JP2012063534A - Toner manufacturing method, toner, and developer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner manufacturing method for stably manufacturing toner having small particle diameter and sharp particle size distribution, as well as excellent low-temperature fixability, heat-resistance storage stability, and high-temperature offset resistance.SOLUTION: A toner manufacturing method includes: a toner manufacturing process of dissolving a crystalline polyester resin by heating in an organic solvent; recrystallizing the crystalline polyester resin by cooling the resulting solution to obtain a crystalline polyester resin dispersion liquid; and dissolving a non-crystalline polyester resin into the dispersion liquid to be crashed into fine particles to produce a crystalline polyester resin dispersion liquid having the crystalline polyester resin with volume average particle diameter of 0.1 to 1.0 μm.

Description

  The present invention relates to a method for producing a toner used in an electrophotographic apparatus, an electrostatic recording apparatus, etc., a toner obtained by this production method, and a developer using the toner.

In recent years, toners are required to have a small particle size for improving the quality of output images and to improve low-temperature fixability for energy saving.
The toner obtained by the conventional kneading and pulverization method has difficulty in reducing the particle size, its shape is indefinite, and its particle size distribution is broad. In addition, there is a problem that a high fixing temperature is required and energy saving is difficult. Furthermore, in the kneading and pulverizing method, during the pulverization, cracking occurs at the interface of the release agent (wax), so that a lot of the release agent (wax) is present on the toner surface. For this reason, a releasing effect at the time of fixing is produced, but toner tends to adhere to the carrier, the photoconductor, and the blade, and the performance is not satisfactory in view of the entire image forming process.

  On the other hand, in order to overcome the problems associated with the kneading and pulverizing method, a toner manufacturing method using a polymerization method has been proposed. The toner produced by the polymerization method can be easily reduced in particle size, the particle size distribution is sharper than the particle size distribution of the toner obtained by the pulverization method, and wax can be included.

  It is desired to improve the low-temperature fixability for energy saving by such a polymerization method. Furthermore, it is desired that the heat-resistant storage stability and hot offset resistance of the toner are not inhibited as the low-temperature fixability is improved.

  Patent Document 1 discloses a technique in which a crystalline polyester is introduced into a toner using a dispersion of crystalline polyester by a polymerization method. Since the crystalline polyester resin in the toner has crystallinity, it exhibits a heat-melting characteristic that shows a rapid viscosity decrease near the fixing start temperature. In other words, the heat-resistant storage stability due to crystallinity is good until just before the melting start temperature, and at the melting start temperature, a sharp viscosity drop (sharp melt property) is caused and fixing is performed. Toner can be designed. Also, good results can be shown for the release width (difference between the fixing lower limit temperature and the hot offset occurrence temperature).

  As a method for producing a crystalline polyester dispersion, Patent Document 2 discloses a method for producing a dispersion using a phase separation solvent. However, in this production method, only a coarse dispersion having a dispersed particle diameter of several tens to several hundreds of μm can be produced, and a dispersion having a volume average particle diameter of 1.0 μm or less that can be used for toner cannot be obtained. .

  On the other hand, in Patent Document 1, as a method for producing a dispersion of crystalline polyester, a crystalline polyester alone is mixed in a solvent, and a coarse dispersion is prepared by heating and cooling. And a dispersion liquid having a small particle diameter of 0.2 μm to 1 μm suitable for use in toner.

However, it has been found that it is difficult to stably produce a dispersion having a small particle size that can be used for a toner even in the method for producing a dispersion of crystalline polyester disclosed in Patent Document 1. This is because when the crystalline polyester resin is dispersed in a solvent, the solution viscosity increases as the dispersed particle size decreases. A high-viscosity solution is harder to handle than a low-viscosity solution, and it is difficult to control the particle size by pulverization with a mechanical pulverizer. When a dispersion liquid with insufficient particle size control is used, there arises a problem that it is difficult to obtain a toner having a sharp particle size distribution.

  The present invention has been made in view of the above problems, and its object is to stably produce a toner having good low-temperature fixability, heat-resistant storage stability, hot-offset resistance, and a sharp particle size distribution. A toner production method, a toner obtained by the production method, and a developer using the toner are provided.

In order to achieve the above object, the invention of claim 1 is to disperse, in an aqueous medium, an oil phase comprising at least a crystalline polyester resin and an amorphous polyester resin as a binder resin component in an organic solvent. In the toner production method of obtaining toner by removing the organic solvent from the obtained dispersion, the crystalline polyester resin is heated and dissolved in the organic solvent during the toner production process, and the resulting solution is cooled. Recrystallizing the crystalline polyester resin to obtain a dispersion of the crystalline polyester resin, and dissolving the amorphous polyester resin in the dispersion, and finely pulverizing it with a mechanical pulverizer; And a step of producing a crystalline polyester dispersion of 0.1 to 1.0 μm.
In the toner production method of claim 1, the endothermic shoulder temperature calculated from the second temperature increase of the differential scanning calorimetry (DSC) of the crystalline polyester in the toner production method of claim 1 is (T2-cs1). In the step of preparing a crystalline polyester dispersion by micronizing with the mechanical pulverizer, the slurry temperature is less than the above (T2-cs1).
According to a third aspect of the present invention, in the toner manufacturing method of the first aspect, the DSC endothermic peak temperature of the crystalline polyester resin is 50 to 130 ° C.
According to a fourth aspect of the present invention, in the toner production method according to any one of the first to third aspects, the oil phase contains a binder resin precursor as a binder resin component.
The invention according to claim 5 is the toner manufacturing method according to any one of claims 1 to 4, comprising at least a colorant, a release agent, the crystalline polyester resin dispersion, and a modified polyester resin in an organic solvent. The oil phase obtained by dissolving and dispersing the binder resin precursor and other binder resin components is dissolved in the oil phase and then the oil phase is dispersed in the oil phase. An emulsified dispersion is obtained by dispersing in an aqueous medium containing an agent, and the binder resin precursor is subjected to a crosslinking reaction and / or an extension reaction in the emulsified dispersion to remove the organic solvent. It is.
The invention according to claim 6 is the toner production method according to any one of claims 1 to 5, wherein the molecular weight distribution by GPC of the soluble portion of ortho-dichlorobenzene in the crystalline polyester resin is a weight average molecular weight (Mw). 1000 to 30000, number average molecular weight (Mn) is 500 to 6000, and Mw / Mn is 2 to 10.
The invention according to claim 7 is the toner manufacturing method according to any one of claims 1 to 6, wherein the binder resin component is a polyester resin.
The invention according to claim 8 is the toner manufacturing method according to any one of claims 1 to 7, wherein the acid value of the non-crystalline polyester resin is 1 mgKOH / g or more and 50 mgKOH / g or less. is there.
The invention of claim 9 is characterized in that, in the toner manufacturing method of any one of claims 1 to 8, the volume average particle size of the toner is 3 μm or more and 7 μm or less.
The invention of claim 10 is characterized in that, in the toner manufacturing method of any one of claims 1 to 9, the ratio of the volume average particle diameter to the number average particle diameter of the toner is 1.2 or less. is there.
According to an eleventh aspect of the present invention, in the toner manufacturing method according to any one of the first to tenth aspects, the number of components having a toner particle size of 2 μm or less is 10% by number or less.
The invention of claim 12 is characterized in that, in the toner manufacturing method of any one of claims 1 to 11, the acid value of the toner is 0.5 mgKOH / g or more and 40 mgKOH / g or less.
A thirteenth aspect of the invention is characterized in that, in the toner manufacturing method according to any one of the first to twelfth aspects, the glass transition point of the toner is 40 ° C. or higher and 70 ° C. or lower.
A fourteenth aspect of the invention is a toner used in an image forming apparatus, which is obtained by the toner manufacturing method according to any one of the first to thirteenth aspects.
A fifteenth aspect of the invention is a developer for use in the image forming apparatus, and is characterized by comprising the toner obtained by the toner manufacturing method according to any one of the first to thirteenth aspects.
According to a sixteenth aspect of the present invention, there is provided a developer for use in the image forming apparatus, comprising the toner obtained by the toner manufacturing method according to any one of the first to thirteenth aspects and a carrier. is there.

In the present invention, in order to prepare a dispersion of a crystalline polyester resin, a step of heating and dissolving / cooling the crystalline polyester resin to recrystallize, and dissolving and pulverizing the amorphous polyester resin in this dispersion And a step of preparing a crystalline polyester dispersion having a volume average particle size of 0.1 to 1.0 μm.
The crystalline polyester resin is dissolved by raising the temperature in an organic solvent and recrystallized by cooling. At that time, the crystalline polyester resin is heated and dissolved / cooled alone. If an amorphous polyester resin is mixed in this step, the crystalline polyester and the amorphous polyester are compatible with each other at the time of heating and dissolving, and the sharp melt property of the crystalline polyester may not be utilized in the toner. For this reason, the step of heating / dissolving / cooling is carried out with crystalline polyester alone. Further, the dispersed particle diameter of the crystalline polyester resin precipitated in the cooling process can be controlled by the concentration of the solution and the cooling rate.
Further, the amorphous polyester resin is dissolved in the dispersion after cooling, and is made into fine particles with a mechanical pulverizer to produce a crystalline polyester dispersion. This is because when the crystalline polyester resin alone is dispersed in an organic solvent, the solution viscosity increases as the dispersed particle size becomes smaller, and can be controlled to 0.1 to 1.0 μm suitable for use in toner. It becomes difficult. In order to reduce the solution viscosity, it is conceivable to reduce the concentration of the solution, but it is actually difficult. For this reason, particle size control is facilitated by mechanically pulverizing amorphous polyester by dissolving it in a dispersion after cooling and controlling the solution viscosity.
In such a process, a dispersion of a crystalline polyester resin having a particle diameter controlled stably to 0.1 to 1.0 μm suitable for use in a toner is obtained, and this dispersion is used for polymerization. Crystalline polyester is introduced into the toner. The obtained toner has a sharp particle size distribution as compared with a toner produced using a conventional dispersion. Further, as described above, it has both good heat-resistant storage stability and low-temperature fixability, and good results can be shown for the release width (difference between the minimum fixing temperature and the hot offset occurrence temperature).

  According to the present invention, a toner production method for stably producing a toner having good low-temperature fixability, heat-resistant storage stability, hot offset resistance, and a sharp particle size distribution, a toner obtained by the production method, and In addition, there is an excellent effect that a developer having the toner can be provided.

The graph which shows the DSC measurement example of crystalline polyester.

A mode for carrying out the present invention will be described.
The toner production method of the present invention is obtained by dispersing an oil phase comprising at least a crystalline polyester resin and an amorphous polyester resin as binder resin components in an organic solvent in an aqueous medium. A method for producing a toner in which toner is obtained by removing an organic solvent from the solution, wherein the crystalline polyester resin is heated and dissolved in the organic solvent during the toner production process, and the solution is cooled to obtain the crystalline polyester resin. Recrystallizing into a dispersion of a crystalline polyester resin, dissolving the amorphous polyester resin in the dispersion, finely pulverizing with a mechanical pulverizer, and having a volume average particle size of 0.1 to 1.0 μm; And a step of producing a crystalline polyester dispersion.

This production method enables fine dispersion of the crystalline polyester resin. By setting the volume average particle size of the crystalline polyester resin in the crystalline polyester dispersion to 0.1 to 1.0 μm, the toner particle size distribution is consequently obtained. The toner can be sharpened, and the low-temperature fixability and heat-resistant storage stability of the toner can be achieved.
The crystalline polyester resin is preferably dispersed by the dispersion step before being added to the organic solvent that forms the oil phase, and the crystalline polyester dispersion obtained in the dispersion step may be added to the oil phase as it is. Preferred and preferred.

(Effect of crystalline polyester resin)
Since the crystalline polyester resin in the toner of the present invention has crystallinity, it exhibits a heat-melting characteristic that shows a sudden decrease in viscosity near the fixing start temperature. In other words, the heat-resistant storage stability due to crystallinity is good until just before the melting start temperature, and at the melting start temperature, a sharp viscosity drop (sharp melt property) is caused and fixing is performed. Toner can be designed. It was also found that good results were obtained with respect to the release width (difference between the fixing lower limit temperature and the hot offset occurrence temperature).

(Organic solvent)
As the organic solvent used in the crystalline polyester dispersion process, the crystalline polyester resin is completely dissolved at a high temperature to form a uniform solution. On the other hand, when cooled to a low temperature, the crystalline polyester resin phase-separates and becomes an opaque non-uniformity. Those that form a solution are used. Specifically, it is only necessary that the non-solvent characteristic is exhibited at a temperature lower than (Tm-40) ° C. and the good solvent characteristic is exhibited at a temperature higher than that based on the melting temperature (Tm) of the crystalline polyester resin. As specific examples, toluene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more.

(Heat dissolution / cooling of crystalline polyester resin)
The crystalline polyester resin is dissolved by raising the temperature in an organic solvent and recrystallized by cooling. At that time, the crystalline polyester resin is heated and dissolved and cooled alone. If an amorphous polyester resin is mixed in this step, the crystalline polyester and the amorphous polyester are compatible with each other when heated and dissolved, and the sharp melt property of the crystalline polyester cannot be utilized in the toner. Therefore, it is necessary to carry out the crystalline polyester alone in the organic solvent in the heating dissolution / cooling step. Further, the dispersed particle diameter of the crystalline polyester resin precipitated in the cooling process is determined by the concentration of the solution and the cooling rate.

(Dissolution and grinding of non-crystalline polyester resin)
Further, after cooling, the non-crystalline polyester resin is dissolved in the dispersion liquid, and finely divided by a mechanical pulverizer to prepare a crystalline polyester dispersion liquid. When the crystalline polyester resin alone is dispersed in the organic solvent, the solution viscosity becomes higher as the dispersed particle size becomes smaller, and it becomes difficult to control to the ideal 0.1 to 1.0 μm. Although there is a measure to reduce the concentration of the solution in order to reduce the solution viscosity, it is not realistic. Therefore, mechanical pulverization is performed by dissolving the amorphous polyester in the dispersion after cooling and controlling the solution viscosity.

The slurry temperature in mechanical pulverization is (T2-cs1) when the endothermic shoulder temperature (T2-cs1) calculated from the second temperature increase in the differential scanning calorimetry (hereinafter referred to as DSC) of the crystalline polyester is used. Must be less than. If the slurry temperature is (T2-cs1) or higher, the crystalline polyester is partially dissolved and compatible with the amorphous polyester. As a result, the toner Tg is lowered and the heat resistant storage stability is deteriorated.
If the dispersed particle diameter exceeds 1.0 μm, it becomes difficult to granulate the toner, and the particle size distribution tends to be broad. Therefore, the dispersed particle diameter needs to be 1.0 μm.

  The solution concentration is preferably 1 to 20% by weight of a crystalline polyester resin in an organic solvent at high temperature dissolution / cooling, and the ratio of crystalline polyester resin / amorphous polyester resin at mechanical grinding is 10 / It is desirable to mix the amorphous polyester so as to be 90 to 90/10.

(Mechanical grinding device)
Examples of the mechanical pulverization apparatus used in the step of micronizing the crystalline polyester resin precipitated in the cooling process include commercially available pulverization apparatuses such as a bead mill apparatus, a ball mill apparatus, a wet pulverization apparatus (Altima manufactured by Sugino Machine). An example of such a device is an Iser device).

(Crystalline polyester resin)
As an example, the crystalline polyester resin contains 80 mol% or more, preferably 85 to 100 mol% of a diol compound having 2 to 6 carbon atoms, particularly 1,4-butanediol, 1,6-hexanediol and derivatives thereof as an alcohol component. A compound represented by the following general formula (1) synthesized by using fumaric acid or a carboxylic acid having a double bond (C═C bond) as an acidic component, and derivatives thereof: Examples thereof include, but are not limited to, crystalline polyester resins.
General formula (1)
_{[-O-CO- (CR 1 =} CR 2) l-CO-O- (CH 2) n-] m
(Here, n and m are the number of repeating units. L is an integer of ₁ to _3. R ₁ and R ₂ are hydrogen atoms or hydrocarbon groups, which may be the same or different.)

In addition, as a method for controlling the crystallinity and softening point of the crystalline polyester resin, a trivalent or higher polyhydric alcohol such as glycerin as an alcohol component and a trivalent or higher polyvalent such as trimellitic anhydride as an acid component can be used during polyester synthesis. Examples thereof include a method of designing and using a non-linear polyester that has been subjected to condensation polymerization by adding a polyvalent carboxylic acid.
The molecular structure of the crystalline polyester resin of the present invention can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc. in addition to NMR measurement by solution or solid. In this case, a material having absorption at 965 ± 10 cm ⁻¹ or 990 ± 10 cm ⁻¹ based on δCH (out-of-plane variable angular vibration) of olefin can be given as an example.

As for the molecular weight, from the viewpoint that the above-mentioned molecular weight distribution is sharp and the low molecular weight is excellent in low-temperature fixability, as a result of intensive studies, the molecular weight distribution by GPC of the soluble part of o-dichlorobenzene is indicated by the log ( M), the peak position of the molecular weight distribution chart in which the vertical axis is expressed in weight% is in the range of 3.5 to 4.0, the half width of the peak is 1.5 or less, and the weight average molecular weight (Mw) is 1000. It is preferable that -30000, number average molecular weight (Mn) is 500-6000, and Mw / Mn is 2-10.
The melting temperature and F1 _{/ 2} temperature are desirably low as long as the heat resistant storage stability is not deteriorated, and the DSC endothermic peak temperature is preferably 50 to 130 ° C. When the DSC endothermic peak temperature is less than 50 ° C., the heat resistant storage stability is deteriorated, and blocking tends to occur at the temperature inside the developing device. It becomes impossible. By setting the F1 _{/ 2} temperature to 120 ° C. to 135 ° C., it is possible to achieve both separation at fixing and low temperature fixing. If the F1 _{/ 2} temperature is 120 ° C. or lower, the thermal characteristics of the toner during fixing deteriorate, and the separability deteriorates. When the F _1/2 temperature is 135 ° C. or higher, the softening start temperature of the toner becomes high and low temperature fixability cannot be obtained.

  The acid value of the crystalline polyester resin is 5 mgKOH / g or more, more preferably 10 mgKOH / g or more in order to achieve the desired low-temperature fixability from the viewpoint of the affinity between paper and resin. On the other hand, in order to improve the hot offset property, it is preferably 45 mgKOH / g or less. Further, the hydroxyl value of the crystalline polymer is preferably 0 to 50 mgKOH / g, more preferably 5 to 50 mgKOH / g in order to achieve a predetermined low-temperature fixability and to achieve good charging characteristics. .

The binder resin component preferably contains a binder resin precursor.
In addition, the toner production method of the present invention includes, in an organic solvent, at least a colorant, a release agent, a crystalline polyester dispersion, a binder resin precursor composed of a modified polyester resin, and other binder resin components. After dissolving the binder resin precursor and the compound that extends or crosslinks in the oil phase obtained by dissolving the oil, the oil phase is dispersed in an aqueous medium in which a fine particle dispersant is present to obtain an emulsified dispersion. A production method in which the binder resin precursor is subjected to a crosslinking reaction and / or elongation reaction in the emulsified dispersion to remove the organic solvent is preferable.

(Binder resin precursor)
As the binder resin precursor, a binder resin precursor made of a modified polyester resin is preferable, and examples thereof include a polyester prepolymer modified with isocyanate or epoxy. This undergoes an extension reaction with a compound having an active hydrogen group (such as amines), and has an effect of improving the release width (difference between the minimum fixing temperature and the hot offset generation temperature). As a method for synthesizing the polyester prepolymer, the polyester prepolymer can be easily synthesized by reacting a base polyester resin with a conventionally known isocyanate agent or epoxidizing agent. Isocyanating agents include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic diisocyanates (Tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; block the polyisocyanates with phenol derivatives, oximes, caprolactam, etc. And combinations of two or more of these. Moreover, epichlorohydrin etc. can be mentioned as the representative example as an epoxidizing agent.

The ratio of the isocyanate agent is usually 5/1 to 1/1, preferably 4/1 to 1 as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the base polyester. 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. When the molar ratio of [NCO] is less than 1, the urea content of this polyester prepolymer becomes low, and the hot offset resistance deteriorates.
The content of the isocyanate agent in the polyester prepolymer is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, and more preferably 2 to 20% by weight. If it is less than 0.5% by weight, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40% by weight, the low-temperature fixability deteriorates.

The number of isocyanate groups contained per molecule in the polyester prepolymer is usually 1 or more, preferably 1.5 to 3 on average, and more preferably 1.8 to 2.5 on average. If it is less than 1 per molecule, the molecular weight of the urea-modified polyester resin after the elongation reaction is lowered, and the hot offset resistance is deteriorated.
The binder resin precursor preferably has a weight average molecular weight of 1 × 10 ⁴ or more and 3 × 10 ⁵ or less.

(Compound that stretches or crosslinks with binder resin precursor)
Examples of the compound that extends or crosslinks with the binder resin precursor include compounds having an active hydrogen group, and typical examples thereof include amines. Examples of amines include diamine compounds, trivalent or higher polyamine compounds, amino alcohol compounds, amino mercaptan compounds, amino acid compounds, and compounds in which these amino groups are blocked. Examples of diamine compounds include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, isophoronediamine). Etc.); and aliphatic diamines (ethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.) and the like. Examples of the trivalent or higher polyamine compound include diethylenetriamine and triethylenetetramine. Examples of amino alcohol compounds include ethanolamine and hydroxyethylaniline. Examples of the amino mercaptan compound include aminoethyl mercaptan and aminopropyl mercaptan.

  Examples of amino acid compounds include aminopropionic acid and aminocaproic acid. Examples of the compounds in which these amino groups are blocked include ketimine compounds and oxazoline compounds obtained from the amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines, preferred are a diamine compound and a mixture of a diamine compound and a small amount of a polyamine compound.

(Coloring agent)
As the colorant of the present invention, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher , Yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan fast yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Phi Se Red, Para Chlorortonito Aniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine B, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R , Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone red Polyazo Red, Chrome Vermillion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), indigo, ultramarine blue, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Lid Russian nin green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

  The colorant used in the present invention can also be used as a master batch combined with a resin. As the binder resin to be kneaded together with the production of the masterbatch or the masterbatch, in addition to the modified and unmodified polyester resins mentioned above, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and polymers of substituted products thereof; Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α- Chloromethyl methacrylate copolymer, Tylene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-malein Styrene copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, poly Acrylic resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. The

  This master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force to obtain a master batch. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. Also, a so-called flushing method called watering paste containing water of a colorant is mixed and kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove moisture and organic solvent components. Since it can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

(Release agent)
The release agent is preferably a wax having a melting point of 50 to 120 ° C.
Since such a wax can effectively act as a release agent between the fixing roller and the toner interface, high temperature offset resistance can be improved without applying a release agent such as oil to the fixing roller. be able to.
In addition, melting | fusing point of wax is calculated | required by measuring the maximum endothermic peak using TG-DSC system TAS-100 (made by Rigaku Corporation) which is a differential scanning calorimeter.

As the mold release agent, the following materials can be used.
As waxes and waxes, plant waxes such as carnauba wax, cotton wax, wood wax, rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cercin; paraffin, microcrystalline, petrolatum, etc. And petroleum wax.
In addition, examples of mold release agents other than these natural waxes include synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax; and synthetic waxes such as esters, ketones, and ethers.
Furthermore, fatty acid amides such as 1,2-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbons; low molecular weight crystalline polymer, poly (n-stearyl methacrylate), poly (methacrylic acid n) -A crystalline polymer having a long-chain alkyl group in the side chain, such as a homopolymer or copolymer of polyacrylate such as lauryl (for example, n-stearyl acrylate-ethyl methacrylate copolymer) is also used as a release agent. Can do.

(Charge control agent)
The toner of the present invention may contain a charge control agent as necessary. All known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified). Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives.

  Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit), copper phthalocyanine, perylene, quinacridone Azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.

  The amount of the charge control agent used is determined by the toner production method including the type of binder resin, the presence or absence of additives used as necessary, and the dispersion method, but is not uniquely limited. Preferably, it is used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline. These charge control agents can be dissolved and dispersed after being melt-kneaded with a masterbatch and resin, and of course, they can be added directly when dissolved and dispersed in an organic solvent, or fixed on the toner surface after preparation of toner particles. May be.

(Unmodified polyester resin)
In the present invention, an amorphous unmodified polyester resin can be used as the binder resin component. It is preferable that at least a part of the modified polyester resin obtained by crosslinking and / or elongation reaction of the binder resin precursor made of the modified polyester resin is compatible with the unmodified polyester resin. Thereby, low temperature fixability and hot offset resistance can be improved. For this reason, it is preferable that the polyol and polycarboxylic acid of the modified polyester resin and the unmodified polyester resin have similar compositions. Further, as the unmodified polyester resin, the non-modified polyester resin used in the crystalline polyester dispersion can also be used as long as it is unmodified.

  The acid value of the unmodified polyester resin is usually 1 to 50 mgKOH / g, preferably 5 to 30 mgKOH / g. Thereby, since the acid value is 1 mgKOH / g or more, the toner is likely to be negatively charged, and further, the affinity between the paper and the toner is improved at the time of fixing to the paper, and the low-temperature fixability can be improved. . However, when the acid value exceeds 50 mgKOH / g, the charging stability, particularly the charging stability against environmental fluctuations may be lowered. In the present invention, the unmodified polyester resin preferably has an acid value of 1 to 50 mgKOH / g.

The hydroxyl value of the unmodified polyester resin is preferably 5 mgKOH / g or more.
The hydroxyl value is measured using a method based on JIS K0070-1966.
Specifically, first, 0.5 g of a sample is precisely weighed into a 100 ml volumetric flask, and 5 ml of an acetylating reagent is added thereto. Next, after heating in a 100 ± 5 ° C. warm bath for 1-2 hours, the flask is removed from the warm bath and allowed to cool. Furthermore, acetic anhydride is decomposed by adding water and shaking. Next, in order to completely decompose acetic anhydride, the flask is again heated in a warm bath for 10 minutes or more and allowed to cool, and then the wall of the flask is thoroughly washed with an organic solvent.
Furthermore, the hydroxyl value was measured at 23 ° C. using an automatic potentiometric titrator DL-53 Titrator (manufactured by METTLER TOLEDO) and electrode DG113-SC (manufactured by METTLER TOLEDO), and analysis software LabX Light Version 1.00 Analyze using .000. For calibration of the apparatus, a mixed solvent of 120 ml of toluene and 30 ml of ethanol is used.

At this time, the measurement conditions are as follows.
Stir
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH ₃ ONa
Concentration [mol / L] 0.1
Sensor DG115
Unit of measurement mV
Predispensing to volume
Volume [mL] 1.0
Wait time [s] 0
Titrant addition Dynamic
dE (set) [mV] 8.0
dV (min) [mL] 0.03
dV (max) [mL] 0.5
Measurement mode Equilibrium controlled
dE [mV] 0.5
dt [s] 1.0
t (min) [s] 2.0
t (max) [s] 20.0
Recognition
Threshold 100.0
Steppes jump only No
Range No
Tendency None
Termination
at maximum volume [mL] 10.0
at potential No
at slope No
after number EQPs Yes
n = 1
comb. termination conditions No
Evaluation
Procedure Standard
Potential1 No
Potentialial No
Stop for revaluation No

  The urea-modified polyester resin can be used in combination with a polyester resin modified with a chemical bond other than a urea bond, for example, a polyester resin modified with a urethane bond, in addition to an unmodified polyester resin.

When the toner composition contains a modified polyester resin such as a urea-modified polyester resin, the modified polyester resin can be produced by a one-shot method or the like.
As an example, a method for producing a urea-modified polyester resin will be described.
First, a polyol and a polycarboxylic acid are heated to 150 to 280 ° C. in the presence of a catalyst such as tetrabutoxy titanate or dibutyltin oxide, and if necessary, water generated while removing pressure is removed to have a hydroxyl group. A polyester resin is obtained. Next, a polyester resin having a hydroxyl group is reacted with polyisocyanate at 40 to 140 ° C. to obtain a polyester prepolymer having an isocyanate group. Furthermore, the polyester prepolymer having an isocyanate group is reacted with amines at 0 to 140 ° C. to obtain a urea-modified polyester resin.
The number average molecular weight of the urea-modified polyester resin is usually 1000 to 10000, preferably 1500 to 6000.

In addition, when making the polyester resin which has a hydroxyl group and polyisocyanate react, and when making the polyester prepolymer which has an isocyanate group, and amines react, a solvent can also be used as needed.
Solvents include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.); ethers (tetrahydrofuran) And the like which are inert with respect to the isocyanate group.
In addition, when using unmodified polyester resin together, you may mix to the solution after reaction of the urea modified polyester resin what was manufactured similarly to the polyester resin which has a hydroxyl group.

In the present invention, as the binder resin component contained in the oil phase, a crystalline polyester resin, an amorphous polyester resin, a binder resin precursor, and an unmodified polyester resin may be used in combination. Other binder resin components may be contained. The binder resin component preferably contains a polyester resin, and more preferably contains 50% by weight or more of the polyester resin. If the content of the polyester resin is less than 50% by weight, the low-temperature fixability may be lowered. It is particularly preferable that all of the binder resin components are polyester resins.
Examples of binder resin components other than polyester resins include polystyrene, poly (p-chlorostyrene), styrene-substituted polymers such as polyvinyltoluene, styrene-substituted polymers, styrene-p-chlorostyrene copolymers, and styrene-propylene copolymers. Polymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-acrylic acid Octyl copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer , Styrene-vinyl methyl ketone copolymer Styrene copolymers such as styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; Methyl acid, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, epoxy resin, epoxy polyol resin, polyurethane resin, polyamide resin, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, fat Aromatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like.

(Toner production method in aqueous medium)
The aqueous medium used in the present invention may be water alone, or a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.

  The binder resin precursor, colorant, release agent, crystalline polyester dispersion, charge control agent, unmodified polyester resin, etc. that form toner particles are mixed when forming the dispersion in an aqueous medium. However, it is more preferable to mix these toner raw materials in advance and then add and disperse the mixture in an aqueous medium. In the present invention, other toner materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in an aqueous medium, but after the particles are formed. , May be added. For example, after forming particles containing no colorant, the colorant can be added by a known dyeing method.

  The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 60 minutes. The temperature during dispersion is usually 0 to 80 ° C. (under pressure), preferably 10 to 40 ° C.

  The amount of the aqueous medium used is usually 100 to 1000 parts by weight with respect to 100 parts by weight of the toner composition. If the amount is less than 100 parts by weight, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 1000 parts by weight, it is not economical. Moreover, a dispersing agent can also be used as needed. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

  As a method of reacting the polyester prepolymer and the compound having active hydrogen groups, the compound having active hydrogen groups may be added and reacted before dispersing the toner composition in the aqueous medium, or dispersed in the aqueous medium. Then, a compound having an active hydrogen group may be added to cause a reaction from the particle interface. In this case, a polyester modified with a polyester prepolymer is preferentially produced on the surface of the toner to be produced, and a concentration gradient can be provided inside the particles.

  Anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamines, etc. as dispersants for emulsifying and dispersing the oil phase in which the toner composition is dispersed in a liquid containing water Amine salts such as salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, etc. Nonionic surfactants such as quaternary ammonium salt type cationic surfactants, fatty acid amide derivatives, polyhydric alcohol derivatives such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl- Amphoteric surfactants such as N- dimethyl ammonium betaine.

  Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acids and metal salts thereof, perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- (2-hydroxyethyl ) Perfluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate Etc.

  Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (Daikin Kogyo Co., Ltd.), Mega-Fac F-l0, F-l20, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF-102 , 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fagento F-100, F150 (manufactured by Neos).

  Examples of cationic surfactants include aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts, and benzaza. Luconium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (Asahi Glass), Florard FC-135 (Sumitomo 3M), Unidyne DS-202 (Daikin Industries) , Megafac F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products Co., Ltd.), Footgent F-300 (Neos Co., Ltd.), and the like.

Further, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like can be used as an inorganic compound dispersant which is hardly soluble in water.
Further, the dispersed droplets may be stabilized by a polymer protective colloid or organic fine particles insoluble in water. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Bodies such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-acrylate Chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N- Methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or esters of compounds containing vinyl alcohol and a carboxyl group, For example, vinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine Homopolymers or copolymers such as those having a nitrogen atom or its heterocyclic ring, polyoxyethylene, polyoxypropylene, poly Xylethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonylphenyl Polyoxyethylenes such as esters, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

In addition, when an acid such as calcium phosphate salt or an alkali-soluble substance is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. To do. It can also be removed by operations such as enzymatic degradation.
When a dispersant is used, the dispersant can remain on the surface of the toner particles. However, it is preferable from the charged surface of the toner to wash away after the reaction.

  Further, in order to lower the viscosity of the toner composition, a solvent in which the polyester prepolymer reacts and is modified with a modified polyester can be used. The use of a solvent is preferable in that the particle size distribution becomes sharp. The solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal. Examples of the solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, and methyl ethyl ketone. , Methyl isobutyl ketone and the like can be used alone or in combination of two or more.

  In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable. The usage-amount of the solvent with respect to 100 parts of polyester prepolymers is 0-300 parts normally, Preferably it is 0-100 parts, More preferably, it is 25-70 parts. When a solvent is used, it is removed by heating under normal pressure or reduced pressure after elongation and / or crosslinking reaction.

  The elongation and / or crosslinking reaction time is selected depending on the reactivity depending on the combination of the polyester prepolymer and the compound having an active hydrogen group, and is usually 10 minutes to 40 hours, preferably 30 minutes to 24 hours. The reaction temperature is usually 0 to 100 ° C., preferably 10 to 50 ° C. Moreover, a well-known catalyst can also be used as needed. Specific examples include tertiary amines such as triethylamine and imidazoles.

  In order to remove the organic solvent from the obtained emulsified dispersion, a method in which the temperature of the entire system is gradually raised to completely evaporate and remove the organic solvent in the droplets can be employed. Alternatively, the emulsified dispersion can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and the aqueous dispersant can be removed by evaporation together. . As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air currents heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used is generally used. Sufficient quality can be obtained with a short treatment such as spray dryer, belt dryer, rotary kiln.

When the particle size distribution at the time of emulsification dispersion is wide and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classifying into a desired particle size distribution.
In the classification operation, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Of course, the classification operation may be performed after obtaining the powder as a powder after drying. The unnecessary fine particles or coarse particles obtained can be returned to the kneading step and used for the formation of particles. At that time, fine particles or coarse particles may be wet.
The dispersant used is preferably removed from the obtained dispersion as much as possible, but it is preferable to carry out it simultaneously with the classification operation described above.

  The resulting dried toner powder is mixed with dissimilar particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles, or mechanical impact force is applied to the mixed powder. As a result, it is possible to prevent the dissociation of the foreign particles from the surface of the composite particle obtained by immobilizing and fusing on the surface.

  Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) has been modified to reduce the pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, etc.

(External additive)
The toner of the present invention may contain an external additive in order to assist fluidity, developability and chargeability.
As the external additive, inorganic fine particles can be preferably used. The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and particularly preferably 5 nm to 500 nm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The proportion of the inorganic fine particles used is preferably 0.01 to 5% by weight of the toner, and particularly preferably 0.01 to 2.0% by weight. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

  Other polymer fine particles such as polystyrene, methacrylic acid ester and acrylic acid ester copolymer obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, polycondensation systems such as silicone, benzoguanamine, and nylon, and thermosetting resins Examples include polymer particles.

  Such a fluidizing agent can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .

  Examples of the cleaning property improver for removing the developer after transfer remaining on the photoreceptor or the primary transfer medium include, for example, zinc stearate, calcium stearate, fatty acid metal salts such as stearic acid, such as polymethyl methacrylate fine particles, polystyrene fine particles, etc. And polymer fine particles produced by soap-free emulsion polymerization. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

In the present invention, the acid value is measured using a method based on JIS K0070-1992.
Specifically, first, 0.5 g of a sample (0.3 g in the case where ethyl acetate is soluble) is added to 120 ml of toluene and dissolved by stirring at 23 ° C. for about 10 hours. Next, 30 ml of ethanol is added to prepare a sample solution. When the sample does not dissolve, a solvent such as dioxane or tetrahydrofuran is used. Furthermore, the acid value was measured at 23 ° C. using an automatic potentiometric titrator DL-53 Titrator (manufactured by METTLER TOLEDO) and electrode DG113-SC (manufactured by METTLER TOLEDO), and analysis software LabX Light Version 1.00 Analyze using .000.
For calibration of the apparatus, a mixed solvent of 120 ml of toluene and 30 ml of ethanol is used.
At this time, the measurement conditions are the same as in the case of the hydroxyl value.
The acid value can be measured as described above. Specifically, the acid value is titrated with a 0.1N potassium hydroxide / alcohol solution standardized in advance, and the formula acid value [mg KOH / g] is determined from the titration amount. = Titrate [ml] x N x 56.1 [mg / ml] / sample weight [g] (where N is a factor of 0.1 N potassium hydroxide / alcohol solution).

  In the present invention, the polyester resin preferably has a glass transition point of 40 to 70 ° C. When the glass transition point is less than 40 ° C., the heat-resistant storage stability may be lowered, and when it exceeds 70 ° C., the low-temperature fixability may be lowered.

In the present invention, the endothermic peak temperature and endothermic shoulder temperature of crystalline polyester, amorphous polyester, and toner are measured using, for example, a DSC system (differential scanning calorimeter) (“DSC-60”, manufactured by Shimadzu Corporation). Can be measured.
Specifically, the endothermic shoulder 1, endothermic peak, and endothermic shoulder 2 of the target sample can be measured by the following procedure. First, about 5.0 mg of polyester resin is put in an aluminum sample container, the sample container is placed on a holder unit, and set in an electric furnace. Next, heating is performed from 0 ° C. to 150 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere. Thereafter, the sample is cooled from 150 ° C. to 0 ° C. at a temperature decrease rate of 10 ° C./min, and further heated to 150 ° C. at a temperature increase rate of 10 ° C./min, and a differential scanning calorimeter (“DSC-60”, manufactured by Shimadzu Corporation) The DSC curve is measured using From the obtained DSC curve, use the analysis program in the DSC-60 system to select the DSC curve at the first temperature rise, and use the “endothermic shoulder temperature” in the analysis program to raise the temperature of the target sample. Select endothermic shoulder 1 and endothermic shoulder 2 at the first time, DSC curve at the second temperature increase, and use “endothermic shoulder temperature” to determine the endothermic shoulder 1 and endothermic shoulder 2 at the second temperature increase of the target sample. You can ask. The shoulder temperature is defined as an endothermic shoulder 1, an endothermic shoulder 2,. Further, from the obtained DSC curve, using the analysis program in the DSC-60 system, using the “endothermic peak temperature” in the analysis program, the DSC curve at the first temperature rise is selected, and the target sample By selecting the endothermic peak at the first temperature increase and the DSC curve at the second temperature increase and using the “endothermic peak temperature” in the analysis program, the endothermic peak at the second temperature increase of the target sample can be obtained. . FIG. 1 shows an example of DSC measurement of crystalline polyester.

(1 component developer, 2 component developer)
When the toner of the present invention is used for a two-component developer, it may be used by mixing with a magnetic carrier. The carrier to toner content ratio in the developer is 1 to 10 weights of toner with respect to 100 parts by weight of carrier. Part is preferred. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, and polyamide resin.

  Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resins such as vinyl, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, polyhexafluoro Propylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride Fluoro such as terpolymers of non-fluoride monomers including, and silicone resins, epoxy resins, and the like and.

Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.
The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

In the present invention, the particle size distribution is measured using a Coulter counter method.
Examples of the particle size distribution measuring apparatus include Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter).
In the present invention, a PC-9801 personal computer (manufactured by NEC Corporation) is connected to the Coulter Counter TA-II type measuring device via an interface (manufactured by Nikka Giken) which outputs the number distribution and volume distribution. Measure the particle size distribution.
Specifically, first, 0.1 to 5 ml of a surfactant (preferably alkyl benzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic solution. The electrolytic solution is prepared by preparing an aqueous solution of about 1% by weight using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Next, 2 to 20 mg of the sample is added and suspended, and then dispersed with an ultrasonic disperser for 1 to 3 minutes. Using the 100 μm aperture, the volume and number of toners are measured from the obtained dispersion, and the volume distribution and number distribution are calculated.
The channel is 2.00 μm or more and less than 2.52 μm, 2.52 μm or more and less than 3.17 μm, 3.17 μm or more and less than 4.00 μm, 4.00 μm or more and less than 5.04 μm, 5.04 μm or more and less than 6.35 μm, 6.35 μm or more and less than 8.00 μm, 8.00 μm or more and less than 10.08 μm, 10.08 μm or more and less than 12.70 μm, 12.70 μm or more and less than 16.00 μm, 16.00 μm or more and less than 20.20 μm, 20.20 μm or more and 25 or more The target is particles having a particle size of 2.00 μm or more and less than 40.30 μm using 13 channels of less than 40 μm, 25.40 μm or more and less than 32.00 μm and 32.00 μm or more and less than 40.30 μm.
The volume average particle size of the toner of the present invention is preferably 3 μm or more and 7 μm or less, and the ratio of the volume average particle size to the number average particle size is preferably 1.2 or less. Moreover, it is preferable that the component whose particle size is 2 micrometers or less is 10 number% or less.

The acid value of the toner of the present invention is an important index for low-temperature fixability and hot offset resistance, and is derived from the terminal carboxyl group of the unmodified polyester resin. In order to control the offset generation temperature or the like, it is preferably 0.5 to 40 mgKOH / g.
When the acid value exceeds 40 mgKOH / g, the extension reaction and / or the crosslinking reaction of the reactive modified polyester resin may be insufficient, and the hot offset resistance may be lowered. On the other hand, if the acid value is less than 0.5 mgKOH / g, the effect of improving the dispersion stability by the base at the time of production cannot be obtained, or the elongation reaction and / or the crosslinking reaction of the reactive modified polyester resin can easily proceed. As a result, the production stability may be reduced.

The toner of the present invention preferably has a glass transition point of 40 to 70 ° C. Thereby, low temperature fixability, heat resistant storage stability and high durability can be obtained.
If the glass transition point is less than 40 ° C., blocking in the developing machine or filming to the photoreceptor may occur, and if it exceeds 70 ° C., the low-temperature fixability may be deteriorated.

  The developer of the present invention is preferably a two-component developer having the toner of the present invention but further having a carrier. At this time, the toner content is preferably 1 to 10% by weight based on the carrier.

As the carrier, iron powder, ferrite powder, magnetite powder or the like having a particle size of about 20 to 200 μm can be used.
Carriers include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin; epoxy resin; acrylic resin, polymethyl methacrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, etc. Polyvinyl resin; Polyvinylidene resin; Polystyrene resin such as polystyrene and styrene acrylic copolymer resin; Halogenated olefin resin such as polyvinyl chloride; Polyester resin such as polyethylene terephthalate and polybutylene terephthalate; Polycarbonate resin, polyethylene, Polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, polyhexafluoropropylene, copolymer of vinylidene fluoride and acrylic monomer, fluoride Vinylidene and copolymers of vinyl fluoride, fluoro terpolymers such as terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomer, may be coated with a coating resin such as silicone resin.
Moreover, the coating resin may contain conductive powder such as metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide, if necessary.
The conductive powder preferably has an average particle size of 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control the electric resistance.

  Further, the developer of the present invention may be a one-component developer having no carrier, that is, a magnetic toner or a non-magnetic toner.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Hereinafter, a part shows a weight part.

Example 1
Production Example 1
-Synthesis of crystalline polyester resin 1-
Into a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, 1,4-butanediol 2010 g, fumaric acid 2520 g, trimellitic anhydride 285 g, hydroquinone 4.9 g were added, and 160 After reacting at 6 ° C. for 6 hours, the temperature was raised to 200 ° C. and reacted for 2 hours, and further reacted at 8.3 kPa for 1 hour to obtain [Crystalline Polyester Resin 1]. As shown in Table 1 below, the endothermic peak temperatures of DSC were 115 ° C., Mn 1100, and Mw 7000. The endothermic shoulder temperature (T2-cs1) was 65 ° C.

-Synthesis of crystalline polyester resin 2-
In the synthesis of the crystalline polyester resin 1, the [crystalline polyester resin 2] was synthesized in the same manner except that the types and amounts of the alcohol component and the acid component were changed. The characteristics are shown in Table 1 below.

Production Example 2
-Synthesis of non-crystalline polyester (low molecular polyester) resin-
240 parts of side 2 mol adduct, 527 parts of bisphenol A propylene oxide 3 mol adduct, 210 parts of terephthalic acid, 46 parts of adipic acid and 2 parts of dibutyltin oxide were added and reacted at normal pressure at 230 ° C. for 8 hours. After reacting at a reduced pressure of ˜15 mmHg for 6 hours, 44 parts of trimellitic anhydride was placed in the reaction vessel and reacted at 180 ° C. and normal pressure for 2 hours to obtain [Low molecular weight polyester 1]. [Low molecular polyester 1] had a number average molecular weight of 2300, a weight average molecular weight of 6000, a Tg of 47 ° C., and an acid value of 25.

Production Example 3
~ Synthesis of polyester prepolymer ~
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 Part and 2 parts of dibutyltin oxide were added, reacted at 230 ° C. under normal pressure for 8 hours, and further reacted for 6 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2100, a weight average molecular weight of 9000, Tg of 58 ° C., an acid value of 0.5, and a hydroxyl value of 51.
Next, 410 parts of [Intermediate Polyester 1], 89 parts of isophorone diisocyanate and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight% of 1.53%.

Production Example 4
~ Synthesis of ketimine ~
In a reaction vessel equipped with a stirrer and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 418.

Production Example 5
~ Synthesis of master batch (MB) ~
1200 parts of water, carbon black (manufactured by Printex 35 Dexa) [DBP oil absorption = 42 ml / 100 mg, pH = 9.5], 540 parts, polyester resin 1200 parts are added and mixed with a Henschel mixer (Mitsui Mining Co., Ltd.). After kneading at 150 ° C. for 30 minutes using two rolls, rolling and cooling and pulverization with a pulverizer gave [Masterbatch 1].

Production Example 6
~ Creation of oil phase ~
In a container equipped with a stirrer and a thermometer, 378 parts of [Low molecular weight polyester 1], 105 parts of Carnauba WAX, 22 parts of CCA (salicylic acid metal complex E-84: Orient Chemical Industry), and 940 parts of ethyl acetate were charged with stirring. The temperature was raised to 0 ° C., kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw material solution 1] 1320 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feed speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. Carbon black and WAX were dispersed under conditions of filling and 3 passes. Next, 1042 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, and one pass was performed with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1]. The solid content concentration of [Pigment / WAX Dispersion 1] (130 ° C., 30 minutes) was 50%.

Production Example 7
-Preparation of dispersion 1 of crystalline polyester-
[Crystalline polyester resin no. 1] and 100 g of ethyl acetate were taken and dissolved by heating at 70 ° C., and then cooled to 20 ° C. at a rate of 20 ° C./min in an ice-water bath. When the cooling liquid was observed, it was confirmed that the crystalline polyester was recrystallized. After cooling, 100 g of [low molecular weight polyester 1] is dissolved in the dispersion, 500 ml of glass beads (3 mmφ) are added thereto, and the mixture is pulverized for 10 hours with a batch type sand mill (made by Campehapio Co., Ltd.). 3 [mu] m of [Crystalline Polyester Dispersion 1] was obtained. The maximum slurry temperature during pulverization was 30 ° C.

-Preparation of dispersion 2 of crystalline polyester-
[Crystalline polyester resin no. 1] and 100 g of ethyl acetate were taken and dissolved by heating at 75 ° C., and then cooled to 15 ° C. at a rate of 5 ° C./min in a water bath. When the cooling liquid was observed, it was confirmed that the crystalline polyester was recrystallized. After cooling, 100 g of [low molecular weight polyester 1] is dissolved in the dispersion, 500 ml of glass beads (3 mmφ) are added thereto, and the mixture is pulverized for 3 hours by a batch type sand mill (made by Campehapio Co., Ltd.). 9 μm of [Crystalline Polyester Dispersion 2] was obtained. The maximum slurry temperature during pulverization was 30 ° C.

~ Preparation of crystalline polyester dispersion 3 ~
[Crystalline polyester resin no. 1] and 100 g of ethyl acetate were taken and dissolved by heating at 70 ° C., and then cooled to 20 ° C. at a rate of 20 ° C./min in an ice-water bath. When the cooling liquid was observed, it was confirmed that the crystalline polyester was recrystallized. After cooling, 100 g of [low molecular weight polyester 1] is dissolved in the dispersion, 500 ml of glass beads (3 mmφ) are added thereto, and pulverized for 1 hour with a batch type sand mill (made by Campehapio Co., Ltd.). 5 μm of [Crystalline Polyester Dispersion 3] was obtained. The maximum slurry temperature during pulverization was 30 ° C.

-Preparation of dispersion 4 of crystalline polyester-
[Crystalline polyester resin no. 1] 100 g, [low molecular weight polyester 1] 200 g, and ethyl acetate 400 g were dissolved by heating at 70 ° C., and then cooled to 20 ° C. at a rate of 20 ° C./min in an ice-water bath. When the cooling liquid was observed, it was confirmed that the crystalline polyester was recrystallized. After cooling, 500 ml of glass beads (3 mmφ) was added to the dispersion, and the mixture was pulverized for 10 hours with a batch sand mill (manufactured by Campehapio) to obtain [Crystalline Polyester Dispersion 4] having a volume average particle size of 0.7 μm. . The maximum slurry temperature during pulverization was 30 ° C.

-Preparation of dispersion 5 of crystalline polyester-
[Crystalline polyester resin no. 1] and 100 g of ethyl acetate were taken and dissolved by heating at 75 ° C., and then cooled to 15 ° C. at a rate of 5 ° C./min in a water bath. When the cooling liquid was observed, it was confirmed that the crystalline polyester was recrystallized. After cooling, 100 g of [low molecular weight polyester 1] is dissolved in the dispersion, 500 ml of zirconia beads (0.5 mmφ) is added thereto, and pulverized for 15 hours with a batch type sand mill (made by Campehapio Co., Ltd.). [Crystalline polyester dispersion 5] of 1.7 μm was obtained. The maximum slurry temperature during pulverization was 68 ° C.

-Production of crystalline polyester dispersion 6-
[Crystalline polyester resin no. 2] and 100 g of ethyl acetate were taken and dissolved by heating at 60 ° C., and then cooled to 15 ° C. at a rate of 20 ° C./min in an ice-water bath. When the cooling liquid was observed, it was confirmed that the crystalline polyester was recrystallized. After cooling, 100 g of [low molecular weight polyester 1] is dissolved in the dispersion, 500 ml of glass beads (3 mmφ) are added thereto, and the mixture is pulverized for 10 hours with a batch type sand mill (made by Campehapio Co., Ltd.). 2 μm of [Crystalline Polyester Dispersion 6] was obtained. The maximum slurry temperature during pulverization was 34 ° C.

-Preparation of dispersion 7 of crystalline polyester-
[Crystalline polyester resin no. 2] and 400 g of ethyl acetate were taken and dissolved by heating at 70 ° C., and then cooled to 20 ° C. at a rate of 20 ° C./min in an ice-water bath. When the cooling liquid was observed, it was confirmed that the crystalline polyester was recrystallized. After cooling, 100 g of [low molecular weight polyester 1] is dissolved in the dispersion, 500 ml of glass beads (3 mmφ) are added thereto, and the mixture is pulverized for 5 hours with a batch type sand mill (made by Campehapio Co., Ltd.). 6 μm of [Crystalline Polyester Dispersion 7] was obtained. The maximum slurry temperature during pulverization was 31 ° C.

-Preparation of crystalline polyester dispersion 8-
[Crystalline polyester resin no. 2] and 400 g of ethyl acetate were taken and dissolved by heating at 70 ° C., and then cooled to 20 ° C. at a rate of 20 ° C./min in an ice-water bath. When the cooling liquid was observed, it was confirmed that the crystalline polyester was recrystallized. After cooling, 100 g of [low molecular weight polyester 1] is dissolved in the dispersion, 500 ml of zirconia beads (0.5 mmφ) is added thereto, and pulverized for 5 hours with a batch type sand mill (made by Campehapio Co., Ltd.). 0.9 μm of [Crystalline Polyester Dispersion 8] was obtained. The maximum slurry temperature during pulverization was 56 ° C.

Production Example 8
~ Synthesis of organic fine particle emulsion ~
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30: manufactured by Sanyo Chemical Industries), 138 parts of styrene, 138 parts of methacrylic acid, When 1 part of ammonium persulfate was charged and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous dispersion of a vinyl resin (a copolymer of styrene-methacrylic acid-methacrylic acid ethylene oxide adduct sulfate sodium salt) [fine particles Dispersion 1] was obtained. The volume average particle diameter of the [fine particle dispersion 1] measured by LA-920 was 0.14 μm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component.

Production Example 9
-Adjustment of aqueous phase-
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of a 48.5% aqueous solution of dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate are mixed and stirred to give a milky white liquid. Got. This is designated [Aqueous Phase 1].

Production Example 9
-Emulsification / solvent removal-
[Pigment / WAX Dispersion 1] 664 parts, [Prepolymer 1] 109.4 parts, [Crystalline Polyester Dispersion 1] 73.9 parts, [Ketimine Compound 1] 4.6 parts, After mixing for 1 minute at 5,000 rpm with a TK homomixer (made by Tokushu Kika), add 1200 parts of [Aqueous Phase 1] to the container and mix for 5 minutes at 11,000 rpm with a TK homomixer [emulsified slurry 1] was obtained.
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain [Dispersion slurry 1].

~ Washing and drying ~
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(4): Add 300 parts of ion-exchanged water to the filter cake of (3), mix with a TK homomixer (10 minutes at 12,000 rpm) and then filter twice to obtain [Filter cake 1]. It was.
[Filtration cake 1] was dried at 45 ° C. for 48 hours in a circulating drier, and sieved with an opening of 75 μm mesh to obtain [Toner 1].

(Examples 2-4, Comparative Examples 1-4)
[Toners 2 to 8] were obtained in the same manner as in Example 1 except that the crystalline polyester dispersion used in Production Example 9 was changed as shown in Table 2 in Example 1.

(Comparative Example 5)
In Example 1, [Toner 9] was obtained in the same manner as in Example 1 except that the crystalline polyester dispersion was not used in Production Example 9.

To 100 parts of the toner thus obtained, 0.7 part of hydrophobic silica and 0.3 part of hydrophobic titanium oxide were mixed with a Henschel mixer. The evaluation results of the obtained toner are shown in Table 2.
A developer composed of 5% by weight of toner subjected to external additive treatment and 95% by weight of a copper-zinc ferrite carrier coated with a silicone resin and having an average particle diameter of 40 μm can be prepared, and 45 sheets of A4 size paper can be printed per minute. Using a RICOH Imagio Neo 450, the surface temperature of the fixing roller was controlled at 130 ° C., and continuous printing was performed and evaluated according to the following criteria.

(Evaluation item)
(Granularity)
The particle diameter of the toner was measured using a particle size measuring device “Coulter Counter TAII” manufactured by Coulter Electronics Co., Ltd., with an aperture diameter of 100 μm. The volume average particle diameter and the number average particle diameter were determined by the particle size measuring instrument.

(Heat resistant storage stability)
The toner was stored at 50 ° C. for 8 hours and then sieved with a 42 mesh sieve for 2 minutes, and the residual rate on the wire mesh was measured.
At this time, the toner having better heat-resistant storage stability has a smaller remaining rate.
The heat-resistant storage stability is ◎ when the residual rate is less than 10%, ◯ when the residual rate is 10% or more and less than 20%, Δ when the residual rate is 20% or more and less than 30%, 30 The case where it was% or more was determined as x.

(Fixing limit)
When the obtained sample image is not peeled off every 10,000 sheets, the image density remaining rate after fixing with a fixing pad is 85% or more, and the image density remaining rate is 70 to 85%. Δ, an image withered or an image density remaining rate of 70% or less was marked as x.

(Hot offset)
The run image was confirmed and it was confirmed that there was no image after the fixing circumference. What did not generate | occur | produced was set to (circle), and what generate | occur | produced was set to x.

  From the results shown in Table 2, all of the toners of Examples 1, 2, 3, and 4 have a small particle size and a sharp particle size distribution. Further, the toners of Examples 1, 2, 3, and 4 all exhibited satisfactory characteristics with respect to all of the low-temperature fixability, heat-resistant storage stability, and hot offset resistance. On the other hand, in the toner of the comparative example, there is a toner whose particle size distribution is not sharp. Further, none of the properties satisfying all of the low-temperature fixability, heat-resistant storage stability, and hot offset resistance were obtained.

As described above, in the present embodiment, an oil phase comprising at least a crystalline polyester resin and an amorphous polyester resin as a binder resin component is dispersed in an aqueous medium in an organic solvent, and an organic solvent is obtained from the obtained dispersion. A toner manufacturing method for obtaining a toner by removing a solvent, wherein a crystalline polyester resin is heated and dissolved in an organic solvent in a toner manufacturing process, and the resulting solution is cooled to obtain a crystalline polyester resin. Recrystallizing into a dispersion of a crystalline polyester resin, dissolving the amorphous polyester resin in the dispersion, finely pulverizing with a mechanical pulverizer, and having a volume average particle size of 0.1 to 1.0 μm; A step of producing a crystalline polyester dispersion liquid. In order to prepare a dispersion of the crystalline polyester resin, the crystalline polyester resin can be finely dispersed by using the above-described process of heating and dissolving / cooling the crystalline polyester resin for recrystallization. Furthermore, by having the step of dissolving and pulverizing the amorphous polyester resin in this dispersion, the particle size control in the pulverization step becomes easy, and the volume average particle suitable for use in the toner is stable. A crystalline polyester dispersion having a diameter of 0.1 to 1.0 μm can be obtained. By using such a crystalline polyester dispersion, the toner particle size distribution can be sharpened.
Further, in this embodiment, when the endothermic shoulder temperature calculated from the second temperature increase in the differential scanning calorimetry (DSC) of the crystalline polyester is (T2-cs1), the crystalline polyester is made fine by a mechanical pulverizer. In the step of preparing the polyester dispersion, the slurry temperature is less than (T2-cs1). Thereby, heat-resistant storage stability is made favorable. This is because when the slurry temperature is (T2-cs1) or higher, the crystalline polyester partially dissolves and becomes compatible with the amorphous polyester, resulting in a decrease in the toner Tg and deterioration of heat resistant storage stability. It is because it ends.
Moreover, according to this embodiment, the endothermic peak temperature of differential scanning calorimetry (DSC) of the crystalline polyester resin is set to 50 to 130 ° C. As a result, both heat-resistant storage stability and low-temperature fixability are improved. When the DSC endothermic peak temperature is less than 50 ° C., the heat resistant storage stability is deteriorated, and blocking tends to occur at the temperature inside the developing device. It becomes impossible.
Moreover, according to this embodiment, an oil phase contains a binder resin precursor as a binder resin component. Also obtained by dissolving and dispersing at least a colorant, a release agent, the crystalline polyester resin dispersion, a binder resin precursor composed of a modified polyester resin, and other binder resin components in an organic solvent. In the oil phase, the binder resin precursor and a compound that extends or crosslinks are dissolved, and then the oil phase is dispersed in an aqueous medium in which a fine particle dispersant is present to obtain an emulsified dispersion, and the emulsified dispersion The binder resin precursor is subjected to a crosslinking reaction and / or an extension reaction in order to remove the organic solvent. Such a binder resin precursor undergoes an extension reaction with a compound having an active hydrogen group (such as amines), and has an effect of improving the release width (difference between the minimum fixing temperature and the hot offset generation temperature).
Moreover, according to this embodiment, the molecular weight distribution by GPC of the soluble part of the ortho dichlorobenzene of crystalline polyester resin is 1000-30000 in a weight average molecular weight (Mw), 500-6000 in a number average molecular weight (Mn), Mw / Mn is 2-10. Regarding the molecular weight of the crystalline polyester resin, those having a sharp molecular weight distribution and a low molecular weight are excellent in low-temperature fixability, and the above range is particularly preferred.
Moreover, according to this embodiment, it is preferable that all the binder resin components are polyester resins.
According to this embodiment, the non-crystalline polyester resin has an acid value of 1 mgKOH / g or more and 50 mgKOH / g or less. When the acid value is 1 mgKOH / g or more, the toner tends to be negatively charged, and at the time of fixing to paper, the affinity between the paper and the toner is improved, and the low-temperature fixability can be improved. On the other hand, when the acid value exceeds 50 mgKOH / g, the charging stability, particularly the charging stability against environmental fluctuations may be lowered. Therefore, it is preferable that the non-crystalline polyester resin has an acid value of 1 to 50 mgKOH / g.
Further, according to the present exemplary embodiment, the toner has a small particle size with a volume average particle size of 3 μm or more and 7 μm or less. Further, the ratio of the volume average particle diameter to the number average particle diameter is 1.2 or less. Further, the number of components having a particle size of 2 μm or less is 10% by number or less. As a result, it is possible to cope with high quality of the output image.
Further, according to the present exemplary embodiment, when the toner has an acid value of 0.5 mgKOH / g or more and 40 mgKOH / g or less, low-temperature fixability and hot offset resistance can be favorably obtained. When the acid value exceeds 40 mgKOH / g, the extension reaction and / or the crosslinking reaction of the reactive modified polyester resin may be insufficient, and the hot offset resistance may be lowered. On the other hand, if the acid value is less than 0.5 mgKOH / g, the effect of improving the dispersion stability by the base at the time of production cannot be obtained, or the elongation reaction and / or the crosslinking reaction of the reactive modified polyester resin can easily proceed. As a result, the production stability may be reduced.
Further, according to the present exemplary embodiment, since the glass transition point of the toner is 40 ° C. or higher and 70 ° C. or lower, low temperature fixability, heat resistant storage stability and high durability can be obtained favorably. If the glass transition point is less than 40 ° C., blocking in the developing machine or filming to the photoreceptor may occur, and if it exceeds 70 ° C., the low-temperature fixability may be deteriorated.
In addition, according to this embodiment, the toner obtained by the above-described manufacturing method has good low-temperature fixability, heat-resistant storage resistance, and hot offset resistance, and has a small particle size and a sharp particle size distribution. it can.
Further, the toner of this embodiment can be used as a one-component developer to obtain a high-quality image. can do.
In addition, the toner of this embodiment can be used as a two-component developer composed of a toner and a carrier to obtain a high-quality image.

Japanese Patent Laid-Open No. 2005-15589 JP-A-8-176310

Claims (16)

A toner is prepared by dispersing an oil phase containing at least a crystalline polyester resin and an amorphous polyester resin as binder resin components in an organic solvent in an aqueous medium, and removing the organic solvent from the obtained dispersion. In the method for producing a toner to obtain
During the toner manufacturing process, the crystalline polyester resin is dissolved by heating in an organic solvent, and the resulting solution is cooled to recrystallize the crystalline polyester resin to obtain a dispersion of the crystalline polyester resin; And a step of dissolving a non-crystalline polyester resin in the dispersion and making it into fine particles with a mechanical pulverizer to produce a crystalline polyester dispersion having a volume average particle size of 0.1 to 1.0 μm. A toner manufacturing method.   2. The toner manufacturing method according to claim 1, wherein when the endothermic shoulder temperature calculated from the second temperature increase in differential scanning calorimetry (DSC) of the crystalline polyester is (T2-cs1), the mechanical pulverizer uses the fine particles. A method for producing a toner, wherein the slurry temperature is less than the above (T2-cs1) in the step of preparing the crystalline polyester dispersion by crystallization.   2. The toner production method according to claim 1, wherein the crystalline polyester resin has a DSC endothermic peak temperature of 50 to 130 ° C. 3.   4. The toner production method according to claim 1, wherein the oil phase contains a binder resin precursor as a binder resin component.   5. The toner production method according to claim 1, wherein, in an organic solvent, at least a colorant, a release agent, the crystalline polyester resin dispersion, a binder resin precursor composed of a modified polyester resin, and the others. In the oil phase obtained by dissolving and dispersing the binder resin component, the binder resin precursor and a compound that extends or crosslinks are dissolved, and then the oil phase is dispersed in an aqueous medium containing a fine particle dispersant. A method for producing a toner, comprising: obtaining an emulsified dispersion, causing the binder resin precursor to undergo a crosslinking reaction and / or elongation reaction in the emulsified dispersion, and removing the organic solvent.   6. The toner production method according to claim 1, wherein the molecular weight distribution by GPC of the soluble portion of the ortho-dichlorobenzene of the crystalline polyester resin is 1000 to 30000 in terms of weight average molecular weight (Mw), and the number average molecular weight (Mn). ) And 500 to 6000, and Mw / Mn is 2 to 10.   7. The toner manufacturing method according to claim 1, wherein all of the binder resin components are polyester resins.   8. The toner manufacturing method according to claim 1, wherein the acid value of the non-crystalline polyester resin is 1 mgKOH / g or more and 50 mgKOH / g or less. 9. The toner manufacturing method according to claim 1, wherein the volume average particle diameter of the toner is 3 μm or more and 7 μm or less.   10. The toner manufacturing method according to claim 1, wherein the ratio of the volume average particle diameter to the number average particle diameter of the toner is 1.2 or less.   11. The toner manufacturing method according to claim 1, wherein a component having a toner particle size of 2 μm or less is 10% by number or less. 12. The toner production method according to claim 1, wherein the toner has an acid value of 0.5 mgKOH / g or more and 40 mgKOH / g or less. 13. The toner manufacturing method according to claim 1, wherein the glass transition point of the toner is 40 ° C. or higher and 70 ° C. or lower. A toner used in an image forming apparatus, wherein the toner is obtained by the toner manufacturing method according to claim 1. A developer for use in an image forming apparatus, comprising a toner obtained by the toner production method according to claim 1.   A developer for use in an image forming apparatus, comprising: a toner obtained by the toner production method according to claim 1; and a carrier.

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