WO2016148183A1 - Black toner for electrostatic-image development - Google Patents

Black toner for electrostatic-image development Download PDF

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Publication number
WO2016148183A1
WO2016148183A1 PCT/JP2016/058305 JP2016058305W WO2016148183A1 WO 2016148183 A1 WO2016148183 A1 WO 2016148183A1 JP 2016058305 W JP2016058305 W JP 2016058305W WO 2016148183 A1 WO2016148183 A1 WO 2016148183A1
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Prior art keywords
toner
black
particles
dispersion
black pigment
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PCT/JP2016/058305
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French (fr)
Japanese (ja)
Inventor
佐野　志穂
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三菱化学株式会社
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Publication of WO2016148183A1 publication Critical patent/WO2016148183A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/09—Colouring agents for toner particles

Definitions

  • the present invention relates to a black toner for developing an electrostatic image used in an image forming method by electrophotography.
  • Patent Documents 1 to 4 carbon black is widely used as a pigment (colorant) for obtaining a black image.
  • Patent Documents 1 to 4 Japanese Unexamined Patent Application Publication No. 2009-133974 (Patent Document 5) discloses using together with carbon black, a nigrosine dye as a charge control agent and a blue pigment as a tint adjusting agent.
  • Patent Document 6 discloses carbon black and C.I. I. It is disclosed that any of cyan pigments of CI Pigment Blue 15: 1, 15: 2, and 15: 3 is used in combination.
  • Japanese Laid-Open Patent Publication No. 8-171235 Japanese Laid-Open Patent Publication No. 9-211889 Japanese Unexamined Patent Publication No. 9-230620 Japanese Unexamined Patent Publication No. 2000-347460 Japanese Unexamined Patent Publication No. 2009-133974 Japanese Unexamined Patent Publication No. 2009-301026
  • the toner of a dry developer which is a toner for developing an electrostatic latent image used in an electrophotographic image forming apparatus, contains a resin and a pigment as main components, but the ratio of the pigment contained in the toner is usually 10 masses. %, Most is 4 to 8% by mass. This ratio is determined by the relationship between the toner particle size and the desired image density. This is because the toner adhesion amount on the recording material such as paper, that is, the image film thickness is usually approximately the thickness of a single toner particle layer, and therefore the toner particle size is reflected in the image density.
  • a mixture of a nigrosine dye and a blue pigment as disclosed in Patent Document 1 or a mixture of a cyan pigment as disclosed in Patent Document 2 causes carbon black.
  • the electric resistance can be increased more than the case of only the case, particularly when the blending ratio of the pigment is increased, the resistance cannot be adjusted sufficiently, and transfer failure may occur. Transfer defects are particularly likely to occur in a high temperature and high humidity environment.
  • the electric resistance is adjusted with a cyan pigment or a nigrosine dye, an appropriate hue may not be obtained depending on the addition ratio.
  • the present invention has been made in view of such circumstances, and the object thereof is to satisfy image density and hue, even when exposed to a high temperature and high humidity environment for a long time.
  • An object of the present invention is to provide a black toner for developing an electrostatic latent image that can suppress transfer defects.
  • carbon black is an appropriate pigment in the toner so that the black toner does not impair the transferability and can maintain the hue as black.
  • the knowledge that it is most effective to maintain the dispersion diameter was obtained, and further studies were made based on this knowledge, thereby completing the present invention.
  • the gist of the present invention is as follows.
  • a black toner for developing an electrostatic charge image containing a black pigment and a binder resin, wherein an average value of the area of black pigment particles in a TEM image having a magnification of 50,000 times the cross section of the toner is 1.0 ⁇ 10 ⁇
  • a black toner for developing an electrostatic image which is: [5] The black toner for developing electrostatic images according to [4], wherein the maximum area of the black pigment particles is 5.0 ⁇ 10 ⁇ 3 ⁇ m 2 or less.
  • the TEM image is corrected with a gamma value of 0.5 using image processing software Win ROOF 5.7.1 (MITANI Corporation) and set to threshold values 60 and 100.
  • FIG. 1 is a TEM photograph of a magnification of 50000 times of a 0.4 ⁇ m ultrathin section of the developing toner G1.
  • FIG. 2 is a TEM photograph of an ultrathin section of 0.4 ⁇ m of the developing toner G2 with a magnification of 50000 times.
  • FIG. 3 is a TEM photograph of an ultrathin section of 0.4 ⁇ m of the developing toner G3 with a magnification of 50000 times.
  • FIG. 4 is a TEM photograph of a magnification of 50000 times of a 0.4 ⁇ m ultrathin section of the developing toner G4.
  • FIG. 5 is a TEM photograph of a magnification of 50000 times of a 0.4 ⁇ m ultrathin section of the developing toner G5.
  • black toner for developing an electrostatic image may be simply abbreviated as “black toner” or “toner”.
  • the toner before the external additive is fixed or adhered is referred to as “toner mother particles”.
  • all percentages and parts expressed by mass are the same as percentages and parts expressed by weight.
  • the first aspect of the black toner of the present invention contains a black pigment and a binder resin, and the average value of the area of the black pigment particles in a TEM image having a magnification of 50,000 times the cross section of the toner is 1.0 ⁇ 10 ⁇ 6. It is characterized by being not less than ⁇ m 2 and not more than 1.0 ⁇ 10 ⁇ 4 ⁇ m 2 .
  • the second embodiment of the black toner of the present invention contains a black pigment and a binder resin, and the peripheral length of the black pigment particles in a TEM image having a magnification of 50,000 times the cross section of the toner is 3.0 ⁇ 10 ⁇ 2 ⁇ m or less. It is characterized by being.
  • the black pigment particle means a primary particle of black pigment or a composite particle in which primary particles of black pigment are aggregated.
  • the average value and the perimeter of the black pigment particle area in the TEM image with a magnification of 50,000 times of the cross section of the toner are considered to represent the approximate size of the black pigment particles dispersed and present in the toner base particles.
  • the average value of the area of the black pigment particles in the TEM image with a magnification of 50,000 times in the cross section of the toner satisfies 1.0 ⁇ 10 ⁇ 6 ⁇ m 2 or more and 1.0 ⁇ 10 ⁇ 4 ⁇ m 2 or less, or the black pigment particles
  • the fact that the perimeter length satisfies 3.0 ⁇ 10 ⁇ 2 ⁇ m or less is considered to be a state in which the pigment dispersion diameter of the black pigment particles is relatively small in the toner base particles. Specifically, it is theoretically considered that the dispersion diameter of the black pigment particles is equivalent to 1.1 ⁇ 10 ⁇ 2 ⁇ m or less.
  • the toner of the present invention preferably has a maximum area of black pigment particles of 5.0 ⁇ 10 ⁇ 3 ⁇ m 2 or less in a TEM image with a magnification of 50,000 times in the cross section of the toner.
  • a black toner it is considered that there are no large black pigment particles having a pigment dispersion diameter exceeding 1.1 ⁇ 10 ⁇ 2 ⁇ m over the entire toner base particles.
  • the standard deviation value of the area of black pigment particles in a TEM image having a magnification of 50,000 times in the cross section of the toner is more preferably 1.0 ⁇ 10 ⁇ 3 ⁇ m 2 or less.
  • Such a black toner is considered to represent a state in which the distribution of the dispersed particle size of the black pigment particles in the toner base particles is narrow and the black pigment particles are finely dispersed.
  • the standard deviation value of the area of the black pigment particles is preferably 1.0 ⁇ 10 ⁇ 5 ⁇ m 2 or more.
  • the peripheral length of the black pigment particles is preferably 2.5 ⁇ 10 ⁇ 2 ⁇ m or less.
  • the peripheral length of the black pigment particles is preferably 1.0 ⁇ 10 ⁇ 3 ⁇ m or more.
  • the TEM image is obtained by correcting the gamma value to 0.5 using image processing software such as Win ROOF 5.7.1 (MITANI Corporation) and setting the threshold values to 60 and 100. It is preferable that the binarization process is performed.
  • the black toner of the present invention aggregates submicron-sized polymer primary particles represented by the emulsion polymerization aggregation method and the emulsion aggregation method to a micron size, which is the toner size, as will be described in detail in ⁇ Toner configuration> described later. It is obtained by using the method.
  • a monomer having an unsaturated double bond is radically polymerized in an aqueous medium to obtain submicron-sized polymer primary particles smaller than the toner size, and then the polymer primary particles are converted to a toner size of micron. It is a method of agglomerating to size.
  • polyester resin or the like is finely divided into water in high-pressure conditions and / or in the presence of a solvent to form submicron-sized polymer primary particles that are smaller than the toner size, and then the polymer primary particles are reduced to micron size that is the toner size.
  • It is a method of aggregation.
  • the aggregation step of agglomerating to micron size at least black pigment particles and polymer primary particles are agglomerated to form particle aggregates. Thereafter, through a ripening and fusing process, the particle aggregate is rounded to obtain toner mother particles.
  • the black toner base particles In order to obtain a black toner satisfying the range specified in the present invention described in detail in ⁇ About the present invention>, it is necessary to uniformly disperse the black pigment particles in the toner base particles. In order to uniformly disperse the black pigment particles in the toner base particles, it is possible to control so that the black pigment particles do not aggregate with each other but aggregate with the polymer primary particles in the initial stage of the production of the particle aggregate. is important. In other words, in the initial stage of the particle aggregate preparation, the aggregation rate of the polymer primary particles is made equal to the aggregation rate of the black pigment particles, or the aggregation rate of the polymer primary particles is set higher than the aggregation rate of the black pigment particles. Control such as speeding up is important.
  • the black pigment particles are finely and uniformly dispersed throughout the toner base particles as in the present invention, the primary particle diameter of the black pigment particles is reduced and the aggregation rate of the black pigment is increased.
  • the polymer primary particles and the black pigment particles are easily aggregated alternately. It is necessary to set conditions for the aggregation process that reduces the difference between the aggregation rate of the primary particles and the aggregation rate of the black pigment particles.
  • the black pigment particles can be finely and uniformly dispersed throughout the toner base particles by setting the conditions of the aggregation process to any of the following conditions.
  • the aggregation rate of the polymer primary particles becomes faster than the aggregation rate of the black pigment particles, and the black pigment is less likely to be taken into the toner base particles, resulting in low color strength. There is a risk of becoming toner.
  • the difference in the aggregation speed is controlled by setting the rotational speed of the stirring blade provided in the stirring tank to be lower than a certain speed. For example, when 1200 g of material is put into a container having a diameter of 12.5 cm and stirring is performed with a stirring blade having an diameter of 11 cm, the rotation speed is set to 250 rpm or less. When the stirring speed is faster than the rotation speed range, the aggregation speed of the black pigment particles becomes faster than the aggregation speed of the polymer primary particles, and the black pigment dispersed particle size in the toner base particles may be increased.
  • the stirring speed is slower than the rotation speed range, the aggregation speed of the polymer primary particles becomes faster than the aggregation speed of the black pigment particles, making it difficult for the black pigment to be taken into the toner base particles, resulting in a toner having low color strength. There is a risk.
  • the addition amount of the salt is 0.1 in terms of solid content with respect to 100 parts by mass of the polymer primary particles.
  • the mass is made not less than 1.0 part by mass.
  • the addition amount of the flocculant is less than 0.1 parts by mass, the aggregation rate of the black pigment particles may be faster than the aggregation rate of the polymer primary particles, and the black pigment dispersion particle size in the toner base particles may increase. is there.
  • the addition amount of the flocculant is more than 1.0 part by mass, the aggregation rate of the polymer primary particles becomes faster than the aggregation rate of the black pigment particles, and the black pigment is less likely to be taken into the toner base particles, and the color strength.
  • the toner may be low.
  • the volume average primary particle size of the black pigment particles used in the black pigment dispersion is 20 nm or less.
  • carbon black having a volatile content of 2.0% or less is used as the black pigment.
  • carbon black having a pigment surface pH of 6 to 8 is used as the black pigment.
  • the carbon black satisfying such a range has a small amount of functional groups on the surface of the carbon black, and it is estimated that the carbon blacks hardly aggregate when the black pigment dispersion is prepared. Thereby, it is considered that the dispersibility of the carbon black in the toner can be maintained well even when the toner is used.
  • the condition of the aggregation process is set to at least one of the above conditions (1) to (4).
  • the black pigment can be finely and uniformly dispersed throughout the particles.
  • the black toner of the present invention thus obtained has the effect that the charging property is lower than that of the conventional black toner, the change in charging property with time is small, and it is difficult to be influenced by the environment such as temperature and humidity. . Therefore, in addition to the color intensity, printing characteristics such as fogging, blurring, and scattering are not affected by changes over time or environmental changes, and a toner with stable performance can be provided.
  • the black toner produced according to the present invention contains at least a binder resin and a black pigment.
  • the binder resin constituting the black toner may be appropriately selected from those known to be usable for toner.
  • styrene resin vinyl chloride resin, rosin modified maleic acid resin, phenol resin, epoxy resin, saturated or unsaturated polyester resin, polyethylene resin, polypropylene resin, ionomer resin, polyurethane resin, silicone resin, ketone resin, Ethylene-acrylate copolymer, xylene resin, polyvinyl butyral resin, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-anhydrous malein An acid copolymer etc. can be mentioned. These resins can be used alone or in combination.
  • the polymer primary particles are used in the aggregation step in a state of being dispersed in a solvent such as water.
  • the polymer primary particles having a styrene or (meth) acrylic monomer as a constituent element are styrene or (meth) acrylic.
  • a polymer primary particle dispersion is obtained by emulsion polymerization of a monomer and, if necessary, a chain transfer agent using an emulsifier.
  • the binder resin is obtained by a method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc., as in the case of producing a toner by a conventional emulsion aggregation method, Mixing with an aqueous medium, heating to a temperature higher than either the melting point of the resin or the glass transition temperature to lower the viscosity of the resin, emulsifying by applying a shearing force, a polymer primary particle dispersion can be obtained.
  • the emulsifier for applying a shearing force include a homogenizer, a homomixer, a pressure kneader, an extruder, and a media disperser.
  • the binder resin constituting the polymer primary particles used in the emulsion polymerization aggregation method one or more polymerizable monomers that can be polymerized by the emulsion polymerization method may be appropriately used.
  • each polymerizable monomer may be added separately, or a plurality of polymerizable monomers may be mixed in advance and added simultaneously.
  • the polymerizable monomer may be added as it is, or may be added as an emulsion prepared by mixing with water or an emulsifier in advance.
  • the ratio of the total amount of monomers having acidic groups in 100% by mass of all polymerizable monomers constituting the binder resin as the polymer primary particles is preferably 0.05% by mass or more, more preferably 0.3% by mass. Above, especially preferably 0.5% by mass or more, and more preferably 1% by mass or more.
  • the upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 2% by mass or less.
  • styrene such as styrene, methyl styrene, chlorostyrene, p-tert-butyl styrene, pn-butyl styrene, pn-nonyl styrene, methyl acrylate, ethyl acrylate, propyl acrylate
  • Acrylates such as n-butyl acrylate, isobutyl acrylate, hydroxyethyl acrylate, ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacrylic acid Methacrylic acid esters such as hydroxyethyl and ethylhexyl methacrylate, acrylamide, N-propylacrylamide, N, N-dimethylacrylamide, N, N-d
  • an acidic monomer and another monomer may be used in combination. More preferably, (meth) acrylic acid is used as the acidic monomer, and a polymerizable monomer selected from styrenes and (meth) acrylic acid esters is used as the other monomer. It is preferable to use (meth) acrylic acid as the monomer, and use a combination of styrene and (meth) acrylic acid esters as the other monomer, and particularly preferably use (meth) acrylic acid as the acidic monomer and other monomers. As a combination of styrene and n-butyl acrylate. In addition, (meth) acrylic acid means acrylic acid or methacrylic acid.
  • a crosslinked resin as the binder resin constituting the polymer primary particles.
  • a polyfunctional monomer having radical polymerizability is used as a crosslinking agent shared with the above polymerizable monomer.
  • the multifunctional monomer include divinylbenzene, hexanediol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol acrylate, diallyl phthalate, and the like. Is mentioned.
  • a polymerizable monomer having a reactive group in a pendant group such as glycidyl methacrylate, methylol acrylamide, acrolein or the like can be used as a crosslinking agent.
  • radically polymerizable bifunctional monomers are preferable, and divinylbenzene and hexanediol diacrylate are particularly preferable.
  • crosslinking agents such as polyfunctional monomers may be used alone or in combination.
  • the blending ratio of the crosslinking agent such as a polyfunctional monomer in the total polymerizable monomer constituting the resin is preferably 0.005% by mass or more, More preferably, it is 0.1 mass% or more, More preferably, it is 0.3 mass% or more, Preferably it is 5 mass% or less, More preferably, it is 3 mass% or less, More preferably, it is 1 mass% or less.
  • emulsifiers can be used for the emulsion polymerization, but one or more emulsifiers selected from the group consisting of cationic surfactants, anionic surfactants and nonionic surfactants are used in combination. Can be used.
  • Examples of the cationic surfactant include dodecyl ammonium chloride, dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, dodecyl pyridinium bromide, hexadecyl trimethyl ammonium bromide and the like.
  • anionic surfactant examples include fatty acid soaps such as sodium stearate and sodium dodecanoate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, and sodium lauryl sulfate.
  • Nonionic surfactants include, for example, polyoxyethylene dodecyl ether, polyoxyethylene hexadecyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene sorbitan monooleate ether, monodecanoyl sucrose, etc. Is mentioned.
  • the amount of the emulsifier is usually 1 to 10 parts by mass with respect to 100 parts by mass of the polymerizable monomer, and these emulsifiers include, for example, partially or fully saponified polyvinyl alcohol such as saponified polyvinyl alcohol, hydroxy One type or two or more types of cellulose derivatives such as ethyl cellulose can be used in combination as a protective colloid.
  • polymerization initiator examples include hydrogen peroxide; persulfates such as potassium persulfate; organic peroxides such as benzoyl peroxide and lauroyl peroxide; 2,2′-azobisisobutyronitrile, 2, Azo compounds such as 2′-azobis (2,4-dimethylvaleronitrile); redox initiators and the like are used. One or more of them are usually used in an amount of about 0.1 to 3 parts by mass with respect to 100 parts by mass of the polymerizable monomer. Among them, it is preferable that at least a part or all of the polymerization initiator is hydrogen peroxide or organic peroxides. Any of the polymerization initiators may be added to the polymerization system before, simultaneously with, or after the addition of the polymerizable monomer, and these addition methods may be combined as necessary.
  • a known chain transfer agent may be used as necessary.
  • a chain transfer agent include t-dodecyl mercaptan, 2-mercaptoethanol, diisopropyl xanthogen, four Examples thereof include carbon chloride and trichlorobromomethane.
  • the chain transfer agent may be used alone or in combination of two or more, and is usually used in a range of 5% by mass or less based on the total polymerizable monomer.
  • a pH adjuster, a polymerization degree adjuster, an antifoaming agent, etc. can be further mix
  • the polymerizable monomer is polymerized in the presence of a polymerization initiator, and the polymerization temperature is usually 50 to 120 ° C., preferably 60 to 100 ° C., more preferably 70 to 90 ° C.
  • the volume average diameter (Mv) of the polymer primary particles obtained by emulsion polymerization is usually 0.02 ⁇ m or more, preferably 0.05 ⁇ m or more, more preferably 0.1 ⁇ m or more, and usually 3 ⁇ m or less, preferably 2 ⁇ m or less. More preferably, it is 1 ⁇ m or less.
  • the particle size is less than the above range, it may be difficult to control the aggregation rate.
  • the particle size exceeds the above range the particle size of the toner obtained by aggregation tends to be large, and a toner having a target particle size can be obtained. It can be difficult.
  • the black pigment is not particularly limited, and examples of the black pigment include carbon black.
  • the carbon black is as described in “(4) Preparation of black pigment” in ⁇ Method for obtaining the present invention> described above.
  • the black pigment dispersion is prepared by a known method by adding 10 to 30 parts by weight of a black pigment and 1 to 15 parts by weight of an emulsifier with respect to 100 parts by weight of water.
  • the volume average diameter of the black pigment dispersion in the black pigment dispersion is monitored while preparing the dispersion, and finally the volume average diameter (Mv) of the black pigment dispersion in the black pigment dispersion is set to 0.
  • Mv volume average diameter of the black pigment dispersion in the black pigment dispersion
  • the thickness is set to be not less than 01 ⁇ m and not more than 3 ⁇ m, and more preferably controlled in a range of not less than 0.05 ⁇ m and not more than 0.5 ⁇ m.
  • a dispersion liquid containing primary particles of polymer obtained by emulsion polymerization is added with a black pigment dispersion liquid and, if necessary, a dispersion liquid such as a charge control agent and a wax described later to obtain a mixed dispersion liquid.
  • a dispersion liquid such as a charge control agent and a wax described later.
  • the primary particles in the mixed dispersion are agglomerated to form core particles, and resin particles are fixed or adhered to the core particles, and the particles obtained by fusing are washed and dried to obtain a toner base. It is preferred to obtain particles.
  • the resin fine particles may be produced by the same method as the above polymer primary particles, and the structure thereof is not particularly limited, but the polar monomer occupies in 100% by mass of the total polymerizable monomer constituting the binder resin as the resin fine particles.
  • the ratio of the total amount is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.2% by mass or more.
  • the upper limit is preferably 3% by mass or less, more preferably 1.5% by mass or less.
  • the proportion of the total amount of polar monomers in 100% by mass of the total polymerizable monomer constituting the binder resin as the resin fine particles is in 100% by mass of the total polymerizable monomer constituting the binder resin as the polymer primary particle. It is preferable that the ratio is smaller than the ratio of the total amount of polar monomers in view of easy adjustment of the particle shape and particle diameter in the aggregation process, generation of fine powder can be suppressed, and excellent charging characteristics.
  • the Tg of the binder resin as the resin fine particles is higher than the Tg of the binder resin as the polymer primary particles.
  • the content ratio of the black pigment may be an amount sufficient for the obtained toner to form a visible image by development.
  • the content is preferably in the range of 1 to 25 parts by mass, more preferably 1 to 15 parts by mass, particularly preferably 3 to 12 parts by mass.
  • wax it is preferable to add a wax to the black toner to impart releasability.
  • Any wax can be used as long as it has releasability, and is not particularly limited.
  • olefin waxes such as low molecular weight polyethylene, low molecular weight polypropylene, and copolymer polyethylene; paraffin wax; ester waxes having a long-chain aliphatic group such as behenyl behenate, montanate ester, stearyl stearate; water Plant waxes such as soy castor oil and carnauba wax; ketones having long chain alkyl groups such as distearyl ketone; silicones having alkyl groups; higher fatty acids such as stearic acid; long chain aliphatic alcohols such as eicosanol; glycerin and pentaerythritol Examples include carboxylic acid esters or partial esters of polyhydric alcohols obtained from polyhydric alcohols such as polyhydr
  • the melting point of the wax is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and particularly preferably 50 ° C. or higher.
  • the melting point of the wax is preferably 100 ° C. or lower, more preferably 90 ° C. or lower, and particularly preferably 80 ° C. or lower. If the melting point is too low, the wax tends to be exposed and sticky after fixing, and if the melting point is too high, the fixability at low temperatures is poor.
  • ester waxes obtained from aliphatic carboxylic acids and mono- or polyhydric alcohols are preferred, and ester waxes having 20 to 100 carbon atoms are preferred.
  • the above waxes may be used alone or in combination. Further, the melting point of the wax compound can be appropriately selected depending on the fixing temperature for fixing the toner.
  • the amount of the wax used is preferably 4 to 20 parts by weight, particularly preferably 6 to 18 parts by weight, and more preferably 8 to 15 parts by weight with respect to 100 parts by weight of the toner.
  • Dv50 volume median diameter
  • the toner of the present invention has a small particle size with a sharp particle size distribution that does not cause deterioration of the toner characteristics as compared with conventional toners even when the amount of wax used is large as in the above range. It is.
  • the wax may be contained in the polymer primary particles or in the resin fine particles.
  • a wax dispersion that has been previously emulsified and dispersed in water at a volume average diameter (Mv) of 0.01 to 2.0 ⁇ m, more preferably 0.01 to 0.5 ⁇ m is emulsified. It is preferable to add at the time of superposition
  • the wax in order to disperse the wax with a suitable dispersed particle diameter in the toner, it is preferable to add the wax as a seed during emulsion polymerization.
  • the wax content in the polymer primary particles is preferably calculated to be 4 to 30% by mass, more preferably 5 to 20% by mass, and particularly preferably 7 to 15% by mass.
  • the black toner may be blended with a charge control agent to impart charge amount and charge stability.
  • a charge control agent Conventionally known compounds are used as the charge control agent. Examples thereof include hydroxycarboxylic acid metal complexes, azo compound metal complexes, naphthol compounds, naphthol compound metal compounds, nigrosine dyes, quaternary ammonium salts, and mixtures thereof.
  • the blending amount of the charge control agent is preferably in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the resin.
  • the charge control agent When a charge control agent is contained in the toner in the emulsion polymerization aggregation method, the charge control agent is blended with a polymerizable monomer or the like at the time of emulsion polymerization, or is blended in the aggregation process with the polymer primary particles and the colorant.
  • the blended primary particles, the colorant, and the like can be blended by a method such as blending after agglomeration to obtain an appropriate particle size as a toner.
  • the charge control agent is preferably emulsified and dispersed in water using an emulsifier, and used as an emulsified dispersion having a volume average diameter (Mv) of 0.01 ⁇ m to 3 ⁇ m.
  • Mv volume average diameter
  • the volume average diameter (Mv) of the polymer primary particles, the colorant dispersed particles, the wax dispersed particles, the charge control agent dispersed particles and the like in the dispersion is measured using a nanotrack by the method described in the Examples, It is defined as the measured value.
  • the blended components such as the polymer primary particles, the black pigment particles, and the charge control agent and the wax as necessary are mixed simultaneously or sequentially.
  • Dispersions that is, polymer primary particle dispersion, colorant particle dispersion, charge control agent dispersion, and wax fine particle dispersion are prepared.
  • the black pigment dispersion is added dropwise at a constant speed with a pump. At that time, the flow rate of the pump is adjusted to control the addition time of the black pigment dispersion. Thereafter, this is aggregated to form particle aggregates.
  • the black pigment is preferably used in a state emulsified in water by a mechanical means such as a sand mill or a bead mill in the presence of an emulsifier.
  • the blend of the colorant dispersion at the time of emulsion aggregation is calculated and used so as to be 2 to 10% by mass in the finished toner base particles after aggregation.
  • the agglomeration treatment usually includes a method of heating in a stirring tank, a method of adding an electrolyte, a method of combining these, and the like.
  • the particle size of the particle agglomerates is controlled from the balance between the agglomeration force between the particles and the shearing force due to agitation.
  • the cohesive force can be increased by heating or adding an electrolyte.
  • the aggregating agent include NaCl, KCl, LiCl, Na 2 SO 4 , K 2 SO 4 , Li 2 SO 4 , MgCl 2 , CaCl 2 , MgSO 4 , CaSO 4 , ZnSO 4 , Al 2 (SO 4 ) 3 , Fe 2 (SO 4 ) 3 , CH 3 COONa, C 6 H 5 SO 3 Na, and other electrolytes.
  • inorganic salts having a divalent or higher polyvalent metal cation are preferred.
  • the amount of the electrolyte blended varies depending on the type of electrolyte, target particle size, and the like, but is usually 0.05 to 25 parts by mass, preferably 0.1 to 15 parts per 100 parts by mass of the solid component of the mixed dispersion. Part by mass, more preferably 0.1 to 10 parts by mass.
  • the blending amount is less than the above range, the progress of the agglutination reaction is slow, and fine powders of 1 ⁇ m or less remain after the agglomeration reaction, the average particle diameter of the obtained particle aggregate does not reach the target particle diameter, etc. There are cases.
  • the upper limit of the above range is exceeded, rapid agglomeration tends to occur and it becomes difficult to control the particle size, and the resulting agglomerated particles may cause problems such as inclusion of coarse powder or irregular shapes. .
  • a method of suppressing the amount of the electrolyte may be employed as a method of controlling the particle size of the toner base particles in a specific range.
  • the particle growth rate is slow, which is not industrially preferable in terms of production efficiency.
  • the aggregation temperature when the electrolyte is added for aggregation is preferably 20 to 70 ° C, more preferably 30 to 60 ° C.
  • controlling the temperature before the aggregation step is one of the methods for controlling the particle size of the toner base particles within a specific range.
  • the aggregation of the black pigments is more likely to occur than the aggregation between the black pigment and the polymer primary particles at a temperature lower than 20 ° C. As a result, the dispersion state of the black pigment in the toner is deteriorated. Therefore, the temperature in the reaction vessel at the time of adding the black pigment during the aggregation process is adjusted to 20 ° C. to 30 ° C.
  • the temperature in the reaction vessel is adjusted to 30 ° C. to 60 ° C.
  • toner base particles having a good dispersion state of the black pigment, a sharp particle size distribution, and few fine powders and coarse powders can be produced.
  • the time required for agglomeration is optimized depending on the shape of the apparatus and the processing scale, but in order to reach the target particle size, the toner base particles are usually held at a temperature within the above range for at least 30 minutes. It is desirable.
  • the temperature rise until reaching the predetermined temperature may be raised at a constant rate, or may be raised stepwise.
  • a resin having a core-shell structure is prepared by adding a resin fine particle (polymer primary particle) dispersion to the particle aggregate after the aggregation treatment, if necessary, so that the resin fine particles adhere or adhere to the particle aggregate. Mother particles can be formed.
  • the production method of the present invention is preferably applied to the case where the core layer is formed when forming the core-shell toner base particles having the core layer and the shell layer.
  • the charge control agent When the charge control agent is added after the aggregation treatment, it is preferable to add the resin fine particles after adding the charge control agent to the dispersion containing the particle aggregate.
  • an emulsifier and a pH adjuster are added as a dispersion stabilizer to reduce the cohesive force between the particles, thereby growing the toner base particles. It is preferable to add an aging step for causing fusion between the agglomerated particles after stopping.
  • the toner of the present invention preferably has a sharp particle size distribution.
  • the stirring rotational speed is reduced before the step of adding an emulsifier or a pH adjuster in the aging step. That is, there is a method of reducing the shearing force by stirring.
  • the viscosity of the binder resin is lowered by heating to be circularized, but if heated as it is, the growth of the toner base particle size does not stop, so for the purpose of stopping the particle size growth by heating, usually as a dispersion stabilizer Further, it is possible to apply a shearing force by adding an emulsifier or a pH adjusting agent or increasing a stirring rotational speed.
  • a toner having a specific particle size distribution can be obtained even if the stirring rotational speed is lowered to reduce the shearing force to the aggregated particles.
  • the temperature of the aging step is preferably not less than Tg of the binder resin constituting the primary particles, more preferably not less than 5 ° C higher than the Tg, and preferably not more than 80 ° C higher than the Tg, more preferably The temperature is 50 ° C. or higher than Tg.
  • the time required for the ripening step varies depending on the shape of the target toner, but is usually 0.1 to 10 hours, preferably 1 to 6 hours after reaching the glass transition temperature of the polymer constituting the primary particles. It is desirable to hold.
  • the emulsifier used here one or more kinds of emulsifiers that can be used when producing the polymer primary particles can be selected and used, and particularly used when the polymer primary particles are produced. It is preferable to use the same emulsifier.
  • the blending amount in the case of blending the emulsifier is not limited, but is preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, further preferably 3 parts by weight or more with respect to 100 parts by weight of the solid component of the mixed dispersion. Moreover, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less.
  • the primary particles in the aggregate are fused and integrated, and the shape of the toner base particles as the aggregate becomes close to a spherical shape.
  • the particle aggregate before the aging step is considered to be an aggregate due to electrostatic or physical aggregation of the primary particles, but after the aging step, the polymer primary particles constituting the particle aggregate are fused together.
  • the shape of the toner base particles can be made nearly spherical. According to such a ripening step, by controlling the temperature and time of the ripening step, a cocoon shape in which primary particles are aggregated, a potato type in which fusion has progressed, a spherical shape in which fusion has further progressed, etc.
  • Various shapes of toner can be produced according to the purpose.
  • the particle aggregate obtained through each of the above steps is subjected to solid / liquid separation according to a known method, the particle aggregate is recovered, then washed as necessary, and then dried. Toner mother particles can be obtained.
  • an outer layer mainly composed of a polymer is further formed on the surface of the particles obtained by the emulsion polymerization aggregation method by, for example, a spray drying method, an in-situ method, or a submerged particle coating method. It is also possible to form encapsulated toner base particles by forming them with a thickness of preferably 0.01 to 0.5 ⁇ m.
  • the average circularity measured using a flow type particle image analyzer FPIA-3000 is preferably 0.90 or more, more preferably 0.92 or more, and still more preferably. Is 0.95 or more.
  • the average circularity is Preferably it is 0.995 or less, More preferably, it is 0.990 or less.
  • At least one of the peak molecular weights in gel permeation chromatography (hereinafter sometimes abbreviated as “GPC”) of the tetrahydrofuran (THF) soluble content of the toner is preferably 10,000 or more, more preferably 1. It is 50,000 or more, more preferably 20,000 or more, preferably 100,000 or less, more preferably 80,000 or less, and still more preferably 50,000 or less.
  • GPC gel permeation chromatography
  • the THF insoluble content of the toner is preferably 1% by mass or more, more preferably 2% by mass or more, and preferably 20% by mass or less, more preferably, when measured by a mass method by celite filtration. It is good that it is 10 mass% or less. If it is not within the above range, it may be difficult to achieve both mechanical durability and low-temperature fixability.
  • the chargeability of the emulsion polymerization aggregation method toner may be positively charged or negatively charged.
  • Control of the chargeability of the toner may include the selection and content of a charge control agent, the selection and blending amount of an external additive, etc. Can be adjusted by.
  • the toner base particles thus obtained may be made into a toner by mixing known external additives on the surface of the toner base particles in order to control fluidity and developability.
  • External additives include metal oxides and hydroxides such as alumina, silica, titania, zinc oxide, zirconium oxide, cerium oxide, talc and hydrotalcite, titanium such as calcium titanate, strontium titanate and barium titanate.
  • Examples thereof include acid metal salts, nitrides such as titanium nitride and silicon nitride, carbides such as titanium carbide and silicon carbide, and organic particles such as acrylic resins and melamine resins.
  • silica, titania, and alumina are preferable, and those that have been surface-treated with, for example, a silane coupling agent or silicone oil are more preferable.
  • the average primary particle diameter is preferably in the range of 1 to 500 nm, more preferably in the range of 5 to 100 nm. It is also preferable to use a combination of a small particle size and a large particle size in the particle size range.
  • the total amount of the external additive is preferably in the range of 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the toner base particles.
  • the toner for developing an electrostatic image of the present invention is a magnetic two-component developer in which a carrier for conveying the toner to the electrostatic latent image portion by a magnetic force coexists, or a magnetic toner containing a magnetic powder in the toner. It may be used for either a component developer or a non-magnetic one-component developer that does not use magnetic powder as a developer. In order to express the effect of the present invention remarkably, it is particularly preferable to use as a developer for a non-magnetic one-component development system.
  • the carrier that is mixed with the toner to form the developer is a known magnetic substance such as an iron powder type, ferrite type, or magnetite type carrier, or a resin coating on the surface thereof.
  • a magnetic resin carrier can be used.
  • the carrier coating resin generally known styrene resins, acrylic resins, styrene acrylic copolymer resins, silicone resins, modified silicone resins, fluorine resins, and the like can be used, but are not limited thereto. It is not a thing.
  • the average particle size of the carrier is not particularly limited, but preferably has an average particle size of 10 to 200 ⁇ m. These carriers are preferably used in an amount of 5 to 100 parts by mass with respect to 1 part by mass of the toner.
  • Other setting conditions were particle refractive index: 1.59, transparency: transmission, shape: true sphere, density: 1.05.
  • volume median particle size (Dv50) of the particles having a volume median particle size (Dv50) of 1 micron or more is obtained by using Multisizer III (aperture diameter 100 ⁇ m: hereinafter abbreviated as Multisizer) manufactured by Beckman Coulter, It was measured by isoton II as a dispersion medium and dispersed to a dispersoid concentration of 0.03%.
  • Multisizer III aperture diameter 100 ⁇ m: hereinafter abbreviated as Multisizer
  • ⁇ Average circularity measurement> The average circularity is determined by dispersing the dispersoid in a dispersion medium (Cell Sheath: Sysmex) at 5720-7140 / ⁇ l, and using a flow particle analyzer (FPIA 3000: Sysmex), HPF (High In the (magnification imaging) mode, the measurement was performed under the conditions of an HPF analysis amount of 0.35 ⁇ l and an HPF detection amount of 2000 to 2500.
  • a dispersion medium Cell Sheath: Sysmex
  • FPIA 3000 Sysmex
  • HPF High In the (magnification imaging) mode
  • THF soluble components of the dried polymer primary particle dispersion and shell particle dispersion were measured by gel permeation chromatography (GPC) under the following conditions.
  • GPC gel permeation chromatography
  • Apparatus GPC apparatus HLC-8020 manufactured by Tosoh Corporation, column: PL-gelMixed-B 10 ⁇ manufactured by Polymer Laboratory, solvent: THF, sample concentration: 0.1% by mass, calibration curve: standard polystyrene
  • Tg glass transition temperature
  • Example 1 ⁇ Preparation of Black Colorant Dispersion Bk1>
  • the container stirrer with a propeller blade Mitsubishi Carbon Black # 960 (manufactured by Mitsubishi Chemical Corporation, N 2 adsorption specific surface area 260m 2 / g DBP (dibutyl phthalate) absorption 69cm 3/100 g volatiles 1.5%) 20 parts 1 part of a 20% sodium dodecylbenzenesulfonate aqueous solution (hereinafter abbreviated as 20% DBS aqueous solution), 4 parts of a nonionic surfactant (Emalgen 120, manufactured by Kao Corporation), 75 parts of ion-exchanged water having a conductivity of 2 ⁇ S / cm And predispersed to obtain a pigment premix solution.
  • 20% DBS aqueous solution a 20% sodium dodecylbenzenesulfonate aqueous solution
  • Emalgen 120 manufactured by Kao Corporation
  • the volume cumulative 50% diameter Dv50 of the carbon black in the dispersion after the premix was about 90 ⁇ m.
  • the premix solution was supplied as a raw material slurry to a wet bead mill and subjected to one-pass dispersion. Note that zirconia beads (true density of 6.0 g / cm 3 ) having a diameter of 120 mm ⁇ , a separator having a diameter of 60 mm ⁇ , and a diameter of 50 ⁇ m were used as a dispersion medium. Since the effective internal volume of the stator is about 2 liters and the media filling volume is 1.4 liters, the media filling rate is 70%.
  • the premix slurry is supplied from the supply port by a non-pulsating metering pump at a supply speed of about 40 liters / hr and reaches a predetermined particle size.
  • the product was acquired from the outlet.
  • cooling water at about 10 ° C. was circulated from the jacket to obtain a black colorant dispersion Bk1.
  • a polymer primary particle dispersion B2 was obtained in the same manner as the polymer primary particle dispersion B1, except that the wax dispersion A1 was changed to the wax dispersion A2 and the monomers were changed as follows.
  • the median diameter (D50) measured using nanotrack was 205 nm.
  • the weight average molecular weight (Mw) was 304000.
  • Tg was 38 ° C. [Monomers] Styrene 65.5 parts Butyl acrylate 34.5 parts Acrylic acid 1.5 parts Trichlorobromomethane 1.0 part Hexanediol diacrylate 0.7 part
  • the obtained dispersion was extracted and suction filtered with an aspirator using 5 types C (No. 5C manufactured by Toyo Roshi Kaisha, Ltd.) filter paper.
  • the cake remaining on the filter paper was transferred to a stainless steel container equipped with a stirrer (propeller blade), and ion-exchanged water having an electric conductivity of 1 ⁇ S / cm was added and stirred uniformly, and then stirred for 30 minutes. This process is repeated until the electric conductivity of the filtrate reaches 10 ⁇ S / cm, and then ion-exchanged water having an electric conductivity of 1 ⁇ S / cm is added to the cake remaining on the filter paper so that the dispersion concentration becomes 20% and stirred. As a result, a core particle dispersion C1 was obtained.
  • Styrene / acrylic acid 2-ethylhexyl-2-acrylamido-2-methylpropanesulfonic acid copolymer aqueous dispersion (containing 2.7% by weight of 2-acrylamido-2-methylpropanesulfonic acid, polymerization average molecular weight (Mw): 14, 200, Tg: 70 ° C., 5 parts (solid content) (medium diameter (D50): 24 nm, solid content concentration: 20% by mass) measured using Nanotrac) was added dropwise and stirred at room temperature for 15 minutes.
  • the dispersion was added dropwise at an addition amount of 10 g / 1 L dispersion volume of 1N-HNO 3 aqueous solution, and after stirring for 15 minutes, the dispersion liquid was heated to an internal temperature of 45 ° C., held for 60 minutes, and then cooled to 30 ° C. did.
  • the volume median particle size (Dv50) measured using Multisizer III before washing was 7.44 ⁇ m, and the average circularity measured by a flow particle analyzer was 0.972.
  • the obtained dispersion was extracted and suction filtered with an aspirator using 5 types C filter paper.
  • the cake remaining on the filter paper was transferred to a stainless steel container equipped with a stirrer (propeller blade), demineralized water having an electric conductivity of 1 ⁇ S / cm was added, and the mixture was uniformly dispersed by stirring at 50 rpm, and then stirred for 60 minutes. This process was repeated until the electric conductivity of the filtrate reached 2 ⁇ S / cm, and then the obtained cake was dried for 48 hours in an air dryer set at 40 ° C., thereby obtaining toner mother particles F1.
  • Example 2 ⁇ Preparation of Black Colorant Dispersion Bk2>
  • a non-ionic surfactant (Emogen A90 manufactured by Kao Co., Ltd.) is used instead of a nonionic surfactant (Emogen A120 manufactured by Kao Co., Ltd.), and the coloring is black except that a 20% DBS aqueous solution is not used.
  • a black colorant dispersion Bk2 was obtained in the same manner as the agent dispersion Bk1.
  • a core particle dispersion C2 was obtained in the same manner as the core particle dispersion C1, except that the black colorant dispersion Bk2 was used instead of the black colorant dispersion Bk1.
  • Toner base particles F2 were obtained in the same manner as toner base particles F1, except that core particle dispersion C2 was used instead of core particle dispersion C1.
  • the volume median particle diameter (Dv50) measured using Multisizer III before washing was 8.76 ⁇ m, and the average circularity measured by a flow particle analyzer was 0.967.
  • a developing toner G2 was obtained in the same manner as the developing toner G1, except that the toner base particles F2 were used instead of the toner base particles F1.
  • volume-median particle size was measured using a multisizer and found to be 6.99 ⁇ m.
  • Toner base particles F3 were obtained in the same manner as toner base particles F1, except that core particle dispersion C3 was used instead of core particle dispersion C1.
  • the volume median particle size (Dv50) measured using Multisizer III before washing was 7.02 ⁇ m, and the average circularity measured by a flow particle analyzer was 0.975.
  • a developing toner G3 was obtained in the same manner as the developing toner G1, except that the toner base particles F3 were used instead of the toner base particles F1.
  • a core particle dispersion C4 was obtained in the same manner as the core particle dispersion C3, except that the black colorant dispersion Bk4 was used instead of the black colorant dispersion Bk3.
  • Toner base particles F4 were obtained in the same manner as toner base particles F1, except that core particle dispersion C4 was used instead of core particle dispersion C1.
  • the volume median particle size (Dv50) measured using Multisizer III before washing was 7.15 ⁇ m, and the average circularity measured by a flow particle analyzer was 0.974.
  • a developing toner G4 was obtained in the same manner as the developing toner G1, except that the toner base particles F4 were used instead of the toner base particles F1.
  • a core particle dispersion C5 was obtained in the same manner as the core particle dispersion C3, except that the black colorant dispersion Bk5 was used instead of the black colorant dispersion Bk1.
  • Toner base particles F5 were obtained in the same manner as toner base particles F1, except that core particle dispersion C5 was used instead of core particle dispersion C1.
  • the volume median particle size (Dv50) measured using Multisizer III before washing was 7.45 ⁇ m, and the average circularity measured by a flow particle analyzer was 0.971.
  • a developing toner G5 was obtained in the same manner as the developing toner G1, except that the toner base particles F5 were used instead of the toner base particles F1.
  • FIG. 1 is a TEM photograph of the developing toner G1
  • FIG. 2 is a TEM photograph of the developing toner G2
  • FIG. 3 is a TEM photograph of the developing toner G3
  • FIG. 4 is a TEM photograph of the developing toner G4, and
  • FIG. It is a TEM photograph of G5.
  • a recording paper carrying an unfixed toner image (Excellent White manufactured by Oki Data Corporation) was prepared and tested as follows using a heat roll fixing type fixing machine.
  • the fixing machine has a roller diameter of 27 mm, a nip width of 9 mm, a fixing speed of 229 mm / sec, a heater on the upper roller, and the roller surface is composed of PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer). Silicone oil is not applied.

Abstract

The purpose of the present invention is to provide a black toner for electrostatic-image development which can satisfy image density and hue and can be inhibited from causing transfer failure even when exposed to a high-temperature high-humidity environment for a long period. The present inventors diligently made investigations in order to solve the problem. As a result, the inventors discovered that for obtaining a black toner which retains intact transferability and can retain the black hue, it is most effective to make the carbon black retain a moderate dispersed-pigment diameter in the toner. The inventors further made investigations on the basis of this finding and, as a result, have completed the invention.

Description

静電荷像現像用ブラックトナーBlack toner for developing electrostatic images
　本発明は電子写真法による画像形成方法に用いられる静電荷像現像用ブラックトナーに関するものである。 The present invention relates to a black toner for developing an electrostatic image used in an image forming method by electrophotography.
　電子写真方式の画像形成装置に用いられる静電潜像現像用トナーにおいて、黒色の画像を得るものとしては、顔料（着色剤）としてカーボンブラックが広く用いられている（特許文献１～４）。たとえば、日本国特開２００９－１３３９７３号公報（特許文献５）には、カーボンブラックとともに、電荷制御剤としてニグロシン系染料を、色味調整剤として青色系顔料を併用することが開示されている。また、日本国特開２００９－３０１０２６号公報（特許文献６）には、着色剤を均一に分散させるためにカーボンブラックと、Ｃ．Ｉ．ピグメントブルー１５：１、同１５：２、同１５：３のいずれかのシアン顔料を併用することが開示されている。 In the toner for developing an electrostatic latent image used in an electrophotographic image forming apparatus, carbon black is widely used as a pigment (colorant) for obtaining a black image (Patent Documents 1 to 4). For example, Japanese Unexamined Patent Application Publication No. 2009-133974 (Patent Document 5) discloses using together with carbon black, a nigrosine dye as a charge control agent and a blue pigment as a tint adjusting agent. Japanese Patent Application Laid-Open No. 2009-301026 (Patent Document 6) discloses carbon black and C.I. I. It is disclosed that any of cyan pigments of CI Pigment Blue 15: 1, 15: 2, and 15: 3 is used in combination.
日本国特開平８－１７１２３５号公報Japanese Laid-Open Patent Publication No. 8-171235 日本国特開平９－２１１８８９号公報Japanese Laid-Open Patent Publication No. 9-211889 日本国特開平９－２３０６２０号公報Japanese Unexamined Patent Publication No. 9-230620 日本国特開２０００－３４７４６０号公報Japanese Unexamined Patent Publication No. 2000-347460 日本国特開２００９－１３３９７３号公報Japanese Unexamined Patent Publication No. 2009-133974 日本国特開２００９－３０１０２６号公報Japanese Unexamined Patent Publication No. 2009-301026
　電子写真方式の画像形成装置に用いられる静電潜像現像用トナーである、乾式現像剤のトナーは、樹脂と顔料とを主成分として含むが、トナー中に含まれる顔料の割合は通常１０質量％未満、多くは４～８質量％である。この割合は、トナーの粒径と所望の画像濃度との関係で決まる。紙等の記録材上のトナーの付着量、すなわち画像膜厚は、通常おおよそトナー粒子単層の厚みとなることから、トナーの粒径が画像濃度に反映されるためである。 The toner of a dry developer, which is a toner for developing an electrostatic latent image used in an electrophotographic image forming apparatus, contains a resin and a pigment as main components, but the ratio of the pigment contained in the toner is usually 10 masses. %, Most is 4 to 8% by mass. This ratio is determined by the relationship between the toner particle size and the desired image density. This is because the toner adhesion amount on the recording material such as paper, that is, the image film thickness is usually approximately the thickness of a single toner particle layer, and therefore the toner particle size is reflected in the image density.
　また近年、画像の品質を向上させるためにトナーの小粒径化が求められているが、記録材上の画像濃度を確保するためにはトナーの粒径が小さくなるのに相応して顔料の割合を高める必要がある。したがって、通常、小粒径のトナーは比較的高い割合の顔料を含む。 In recent years, in order to improve the image quality, it is required to reduce the particle size of the toner. However, in order to ensure the image density on the recording material, the pigment particle size corresponding to the smaller particle size of the toner is required. It is necessary to increase the ratio. Thus, usually small particle size toners contain a relatively high proportion of pigment.
　しかしながら、黒色の画像を得るための静電潜像現像用トナーでは、十分な画像濃度を確保するために、トナーにおけるカーボンブラックの含有量を増やすと、トナーの電気抵抗が小さくなり、電子写真方式の画像形成において転写不良が発生するという問題がある。 However, in the toner for developing an electrostatic latent image for obtaining a black image, if the carbon black content in the toner is increased in order to ensure a sufficient image density, the electric resistance of the toner decreases, and the electrophotographic system There is a problem that a transfer failure occurs in the image formation.
　このような転写不良の問題に対し、特許文献１に開示されているようなニグロシン系染料と青色系顔料の混合、または特許文献２に開示されているようなシアン顔料の混合によると、カーボンブラックのみの場合より電気抵抗を大きくすることができるものの、特に顔料の配合割合を高くした場合には十分に抵抗を調整することができず、転写不良が発生する場合がある。転写不良は、高温高湿の環境下では特に生じやすい。また、シアン顔料やニグロシン系染料により電気抵抗を調整する場合、その添加割合によっては適正な色相が得られない場合がある。 In order to solve such a transfer failure problem, a mixture of a nigrosine dye and a blue pigment as disclosed in Patent Document 1 or a mixture of a cyan pigment as disclosed in Patent Document 2 causes carbon black. Although the electric resistance can be increased more than the case of only the case, particularly when the blending ratio of the pigment is increased, the resistance cannot be adjusted sufficiently, and transfer failure may occur. Transfer defects are particularly likely to occur in a high temperature and high humidity environment. In addition, when the electric resistance is adjusted with a cyan pigment or a nigrosine dye, an appropriate hue may not be obtained depending on the addition ratio.
　本発明は、このような状況に鑑みなされたものであって、その目的とすることは、画像濃度および色相を満足させるとともに、高温高湿の環境下に長期間晒された場合であっても転写不良を抑制することができる静電潜像現像用ブラックトナーを提供することにある。 The present invention has been made in view of such circumstances, and the object thereof is to satisfy image density and hue, even when exposed to a high temperature and high humidity environment for a long time. An object of the present invention is to provide a black toner for developing an electrostatic latent image that can suppress transfer defects.
　本発明者は、上記課題を解決するために鋭意研究を行なったところ、ブラックトナーが転写性を害さず、かつ黒色としての色相を保持し得るためには、カーボンブラックがトナー中で適度な顔料分散径を維持することが最も有効であるとの知見を得、この知見に基づきさらに検討を重ねたことにより本発明の完成に至った。 The present inventor has conducted extensive research to solve the above-mentioned problems. As a result, carbon black is an appropriate pigment in the toner so that the black toner does not impair the transferability and can maintain the hue as black. The knowledge that it is most effective to maintain the dispersion diameter was obtained, and further studies were made based on this knowledge, thereby completing the present invention.
　すなわち、本発明の要旨は以下にある。
［１］ブラック顔料及び結着樹脂を含有する静電荷像現像用ブラックトナーであって、トナー断面の倍率５万倍のＴＥＭ画像におけるブラック顔料粒子の面積の平均値が、１．０×１０－６μｍ２以上１．０×１０－４μｍ２以下である静電荷像現像用ブラックトナー。
［２］前記ブラック顔料粒子の面積の最大値が５．０×１０－３μｍ２以下である、前記［１］に記載の静電荷像現像用ブラックトナー。
［３］前記ブラック顔料粒子の面積の標準偏差値が１．０×１０－３μｍ２以下である、前記［２］記載の静電荷像現像用ブラックトナー。
［４］ブラック顔料及び結着樹脂を含有する静電荷像現像用ブラックトナーであって、トナー断面の倍率５万倍のＴＥＭ画像におけるブラック顔料粒子の周囲長が、３．０×１０－２μｍ以下である静電荷像現像用ブラックトナー。
［５］前記ブラック顔料粒子の面積の最大値が５．０×１０－３μｍ２以下である、前記［４］に記載の静電荷像現像用ブラックトナー。
［６］前記ブラック顔料粒子の面積の標準偏差値が１．０×１０－３μｍ２以下である、前記［５］記載の静電荷像現像用ブラックトナー。
［７］前記ＴＥＭ画像は、画像処理ソフト　Ｗｉｎ　ＲＯＯＦ　５．７．１（ＭＩＴＡＮＩ　Ｃｏｒｐｏｒａｔｉｏｎ）を用いて、ガンマ値を０．５に補正し、閾値６０、１００に設定した後、２つの閾値による２値化処理を行なったものである、前記［１］～［６］のいずれか１つに記載の静電荷像現像用ブラックトナー。 That is, the gist of the present invention is as follows.
[1] A black toner for developing an electrostatic charge image containing a black pigment and a binder resin, wherein an average value of the area of black pigment particles in a TEM image having a magnification of 50,000 times the cross section of the toner is 1.0 × 10 − A black toner for developing electrostatic images having a size of 6 μm 2 or more and 1.0 × 10 −4 μm 2 or less.
[2] The black toner for developing an electrostatic charge image according to [1], wherein the maximum area of the black pigment particles is 5.0 × 10 −3 μm 2 or less.
[3] The black toner for developing an electrostatic charge image according to [2], wherein the standard deviation value of the area of the black pigment particles is 1.0 × 10 −3 μm 2 or less.
[4] A black toner for developing an electrostatic charge image containing a black pigment and a binder resin, wherein the peripheral length of the black pigment particles in a TEM image with a magnification of 50,000 times the cross section of the toner is 3.0 × 10 −2 μm A black toner for developing an electrostatic image which is:
[5] The black toner for developing electrostatic images according to [4], wherein the maximum area of the black pigment particles is 5.0 × 10 −3 μm 2 or less.
[6] The black toner for developing an electrostatic charge image according to [5], wherein the standard deviation value of the area of the black pigment particles is 1.0 × 10 −3 μm 2 or less.
[7] The TEM image is corrected with a gamma value of 0.5 using image processing software Win ROOF 5.7.1 (MITANI Corporation) and set to threshold values 60 and 100. The black toner for developing electrostatic images according to any one of [1] to [6], which has been subjected to a valuation process.
　本発明によれば、複数のトナー層を形成しなくても画像濃度および色相を満足させるとともに、高温高湿に長期間晒された場合であっても転写不良の問題を防止するという優れた効果を有する静電荷像現像用ブラックトナーを提供できる。 According to the present invention, an excellent effect of satisfying image density and hue without forming a plurality of toner layers and preventing the problem of transfer failure even when exposed to high temperature and high humidity for a long period of time. It is possible to provide a black toner for developing an electrostatic charge image.
図１は、現像用トナーＧ１の０．４μｍ超薄切片の倍率５００００倍のＴＥＭ写真である。FIG. 1 is a TEM photograph of a magnification of 50000 times of a 0.4 μm ultrathin section of the developing toner G1. 図２は、現像用トナーＧ２の０．４μｍ超薄切片の倍率５００００倍のＴＥＭ写真である。FIG. 2 is a TEM photograph of an ultrathin section of 0.4 μm of the developing toner G2 with a magnification of 50000 times. 図３は、現像用トナーＧ３の０．４μｍ超薄切片の倍率５００００倍のＴＥＭ写真である。FIG. 3 is a TEM photograph of an ultrathin section of 0.4 μm of the developing toner G3 with a magnification of 50000 times. 図４は、現像用トナーＧ４の０．４μｍ超薄切片の倍率５００００倍のＴＥＭ写真である。FIG. 4 is a TEM photograph of a magnification of 50000 times of a 0.4 μm ultrathin section of the developing toner G4. 図５は、現像用トナーＧ５の０．４μｍ超薄切片の倍率５００００倍のＴＥＭ写真である。FIG. 5 is a TEM photograph of a magnification of 50000 times of a 0.4 μm ultrathin section of the developing toner G5.
　以下に本発明を詳細に説明するが、本発明は以下の実施形態に限定されるものではなく、本発明の要旨を逸脱しない範囲において、任意に変形して実施することができる。
　以下、「静電荷像現像用ブラックトナー」を単に「ブラックトナー」あるいは「トナー」と、略記する場合がある。外添剤を固着又は付着させる前のトナーを「トナー母粒子」と称する。
　また、本明細書において、質量で表される全ての百分率や部は、重量で表される百分率や部と同様である。 Hereinafter, the present invention will be described in detail, but the present invention is not limited to the following embodiments, and can be arbitrarily modified without departing from the gist of the present invention.
Hereinafter, “black toner for developing an electrostatic image” may be simply abbreviated as “black toner” or “toner”. The toner before the external additive is fixed or adhered is referred to as “toner mother particles”.
In the present specification, all percentages and parts expressed by mass are the same as percentages and parts expressed by weight.
＜本発明について＞
　本発明のブラックトナーの第１の態様は、ブラック顔料及び結着樹脂を含有し、トナー断面の倍率５万倍のＴＥＭ画像におけるブラック顔料粒子の面積の平均値が、１．０×１０－６μｍ２以上１．０×１０－４μｍ２以下であることを特徴とする。本発明のブラックトナーの第２の態様は、ブラック顔料及び結着樹脂を含有し、トナー断面の倍率５万倍のＴＥＭ画像におけるブラック顔料粒子の周囲長が、３．０×１０－２μｍ以下であることを特徴とする。 <About the present invention>
The first aspect of the black toner of the present invention contains a black pigment and a binder resin, and the average value of the area of the black pigment particles in a TEM image having a magnification of 50,000 times the cross section of the toner is 1.0 × 10 −6. It is characterized by being not less than μm 2 and not more than 1.0 × 10 −4 μm 2 . The second embodiment of the black toner of the present invention contains a black pigment and a binder resin, and the peripheral length of the black pigment particles in a TEM image having a magnification of 50,000 times the cross section of the toner is 3.0 × 10 −2 μm or less. It is characterized by being.
　ここで、前記ブラック顔料粒子とは、ブラック顔料の一次粒子又はブラック顔料の一次粒子が凝集した複次粒子を意味する。トナー断面の倍率５万倍のＴＥＭ画像におけるブラック顔料粒子の面積の前記平均値及び周囲長は、トナー母粒子中に分散して存在するブラック顔料粒子の大凡の大きさを表すものと考えられる。すなわち、トナー断面の倍率５万倍のＴＥＭ画像におけるブラック顔料粒子の面積の平均値が１．０×１０－６μｍ２以上１．０×１０－４μｍ２以下を満たすこと又はブラック顔料粒子の周囲長が３．０×１０－２μｍ以下を満たすことは、トナー母粒子中においてブラック顔料粒子の顔料分散径が比較的に小さい状態であると考えられる。具体的には、ブラック顔料粒子の分散径は、１．１×１０－２μｍ以下相当であると理論的に考えられる。 Here, the black pigment particle means a primary particle of black pigment or a composite particle in which primary particles of black pigment are aggregated. The average value and the perimeter of the black pigment particle area in the TEM image with a magnification of 50,000 times of the cross section of the toner are considered to represent the approximate size of the black pigment particles dispersed and present in the toner base particles. That is, the average value of the area of the black pigment particles in the TEM image with a magnification of 50,000 times in the cross section of the toner satisfies 1.0 × 10 −6 μm 2 or more and 1.0 × 10 −4 μm 2 or less, or the black pigment particles The fact that the perimeter length satisfies 3.0 × 10 −2 μm or less is considered to be a state in which the pigment dispersion diameter of the black pigment particles is relatively small in the toner base particles. Specifically, it is theoretically considered that the dispersion diameter of the black pigment particles is equivalent to 1.1 × 10 −2 μm or less.
　このような本発明のトナーの第１の態様あるいは第２の態様を用いて画像形成を行うことにより、画像濃度や色相に優れた画像を提供することが可能となる。 It is possible to provide an image excellent in image density and hue by performing image formation using the first aspect or the second aspect of the toner of the present invention.
　本発明のトナーは、トナー断面の倍率５万倍のＴＥＭ画像におけるブラック顔料粒子の面積の最大値が５．０×１０－３μｍ２以下であることが好ましい。このようなブラックトナーは、トナー母粒子全体に渡って、顔料分散径が１．１×１０－２μｍを超える大きなブラック顔料粒子が存在しないものと考えられる。また、本発明のトナーは、トナー断面の倍率５万倍のＴＥＭ画像におけるブラック顔料粒子の面積の標準偏差値が１．０×１０－３μｍ２以下であることがより好ましい。このようなブラックトナーは、ブラック顔料粒子のトナー母粒子中における分散粒径の分布が狭く、ブラック顔料粒子が微分散された状態を表すものと考えられる。前記最大値の範囲又は前記最大値の範囲と前記標準偏差値の範囲の両方の値の範囲を満たすブラックトナーとすることにより、より色相に優れた画像を得ることができる。また、帯電性の観点からは、ブラック顔料粒子の面積の標準偏差値が１．０×１０－５μｍ２以上であることが好ましい。また、色相の観点からブラック顔料粒子の周囲長は２．５×１０－２μｍ以下であることが好ましい。帯電性の観点からは、ブラック顔料粒子の周囲長が１．０×１０－３μｍ以上が好ましい。 The toner of the present invention preferably has a maximum area of black pigment particles of 5.0 × 10 −3 μm 2 or less in a TEM image with a magnification of 50,000 times in the cross section of the toner. In such a black toner, it is considered that there are no large black pigment particles having a pigment dispersion diameter exceeding 1.1 × 10 −2 μm over the entire toner base particles. In the toner of the present invention, the standard deviation value of the area of black pigment particles in a TEM image having a magnification of 50,000 times in the cross section of the toner is more preferably 1.0 × 10 −3 μm 2 or less. Such a black toner is considered to represent a state in which the distribution of the dispersed particle size of the black pigment particles in the toner base particles is narrow and the black pigment particles are finely dispersed. By using black toner that satisfies the maximum value range or both the maximum value range and the standard deviation value range, it is possible to obtain an image with more excellent hue. From the viewpoint of chargeability, the standard deviation value of the area of the black pigment particles is preferably 1.0 × 10 −5 μm 2 or more. From the viewpoint of hue, the peripheral length of the black pigment particles is preferably 2.5 × 10 −2 μm or less. From the viewpoint of chargeability, the peripheral length of the black pigment particles is preferably 1.0 × 10 −3 μm or more.
　尚、前記ＴＥＭ画像は、画像処理ソフト、例えば、Ｗｉｎ　ＲＯＯＦ　５．７．１（ＭＩＴＡＮＩ　Ｃｏｒｐｏｒａｔｉｏｎ）を用いて、ガンマ値を０．５に補正し、閾値６０、１００に設定した後、２つの閾値による２値化処理を行なったものであることが好ましい。 The TEM image is obtained by correcting the gamma value to 0.5 using image processing software such as Win ROOF 5.7.1 (MITANI Corporation) and setting the threshold values to 60 and 100. It is preferable that the binarization process is performed.
＜本発明を得るための方法について＞
　本発明のブラックトナーは、後述の＜トナーの構成＞で詳述するように、乳化重合凝集法や乳化凝集法に代表されるサブミクロンサイズの重合体一次粒子をトナーサイズであるミクロンサイズまで凝集させる方法を用いて得られる。
　乳化重合凝集法は、水系媒体中で不飽和二重結合を有するモノマーをラジカル重合しトナーサイズ以下のサブミクロンサイズの重合体一次粒子を得た後、その重合体一次粒子をトナーサイズであるミクロンサイズまで凝集させる方法である。乳化凝集法は、ポリエステル樹脂等を高圧条件及びまたは溶剤存在下で水中に微粒子化しトナーサイズ以下であるサブミクロンサイズの重合体一次粒子とし、その後その重合体一次粒子をトナーサイズであるミクロンサイズまで凝集させる方法である。
　いずれの方法においても、ミクロンサイズまで凝集させる凝集工程では、少なくともブラック顔料粒子と重合体一次粒子とを凝集させて、粒子凝集体を作成する。その後、熟成・融着工程を経て、粒子凝集体の円形化を行い、トナー母粒子を得る。 <About the method for obtaining this invention>
The black toner of the present invention aggregates submicron-sized polymer primary particles represented by the emulsion polymerization aggregation method and the emulsion aggregation method to a micron size, which is the toner size, as will be described in detail in <Toner configuration> described later. It is obtained by using the method.
In the emulsion polymerization aggregation method, a monomer having an unsaturated double bond is radically polymerized in an aqueous medium to obtain submicron-sized polymer primary particles smaller than the toner size, and then the polymer primary particles are converted to a toner size of micron. It is a method of agglomerating to size. In the emulsion aggregation method, polyester resin or the like is finely divided into water in high-pressure conditions and / or in the presence of a solvent to form submicron-sized polymer primary particles that are smaller than the toner size, and then the polymer primary particles are reduced to micron size that is the toner size. It is a method of aggregation.
In any method, in the aggregation step of agglomerating to micron size, at least black pigment particles and polymer primary particles are agglomerated to form particle aggregates. Thereafter, through a ripening and fusing process, the particle aggregate is rounded to obtain toner mother particles.
　＜本発明について＞にて詳述した本発明で規定する範囲を満たすブラックトナーを得るには、トナー母粒子中にブラック顔料粒子を均一に分散させる必要がある。トナー母粒子中にブラック顔料粒子を均一に分散させるためには、前記粒子凝集体の作製の初期段階で、ブラック顔料粒子同士で凝集せず、重合体一次粒子と凝集するように制御することが重要である。換言すれば、粒子凝集体の作成の初期段階において、重合体一次粒子の凝集速度をブラック顔料粒子の凝集速度と同等とする、あるいは、重合体一次粒子の凝集速度をブラック顔料粒子の凝集速度より速くするといった制御が重要である。 In order to obtain a black toner satisfying the range specified in the present invention described in detail in <About the present invention>, it is necessary to uniformly disperse the black pigment particles in the toner base particles. In order to uniformly disperse the black pigment particles in the toner base particles, it is possible to control so that the black pigment particles do not aggregate with each other but aggregate with the polymer primary particles in the initial stage of the production of the particle aggregate. is important. In other words, in the initial stage of the particle aggregate preparation, the aggregation rate of the polymer primary particles is made equal to the aggregation rate of the black pigment particles, or the aggregation rate of the polymer primary particles is set higher than the aggregation rate of the black pigment particles. Control such as speeding up is important.
　本発明のように、トナー母粒子全体にブラック顔料粒子を細かく均一に分散させる場合、ブラック顔料粒子の一次粒子径が小さくなり、ブラック顔料の凝集速度が速くなる。この状況において、ブラック顔料同士が凝集してトナー母粒子中のブラック顔料粒子の粒径が大きくなることを防ぐために、重合体一次粒子とブラック顔料粒子が交互に凝集しやすくなるように、重合体一次粒子の凝集速度とブラック顔料粒子の凝集速度との差を小さくする凝集工程の条件を設定する必要がある。 When the black pigment particles are finely and uniformly dispersed throughout the toner base particles as in the present invention, the primary particle diameter of the black pigment particles is reduced and the aggregation rate of the black pigment is increased. In this situation, in order to prevent the black pigments from aggregating to increase the particle size of the black pigment particles in the toner base particles, the polymer primary particles and the black pigment particles are easily aggregated alternately. It is necessary to set conditions for the aggregation process that reduces the difference between the aggregation rate of the primary particles and the aggregation rate of the black pigment particles.
　本発明者の検討の結果、凝集工程の条件を以下のいずれかの条件に設定することにより、トナー母粒子全体にブラック顔料粒子を細かく均一に分散させることが可能であると分かった。 As a result of the study by the present inventors, it was found that the black pigment particles can be finely and uniformly dispersed throughout the toner base particles by setting the conditions of the aggregation process to any of the following conditions.
（１）ブラック顔料添加時の温度調整
　凝集工程を行う際に、重合体一次粒子の分散液を撹拌槽に仕込んでおき、該撹拌槽系の内温を２５℃から３０℃に調整した上で、ブラック顔料分散液を滴下して添加することで、前記凝集速度の差を制御する。
　撹拌槽系の内温が２５℃よりも低いときは、ブラック顔料粒子の凝集速度が重合体一次粒子の凝集速度より速くなり、トナー母粒子中のブラック顔料分散粒径が大きくなるおそれがある。
　撹拌槽系の内温が３０℃よりも高いときは、重合体一次粒子の凝集速度がブラック顔料粒子の凝集速度より速くなり、ブラック顔料がトナー母粒子中に取り込まれにくくなり、色強度の低いトナーになるおそれがある。 (1) Temperature adjustment at the time of adding a black pigment When the aggregation process is performed, a dispersion of polymer primary particles is charged into a stirring tank, and the internal temperature of the stirring tank system is adjusted from 25 ° C to 30 ° C. The difference in the aggregation rate is controlled by adding the black pigment dispersion dropwise.
When the internal temperature of the stirring tank system is lower than 25 ° C., the aggregation rate of the black pigment particles becomes faster than the aggregation rate of the polymer primary particles, and the black pigment dispersed particle size in the toner base particles may be increased.
When the internal temperature of the stirring tank system is higher than 30 ° C., the aggregation rate of the polymer primary particles becomes faster than the aggregation rate of the black pigment particles, and the black pigment is less likely to be taken into the toner base particles, resulting in low color strength. There is a risk of becoming toner.
（２）撹拌速度を低速に調整
　凝集工程を行う際に、撹拌槽に備えられた撹拌翼の回転速度を一定の速度以下と低く設定することで、前記凝集速度の差を制御する。
　たとえば直径１２．５ｃｍの容器に１２００ｇの材料を投入し、直径１１ｃｍの撹拌翼で撹拌する場合、回転数を２５０ｒｐｍ以下にする。
　撹拌速度が前記回転数の範囲より速い場合は、ブラック顔料粒子の凝集速度が重合体一次粒子の凝集速度より速くなり、トナー母粒子中のブラック顔料分散粒径が大きくなるおそれがある。
　撹拌速度が前記回転数の範囲より遅い場合は、重合体一次粒子の凝集速度がブラック顔料粒子の凝集速度より速くなり、ブラック顔料がトナー母粒子中に取り込まれにくくなり、色強度の低いトナーになるおそれがある。 (2) Adjusting the stirring speed to a low speed When performing the aggregation process, the difference in the aggregation speed is controlled by setting the rotational speed of the stirring blade provided in the stirring tank to be lower than a certain speed.
For example, when 1200 g of material is put into a container having a diameter of 12.5 cm and stirring is performed with a stirring blade having an diameter of 11 cm, the rotation speed is set to 250 rpm or less.
When the stirring speed is faster than the rotation speed range, the aggregation speed of the black pigment particles becomes faster than the aggregation speed of the polymer primary particles, and the black pigment dispersed particle size in the toner base particles may be increased.
When the stirring speed is slower than the rotation speed range, the aggregation speed of the polymer primary particles becomes faster than the aggregation speed of the black pigment particles, making it difficult for the black pigment to be taken into the toner base particles, resulting in a toner having low color strength. There is a risk.
（３）凝集剤の添加量を調整
　凝集剤として、２価または３価の塩を添加する際に、塩の添加量を重合体一次粒子１００質量部に対して、固形分比で０．１質量部以上１．０質量部以下にする。
　凝集剤の添加量が０．１質量部よりも少ないときは、ブラック顔料粒子の凝集速度が重合体一次粒子の凝集速度より速くなり、トナー母粒子中のブラック顔料分散粒径が大きくなるおそれがある。
　凝集剤の添加量が１．０質量部よりも多いときは、重合体一次粒子の凝集速度がブラック顔料粒子の凝集速度より速くなり、ブラック顔料がトナー母粒子中に取り込まれにくくなり、色強度の低いトナーになるおそれがある。 (3) Adjustment of addition amount of flocculant When adding a divalent or trivalent salt as a flocculant, the addition amount of the salt is 0.1 in terms of solid content with respect to 100 parts by mass of the polymer primary particles. The mass is made not less than 1.0 part by mass.
When the addition amount of the flocculant is less than 0.1 parts by mass, the aggregation rate of the black pigment particles may be faster than the aggregation rate of the polymer primary particles, and the black pigment dispersion particle size in the toner base particles may increase. is there.
When the addition amount of the flocculant is more than 1.0 part by mass, the aggregation rate of the polymer primary particles becomes faster than the aggregation rate of the black pigment particles, and the black pigment is less likely to be taken into the toner base particles, and the color strength. The toner may be low.
（４）ブラック顔料の調整
　ブラック顔料分散液に用いるブラック顔料粒子の体積平均一次粒径を２０ｎｍ以下とする。好ましくは、ブラック顔料として、揮発分２．０％以下のカーボンブラックを用いる。更に好ましくは、ブラック顔料として、顔料表面のｐＨが６以上８以下のカーボンブラックを用いる。このような範囲を満たすカーボンブラックは、カーボンブラック表面の官能基量が少なく、ブラック顔料分散液を調製した際に、カーボンブラック同士が凝集し難いものと推定される。これにより、トナーとした際にも、トナー中におけるカーボンブラックの分散性を良好に維持することができるものと考えられる。 (4) Preparation of black pigment The volume average primary particle size of the black pigment particles used in the black pigment dispersion is 20 nm or less. Preferably, carbon black having a volatile content of 2.0% or less is used as the black pigment. More preferably, carbon black having a pigment surface pH of 6 to 8 is used as the black pigment. The carbon black satisfying such a range has a small amount of functional groups on the surface of the carbon black, and it is estimated that the carbon blacks hardly aggregate when the black pigment dispersion is prepared. Thereby, it is considered that the dispersibility of the carbon black in the toner can be maintained well even when the toner is used.
　サブミクロンサイズの重合体一次粒子をトナーサイズであるミクロンサイズまで凝集させるトナー製造過程において、凝集工程の条件を上記（１）乃至（４）の少なくともいずれかの条件に設定することにより、トナー母粒子全体にブラック顔料を細かく均一に分散させることができる。このようにして得られた本発明のブラックトナーは、従来のブラックトナーよりも帯電性が低く、また帯電性の経時変化が少なく、温度及び湿度などの環境からの影響を受けにくいといった効果を奏する。そのため、色強度以外にも、かぶり、カスレ、飛散などの印刷特性が経時変化や環境変化を受けず、安定な性能のトナーを提供することができる。 In the toner manufacturing process of aggregating the submicron-sized polymer primary particles to the micron size, which is the toner size, the condition of the aggregation process is set to at least one of the above conditions (1) to (4). The black pigment can be finely and uniformly dispersed throughout the particles. The black toner of the present invention thus obtained has the effect that the charging property is lower than that of the conventional black toner, the change in charging property with time is small, and it is difficult to be influenced by the environment such as temperature and humidity. . Therefore, in addition to the color intensity, printing characteristics such as fogging, blurring, and scattering are not affected by changes over time or environmental changes, and a toner with stable performance can be provided.
＜トナーの構成、トナー母粒子及びトナーの製造方法について＞
　本発明により製造されるブラックトナーは、少なくとも結着樹脂及びブラック顔料を含む。
［結着樹脂］
　ブラックトナーを構成する結着樹脂としては、トナーに用い得ることが知られているもののなかから適宜選択して用いればよい。例えば、スチレン系樹脂、塩化ビニル系樹脂、ロジン変性マレイン酸樹脂、フェノール樹脂、エポキシ樹脂、飽和又は不飽和ポリエステル樹脂、ポリエチレン系樹脂、ポリプロピレン系樹脂、アイオノマー樹脂、ポリウレタン樹脂、シリコーン樹脂、ケトン樹脂、エチレン－アクリレート共重合体、キシレン樹脂、ポリビニルブチラール樹脂、スチレン－アクリル酸アルキル共重合体、スチレン－メタクリル酸アルキル共重合体、スチレン－アクリロニトリル共重合体、スチレン－ブタジエン共重合体、スチレン－無水マレイン酸共重合体等を挙げることができる。これらの樹脂は単独で用いることも、いくつかを併用することもできる。 <Regarding Toner Configuration, Toner Base Particles, and Toner Production Method>
The black toner produced according to the present invention contains at least a binder resin and a black pigment.
[Binder resin]
The binder resin constituting the black toner may be appropriately selected from those known to be usable for toner. For example, styrene resin, vinyl chloride resin, rosin modified maleic acid resin, phenol resin, epoxy resin, saturated or unsaturated polyester resin, polyethylene resin, polypropylene resin, ionomer resin, polyurethane resin, silicone resin, ketone resin, Ethylene-acrylate copolymer, xylene resin, polyvinyl butyral resin, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-anhydrous malein An acid copolymer etc. can be mentioned. These resins can be used alone or in combination.
［重合体一次粒子］
　重合体一次粒子は水等の溶媒中に分散された状態で前記凝集工程に用いられる。 [Polymer primary particles]
The polymer primary particles are used in the aggregation step in a state of being dispersed in a solvent such as water.
　重合体一次粒子分散液の調製方法としては、いくつかの方法が挙げられる。
　例えば、後に記載する従来の乳化重合凝集法によりトナーを製造する場合には、スチレン系あるいは（メタ）アクリル系単量体を構成要素とする重合体一次粒子は、スチレン系あるいは（メタ）アクリル系単量体と、必要に応じ連鎖移動剤を、乳化剤を用いて乳化重合することによって重合体一次粒子分散液が得られる。 There are several methods for preparing the polymer primary particle dispersion.
For example, when a toner is produced by the conventional emulsion polymerization aggregation method described later, the polymer primary particles having a styrene or (meth) acrylic monomer as a constituent element are styrene or (meth) acrylic. A polymer primary particle dispersion is obtained by emulsion polymerization of a monomer and, if necessary, a chain transfer agent using an emulsifier.
　また、別の方法としては、従来の乳化凝集法によりトナーを製造する場合に行われるように、塊状重合、溶液重合、懸濁重合、乳化重合などの方法で前記結着樹脂を得た後、水系媒体と混合し、樹脂の融点かガラス転移温度のいずれかの高い温度以上に加熱して樹脂の粘性を下げて、剪断力を与えて乳化することで、重合体一次粒子分散液が得られる。剪断力を与えるための乳化機としては、例えば、ホモジナイザー、ホモミキサー、加圧ニーダー、エクストルーダー、メディア分散機等が挙げられる。 Further, as another method, after the binder resin is obtained by a method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc., as in the case of producing a toner by a conventional emulsion aggregation method, Mixing with an aqueous medium, heating to a temperature higher than either the melting point of the resin or the glass transition temperature to lower the viscosity of the resin, emulsifying by applying a shearing force, a polymer primary particle dispersion can be obtained. . Examples of the emulsifier for applying a shearing force include a homogenizer, a homomixer, a pressure kneader, an extruder, and a media disperser.
　乳化重合凝集法に用いられる重合体一次粒子を構成するバインダー樹脂は乳化重合法により重合可能な１種又は２種以上の重合性モノマーを適宜用いればよい。
　この際、各重合性モノマーは別々に加えても、予め複数の重合性モノマーを混合しておいて同時に添加してもよい。更に、重合性モノマー添加途中で重合性モノマー組成を変化させることも可能である。また、重合性モノマーはそのまま添加してもよいし、予め水や乳化剤等と混合、調製した乳化液として添加することもできる。 As the binder resin constituting the polymer primary particles used in the emulsion polymerization aggregation method, one or more polymerizable monomers that can be polymerized by the emulsion polymerization method may be appropriately used.
At this time, each polymerizable monomer may be added separately, or a plurality of polymerizable monomers may be mixed in advance and added simultaneously. Furthermore, it is also possible to change the polymerizable monomer composition during the addition of the polymerizable monomer. Further, the polymerizable monomer may be added as it is, or may be added as an emulsion prepared by mixing with water or an emulsifier in advance.
　重合性モノマー中には、酸性基を有するモノマー、とくに（メタ）アクリル酸があるのがよい。重合体一次粒子としてのバインダー樹脂を構成する全重合性モノマー１００質量％中に占める酸性基を有するモノマーの合計量の割合は、好ましくは０．０５質量％以上、より好ましくは０．３質量％以上、特に好ましくは０．５質量％以上、更に好ましくは１質量％以上である。上限は、好ましくは１０質量％以下、より好ましくは５質量％以下、特に好ましくは２質量％以下である。
　上記範囲である場合、得られる重合体一次粒子の分散安定性が向上し、凝集工程において粒子形状や粒子径の調整を行いやすくなる。 Among the polymerizable monomers, monomers having an acidic group, particularly (meth) acrylic acid are preferred. The ratio of the total amount of monomers having acidic groups in 100% by mass of all polymerizable monomers constituting the binder resin as the polymer primary particles is preferably 0.05% by mass or more, more preferably 0.3% by mass. Above, especially preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 2% by mass or less.
When it is in the above range, the dispersion stability of the obtained polymer primary particles is improved, and the particle shape and particle diameter can be easily adjusted in the aggregation step.
　その他のモノマーとしては、スチレン、メチルスチレン、クロロスチレン、ｐ－ｔｅｒｔ－ブチルスチレン、ｐ－ｎ－ブチルスチレン、ｐ－ｎ－ノニルスチレン等のスチレン類、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ｎ－ブチル、アクリル酸イソブチル、アクリル酸ヒドロキシエチル、アクリル酸エチルヘキシル等のアクリル酸エステル類、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ｎ－ブチル、メタクリル酸イソブチル、メタクリル酸ヒドロキシエチル、メタクリル酸エチルヘキシル等のメタクリル酸エステル類、アクリルアミド、Ｎ－プロピルアクリルアミド、Ｎ，Ｎ－ジメチルアクリルアミド、Ｎ，Ｎ－ジプロピルアクリルアミド、Ｎ，Ｎ－ジブチルアクリルアミド、アクリル酸アミド等が挙げられる。重合性モノマーは、単独で用いてもよく、また複数を組み合わせて用いてもよい。 Other monomers include styrene such as styrene, methyl styrene, chlorostyrene, p-tert-butyl styrene, pn-butyl styrene, pn-nonyl styrene, methyl acrylate, ethyl acrylate, propyl acrylate Acrylates such as n-butyl acrylate, isobutyl acrylate, hydroxyethyl acrylate, ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacrylic acid Methacrylic acid esters such as hydroxyethyl and ethylhexyl methacrylate, acrylamide, N-propylacrylamide, N, N-dimethylacrylamide, N, N-dipropylacrylamide, N, N-dibutylacrylic Amide, acrylic acid amide and the like. A polymerizable monomer may be used independently and may be used in combination of multiple.
　また、上述した重合性モノマー等を組み合わせて用いる中でも、好ましい実施態様として酸性モノマーとその他のモノマーを組み合わせて用いるのがよい。より好適には、酸性モノマーとして（メタ）アクリル酸を用い、その他のモノマーとしてスチレン類、（メタ）アクリル酸エステル類の中から選択される重合性モノマーを用いるのがよく、更に好適には酸性モノマーとして（メタ）アクリル酸を用い、その他のモノマーとしてスチレンと（メタ）アクリル酸エステル類との組み合わせを用いるのがよく、特に好適には酸性モノマーとして（メタ）アクリル酸を用い、その他のモノマーとしてスチレンとアクリル酸ｎ－ブチルとの組み合わせで用いるのがよい。尚、（メタ）アクリル酸とはアクリル酸又はメタクリル酸を意味する。 Also, among the above-described polymerizable monomers used in combination, as a preferred embodiment, an acidic monomer and another monomer may be used in combination. More preferably, (meth) acrylic acid is used as the acidic monomer, and a polymerizable monomer selected from styrenes and (meth) acrylic acid esters is used as the other monomer. It is preferable to use (meth) acrylic acid as the monomer, and use a combination of styrene and (meth) acrylic acid esters as the other monomer, and particularly preferably use (meth) acrylic acid as the acidic monomer and other monomers. As a combination of styrene and n-butyl acrylate. In addition, (meth) acrylic acid means acrylic acid or methacrylic acid.
　更に、重合体一次粒子を構成するバインダー樹脂として架橋樹脂を用いることも好ましい。その場合、上述の重合性モノマーと共用される架橋剤としてラジカル重合性を有する多官能性モノマーが用いられる。多官能性モノマーとしては、例えば、ジビニルベンゼン、ヘキサンジオールジアクリレート、エチレングリコールジメタクリレート、ジエチレングリコールジメタクリレート、ジエチレングリコールジアクリレート、トリエチレングリコールジアクリレート、ネオペンチルグリコールジメタクリレート、ネオペンチルグリコールアクリレート、ジアリルフタレート等が挙げられる。また、架橋剤として反応性基をペンダントグループに有する重合性モノマー、例えばグリシジルメタクリレート、メチロールアクリルアミド、アクロレイン等を用いることも可能である。中でもラジカル重合性の２官能性モノマーが好ましく、ジビニルベンゼン、ヘキサンジオールジアクリレートが特に好ましい。 Furthermore, it is also preferable to use a crosslinked resin as the binder resin constituting the polymer primary particles. In that case, a polyfunctional monomer having radical polymerizability is used as a crosslinking agent shared with the above polymerizable monomer. Examples of the multifunctional monomer include divinylbenzene, hexanediol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol acrylate, diallyl phthalate, and the like. Is mentioned. In addition, a polymerizable monomer having a reactive group in a pendant group such as glycidyl methacrylate, methylol acrylamide, acrolein or the like can be used as a crosslinking agent. Among them, radically polymerizable bifunctional monomers are preferable, and divinylbenzene and hexanediol diacrylate are particularly preferable.
　これら多官能性モノマー等の架橋剤は、単独で用いても複数を混合して用いてもよい。重合体一次粒子を構成するバインダー樹脂として架橋樹脂を用いる場合は、樹脂を構成する全重合性モノマー中に占める多官能性モノマー等の架橋剤の配合率は、好ましくは０．００５質量％以上、より好ましくは０．１質量％以上であり、更に好ましくは０．３質量％以上であり、好ましくは５質量％以下、より好ましくは３質量％以下、更に好ましくは１質量％以下である。 These crosslinking agents such as polyfunctional monomers may be used alone or in combination. When a crosslinked resin is used as the binder resin constituting the polymer primary particles, the blending ratio of the crosslinking agent such as a polyfunctional monomer in the total polymerizable monomer constituting the resin is preferably 0.005% by mass or more, More preferably, it is 0.1 mass% or more, More preferably, it is 0.3 mass% or more, Preferably it is 5 mass% or less, More preferably, it is 3 mass% or less, More preferably, it is 1 mass% or less.
　乳化重合に用いる乳化剤としては公知のものが使用できるが、カチオン性界面活性剤、アニオン性界面活性剤及びノニオン性界面活性剤からなる群の中から選ばれる１種又は２種以上の乳化剤を併用して用いることができる。 Known emulsifiers can be used for the emulsion polymerization, but one or more emulsifiers selected from the group consisting of cationic surfactants, anionic surfactants and nonionic surfactants are used in combination. Can be used.
　カチオン性界面活性剤としては、例えば、ドデシルアンモニウムクロライド、ドデシルアンモニウムブロマイド、ドデシルトリメチルアンモニウムブロマイド、ドデシルピリジニウムクロライド、ドデシルピリジニウムブロマイド、ヘキサデシルトリメチルアンモニウムブロマイド等が挙げられる。 Examples of the cationic surfactant include dodecyl ammonium chloride, dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, dodecyl pyridinium bromide, hexadecyl trimethyl ammonium bromide and the like.
　アニオン性界面活性剤としては、例えば、ステアリン酸ナトリウム、ドデカン酸ナトリウム等の脂肪酸石けん、硫酸ドデシルナトリウム、ドデシルベンゼンスルホン酸ナトリウム、ラウリル硫酸ナトリウム等が挙げられる。 Examples of the anionic surfactant include fatty acid soaps such as sodium stearate and sodium dodecanoate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, and sodium lauryl sulfate.
　ノニオン界面活性剤としては、例えば、ポリオキシエチレンドデシルエーテル、ポリオキシエチレンヘキサデシルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンソルビタンモノオレアートエーテル、モノデカノイルショ糖等が挙げられる。 Nonionic surfactants include, for example, polyoxyethylene dodecyl ether, polyoxyethylene hexadecyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene sorbitan monooleate ether, monodecanoyl sucrose, etc. Is mentioned.
　乳化剤の使用量は、通常、重合性単量体１００質量部に対して１～１０質量部とされ、また、これらの乳化剤に、例えば、部分又は完全ケン化ポリビニルアルコール等のポリビニルアルコール類、ヒドロキシエチルセルロース等のセルロース誘導体類等の１種又は２種以上を保護コロイドとして併用することができる。
　重合開始剤としては、例えば、過酸化水素；過硫酸カリウム等の過硫酸塩類；ベンゾイルパーオキシド、ラウロイルパーオキシド等の有機過酸化物類；２，２’－アゾビスイソブチロニトリル、２，２’－アゾビス（２，４－ジメチルバレロニトリル）等のアゾ系化合物類；レドックス系開始剤等が用いられる。それらは１種又は２種以上が、通常、重合性単量体１００質量部に対して０．１～３質量部程度の量で用いられる。中でも、重合開始剤としては少なくとも一部又は全部が過酸化水素又は有機過酸化物類であるのが好ましい。
　前記重合開始剤は、何れも重合性モノマー添加前、添加と同時、添加後の何れの時期に重合系に添加してもよく、必要に応じてこれらの添加方法を組み合わせてもよい。 The amount of the emulsifier is usually 1 to 10 parts by mass with respect to 100 parts by mass of the polymerizable monomer, and these emulsifiers include, for example, partially or fully saponified polyvinyl alcohol such as saponified polyvinyl alcohol, hydroxy One type or two or more types of cellulose derivatives such as ethyl cellulose can be used in combination as a protective colloid.
Examples of the polymerization initiator include hydrogen peroxide; persulfates such as potassium persulfate; organic peroxides such as benzoyl peroxide and lauroyl peroxide; 2,2′-azobisisobutyronitrile, 2, Azo compounds such as 2′-azobis (2,4-dimethylvaleronitrile); redox initiators and the like are used. One or more of them are usually used in an amount of about 0.1 to 3 parts by mass with respect to 100 parts by mass of the polymerizable monomer. Among them, it is preferable that at least a part or all of the polymerization initiator is hydrogen peroxide or organic peroxides.
Any of the polymerization initiators may be added to the polymerization system before, simultaneously with, or after the addition of the polymerizable monomer, and these addition methods may be combined as necessary.
　乳化重合に際しては、必要に応じて公知の連鎖移動剤を使用することもできるが、その様な連鎖移動剤の具体的な例としては、ｔ－ドデシルメルカプタン、２－メルカプトエタノール、ジイソプロピルキサントゲン、四塩化炭素、トリクロロブロモメタン等が挙げられる。連鎖移動剤は単独又は２種類以上の併用でもよく、全重合性モノマーに対して通常５質量％以下の範囲で用いられる。また、反応系には、更に、ｐＨ調整剤、重合度調節剤、消泡剤等を適宜配合することができる。 In the emulsion polymerization, a known chain transfer agent may be used as necessary. Specific examples of such a chain transfer agent include t-dodecyl mercaptan, 2-mercaptoethanol, diisopropyl xanthogen, four Examples thereof include carbon chloride and trichlorobromomethane. The chain transfer agent may be used alone or in combination of two or more, and is usually used in a range of 5% by mass or less based on the total polymerizable monomer. Moreover, a pH adjuster, a polymerization degree adjuster, an antifoaming agent, etc. can be further mix | blended with a reaction system suitably.
　乳化重合は、上記の重合性モノマーを重合開始剤の存在下で重合するが、重合温度は、通常５０～１２０℃、好ましくは６０～１００℃、更に好ましくは７０～９０℃である。乳化重合により得られた重合体一次粒子の体積平均径（Ｍｖ）は、通常０．０２μｍ以上、好ましくは０．０５μｍ以上、更に好ましくは０．１μｍ以上であり、通常３μｍ以下、好ましくは２μｍ以下、更に好ましくは１μｍ以下である。粒径が前記範囲未満では、凝集速度の制御が困難となる場合があり、前記範囲超過では、凝集して得られるトナーの粒径が大きくなりやすく、目的とする粒径のトナーを得ることが困難となる場合がある。 In emulsion polymerization, the polymerizable monomer is polymerized in the presence of a polymerization initiator, and the polymerization temperature is usually 50 to 120 ° C., preferably 60 to 100 ° C., more preferably 70 to 90 ° C. The volume average diameter (Mv) of the polymer primary particles obtained by emulsion polymerization is usually 0.02 μm or more, preferably 0.05 μm or more, more preferably 0.1 μm or more, and usually 3 μm or less, preferably 2 μm or less. More preferably, it is 1 μm or less. When the particle size is less than the above range, it may be difficult to control the aggregation rate. When the particle size exceeds the above range, the particle size of the toner obtained by aggregation tends to be large, and a toner having a target particle size can be obtained. It can be difficult.
［ブラック顔料］
　本発明において、ブラック顔料は特に限定されないが、ブラック顔料としては、カーボンブラックが挙げられる。カーボンブラックについては、前述した＜本発明を得るための方法について＞の「（４）ブラック顔料の調整」に記載の通りである。 [Black pigment]
In the present invention, the black pigment is not particularly limited, and examples of the black pigment include carbon black. The carbon black is as described in “(4) Preparation of black pigment” in <Method for obtaining the present invention> described above.
　前記ブラック顔料分散液は、水１００質量部に対して、ブラック顔料を１０～３０質量部、乳化剤を１～１５質量部加えて公知の方法にて調製される。
　ブラック顔料分散液中のブラック顔料分散体の体積平均径は、分散液の調製途中でモニターしながら行い、最終的にブラック顔料分散液中のブラック顔料分散体の体積平均径（Ｍｖ）を０．０１μｍ以上３μｍ以下とするのがよく、より好適には０．０５μｍ以上０．５μｍ以下の範囲に制御することが好ましい。 The black pigment dispersion is prepared by a known method by adding 10 to 30 parts by weight of a black pigment and 1 to 15 parts by weight of an emulsifier with respect to 100 parts by weight of water.
The volume average diameter of the black pigment dispersion in the black pigment dispersion is monitored while preparing the dispersion, and finally the volume average diameter (Mv) of the black pigment dispersion in the black pigment dispersion is set to 0. It is preferable that the thickness is set to be not less than 01 μm and not more than 3 μm, and more preferably controlled in a range of not less than 0.05 μm and not more than 0.5 μm.
［樹脂微粒子］
　本発明においては、乳化重合により得た重合体一次粒子を含む分散液に、ブラック顔料分散液と、必要に応じて、後述する帯電制御剤、ワックス等の分散液を添加して混合分散液を調製し、次いで、この混合分散液中の一次粒子を凝集させて芯粒子とし、芯粒子に樹脂微粒子等を固着又は付着させ、融着させて得られた粒子を洗浄、乾燥することによりトナー母粒子を得ることが好ましい。
　樹脂微粒子は、上記重合体一次粒子と同様の方法で製造してもよく、その構成は特に限定されないが、樹脂微粒子としてのバインダー樹脂を構成する全重合性モノマー１００質量％中に占める極性モノマーの合計量の割合は、好ましくは０．０５質量％以上、より好ましくは０．１質量％以上、更に好ましくは０．２質量％以上である。上限は、好ましくは３質量％以下、より好ましくは１．５質量％以下である。上記範囲である場合、得られる樹脂微粒子の分散安定性が向上し、凝集工程において粒子形状や粒子径の調整を行いやすくなる。 [Resin fine particles]
In the present invention, a dispersion liquid containing primary particles of polymer obtained by emulsion polymerization is added with a black pigment dispersion liquid and, if necessary, a dispersion liquid such as a charge control agent and a wax described later to obtain a mixed dispersion liquid. Next, the primary particles in the mixed dispersion are agglomerated to form core particles, and resin particles are fixed or adhered to the core particles, and the particles obtained by fusing are washed and dried to obtain a toner base. It is preferred to obtain particles.
The resin fine particles may be produced by the same method as the above polymer primary particles, and the structure thereof is not particularly limited, but the polar monomer occupies in 100% by mass of the total polymerizable monomer constituting the binder resin as the resin fine particles. The ratio of the total amount is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.2% by mass or more. The upper limit is preferably 3% by mass or less, more preferably 1.5% by mass or less. When it is in the above range, the dispersion stability of the obtained resin fine particles is improved, and it becomes easy to adjust the particle shape and particle diameter in the aggregation process.
　また、樹脂微粒子としてのバインダー樹脂を構成する全重合性モノマー１００質量％中に占める極性モノマーの合計量の割合が、重合体一次粒子としてのバインダー樹脂を構成する全重合性モノマー１００質量％中に占める極性モノマーの合計量の割合よりも小さい方が、凝集工程において粒子形状や粒子径の調整を行いやすくなり、微粉の発生が抑制でき、帯電特性に優れたものとなる点で好ましい。 Further, the proportion of the total amount of polar monomers in 100% by mass of the total polymerizable monomer constituting the binder resin as the resin fine particles is in 100% by mass of the total polymerizable monomer constituting the binder resin as the polymer primary particle. It is preferable that the ratio is smaller than the ratio of the total amount of polar monomers in view of easy adjustment of the particle shape and particle diameter in the aggregation process, generation of fine powder can be suppressed, and excellent charging characteristics.
　また、樹脂微粒子としてのバインダー樹脂のＴｇが、重合体一次粒子としてのバインダー樹脂のＴｇよりも高い方が、保存安定性等の点から好ましい。 Also, it is preferable from the viewpoint of storage stability that the Tg of the binder resin as the resin fine particles is higher than the Tg of the binder resin as the polymer primary particles.
　前記ブラック顔料の含有割合は、得られるトナーが現像により可視像を形成するのに十分な量であればよく、例えば、トナー中に１～２５質量部の範囲が好ましく、更に好ましくは１～１５質量部、特に好ましくは３～１２質量部である。 The content ratio of the black pigment may be an amount sufficient for the obtained toner to form a visible image by development. For example, the content is preferably in the range of 1 to 25 parts by mass, more preferably 1 to 15 parts by mass, particularly preferably 3 to 12 parts by mass.
［ワックス］
　ブラックトナーには、離型性付与のためワックスを配合することが好ましい。ワックスとしては、離型性を有するものであればいかなるものも使用可能であり、特に限定はされない。具体的には、低分子量ポリエチレン、低分子量ポリプロピレン、共重合ポリエチレン等のオレフィン系ワックス；パラフィンワックス；ベヘン酸ベヘニル、モンタン酸エステル、ステアリン酸ステアリル等の長鎖脂肪族基を有するエステル系ワックス；水添ひまし油、カルナバワックス等の植物系ワックス；ジステアリルケトン等の長鎖アルキル基を有するケトン；アルキル基を有するシリコーン；ステアリン酸等の高級脂肪酸；エイコサノール等の長鎖脂肪族アルコール；グリセリン、ペンタエリスリトール等の多価アルコールと長鎖脂肪酸により得られる多価アルコールのカルボン酸エステル、又は部分エステル；オレイン酸アミド、ステアリン酸アミド等の高級脂肪酸アミド；低分子量ポリエステル等が例示される。 [wax]
It is preferable to add a wax to the black toner to impart releasability. Any wax can be used as long as it has releasability, and is not particularly limited. Specifically, olefin waxes such as low molecular weight polyethylene, low molecular weight polypropylene, and copolymer polyethylene; paraffin wax; ester waxes having a long-chain aliphatic group such as behenyl behenate, montanate ester, stearyl stearate; water Plant waxes such as soy castor oil and carnauba wax; ketones having long chain alkyl groups such as distearyl ketone; silicones having alkyl groups; higher fatty acids such as stearic acid; long chain aliphatic alcohols such as eicosanol; glycerin and pentaerythritol Examples include carboxylic acid esters or partial esters of polyhydric alcohols obtained from polyhydric alcohols such as polyhydric alcohols and long chain fatty acids; higher fatty acid amides such as oleic acid amides and stearic acid amides; low molecular weight polyesters and the like.
　これらのワックスの中で定着性を改善するためには、ワックスの融点は３０℃以上が好ましく、４０℃以上が更に好ましく、５０℃以上が特に好ましい。また、ワックスの融点は１００℃以下が好ましく、９０℃以下が更に好ましく、８０℃以下が特に好ましい。融点が低すぎると定着後にワックスが表面に露出しべたつきを生じやすく、融点が高すぎると低温での定着性が劣る。また更に、ワックスの化合物種としては、脂肪族カルボン酸と一価若しくは多価アルコールとから得られるエステル系ワックスが好ましく、エステル系ワックスの中でも炭素数が２０～１００のものが好ましい。 In order to improve fixability among these waxes, the melting point of the wax is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and particularly preferably 50 ° C. or higher. The melting point of the wax is preferably 100 ° C. or lower, more preferably 90 ° C. or lower, and particularly preferably 80 ° C. or lower. If the melting point is too low, the wax tends to be exposed and sticky after fixing, and if the melting point is too high, the fixability at low temperatures is poor. Furthermore, as the wax compound species, ester waxes obtained from aliphatic carboxylic acids and mono- or polyhydric alcohols are preferred, and ester waxes having 20 to 100 carbon atoms are preferred.
　上記ワックスは単独で用いてもよく、混合して用いてもよい。また、トナーを定着する定着温度により、ワックス化合物の融点を適宜選択することができる。ワックスの使用量はトナー１００質量部に対して、好ましくは４～２０質量部、特に好ましくは６～１８質量部、更に好ましくは８～１５質量部である。また、トナーの体積中位径（Ｄｖ５０）が７μｍ以下の場合、即ち、トナーが小粒径である場合には、ワックスの使用量の増加に伴いワックスのトナー表面への露出が極端に激しくなりトナーの保存安定性が悪くなる。本発明のトナーは、上記範囲のようにワックスの使用量が多い場合であっても、従来のトナーと比較して上記トナー特性の悪化を招くことがない粒度分布がシャープな小粒径のトナーである。 The above waxes may be used alone or in combination. Further, the melting point of the wax compound can be appropriately selected depending on the fixing temperature for fixing the toner. The amount of the wax used is preferably 4 to 20 parts by weight, particularly preferably 6 to 18 parts by weight, and more preferably 8 to 15 parts by weight with respect to 100 parts by weight of the toner. In addition, when the volume median diameter (Dv50) of the toner is 7 μm or less, that is, when the toner has a small particle diameter, the exposure of the wax to the toner surface becomes extremely intense as the amount of the wax used increases. The storage stability of the toner is deteriorated. The toner of the present invention has a small particle size with a sharp particle size distribution that does not cause deterioration of the toner characteristics as compared with conventional toners even when the amount of wax used is large as in the above range. It is.
　ワックスは重合体一次粒子に含有させても、樹脂微粒子に含有させてもよい。ただし、通常はワックスの使用量の増加に伴い凝集制御が悪化して粒子径分布がブロードになる傾向にある。
　そのため、乳化重合凝集法におけるワックスの配合方法としては、予め水中に体積平均径（Ｍｖ）０．０１～２．０μｍ、より好ましくは０．０１～０．５μｍに乳化分散したワックス分散液を乳化重合時に添加するか、又は凝集工程で添加することが好ましい。トナー中に好適な分散粒径でワックスを分散させるためには、乳化重合時にワックスをシードとして添加することが好ましい。シードとして添加することにより、ワックスが内包された重合体一次粒子が得られるので、ワックスがトナー表面に多量に存在することがなく、トナーの帯電性や耐熱性の悪化を抑制することができる。重合体一次粒子に占めるワックス含有量は、好ましくは４～３０質量％、より好ましくは５～２０質量％、特に好ましくは７～１５質量％となるよう計算して用いられる。 The wax may be contained in the polymer primary particles or in the resin fine particles. However, in general, as the amount of wax used increases, aggregation control tends to deteriorate and the particle size distribution tends to become broader.
Therefore, as a method of blending the wax in the emulsion polymerization aggregation method, a wax dispersion that has been previously emulsified and dispersed in water at a volume average diameter (Mv) of 0.01 to 2.0 μm, more preferably 0.01 to 0.5 μm, is emulsified. It is preferable to add at the time of superposition | polymerization or to add at the aggregation process. In order to disperse the wax with a suitable dispersed particle diameter in the toner, it is preferable to add the wax as a seed during emulsion polymerization. By adding as a seed, polymer primary particles in which wax is encapsulated can be obtained, so that a large amount of wax does not exist on the toner surface, and deterioration of chargeability and heat resistance of the toner can be suppressed. The wax content in the polymer primary particles is preferably calculated to be 4 to 30% by mass, more preferably 5 to 20% by mass, and particularly preferably 7 to 15% by mass.
［帯電制御剤］
　ブラックトナーには、帯電量、帯電安定性付与のため、帯電制御剤を配合してもよい。帯電制御剤としては、従来公知の化合物が使用される。例えば、ヒドロキシカルボン酸の金属錯体、アゾ化合物の金属錯体、ナフトール系化合物、ナフトール系化合物の金属化合物、ニグロシン系染料、第４級アンモニウム塩及びこれらの混合物が挙げられる。
　帯電制御剤の配合量は樹脂１００質量部に対し、０．１～５質量部の範囲が好ましい。 [Charge control agent]
The black toner may be blended with a charge control agent to impart charge amount and charge stability. Conventionally known compounds are used as the charge control agent. Examples thereof include hydroxycarboxylic acid metal complexes, azo compound metal complexes, naphthol compounds, naphthol compound metal compounds, nigrosine dyes, quaternary ammonium salts, and mixtures thereof.
The blending amount of the charge control agent is preferably in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the resin.
　乳化重合凝集法においてトナー中に帯電制御剤を含有させる場合は、乳化重合時に重合性モノマー等とともに帯電制御剤を配合するか、重合体一次粒子及び着色剤等とともに凝集工程で配合するか、重合体一次粒子及び着色剤等を凝集させてほぼトナーとして適当な粒径となった後に配合する等の方法によって配合することができる。これらのうち、帯電制御剤を、乳化剤を用いて水中で乳化分散させ、体積平均径（Ｍｖ）０．０１μｍ～３μｍの乳化分散液として使用することが好ましい。乳化凝集時における帯電制御剤分散液の配合は、凝集後のでき上がりのトナー母粒子中に０．１～５質量％となるように計算して用いられる。 When a charge control agent is contained in the toner in the emulsion polymerization aggregation method, the charge control agent is blended with a polymerizable monomer or the like at the time of emulsion polymerization, or is blended in the aggregation process with the polymer primary particles and the colorant. The blended primary particles, the colorant, and the like can be blended by a method such as blending after agglomeration to obtain an appropriate particle size as a toner. Of these, the charge control agent is preferably emulsified and dispersed in water using an emulsifier, and used as an emulsified dispersion having a volume average diameter (Mv) of 0.01 μm to 3 μm. The blending of the charge control agent dispersion at the time of emulsion aggregation is calculated and used so as to be 0.1 to 5% by mass in the finished toner base particles after aggregation.
　前記の分散液中の重合体一次粒子、着色剤分散粒子、ワックス分散粒子、帯電制御剤分散粒子等の体積平均径（Ｍｖ）は、実施例に記載の方法でナノトラックを用いて測定し、その測定値として定義される。 The volume average diameter (Mv) of the polymer primary particles, the colorant dispersed particles, the wax dispersed particles, the charge control agent dispersed particles and the like in the dispersion is measured using a nanotrack by the method described in the Examples, It is defined as the measured value.
［凝集工程］
　乳化重合凝集法における凝集工程においては、上述した、重合体一次粒子、ブラック顔料粒子、必要に応じて帯電制御剤、ワックス等の配合成分は、同時にあるいは逐次に混合するが、予めそれぞれの成分の分散液、即ち、重合体一次粒子分散液、着色剤粒子分散液、帯電制御剤分散液、ワックス微粒子分散液を各々作製しておく。 [Aggregation process]
In the flocculation step in the emulsion polymerization flocculation method, the blended components such as the polymer primary particles, the black pigment particles, and the charge control agent and the wax as necessary are mixed simultaneously or sequentially. Dispersions, that is, polymer primary particle dispersion, colorant particle dispersion, charge control agent dispersion, and wax fine particle dispersion are prepared.
　乳化重合凝集法におけるブラック顔料の配合方法としては、重合体一次粒子分散液を仕込んだのち、ブラック顔料分散液をポンプで一定速度にて滴下して添加する。その際、ポンプの流速を調整して、ブラック顔料分散液の添加時間を制御する。その後、これを凝集させて粒子凝集体とする。ブラック顔料は、乳化剤の存在下で水中にサンドミル、ビーズミル等の機械的手段により乳化させた状態で用いるのが好ましい。乳化凝集時における着色剤分散液の配合は、凝集後のでき上がりのトナー母粒子中に２～１０質量％となるように計算して用いられる。 As a method for blending the black pigment in the emulsion polymerization aggregation method, after preparing the polymer primary particle dispersion, the black pigment dispersion is added dropwise at a constant speed with a pump. At that time, the flow rate of the pump is adjusted to control the addition time of the black pigment dispersion. Thereafter, this is aggregated to form particle aggregates. The black pigment is preferably used in a state emulsified in water by a mechanical means such as a sand mill or a bead mill in the presence of an emulsifier. The blend of the colorant dispersion at the time of emulsion aggregation is calculated and used so as to be 2 to 10% by mass in the finished toner base particles after aggregation.
　前記の凝集処理は通常、攪拌槽内で、加熱する方法、電解質を加える方法、これらを組み合わせる方法等がある。一次粒子を攪拌下に凝集してほぼトナーの大きさに近い粒子凝集体を得ようとする場合、粒子同士の凝集力と攪拌による剪断力とのバランスから粒子凝集体の粒径が制御されるが、加熱するか又は電解質を加えることによって凝集力を大きくすることができる。 The agglomeration treatment usually includes a method of heating in a stirring tank, a method of adding an electrolyte, a method of combining these, and the like. When primary particles are agglomerated under stirring to obtain particle agglomerates that are approximately the size of the toner, the particle size of the particle agglomerates is controlled from the balance between the agglomeration force between the particles and the shearing force due to agitation. However, the cohesive force can be increased by heating or adding an electrolyte.
　凝集剤として、具体的には、ＮａＣｌ、ＫＣｌ、ＬｉＣｌ、Ｎａ２ＳＯ４、Ｋ２ＳＯ４、Ｌｉ２ＳＯ４、ＭｇＣｌ２、ＣａＣｌ２、ＭｇＳＯ４、ＣａＳＯ４、ＺｎＳＯ４、Ａｌ２（ＳＯ４）３、Ｆｅ２（ＳＯ４）３、ＣＨ３ＣＯＯＮａ、Ｃ６Ｈ５ＳＯ３Ｎａ等の電解質が挙げられる。これらのうち、２価以上の多価の金属カチオンを有する無機塩が好ましい。 Specific examples of the aggregating agent include NaCl, KCl, LiCl, Na 2 SO 4 , K 2 SO 4 , Li 2 SO 4 , MgCl 2 , CaCl 2 , MgSO 4 , CaSO 4 , ZnSO 4 , Al 2 (SO 4 ) 3 , Fe 2 (SO 4 ) 3 , CH 3 COONa, C 6 H 5 SO 3 Na, and other electrolytes. Of these, inorganic salts having a divalent or higher polyvalent metal cation are preferred.
　前記電解質の配合量は、電解質の種類、目的とする粒径等によって異なるが、混合分散液の固形成分１００質量部に対して、通常０．０５～２５質量部、好ましくは０．１～１５質量部、更に好ましくは０．１～１０質量部である。配合量が前記範囲未満の場合は、凝集反応の進行が遅くなり、凝集反応後も１μｍ以下の微粉が残る場合や、得られた粒子凝集体の平均粒径が目的の粒径に達しない等の場合がある。また、前記範囲の上限を超えた場合は、急速な凝集となりやすく粒径の制御が困難となり、得られた凝集粒子中に粗粉や不定形のものが含まれる等の問題を生じる場合がある。 The amount of the electrolyte blended varies depending on the type of electrolyte, target particle size, and the like, but is usually 0.05 to 25 parts by mass, preferably 0.1 to 15 parts per 100 parts by mass of the solid component of the mixed dispersion. Part by mass, more preferably 0.1 to 10 parts by mass. When the blending amount is less than the above range, the progress of the agglutination reaction is slow, and fine powders of 1 μm or less remain after the agglomeration reaction, the average particle diameter of the obtained particle aggregate does not reach the target particle diameter, etc. There are cases. In addition, when the upper limit of the above range is exceeded, rapid agglomeration tends to occur and it becomes difficult to control the particle size, and the resulting agglomerated particles may cause problems such as inclusion of coarse powder or irregular shapes. .
　ここで、特定範囲のトナー母粒子の粒径に制御する方法として、電解質の配合量を抑える方法を採用してもよい。一般に、電解質の配合量を抑えると粒子の成長速度が遅くなり、生産効率の点で工業的に好ましくない。しかしながら、工業的見地に反して、敢えて電解質の配合量を抑えることによっても特定範囲の粒径に制御できる。 Here, as a method of controlling the particle size of the toner base particles in a specific range, a method of suppressing the amount of the electrolyte may be employed. In general, if the amount of the electrolyte is suppressed, the particle growth rate is slow, which is not industrially preferable in terms of production efficiency. However, contrary to the industrial point of view, it is possible to control the particle size within a specific range by intentionally suppressing the amount of electrolyte.
　また、電解質を加えて凝集を行う場合の凝集温度は、２０～７０℃が好ましく、３０～６０℃が更に好ましい。
　ここで、凝集工程前の温度を制御することも特定範囲のトナー母粒子の粒径に制御する方法の一つである。
　ブラック顔料分散液は、２０℃未満の低い温度では、ブラック顔料と重合体一次粒子間の凝集よりもブラック顔料同士の凝集が起こりやすい。その結果、トナー中でのブラック顔料の分散状態が悪くなる。
　そこで、凝集工程中におけるブラック顔料添加時の反応槽内の温度を２０℃～３０℃に調整し、ブラック顔料添加後さらに、凝集剤として電解質を添加した後に反応槽内の温度を３０℃～６０℃に加温し、凝集反応による粒径成長を進めることで、ブラック顔料の分散状態が良好で且つ粒度分布がシャープで微粉および粗粉が少ないトナー母粒子を作製することができる。 In addition, the aggregation temperature when the electrolyte is added for aggregation is preferably 20 to 70 ° C, more preferably 30 to 60 ° C.
Here, controlling the temperature before the aggregation step is one of the methods for controlling the particle size of the toner base particles within a specific range.
In the black pigment dispersion, the aggregation of the black pigments is more likely to occur than the aggregation between the black pigment and the polymer primary particles at a temperature lower than 20 ° C. As a result, the dispersion state of the black pigment in the toner is deteriorated.
Therefore, the temperature in the reaction vessel at the time of adding the black pigment during the aggregation process is adjusted to 20 ° C. to 30 ° C. After the addition of the black pigment and the electrolyte as an aggregating agent, the temperature in the reaction vessel is adjusted to 30 ° C. to 60 ° C. By heating to 0 ° C. and advancing particle size growth by agglomeration reaction, toner base particles having a good dispersion state of the black pigment, a sharp particle size distribution, and few fine powders and coarse powders can be produced.
　凝集に要する時間は装置形状や処理スケールにより最適化されるが、トナー母粒子の粒径を目的とする粒径に到達するためには、前記範囲内の温度で通常、少なくとも３０分以上保持することが望ましい。所定の温度へ到達するまでの昇温は、一定速度で昇温してもよいし、段階的に昇温することもできる。 The time required for agglomeration is optimized depending on the shape of the apparatus and the processing scale, but in order to reach the target particle size, the toner base particles are usually held at a temperature within the above range for at least 30 minutes. It is desirable. The temperature rise until reaching the predetermined temperature may be raised at a constant rate, or may be raised stepwise.
　本発明においては、上述の凝集処理後の粒子凝集体に、必要に応じて樹脂微粒子（重合体一次粒子）分散液を添加して粒子凝集体に樹脂微粒子を付着又は固着させてコアシェル構造のトナー母粒子を形成することができる。本発明の製造方法は、コア層とシェル層を有するコアシェル構造のトナー母粒子を形成する場合に、コア層を形成する場合に適用することが好ましい。 In the present invention, a resin having a core-shell structure is prepared by adding a resin fine particle (polymer primary particle) dispersion to the particle aggregate after the aggregation treatment, if necessary, so that the resin fine particles adhere or adhere to the particle aggregate. Mother particles can be formed. The production method of the present invention is preferably applied to the case where the core layer is formed when forming the core-shell toner base particles having the core layer and the shell layer.
　前記の帯電制御剤を凝集処理後に加える場合には、粒子凝集体を含む分散液に帯電制御剤を加えた後に樹脂微粒子を加えることが好ましい。 When the charge control agent is added after the aggregation treatment, it is preferable to add the resin fine particles after adding the charge control agent to the dispersion containing the particle aggregate.
［熟成工程］
　乳化重合凝集法においては、凝集で得られた粒子凝集体の安定性を増すために、分散安定剤として乳化剤やｐＨ調整剤を添加して粒子同士の凝集力を低下させ、トナー母粒子の成長を止めた後に、凝集した粒子間の融着を起こす熟成工程を加えることが好ましい。 [Aging process]
In the emulsion polymerization aggregation method, in order to increase the stability of the particle aggregate obtained by aggregation, an emulsifier and a pH adjuster are added as a dispersion stabilizer to reduce the cohesive force between the particles, thereby growing the toner base particles. It is preferable to add an aging step for causing fusion between the agglomerated particles after stopping.
　ここで、本発明のトナーは、粒度分布がシャープであることが好ましく、特定範囲の粒径に制御する方法として、熟成工程で乳化剤やｐＨ調整剤を添加する工程の前に攪拌回転数を低下させる、即ち、攪拌によるせん断力を下げる方法が挙げられる。 Here, the toner of the present invention preferably has a sharp particle size distribution. As a method for controlling the particle size within a specific range, the stirring rotational speed is reduced before the step of adding an emulsifier or a pH adjuster in the aging step. That is, there is a method of reducing the shearing force by stirring.
　熟成工程では、加熱により結着樹脂の粘度を下げ円形化させるが、そのまま加熱するとトナー母粒子径の成長が停止しないため、加熱による粒子径の成長を停止させる目的で、通常、分散安定剤として、乳化剤やｐＨ調整剤を添加したり、攪拌回転数を上げたりしてせん断力をかけることができる。 In the ripening step, the viscosity of the binder resin is lowered by heating to be circularized, but if heated as it is, the growth of the toner base particle size does not stop, so for the purpose of stopping the particle size growth by heating, usually as a dispersion stabilizer Further, it is possible to apply a shearing force by adding an emulsifier or a pH adjusting agent or increasing a stirring rotational speed.
　また、分散安定剤を添加する工程の前でなくとも、攪拌回転数を下げて凝集粒子へのせん断力を低減させても特定の粒度分布のトナーを得ることができる。ただし、分散安定剤の配合量を調整できる点を考慮すると、分散安定剤を添加する工程の前に行うことの方が好ましい。 Also, even before the step of adding the dispersion stabilizer, a toner having a specific particle size distribution can be obtained even if the stirring rotational speed is lowered to reduce the shearing force to the aggregated particles. However, in consideration of the point that the amount of the dispersion stabilizer can be adjusted, it is preferable to perform it before the step of adding the dispersion stabilizer.
　熟成工程の温度は、好ましくは一次粒子を構成するバインダー樹脂のＴｇ以上、より好ましくは前記Ｔｇより５℃高い温度以上であり、また、好ましくは前記Ｔｇより８０℃高い温度以下、より好ましくは前記Ｔｇより５０℃高い温度以下である。また、熟成工程に要する時間は、目的とするトナーの形状により異なるが、一次粒子を構成する重合体のガラス転移温度以上に到達した後、通常０．１～１０時間、好ましくは１～６時間保持することが望ましい。 The temperature of the aging step is preferably not less than Tg of the binder resin constituting the primary particles, more preferably not less than 5 ° C higher than the Tg, and preferably not more than 80 ° C higher than the Tg, more preferably The temperature is 50 ° C. or higher than Tg. The time required for the ripening step varies depending on the shape of the target toner, but is usually 0.1 to 10 hours, preferably 1 to 6 hours after reaching the glass transition temperature of the polymer constituting the primary particles. It is desirable to hold.
　なお、乳化重合凝集法においては、前記凝集工程以降、好ましくは熟成工程以前又は熟成工程中の段階で、乳化剤を添加するか、凝集液のｐＨ値を上げることが好ましい。ここで用いられる乳化剤としては、前記の重合体一次粒子を製造する際に用いることのできる乳化剤から１種以上を選択して用いることができるが、特に重合体一次粒子を製造した際に用いた乳化剤と同じものを用いることが好ましい。 In the emulsion polymerization flocculation method, it is preferable to add an emulsifier or raise the pH value of the flocculated liquid after the flocculation step, preferably before or during the ripening step. As the emulsifier used here, one or more kinds of emulsifiers that can be used when producing the polymer primary particles can be selected and used, and particularly used when the polymer primary particles are produced. It is preferable to use the same emulsifier.
　乳化剤を配合する場合の配合量は限定されないが、混合分散液の固形成分１００質量部に対して、好ましくは０．１質量部以上、より好ましくは１質量部以上、更に好ましくは３質量部以上であり、また、好ましくは２０質量部以下、より好ましくは１５質量部以下、更に好ましくは１０質量部以下である。凝集工程以降、熟成工程の完了前の間に乳化剤を添加するか、凝集液のｐＨ値を上げることにより、凝集工程で凝集した粒子凝集体同士の凝集等を抑制することができ、熟成工程後のトナー中に粗大粒子が生じることを抑制できる。 The blending amount in the case of blending the emulsifier is not limited, but is preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, further preferably 3 parts by weight or more with respect to 100 parts by weight of the solid component of the mixed dispersion. Moreover, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less. After the aggregation process, before the completion of the ripening process, by adding an emulsifier or by increasing the pH value of the flocculation liquid, aggregation of the particle aggregates aggregated in the aggregation process can be suppressed. The generation of coarse particles in the toner can be suppressed.
　このような加熱処理により、凝集体における一次粒子同士の融着一体化がなされ、凝集体としてのトナー母粒子形状も球形に近いものとなる。熟成工程前の粒子凝集体は、一次粒子の静電的あるいは物理的凝集による集合体であると考えられるが、熟成工程後は、粒子凝集体を構成する重合体一次粒子は互いに融着しており、トナー母粒子の形状も球状に近いものとすることが可能となる。この様な熟成工程によれば、熟成工程の温度及び時間等を制御することにより、一次粒子が凝集した形状である葡萄型、融着が進んだジャガイモ型、更に融着が進んだ球状等、目的に応じて様々な形状のトナーを製造することができる。 By such heat treatment, the primary particles in the aggregate are fused and integrated, and the shape of the toner base particles as the aggregate becomes close to a spherical shape. The particle aggregate before the aging step is considered to be an aggregate due to electrostatic or physical aggregation of the primary particles, but after the aging step, the polymer primary particles constituting the particle aggregate are fused together. In addition, the shape of the toner base particles can be made nearly spherical. According to such a ripening step, by controlling the temperature and time of the ripening step, a cocoon shape in which primary particles are aggregated, a potato type in which fusion has progressed, a spherical shape in which fusion has further progressed, etc. Various shapes of toner can be produced according to the purpose.
　前記の各工程を経ることにより得た粒子凝集体は、公知の方法に従って固／液分離し、粒子凝集体を回収し、次いで、これを必要に応じて洗浄した後、乾燥することにより目的とするトナー母粒子を得ることができる。 The particle aggregate obtained through each of the above steps is subjected to solid / liquid separation according to a known method, the particle aggregate is recovered, then washed as necessary, and then dried. Toner mother particles can be obtained.
　また、前記の乳化重合凝集法により得られた粒子の表面に、例えば、スプレードライ法、ｉｎ－ｓｉｔｕ法、或いは液中粒子被覆法等の方法によって、更に、重合体を主成分とする外層を、好ましくは０．０１～０．５μｍの厚みで形成させることによって、カプセル化されたトナー母粒子とすることもできる。 Further, an outer layer mainly composed of a polymer is further formed on the surface of the particles obtained by the emulsion polymerization aggregation method by, for example, a spray drying method, an in-situ method, or a submerged particle coating method. It is also possible to form encapsulated toner base particles by forming them with a thickness of preferably 0.01 to 0.5 μm.
　また、乳化重合凝集法トナーにおいては、フロー式粒子像分析装置ＦＰＩＡ－３０００（マルバーン社製）を用いて測定した平均円形度が好ましくは０．９０以上、より好ましくは０．９２以上、更に好ましくは０．９５以上である。球形に近いほど粒子内での帯電量の局在化が起こりにくく、現像性が均一になる傾向にあるが、完全な球状トナーを作ることは製造上困難であるので、前記平均円形度は、好ましくは０．９９５以下、より好ましくは０．９９０以下である。 In the emulsion polymerization aggregation method toner, the average circularity measured using a flow type particle image analyzer FPIA-3000 (manufactured by Malvern) is preferably 0.90 or more, more preferably 0.92 or more, and still more preferably. Is 0.95 or more. The closer to a sphere, the less the localization of the charge amount in the particles and the developability tends to be uniform, but since it is difficult to produce a perfect spherical toner, the average circularity is Preferably it is 0.995 or less, More preferably, it is 0.990 or less.
　また、トナーのテトラヒドロフラン（ＴＨＦ）可溶分のゲルパーミエーションクロマトグラフィー（以下、「ＧＰＣ」と略す場合がある。）におけるピーク分子量のうち少なくとも１つが、好ましくは１万以上、より好ましくは１．５万以上、更に好ましくは２万以上であり、好ましくは１０万以下、より好ましくは８万以下、更に好ましくは５万以下である。ピーク分子量が何れも前記範囲より低い場合は、非磁性一成分現像方式における機械的耐久性が悪化する場合があり、ピーク分子量が何れも前記範囲より高い場合は、低温定着性や定着強度が悪化する場合がある。 In addition, at least one of the peak molecular weights in gel permeation chromatography (hereinafter sometimes abbreviated as “GPC”) of the tetrahydrofuran (THF) soluble content of the toner is preferably 10,000 or more, more preferably 1. It is 50,000 or more, more preferably 20,000 or more, preferably 100,000 or less, more preferably 80,000 or less, and still more preferably 50,000 or less. When the peak molecular weight is lower than the above range, the mechanical durability in the non-magnetic one-component development method may be deteriorated. When the peak molecular weight is higher than the above range, the low temperature fixability and the fixing strength are deteriorated. There is a case.
　トナーのＴＨＦ不溶分は、セライト濾過による質量法で測定した場合、好ましくは１質量％以上であり、より好ましくは２質量％以上であり、また、好ましくは２０質量％以下であり、より好ましくは１０質量％以下であるのがよい。前記範囲にない場合は、機械的耐久性と低温定着性の両立が困難となる場合がある。 The THF insoluble content of the toner is preferably 1% by mass or more, more preferably 2% by mass or more, and preferably 20% by mass or less, more preferably, when measured by a mass method by celite filtration. It is good that it is 10 mass% or less. If it is not within the above range, it may be difficult to achieve both mechanical durability and low-temperature fixability.
　乳化重合凝集法トナーの帯電性は、正帯電であっても負帯電であってもよく、トナーの帯電性の制御は、帯電制御剤の選択及び含有量、外添剤の選択及び配合量等によって調整することができる。 The chargeability of the emulsion polymerization aggregation method toner may be positively charged or negatively charged. Control of the chargeability of the toner may include the selection and content of a charge control agent, the selection and blending amount of an external additive, etc. Can be adjusted by.
［外添剤及びトナー化］
　こうして得られたトナー母粒子には、流動性や現像性を制御する為に、トナー母粒子表面に公知の外添剤が配合されてトナーとなっていてもよい。外添剤としては、アルミナ、シリカ、チタニア、酸化亜鉛、酸化ジルコニウム、酸化セリウム、タルク、ハイドロタルサイト等の金属酸化物や水酸化物、チタン酸カルシウム、チタン酸ストロンチウム、チタン酸バリウム等のチタン酸金属塩、窒化チタン、窒化珪素等の窒化物、炭化チタン、炭化珪素等の炭化物、アクリル系樹脂やメラミン樹脂等の有機粒子等が挙げられ、複数組み合わせることが可能である。中でも、シリカ、チタニア、アルミナが好ましく、また、例えばシランカップリング剤やシリコーンオイル等で表面処理されたものがより好ましい。
　その平均一次粒子径は１～５００ｎｍの範囲が好ましく、より好ましくは５～１００ｎｍの範囲がよい。また、前記粒径範囲において小粒径のものと大粒径のものとを併用することも好ましい。外添剤の配合量の総量は、トナー母粒子１００質量部に対して０．０５～１０質量部の範囲が好ましく、より好ましくは０．１～５質量部である。 [External additives and toner]
The toner base particles thus obtained may be made into a toner by mixing known external additives on the surface of the toner base particles in order to control fluidity and developability. External additives include metal oxides and hydroxides such as alumina, silica, titania, zinc oxide, zirconium oxide, cerium oxide, talc and hydrotalcite, titanium such as calcium titanate, strontium titanate and barium titanate. Examples thereof include acid metal salts, nitrides such as titanium nitride and silicon nitride, carbides such as titanium carbide and silicon carbide, and organic particles such as acrylic resins and melamine resins. Among these, silica, titania, and alumina are preferable, and those that have been surface-treated with, for example, a silane coupling agent or silicone oil are more preferable.
The average primary particle diameter is preferably in the range of 1 to 500 nm, more preferably in the range of 5 to 100 nm. It is also preferable to use a combination of a small particle size and a large particle size in the particle size range. The total amount of the external additive is preferably in the range of 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the toner base particles.
［その他］
　本発明の静電荷像現像用トナーは、トナーを磁力により静電潜像部に搬送するためのキャリアを共存させた磁性二成分現像剤用、又は、磁性粉をトナー中に含有させた磁性一成分現像剤用、或いは、現像剤に磁性粉を用いない非磁性一成分現像剤用の何れに用いてもよい。本発明の効果を顕著に発現するためには、特に非磁性一成分現像方式用の現像剤として用いるのが好ましい。 [Others]
The toner for developing an electrostatic image of the present invention is a magnetic two-component developer in which a carrier for conveying the toner to the electrostatic latent image portion by a magnetic force coexists, or a magnetic toner containing a magnetic powder in the toner. It may be used for either a component developer or a non-magnetic one-component developer that does not use magnetic powder as a developer. In order to express the effect of the present invention remarkably, it is particularly preferable to use as a developer for a non-magnetic one-component development system.
　前記磁性二成分現像剤として用いる場合には、トナーと混合して現像剤を形成するキャリアとしては、公知の鉄粉系、フェライト系、マグネタイト系キャリア等の磁性物質又は、それらの表面に樹脂コーティングを施したものや磁性樹脂キャリアを用いることができる。キャリアの被覆樹脂としては、一般的に知られているスチレン系樹脂、アクリル樹脂、スチレンアクリル共重合樹脂、シリコーン系樹脂、変性シリコーン系樹脂、フッ素系樹脂等が利用できるが、これらに限定されるものではない。キャリアの平均粒径は、特に制限はないが１０～２００μｍの平均粒径を有するものが好ましい。これらのキャリアは、トナー１質量部に対して５～１００質量部使用することが好ましい。 When used as the magnetic two-component developer, the carrier that is mixed with the toner to form the developer is a known magnetic substance such as an iron powder type, ferrite type, or magnetite type carrier, or a resin coating on the surface thereof. Or a magnetic resin carrier can be used. As the carrier coating resin, generally known styrene resins, acrylic resins, styrene acrylic copolymer resins, silicone resins, modified silicone resins, fluorine resins, and the like can be used, but are not limited thereto. It is not a thing. The average particle size of the carrier is not particularly limited, but preferably has an average particle size of 10 to 200 μm. These carriers are preferably used in an amount of 5 to 100 parts by mass with respect to 1 part by mass of the toner.
　以下、本発明を実施例によりさらに具体的に説明するが、本発明はその要旨を越えない限り、以下の実施例に限定されるものではない。以下の例で「部」とあるのは「質量部」を意味する。
　各粒子径及び円形度、電気伝導度、熱特性等は次のように測定した。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the following examples, “part” means “part by mass”.
Each particle diameter, circularity, electrical conductivity, thermal characteristics, etc. were measured as follows.
＜中位径測定（Ｄ５０）＞
　１ミクロン未満の中位径（Ｄ５０）を有す粒子の中位径（Ｄ５０）は、日機装株式会社製型式ＭｉｃｒｏｔｒａｃＮａｎｏｔｒａｃ１５０（以下ナノトラックと略す）および同社解析ソフトＭｉｃｒｏｔｒａｃＰａｒｔｉｃｌｅ　Ａｎａｌｙｚｅｒ　Ｖｅｒ１０．１．２－０１９ＥＥを用い、電気伝導度が０．５μＳ／ｃｍのイオン交換水を溶媒とし、溶媒屈折率：１．３３３、測定時間：１２０秒、測定回数：５回の測定条件で取り扱い説明書に記載された方法で測定し、その平均値を求めた。その他の設定条件は、粒子屈折率：１．５９、透過性：透過、形状：真球形、密度：１．０５とした。 <Medium diameter measurement (D50)>
The median diameter (D50) of the particles having a median diameter (D50) of less than 1 micron is obtained from Nikkiso Co., Ltd. model Microtrac Nanotrac 150 (hereinafter abbreviated as “Nanotrack”) and the company's analysis software Microtrac Particle Analyzer Ver10.1.2-019EE. The method described in the instruction manual using the ion-exchange water having an electric conductivity of 0.5 μS / cm as the solvent, the solvent refractive index: 1.333, the measurement time: 120 seconds, and the number of measurements: 5 times. The average value was obtained. Other setting conditions were particle refractive index: 1.59, transparency: transmission, shape: true sphere, density: 1.05.
＜体積中位粒径測定（Ｄｖ５０）＞
　１ミクロン以上の体積中位粒径（Ｄｖ５０）を有す粒子の体積中位粒径（Ｄｖ５０）は、ベックマン・コールター社製マルチサイザーＩＩＩ（アパーチャー径１００μｍ：以下、マルチサイザーと略す）を用い、同社アイソトンＩＩを分散媒として、分散質濃度０．０３％になるように分散させて測定した。 <Volume Median Particle Size Measurement (Dv50)>
The volume median particle size (Dv50) of the particles having a volume median particle size (Dv50) of 1 micron or more is obtained by using Multisizer III (aperture diameter 100 μm: hereinafter abbreviated as Multisizer) manufactured by Beckman Coulter, It was measured by isoton II as a dispersion medium and dispersed to a dispersoid concentration of 0.03%.
＜平均円形度測定＞
　平均円形度は、分散質を分散媒（セルシース：シスメックス社製）に５７２０～７１４０個／μｌとなるように分散させ、フロー式粒子分析装置（ＦＰＩＡ３０００：シスメックス社製）を用いて、ＨＰＦ（高倍率撮像）モードにより、ＨＰＦ分析量０．３５μｌ、ＨＰＦ検出量２０００～２５００個の条件下で測定した。 <Average circularity measurement>
The average circularity is determined by dispersing the dispersoid in a dispersion medium (Cell Sheath: Sysmex) at 5720-7140 / μl, and using a flow particle analyzer (FPIA 3000: Sysmex), HPF (High In the (magnification imaging) mode, the measurement was performed under the conditions of an HPF analysis amount of 0.35 μl and an HPF detection amount of 2000 to 2500.
＜電気伝導度測定＞
　電気伝導度の測定は、導電率計（アズワン株式会社製のＣｙｂｅｒＳｃａｎＣＯＮ１００）を用いて行なった。 <Electrical conductivity measurement>
The electrical conductivity was measured using a conductivity meter (CyberScanCON100 manufactured by ASONE Corporation).
＜重量平均分子量（Ｍｗ）＞
　重合体一次粒子分散液、シェル粒子分散液の乾燥品のＴＨＦ可溶成分を、以下の条件でゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定した。
　装置：東ソー社製ＧＰＣ装置　ＨＬＣ－８０２０、カラム：ポリマーラボラトリー社製ＰＬ－ｇｅｌＭｉｘｅｄ－Ｂ　１０μ、溶媒：ＴＨＦ、試料濃度：０．１質量％、検量線：標準ポリスチレン <Weight average molecular weight (Mw)>
The THF soluble components of the dried polymer primary particle dispersion and shell particle dispersion were measured by gel permeation chromatography (GPC) under the following conditions.
Apparatus: GPC apparatus HLC-8020 manufactured by Tosoh Corporation, column: PL-gelMixed-B 10μ manufactured by Polymer Laboratory, solvent: THF, sample concentration: 0.1% by mass, calibration curve: standard polystyrene
＜ガラス転移温度（Ｔｇ）測定＞
　セイコ－電子工業株式会社製の示差熱分析装置（ＤＳＣ２００）を用いて、昇温速度１０℃／分の条件で測定した。Ｔｇは、ＤＳＣ曲線のベースラインの延長線と吸熱カーブで最大傾斜を示す接線との交点から求めた。 <Measurement of glass transition temperature (Tg)>
Using a differential thermal analyzer (DSC200) manufactured by Seiko Denshi Kogyo Co., Ltd., the temperature was measured at a temperature rising rate of 10 ° C./min. Tg was determined from the intersection of the base line extension of the DSC curve and the tangent line showing the maximum slope in the endothermic curve.
＜ＢＥＴ（Ｎ２吸着比表面積）の測定＞
　Ｍｏｕｎｔｅｃｈ社のＡｕｔｏｍａｔｉｃ　Ｓｕｒｆａｃｅ　Ａｒｅａ　Ａｎａｌｙｚｅｒで、キャリアガスにヘリウムを用いて、サンプル０．５ｇを２００℃で２０ｍｉｎ脱気したのち測定した。 <Measurement of BET (N 2 adsorption specific surface area)>
Measurement was performed with an Automatic Surface Area Analyzer manufactured by Mounttech using a helium carrier gas and degassing a 0.5 g sample at 200 ° C. for 20 minutes.
［実施例１］
＜ブラック着色剤分散液Ｂｋ１の調製＞
　プロペラ翼を備えた攪拌機の容器に、三菱カーボンブラック＃９６０（三菱化学社製、Ｎ２吸着比表面積２６０ｍ２／ｇ　ＤＢＰ（ジブチルフタレート）吸収量６９ｃｍ３／１００ｇ　揮発分１．５％）２０部、２０％ドデシルベンゼンスルホン酸ナトリウム水溶液（以下、２０％ＤＢＳ水溶液と略す）１部、非イオン界面活性剤（花王社製、エマルゲン１２０）４部、導電率が２μＳ／ｃｍのイオン交換水７５部を加えて予備分散して顔料プレミックス液を得た。プレミックス後の分散液中カーボンブラックの体積累積５０％径Ｄｖ５０は約９０μｍであった。上記プレミックス液を原料スラリーとして湿式ビーズミルに供給し、ワンパス分散を行った。なお、ステータの内径は１２０ｍｍφ、セパレータの径が６０ｍｍφ、分散用のメディアとして直径が５０μｍのジルコニアビーズ（真密度６．０ｇ／ｃｍ３）を用いた。ステータの有効内容積は約２リットルであり、メデイアの充填容積は１．４リットルとしたので、メディア充填率は７０％である。ロータの回転速度を一定（ロータ先端の周速が約１１ｍ／ｓｅｃ）として、供給口より前記プレミックススラリーを無脈動定量ポンプにより供給速度約４０リットル／ｈｒで供給し、所定粒度に達した時点で排出口より製品を取得した。なお、運転時にはジャケットから約１０℃の冷却水を循環させながら行い、ブラック着色剤分散液Ｂｋ１を得た。 [Example 1]
<Preparation of Black Colorant Dispersion Bk1>
The container stirrer with a propeller blade, Mitsubishi Carbon Black # 960 (manufactured by Mitsubishi Chemical Corporation, N 2 adsorption specific surface area 260m 2 / g DBP (dibutyl phthalate) absorption 69cm 3/100 g volatiles 1.5%) 20 parts 1 part of a 20% sodium dodecylbenzenesulfonate aqueous solution (hereinafter abbreviated as 20% DBS aqueous solution), 4 parts of a nonionic surfactant (Emalgen 120, manufactured by Kao Corporation), 75 parts of ion-exchanged water having a conductivity of 2 μS / cm And predispersed to obtain a pigment premix solution. The volume cumulative 50% diameter Dv50 of the carbon black in the dispersion after the premix was about 90 μm. The premix solution was supplied as a raw material slurry to a wet bead mill and subjected to one-pass dispersion. Note that zirconia beads (true density of 6.0 g / cm 3 ) having a diameter of 120 mmφ, a separator having a diameter of 60 mmφ, and a diameter of 50 μm were used as a dispersion medium. Since the effective internal volume of the stator is about 2 liters and the media filling volume is 1.4 liters, the media filling rate is 70%. When the rotational speed of the rotor is constant (the peripheral speed at the tip of the rotor is about 11 m / sec), the premix slurry is supplied from the supply port by a non-pulsating metering pump at a supply speed of about 40 liters / hr and reaches a predetermined particle size. The product was acquired from the outlet. In operation, cooling water at about 10 ° C. was circulated from the jacket to obtain a black colorant dispersion Bk1.
＜ワックス分散液Ａ１の調製＞
　エステルワックス　ニッサンエレクトールＷＥ－１０（日油社製、カタログ値融点６９℃、０．１％重量減少時間１９分）２９．８部、デカグリセリンデカベヘネート（酸価３．２ｍｇＫＯＨ／ｇ、水酸基価２７ｍｇＫＯＨ／ｇ）０．２４部、２０％ＤＢＳ水溶液２．７５部、脱塩水６７．２５部を９０℃に加熱して２０分間攪拌した。次いで、１００℃加熱下で、高圧乳化機を用いて３０ＭＰａの加圧条件で循環乳化を開始し、ナノトラックで粒子径を測定し中位径（Ｄ５０）が２４５ｎｍ以下になるまで分散してワックス分散液Ａ１を作製した。最終粒径（Ｄ５０）は、２３２ｎｍであった。 <Preparation of wax dispersion A1>
Ester wax Nissan Electol WE-10 (manufactured by NOF Corporation, catalog value melting point 69 ° C., 0.1% weight loss time 19 minutes) 29.8 parts, decaglycerin dekabehenate (acid value 3.2 mg KOH / g, Hydroxyl value 27 mg KOH / g) 0.24 parts, 20% DBS aqueous solution 2.75 parts, demineralized water 67.25 parts were heated to 90 ° C. and stirred for 20 minutes. Next, under 100 ° C. heating, circulation emulsification is started using a high-pressure emulsifier under a pressure of 30 MPa, the particle diameter is measured with Nanotrac, and dispersed until the median diameter (D50) is 245 nm or less. Dispersion A1 was produced. The final particle size (D50) was 232 nm.
＜重合体一次粒子分散液Ｂ１の調製＞
　攪拌装置（３枚翼）、加熱冷却装置、濃縮装置、及び各原料・助剤仕込み装置を備えた反応器にワックス分散液Ａ１　３６．３部、脱塩水２６０部を仕込み、攪拌しながら窒素気流下で９０℃に昇温した。
　その後、攪拌を続けたまま下記のモノマー類・乳化剤水溶液の混合物を３００分かけて添加した。このモノマー類・乳化剤水溶液の混合物を添加開始した時間を重合開始とし、下記の開始剤水溶液１を重合開始３０分後から２７０分かけて添加した。その後開始剤水溶液２を１２０分かけて添加した。その後、攪拌下で内温９０℃のまま６０分保持した。
［モノマー類］
　　スチレン　　　　　　　　　　　　　　　６９．１部
　　アクリル酸ブチル　　　　　　　　　　　３０．９部
　　アクリル酸　　　　　　　　　　　　　　１．５部
　　トリクロロブロモメタン　　　　　　　　１．０部
　　ヘキサンジオールジアクリレート　　　　０．５部
［乳化剤水溶液］
　　２０％ＤＢＳ水溶液　　　　　　　　　　１．０部
　　脱塩水　　　　　　　　　　　　　　　　６７．５部
［開始剤水溶液１］
　　８％過酸化水素水溶液　　　　　　　　　１５．５部
　　８％Ｌ－（＋）アスコルビン酸水溶液　　１５．５部
［開始剤水溶液２］
　　８％Ｌ－（＋）アスコルビン酸水溶液　　１４．２部
　重合反応終了後冷却し、乳白色の重合体一次粒子分散液Ｂ１を得た。ナノトラックを用いて測定した中位径（Ｄ５０）は２０３ｎｍだった。重量平均分子量（Ｍｗ）は４０３００だった。Ｔｇは３７℃だった。 <Preparation of polymer primary particle dispersion B1>
A reactor equipped with a stirrer (three blades), a heating / cooling device, a concentrating device, and a raw material / auxiliary charging device was charged with 36.3 parts of wax dispersion A1 and 260 parts of demineralized water, and a nitrogen stream while stirring. The temperature was raised to 90 ° C.
Then, the mixture of the following monomers and emulsifier aqueous solution was added over 300 minutes, continuing stirring. The time when the addition of the monomer / emulsifier aqueous solution started to be added was regarded as polymerization start, and the following initiator aqueous solution 1 was added over 270 minutes after 30 minutes from the start of polymerization. Thereafter, the initiator aqueous solution 2 was added over 120 minutes. Thereafter, the inner temperature was maintained at 90 ° C. for 60 minutes under stirring.
[Monomers]
Styrene 69.1 parts Butyl acrylate 30.9 parts Acrylic acid 1.5 parts Trichlorobromomethane 1.0 part Hexanediol diacrylate 0.5 part [Emulsifier aqueous solution]
20% DBS aqueous solution 1.0 part Demineralized water 67.5 parts [Initiator aqueous solution 1]
8% aqueous hydrogen peroxide solution 15.5 parts 8% L-(+) ascorbic acid aqueous solution 15.5 parts [initiator aqueous solution 2]
8% L-(+) ascorbic acid aqueous solution 14.2 parts After the completion of the polymerization reaction, the mixture was cooled to obtain a milky white primary polymer particle dispersion B1. The median diameter (D50) measured using the nanotrack was 203 nm. The weight average molecular weight (Mw) was 40300. Tg was 37 ° C.
＜ワックス分散液Ａ２の調製＞
　ニッサンエレクトールＷＥ－１０の代わりにニッサンエレクトールＷＥＰ－５（日油社製、カタログ値融点８２℃、０．１％重量減少時間５５分）を用いる以外はワックス分散液Ａ１と同様にして、ワックス分散液Ａ２を作製した。最終粒径（Ｄ５０）は、２３８ｎｍであった。 <Preparation of wax dispersion A2>
In the same manner as in the wax dispersion A1, except that Nissan Electol WEP-5 (manufactured by NOF Corporation, catalog value melting point 82 ° C., 0.1% weight reduction time 55 minutes) is used instead of Nissan Electol WE-10. A wax dispersion A2 was prepared. The final particle size (D50) was 238 nm.
＜重合体一次粒子分散液Ｂ２の調製＞
　ワックス分散液Ａ１をワックス分散液Ａ２に、モノマー類を以下のように変更した以外は重合体一次粒子分散液Ｂ１と同様の方法で、重合体一次粒子分散液Ｂ２を得た。ナノトラックを用いて測定した中位径（Ｄ５０）は２０５ｎｍだった。重量平均分子量（Ｍｗ）は３０４０００だった。Ｔｇは３８℃だった。
［モノマー類］
　　スチレン　　　　　　　　　　　　　　　６５．５部
　　アクリル酸ブチル　　　　　　　　　　　３４．５部
　　アクリル酸　　　　　　　　　　　　　　１．５部
　　トリクロロブロモメタン　　　　　　　　１．０部
　　ヘキサンジオールジアクリレート　　　　０．７部 <Preparation of polymer primary particle dispersion B2>
A polymer primary particle dispersion B2 was obtained in the same manner as the polymer primary particle dispersion B1, except that the wax dispersion A1 was changed to the wax dispersion A2 and the monomers were changed as follows. The median diameter (D50) measured using nanotrack was 205 nm. The weight average molecular weight (Mw) was 304000. Tg was 38 ° C.
[Monomers]
Styrene 65.5 parts Butyl acrylate 34.5 parts Acrylic acid 1.5 parts Trichlorobromomethane 1.0 part Hexanediol diacrylate 0.7 part
＜コア粒子分散液Ｃ１の調製＞
　攪拌装置、加熱冷却装置、及び各原料・助剤仕込み装置を備えた直径１２．５ｃｍの丸底ガラス混合器に重合体一次粒子分散液Ｂ１　８５部（固形分）、重量としては１２００ｇを投入した。直径１１ｃｍの撹拌棒で、２５０ｒｐｍで撹拌しながら内温を２５℃に調整した後、硫酸鉄７水和物の５％水溶液を０．５部（固形分）添加し、ブラック着色剤分散液Ｂｋ１　６．０部を５分かけて添加して均一に混合した後、０．５％硫酸アルミニウム水溶液０．３部（固形分）を１５分かけて添加した。更に１３１分かけて内温４４℃まで昇温した。ここでマルチサイザーを用いて体積中位粒径（Ｄｖ５０）を測定したところ、５．９５μｍであった。その後、重合体一次粒子分散液Ｂ２を１５部（固形分）、１２分かけて添加した後、３０分撹拌を継続した。その後、２０％ＤＢＳ水溶液４．０部を添加してから、３８分かけて８１℃まで昇温し、５０分保持し、その後３０℃まで冷却した。ここでマルチサイザーを用いて体積中位粒径（Ｄｖ５０）を測定したところ、７．２８μｍであった。 <Preparation of core particle dispersion C1>
85 parts (solid content) of the polymer primary particle dispersion B1 (solid content) and 1200 g as a weight were put into a 12.5 cm diameter round bottom glass mixer equipped with a stirrer, a heating / cooling device, and raw material / auxiliary charging devices. . After adjusting the internal temperature to 25 ° C. while stirring at 250 rpm with a stirring rod having a diameter of 11 cm, 0.5 part (solid content) of a 5% aqueous solution of iron sulfate heptahydrate was added, and black colorant dispersion Bk1 After adding 6.0 parts over 5 minutes and mixing uniformly, 0.3 part (solid content) of 0.5% aluminum sulfate aqueous solution was added over 15 minutes. The temperature was further increased to 44 ° C. over 131 minutes. Here, the volume median particle diameter (Dv50) was measured using a multisizer, and it was 5.95 μm. Thereafter, 15 parts (solid content) of polymer primary particle dispersion B2 was added over 12 minutes, and then stirring was continued for 30 minutes. Then, after adding 4.0 parts of 20% DBS aqueous solution, it heated up to 81 degreeC over 38 minutes, hold | maintained for 50 minutes, and cooled to 30 degreeC after that. Here, the volume median particle diameter (Dv50) was measured using a multisizer, and it was 7.28 μm.
　得られた分散液を抜き出し、５種Ｃ（東洋濾紙社製　Ｎｏ．５Ｃ）の濾紙を用いてアスピレーターにより吸引ろ過した。濾紙上に残ったケーキを攪拌機（プロペラ翼）を備えたステンレス容器に移し、電気伝導度が１μＳ／ｃｍのイオン交換水を加え攪拌することにより均一に分散させ、その後３０分間攪拌した。この工程をろ液の電気伝導度が１０μＳ／ｃｍになるまで繰り返した後、濾紙上に残ったケーキに電気伝導度が１μＳ／ｃｍのイオン交換水を分散液濃度２０％になるように加え攪拌することによりコア粒子分散液Ｃ１を得た。 The obtained dispersion was extracted and suction filtered with an aspirator using 5 types C (No. 5C manufactured by Toyo Roshi Kaisha, Ltd.) filter paper. The cake remaining on the filter paper was transferred to a stainless steel container equipped with a stirrer (propeller blade), and ion-exchanged water having an electric conductivity of 1 μS / cm was added and stirred uniformly, and then stirred for 30 minutes. This process is repeated until the electric conductivity of the filtrate reaches 10 μS / cm, and then ion-exchanged water having an electric conductivity of 1 μS / cm is added to the cake remaining on the filter paper so that the dispersion concentration becomes 20% and stirred. As a result, a core particle dispersion C1 was obtained.
＜トナー母粒子Ｆ１の製造＞
　攪拌装置、加熱冷却装置を備えた反応器にコア粒子分散液Ｃ１を７０部（固形分）、脱塩水３０部を仕込み、室温で攪拌しながらＰＡＳ－Ｊ－８１（ニットーボーメディカル社製、ジアリルジメチルアンモニウムクロリド・アクリルアミド共重合体２５％水溶液、カタログ値重量平均分子量（Ｍｗ）８７０，０００）０．１０７部（固形分）を添加し、室温で１５分撹拌した。その後、１Ｎ－ＮａＯＨ水溶液７．５ｇ／１Ｌ分散液体積の添加量で添加した後、１５分撹拌を継続した。スチレン・アクリル酸２－エチルヘキシル・２－アクリルアミド－２－メチルプロパンスルホン酸共重合体水分散液（２－アクリルアミド－２メチルプロパンスルホン酸２．７質量％含有、重合平均分子量（Ｍｗ）：１４，２００、Ｔｇ：７０℃、ナノトラックを用いて測定した中位径（Ｄ５０）：２４ｎｍ、固形分濃度：２０質量％）５部（固形分）を滴下し、室温で１５分撹拌した。その後、１Ｎ－ＨＮＯ３水溶液１０ｇ／１Ｌ分散液体積の添加量で滴下し、１５分撹拌を継続した後、分散液を内温４５℃まで昇温し、６０分保持した後、３０℃まで冷却した。洗浄前にマルチサイザーＩＩＩを用いて測定した体積中位粒径（Ｄｖ５０）は７．４４μｍであり、フロー式粒子分析装置で測定した平均円形度は０．９７２であった。 <Manufacture of toner mother particles F1>
A reactor equipped with a stirrer and a heating / cooling device was charged with 70 parts of the core particle dispersion C1 (solid content) and 30 parts of demineralized water, and PAS-J-81 (manufactured by Nitto Bo Medical, diallyldimethyl) while stirring at room temperature. Ammonium chloride / acrylamide copolymer 25% aqueous solution, catalog value weight average molecular weight (Mw) 870,000) 0.107 parts (solid content) was added, and the mixture was stirred at room temperature for 15 minutes. Thereafter, 1N-NaOH aqueous solution was added in an amount of 7.5 g / 1 L dispersion volume, and stirring was continued for 15 minutes. Styrene / acrylic acid 2-ethylhexyl-2-acrylamido-2-methylpropanesulfonic acid copolymer aqueous dispersion (containing 2.7% by weight of 2-acrylamido-2-methylpropanesulfonic acid, polymerization average molecular weight (Mw): 14, 200, Tg: 70 ° C., 5 parts (solid content) (medium diameter (D50): 24 nm, solid content concentration: 20% by mass) measured using Nanotrac) was added dropwise and stirred at room temperature for 15 minutes. Thereafter, the dispersion was added dropwise at an addition amount of 10 g / 1 L dispersion volume of 1N-HNO 3 aqueous solution, and after stirring for 15 minutes, the dispersion liquid was heated to an internal temperature of 45 ° C., held for 60 minutes, and then cooled to 30 ° C. did. The volume median particle size (Dv50) measured using Multisizer III before washing was 7.44 μm, and the average circularity measured by a flow particle analyzer was 0.972.
　得られた分散液を抜き出し、５種Ｃの濾紙を用いてアスピレーターにより吸引ろ過をした。濾紙上に残ったケーキを攪拌機（プロペラ翼）を備えたステンレス容器に移し、電気伝導度が１μＳ／ｃｍの脱塩水を加え５０ｒｐｍで攪拌することにより均一に分散させ、その後６０分間攪拌した。
　この工程を濾液の電気伝導度が２μＳ／ｃｍになるまで繰り返した後、得られたケーキを４０℃に設定された送風乾燥機内で４８時間乾燥することにより、トナー母粒子Ｆ１を得た。 The obtained dispersion was extracted and suction filtered with an aspirator using 5 types C filter paper. The cake remaining on the filter paper was transferred to a stainless steel container equipped with a stirrer (propeller blade), demineralized water having an electric conductivity of 1 μS / cm was added, and the mixture was uniformly dispersed by stirring at 50 rpm, and then stirred for 60 minutes.
This process was repeated until the electric conductivity of the filtrate reached 2 μS / cm, and then the obtained cake was dried for 48 hours in an air dryer set at 40 ° C., thereby obtaining toner mother particles F1.
＜現像用トナーＧ１の製造＞
　協立理工社製サンプルミルＫＲ－３内に、トナー母粒子Ｆ１を１００部投入し、続いて体積平均一次粒径０．１μｍでＰＤＭＳ（ポリジメチルシロキサン）処理されたシリカ微粒子０．８部、体積平均一次粒径０．１２μｍでＰＤＭＳ処理されたシリカ微粒子０．８部を添加し計１．５分間撹拌、混合した。その後、体積平均一次粒径０．０１４μｍでアルキルシラン処理されたチタニア微粒子０．３部、体積平均一次粒径０．０１５μｍでＰＤＭＳ処理されたシリカ微粒子０．４部、体積平均一次粒径０．０１μｍでＰＤＭＳ／アミノシラン処理されたシリカ微粒子０．２部を添加し計１．５分間撹拌、混合した。その後、体積一次粒径０．２μｍの樹脂ビーズ０．２部を１．５分間撹拌、混合し、篩別することにより現像用トナーＧ１を得た。 <Manufacture of developing toner G1>
In a sample mill KR-3 manufactured by Kyoritsu Riko Co., Ltd., 100 parts of toner mother particles F1 were charged, and then 0.8 parts of silica fine particles treated with PDMS (polydimethylsiloxane) with a volume average primary particle size of 0.1 μm, 0.8 parts of silica fine particles treated with PDMS at a volume average primary particle size of 0.12 μm were added and stirred and mixed for a total of 1.5 minutes. Thereafter, 0.3 part of titania fine particles treated with alkylsilane with a volume average primary particle size of 0.014 μm, 0.4 part of silica fine particles treated with PDMS with a volume average primary particle size of 0.015 μm, and a volume average primary particle size of 0.1 parts. 0.2 parts of silica fine particles treated with PDMS / aminosilane at 01 μm were added and stirred and mixed for a total of 1.5 minutes. Thereafter, 0.2 parts of resin beads having a volume primary particle size of 0.2 μm were stirred for 1.5 minutes, mixed and sieved to obtain a developing toner G1.
［実施例２］
＜ブラック着色剤分散液Ｂｋ２の調製＞
　分散剤として、非イオン界面活性剤（花王社製、エマルゲン１２０）の代わりに非イオン界面活性剤（花王社製、エマルゲンＡ９０）を使用し、２０％ＤＢＳ水溶液を使用しないこと以外は、ブラック着色剤分散液Ｂｋ１と同様の方法でブラック着色剤分散液Ｂｋ２を得た。 [Example 2]
<Preparation of Black Colorant Dispersion Bk2>
As a dispersant, a non-ionic surfactant (Emogen A90 manufactured by Kao Co., Ltd.) is used instead of a nonionic surfactant (Emogen A120 manufactured by Kao Co., Ltd.), and the coloring is black except that a 20% DBS aqueous solution is not used. A black colorant dispersion Bk2 was obtained in the same manner as the agent dispersion Bk1.
＜コア粒子分散液Ｃ２の調製＞
　ブラック着色剤分散液Ｂｋ１のかわりにブラック着色剤分散液Ｂｋ２を使用する以外は、コア粒子分散液Ｃ１と同様の方法でコア粒子分散液Ｃ２を得た。 <Preparation of core particle dispersion C2>
A core particle dispersion C2 was obtained in the same manner as the core particle dispersion C1, except that the black colorant dispersion Bk2 was used instead of the black colorant dispersion Bk1.
＜トナー母粒子Ｆ２の製造＞
　コア粒子分散液Ｃ１のかわりにコア粒子分散液Ｃ２を使用する以外は、トナー母粒子Ｆ１と同様の方法でトナー母粒子Ｆ２を得た。
　洗浄前にマルチサイザーＩＩＩを用いて測定した体積中位粒径（Ｄｖ５０）は８．７６μｍであり、フロー式粒子分析装置で測定した平均円形度は０．９６７であった。 <Manufacture of toner mother particles F2>
Toner base particles F2 were obtained in the same manner as toner base particles F1, except that core particle dispersion C2 was used instead of core particle dispersion C1.
The volume median particle diameter (Dv50) measured using Multisizer III before washing was 8.76 μm, and the average circularity measured by a flow particle analyzer was 0.967.
＜現像用トナーＧ２の製造＞
　トナー母粒子Ｆ１のかわりにトナー母粒子Ｆ２を使用する以外は、現像用トナーＧ１と同様の方法で現像用トナーＧ２を得た。 <Manufacture of developing toner G2>
A developing toner G2 was obtained in the same manner as the developing toner G1, except that the toner base particles F2 were used instead of the toner base particles F1.
［比較例１］
＜ブラック着色剤分散液Ｂｋ３の調製＞
　カーボンブラックとして、＃９６０の代わりにリーガル３３０Ｒ（キャボット社製、Ｎ２吸着比表面積８８ｍ２／ｇ　ＤＢＰ吸収量７０ｃｍ３／１００ｇ）を使用した以外はブラック着色剤分散液Ｂｋ１と同様の方法でブラック着色剤分散液Ｂｋ３を得た。 [Comparative Example 1]
<Preparation of Black Colorant Dispersion Bk3>
Black as the carbon black, REGAL 330R (Cabot Corporation, N 2 adsorption specific surface area 88m 2 / g DBP absorption 70cm 3/100 g) instead of # 960 in the same manner as the black colorant dispersion Bk1 except using A colorant dispersion Bk3 was obtained.
＜コア粒子分散液Ｃ３の調製＞
　攪拌装置、加熱冷却装置、及び各原料・助剤仕込み装置を備えた直径１２．５ｃｍの丸底ガラス混合器に重合体一次粒子分散液Ｂ１　８５部（固形分）、重量としては１２００ｇを投入した。直径１１ｃｍの撹拌棒で、３７０ｒｐｍで撹拌しながら内温を１０℃に調整した後、硫酸鉄７水和物の５％水溶液を０．５部（固形分）添加、ブラック着色剤分散液Ｂｋ３　６．０部を５分かけて添加して均一に混合した後、０．５％硫酸アルミニウム水溶液０．０５部（固形分）を１５分かけて添加した。更に１８２分かけて内温４３．４℃まで昇温した。ここでマルチサイザーを用いて体積中位粒径（Ｄｖ５０）を測定したところ、５．４９μｍであった。その後、重合体一次粒子分散液Ｂ２を１５部（固形分）、１２分かけて添加した後、３０分撹拌を継続した。その後、２０％ＤＢＳ水溶液４．０部を添加してから、４９分かけて８１℃まで昇温し、５０分保持し、その後３０℃まで冷却した。ここでマルチサイザーを用いて体積中位粒径（Ｄｖ５０）を測定したところ、６．９９μｍであった。 <Preparation of core particle dispersion C3>
85 parts (solid content) of the polymer primary particle dispersion B1 (solid content) and 1200 g as a weight were put into a 12.5 cm diameter round bottom glass mixer equipped with a stirrer, a heating / cooling device, and raw material / auxiliary charging devices. . After adjusting the internal temperature to 10 ° C. while stirring at 370 rpm with a stirring rod having a diameter of 11 cm, 0.5 part (solid content) of 5% aqueous solution of iron sulfate heptahydrate was added, and black colorant dispersion Bk3 6 After adding 0.0 part over 5 minutes and mixing uniformly, 0.05 part (solid content) of 0.5% aluminum sulfate aqueous solution was added over 15 minutes. The temperature was further increased to 43.4 ° C. over 182 minutes. Here, the volume-median particle size (Dv50) was measured using a multisizer and found to be 5.49 μm. Thereafter, 15 parts (solid content) of polymer primary particle dispersion B2 was added over 12 minutes, and then stirring was continued for 30 minutes. Then, after adding 4.0 parts of 20% DBS aqueous solution, it heated up to 81 degreeC over 49 minutes, hold | maintained for 50 minutes, and cooled to 30 degreeC after that. Here, the volume-median particle size (Dv50) was measured using a multisizer and found to be 6.99 μm.
＜トナー母粒子Ｆ３の製造＞
　コア粒子分散液Ｃ１のかわりにコア粒子分散液Ｃ３を使用する以外は、トナー母粒子Ｆ１と同様の方法でトナー母粒子Ｆ３を得た。
　洗浄前にマルチサイザーＩＩＩを用いて測定した体積中位粒径（Ｄｖ５０）は７．０２μｍであり、フロー式粒子分析装置で測定した平均円形度は０．９７５であった。 <Manufacture of toner mother particles F3>
Toner base particles F3 were obtained in the same manner as toner base particles F1, except that core particle dispersion C3 was used instead of core particle dispersion C1.
The volume median particle size (Dv50) measured using Multisizer III before washing was 7.02 μm, and the average circularity measured by a flow particle analyzer was 0.975.
＜現像用トナーＧ３の製造＞
　トナー母粒子Ｆ１のかわりにトナー母粒子Ｆ３を使用する以外は、現像用トナーＧ１と同様の方法で現像用トナーＧ３を得た。 <Manufacture of developing toner G3>
A developing toner G3 was obtained in the same manner as the developing toner G1, except that the toner base particles F3 were used instead of the toner base particles F1.
［比較例２］
＜ブラック着色剤分散液Ｂｋ４の調製＞
　カーボンブラックとして、＃９６０の代わりに＃４４（三菱化学社製、Ｎ２吸着比表面積１１０ｍ２／ｇ　ＤＢＰ吸収量７８ｃｍ３／１００ｇ　揮発分０．８％）を使用した以外は、ブラック着色剤分散液Ｂｋ１と同様の方法でブラック着色剤分散液Ｂｋ４を得た。 [Comparative Example 2]
<Preparation of black colorant dispersion Bk4>
As the carbon black, except for using a # 44 instead of # 960 (manufactured by Mitsubishi Chemical Corporation, N 2 adsorption specific surface area 110m 2 / g DBP absorption 78cm 3/100 g volatiles 0.8%), black colorant dispersion A black colorant dispersion liquid Bk4 was obtained in the same manner as liquid Bk1.
＜コア粒子分散液Ｃ４の調製＞
　ブラック着色剤分散液Ｂｋ３のかわりにブラック着色剤分散液Ｂｋ４を使用する以外は、コア粒子分散液Ｃ３と同様の方法でコア粒子分散液Ｃ４を得た。 <Preparation of core particle dispersion C4>
A core particle dispersion C4 was obtained in the same manner as the core particle dispersion C3, except that the black colorant dispersion Bk4 was used instead of the black colorant dispersion Bk3.
＜トナー母粒子Ｆ４の製造＞
　コア粒子分散液Ｃ１のかわりにコア粒子分散液Ｃ４を使用する以外は、トナー母粒子Ｆ１と同様の方法でトナー母粒子Ｆ４を得た。
　洗浄前にマルチサイザーＩＩＩを用いて測定した体積中位粒径（Ｄｖ５０）は７．１５μｍであり、フロー式粒子分析装置で測定した平均円形度は０．９７４であった。 <Manufacture of toner mother particles F4>
Toner base particles F4 were obtained in the same manner as toner base particles F1, except that core particle dispersion C4 was used instead of core particle dispersion C1.
The volume median particle size (Dv50) measured using Multisizer III before washing was 7.15 μm, and the average circularity measured by a flow particle analyzer was 0.974.
＜現像用トナーＧ４の製造＞
　トナー母粒子Ｆ１のかわりにトナー母粒子Ｆ４を使用する以外は、現像用トナーＧ１と同様の方法で現像用トナーＧ４を得た。 <Manufacture of developing toner G4>
A developing toner G4 was obtained in the same manner as the developing toner G1, except that the toner base particles F4 were used instead of the toner base particles F1.
［比較例３］
＜ブラック着色剤分散液Ｂｋ５の調製＞
　カーボンブラックとして、＃９６０の代わりにＭＡ０７７（三菱化学社製、Ｎ２吸着比表面積１３０ｍ２／ｇ　ＤＢＰ吸収量６８ｃｍ３／１００ｇ　揮発分２．８％）を使用した以外は、ブラック着色剤分散液Ｂｋ１と同様の方法でブラック着色剤分散液Ｂｋ５を得た。 [Comparative Example 3]
<Preparation of black colorant dispersion Bk5>
As the carbon black, except using MA077 instead of # 960 (manufactured by Mitsubishi Chemical Corporation, N 2 adsorption specific surface area 130m 2 / g DBP absorption 68cm 3/100 g volatiles 2.8%), black colorant dispersion A black colorant dispersion Bk5 was obtained in the same manner as Bk1.
＜コア粒子分散液Ｃ５の調製＞
　ブラック着色剤分散液Ｂｋ１のかわりにブラック着色剤分散液Ｂｋ５を使用する以外は、コア粒子分散液Ｃ３と同様の方法でコア粒子分散液Ｃ５を得た。 <Preparation of core particle dispersion C5>
A core particle dispersion C5 was obtained in the same manner as the core particle dispersion C3, except that the black colorant dispersion Bk5 was used instead of the black colorant dispersion Bk1.
＜トナー母粒子Ｆ５の製造＞
　コア粒子分散液Ｃ１のかわりにコア粒子分散液Ｃ５を使用する以外は、トナー母粒子Ｆ１と同様の方法でトナー母粒子Ｆ５を得た。
　洗浄前にマルチサイザーＩＩＩを用いて測定した体積中位粒径（Ｄｖ５０）は７．４５μｍであり、フロー式粒子分析装置で測定した平均円形度は０．９７１であった。 <Manufacture of toner mother particles F5>
Toner base particles F5 were obtained in the same manner as toner base particles F1, except that core particle dispersion C5 was used instead of core particle dispersion C1.
The volume median particle size (Dv50) measured using Multisizer III before washing was 7.45 μm, and the average circularity measured by a flow particle analyzer was 0.971.
＜現像用トナーＧ５の製造＞
　トナー母粒子Ｆ１のかわりにトナー母粒子Ｆ５を使用する以外は、現像用トナーＧ１と同様の方法で現像用トナーＧ５を得た。 <Manufacture of developing toner G5>
A developing toner G5 was obtained in the same manner as the developing toner G1, except that the toner base particles F5 were used instead of the toner base particles F1.
＜ＴＥＭ観察＞
　（株）日立製作所製のＨＩＴＡＣＨＩ　Ｈ－７５００形透過電子顕微鏡を用いて観察した。
　トナーをショ糖溶液に混合し、２ｍｍ径の試料台にのせて、液体窒素で凍結した後、クライオウルトラミクロトームを用いてダイヤモンドナイフで０．４μｍ超薄切片を作製した。その切片をメッシュにのせて、倍率５００００で、ＴＥＭ観察を行なった。結果を図１～５に示す。図１は現像用トナーＧ１のＴＥＭ写真、図２は現像用トナーＧ２のＴＥＭ写真、図３は現像用トナーＧ３のＴＥＭ写真、図４は現像用トナーＧ４のＴＥＭ写真、図５は現像用トナーＧ５のＴＥＭ写真である。 <TEM observation>
Observation was performed using a Hitachi Hitachi 7500 transmission electron microscope manufactured by Hitachi, Ltd.
The toner was mixed with a sucrose solution, placed on a 2 mm diameter sample stage and frozen with liquid nitrogen, and then a 0.4 μm ultrathin section was prepared with a diamond knife using a cryoultramicrotome. The section was placed on a mesh and subjected to TEM observation at a magnification of 50000. The results are shown in FIGS. FIG. 1 is a TEM photograph of the developing toner G1, FIG. 2 is a TEM photograph of the developing toner G2, FIG. 3 is a TEM photograph of the developing toner G3, FIG. 4 is a TEM photograph of the developing toner G4, and FIG. It is a TEM photograph of G5.
＜ＴＥＭ写真の画像処理＞
　トナー断面の５０ＫのＴＥＭ写真を以下の手順で画像処理し、ブラック顔料粒子の面積データを得た。
　画像処理ソフト　Ｗｉｎ　ＲＯＯＦ　５．７．１　（ＭＩＴＡＮＩ　Ｃｏｒｐｏｒａｔｉｏｎ）を用いた。
　画像処理の強調を行いガンマ値を０．５に補正した。
　閾値６０、１００に設定して、２つの閾値による２値化処理を行なった。
　自動計測により、ＴＥＭ写真中のブラック顔料の面積、周囲長を測定した。
　測定値のうち、１ピクセルのデータはノイズとみなして消去した。
　残りのデータから面積の平均値、標準偏差値、最大値、および平均周囲長を求めた。
　１サンプルにつき３枚のＴＥＭ写真について同様の画像処理を行ない、平均値を求めた。結果を表１に示した。 <Image processing of TEM photographs>
A 50K TEM photograph of the cross section of the toner was subjected to image processing according to the following procedure to obtain area data of black pigment particles.
Image processing software Win ROOF 5.7.1 (MITANI Corporation) was used.
Image processing was enhanced and the gamma value was corrected to 0.5.
The threshold values 60 and 100 were set, and binarization processing with two threshold values was performed.
The area and perimeter of the black pigment in the TEM photograph were measured by automatic measurement.
Of the measured values, 1 pixel data was considered as noise and erased.
The average value, standard deviation value, maximum value, and average perimeter of the area were obtained from the remaining data.
Similar image processing was performed on three TEM photographs per sample, and an average value was obtained. The results are shown in Table 1.
＜耐ブロッキング性＞
　現像用トナー１０ｇを内径３ｃｍ、高さ６ｃｍの円筒形の容器に入れ、２０ｇの荷重をのせ、温度５０℃、湿度５５％の環境下に４８時間放置した後、トナーを容器から取り出し、上から荷重をかけることで凝集の程度を確認した。判定は以下の通りである。結果を表１に示した。
　　〇：１００ｇ未満の荷重で崩れる。
　　△：２００ｇ未満の荷重で崩れる。
　　×：凝集しており、２００ｇ以上の荷重をかけないと崩れない。 <Blocking resistance>
10 g of developing toner is put into a cylindrical container having an inner diameter of 3 cm and a height of 6 cm, a load of 20 g is put on it, and left in an environment of a temperature of 50 ° C. and a humidity of 55% for 48 hours. The degree of aggregation was confirmed by applying a load. The determination is as follows. The results are shown in Table 1.
○: It collapses with a load of less than 100 g.
Δ: Breaks with a load of less than 200 g.
X: Aggregates and does not collapse unless a load of 200 g or more is applied.
＜定着試験＞
　未定着のトナー像を担持した記録紙（（株）沖データ社製エクセレントホワイト）を用意し、熱ロール定着方式の定着機を用い、以下のように試験した。
　定着機は、ローラー直径２７ｍｍ、ニップ幅９ｍｍ、定着速度２２９ｍｍ／ｓｅｃであり、上ローラーにヒーターを有し、ローラー表面がＰＦＡ（テトラフルオロエチレン－パーフルオロアルキルビニルエーテル共重合体）で構成されており、シリコーンオイルは塗布されていない。 <Fixing test>
A recording paper carrying an unfixed toner image (Excellent White manufactured by Oki Data Corporation) was prepared and tested as follows using a heat roll fixing type fixing machine.
The fixing machine has a roller diameter of 27 mm, a nip width of 9 mm, a fixing speed of 229 mm / sec, a heater on the upper roller, and the roller surface is composed of PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer). Silicone oil is not applied.
＜耐ホットオフセット（ＨＯＳ）性試験＞
　ローラーの表面温度を１７５℃から５℃刻みで昇温しながら、付着量約１．０ｍｇ／ｃｍ２の未定着のトナー像を担持した記録紙を定着ニップ部に搬送し、各定着温度での画像を得た。以下のように耐オフセット性を判定した。結果を表１に示した。
　　○：２０５℃でオフセットしない
　　△：２００℃でオフセットしない
　　×：１９５℃でオフセットする <Hot offset resistance test>
While increasing the surface temperature of the roller from 175 ° C. in increments of 5 ° C., the recording paper carrying the unfixed toner image with an adhesion amount of about 1.0 mg / cm 2 is conveyed to the fixing nip portion, and at each fixing temperature. I got an image. The offset resistance was determined as follows. The results are shown in Table 1.
○: No offset at 205 ° C Δ: No offset at 200 ° C ×: Offset at 195 ° C
＜印字色相の測定＞
　ローラーの表面温度を１７０℃に調整し、付着量約０．４ｍｇ／ｃｍ２の未定着のトナー像を担持した記録紙を定着ニップ部に搬送し、定着画像を得た。
　Ｘ－ｒｉｔｅ９３８（Ｘ－ｒｉｔｅ社）を用いて、定着画像の固定位置で印字濃度を測定した。３点測定し、平均値を求めた。判定は以下のとおりである。結果を表１に示した。
　　〇：Ｌ値が１５．０以下
　　×：Ｌ値が１５．０よりも大きい <Measurement of printing hue>
The surface temperature of the roller was adjusted to 170 ° C., and a recording paper carrying an unfixed toner image having an adhesion amount of about 0.4 mg / cm 2 was conveyed to the fixing nip portion to obtain a fixed image.
The print density was measured at a fixed position of the fixed image using X-rite 938 (X-rite). Three points were measured and the average value was determined. The determination is as follows. The results are shown in Table 1.
◯: L value is 15.0 or less ×: L value is larger than 15.0
＜紛体色相の測定＞
　各トナー粒子を所定の容器に３ｇ充填し、分光光度計ＳＺ　Ｏｐｔｉｃａｌ　Ｓｅｎｓｏｒ（（株）日本電色）を用いて測定した。判定は以下のとおりである。結果を表１に示した。
　　〇：Ｌ値が１２．０以下
　　×：Ｌ値が１２．０よりも大きい <Measurement of powder hue>
Each toner particle was filled in 3 g in a predetermined container and measured using a spectrophotometer SZ Optical Sensor (Nippon Denshoku Co., Ltd.). The determination is as follows. The results are shown in Table 1.
◯: L value is 12.0 or less ×: L value is larger than 12.0
＜帯電性＞
　キャリアとして関東電化工業（株）製ＦＭＵ６５を使用し、現像用トナーとキャリアとの質量比１：２４の混合物１０ｇをガラス製サンプル瓶に入れ、タイテック社製ＮＲ－１にて３０ｍｉｎ間振盪した後、そのうち０．１ｇを用いて東芝ケミカル（株）製ブローオフ帯電量測定装置を用い、吸引ブローオフ法にて帯電量を測定した。
　　ブロー条件：０．０５ｋｇｆ／ｃｍ２×３秒
　　吸引圧力　：３５０～４００ｍｍＨ２Ｏ
　　スクリーン：４００メッシュ
　帯電量を以下のように判定した。結果を表１に示した。
　　〇：帯電値が１５．０μＣ／ｇ以下
　　×：帯電値が１５．０μＣ／ｇよりも大きい <Chargeability>
FMU65 manufactured by Kanto Denka Kogyo Co., Ltd. was used as the carrier, and 10 g of a mixture of developing toner and carrier in a mass ratio of 1:24 was placed in a glass sample bottle and shaken with NR-1 manufactured by Tytec for 30 minutes. Of these, 0.1 g was used to measure the charge amount by a suction blow-off method using a blow-off charge amount measuring device manufactured by Toshiba Chemical Corporation.
Blowing conditions: 0.05 kgf / cm 2 × 3 seconds Suction pressure: 350 to 400 mmH 2 O
Screen: 400 mesh The charge amount was determined as follows. The results are shown in Table 1.
◯: Charge value is 15.0 μC / g or less ×: Charge value is greater than 15.0 μC / g
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　本発明を詳細にまた特定の実施形態を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。本出願は、２０１５年３月１７日出願の日本特許出願（特願２０１５－０５３４２４）に基づくものであり、その内容はここに参照として取り込まれる。 Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on Mar. 17, 2015 (Japanese Patent Application No. 2015-053424), the contents of which are incorporated herein by reference.

Claims (7)

  1. 　ブラック顔料及び結着樹脂を含有する静電荷像現像用ブラックトナーであって、
    　トナー断面の倍率５万倍のＴＥＭ画像におけるブラック顔料粒子の面積の平均値が、１．０×１０－６μｍ２以上１．０×１０－４μｍ２以下である静電荷像現像用ブラックトナー。     A black toner for developing an electrostatic image containing a black pigment and a binder resin,
    Black toner for developing electrostatic images having an average area of black pigment particles in a TEM image with a magnification of 50,000 times in the cross section of the toner of 1.0 × 10 −6 μm 2 or more and 1.0 × 10 −4 μm 2 or less. .
  2. 　前記ブラック顔料粒子の面積の最大値が５．０×１０－３μｍ２以下である、請求項１に記載の静電荷像現像用ブラックトナー。 The black toner for developing electrostatic images according to claim 1, wherein the maximum value of the area of the black pigment particles is 5.0 × 10 −3 μm 2 or less.
  3. 　前記ブラック顔料粒子の面積の標準偏差値が１．０×１０－３μｍ２以下である、請求項２記載の静電荷像現像用ブラックトナー。 The black toner for developing electrostatic images according to claim 2, wherein the standard deviation value of the area of the black pigment particles is 1.0 × 10 −3 μm 2 or less.
  4. 　ブラック顔料及び結着樹脂を含有する静電荷像現像用ブラックトナーであって、
    　トナー断面の倍率５万倍のＴＥＭ画像におけるブラック顔料粒子の周囲長が、３．０×１０－２μｍ以下である静電荷像現像用ブラックトナー。     A black toner for developing an electrostatic image containing a black pigment and a binder resin,
    A black toner for developing an electrostatic charge image, in which a peripheral length of black pigment particles in a TEM image having a magnification of 50,000 times in a cross section of the toner is 3.0 × 10 −2 μm or less
  5. 　前記ブラック顔料粒子の面積の最大値が５．０×１０－３μｍ２以下である、請求項４に記載の静電荷像現像用ブラックトナー。 The electrostatic charge image developing black toner according to claim 4, wherein the maximum area of the black pigment particles is 5.0 × 10 −3 μm 2 or less.
  6. 　前記ブラック顔料粒子の面積の標準偏差値が１．０×１０－３μｍ２以下である、請求項５記載の静電荷像現像用ブラックトナー。 6. The black toner for developing electrostatic images according to claim 5, wherein the standard deviation value of the area of the black pigment particles is 1.0 × 10 −3 μm 2 or less.
  7. 　前記ＴＥＭ画像は、画像処理ソフト　Ｗｉｎ　ＲＯＯＦ　５．７．１　（ＭＩＴＡＮＩ　Ｃｏｒｐｏｒａｔｉｏｎ）を用いて、ガンマ値を０．５に補正し、閾値６０、１００に設定した後、２つの閾値による２値化処理を行なったものである、請求項１～６のいずれか１項に記載の静電荷像現像用ブラックトナー。 The TEM image is binarized by two threshold values after correcting the gamma value to 0.5 using image processing software Win ROOF 5.7.1 (MITANI Corporation) and setting the threshold values to 60 and 100. The black toner for developing an electrostatic charge image according to any one of claims 1 to 6, wherein
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