JP6036451B2 - Toner for developing electrostatic image and method for producing the same - Google Patents

Description

  The present invention relates to an electrostatic image developing toner used for electrophotographic image formation and a method for producing the same.

  Conventionally, a crystalline organic compound, particularly a crystalline polyester resin, has been included in the toner in order to achieve low-temperature fixing of an electrostatic charge image developing toner (hereinafter also simply referred to as “toner”). . For example, Patent Document 1 and Patent Document 2 disclose a block copolymer or graft copolymer in which a crystalline polyester resin and an amorphous vinyl polymer having a functional group capable of binding thereto are chemically bonded. A toner containing as a main component is disclosed.

  However, in such a toner, the free crystalline polyester resin migrates to the surface of the toner particles due to imperfect bonding between the amorphous vinyl polymer and the crystalline polyester resin. As a result, there is a problem that the storage stability of the toner is low.

  In order to solve such a problem of low storage stability, for example, Patent Document 3 discloses that the solubility parameter is controlled by changing the structure of a crystalline polyester resin or an amorphous resin, and the blending of both is further performed. A technique for improving storage stability by controlling the ratio is disclosed.

However, in the method of Patent Document 3, it is inevitable that the migration of crystalline polyester proceeds in a span of several months, and it cannot be said that improvement in storage stability over a long period of time has been achieved.
For this reason, improvement in long-term storage stability has been demanded in order to eliminate the need for strict temperature control during cargo ship transportation and warehouse storage.

  Similarly, in order to solve the problem of low storage stability, for example, a seed polymerization method in which a crystalline polyester resin is used as a seed and is coated with a styrene resin has been proposed (see Patent Document 4).

  However, similarly to the method disclosed in Patent Document 3, the occurrence of migration of the crystalline polyester resin cannot be sufficiently suppressed, and there is a problem that the storage stability cannot be obtained stably over a long period of time. .

  In this way, a crystalline resin is contained so that sufficient low-temperature fixability is ensured, while storage stability is stably obtained over a long period of time, and a temperature-controlled refrigerated container is not used. It can be said that there is still no toner that can be transported by cargo ship.

JP 63-27855 A US Pat. No. 7,547,499 JP 2006-251564 A JP 2011-197659 A

  The present invention has been made based on the above circumstances, and its purpose is to achieve excellent long-term storage stability while ensuring sufficient low-temperature fixability, and tough temperatures during transportation and storage in a warehouse. An object of the present invention is to provide a toner for developing an electrostatic charge image that does not require management and a method for producing the same.

The method for producing an electrostatic image developing toner of the present invention is a method for producing an electrostatic image developing toner comprising toner particles containing an amorphous resin, a crystalline resin and an ester wax,
The peak molecular weight of the crystalline resin is 3,000 to 32,000,
(A) Crystalline organic substance solution preparation step of preparing crystalline organic substance solution by dissolving crystalline resin and ester wax in organic solvent,
(B) An oil droplet forming step of forming an oil droplet comprising the crystalline organic material solution by emulsifying and dispersing the crystalline organic material solution in an aqueous medium at a temperature equal to or higher than the melting point of the ester wax.
(C) a solvent removal step of generating composite fine particles by distilling off the organic solvent from the oil droplets at a temperature not higher than the melting point of the ester wax or the melting point of the crystalline resin,
(D) a reheating step of reheating the composite fine particles at a temperature equal to or higher than the melting point of the crystalline resin to obtain heated composite fine particles;
and,
(E) A toner particle forming step of forming toner particles by aggregating and fusing the heated composite fine particles and fine particles made of an amorphous resin is performed.

  In the method for producing a toner for developing an electrostatic charge image according to the present invention, in the reheating step, a polymerizable monomer containing a dissociative polymerizable monomer is added to an aqueous medium, and the melting point of the crystalline resin or higher. The reheating is also preferably performed by polymerizing the polymerizable monomer at the temperature.

The method for producing an electrostatic image developing toner of the present invention is a method for producing an electrostatic image developing toner comprising toner particles containing an amorphous resin, a crystalline resin and an ester wax,
The peak molecular weight of the crystalline resin is 3,000 to 32,000,
(A) a crystalline organic solution preparing step of preparing a crystalline organic solution by dissolving a crystalline resin and an ester wax in an organic solvent;
(B) an oil droplet forming step of forming an oil droplet comprising the crystalline organic material solution by emulsifying and dispersing the crystalline organic material solution in an aqueous medium at a temperature equal to or higher than the melting point of the ester wax;
(C) a solvent removal step of generating composite fine particles by distilling the organic solvent from the oil droplets at a temperature not higher than the melting point of the ester wax or the melting point of the crystalline resin,
and,
(D) Aggregating the composite fine particles and fine particles made of an amorphous resin at a temperature equal to or higher than the melting point of the crystalline resin, and melting the composite fine particles while reheating at a temperature equal to or higher than the melting point of the crystalline resin. A toner particle forming step of forming toner particles by applying the toner particles is performed.

  In the method for producing a toner for developing an electrostatic image according to the present invention, the crystalline resin is preferably a crystalline polyester resin.

The electrostatic image developing toner of the present invention is an electrostatic image developing toner comprising toner particles containing an amorphous resin, a crystalline resin and an ester wax,
The peak molecular weight of the crystalline resin is 3,000 to 32,000,
The toner particles are characterized in that the crystalline resin has fine particles included in an ester wax layer of ester wax.

  According to the method for producing a toner for developing an electrostatic charge image of the present invention, the step of heating composite fine particles comprising a crystalline resin having a specific peak molecular weight and an ester wax to a temperature not lower than the melting point of the crystalline resin. As a result, it is possible to produce a toner for developing an electrostatic charge image that provides excellent long-term storage stability while ensuring sufficient low-temperature fixability and does not require strict temperature control during transportation and storage in a warehouse.

FIG. 3 is a schematic cross-sectional view illustrating an example of a configuration of an electrostatic charge image developing toner of the present invention.

  Hereinafter, the present invention will be described in detail.

  The method for producing a toner for developing an electrostatic charge image (hereinafter also simply referred to as “toner”) of the present invention is a method for producing a toner comprising toner particles containing an amorphous resin, a crystalline resin and an ester wax. .

<First Embodiment>
The first embodiment of the toner production method of the present invention is:
(A) a crystalline organic solution preparing step of preparing a crystalline organic solution by dissolving a crystalline resin having a peak molecular weight of 3,000 to 32,000 and an ester wax in an organic solvent;
(B) an oil droplet forming step of forming an oil droplet comprising a crystalline organic material solution by emulsifying and dispersing the crystalline organic material solution in an aqueous medium at a temperature equal to or higher than the melting point of the ester wax.
(C) a solvent removal step of producing composite fine particles by distilling the organic solvent from the oil droplets at a temperature not higher than either the melting point of the ester wax or the melting point of the crystalline resin,
(D) a reheating step of reheating the composite fine particles at a temperature equal to or higher than the melting point of the crystalline resin to obtain heated composite fine particles;
(E) a toner particle forming step of forming toner particles by agglomerating and fusing the fine particles of the heat composite fine particles and the amorphous resin; specifically, (F) a dispersion of toner particles The toner particles are separated from the toner particles by solid-liquid separation, and a filtration and washing step for removing the surfactant from the toner particles.
(G) a drying process for drying the washed toner particles;
(H) It is preferable to go through an external additive addition step of adding an external additive to the dried toner particles.
Hereinafter, an ester wax that forms composite fine particles together with a crystalline resin is referred to as a “layer forming ester wax”.

[Configuration of toner particles]
By using the above manufacturing method, as shown in FIG. 1, the inclusion fine particles H in which the crystalline particles Cr by the crystalline resin are included in the ester wax block layer Wx by the ester wax for layer formation are non- A state in which the amorphous resin and the crystalline resin are phase-separated from each other by partitioning the crystalline resin and the amorphous resin by the ester wax block layer Wx. Toner particles T having the following characteristics are obtained.
Here, from the viewpoint of surely obtaining the effect of suppressing the degree of compatibility between the crystalline resin and the amorphous resin when the inclusion fine particles H are subjected to a thermal history as described later, the ester wax block layer is surely obtained. It is preferable that Wx has a form in which the crystalline particles Cr are completely covered, but the above-described effect of suppressing the compatibility can be obtained to some extent even in a form in which a part of the crystalline particles Cr is covered. Therefore, you may have such a form.

  The structure of such toner particles T can be confirmed using a known means such as a transmission electron microscope (TEM). Specifically, first, the toner is embedded in a photo-curing resin and subjected to a dyeing treatment as necessary. This can be confirmed by preparing a thin section and taking a cross-sectional photograph at a magnification of 10,000 times with a transmission electron microscope (TEM) “2000FX” (manufactured by JEOL Ltd.).

In the above manufacturing method, the reason why the inclusion fine particles H in which the crystalline particles Cr are included in the ester wax block layer Wx is formed is considered as follows.
That is, in the composite fine particles, it is considered that the phase due to the crystalline resin and the phase due to the layer forming ester wax each form a fine domain and are phase-separated, and in the reheating step When the composite fine particles are heated to a temperature equal to or higher than the melting point of the crystalline resin, the crystalline resin having a relatively high melt viscosity in the composite fine particles moves to gather in the center while extruding the ester wax for layer formation, and crystallizes. As a result of the formation of the crystalline particles Cr, it is presumed that the layer forming ester wax remains on the outer shell side of the composite fine particles in a state including the crystalline particles Cr, and thereby the ester wax block layer Wx is formed. .

  Therefore, the toner of the present invention as described above can obtain long-term storage stability while maintaining low-temperature fixability because the crystalline resin having a low glass transition point does not migrate to the surface of the toner particles. Can do. In addition, since the degree of compatibility between the crystalline resin and the amorphous resin in the toner manufacturing process is suppressed to a small level, the crystalline resin and the amorphous resin can be used even when the heating conditions are changed in the toner manufacturing process. Since the fluctuation of the glass transition point due to the compatibility with is suppressed, excellent production stability can be obtained.

(A) Crystalline organic substance solution preparation step [crystalline resin]
The crystalline resin contained in the toner particles constituting the toner of the present invention has a peak molecular weight of 3,000 to 32,000, preferably a peak molecular weight of 3,200 to 14,000.
When the peak molecular weight of the crystalline resin is in the above range, the crystalline resin has a higher melt viscosity than the ester-forming wax for layer formation, so that the compatibility between the crystalline resin and the amorphous resin is ensured. An ester wax block layer Wx effective for the effect of suppressing the above can be formed. On the other hand, when the peak molecular weight of the crystalline resin is less than 3,000 or more than 32,000, the compatibility between the crystalline resin and the amorphous resin cannot be sufficiently suppressed, and the resulting toner is heat resistant. The storage property is inferior, and sufficient low-temperature fixability cannot be obtained. This is because the aggregation of the crystalline resin to the central part cannot be sufficiently performed in the reheating step, and the resulting ester wax block layer is effective in suppressing the compatibility between the crystalline resin and the amorphous resin. It is presumed that it is not effective.
In the toner particles constituting the toner of the present invention, the crystalline resin is used in combination with a binder resin made of an amorphous resin, but the toner can be compatible with the amorphous resin. Gradually, a phase-separated region can be formed, and has a function of quickly reducing the melt viscosity of the toner during heat fixing. On the other hand, it is clearly phase-separated from the mold release agent and essentially does not function as a mold release agent.

  The peak molecular weight is obtained from a molecular weight distribution based on a styrene-converted molecular weight measured by gel permeation chromatography (GPC), and the peak molecular weight is a molecular weight corresponding to the elution time of the peak top in the molecular weight distribution. When there are a plurality of peak tops in the molecular weight distribution, the molecular weight corresponds to the elution time of the peak top having the largest peak area ratio.

  Moreover, it is preferable that the weight average molecular weights measured by the gel permeation chromatography (GPC) of crystalline resin are 7,000-30,000.

  Specifically, the measurement of the peak molecular weight and the weight average molecular weight by gel permeation chromatography (GPC) is performed using an apparatus “HLC-8220” (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) as a carrier solvent was allowed to flow at a flow rate of 0.2 ml / min, and the measurement sample was treated at room temperature for 5 minutes using an ultrasonic disperser at a concentration of 1 mg. / Ml, and then treated with a membrane filter having a pore size of 0.2 μm to obtain a sample solution. 10 μL of this sample solution is injected into the apparatus together with the carrier solvent, and a refractive index detector ( Detect and measure using RI detector The molecular weight distribution of the sample is calculated using a calibration curve measured using monodisperse polystyrene standard particles. Ten polystyrenes were used for calibration curve measurement.

It is preferable that melting | fusing point of crystalline resin is 40-100 degreeC, More preferably, it is 56-75 degreeC.
When the melting point of the crystalline resin is within the above range, sufficient low-temperature fixability and excellent storage stability can be obtained.

  Here, the melting point of the crystalline resin is specifically the first temperature that is raised from 0 ° C. to 200 ° C. at a rising / lowering speed of 10 ° C./min using a differential scanning calorimeter “Diamond DSC” (manufactured by PerkinElmer). Measurement conditions for passing through a temperature raising process, a cooling process for cooling from 200 ° C. to 0 ° C. at a cooling rate of 10 ° C./min, and a second temperature raising process for raising the temperature from 0 ° C. to 200 ° C. at a lifting speed of 10 ° C./min. Based on the DSC curve obtained by this measurement, the endothermic peak top temperature derived from the crystalline resin in the first temperature raising process is taken as the melting point. . As a measurement procedure, 3.0 mg of crystalline resin is sealed in an aluminum pan and set in a diamond DSC sample holder. The reference used an empty aluminum pan.

Examples of the crystalline resin include a crystalline polyester resin, a crystalline polyurethane resin, a crystalline polyurea resin, a crystalline polyamide resin, and a crystalline polyether resin. In particular, it is preferable to use a crystalline polyester resin.
In the present invention, the crystalline resin means a resin having a clear endothermic peak in a DSC curve measured using the above-mentioned differential scanning calorimeter “Diamond DSC” (manufactured by PerkinElmer).

(Crystalline polyester resin)
The crystalline polyester resin is preferably a polycondensate of a diol component and a dicarboxylic acid component, and may use a polyol component or a polycarboxylic acid component as necessary. A lactone ring-opening polymer or polyhydroxycarboxylic acid can also be used.

(Diol component)
As a diol component for obtaining a crystalline polyester resin, an aliphatic diol is preferably used because of its high crystallinity and excellent heat-resistant storage stability, and an aliphatic diol having 2 to 12 carbon atoms is particularly preferable. Moreover, it is preferable to use a linear aliphatic diol. A branched aliphatic diol or an alicyclic aliphatic diol can also be used.

  Examples of the linear aliphatic diol 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-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1, Examples thereof include 18-octadecanediol and 1,2-eicosanediol. Among these, it is preferable to use ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol.

As the diol component for obtaining the crystalline polyester resin, other diols can be used as required in addition to the above.
Other diols include carbon such as 1,2-propylene glycol, butanediol, hexanediol, octanediol, decanediol, dodecanediol, tetradecandiol, neopentyl glycol, 2,2-diethyl-1,3-propanediol A branched aliphatic diol having 2 to 12 carbon atoms; an alicyclic diol having 4 to 12 carbon atoms such as 1,4-cyclohexanedimethanol and 1,4-adamantyldimethanol; ethylene oxide (EO) of these alicyclic diols ) Adducts, propylene oxide (PO) adducts, alkylene oxide (AO) adducts such as butylene oxide (BO) adducts (addition moles 1 to 3); polylactone diols such as poly-ε-caprolactone diol; polybutadiene diols Etc.

(Dicarboxylic acid component)
As the dicarboxylic acid component for obtaining a crystalline polyester resin, it is preferable to use an aliphatic dicarboxylic acid, and it is particularly preferable to use a linear aliphatic dicarboxylic acid.
Examples of the aliphatic dicarboxylic acid include alkane dicarboxylic acids having 4 to 12 carbon atoms such as succinic acid, adipic acid, sebacic acid, azelaic acid and dodecanedicarboxylic acid; and 4 to 6 carbon atoms such as maleic acid, fumaric acid and citraconic acid. Alkene dicarboxylic acid etc. are mentioned.

  Among these, it is preferable to use an aliphatic dicarboxylic acid, particularly a linear aliphatic dicarboxylic acid alone. As the aliphatic dicarboxylic acid, adipic acid, sebacic acid, dodecane are used from the viewpoint of crystallinity of the crystalline resin. It is preferable to use a dicarboxylic acid. When using an aromatic dicarboxylic acid together with an aliphatic dicarboxylic acid, it is preferable to use terephthalic acid or isophthalic acid.

(Lactone)
Examples of lactones for obtaining crystalline polyester resins include monolactone rings having 3 to 12 carbon atoms such as β-propiolactone, γ-butyrolactone, δ-valerolactone, and ε-caprolactone (one ester group in the ring). ) And the like. From the viewpoint of crystallinity of the crystalline resin, it is preferable to use ε-caprolactone.

  Specifically, a ring-opening polymerization product of a lactone is a ring-opening polymerization using the above lactone as a catalyst with an organic metal compound such as a metal oxide, an organic tin compound, an organic titanium compound, an organic tin halide compound, or the like. Can be obtained by doing The addition amount of the catalyst is usually 0.1 to 5,000 ppm. Moreover, reaction temperature shall be 100-230 degreeC. The ring-opening polymerization of the lactone is preferably performed in an inert atmosphere.

The ring-opening polymer of lactone may have a hydroxyl group at the terminal, and such ring-opening polymer uses glycols such as ethylene glycol and propylene glycol as a polymerization initiator for ring-opening polymerization. Obtained by.
Moreover, you may have a carboxyl group at the terminal.

(Polyhydroxycarboxylic acid)
The polyhydroxycarboxylic acid constituting the crystalline polyester resin can be obtained by directly dehydrating and condensing hydroxycarboxylic acids such as glycolic acid and lactic acid (D-form, L-form, racemic form). However, a cyclic ester having 4 to 12 carbon atoms corresponding to a bimolecular or trimolecular dehydration condensate of a hydroxycarboxylic acid such as glycolide or lactide (D-form, L-form, racemate) (number of esters in the ring is 2 to 2). It is preferable from the viewpoint of controllability of the molecular weight of the crystalline polyester resin that a ring-opening polymerization method using a catalyst such as a metal oxide or an organometallic compound is used.
From the viewpoint of adjusting the crystallinity of the crystalline polyester resin, it is preferable to use L-lactide and D-lactide.

(Crystalline polyurethane resin)
The crystalline polyurethane resin is preferably synthesized from a diol component and a diisocyanate component, and may be one using a polyol component or a polyisocyanate component as necessary.

  As the diol component and polyol component for obtaining the crystalline polyurethane resin, the same ones as described above can be used.

(Diisocyanate component)
Examples of the diisocyanate component for obtaining the crystalline polyurethane resin include aromatic diisocyanates having 6 to 20 carbon atoms (excluding carbon in the NCO group), aliphatic diisocyanates having 2 to 18 carbon atoms, and fats having 4 to 15 carbon atoms. Examples thereof include cyclic diisocyanates, araliphatic diisocyanates having 8 to 15 carbon atoms, and modified products of these diisocyanates. These may be used alone or in combination of two or more.
As a diisocyanate component for obtaining a crystalline polyurethane resin, a triisocyanate or higher polyisocyanate may be used together with the above diisocyanate.

Aromatic diisocyanates include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), 2,4′- and / or 4,4 ′. -Diphenylmethane diisocyanate (MDI), polyallyl polyisocyanate (PAPI), 1,5-naphthylene diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, m- and p-isocyanatophenylsulfonyl isocyanate It is done.
Aliphatic diisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodemethylene diisocyanate, 1,6,11-undecane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2, Examples include 6-diisocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-dicyanatohexanoate.
Examples of the alicyclic diisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), and bis (2-isocyanatoethyl). Examples include -4-cyclohexene-1,2-dicarboxylate, 2,5- and / or 2,6-norbornane diisocyanate.
Examples of the araliphatic diisocyanate include m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate.
Examples of the modified product of diisocyanate include modified products of urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uresiimine group, isocyanurate group, and oxazolidone group. Specific examples include urethane-modified MDI, urethane-modified TDI, carbodiimide-modified MDI, and trihydrocarbyl phosphate-modified MDI. These can be used alone or in combination of two or more.

  Among these, it is preferable to use an aromatic diisocyanate having 6 to 15 carbon atoms, an aliphatic diisocyanate having 4 to 12 carbon atoms, and an alicyclic diisocyanate having 4 to 15 carbon atoms, particularly preferably TDI, MDI, HDI, water. They are MDI and IPDI.

[Crystalline polyamide resin]
The crystalline polyamide resin is preferably obtained from a reaction between a diamine component and a dicarboxylic acid component, and may be a polyamine component or a polycarboxylic acid component as required.

  As the dicarboxylic acid component and polycarboxylic acid component for obtaining the crystalline polyamide resin, the same ones as described above can be used.

(Diamine component)
As a diamine component and a polyamine component for obtaining a crystalline polyamide resin, an aliphatic diamine or an aliphatic polyamine is preferably used, and an aromatic diamine can also be used.

Examples of the aliphatic diamine and aliphatic polyamine include the following.
(1) Linear aliphatic diamines One having 2 to 6 carbon atoms such as ethylenediamine, propylenediamine, trimethylenecyamine, tetramethylenediamine, hexamethylenediamine.
(2) Aliphatic polyamines having 2 to 6 carbon atoms such as diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine.
(3) Branched aliphatic diamine dialkyl (1 to 3 carbon atoms) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-hexamethylenediamine, methyliminobispropylamine.
(4) Alicyclic diamines having 4 to 15 carbon atoms such as 1,3-diaminocyclohexane, isophoronediamine, mensendiamine, 4,4′-methylenedicyclohexanediamine (hydrogenated melendiamine).
(5) Heterocyclic diamine piperazine, 4-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4-bis (2-amino-2-methylpropyl) piperazine, 3,9-bis (3-aminopropyl) ) Those having 4 to 15 carbon atoms such as -2,4,8,10-tetraoxaspiro [5,5] undecane.
(6) Aromatic ring-containing aliphatic diamines having 8 to 15 carbon atoms such as xylylenediamine and tetrachloro-p-xylylenediamine.

Examples of the aromatic diamine that can be used in combination with the aliphatic diamine and the aliphatic polyamine include those having 6 to 20 carbon atoms. Specifically, the following are preferably used.
(7) unsubstituted aromatic diamine 1,2-, 1,3- and 1,4-phenylenediamine, 2,4′- and 4,4′-diphenylmethanediamine, polyphenylpolymethylenepolyamine, diaminodiphenylsulfone, Thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4,4 ′, 4 ″ -triamine, naphthylenediamine and the like.
(8) Aromatic diamines substituted with an alkyl group having 1 to 4 carbon atoms 2,4-tolylenediamine, 2,6-tolylenediamine, ethyltolylenediamine, 4,4'-diamino-3,3 '-Dimethyldiphenylmethane, 4,4'-bis (o-toluidine), dianisidine, diaminoditolyl sulfone, 1,3-dimethyl-2,4-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene, 2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,4,3,3 ′, 5.5′-tetramethylbenzidine, 3,3 ′, 5,5′-tetramethyl 4,4 '-Dimethyldiphenylmethane, 3,5-diethyl-3'-methyl-2', 4-diaminodiphenylmethane, 3,3'-diethyl-2.2'-aminodiphenylmethane, 4,4'-diamino-3 3′-dimethyldiphenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminobenzophenone, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenyl ether, 3,3 ′ , 5,5'-tetraisopropyl-4,4'-diaminodiphenyl sulfone and mixtures of these isomers.
A part or all of the amino groups of the aromatic diamines of the above (7) to (8) are —NH—R ¹ (wherein R ¹ is substituted with a lower alkyl group such as a methyl group or an ethyl group, 4'-di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene and the like.

Moreover, as a polyamine component for obtaining a crystalline polyamide resin, the following other polyamine components can also be used.
(9) Other polyamines Low molecular weight polyamide polyamines obtained by condensation of dicarboxylic acids such as dimer acids and excess aliphatic polyamines (more than 2 moles per mole of dicarboxylic acid), cyanoethyl polyols such as polyalkylene glycols Polyether polyamines such as hydrides.

(Crystalline polyurea resin)
The crystalline polyurea resin is preferably obtained from a reaction between a diamine component and a diisocyanate component, and may be a polyamine component or a polyisocyanate component as required.

As the diamine component and polyamine component for obtaining the crystalline polyurea resin, the same ones as described above can be used.
In addition, as the diisocyanate component and polyisocyanate component for obtaining the crystalline polyurea resin, the same ones as described above can be used.

[Crystalline polyether resin]
As the crystalline polyether resin, a crystalline polyoxyalkylene polyol or the like can be used.
Examples of the alkylene oxide (AO) used for the production of the crystalline polyoxyalkylene polyol include those having 3 to 9 carbon atoms.
Specifically, examples of the alkylene oxide (AO) having 3 carbon atoms include propylene oxide, 1-chlorooctacene, 1,2-dichlorooctacene, epichlorohydrin, epibromohydrin, and the like.
Examples of the alkylene oxide (AO) having 4 carbon atoms include 1,2-butylene oxide and methyl glycidyl ether.
Examples of the alkylene oxide (AO) having 5 carbon atoms include 1,2-pentylene oxide, 2,3-pentylene oxide, 3-methyl-1,2-butylene oxide, and the like.
Examples of the alkylene oxide (AO) having 6 carbon atoms include cyclohexene oxide, 1,2-hexylene oxide, 2,3-hexylene oxide, 3-methyl-1,2-pentylene oxide, 4-methyl-2,3 -Pentylene oxide, allyl glycidyl ether, etc. are mentioned.
Examples of the alkylene oxide (AO) having 7 carbon atoms include 1,2-hexylene oxide.
Styrene oxide is mentioned as a C8 alkylene oxide (AO).
Examples of the alkylene oxide (AO) having 9 carbon atoms include phenyl glycidyl ether.
Of these alkylene oxides, it is preferable to use propylene oxide, 1,2-butylene oxide, styrene oxide, cyclohexene oxide, and particularly preferably propylene oxide, 1,2-butylene oxide, cyclohexene oxide, and the polymerization rate is high. Most preferred is propylene oxide because it is high. These alkylene oxides (AO) can be used alone or in combination of two or more.

  As a method for synthesizing the crystalline polyoxyalkylene polyol, various conventionally known methods can be used. Specifically, Journal of the American Chemical Society 78, 18, p. A method of ring-opening polymerization of a chiral alkylene oxide (AO) disclosed in 4787-4792 (1956) using a catalyst usually used in the polymerization of alkylene oxide (AO), disclosed in JP-A-11-12353 And a method of using as a catalyst a compound obtained by contacting a sterically bulky lanthanide complex and an organoaluminum, and reacting a bimetal μ-oxoalkoxide and a boroxyl compound disclosed in JP-T-2001-521957 in advance. Methods, Journal of the American Chemical Society 127, 33, p. 11566-11567 (2005), and a method for obtaining a polyoxyalkylene polyol having a high isocity is mentioned.

In the method of ring-opening polymerization of a chiral alkylene oxide (AO), a polyoxyalkylene glycol having a hydroxyl group at the terminal and having an isotacticity of 50% or more can be obtained by using glycol or water as a polymerization initiator. . The end of the polyoxyalkylene glycol having an isotacticity of 50% or more may be modified with a carboxyl group. Usually, when the isotacticity is 50% or more, it becomes crystalline.
The isotacticity is more preferably 70% or more, further preferably 80% or more, and particularly preferably 90% or more from the viewpoint of obtaining high sharp melt properties and blocking resistance.

Isotacticity is described in Macromolecule, 35, 6, p. 2389-2392 (2002).
Specifically, 30 mg of a measurement sample was weighed into a ¹³ C-NMR sample tube having a diameter of 5 mm, and 0.5 ml of a deuterated solvent (deuterated chloroform, deuterated toluene, deuterated dimethylformamide, deuterated). A solvent capable of dissolving the sample such as dimethyl sulfoxide) is added and dissolved, and the signal derived from the methine group of the ¹³ C-NMR tripods, respectively, syndiotactic value: around 75.1 ppm, heterotactic value: 75 .About.3 ppm, isotactic value: around 75.5 ppm can be observed and calculated from the following formula (a).
Formula (a): Isotacticity (%) = [I / (I + S + H)] × 100
[I: integrated value of isotactic value, S: integrated value of syndiotactic value, H: integrated value of heterotactic value]

  The above crystalline resins may have a structure in which two or more of them are bonded as a block copolymer.

  The content of the crystalline resin in the toner particles constituting the toner of the present invention is 10 to 60% by mass with respect to the total resin constituting the toner particles from the viewpoint of obtaining sufficient low-temperature fixability and excellent storage stability. It is preferable that

[Ester wax for layer formation]
Specific examples of the layer-forming ester wax that forms composite fine particles with the crystalline resin include, for example, behenyl behenate, stearyl stearate, pentaerythritol tetrabehenate, pentaerythritol tetrastearate, dipentaerythritol. Tetrastearate, glycerol tribehenate, glycerol tristearate, diglycerol hexabehenate, stearyl sebacate, trimethylolpropane behenate, distearyl succinate, glycerol 1,2 hydrostearate, glycerol monobe Henates, tristearyl citrate and the like can be used. Among these, it is particularly preferable to use behenyl behenate and glycerin monobehenate from the viewpoint of obtaining image storage stability.

  By using an ester wax as the ester wax for layer formation, the ester wax has an extremely low melt viscosity. Therefore, when the ester wax is heated above the melting point of the ester wax for layer formation in the reheating step, the ester for layer formation is used. Since the exudation of the wax to the outer shell can be sufficiently advanced, it is possible to reliably form the ester wax block layer Wx effective in suppressing the compatibility between the crystalline resin and the amorphous resin. .

As the layer forming ester wax, it is preferable to use an ester wax whose melting point is higher by 10 to 40 ° C. than the melting point of the crystalline resin.
By using an ester wax having a melting point higher by 10 to 40 ° C. than the melting point of the crystalline resin, the ester wax block layer Wx effective for suppressing the compatibility between the crystalline resin and the amorphous resin is reliably formed. can do.

The content of the ester wax for layer formation in the toner particles constituting the toner of the present invention is a mass ratio with respect to the crystalline resin, and the ratio of crystalline resin: layer formation ester wax is 9: 1 to 6: 4. Preferably, it is 8: 2 to 7: 3.
When the content of the layer-forming ester wax is in the above range, the ester wax block layer Wx effective for suppressing the compatibility between the crystalline resin and the amorphous resin can be reliably formed. On the other hand, when the content of the ester wax for layer formation is excessive, there is a possibility that it cannot be completely dissolved in the organic solvent, and when the content of the ester wax for layer formation is excessive, it is obtained. There is a possibility that the ester wax block layer may not be effective in suppressing the compatibility between the crystalline resin and the amorphous resin.

〔Organic solvent〕
The organic solvent may be any one that dissolves the crystalline resin and the layer-forming ester wax and has a boiling point higher than the melting point of the layer-forming ester wax or the crystalline resin, such as ethyl acetate, methyl ethyl ketone, and toluene. In particular, it is preferable to use ethyl acetate because it is preferable to control the temperature at which the organic solvent is distilled off in the solvent removal step to 30 to 50 ° C. under a practical reduced pressure.

  The temperature at which the crystalline resin and the layer forming ester wax are dissolved in the organic solvent is preferably higher than the melting point of the crystalline resin and higher than the melting point of the layer forming ester wax.

(B) Oil Drop Forming Step In this step, oil droplets composed of the crystalline organic matter solution are formed by emulsifying and dispersing the crystalline organic matter solution in the aqueous medium at a temperature equal to or higher than the melting point of the layer forming ester wax. The
In this step, it is preferable to gradually add the crystalline organic substance solution to the aqueous medium, but a phase inversion emulsification method in which the aqueous medium is gradually added to the crystalline organic solution may be performed.
Specifically, after heating the aqueous medium to the melting point of the layer forming ester wax or higher, the crystalline organic solution is added to the aqueous medium, or the aqueous medium is heated to the melting point of the layer forming ester wax or higher. It is preferable to add this to the crystalline organic substance solution after heating.

  In the present invention, since the crystalline organic solution for forming oil droplets has a lower melt viscosity than that of only a crystalline resin, high dispersion stability is achieved in oil droplets formed by emulsification and dispersion. Therefore, it is presumed that migration of the crystalline resin to the surface of the toner particles is suppressed, and as a result, excellent storage stability can be obtained.

  In the present invention, the “aqueous medium” refers to a medium comprising 50 to 100% by mass of water and 0 to 50% by mass of a water-soluble organic solvent. Examples of the water-soluble organic solvent include methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, and tetrahydrofuran. It is preferable to use an alcohol-based organic solvent that does not dissolve the resin.

  In addition, amine or ammonia may be dissolved in the aqueous medium as necessary.

[Surfactant]
In the above aqueous medium, a surfactant such as a normal cationic surfactant, an anionic surfactant, an amphoteric surfactant, and a nonionic surfactant may be dissolved as necessary. As the surfactant, it is preferable to use an anionic surfactant because it is excellent in dispersion stability of oil droplets by the crystalline organic substance solution and stability against temperature change is obtained.

  Examples of the anionic surfactant include higher fatty acid salts such as sodium oleate; alkyl aryl sulfonates such as sodium dodecylbenzene sulfonate; alkyl sulfate salts such as sodium lauryl sulfate; polyethoxyethylene lauryl ether sodium sulfate Polyoxyethylene alkyl ether sulfate salts of polyoxyethylene alkylaryl ether sulfate salts such as sodium polyoxyethylene nonylphenyl ether sulfate; sodium monooctyl sulfosuccinate, sodium dioctyl sulfosuccinate, sodium polyoxyethylene lauryl sulfosuccinate, etc. Examples thereof include alkyl sulfosuccinic acid ester salts and derivatives thereof.

  The above surfactants can be used singly or in combination of two or more as desired.

  Specific means for emulsifying and dispersing includes applying mechanical energy, and the dispersing device for applying mechanical energy is not particularly limited, and includes, for example, a rotor capable of high-speed rotation. A stirrer, an ultrasonic dispersion device, a mechanical homogenizer, a manton gourin, a pressure homogenizer, or the like can be used.

(C) Solvent removal step In this step, composite fine particles are produced by distilling the organic solvent from the oil droplets at a temperature not higher than the melting point of the ester wax for layer formation or the melting point of the crystalline resin. .
Since the organic solvent is distilled off at a temperature lower than the melting point of the layer forming ester wax or the crystalline resin, at least one of the layer forming ester wax and the crystalline resin is in a solid state. In addition, the phase separation state of the layer forming ester wax and the crystalline resin is obtained. As a result, the ester wax block layer Wx can be formed in the reheating step. On the other hand, when the organic solvent is distilled off at a temperature equal to or higher than the melting point of the layer-forming ester wax and higher than the melting point of the crystalline resin, the phase between the inclusion fine particles H and the phase due to the crystalline particles Cr Separation is incomplete and the desired ester wax block layer cannot be formed in the reheating process.

  Specifically, the organic solvent is preferably distilled off at a temperature of 30 to 50 ° C. in a state where the degree of vacuum is set to 400 to 50,000 Pa.

[Composite fine particles]
The particle diameter of the composite fine particles is preferably in the range of 30 to 500 nm, for example, by volume-based median diameter.
The particle diameter of the composite fine particles is measured by a dynamic light scattering method using “Microtrac UPA-150” (manufactured by Nikkiso Co., Ltd.).

(D) Reheating process In this process, a heating composite microparticle is obtained by reheating the composite microparticle produced | generated in the solvent removal process at the temperature more than melting | fusing point of crystalline resin.
The reheating temperature needs to be higher than the melting point of the crystalline resin.
When the reheating temperature is equal to or higher than the melting point of the crystalline resin, the crystalline resin can be gathered at the center, and the crystalline resin and the amorphous resin are partitioned by the ester wax block layer Wx. A state in which phases are separated from each other can be formed.
The reheating temperature is preferably not less than the melting point of the layer-forming ester wax, that is, not less than the melting point of the composite fine particles.
When the reheating temperature is equal to or higher than the melting point of the composite fine particles, the layer-forming ester wax can also be in a molten state, and the layer-forming ester wax has a low melt viscosity together with the aggregation at the center of the crystalline resin. Therefore, the ester wax block layer Wx effective for suppressing the compatibility between the crystalline resin and the amorphous resin can be reliably formed.

  The reheating time can be, for example, 1 to 6 hours.

(E) Toner Particle Formation Step In this step, the heated composite fine particles and fine particles comprising amorphous resin (hereinafter also referred to as “amorphous resin fine particles”) obtained in the reheating step are aggregated and fused. As a result, toner particles are formed.

  As a specific method for agglomerating and fusing the heated composite fine particles and the amorphous resin fine particles, a flocculant is added to the aqueous medium so as to have a critical aggregation concentration or more, and then the glass transition point of the amorphous resin fine particles. By heating to a temperature equal to or higher than the melting peak temperature (° C.) of these mixtures, the salting of the heated composite fine particles and the amorphous resin fine particles proceeds, and at the same time, the fusion is advanced in parallel. There is a method of adding a coagulation terminator to stop particle growth when it has grown to a desired particle size, and further continuing heating to control the particle shape as necessary.

[Amorphous resin]
As the amorphous resin according to the toner of the present invention, various known resins can be used. Specifically, for example, an amorphous polyester resin, a styrene acrylic resin, or the like can be used. From the viewpoint of obtaining image storage resistance, it is preferable to use an amorphous polyester resin. As an amorphous resin, it can use individually by 1 type or in combination of 2 or more types.
In the present invention, the amorphous resin refers to a resin having no clear endothermic peak in a DSC curve measured using the above-mentioned differential scanning calorimeter “Diamond DSC” (manufactured by PerkinElmer).

The amorphous resin according to the present invention preferably has a glass transition point of 25 to 60 ° C, more preferably 35 to 45 ° C.
When the glass transition point of the amorphous resin is in the above range, sufficient low-temperature fixability and excellent storage stability can be obtained.

The glass transition point of the amorphous resin is measured using “Diamond DSC” (Perkin Elmer).
As a measurement procedure, 3.0 mg of a 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 endothermic peak, and a tangent line indicating the maximum slope between the rise of the first peak and the peak apex, The intersection point is shown as the glass transition point.

  As a method for producing the amorphous resin fine particles, it is preferable to use a method of performing emulsion polymerization or miniemulsion polymerization using an appropriate polymerizable monomer in an aqueous medium from the viewpoint of reducing energy cost during production.

  Amorphous resin fine particles may be composed of two or more layers of resins having different compositions. In this case, the dispersion of the first resin fine particles prepared by emulsion polymerization treatment (first-stage polymerization) according to a conventional method. A multi-stage polymerization method in which a polymerization initiator and a polymerizable monomer are added to the liquid and this system is polymerized (second-stage polymerization) can be employed.

The amorphous resin fine particles preferably have a volume-based median diameter of 50 to 300 nm.
The particle diameter of the amorphous resin fine particles is measured by a dynamic light scattering method using “Microtrac UPA-150” (manufactured by Nikkiso Co., Ltd.).

[Flocculant]
As the flocculant, alkali metal salts and alkaline earth metal salts can be used.
Examples of the alkali metal constituting the flocculant include lithium, potassium and sodium, and examples of the alkaline earth metal constituting the flocculant include magnesium, calcium, strontium and barium. Of these, potassium, sodium, magnesium, calcium, and barium are preferable.
In addition, examples of the counter ions (anions constituting the salt) of these alkali metals or alkaline earth metals include chloride ions, bromide ions, iodide ions, carbonate ions, sulfate ions, and the like.

The temperature of the dispersion when adding the flocculant to the dispersion in which the amorphous resin fine particles and the heated composite fine particles are dispersed is preferably equal to or lower than the glass transition point of the amorphous resin fine particles.
When the temperature of the dispersion liquid when adding the flocculant exceeds the glass transition point of the amorphous resin fine particles, it is difficult to control the particle size, and large particles are likely to be generated.
Thus, in this step, the dispersion is stirred when the temperature of the dispersion in which the amorphous resin fine particles and the heated composite fine particles are dispersed is equal to or lower than the glass transition point of the amorphous resin fine particles. While adding the flocculant, it is necessary to immediately start heating the dispersion to a temperature equal to or higher than the glass transition point of the amorphous resin fine particles.

  The range of the heating temperature in this toner particle forming step is (the glass transition point of the amorphous resin fine particles + 10 ° C.) to (the glass transition point of the amorphous resin fine particles + 50 ° C.), particularly preferably (amorphous). The glass transition point of resin fine particles + 15 ° C.) to (the glass transition point of amorphous resin fine particles + 40 ° C.).

The toner particles constituting the toner of the present invention may have a core-shell structure composed of core particles containing a crystalline resin and an ester wax, and a shell layer that covers the surface of the core particles with a resin. Since the toner particles have a core-shell structure, high production stability and storage stability can be expected.
Here, the core-shell structure is not limited as long as the shell layer covers the core particles, and the shell layer completely covers the core particles as well as a part of the core particles. There may be. The shell layer may have a multilayer structure of two or more layers made of resins having different compositions.
In the toner having such a configuration, the content ratio of the resin constituting the shell layer (shell resin) is preferably 5% by mass or more and 30% by mass or less with respect to the whole toner.
As the shell resin, a resin having a high glass transition point that is incompatible with a resin other than the crystalline resin constituting the core particle is used.
Here, as a shell resin, it is preferable that the glass transition point is 45 degreeC or more and 60 degrees C or less. Moreover, it is preferable that the weight average molecular weight is 8,000 or more and 50,000 or less.

  When the toner particles have a core-shell structure as described above, first, the amorphous resin fine particles and the heated composite fine particles are aggregated to form core particles, and then the fine particles made of the shell resin are formed on the core particles. It can manufacture by performing the shelling process to aggregate.

  The toner particles constituting the toner of the present invention may contain an internal additive such as a colorant, magnetic powder, a charge control agent, and a release agent, if necessary.

  In this way, when the toner particles contain an internal additive such as a colorant, a release agent, a charge control agent, and magnetic powder, the amorphous resin fine particles are formed as containing these internal additives. By doing so, it can be introduced into the toner particles. It is also possible to prepare a dispersion of the internal additive fine particles, add this in the toner particle forming step, and agglomerate and fuse together with the amorphous fine particles and the heated composite fine particles to be introduced into the toner particles. Moreover, you may combine these methods.

[Colorant]
As the colorant, a known inorganic or organic colorant can be used. Specific colorants are shown below.
Examples of the black colorant include carbon black such as furnace black, channel black, acetylene black, thermal black and lamp black, and magnetic powder such as magnetite and ferrite.
Examples of the colorant for magenta or red include C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 139, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. And CI Pigment Red 222.
Examples of the colorant for orange or yellow include C.I. I. Pigment orange 31, C.I. I. Pigment orange 43, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 138, and the like.
Examples of the colorant for green or cyan include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 16, C.I. I. Pigment blue 60, C.I. I. Pigment blue 62, C.I. I. Pigment blue 66, C.I. I. And CI Pigment Green 7.
These colorants can be used alone or in combination of two or more.

〔Release agent〕
As the release agent, various known waxes can be used, and the same ester wax as the layer-forming ester wax can also be used.
Specific examples of the wax include polyolefin waxes such as polyethylene wax and polypropylene wax; branched hydrocarbon waxes such as microcrystalline wax; long-chain hydrocarbon waxes such as paraffin wax and sazol wax; distearyl ketone and the like Dialkyl ketone waxes: carnauba wax, montan wax, behenyl behenate, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerol tribehenate, 1,18-octadecane Ester waxes such as diol distearate, tristearyl trimellitic acid and distearyl maleate; ethylenediamine behenylamide, trimearic acid tristearate Such as amide-based waxes such as Ruamido the like.

(F) Filtration, washing process, (G) Drying process The filtration, washing process and drying process can be carried out by employing various known methods.

[Toner particle size]
The particle diameter of the toner particles constituting the toner of the present invention is preferably 3 to 10 μm, and more preferably 5 to 8 μm, for example, on a volume basis median diameter.
When the volume-based median diameter is in the above range, the transfer efficiency is increased, the image quality of halftone is improved, and the image quality of fine lines and dots is improved.

The volume-based median diameter of toner particles is measured and calculated using a measuring apparatus in which a computer system for data processing (Beckman Coulter, Inc.) is connected to “Coulter Multisizer 3” (Beckman Coulter, Inc.). .
Specifically, 0.02 g of toner is added to 20 mL of a surfactant solution (for example, a surfactant solution in which a neutral detergent containing a surfactant component is diluted 10-fold with pure water for the purpose of dispersing the toner). Then, ultrasonic dispersion treatment was performed for 1 minute to prepare a toner particle dispersion, and this toner particle dispersion was 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 5% to 10%. 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 a volume-based median diameter.

[Toner circularity]
The toner particles constituting the toner of the present invention preferably have an average circularity of 0.930 to 1.000, more preferably 0.950 to 0.995, from the viewpoint of improving transfer efficiency.

The circularity of the toner is a value measured by “FPIA-2100” (manufactured by Sysmex).
Specifically, after adding a sample (toner) to a commercially available special sheath solution in which a surfactant is dissolved, the sample is sonicated for 1 minute to prepare a dispersion. With respect to the liquid, using “FPIA-2100”, the measurement conditions are set to the HPF (high magnification imaging) mode, and the measurement is performed at an appropriate concentration of 3000 to 10,000 HPF detections. Here, a reproducible measurement value can be obtained by using this range. And based on the measured value obtained by this measurement, the circularity shown by the following formula (T) is calculated.
Formula (T): Circularity = (perimeter of a circle having the same projection area as the particle image) / (perimeter of the particle projection image)
Further, the average circularity is calculated by adding the average value of the circularity of each toner particle that is the measurement target of the above-mentioned circularity, that is, the circularity of each toner particle, and dividing by the total number of toner particles.

(H) External additive addition step This external additive addition step is a step of adding and mixing external additives as necessary to the dried toner particles.
The toner particles prepared through the steps up to the drying step can be used as toners as they are, but from the viewpoint of improving the charging performance, fluidity, or cleaning properties of the toner, a known inorganic surface is used on the surface. It is preferable to add particles such as fine particles and organic fine particles, and a lubricant as external additives.

Specific examples of the external additive include inorganic oxide fine particles such as silica fine particles, alumina fine particles and titanium oxide fine particles, inorganic stearate compound fine particles such as aluminum stearate fine particles and zinc stearate fine particles, or strontium titanate and titanium. Examples include inorganic fine particles such as inorganic titanic acid compound fine particles such as zinc oxide.
These inorganic fine particles are preferably those subjected to surface treatment with a silane coupling agent, a titanium coupling agent, a higher fatty acid, silicone oil, or the like from the viewpoint of heat-resistant storage stability and environmental stability.

The addition amount of the external additive is 0.05 to 5 parts by mass, preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the toner. In addition, various external additives may be used in combination.
Examples of the method for adding the external additive include a dry method in which the external additive is added in powder form to the dried toner particles. Examples of the mixing device include mechanical mixing devices such as a Henschel mixer and a coffee mill. .

(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.
In the case where the toner of the present invention is used as a two-component developer, the carrier is conventionally a ferromagnetic metal such as iron, a ferromagnetic metal and an alloy such as aluminum and lead, and a compound of a ferromagnetic metal such as ferrite and magnetite. Magnetic particles made of known materials can be used, and ferrite particles are particularly preferable. As the carrier, a coated carrier in which the surface of magnetic particles is coated with a coating agent such as a resin, a binder type carrier in which magnetic fine powder is dispersed in a binder resin, and the like can also be used. The coating resin constituting the coat carrier is not particularly limited, and examples thereof include olefin resins, styrene resins, styrene-acrylic resins, silicone resins, ester resins, and fluorine resins. Moreover, it does not specifically limit as resin which comprises a resin dispersion type carrier, A well-known thing can be used, For example, a styrene-acrylic-type resin, a polyester resin, a fluororesin, a phenol resin etc. can be used.

The volume-based median diameter of the carrier is preferably 20 to 100 μm, and more preferably 20 to 60 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.

  According to the method for producing a toner of the present invention as described above, the composite fine particles composed of a crystalline resin having a specific peak molecular weight and an ester wax are heated to a temperature equal to or higher than the melting point of the crystalline resin. Thus, it is possible to produce a toner that has excellent long-term storage stability while ensuring sufficient low-temperature fixability and does not require strict temperature control during transportation and storage in a warehouse.

<Second Embodiment>
The second embodiment of the toner production method of the present invention is the same as the first embodiment except that a polymerizable monomer containing a dissociable polymerizable monomer is polymerized in the reheating step in the first embodiment. This method has the same steps as those in the embodiment.
Specifically, a polymerizable monomer containing a dissociable polymerizable monomer is added to an aqueous medium in which composite fine particles are dispersed, and the aqueous resin is heated by reheating, that is, a crystalline resin. By reheating at a temperature higher than the melting point of the resin, the ester wax block layer Wx is formed in the composite fine particles, and at the same time, the composite monomer is used as a base particle and a polymerizable monomer containing the dissociative polymerizable monomer is seed-polymerized. Thus, a shell layer is formed, thereby obtaining heated composite fine particles.
The polymerizable monomer including the dissociable polymerizable monomer, and the polymerization initiator used as necessary are preliminarily placed in the aqueous medium in any of the crystalline organic solution preparation step, the oil droplet formation step, and the solvent removal step. It may be added.

  According to the toner manufacturing method according to the second embodiment as described above, the same effects as those in the first embodiment can be obtained.

<Third Embodiment>
In the third embodiment of the toner manufacturing method of the present invention, the reheating step in the first embodiment is not performed, and in the toner particle forming step, fine particles composed of composite fine particles and amorphous resin are made of crystalline resin. This is a method having the same steps as in the first embodiment, except that the particles are aggregated at a temperature higher than the melting point and the composite fine particles are fused while being reheated at a temperature higher than the melting point of the crystalline resin.

  According to the toner manufacturing method according to the third embodiment as described above, it is possible to obtain the same effect as that of the first embodiment.

  Although the embodiments of the toner and the manufacturing method thereof according to the present invention have been described above, the present invention is not limited to the above-described embodiments, and various modifications can be added.

  Specific examples of the present invention will be described below, but the present invention is not limited to these examples.

[Synthesis Example 1 of crystalline polyester resin]
156 parts by mass of sebacic acid, 11 parts by mass of adipic acid and 108 parts by mass of 1,4-butanediol, catalyst: titanium dihydroxybis (triethanolaminate) 0.5 parts by mass was added, and the reaction was carried out for 8 hours while distilling off the water produced at 180 ° C. under a nitrogen stream.
Next, while gradually raising the temperature to 225 ° C., the reaction was carried out for 4 hours while distilling off the generated water and 1,4-butanediol under a nitrogen stream. Furthermore, after reacting under reduced pressure of 665-2660 Pa, it took out from the reaction tank and cooled to room temperature, and crystalline polyester resin [PEs1] was obtained. The crystalline polyester resin [PEs1] had a peak molecular weight of 5,200, a weight average molecular weight of 10,000, and a melting point of 57.2 ° C.

[Synthesis Example 2 of Crystalline Polyester Resin]
286 parts by mass of dodecanedioic acid, 190 parts by mass of 1,6-hexanediol, catalyst: 1 part by mass of titanium dihydroxybis (triethanolaminate) are placed in a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe and a stirring device. The reaction was carried out for 8 hours while distilling off the water produced at 180 ° C. under a nitrogen stream.
Next, the mixture was allowed to react for 4 hours while distilling off the generated water under a nitrogen stream while gradually raising the temperature to 220 ° C. Furthermore, after reacting under reduced pressure of 665-2660 Pa, it took out from the reaction tank, and it cooled to room temperature, and obtained crystalline polyester resin [PEs2]. The crystalline polyester resin [PEs2] had a peak molecular weight of 4,700, a weight average molecular weight of 10,000, and a melting point of 67.5 ° C.

[Synthesis Example 3 of Crystalline Polyester Resin]
In a reaction apparatus equipped with a stirrer, a thermometer, and an outflow cooler, 230.3 parts by mass of 1,4-decanedicarboxylic acid, 106.1 parts by mass of diethylene glycol, and 0.50 parts by mass of tetrabutyl titanate were added. Then, the temperature was raised to 220 ° C., the pressure inside the system was gradually reduced, and a polycondensation reaction was carried out at 150 Pa to obtain a crystalline polyester resin [PEs3]. The crystalline polyester resin [PEs3] had a peak molecular weight of 6,100, a weight average molecular weight of 13,100, and a melting point of 81.0 ° C.

[Synthesis Example 4 of Crystalline Polyester Resin]
A 5 L reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe and a nitrogen introducing device was charged with 220 parts by mass of sebacic acid and 157 parts by mass of 1,4-butanediol, and the system was stirred for 1 hour. The internal temperature was raised to 190 ° C. and it was confirmed that the mixture was uniformly stirred, and then Ti (OBu) ₄ was added as a catalyst in an amount of 0.003% by mass with respect to the charged amount of sebacic acid. I put it in. Then, while distilling off the water produced, the internal temperature is raised from 190 ° C. to 240 ° C. over 6 hours, and polymerization is carried out by continuing the dehydration condensation reaction over 6 hours under the condition of 240 ° C. As a result, a crystalline polyester resin [PEs4] was obtained. The crystalline polyester resin [PEs4] had a peak molecular weight of 12,600, a weight average molecular weight of 27,100, and a melting point of 65.8 ° C.

[Synthesis Example 5 of Crystalline Polyester Resin]
In Synthesis Example 4 of crystalline polyester resin, 230.3 parts by mass of 1,4-decanedicarboxylic acid was used instead of 220 parts by mass of sebacic acid, and 68 parts by mass of ethylene glycol instead of 157 parts by mass of 1,4-butanediol. A crystalline polyester resin [PEs5] was obtained in the same manner except that the part was used. The crystalline polyester resin [PEs5] had a peak molecular weight of 32,000, a weight average molecular weight of 69,800, and a melting point of 75.0 ° C.

[Synthesis Example 6 of Crystalline Polyester Resin]
1260 parts by weight of butanediol, 3068 parts by weight of 1,6-hexanediol, 4826 parts by weight of fumaric acid, 18 parts by weight of dibutyltin oxide and 4.5 parts by weight of hydroquinone By putting it in a four-necked flask for 10 liters equipped and reacting at 160 ° C. for 5 hours, raising the temperature to 200 ° C. and reacting for 1 hour, and then reacting under reduced pressure of 8300 Pa for further 1 hour, -Soluble polyester resin [PEs6] was obtained. The crystalline polyester resin [PEs6] had a peak molecular weight of 3,740, a weight average molecular weight of 8,100, and a melting point of 81.6 ° C.

[Synthesis Example 7 of Crystalline Polyester Resin]
1418 parts by mass of 1,4-butanediol, 3452 parts by mass of 1,6-hexanediol, 5324 parts by mass of fumaric acid, 5 parts by mass of hydroquinone and 20 parts by mass of dibutyltin oxide were added to a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple. In a 10-liter four-necked flask equipped with a reaction vessel, reacted at 160 ° C. for 5 hours, heated to 200 ° C. and reacted for 1 hour, and then further reacted for 1 hour under a reduced pressure of 8300 Pa, Crystalline polyester resin [PEs7] was obtained. The crystalline polyester resin [PEs7] had a peak molecular weight of 4,520, a weight average molecular weight of 9,700, and a melting point of 85.5 ° C.

[Synthesis Example 8 of Crystalline Polyester Resin]
In a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, and a stirrer, 2,253 parts by mass of 1,4-butanediol, 3,063 parts by mass of fumaric acid, 5.3 parts by mass of hydroquinone and dibutyltin oxide 2 After adding a mass part and making it react at 150 degreeC for 5 hours, it heated up at 200 degreeC and made it react for 1 hour, and also by making it react at 85,000 Pa for 1 hour, crystalline polyester resin [PEs8] was obtained. The crystalline polyester resin [PEs8] had a peak molecular weight of 3,170, a weight average molecular weight of 6,970, and a melting point of 96.0 ° C.

[Synthesis Example 9 of Crystalline Polyester Resin]
In a reaction vessel equipped with a stirrer and a dehydrator, 2 parts by mass of 1,4-butanediol, 650 parts by mass of ε-caprolactam and 2 parts by mass of dibutyltin oxide were added at 150 ° C. under normal pressure and nitrogen atmosphere. By reacting for a time and cooling to room temperature, a crystalline polyester resin [PEs9], which is a lactone ring-opening polymer, was obtained. The crystalline polyester resin [PEs9] had a peak molecular weight of 4,600, a weight average molecular weight of 10,160, and a melting point of 60.0 ° C.

[Synthesis Example 10 of Crystalline Polyester Resin]
In a reaction vessel equipped with a stirrer and a dehydrator, 2 parts by mass of ethylene glycol, 400 parts by mass of L-lactide, 150 parts by mass of glycolide and 2 parts by mass of dibutyltin oxide were placed at 150 ° C. under normal pressure and nitrogen atmosphere. By reacting for 10 hours and cooling to room temperature, a crystalline polyester resin [PEs10], which is a polyhydroxycarboxylic acid, was obtained. The crystalline polyester resin [PEs10] had a peak molecular weight of 5,100, a weight average molecular weight of 11,220, and a melting point of 60.0 ° C.

[Synthesis Example 1 of crystalline polyurethane resin]
A reaction vessel equipped with a condenser, a stirrer, and a thermometer was charged with 66 parts by mass of 1,4-butanediol, 86 parts by mass of 1,6-hexanediol, and 40 parts by mass of methyl ethyl ketone (MEK). After adding 248 parts by mass of diisocyanate (HDI) and reacting at 80 ° C. for 5 hours, MEK was removed to obtain a crystalline polyurethane resin [PU1]. The crystalline polyurethane resin [PU1] had a peak molecular weight of 4,800, a weight average molecular weight of 10,560, and a melting point of 56.0 ° C.

[Synthesis Example 1 of Crystalline Polyether Resin]
(S)-(−)-Propylene oxide (180 parts by mass) and potassium hydroxide (30 parts by mass) were charged into a 1 L autoclave, stirred at room temperature for 48 hours, and the resulting polymer was heated to 70 ° C. and melted. 100 parts by mass of toluene and 100 parts by mass of water were added, and liquid separation was repeated three times to remove potassium hydroxide, the toluene phase was neutralized with 0.1 mol / L hydrochloric acid, and 100 parts by mass of water was added to each. After performing the liquid separation three times, toluene in the toluene phase was distilled off and cooled to room temperature to obtain a crystalline polyether resin [PE1]. The crystalline polyether resin [PE1] had a peak molecular weight of 4,200, a weight average molecular weight of 9,240, a melting point of 55.0 ° C., and an isotacticity of 99%.

[Synthesis Example 11 of crystalline polyester resin (for comparison)]
Put 1500 parts by weight of sebacic acid, 964 parts by weight of hexamethylene glycol and 2 parts by weight of dibutyltin oxide into a reactor consisting of a round bottom flask equipped with a thermometer, stirrer, nitrogen gas inlet tube and fluidized condenser, The reactor was placed in a mantle heater, and the temperature was raised to 150 ° C. for reaction while the inside of the reactor was kept in a nitrogen gas atmosphere. The reaction was stopped when the amount of water distilled by this esterification reaction reached 250 parts by mass, the reaction system was cooled to room temperature, and a comparative hexamerethylene sebacate having a hydroxyl group at the molecular end was used. Crystalline polyester resin [PEs11] was obtained. The comparative crystalline polyester resin [PEs11] had a peak molecular weight of 2,840, a weight average molecular weight of 6,530, and a melting point of 64.0 ° C.

[Synthesis Example 12 of crystalline polyester resin (for comparison)]
In the same manner as in Synthesis Example 5 of crystalline polyester resin, except that 460.6 parts by mass of octadecanediol and 68 parts by mass of ethylene glycol were used instead of 68 parts by mass of ethylene glycol, a comparative crystalline polyester resin [ PEs12] was obtained. The comparative crystalline polyester resin [PEs12] had a peak molecular weight of 33,400, a weight average molecular weight of 73,480, and a melting point of 75.0 ° C.

<Example 1: Preparation Example 1 of toner>
(A) Preparation of composite fine particles (crystalline organic matter solution preparation step, oil droplet formation step, solvent removal step)
By dissolving 16 g of crystalline polyester resin [PEs1] and 4 g of ester wax for layer formation: behenyl behenate (melting point: 71.2 ° C.) in 450 g of ethyl acetate heated to 75 ° C., a crystalline organic solution [S- 1] was obtained.
Next, after heating 750 g of an aqueous solution containing 8 g of a surfactant “AQUALON KH-05” (Daiichi Kogyo Seiyaku Co., Ltd.) to 75 ° C., the crystalline organic solution [S-1] was dropped and stirred, The mixture was emulsified for 20 minutes using “Digital Sonifier 250D Advanced 20 kHz 200W” (manufactured by Branson). Thereafter, the emulsion is cooled to 40 ° C., and in this state, ethyl acetate is removed using a rotary evaporator, thereby containing composite fine particles [H1-1] composed of crystalline polyester resin [PEs1] and behenate wax. To obtain a composite fine particle dispersion [H1-1]. The volume-based median diameter of the composite fine particles [H1-1] was 40 nm.

(B) Preparation of Amorphous Polyester Resin Dispersion Liquid
Terephthalic acid 30mol%
Fumaric acid 70mol%
Bisphenol A ethylene oxide 2 mol adduct 20 mol%
Bisphenol A propylene oxide 2 mol adduct 80 mol%
Was added to the mixture, and the internal temperature was raised to 190 ° C. over 1 hour. After confirming that the reaction system was uniformly stirred, 1.2 mol% of dibutyltin oxide was added. did. Further, while distilling off the generated water, the temperature was raised to 240 ° C. over 6 hours from the same temperature, and the dehydration condensation reaction was continued at 240 ° C. for another 3 hours. The acid value was 12.0 mgKOH / g and the weight average molecular weight. Amorphous polyester resin having an A of 9,700 was obtained. Subsequently, this was transferred in a molten state to Cavitron CD1010 (manufactured by Eurotech Co., Ltd.) at a rate of 100 g / min. Separately prepared aqueous medium tank is filled with 0.37 wt% diluted ammonia water diluted with ion-exchanged water with reagent-exchanged water, and heated at 120 ° C with a heat exchanger at a rate of 0.1 liter per minute. The melt was transferred to Cavitron CD1010 (manufactured by Eurotech Co., Ltd.) simultaneously with the melt of the amorphous polyester resin. Amorphous polyester resin dispersion [Am1] in which a Cavitron is operated under conditions of a rotor rotation speed of 60 Hz and a pressure of 5 kg / cm ² to disperse amorphous polyester resin fine particles having a volume average particle size of 0.16 μm. Got.

(C) Preparation of Release Agent Fine Particle Dispersion 60 parts by mass of behenyl behenate (melting point: 71.2 ° C.) as a release agent, and 5 mass of ionic surfactant “Neogen RK” (Daiichi Kogyo Seiyaku Co., Ltd.) And a solution obtained by mixing 240 parts by mass of ion-exchanged water are heated to 95 ° C. and sufficiently dispersed using a homogenizer “Ultratax T50” (manufactured by IKA), and then dispersed using a pressure discharge type gorin homogenizer. By processing, a release agent fine particle dispersion [W] having a volume average diameter of 240 nm and a solid mass of 20 parts by mass was prepared.

(D) Preparation of Colorant Fine Particle Dispersion Carbon Black “Regal 330” (manufactured by Cabot Corporation) 10 parts by mass C.I. I. Pigment Blue 15: 3 40 parts by weight Ionic surfactant (sodium n-dodecylbenzenesulfonate) 8 parts by weight 250 parts by weight of ion-exchanged water is mixed and dissolved, and “Ultra Turrax T50” (manufactured by IKA) is used for 10 minutes. After the dispersion treatment, a black colorant fine particle dispersion [K] in which colorant fine particles having a volume-based median diameter of 310 nm are dispersed was prepared by treatment with an ultrasonic disperser for 20 minutes.

(E) Formation of toner particles (toner particle forming step)
Amorphous polyester resin dispersion [Am1] (solid content conversion) 560 parts by mass Composite fine particles [H1-1] 340 parts by mass Release agent fine particle dispersion [W] 65 parts by mass Black colorant fine particle dispersion [K] 80 Part by mass was put into a round stainless steel flask and adjusted to 20 ° C. while stirring with 300 parts by mass of ion-exchanged water. Thereafter, the mixture was sufficiently mixed and dispersed by “Ultra Turrax T50” (manufactured by IKA) to prepare a dispersion. Next, 0.1 part by mass of polyaluminum chloride was added to the dispersion, and the dispersion treatment was continued with “Ultra Turrax T50” (manufactured by IKA). After the dispersion treatment, the flask was put into a heating oil bath, and the flask was heated to 45 ° C. with stirring. After maintaining the flask at 45 ° C. for 60 minutes, 200 parts by mass (in terms of solid content) of amorphous polyester resin dispersion [Am1] was slowly added to the dispersion.

(F) Step of forming heated composite fine particles while forming toner particles Further, the pH of the system is adjusted to 8 with a 0.5 mol / liter sodium hydroxide aqueous solution, and then the composite fine particles are reheated. The stainless steel flask was sealed and heated to 90 ° C. while continuing to stir with a magnetic seal, and the pH in the system was adjusted to 7 with 0.5 mol / liter of nitric acid, and the reaction was continued for 30 minutes. In this way, toner particles [1] were formed.
After completion of the reaction, a multi-tubular heat exchanger was used (refrigerant was cold water at 5 ° C.), and the flow rate of cold water was adjusted to a cooling rate of −25 ° C./min and rapidly cooled to 30 ° C. After rapid cooling, the mixture was filtered and thoroughly washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. Further, the separated particles were redispersed in 3 liters of ion exchange water at 43 ° C., and washed with stirring for 15 minutes at 300 rpm.
To 100 parts by mass of toner particles [1] air-dried at 42 ° C., 0.6 part by mass of hydrophobic silica having an average primary particle diameter of 17 nm and 1.0 part by mass of hydrophobic silica having an average primary particle diameter of 80 nm are added, The outer peripheral speed of the Henschel mixer was set to 35 m / sec, and the external additive was mixed for 20 minutes, and then passed through a 400 mesh stainless steel sieve to obtain toner [1].
The volume-based median diameter of the toner [1] was 6.5 μm.

<Example 2: Toner preparation example 2>
Other than using 340 parts by mass of composite fine particles [H1-2] prepared as described below in place of 340 parts by mass of composite fine particles [H1-1] in the toner particle forming step (d) of toner preparation example 1 Made toner [2] in the same manner. The volume-based median diameter of the toner [2] was 6.2 μm.

[Preparation of composite fine particles [H1-2]]
The composite fine particle dispersion [H1-1] was heated and stirred at 75 ° C. for 1 hour to perform a reheating step. Let the dispersion liquid which passed through this reheating process be a composite fine particle dispersion liquid [H1-2].

<Example 3: Preparation Example 3 of toner>
Other than using 442 parts by mass of composite fine particles [H1-3] prepared as described below in place of 340 parts by mass of composite fine particles [H1-1] in the toner particle formation step (d) of toner preparation example 1 In the same manner, a toner [3] was produced. The volume-based median diameter of the toner [3] was 6.4 μm.

[Preparation of composite fine particles [H1-3]]
Into a 5 L reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe and a nitrogen introducing device, 1450 parts by mass of a composite fine particle dispersion [H1-1] not reheated and 1250 parts by mass of ion-exchanged water were charged. Further, a polymerization initiator solution in which 10.3 parts by mass of potassium persulfate was dissolved in 210 parts by mass of ion-exchanged water was added, and 300.1 parts by mass of styrene and 123.2 n-butyl acrylate were obtained at a temperature of 80 ° C. A polymerizable monomer mixture composed of a radically polymerizable monomer composition consisting of 2 parts by mass and 21.8 parts by mass of methacrylic acid and 8.2 parts by mass of n-octyl mercaptan was added dropwise over 2 hours, and then 2 at 80 ° C. Polymerization is performed by heating and stirring over time and a reheating step is performed, and then the mixture is cooled to 28 ° C., thereby heating composite fine particles [H1-3] To give composite fine particles dispersion [H1-3] containing.
The volume-based median diameter of the composite fine particles [H1-3] was 120 nm, and coarse particles of 500 nm or more were not detected.
The composite fine particles [H1-3] had a peak molecular weight of 9,100 and a weight average molecular weight of 19,500. Further, the glass transition point of the composite fine particles [H1-3], that is, the glass transition point of the amorphous resin constituting the composite fine particles [H1-3] was 39 ° C.

<Example 4: Toner Preparation Example 4>
(A) Preparation of resin fine particles for core part (1) First stage polymerization 4 mass of sodium polyoxyethylene-2-dodecyl ether sulfate in a 5 L reaction vessel equipped with a stirrer, temperature sensor, cooling tube and nitrogen introducing device A surfactant solution in which 30 parts by mass of ion-exchanged water was dissolved was charged, and the internal temperature was raised to 80 ° C. while stirring at a stirring speed of 230 rpm under a nitrogen stream. To this surfactant solution, an initiator solution in which 10 parts by mass of a polymerization initiator (potassium persulfate: KPS) was dissolved in 400 parts by mass of ion-exchanged water was added to a temperature of 75 ° C., and then 532 parts by mass of styrene. A monomer mixture composed of 200 parts by mass of n-butyl acrylate, 68 parts by mass of methacrylic acid and 16.4 parts by mass of n-octyl mercaptan was dropped over 1 hour, and the system was heated at 75 ° C. for 2 hours. Then, polymerization (first stage polymerization) was carried out by stirring to prepare a dispersion of resin fine particles [A1]. The weight average molecular weight of the resin fine particles [A1] was 16,500.
(2) Second stage polymerization (formation of intermediate layer)
In a flask equipped with a stirrer, a monomer mixture comprising 101.1 parts by mass of styrene, 62.2 parts by mass of n-butyl acrylate, 12.3 parts by mass of methacrylic acid, and 1.75 parts by mass of n-octyl mercaptan As a release agent, 93.8 parts by mass of paraffin wax “HNP-57” (manufactured by Nippon Seiki Co., Ltd.) was added, and the mixture was heated to 90 ° C. and dissolved to prepare a monomer solution.
On the other hand, a surfactant solution in which 3 parts by mass of sodium polyoxyethylene-2-dodecyl ether sulfate was dissolved in 1560 parts by mass of ion-exchanged water was heated to 98 ° C., and the resin fine particles [A1 32.8 parts by mass in terms of solid content is added, and then the above monomer solution is mixed and dispersed for 8 hours using a mechanical disperser “CLEAMIX” (manufactured by M Technique Co., Ltd.) having a circulation path. Thus, a dispersion liquid in which emulsified particles having a dispersed particle diameter of 340 nm were dispersed was prepared.
Next, an initiator solution in which 6 parts by mass of potassium persulfate is dissolved in 200 parts by mass of ion-exchanged water is added to this dispersion, and this system is polymerized by heating and stirring at 98 ° C. for 12 hours (second). Step polymerization) was performed to prepare a dispersion of resin fine particles [A2]. The resin fine particles [A2] had a weight average molecular weight of 23,000.
(3) Third stage polymerization (formation of outer layer)
An initiator solution obtained by dissolving 5.45 parts by mass of potassium persulfate in 220 parts by mass of ion-exchanged water is added to the dispersion of the resin fine particles [A2], and styrene 293.8 is used at a temperature of 80 ° C. A monomer mixed solution consisting of parts by mass, n-butyl acrylate 154.1 parts by mass, and n-octyl mercaptan 7.08 parts by mass was added dropwise over 1 hour. After completion of the dropwise addition, polymerization (third stage polymerization) was performed by heating and stirring for 2 hours, and then cooled to 28 ° C. to obtain a dispersion of resin fine particles [1] for the core part. The core part resin fine particles [A3] had a weight average molecular weight of 26,800.
The core resin fine particles [1] had a volume-based median diameter of 125 nm and a glass transition point of 28.1 ° C.

(B) Production of resin fine particles for shell layer In the first stage polymerization in the production step of the resin fine particles for core part, 624 parts by mass of styrene, 120 parts by mass of 2-ethylhexyl acrylate, 56 parts by mass of methacrylic acid, Resin fine particles for shell layer [1] were prepared by carrying out the polymerization reaction and the post-reaction treatment in the same manner except that the monomer mixed solution in which n-octyl mercaptan was changed to 16.4 parts by mass was used. .

(C) Toner particle forming step In a 5 L reaction vessel equipped with a stirrer, a temperature sensor, a cooling tube, and a nitrogen introducing device, resin fine particles for core part [1] 300 (solid content conversion) g, composite fine particles [H1-3 ] 100 g, 1400 g of ion-exchanged water, and 120 g of a black colorant fine particle dispersion [K] were mixed, the liquid temperature was adjusted to 30 ° C., and then the pH was adjusted to 8 by adding a 5N aqueous sodium hydroxide solution. Next, an aqueous solution in which 35 g of magnesium chloride was dissolved in 35 ml of ion-exchanged water was added over 10 minutes at 30 ° C. with stirring. After holding for 3 minutes, the temperature was raised and the system was heated to 75 ° C. over 60 minutes, and the particle growth reaction was continued while maintaining 75 ° C. In this state, the particle size of the associated particles is measured with “Coulter Multisizer 3” (manufactured by Beckman Coulter, Inc.). When the volume-based median diameter becomes 2.0 μm, the resin fine particles for shell layer [1 100 g (in terms of solid content) was added, and the particle growth reaction was continued. When the volume-based median diameter reaches 6.2 μm, an aqueous solution in which 150 g of sodium chloride is dissolved in 600 ml of ion-exchanged water is added to stop particle growth, and further, the mixture is heated and stirred at a liquid temperature of 75 ° C. The fusion between the particles was advanced. Thereafter, the solution was cooled to 30 ° C., hydrochloric acid was added to adjust the pH to 7.0, stirring was stopped, and toner [4] was obtained. The volume-based median diameter of the toner [4] was 6.2 μm.

Example 5: Toner preparation example 5
In the preparation process of the composite fine particles (a) of the toner preparation example 1, the composite fine particle dispersion [H2-1] obtained using the crystalline polyester resin [PEs2] instead of the crystalline polyester resin [PEs1] is used. Toner [5] was obtained in the same manner except that glycerin monobehenate (melting point: 74.0 ° C.) was used as the layer forming ester wax instead of behenyl behenate. The volume-based median diameter of the toner [5] was 6.5 μm.

<Example 6: Preparation example 6 of toner>
In the toner production example 2, the toner [ 6] was obtained. The volume-based median diameter of the toner [6] was 6.5 μm.

<Example 7: Toner preparation example 7>
In Toner Preparation Example 3, composite fine particle dispersion [H4-3] obtained using crystalline polyester resin [PEs4] instead of crystalline polyester resin [PEs1] was used, and behenic acid was used as the layer forming ester wax. Toner [7] was obtained in the same manner except that stearyl stearate (melting point: 69.9 ° C.) was used instead of behenyl. The volume-based median diameter of the toner [7] was 6.4 μm.

<Example 8: Preparation example 8 of toner>
In the toner preparation example (a) composite fine particle preparation step, the composite fine particle dispersion [H5-1] obtained using the crystalline polyester resin [PEs5] instead of the crystalline polyester resin [PEs1] is used. Toner [8] was obtained in the same manner except that glycerol tristearate (melting point: 81.0 ° C.) was used as the layer forming ester wax instead of behenyl behenate. The volume-based median diameter of the toner [8] was 6.2 μm.

<Example 9: Toner preparation example 9>
In Toner Preparation Example 2, composite fine particle dispersion [H6-2] obtained using crystalline polyester resin [PEs6] instead of crystalline polyester resin [PEs1] was used, and behenic acid was used as an ester wax for layer formation. Toner [9] was obtained in the same manner except that glycerol monostearate (melting point: 79.0 ° C.) was used instead of behenyl. The volume-based median diameter of the toner [9] was 6.5 μm.

<Example 10: Preparation example 10 of toner>
In Toner Preparation Example 3, the composite fine particle dispersion [H7-3] obtained using the crystalline polyester resin [PEs7] instead of the crystalline polyester resin [PEs1] was used, and pentaerythritol was used as the layer forming ester wax. Toner [10] was obtained in the same manner except that tetrastearic acid ester (melting point: 80.2 ° C.) was used. The volume-based median diameter of the toner [10] was 6.5 μm.

Example 11 Toner Preparation Example 11
In the preparation process of (a) composite fine particles in toner preparation example 1, the composite fine particle dispersion [H8-1] obtained using the crystalline polyester resin [PEs8] instead of the crystalline polyester resin [PEs1] is used. A toner [11] was obtained in the same manner except that tristearyl citrate (melting point: 73.0 ° C.) was used in place of behenyl behenate as the ester wax for layer formation. The volume-based median diameter of the toner [11] was 6.4 μm.

Example 12: Toner Preparation Example 12
In the toner preparation example 2, the toner [ 12] was obtained. The volume-based median diameter of the toner [12] was 6.5 μm.

Example 13 Toner Preparation Example 13
In the preparation step of (a) composite fine particles of toner preparation example 1, the composite fine particle dispersion [H10-1] obtained using the crystalline polyester resin [PEs10] instead of the crystalline polyester resin [PEs1] was used. Except that, Toner [13] was obtained. The volume-based median diameter of the toner [13] was 6.3 μm.

Example 14 Toner Preparation Example 14
In the toner production example 2, the toner [H21-2] was used in the same manner except that the composite fine particle dispersion [H21-2] obtained using the crystalline polyurethane resin [PU1] instead of the crystalline polyester resin [PEs1] was used. 14]. The volume-based median diameter of the toner [14] was 6.3 μm.

<Example 15: Toner preparation example 15>
In the same manner as in Toner Preparation Example 2, except that the composite fine particle dispersion [H22-2] obtained using the crystalline polyether resin [PE1] instead of the crystalline polyester resin [PEs1] was used. [15] was obtained. The volume-based median diameter of the toner [15] was 6.3 μm.

<Comparative Example 1: Toner Preparation Example 16>
In the toner production example 2, the composite fine particle dispersion [h1-2] obtained by using the crystalline polyester resin [PEs11] for comparison instead of the crystalline polyester resin [PEs1] was used in the same manner. A comparative toner [16] was obtained. The volume-based median diameter of the toner [16] was 6.5 μm.

<Comparative Example 2: Toner Preparation Example 17>
In the toner production example 2, the composite fine particle dispersion [h2-2] obtained using the crystalline polyester resin [PEs12] for comparison instead of the crystalline polyester resin [PEs1] was used in the same manner. A comparative toner [17] was obtained. The volume-based median diameter of the toner [17] was 6.1 μm.

<Comparative Example 3: Toner Preparation Example 18: Mode in which layer forming ester wax is not used>
In the same manner as Example 1 of toner preparation (a), except that only 16 g of crystalline polyester resin [PEs1] was used and 4 g of layer forming ester wax was not added. A fine particle dispersion [P1-1] made of resin [PEs1] was obtained. The volume-based median diameter of the fine particles made of the crystalline polyester resin [PEs1] was 40 nm. In the subsequent steps, a comparative toner [18] was prepared in the same manner as in Preparation Example 1 except that the dispersion [P1-1] was used instead of the composite fine particle dispersion [H1-1]. Obtained. The volume-based median diameter of the toner [18] was 6.5 μm.

<Comparative Example 4: Toner Preparation Example 19: Mode in which paraffin wax is used instead of ester forming wax>
The crystalline polyester resin [PEs1] was prepared in the same manner as in Example 1 of toner preparation except that paraffin wax (melting point: 87.0 ° C.) was used instead of 4 g of layer forming ester wax. ] And a dispersion [P2-1] in which fine particles [P2-1] made of paraffin wax are dispersed. The volume-based median diameter of the fine particles [P2-1] was 40 nm. In the subsequent steps, a comparative toner [19] was prepared in the same manner as in Preparation Example 1 except that the dispersion [P2-1] was used instead of the composite fine particle dispersion [H1-1]. Obtained. The volume-based median diameter of the toner [19] was 6.5 μm.

<Comparative Example 5: Toner Preparation Example 20: Aspect of Patent Document 3>
A dispersion [P1-1] was prepared in the same manner as in Toner Preparation Example 18.
In a 5 L reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe and a nitrogen introducing device, 1450 parts by mass of this dispersion [P1-1], 650 parts by mass of the release agent fine particle dispersion [W], and ion exchange 1250 parts by weight of water, and a polymerization initiator solution in which 1.3 parts by weight of potassium persulfate was dissolved in 210 parts by weight of ion-exchanged water were added, and 274.1 parts by weight of styrene under a temperature condition of 80 ° C. And a polymerizable monomer mixed solution composed of radically polymerizable monomer unit consisting of 139.2 parts by mass of n-butyl acrylate and 21.8 parts by mass of methacrylic acid and 8.2 parts by mass of n-octyl mercaptan over 2 hours. After dropping, seed polymerization is performed by heating and stirring at 80 ° C. for 2 hours. After the polymerization is completed, the polymer is cooled to 28 ° C. A binder resin fine particle having a core / shell structure in which an amorphous resin is coated on a core particle made of a resin resin [PEs1], and an amorphous resin is coated on a core particle made of a release agent fine particle. An aqueous dispersion (hereinafter referred to as “comparative binder resin particle dispersion [P1-2]”) in which the binder resin fine particles having a core / shell structure having the above structure coexist was prepared.
In the toner production example 1 (e) toner particle formation (toner particle forming step), the comparative binder resin particle dispersion [P1-2] was used instead of the composite fine particle dispersion [H1-1]. A comparative toner [20] was obtained in the same manner as in Toner Preparation Example 1 except for the above. The volume-based median diameter of the toner [20] was 6.7 μm.

(Development of developer)
A ferrite carrier having a volume-based median diameter of 60 μm and coated with a silicone resin is mixed with the obtained toners [1] to [20] using a V-type mixer so that the toner concentration becomes 6% by mass. As a result, developers [1] to [20] were obtained.

(Evaluation 1) Low-temperature fixability In a commercially available multifunction machine “bizhub PRO C6500” (manufactured by Konica Minolta Business Technologies) as an image forming apparatus, the surface temperature of the fixing heating member in the fixing device of the hot roll fixing method is 80 to 150 ° C. In the environment of room temperature and normal humidity (temperature 20 ° C., humidity 50% RH) using the developer [1] to [20] modified so that it can be changed within the range of The fixing experiment for fixing a solid image with an image density of 0.8 on a paper weighing 350 g was changed to increase the set fixing temperature (surface temperature of the fixing heating member) from 80 ° C. to 150 ° C. in increments of 5 ° C. Repeatedly.
The obtained solid image is folded by a folding machine so that a load is applied to the solid image, and air with a pressure of 0.35 MPa is blown onto the solid image. The fixing temperature in the fixing experiment of rank 3 was defined as the lower limit fixing temperature. The results are shown in Table 1.

-Evaluation criteria-
Rank 1: There is a large separation in the image (there is also a portion other than the crease).
Rank 2: There is a thick linear peeling according to the crease.
Rank 3: There is thin linear peeling according to the crease.
Rank 4: There is peeling according to the crease at a part of the crease.
Rank 5: There is no peeling at the folds.

(Evaluation 2) Long-term storage stability-Heat cycle test assuming cargo ship transportation-
For each of the toners [1] to [20], 50 g of toner was filled in a polyethylene bottle, and the lid was closed and shaken 50 times with a “Tap Denser KYT-2000” (manufactured by Seishin Enterprise). Next, a polyethylene bottle containing 50 g of toner was placed in a thermostatic bath, and a heat cycle test was performed assuming dry container cargo ship transportation (on-deck top loading).
Specifically, after storing for 24 hours in an environment at a temperature of 30 ° C., the temperature is increased from 30 ° C. to 60 ° C. over 6 hours and then returned to 60 ° C. to 30 ° C. over 6 hours 90 times. went.
After performing this heat cycle test, place the toner on a 48 mesh (350 μm mesh) sieve with care not to crush it, set the sieve on a “powder tester” (manufactured by Hosokawa Micron), and press the bar. After fixing with a knob nut, adjusting the vibration intensity to a feed width of 1 mm and applying vibration for 10 seconds, the amount of residual toner remaining on the sieve was measured, and the toner aggregation rate was calculated and evaluated by the following formula (1). . The results are shown in Table 1.
When the toner aggregation rate is 20% by mass or less, it is determined as an acceptable level, and when it is less than 15% by mass, it is determined that the long-term storage stability is extremely good.
Formula (1): toner aggregation rate (mass%) = {residual toner amount (g) / 50 (g)} × 100

Cr crystalline particles H inclusion fine particles T toner particles Wx ester wax block layer

Claims (5)

A method for producing an electrostatic image developing toner comprising toner particles containing an amorphous resin, a crystalline resin and an ester wax,
The peak molecular weight of the crystalline resin is 3,000 to 32,000,
(A) Crystalline organic substance solution preparation step of preparing crystalline organic substance solution by dissolving crystalline resin and ester wax in organic solvent,
(B) An oil droplet forming step of forming an oil droplet comprising the crystalline organic material solution by emulsifying and dispersing the crystalline organic material solution in an aqueous medium at a temperature equal to or higher than the melting point of the ester wax.
(C) a solvent removal step of generating composite fine particles by distilling off the organic solvent from the oil droplets at a temperature not higher than the melting point of the ester wax or the melting point of the crystalline resin,
(D) a reheating step of reheating the composite fine particles at a temperature equal to or higher than the melting point of the crystalline resin to obtain heated composite fine particles;
and,
(E) A method for producing a toner for developing an electrostatic charge image, comprising performing a toner particle forming step of aggregating and fusing the heated composite fine particles and fine particles comprising an amorphous resin to form toner particles. .   In the reheating step, by adding a polymerizable monomer containing a dissociable polymerizable monomer in an aqueous medium, and polymerizing the polymerizable monomer at a temperature equal to or higher than the melting point of the crystalline resin, 2. The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the reheating is also performed. A method for producing an electrostatic image developing toner comprising toner particles containing an amorphous resin, a crystalline resin and an ester wax,
The peak molecular weight of the crystalline resin is 3,000 to 32,000,
(A) a crystalline organic solution preparing step of preparing a crystalline organic solution by dissolving a crystalline resin and an ester wax in an organic solvent;
(B) an oil droplet forming step of forming an oil droplet comprising the crystalline organic material solution by emulsifying and dispersing the crystalline organic material solution in an aqueous medium at a temperature equal to or higher than the melting point of the ester wax;
(C) a solvent removal step of generating composite fine particles by distilling the organic solvent from the oil droplets at a temperature not higher than the melting point of the ester wax or the melting point of the crystalline resin,
and,
(D) The composite fine particles and the fine particles made of an amorphous resin are aggregated at a temperature equal to or higher than the melting point of the crystalline resin, and the composite fine particles are melted while being reheated at a temperature equal to or higher than the melting point of the crystalline resin. A method for producing a toner for developing an electrostatic charge image, comprising performing a toner particle forming step of forming toner particles by applying the toner particles.   The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 3, wherein the crystalline resin is a crystalline polyester resin. An electrostatic charge image developing toner comprising toner particles containing an amorphous resin, a crystalline resin and an ester wax,
The peak molecular weight of the crystalline resin is 3,000 to 32,000,
A toner for developing an electrostatic charge image, wherein the toner particles include fine particles in which a crystalline resin is included in an ester wax layer of an ester wax.

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