JP4981434B2 - toner - Google Patents

Description

  The present invention relates to a toner used in electrophotography, electrostatic recording, and magnetic recording. More specifically, the present invention relates to an electrostatic image developing toner (hereinafter abbreviated as toner) used in an image recording apparatus that can be used in a copying machine, a printer, a facsimile, a plotter, and the like.

  A technique for visualizing image information through an electrostatic latent image, such as electrophotography, is used in various fields such as a copying machine and a printer. With the development of technology, demands from users are becoming stricter year by year, and higher image quality, energy saving, and longer life are required more than ever. Numerous measures have been taken for individual issues.

  For example, from the viewpoint of high image quality and energy saving, the toner contains a low molecular weight resin having a peak or shoulder in a specific molecular weight region and a high molecular weight resin having a peak or shoulder in a specific molecular weight region, and a polyolefin-based resin. Measures such as inclusion of wax have been performed (Patent Document 1). In addition, attempts have been made to improve low-temperature fixability by defining the molecular weight distribution by GPC of the THF-soluble component of the binder resin and the glass transition point of the binder resin and toner (Patent Document 2). . In terms of long life, a measure has been taken such that a thermoplastic resin having a tensile breaking elongation of 200 to 1000% and a softening temperature (Vicat method) of 55 to 120 ° C. is contained (Patent Document 3).

  Certainly, such a measure has made it possible to obtain a stable image with a great effect on each problem. However, as a result of intensive studies by the present inventors, it has been found that it is still insufficient in terms of satisfying both high image quality and long life. Since there are portions where the fixability and the developability are inconsistent, it is difficult to achieve both, and it is actually necessary to improve various characteristics of the toner.

JP 2002-6553 Patent No. 2630972 JP2004-101579

  The present invention is to provide a toner that solves the above background art. That is, an object is to provide a toner that satisfies energy-saving fixing, long life, and high durability.

The present invention relates to a toner having inorganic particles and toner particles containing at least a binder resin, a colorant, and a release agent.
The toner particles are
(I) a dispersion step of dissolving and dispersing the release agent, the colorant, the charge control agent and the polar resin in at least the polymerizable monomer by a disperser to obtain a polymerizable monomer composition;
(Ii) Granulation in which the polymerizable monomer composition obtained in the dispersion step is dispersed in an aqueous phase containing a dispersion stabilizer with a stirrer to produce droplets of the polymerizable monomer composition. Process,
(Iii) a polymerization step for polymerizing the polymerizable monomer in the droplet; and
(Iv) a drying step in which the particles obtained in the polymerization step are washed and the wet particles are collected and then dried;
Is obtained through
As the polymerizable monomer, styrene and (meth) acrylic acid ester monomers are used,
The polar resin has an acid value of 4 to 20 mgKOH / g,
The toner is directed molecular weight distribution measured by tetrahydrofuran (THF) soluble matter of gel permeation chromatography (GPC),
(I) The molecular weight (M1) of the main peak is 10,000 to 80,000,
(Ii) In the molecular weight distribution chart, when the height of the molecular weight (M1) of the main peak is H (M1) and the height of the molecular weight 4,000 is H (4,000),
H (4,000): H (M1) = (0.100 to 0.950): 1.00
And
(Iii) having a sub-peak P (M2) in the region of molecular weight 600 to 6000 ,
The toner is zeta potential measurement in a state dispersed in methanol (measurement conditions: Dielectric Constant: 25.00, Temperature: 25 ℃) in, zeta potential at -110.0 to -50.0M V Yes ,
This invention relates to a toner.

  According to the present invention, a high quality image having both fixability and developability can be obtained. That is, it is possible to obtain a long-life toner that achieves low-temperature fixability and high gloss and does not cause development streaks and member contamination.

  Hereinafter, the present invention will be described in detail.

As a result of intensive studies on the above problems, the present inventors have determined the molecular weight distribution of the tetrahydrofuran (THF) soluble part of the toner measured by gel permeation chromatography (GPC) and the zeta potential of the toner in a methanol medium. By setting a specific value, an excellent toner having excellent fixability and developability was obtained.
First, the structural features and materials of the toner will be described.

  The toner of the present invention is a toner having toner particles containing at least a binder resin, a colorant, and a release agent, and an inorganic fine powder, and gel permeation chromatography (GPC) soluble in tetrahydrofuran (THF) of the toner. The molecular weight (M1) of the main peak measured by the above is 10,000 to 80,000, the molecular weight (M1) height of the main peak is H (M1), and the molecular weight is 4,000 in the molecular weight distribution chart. Is H (4,000), it is essential that H (4,000): H (M1) = (0.100 to 0.950): 1.00. Demonstrates great effect on fixability. The reason is that the toner of the present invention blends components having specific molecular weights in a well-balanced manner by defining the ratio of molecular weight heights H (4000): H (M1) within a predetermined range. By setting the molecular weight of the main peak in the region of 10,000 to 80,000, the binder resin component in the region of molecular weight 15,000 to 60,000 is a wax present in the toner, a low molecular weight polymer having a molecular weight of less than 15,000, or Compared to low molecular weight copolymers, the viscosity change due to temperature change is small, so a wide fixing temperature range is possible. The toner of the present invention also contains components in a molecular weight range of 4000 to 15000 in a well-balanced manner. A low molecular component having a molecular weight of 4000 to 15000 exhibits an effect on low-temperature fixability, and a high gloss image can be obtained because of low melt viscosity.

  A more preferable molecular weight distribution in the present invention preferably has a sub-peak (P (M2)) in addition to the main peak in the molecular weight region of 16000 to 60,000. Further, it is preferable that the sub-peak has a molecular weight of 600 to 6000. A toner containing a component having a molecular weight of 600 to 6000 can further improve the low-temperature fixability. By having a peak in the molecular weight M2, which is an extremely low molecular region, the melt viscosity of the toner at low temperatures can be lowered more effectively, the low temperature fixability can be improved, and a high gloss image can be obtained.

Moreover, it is preferable to have the maximum point P (M3) in a region having a molecular weight of 2500 or more and less than 15000. Further, in the molecular weight distribution chart measured by GPC of the THF soluble content of the toner, the height of the maximum point P (M3) is H (M3), and the maximum point P (M3) and the main peak H (M3), H (L1), and H (M1) are H (L1), where H (L1) is the height of the minimum point P (L1) when the minimum point P (L1) exists between them. The following conditions H (M3): H (L1): H (M1) = (0.10 to 0.95) :( 0.20 to 0.99): 1.00
By satisfying the above, the interaction between the resin component contained in a region having a molecular weight of 2500 or more and less than 15000 and the resin component contained in a region having a molecular weight of 15000 or more (particularly a molecular weight of 15000 or more and less than 200,000) is moderately moderated. Therefore, the softening and oozing of the wax, the low molecular weight polymer having a molecular weight of less than 15000, or the low molecular weight copolymer can be effectively increased, and the excellent effects of low temperature fixability and expansion of the fixable temperature range are exhibited.

  An example of the molecular weight distribution chart of the THF soluble content of the preferred toner in the present invention is shown in FIGS.

  In the molecular weight distribution chart measured by GPC of the THF soluble part of the toner, the molecular weight distribution when the molecular weight at the main peak p (M1) is M1 and the height at that time is h (M1) [mV] is shown. It was shown in FIG. Here, h (M2) represents the height at the subpeak p (M2), and h (4000) represents the height at a molecular weight of 4000. As shown in FIG. 1, the toner of the present invention has the main peak in a molecular weight region of 16000 to 60,000.

  In the molecular weight distribution chart measured by GPC of the THF soluble part of the toner shown in FIG. 1, the molecular weight distribution chart when the height is converted to h (M1) [mV] = 1.00 is shown in FIG. Show.

  In FIG. 2, the height at the main peak P (M1) is H (M1) (the molecular weight at the main peak is M1), the height at the subpeak P (M2) is H (M2) (the molecular weight at the subpeak is M2). ). In FIG. 2, the height at a molecular weight of 4000 is indicated by H (4000).

  FIG. 3 shows a chart of the molecular weight distribution measured by GPC of the THF soluble matter of the toner in the case where the maximum point p (M3) is between the main peak p (M1) and the sub peak p (M2). . Moreover, the minimum value between the main peak p (M1) and the maximum value p (M3) was set to p (L1). Here, h (M3) represents the height at the maximum value p (M3), and h (L1) represents the height at the minimum value p (L1).

  In the molecular weight distribution chart measured by GPC of the THF soluble part of the toner shown in FIG. 3, the molecular weight distribution chart when the height is converted to h (M1) [mV] = 1.00 is shown in FIG. Indicated.

  In FIG. 4, the height at the main peak P (M1) is H (M1) (the molecular weight at the main peak is M1), the height at the subpeak P (M2) is H (M2) (the molecular weight at the subpeak is M2) ). In FIG. 4, the height at the maximum point P (M3) between the main peak P (M1) and the sub peak P (M2) is H (M3) (the molecular weight at the maximum point P (M3) is M3 (M3). > M2)). In FIG. 4, the height at a molecular weight of 4000 is indicated by H (4000). Moreover, the minimum value between the main peak P (M1) and the maximum value P (M3) was set to P (L1). Here, H (L1) indicates the height at the minimum value P (L1).

  The chart of the molecular weight distribution of the THF soluble content of the toner of the present invention can be measured under the following measurement conditions using a GPC measuring apparatus (HLC-8120 GPC manufactured by Tosoh Corporation).

<Measurement conditions>
Column (manufactured by Showa Denko KK): Shodex GPC KF-801, Shodex GPC KF-802, Shodex GPC KF-803, Shodex GPC KF-804, Shodex GPC KF-805, Shodex GPC KF-806, G 807 (diameter: 8.0mm, length: 30cm), 7 stations, temperature: 40 ° C
・ Flow rate: 0.6ml / min
・ Detector: RI
Sample concentration: 10 μl of 0.1% by mass sample

  Sample preparation is performed by placing a toner sample to be measured in tetrahydrofuran (THF), allowing it to stand for 6 hours, and then shaking it sufficiently (until the sample is no longer integrated), and then allowing it to stand for 1 day or longer. And let what passed the sample processing filter (pore size 0.45 micrometer) be a sample for GPC measurement. The calibration curve uses a molecular weight calibration curve created with a monodisperse polystyrene standard sample.

However, although the toner configuration alone has a great effect on the fixing property, it has not yet achieved the high durability required by the current market. In particular, a toner containing a large amount of components in the molecular weight region of 4000 to 15000, which has a great effect on low-temperature fixability and high glossiness, has low durability. The reason is that the smaller the molecular weight, the lower the thermal durability and strength, causing cracking and breakage of the toner, exposure of low molecular weight components to the toner surface, and further development by promoting exposure of the wax to the surface. High durability cannot be obtained because it causes streak and member contamination. However, even if the toner of the present invention is a toner having the above-described configuration, the zeta potential of the toner is measured in the range of −110.0 to −50.0 mV in the measurement of the zeta potential in a state dispersed in methanol. It is possible to further improve without impairing. When the zeta potential of the toner in methanol is in the range of -110.0 to -50.0 mV, it indicates that the binder resin, wax, etc. in the toner particles are present in a desirable state. When the zeta potential exceeds −50 mV, since the wax and low molecular components are exposed on the toner surface, development streaks and member contamination occur due to temperature rise in the machine, mechanical stress, and the like. Conversely, when the zeta potential is less than −110 mV, image unevenness due to charge-up occurs. More preferably, it is in the range of −100.0 to −60.0 mV, and the balance between durability and fixability is further improved. The standard deviation of the zeta potential ( zeta SD ) is preferably 10 mV or less. It is suggested that the smaller the numerical value of the zeta SD, the less the variation in the zeta potential of the toner and the more stable the chargeability. By setting the zeta SD to 10 mV or less, more stable image quality can be obtained.

  In the present invention, by optimizing the drying process, which will be described later, the thermal deterioration (durability deterioration) factor is suppressed, and even in the case of toner containing many low molecular components having low heat durability and strength, each component is brought into a desired presence state. Therefore, high image quality can be obtained without impairing durability. In other words, both fixability and developability can be achieved.

  The zeta potential of the toner of the present invention can be measured under the following measurement conditions using a Zetasizer Nano-ZS (manufactured by MALERN).

<Measurement conditions>
Cell: DTS1060-Green disposablezecell
・ Model: Smolchowski
・ Dispersant: Me OH
-Dielectric Constant: 25.00
・ Temperature: 25 ° C
・ Result Calculation: General Purpose

Adjustment of the sample, put the toner samples 10mg to be measured in methanol 20 ml, dispersed for 5 minutes using a homogenizer (SMT Co., Ltd.).

  Next, the toner material will be described.

[Binder resin]
Specific examples of the binder resin contained in the toner of the present invention include styrene- (meth) acrylic copolymers, polyester resins, epoxy resins, and styrene-butadiene copolymers. In a method for directly obtaining toner particles by a polymerization method, a monomer for forming a binder resin is used. Specifically, styrene; styrene monomers such as o- (m-, p-) methylstyrene, m- (p-) ethylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, ( Meth) propyl acrylate, butyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (Meth) acrylic acid ester monomers such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; ene monomers such as butadiene, isoprene, cyclohexene, (meth) acrylonitrile, and acrylamide Is preferably used. These monomers are used alone or in general so that the theoretical glass transition temperature (Tg) described in Polymer Handbook 2nd edition III-P139 to 192 (manufactured by John Wiley & Sons) is 40 to 75 ° C. It is used by mixing appropriately. When the theoretical glass transition temperature (Tg) is less than 40 ° C., problems are likely to occur from the viewpoint of storage stability and durability stability of the toner, while when it exceeds 75 ° C., the fixing point of the toner is increased.

  Further, in the present invention, it is possible to use a crosslinking agent during the synthesis of the binder resin in order to increase the mechanical strength of the toner particles.

  Among the crosslinking agents used in the toner of the present invention, difunctional linking agents such as divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4 -Butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200 , # 400, # 600 diacrylate, dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester type diacrylate (MANDA Honkakusuri), and those obtained by changing the methacrylates of the above diacrylate.

  Polyfunctional crosslinkers include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate and its methacrylate, 2,2-bis (4-methacryloxy, polyethoxy Phenyl) propane, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate and triallyl trimellitate.

  These crosslinking agents are 0.01 to 10 parts by mass, preferably 0.05 to 4 parts by mass, with respect to 100 parts by mass of the polymerizable monomer constituting the binder resin.

  The toner of the present invention can be polymerized by adding a low molecular weight resin to the polymerizable monomer composition. Low molecular weight resins that can be added to the toner of the present invention include random copolymers, block copolymers, and graft copolymers of a monomer component containing a hydrophilic functional group and a vinyl compound such as styrene or ethylene. Such a copolymer is mentioned. Further, it can be used in the form of the above-mentioned monomer component containing a hydrophilic functional group and a polycondensate such as polyester and polyamide, or an addition polymer such as polyether and polyimine. Examples of hydrophilic functional groups include amino groups, carboxylic acid groups, hydroxyl groups, sulfonic acid groups, glycidyl groups, and nitrile groups.

  In addition to the above, examples of the low molecular weight resin that can be added to the polymerizable monomer composition include the following. Homopolymers of styrene such as polystyrene and polyvinyltoluene and substituted products thereof; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene- Ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate Copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer , Styrene-butadi Copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene copolymer such as styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, Polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin. In addition, the said low molecular weight resin can be used individually or in mixture.

  Among these low molecular weight resins, the glass transition point of the low molecular weight resin is preferably 40 to 100 ° C. When the glass transition point is less than 40 ° C., the strength of the entire toner particles is lowered, and the transferability and development characteristics are liable to be lowered during a multi-endurance test. Further, the toner particles are aggregated in a high-temperature and high-humidity environment, resulting in a problem that storage stability is lowered. On the other hand, if the glass transition point exceeds 100 ° C., the problem of poor fixing tends to occur.

  The glass transition point of the low molecular weight resin is preferably 40 to 70 ° C., more preferably 40 to 65 ° C., from the viewpoints of low-temperature fixability and high gloss image.

  The addition amount of the low molecular weight resin is preferably 0.1 to 60 parts by mass in 100 parts by mass of the binder resin in the toner particles. When the amount is less than 0.1 part by mass in 100 parts by mass of the binder resin in the toner particles, the effect of adding the low molecular weight resin is small.

[Polar resin]
In the present invention, a resin having polarity (hereinafter referred to as “polar resin”) such as a polyester resin and a polycarbonate resin can be used in combination with the above-described binder resin. By adding a polar resin in the toner, it becomes easier to control the presence state of the wax in the toner to a desired state.

  For example, when a toner is directly produced by a suspension polymerization method, which will be described later, a polymerizable monomer composition that becomes toner particles when a polar resin as described above is added during the polymerization reaction from the dispersion step to the polymerization step. Depending on the balance of polarity exhibited by the aqueous dispersion medium, the added polar resin can be controlled so that a thin layer is formed on the surface of the toner particles, or that there is an inclination from the toner particle surface toward the center. By controlling the inclination, functional separation in the toner particles can be achieved. That is, it is possible to make the presence state of the binder resin and the wax into a desirable form while controlling the state of exposure of the wax to the toner particle surface. In particular, it is preferable to use a polar resin having an acid value of 4 to 20 mgKOH / g.

  In the present invention, the addition amount of the polar resin is preferably 1 to 25 parts by mass, more preferably 2 to 15 parts by mass with respect to 100 parts by mass of the binder resin. If the addition amount of the polar resin is less than 1 part by mass, the presence state of the polar resin in the toner particles becomes non-uniform. On the contrary, when the amount exceeds 25 parts by mass, the thin layer of polar resin formed on the surface of the toner particles becomes thick, and in any case, the performance required for the toner cannot be expressed in a balanced manner.

  The polar resins as described above are not limited to one type of polymer. For example, two or more types of reactive polyester resins can be used simultaneously, or two or more types of vinyl polymers can be used. Yes, and a completely different kind of polymer, such as non-reactive polyester resin, epoxy resin, polycarbonate resin, polyolefin, polyvinyl acetate, polyvinyl chloride, polyalkyl vinyl ether, polyalkyl vinyl ketone, polystyrene, poly (meth) acrylic Various polymers such as ester, melamine formaldehyde resin, polyethylene terephthalate, nylon, and polyurethane can be added to the binder resin as necessary.

[Release agent]
For the toner of the present invention, known wax components can be used. Specifically, petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam and derivatives thereof, montan wax and derivatives thereof, and Fischer-Tropsch method. Examples include hydrocarbon waxes and derivatives thereof, polyolefin waxes and derivatives thereof typified by polyethylene, natural waxes such as carnauba wax and candelilla wax, and derivatives thereof. Derivatives include block copolymers with oxides and vinyl monomers. Polymerized products and graft-modified products are also included. Further, alcohols such as higher aliphatic alcohols; fatty acids such as stearic acid and palmitic acid or compounds thereof; acid amides, esters, ketones, hydrogenated castor oil and derivatives thereof, vegetable waxes, and animal waxes. These can be used alone or in combination.

  Among these, when polyolefin, hydrocarbon wax by Fischer-Tropsch method, or petroleum wax is used, the effect of improving developability and transferability is further enhanced. These wax components may be added with an antioxidant within a range that does not affect the chargeability of the toner. In addition, these wax components are preferably used in an amount of 1 to 30 parts by mass with respect to 100 parts by mass of the binder resin.

  The melting point of the wax component used in the present invention is preferably in the range of 30 to 120 ° C, more preferably in the range of 60 to 100 ° C.

  By using the wax component exhibiting the thermal characteristics as described above, not only good fixability of the obtained toner but also a release effect by the wax component is efficiently expressed, and a sufficient fixing region is secured. Furthermore, it is possible to eliminate developability, blocking resistance and adverse effects on the image forming apparatus due to conventionally known wax components.

  The melting point of the wax component used in the present invention means a main endothermic peak temperature in a DSC curve measured according to “ASTM D3418-82”, and is measured by, for example, “DSC-7” (Perkin Elmer). The At this time, the melting point of iridium and zinc is used for the temperature correction of the device detection unit, and the heat of fusion of iridium is used for the correction of the heat quantity. In the measurement, a measurement sample placed in an aluminum pan and an aluminum pan only (empty pan) were set as a control, and the measurement range of 20 to 180 ° C. was increased at a rate of temperature increase of 10 ° C./min. The melting point is determined from the main endothermic peak temperature of the DSC curve obtained when heated. In the case of measuring only the wax component, the measurement is started after the temperature is raised and lowered under the same conditions as in the measurement to remove the previous history. When measuring the wax component contained in the toner, the measurement is performed as it is without performing the operation of removing the previous history.

[Charge control agent]
A known charge control agent can be used in combination with the toner of the present invention. In particular, a charge control agent that has a high charging speed and can stably maintain a constant charge amount is preferably used. Further, when the toner particles are directly produced by a polymerization method, a charge control agent having no polymerization inhibitory property and having no solubilized product in an aqueous dispersion medium is preferable. Specific compounds include metal compounds of carboxylic acids such as salicylic acid, naphthoic acid, and dicarboxylic acid as negative charge control agents; polymer compounds having sulfonic acid or carboxylic acid groups in the side chain; boron compounds; urea compounds; Silicon compound; calixarene and the like. Examples of the positive charge control agent include quaternary ammonium salts; polymer type compounds having the quaternary ammonium salt in the side chain; guanidine compounds; imidazole compounds. The metal compounds or polymer compounds described above can be used alone, but more preferably used in combination.

[Colorant]
The colorant of the toner of the present invention may be any of a cyan colorant, a magenta colorant, a yellow colorant, and carbon black. The following are mentioned as an organic pigment or dye preferably used.

  As an organic pigment or organic dye that can be used as a cyan colorant, a copper phthalocyanine compound and a derivative thereof, an anthraquinone compound, a basic dye lake compound, or the like can be used. Specifically, C.I. I. Pigment blue 1, C.I. I. Pigment blue 7, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, 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 60, C.I. I. Pigment blue 62, C.I. I. And CI Pigment Blue 66.

  Organic pigments or organic dyes that can be used as magenta colorants include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds. Is used. Specifically, 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 violet 19, C.I. I. Pigment red 23, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 150, C.I. I. Pigment red 166, C.I. I. Pigment red 169, C.I. I. Pigment red 177, C.I. I. Pigment red 184, C.I. I. Pigment red 185, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. And CI Pigment Red 254.

  Examples of organic pigments or organic dyes that can be used as yellow colorants include compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, 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 17, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 111, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 127, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 174, C.I. I. Pigment yellow 175, C.I. I. Pigment yellow 176, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 181, C.I. I. Pigment yellow 191, C.I. I. And CI Pigment Yellow 194.

  As the black colorant, carbon black and the one prepared by using the above yellow / magenta / cyan colorant to be blackened are used.

  Among them, carbon black and those that are toned in black by the above-mentioned preferred yellow / magenta / cyan colorant combination are preferable in order to satisfy the organic volatile component amount of the present invention.

  These colorants can be used alone or mixed and further used in the form of a solid solution. The colorant used in the toner of the present invention is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in the toner.

  A preferable content of the colorant in the toner particles is 1 to 20 parts by mass with respect to 100 parts by mass of a binder resin (consisting of a vinyl polymer manufactured using the organic peroxide and other resins). It is.

  As will be described later, the toner particles of the present invention are produced using a polymerization method. When obtaining toner particles by a polymerization method, it is necessary to pay attention to the polymerization inhibition property and water phase transfer property of the colorant. Therefore, the colorant is preferably subjected to surface modification, for example, a hydrophobic treatment with a substance having no polymerization inhibitory property. In particular, many dye-based colorants and carbon black have a polymerization inhibitory property, and when toner particles are produced by a polymerization method, care must be taken when used.

  The surface treatment of the dye-based colorant can be performed by polymerizing an arbitrary polymerizable monomer in the presence of these dyes. The toner particles may be produced by a polymerization method using the colored polymer thus obtained as a colorant.

  The surface treatment of carbon black may be a treatment with a substance that reacts with the surface functional group of carbon black, such as polyorganosiloxane, in addition to the same treatment as that for the dye-based colorant.

Next, the production method for producing the toner of the present invention, which will be described below with respect to the production method of the toner, is a method for producing the toner directly in the medium, such as suspension polymerization method and emulsion polymerization aggregation method (hereinafter referred to as heavy weight production method). (It is also referred to as legal). Among the above polymerization methods, the suspension polymerization method is particularly preferable.

  In the present invention, the suspension polymerization method includes at least a release agent, a colorant, a charge control agent, and other additives in the polymerizable monomer, and is uniformly dissolved and dispersed by a disperser such as a homogenizer or an ultrasonic disperser. Dispersing step of dispersing, the polymerizable monomer composition obtained in the dispersing step is dispersed in a water phase containing a dispersion stabilizer by a known stirrer, homomixer or homogenizer, and the polymerizable monomer composition A granulation step for producing droplets of the product, a polymerization step for polymerizing the polymerizable monomer in the droplets, washing the particles obtained in the polymerization step, and suitable filtration, decantation, centrifugation, etc. This is a polymerization method in which toner particles are produced by at least a step of drying after collecting wet particles (hereinafter referred to as wet particles).

  In the present invention, it is necessary to perform the drying step under conditions suitable for the toner of the present invention. A known apparatus is used as a dryer used in the drying process. For example, a fluidized bed dryer (Japanese Patent Laid-Open No. 4-31966) and a continuous instantaneous air flow dryer (Japanese Patent Laid-Open No. 2000-275903) are used. When the wet particles are dried by the dryer, the amount of heat received from the dryer includes the amount of heat (Q1) accompanying the temperature rise of the toner particles, the amount of heat (Q2) accompanying the temperature rise of the water, and the amount of heat for evaporating the water. (Q3) can be broadly divided into three.

  Since the toner of the present invention contains a large amount of low-molecular components that are vulnerable to heat, it is necessary to provide the heat amounts Q2 and Q3 while suppressing the heat amount Q1 as much as possible. When using a continuous instantaneous air dryer as one of the methods, the wet particles are heated to a specific temperature in advance, and the amount of heat given from the dryer is made the minimum amount of heat necessary for evaporation of moisture, Drying can be performed while suppressing thermal deterioration of the toner. As a result, a durability deterioration factor does not occur and high durability is obtained. The temperature of the wet particles is preferably 40 ° C to 60 ° C. The dryer temperature is preferably 50 ° C to 70 ° C.

<Other configuration>
The inorganic fine powder contained in the toner of the present invention acts as an external additive for the toner, and can improve the fluidity of the toner or make the charge uniform.

  The average primary particle size of the inorganic fine powder is preferably 4 to 80 nm, and more preferably 6 to 35 nm. When the average primary particle size of the inorganic fine powder is larger than 80 nm, it is difficult to sufficiently improve the fluidity of the toner, and the adhesion to the toner particles is likely to be non-uniform, and the triboelectric chargeability under low humidity is non-uniform. Leads to. For this reason, problems such as an increase in fog, a decrease in image density, or a decrease in durability are likely to occur. On the other hand, when the average primary particle size of the inorganic fine powder is smaller than 4 nm, the agglomeration property of the inorganic fine particles is increased, and the aggregate is not a primary particle but an aggregate having a wide particle size distribution having a strong agglomeration property that is difficult to break even by crushing treatment. It becomes easy to behave as. Image defects are likely to occur when the aggregate is developed or the image carrier or toner carrier is damaged.

  The average primary particle size of the inorganic fine powder is a photograph of the toner magnified by a scanning electron microscope, and is further mapped by the element contained in the inorganic fine powder by an elemental analysis means such as XMA attached to the scanning electron microscope. It can be measured by measuring 100 or more primary particles of the inorganic fine powder present on the toner surface while adhering to or separating from the toner image, and determining the number average particle diameter.

  Examples of the inorganic fine powder contained in the toner of the present invention include silica, titanium oxide, alumina, or double oxides thereof.

As the silica, for example, any of so-called dry silica produced by vapor phase oxidation of silicon halides, dry silica called fumed silica, and so-called wet silica produced from water glass can be used. However, dry silica having less silanol groups on the surface and inside the silica fine powder and less production residue such as Na ₂ O, SO ₃ ²⁻ is more preferable.

  Here, dry silica also includes composite fine powders of silica and other metal oxides obtained by using other metal halogen compounds such as aluminum chloride and titanium chloride in combination with silicon halogen compounds in the production process. To do.

  The inorganic fine powder is preferably hydrophobized from the viewpoint of improving the properties of the toner in a high humidity environment. When the inorganic fine powder added to the toner absorbs moisture, the charge amount of the toner is remarkably lowered, and the developability and transferability are easily lowered.

  Examples of the treatment agent used for the hydrophobizing treatment include silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, and organic titanium compounds. It is done. These can be hydrophobized alone or in combination of two or more.

  The hydrophobic treatment is particularly preferably a treatment with silicone oil. More preferably, the inorganic fine powder is hydrophobized with silicone oil at the same time or after the hydrophobizing treatment by any method. The inorganic fine powder obtained in this way can maintain a high charge amount of the toner in a high humidity environment, and is preferable for suppressing selective development.

  As a more preferable hydrophobic treatment of the inorganic fine powder, for example, a silylation reaction is performed using a silylating agent as a first-stage treatment reaction, and a hydrophobic thin film is formed on the surface with silicone oil as a second-stage treatment reaction.

  The amount of the silylating agent used is preferably 5 to 50 parts by mass with respect to 100 parts by mass of the inorganic fine powder. If the amount is less than 5 parts by mass, it is not sufficient to eliminate the active hydrogen on the surface of the inorganic fine particles. If the amount exceeds 50 parts by mass, the siloxane compound produced by the reaction between the excess silylating agents acts as a paste to prevent the inorganic fine particles from Aggregation occurs and image defects are likely to occur.

Viscosity at 25 ° C. of the silicone oil is preferably from 10 to 200,000 mm ² / s, more preferably 3,000 to 80,000mm ² / s. If it is less than 10 mm ² / s, the inorganic fine powder becomes unstable, and the image quality of the image formed using the toner containing it tends to deteriorate due to heat and mechanical stress. With silicone oil exceeding 200,000 mm ² / s, it may be difficult to uniformly treat the inorganic fine powder.

  As a method for hydrophobizing inorganic fine powder with silicone oil, for example, inorganic fine powder treated with a silane compound and silicone oil may be directly mixed using a mixer such as a Henschel mixer, or inorganic fine powder. A method of spraying silicone oil on the body may be used. Alternatively, after dissolving or dispersing silicone oil in a suitable solvent, an inorganic fine powder may be added and mixed, and then the solvent may be removed. A method using a sprayer is more preferable in that the formation of inorganic fine powder aggregates is relatively small.

  The treatment amount of the silicone oil is preferably 1 to 23 parts by mass, more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the inorganic fine powder. If the amount of the silicone oil is too small, good hydrophobicity cannot be obtained, and if it is too large, aggregation of inorganic fine particles tends to occur.

  The content (namely, addition amount) of the inorganic fine powder in the toner of the present invention is preferably 0.1 to 4.0 parts by mass with respect to 100 parts by mass of the toner particles. When the addition amount is less than 0.1 parts by mass, the effect of the inorganic fine powder is not sufficiently achieved, and when it exceeds 4.0 parts by mass, the toner fixing property tends to be lowered. The content of the inorganic fine powder can be quantified using a calibration curve prepared from a standard sample using fluorescent X-ray analysis.

The toner of the present invention preferably has a primary particle size of more than 30 nm (preferably a BET specific surface area of less than 50 m ² / g), more preferably a primary particle size of 50 nm or more (preferably a BET ratio) for the purpose of improving cleaning properties. It is preferable to further add inorganic or organic fine particles having a surface area of less than 30 m ² / g). For example, spherical silica particles, spherical polymethylsilsesquioxane particles, spherical resin particles and the like are preferably used.

  The toner of the present invention can be produced by mixing the toner particles with the inorganic fine powder and, if necessary, other fine particles and attaching them to the surface. The mixing can be performed using ordinary processing.

  The toner of the present invention has a weight average particle diameter of preferably 3 to 9 μm, and more preferably 4 to 7.8 μm. This is because finer latent image dots are faithfully developed in order to obtain a higher quality image. When the weight average particle diameter is less than 3 μm, there is a tendency that the amount of residual toner on the photosensitive member increases due to a decrease in transfer efficiency. Furthermore, when the amount of transfer residual toner on the photoconductor increases, it may be difficult to suppress photoconductor scraping and toner fusion in the contact charging process. Further, in addition to an increase in the surface area of the entire toner, the fluidity and agitation as a powder decrease, making it difficult to uniformly charge individual toner particles, and fog and transferability tend to deteriorate. Therefore, it tends to cause non-uniform image unevenness other than shaving and fusion.

  On the other hand, when the weight average particle diameter of the toner exceeds 9 μm, the characters and the line image are likely to be scattered and high resolution is difficult to obtain.

  The weight average particle diameter and number average particle diameter of the toner of the present invention can be measured with a Coulter Counter TA-II type or Coulter Multisizer (manufactured by Coulter Co.). Specifically, it can be measured as follows. Using a Coulter Multisizer (manufactured by Coulter), an interface (manufactured by Nikki) that outputs number distribution and volume distribution and a PC 9801 personal computer (manufactured by NEC) are connected. As the electrolytic solution, a 1% NaCl aqueous solution prepared using primary sodium chloride can be used. For example, ISOTON R-II (manufactured by Coulter Scientific Japan) can be used. The specific measurement procedure is as follows.

  100 ml of the electrolytic aqueous solution is added, and 2 mg of a measurement sample (toner) is further added. The electrolytic solution in which the sample is suspended is dispersed for about 1 minute with an ultrasonic disperser, and the volume and number distribution of the toner is measured by measuring the volume and number of toner of 2 μm or more using the Coulter Multisizer with a 100 μm aperture. calculate. From this, the weight average particle diameter (D4) and the number average particle diameter (D1) are determined.

  The toner of the present invention preferably has an average circularity of 0.970 to 1.000 and a mode circularity of 0.980 to 1.000 for particles of 3 μm or more.

Here, “circularity” in the present invention is used as a simple method for quantitatively expressing the shape of the particles. In the present invention, flow type particle image analyzer FPIA-2100 manufactured by Toa Medical Electronics is used. The value obtained from the following equation is defined as circularity.
Circularity a = L ₀ / L
L ₀ : Perimeter of a circle having the same projection area as the particle image L: Perimeter of the particle image (L ₀ ; Perimeter of a circle having the same projection area as the particle image, L: Perimeter of the projection image of the particle)

  The circularity in the present invention is an index of the degree of unevenness of the toner. When the toner is a perfect sphere, the circularity is 1.000, and the circularity becomes smaller as the surface shape becomes more complicated.

  A toner having an average circularity of 0.970 to 1.000 is preferred because it has excellent transferability. This is presumably because the contact area between the toner and the photoconductor is small and the adhesion force of the toner to the photoconductor due to mirror image force, van der Waals force, etc. is reduced. Therefore, if such a toner is used, the transfer rate is high and the residual toner is greatly reduced. Therefore, the toner in the pressure contact portion between the charging member and the photosensitive member is very little, toner fusion is prevented, and image defects are prevented. It is considered to be significantly suppressed.

  These effects are more prominent in an image forming method including a contact transfer process in which transfer loss is likely to occur.

  In the circularity distribution of the toner, the mode circularity of 0.98 to 1.00 means that most of the toner particles have a shape close to a true sphere. In this case, the reduction in the adhesion force of the toner to the photosensitive member due to the mirror image force, van der Waals force, etc. becomes more remarkable, and the transfer efficiency becomes very high, which is preferable.

  Here, the mode circularity is as follows. First, the circularity from 0.40 to 1.00 is 0.40 or more and less than 0.41, 0.41 or more and less than 0.42, ..., 0.99 or more and less than 1.00, and 1.00. Thus, 61 is divided every 0.01. Then, the measured circularity of each particle is assigned to each divided range, and the circularity of the divided range where the frequency value is maximum in the circularity frequency distribution is referred to as mode circularity.

  Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the examples. In addition, all the parts used in an Example show a mass part.

[Production of polymer type compound charge control agent]
In a pressurizable reaction vessel equipped with a reflux tube, a stirrer, a thermometer, a nitrogen introduction tube, a dropping device and a decompression device, 250 parts of methanol as a solvent, 150 parts of 2-butanone and 100 parts of 2-propanol, styrene as a monomer 77 parts, 15 parts of 2-ethylhexyl acrylate, and 8 parts of 2-acrylamido-2-methylpropanesulfonic acid were added and heated to reflux temperature with stirring. A solution obtained by diluting 1 part of t-butylperoxy-2-ethylhexanoate as a polymerization initiator with 20 parts of 2-butanone was added dropwise over 30 minutes, and stirring was continued for 5 hours. Further, t-butylperoxy-2 was further added. -A solution obtained by diluting 1 part of ethylhexanoate with 20 parts of 2-butanone was added dropwise over 30 minutes, and the mixture was further stirred for 5 hours to complete the polymerization. Further, 500 parts of deionized water was added while maintaining the temperature, and the mixture was stirred at 100 rpm for 2 hours so as not to disturb the interface between the organic layer and the aqueous layer. The layer was discarded, and anhydrous sodium sulfate was added to the organic layer for dehydration.

  Next, a resin having sulfur atoms obtained by roughly pulverizing the polymer obtained after distilling off the polymerization solvent under reduced pressure to 100 μm or less using a cutter mill equipped with a 150-mesh screen is referred to as Resin R. The obtained resin R had a peak molecular weight (Mp) of 13,000, an average molecular weight (Mw) of 30,000, and a glass transition point (Tg) of 58 ° C.

[Manufacture of styrene resin (low molecular weight resin)]
[Production of low-molecular resin 1]
A reactor equipped with a dropping funnel, a Liebig condenser and a stirrer was charged with 600.0 parts of xylene and heated to 135 ° C. A mixture of 100.0 parts of styrene monomer, 0.1 part of n-butyl acrylate and 15.0 parts of di-tert-butyl peroxide was charged into a dropping funnel, and dropped into xylene at 135 ° C. over 2 hours. Further, the solution polymerization was completed under reflux of xylene (137 ° C. to 145 ° C.) to remove xylene, and low molecular resin 1 was obtained. The obtained low molecular weight resin 1 had a weight average molecular weight (Mw) of 2900, Mw / Mn of 1.19, and a glass transition point (Tg) of 55 ° C. The physical properties are shown in Table 1.

[Production of low-molecular resins 2 to 5]
The low molecular weight resins 2 to 5 were prepared using the same production method as the low molecular weight resin 1 except that styrene monomer, n-butyl acrylate, di-tert-butyl peroxide, and xylene were used in the addition amounts shown in Table 1. Manufactured. Table 1 shows the weight average molecular weight (Mw), Mw / Mn, and glass transition point (Tg) of the obtained low molecular weight resins 2 to 5. In addition, "-" of Table 1 means not adding.

[Production of polyester resin (polar resin)]
[Production of Polar Resin 1]
In an autoclave equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device, terephthalic acid: 48 parts, bisphenol A-propylene oxide 2 mol adduct: 55 parts, bisphenol A-propylene oxide 3 Mole adduct: 64 parts, dibutyltin oxide: 0.030 part, charged under nitrogen atmosphere and normal pressure at 200 ° C. for 10 hours, then reacted at 220 ° C. for 3 hours, and further under reduced pressure of 10 to 20 mmHg For 2 hours. Thereafter, the temperature was lowered to 170 ° C., 0.7 part of trimellitic anhydride was added, and the mixture was reacted at 170 ° C. for 1.5 hours to obtain Polar Resin 1. The physical properties of the obtained polar resin 1 are shown in Table 2.

[Production of Polar Resin 2]
In an autoclave equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device, terephthalic acid: 46 parts, bisphenol A-propylene oxide 2 mol adduct: 50 parts, bisphenol A-propylene oxide 3 Mole adduct: 59 parts, dibutyltin oxide: 0.030 part were charged, reacted at 200 ° C. for 7 hours under a nitrogen atmosphere and at normal pressure, then reacted at 220 ° C. for 3 hours, and further under reduced pressure of 10 to 20 mmHg. For 2 hours to obtain polar resin 2. The physical properties of the obtained polar resin 2 are shown in Table 2.

[Production of Polar Resin 3]
In an autoclave equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device, terephthalic acid: 48 parts, bisphenol A-propylene oxide 2 mol adduct: 55 parts, bisphenol A-propylene oxide 3 Mole adduct: 64 parts, dibutyltin oxide: 0.030 part, charged under nitrogen atmosphere and normal pressure at 200 ° C. for 10 hours, then reacted at 220 ° C. for 3 hours, and further under reduced pressure of 10 to 20 mmHg For 2 hours. Thereafter, the temperature was lowered to 170 ° C., 1.8 parts of trimellitic anhydride was added, and the mixture was reacted at 170 ° C. for 1.5 hours to obtain Polar Resin 3. The physical properties of the obtained polar resin 3 are shown in Table 2.

<Toner Production Example 1>
In a four-necked vessel, 710 parts of ion-exchanged water and 850 parts of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution were added, and the mixture was stirred at 12,000 rpm using a high-speed stirrer TK-homomixer at 60 ° C. Held on. To this, 68 parts of a 1.0 mol / liter-CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

Styrene monomer 125.0 parts n-butyl acrylate 35.0 parts Copper phthalocyanine pigment 13.0 parts Low molecular resin 1 (styrene resin) 40.0 parts (Mw = 3200, Mw / Mn = 1.19)
Polar resin 1 (polyester resin) 10.0 parts (terephthalic acid-propylene oxide modified bisphenol A (2 mol adduct) -ethylene oxide modified bisphenol A (2 mol adduct) (molar ratio 51:30:20); acid 9: Glass transition point 60 ° C. Mw = 10000, Mw / Mn = 3.20)
Negatively charged control agent Bontron E-88 (metal compound) 0.8 parts
Resin R (polymer compound) 1.0 part wax [Fischer-Tropsch wax (1), melting point 78.0 ° C.] 15.0 parts The monomer mixture 1 was dispersed for 3 hours using an attritor. A polymerizable monomer composition obtained by adding 20.0 parts of 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate (toluene solution 50%) as a polymerization initiator to the monomer mixture 1 The product was put into an aqueous dispersion medium. And it granulated for 5 minutes, maintaining the rotation speed of a stirrer at 10,000 rpm. Thereafter, the high-speed stirrer was changed to a propeller stirrer, the internal temperature was raised to 70 ° C., and the reaction was allowed to proceed for 6 hours with slow stirring.

  Next, the temperature in the container was raised to 80 ° C. and maintained for 4 hours, and then gradually cooled to 30 ° C. at a cooling rate of 1 ° C. per minute to obtain slurry 1. Dilute hydrochloric acid was added to the container containing the slurry 1 to remove the dispersion stabilizer. Further, after washing, filtration was performed to obtain wet particles. The moisture content of the wet particles was 26.2%. The moisture content here means the moisture content moisture content, that is, the ratio of the moisture mass to the total mass (the sum of the dry toner mass and the moisture mass), and is a value obtained by a heat loss method at 105 ° C. is there.

  The wet particles were heated to 48 ° C. and held for 1 h so that the temperature of the entire particles was uniform. Then, using a continuous instantaneous air dryer (flash jet dryer FJD-4: manufactured by Seishin Enterprise Co., Ltd.), air at 60 ° C. was blown at a linear velocity of 16.5 m / sec, and wet particles were continuously supplied at 15 kg / hr. And dried to obtain polymer particles (toner particles 1) having a weight average particle diameter of 6.2 μm. Toner particle 1 was 0.2%.

The obtained toner particles 1 (100.0 parts), titanium oxide specific surface area by hydrophobic silica 2.0 parts of BET method is 100 m ² / g is the specific surface area by BET method is 200 meters ² / g The toner of Example 1 was obtained by externally adding 0.1 part. Table 3 shows toner production conditions. In addition, Table 4 shows the physical properties of Toner 1 of the obtained Example.

<Toner Production Example 2>
The toner obtained in the same manner as in Example 1 except that the raw materials shown in Table 3-1 were used is referred to as Example Toner 2. Table 4 shows the physical properties of Toner 2 of the obtained Example.

<Toner Production Example 3>
The toner obtained in the same manner as in Example 1 except that the raw materials shown in Table 3-1 were used is referred to as Example toner 3. Table 4 shows the physical properties of Toner 3 of the obtained Example.

<Toner Production Example 4>
The toner obtained by changing the raw materials and drying conditions shown in Table 3-1 is referred to as Example toner 4. Table 4 shows the physical properties of Toner 4 of the obtained Example.

<Toner Production Example 5>
The toner obtained by changing the raw materials and drying conditions shown in Table 3-1 is referred to as Example toner 5. Table 4 shows the physical properties of Toner 5 of the obtained Example.

<Toner Production Example 6>
The toner obtained by changing the raw materials and drying conditions shown in Table 3-2 is referred to as Example toner 6. Table 4 shows the physical properties of Toner 6 of the obtained Example.

<Toner Production Example 7>
The toner obtained by changing the raw materials and drying conditions shown in Table 3-2 is referred to as Example toner 7. Table 4 shows the physical properties of Toner 7 of the obtained Example.

<Toner Production Example 8>
The toner obtained in the same manner as in Example 1 except that the raw materials shown in Table 3-2 are used is referred to as Example Toner 8. Table 4 shows the physical properties of Toner 8 thus obtained.

<Toner Production Example 9>
The toner obtained by changing the raw materials and drying conditions shown in Table 3-2 is referred to as Example toner 9. Table 4 shows the physical properties of Toner 9 of the obtained Example.

<Toner Production Example 10>
The toner obtained by changing the raw materials and drying conditions shown in Table 3-2 is referred to as Example toner 10. Table 4 shows the toner physical properties of Example toner 10 thus obtained.

<Toner Production Example 11>
The toner obtained in the same manner as in Example 1 except that the raw materials shown in Table 3-3 are used is referred to as Example toner 11. Table 4 shows the toner physical properties of Example toner 11 obtained.

<Toner Production Example 12>
The toner obtained in the same manner as in Example 1 except that the raw materials shown in Table 3-3 are used is referred to as Example Toner 12. Table 4 shows the toner physical properties of Example toner 12 obtained.

<Toner Production Example 13>
The toner obtained by changing the raw materials and drying conditions shown in Table 3-3 is referred to as Example Toner 13. Table 4 shows the toner physical properties of Example toner 13 obtained.

<Toner Production Example 14>
The toner obtained by changing the raw materials and drying conditions shown in Table 3-3 is referred to as Example toner 14. Table 4 shows the toner physical properties of Example toner 14 obtained.

<Comparative Toner Production Example 1>
A toner obtained in the same manner as in Example 1 except that the raw materials shown in Table 3-4 are used is referred to as Comparative Example Toner 1. Table 4 shows the physical properties of Toner 1 of Comparative Example obtained.

<Comparative Toner Production Example 2>
A toner obtained in the same manner as in Example 1 except that the raw materials shown in Table 3-4 are used is referred to as Comparative Example Toner 2. Table 4 shows the physical properties of Toner 2 of Comparative Example obtained.

<Comparative Toner Production Example 3>
The toner obtained by changing the raw materials and drying conditions shown in Table 3-4 is referred to as Comparative Example Toner 3. Table 4 shows the physical properties of Toner 3 of the obtained Comparative Example.

<Comparative Toner Production Example 4>
The toner obtained by changing the raw materials and drying conditions shown in Table 3-4 is referred to as Comparative Example Toner 4. Table 4 shows the physical properties of Toner 4 of Comparative Example obtained.

<Comparative Toner Production Example 5>
The toner obtained by changing the raw materials and drying conditions shown in Table 3-4 is referred to as Comparative Example Toner 5. Table 4 shows the physical properties of Toner 5 of Comparative Example obtained.

◎ <Image evaluation>
The image evaluation was performed using a commercially available color laser printer HP Color Laser Jet 3800 (manufactured by HP).

The toner contained in the cartridge was taken out from the commercially available cartridge, the inside was cleaned by air blow, and the test toner (300 g) was filled. This cartridge was allowed to stand for one day in a normal humidity and normal temperature environment, and then the fixing property was evaluated. Further, the cartridge filled with each test toner was left in a high-temperature and high-humidity environment (40 ° C./60 RH) for one day, and durability was evaluated in the environment. Only the test toners that had good development levels through durability in a high temperature and high humidity environment were subsequently evaluated in a low temperature and low humidity environment (15 ° C./10% RH). The image evaluation items are as follows, and the image evaluation was performed after printing 10,000, 20000, and 30,000 images with a printing rate of 1% in the initial and horizontal lines. LETTER size XEROX 4024 paper (manufactured by XEROX, 75 g / m ² ) was used as the transfer material.

  In addition, the machine has been improved so that it can operate even when only one color process cartridge is installed. Also, the fixing unit has been improved so that the fixing temperature can be adjusted.

[Fixability test]
(Low temperature fixability)
A solid image (toner loading: 0.6 mg / cm ² ) on the transfer material was evaluated at different fixing temperatures (125 to 135 ° C.). The fixing temperature is a value obtained by measuring the surface of the fixing roller using a non-contact thermometer. LETTER size XEROX 4024 paper (manufactured by XEROX, 75 g / m ² ) was used as the transfer material.
A: No offset at 125 ° C B: Offset generated at 125 ° C C: Offset generated at 130 ° C D: Offset generated at 135 ° C

(High temperature fixability)
A solid image (toner loading amount: 0.6 mg / cm ² ) on the transfer material was evaluated by changing the fixing temperature (200 to 220 ° C.). The fixing temperature is a value obtained by measuring the surface of the fixing roller using a non-contact thermometer. LETTER size XEROX 4024 paper (manufactured by XEROX, 75 g / m ² ) was used as the transfer material.
A: No offset at 220 ° C. B: Offset generated at 220 ° C. C: Offset generated at 210 ° C. D: Offset generated at 200 ° C.

[Gross evaluation]
The gloss value of a solid image (toner loading: 0.6 mg / cm ² ) at a fixing temperature of 170 ° C. was measured using PG-3D (manufactured by Nippon Denshoku Industries Co., Ltd.).
A: Gloss 30 or more and less than 40 B: Gloss 20 or more and less than 30 C: Gloss 15 to less than 20 D: Less than 15

[Durability test]
[Image density]
After the initial printout test of 10,000 sheets, 20,000 sheets, and 30,000 sheets, evaluation was performed based on the image density of the solid portion. The image density was measured by using a “Macbeth reflection densitometer RD918” (manufactured by Macbeth Co., Ltd.) to measure a relative density with respect to a printout image of a white background portion having a document density of 0.00.
A: 1.40 or more B: 1.35 or more, less than 1.40 C: 1.00 or more, less than 1.35 D: less than 1.00

[Development stripes]
Initially, after completion of the printout test of 10,000 sheets, 20,000 sheets, and 30,000 sheets, an image of HT image (toner loading amount: 0.6 mg / cm ² ) on transfer paper (75 g / m ² , A4 size paper) Was printed out and evaluated by the number of development lines.
A: Not generated B: 1 or more, 3 or less C: 4 or more, 6 or less D: 7 or more, or a line having a width of 0.5 mm or more

[Development member contamination]
After completing the 30,000-sheet printout test, remove the developing roller, blow off the toner with air, tap the developing member with a mending tape (manufactured by Sumitomo 3M Co., Ltd.) to peel off the contaminants, and the “Macbeth reflection densitometer RD918” Measurement was performed using (made by Macbeth Co.), and evaluation was performed using a value (%) subtracted from the value of an unused mending tape.
A: Less than 0.0% B: 0.02% or more, less than 0.04% C: 0.04% or more, less than 0.06% D: 0.06% or more

[Resolution]
The resolution was evaluated by the reproducibility of a small-diameter isolated 1 dot at 600 dpi, which is easy to close due to the latent image electric field and difficult to reproduce.
A: Less than 5 defects in 100 B: 5 or more and less than 10 defects in 100 C: 10 or more and less than 20 defects in 100 D: 20 or more defects in 100

[Fog]
The reflectance (%) of the non-image portion of the printout image is measured with “REFLECTOMETER MODEL TC-6DS” (manufactured by Tokyo Denshoku Co., Ltd.). The obtained reflectance was evaluated using a numerical value (%) subtracted from the reflectance (%) of unused printout paper (standard paper) measured in the same manner. The smaller the numerical value, the more image fog is suppressed.
A: Less than 0.5 B: 0.5 or more, less than 1.0 C: 1.0 or more, less than 3.0 D: 3.0 or more

<Example 1>
The fixing evaluation of the toner of Example 1 was performed by the above evaluation method. As a result, good results were obtained for each item. Next, as a result of evaluating 30,000 printout images in each environment, good results were obtained for each item. The evaluation results are shown in Table 5.

<Example 2>
The toner of Example 2 was evaluated by the above evaluation method. As a result, good results were obtained for each item. The evaluation results are shown in Table 5.

<Example 3>
The toner of Example 3 was evaluated by the above evaluation method. As a result, good results were obtained for each item. The evaluation results are shown in Table 5.

<Example 4>
The toner of Example 4 was evaluated by the above evaluation method. As a result, good results were obtained for each item. The evaluation results are shown in Table 5.

<Example 5>
The toner of Example 5 was evaluated by the above evaluation method. As a result, although the developability was slightly deteriorated, generally good results were obtained in each item. The evaluation results are shown in Table 5.

<Example 6>
The toner of Example 6 was evaluated by the above evaluation method. As a result, good results were obtained for each item. The evaluation results are shown in Table 5.

<Example 7>
The toner of Example 7 was evaluated by the above evaluation method. As a result, good results were obtained for each item. The evaluation results are shown in Table 5.

<Example 8>
The toner of Example 8 was evaluated by the above evaluation method. As a result, the concentration in a low temperature and low humidity environment deteriorated. The evaluation results are shown in Table 5.

<Example 9>
The toner of Example 9 was evaluated by the above evaluation method. As a result, although it was not a problem level in a high temperature and high humidity environment, the image quality was deteriorated. Therefore, evaluation under a low temperature and low humidity environment was not performed. The evaluation results are shown in Table 5.

<Example 10>
The toner of Example 10 was evaluated by the above evaluation method. As a result, good results were obtained for each item. The evaluation results are shown in Table 5. The evaluation results are shown in Table 5.

<Example 11>
The toner of Example 11 was evaluated by the above evaluation method. As a result, although it was not a problem level in a high temperature and high humidity environment, the developability deteriorated. Therefore, evaluation under a low temperature and low humidity environment was not performed. The evaluation results are shown in Table 5.

<Example 12>
The toner of Example 12 was evaluated by the above evaluation method. As a result, although it was not a problem level, the fixing property was deteriorated, so evaluation under a low temperature and low humidity environment was not performed. The evaluation results are shown in Table 5.

<Example 13>
The toner of Example 13 was evaluated by the above evaluation method. As a result, although it was not a problem level, the fixing property was deteriorated, so evaluation under a low temperature and low humidity environment was not performed. The evaluation results are shown in Table 5.

<Example 14>
The toner of Example 14 was evaluated by the above evaluation method. As a result, although it was not a problem level in a high temperature and high humidity environment, the developability deteriorated. Therefore, evaluation under a low temperature and low humidity environment was not performed. The evaluation results are shown in Table 5.

<Comparative Example 1>
Comparative Example Toner 1 was evaluated by the above evaluation method. As a result, the fixability was remarkably deteriorated, so evaluation under a low temperature and low humidity environment was not performed. The evaluation results are shown in Table 5.

<Comparative example 2>
The comparative toner 2 was evaluated by the above evaluation method. As a result, the fixability and developability deteriorated remarkably, so evaluation was not performed in a low temperature and low humidity environment. The evaluation results are shown in Table 5.

<Comparative Example 3>
The comparative toner 3 was evaluated by the above evaluation method. As a result, the fixability was remarkably deteriorated, so evaluation under a low temperature and low humidity environment was not performed. The evaluation results are shown in Table 5.

<Comparative example 4>
The comparative toner 4 was evaluated by the above evaluation method. As a result, the developability was remarkably deteriorated in a high-temperature and high-humidity environment. Therefore, evaluation under a low-temperature and low-humidity environment was not performed. The evaluation results are shown in Table 5.

<Comparative Example 5>
Comparative toner 5 was evaluated by the above evaluation method. As a result, the developability was remarkably deteriorated in a high-temperature and high-humidity environment. Therefore, evaluation under a low-temperature and low-humidity environment was not performed. The evaluation results are shown in Table 5.

It is a figure which shows an example of the chart of the molecular weight distribution measured by GPC of the THF soluble part of a toner. FIG. 2 is a view showing a chart of molecular weight distribution measured by GPC of a THF soluble part of the toner shown in FIG. 1 when a main peak height is 1.00. It is a figure which shows an example of the chart of the molecular weight distribution measured by GPC of the THF soluble part of a toner. FIG. 5 is a diagram illustrating an example of a chart of molecular weight distribution measured by GPC of a THF soluble portion of the toner illustrated in FIG. 4 when a main peak height is 1.00.

Claims (5)

In a toner having toner particles and inorganic fine powder containing at least a binder resin, a colorant, and a release agent,
The toner particles are
(I) a dispersion step of dissolving and dispersing the release agent, the colorant, the charge control agent and the polar resin in at least the polymerizable monomer by a disperser to obtain a polymerizable monomer composition;
(Ii) Granulation in which the polymerizable monomer composition obtained in the dispersion step is dispersed in an aqueous phase containing a dispersion stabilizer with a stirrer to produce droplets of the polymerizable monomer composition. Process,
(Iii) a polymerization step for polymerizing the polymerizable monomer in the droplet; and
(Iv) a drying step in which the particles obtained in the polymerization step are washed and the wet particles are collected and then dried;
Is obtained through
As the polymerizable monomer, styrene and (meth) acrylic acid ester monomers are used,
The polar resin has an acid value of 4 to 20 mgKOH / g,
The toner is directed molecular weight distribution measured by tetrahydrofuran (THF) soluble matter of gel permeation chromatography (GPC),
(I) The molecular weight (M1) of the main peak is 10,000 to 80,000,
(Ii) In the molecular weight distribution chart, when the height of the molecular weight (M1) of the main peak is H (M1) and the height of the molecular weight 4,000 is H (4,000),
H (4,000): H (M1) = (0.100 to 0.950): 1.00
And
(Iii) having a sub-peak P (M2) in the region of molecular weight 600 to 6000 ,
The toner is zeta potential measurement in a state dispersed in methanol (measurement conditions: Dielectric Constant: 25.00, Temperature: 25 ℃) in, zeta potential at -110.0 to -50.0M V Yes ,
Toner characterized by the above.   The toner according to claim 1, wherein a standard deviation of zeta potential of the toner is 10 mV or less.   3. The toner according to claim 1, wherein the toner has at least a maximum point P (M3) in a region having a molecular weight of 2500 or more and less than 15000 in a molecular weight distribution chart measured by GPC of a THF-soluble component of the toner. . In the molecular weight distribution chart measured by GPC of the THF soluble part of the toner, the height of the maximum point P (M3) is H (M3), and the maximum point P (M3) and the main peak P (M1) H (M3), H (L1), and H (M1) are H (L1) when the height of the minimum point P (L1) is H (L1). The following conditions H (M3): H (L1) :: H (M1) = (0.10 to 0.95) :( 0.20 to 0.99): 1.00
The toner according to claim 3, wherein:   The toner according to claim 1, wherein the toner has a zeta potential of −100 to −60 mV.

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