structure.

<Preparation of Toner 17>
In the production of “Toner 1”, when the median diameter (D ₅₀ ) on the volume basis of the particles becomes 5.8 μm after starting the aggregation reaction of the resin particles and the colorant particles, the exemplified compound (6-1) 26 “Toner 17” was prepared in the same manner except that 4 parts by mass was changed to 73.8 parts by mass of the exemplified compound (B) having the following structure.

Table 1 shows the tricarboxylic acid compounds or comparative compounds used in the production of “Toners 1 to 17”, the addition amount during toner production, the amount contained in the toner, the sodium content, the divalent or trivalent metal. The content and the median diameter (D ₅₀ ) based on the volume of the toner are shown.

<Non-magnetic one-component developer>
“Toners 1 to 17” produced above were used as non-magnetic one-component developers.

<Evaluation>
<Image forming device>
As an image forming apparatus for evaluation, a commercially available color laser printer “Magicor 5430DL” (manufactured by Konica Minolta Business Technologies Co., Ltd.) is modified so that only magenta toner can be output, and the printing speed (linear speed) is commercially available. Remodeled to about twice the setting (300 mm / sec) and evaluated under high-spec conditions. The evaluation with only magenta toner is because the problem to be solved by the present invention, in particular, the evaluation mode in which filming of the developing roller is easy to detect (conspicuous when filming occurs).

  When the remaining amount of toner was low, the toner cartridge was temporarily stopped, the toner was added, and the evaluation was continued without replacing the developing roller.

<Evaluation item>
(Image density decrease under low temperature and low humidity)
The decrease in image density under low temperature and low humidity is 5,000 sheets printed on high-quality A4 size paper (65 g / m ² ) under low temperature and low humidity (10 ° C, 20% RH) environmental conditions. The image density of the solid image area at the end of printing was measured and evaluated. The image density was measured using a reflection densitometer “RD-918” (manufactured by Macbeth).

Evaluation Criteria A: Excellent when the image density drop is less than 0.04 at the start and at the end of printing 5,000 sheets ○: Good when the image density drop is less than 0.07 at the start and at the end of printing 5,000 sheets X: Deterioration in image density was poor at 0.07 or more at the start and at the end of printing 5,000 sheets.

(Filming of developing roller)
Filming of the developing roller is performed at a high temperature and high humidity (30 ° C., 80% RH) environmental condition, printing at a pixel rate of 2%, and visually confirming the number of halftone density irregularities at the developing roller pitch. The determination was made according to the following criteria.

Evaluation criteria A: Up to 10,000 prints, no filming and density unevenness of developing roller pitch occurred. O: Minor filming occurred at 5000 prints or more and 10,000 prints or less. Density unevenness of the developing roller pitch does not occur until 10000 prints. Δ: Filming occurs at 2000 prints or more and 5000 prints or less. Minor density unevenness of developing roller pitch occurs when printing 5000 sheets or more. X: Filming occurs when printing is less than 2000 sheets. Density unevenness of developing roller pitch occurs in halftone (Fixability of high whiteness paper)
The fixability was evaluated by performing printing using transfer paper (80 g / m ² ) having a calcium carbonate content of 20% by mass under ambient conditions of normal temperature and humidity (20 ° C., 55% RH).

  The fixing strength was evaluated by a tape peeling test.

  A solid image having an initial density of 1.0 to 1.2 was printed at a fixing speed of 80 mm / sec and a surface temperature of the transfer material of 100 ° C. After pasting a “mending tape” (manufactured by Sumitomo 3M) on the solid image, the image density of the peeled portion was measured, the ratio with the initial image density was calculated, and the fixing strength by the tape peeling method was evaluated. For the measurement of the image density, a reflection densitometer “RD-918” (manufactured by Macbeth) was used.

Tape peeling method (1) Measure absolute reflection density D0 of solid black of 5 mm square (2) Lightly affix "Mending tape" (manufactured by Sumitomo 3M: No.810-3-12) (3) 1 kPa (4) The tape is peeled off at an angle of 180 ° and a force of 200 g. (5) The absolute reflection density D1 after peeling is measured. (6) Fixing strength = 100 × D1 / D0 (%)
Evaluation Criteria A: Fixing strength is 95% or more, good ○: Fixing strength is 90% or more, no practical problem ×: Fixing strength is less than 90%.

(Laminate floating)
A commercially available laminating machine was used to print a double-sided image with a pixel rate of 70% on a transfer paper (A4 size, 80 g / m ² ) with a calcium carbonate content of 20% by mass under environmental conditions of normal temperature and humidity (20 ° C., 55% RH). The laminate was used and left in an environment of 30 ° C. and 80% RH for 7 days. Thereafter, the side of the laminate image was dropped 6 times from a height of 20 cm, and the presence or absence of a portion where the toner and the laminate material were peeled off from the transfer paper was visually evaluated.

Evaluation criteria ○: There is no part where the toner and the laminate material are peeled off from the transfer paper. ×: There is a part where the toner and the laminate material are peeled off from the transfer paper.

  Table 2 shows the evaluation results.

  From the evaluation results of Table 2, the “toners 1 to 9” of Examples 1 to 9 had a smaller crushing strength index than the comparative examples and were good in all the evaluation items. No. 17 ”indicates that the crushing strength index is larger than that of the example, and any of the evaluation items has a problem.

It is a schematic sectional drawing which shows an example of the developing device for nonmagnetic one-component developers. 1 is a cross-sectional view illustrating an example of a full-color image forming apparatus that forms an image using the toner of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 14 Developing device 14a Developing roller 3 Hopper 4 Supply roller 5 Toner regulating blade 7 Bias power supply 10 Latent image holder (photosensitive drum)
T Toner

Claims (4)

An electrostatic charge image developing toner comprising at least a resin and a colorant,
In the step of aggregating the resin particles at the time of producing the electrostatic image developing toner,
The resin particles contain a vinyl polymer,
Tricarboxylic acid or a salt thereof having a hydroxyl group, or by adding tricarboxylic acid or its salt shown below,
Tricarboxylic acid or a salt thereof having a hydroxyl group in the electrostatic toner for electrostatic image development, or electrostatic image, characterized in that the tricarboxylic acid or its salt is obtained by incorporating 20ppm or 264ppm below Developing toner.

2. The electrostatic charge image developing toner according to claim 1, wherein the electrostatic charge image developing toner contains 1 ppm to 134 ppm of a sodium element and 600 ppm to 1800 ppm of a divalent or trivalent metal element. . 3. The electrostatic image developing toner according to claim 1, wherein the electrostatic image developing toner is used in a non-magnetic one-component image forming method. A method for producing an electrostatic image developing toner comprising at least a resin and a colorant,
In the step of aggregating the resin particles at the time of producing the electrostatic image developing toner,
The resin particles contain a vinyl polymer,
When the diameter of the resin particles reaches the diameter of the electrostatic image developing toner,
Tricarboxylic acid or a salt thereof having a hydroxyl group, or by adding tricarboxylic acid or its salt shown below,
Tricarboxylic acid or a salt thereof having a hydroxyl group in the electrostatic toner for electrostatic image development, or electrostatic image, characterized in that the tricarboxylic acid or its salt is obtained by incorporating 20ppm or 264ppm below A method for producing a developing toner.

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