JP2017083603A - Manufacturing method of toner particle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of toner particles in a suspension polymerization method, the manufacturing method of toner particles suppressing microparticles being the cause of generation of image defects including development streaks, and achieving a high aspect ratio for suppressing fogging caused by composite particles having an ununiform charge amount distribution.SOLUTION: There is provided a manufacturing method of toner particles including: a granulation step of forming, in a first aqueous medium containing a dispersion stabilizer A, particles of a polymerizable monomer composition containing a polymerizable monomer, colorant, and polyester resin; and a polymerization step of polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition to obtain toner particles, wherein the polyester resin has an acid value of 0.3 mgKOH/g or more and 1.5 mgKOH/g or less; the toner contains the polyester resin in an amount of 5.0 mass% or more and 20.0 mass% or less based on the polymerizable monomer composition; the first aqueous medium contains sodium chloride in an amount of 1.5 mass% or more and 5.9 mass% or less based on the polymerizable monomer composition.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing toner particles used in electrophotography.

  In recent years, as a method for producing toner particles, a toner manufactured by a wet method such as a suspension polymerization method using a polymerizable monomer, an emulsion polymerization aggregation method, or a dissolution suspension method in which a binder resin is granulated in a solvent. Many proposals have been made. For example, in the suspension polymerization method, a polymerizable monomer, a colorant, a release agent and a polymerization initiator, and further, if necessary, a resin, a crosslinking agent, a charge control agent and other additives are uniformly dissolved or dispersed. Let it be a polymerizable monomer composition. This is dispersed in an aqueous medium containing a dispersion stabilizer using an appropriate stirrer, and a polymerizable monomer is polymerized to obtain toner particles having a desired particle size.

  The toner particles produced in this way have a very sharp particle size distribution, so that not only high developability and high transferability can be achieved, but also high yields can be achieved, which is excellent from the viewpoint of productivity. Yes.

  Under these circumstances, a method for producing toner particles having high circularity has been proposed in order to make the charge amount distribution uniform in addition to the sharp particle size distribution (for example, Patent Document 1).

  This technique has a step of forming droplets of a polymerizable monomer composition and a step of polymerizing the polymerizable monomer composition to obtain toner particles, and in each step, a dispersion stabilizer is added. Use aqueous medium. By using an aqueous medium containing a dispersion stabilizer in the polymerization step, toner particles with high circularity are obtained. However, when an aqueous medium containing a dispersion stabilizer is used in the polymerization process, toner particles having high circularity can be obtained, but at the same time, there is a tendency that fine particles are likely to be generated. When toner containing fine particles is used for electrophotography, an image such as a development streak is caused by adhesion or fixation of fine particles to a rubbing portion in a cartridge, particularly a rubbing portion between a developer carrying member and a developer regulating member. Defects may occur.

  On the other hand, as means for suppressing the generation of fine particles, an inorganic compound serving as a dispersion stabilizer and a toner particle production method devised as a method for adding an inorganic compound have been proposed (for example, Patent Documents 2 to 4).

  Although these methods can improve the properties of the dispersion stabilizer, it is possible to suppress the generation of fine particles, but the stability of the droplets of the polymerizable monomer composition in the aqueous medium is improved. And may cause coalesced toner particles. When these united toner particles are used in electrophotography, the charge amount distribution is likely to be non-uniform, and this may cause image defects such as a phenomenon of developing on a white background on an image, so-called fog.

  Therefore, from the viewpoint of improving image defects such as fogging and development streaks, it can be said that studies on a method for producing toner particles that can achieve high circularity while suppressing fine particles are still insufficient.

Japanese Patent No. 3972709 JP 2005-134411 A JP 2007-127678 A JP 2008-9092 A

  It is an object of the present invention to suppress fogging caused by coalesced particles having a non-uniform charge distribution while suppressing fine particles that cause image defects such as development streaks in a method for producing toner particles in a suspension polymerization method. Therefore, an object of the present invention is to provide a toner particle manufacturing method that achieves a high aspect ratio.

The present invention relates to a granulating step of forming particles of a polymerizable monomer composition containing a polymerizable monomer, a colorant and a polyester resin in a first aqueous medium containing a dispersion stabilizer A, the polymerizable property A polymerization step of polymerizing the polymerizable monomer contained in the particles of a monomer composition to obtain toner particles,
The polyester resin has an acid value of 0.3 mgKOH / g or more and 1.5 mgKOH / g or less, and the toner is 5.0% by mass or more and 20% by mass or less based on the polymerizable monomer composition. A toner particle comprising: a resin, wherein the first aqueous medium contains 1.5% by mass or more and 5.9% by mass or less of sodium chloride based on the polymerizable monomer composition It relates to a manufacturing method.

  The present invention further includes a step of mixing the particles of the polymerizable monomer composition obtained in the granulation step and a second aqueous medium, and the second aqueous medium is the dispersion stabilizer A. And 5.0% by weight or more and 40% by weight or less of dispersion stabilizer B based on the above.

  The present invention also relates to a method for producing toner particles, wherein the sodium chloride content of the first aqueous medium is adjusted by adding sodium chloride to the first aqueous medium.

  The present invention further relates to a method for producing toner particles, wherein the dispersion stabilizer A is prepared by mixing an aqueous calcium chloride solution and an aqueous sodium phosphate solution.

  According to the present invention, it is possible to provide a method for producing toner particles that does not cause image defects such as development streaks and fog by achieving a high aspect ratio while suppressing fine particles.

  Hereinafter, embodiments for carrying out the present invention will be described in detail.

  The present invention relates to a granulating step of forming particles of a polymerizable monomer composition containing a polymerizable monomer, a colorant and a polyester resin in a first aqueous medium containing a dispersion stabilizer A, the polymerizable property A method of producing toner particles comprising polymerizing the polymerizable monomer contained in the particles of the monomer composition to obtain toner particles, wherein the acid value of the polyester resin is 0.3 mgKOH / g or more 1.5 mg KOH / g or less, and the toner contains 5.0% by mass or more and 20.0% by mass or less of the polyester resin based on the polymerizable monomer composition, and the first aqueous medium contains And 1.5% by weight or more and 5.9% by weight or less of sodium chloride based on the polymerizable monomer composition.

  The toner particle production method of the present invention has a low acid value of 0.3 mgKOH / g or less and an acid value of the polyester resin, and the content is based on the polymerizable monomer composition. It is important for obtaining toner particles having a high aspect ratio to be 5.0% by mass or more and 20% by mass or less. The reason is not clear, but by containing a large amount of low acid value polyester resin, the dispersibility of the colorant in the polymerizable monomer composition in the granulation step and the polymerization step is improved, and the polymerizable single amount It is considered that the particles of the body composition are stabilized in the aqueous medium. Thereby, the coalescence of the particles is suppressed, and it is considered that toner particles having a high aspect ratio can be obtained.

  On the other hand, when a high acid value polyester resin is contained in a large amount, the particle size distribution becomes broad. Conventionally, it has been considered that the resin contained in the polymerizable monomer has a high acid value, so that it becomes easy to orient at the interface between the aqueous phase and the oil phase and stabilize the particles. However, if it is added too much, the dispersibility of the colorant in the polymerizable monomer composition may be lowered and the stability of the droplets may be impaired.

  Therefore, the content of the low acid value polyester resin needs to be 5.0% by mass or more and 20.0% by mass or less based on the polymerizable monomer composition. When the content is less than 5.0% by mass, the aspect ratio of the toner particles is insufficient, and even when the content exceeds 20.0% by mass, the effect of the aspect ratio of the toner particles cannot be further obtained. Since the viscosity of the polymerizable monomer composition is increased, the production stability may be decreased, which is not preferable.

  The toner particle production method of the present invention includes the control of the content of the low acid value polyester, and 1.5% by mass or more and 5.9% by mass or less based on the polymerizable monomer composition in the aqueous medium. It is important to contain sodium chloride in order to suppress fine particles. By containing a large amount of sodium chloride in the aqueous medium, it is possible to prevent the monomer of the polymerizable monomer from dissolving in the aqueous medium from the particles of the polymerizable monomer composition due to the salting out effect. If the monomer of the polymerizable monomer is dissolved in the aqueous medium, a dispersion stabilizer adheres to the monomer and fine particles such as so-called emulsified particles are generated. Moreover, the particle | grains of the polymerizable monomer composition which have a desired particle size may be adhere | attached starting from an emulsified particle | grain, and a coalesced particle may be generated.

  Therefore, the content of sodium chloride needs to be 1.5% by mass or more and 5.9% by mass or less based on the polymerizable monomer composition. Conventional dispersion stabilizers produce by-product salts in aqueous media. However, the content of the by-product salt is small for the salting out effect. On the other hand, when the amount of the dispersion stabilizer added is large, toner particles having a desired particle diameter cannot be obtained, and it is preferable to add sodium chloride. The content of sodium chloride defined in the present invention is the total amount of by-product salt and added sodium chloride, and if it is less than 1.5% by mass, the suppression of fine particles becomes insufficient. Even if it exceeds .9% by mass, the effect of suppressing fine particles cannot be obtained any more, and the content of sodium chloride remaining in the toner particles increases, so the chargeability of the toner decreases. Since there is a case, it is not preferable.

  The present invention further includes a step of mixing the particles of the polymerizable monomer composition obtained in the granulation step and a second aqueous medium, and the second aqueous medium is the dispersion stabilizer A. The dispersion stabilizer B is preferably contained in an amount of 5.0% by mass or more and 40.0% by mass or less based on the above. By containing the above-mentioned content of the dispersion stabilizer B in the second aqueous medium, it becomes possible to compensate for the dispersion stabilizer that is insufficient during granulation and to obtain toner particles having a higher aspect ratio. However, when the content of the dispersion stabilizer B is less than 5.0% by mass based on the dispersion stabilizer A, the effect of further improving the aspect ratio is insufficient. On the other hand, if it exceeds 40.0% by mass, the excessive dispersion stabilizer B tends to adhere to the volatile monomer of the polymerizable monomer during polymerization and increase the fine particles, which is not preferable.

  Moreover, as for this invention, it is preferable to adjust content of this sodium chloride of this 1st aqueous medium by adding sodium chloride to this 1st aqueous medium as mentioned above.

In the present invention, the dispersion stabilizer A is preferably prepared by mixing an aqueous calcium chloride solution and an aqueous sodium phosphate solution. From calcium chloride and calcium phosphate, as shown in the following formula (1), hydroxyapatite and sodium chloride as a by-product salt are generated. Hydroxyapatite is a preferred dispersion stabilizer for stabilizing the particles of the polymerizable monomer composition. Moreover, since sodium chloride is produced as a by-product salt, it is preferably used in the present invention in order to express a salting-out effect for suppressing fine particles. In the examples described later, the amount of by-product salt is calculated according to the following formula (1).
6Na ₃ PO ₄ + 10CaCl ₂ + 2H ₂ O → [Ca ₃ (PO ₄ ) ₂ ] ₃ Ca (OH) ₂ + 18NaCl + 2HCl Formula (1)

  Hereinafter, a material configuration and a manufacturing method for carrying out the present invention will be described in detail.

  In the present invention, it is produced by a suspension polymerization method in which a polymerizable monomer composition is granulated in an aqueous medium to form particles of the polymerizable monomer composition.

  As the polymerizable monomer, a vinyl monomer capable of radical polymerization is used. As the vinyl monomer, a monofunctional monomer or a polyfunctional monomer can be used.

  Monofunctional monomers include styrene; styrene derivatives such as α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene; methyl Acrylic polymerizable monomers such as acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, dibutyl Methacrylic polymerizable monomers such as phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl esters such as vinyl acetate and vinyl propionate; vinyl methyl ether; Sulfonyl ethyl ether, vinyl ether such as vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone, and vinyl ketones such as vinyl isopropyl ketone.

  Among the above, the polymerizable monomer preferably contains styrene or a styrene derivative.

  Examples of the polyfunctional monomer include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinyl ether and the like.

  You may use the above-mentioned monofunctional monomer individually or in combination of 2 or more types, or combining the above-mentioned monofunctional monomer and polyfunctional monomer. Polyfunctional monomers can also be used as crosslinking agents.

  As the polymerization initiator used in the present invention, an oil-soluble initiator and / or a water-soluble initiator is used. Preferably, the half-life at the reaction temperature during the polymerization reaction is 0.5 to 30 hours. Further, when the polymerization reaction is carried out at an addition amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer, a polymer having a maximum value between 10,000 and 100,000 is usually obtained. It is preferable because toner particles having excellent strength and melting characteristics can be obtained.

  As polymerization initiators, the following 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbohydrate) were used. Nitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azo or diazo polymerization initiators such as azobisisobutyronitrile; benzoyl peroxide, t-butylperoxy 2- Ethyl hexanoate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4- Peroxidation such as dichlorobenzoyl peroxide and lauroyl peroxide System polymerization initiators and the like.

  In the present invention, in order to control the degree of polymerization of the polymerizable monomer, a known chain transfer agent, polymerization inhibitor or the like can be further added and used.

  In the present invention, the polymerizable monomer composition contains a polyester resin.

  Examples of the polyester resin used in the present invention include the following.

  Examples of the divalent acid component include the following dicarboxylic acids or derivatives thereof. Benzene dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride or their anhydrides or lower alkyl esters thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid or their anhydrides or lower thereof Alkyl esters; alkenyl succinic acids or alkyl succinic acids such as n-dodecenyl succinic acid, n-dodecyl succinic acid, or anhydrides thereof or lower alkyl esters thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, itaconic acid Or its anhydride or its lower alkyl ester.

  The following are mentioned as a bivalent alcohol component. Ethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol (CHDM), hydrogenated bisphenol A, formula (I) ) Bisphenol and its derivatives:

（式中、Ｒはエチレンまたはプロピレン基であり、ｘ、ｙはそれぞれ０以上の整数であり、かつ、ｘ＋ｙの平均値は０乃至１０である。）

(In the formula, R is an ethylene or propylene group, x and y are each an integer of 0 or more, and the average value of x + y is 0 to 10.)

  The polyester resin that can be used in the present invention includes a monovalent carboxylic acid compound, a monovalent alcohol compound, a trivalent or higher carboxylic acid compound, in addition to the above-described divalent carboxylic acid compound and divalent alcohol compound. You may contain the alcohol compound more than a valence as a structural component.

  Examples of the monovalent carboxylic acid compound include aromatic carboxylic acids having 30 or less carbon atoms such as benzoic acid and p-methylbenzoic acid, and aliphatic carboxylic acids having 30 or less carbon atoms such as stearic acid and behenic acid. .

  Examples of monovalent alcohol compounds include aromatic alcohols having 30 or less carbon atoms such as benzyl alcohol, and aliphatic alcohols having 30 or less carbon atoms such as lauryl alcohol, cetyl alcohol, stearyl alcohol, and behenyl alcohol. It is done.

  Although it does not restrict | limit especially as a trivalent or more carboxylic acid compound, A trimellitic acid, trimellitic anhydride, pyromellitic acid, etc. are mentioned.

  Examples of the trivalent or higher alcohol compound include trimethylolpropane, pentaerythritol, and glycerin.

  The production method of the polyester resin that can be used in the present invention is not particularly limited, and a known method can be used.

  The polyester resin that can be used in the present invention may be a crystalline polyester resin.

  As the alcohol component used for the raw material monomer of the crystalline polyester resin, an aliphatic diol having 6 to 18 carbon atoms is preferably used from the viewpoint of enhancing crystallinity. Among these, aliphatic diols having 6 to 12 carbon atoms are preferable from the viewpoints of fixability and heat stability. Examples of the aliphatic diol include 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1, Examples include 12-dodecanediol. The content of the aliphatic diol is preferably 80.0 mol% or more and 100.0 mol% or less in the alcohol component from the viewpoint of further improving the crystallinity of the crystalline polyester resin.

  As an alcohol component for obtaining crystalline polyester resin, you may contain polyhydric alcohol components other than said aliphatic diol. For example, the polyoxypropylene adduct of 2,2-bis (4-hydroxyphenyl) propane and the polyoxyethylene adduct of 2,2-bis (4-hydroxyphenyl) propane are represented by the above formula (I). Aromatic diols such as alkylene oxide adducts of bisphenol A; trivalent or higher alcohols such as glycerin, pentaerythritol, and trimethylolpropane.

  As the carboxylic acid component used for the raw material monomer of the crystalline polyester resin, an aliphatic dicarboxylic acid compound having 6 to 18 carbon atoms is preferably used. Among these, aliphatic dicarboxylic acid compounds having 6 to 12 carbon atoms are preferable from the viewpoint of toner fixing properties and heat stability. Examples of the aliphatic dicarboxylic acid compound include 1,8-octanedioic acid, 1,9-nonanedioic acid, 1,10-decanedioic acid, 1,11-undecanedioic acid, 1,12-dodecanedioic acid, and the like. It is done. The content of the aliphatic dicarboxylic acid compound having 6 to 18 carbon atoms is preferably 80.0 mol% or more and 100.0 mol% or less in the carboxylic acid component.

  As a carboxylic acid component for obtaining a crystalline polyester resin, a carboxylic acid component other than the aliphatic dicarboxylic acid compound may be contained. For example, an aromatic dicarboxylic acid compound, a trivalent or higher valent aromatic polycarboxylic acid compound, and the like can be mentioned, but the invention is not particularly limited thereto. The aromatic dicarboxylic acid compound also includes an aromatic dicarboxylic acid derivative. Specific examples of the aromatic dicarboxylic acid compound include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid, anhydrides of these acids, and alkyl (1 to 3 carbon atoms) esters thereof. . Examples of the alkyl group in the alkyl ester include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Examples of the trivalent or higher polyvalent carboxylic acid compounds include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, and aromatic carboxylic acids such as pyromellitic acid, and these Derivatives such as acid anhydrides and alkyl (having 1 to 3 carbon atoms) esters may be mentioned.

  In the present invention, the polymerizable monomer composition may contain a wax as a release agent.

  The wax is preferably a hydrocarbon wax such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, or paraffin wax from the viewpoint of high releasability. If necessary, two or more kinds of waxes may be used in combination.

  Specific examples of the wax include the following. Biscol (registered trademark) 330-P, 550-P, 660-P, TS-200 (Sanyo Chemical Industries), High Wax 400P, 200P, 100P, 410P, 420P, 320P, 220P, 210P, 110P (Mitsui Chemicals) ), Sazole H1, H2, C80, C105, C77 (Schumann Sazol), HNP-1, HNP-3, HNP-9, HNP-10, HNP-11, HNP-12 (Nippon Seiki Co., Ltd.), Unilin (registered trademark) 350, 425, 550, 700, Unicid (registered trademark), Unicid (registered trademark) 350, 425, 550, 700 (Toyo Adre Co., Ltd.), wood wax, beeswax, rice wax, candelilla wax Carnauba wax (available from Celerica NODA).

  The amount of the wax added is preferably 1.0 to 20.0 parts by mass of wax with respect to 100 parts by mass of the binder resin.

  The toner particles of the present invention may be magnetic toner particles or non-magnetic toner particles.

  When manufacturing as magnetic toner particles, it is preferable to use magnetic iron oxide as the magnetic material. As the magnetic iron oxide, iron oxides such as magnetite, maghematite, and ferrite are used. The amount of magnetic iron oxide contained in the toner is preferably 25 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the binder resin.

  When producing non-magnetic toner particles, carbon black or other known pigments or dyes can be used as the colorant. Further, only one kind of pigment or dye may be used, or two or more kinds may be used in combination. The colorant contained in the toner is preferably 0.1 parts by mass or more and 60.0 parts by mass or less, more preferably 0.5 parts by mass or more and 50.0 parts by mass with respect to 100 parts by mass of the binder resin. Or less.

  In the method for producing toner particles by the suspension polymerization method, in addition to the materials described above, a known charge control agent, conductivity imparting agent, lubricant, abrasive, and the like may be added.

  In the suspension polymerization toner particles, these additives are uniformly dissolved or dispersed to form a polymerizable monomer composition. Thereafter, the polymerizable monomer composition is dispersed in an aqueous medium containing a dispersion stabilizer using an appropriate stirrer, and if necessary, an aromatic solvent and a polymerization initiator are added to perform a polymerization reaction. To obtain toner particles having a desired particle diameter.

  After the polymerization of the toner particles, the toner is obtained by filtering, washing and drying by a known method, and if necessary, mixing inorganic fine powder as a fluidity improver and adhering it to the surface.

  Known inorganic fine powders can be used. Preferred are silica fine particles such as titania fine particles, wet-processed silica, and dry-process silica, and inorganic fine powders obtained by surface-treating these silicas with a silane coupling agent, a titanium coupling agent, or silicone oil. The inorganic fine powder subjected to the surface treatment preferably has a degree of hydrophobicity of 30 or more and 98 or less titrated by a methanol titration test.

  A method for measuring physical properties of the obtained toner particles and toner is as follows. Also in the examples described later, the physical property values are measured based on these methods.

<Measurement of Tg of Resin>
The Tg of the resin is measured in accordance with ASTM D3418-82 using a differential scanning calorimeter “Q2000” (manufactured by TA Instruments). The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium. Specifically, about 2 mg of a sample is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference. Measurement is performed at ° C / min. In the measurement, the temperature is once raised to 200 ° C., subsequently lowered to 30 ° C., and then the temperature is raised again. A specific heat change is obtained in the temperature range of 40 ° C. to 100 ° C. in the second temperature raising process. At this time, the point of intersection between the line of the midpoint of the baseline before and after the change in specific heat and the differential heat curve is defined as the glass transition temperature Tg of the resin.

<Measurement of softening point of resin>
The softening point of the resin is measured by using a constant load extrusion type capillary rheometer “Flow Characteristic Evaluation Device Flow Tester CFT-500D” (manufactured by Shimadzu Corporation) according to the manual attached to the device. In this device, while applying a constant load from the top of the measurement sample with the piston, the measurement sample filled in the cylinder is heated and melted, and the melted measurement sample is pushed out from the die at the bottom of the cylinder, and the piston drop amount at this time A flow curve showing the relationship between temperature and temperature can be obtained.

  The “melting temperature in the 1/2 method” described in the manual attached to the “flow characteristic evaluation device Flow Tester CFT-500D” is defined as the softening point. The melting temperature in the 1/2 method is calculated as follows. First, ½ of the difference between the piston lowering amount Smax at the time when the outflow ends and the piston lowering amount Smin at the time when the outflow starts is obtained (this is X. X = (Smax−Smin) / 2). And the temperature of the flow curve when the amount of descending piston is the sum of X and Smin in the flow curve is the melting temperature in the 1/2 method.

  As a measurement sample, about 1.0 g of a sample is compression-molded at about 10 MPa for about 60 seconds using a tablet molding compressor (for example, NT-100H, manufactured by NPA System) in an environment of 25 ° C. A cylindrical shape having a diameter of about 8 mm is used.

The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rising method temperature rising rate: 4 ° C./min
Starting temperature: 50 ° C
Achieving temperature: 200 ° C

<Measurement of acid value of resin>
The acid value of the resin is the number of mg of potassium hydroxide necessary to neutralize the acid contained in 1 g of the sample. The acid value of the polyester resin is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.

(1) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 ml of ethyl alcohol (95 vol%), and ion exchanged water is added to make 100 ml to obtain a phenolphthalein solution.

  7 g of special grade potassium hydroxide is dissolved in 5 ml of water, and ethyl alcohol (95 vol%) is added to make 1 l. In order not to touch carbon dioxide, etc., put in an alkali-resistant container and let stand for 3 days, then filter to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was as follows: 25 ml of 0.1 mol / l hydrochloric acid was placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution were added, titrated with the potassium hydroxide solution, and the hydroxide required for neutralization. Determined from the amount of potassium solution. As the 0.1 mol / l hydrochloric acid, one prepared according to JIS K 8001-1998 is used.

(2) Operation (A) Main test 2.0 g of a pulverized polyester resin sample is precisely weighed into a 200 ml Erlenmeyer flask, and 100 ml of a mixed solution of toluene / ethanol (2: 1) is added and dissolved over 5 hours. Subsequently, several drops of the phenolphthalein solution is added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of titration is when the light red color of the indicator lasts for about 30 seconds.

(B) Blank test Titration is performed in the same manner as above except that no sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).

(3) The acid value is calculated by substituting the obtained result into the following formula.
A = [(C−B) × f × 5.61] / S

  Here, A: acid value (mgKOH / g), B: addition amount (ml) of a potassium hydroxide solution in a blank test, C: addition amount (ml) of a potassium hydroxide solution in this test, f: potassium hydroxide Solution factor, S: sample (g).

<Measurement of hydroxyl value of binder resin>
The hydroxyl value is the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when 1 g of a sample is acetylated. The hydroxyl value of the binder resin is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.

(1) Preparation of reagent 25 g of special grade acetic anhydride is placed in a 100 ml volumetric flask, pyridine is added to make a total volume of 100 ml, and shaken sufficiently to obtain an acetylating reagent. The obtained acetylating reagent is stored in a brown bottle so as not to come into contact with moisture, carbon dioxide gas and the like.

  Dissolve 1.0 g of phenolphthalein in 90 ml of ethyl alcohol (95 vol%) and add ion exchange water to make 100 ml to obtain a phenolphthalein solution.

  Dissolve 35 g of special grade potassium hydroxide in 20 ml of water and add ethyl alcohol (95 vol%) to make 1 liter. In order not to touch carbon dioxide, etc., put in an alkali-resistant container and let stand for 3 days, then filter to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was as follows: 25 ml of 0.5 mol / l hydrochloric acid was placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution were added, titrated with the potassium hydroxide solution, and the hydroxide required for neutralization. Determined from the amount of potassium solution. As the 0.5 mol / l hydrochloric acid, one prepared according to JIS K 8001-1998 is used.

(2) Operation (A) Main test A 1.0 g sample of the pulverized binder resin is precisely weighed into a 200 ml round bottom flask, and 5.0 ml of the acetylating reagent is accurately added to the sample using a whole pipette. At this time, if the sample is difficult to dissolve in the acetylating reagent, a small amount of special grade toluene is added and dissolved.

  A small funnel is placed on the mouth of the flask, and the bottom of the flask is immersed in a glycerin bath at about 97 ° C. and heated. At this time, in order to prevent the temperature of the neck of the flask from rising due to the heat of the bath, it is preferable to cover the base of the neck of the flask with a cardboard having a round hole.

  After 1 hour, the flask is removed from the glycerin bath and allowed to cool. After standing to cool, 1 ml of water is added from the funnel and shaken to hydrolyze acetic anhydride. The flask is again heated in the glycerin bath for 10 minutes for further complete hydrolysis. After cooling, wash the funnel and flask walls with 5 ml of ethyl alcohol.

  Add several drops of the phenolphthalein solution as an indicator and titrate with the potassium hydroxide solution. The end point of titration is when the light red color of the indicator lasts for about 30 seconds.

(B) Blank test Titration similar to the above operation is performed except that no binder resin sample is used.

(3) Substituting the obtained results into the following formula to calculate the hydroxyl value.
A = [{(BC) × 28.05 × f} / S] + D

  Here, A: hydroxyl value (mg KOH / g), B: addition amount (ml) of potassium hydroxide solution in blank test, C: addition amount (ml) of potassium hydroxide solution in this test, f: potassium hydroxide Factor of solution, S: sample (g), D: acid value of binder resin (mgKOH / g).

<Measurement method of weight average particle diameter (D4)>
The weight average particle diameter (D4) of the toner is determined based on the precise particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) having a 100 μm aperture tube. Using the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) for setting and analyzing the measurement data, the measurement data is measured with 25,000 effective channels. Analysis was performed and calculated.

  As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, dedicated software was set up as follows.

  In the “Standard Measurement Method (SOM) Change Screen” of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash after measurement is checked.

  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 to 60 μm.

The specific measurement method is as follows.
1. About 200 ml of the electrolytic solution is placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.
2. About 30 ml of the electrolytic aqueous solution is put in a glass 100 ml flat bottom beaker, and “Contaminone N” (a nonionic surfactant, an anionic surfactant, and an organic builder for pH 7 precision measuring instrument washing is used as a dispersant therein. About 0.3 ml of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent (manufactured by Wako Pure Chemical Industries, Ltd.) with ion-exchanged water 3 times by mass is added.
3. Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and a predetermined amount of ions are contained in the water tank of an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) with an electrical output of 120 W. Exchange water is added, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.
4). 2. Is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
5. 4. above. In the state where the electrolytic aqueous solution in the beaker is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
6). The above 1. installed in the sample stand. The toner was dispersed in a round bottom beaker using a pipette. The aqueous electrolyte solution is dropped to adjust the measured concentration to about 5%. The measurement is performed until the number of measured particles reaches 50,000.
7). Constant data is analyzed with the dedicated software attached to the apparatus, and each average particle size is calculated. When the graph / volume% is set in the dedicated software, the “arithmetic diameter” on the analysis / volume statistics screen is the weight average particle diameter D4 and the “50% D diameter” is D50. The number average particle diameter D1 is calculated in the same manner.

<Measurement method of aspect ratio and small particle ratio>
The average circularity of the toner particles was measured with a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) under the measurement and analysis conditions during the calibration operation.

  A specific measurement method is as follows. First, about 20 ml of ion-exchanged water from which impure solids are removed in advance is put in a glass container. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.2 ml of a diluted solution obtained by diluting the solution with ion exchange water about 3 times by mass. Further, about 0.02 g of a measurement sample is added, and dispersion treatment is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of a dispersion liquid may become 10 to 40 degreeC. As the ultrasonic disperser, a desktop type ultrasonic cleaner disperser (for example, “VS-150” (manufactured by VervoCrea)) having an oscillation frequency of 50 kHz and an electric output of 150 W is used. Ion exchange water is added, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.

  For the measurement, the above-mentioned flow type particle image analyzer equipped with “LUCPLFLN” (magnification 20 ×, numerical aperture 0.40) as an objective lens is used, and particle sheath “PSE-900A” (manufactured by Sysmex Corporation) is used as the sheath liquid. It was used. The dispersion prepared in accordance with the above procedure is introduced into the flow type particle image analyzer, and 2000 toner particles are measured in the HPF measurement mode and in the total count mode. Then, the binarization threshold at the time of particle analysis was set to 85%, the analysis particle diameter was limited to a circle equivalent diameter of 1.977 μm or more and less than 39.54 μm, and the aspect ratio and small particle ratio of toner particles were obtained.

  In the measurement, automatic focus adjustment is performed using standard latex particles (eg, “RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5100A” manufactured by Duke Scientific) diluted with ion-exchanged water before starting the measurement. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.

  In the examples of the present application, a flow-type particle image analyzer that has been issued a calibration certificate issued by Sysmex Corporation, which has been calibrated by Sysmex Corporation, was used. Measurement was performed under the measurement and analysis conditions when the calibration certificate was received, except that the analysis particle diameter was limited to a circle equivalent diameter of 1.977 μm or more and less than 39.54 μm.

  Examples are shown below.

  The toner and the toner particle manufacturing method will be described in detail.

<Example of production of polyester resin B1>
Into a reaction vessel equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, after using the amount of monomer shown in Table 1, 1.5 mass of dibutyltin as a catalyst with respect to 100 mass parts of the total amount of monomers. Part was added. Next, the temperature was quickly raised to 180 ° C. under normal pressure in a nitrogen atmosphere, and then water was distilled off while heating from 180 ° C. to 210 ° C. at a rate of 10 ° C./hour to perform polycondensation. After reaching 210 ° C., the pressure in the reaction vessel was reduced to 5 kPa or less, and polycondensation was performed under the conditions of 210 ° C. and 5 kPa or less to obtain polyester resin B1. At that time, the polymerization time was adjusted so that the softening point of the obtained polyester resin B1 was the value shown in Table 2 (125 ° C.). Table 2 shows the physical properties of the polyester resin B1.

<Example of production of polyester resins B2 to B4>
Monomers and amounts used were changed as shown in Table 1, and polyester resins B2 to B4 were obtained in the same manner as polyester resin B1 except that. Table 2 shows the physical properties of the polyester resins B2 to B4.

<Production example of magnetic body 1>
During an aqueous ferrous sulfate solution, 1.10 eq of sodium hydroxide solution from 1.00 relative to iron element, the amount of P ₂ O ₅ to an iron element to be 0.15% by mass in terms of phosphorus, the iron element On the other hand, SiO ₂ in an amount of 0.50% by mass in terms of silicon element was mixed to prepare an aqueous solution containing ferrous hydroxide. The pH of the aqueous solution was 8.0, and an oxidation reaction was performed at 85 ° C. while blowing air to prepare a slurry liquid having seed crystals.

  Subsequently, after adding ferrous sulfate aqueous solution so that it may become 0.90 to 1.20 equivalent with respect to the original alkali amount (sodium component of caustic soda) to this slurry liquid, the slurry liquid is maintained at pH 7.6, The oxidation reaction was promoted while blowing air to obtain a slurry liquid containing magnetic iron oxide. After filtration and washing, the water-containing slurry was once taken out. At this time, a small amount of water-containing sample was collected and the water content was measured. Next, this water-containing sample is put into another aqueous medium without being dried, stirred and redispersed with a pin mill while circulating the slurry, and the pH of the redispersed liquid is adjusted to about 4.8. Then, 1.6 parts by mass of n-hexyltrimethoxysilane coupling agent with respect to 100 parts by mass of magnetic iron oxide (the amount of magnetic iron oxide was calculated as a value obtained by subtracting the water content from the water-containing sample) was added with stirring. Hydrolysis was performed. Thereafter, the mixture was sufficiently stirred, and the dispersion was subjected to surface treatment at a pH of 8.6. The produced hydrophobic magnetic material is filtered with a filter press, washed with a large amount of water, dried at 100 ° C. for 15 minutes, and then at 90 ° C. for 30 minutes. 0.21 μm magnetic body 1 was obtained.

<Production Example of Toner 1>
Toner particles and toner were produced by the following procedure.

(Preparation of the first aqueous medium)
Into 342.8 parts by mass of ion-exchanged water, 3.1 parts by mass of sodium phosphate 12 hydrate was added and heated to 60 ° C. with stirring using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). After that, calcium chloride aqueous solution in which 1.8 parts by mass of calcium chloride dihydrate was added to 12.7 parts by mass of ion-exchanged water, and 4.3 parts by mass of sodium chloride were added to 14.5 parts by mass of ion-exchanged water. A sodium chloride aqueous solution was added and stirring was continued to obtain a first aqueous medium containing the dispersion stabilizer A.

(Preparation of polymerizable monomer composition)
Styrene 74.0 parts by mass n-butyl acrylate 26.0 parts by mass 1-6 hexanediol diacrylate 0.5 parts by mass Aluminum salicylate compound (E-101: manufactured by Orient Chemical Co., Ltd.) 0.5 parts by mass Colorant: 65.0 parts by mass of magnetic material 1 and 20.0 parts by mass of polyester resin B1 The above materials are uniformly dispersed and mixed using an attritor (manufactured by Mitsui Miike Chemical Co., Ltd.), and then heated to 60 ° C. Then, 15.0 parts by mass of paraffin wax (DSC peak temperature: 80 ° C.) was added, mixed and dissolved to obtain a polymerizable monomer composition.

(Preparation of second aqueous medium)
0.9 parts by mass of sodium phosphate dodecahydrate is added to 164.7 parts by mass of ion-exchanged water and heated to 60 ° C. with stirring using a paddle stirring blade, and then 3.8 parts by mass of ion-exchanged water. Then, a calcium chloride aqueous solution added with 0.5 parts by mass of calcium chloride dihydrate was added to the mixture, followed by stirring to obtain a second aqueous medium containing the dispersion stabilizer B.

(Granulation)
Said the polymerizable monomer composition and t- butyl peroxypivalate 7.0 part by weight as a polymerization initiator was introduced into the first aqueous medium, 60 ° C., TK homomixer (Special under N ₂ atmosphere Granulation was carried out at 12000 rpm for 10 minutes at Meka Kogyo Co., Ltd. to obtain a granulated liquid containing droplets of the polymerizable monomer composition.

(Polymerization / distillation / drying / external addition)
The granulation liquid was put into the second aqueous medium and reacted at 74 ° C. for 3 hours while stirring with a paddle stirring blade. After completion of the reaction, the mixture was distilled at 98 ° C. for 3 hours, and then the suspension was cooled, washed with hydrochloric acid, filtered and dried to obtain toner particles having a weight average particle diameter of 8.0 μm.

To 100 parts by mass of the obtained toner particles, the following materials were mixed with a Henschel mixer (FM-10 model manufactured by Mitsui Miike Chemical Co., Ltd.) to obtain toner 1. The temperature of the Henschel mixer jacket was adjusted to 45 ° C.
-Hydrophobic silica fine particles having a number average particle size of 20 nm of primary particles surface-treated with 25% by mass of hexamethyldisilazane 0.5 parts by mass-Number average particle size of primary particles surface-treated with 15% by mass of hexamethyldisilazane 110 nm 0.5 part by mass of hydrophobic silica fine particles obtained The toner had a particle size distribution (D50 / D1) of 1.10, an aspect ratio of 0.930, and a small particle ratio of 4.5%.

  Table 3 shows the main production conditions of the toner. In Table 3, “polyester resin content” is based on the polymerizable monomer composition, “dispersion of dispersion stabilizer B” is based on the dispersion stabilizer A, “ The “content of sodium chloride” is based on the polymerizable monomer composition.

<Production Example of Toner 2>
Toner 2 was obtained in the same manner as in Toner 1 except that the amount of sodium chloride added was 2.3 parts by mass in Toner 1 Production Example. The production conditions of the obtained toner are shown in Table 3, and the physical properties are shown in Table 4.

<Production Example of Toner 3>
Toner 3 was obtained in the same manner as in Toner 1 except that the amount of sodium chloride added was 9.2 parts by weight. The production conditions of the obtained toner are shown in Table 3, and the physical properties are shown in Table 4.

<Production Example of Toner 4>
In the toner 1 production example, toner 4 was obtained in the same manner as in the toner 1 production example, except that the addition part of the polyester resin B1 was 10.0 parts by mass. The production conditions of the obtained toner are shown in Table 3, and the physical properties are shown in Table 4.

<Production Example of Toner 5>
In the toner 1 production example, toner 5 was obtained in the same manner as in the toner 1 production example, except that the addition part of the polyester resin B1 was changed to 47.0 parts by mass. The production conditions of the obtained toner are shown in Table 3, and the physical properties are shown in Table 4.

<Production Example of Toner 6>
A toner 6 was obtained in the same manner as in the production example of the toner 1 except that the polyester resin B1 was changed to the polyester resin B2 in the production example of the toner 1. The production conditions of the obtained toner are shown in Table 3, and the physical properties are shown in Table 4.

<Production Example of Toner 7>
A toner 7 was obtained in the same manner as in the production example of the toner 1 except that the polyester resin B1 was changed to the polyester resin B3 in the production example of the toner 1. The production conditions of the obtained toner are shown in Table 3, and the physical properties are shown in Table 4.

<Production Example of Toner 8>
In the production example of Toner 1, the added amount of sodium phosphate dodecahydrate used for adjusting the second aqueous medium was 0.15 parts by mass, and the added part of calcium chloride dihydrate was 0.08 parts by mass. Except for the above, Toner 8 was obtained in the same manner as in Toner 1 Production Example. The production conditions of the obtained toner are shown in Table 3, and the physical properties are shown in Table 4.

<Production Example of Toner 9>
In the production example of Toner 1, the added amount of sodium phosphate dodecahydrate used for adjusting the second aqueous medium was 1.2 parts by mass, and the added part of calcium chloride dihydrate was 0.67 parts by mass. Except for the above, Toner 9 was obtained in the same manner as in Toner 1 Production Example. The production conditions of the obtained toner are shown in Table 3, and the physical properties are shown in Table 4.

<Production Example of Toner 10>
In the production example of Toner 1, the added amount of sodium phosphate dodecahydrate used for adjusting the second aqueous medium was 0.06 parts by mass, and the added part of calcium chloride dihydrate was 0.03 parts by mass. Except for the above, Toner 10 was obtained in the same manner as in Toner 1 Production Example. The production conditions of the obtained toner are shown in Table 3, and the physical properties are shown in Table 4.

<Production Example of Toner 11>
In the toner 1 production example, the added amount of sodium phosphate dodecahydrate used for adjusting the second aqueous medium was 1.5 parts by mass, and the added part of calcium chloride dihydrate was 0.83 parts by mass. Except for the above, Toner 11 was obtained in the same manner as in Toner 1 Production Example. The production conditions of the obtained toner are shown in Table 3, and the physical properties are shown in Table 4.

<Production Example of Toner 12>
In the production example of the toner 10, the toner 12 is produced in the same manner as in the production example of the toner 10 except that the calcium chloride dihydrate is changed to magnesium chloride dihydrate for the adjustment of the first aqueous medium and the second aqueous medium. Got. The production conditions of the obtained toner are shown in Table 3, and the physical properties are shown in Table 4.

<Production Example of Toner 13>
A toner 13 was obtained in the same manner as in the production example of the toner 1 except that the magnetic material 1 was changed to 6 parts by mass of carbon black in the production example of the toner 1. The production conditions of the obtained toner are shown in Table 3, and the physical properties are shown in Table 4.

<Production Example of Toner 14>
A toner 14 was obtained in the same manner as in the production example of the toner 12 except that the polyester resin B1 was changed to the polyester resin B4 in the production example of the toner 12. The production conditions of the obtained toner are shown in Table 3, and the physical properties are shown in Table 4.

<Production Example of Toner 15>
In the toner 12 production example, a toner 15 was obtained in the same manner as in the toner 12 production example, except that the addition part of the polyester resin B1 was 4.0 parts by mass. The production conditions of the obtained toner are shown in Table 3, and the physical properties are shown in Table 4.

<Production Example of Toner 16>
In the toner 12 production example, a toner 16 was obtained in the same manner as in the toner 12 production example, except that the amount of sodium chloride added was 1.8 parts by mass. The production conditions of the obtained toner are shown in Table 3, and the physical properties are shown in Table 4.

<Production Example of Toner 17>
In the toner 12 production example, toner 17 was obtained in the same manner as in the toner 12 production example, except that the amount of sodium chloride added was 9.7 parts by mass. The production conditions of the obtained toner are shown in Table 3, and the physical properties are shown in Table 4.

[Example 1]
A commercially available laser printer LASERJET PRO P1606 (manufactured by HP) was used for image evaluation in the examples.

  The process cartridge of the evaluation machine was taken out, the product toner was extracted from the cartridge, and 150 g of toner 1 was filled. The cartridge was left in a high-temperature and high-humidity environment with a temperature of 32.5 ° C. and a relative humidity of 80% for 24 hours, and then image evaluation was performed. As for image output evaluation, the following evaluation was performed and the following indicators were used. The evaluation results are shown in Table 4.

Fog (high temperature and high humidity)
An image having a printing ratio of 2% was output, and paper was passed until the remaining amount of the filled toner reached 50 g. When the toner remaining amount reached 50 g, a solid black image was printed, and the fog toner on the photoconductor in the white background immediately after the solid black portion was developed was taped. Taped tape was affixed to white paper, and the fog density (%) was calculated from the difference from the tape without taping. For fog measurement, TC-6DS (manufactured by Tokyo Denshoku Co., Ltd.) was used, and the average value of 5 points was taken as the fog density (%), and the following index was used for judgment.
A: Fog less than 2.5% B: Fog 2.5% or more, less than 5.0% C: Fog 5.0% or more, less than 7.5% D: Fog 7.5% or more, less than 10.0% E: Fog 10.0% or more

Development stripe (under high temperature and high humidity)
Subsequently, the toner coat property and the solid image on the developer carrying member were visually observed and judged by the following indices.
A: No streaks on the developer carrying member B: Minor streaks can be seen on the developer carrying member C: Streaks can be seen on the developer carrying member, but not on solid images D: On solid images Minor streaks can be seen E: There are clear streaks on solid images.

[Examples 2 to 12, Comparative Examples 1 to 4]
Evaluation was performed in the same manner as in Example 1 except that the toner was changed as shown in Table 3. The evaluation results are shown in Table 4.

Example 13
Evaluation was performed in the same manner as in Example 1 except that a commercially available color laser printer Color Laser Jet CP4525 (manufactured by hp) was used and image evaluation was performed using a black cartridge. The evaluation results are shown in Table 4.

Claims (4)

A granulating step of forming particles of a polymerizable monomer composition containing a polymerizable monomer, a colorant and a polyester resin in a first aqueous medium containing the dispersion stabilizer A, the polymerizable monomer composition A polymerization step of polymerizing the polymerizable monomer contained in the particles of the product to obtain toner particles,
The acid value of the polyester resin is 0.3 mgKOH / g or more and 1.5 mgKOH / g or less,
The toner contains 5.0% by mass or more and 20.0% by mass or less of the polyester resin based on the polymerizable monomer composition;
The method for producing toner particles, wherein the first aqueous medium contains 1.5% by mass or more and 5.9% by mass or less of sodium chloride based on the polymerizable monomer composition. A step of mixing the particles of the polymerizable monomer composition obtained in the granulation step and a second aqueous medium;
2. The toner particle production according to claim 1, wherein the second aqueous medium contains 5.0% by mass or more and 40.0% by mass or less of a dispersion stabilizer B based on the dispersion stabilizer A. 3. Method.   3. The method for producing toner particles according to claim 1, wherein the content of the sodium chloride in the first aqueous medium is adjusted by adding sodium chloride to the first aqueous medium.   The method for producing toner particles according to claim 1, wherein the dispersion stabilizer A is prepared by mixing an aqueous calcium chloride solution and an aqueous sodium phosphate solution. .