JP2018072407A - Method for manufacturing toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing toner with which a toner excellent in hot offset resistance can be manufactured without deteriorating low-temperature fixability and expanding a particle size distribution.SOLUTION: There is provided a method for manufacturing a toner including toner particles containing a binder resin and a hydrocarbon wax, the manufacturing method including: a granulation step of forming particles of polymerizable monomer composition in an aqueous medium; and a polymerization step of polymerizing the polymerizable monomer to obtain resin particles. The polymerizable monomer composition contains a polymerizable monomer that can form the binder resin, the hydrocarbon wax, and a non-polymerizable organic solvent; the difference Rar in Hansen solubility parameter (HSP) between the non-polymerizable organic solvent and the hydrocarbon wax is 2.00 or less; the difference Raw in Hansen solubility parameter (HSP) between the non-polymerizable organic solvent and the aqueous medium is 41.00 or more and 45.20 or less; the melting point Tr(°C) of the hydrocarbon wax satisfies the following formula (1). (1) Tp+15≤Tr≤Tp+30(°C). (In the formula, Tp represents the average temperature of the aqueous medium in the granulation step and the polymerization step).SELECTED DRAWING: None

Description

  The present invention relates to a method for producing toner used to form a toner image by developing an electrostatic latent image formed by a method such as electrophotography, electrostatic recording, or toner jet recording.

In an electrophotographic process, in which toner is heated and pressurized and fixed on a recording medium (fixing process), a toner containing wax as a release agent in order to suppress a phenomenon that the toner adheres to a fixing member, so-called offset Has been devised.
The suspension polymerization method, which is one of the toner production methods, uses a granulator equipped with a high shear stirrer to granulate a composition containing a polymerizable monomer in an aqueous medium to produce toner particles. How to get.
In producing a toner in which wax is encapsulated in the suspension polymerization method, a method in which a wax is contained in a composition containing a polymerizable monomer is generally used.
The optimum melting point of this wax is determined from the viewpoints of the meltability in the fixing process by heating, the solubility in the granulation step of the suspension polymerization method, and the blocking resistance during toner storage. However, the wax having such a melting point tends to be compatible with the wax and the binder resin when the toner is heated at a high temperature, and the wax is difficult to exude. Further, since the elastic modulus of the binder resin is greatly reduced by the compatibility of the wax and the binder resin, an offset (hot offset) that occurs when the fixing member is at a high temperature is likely to occur.
Patent Document 1 discloses a suspension polymerization toner containing a wax having a melting point of 75 ° C. or higher and 140 ° C. or lower as a release agent.
Patent Document 2 discloses a method for producing a suspension polymerization toner using polyethylene wax.
Patent Document 3 discloses a method for producing a toner in which a wax having a melting point of 80 ° C. or higher and 120 ° C. or lower is wet pulverized to prepare a wax dispersion, and a polymer composition to which the wax is added is granulated and polymerized in an aqueous medium. It is disclosed.

Japanese Patent No. 2748183 Japanese Patent Laid-Open No. 1-100562 Japanese Patent No. 5645580

In the toner described in Patent Document 1, suspension polymerization is performed by adding a hydrocarbon wax having a relatively high melting point to the polymerizable monomer composition. A hydrocarbon wax having a high melting point is less compatible with the binder resin when the toner is heated at a high temperature. Due to such characteristics, it is considered that when heated at a high temperature, the wax easily oozes out between the melted toner and the fixing member, and hot offset hardly occurs. In this toner production example, in order to dissolve the wax in the polymerizable monomer composition, the polymerizable monomer is heated to near the melting point of the wax for granulation and polymerization. Thus, in the toner prepared by granulation and polymerization at a temperature near the melting point of the wax, the wax tends to exist in a single domain in the toner particles. For this reason, the efficiency with which the wax oozes out during fixing is poor, and there are problems with hot offset resistance and low-temperature fixability.
Further, the method for producing a toner described in Patent Document 2 includes a step of adding an organic solvent to a polymerizable monomer containing a polyethylene wax having a relatively high melting point, and as a result, the wax is added to the polymerizable monomer. Increases solubility. By such a production method, the wax can be dissolved to some extent without heating to near the melting point of the wax. However, since the melting point of the wax is excessively high with respect to the granulation temperature, it is considered that there is a solid wax that cannot be dissolved in the polymerizable monomer composition. In such a case, a solid wax is present at the interface between the droplet of the polymerizable monomer composition and the aqueous medium, and the stability of the interface is impaired. Is not suitable for producing a narrow particle size distribution. In addition, if the wax is not sufficiently dissolved in the polymerizable monomer, the wax does not disperse in the toner particles and tends to exist in a small number of domains. There is no effect.
In the toner described in Patent Document 3, a hydrocarbon wax having a melting point of 80 ° C. or higher and 120 ° C. or lower is dispersed in toner particles, so that the wax exuding property at the time of fixing is improved and the low temperature fixing property is improved. The hot offset is less likely to occur. However, pulverized wax particles exist at the time of granulation, and the granulation property was insufficient.
The present invention provides a toner manufacturing method that solves the conventional problems. That is, the present invention provides a toner production method capable of producing a toner excellent in hot offset resistance while maintaining granulation properties and low-temperature fixability.

The present invention is a method for producing a toner having toner particles containing a binder resin and a hydrocarbon wax,
The manufacturing method is as follows:
A granulating step of forming particles of a polymerizable monomer composition containing a polymerizable monomer capable of forming the binder resin, the hydrocarbon wax, and a non-polymerizable organic solvent in an aqueous medium; ,
Polymerizing the polymerizable monomer to obtain resin particles, and
The difference Rar of Hansen solubility parameter (HSP) between the non-polymerizable organic solvent and the hydrocarbon wax is 2.00 or less,
The difference Raw between the Hansen solubility parameter (HSP) of the non-polymerizable organic solvent and the aqueous medium is 41.00 or more and 45.20 or less,
The hydrocarbon wax has a melting point Tr (° C.) satisfying the following formula (1).
Tp + 15 ≦ Tr ≦ Tp + 30 (° C.) Formula (1)
(In the formula, Tp represents the average temperature of the aqueous medium in the granulation step and the polymerization step.)

  According to the present invention, in the suspension polymerization method, it is possible to provide a method for producing a toner excellent in hot offset resistance while maintaining granulation property and low-temperature fixability.

  In the suspension polymerization method, the present inventors have intensively studied a method for producing a toner excellent in hot offset resistance while maintaining granulation property and low-temperature fixability. As a result, non-polymerization in which the distance (HSP difference) in the Hansen solubility parameter (HSP) space with respect to the hydrocarbon wax and the aqueous medium is in a specific range is applied to the polymerizable monomer composition containing the hydrocarbon wax. In order to obtain a toner that solves the above problems by adding a hydrophilic organic solvent and controlling the relationship between the melting point of the hydrocarbon wax and the temperature of the granulation step and the polymerization step to be within a specific range. It came.

  The present inventors consider these reasons as follows. In the initial stage of the granulation step and the polymerization step, the polymerizable monomer composition containing the hydrocarbon wax contains a large amount of a non-polymerizable organic solvent, and the hydrocarbon wax and the non-polymerizable organic solvent Since the HSP distance is small, the wax is in a sufficiently dissolved state. In such a case, the precipitated wax is unlikely to exist at the interface between the droplet made of the polymerizable monomer composition and the aqueous medium. Therefore, it is difficult to destabilize the interface between the droplet and the aqueous medium, and the granulation property is improved. In addition, the present invention is characterized in that the melting point of the hydrocarbon wax is higher in the range of 15 ° C. or more and 30 ° C. or less with respect to the average temperature of the aqueous medium in the granulation step and the polymerization step. In general, hydrocarbon waxes have low solubility in polymerizable monomers. However, in the present invention, the solubility can be enhanced by adding the non-polymerizable organic solvent in which the difference Rar of HSP with the hydrocarbon wax is in a specific range. Here, when the non-polymerizable organic solvent shifts from the droplets to the aqueous medium as the polymerization proceeds, the solubility of the wax rapidly decreases and the precipitation of the wax is promoted. The non-polymerizable organic solvent added in the present invention is such that the difference Raw of the HSP with the aqueous medium is within a specific range, so that the non-polymerizable organic solvent is contained in droplets at the initial stage of the granulation process or polymerization process. A large amount is included, and it is considered that the aqueous medium gradually moves as the polymerization process proceeds.

  Therefore, in the initial stage of the granulation process and the polymerization process, the wax is sufficiently dissolved, and as the polymerization proceeds, the solubility of the wax decreases and the precipitation of the wax is promoted. By such a production method, it is possible to obtain toner particles containing a wax having a melting point higher than that used in a usual suspension polymerization method without widening the particle size distribution, and further, the wax is in a dissolved state. By precipitating quickly, it is considered that the dispersibility of the wax is increased and the hot offset can be improved without deteriorating the low-temperature fixability.

  Although an example of the manufacturing method of this invention is demonstrated concretely below, it is not limited to this.

(Polymerizable monomer composition preparation process)
A polymerizable monomer, a hydrocarbon wax, a non-polymerizable organic solvent, and the like are mixed to prepare a polymerizable monomer composition. A polar resin, a colorant, a charge control agent, and the like can be appropriately added to the polymerizable monomer composition as necessary.

(Granulation process)
Prepare an aqueous dispersion medium containing a dispersion stabilizer, put it in a stirring tank equipped with a stirrer having high shearing force, add the polymerizable monomer composition to this, and disperse by stirring to polymerize. Form particles of the monomer composition. Since the particle size distribution of the polymerizable monomer composition is directly reflected in the particle size distribution of the obtained toner particles, it is important to make the particle size of the polymerizable monomer composition uniform. .

(Polymerization process)
Subsequent to the granulation step, the polymerizable monomer in the particles of the polymerizable monomer composition is polymerized to obtain resin particles. In the polymerization step in the present invention, a general stirring tank capable of adjusting the temperature can be used.

  Any stirring blade may be used as long as the stirring blade used for stirring floats the dispersion having resin particles without stagnation and can keep the temperature in the tank uniform.

  In the present invention, it is necessary to control the average temperature of the aqueous medium in the granulation step and the polymerization step so that the melting point of the hydrocarbon wax to be added has a specific relationship. When the granulation step and the polymerization step are performed at a constant temperature, the average temperature of the aqueous medium in the granulation step and the polymerization step is defined as the average temperature. Moreover, when performing a granulation process and a superposition | polymerization process, changing temperature, it can calculate by recording the temperature of an aqueous medium with a fixed period during a process, and taking the average value of the recorded temperature. In that case, it is only necessary to perform recording by recording at an appropriate cycle according to the change rate of temperature.

  The temperature of the aqueous medium in the granulation step and the polymerization step may be a constant temperature as long as the average temperature is within a specified range. The temperature may be changed by a temperature gradient or the like. However, the difference between the maximum temperature and the minimum temperature is 15 ° C. from the viewpoint of wax solubility, wax precipitation and resulting wax dispersibility, polymerization reaction stability, and evaporability of the non-polymerizable organic solvent to be added. Is preferably within 10 ° C., more preferably within 10 ° C.

  The average temperature of the aqueous medium in the granulation step and the polymerization step is preferably 60 ° C. or higher and 80 ° C. or lower, and more preferably 65 ° C. or higher and 75 ° C. or lower. By being within such a range, the polymerization reaction proceeds sufficiently so that the unreacted polymerizable monomer is less likely to remain in the toner particles, and the low molecular weight component of the binder resin is reduced. Further, it is possible to improve the blocking resistance when storing the toner.

(High temperature treatment process)
It is preferable to heat-treat the aqueous medium in which the resin particles after the polymerization step are dispersed at a high temperature. The high temperature heat treatment is performed by raising the temperature while stirring the resin particle dispersion in a stirring tank provided with a stirring means. The high temperature heat treatment has an effect of reducing the amount of the non-polymerizable organic solvent contained in the aqueous medium and the toner particles obtained after the high temperature heat treatment step. By reducing the amount of the non-polymerizable organic solvent, it is possible to further suppress the adverse effect that the particles are united and the particle size distribution is broadened, and blocking when the toner is stored at high temperature. By performing a high temperature heat treatment, a dispersion of toner particles can be obtained.

  Further, the toner particles obtained by the production method of the present invention are likely to be present in a state where wax is dispersed in the particles. Usually, toner particles in which wax is dispersed tend to expose the wax on the surface, and the particles are coalesced by the post-polymerization process, resulting in a wide particle size distribution and a problem that blocking during high-temperature storage is likely to occur. It's easy to do. When high-temperature heat treatment is performed in an aqueous medium, the mobility of the composition in the particles is increased, and the hydrophobic wax is less likely to be present on the outermost surface of the toner particles, so that the above-described adverse effects are less likely to occur. This effect can be further enhanced by including a polar resin as described later.

  Furthermore, it is preferable to perform a high-temperature heat treatment in an aqueous medium because the spheroidization of particles proceeds and the fluidity of the obtained toner is improved. The high temperature heat treatment is preferably performed at a temperature of 95 ° C. or higher for 2 hours or longer.

(Solid-liquid separation process, washing process and drying process)
In order to remove the dispersion stabilizer adhering to the toner particle surface, the toner particle dispersion is treated with an acid or an alkali. After the dispersion stabilizer is removed from the toner particles, the toner particles are separated from the aqueous medium by a general solid-liquid separation method. However, in order to completely remove the acid or alkali and the dispersion stabilizer component dissolved in them, It is preferable to add toner to wash the toner particles. This washing process is repeated several times, and after sufficient washing, solid-liquid separation is performed again to obtain toner particles. If necessary, the obtained toner particles may be dried by a known drying means.

(Classification process)
When the toner particles obtained in this way are required to have a narrower particle size distribution, a particle separation process using an air classifier or the like can be performed to separate and remove particles that deviate from the desired particle size distribution.

(External addition process)
An external additive may be added to the obtained toner particles for the purpose of improving fluidity, chargeability, storage stability in a high temperature environment, and the like. The external addition step is performed by putting the external additive and the toner particles in a mixing device having blades that rotate at high speed and sufficiently mixing them, whereby a toner in which the external additive is added to the toner particles can be obtained. .

  Below, the material used for the manufacturing method of this invention is demonstrated.

  In the present invention, a hydrocarbon wax is used. Hydrocarbon wax has low compatibility with the binder resin and excellent exudability at the time of fixing, so it has a high effect of improving low-temperature fixability and hot offset resistance, and is preferably used as a release agent. it can.

The melting point Tr (° C.) of the hydrocarbon wax used in the present invention is given by the following formula (1)
Tp + 15 ≦ Tr ≦ Tp + 30 (° C.) Formula (1)
(In the formula, Tp represents the average temperature of the aqueous medium in the granulation step and the polymerization step.)
It is necessary to satisfy. When the melting point Tr (° C.) of the hydrocarbon wax is within the above range, phase separation due to precipitation of the hydrocarbon wax is likely to occur during the polymerization reaction of the polymerizable monomer. Compared with the case where the polymerizable monomer and the wax are both likely to phase separate in a liquid state, the dispersibility of the wax in the resulting toner particles is higher when phase separation due to precipitation is likely to occur. Therefore, the effect of improving the low-temperature fixability and hot offset resistance is particularly enhanced.

  If the melting point Tr (° C.) of the hydrocarbon wax is within this range, the hydrocarbon wax is highly soluble at the initial stage of the granulation step and the polymerization step, so that wax precipitation occurs in the granulation step. It is difficult to obtain toner particles having a narrow particle size distribution.

  The melting point Tr (° C.) of the hydrocarbon wax used in the present invention is preferably 85 ° C. or higher and 100 ° C. or lower, and more preferably 88 ° C. or higher and 97 ° C. or lower. Within this range, the meltability in the fixing process is excellent, and good hot offset resistance can be obtained without deteriorating the low-temperature fixability. In general, hydrocarbon waxes contain a low melting point component, but hydrocarbon waxes within the above melting point range have few low melting point components that melt when stored in a high temperature environment, and are resistant to resistance. A toner having excellent blocking properties can be obtained.

  The hydrocarbon wax used in the present invention is not particularly limited as long as the relationship between the melting point and the average temperature of the aqueous medium in the granulation step and the polymerization step is satisfied. For example, the following can be used. A polyolefin obtained by purifying a low molecular weight by-product obtained at the time of polymerizing a high molecular weight polyolefin; a polyolefin polymerized using a catalyst such as a Ziegler catalyst or a metallocene catalyst; a paraffin wax, a Fischer-Tropsch wax; Synthetic hydrocarbon waxes synthesized by the hydrocol method or the age method; synthetic waxes using a compound having one carbon atom as a monomer; hydrocarbon waxes having functional groups such as hydroxyl groups and carboxyl groups; hydrocarbon waxes and functional groups Mention may be made of mixtures with hydrocarbon waxes. In addition, these waxes have a sharp molecular weight distribution using techniques such as the press sweating method, solvent method, recrystallization method, vacuum distillation method, supercritical gas extraction method, and melt liquid crystal deposition method, and low molecular weight solid fatty acids. , Low molecular weight solid alcohol, low molecular weight solid compound, and other impurities are used. Among them, those preferably used are paraffin wax, Fischer-Tropsch wax, microcrystalline wax, polyethylene synthesized using a metallocene catalyst, low molecular weight by-product distillation purified product obtained during polyethylene polymerization, synthesized using a metallocene catalyst. It is a distillation purified product of low molecular weight by-products obtained during polymerization of polypropylene and polyethylene. Furthermore, as the wax used in the present invention, paraffin wax, Fischer-Tropsch wax, and microcrystalline wax are particularly preferably used from the viewpoint of the bleeding property at the time of storage in a high temperature environment and fixing.

  The added amount of the hydrocarbon wax in the present invention is 1.5 parts by mass or more and 20.0 parts by mass or less with respect to 100.0 parts by mass of the total amount of the polymerizable monomer and the non-polymerizable organic solvent. Preferably, it is 5.0 parts by weight or more and 15.0 parts by weight or less. Within this range, a sufficient amount of wax functions as a release agent in the fixing process and does not deteriorate the low-temperature fixability. Further, if it is within this range, the precipitation of wax during granulation is reduced, and toner particles having a narrower particle size distribution can be produced.

  Further, in the present invention, in addition to the hydrocarbon wax as described above, other waxes can be further contained. Other waxes may be added as release agents, and become plasticizers that are compatible with the binder resin in the fixing process to improve the thermoplasticity of the toner and improve the low-temperature fixability. You can add things. Further, a wax having other functions such as improving the glossiness of an image can be contained, and a wax having a plurality of different functions can also be contained.

  Such a wax is not particularly limited. For example, a wax mainly composed of a fatty acid ester such as carnauba wax, an ester wax, or a montanic acid ester wax; or a part or all of a fatty acid ester such as deoxidized carnauba wax is removed. Oxidized products; partially esterified products of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; methyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable oils and the like.

  As an aqueous medium used in the present invention, water alone may be used, or a solvent miscible with water may be added. Examples of the water-miscible solvent include alcohol (methanol, ethanol, 2-propanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, lower ketones (acetone, 1-butanone, etc.) and the like.

  A known resin can be used as the binder resin used in the toner of the present invention.

  Specific examples include: vinyl resins; polyester resins; polyamide resins; furan resins; epoxy resins; xylene resins; These resins can be used alone or in combination. As the vinyl resin, styrene monomers represented by styrene, α-methylstyrene, divinylbenzene, etc .; methyl acrylate, butyl acrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, t-methacrylic acid t- Unsaturated carboxylic acid esters typified by butyl, 2-ethylhexyl methacrylate, etc .; Unsaturated carboxylic acids typified by acrylic acid, methacrylic acid, etc .; Unsaturated dicarboxylic acids typified by maleic acid, etc .; Maleic anhydride, etc. A homopolymer or copolymer of a polymerizable monomer such as an unsaturated dicarboxylic acid anhydride represented by nitrile; a nitrile vinyl monomer represented by acrylonitrile or the like;

  Among these binder resins, a styrene acrylic resin is particularly preferable from the viewpoint of productivity when granulating a polymerizable monomer capable of forming the binder resin in an aqueous medium. Further, the ratio between the polymerization monomer styrene and the acrylic monomer may be adjusted in consideration of the desired binder resin and the glass transition temperature of the toner particles.

  In the present invention, a non-polymerizable organic solvent having an HSP difference Rar of 2.00 or less, preferably 1.80 or less, from the hydrocarbon wax is used. When the difference Rar of HSP with the hydrocarbon wax is in the above range, the solubility of the hydrocarbon wax at the initial stage of the granulation step and the polymerization step is sufficiently high, and good granulation property can be obtained. . Further, since the solubility is high, it is possible to prevent the wax that cannot be completely dissolved from becoming a large domain in the toner particles. As a result, the dispersibility of the wax can be improved, so that the low-temperature fixability and the hot offset resistance can be improved.

  In addition, as the non-polymerizable organic solvent used in the present invention, a solvent having an HSP difference Raw with respect to an aqueous medium of 41.00 to 45.20, preferably 44.00 to 45.10 is used. Within such a range, the non-polymerizable organic solvent contained in the particles of the polymerizable monomer composition moves into the aqueous medium at an appropriate rate. When the polymerization reaction of the polymerizable monomer and the transfer of the non-polymerizable organic solvent into the aqueous medium are at an appropriate rate, the solubility of the hydrocarbon wax is sufficiently high at the initial stage of the granulation step and the polymerization step. Further, it is considered that the polymerization reaction and the migration of the non-polymerizable organic solvent to the aqueous medium proceed at the same time, so that precipitation of the dissolved wax is promoted and the dispersion state of the wax in the obtained toner particles is improved. .

  The non-polymerizable organic solvent used in the present invention is not limited as long as the non-polymerizable organic solvent satisfies the range of the above HSP, and for example, cyclohexane, methylcyclohexane, n-butylcyclohexane, cyclohexene, and p-diethylbenzene can be used. . Among these, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, and n-butylcyclohexane are preferable because the HSP difference Rar with the hydrocarbon wax and the HSP difference Raw with the aqueous medium can be easily adjusted. Furthermore, cyclohexane and methylcyclohexane are more preferable. Two or more non-polymerizable organic solvents can be used at the same time.

  The addition amount of the non-polymerizable organic solvent in the present invention is preferably 5.0 parts by mass or more and 50.0 parts by mass or less, preferably 10.0 parts by mass or more and 40 parts by mass or less with respect to 100.0 parts by mass of the polymerizable monomer. More preferably, it is 0.0 parts by mass or less. Within this range, the wax solubility at the initial stage of the granulation step and the polymerization step can be improved, and toner particles having a narrow particle size distribution can be obtained. In addition, the amount of the non-polymerizable organic solvent remaining in the toner particles after production is small, and blocking due to bleeding of the non-polymerizable organic solvent is difficult even when stored in a high-temperature environment.

  Various polymerization initiators such as peroxide polymerization initiators and azo polymerization initiators can be used as the polymerization initiator used in the binder resin and toner particle production. Examples of peroxide polymerization initiators that can be used include peroxyesters, peroxydicarbonates, dialkyl peroxides, peroxyketals, ketone peroxides, hydroperoxides, and diacyl peroxides. Examples of the inorganic system include persulfate and hydrogen peroxide. Specifically, t-butyl peroxyacetate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-hexyl peroxyacetate, t-hexyl peroxypivalate, t-hexyl peroxyiso Peroxyesters such as butyrate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate; diacyl peroxides such as benzoyl peroxide; peroxydicarbonates such as diisopropyl peroxydicarbonate; 1 , 1-di-t-hexylperoxycyclohexane and other peroxyketals; di-t-butyl peroxide and other dialkyl peroxides; and other t-butyl peroxyallyl monocarbonate and the like It is below. Examples of the azo polymerization initiator that can be used include 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-methylpropionate), etc. Illustrated.

  If necessary, two or more of these polymerization initiators can be used simultaneously. The amount of the polymerization initiator used at this time is preferably 0.10 parts by mass or more and 20.0 parts by mass or less with respect to 100.0 parts by mass of the polymerizable monomer.

  The toner may contain a polar resin. When granulating in an aqueous medium, if a polar resin is present, the polar resin tends to migrate to the vicinity of the interface between the aqueous medium and other components due to the difference in affinity for water. Polar resin will be unevenly distributed. As a result, the resulting toner particles have a core-shell structure.

  When the wax is dispersed in the toner particles, the wax is usually easily exposed on the surface of the toner particles. However, when the toner particles have a core-shell structure, the exposure of wax can be reduced. This effect is further enhanced by performing a process of treating the aqueous medium in which the particles are dispersed at a high temperature after the polymerization is substantially completed.

  As the polar resin, a saturated or unsaturated polyester resin is preferable. By using a saturated or unsaturated polyester resin as the polar resin, when the resin is unevenly distributed on the surface of the toner particles to form a shell, the lubricity of the resin itself can be expected.

  As the polyester resin, for example, a resin obtained by condensation polymerization of an acid component monomer and an alcohol component monomer described below can be used. Acid monomers include terephthalic acid, isophthalic acid, phthalic acid, fumaric acid, maleic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, camphor Examples include acids, cyclohexanedicarboxylic acid, and trimellitic acid.

  Examples of alcohol component monomers include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, and 1,4-bis (hydroxymethyl). ) Alkylene glycols such as cyclohexane and polyalkylene glycols, bisphenol A, hydrogenated bisphenol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, glycerin, trimethylolpropane, and pentaerythritol.

  The content of the polar resin is preferably 0.2 parts by mass or more and 20.0 parts by mass or less with respect to 100.0 parts by mass of the polymerizable monomer. Within this range, the exposure of the wax to the toner surface is suppressed, and the storage stability in a high temperature environment is reduced little. Further, if it is within this range, the exudation of wax in the fixing process is not inhibited.

  The toner of the present invention may contain a colorant. As the colorant, known colorants such as various conventionally known dyes and pigments can be used.

  As the black colorant, carbon black, a magnetic material, or a color toned to black using a yellow / magenta / cyan colorant shown below is used.

  Examples of the yellow colorant include compounds represented by monoazo compounds, disazo compounds, condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complex methine compounds, and allylamide compounds. Specifically, C.I. I. Pigment yellow 74, 93, 95, 109, 111, 128, 155, 174, 180, 185.

  Examples of the magenta colorant include monoazo compounds, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, C.I. I. Pigment Red 2,3,5,6,7,23,48: 2,48: 3,48: 4,57: 1,81: 1,122,144,146,150,166,169,177,184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. Pigment Bio Red 19 and the like can be exemplified.

  As the cyan colorant, for example, a copper phthalocyanine compound and a derivative thereof, an anthraquinone compound, and a basic dye lake compound can be used. Specifically, C.I. I. Pigment blue 1,7,15,15: 1,15: 2,15: 3,15: 4,60,62,66.

  When the toner of the present invention is used as a magnetic toner, the toner particles may contain a magnetic material. In this case, the magnetic material can also serve as a colorant. In the present invention, examples of the magnetic material include iron oxides such as magnetite, hematite, and ferrite; and metals such as iron, cobalt, and nickel. Or alloys of these metals with metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium and mixtures thereof. .

  The colorant is selected from the viewpoints of hue angle, saturation, lightness, light resistance, OHP transparency, and dispersibility in toner particles. These colorants can be used alone or in combination, and further in a solid solution state. The colorant is preferably used in an amount of 1.0 to 20.0 parts by mass with respect to 100.0 parts by mass of the polymerizable monomer.

  The toner of the present invention may further contain a charge control agent in order to improve toner characteristics. Specific examples of the charge control agent for negative charge include the following metal compounds of aromatic carboxylic acids represented by salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid, etc .; sulfonic acid groups, sulfonic acid groups or Examples thereof include polymers or copolymers having a sulfonate group; metal salts or metal complexes of azo dyes or azo pigments; boron compounds, silicon compounds, calixarenes, and the like. Examples of the positive charge control agent include the following quaternary ammonium salts, polymer compounds having a quaternary ammonium salt in the side chain; guanidine compounds; nigrosine compounds; imidazole compounds. Examples of the polymer or copolymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group include styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and 2-methacrylamide-2-methylpropanesulfone. A homopolymer of a sulfonic acid group-containing vinyl monomer represented by acid, vinyl sulfonic acid, methacryl sulfonic acid or the like, or a copolymer of the vinyl monomer shown in the section of the binder resin and the sulfonic acid group-containing vinyl monomer Etc. can be used.

  The addition amount of the charge control agent is preferably 0.1 parts by mass or more and 10.0 parts by mass or less with respect to 100.0 parts by mass of the polymerizable monomer.

  It is preferable to add an external additive to the toner particles in order to improve the image quality. As the external additive, inorganic fine particles such as silicate fine particles, titanium oxide, and aluminum oxide are preferably used. These inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane coupling agent, silicone oil or a mixture thereof. The external additive is preferably used in an amount of 0.1 parts by weight or more and 5.0 parts by weight or less based on 100.0 parts by weight of the toner particles, and is used in an amount of 0.1 parts by weight or more and 3.0 parts by weight or less. Is more preferable.

  As the dispersion stabilizer added to the aqueous medium, known surfactants, organic dispersants, and inorganic dispersants can be used. Among these, inorganic dispersants can be suitably used because they are less likely to lose stability depending on the polymerization temperature and the passage of time, are easy to wash and do not adversely affect the toner. The following are mentioned as an inorganic dispersing agent. Polyvalent metal phosphates such as calcium phosphate, magnesium phosphate, aluminum phosphate and zinc phosphate; carbonates such as calcium carbonate and magnesium carbonate; inorganic salts such as calcium metasuccinate, calcium sulfate and barium sulfate; calcium hydroxide Inorganic oxides such as magnesium hydroxide, aluminum hydroxide, silica, bentonite and alumina. These inorganic dispersants can be almost completely removed by adding an acid or an alkali after the polymerization and dissolving.

  A method for calculating the distance in the Hansen solubility parameter space and the toner particle size distribution will be described below.

(Distance in Hansen Solubility Parameter Space)
In the toner manufacturing method of the present invention, it is necessary to determine the component to be added so that the distance (HSP difference) in the Hansen solubility parameter (HSP) space is within a specific range.

  HSP is a three-dimensional vector quantity composed of a dispersion term, a polar term, and a hydrogen bond term. When a dispersion term value of an HSP of a substance is δd, a polar term value is δp, and a hydrogen bond term value is δh, it is expressed as [δd, δp, δh] in this specification.

  The difference in HSP is a calculated value indicating the ease of dissolution of a solute in a solvent or the ease of mixing a plurality of solvents from the viewpoint of intermolecular interaction. It is presumed that the closer the difference in HSP between two substances is to 0, the higher the affinity between the substances and the higher the solubility and miscibility.

Focusing on two substances, when the HSP of one substance is [δdA, δpA, δhA] and the HSP of the other substance is [δdB, δpB, δhB], the difference Ra between the two substances is: The following formula:
Ra = {4 (δdA−δdB) ² + (δpA−δpB) ² + (δhA−δhB) ² } ^1/2
It is represented by

  In the present invention, the HSP of the non-polymerizable organic solvent and the aqueous medium is included in the calculation software “Hansen Solubility Parameters in Practice (HSPiP) Version 4.1.03” (Steven Abbott, Charles M. Hansen, Hiroshi). Database values were used. The wax HSP is calculated by inputting the chemical structural formula of the wax using the calculation software. The HSP of the hydrocarbon wax is calculated by inputting the structure of the linear alkane closest to the weight average molecular weight of the hydrocarbon wax into the calculation software, and uses the value.

  The HSP in the case of using a plurality of solvents is treated as having one HSP as a mixed solvent if the mixture of the plurality of solvents exhibits a uniform appearance. In that case, HSP as a mixed solvent is calculated from the volume ratio of each solvent and the HSP of each solvent.

The HSP of the mixed solvent is calculated as follows. For example, when two types of solvents are used, the HSP of one solvent is [δd1, δp1, δh1], the HSP of the other solvent is [δd2, δp2, δh2], and the volume ratio of each solvent is v1 and v2. Then, each component of HSP [δdm, δpm, δhm] of the mixed solvent is represented by the following formulas:
δdm = (v1 × δd1 + v2 × δd2) ÷ (v1 + v2)
δpm = (v1 × δp1 + v2 × δp2) ÷ (v1 + v2)
δhm = (v1 × δh1 + v2 × δh2) ÷ (v1 + v2)
It is represented by

  If the mixture of solvents does not exhibit a uniform appearance, each solvent is treated as having an independent HSP.

(Particle size distribution of toner particles)
The particle size distribution of the toner particles is calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with an aperture tube of 100 μm is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. The measurement is performed with 25,000 effective measurement channels.

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

  Prior to measurement and analysis, the dedicated software is set as follows.

  On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush 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) Put 200 mL of the electrolytic solution in a glass 250 mL round-bottom beaker dedicated to Multisizer 3, set it on a sample stand, and stir the stirrer rod counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) Put 30 mL of the electrolytic aqueous solution into a glass 100 mL flat bottom beaker. 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. ) Is diluted 0.3 times with ion-exchanged water at a mass ratio of 0.3 mL.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) having an electrical output of 120 W is prepared. Put 3.3 L of ion exchange water in the water tank of the ultrasonic disperser, and add 2 mL of Contaminone N into this water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser 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.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, toner particles or a dispersion of toner particles are added to the electrolytic aqueous solution little by little so that the toner becomes 10 mg, and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In 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) To the round bottom beaker (1) installed in a sample stand, the electrolyte aqueous solution (5) in which toner is dispersed using a pipette is dropped to prepare a measurement concentration of 5%. . Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated.

The present invention will be specifically described with reference to the following examples. However, this does not limit the present invention in any way.

  The toner production method will be described below. All parts in the production examples are based on mass unless otherwise specified.

[Example of toner production]
<Example 1>
(Preparation of polymerizable monomer composition)
A toner was produced by the following method.
-Styrene 75.0 parts-n-butyl acrylate 25.0 parts-Divinylbenzene 0.5 parts-Copper phthalocyanine pigment (CI Pigment Blue 15: 3) 5.0 parts-Aluminum salicylate compound 0.7 parts ( Bontron E-88: manufactured by Orient Chemical Co., Ltd.)
-5.0 parts of polar resin (acid value 3.9 mgKOH / g, glass transition point 69 ° C., weight average molecular weight 9500)
Hydrocarbon wax (melting point 90 ° C.) A mixture of polymerizable monomers consisting of 10.0 parts was prepared. 15 mm ceramic beads were put into this, and dispersed for 2 hours using a wet attritor (manufactured by Nippon Coke Industries) to obtain a polymerizable monomer composition.

(Granulation process)
6.3 parts of sodium phosphate (Na ₃ PO ₄ ) was added to 414.0 parts of ion-exchanged water, and the aqueous medium was heated to 70 ° C. while stirring using CLEARMIX (M Technique). . Thereafter, an aqueous calcium chloride solution in which 3.6 parts of calcium chloride (CaCl ₂ ) was dissolved in 25.5 parts of ion-exchanged water was added and stirring was continued to prepare an aqueous medium containing calcium phosphate as a dispersion stabilizer. To the above polymerizable monomer composition, 30.0 parts of cyclohexane and 10.0 parts of t-butyl peroxypivalate were added as a non-polymerizable organic solvent, and this was added to the aqueous dispersion medium. The granulation process was performed for 10 minutes while maintaining 12,000 rotations / minute with the CLEARMIX.

(Polymerization process)
Then, it superposed | polymerized for 8 hours, hold | maintaining an aqueous medium at 70 degreeC, stirring with the stirring tank provided with the general stirrer, and obtained the resin particle dispersion liquid.

(High temperature heat treatment process)
While stirring, the temperature of the resin particle dispersion was raised to 98 ° C. and held for 3 hours to obtain a toner particle dispersion.

(Solid-liquid separation process, washing process and drying process)
After cooling the toner particle dispersion, hydrochloric acid was added to adjust the pH to 1.4 or less, the dispersion stabilizer was dissolved, and the toner particles were obtained by filtration, washing and drying.

(External addition process)
To 100.0 parts of the obtained toner particles, 0.3 part of hydrophobic titanium oxide is added and mixed with an FM mixer (manufactured by Nippon Coke Industries), and then 1.5 parts of hydrophobic silica is added and mixed with an FM mixer. Thus, Toner 1 having an external additive was obtained.

<Example 2>
In Example 1, the temperature of the aqueous medium in the granulation step and the polymerization step was changed to 62 ° C, and the hydrocarbon wax (melting point 90 ° C) was changed to the hydrocarbon wax (melting point 88 ° C). Toner 2 was obtained.

<Example 3>
In Example 1, the temperature of the aqueous medium in the granulation step and the polymerization step was changed to 78 ° C, and the hydrocarbon wax (melting point 90 ° C) was changed to the hydrocarbon wax (melting point 96 ° C). Toner 3 was obtained.

<Example 4>
In Example 1, the temperature of the aqueous medium in the granulation step and the polymerization step was set to 59 ° C., and the hydrocarbon wax (melting point: 90 ° C.) was changed to the hydrocarbon wax (melting point: 88 ° C.). Toner 4 was obtained.

<Example 5>
In Example 1, the temperature of the aqueous medium in the granulation step and the polymerization step was changed to 81 ° C., and the hydrocarbon wax (melting point 90 ° C.) was changed to the hydrocarbon wax (melting point 97 ° C.). Toner 5 was obtained.

<Example 6>
In Example 1, the temperature of the aqueous medium in the granulation step and the polymerization step was changed to 65 ° C., and the hydrocarbon wax (melting point 90 ° C.) was changed to the hydrocarbon wax (melting point 85 ° C.). Toner 6 was obtained.

<Example 7>
In Example 1, the temperature of the aqueous medium in the granulation step and the polymerization step was set to 75 ° C, and the hydrocarbon wax (melting point 90 ° C) was changed to the hydrocarbon wax (melting point 98 ° C). Toner 7 was obtained.

<Example 8>
In Example 1, the temperature of the aqueous medium in the granulation step and the polymerization step was set to 65 ° C., and the hydrocarbon wax (melting point 90 ° C.) was changed to the hydrocarbon wax (melting point 81 ° C.). Toner 8 was obtained.

<Example 9>
In Example 1, the temperature of the aqueous medium in the granulation step and the polymerization step was changed to 75 ° C, and the hydrocarbon wax (melting point 90 ° C) was changed to the hydrocarbon wax (melting point 102 ° C). Toner 9 was obtained.

<Example 10>
Toner 10 was obtained in the same manner as in Example 1, except that the amount of hydrocarbon wax (melting point 90 ° C.) was 2.0 parts.

<Example 11>
Toner 11 was obtained in the same manner as in Example 1, except that the addition amount of hydrocarbon wax (melting point 90 ° C.) was 25.0 parts.

<Example 12>
Toner 12 was obtained in the same manner as in Example 1, except that the amount of hydrocarbon wax (melting point 90 ° C.) added was 1.2 parts.

<Example 13>
Toner 13 was obtained in the same manner as in Example 1, except that the addition amount of hydrocarbon wax (melting point 90 ° C.) was 30.0 parts and the addition amount of cyclohexane was 15.0 parts.

<Example 14>
Toner 14 was obtained in the same manner as in Example 1, except that the amount of cyclohexane added was 7.0 parts.

<Example 15>
Toner 15 was obtained in the same manner as in Example 1, except that the amount of cyclohexane added was 48.0 parts.

<Example 16>
Toner 16 was obtained in the same manner as in Example 1, except that the amount of cyclohexane added was 3.0 parts.

<Example 17>
Toner 17 was obtained in the same manner as in Example 1 except that the amount of cyclohexane added was 55.0 parts.

<Example 18>
A toner 18 was obtained in the same manner as in Example 1 except that, in the high-temperature heat treatment step, the holding time after raising the temperature was 2 hours.

<Example 19>
A toner 19 was obtained in the same manner as in Example 1 except that the temperature of the high-temperature heat treatment step was 95 ° C.

<Example 20>
A toner 20 was obtained in the same manner as in Example 1 except that in the high-temperature heat treatment step, the holding time after raising the temperature was 1 hour.

<Example 21>
In Example 1, Toner 21 was obtained in the same manner except that the temperature of the high-temperature heat treatment step was 90 ° C.

<Example 22>
Toner 22 was obtained in the same manner as in Example 1 except that methylcyclohexane was used instead of cyclohexane, and the time of holding after the temperature increase in the high-temperature heat treatment step was 8 hours.

<Example 23>
A toner 23 was obtained in the same manner as in Example 1 except that cyclopentane was used instead of cyclohexane.

<Example 24>
In Example 1, the temperature of the aqueous medium in the granulation step and the polymerization step was changed to 77 ° C., the hydrocarbon wax (melting point 90 ° C.) was changed to the hydrocarbon wax (melting point 102 ° C.), and p-diethylbenzene was used instead of cyclohexane. The toner 24 was obtained in the same manner except that the temperature was raised and held for 8 hours.

<Comparative Example 1>
The toner 25 was obtained in the same manner as in Example 1 except that the hydrocarbon wax (melting point 90 ° C.) was changed to dibehenyl terephthalate (melting point 89 ° C.) and cyclohexene was used instead of cyclohexane.

<Comparative example 2>
In Example 1, the temperature of the aqueous medium in the granulation step and the polymerization step was set to 75 ° C, and the hydrocarbon wax (melting point 90 ° C) was changed to the hydrocarbon wax (melting point 88 ° C). Toner 26 was obtained.

<Comparative Example 3>
In Example 1, the temperature of the aqueous medium in the granulation step and the polymerization step was set to 65 ° C., and the hydrocarbon wax (melting point 90 ° C.) was changed to the hydrocarbon wax (melting point 97 ° C.). Toner 27 was obtained.

<Comparative Example 4>
A toner 28 was obtained in the same manner as in Example 1 except that hexane was used instead of cyclohexane.

<Comparative Example 5>
A toner 29 was obtained in the same manner as in Example 1 except that heptane was used instead of cyclohexane.

<Comparative Example 6>
A toner 30 was obtained in the same manner as in Example 1 except that toluene was used instead of cyclohexane.

<Comparative Example 7>
A toner 31 was obtained in the same manner as in Example 1 except that ethanol was used instead of cyclohexane.

<Comparative Example 8>
A toner 32 was obtained in the same manner as in Example 1 except that 2-propanol was used instead of cyclohexane.

  The production conditions for each example are shown in Table 1.

[Toner evaluation]
Each obtained toner was evaluated by the following method. The evaluation results are shown in Table 2.

  In the following hot offset resistance test and low-temperature fixability test, a color laser printer (HP Color LaserJet 3525dn; manufactured by HP) was used as an image forming apparatus. In order to output an unfixed toner image, the fixing unit was removed, and the removed fixing unit was modified so that the fixing temperature, process speed, and fixing linear pressure could be adjusted, and used for evaluation.

  The toner cartridge was used by taking out the toner from the cyan cartridge and filling it with a toner to be evaluated instead.

As the image receiving paper, A4 size, 81.4 g / m ² Canon color laser copier paper (manufactured by Canon Inc.) was used.

[Hot offset resistance and low-temperature fixability]
Using the filled toner on the image receiving paper, an unfixed toner image of 5.0 cm in length and 5.0 cm in width (toner loading: 0.7 mg / cm ² ) is 1.0 cm from the upper end in the sheet passing direction. In the direction perpendicular to the paper passing direction, the central portion is formed. Next, a fixing test of an unfixed image was performed using the modified fixing unit.

  First, in a normal temperature and humidity environment (23 ° C., 60% RH), the process speed is set to 240 mm / s, the initial temperature of the fixing roller is set to 140 ° C., and the set temperature is sequentially increased by 5 ° C. The unfixed image was fixed.

Evaluation criteria for hot offset resistance are as follows. The high temperature side fixing upper limit temperature is an upper limit temperature at which a phenomenon (offset) in which molten toner adheres to the fixing roller is not observed.
A: High temperature side fixing upper limit temperature is 230 ° C. or higher B: High temperature side fixing upper limit temperature is 220 ° C. or higher and 225 ° C. or lower C: High temperature side fixing upper limit temperature is 210 ° C. or higher and 215 ° C. or lower D: High temperature side fixing upper limit temperature is 200 ° C. or higher 205 ° C. or less E: High-temperature side fixing upper limit temperature is 195 ° C. or less

The evaluation criteria for low-temperature fixability are as follows. The low-temperature fixing lower limit temperature is a lower limit temperature at which no offset or blister (fixed image blistering) is observed.
A: Low temperature side fixing lower limit temperature is 150 ° C. or lower B: Low temperature side fixing lower limit temperature is 155 ° C. or higher and 160 ° C. or lower C: Low temperature side fixing lower limit temperature is 165 ° C. or higher and 170 ° C. or lower D: Low temperature side fixing lower limit temperature is 175 ° C. or higher 180 ° C. or lower E: Lower limit fixing temperature on the low temperature side is 185 ° C. or higher.

[Heat resistant storage stability]
1.0 g of the toner to be evaluated was weighed into a 50 cc polycup and allowed to stand for 72 hours in a thermostatic bath set at a temperature of 60 ° C. and a humidity of 10% RH. Thereafter, the degree of toner aggregation was evaluated according to the following criteria.
A: When the polycup is tilted, the toner flows.
B: Although the toner does not flow even when the polycup is tilted, the toner flows when an impact is applied.
C: Some toner does not flow even when an impact is applied to the polycup, but non-flowing toner is easily loosened when pressed with a finger.
D: Toner that does not flow exists and is not easily unraveled when pressed with a finger, but unraveled when pressed hard.
E: There is toner that does not flow, and it does not loosen even when pressed strongly with a finger

[Granulation]
In the toner particle production process, the ratio D4 / D1 between the weight average particle diameter D4 (μm) and the number average particle diameter D1 (μm) of the toner particles after the drying process was evaluated according to the following criteria. The closer the value of the ratio D4 / D1 is to 1.00, the narrower the particle size distribution.
A: D4 / D1 is less than 1.20 B: D4 / D1 is 1.20 or more and less than 1.25 C: D4 / D1 is 1.25 or more and less than 1.30 D: D4 / D1 is 1.30 or more and 1. Less than 35 E: D4 / D1 is 1.35 or more and less than 1.40

Claims (7)

A method for producing a toner having toner particles containing a binder resin and a hydrocarbon wax,
The manufacturing method is as follows:
A granulating step of forming particles of a polymerizable monomer composition containing a polymerizable monomer capable of forming the binder resin, the hydrocarbon wax, and a non-polymerizable organic solvent in an aqueous medium; ,
Polymerizing the polymerizable monomer to obtain resin particles, and
The difference Rar of Hansen solubility parameter (HSP) between the non-polymerizable organic solvent and the hydrocarbon wax is 2.00 or less,
The difference Raw between the Hansen solubility parameter (HSP) of the non-polymerizable organic solvent and the aqueous medium is 41.00 or more and 45.20 or less,
A method for producing a toner, wherein a melting point Tr (° C.) of the hydrocarbon wax satisfies the following formula (1).
Tp + 15 ≦ Tr ≦ Tp + 30 (° C.) Formula (1)
(In the formula, Tp represents the average temperature of the aqueous medium in the granulation step and the polymerization step.)   The toner production method according to claim 1, further comprising a step of heating the aqueous medium in which the resin particles are dispersed after the polymerization step at a temperature of 95 ° C. or more for 2 hours or more.   The method for producing a toner according to claim 1 or 2, wherein the addition amount of the non-polymerizable organic solvent is 5.0 parts by mass or more and 50.0 parts by mass or less with respect to 100.0 parts by mass of the polymerizable monomer. .   The addition amount of the hydrocarbon wax is 1.5 parts by mass or more and 20.0 parts by mass or less with respect to 100.0 parts by mass of the total amount of the polymerizable monomer and the non-polymerizable organic solvent. The method for producing a toner according to any one of items 1 to 3.   The method for producing a toner according to claim 1, wherein the hydrocarbon wax has a melting point of 85 ° C. or higher and 100 ° C. or lower.   The toner manufacturing method according to claim 1, wherein an average temperature of the aqueous medium in the granulation step and the polymerization step is 60 ° C. or more and 80 ° C. or less.   The method for producing a toner according to claim 1, wherein the non-polymerizable organic solvent is an alicyclic hydrocarbon.