JP6337638B2 - Toner for electrostatic image development - Google Patents

Description

  The present invention relates to an electrostatic charge image developing toner used for electrophotographic image formation.

In recent years, electrophotographic image forming apparatuses have been required to reduce thermal energy during fixing in order to increase printing speed and reduce environmental burden.
In response to such a demand, as an electrostatic charge image developing toner (hereinafter, also simply referred to as “toner”) used for electrophotographic image formation, a crystalline polyester excellent in sharp melt property as a binder resin, etc. It is known to use a crystalline resin.

  For example, in the case where a crystalline polyester resin and an amorphous resin are mixed and used as the binder resin, the crystalline component melts when the temperature history at the time of heat fixing exceeds the melting point of the crystalline polyester resin. By being compatible with the water-soluble component, it is possible to promote the thermal melting of the amorphous resin and fix it at a low temperature.

In general, a release agent is added to the toner in order to ensure fixing separation.
The toner passes through the fixing nip portion during heat fixing, and the binder resin in the toner is melted by heat to be fixed on an image support such as paper. At this time, the binder resin is heat-melted to cause stickiness, but if the adhesiveness to the fixing member is higher than the adhesiveness to the image support or the toner has a low internal cohesive force, the toner Is transferred to the fixing member, and there is a problem that fixing separation property cannot be obtained. In order to obtain the fixing separation property, it is necessary that the release agent sufficiently oozes out on the surface of the molten toner when the binder resin is melted by heat.
In the case of using a mixture of an amorphous resin and a crystalline polyester resin as the binder resin, the crystalline polyester resin melts when heated to a temperature exceeding the melting point of the crystalline polyester resin, and the amorphous component By being compatible with (amorphous resin), thermal melting of the amorphous resin is promoted. Therefore, the melting point is preferably equal to or lower than the melting point of the crystalline polyester resin from the viewpoint of leaching of the release agent.
On the other hand, when the release agent is heated excessively beyond its melting point, it volatilizes and recrystallizes in the air to generate ultra fine particles (UFP). Furthermore, the release of the release agent to the surface of the molten toner becomes excessive and adheres to a fixing member such as a fixing roller or a fixing belt, and the release agent attached to the fixing member acts on the image portion of the second round. Cause uneven gloss.

As means for solving such a problem, Patent Document 1 has a binder resin, a colorant, and an ester wax containing 50 to 95% by weight of an ester compound having the same total carbon number. Toner is disclosed. However, no consideration has been given to high-speed printing, and neither suppression of volatile components nor image quality is mentioned.
Further, Patent Document 2 discloses a toner in which the complex viscosity (Pa · s) obtained from the dynamic viscoelasticity measurement of the release agent is defined with a complex viscosity relationship at a specific frequency. However, there is no mention of the relationship between the glass transition point of the binder resin and the melting point of the release agent and the crystalline polyester.

Japanese Patent No. 3287733 JP 2013-15673 A

  The present invention has been made in consideration of the above-described circumstances. The object of the present invention is to ensure fixing separation property while having excellent low-temperature fixability, and to generate UFP and uneven gloss. An object of the present invention is to provide a toner for developing an electrostatic image in which the toner is suppressed.

The electrostatic image developing toner of the present invention is an electrostatic image developing toner comprising toner particles containing a binder resin and a release agent.
The binder resin includes an amorphous resin and a crystalline polyester resin,
The temperature of the melting peak derived from the crystalline polyester resin in the temperature rising process in the differential scanning calorimetry of the toner for developing an electrostatic charge image is Tmc (° C.), and the temperature of the melting peak derived from the release agent is Tmw (° C.). When the glass transition point of the toner is Tg (° C.), the following formula (1) is satisfied, and
The melting peak temperature Tmc derived from the crystalline polyester resin is 60 to 95 ° C.,
The release agent is composed of at least an ester wax, the melting peak temperature Tmw derived from the release agent is 60 to 80 ° C., and the release agent is composed of a plurality of components having different carbon chain lengths. In the carbon chain length distribution of the agent, the content of the carbon chain length component having the largest content is 80% by mass or more, and the carbon chain length of the release agent is the total number of carbon atoms of the fatty acid and the aliphatic alcohol. It is characterized by.
Formula (1): Tg <Tmw ≦ Tmc

  In the electrostatic image developing toner of the present invention, the melting peak temperature Tmc derived from the crystalline polyester resin is preferably in the range of 60 to 80 ° C.

  The electrostatic image developing toner of the present invention is an electrostatic image developing toner comprising toner particles containing a binder resin and a release agent.
  The binder resin includes an amorphous resin and a crystalline polyester resin,
  The temperature of the melting peak derived from the crystalline polyester resin in the temperature rising process in the differential scanning calorimetry of the toner for developing an electrostatic charge image is Tmc (° C.), and the temperature of the melting peak derived from the release agent is Tmw (° C.). When the glass transition point of the toner is Tg (° C.), the following formula (1) is satisfied, and
  The melting peak temperature Tmc derived from the crystalline polyester resin is 60 to 95 ° C.,
  The release agent is composed of at least a hydrocarbon wax, the melting peak temperature Tmw derived from the release agent is 75 to 95 ° C., and the release agent is composed of a plurality of components having different carbon chain lengths. In the carbon chain length distribution of the mold, the content of the carbon chain length component having the largest content is 5% by mass or more.
  Formula (1): Tg <Tmw ≦ Tmc

  In the toner for developing an electrostatic image, the content of the carbon chain length component having the largest content is preferably 7% by mass or more.

  According to the electrostatic image developing toner of the present invention, the melting peak temperature Tmc derived from the crystalline polyester resin, the melting peak temperature Tmw derived from the release agent, and the glass transition point Tg of the toner are in a specific range, Further, by satisfying the formula (1), the fixing separation property is ensured while having excellent low-temperature fixing property, and the occurrence of UFP and uneven glossiness is suppressed.

  Hereinafter, the present invention will be described in detail.

〔toner〕
The toner of the present invention comprises toner particles containing a binder resin containing at least an amorphous resin and a crystalline polyester resin, and a release agent. It may contain other toner constituents such as powder and charge control agent. Further, external additives such as a fluidizing agent and a cleaning aid may be added to the toner particles.

In the toner of the present invention, the temperature of the melting peak derived from the crystalline polyester resin in the temperature rising process in the differential scanning calorimetry of the toner is Tmc (° C.), and the temperature of the melting peak derived from the release agent is Tmw (° C.). When the glass transition point of the toner is Tg (° C.), the following formula (1) is satisfied.
Formula (1): Tg <Tmw ≦ Tmc
In the toner of the present invention, since the melting peak temperature Tmw derived from the release agent is higher than the glass transition point Tg of the toner, the release agent is not excessively heated even when heated to the toner fixing temperature. UFP and gloss unevenness are suppressed. Further, when the melting peak temperature Tmw derived from the release agent is equal to or lower than the melting peak temperature Tmc derived from the crystalline polyester resin, the release agent is thermally melted prior to or simultaneously with the crystalline polyester resin when passing through the fixing nip portion, Since wetting and spreading between the surface of the molten toner and the fixing member, even if the crystalline polyester resin is melted by heat and is compatible with the amorphous resin to cause stickiness, fixing separation is ensured.

  From the above, in the toner of the present invention, since the crystalline resin is contained in the binder resin, the heat melting of the amorphous resin is promoted at the time of heat fixing. Sex is obtained. Further, since the melting peak temperature Tmw derived from the release agent is higher than the glass transition point Tg of the toner, the generation of UFP and the occurrence of uneven gloss are suppressed. Furthermore, fixing separation property is ensured when the melting peak temperature Tmw derived from the release agent is equal to or lower than the melting peak temperature Tmc derived from the crystalline polyester resin. Even if the passage time of the fixing nip is shortened as the printing speed is increased, the release agent is thermally melted before or at the same time as the crystalline polyester resin, and between the surface of the molten toner and the fixing member. Since wetting and spreading, even if the crystalline polyester resin or amorphous resin is hot melted and becomes sticky, it can be reliably prevented from moving to the fixing member, and fixing separation can be ensured. it can.

In the toner of the present invention, the difference between the melting peak temperature Tmw derived from the release agent and the glass transition point Tg of the toner is preferably 10 to 50 ° C. Further, the difference between the melting peak temperature Tmw derived from the release agent and the melting peak temperature Tmc derived from the crystalline polyester resin is preferably 0 to 30 ° C, more preferably 0 to 10 ° C.
Specifically, the glass transition point Tg of the toner is preferably 25 to 65 ° C, more preferably 35 to 55 ° C. The melting peak temperature Tmw derived from the release agent is 75 to 95 ° C. when the release agent is made of a hydrocarbon wax, and is 60 to 80 ° C. when the release agent is an ester wax. Furthermore, the melting peak temperature Tmc derived from the crystalline polyester resin is 60 to 95 ° C, preferably 60 to 80 ° C, more preferably 70 to 80 ° C.
When the glass transition point Tg of the toner, the melting peak temperature Tmw derived from the release agent, and the melting peak temperature Tmc derived from the crystalline polyester resin are within the above ranges, the low-temperature fixing property and the fixing separation property can be reliably obtained.

Here, the melting peak temperature Tmc derived from the crystalline polyester resin and the melting peak temperature Tmw derived from the release agent are values measured in the temperature rising process in the differential scanning calorimetry of the toner, specifically, "DSC-7 differential scanning calorimeter" (manufactured by PerkinElmer), "TAC7 / DX thermal analyzer controller" (manufactured by PerkinElmer) can be used.
As a measurement procedure, toner 4.5 mg to 5.0 mg is precisely weighed to two decimal places, sealed in an aluminum pan (KITNO.0219-0041), and set in a DSC-7 sample holder. The reference uses an empty aluminum pan. The measurement conditions were a measurement temperature of 0 ° C. to 200 ° C., a temperature increase rate of 10 ° C./min, a temperature decrease rate of 10 ° C./min, and heat-cool-heat temperature control. Analysis is performed based on the data in Heat. The melting peak temperature is the peak top temperature.

Further, the glass transition point Tg of the toner is a value measured as follows.
In the differential scanning calorimetry described above, an extension of the baseline before the rise of the first melting peak and a tangent line indicating the maximum slope between the rising portion of the first melting peak and the peak apex are drawn, and the intersection is obtained. The glass transition point.

[Binder resin]
In the toner of the present invention, the binder resin contains at least an amorphous resin and a crystalline polyester resin. Here, the term “polyester resin” includes the meanings of both a polyester polymer segment only and a modified resin in which other components are bound at a ratio of 50% by mass or less. As said other component couple | bonded with a polyester polymerization segment, it is preferable to use a vinyl-type polymerization segment.

(Amorphous resin)
The amorphous resin constituting the binder resin is configured as a main component in the binder resin. The amorphous resin is not particularly limited. Specifically, vinyl resins such as styrene resin, acrylic resin, and styrene acrylic copolymer resin, and amorphous polyester resin are used for fixing and heat resistance of the toner. From the viewpoint of storability and heat resistance of a fixed image, it is preferable. As the amorphous resin, vinyl resins other than the above such as olefin resins, polyamide resins, polycarbonate resins, polyether resins, polyvinyl acetate resins, polysulfone resins, epoxy resins, polyurethane resins, urea resins, etc. are used. You can also
Amorphous resins can be used singly or in combination of two or more.

Examples of the monomer for forming a vinyl resin such as a styrene resin, an acrylic resin, and a styrene acrylic copolymer resin include vinyl monomers.
The following can be used as the vinyl monomer. As a vinyl monomer, it can be used individually by 1 type or in combination of 2 or more types.
(1) Styrene monomer Styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-tert -Butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, and derivatives thereof.
(2) (meth) acrylic acid ester monomer (meth) methyl acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, T-butyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, phenyl (meth) acrylate, (meth ) Diethylaminoethyl acrylate, dimethylaminoethyl (meth) acrylate, and derivatives thereof.
(3) Vinyl esters Vinyl propionate, vinyl acetate, vinyl benzoate and the like.
(4) Vinyl ethers Vinyl methyl ether, vinyl ethyl ether and the like.
(5) Vinyl ketones Vinyl methyl ketone, vinyl ethyl ketone, vinyl hexyl ketone and the like.
(6) N-vinyl compounds N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone and the like.
(7) Others Vinyl compounds such as vinyl naphthalene and vinyl pyridine, acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.

Moreover, as a vinyl monomer, it is preferable to use the monomer which has ionic dissociation groups, such as a carboxy group, a sulfonic acid group, and a phosphoric acid group, for example. Specifically, there are the following.
Examples of the monomer having a carboxy group include acrylic acid, methacrylic acid, maleic acid, itaconic acid, cinnamic acid, fumaric acid, maleic acid monoalkyl ester, itaconic acid monoalkyl ester, and the like. Examples of the monomer having a sulfonic acid group include styrene sulfonic acid, allyl sulfosuccinic acid, 2-acrylamido-2-methylpropane sulfonic acid, and the like. Furthermore, examples of the monomer having a phosphate group include acid phosphooxyethyl methacrylate.

  Furthermore, polyfunctional vinyls can be used as the vinyl monomer, and the vinyl resin can have a crosslinked structure. Examples of the polyfunctional vinyls include divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neo Examples include pentyl glycol diacrylate.

  Amorphous polyester resin is a differential scanning calorimetry among known polyester resins obtained by polycondensation reaction of divalent or higher carboxylic acid (polyvalent carboxylic acid) and divalent or higher alcohol (polyhydric alcohol). In (DSC), it does not show a clear melting peak. Here, the clear melting peak is specifically a peak whose half-width of the melting peak is within 15 ° C. when measured at a temperature rising rate of 10 ° C./min in differential scanning calorimetry (DSC). Means that.

The polyvalent carboxylic acid is a compound containing two or more carboxy groups in one molecule.
Examples of the polyvalent carboxylic acid for forming the amorphous polyester resin include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelic acid, sebacic acid, 1,9- Nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecane Saturated aliphatic dicarboxylic acids such as dicarboxylic acid and 1,18-octadecanedicarboxylic acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid and naphthalenedicarboxylic acid; maleic acid, fumaric acid, itaconic acid, citraconic acid, glutacone Acid, isododecenyl succinic acid, n-dodecenyl succinic acid, n- Unsaturated aliphatic dicarboxylic acids such as octenyl succinic acid; trivalent or higher polyvalent carboxylic acids such as trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, pyrenetetracarboxylic acid, etc. Can do.
These may be used individually by 1 type and may be used in combination of 2 or more type.

A polyhydric alcohol is a compound containing two or more hydroxyl groups in one molecule.
Examples of the polyhydric alcohol for forming the amorphous polyester resin include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1 , 7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-dodecanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, , 14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol, and the like; bisphenols such as bisphenol A and bisphenol F, and ethylene oxide adducts, propylene oxide adducts, etc. Alkylene oxide of bisphenols Addendum; glycerol, pentaerythritol, hexamethylol melamine, can be cited hexa ethyl melamine, tetramethylol benzoguanamine, etc. trihydric or higher polyols, such as tetra-ethyl benzoguanamine the.
These may be used individually by 1 type and may be used in combination of 2 or more type.

The glass transition point of the amorphous resin is preferably 20 to 65 ° C, more preferably 30 to 63 ° C.
When the glass transition point of the amorphous resin is in the above range, low temperature fixability is ensured.

In the present invention, the glass transition point of the amorphous resin is a value measured using “Diamond DSC” (manufactured by PerkinElmer).
As a measurement procedure, 3.0 mg of a measurement sample (amorphous resin) is sealed in an aluminum pan and set in a holder. The reference used an empty aluminum pan. The measurement conditions were a measurement temperature of 0 ° C. to 200 ° C., a temperature increase rate of 10 ° C./min, a temperature decrease rate of 10 ° C./min, and heat-cool-heat temperature control. Perform analysis based on the data in Heat, draw a baseline extension before the rise of the first melting peak, and a tangent line indicating the maximum slope between the rise of the first peak and the peak apex, Let the intersection be the glass transition point.

  The softening point of the amorphous resin is preferably 80 to 120 ° C., more preferably 90 to 110 ° C., from the viewpoint of obtaining low-temperature fixability for the toner.

In the present invention, the softening point of the amorphous resin is a value measured by a flow tester.
Specifically, first, in an environment of 20 ° C. and 50% RH, 1.1 g of a measurement sample (amorphous resin) was placed in a petri dish and left flat for 12 hours or more. 10A "(manufactured by Shimadzu Corporation) with a pressure of 3820 kg / cm ² for 30 seconds to produce a cylindrical molded sample having a diameter of 1 cm, and this molded sample is then subjected to an environment of 24 ° C. and 50% RH. Using a flow tester “CFT-500D” (manufactured by Shimadzu Corporation), a cylindrical die hole (1 mm) under the conditions of a load of 196 N (20 kgf), a starting temperature of 60 ° C., a preheating time of 300 seconds, and a temperature rising rate of 6 ° C. than the diameter × 1 mm), extruded from the time of preheating ends with piston diameter 1 cm, offset method temperature T _offset is softened as measured by setting the offset value 5mm at a melt temperature measurement method of temperature ramps It is.

The molecular weight of the amorphous resin measured by gel permeation chromatography (GPC) is preferably 10,000 to 50,000, more preferably 25,000 to 35,000 in terms of weight average molecular weight (Mw). It is. The number average molecular weight (Mn) is preferably 5,000 to 20,000, more preferably 6,500 to 12,000.
When the molecular weight of the amorphous resin is in the above range, the low temperature fixing property and the fixing separation property can be reliably obtained.
When the molecular weight of the amorphous resin is excessive, there is a possibility that the low-temperature fixability cannot be obtained sufficiently. On the other hand, when the molecular weight of the amorphous resin is too small, there is a possibility that the fixing separation property cannot be obtained sufficiently.

In the present invention, the molecular weight of the amorphous resin by gel permeation chromatography (GPC) is a value measured as follows.
Specifically, using an apparatus “HLC-8120GPC” (manufactured by Tosoh Corporation) and a column “TSKguardcolumn + TSKgelSuperHZ-M3 series” (manufactured by Tosoh Corporation), while maintaining the column temperature at 40 ° C., tetrahydrofuran (THF) was used as a carrier solvent. The sample was flowed at a flow rate of 0.2 ml / min, and the measurement sample (amorphous resin) was dissolved in tetrahydrofuran to a concentration of 1 mg / ml under a dissolution condition in which treatment was performed for 5 minutes using an ultrasonic disperser at room temperature. A sample solution is obtained by processing with a membrane filter having a pore size of 0.2 μm, and 10 μL of this sample solution is injected into the apparatus together with the carrier solvent described above, and detected using a refractive index detector (RI detector). A calibration curve obtained by measuring the molecular weight distribution using monodisperse polystyrene standard particles Is used to calculate. Ten polystyrenes were used for calibration curve measurement.

The content ratio of the amorphous resin is preferably 70 to 99% by mass in the binder resin.
When the amorphous resin content is in the above range, when used as a binder resin together with a crystalline polyester resin, sufficient fixing properties, sufficient heat storage stability of the toner and heat resistance of the fixed image are obtained. Can be secured.

(Crystalline polyester resin)
The crystalline polyester resin constituting the binder resin is a known polyester resin obtained by a polycondensation reaction between a divalent or higher carboxylic acid (polyvalent carboxylic acid) and a divalent or higher alcohol (polyhydric alcohol). In differential scanning calorimetry (DSC), it refers to a resin having a clear melting peak rather than a stepwise endothermic change. Here, the clear melting peak is specifically a peak whose half-width of the melting peak is within 15 ° C. when measured at a temperature rising rate of 10 ° C./min in differential scanning calorimetry (DSC). Means that.

Examples of the polyvalent carboxylic acid for forming the crystalline polyester resin include saturated aliphatic dicarboxylic acids such as succinic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; aromatics such as phthalic acid, isophthalic acid, and terephthalic acid. Group dicarboxylic acids; trivalent or higher polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid; and anhydrides of these carboxylic acid compounds or alkyl esters having 1 to 3 carbon atoms.
These may be used individually by 1 type and may be used in combination of 2 or more type.

Examples of the polyhydric alcohol for forming the crystalline polyester resin include 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexane. Aliphatic diols such as xanthdiol, 1,7-heptanediol, 1,8-octanediol, neopentyl glycol, 1,4-butenediol; trivalent or higher valents such as glycerin, pentaerythritol, trimethylolpropane, sorbitol A polyhydric alcohol etc. are mentioned.
These may be used individually by 1 type and may be used in combination of 2 or more type.

The melting point of the crystalline polyester resin is preferably 60 to 95 ° C, more preferably 60 to 80 ° C.
When the melting point of the crystalline polyester resin is in the above range, the thermal melting of the amorphous resin during heat fixing is promoted, and sufficient low-temperature fixability can be obtained even when the printing speed is increased.

The melting point of the crystalline polyester resin is a value measured as follows.
The melting point of the crystalline polyester indicates the temperature at the peak top of the melting peak, and is measured by DSC by differential scanning calorimetry using “Diamond DSC” (manufactured by PerkinElmer).
Specifically, 1.0 mg of a measurement sample (crystalline polyester resin) is sealed in an aluminum pan (KITNO.B0143013), and this is set in a sample holder of “Diamond DSC” at a measurement temperature of 0 to 200 ° C. The temperature control of heating-cooling-heating is performed under the measurement conditions of a heating rate of 10 ° C./min and a cooling rate of 10 ° C./min, and the analysis is performed based on the second heating data.

  The molecular weight measured by gel permeation chromatography (GPC) of the crystalline polyester resin is 12,000 to 30,000 in terms of weight average molecular weight (Mw) and 3,000 to 10,000 in terms of number average molecular weight (Mn). Preferably there is.

  The molecular weight of the crystalline polyester resin measured by gel permeation chromatography (GPC) is measured in the same manner as described above except that the crystalline polyester resin is used as a measurement sample.

The crystalline polyester resin is preferably contained in the binder resin at a ratio of 1 to 30% by mass, and more preferably 5 to 20% by mass.
When the content of the crystalline polyester resin in the toner particles is within the above range, an amount of the crystalline polyester resin that can achieve low-temperature fixability can be introduced into the toner particles.

〔Release agent〕
In the toner of the present invention, a release agent is contained in order to ensure fixing separation.
As the release agent, ester wax or hydrocarbon wax can be used. As such a wax, a synthesized wax may be used, or a commercially available wax may be purified and used. Examples of the purification method include a method of recrystallization by dissolving in n-hexane or heptane. Furthermore, these release agents may be used alone or in combination. In that case, the release agent satisfying the above formula (1): Tg <Tmw ≦ Tmc is preferably 10% by mass or more, more preferably 15% by mass or more, based on the total amount of the release agent. As a result, it is possible to ensure fixing separation by oozing out before the crystalline polyester.
Examples of ester waxes include carnauba wax, montan wax, behenate behenate, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18-octadecane. Examples thereof include diol distearate, tristearyl trimellitic acid, and distearyl maleate.
Examples of hydrocarbon waxes include polyolefin waxes such as polyethylene wax and polypropylene wax, petroleum-derived paraffin wax, microcrystalline wax, and synthetic waxes such as Fischer-Tropsch wax and polyethylene wax.

The ester wax or hydrocarbon wax constituting the release agent is composed of a plurality of components having different carbon chain lengths, and the content of the carbon chain length component having the highest content in the carbon chain length distribution of the release agent. [Cm] is preferably 70% by mass or more, more preferably 80% by mass or more when the release agent is an ester wax. In the case where the release agent is a hydrocarbon wax, the content [Cm] of the carbon chain length component having the largest content is preferably 5% by mass or more, more preferably 7% by mass or more. is there.
In the release agent, when the content [Cm] of the carbon chain length component having the largest content is in the above range, the release agent has less volatile components, and the generation of UFP is reliably suppressed. In addition, since the amount of the release agent that oozes on the surface of the molten toner does not become excessive, the occurrence of uneven gloss is reliably suppressed.

Here, the carbon chain length distribution of the release agent indicates a variation in the total carbon number (carbon chain length) of the ester or paraffin chain alkyl skeleton constituting the release agent. In the carbon chain length distribution, the total carbon number of the chain alkyl skeleton constituting the release agent is the total number of carbon atoms of fatty acid and aliphatic alcohol in the case of ester wax, and in the case of hydrocarbon wax. Is the carbon number of the alkane.
The content [Cm] of the carbon chain length component having the largest content in the release agent is such that when the release agent is an ester wax, the carbon chain length distribution is monodisperse, or In the case where the release agent is a hydrocarbon wax, it can be controlled by purifying a commercially available wax.

In the present invention, the carbon chain length distribution of the release agent is measured by gel permeation chromatography (GPC).
Specifically, the measurement is performed under the following measurement conditions.
-Measurement conditions-
The measurement sample (release agent) was dissolved in 145 ° C. o-dichlorobenzene, and then filtered through a sintered filter having a pore size of 1.0 μm.
GPC equipment: HLC-8121GPC / HT (manufactured by Tosoh Corporation)
Column: TSKgel G2000HHR (20) HT (inner diameter 7.8 mm × 30 cm) triple (manufactured by Tosoh Corporation)
Column temperature: 140 ° C
Solvent: o-dichlorobenzene Flow rate: 1.0 m / min
Sample concentration: 0.1% (v / w)
Sample injection volume: 500 μl
Detector: Refractive index detector (RI detector)
Calibration curve: standard polystyrene, n-hexylbenzene The detection level in the above column is 10,000 in terms of polystyrene.

The melting point of the release agent is 75 to 95 ° C., preferably 78 to 88 ° C. when the release agent is made of hydrocarbon wax, and 60 to 80 ° C. when the release agent is made of ester wax. , Preferably it is 63-78 degreeC.
If the melting point of the release agent is too small, image defects may occur. On the other hand, when the melting point of the release agent is excessive, it may be difficult to ensure the fixing and separating property.

The melting point of the release agent is a value measured using “Diamond DSC” (Perkin Elmer).
As a measurement procedure, 3.0 mg of a measurement sample (release agent) is sealed in an aluminum pan and set in a holder. The reference uses an empty aluminum pan. The measurement conditions were a measurement temperature of 0 ° C. to 200 ° C., a temperature increase rate of 10 ° C./min, a temperature decrease rate of 10 ° C./min, and heat-cool-heat temperature control. Analysis is performed based on the data in Heat, and the peak apex of the melting peak derived from the release agent is shown as the melting point.

  The content of the release agent is preferably 1 to 20% by mass, more preferably 5 to 20% by mass in the toner particles. When the content ratio of the release agent in the toner particles is within the above range, both the separation property and the fixing property can be reliably obtained.

In the toner of the present invention, the form of the toner particles is not particularly limited, and examples thereof include a single layer structure, a core-shell structure, a multilayer structure, and a domain-matrix structure. In particular, a core-shell structure is preferable from the viewpoint of ensuring heat-resistant storage properties.
The shell layer is not limited to completely covering the core particles, and a part of the core particle surface may be exposed.

  Although it does not specifically limit as resin which comprises a shell layer, Amorphous polyester resin, vinyl resin, etc. are preferable.

The layer thickness of the shell layer is preferably 0.1 to 1 μm.
In the present invention, the thickness of the shell layer is a value measured by an observation image of a transmission electron microscope (TEM).
Further, the content ratio of the resin constituting the shell layer is preferably 5 to 30% by mass in the toner particles.

[Colorant]
When the toner particles are configured to contain a colorant, various known colorants such as carbon black, black iron oxide, dyes, and pigments can be used as the colorant.
Examples of carbon black include channel black, furnace black, acetylene black, thermal black, and lamp black. Examples of black iron oxide include magnetite, hematite, and iron iron trioxide.
Examples of the dye include C.I. I. Solvent Red 1, 49, 52, 58, 63, 111, 122, C.I. I. Solvent Yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162, C.I. I. Solvent Blue 25, 36, 60, 70, 93, 95 and the like.
Examples of the pigment include C.I. I. Pigment Red 5, 48: 1, 48: 3, 53: 1, 57: 1, 81: 4, 122, 139, 144, 149, 150, 166, 177, 178, 222, 238, 269, C.I. I. Pigment Orange 31 and 43, C.I. I. Pigment yellow 14, 17, 74, 93, 94, 138, 155, 156, 158, 180, 185, C.I. I. Pigment green 7, C.I. I. Pigment Blue 15: 3, 60, and the like.
The colorant for obtaining the toner of each color can be used singly or in combination of two or more for each color.

  The content ratio of the colorant is preferably 1 to 10% by mass in the toner particles, and more preferably 2 to 8% by mass. If the content of the colorant is too small, the resulting toner may not have the desired coloring power. On the other hand, if the content of the colorant is excessive, it may be released to the colorant or to the carrier. May occur, which may affect the chargeability.

[Charge control agent]
In the toner of the present invention, when the toner particles are configured to contain a charge control agent, various known compounds can be used as the charge control agent.
The content of the charge control agent is preferably 0.1 to 10% by mass in the toner particles, and more preferably 1 to 5% by mass.

(External additive)
In the toner of the present invention, the toner particles can be used as toners as they are. However, in order to improve fluidity, chargeability, cleaning properties, etc., the toner particles may contain so-called fluidizing agents, cleaning aids, etc. An external additive may be added.
Various external additives may be used in combination.
The total addition amount of these external additives is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the toner particles.

[Toner particle size]
In the toner of the present invention, the average particle diameter is preferably 3 to 10 μm, and more preferably 5 to 8 μm, for example, on a volume basis median diameter. This average particle size can be controlled by the concentration of the flocculant used during production, the amount of organic solvent added, the fusing time, the composition of the binder resin, and the like.
When the volume-based median diameter is in the above range, a very small dot image of 1200 dpi level can be faithfully reproduced.

  The volume-based median diameter of the toner is measured and calculated using a measuring apparatus in which a computer system equipped with data processing software “Software V3.51” is connected to “Multisizer 3” (manufactured by Beckman Coulter). Is. Specifically, 0.02 g of a measurement sample (toner) was added to 20 mL of a surfactant solution (for example, a surfactant obtained by diluting a neutral detergent containing a surfactant component 10 times with pure water for the purpose of dispersing toner particles). After adding the solution to the solution), ultrasonic dispersion is performed for 1 minute to prepare a toner dispersion, and this toner dispersion is added to a beaker containing “ISOTONII” (manufactured by Beckman Coulter) in a sample stand. Then, inject with a pipette until the displayed concentration of the measuring device is 8%. Here, a reproducible measurement value can be obtained by setting the concentration range. In the measuring apparatus, the measurement particle count number is 25000, the aperture diameter is 100 μm, and the frequency value is calculated by dividing the range of 2 to 60 μm, which is the measurement range, into 256 parts. % Particle diameter is defined as the volume-based median diameter.

[Average circularity of toner]
In the toner of the present invention, the individual toner particles constituting the toner preferably have an average circularity of 0.930 to 1.000 from the viewpoints of stability of charging characteristics and low-temperature fixability. More preferably, it is 950 to 0.995.
When the average circularity is within the above range, the individual toner particles are less likely to be crushed, the contamination of the frictional charge imparting member is suppressed, the toner chargeability is stabilized, and the image quality of the formed image is high. It will be a thing.

The average circularity of the toner is a value measured using “FPIA-2100” (manufactured by Sysmex). Specifically, the measurement sample (toner) was blended with an aqueous solution containing a surfactant, dispersed by performing ultrasonic dispersion for 1 minute, and then subjected to measurement conditions HPF by “FPIA-2100” (manufactured by Sysmex). In the (high magnification imaging) mode, photographing is performed at an appropriate density of 3,000 to 10,000 HPF detections, and the circularity of each toner particle is calculated according to the following formula (y). This is a value calculated by adding the degree and dividing by the total number of toner particles. If the number of HPF detections is in the above range, reproducibility can be obtained.
Formula (y): Circularity = (perimeter of a circle having the same projection area as the particle image) / (perimeter of the particle projection image)

(Developer)
The toner of the present invention can be used as a magnetic or non-magnetic one-component developer, but may be mixed with a carrier and used as a two-component developer. When the toner is used as a two-component developer, the carrier includes magnetic particles made of conventionally known materials such as metals such as iron, ferrite and magnetite, and alloys of these metals with metals such as aluminum and lead. In particular, ferrite particles are preferable. Further, as the carrier, a coated carrier in which the surface of magnetic particles is coated with a coating agent such as a resin, a dispersion type carrier in which a magnetic fine powder is dispersed in a binder resin, or the like may be used.
The volume-based median diameter of the carrier is preferably 20 to 100 μm, more preferably 25 to 80 μm. The volume-based median diameter of the carrier can be typically measured by a laser diffraction particle size distribution measuring apparatus “HELOS” (manufactured by SYMPATEC) equipped with a wet disperser.

  In the above toner, the melting peak temperature Tmc derived from the crystalline polyester resin, the melting peak temperature Tmw derived from the release agent, and the glass transition point Tg of the toner satisfy the formula (1), thereby achieving excellent low-temperature fixing. However, the fixing separation property is ensured and the occurrence of UFP and uneven gloss are suppressed.

[Toner Production Method]
The method for producing the toner of the present invention is not particularly limited, and examples thereof include a pulverization method, an emulsion dispersion method, a suspension polymerization method, a dispersion polymerization method, an emulsion polymerization method, an emulsion polymerization aggregation method, and other known methods. It is done. In particular, the emulsion polymerization aggregation method is preferable from the viewpoint of production cost and production stability.

  The method for producing the toner of the present invention by the emulsion polymerization aggregation method includes an aqueous dispersion in which fine particles of a binder resin (hereinafter also referred to as “binder resin fine particles”) are dispersed in an aqueous medium, and fine particles of a colorant. (Hereinafter also referred to as “colorant fine particles”) is mixed with an aqueous dispersion, and the toner particles are formed by aggregating and thermally fusing the binder resin fine particles and the colorant fine particles. .

  The binder resin fine particles may have a multilayer structure of two or more layers made of binder resins having different compositions. For example, a binder resin fine particle having such a structure has a two-layer structure. A dispersion of resin fine particles is prepared by polymerization treatment (first-stage polymerization) according to the method, a polymerization initiator and a polymerizable monomer are added to the dispersion, and this system is polymerized (second-stage polymerization). ).

  Here, the “aqueous dispersion” is a dispersion in which a dispersion (particles) is dispersed in an aqueous medium, and the aqueous medium is one in which a main component (50% by mass or more) is made of water. . Examples of components other than water include organic solvents that dissolve in water, such as methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, and tetrahydrofuran. Among these, alcohol-based organic solvents such as methanol, ethanol, isopropanol, and butanol, which are organic solvents that do not dissolve the resin, are particularly preferable.

Specifically, an example of the toner production method of the present invention by the emulsion polymerization aggregation method is as follows:
(A) a step of preparing an aqueous dispersion in which fine particles of amorphous resin (hereinafter also referred to as “amorphous resin fine particles”) are dispersed in an aqueous medium;
(B) a step of preparing an aqueous dispersion in which fine particles of a crystalline polyester resin (hereinafter also referred to as “crystalline polyester resin fine particles”) are dispersed in an aqueous medium;
(C) a step of preparing an aqueous dispersion in which colorant fine particles are dispersed in an aqueous medium;
(D) a step of aggregating and fusing amorphous resin fine particles, crystalline polyester resin fine particles and colorant fine particles in an aqueous medium to form associated particles;
(E) aging associated particles with thermal energy to control the shape to obtain toner particles;
(F) a step of cooling the dispersion of toner particles;
(G) a step of filtering the toner particles from the aqueous medium and removing the surfactant from the toner particles;
(H) drying the washed toner particles;
As necessary,
(I) A step of adding an external additive to the dried toner particles can be added.

(A) Step of preparing an aqueous dispersion of amorphous resin fine particles In this step, an aqueous dispersion of amorphous resin fine particles of an amorphous resin is prepared.
For example, when the amorphous resin is a vinyl resin such as a styrene-acrylic copolymer resin, an aqueous dispersion of the amorphous resin fine particles can be obtained by using a vinyl monomer for obtaining the amorphous resin. It can be prepared by an emulsion polymerization method. That is, for example, a vinyl monomer is added to an aqueous medium containing a surfactant, mechanical energy is applied to form droplets, and then the radicals from the water-soluble radical polymerization initiator The polymerization reaction is allowed to proceed. Note that an oil-soluble polymerization initiator may be contained in the droplet.

[Surfactant]
As the surfactant used in this step, conventionally known various anionic surfactants, cationic surfactants, nonionic surfactants and the like can be used.

(Polymerization initiator)
As the polymerization initiator used in this step, various conventionally known polymerization initiators can be used. As specific examples of the polymerization initiator, for example, persulfates (potassium persulfate, ammonium persulfate, etc.) are preferably used. In addition, azo compounds (4,4′-azobis-4-cyanovaleric acid and its salts, 2,2′-azobis (2-amidinopropane) salts, etc.), peroxide compounds, azobisisobutyronitrile, etc. Also good.

[Chain transfer agent]
In this step, a commonly used chain transfer agent can be used for the purpose of adjusting the molecular weight of the amorphous resin. The chain transfer agent is not particularly limited, and examples thereof include mercaptans such as 2-chloroethanol, octyl mercaptan, dodecyl mercaptan, and t-dodecyl mercaptan, and styrene dimers.

  In addition, for example, when the amorphous resin is an amorphous polyester resin, the aqueous dispersion of the amorphous resin fine particles is synthesized with an amorphous polyester resin, and the amorphous polyester resin is placed in an aqueous medium. It can be prepared by dispersing in fine particles. Specifically, an amorphous polyester resin is dissolved or dispersed in an organic solvent to prepare an oil phase liquid, and the oil phase liquid is dispersed in an aqueous medium by phase inversion emulsification or the like to obtain a desired particle size. After forming oil droplets in a controlled state, it can be prepared by removing the organic solvent.

The amount of the aqueous medium used is preferably 50 to 2,000 parts by mass and more preferably 100 to 1,000 parts by mass with respect to 100 parts by mass of the oil phase liquid.
A surfactant or the like may be added to the aqueous medium for the purpose of improving the dispersion stability of the oil droplets. As surfactant, the thing similar to what was mentioned in said process can be mentioned.

The organic solvent used for the preparation of the oil phase liquid is preferably one having a low boiling point and low solubility in water from the viewpoint of easy removal treatment after formation of oil droplets. Examples thereof include methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene and the like. These can be used alone or in combination of two or more. The usage-amount of an organic solvent is 1-300 mass parts normally with respect to 100 mass parts of amorphous polyester resins.
The emulsification and dispersion of the oil phase liquid can be performed using mechanical energy.

The toner particles according to the present invention contain a release agent. For example, in this step, the release agent is a vinyl monomer solution or an amorphous material for forming a vinyl resin in advance. It can be introduced into the toner particles by dissolving or dispersing it in the oil phase liquid of the conductive polyester resin.
In addition, a release agent is prepared by separately preparing a dispersion of release agent fine particles consisting of only a release agent, and the release agent together with amorphous resin fine particles, crystalline polyester resin fine particles and colorant fine particles in the aggregation / fusion process. Although it is possible to introduce the toner particles into the toner particles by aggregating the agent fine particles, it is preferable to adopt a method of introducing them in advance in this step.

In addition, the toner particles according to the present invention may contain other internal additives such as a charge control agent, if necessary. Such internal additives are preliminarily used in this step, for example. It can be introduced into the toner particles by dissolving or dispersing in a vinyl monomer solution (or an oil phase liquid of an amorphous polyester resin) for forming an amorphous resin.
Such an internal additive is prepared by separately preparing a dispersion of internal additive fine particles consisting only of the internal additive, together with the amorphous resin fine particles, the crystalline polyester resin fine particles and the colorant fine particles in the aggregation / fusion process. Although it is possible to introduce into the toner particles by aggregating the additive fine particles, it is preferable to adopt a method of introducing in advance in this step.

The average particle diameter of the amorphous resin fine particles is preferably in the range of 100 to 400 nm in terms of volume-based median diameter.
In the present invention, the volume-based median diameter of the amorphous resin fine particles is a value measured using “Microtrac UPA-150” (manufactured by Nikkiso Co., Ltd.).

(B) Preparation Step of Aqueous Dispersion of Crystalline Polyester Resin Fine Particles In this step, an aqueous dispersion of crystalline polyester resin fine particles using a crystalline polyester resin is prepared.
The aqueous dispersion of crystalline polyester resin fine particles can be prepared by synthesizing a crystalline polyester resin and dispersing the crystalline polyester resin in an aqueous medium in the form of fine particles. Specifically, an oil phase liquid is prepared by dissolving or dispersing a crystalline polyester resin in an organic solvent, and the oil phase liquid is dispersed in an aqueous medium by phase inversion emulsification or the like to control to a desired particle size. It can be prepared by removing the organic solvent after forming the oil droplets in the finished state.

The amount of the aqueous medium used is preferably 50 to 2,000 parts by mass and more preferably 100 to 1,000 parts by mass with respect to 100 parts by mass of the oil phase liquid.
A surfactant or the like may be added to the aqueous medium for the purpose of improving the dispersion stability of the oil droplets. As surfactant, the thing similar to what was mentioned in said process can be mentioned.

The organic solvent used for the preparation of the oil phase liquid is preferably one having a low boiling point and low solubility in water from the viewpoint of easy removal treatment after formation of oil droplets. Examples thereof include methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene and the like. These can be used alone or in combination of two or more. The usage-amount of an organic solvent is 1-300 mass parts normally with respect to 100 mass parts of crystalline polyester resins.
The emulsification and dispersion of the oil phase liquid can be performed using mechanical energy.

The average particle diameter of the crystalline polyester resin fine particles is preferably in the range of 100 to 400 nm in terms of volume-based median diameter.
In the present invention, the volume-based median diameter of the crystalline polyester resin fine particles is a value measured using “Microtrack UPA-150” (manufactured by Nikkiso Co., Ltd.).

(C) Preparation Step of Aqueous Dispersion of Colorant Fine Particles This step is a step that is performed as necessary when toner particles containing a colorant are desired, and the colorant is finely divided in an aqueous medium. In which an aqueous dispersion of fine colorant particles is prepared.

The aqueous dispersion of colorant fine particles can be obtained by dispersing the colorant in an aqueous medium in which a surfactant is added to a critical micelle concentration (CMC) or higher.
The colorant can be dispersed using mechanical energy, and the disperser to be used is not particularly limited. However, an ultrasonic disperser, a mechanical homogenizer, a manton gourin or a pressure homogenizer is preferably used. Examples thereof include medium dispersers such as a pressure disperser, a sand grinder, a Getzman mill, and a diamond fine mill.

The colorant fine particles preferably have a volume-based median diameter of 10 to 300 nm in a dispersed state, more preferably 100 to 200 nm, and particularly preferably 100 to 150 nm.
In the present invention, the volume-based median diameter of the colorant fine particles is a value measured using an electrophoretic light scattering photometer “ELS-800” (manufactured by Otsuka Electronics Co., Ltd.).

(D) Aggregation / fusion process In this process, the amorphous resin fine particles, the crystalline polyester resin fine particles and the colorant fine particles, and if necessary, fine particles of other toner components are agglomerated and further fused by heating. Put on.
Specifically, in an aqueous dispersion in which the above fine particles are dispersed in an aqueous medium, an aggregating agent having a critical aggregation concentration or higher is added, and the temperature is set to a temperature higher than the glass transition point of the amorphous resin. And fuse.

  The fusing temperature for fusing the amorphous resin fine particles and the crystalline polyester resin fine particles may be equal to or higher than the glass transition point of the amorphous resin. In particular, (the glass transition point of the amorphous resin + 10 ° C) to (glass transition point of amorphous resin + 50 ° C), particularly preferably (glass transition point of amorphous resin + 15 ° C) to (glass transition point of amorphous resin + 40 ° C).

[Flocculant]
The flocculant used in this step is not particularly limited, but those selected from metal salts such as alkali metal salts and alkaline earth metal salts are preferably used. Examples of the metal salt include monovalent metal salts such as sodium, potassium, and lithium; divalent metal salts such as calcium, magnesium, manganese, and copper; and trivalent metal salts such as iron and aluminum. Specific metal salts can include sodium chloride, potassium chloride, lithium chloride, calcium chloride, magnesium chloride, zinc chloride, copper sulfate, magnesium sulfate, manganese sulfate, and the like. It is particularly preferable to use a divalent metal salt. These can be used individually by 1 type or in combination of 2 or more types.

  In the case where the toner particles have a core-shell structure, for example, in this step, the amorphous resin fine particles, the crystalline polyester resin fine particles and the colorant fine particles are aggregated and fused to form core particles, and then the shell is formed. It can be formed by aggregating and fusing the resin fine particles for shell for forming the layer into the core particles.

(E) Ripening step This step is performed as necessary, and in the maturing step, the toner particles obtained by the aggregation / fusion step are aged by heat energy until a desired shape is obtained. An aging process for forming toner particles is performed.
Specifically, the aging treatment is performed by adjusting the heating temperature, stirring speed, heating time, and the like until the shape of the associated particles reaches a desired circularity by heating and stirring the system in which the associated particles are dispersed. Done.

(F) Cooling Step This step is a step of cooling the toner particle dispersion. As a condition for the cooling treatment, it is preferable to cool at a cooling rate of 1 to 20 ° C./min. The specific method of the cooling treatment is not particularly limited, and examples include a method of cooling by introducing a refrigerant from the outside of the reaction vessel, a method of cooling by directly introducing cold water into the reaction system, and the like. it can.

(G) Filtration / Washing Step This step involves solid-liquid separation of the toner particles from the cooled dispersion of toner particles, and a toner cake obtained by solid-liquid separation (aggregating toner particles in a wet state into a cake form) This is a step of removing adhering substances such as a surfactant and an aggregating agent from the aggregate).
The solid-liquid separation is not particularly limited, and a centrifugal separation method, a vacuum filtration method using Nutsche or the like, a filtration method using a filter press, or the like can be used. Further, in washing, it is preferable to wash with water until the electric conductivity of the filtrate reaches 10 μS / cm.

(H) Drying Step This step is a step of drying the washed toner cake, and can be carried out according to a drying step in a generally known method for producing toner particles.
Specifically, examples of the dryer used for drying the toner cake include a spray dryer, a vacuum freeze dryer, and a vacuum dryer, and a stationary shelf dryer, a mobile shelf dryer, a fluidized bed, and the like. It is preferable to use a dryer, a rotary dryer, a stirring dryer or the like.
The moisture of the dried toner particles is preferably 5% by mass or less, more preferably 2% by mass or less. In addition, when the dried toner particles are aggregated by a weak interparticle attractive force, the aggregate may be crushed. Here, as the crushing treatment apparatus, a mechanical crushing apparatus such as a jet mill, a Henschel mixer, a coffee mill, or a food processor can be used.

(I) External additive addition step This step is a step that is performed as necessary when an external additive is added to the toner particles.
The above toner particles can be used as toners as they are, but in order to improve fluidity, chargeability, cleaning properties, etc., external additives such as fluidizing agents and cleaning aids are added to the toner particles. You may use it in the state.
Various external additives may be used in combination.
The total addition amount of these external additives is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the toner particles.
As the external additive mixing device, a mechanical mixing device such as a Henschel mixer or a coffee mill can be used.

  Although the embodiments of the present invention have been specifically described above, the embodiments of the present invention are not limited to the above examples, and various modifications can be made.

  Hereinafter, specific examples of the present invention will be described, but the present invention is not limited thereto.

<Toner Production Example 1: Example 1>
(1-1) Synthesis of Release Agent In a 5 L reaction vessel equipped with a stirrer, a temperature sensor, a cooling tube and a nitrogen introducing device, 170 parts by mass of behenic acid (molecular weight 340.6) and behenyl alcohol (molecular weight 326.6) ) 163 parts by mass, and while stirring this system, the internal temperature was raised to 190 ° C. over 1 hour. After confirming that the system was uniformly stirred, sulfuric acid was added as a catalyst to carboxylic acid. Was added in an amount of 0.05% by mass with respect to the amount of preparation. Thereafter, the internal temperature is raised from 190 ° C. to 240 ° C. over 6 hours while distilling off the generated water, and the dehydration condensation reaction is continued over 6 hours under the condition of a temperature of 240 ° C. for polymerization. Thus, a release agent [W1] composed of behenyl behenate was obtained.
This release agent [W1] had a carbon chain length component content [Cm] of 88% by mass and a melting point of 69 ° C. with the highest content.

(1-2) Preparation of release agent fine particle dispersion 200 parts by weight of the release agent [W1] was heated to 75 ° C. and dissolved. This was further added to a surfactant aqueous solution dissolved in 800 parts by mass of ion-exchanged water so that the sodium alkyldiphenyl ether disulfonate had a concentration of 3% by mass, followed by dispersion treatment using an ultrasonic homogenizer. The solid content concentration was adjusted to 20% by mass. Thus, a release agent fine particle dispersion [Wm1] in which release agent fine particles are dispersed in an aqueous medium was prepared.
The volume-based median diameter of the release agent fine particles in the release agent fine particle dispersion [Wm1] was measured using a Microtrac particle size distribution measuring device “UPA-150” (manufactured by Nikkiso Co., Ltd.).

(2-1) Synthesis of amorphous resin In a reaction vessel equipped with a stirrer, a nitrogen introduction tube, a temperature sensor and a rectifying tower, 85 parts by mass of terephthalic acid, 6 parts by mass of trimellitic acid, 18 parts by mass of fumaric acid and 80 parts by mass of dodecenyl succinic anhydride, 381 parts by mass of bisphenol A propylene oxide adduct and 62 parts by mass of bisphenol A ethylene oxide adduct are added as polyhydric alcohol, and the temperature of the reaction system is increased over 1 hour. After raising the temperature to 190 ° C. and confirming that the inside of the reaction system is uniformly stirred, Ti (OBu) ₄ was added as a catalyst in an amount of 0.006% by mass relative to the total amount of polyvalent carboxylic acid. Further, the temperature of the reaction system was increased from the same temperature to 240 ° C. over 6 hours while distilling off the generated water, and further maintained at 240 ° C. By performing continuous polymerization reaction time dehydration condensation reaction to obtain a noncrystalline polyester resin [A1].
This amorphous polyester resin [A1] had a number average molecular weight (Mn) of 3,100 and a glass transition point of 63 ° C. The molecular weight and glass transition point of the amorphous resin were measured as described above. The same shall apply hereinafter.

(2-2) Preparation of Amorphous Polyester Resin Fine Particle Dispersion Dissolve 200 parts by mass of amorphous polyester resin [A1] in 200 parts by mass of ethyl acetate, and stir the solution to 800 parts by mass of ion-exchanged water. An aqueous solution in which sodium polyoxyethylene lauryl ether sulfate was dissolved to a concentration of 1% by mass was slowly added dropwise. After removing ethyl acetate from the solution under reduced pressure, the pH was adjusted to 8.5 with ammonia. Thereafter, the solid content concentration was adjusted to 20% by mass. Thus, an amorphous polyester resin fine particle dispersion [Am1] in which fine particles of the amorphous polyester resin [A1] were dispersed in an aqueous medium was prepared.
The volume-based median diameter of the fine particles of the amorphous polyester resin [A1] was 230 nm.

(3-1) Synthesis of crystalline polyester resin In a reaction vessel equipped with a stirrer, a nitrogen introduction tube, a temperature sensor, and a rectifying tower, 200 parts by mass of sebacic acid as a polyvalent carboxylic acid and 1,12 as a polyhydric alcohol -140 parts by weight of dodecanediol was charged, the temperature of the reaction system was raised to 190 ° C over 1 hour, and after confirming that the inside of the reaction system was uniformly stirred, Ti (OBu) ₄ was used as a catalyst. An amount of 0.006% by mass with respect to the total amount of the polyvalent carboxylic acid is added, and the temperature of the reaction system is increased from the same temperature to 240 ° C. over 6 hours while distilling off the generated water. Crystallization polyester resin [B1] was obtained by continuing a dehydration condensation reaction for 6 hours in the state maintained at 240 degreeC, and performing a polymerization reaction.
This crystalline polyester resin [B1] had a number average molecular weight (Mn) of 3,500 and a melting point of 70 ° C. The molecular weight and melting point of the crystalline polyester resin were measured as described above. The same shall apply hereinafter.

(3-2) Preparation of Crystalline Polyester Resin Fine Particle Dispersion Dissolve 200 parts by mass of crystalline polyester resin [B1] in 200 parts by mass of ethyl acetate, and stir this solution to 800 parts by mass of ion-exchanged water. An aqueous solution in which sodium ethylene lauryl ether sulfate was dissolved to a concentration of 1% by mass was slowly added dropwise. After removing ethyl acetate from the solution under reduced pressure, the pH was adjusted to 8.5 with ammonia. Thereafter, the solid content concentration was adjusted to 20% by mass. Thus, a crystalline polyester resin fine particle dispersion [Bm1] in which fine particles of the crystalline polyester resin [B1] were dispersed in an aqueous medium was prepared.
The volume-based median diameter of the fine particles of the crystalline polyester resin [B1] was 210 nm.

(4) Preparation of Colorant Fine Particle Dispersion Solution 50 parts by mass of copper phthalocyanine (CI Pigment Blue 15: 3) was dissolved in 200 parts by mass of ion-exchanged water so as to have a concentration of 1% by mass of sodium alkyldiphenyl ether disulfonate. After throwing it into the surfactant aqueous solution, dispersion treatment was performed using an ultrasonic homogenizer. The solid content concentration was adjusted to 20% by mass. Thereby, a colorant fine particle dispersion [1] in which colorant fine particles are dispersed in an aqueous medium was prepared.
When the volume-based median diameter of the colorant fine particles in the colorant fine particle dispersion [1] was measured using a Microtrac particle size distribution measuring device “UPA-150” (manufactured by Nikkiso Co., Ltd.), it was 150 nm.

(5) Formation of toner particles Amorphous polyester resin fine particle dispersion [Am1] 70.8 parts by mass, crystalline polyester resin fine particle dispersion [Bm1] 86.4 parts by mass, release agent fine particle dispersion [Wm1] 15 .5 parts by mass, colorant fine particle dispersion [1] 58.5 parts by mass, 45 parts by mass of ion-exchanged water and 0.5 parts by mass of sodium polyoxyethylene lauryl ether sulfate, equipped with a stirrer, a condenser tube and a thermometer The reaction vessel was put into a reaction vessel, and the pH was adjusted to 10 by adding a 0.1N sodium hydroxide aqueous solution while stirring. Next, an aqueous solution in which 11.6 parts by mass of magnesium chloride hexahydrate was dissolved in 11.6 parts by mass of ion-exchanged water was dropped over 10 minutes, and then the internal temperature was raised to 60 ° C. while stirring. Sampling was performed at this point, and the particle size of the associated particles was measured with “Multisizer 3” (manufactured by Beckman Coulter). The volume-based median diameter was 2.05 μm.
After maintaining at 60 ° C. for 1 hour, in a mixed liquid of 275.4 parts by mass of amorphous polyester resin fine particle dispersion [Am1], 180 parts by mass of ion-exchanged water and 2 parts by mass of sodium polyoxyethylene lauryl ether sulfate, 0. A solution adjusted to pH 5 by adding 1N aqueous sodium hydroxide solution was added dropwise over 1 hour. The temperature was further raised to 75 ° C. to maintain the internal temperature, and the particle size of the associated particles was measured with “Multisizer 3” (manufactured by Beckman Coulter). When the volume-based median diameter reached 5.3 μm. The particle size growth was stopped by adding a sodium chloride aqueous solution in which 15.8 parts by mass of sodium chloride was dissolved in 63.3 parts by mass of ion-exchanged water. Furthermore, the internal temperature was raised to 85 ° C., and when “FPIA-2000” (manufactured by Sysmex) was used, the average circularity reached 0.964, and the temperature was cooled to room temperature at a rate of 10 ° C./min.

(6) Filtration / Washing / Drying Next, the operation of solid-liquid separation, re-dispersing the dehydrated toner cake in ion-exchanged water, and solid-liquid separation was repeated three times, followed by drying at 40 ° C. for 24 hours. Toner particles [1] were obtained.
The toner particles [1] had a volume-based median diameter of 5.2 μm and an average circularity of 0.964. The particle size and average circularity of the toner particles were measured as described above. The same shall apply hereinafter.

(7) Addition of external additive To 100 parts by mass of the obtained toner particles [1], 0.6 parts by mass of hydrophobic silica particles (number average primary particle size = 12 nm, degree of hydrophobicity = 68) and hydrophobic titanium oxide 1.0 parts by mass of particles (number average primary particle size = 20 nm, degree of hydrophobicity = 63) were added, and “Henshell mixer” (manufactured by Mitsui Miike Chemical Co., Ltd.) was used. After mixing for a minute, toner [1] was produced by applying an external additive treatment to remove coarse particles using a sieve having an opening of 45 μm. In toner [1], the shape and particle size of the toner particles did not change with the addition of the external additive.
With respect to the toner [1], the melting peak temperature Tmc (° C.) derived from the crystalline polyester resin, the melting peak temperature Tmw (° C.) derived from the release agent, the glass transition point in the temperature rising process in the differential scanning calorimetry of the toner Tg (° C.) was measured. The results are shown in Table 1.

<Toner Production Example 2: Example 2>
In Toner Production Example 1, (3-1) Crystalline polyester resin [B2] was synthesized by changing polyvalent carboxylic acid and polyhydric alcohol in the synthesis of crystalline polyester resin to dodecanedioic acid and ethylene glycol, Toner [2] was produced in the same manner except that this was used. The crystalline polyester resin [B2] had a number average molecular weight (Mn) of 3,600 and a melting point of 80 ° C.
With respect to this toner [2], the melting peak temperature Tmc (° C.) derived from the crystalline polyester resin in the temperature rising step in the differential scanning calorimetry of the toner, the melting peak temperature Tmw (° C.) derived from the release agent, and the glass transition point Tg (° C.) was measured. The results are shown in Table 1.

<Toner Production Example 3: Example 3>
In toner production example 1, (3-1) changing the polyvalent carboxylic acid and polyhydric alcohol in the synthesis of the crystalline polyester resin to succinic acid and 1,6-hexanediol, the crystalline polyester resin [B3] A toner [3] was produced in the same manner except that it was synthesized and used. The crystalline polyester resin [B3] had a number average molecular weight (Mn) of 3,700 and a melting point of 83 ° C.
For this toner [3], the melting peak temperature Tmc (° C.) derived from the crystalline polyester resin, the melting peak temperature Tmw (° C.) derived from the release agent, the glass transition point in the temperature rising process in the differential scanning calorimetry of the toner Tg (° C.) was measured. The results are shown in Table 1.

<Toner Production Example 4: Example 4>
(1) Synthesis of mold release agent In a 5 L reaction vessel equipped with a stirrer, temperature sensor, cooling pipe and nitrogen introducing device, 170 parts by mass of stearic acid (molecular weight 284.48) and stearyl alcohol (molecular weight 270.49) 163 parts by mass, and while stirring this system, the internal temperature was raised to 190 ° C. over 1 hour. After confirming that the system was uniformly stirred, sulfuric acid was added as a catalyst to the carboxylic acid. The amount added was 0.05% by mass with respect to the charged amount. Thereafter, the internal temperature is raised from 190 ° C. to 240 ° C. over 6 hours while distilling off the generated water, and the dehydration condensation reaction is continued over 6 hours under the condition of a temperature of 240 ° C. for polymerization. Thus, a release agent [W2] made of stearyl stearate was obtained.
This release agent [W2] had a carbon chain length component content [Cm] of 85% by mass and a melting point of 60 ° C. with the highest content.

(2) Preparation of aqueous dispersion of amorphous resin fine particles (first stage polymerization)
A 5 L reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe and a nitrogen introducing device was charged with a solution prepared by dissolving 8 g of sodium dodecyl sulfate in 3 L of ion-exchanged water, and stirred at a stirring speed of 230 rpm under a nitrogen stream. After the internal temperature was raised to 80 ° C., a solution in which 10 g of potassium persulfate was dissolved in 200 g of ion-exchanged water was added, the liquid temperature was again adjusted to 80 ° C., 480 g of styrene, 250 g of n-butyl acrylate and 68 g of methacrylic acid. After dropping a vinyl monomer solution consisting of 1 hour over 1 hour, polymerization was performed by heating and stirring at 80 ° C. for 2 hours to obtain resin fine particles [a1].

(Second stage polymerization)
A 5 L reaction vessel equipped with a stirrer, temperature sensor, cooling tube and nitrogen introducing device was charged with a solution of 7 g of polyoxyethylene (2) sodium dodecyl ether sulfate in 800 ml of ion-exchanged water and heated to 98 ° C. 260 g of the above resin fine particles [a1], 284 g of styrene, 92 g of n-butyl acrylate and 13 g of methacrylic acid, 1.5 g of n-octyl-3-mercaptopropionate, and a release agent [W2] 190 g of a mixed solution dissolved and mixed at 90 ° C. was added, and the mixture was dispersed and dispersed for 1 hour by a mechanical disperser “CLEARMIX” (manufactured by M Technique Co., Ltd.) having a circulation path. A dispersion containing a droplet) was prepared.
Next, an initiator solution in which 6 g of potassium persulfate was dissolved in 200 ml of ion-exchanged water was added to this dispersion, and the system was polymerized by heating and stirring at 84 ° C. for 1 hour to obtain resin fine particles [a2]. Got.

(3rd stage polymerization)
A solution prepared by dissolving 11 g of potassium persulfate in 400 ml of ion-exchanged water is added to the resin fine particles [a2], and styrene 400 g, n-butyl acrylate 128 g, methacrylic acid 28 g, and methacrylic acid are added at a temperature of 82 ° C. A mixed solution of a vinyl monomer solution consisting of 45 g of methyl and 8 g of n-octyl-3-mercaptopropionate was added dropwise over 1 hour. After completion of the dropwise addition, polymerization was carried out by heating and stirring for 2 hours, followed by cooling to 28 ° C., thereby preparing an aqueous dispersion [A2] of amorphous resin fine particles made of a styrene acrylic copolymer resin. .
The amorphous resin fine particles had a volume-based median diameter of 220 nm, a weight average molecular weight (Mw) of 25,000, and a glass transition point of 50 ° C.

(3) Synthesis of crystalline polyester resin In a 5 L reaction vessel equipped with a stirrer, a temperature sensor, a cooling tube and a nitrogen introducing device, 300 parts by mass of sebacic acid as polyvalent carboxylic acid and 1,12- as polyhydric alcohol After adding 170 parts by mass of dodecanediol and stirring the system, the internal temperature was raised to 190 ° C. over 1 hour. After confirming that the system was uniformly stirred, Ti (OBu) was used as a catalyst. ₄ was added in an amount of 0.003% by mass based on the charged amount of polycarboxylic acid. Thereafter, the internal temperature is raised from 190 ° C. to 240 ° C. over 6 hours while distilling off the generated water, and the dehydration condensation reaction is continued over 6 hours under the condition of a temperature of 240 ° C. for polymerization. As a result, a crystalline polyester resin [B4] was obtained.
This crystalline polyester resin [B4] had a number average molecular weight (Mn) of 3,400 and a melting point of 70 ° C.

(4) Preparation of Aqueous Dispersion of Crystalline Polyester Resin Fine Particles Crystalline polyester resin [B4] 30 parts by mass are melted and left in a molten state with respect to an emulsification disperser “Cavitron CD1010” (manufactured by Eurotech Co., Ltd.) It was transferred at a transfer rate of 100 parts by mass per minute. Simultaneously with the transfer of the crystalline polyester resin [B4] in the molten state, 70 mass parts of reagent ammonia water was diluted with ion-exchanged water in an aqueous solvent tank with respect to the emulsification disperser, and the concentration was 0.37 mass%. The diluted ammonia water was transferred at a transfer rate of 0.1 liter per minute while being heated to 100 ° C. with a heat exchanger. Then, by operating this emulsification disperser under the conditions of a rotor rotation speed of 60 Hz and a pressure of 5 kg / cm ² , an aqueous system of crystalline polyester resin fine particles having a volume-based median diameter of 200 nm and a solid content of 30 parts by mass. A dispersion [Bm4] was prepared.

(5) Preparation of aqueous dispersion of composite fine particles In a 5 L reaction vessel equipped with a stirrer, a temperature sensor, a cooling tube and a nitrogen introduction device, 2000 parts by mass of crystalline polyester resin fine particle dispersion [Bm4] and ion-exchanged water 1150 A polymerization initiator solution prepared by dissolving 10.3 parts by mass of potassium persulfate in 210 parts by mass of ion-exchanged water, and 390 parts by mass of styrene (St) under a temperature condition of 80 ° C. A monomer mixture composed of 143 parts by mass of n-butyl acrylate (BA), 27 parts by mass of methacrylic acid (MAA) and 40 parts by mass of methyl methacrylate (MMA) was added dropwise over 2 hours, and then at 80 ° C. for 2 hours. The seed polymerization is carried out by heating and stirring, and after the polymerization is completed, the crystalline polyester resin [B4 An aqueous dispersion [SB4] of composite fine particles [SB4] enclosing the fine particles obtained by
With respect to this aqueous dispersion [SB4], the volume-based median diameter of the composite fine particles [SB4] was 250 nm.

(6) Preparation of aqueous dispersion of colorant fine particles [Bk] 90 parts by mass of sodium dodecyl sulfate was added to 1600 parts by mass of ion-exchanged water. While stirring this solution, 420 parts by mass of carbon black (Regal 330R: manufactured by Cabot) is gradually added, and then dispersed using a stirring device “CLEARMIX” (manufactured by M Technique Co., Ltd.). Thus, an aqueous dispersion [Bk] of fine colorant particles was prepared.
With respect to the obtained aqueous dispersion [Bk], the average particle diameter (volume-based median diameter) of the colorant fine particles was 110 nm.

(7) Preparation of aqueous dispersion of resin fine particles [S1] for shells 8 g of sodium dodecyl sulfate and 3 L of ion-exchanged water were charged into a 5 L reaction vessel equipped with a stirrer, a temperature sensor, a cooling tube, and a nitrogen introducing device. The internal temperature was raised to 80 ° C. while stirring at a stirring speed of 230 rpm under an air flow. After heating, 10 g of potassium persulfate dissolved in 200 g of ion-exchanged water was added, the liquid temperature was again 80 ° C., the following monomer mixture was added dropwise over 1 hour, and then heated at 80 ° C. for 2 hours. Then, polymerization was carried out by stirring to prepare an aqueous dispersion [S1] of resin fine particles for shell.
The resin fine particles for shell had a volume-based median diameter of 100 nm, a weight average molecular weight (Mw) of 28,000, and a glass transition point of 60 ° C.
Styrene 480g
n-Butyl acrylate 250g
Methacrylic acid 68g
n-octyl-3-mercaptopropionate 0.5 g

(8) Preparation of toner particles An aqueous dispersion [A2] in which 600 parts by mass of amorphous resin fine particles are dispersed in a zebra flask equipped with a stirrer, a temperature sensor, a cooling tube and a nitrogen introducing device, and crystalline polyester resin fine particles 90 parts by mass (SB4) of an aqueous dispersion of composite fine particles [SB4] according to [B4], 2500 parts by mass of ion-exchanged water, and 500 parts by mass of an aqueous dispersion [Bk] of colorant fine particles After adjusting the liquid temperature to 25 ° C., an aqueous sodium hydroxide solution having a concentration of 25% by mass was added to adjust the pH to 10.
Next, an aqueous solution in which 54.3 parts by mass of magnesium chloride hexahydrate is dissolved in 54.3 parts by mass of ion-exchanged water is added, and then the temperature of the system is raised to 97 ° C. to thereby form each resin fine particle. And agglomeration reaction of the colorant fine particles was started.
After the start of this agglutination reaction, sampling is performed periodically, and the volume-based median diameter of the colored particles is measured using a particle size distribution measuring device “Coulter Multisizer 3” (manufactured by Beckman Coulter). Aggregation was continued while stirring was continued until 6.3 μm.
Next, an aqueous solution in which 11.5 parts by mass of sodium chloride is dissolved in 46 parts by mass of ion-exchanged water is added, and an aqueous dispersion [S1] in which 10 parts by mass of resin fine particles for shell are dispersed is added. The resin fine particles for the shell were adhered to.
Thereafter, an aqueous solution in which 11.5 parts by mass of sodium chloride was dissolved in 46 parts by mass of ion-exchanged water was added, the temperature of the system was kept at 95 ° C., and stirring was continued for 4 hours, and a flow-type particle image analyzer “FPIA-2100” When the circularity reached 0.946 as measured by (Sysmex), the reaction was stopped by cooling to 30 ° C. under conditions of 6 ° C./min to obtain a dispersion of toner particles. The toner particles after cooling had a particle size of 6.1 μm and a circularity of 0.946.
The toner particle dispersion thus obtained was subjected to solid-liquid separation using a basket-type centrifuge “MARK III Model No. 60 × 40” (manufactured by Matsumoto Kikai Co., Ltd.) to form a wet cake. This wet cake was repeatedly washed and solid-liquid separated with the basket-type centrifuge until the electric conductivity of the filtrate reached 15 μS / cm. Thereafter, a “flash jet dryer” (manufactured by Seishin Enterprise Co., Ltd.) was used, and the temperature was 40 The toner particles [4] were obtained by drying until the water content became 0.5% by mass by blowing an air flow of 20 ° C. and a humidity of 20% RH, and cooling to 24 ° C. The toner particles [4] had a volume-based median diameter of 6.1 μm and an average circularity of 0.946.

(9) Addition of external additive To the obtained toner particles [4], 1% by mass of hydrophobic silica particles and 1.2% by mass of hydrophobic titanium oxide particles were added, and a Henschel mixer was used. Then, the mixture was mixed for 20 minutes under the condition of the peripheral speed of the rotating blades of 24 m / s, and the external additive was added by passing through a 400 mesh screen to obtain toner [4]. In toner [4], the shape and particle size of the toner particles did not change with the addition of the external additive.
For this toner [4], the melting peak temperature Tmc (° C.) derived from the crystalline polyester resin, the melting peak temperature Tmw (° C.) derived from the release agent, the glass transition point in the temperature rising process in the differential scanning calorimetry of the toner Tg (° C.) was measured. The results are shown in Table 1.

<Toner Production Example 5: Example 5>
In Toner Production Example 4, the same procedure was performed except that (2) the release agent [W2] in the second stage polymerization in the preparation of the aqueous dispersion of amorphous resin fine particles was changed to the release agent [W1]. Toner [5] was produced.
For this toner [5], the melting peak temperature Tmc (° C.) derived from the crystalline polyester resin in the temperature rising process in the differential scanning calorimetry of the toner, the melting peak temperature Tmw (° C.) derived from the release agent, and the glass transition point Tg (° C.) was measured. The results are shown in Table 1.

<Toner Production Example 6: Example 6>
In Toner Production Example 4, (2) the release agent [W2] in the second stage polymerization in the preparation of the aqueous dispersion of amorphous resin fine particles was changed to the release agent [W3] shown in the synthesis example below, and (3) Composite fine particles containing fine particles of crystalline polyester resin [B5] by changing polyvalent carboxylic acid and polyhydric alcohol in the synthesis of crystalline polyester resin to succinic acid and 1,6-hexanediol [ An aqueous dispersion [SB5] of SB5] was prepared, and a toner [6] was produced in the same manner except that this was used. The crystalline polyester resin [B5] had a number average molecular weight (Mn) of 3,900 and a melting point of 83 ° C.
For this toner [6], the melting peak temperature Tmc (° C.) derived from the crystalline polyester resin, the melting peak temperature Tmw (° C.) derived from the release agent, the glass transition point in the temperature rising process in the differential scanning calorimetry of the toner Tg (° C.) was measured. The results are shown in Table 1.

〔Release agent〕
A release agent [W3] was obtained by dissolving paraffin wax “HNP-0190” (manufactured by Nippon Seiwa Co., Ltd.) in n-hexane and recrystallization.
The release agent [W3] had a carbon chain length component content [Cm] of 8% by mass and a melting point of 83 ° C. with the highest content.

<Toner Production Example 7: Comparative Example 1>
In Toner Production Example 1, (3-1) Crystalline polyester resin [B6] is obtained by changing polycarboxylic acid and polyhydric alcohol in the synthesis of crystalline polyester resin to dodecanedioic acid and 1,9-nonanediol. A toner [7] was produced in the same manner except that this was used. The crystalline polyester resin [B6] had a number average molecular weight (Mn) of 4,000 and a melting point of 65 ° C.
For this toner [7], the melting peak temperature Tmc (° C.) derived from the crystalline polyester resin, the melting peak temperature Tmw (° C.) derived from the release agent, the glass transition point in the temperature rising process in the differential scanning calorimetry of the toner Tg (° C.) was measured. The results are shown in Table 1.

<Toner Production Example 8: Comparative Example 2>
The same procedure as in toner production example 1 except that the release agent [W4] shown in the following synthesis example was used instead of the release agent [W1], and that the crystalline polyester resin [B6] was used. Toner [8] was produced.
With respect to the toner [8], the melting peak temperature Tmc (° C.) derived from the crystalline polyester resin in the temperature rising process in the differential scanning calorimetry of the toner, the melting peak temperature Tmw (° C.) derived from the release agent, and the glass transition point Tg (° C.) was measured. The results are shown in Table 1.

[Synthesis Example of Release Agent [W4]]
In a 5 L reaction vessel equipped with a stirrer, a temperature sensor, a condenser tube and a nitrogen introducing device, 90 parts by mass of behenic acid (molecular weight 340.6), 80 parts by mass of stearic acid (molecular weight 284.48), and behenyl alcohol (molecular weight 326). .6) 85 parts by mass and 80 parts by mass of stearyl alcohol (molecular weight 270.49) were charged, and while stirring this system, the internal temperature was raised to 190 ° C. over 1 hour, and the system was uniformly stirred. After confirming that it was present, sulfuric acid was added as a catalyst in an amount of 0.05% by mass relative to the charged amount of carboxylic acid. Thereafter, the internal temperature is raised from 190 ° C. to 240 ° C. over 6 hours while distilling off the generated water, and the dehydration condensation reaction is continued over 6 hours under the condition of a temperature of 240 ° C. for polymerization. Thus, a release agent [W4] in which the component having the longest carbon chain length was behenyl behenate was obtained.
In this release agent [W4], the content [Cm] of the carbon chain length component having the largest content was 57 mass%, and the melting point was 66 ° C.

<Toner Production Example 9: Comparative Example 3>
In toner production example 4, (2) the release agent [W2] in the second stage polymerization in the preparation of the aqueous dispersion of amorphous resin fine particles was changed to the release agent [W4], and (3) the crystal Dispersion of composite fine particles [SB7] containing fine particles of crystalline polyester resin [B7] by changing the polycarboxylic acid and polyhydric alcohol in the synthesis of the crystalline polyester resin to adipic acid and 1,6-hexanediol A toner [9] was produced in the same manner except that a liquid [SB7] was prepared and used. The crystalline polyester resin [B7] had a number average molecular weight (Mn) of 3,000 and a melting point of 52 ° C.
For this toner [9], the melting peak temperature Tmc (° C.) derived from the crystalline polyester resin, the melting peak temperature Tmw (° C.) derived from the release agent, the glass transition point in the temperature rising process in the differential scanning calorimetry of the toner Tg (° C.) was measured. The results are shown in Table 1.

<Toner Production Example 10: Comparative Example 4>
In toner production example 4, (2) the release agent [W2] in the second stage polymerization in the preparation of the aqueous dispersion of amorphous resin fine particles was changed to the release agent [W5] shown below, and ( 3) Composite fine particles [SB8] containing fine particles of crystalline polyester resin [B8] by changing polyvalent carboxylic acid and polyhydric alcohol in the synthesis of crystalline polyester resin to adipic acid and 1,10-dodecanediol An aqueous dispersion [SB8] was prepared, and a toner [10] was produced in the same manner except that this was used. The crystalline polyester resin [B8] had a number average molecular weight (Mn) of 3,300 and a melting point of 60 ° C.
For this toner [10], the melting peak temperature Tmc (° C.) derived from the crystalline polyester resin, the melting peak temperature Tmw (° C.) derived from the release agent, the glass transition point in the temperature rising process in the differential scanning calorimetry of the toner Tg (° C.) was measured. The results are shown in Table 1.

〔Release agent〕
Paraffin wax “HNP-0190” (manufactured by Nippon Seiwa Co., Ltd.) was used as a release agent [W5].
In this release agent [W5], the content [Cm] of the carbon chain length component having the largest content was 4% by mass and the melting point was 82 ° C.

[Developer Production Examples 1 to 10]
To each of the toners [1] to [10], a ferrite carrier having a volume-based median diameter of 60 μm coated with a silicone resin is added so that the toner concentration becomes 6% by mass, and mixed by a V-type mixer. As a result, developers [1] to [10] were produced.

(1) Evaluation of low-temperature fixability The low-temperature fixability is measured by measuring the surface temperature (measured at the center of the roller) of the heat-fixing roller in a commercially available copying machine “bizhub PRO C6505” (manufactured by Konica Minolta) as an image evaluation apparatus. Using the one modified so that it can be changed to the range of 200 ° C., each of the developers [1] to [10] is mounted as a developer, and in a room temperature and normal humidity (temperature 20 ° C., humidity 50% RH) environment, A fixing experiment in which a solid image having a toner adhesion amount of 8 mg / cm ² was fixed on high-quality paper of A4 size was repeated up to 200 ° C. while changing the fixing temperature to be increased from 120 ° C. in increments of 5 ° C. Of fixing experiments in which image stain due to low temperature offset was not visually observed, the lowest temperature was evaluated as the lowest fixing temperature. A case where the minimum fixing temperature is 150 ° C. or lower is regarded as acceptable. The results are shown in Table 2.

(2) Evaluation of fixing separability Using an image evaluation apparatus similar to the evaluation of low-temperature fixing property, the surface temperature of the heat fixing roller is 160 ° C., and a solid black belt-like image having a width of 5 cm is perpendicular to the conveying direction. The separation between the image-side heat-fixing roller and the paper when the A4 paper was conveyed by vertical feeding was evaluated according to the following evaluation criteria. The results are shown in Table 2.
-Evaluation criteria-
A: Paper separates from the heat fixing roller without curling B: Paper separates from the heat fixing roller, but the paper tip slightly curls (no problem in practice)
C: The paper is separated from the heat fixing roller, and the gloss of the image surface is uneven, or the paper is wrapped around the heat fixing roller and cannot be separated from the heat fixing roller.

(3) Evaluation of gloss unevenness Using the same image evaluation apparatus as the evaluation of low temperature fixability, the minimum fixing temperature in the evaluation of low temperature fixability + 20 ° C. is set as the fixing temperature, and after 10,000 sheets of durable printing, toner A solid pattern having an adhesion amount of 12.5 ± 0.5 g / m ² was drawn, and the state of uneven gloss was visually evaluated according to the following evaluation criteria. The results are shown in Table 2.
-Evaluation criteria-
A: The difference between the maximum glossiness and the minimum glossiness is almost unknown. B: There is a slight difference between the maximum glossiness and the minimum glossiness, but there is no practical problem. C: The difference between the maximum glossiness and the minimum glossiness is clear. There are practical problems

(4) Evaluation of UFP generation Using an image evaluation apparatus similar to the evaluation of low-temperature fixability, a particle counter (Particle Sizer FMPS 3091, manufactured by Tokyo Direc Co., Ltd.) is attached to the exhaust port of the image evaluation apparatus main body, and the printing area is An image which is 20% of A4 size paper was evaluated by the amount of particles (pieces) when 250 sheets were output at a fixing temperature of 180 ° C. The case where the amount of particles is 10 × 10 ⁵ or less is regarded as acceptable. The results are shown in Table 2.

Claims (4)

In an electrostatic charge image developing toner comprising toner particles containing a binder resin and a release agent,
The binder resin includes an amorphous resin and a crystalline polyester resin,
The temperature of the melting peak derived from the crystalline polyester resin in the temperature rising process in the differential scanning calorimetry of the toner for developing an electrostatic charge image is Tmc (° C.), and the temperature of the melting peak derived from the release agent is Tmw (° C.). When the glass transition point of the toner is Tg (° C.), the following formula (1) is satisfied, and
The melting peak temperature Tmc derived from the crystalline polyester resin is 60 to 95 ° C.,
The release agent is composed of at least an ester wax, the melting peak temperature Tmw derived from the release agent is 60 to 80 ° C., and the release agent is composed of a plurality of components having different carbon chain lengths. In the carbon chain length distribution of the agent, the content of the carbon chain length component having the largest content is 80% by mass or more, and the carbon chain length of the release agent is the total number of carbon atoms of the fatty acid and the aliphatic alcohol. A toner for developing an electrostatic charge image.
Formula (1): Tg <Tmw ≦ Tmc   In an electrostatic charge image developing toner comprising toner particles containing a binder resin and a release agent,
  The binder resin includes an amorphous resin and a crystalline polyester resin,
  The temperature of the melting peak derived from the crystalline polyester resin in the temperature rising process in the differential scanning calorimetry of the toner for developing an electrostatic charge image is Tmc (° C.), and the temperature of the melting peak derived from the release agent is Tmw (° C.). When the glass transition point of the toner is Tg (° C.), the following formula (1) is satisfied, and
  The melting peak temperature Tmc derived from the crystalline polyester resin is 60 to 95 ° C.,
  The release agent is composed of at least a hydrocarbon wax, the melting peak temperature Tmw derived from the release agent is 75 to 95 ° C., and the release agent is composed of a plurality of components having different carbon chain lengths. A toner for developing an electrostatic charge image, wherein the content of the carbon chain length component having the largest content in the carbon chain length distribution of the mold is 5% by mass or more.
  Formula (1): Tg <Tmw ≦ Tmc The electrostatic charge image developing toner according to claim 1 or 2, wherein the melting peak temperature Tmc derived from the crystalline polyester resin is in a range of 60 to 80 ° C. The electrostatic image developing toner according to claim 2 , wherein the content of the carbon chain length component having the largest content is 7% by mass or more.