JP2005084407A - Method for producing resin dispersion, image forming toner, developer and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a resin dispersion by which a resin dispersion containing a crystalline polyester resin and having a small particle diameter and a narrow particle size distribution can easily be produced. <P>SOLUTION: The method for producing a resin dispersion comprises (a) a step of preparing a solution by heating at least a crystalline polyester resin and a release agent in an organic solvent, (b) a step of preparing a crude dispersion by precipitating the crystalline polyester resin and the release agent by cooling the solution, and (c) a step of preparing a dispersion having a volume average particle diameter of 0.2-2 μm by further comminuting the crude dispersion with a mechanical comminuting apparatus. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing a resin dispersion containing a crystalline polyester resin, and more particularly to a method for producing a resin dispersion having a small particle size and a narrow particle size distribution. The present invention also relates to an image forming toner used in an electrophotographic apparatus or an electrostatic recording apparatus manufactured using the dispersion obtained by the manufacturing method, a developer using the toner, and an image forming method. .

  In general, vinyl-based thermoplastic resins synthesized by addition polymerization can be directly produced as dispersions by suspension polymerization or emulsion polymerization, but thermoplastics synthesized by condensation polymerization like polyester resins. The resin is polymerized in a lump, and it is impossible to produce a dispersion by the polymerization process itself. In order to produce a polyester resin dispersion, it is necessary to add a dispersion step separately.

As a method for producing a dispersion of a crystalline polyester resin, Patent Document 1 discloses a method for producing a dispersion using a phase separation solvent. In this method, the dispersion particle size is from several tens to several hundreds of μm. Only a coarse dispersion can be produced, and a dispersion having a volume average particle size of around 1.0 μm that can be used in toner production cannot be obtained.
In addition, the dispersion of crystalline polyester resin alone has strong thixotropy, and the dispersion particle size becomes small and the increase in viscosity is remarkably high, so that it takes a long time to disperse and the handling in manufacturing becomes difficult. was there.

JP-A-8-176310

  In view of the above problems, the present invention provides a method for producing a resin dispersion which can easily produce a resin dispersion containing a crystalline polyester resin and having a small particle size and a narrow particle size distribution. And It is another object of the present invention to provide an image forming toner manufactured using the resin dispersion, a developer using the toner, and an image forming apparatus.

In order to solve the above problems, the present invention is characterized by the following.
1. The present invention is a method for producing a resin dispersion characterized by comprising the following steps (a), (b), and (c).
(A) A step of heating at least the crystalline polyester resin and the release agent in an organic solvent to obtain a solution.
(B) A step of cooling the solution to precipitate a crystalline polyester resin and a release agent to obtain a coarse dispersion.
(C) A step of further pulverizing the coarse dispersion with a mechanical pulverizer to obtain a dispersion having a volume average particle size of 0.2 to 2 μm.

2. In the method for producing the resin dispersion, the crystalline polyester resin has a DSC endothermic peak temperature of 50 to 150 ° C.
3. In the method for producing the resin dispersion, the crystalline polyester resin has a weight average molecular weight (Mw) of 1000 to 30000 as determined by gel permeation chromatography (GPC) of a soluble portion of orthodichlorobenzene, and a number average molecular weight (Mn). Is 500 to 6000, and the molecular weight distribution (Mw / Mn) is 2 to 8.

（ここでｎ、ｍは繰り返し単位の数である。ｌは１〜３の整数である。Ｒ_１、Ｒ_２は水素原子もしくは炭化水素基であり、それぞれ同一でも異なっていてもよい。） 4). In the production method of the resin dispersion, wherein the crystalline polyester resin is in the infrared (IR) absorption spectrum, the absorption based on olefin? Ch (out-of-plane deformation vibration) to 965 ± 10 cm ^-1 or 990 ± 10 cm ^-1 It is characterized by having.
5). In the method for producing the resin dispersion, the crystalline polyester resin has a structure represented by the following general formula (1).

(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.)

6). In the method for producing the resin dispersion, the crystalline polyester resin contains a diol compound having 2 to 6 carbon atoms as an alcohol component and at least fumaric acid and one of its derivatives as an acid component.
7). In the method for producing the resin dispersion, the alcohol component of the crystalline polyester resin contains at least one of 1,4-butanediol, 1,6-hexanediol, and derivatives thereof. .

8). In the method for producing the resin dispersion, the release agent is selected from the group consisting of polyolefin wax, long-chain hydrocarbon wax, and carbonyl group-containing wax.
9. In the method for producing the resin dispersion, the organic solvent exhibits non-solvent characteristics at a temperature lower than (Tm-40) ° C. based on the melting temperature (Tm) of the crystalline polyester resin or the release agent. It is characterized by exhibiting good solvent characteristics at higher temperatures.
10. In the method for producing a resin dispersion, the organic solvent is selected from the group consisting of toluene, ethyl acetate, and methyl ethyl ketone.

11. In the method for producing the resin dispersion, the crystalline polyester resin and the release agent are dissolved in an organic solvent in an amount of 1 to 50% by weight in the step (a), and the solution is 0.1 to 30 ° C. in the step (b). It is characterized by cooling at a rate of / min.
12 In the method for producing the resin dispersion, the mechanical pulverization apparatus is selected from the group consisting of a ball mill apparatus, a sand mill apparatus, and a wet microparticulation apparatus.

13. The present invention also provides a polymer dispersion having a site capable of reacting with a compound having an active hydrogen group in at least an organic solvent, a colorant, and a resin dispersion produced by any one of the methods for producing a resin dispersion. Is dissolved or dispersed, the solution or dispersion is dispersed in an aqueous medium, the polymer having a site capable of reacting with the compound having an active hydrogen group is reacted, or while reacting, the organic solvent is removed. It is an image forming toner obtained by removing, washing and drying.

14 Furthermore, the present invention is a one-component developer comprising the image forming toner.
15. The present invention also provides a two-component developer comprising the image forming toner and a magnetic carrier.

16. Further, the present invention develops an electrostatic latent image formed on an image carrier with toner, transfers the toner image formed on the image carrier to an image support, and transfers the transferred toner image to a roller shape. Alternatively, in the image forming method including a step of obtaining a fixed image by heat and pressure fixing with a belt-shaped fixing member, the image forming method uses any one of the above-described developers.

17. Further, according to the present invention, in a process cartridge that includes at least an image carrier and a developing unit and is integrally supported and detachable from the main body of the image forming apparatus, the developing unit holds any one of the developers. Process cartridge.

  According to the present invention, a method for producing a crystalline polyester resin dispersion for dispersing a crystalline polyester resin effective in low-temperature fixability and heat-resistant storage stability of the toner in the toner, and toner and development using the dispersion Agents and image forming methods can be provided. In particular, it is a low-temperature fixing toner that has good print quality with the toner, excellent image quality stability in continuous printing, stable cleaning properties, and prevents filming contamination on the photoreceptor, developing roller, etc. is there.

Hereinafter, embodiments of the present invention will be described.
The present invention is a method for producing a resin dispersion characterized by comprising the following steps (a), (b), and (c).
(A) A step of heating at least the crystalline polyester resin and the release agent in an organic solvent to obtain a solution.
(B) A step of cooling the solution to precipitate a crystalline polyester resin and a release agent to obtain a coarse dispersion.
(C) A step of further pulverizing the coarse dispersion with a mechanical pulverizer to obtain a dispersion having a volume average particle size of 0.2 to 2 μm.
Since the crystalline polyester resin has crystallinity, the crystalline polyester resin exhibits a heat-melting characteristic showing 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 are shown for the release width (difference between the minimum fixing temperature and the hot offset occurrence temperature).
On the other hand, the dispersion of the crystalline polyester resin alone is strong in thixotropy, and the dispersion particle size becomes small and the increase in viscosity becomes remarkably high. Therefore, the small particle size dispersion having a volume average particle size of 0.2 to 2 μm. Is difficult to produce. Therefore, in the method for producing a resin dispersion according to the present invention, a release agent is added together with the crystalline polyester resin in an organic solvent to reduce the dispersed particle size of the crystalline polyester resin in the coarse dispersion, and The thixotropic property is lowered and a resin dispersion having a small particle diameter is easily produced.

（ここでｎ、ｍは繰り返し単位の数である。Ｌは１〜３の整数である。Ｒ₁、Ｒ₂は水素原子もしくは炭化水素基であり、それぞれ同一でも異なっていてもよい。） Below, each material required for preparation of a resin dispersion liquid is demonstrated.
(Crystalline polyester)
The crystalline polyester resin contains a diol compound having 2 to 6 carbon atoms as an alcohol component, particularly 1,4-butanediol, 1,6-hexanediol and derivatives thereof of 80 mol% or more, preferably 85 to 100 mol%. And at least an acidic component such as fumaric acid or a carboxylic acid having a double bond (C = C bond), and a course represented by the following general formula (1) synthesized using these derivatives Crystalline polyester resins are preferred.

(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 can be confirmed by X-ray diffraction, GC / MS, LC / MS, infrared absorption (IR) measurement, etc. in addition to NMR measurement by solution or solid, Examples of the spectrum include those having absorption at 965 ± 10 cm ⁻¹ or 990 ± 10 cm ⁻¹ based on δCH (out-of-plane variable angular vibration) of olefin.

  As for the molecular weight, 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 obtained by gel permeation chromatography (GPC) of the soluble portion of orthodichlorobenzene The peak position of the molecular weight distribution diagram with log (M) on the horizontal axis and weight% on the vertical axis 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 It is preferable that the molecular weight (Mw) is 1000 to 30000, the number average molecular weight (Mn) is 500 to 6000, and Mw / Mn is 2 to 8. If the molecular weight is smaller than this, sufficient properties as a binder resin cannot be obtained, and if the molecular weight is larger than this, or if the molecular weight distribution is widened, the sharp melt property is deteriorated, so that good fixability cannot be obtained.

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 150 ° C. When the melting temperature and F1 _{/ 2} temperature are 50 ° C. or lower, the heat-resistant storage stability is deteriorated, and blocking tends to occur at the temperature inside the developing device. 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. .

(Release agent)
Known waxes can be used as the release agent. Among them, polyolefin wax (polyethylene wax, polypropylene wax, etc.); long-chain hydrocarbon wax (paraffin) because of its good affinity with crystalline polyester resin. Preferred examples include waxes and sazol waxes; and carbonyl group-containing waxes. Among these, a carbonyl group-containing wax is more preferable. Examples of the carbonyl group-containing wax include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18. -Octadecanediol distearate, etc.); polyalkanol esters (trimellitic acid tristearyl, distearyl maleate, etc.); polyalkanoic acid amides (ethylenediamine dibehenyl amide, etc.); polyalkylamides (trimellitic acid tristearyl amide, etc.) And dialkyl ketones (such as distearyl ketone). Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred.
The melting point of the wax is usually 40 to 160 ° C, preferably 50 to 120 ° C, more preferably 60 to 90 ° C. A wax having a melting point of less than 40 ° C. has an adverse effect on heat resistant storage stability, and a wax having a melting point of more than 160 ° C. tends to cause a cold offset when fixing at a low temperature. Further, the melt viscosity of the wax is preferably 5 to 1000 cps, more preferably 10 to 100 cps as a measured value at a temperature 20 ° C. higher than the melting point. Waxes exceeding 1000 cps have poor effects for improving hot offset resistance and low-temperature fixability. The content of the wax in the toner is usually 0 to 40% by weight, preferably 3 to 30% by weight.
The wax is contained in the resin dispersion, and can also be added during the toner preparation process according to the toner formulation. In this case, the wax to be used is not limited to the above wax, plant wax such as carnauba wax, cotton wax, wood wax and rice wax, animal wax such as beeswax and lanolin, mineral wax such as ozokerite and cercin, and Petroleum waxes such as paraffin, microcrystalline, and petrolatum may be used.

(Organic solvent)
As an organic solvent, the crystalline polyester resin is completely dissolved at a high temperature to form a transparent uniform solution. On the other hand, when cooled to a low temperature, the crystalline polyester resin is phase-separated to form an opaque heterogeneous solution. Is used. Specifically, it is only necessary that the non-solvent property is exhibited at a temperature lower than (Tm-40) ° C. and the good solvent property 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.

(Solid content concentration and cooling rate of crystalline polyester)
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. The higher the solution concentration, the larger the particle size, but the efficiency of mechanical pulverization in the next step becomes worse. In addition, the smaller the solution concentration, the smaller the particle size and the higher the efficiency of mechanical grinding, but the lower the concentration of the resulting dispersion, the worse the overall production efficiency. As a result of intensive studies, the crystalline polyester resin is preferably added to the organic solvent in an amount of preferably 1 to 50% by weight, more preferably 5 to 40% by weight, and still more preferably 10 to 30% by weight. And it stirs for about 30 minutes below the normal-pressure boiling point of the organic solvent using this mixture, and it is set as a transparent uniform solution.
The subsequent cooling of the solution is preferably 0.1 to 30 ° C./min, more preferably 0.5 to 25 ° C./min, and even more preferably 1 to 20 ° C./min. When the cooling rate is slower than 0.1 ° C./minute, the dispersed particle size of the precipitated crystalline polyester resin becomes large, and the efficiency of mechanical pulverization in the next step is deteriorated. Further, it is not preferable in terms of cost to make the cooling rate faster than 30 ° C./min because a special cooling device is required.

(Mechanical grinding device)
As the mechanical pulverization apparatus, a commercially available mechanical pulverization apparatus can be mentioned, but in particular, as a pulverization apparatus suitable for efficiently dispersing the particles of the coarse dispersion liquid and preparing a resin dispersion liquid having a small particle diameter. , A ball mill device, a sand mill device, a wet micronizing device, and the like.

  Next, the toner of the present invention will be described. The toner of the present invention is produced using the resin dispersion described above, and is manufactured using other materials such as those shown below.

(Polymer having a site capable of reacting with a compound having an active hydrogen group)
Examples of the polymer having a site capable of reacting with a compound having an active hydrogen group 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 the 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 the polyester prepolymer becomes low and the hot offset resistance is deteriorated. 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. When the number is less than 1 per molecule, the molecular weight of the urea-modified polyester after the elongation reaction becomes low, and the hot offset resistance deteriorates.

(Compound having an active hydrogen group)
A representative example of the compound having an active hydrogen group is an amine. 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 the diamine compound include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diaminecyclohexane, Isophorone diamine etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine 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, 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, parachlor ortho nitro Nirin Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmin Min BS, 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, Pogment 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, Thio Indigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone red, Riazo 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, Phthalo Cyanine 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 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
The master batch can be obtained by mixing and kneading the resin for the master batch and the colorant under high shearing force and kneading. 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.

(Charge control agent)
The toner 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 NEG VP2036 of quaternary ammonium salt, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit), copper phthalocyanine, perylene, quinacridone, Zone-based pigment, a sulfonic acid group, a 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. More preferably, the range of 0.2 to 5 parts by weight is good. 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. May be.

(External additive)
The toner may contain an external additive 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 mμ to 2 μm, and particularly preferably 5 mμ to 500 mμ. 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, quartz 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.
In addition, polymer fine particles, such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, methacrylate esters, acrylate copolymers, polycondensation systems such as silicone, benzoguanamine, and nylon, thermosetting Examples thereof include polymer particles made of a resin.
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 toner after transfer remaining on the photosensitive member or the primary transfer medium include fatty acid metal salts such as zinc stearate and calcium stearate such as polymethyl methacrylate fine particles and polystyrene fine particles. Examples thereof include fine polymer 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.

(Unmodified polyester)
In the toner of the present invention, not only the polyester prepolymer but also unmodified polyester can be contained as a toner binder component. By using the unmodified polyester in combination, the low-temperature fixability and the gloss when used in a full color apparatus are improved, which is preferable to the single use. The polyester prepolymer and the unmodified polyester are preferably at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Therefore, a similar composition is preferable for the polyester component of the polyester prepolymer and the unmodified polyester. The weight average molecular weight of the unmodified polyester is usually 1000 to 30000, preferably 1500 to 10000, and more preferably 2000 to 8000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 10,000, low-temperature fixability will deteriorate. The hydroxyl value is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. An acid value is 1-30 normally, Preferably it is 3-25. By having an acid value, it tends to be negatively charged. Further, those having an acid value and a hydroxyl value exceeding these ranges are easily affected by the environment under high temperature and high humidity and low temperature and low humidity, and are liable to cause image deterioration.

The image forming toner of the present invention is produced, for example, by the following production method.
(Toner production method in aqueous medium)
As an aqueous medium, water alone may be used, but 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.
A polymer having a site capable of reacting with a compound having an active hydrogen group in an aqueous medium, forming a toner particle, a colorant, a release agent, a crystalline polyester dispersion, a charge control agent, an unmodified polyester resin, etc. Although mixing may be performed when forming the dispersion in the aqueous medium, it is more preferable to mix these toner raw materials in advance and then add and disperse the mixture in the 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 that do not contain a 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 50 ° C. The amount of the aqueous medium used relative to 100 parts of the toner composition is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight. If the amount is less than 50 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 20000 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, and alkylamines 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 and the like.

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, perfluoroalkyl carboxylic 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. Is mentioned.
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 (manufactured by Taikin Kogyo Co., Ltd.), Mega-Fac F-ll0, F-120, 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).
In addition, as the cationic surfactant, aliphatic primary, secondary or secondary amine acids that right the fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, Benzalkonium 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) ), Megafuck 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, etc., or esters of compounds containing vinyl alcohol and carboxyl groups, such as Vinyl acetate, vinyl propionate, vinyl butyrate, etc., 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, etc. Homopolymers or copolymers such as those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylene, polyoxypropylene, Oxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl phenyl ester Polyoxyethylenes such as, 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, but 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, 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 or 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.

  By mixing the obtained powder of toner after drying with different kinds of particles such as fine particles of release agent, fine particles of charge control agent, fine particles of fluidizing agent, fine particles of colorant, or applying mechanical impact force to the mixed powder By immobilizing and fusing on the surface, it is possible to prevent detachment of the foreign particles from the surface of the resulting composite particle. 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.) is 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.

(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, polyamide resin, and epoxy 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, polyhexafluoropropylene resins , Copolymers of vinylidene fluoride and acrylic monomers, copolymers of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinyl Fluoro terpolymers, and silicone resins terpolymers etc. of vinylidene fluoride and non-fluorinated monomer. 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.

The image forming method using the developer of the present invention is as follows. FIG. 7 is a diagram illustrating a schematic configuration of an image forming apparatus as an example. The surface of the photoreceptor 1 as an image carrier is uniformly charged by a charging roller 2 and an electrostatic latent image is written by exposure light L from an exposure device (not shown). The electrostatic latent image is developed by the developing device 4. The developing device 4 holds the developer of the present invention. The developer is supplied to the developing roller 5 while being stirred by the stirring screw 14. The developing roller 5 rotates while carrying the developer, and develops the toner into an electrostatic latent image on the photosensitive member 1 by a developing electric field formed on the surface facing the photosensitive member 1. The toner image on the photoreceptor 1 is transferred at a nip portion with the photoreceptor 1 while being transported to a transfer belt 6 on a sheet fed from a sheet feeding device (not shown). Thereafter, the toner image on the paper is fixed by receiving heat and pressure by a fixing device (not shown).
On the other hand, on the surface of the photoreceptor 1 after the toner image is transferred, the transfer residual toner is scraped off by the cleaning blade 7 and the residual charge is erased by the charge eliminating lamp 20 to prepare for the next image forming process.

  Further, the developer of the present invention can be a process cartridge that is held in a developing device, includes at least a photosensitive member and a developing device, is integrally supported, and is detachably formed on the main body of the image forming apparatus. In addition to this, the process cartridge may include a charging device and a cleaning device. Thereby, the maintainability of the image forming apparatus can be improved.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. Moreover, a part shows a weight part.
(Production Example 1)
~ Synthesis of crystalline polyester resin ~
In a 5-liter four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer and thermocouple, 2070 g of 1,4-butanediol, 2535 g of fumaric acid, 291 g of trimellitic anhydride, and 4.9 g of hydroquinone were added. After reacting at 5 ° C. for 5 hours, the temperature was raised to 200 ° C. and reacted for 1 hour, and further reacted at 8.3 kPa for 1 hour to obtain a crystalline polyester resin. The endothermic peak temperature of DSC was 123 ° C., the number average molecular weight Mn was 710, and the weight average molecular weight Mw was 2100.

(Production Example 2)
In Production Example 1, crystalline polyester resins 1 to 6 were synthesized in the same manner as in Production Example 1 except that the types and amounts of the alcohol component and the acidic component were changed. The physical property values of the obtained crystalline polyester resin are shown in Table 1. In addition, IR spectrum charts are shown in FIGS.

<Example 1>
~ Preparation of crystalline polyester resin dispersion ~
The crystalline 2L container shown in Table 1 [Crystalline Polyester Resin No. 4], 100 g of pentaerythritol tetrabehenate, and 400 g of ethyl acetate were dissolved by heating at 79 ° C., and then rapidly cooled in an ice-water bath at a rate of 27 ° C./min. A [crude dispersion] was obtained. To this, 500 ml of glass beads (3 mmφ) was added, and pulverized for 4 hours with a batch type sand mill (manufactured by Campehapio) to obtain [resin dispersion 1] having a volume average particle diameter of 0.4 μm.

<Examples 2 to 6>
In Example 1, except having changed dispersion conditions into Table 2, it operated similarly to Example 1 and obtained [resin dispersion liquids 2-6]. Table 2 also shows the dispersion state of each resin dispersion.

<Comparative Examples 1-6>
In Examples 1 to 6, operations were performed in the same manner as in Examples 1 to 6 except that a resin dispersion was prepared without containing a release agent. Each dispersion condition and the dispersion state of the obtained resin dispersion are shown together in Table 2.

  As a result, the resin dispersions of Examples 1 to 6 in which the crystalline polyester resin was dissolved and crystallized together with the release agent were compared with the resin dispersions of Comparative Examples 1 to 6 in which the crystalline polyester resin alone was used. As the volume average particle size becomes smaller and the thixotropy of the dispersion also decreases, it has been found that the subsequent dispersion time by the mechanical pulverization apparatus can be greatly shortened.

<Example 7>
~ Preparation of crystalline polyester resin dispersion ~
In Example 1, the crystalline polyester resin no. Crystals having a volume average particle diameter of 0.6 μm were the same as in Example 1 except that 4 was changed to 320 g, pentaerythritol tetrabehenate 80 g, ethyl acetate 400 g, and the grinding time by the sand mill was changed to 15 hours. -Based polyester resin dispersion No. 7 was obtained.
~ Synthesis of organic fine particle emulsion ~
In a reaction vessel equipped with a stirrer 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 sodium salt of styrene-methacrylic acid-methacrylic acid ethylene oxide adduct sulfate) [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. The resin content Tg was 152 ° C.

-Adjustment of aqueous phase-
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7: Sanyo Chemical Industries) and 90 parts of ethyl acetate are mixed and stirred to give a milky white liquid. Got. This is designated as [Aqueous Phase 1].
~ Synthesis of low molecular weight polyester ~
229 parts of bisphenol A ethylene oxide 2 mol adduct, 529 parts of bisphenol A propylene oxide 3 mol adduct, 208 parts of terephthalic acid, 46 parts of adipic acid and 2 parts of dibutyltin oxide were reacted at 230 ° C. for 8 hours under normal pressure. Furthermore, after 5 hours of reaction under reduced pressure of 10 to 15 mmHg, 44 parts of trimellitic anhydride was put in a reaction vessel and reacted at 180 ° C. under normal pressure for 2 hours to obtain [Low molecular weight polyester 1]. [Low molecular polyester 1] had a number average molecular weight Mn of 2500, a weight average molecular weight Mw of 6700, a Tg of 43 ° C., and an acid value of 25.

~ Synthesis of polyester prepolymer ~
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 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, 22 parts of trimellitic anhydride And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. for 8 hours under normal pressure, and further reacted for 5 hours under reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight Mn of 2100, a weight average molecular weight Mw of 9500, a Tg of 55 ° 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 percentage of 1.53%.

~ 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.
~ Master batch synthesis ~
Add 1200 parts of water, 540 parts of carbon black (Printex35: manufactured by Dexa) [DBP oil absorption = 42 ml / 100 mg, pH = 9.5], 1200 parts of polyester resin, and mix with a Henschel mixer (made by Mitsui Mining Co., Ltd.). Was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1].

~ Preparation of oil phase ~
In a container equipped with a stir bar and a thermometer, 378 parts of [Low molecular weight polyester 1], 92 parts of carnauba wax, 22 parts of a salicylic acid metal complex (E-84: manufactured by Orient Chemical Industries), and 947 parts of ethyl acetate are charged and stirred. The temperature was raised to 80 ° C., kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. in 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were placed in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw Material Solution 1] 1324 parts were transferred to a container, and using a bead mill (Ultra Visco Mill: manufactured by Imex Co., Ltd.), liquid feeding speed 1 kg / hr, disk peripheral speed 6 m / sec, 0.5 mm zirconia beads 80% by volume. Carbon black and wax were dispersed under conditions of filling and 3 passes. Next, 1042.3 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, followed by one pass 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%.

<Example 8>
~ Emulsification, solvent removal ~
[Pigment / Wax Dispersion 1] 664 parts, [Prepolymer 1] 109.4 parts, [Example 7 Dispersion 7] 92.4 parts, [Ketimine Compound 1] 4.6 parts in a container 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 with a TK homomixer at 13,000 rpm for 20 minutes. An 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, drying ~
[Emulsified slurry 1] After 100 parts of vacuum filtration,
(I) 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(Ii) 100 parts of a 10% sodium hydroxide aqueous solution was added to the filter cake of (i), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(Iii) 100 parts of 10% hydrochloric acid was added to the filter cake of (i), mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(Iv) Add 300 parts of ion exchanged water to the filter cake of (iii), 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 with a circulating drier, and sieved with a mesh of 75 μm to obtain [Toner 1].

<Comparative Example 7>
[Toner 2] was obtained in the same manner as in Example 8, except that [Dispersion 7 of Example 7] was not used.

  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 obtained toner physical properties are shown in Table 3.

  A developer composed of 5% by weight of toner treated with an external additive and 95% by weight of a copper-zinc ferrite carrier coated with a silicone resin and having an average particle diameter of 40 μm is prepared, and 45 sheets of A4 size paper are printed per minute. Using Ricoh's imagio Neo 450, which was continuously printed and evaluated according to the following criteria, the results are shown in Table 4.

The evaluation items in Tables 3 and 4 are as follows.
(Evaluation item)
(A) Particle size The particle size of the toner was measured with 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.
(B) Circularity Measured using a flow particle image analyzer FPIA-1000 (manufactured by Toa Medical Electronics Co., Ltd.). As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably alkylbenzene sulfonate is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance, and further measurement is performed. Add about 0.1-0.5g of sample. The suspension in which the sample was dispersed was subjected to dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the shape and distribution of the toner were measured with the above apparatus at a dispersion concentration of 3000 to 10,000 / μl. .
(C) Charge amount 6 g of developer was weighed, charged into a metal cylinder that could be sealed, and blown to obtain the charge amount. The toner concentration was adjusted to 4.5 to 5.5 wt%.
(D) Toner thermal characteristics (flow tester characteristics)
Measurement was performed using an elevated flow tester CFT500 manufactured by Shimadzu Corporation. The flow curve of this flow tester becomes the data shown in FIGS. 8A and 8B, from which each temperature can be read. In the figure, Ts is the softening temperature, Tfb is the outflow start temperature, and the melting temperature in the 1/2 method is the T1 / 2 temperature.
[Measurement condition]
Load: 10 kg / cm ² , temperature rising rate: 3.0 ° C./min,
Die diameter: 0.50 mm, Die length: 10.0 mm
(E) Fixability Using Ricoh imagio Neo 450, 1.0 ± 0.1 mg as a solid image on plain paper and cardboard transfer paper (Ricoh Type 6200 and NBS Ricoh Copy Printing Paper <135>) Adjustment was made so that toner of / cm ² was developed, and adjustment was made so that the temperature of the fixing belt was variable, and the temperature at which no offset occurred on plain paper and the lower limit fixing temperature on thick paper were measured. The lower limit fixing temperature was determined as the fixing lower limit temperature at the fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more.
(F) Image density After outputting a solid image, the image density was measured by X-Rite (manufactured by X-Rite). This was measured at five points for each color alone, and the average was obtained for each color.
(G) Background stain A blank image is stopped during development, the developer on the developed photoreceptor is tape transferred, and the difference from the image density of the untransferred tape is determined by 938 Spectrodensitometer (manufactured by X-Rite) ).
(H) Cleaning property The transfer residual toner on the photosensitive member that has passed the cleaning process is transferred to white paper with a scotch tape (manufactured by Sumitomo 3M Co.), measured with a Macbeth reflection densitometer RD514, and the difference from the blank is 0. The evaluations were evaluated as “◯ (good)” for those below 01 and “× (defect)” for those exceeding that.
(I) Filming The presence or absence of toner filming on the developing roller or the photoreceptor was observed. The state where there was no filming was evaluated as “◯”, the state where streaky filming was observed was evaluated as “Δ”, and the state where filming was present as a whole was evaluated as “x”.

  As can be seen from Tables 3 and 4, the toner no. No. 1 has excellent low-temperature fixability, good heat-resistant storage stability, good print quality, excellent image quality stability during continuous printing, stable cleaning on the photoreceptor, and occurrence of filming. It is a toner that can be prevented.

Crystalline polyester resin no. 1 is an IR spectrum chart of 1; Crystalline polyester resin no. 2 is an IR spectrum chart of No. 2; Crystalline polyester resin no. 3 is an IR spectrum chart of FIG. Crystalline polyester resin no. 4 is an IR spectrum chart of No. 4; Crystalline polyester resin no. 5 is an IR spectrum chart of FIG. Crystalline polyester resin no. 6 is an IR spectrum chart of FIG. 1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to the present invention. It is a figure which shows the flow curve of a flow tester.

Explanation of symbols

1 Photoconductor (image carrier)
2 Charging roller 4 Developing device 5 Developing roller 6 Transfer belt 7 Cleaning blade L Exposure light

Claims (17)

A method for producing a resin dispersion, comprising the following steps (a), (b), and (c).
(A) A step of heating at least the crystalline polyester resin and the release agent in an organic solvent to obtain a solution.
(B) A step of cooling the solution to precipitate a crystalline polyester resin and a release agent to obtain a coarse dispersion.
(C) A step of further pulverizing the coarse dispersion with a mechanical pulverizer to obtain a dispersion having a volume average particle size of 0.2 to 2 μm.   The method for producing a resin dispersion according to claim 1, wherein the crystalline polyester resin has an endothermic peak temperature in differential scanning calorimetry (DSC) of 50 to 150 ° C.   The crystalline polyester resin has a weight average molecular weight (Mw) of 1000 to 30000, a number average molecular weight (Mn) of 500 to 6000, and a molecular weight distribution (Mw) as determined by gel permeation chromatography (GPC) of the soluble portion of orthodichlorobenzene. / Mn) is 2-8, The manufacturing method of the resin dispersion liquid of Claim 1 or 2 characterized by the above-mentioned. The crystalline polyester resin is in the infrared (IR) absorption spectrum, according to claim 1, characterized in that an absorption based on the olefin? Ch (out-of-plane deformation vibration) to 965 ± 10 cm ^-1 or 990 ± 10 cm ^-1 4. A method for producing a resin dispersion according to any one of items 3 to 3. The method for producing a resin dispersion according to any one of claims 1 to 4, wherein the crystalline polyester resin has a structure represented by the following general formula (1).

(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.)   The crystalline polyester resin contains a diol compound having 2 to 6 carbon atoms as an alcohol component, and at least fumaric acid and one of its derivatives as an acid component. A method for producing a resin dispersion.   The alcohol component of the crystalline polyester resin contains at least one of 1,4-butanediol, 1,6-hexanediol, and derivatives thereof, according to any one of claims 1 to 6. The manufacturing method of the resin dispersion of description.   8. The resin dispersion according to claim 1, wherein the release agent is selected from the group consisting of polyolefin wax, long-chain hydrocarbon wax and carbonyl group-containing wax. Method.   The organic solvent exhibits non-solvent characteristics at a temperature lower than (Tm-40) ° C. based on the melting temperature (Tm) of the crystalline polyester resin or the release agent, and is a good solvent at a temperature higher than that. The method for producing a resin dispersion according to any one of claims 1 to 8, wherein the resin dispersion exhibits characteristics.   10. The method for producing a resin dispersion according to claim 1, wherein the organic solvent is selected from the group consisting of toluene, ethyl acetate, and methyl ethyl ketone.   In the step (a), 1 to 50% by weight of the crystalline polyester resin and the release agent are dissolved in an organic solvent, and in the step (b), the solution is cooled at a rate of 0.1 to 30 ° C./min. The method for producing a resin dispersion according to any one of claims 1 to 10.   The method for producing a resin dispersion according to any one of claims 1 to 11, wherein the mechanical pulverization apparatus is selected from the group of a ball mill apparatus, a sand mill apparatus, and a wet microparticulation apparatus.   A polymer having a site capable of reacting with a compound having an active hydrogen group in at least an organic solvent, a colorant, and a resin dispersion produced by the method for producing a resin dispersion according to any one of claims 1 to 12 The organic solvent is dissolved or dispersed, and the solution or dispersion is dispersed in an aqueous medium, and the polymer having a site capable of reacting with the compound having an active hydrogen group is reacted or while reacting. An image-forming toner obtained by removing water, washing and drying.   A one-component developer comprising the image forming toner according to claim 13.   A two-component developer comprising the image forming toner according to claim 13 and a magnetic carrier.   The electrostatic latent image formed on the image carrier is developed with toner, the toner image formed on the image carrier is transferred to an image support, and the transferred toner image is a roller-shaped or belt-shaped fixing member. An image forming method comprising using the developer according to claim 14 or 15 in an image forming method including a step of obtaining a fixed image by heat and pressure fixing.   16. In a process cartridge that includes at least an image carrier and a developing unit and is integrally supported and detachably attached to an image forming apparatus main body, the developing unit holds the developer according to claim 14 or 15. Feature process cartridge.

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