JP6541481B2 - Toner and manufacturing method thereof - Google Patents

Description

  The present invention relates to a toner, and more particularly, to a toner used when forming a toner image in an image forming method such as electrophotography and electrostatic printing or an image forming method using a toner jet method, and a manufacturing method thereof.

  Conventionally, studies for improving the triboelectric charging characteristics of toner have been actively conducted. In particular, in recent years, a proposal has been made to use a resin having a charge control function (charge control resin) as a raw material for toner, in consideration of environmental considerations, requirements for more stable chargeability, manufacturing costs, etc. There is. Patent Documents 1 and 2 propose a toner in which a resin containing a sulfonic acid group is used as a charge control resin and is internally added to the toner. According to this method, it is supposed that a toner having a stable charging characteristic can be obtained with a small change in the amount of charge due to environmental changes. On the other hand, Patent Document 3 proposes a toner in which a charge control resin is present on the outermost surface of the toner as a method of enhancing the effect of the charge control function.

JP-A-11-327208 Unexamined-Japanese-Patent No. 03-56974 JP 2005-258075 A

  However, when the charge function is concentrated on the outermost surface of the toner, the hydrophilic charge control agent is strongly affected by moisture under high humidity, and it is necessary to improve the stability due to the environmental difference. Then, when the present inventors intensively studied, it became clear that there is room for improvement in the stability of the charge when printing out a large number of sheets, in particular, the stability of the charge amount under high temperature and high humidity. The

  The present invention has been made in view of the above problems, and an object thereof is a toner excellent in the stability of charging when printing out a large number of sheets, in particular, the stability of charging amount under high temperature and high humidity, and the toner It is in providing a manufacturing method.

  As a result of intensive studies, the present inventors have found that the above-described problems can be solved by the toner of the present invention, and the present invention has been achieved.

That is, the present invention is a toner having toner particles having toner base particles having a binder resin and a colorant, and resin particles provided on the surface of the toner base particles.
The resin particles have a resin A having a unit a derived from 2-acrylamido-2-methylpropane sulfonic acid and a unit b derived from an electron donating compound having a polymerizable unsaturated functional group,
In the resin A, Ri molar ratio n _a / n _b is 1.0 to 10.0 der following said unit a and the unit b,
The present invention relates to a toner characterized in that the electron donating compound is vinylpyridine .

The present invention is also a method of producing a toner for producing the above toner, wherein
The present invention relates to a method for producing a toner in which the resin fine particles are resin fine particles produced in an aqueous medium.

  According to the present invention, it is possible to provide a toner excellent in the stability of charging when printing out a large number of sheets, in particular, the stability of the charging amount under high temperature and high humidity, and a method for producing the same.

It is a figure which shows the structural example of the apparatus used for the measurement of the triboelectric charge of the toner manufactured by the Example or the comparative example. FIG. 6 is a schematic configuration view showing an example of a process cartridge and an image forming apparatus used when performing image formation evaluation of toner manufactured in an embodiment or a comparative example.

The toner of the present invention has toner particles having toner base particles having a binder resin and a colorant, and resin particles provided on the surface of the toner base particles. In the present invention, the resin particles have a resin A having a unit a derived from 2-acrylamido-2-methylpropane sulfonic acid and a unit b derived from an electron donating compound having a polymerizable unsaturated functional group. There is. In the present invention, the resin A, the molar ratio n _a / n _b of the unit a and the unit b is 1.0 to 10.0.

  The present inventors have found that the toner of the present invention having the above-described configuration is excellent in charge stability when printing out a large number of sheets, in particular, the stability of the charge amount under high temperature and high humidity. The present invention has been achieved. Furthermore, by causing resin particles having the resin A to be present intensively on the surface of the toner base particles, the toner of the present invention exerts the charge expression effect by the unit a and the water absorption suppressing effect by the unit b, under high temperature and high humidity. It was found that the reduction of the charge amount in the case of the above was excellent and the stability was excellent.

  Although the mechanism by which the toner of the present invention is excellent in the stability of the charge amount under high temperature and high humidity is not clear, the present inventors think as follows.

  Although the unit a derived from 2-acrylamido-2-methylpropanesulfonic acid in the polymer constituting the resin A exerts an effect on charge generation and charge accumulation, it is easily hydrated because of the sulfonic acid structure. In particular, since the generation and accumulation of electric charge can be suppressed by containing water under high temperature and high humidity, a difference easily occurs between the charge amount under normal temperature and normal humidity and under high temperature and high humidity.

  On the other hand, in the resin A, since a unit a derived from 2-acrylamido-2-methylpropanesulfonic acid and a unit b derived from an electron donor compound having a polymerizable unsaturated functional group coexist, an ion complex is generated. The presence as an ion complex makes it difficult to absorb water as compared to the case where a unit of 2-acrylamido-2-methylpropanesulfonic acid is present alone. It is considered that the generation of the ion complex suppresses the water absorption particularly under high temperature and high humidity, so that a toner having excellent charge stability under high temperature and high humidity can be obtained.

In the present invention, 2-acrylamido-2-methylpropane and unit a derived from sulfonic acid-polymerizable unsaturated molar ratio of the units b derived from an electron-donating compound having a functional group (n _a / n _b) is 1. It is essential that it is 0 or more and 10.0 or less.

  When this molar ratio is less than 1.0, the number of units b is larger than that of units a, and charge generation and accumulation are suppressed. On the other hand, if this molar ratio is larger than 10.0, the amount of unit b required for the generation of ion complex decreases, so that it becomes easy to absorb water under high temperature and high humidity, and the charge amount decreases under high temperature and high humidity May occur.

  In the toner of the present invention, the resin A contained in the resin particles is a polymer including the unit a and the unit b.

  The electron donating compound having a polymerizable unsaturated functional group that can be used in the present invention is not particularly limited as long as it is an electron donating compound having a polymerizable unsaturated functional group and having an unshared electron pair. . The polymerizable unsaturated functional group is not particularly limited as long as it is a substituent that causes a polymerization reaction to occur by a radical or ion (cation, anion), but is preferably a vinyl group. Further, in the present invention, as the electron donor compound, primary to tertiary amines, imines, primary to tertiary amides, imides, aromatic imides (such as pyridine), thiols, thioesters, thionyls, etc. are preferable. It is a compound selected from sulfide and sulfoxide.

  Above all, as electron donating compounds which can be used in the present invention, vinylpyridines such as 4-vinylpyridine and 2-vinylpyridine or derivatives thereof, N-vinylpyrrolidones such as N-vinyl-2-pyrrolidone and derivatives thereof, 4 Acryloyl morpholine such as acryloyl morpholine or a derivative thereof, and the like, and the like, with preference given to vinyl pyridine.

  The specific structure of the polymer constituting the resin A in the toner of the present invention is not particularly limited. For example, vinyl polymers, polyester polymers, polyamide polymers, polyurethane polymers, polyether polymers and the like can be mentioned. It is preferable that the polymer is a vinyl polymer in consideration of easiness of production when manufacturing a charge control resin described later, cost merit and the like.

  In the toner of the present invention, when the resin A is a vinyl polymer, for example, a vinyl copolymer resin, the resin A is a unit other than the unit a and the unit b, for example, a unit derived from a vinyl monomer. (Hereafter, it may be called unit c.) May be included. The vinyl-based monomer from which the unit c is derived is not particularly limited, and specifically, the following compounds can be mentioned. That is, styrene and derivatives thereof such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene and α-methylstyrene; ethylene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; vinyl chloride, chloride Vinyl halides such as vinylidene, vinyl bromide and vinyl fluoride; Vinyl esters of carboxylic acid such as vinyl acetate, vinyl propionate and vinyl benzoate; n-butyl acrylate and acrylic acid such as 2-ethylhexyl acrylate Esters; Methacrylates obtained by converting “acrylic” of the acrylic esters into methacrylic acid; methacrylic acid amino esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; vinyl resins such as vinyl methyl ether and vinyl ethyl ether Vinyl ketones such as vinyl methyl ketone; ethers acrylate; methacrylic acid. It is more preferable that it is a unit derived from styrene among the vinyl type monomers mentioned above. This is because when the resin A is made into fine particles, the resin A itself has a self-emulsifiable property by combining the part containing the unit a which is hydrophilic and the hydrophobic styrene-derived unit, and the production of the fine particles is It is because it becomes easy.

  As a polymerization initiator which can be used when polymerizing the above-mentioned polymerizable monomer component, various things, such as a peroxide system polymerization initiator and an azo system polymerization initiator, can be used. As a peroxide type polymerization initiator which can be used, an organic type thing and an inorganic type thing can be mentioned. Examples of organic peroxide-based polymerization initiators include peroxy esters, peroxy dicarbonates, dialkyl peroxides, peroxy ketals, ketone peroxides, hydroperoxides, and diacyl peroxides. Examples of inorganic peroxide-based polymerization initiators include persulfates and hydrogen peroxide.

  As a peroxide type polymerization initiator which can be used, specifically, t-butyl peroxy acetate, t-butyl peroxy pivalate, t-butyl peroxy isobutyrate, t-hexyl peroxy acetate, t-hexyl Peroxy esters such as peroxypivalate, t-hexylperoxyisobutyrate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, etc .; diacyl peroxides such as benzoyl peroxide; Peroxydicarbonates such as oxydicarbonates; peroxyketals such as 1,1-di-t-hexylperoxycyclohexane; dialkyl peroxides such as di-t-butyl peroxide; t-butylperoxyallyl mono Boneto, and the like.

  Moreover, as an azo polymerization initiator which can be used, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane- 1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile, dimethyl-2,2'-azobis (2-methyl propionate), etc. It is illustrated.

  In addition, two or more types of these polymerization initiators can also be used simultaneously as needed. The amount of the polymerization initiator used at this time is preferably 0.1 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer. Further, as the polymerization method, any method such as solution polymerization, suspension polymerization, emulsion polymerization, dispersion polymerization, precipitation polymerization, bulk polymerization can be used, and it is not particularly limited.

Method of controlling the molar ratio n _a / n _b of the unit b derived from an electron-donating compound having a unit a and a polymerizable unsaturated functional group derived from 2-acrylamido-2-methylpropanesulfonic acid with the resin A, The polymerization may be carried out in the manner described above by controlling the amount charged.

  In the toner of the present invention, the content of the unit a contained in the resin A is determined by quantitative analysis of sulfur atoms by elemental analysis, but the content is 0.01 mmol / g to 0.8 mmol / g. Is preferred.

  If the content of the unit a contained in the resin A is within the above range, an appropriate amount of sulfonic acid group sites are present, so production of resin particles having a sufficient charge amount and adhesion of the resin particles to the toner base particles Can be compatible.

  In the toner of the present invention, the weight average molecular weight of the resin A can be calculated, for example, by gel permeation chromatography (GPC), but the weight average molecular weight (Mw) obtained by this GPC is 2,500 or more and 100,000 or more. It is preferable that it is the following.

  When the weight average molecular weight of the resin A is within the above range, the unit a and the unit b can be uniformly present in the resin A, and the decrease in the charge amount is suppressed even under high temperature and high humidity. Ru. In addition, production of resin particles and adhesion of resin particles to toner base particles are facilitated.

  In the toner of the present invention, as a method of adjusting the weight average molecular weight of the resin A, known methods can be used.

  From the viewpoint of chargeability and fixability, the molecular weight distribution of the resin A is preferably narrow. It is preferable that ratio (Mw / Mn) of the weight average molecular weight Mw and number average molecular weight Mn calculated by gel permeation chromatography is 1.0 or more and 6.0 or less. More preferably, it is 1.0 or more and 4.0 or less.

  In the toner of the present invention, as a means for causing the resin A to be present on the surface of the toner base particles, known methods can be used. For example, there is a method of micronizing resin A, applying mechanical stress, and fixing it on toner.

  Further, in the present invention, from the viewpoint of durability, it is more preferable to add and fix the resin particles having the resin A in an aqueous medium containing toner base particles. At that time, the resin particles can be firmly fixed by controlling the temperature, pH, time, and the conditions of addition of the coagulant of the electrolyte, if necessary, so that the resin particles are released. Durability deterioration can be suppressed. Further, by fixing the resin particles to the toner base particles in an aqueous medium, the resin particles can be fixed uniformly on the surface of the toner particles without bias. Thus, the effect of the present invention can be suitably exhibited by fixing the resin particles uniformly on the surface of the toner particles without any bias.

  The method for preparing the resin particles contained in the toner of the present invention is not particularly limited, and the emulsion polymerization method, or the resin is dissolved or melted in a solvent to be liquefied, and suspended or phase-inverted in an aqueous medium The method of preparing by emulsifying is mentioned. At this time, known surfactants and dispersants can also be used, and the resin forming the resin particles can have self-emulsifiability. In the present invention, it is preferable to produce resin particles in an aqueous medium. When prepared in an aqueous medium, the hydrophilic functional group such as unit a is easily oriented to the water side, so that the charge expression effect can be further improved.

  When preparing the resin particles by dissolving the above-mentioned resin in a solvent, there is no particular limitation on the solvent which can be used, but, for example, hydrocarbon solvents such as toluene and xylene; halogenated such as methylene chloride, chloroform and dichloroethane Hydrocarbon solvents; ester solvents such as methyl acetate, ethyl acetate, butyl acetate and isopropyl acetate; ether solvents such as diethyl ether; ketone solvents such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone and methyl cyclohexane; methanol, ethanol And alcohol solvents such as butanol.

  The binder resin contained in the toner base particles constituting the toner of the present invention is not particularly limited. In the case of producing toner base particles using a suspension polymerization method, a polymer obtained by the polymerization of a polymerizable monomer which is a raw material can be constituted as a binder resin. In this case, the polymerizable monomer is not particularly limited, but the above-mentioned vinyl monomers are suitably used. Moreover, in this case, in addition to the polymerizable monomer in the monomer composition, a vinyl resin or a polyester resin may be added as a constituent material of the binder resin. Examples of vinyl resins that can be used as the binder resin contained in the toner base particles constituting the toner of the present invention include, for example, styrene resins, acrylic resins, methacrylic resins, styrene-acrylic resins, styrene-methacrylic resins Resin, polyethylene resin, polyethylene-vinyl acetate resin, vinyl acetate resin, polybutadiene resin, etc. are mentioned.

  Moreover, as polyester resin which can be used as a binder resin, polyester resin generally manufactured can be used by using polyhydric alcohol and carboxylic acid, carboxylic acid anhydride, or carboxylic acid ester as a raw material monomer, respectively. Specifically, the same polyhydric alcohol component and polyhydric carboxylic acid component as the polyester resin described above can be used. Among them, polyester resins obtained by condensation polymerization of the components listed below are particularly preferable. That is, as a diol component which is a dihydric alcohol, a bisphenol derivative is preferable. Examples of the acid component include carboxylic acids such as lower alkyl esters such as carboxylic acids having two or more valences or acid anhydrides thereof; fumaric acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc. Is preferred.

  As resin which can be used as a binder resin, a phenol resin, a polyurethane resin, a polybutyral resin etc. are mentioned other than the vinyl resin and polyester resin which were mentioned above. In addition, a hybrid resin in which the above-described resins are optionally bonded can also be used.

  Among these, the following are preferably used on the toner characteristics. That is, a styrene resin, an acrylic resin, a methacrylic resin, a styrene-acrylic resin, a styrene-methacrylic resin, a polyester resin, a styrene resin, or a hybrid resin obtained by combining a styrene-methacrylic resin and a polyester resin is preferable. Used.

  In the toner of the present invention, the toner base particles may further contain a wax. Examples of the wax contained in the toner base particles include aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax and paraffin wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax; aliphatic A block copolymer of a hydrocarbon wax; a wax containing a fatty acid ester as a main component such as carnauba wax, Sazole wax, montanic acid ester wax; and deoxidized a part or all of a fatty acid ester such as deacidified carnauba wax And partially esterified products of polyalcohols with fatty acids such as behenic acid monoglyceride; and methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

  As the molecular weight distribution of the wax, the main peak is preferably in the region of molecular weight 400 or more and 2400 or less, and more preferably in the region of 430 or more and 2000 or less. By this, it is possible to impart preferable thermal characteristics to the toner. The amount of the wax added is preferably 2.5 parts by mass or more and 40.0 parts by mass or less in total, and is 3.0 parts by mass or more and 15.0 parts by mass or less with respect to 100 parts by mass of the binder resin. Is more preferred.

  Examples of colorants that can be used in the toner of the present invention include known colorants such as various dyes and pigments conventionally known.

  As a color pigment for magenta, C.I. I. Pigment red 3, 5, 17, 22, 23, 38, 41, 112, 122, 123, 146, 149, 178, 179, 190, 202, C.I. I. Pigment violet 19, 23 and the like. The pigments listed above may be used alone or in combination with dyes.

  As a color pigment for cyan, C.I. I. Pigment Blue 15, 15: 1, 15: 3 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on a phthalocyanine skeleton, and the like.

  As a color pigment for yellow, C.I. I. Pigment yellow 1, 3, 12, 13, 14, 17, 55, 74, 83, 93, 94, 95, 97, 98, 109, 110, 154, 155, 166, 180, 185, and the like.

  As black colorants, carbon black, aniline black, acetylene black, titanium black, and those toned in black using the yellow / magenta / cyan colorants described above can be used.

In the present invention, when the colorant is a magnetic substance, it is possible to use the toner of the present invention as a magnetic substance toner. Specifically, iron oxide such as magnetite, maghemite and ferrite (the iron oxide may contain other metal oxides) as a colorant which is a magnetic substance; Fe, Co, Ni, etc. Examples thereof include metal materials and alloys obtained by combining these metal materials with metals such as Al, Co, Cu, Pb, Mg, Ni, Sn, Zn, Sb, Ca, Mn, Se, and Ti. In addition, you may use the mixture which combines and selects 2 or more types from iron oxide, a metal material, an alloy etc. which were mentioned above. In the present invention, as the colorant which is a magnetic substance, specifically, iron trioxide (Fe ₃ O ₄ ), iron trioxide (γ-Fe ₂ O ₃ ), iron zinc oxide (ZnFe ₂ O ₄ ), Iron oxide copper (CuFe ₂ O ₄ ), iron neodymium oxide (NdFe ₂ O ₃ ), iron barium oxide (BaFe ₁₂ O ₁₉ ), iron magnesium oxide (MgFe ₂ O ₄ ), iron manganese oxide (MnFe ₂ O ₄ ), etc. Can be mentioned. The magnetic materials described above may be used alone or in combination of two or more. Among the magnetic materials listed above, triiron tetraoxide or γ-iron trioxide is particularly preferred. In the present invention, fine powders of the magnetic materials listed above are preferably used. In the present invention, as the magnetic material, particularly preferably, finely powdered triiron tetraoxide or γ-iron trioxide is used.

The magnetic particles described above preferably have an average particle diameter of 0.1 μm or more and 1.0 μm or less, and more preferably 0.1 μm or more and 0.3 μm or less. The magnetic properties at 795.8 kA / m (10 K oersted) application preferably have a coercive force (Hc) of 1.6 kA / m or more and 12 kA / m or less (20 oersted or more and 150 oersted or less). The saturation magnetization (σs) is preferably 5 Am ² / kg or more and 200 Am ² / kg or less, more preferably 50 Am ² / kg or more and 100 Am ² / kg or less. Residual magnetization (.sigma.r) is, 2Am ² / kg or more 20 Am ² / kg or less being preferred.

  The magnetic material described above is preferably used in an amount of 10 parts by mass or more and 200 parts by mass or less, and more preferably 20 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the binder resin.

The method for producing toner base particles is not particularly limited, and known production methods may be used. For example, they are as shown in the following (A) to (I).
(A) A method of directly producing toner base particles using the suspension polymerization method described in JP-B 36-10231, JP-A 59-53856, and JP-A 59-61842;
(B) A method of producing toner base particles by an interfacial polymerization method such as a microcapsule production method;
(C) Method of producing toner mother particles by coacervation method;
(D) A toner mother according to an association polymerization method to obtain particles having a desired particle diameter by aggregating at least one or more kinds of fine particles as disclosed in JP-A-62-106473 and JP-A-63-186253. How to get the particles;
(E) A method of producing toner base particles by dispersion polymerization characterized by monodispersion;
(F) A polymer dissolution (melting) suspension method in which the required resins are dissolved in a water-insoluble organic solvent and then mother particles are formed in water;
(G) A method of obtaining toner base particles by an emulsion dispersion method;
(H) Knead and uniformly disperse toner components using a pressure kneader, extruder, or media disperser, etc., and then cool, and let the kneaded product collide with the target mechanically or under a jet stream to obtain the desired Grinding method to produce toner base particles by finely pulverizing to particle size and further adjusting particle size distribution through classification process;
(I) A method of obtaining toner base particles obtained by spheroidizing the base particles obtained by the grinding method in a solvent by heating or the like;

  In the case of producing toner base particles by a suspension polymerization method, first, a colorant is uniformly dissolved and mixed or dispersed in a polymerizable monomer constituting the binder resin by a stirrer or the like. In particular, when the colorant is a pigment, it is preferable to process with a dispersing machine to obtain a pigment dispersion paste. A polymerizable monomer composition is obtained by uniformly dissolving or dispersing this with a polymerizable monomer, charge control resin, polymerization initiator, wax and other additives as needed using a stirrer or the like. Make. The polymerizable monomer composition thus obtained is added to a dispersion medium (preferably, an aqueous medium) containing a dispersion stabilizer, and a stirring apparatus such as a high speed stirrer, a high speed disperser (for example, super The polymerizable monomer composition is finely dispersed to the toner particle diameter using a sonic dispersion machine or the like (granulation step). Then, toner base particles can be obtained by polymerizing the polymerizable monomer contained in the polymerizable monomer composition finely dispersed in the granulation step with light or heat (polymerization step). The polymerization initiator may be added after the granulation step.

  A known method can be used as a method of dispersing the pigment in the polymerizable monomer composition. For example, there is a method in which a resin, a pigment dispersant and the like are dissolved in the polymerizable monomer as necessary, and the pigment powder is gradually added while stirring to be sufficiently mixed. Furthermore, the pigment can be stably finely dispersed, ie, uniformly dispersed in the form of fine particles, by applying mechanical shear force with a dispersing machine such as a ball mill, paint shaker, dissolver, attritor, sand mill, high speed mill or the like.

  As polymerizable monomers that can be suitably used in the suspension polymerization method, vinyl-based monomers that can be used when producing the above-mentioned charge control resin can be similarly used.

  The dispersion medium which can be used in the suspension polymerization method can be determined from the solubility in a dispersion medium such as a binder resin, a polymerizable monomer, and a charge control resin, but an aqueous dispersion medium is preferable. Examples of usable aqueous dispersion media include water; alcohols such as water; methyl alcohol, ethyl alcohol, denatured ethyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, sec-butyl alcohol, etc .; And ether alcohols such as cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve, diethylene glycol monobutyl ether and the like. Water-soluble solvents other than these can also be used. For example, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate; ethers such as ethyl ether and ethylene glycol; acetals such as methylal and diethyl acetal Selected from acids such as formic acid, acetic acid, propionic acid and the like. Among these solvents, water or alcohols are particularly preferred. Moreover, you may select and use 1 type from these solvent, and it can also be used in mixture of 2 or more types. In the present invention, the concentration of the liquid mixture or polymerizable monomer composition relative to the dispersion medium is preferably 1% by mass to 80% by mass, more preferably 10% by mass to 65% by mass, with respect to the dispersion medium. It is below.

  As a dispersion stabilizer which can be used when using an aqueous dispersion medium, known ones can be used. Specific examples of the inorganic compound include calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate , Bentonite, silica, alumina and the like. As the organic compound, polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, polyacrylic acid and salts thereof, starch and the like can be dispersed in an aqueous phase and used. In the present invention, the concentration of the dispersion stabilizer is preferably 0.2 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the liquid mixture or the polymerizable monomer composition.

  As a polymerization initiator used when producing the toner of the present invention using a suspension polymerization method, a polymerization initiator which can be used when producing the above-mentioned charge control resin can be used similarly.

  When the toner is produced using a suspension polymerization method, a known crosslinking agent may be added. The preferable addition amount of the crosslinking agent is 0 parts by mass or more and 15.0 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer.

To the toner particles contained in the toner of the present invention, a fluidity improver may be added as an external additive. As a flowability improver, fluorine resin powder such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; silica fine powder by wet process, silica fine powder such as silica fine powder by dry process, and the above silica fine powder Treated silica fine powder surface-treated with treating agent such as silane coupling agent, titanium coupling agent, silicone oil; titanium oxide fine powder; alumina fine powder; treated titanium oxide fine powder; treated alumina oxide fine powder etc. Be The flowability improver preferably has a specific surface area of 30 m ² / g or more, more preferably 50 m ² / g or more, as measured by the BET method using nitrogen adsorption. The flowability improver is preferably used in an amount of 0.01 to 8.0 parts by mass with respect to 100 parts by mass of toner particles, and is preferably used in an amount of 0.1 to 4.0 parts by mass. More preferable.

  The weight average particle diameter (D4) of the toner is preferably 3.0 μm or more and 15.0 μm or less, and more preferably 4.0 μm or more and 12.0 μm or less.

  The toner of the present invention can be mixed with a magnetic carrier and used as a two-component developer. As the magnetic carrier, metal particles such as surface oxidized or unoxidized iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, rare earths, etc., alloy particles thereof, oxide particles and ferrite are micronized Can be used.

  In the developing method of applying an alternating current bias to the developing sleeve, it is preferable to use a coated carrier in which the surface of the magnetic carrier core is coated with a resin. As a method of coating the surface of the magnetic carrier core, a method of adhering a coating solution prepared by dissolving or suspending a coating material such as resin in a solvent to the surface of the magnetic carrier core, a magnetic carrier core and a coating material The method of mixing with powder etc. are used.

  As a coating material of the magnetic carrier core, silicone resin, polyester resin, styrene resin, acrylic resin, polyamide, polyvinyl butyral, amino acrylate resin and the like can be mentioned. These coating materials may be used alone or in combination of two or more. Moreover, 0.1 mass% or more and 30 mass% or less are preferable with respect to a carrier core particle, and, as for the processing amount of the said coating material, 0.5 mass% or more and 20 mass% or less are more preferable.

  The average particle diameter of the magnetic carrier is preferably 10 μm or more and 100 μm or less, more preferably 20 μm or more and 70 μm or less in terms of 50% particle diameter (D50) based on volume.

  When a two-component developer is prepared using the toner of the present invention, the mixing ratio of the toner of the present invention in the developer is preferably 2% by mass to 15% by mass, and 4% by mass with respect to the entire developer. More than 13 mass% is more preferable, and a good result is obtained.

[Method of measuring physical properties of toner]
The methods for measuring each physical property value of the toner will be described below.

(1) Molecular Weight Distribution of Charge Control Resin (Resin Particles) The molecular weight and molecular weight distribution of the charge control resin (resin particles) can be measured by gel permeation chromatography (GPC), and are calculated in terms of polystyrene. By the way, when measuring the molecular weight of a resin having an acidic substituent, the column elution rate also depends on the amount of the acidic substituent, so it is necessary to prepare a sample capped with the acidic substituent in advance. There is. Methyl esterification is preferable for capping, and commercially available methyl esterification agents can be used. Specifically, a method of treating with trimethylsilyldiazomethane can be mentioned.

The measurement of the molecular weight by GPC is performed as follows. First, the measurement sample is dissolved in tetrahydrofuran (THF) for 24 hours at room temperature. Then, the obtained THF solution is filtered through a solvent-resistant membrane filter “Mishori Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is 0.8% by mass. For example, the measurement is performed under the following conditions using this sample solution.
Device: HLC8120 GPC (detector: RI) (made by Tosoh Corporation)
Column: 7 series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (made by Showa Denko)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 mL

  In addition, in calculation of the molecular weight of a measurement sample, standard polystyrene resin (For example, brand name "TSK standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, and F-20. , F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 "(manufactured by Tosoh Corporation), and a molecular weight calibration curve is used.

(2) Method for Deriving Composition Ratio of Charge Control Resin (Resin Particles) The composition ratio of the charge control resin (resin particles) is determined by measuring the amount of sulfur element for unit a derived from 2-acrylamido-2-methylpropane sulfonic acid. The unit b derived from the electron donating compound having the unsaturated functional group is derived by NMR measurement.

(3) Measurement of content of unit a derived from 2-acrylamido-2-methylpropanesulfonic acid in charge control resin (resin particle) From 2-acrylamido-2-methylpropanesulfonic acid in charge control resin (resin particle) The content (mmol / g) of the unit a of (a) is calculated from the amount of sulfur element by measuring the amount of sulfur element (ppm) contained in the polymer. Specifically, the resin is used as an automatic sample combustion device (device name: pretreatment device AQF-100 for ion chromatograph (device specification: auto boat controller ABC type, AQF-100, GA-100 integrated type, Dia Co., Ltd. The resin is introduced into Instruments, burned into a gas, and absorbed into an absorbing solution (an aqueous solution containing 30 ppm of H ₂ O ₂ ), and then ion chromatography (Device name: Ion chromatograph ICS 2000, column: The amount of sulfur element (ppm) contained in the resin is calculated by measuring the amount of SO ₄ contained in the absorbing liquid according to IONPAC AS17 (manufactured by Nippon Dionex Co., Ltd.) From the amount of sulfur element (ppm) in the resin Calculate the unit a content (mmol / g) derived from 2-acrylamido-2-methylpropanesulfonic acid Get out.

(4) Measurement of content of unit b derived from electron donating compound having a polymerizable unsaturated functional group in charge control resin (resin particle) Electron having a polymerizable unsaturated functional group in charge control resin (resin particle) The content of the unit b derived from the donor compound is calculated using a nuclear magnetic resonance apparatus ( ¹ H-NMR, ¹³ C-NMR).

The following shows the devices used.
Nuclear magnetic resonance device: FT-NMR JNM-EX400 (use solvent: deuterated chloroform) manufactured by JEOL Ltd.
The content is calculated by the above two types of measurement, and the composition ratio is calculated.

(5) Measurement of Acid Value of Charge Control Resin (Resin Particles) The acid value is the number of mg of potassium hydroxide necessary to neutralize the acid contained in 1 g of the sample. In the present invention, the acid value is measured according to JIS K 0070-1992, and specifically, it is measured according to the following procedure.

  The titration is performed using a 0.1 mol / L potassium hydroxide ethyl alcohol solution (manufactured by Kishida Chemical Co., Ltd.). The factor of the potassium hydroxide ethyl alcohol solution can be determined by using a potentiometric titration apparatus (a potentiometric titration measurement apparatus AT-510 manufactured by Kyoto Denshi Kogyo Co., Ltd.). 100 mL of 0.100 mol / L hydrochloric acid is taken in a 250 mL tall beaker, titrated with the above potassium hydroxide ethyl alcohol solution, and the acid value is determined from the amount of the above potassium hydroxide ethyl alcohol solution required for neutralization. In addition, the said 0.100 mol / L hydrochloric acid uses what was prepared according to JISK 8001-1998.

The specific example of the measurement conditions in the case of an acid value measurement is shown below.
Titration device: Potentiometric titration device AT-510 (manufactured by Kyoto Denshi Kogyo Co., Ltd.)
Electrode: Composite glass electrode double junction type (manufactured by Kyoto Denshi Kogyo Co., Ltd.)
Control software for titrator: AT-WIN
Titration analysis software: Tview
The titration parameters and control parameters at the time of titration are performed as follows.

(5-1) Titration parameter Titration mode: Blank titration Titration mode: Total titration Maximum titration amount: 20 mL
Waiting time before titration: 30 seconds Titration direction: Automatic

(5-2) Control parameter end point judgment potential: 30 dE
End point judgment potential value: 50 dE / dmL
End point detection judgment: Not set Control speed mode: Standard gain: 1
Data collection potential: 4mV
Data collection titer: 0.1 mL

(main exam)
0.100 g of the measurement sample is precisely weighed in a 250 mL tall beaker, 150 mL of a mixed solution of toluene / ethanol (3: 1) is added, and then the measurement sample is dissolved over 1 hour. Next, titration is performed using the potassium hydroxide ethyl alcohol solution using the potentiometric titration apparatus.

(Empty test)
The titration is performed in the same manner as in this test except that the sample is not dissolved (that is, only a mixed solution of toluene / ethanol (3: 1) is used).

The acid value is calculated by substituting the obtained result into the following equation.
A = [(C−B) × f × 5.61] / S
(Wherein, A is the acid value (mg KOH / g), B is the blank potassium hydroxide solution addition amount (mL), C is the potassium hydroxide solution addition test (mL), f is hydroxylation Factor of potassium solution, S is weighing (g) of measurement sample.)

(6) Structural Analysis of Charge Control Resin (Resin Particles) The structure determination of the charge control resin (resin particles) should be performed using a nuclear magnetic resonance apparatus ( ¹ H-NMR, ¹³ C-NMR) and an FT-IR spectrum. Can. The apparatus used below is described.

(I) Nuclear magnetic resonance system FT-NMR JNM-EX400 (use solvent heavy chloroform) made by Nippon Denshi
(Ii) FT-IR Spectrum Thermo Fisher Scientific Inc. AVATAR360FT-IR

(7) Glass Transition Temperatures of Charge Control Resin (Resin Particles) and Toner The glass transition temperatures of the charge control resin (resin particles) and the toner are measured using a differential scanning calorimeter (DSC measurement device).

  The differential scanning calorimeter is measured as follows according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments). First, 3 mg of a measurement sample is weighed. Place it in an aluminum pan and use an empty aluminum pan for control. After equilibrating at 20 ° C. for 5 minutes, measurement is performed at a temperature rising rate of 1.0 ° C./min by applying modulation of 1.0 ° C./min in a measurement range of 20 ° C. to 140 ° C. In the present invention, the glass transition temperature is Rev. It can be determined by the midpoint method using the Heat Flow curve.

(8) Weight average particle diameter (D4) of toner, number average particle diameter (D1)
The weight average particle diameter (D4) and the number average particle diameter (D1) of the toner are calculated as follows. As a measuring apparatus, a precise particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) having a 100 μm aperture tube and using a pore electrical resistance method is used. The setting of measurement conditions and the analysis of measurement data use the attached special software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.). The measurement is performed with 25,000 channels of effective measurement channels.

  As the electrolytic aqueous solution used for the measurement, a solution in which special grade sodium chloride is dissolved in ion exchange water so that the concentration is 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  In addition, before performing measurement and analysis, the setting of the dedicated software is performed as follows. In the "Change Standard Measurement Method (SOM)" screen of the dedicated software, set the total count number in the control mode to 50000 particles, set the number of measurements once, and the Kd value "standard particle 10.0 μm" (Beckman Coulter Set the value obtained using The threshold and noise level are automatically set by pressing the "Threshold / noise level measurement button". Also, set the current to 1600 μA, the gain to 2, and the electrolyte to ISOTON II, and check “Aperture tube flush after measurement”. In the "Pulse to particle size conversion setting" screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm or more and 60 μm or less.

  The specific measurement method is as follows.

  (8-1) Put 200 mL of the above aqueous electrolytic solution in a 250 mL round bottom beaker made of Multisizer 3 and put it on a sample stand, and stir the stirrer rod in a counterclockwise direction at 24 rotations / second. Then, dirt and air bubbles in the aperture tube are removed by the "aperture flush" function of special software.

  (8-2) 30 mL of the above electrolytic aqueous solution is placed in a 100 mL flat bottom beaker made of glass. Among them, “contaminone N” (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH 7 precision measuring instrument cleaning consisting of organic builders as a dispersing agent, Wako Pure Chemical Industries, Ltd. 3.) add 0.3 mL of a diluted solution diluted threefold with deionized water.

  (8-3) Two ultrasonic oscillators with an oscillation frequency of 50 kHz are incorporated 180 degrees out of phase, and an ultrasonic dispersion device with an electrical output of 120 W, "Ultrasonic Dispension System Tetora 150" (manufactured by Nikkaki Bios Co., Ltd.) is prepared Do. Put 3.3 L of ion exchange water into the water tank of the ultrasonic disperser, and add 2 mL of Contaminone N into this water tank.

  (8-4) The beaker of (8-2) is set in the beaker fixing hole of the ultrasonic dispersion device, and the ultrasonic dispersion device is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid surface of the electrolytic aqueous solution in the beaker is maximized.

  (8-5) While the electrolytic aqueous solution in the beaker of (8-4) is irradiated with ultrasonic waves, 10 mg of toner is added little by little to the electrolytic aqueous solution and dispersed. Then, ultrasonic dispersion processing is continued for another 60 seconds. In addition, in ultrasonic dispersion, the water temperature of the water tank is appropriately adjusted so as to be 10 ° C. or more and 40 ° C. or less.

  (8-6) In the round bottom beaker of (8-1) placed in the sample stand, the aqueous electrolyte solution of (8-5) above in which the toner is dispersed using a pipette is dropped, and the measurement concentration is 5%. Adjust to become Then, measurement is performed until the number of measurement particles reaches 50,000.

  (8-7) Analyze the measured data with the dedicated software attached to the device to calculate the weight average particle diameter (D4) and the number average particle diameter (D1), the volume based median diameter, and the number based median diameter.

  The "average diameter" on the "Analysis / volume statistics (arithmetic mean)" screen is "weight average particle diameter (D4)" when "graph / volume%" is set in the above dedicated software, and "middle diameter" “Is the volume-based median diameter (Dv 50). Also, when the graph / number% is set with the dedicated software, the “average diameter” on the “Analysis / number statistics (arithmetic mean)” screen is the number average particle diameter (D1), and the “median diameter” is It is a number standard median diameter (Dn 50).

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. In the following description, "parts" means "parts by mass".

(Production example of resin fine particle 1)
A reaction vessel equipped with a stirrer, a condenser, a thermometer and a nitrogen introduction tube was prepared. Next, 100.0 parts of methyl ethyl ketone and 50.0 parts of methanol were charged in a non-shielded state of the reaction vessel, and then the solvent in the reaction vessel was heated to 60 ° C. under a nitrogen stream.

Next, the following monomers and solvents were mixed to prepare a 2-acrylamido-2-methylpropane sulfonic acid-containing mixed solution (mixed solution A).
2-acrylamido-2-methylpropane sulfonic acid 6.1 parts styrene 83.0 parts 2-ethylhexyl acrylate 9.0 parts 2-butanone 100.0 parts methanol 50.0 parts dimethyl-2,2 1.0 part of '-azobis (2-methyl propionate)

Next, the following monomers and solvents were mixed to prepare a 4-vinylpyridine-containing mixed solution (mixed solution B).
-4-vinylpyridine 1.9 parts-2-butanone 50.0 parts

  Next, mixed solution A and mixed solution B were separately added to the reaction vessel over 60 minutes through separate routes. Next, the reaction solution was heated to 60 ° C. and stirred at this temperature (60 ° C.) for 8 hours, and then the reaction solution was cooled to room temperature. Thus, a polymer-containing composition was obtained.

  Next, the obtained polymer-containing composition was dropped into 1400 parts of methanol to precipitate and crystallize the resin composition. Next, the obtained resin composition was filtered and washed twice with 200 parts of methanol to obtain a powdery resin (resin powder).

  The obtained resin powder was dried at 60 ° C. for 10 hours under reduced pressure to obtain a charge control resin.

  Next, 100.0 parts of the obtained charge control resin, 45.0 parts of methyl ethyl ketone, and 45.0 parts of tetrahydrofuran are charged into a reaction vessel equipped with a stirrer, a condenser, a thermometer and a nitrogen introducing pipe, and 80 The charge control resin was dissolved in a solvent by heating to ° C. Next, while stirring the solution in which the charge control resin is dissolved, 300.0 parts of ion-exchanged water at 80 ° C. was added and dispersed in water. After this, the obtained aqueous dispersion was transferred to a distillation apparatus, and distillation was performed until the fraction temperature reached 100.degree. Next, ion-exchanged water was added to the aqueous dispersion obtained by cooling to room temperature, and the concentration of the resin in the dispersion was adjusted to 20%. Thereby, resin fine particles 1 were obtained in the state of being mixed in the dispersion liquid.

(Production example of resin fine particle 10)
First, the following reagents were mixed to obtain a mixed solution C.
2-acrylamido-2-methylpropane sulfonic acid 6.1 parts styrene 83.0 parts 4-vinylpyridine 1.9 parts anionic surfactant Neogen SC 2.5 parts in 140 parts of demineralized water It was dissolved. Next, after the mixed solution C was dispersed and emulsified in a flask, 100 parts of demineralized water in which 10.0 parts of potassium persulfate was dissolved was added while slowly mixing for 10 minutes. Next, the flask was heated using an oil bath until the contents in the flask reached 70 ° C. while performing nitrogen substitution, and after reacting for 10 hours from the start of polymerization, it was kept for another 30 minutes. Thus, resin fine particles 10 were obtained.

(Production example of resin fine particles 14)
(1) Preparation of Polyester P-1 First, the reagent and solvent shown below were charged in a four-necked flask.
-Bisphenol A-Propylene oxide 2.2 mol adduct 70.0 parts-Terephthalic acid 28.0 parts-Fumaric acid 3.0 parts-Dibutyltin oxide 0.005 parts Next, in a 4-neck flask, use a thermometer, After attaching a stirring rod, a condenser and a nitrogen introducing tube, a polyester resin P-1 was obtained by reacting for 5 hours at 220 ° C. in a nitrogen atmosphere.

(2) Preparation of Resin Fine Particles 14 In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introducing pipe, 200 parts of xylene was charged and refluxed under nitrogen stream. 70 parts of polyester resin P-1 produced by said (1) were thrown in there, and it was made to melt | dissolve.

Next, a mixture D was prepared by mixing the reagents shown below.
2-acrylamido-2-methylpropane sulfonic acid 11.0 parts 4-vinylpyridine 2.0 parts dimethyl-2,2'-azobis (2-methyl propionate) 1.0 part Next, a reaction vessel The mixture D was added dropwise while stirring the internal reaction solution, and the mixture was maintained for 10 hours. Then, the residue obtained by distilling and distilling a solvent off was dried at 40 degreeC under pressure reduction, and resin was obtained. The obtained resin was micronized by the same method as in the production example of resin fine particle 1 to obtain resin fine particle 14.

(Production example of resin fine particles 2 to 9, 11 to 13, 15 to 16)
In the production example of resin fine particle 1, resin fine particles 2 to 2 are prepared in the same manner as the production example of resin fine particle 1 except that the monomer composition, the mixing ratio and the number of parts of the polymerization initiator are changed as described in Table 1. 9, 11 to 13, 15 to 16 were obtained respectively.

  Here, Table 1 shows the configuration of the produced resin particles (resin fine particles 1 to 16), and Table 2 shows physical properties (composition ratio, molecular weight, etc.).

In Table 1, AMPS represents 2-acrylamido-2-methylpropanesulfonic acid, 4-VP represents 4-vinylpyridine, and 2-EHA represents 2-ethylhexyl acrylate. Further, in Table 2, n _a / n _a (molar ratio) means the molar concentration of the unit a derived from 2-acrylamido-2-methylpropanesulfonic acid and the polymerizable unsaturated functional group contained in the resin A (resin fine particles). It represents the ratio to the molar concentration of the unit b derived from the electron donor compound.

Example 1 Production of Toner 1 (1) Preparation of Pigment Dispersion Paste After well premixing the materials shown below in a container, the premixed material is dispersed for 5 hours with a bead mill while keeping the temperature at 20 ° C. or lower. By doing this, a pigment dispersion paste was produced.
Styrene 80.0 parts C.I. I. Pigment blue 15: 3 14.0 parts

(2) Preparation of Toner Base Particles To 1150 parts of ion-exchanged water, 390 parts of a 0.1 mol / liter aqueous solution of Na ₃ PO ₄ was added, and heated to 60 ° C. Made at 11000 rpm. Next, 58 parts of a 1.0 mol / liter aqueous solution of CaCl ₂ was added to obtain a dispersion liquid containing Ca ₃ (PO ₄ ) ₂ .

Next, the reagents and solvents shown below were mixed.
Pigment dispersion paste prepared in the above (1) 38.0 parts Styrene 34.0 parts n-butyl acrylate 15.0 parts Paraffin wax (HNP-9: made by Nippon Seiwa) 8.00 parts saturated polyester Resin _{(Note 1)} 5.00 parts (Note 1: Terephthalic acid-propylene oxide modified bisphenol A copolymer, acid value 11 mg KOH / g, Mw: 14700)
Next, the mixture was heated to 60 ° C., melted and dispersed to prepare a monomer mixture. Next, 5.00 parts of a polymerization initiator (2,2-azobis (2,4-dimethylvaleronitrile)) is added and dissolved while maintaining this monomer mixture at 60 ° C. The composition was prepared.

  Next, the monomer composition was charged into the dispersion. Next, the monomer composition was granulated by stirring at 10000 rpm for 20 minutes using Clearmix at 60 ° C. under a nitrogen atmosphere. Then, the reaction was carried out at 60 ° C. for 5 hours while stirring with a paddle stirring blade, and then the polymerization was terminated by stirring at 80 ° C. for 5 hours. After completion of the polymerization, the obtained polymer fine particle dispersion was heated in an oil bath at 140 ° C. for distillation to remove the polymerizable monomer remaining in the dispersion. Distillation was performed for 8 hours, and ion-exchanged water of the same amount as the fraction was added every hour. A fine particle dispersion (toner base particle dispersion) was obtained by the above steps.

(3) Preparation of Toner Particles After cooling the toner base particle dispersion obtained in the above (2) to 80 ° C., 3.0 parts of resin fine particles relative to 100.0 parts of the solid content of the toner base particle dispersion After 1 was added over 5 minutes, the mixture was stirred at 80 ° C. for 30 minutes. Thereafter, it was cooled to room temperature at a speed of 1 ° C./min. Furthermore, after confirming that the temperature had reached room temperature, 10% hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ in order to remove the dispersion stabilizer. Next, the dispersion is stirred as it is for 2 hours, and after repeating the combination of filtration and washing with water three times, the solid content is recovered and dried in a vacuum dryer at 30 ° C. for 1 day to obtain toner particles. Obtained. Furthermore, toner particles 1 were obtained by performing classification such that particles of 2 μm or more and less than 10 μm were selected with respect to the obtained toner particles. Thus, toner particles in which the resin particles were fixed to the surface of the toner base particles were obtained.

(4) Preparation of Toner The toner particles 1 (100 parts) obtained in the above (3) are surface-treated with hexamethyldisilazane, and then the primary particles treated with silicone oil have a number average particle diameter of 9 nm, Toner 1 was obtained by mixing and externally adding 1 part of a hydrophobic silica fine powder having a BET specific surface area of 180 m ² / g with a Henschel mixer (Mitsui Miike Kako Co., Ltd.).

Example 2
Toner 2 was obtained in the same manner as in Example 1 except that resin fine particle 2 was used in place of resin fine particle 1 in Example 1 (3).

[Example 3]
Toner 3 was obtained in the same manner as in Example 1 except that resin fine particle 3 was used in place of resin fine particle 1 in Example 1 (3).

Example 4
In Example 1 (1), a pigment dispersion paste was prepared using the materials shown below.
-Styrene monomer 80.0 parts-Carbon black 15.0 parts Moreover, in Example 1 (2), the quantity of the pigment paste added when preparing a monomer composition was 47.5 parts. Further, in Example 1 (3), resin fine particles 4 were used in place of the resin fine particles 1. A toner 4 was obtained in the same manner as in Example 1 except for the above.

[Example 5]
A pigment dispersion paste was prepared using the materials shown below in Example 1 (1).
-Styrene monomer 80.0 parts-Quinacridone (Pigment Violet 19) 13.0 parts Moreover, in Example 1 (3), resin fine particles 5 were used in place of resin fine particles 1. A toner 5 was obtained in the same manner as in Example 1 except for the above.

[Example 6]
A pigment dispersion paste was prepared using the materials shown below in Example 1 (1).
-Styrene monomer 80.0 parts-Cu phthalocyanine (Pigment Blue 15: 3) 13.0 parts Further, in Example 1 (3), resin microparticles 1 were used instead of resin microparticles 1 and resin microparticles 6 were used. Toner 6 was obtained in the same manner as in Example 1 except for the above.

[Example 7]
Toner 7 was obtained in the same manner as in Example 1 except that resin fine particle 7 was used in place of resin fine particle 1 in Example 1 (3).

[Example 8]
A toner 8 was obtained in the same manner as in Example 1 except that resin fine particles 8 were used in place of resin fine particles 1 in Example 1 (3).

[Example 9]
In Example 1 (3), resin fine particles 6 are used instead of resin fine particles 1, and the number of added parts of resin fine particles 6 is 1.0 part with respect to 100.0 parts of the solid content of the toner base particle dispersion. Toner 9 was obtained in the same manner as in Example 1 except for the above.

[Example 10]
In Example 1 (3), resin fine particles 6 are used instead of resin fine particles 1, and the number of added parts of the resin fine particles 6 is 0.5 parts to 100.0 parts of the solid content of the toner base particle dispersion. Toner 10 was obtained in the same manner as in Example 1 except for the above.

[Example 11]
Toner 11 was obtained in the same manner as in Example 1 except that resin fine particles 9 were used in place of resin fine particles 1 in Example 1 (3).

[Example 12]
Toner 12 was obtained in the same manner as in Example 1 except that resin fine particle 10 was used in place of resin fine particle 1 in Example 1 (3).

[Example 13]
A toner 13 was obtained in the same manner as in Example 1 except that resin fine particles 11 were used in place of the resin fine particles 1 in Example 1 (3).

Example 14
(1) Preparation of Polyester Resin P-2 The following reagents and solvents were placed in a four-necked flask.
-Bisphenol A-Propylene oxide 2.2 mol adduct 50.0 parts-Bisphenol A-Ethylene oxide 2.2 mol adduct 20.0 parts-Terephthalic acid 10.0 parts-Trimellitic anhydride 8.0 parts-Fumar 12.0 parts of acid and 0.005 parts of dibutyltin oxide Next, attach a thermometer, a stirrer, a condenser, and a nitrogen inlet tube to a four-necked flask, and then react at 220 ° C for 5 hours under a nitrogen atmosphere. Thus, a polyester resin P-2 was obtained. The molecular weight of the obtained resin was Mw = 22500 and Mn = 3600.

(2) Preparation of Toner Base Particles Next, materials shown below were sufficiently premixed with a Henschel mixer (Mitsui Miike Kako Co., Ltd.).
Polyester resin P-2 100.0 parts Cu phthalocyanine (Pigment Blue 15: 3) 5.0 parts Paraffin wax (HNP-7: manufactured by Nippon Seikei Co., Ltd.) 3.0 parts Next, a twin-screw extruder The mixture was melt-kneaded using the above, and after cooling, the kneaded material was roughly crushed to a particle size of about 1 to 2 mm using a hammer mill. Then, it was finely pulverized by an air jet type pulverizer. Further, the finely pulverized product obtained was classified with a multi-division classifier to obtain toner mother particles.

(3) Preparation of Toner Particles Next, using a Henschel mixer, 100 parts by mass of the toner base particles obtained in (2) and resin fine particles 12 (3.0 parts, dispersion liquid) are mixed, and then fluidized bed drying By drying with a machine, toner particles to which resin fine particles were attached were obtained. The toner particles were charged into a type I hybridizer (manufactured by Nara Machinery Co., Ltd.) and processed for 5 minutes at 7,000 rpm to obtain toner particles having the resin particles fixed on the surface.

(4) Preparation of Toner Toner 14 was obtained by externally adding the toner particles obtained in (3) in the same manner as in Example 1 (4).

[Example 15]
A toner 15 was obtained in the same manner as in Example 1 except that resin fine particles 13 were used in place of the resin fine particles 12 in Example 14 (3).

[Example 16]
A toner 16 was obtained in the same manner as in Example 1 except that resin fine particles 14 were used instead of resin fine particles 1 in Example 1 (3).

Comparative Example 1
A toner 17 was obtained in the same manner as in Example 1 except that resin fine particles 15 were used instead of resin fine particles 1 in Example 1 (3).

Comparative Example 2
A toner 18 was obtained in the same manner as in Example 1 except that resin fine particles 16 were used instead of resin fine particles 1 in Example 1 (3).

Comparative Example 3
After confirming that the toner mother particle dispersion liquid obtained in Example 1 (2) had reached room temperature, 10% hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ . Next, the dispersion was stirred as it is for 2 hours, and filtration and washing with water were repeated 3 times, after which the solid content was recovered and dried with a vacuum dryer at 30 ° C. for 1 day to obtain toner particles. Thereafter, external addition is performed in the same manner as in Example 1 (4) to obtain a toner 19.

  The physical properties of the toner obtained above are shown in Table 3.

[Evaluation of Toner]
The triboelectric charge of the toner of the present invention can be determined by the method described below. Specifically, a two-component developer obtained by mixing the toner and a standard carrier for negative charge polarity toner (trade name: N-01, manufactured by Japan Imaging Society) so that the toner concentration is 4% is used. The evaluation was done. The standard carrier for negative charge polarity toner (trade name: N-01, manufactured by Japan Imaging Society) used for the measurement was used after passing 250 mesh.

  In the two-component developer used, the evaluation was carried out after lowering the toner concentration and increasing the absolute value of the frictional charge amount of the toner in order to make the effects of the present invention easier to compare.

  The above toner and two-component developer were evaluated as follows.

(1) Evaluation of environmental dependency 50 g of the two-component developer is separated, and left for 4 days under normal temperature and humidity environment (23.degree. C./60% Rh) and high temperature and high humidity environment (30.degree. C./80% Rh). did. Thereafter, the two-component developer was placed in a 50 cc poly container, shaking was performed 300 times over 2 minutes, and the triboelectric charge amount was measured using the apparatus of FIG. The specific measurement method will be described later. In the evaluation, the absolute value of the triboelectric charge amount at each shaking frequency was measured, the evaluation value was calculated using the following equation (α), and the judgment was made based on the following criteria. The results are shown in Table 4. In addition, if it is an evaluation result of A, B, and C rank, it was set as the level in which the effect of this invention is acquired.

[Evaluation value of environmental dependence]
= [Frictional charge in normal temperature and humidity environment] / [frictional charge in high temperature and high humidity environment] (α)
A rank: evaluation value is 1.00 or more and less than 1.20 B rank: evaluation value is 1.20 or more and less than 1.30 C rank: evaluation value is 1.30 or more and less than 1.40 D rank: evaluation value is 1. 40 or more

(Method of measuring triboelectric charge)
Hereinafter, measurement examples of the frictional charge amount will be described. In a metal measuring container 2 having a screen 3 of 500 mesh (25 μm openings) at the bottom, 0.5 g of a two-component developer to be measured for the triboelectric charge was put, and a metal lid 4 was made. At this time, the mass of the entire measurement container 2 is weighed to obtain W1 (g). Next, in the suction device 1 (the portion in contact with the measurement container 2 is at least an insulator), the pressure of the vacuum gauge 5 is set to 250 mmAq by suctioning from the suction port 7 and adjusting the air volume control valve 6. In this state, suction was carried out sufficiently (preferably, 2 minutes) to suction and remove the toner. The potential of the electrometer 9 at this time is V (volt). Reference numeral 8 is a capacitor, and its capacity is C (μF). Further, the mass of the entire measurement container after suction is weighed to obtain W2 (g). Based on the numerical values obtained by the above-described operation, the triboelectric charge amount (mC / kg) of the toner was calculated using the following formula (β).
Triboelectric charge (mC / kg) = (C x V) / (W 1-W 2) (β)

(2) Evaluation of Image Output Evaluation of the toners of Examples 1 to 16 and Comparative Examples 1 to 3 was performed by the method described below. 100 g of toner was loaded using a toner cartridge of a tandem type laser beam printer LBP 9600C manufactured by Canon Inc. having the configuration as shown in FIG. It was left for 72 hours under each environment of normal temperature and normal humidity (23 ° C./60% RH) and high temperature and high humidity (30 ° C./85% RH).

  The evaluation was performed by mounting the toner cartridge loaded in the above to a cyan station, and mounting a dummy cartridge on the other, and carrying out image evaluation in a normal temperature normal humidity environment and a high temperature high humidity environment.

In the drawing-out test, the first to fifth sheets are initially 1, and the 95th to 100th sheets are initially 2, the 9995th to 10000th sheets are durable, and the image density and fog for each are evaluated. It measured and calculated the average value. In this test, an original chart with an image area ratio of 1% was continuously output using 75 g / m ² A4 plain paper. The results are shown in Table 4.

(2-1) Evaluation of Image Density The image density was evaluated using a Macbeth densitometer (RD-914; manufactured by Macbeth) equipped with an SPI auxiliary filter. The image density of the fixed image portion of the output image was measured, and the image density was evaluated based on the relative density to the printout image of the white area of 0.00 according to the following criteria.
A rank: 1.40 or more B rank: 1.30 or more and less than 1.40 C rank: 1.20 or more and less than 1.30 D rank: 1.10 or more and less than 1.20 E rank: less than 1.10.

(2-2) Evaluation of fogging The fogging density (%) is calculated from the difference between the whiteness of the white area of the printout image and the whiteness of the transfer paper measured by the “Reflectometer” (manufactured by Tokyo Denshoku Co., Ltd.), Image fog was evaluated based on the following criteria.
A rank: less than 0.5% B rank: more than 0.5% less than 1.0% C rank: more than 1.0% less than 1.5% D rank: more than 1.5% less than 2.5% E rank: more than 2.5%

  From Table 4, it is understood that the toners of Examples 1 to 16 according to the present invention are superior to the toners of Comparative Examples 1 to 3 in environmental dependency.

  1: Suction machine 2: 2: Measurement container 3: 3: Screen 4: 4: lid 5: vacuum gauge 6: 6: air flow control valve 7: 7: suction port 8: condenser 9: electrometer 11: photoconductor 12: 12 Developing roller, 13: toner supply roller, 14: toner, 15: regulating blade, 16: developing device, 17: laser beam, 18: charging device, 19: cleaning device, 20: cleaning charging device, 21: stirring blade, 22: drive roller, 23: transfer roller, 24: bias power supply, 25: tension roller, 26: transfer conveyance belt, 27: driven roller, 28: paper, 29: paper feed roller, 30: adsorption roller, 31: fixing device

Claims (8)

A toner having toner particles comprising toner base particles having a binder resin and a colorant, and resin particles provided on the surface of the toner base particles,
The resin particles have a resin A having a unit a derived from 2-acrylamido-2-methylpropane sulfonic acid and a unit b derived from an electron donating compound having a polymerizable unsaturated functional group,
In the resin A, Ri molar ratio n _a / n _b is 1.0 to 10.0 der following said unit a and the unit b,
The toner in which the electron donating compound is vinylpyridine .   The toner according to claim 1, wherein the polymerizable unsaturated functional group is a vinyl group. The resin A toner according to claim 1 or 2 further comprising a unit c from styrene. The toner according to any one of claims 1 to 3 , wherein a content of the unit a in the resin A is 0.01 mmol / g or more and 0.8 mmol / g or less. The toner according to any one of claims 1 to 4 , wherein the weight average molecular weight Mw of the resin A is 2,500 or more and 100,000 or less. The toner according to any one of claims 1 to 5 , wherein the resin particles are fixed to the surface of the toner base particles. A toner manufacturing method for manufacturing the toner according to any one of claims 1 to 6 ,
The manufacturing method of the toner whose resin particles are resin particles manufactured in an aqueous medium. The method according to claim 7 , wherein the toner base particles are produced in an aqueous medium.

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