JP5552927B2 - Toner, developer, developer container, process cartridge, image forming method, and image forming apparatus - Google Patents

Description

  The present invention relates to a toner for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, and the like, a developer using the toner, a container containing the developer, a process cartridge, an image forming method, and an image forming apparatus About.

  Conventionally, in an electrophotographic apparatus, an electrostatic recording apparatus or the like, an electric latent image or a magnetic latent image is visualized with toner. For example, in electrophotography, an electrostatic image (latent image) is formed on a photoreceptor, and then the latent image is developed with toner to form a toner image. The toner image is usually transferred onto a recording medium such as paper and then fixed by a method such as heating. The toner used for electrostatic image development is generally colored particles containing a colorant, a charge control agent, and other additives in a binder resin.

  As a fixing method in the dry development method, a heated heat roller method is widely used because of its energy efficiency. In recent years, in order to save energy by fixing the toner at a low temperature, the thermal energy given to the toner during fixing tends to be lowered. In the 1999 International Energy Agency (IEA) DSM (Demand-Side Management) program, there is a technology procurement project for next-generation copiers, and the required specifications are published. For copiers of 30 cpm or more, achieve dramatic energy savings compared to conventional copiers so that standby time is within 10 seconds and standby power consumption is 10 to 30 watts (depending on the copying speed). Is required. One way to achieve this requirement is to reduce the heat capacity of a fixing member such as a heated heat roller to improve the temperature responsiveness of the toner. It is not possible.

In order to achieve such a requirement and shorten the waiting time, it is considered that it is an essential technical achievement matter to lower the melting start temperature of the toner to lower the fixing temperature when it can be used. In order to cope with such low-temperature fixing, an attempt has been made to use a polyester resin having excellent low-temperature fixability and relatively good heat-resistant storage stability, instead of the styrene-acrylic resins that have been widely used.
Also, as a fixing method in electrophotography, from the viewpoint of excellent thermal efficiency and downsizing, a method of fixing by directly pressing a heating roller against a toner image on a recording medium, that is, a heat roller fixing method is energy efficient. It is widely used because of its good quality. Thus, from the environmental consideration of energy saving, reduction of power consumption of the heat roller used for fixing is desired.

  In recent years, the fixing device has been further improved, and the thermal energy efficiency is increased by reducing the thickness of the roller on the side in contact with the surface that supports the toner image, and the start-up time can be greatly shortened. However, since the specific heat capacity is reduced, the temperature difference between the portion through which the recording medium passes and the portion through which the recording medium does not pass increases, and toner adheres to the fixing roller. For this reason, a so-called hot offset phenomenon occurs in which the toner is fixed to the non-image portion on the recording medium after the fixing roller makes one round. Therefore, the demand for toner with respect to hot offset resistance as well as low-temperature fixability is becoming stricter.

  On the other hand, the methods for producing toner used for electrostatic image development are roughly classified into a pulverization method and a polymerization method. In the pulverization method, a toner composition is prepared by pulverizing and classifying a toner composition in which a colorant, a charge control agent, an anti-offset agent, and the like are melt-mixed and uniformly dispersed in a thermoplastic resin. For this reason, it is possible to produce a toner having some excellent characteristics, but there is a limit to the selection of materials. That is, the toner composition obtained by melt mixing must be pulverized and classified by an economically usable apparatus. From this demand, the melt-mixed toner composition must be sufficiently brittle. For this reason, when the toner composition is pulverized, the particle size distribution tends to be wide, and if an attempt is made to obtain a copy image having good resolution and gradation, for example, fine powder having a particle size of 4 μm or less and coarse particle having a particle size of 15 μm or more. The powder must be removed by classification, and there is a problem that the yield of toner becomes very low. In addition, in the pulverization method, it is difficult to uniformly disperse the colorant, the charge control agent and the like in the thermoplastic resin, and there is a problem in that the fluidity, developability, durability, image quality, etc. of the toner are adversely affected. is there.

In recent years, in order to overcome these problems in the pulverization method, a toner production method by a polymerization method has been proposed. For example, a toner is produced by a suspension polymerization method or an emulsion polymerization aggregation method. However, it is difficult to produce a toner using a polyester resin excellent in low-temperature fixability.
In order to solve this problem, a dry toner composed of particles formed by an extension reaction and / or a crosslinking reaction with an amine (B) in an aqueous medium of an isocyanate group-containing prepolymer (A) is known (patent). Reference 1).
Such a toner is excellent in relatively low-temperature fixability by using a polyester resin as a binder resin, but cannot satisfy the requirement for hot offset resistance only by adding a high molecular weight component to the binder resin. Therefore, it is necessary to contain a release agent in the toner.

In order to improve the offset resistance of the toner, it is desired that the release agent has a low melt viscosity and excellent separability from the resin. In general, examples of the release agent used in the toner include hydrocarbon waxes represented by carnauba wax, montan wax (see Patent Documents 2 to 5), polyethylene, polypropylene, paraffins, and the like (Patent Documents 6 to 6). 8) etc. are known.
Among these, hydrocarbon waxes are resistant to offset because they have a large polarity difference from polyester resin, excellent separation between the fixing member and image, low melt viscosity, and ooze out quickly from the toner to the fixing member. The effect of improving is great.
On the other hand, in a toner obtained by emulsifying or dispersing a liquid (toner material liquid) containing a material constituting the toner in an aqueous medium, a volume mode particle diameter of the dispersoid of the toner material liquid is obtained. It has been revealed that the composition of the base particles and the uniformity of the particle diameter are affected (see Patent Document 9).
At this time, the release agent contained in the toner material liquid has a great influence on the uniformity of the base particles. In addition, if the composition and particle size of the base particles are not uniform, variations in the chargeability, fluidity, and fixability of the toner increase, and image fogging due to uncharged toner and scattering of toner on non-image areas, Occurrence of background stains, adhesion of toner components to the developing unit, offset to the fixing member, and the like are likely to occur. For this reason, it becomes difficult to stably obtain a high-quality image. Therefore, it is desired to finely disperse the release agent.

However, the polarity difference between the organic solvent and the polyester resin and the hydrocarbon wax is large, and there is no functional group having affinity between the hydrocarbon wax and the polyester resin. It is very difficult to finely disperse. Furthermore, in order to improve dispersibility, a very long time is required for the dispersion process, so a great amount of energy is required. In addition, in the toner composition liquid, the release agent is likely to aggregate over time, which makes it difficult to produce toner having a certain quality over a long period of time.
In addition, since the polyester resin is highly soluble and easy to remove, an organic solvent having a relatively high polarity and a low boiling point is often used as the organic solvent. Among them, ester solvents such as ethyl acetate and ketone solvents such as methyl ethyl ketone are often used as main components. However, when such an organic solvent is used, the affinity between the organic solvent and the hydrocarbon wax tends to be further reduced, and therefore it is more difficult to finely disperse the hydrocarbon wax in the toner composition liquid. Become.

Furthermore, in the high-speed printing field, high image quality that is the same as the initial level is required even when a large amount of images are printed with a large image area. On the other hand, when used in an electrophotographic image forming apparatus that prints a large amount of wax with the contents proposed in the past, the hydrocarbon wax having high volatility causes contamination to various image forming apparatus members and transfer. It has been found that problems such as contamination of the medium itself occur.
For example, Patent Document 10 shows an improvement effect by specifying a heating loss at 220 ° C. for storage stability, carrier spent, and photoconductor filming, but does not satisfy the heating loss at this temperature. However, in the case of a toner production method using wax type or water-based granulation, the above problem may not occur. Rather, even when the heat loss characteristics are satisfied, it can be seen that the high-speed printing has insufficient component contamination, and that the transfer medium is not sufficiently separated during high-speed printing, and Even if the weight loss by heating was not satisfied, it was found that satisfying the scope of claims of the present application has an effect on member contamination.
On the other hand, when a high-melting point hydrocarbon wax is simply used, it is difficult to obtain the desired releasability, which reduces image quality such as occurrence of hot offset and decrease in gloss. Met.
Therefore, the actual situation is that the in-machine contamination and the desired fixing property cannot be secured by simply defining the melting point of the hydrocarbon wax.
Also, images for high-speed printing are mostly full-color images with a high image area ratio, and it is necessary to separate the heating medium and the transfer medium at high speed reliably in the fixing process. Ensuring moldability and in-flight contamination are the most important issues.

On the other hand, a toner using a synthetic ester wax as a release agent has also been proposed (Patent Document 11). Ester waxes synthesized from monocarboxylic acids with a certain number of carbon atoms and mono- or polyhydric alcohols exhibit sharp heat-melting behavior, so using them in toner improves blocking and offset resistance. It has been found that the volatility can be reduced. Moreover, it has high affinity with ester solvents such as ethyl acetate and ketone solvents such as methyl ethyl ketone, and it is possible to finely disperse the wax.
However, in the polymerized toner using polyester, there is a problem that the toner material and the release agent are compatible with each other, and the release property and the fixing property are deteriorated.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, a toner that is excellent in releasability and low-temperature fixability, has low in-machine contamination, and is easy to manufacture, as well as a developer, a developer-containing container, a process cartridge, an image forming method, and an image forming apparatus using the toner. The task is to do.

The features of the present invention, which is a means for solving the above problems, are listed below.
The toner of the present invention has a base particles toner material containing a binder resin and a releasing agent is prepared by a liquid which is dissolved or dispersed in an organic solvent, is emulsified or dispersed in water-based media A toner, wherein the binder resin contains a polyester resin, and the release agent is a melt obtained by heating and mixing a hydrocarbon wax with a synthetic ester wax at a weight ratio of 1/9 to 9/1. The hydrocarbon wax has a transparent melting point of 60 to 95 ° C, and the synthetic ester wax has a transparent melting point of 65 to 90 ° C and has a linear monoester and a branched structure. consists esters, when subjected to DSC measurement of the release agent, the glass transition temperature of the hydrocarbon wax during the second time heating the (Tg) Tg _1, T of the synthetic ester wax The Tg _2, when the Tg of the releasing agent was _{Tg 1 + 2, Tg 1>} Tg 1 + 2, and _{characterized} by having the relationship of _{Tg 2>} Tg _{1 +} 2.
Further, in the toner of the present invention, when DSC measurement of the release agent was performed, the glass transition temperature (Tg) of the hydrocarbon wax at the second temperature rise was Tg ₁ , and the Tg of the synthetic ester wax was Tg ₂ , where Tg _{1 + 2} is Tg _{1 + 2} , Tg ₁ −Tg _{1 + 2} > 0.5 and Tg ₂ −Tg _{1 + 2} > 1.0.
Further, in the toner of the present invention, the synthetic ester wax has a transparent melting point of 72 to 80 ° C. and is synthesized from a linear fatty acid and a monovalent higher alcohol. It contains a saturated ester synthesized from a fatty acid and a polyhydric alcohol.
The toner of the present invention, further, the hydrocarbon wax is you being a transparent mp 70 to 88 ° C..
Further, the toner of the present invention further contains, as the binder resin, a modified polyester containing at least an ester bond and a bond unit other than the ester bond, or a resin precursor capable of producing the modified polyester. It is characterized by.
The toner of the present invention further contains, as a resin precursor capable of producing the modified polyester, a compound having an active hydrogen group and a polyester having a functional group capable of reacting with the active hydrogen group of the compound. It is characterized by being.
The toner of the present invention, furthermore, the modified polyester is, it characterized in that it comprises at least an ester bond and a urea bond.

The developer of the present invention is a developer used for forming an image of a latent image in electrophotography, and includes the toner described above.
The developer-containing container of the present invention is a developer-containing container filled with toner used for forming an image of a latent image in electrophotography, and includes the toner described above.

  The process cartridge of the present invention has at least an electrostatic latent image carrier and developing means for developing a latent image formed on the electrostatic latent image carrier using toner to form a visible image. A process cartridge that is attachable to and detachable from an image forming apparatus main body, wherein the toner is the toner according to claim 1.

The image forming method of the present invention includes an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, and developing the electrostatic latent image with toner to form a visible image. An image forming method comprising at least a development step, a transfer step for transferring the visible image to a recording medium, and a fixing step for fixing the transfer image transferred to the recording medium, wherein the toner is any of the above It is the toner described in the above.
An image forming apparatus according to the present invention includes an electrostatic latent image carrier that carries an electrostatic latent image, an exposure device that forms an electrostatic latent image on the electrostatic latent image carrier, and a toner that is transferred to the electrostatic latent image. An image forming apparatus including at least a developing device that forms a visible image by developing, a transfer device that transfers the visible image to a recording medium, and a fixing device that fixes the transferred image transferred to the recording medium The toner is one of the toners described above.

  According to the present invention which is a means for solving the above problems, it is possible to provide a toner which is excellent in releasability and low-temperature fixability, has low in-machine contamination and can be easily produced, and a method for producing the toner. Further, according to the present invention, a developer having the toner, a developer-containing container, a process cartridge, and an image forming method can be provided.

It is a figure which shows an example of the image forming apparatus of this invention. It is a figure which shows the other example of the image forming apparatus of this invention. FIG. 3 is a diagram illustrating the tandem developing device of FIG. 2. It is a figure which shows an example of the process cartridge of this invention.

  The best mode for carrying out the present invention will be described below with reference to the drawings. Note that it is easy for a person skilled in the art to make other embodiments by changing or correcting the present invention within the scope of the claims, and these changes and modifications are included in the scope of the claims. The following description is an example of the best mode of the present invention, and does not limit the scope of the claims.

Next, the best mode for carrying out the present invention will be described with reference to the drawings.
The toner of the present invention is obtained by emulsifying or dispersing a liquid in which a toner material containing a binder resin and a release agent is dissolved or dispersed in an organic solvent (hereinafter referred to as “toner material liquid”) in an aqueous medium. In this case, the release agent is obtained by heating, melting and mixing a hydrocarbon wax to a synthetic ester wax. As a result, the wax can be finely dispersed in the toner material liquid, and high releasability, low-temperature fixability, and low volatility can be maintained.

In the present invention, the release agent contains a synthetic ester wax and a hydrocarbon wax. When DSC measurement of the release agent is performed, the glass transition temperature (Tg) of the hydrocarbon wax is Tg ₁ , the synthetic ester. when the Tg of the wax Tg _2, the Tg of the releasing agent and _{Tg 1 + 2,} the compatibility of the synthetic ester wax and hydrocarbon _{wax, Tg 1>} Tg 1 _{+ 2} and _Tg 2> shows the thermal properties of _{Tg 1 + 2} It is preferable that Tg ₁ −Tg _{1 + 2} > 0.5 and Tg ₂ −Tg _{1 + 2} > 1.0. When the thermal characteristics are not observed, the hydrocarbon wax and the ester wax are not compatible with each other, and there is a possibility that the releasability, the low-temperature fixability, and the in-machine contamination due to wax volatilization from the toner are deteriorated.

Here, the wax was extracted from the toner by the following method.
First, 30 g of toner is poured into 300 ml of ethyl acetate, stirred for 30 minutes at 35 ° C., and the resulting solution is filtered through a membrane filter having an opening of 0.2 μm to remove the resin component. Next, the hexane-soluble component is extracted from the obtained ethyl acetate-insoluble component with a Soxhlet extractor. Place the ethyl acetate insoluble matter in a cylindrical filter paper with an inner diameter of 24 mmφ, set in the extraction tube, put the flask part of a set with a condenser containing 300 ml of hexane in the mantle heater, reflux hexane at 70 ° C, Hexane from the cooling tube was dropped into the ethyl acetate insoluble matter, and the hexane soluble matter was extracted into the flask. After extraction for 10 hours, the hexane in the extract is distilled off under reduced pressure to extract the compatible wax.
Furthermore, this residue was dissolved in chloroform to prepare a sample for gel permeation chromatography (GPC) measurement, and injected into a GPC measurement apparatus (GPC / HLC-8120 manufactured by Tosoh Corporation). Place a fraction collector at the eluate outlet of GPC, collect the eluate at every predetermined count, collect the eluate corresponding to the part where the peak of the GPC chromatograph was obtained, and distill off chloroform from these. An eluate was obtained. Next, for the eluate, a 50 mg sample was dissolved in 5 ml of deuterated chloroform (chloroform-D1, manufactured by Merck & Co., Inc.), the solution was put into a 5 mm diameter NMR glass tube, and a nuclear magnetic resonance apparatus (JNM-ECX, JEOL Ltd.) The spectrum was obtained by integrating 256 times at a temperature of 25 ° C. The peaks of the obtained spectrum are assigned, and a signal derived from the ester group carbonyl (C═O bond) is observed near 160 ppm, a synthetic ester wax, and a signal not observed near 160 ppm is a hydrocarbon. It is obtained as a system wax. In this way, synthetic ester wax and hydrocarbon wax can be extracted from the toner.

  The glass transition temperature (Tg) was measured by the following method using a DSC system (differential scanning calorimeter) (“DSC-60”, manufactured by Shimadzu Corporation). First, about 5.0 mg of resin was put in an aluminum sample container, and the sample container was placed on a holder unit and set in an electric furnace. Subsequently, it heated from 20 degreeC to 150 degreeC with the temperature increase rate of 10 degree-C / min in nitrogen atmosphere. Thereafter, the sample is cooled from 150 ° C. to 0 ° C. at a rate of temperature decrease of 10 ° C./min, and further heated to 150 ° C. at a rate of temperature increase of 10 ° C./min. Thus, the DSC curve was measured. From the obtained DSC curve, using the analysis program in the DSC-60 system, the shoulder of the DSC curve at the second temperature increase was selected, and the glass transition temperature (Tg) of the resin was calculated.

In the present invention, the melting point of the hydrocarbon wax is preferably 60 to 95 ° C, more preferably 70 to 88 ° C, from the viewpoints of storage stability and volatility. When the melting point is lower than 60 ° C., the toner is likely to be blocked during storage, and the heat resistant storage stability may be lowered. In addition, the volatilization amount of the wax may increase, and the in-machine contamination may be deteriorated. When the melting point exceeds 100 ° C., the low-temperature fixability may be deteriorated. In addition, the affinity with the organic solvent is lowered, and the wax may not be finely dispersed. Here, the melting point is a transparent melting point, which refers to the temperature at which one end is crushed into a fine capillary, taken into a closed capillary tube, heated at a constant speed, and melted to become completely transparent. The value measured by the analytical test method (2.2.4.1-1996).
Examples of the hydrocarbon wax include polyolefin waxes such as paraffin wax, sazol wax, polyethylene wax, polypropylene wax, and microcrystalline wax, and two or more kinds may be used in combination.

In the present invention, the synthetic ester wax preferably has a transparent melting point of 60 to 90 ° C, more preferably 72 to 80 ° C. When the melting point is lower than 60 ° C., blocking tends to occur when the toner is stored, and the heat resistant storage stability may be lowered. In addition, the volatilization amount of the wax may increase and the in-machine contamination may deteriorate. When the melting point exceeds 90 ° C., the low-temperature fixability may be deteriorated.
The synthetic ester wax is obtained by dehydrating condensation of a linear monocarboxylic acid and a monohydric higher alcohol or polyhydric alcohol. Examples of linear fatty acids include myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid and the like.

Examples of monovalent higher alcohols include capryl alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, aratidyl alcohol, behenyl alcohol, lignoceryl alcohol, and the like.
Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1 , 6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tri Pentaerythritol, 1,2,4-butanetriol, 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxy Benzene, and the like.

The monoester synthesized from the above linear fatty acid and monohydric alcohol preferably has 30 to 50 carbon atoms from the viewpoint of compatibility with the hydrocarbon wax. Moreover, in the saturated ester synthesize | combined from a linear fatty acid and a polyhydric alcohol, it is preferable to use a C15 or more linear fatty acid from the same viewpoint. The synthetic ester wax is preferably composed of a monoester and a saturated ester from the viewpoint of fixability, releasability and storage stability.
In the present invention, the release agent is obtained by heating and melt-mixing a hydrocarbon wax at a weight ratio of 1/9 to 9/1 with respect to the synthetic ester, and more preferably 8/2 to 5/5. When the weight ratio of the hydrocarbon wax exceeds 5, the content of the hydrocarbon wax with respect to the release agent increases, and the volatilization amount of the wax from the toner may increase.

  In the present invention, the binder resin contains a polyester resin because good low-temperature fixability can be obtained, but more preferably contains an unmodified polyester resin (an unmodified polyester resin). In addition, the molecular weight of a polyester resin, a structural monomer, etc. can be suitably selected according to the objective. The binder resin may further contain a resin other than the polyester resin. Examples of resins other than polyester resins include homopolymers or copolymers such as styrene monomers, acrylic monomers, and methacrylic monomers, polyol resins, phenol resins, silicone resins, polyurethane resins, and polyamides. Resins, furan resins, epoxy resins, xylene resins, terpene resins, coumarone indene resins, polycarbonate resins, petroleum resins and the like may be mentioned, and two or more may be used in combination.

  The polyester resin is obtained by dehydration condensation of a polyhydric alcohol and a polycarboxylic acid. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, bisphenol A And divalent alcohols obtained by adding cyclic ethers such as ethylene oxide and propylene oxide to the above. In order to crosslink the polyester resin, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene, etc. It is preferable to use a trivalent or higher alcohol together.

  Examples of the polyvalent carboxylic acid include benzene dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid or anhydrides thereof, alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid or anhydrides thereof, and maleic acid. Unsaturated dibasic acids such as acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid and mesaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride, etc. Basic acid anhydride, trimet acid, pyrometic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxylic acid -2-methyl-2-methylenecarboxypropane, tetrakis (methylenecarboxy) methane, 1,2,7,8-octanetetracarboxylic acid, empol trimer acid, anhydrides thereof, partial lower alkyl esters and the like. .

  The polyester resin preferably has at least one peak in the molecular weight region of 3000 to 50000 in the molecular weight distribution of the component soluble in THF in terms of toner fixing property and offset resistance, and has a molecular weight of 5000 to 20000. More preferably, the region has at least one peak. Furthermore, the component of the polyester resin soluble in THF preferably has a content of a component having a molecular weight of 100000 or less of 60 to 100% by weight. The molecular weight distribution of the polyester resin is measured by gel permeation chromatography (GPC) using THF as a solvent.

In the present invention, the binder resin preferably contains a polyester resin having a functional group capable of reacting with an active hydrogen group (hereinafter referred to as a polyester prepolymer). As a polyester prepolymer, what has an isocyanate group can be used. Such a polyester prepolymer can be obtained, for example, by reacting a polyester resin having an active hydrogen group with polyisocyanate.
Examples of the active hydrogen group possessed by the polyester resin include hydroxyl groups (alcoholic hydroxyl groups, phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like, with alcoholic hydroxyl groups being preferred.
The polyester resin and the polyester prepolymer are preferably at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Therefore, it is preferable that the compositions of the polyester resin and the polyester prepolymer are similar.

Examples of the polyisocyanate include aliphatic polyisocyanates (for example, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethyl caproate); alicyclic polyisocyanates (for example, isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); Aromatic diisocyanates (for example, tolylene diisocyanate, diphenylmethane diisocyanate, etc.); aromatic aliphatic diisocyanates (for example, α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates You may use together. Moreover, as polyisocyanate, you may use what was blocked with a phenol derivative, oxime, caprolactam, etc.
The equivalent ratio of the isocyanate group to the hydroxyl group when the polyester resin having a hydroxyl group and the polyisocyanate are reacted is usually 1 to 5, preferably 1.2 to 4, and more preferably 1.5 to 2.5. If this equivalent ratio exceeds 5, the low-temperature fixability may decrease. If it is less than 1, the urea content in the modified polyester resin obtained by the crosslinking and / or elongation reaction described later decreases, and resistance to hot offset May decrease.

The content of the component derived from polyisocyanate 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 this content is less than 0.5% by weight, the hot offset resistance is lowered, and it may be disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. May decrease.
Moreover, the number of isocyanate groups (average value) per molecule of the polyester prepolymer is usually 1 or more, preferably 1.5 to 3, more preferably 1.8 to 2.5. When the number of isocyanate groups is less than 1, the molecular weight of the modified polyester resin after crosslinking and / or elongation is lowered, and the hot offset resistance may be lowered.
The weight ratio of the polyester resin to the polyester prepolymer is usually 5/95 to 50/50, more preferably 10/90 to 30/70, and particularly preferably 12/88 to 25/75. It is preferably 5 to 30% by weight. If this content is less than 5/95, the hot offset resistance is lowered, and it may be disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. If it exceeds 50/50, the low-temperature fixability is inferior. Sometimes.

In the present invention, it is preferable to react a polyester prepolymer with a compound having an active hydrogen group (hereinafter referred to as a crosslinking agent and / or an elongation agent) in an aqueous medium (hereinafter referred to as a crosslinking and / or elongation reaction). .
As the cross-linking agent and / or extender, amines can be used. Examples of the amines include divalent amines, trivalent or higher amines, amino alcohols, amino mercaptans, and amino acids. Examples of the divalent amine include aromatic diamines (eg, phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane); alicyclic diamines (eg, 4,4′-diamino-3,3′-dimethyl). Dicyclohexylmethane, diaminocyclohexane, isophoronediamine, etc.); aliphatic diamines (ethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.) and the like. Examples of the trivalent or higher amine include diethylenetriamine and triethylenetetraamine. Examples of amino alcohols include ethanolamine and hydroxyethylaniline. Examples of amino mercaptans include aminoethyl mercaptan and aminopropyl mercaptan. Examples of amino acids include aminopropionic acid and aminocaproic acid. Moreover, as amines, you may use what blocked the amino group (For example, the ketimine compound blocked with ketones (For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), an oxazoline compound). Among these, a divalent amine or a mixture of a divalent amine and a small amount of a trivalent or higher amine is preferable.

Furthermore, when the crosslinking and / or extension reaction is performed, the molecular weight of the modified polyester resin can be adjusted using a terminator as necessary. Stopping agents include monoamines (eg, diethylamine, dibutylamine, butylamine, laurylamine, etc.) and ketimines blocked with monoamines that block the amino group (eg, ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.)) Compound, oxazoline compound) and the like.
The equivalent ratio of the amino group of the amine to the isocyanate group of the polyester prepolymer in the crosslinking and / or elongation reaction is preferably 1/3 to 3, more preferably 1/2 to 2, and more preferably 2/3. -1.5 is particularly preferred. When this equivalent ratio exceeds 3 or less than 1/3, the molecular weight of the modified polyester resin may decrease, and the hot offset resistance may decrease.

The binder resin preferably has a glass transition temperature (Tg) of 35 to 80 ° C., and more preferably 40 to 75 ° C., from the viewpoint of toner storage stability. When Tg is less than 35 ° C., the toner may be easily deteriorated in a high temperature atmosphere, and offset may be easily generated during fixing. On the other hand, when Tg exceeds 80 ° C., fixability may be deteriorated.
In the present invention, the content of the release agent in the base particles is preferably 1 to 20% by weight, and more preferably 3 to 10% by weight. If the content is less than 1% by weight, the effect of the release agent cannot be sufficiently obtained, and the offset resistance may be lowered. If the content exceeds 20% by weight, the fluidity of the toner may be lowered or the development may be performed. It may stick to the device. The content of the release agent is determined by DSC endothermic peak measurement, similarly to the melting point. Specifically, first, DSC measurement of a predetermined weight of the release agent is performed in advance to determine the heat of fusion Qw [J / mg] per unit weight of the release agent. Next, DSC measurement of a predetermined weight of the base particles is performed in the same manner, and from the area of the endothermic peak of the release agent, the heat of fusion Qt [J / mg] of the release agent contained in the base particles of the unit weight is calculated. Ask. Thereby, the content W (x) of the release agent in the base particles can be obtained from W (x) = Qt / Qw × 100 [wt%].

In the present invention, the toner material may further contain a colorant, a charge control agent and the like.
The colorant can be appropriately selected from known dyes and pigments according to the purpose. 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,
Anthrazin Yellow BGL, Isoindolinone Yellow, Bengala, Red Plum, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimony Zhu, Permanent Red 4R, Para Red, Faucet Red, Parachloro Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine 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, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Maroon light, bon maroon medium, eosin rake, rhodamine rake B, rhodamine rake Y, alizarin rake, thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone red, polyazo red, chrome vermilion, 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, anthrac Violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment green B, naphthol green B, green gold, acid green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, lithobon, etc. 2 or more may be used in combination.

The content of the colorant in the toner material is preferably 1 to 15% by weight, and more preferably 3 to 10% by weight. If the content is less than 1% by weight, the coloring power of the toner may be reduced. If the content exceeds 15% by weight, poor dispersion of the pigment in the toner will occur. The characteristics may be degraded.
The colorant may be used as a master batch combined with a resin. Examples of such resins include polyesters, styrene or substituted polymers thereof, styrene copolymers, polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, and epoxy resins. , Epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax 2 or more types may be used in combination.

  Examples of the polymer of styrene or a substituted product thereof include polystyrene, poly (p-chlorostyrene), and polyvinyl toluene. Examples of the styrene copolymer include styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer. Copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-methacrylic copolymer Acid butyl copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene- Acrylonitrile-indene copolymer, steel Down - maleic acid copolymer, styrene - maleic acid ester copolymers and the like.

  The master batch can be manufactured by applying a high shear force and mixing or kneading the resin and the colorant. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. The flushing method is a method in which an aqueous paste containing water of a colorant is mixed or kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove water and the organic solvent. For mixing or kneading, for example, a high shear dispersion device such as a three-roll mill can be used.

Examples of the charge control agent include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts). ), Alkylamide, simple substance or compound of phosphorus, simple substance or compound of tungsten, fluorine-based surfactant, metal salt of salicylic acid, metal salt of salicylic acid derivative, and the like.
Commercially available products may be used as the charge control agent. For example, bontron 03 of nigrosine dye, bontron P-51 of quaternary ammonium salt, bontron S-34 of metal-containing azo dye, oxynaphthoic acid metal complex E-82, E-84 of salicylic acid metal complex, E-89 of phenol-based condensate (above, manufactured by Orient Chemical Co., Ltd.), TP-302, TP-415 of quaternary ammonium salt molybdenum complex (above, Hodogaya) Chemical Industry Co., Ltd.) Quaternary ammonium salt copy charge PSY VP2038, Triphenylmethane derivative copy blue PR, Quaternary ammonium salt copy charge NEG VP2036, Copy charge NX VP434 (above, Hoechst), LRA-901 LR-147 which is a boron complex (manufactured by Nippon Carlit), copper phthalo Cyanine, perylene, quinacridone, azo pigments, a sulfonic acid group, a carboxyl group, such as polymer compounds having a functional group such as quaternary ammonium bases.

  The content of the charge control agent in the toner composition is, for example, preferably 0.1 to 10% by weight, and more preferably 0.2 to 5% by weight with respect to the binder resin. If the content is less than 0.1% by weight, the charge controllability may not be obtained. If the content exceeds 10% by weight, the chargeability of the toner becomes too large and the effect of the main charge control agent is reduced. As a result, the electrostatic attraction force with the developing roller increases, which may lead to a decrease in toner fluidity and a decrease in image density.

The toner of the present invention may further include inorganic fine particles, a cleaning property improver, a magnetic material, and the like.
The inorganic fine particles are used as an external additive for imparting fluidity, developability, chargeability and the like to the toner. Examples of inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth, Examples thereof include chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.
The inorganic fine particles preferably have a primary particle size of 5 nm to 2 μm, more preferably 5 to 500 nm.
The content of the inorganic fine particles in the toner is preferably 0.01 to 5.0% by weight, and more preferably 0.01 to 2.0% by weight.

The inorganic fine particles are preferably surface-treated with a fluidity improver. As a result, the hydrophobicity of the inorganic fine particles is improved, and a decrease in fluidity and chargeability can be suppressed even under high humidity. Examples of fluidity improvers include, for example, silane coupling agents, silylating agents, silane coupling agents having a fluorinated alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils, and the like. Is mentioned. Silica and titanium oxide are preferably surface-treated with a fluidity improver and used as hydrophobic silica and hydrophobic titanium oxide.
The cleaning property improver is used to facilitate removal of toner remaining on the photoreceptor and the primary transfer medium after transfer. Examples of the cleaning improver include fatty acid metal salts such as zinc stearate and calcium stearate, polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and preferably have a volume average particle size of 0.01 to 1 μm.
Examples of the magnetic material include iron powder, magnetite, and ferrite. The magnetic material is preferably white from the viewpoint of the color tone of the toner.

In the present invention, the base particles preferably have a volume average particle diameter (Dv) of 3 to 6 μm, and the ratio of Dv to the number average particle diameter (Dn) (Dv / Dn) is 1.05 to 1.25. Preferably there is. Thereby, it is excellent in all of heat resistant storage stability, low-temperature fixability and hot offset resistance, and particularly when used in a full-color copying machine or the like, it is excellent in image glossiness. In addition, when used in a two-component developer, the toner particle size does not vary even if the toner balance (toner consumption and toner replenishment to compensate for the consumed toner) is performed over a long period of time. Less. As a result, good and stable developability can be obtained even with long-term stirring in the developing device.
Conventionally, for example, a toner having a larger particle diameter is consumed more rapidly, and as a result, after a long-time image forming operation, a phenomenon in which the content of toner having a smaller particle diameter increases may occur. In addition, when used as a one-component developer, even if the balance of the toner is performed, fluctuations in the particle size of the toner are reduced, toner filming on the developing roller, and toner thinning Toner adhesion to a member such as a blade can be suppressed. As a result, good and stable developability and images can be obtained even in the long-term use (stirring) of the developing device.

In general, it is said that the smaller the particle size of the toner, the more advantageous it is for obtaining a high-resolution and high-quality image, but it is disadvantageous for transferability and cleaning property. When a toner having base particles having a Dv of less than 3 μm is used as a two-component developer, the toner may be fused to the surface of the carrier during long-term agitation in the developing device, and the charging ability of the carrier may be reduced. Further, when used as a one-component developer, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner may easily occur.
On the other hand, when Dv of the base particles exceeds 6 μm and Dv / Dn exceeds 1.25, it becomes difficult to obtain a high-resolution and high-quality image, and the balance of toner in the developer is reduced. In many cases, the variation in the particle size of the toner increases.

  In the present invention, Dv and Dn were measured with a particle size analyzer Multisizer III (manufactured by Beckman Coulter, Inc.) with an aperture diameter of 100 μm, and analyzed with analysis software Beckman Coulter Multisizer 3 Version 3.51. Specifically, 0.5 ml of a 10 wt% aqueous solution of alkylbenzene sulfonate Neogen SC-A (Daiichi Kogyo Seiyaku Co., Ltd.) and 0.5 g of base particles were added to a glass 100 ml beaker, and the mixture was stirred with a micropartel. Thereafter, 80 ml of ion exchange water is added. The obtained dispersion was subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser W-113MK-II (manufactured by Honda Electronics Co., Ltd.). Further, the sample dispersion subjected to the dispersion treatment is measured using Multisizer III and a measurement solution Isoton III (manufactured by Beckman Coulter). In the measurement, the sample dispersion was dropped so that the concentration indicated by Multisizer III would be 8 ± 2%. In this measurement method, it is important that the concentration is 8 ± 2% from the viewpoint of measurement reproducibility of the particle diameter.

The toner of the present invention has various physical properties such as shape and size, but preferably has the following penetration, minimum fixing temperature, non-offset temperature, and the like.
The toner of the present invention preferably has a penetration of 15 mm or more, more preferably 20 to 30 mm. When the penetration is less than 15 mm, the heat resistant storage stability may be lowered. The penetration is measured by a penetration test (JIS K2235-1991). Specifically, a 50 ml glass container is filled with toner, left in a thermostat at 50 ° C. for 20 hours, cooled to room temperature, and a penetration test is performed. In addition, heat resistance preservability is excellent, so that the value of penetration is large.
Further, from the viewpoint of low-temperature fixability, it is preferable that the minimum fixing temperature is less than 150 ° C. and the temperature at which no offset occurs is 200 ° C. or more. The minimum fixing temperature means the temperature of the fixing roll at which the residual ratio of the image density becomes 70% or more after a copy test is performed using an image forming apparatus and the obtained fixed image is rubbed with a pad. Also, the offset non-occurrence temperature is adjusted, for example, using an image forming apparatus so that solid images of single colors of yellow, magenta, cyan and black and single colors of red, blue and green are developed as intermediate colors. Then, the temperature at which no offset occurs is measured by changing the temperature of the fixing belt.
The toner of the present invention is not particularly limited, but can be at least one of black toner, cyan toner, magenta toner, and yellow toner by appropriately selecting the type of colorant.

The method for producing a toner of the present invention includes at least a step of dissolving or dispersing a toner material in an organic solvent and a step of emulsifying or dispersing the obtained toner material liquid in an aqueous medium. The following step (1) It is preferable to consist of ~ (6).
(1) Preparation of toner material liquid A toner material liquid is prepared by dissolving or dispersing a toner material in an organic solvent. The organic solvent is not particularly limited but preferably has a boiling point of less than 150 ° C. because it is easy to remove. For example, 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 may be used in combination. Among these, because of excellent solubility of the polyester resin, the organic solvent is preferably a solubility parameter is ^{8~9.8cal 1/2 · m -3/2, 8.5~9.5cal 1/2} · m ^−3/2 is more preferable. Furthermore, since the interaction with the modifying group of the release agent is large and the crystal growth of the release agent can be effectively suppressed, ester solvents and ketone solvents are preferable, and removal is easy. Therefore, ethyl acetate and methyl ethyl ketone are particularly preferable.
The amount of the organic solvent used can be appropriately selected according to the purpose. For example, it is preferably 40 to 300 parts by weight, more preferably 60 to 140 parts by weight, based on 100 parts by weight of the toner material. -120 parts by weight are particularly preferred.
In the present invention, when the toner material liquid is prepared, it is preferable that the binder resin and the release agent are heated and dissolved in an organic solvent, and then the heated and dissolved liquid is cooled. Thereby, a mold release agent can be disperse | distributed further favorably.

(2) Preparation of aqueous medium The aqueous medium can be prepared, for example, by dispersing resin fine particles in an aqueous solvent. The addition amount of the resin fine particles in the aqueous solvent can be appropriately selected according to the purpose, but is preferably 0.5 to 10% by weight.
Examples of the aqueous solvent include water, a solvent miscible with water, and the like, and two or more of them may be used in combination. Examples of the water-miscible solvent include alcohol (eg, methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves, lower ketones (eg, acetone, methyl ethyl ketone, etc.) and the like.
The resin fine particle material is not particularly limited as long as it is a resin that can be dispersed in an aqueous solvent. For example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, A thermoplastic resin or a thermosetting resin such as a phenol resin, a melamine resin, a urea resin, an aniline resin, an ionomer resin, or a polycarbonate resin may be mentioned, and two or more kinds may be used in combination. Among these, vinyl resin, polyurethane resin, epoxy resin, and polyester resin are preferable because an aqueous dispersion of fine spherical resin particles is easily obtained. The vinyl resin is a resin obtained by homopolymerizing or copolymerizing a vinyl monomer. For example, a styrene- (meth) acrylic acid ester copolymer, a styrene-butadiene copolymer, (meth) acrylic acid- An acrylic ester copolymer, a styrene-acrylonitrile copolymer, a styrene-maleic anhydride copolymer, a styrene- (meth) acrylic acid copolymer, and the like can be given.
In addition, resin fine particles can be formed using a monomer having two or more unsaturated groups. Examples of the monomer having two or more unsaturated groups include sodium salt of sulfate ester of methacrylic acid ethylene oxide adduct, divinylbenzene, 1,6-hexanediol diacrylate, and the like.

The resin fine particles can be formed using a known polymerization method, but it is preferably obtained as an aqueous dispersion of resin fine particles. Examples of the method for preparing an aqueous dispersion of resin fine particles include the methods shown in the following (a) to (h).
(A) A method in which an aqueous dispersion of resin fine particles is directly prepared from a vinyl monomer as a starting material by any one of a suspension polymerization method, an emulsion polymerization method, a seed polymerization method and a dispersion polymerization method.
(B) After dispersing a precursor of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin (monomer, oligomer, etc.) or a solvent solution thereof in an aqueous medium in an aqueous medium, A method of preparing an aqueous dispersion of resin fine particles by heating or adding a curing agent to cure.
(C) Polyaddition or condensation resin precursors (monomers, oligomers, etc.) such as polyester resins, polyurethane resins, and epoxy resins, or solvent solutions thereof (preferably liquids, which may be liquefied by heating). A method for preparing an aqueous dispersion of resin fine particles by dissolving a suitable emulsifier in the mixture and then adding water to effect phase inversion emulsification.
(D) A resin synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is pulverized and classified using a mechanical rotary type or jet type fine pulverizer. A method of preparing an aqueous dispersion of resin fine particles by obtaining resin fine particles and then dispersing in water in the presence of an appropriate dispersant.
(E) Fine resin particles are formed by spraying a resin solution in which a resin synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is dissolved in a solvent. Then, resin fine particles are dispersed in water in the presence of a suitable dispersant to prepare an aqueous dispersion of resin fine particles.
(F) A poor solvent is added to a resin solution prepared by previously dissolving a resin synthesized by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent, or heated to a solvent in advance. By cooling the dissolved resin solution, the resin fine particles are precipitated, the solvent is removed to form the resin fine particles, and then the resin fine particles are dispersed in water in the presence of an appropriate dispersant to disperse the resin fine particles in water. A method for preparing a liquid.
(G) A resin solution obtained by dissolving a resin previously synthesized by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent in the presence of an appropriate dispersant. A method of preparing an aqueous dispersion of resin fine particles by dispersing in a solvent and then removing the solvent by heating, decompression or the like.
(H) A suitable emulsifier is dissolved in a resin solution prepared by previously dissolving a resin synthesized by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent, and then water To prepare an aqueous dispersion of resin fine particles by phase inversion emulsification.

In addition, the aqueous medium contains a dispersant as necessary from the viewpoint of stabilizing the oil droplets and obtaining a desired shape while sharpening the particle size distribution when emulsifying or dispersing the toner material liquid. It is preferable. Examples of the dispersant include surfactants, sparingly water-soluble inorganic compound dispersants, polymeric protective colloids, and the like, and two or more of them may be used in combination. Among these, surfactants such as an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant are preferable.
Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters and the like, and those having a fluoroalkyl group are preferable. Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonyl glutamate, 3- [ω-fluoroalkyl (6 carbon atoms). -11) Oxy] -1-alkyl (carbon number 3-4) sodium sulfonate, 3- [ω-fluoroalkanoyl (carbon number 6-8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (Carbon number 11-20) carboxylic acid or its metal salt, perfluoroalkyl carboxylic acid (carbon number 7-13) or its metal salt, perfluoroalkyl (carbon number 4-12) sulfonic acid or its metal salt, perfluoro Octanesulfonic acid diethanolamide, N-propyl-N- (2-hydroxyethyl) par -Fluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number 6-6) 16) Ethyl phosphate and the like. Moreover, as a commercial item of the anionic surfactant which has a fluoroalkyl group, for example, Surflon S-111, S-112, S-113 (above, Asahi Glass Co., Ltd.); Fluorad FC-93, FC-95, FC-98, FC-129 (above, manufactured by Sumitomo 3M); Unidyne DS-101, DS-102 (above, manufactured by Daikin Industries); Megafac F-110, F-120, F-113, F-191 F-812, F-833 (manufactured by Dainippon Ink & Chemicals, Inc.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (Tochem Products) Product); tergent F-100, F150 (manufactured by Neos) and the like.

Examples of the cationic surfactant include amine salt type surfactants and quaternary ammonium salt type surfactants. Examples of amine salt type surfactants include alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like. Examples of the quaternary ammonium salt type surfactant include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, and benzethonium chloride. Among them, aliphatic primary, secondary or tertiary amino acids having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (carbon number 6 to 10) sulfonamidopropyltrimethylammonium salt, benzalkonium salts Benzethonium chloride, pyridinium salt, imidazolinium salt and the like are preferable. Commercially available cationic surfactants include, for example, Surflon S-121 (manufactured by Asahi Glass Co., Ltd.); Florard FC-135 (manufactured by Sumitomo 3M Co.); 150, F-824 (manufactured by Dainippon Ink & Chemicals, Inc.); Xtop EF-132 (manufactured by Tochem Products); and Ftergent F-300 (manufactured by Neos).
Examples of nonionic surfactants include fatty acid amide derivatives and polyhydric alcohol derivatives.
Examples of the amphoteric surfactant include alanine, dodecylbis (aminoethyl) glycine, bis (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine and the like.

Examples of the hardly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.
Examples of the polymeric protective colloid include acid monomers, (meth) acrylic monomers having a hydroxyl group, ethers of vinyl alcohol, esters of compounds having a vinyl alcohol and a carboxyl group, monomers having an amide bond, monomers having an amide bond Homopolymers or copolymers such as methylolates, acid chloride monomers, monomers having nitrogen atoms or heterocycles containing nitrogen atoms, polyoxyethylene resins, celluloses and the like.

Examples of the acid monomer include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and the like.
Examples of the (meth) acrylic monomer having a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, Γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N-methylolacrylamide, N-methylol methacrylamide etc. are mentioned.
Examples of vinyl alcohol ethers include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like.
Examples of the ester of the compound having vinyl alcohol and a carboxyl group include vinyl acetate, vinyl propionate, vinyl butyrate and the like.
Examples of the monomer having an amide bond include acrylamide, methacrylamide, diacetone acrylamide acid and the like.
Examples of the acid chloride monomer include acrylic acid chloride and methacrylic acid chloride.
Examples of the monomer having a nitrogen atom or a heterocyclic ring containing a nitrogen atom include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethyleneimine.

Examples of the polyoxyethylene-based resin include polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples thereof include oxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester.
Examples of celluloses include methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and the like.
When preparing an aqueous dispersion of resin fine particles, a dispersion stabilizer can be used as necessary. Examples of the dispersion stabilizer include acids such as calcium phosphate salts and alkali-soluble compounds.
When the binder resin contains a polyester prepolymer, the aqueous medium can also contain a catalyst for urea reaction such as dibutyltin laurate and dioctyltin laurate, and urethane reaction.

(3) Preparation of Emulsified Slurry The emulsified slurry is prepared by emulsifying or dispersing the toner material liquid in an aqueous medium, but it is preferable to emulsify or disperse while stirring. As an apparatus for emulsifying or dispersing, for example, a homogenizer (manufactured by IKA), a polytron (manufactured by Kinematica), a batch emulsifier such as a TK auto homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), Ebara Milder (Kashihara Seisakusho) ), TK Philmix, TK Pipeline Homo Mixer (above, made by Special Machine Industries Co., Ltd.), Colloid Mill (made by Shinko Pantech Co., Ltd.), Thrasher, Trigonal Wet Fine Crusher (above, made by Mitsui Miike Chemical Co., Ltd.) , Continuous emulsifiers such as Capitolon (manufactured by Eurotech), fine flow mill (manufactured by Taiheiyo Kiko), microfluidizer (manufactured by Mizuho Industries), nanomizer (manufactured by Nanomizer), APV Gaurin (manufactured by Gaurin), etc. Vibration of membrane emulsifiers such as high-pressure emulsifiers, membrane emulsifiers (made by Chilling Industries Co., Ltd.), and vibro mixers (made by Chilling Industries Co., Ltd.) Emulsifier, ultrasonic emulsifier such as an ultrasonic homogenizer (manufactured by Branson Co., Ltd.). Among these, APV Gaurin, homogenizer, TK auto homomixer, Ebara milder, TK fillmix, and TK pipeline homomixer are preferable from the viewpoint of uniform particle size.

(4) Removal of organic solvent When removing the organic solvent from the emulsified slurry, a method of evaporating and removing the organic solvent in the emulsified dispersion by gradually raising the temperature of the entire reaction system, and the emulsified dispersion in a dry atmosphere Examples thereof include a method of spraying in to remove the organic solvent and evaporate and remove the aqueous solvent.

(5) Washing, drying, classification, etc. When the organic solvent is removed from the emulsified slurry, base particles are formed. The base particles can be washed, dried, etc., and further classified if desired. For example, classification may be performed by removing fine particle components by cyclone, decanter, centrifugation, or the like in an aqueous medium, or the base particles after drying may be classified.
In addition, when an acid such as calcium phosphate salt or an alkali-soluble compound is used as the dispersion stabilizer, the dispersion stabilizer is dissolved with an acid such as hydrochloric acid, and then dispersed from the base particles by a method such as washing with water. Stabilizer can be removed.

(6) External addition of inorganic fine particles, etc. The base particles are mixed with inorganic fine particles such as silica and titanium oxide, if necessary, and further applied with a mechanical impact force, whereby inorganic fine particles from the surface of the base particles are applied. Etc. can be suppressed. As a method of applying a mechanical impact force, for example, a method of applying an impact force to particles using a blade rotating at high speed, a particle in which particles are injected into a high-speed air stream and accelerated to form particles or a composite particle And a method in which an impact force is applied by colliding with a suitable collision plate. As a device for applying a mechanical impact force, for example, an ong mill (manufactured by Hosokawa Micron Co., Ltd.), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) and a pulverization air pressure reducing device, a hybridization system ( Nara Machinery Co., Ltd.), Kryptron System (Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.

The toner of the present invention has various properties such as fluidity and fixability, and can achieve both excellent low-temperature fixability and heat-resistant storage stability. Therefore, the toner of the present invention can be used in various fields, and is particularly preferably used for image formation by electrophotography.
The developer of the present invention has the toner of the present invention, but may further have a component such as a carrier, and may be used as a one-component developer composed of toner, a two-component developer composed of toner and carrier, or the like. However, it is preferable to use a two-component developer in the high-speed printer and the like corresponding to the recent improvement in information processing speed from the viewpoint of improving the service life. Such a developer can be used in various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method.
When the developer of the present invention is used as a one-component developer, there is little fluctuation in the particle size of the toner even if the balance of the toner is performed, and the blade for filming the toner on the developing roller and thinning the toner The toner can be prevented from being fused to a member such as the above, and good and stable developability can be obtained even when the developing device is used (stirred) for a long time.

In addition, when the developer of the present invention is used as a two-component developer, even if the toner balance for a long period of time is performed, there is little fluctuation in the particle size of the toner, and it is good and stable even with long-term stirring in the developing device. Developability is obtained.
The content of the carrier in the two-component developer is preferably 90 to 98% by weight, and more preferably 93 to 97% by weight.
The carrier is not particularly limited, but preferably has a core material and a resin layer covering the core material.
Examples of the core material include 50 to 90 emu / g manganese-strontium (Mn—Sr) -based material, manganese-magnesium (Mn—Mg) -based material, and two or more of them may be used in combination. In terms of securing image density, it is preferable to use a highly magnetized material such as iron powder (100 emu / g or more) or magnetite (75 to 120 emu / g) as the core material. In addition, a copper-zinc (Cu-Zn) system (30 to 80 emu / g) is used as a core material in that it can weaken the hitting of the photoconductor in which the toner is in a spiked state, and is advantageous in improving the image quality. It is preferable to use a weakly magnetized material such as

The core material preferably has a volume average particle size of 10 to 150 μm, more preferably 20 to 80 μm. When the volume average particle size is less than 10 μm, the fine particle increases in the particle size distribution of the carrier, so that the magnetization per particle may decrease and carrier scattering may occur. On the other hand, if the volume average particle diameter exceeds 150 μm, the specific surface area of the carrier may be reduced, and toner scattering may occur. As a result, the reproducibility of the solid portion may be deteriorated particularly in a full color with many solid portions.
Examples of the material of the resin layer include amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, polyester resins, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoro Ethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, terpolymer of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomer Examples thereof include fluoroterpolymers such as polymers, silicone resins, and the like, and two or more of them may be used in combination.
Examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, and polyvinyl butyral. Examples of polystyrene resins include polystyrene and styrene-acrylic copolymers. Examples of the halogenated olefin resin include polyvinyl chloride. Examples of the polyester-based resin include polyethylene terephthalate and polybutylene terephthalate.

Moreover, a resin layer may contain conductive powder etc. as needed. Examples of the conductive powder material include metals, carbon black, titanium oxide, tin oxide, and zinc oxide. The conductive powder preferably has an average particle size of 1 μm or less. When the average particle size exceeds 1 μm, it may be difficult to control the electric resistance.
The resin layer is formed, for example, by preparing a coating solution by dissolving a silicone resin or the like in a solvent, and then applying the coating solution to the surface of the core material by a known coating method, followed by drying and baking. Can do. Examples of the application method include a dipping method, a spray method, and a brush coating method. Examples of the solvent include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, celsol butyl acetate and the like. Furthermore, the baking method may be either an external heating method or an internal heating method, for example, a method using a fixed electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, or the like, or using a microwave. Methods and the like.
The content of the resin layer in the carrier is preferably 0.01 to 5.0% by weight. If the content is less than 0.01% by weight, a uniform resin layer may not be formed on the surface of the core material. If the content exceeds 5.0% by weight, the resin layer becomes too thick and the carriers are formed. Particles may be generated and a uniform carrier may not be obtained.

The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method.
The developer-containing container of the present invention contains the toner of the present invention and the developer containing the toner. However, the container is not particularly limited and can be appropriately selected from known ones. The thing which has a main body and a cap etc. are mentioned.
In addition, the size, shape, structure, material, etc. of the container body are not particularly limited, but the shape is preferably cylindrical, etc., spiral irregularities are formed on the inner peripheral surface, and by rotating, It is particularly preferable that the developer as the contents can move to the discharge port side, and that some or all of the spiral irregularities have a bellows function. Furthermore, the material is not particularly limited, but is preferably one having good dimensional accuracy. For example, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, polyacrylic acid, polycarbonate resin, ABS resin, Examples thereof include resin materials such as polyacetal resin.
Since the developer-containing container is easy to store and transport and has excellent handling properties, it can be detachably attached to a process cartridge, an image forming apparatus, etc., which will be described later, and used for replenishing the developer.

The image forming method of the present invention preferably has at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, more preferably a cleaning step. You may have a process, a recycling process, a control process, etc.
The image forming apparatus of the present invention preferably includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing device, and further includes a cleaning device. Preferably, it may have, for example, a static elimination means, a recycling means, a control means, etc. as necessary.
The image forming method of the present invention can be carried out using the image forming apparatus of the present invention, the electrostatic latent image forming step using an electrostatic latent image forming unit, and the developing step using a developing unit. The transfer step can be performed using a transfer unit, the fixing step can be performed using a fixing unit, and the other steps can be performed using other units.

The electrostatic latent image forming step is a step of forming an electrostatic latent image on an electrostatic latent image carrier such as a photoconductive insulator or a photoconductor. The material, shape, structure, size and the like of the electrostatic latent image carrier are not particularly limited and can be appropriately selected from known ones, but the shape is preferably a drum shape. Examples of the photoreceptor include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine. Among these, an amorphous silicon photoconductor is preferable because of its long life.
The electrostatic latent image is formed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then exposing it like an image, and can be formed using electrostatic latent image forming means. The electrostatic latent image forming means includes, for example, a charging device that applies a voltage to the surface of the electrostatic latent image carrier and uniformly charges it, and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Have at least.

The charging device as the charging means is not particularly limited. For example, a known contact charging system including a conductive or semiconductive roll, brush, film, rubber blade, or corona discharge such as corotron or scorotron is used. A non-contact charging method or the like can be used.
The exposure device as the exposure means is not particularly limited as long as it can be exposed like an image to be formed on the surface of the electrostatic latent image carrier charged by the charging device. For example, a copying optical system, a rod lens array Various exposure apparatuses such as an optical system, a laser optical system, and a liquid crystal shutter optical system can be used. In addition, you may employ | adopt the light back system which performs imagewise exposure from the back surface side of an electrostatic latent image carrier.

  The developing step is a step of developing the electrostatic latent image with the developer of the present invention to form a toner image, and the visible image can be formed using a developing device as a developing unit. The developing unit is not particularly limited as long as it can be developed with the developer of the present invention. For example, the developing device can store the developer of the present invention and can apply toner to the electrostatic latent image in a contact or non-contact manner. A developing device equipped with the developer-containing container of the present invention is preferable. The developing device may be either a dry developing method or a wet developing method, and may be either a single color developing device or a multicolor developing device. For example, the developer of the present invention is frictionally stirred. Examples include a stirrer to be charged and a rotatable magnet roller. In the developing device, for example, the toner and the carrier are mixed and stirred, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. The magnet roller is disposed in the vicinity of the electrostatic latent image carrier, and a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted by the electrostatic latent image carrier. Move to the surface. As a result, the electrostatic latent image is developed with toner, and a toner image is formed on the surface of the electrostatic latent image carrier. The developer housed in the developing device is the developer of the present invention, but may be a one-component developer or a two-component developer.

The transfer step is a step of transferring the toner image to a recording medium by charging the electrostatic latent image carrier on which the toner image is formed using, for example, a transfer charging device. Can be used to transfer. At this time, the transfer step preferably includes a primary transfer step of transferring the toner image onto the intermediate transfer member and a secondary transfer step of transferring the toner image transferred onto the intermediate transfer member onto the recording medium. The transfer process includes a primary transfer process in which a toner image of two or more colors, preferably a full color toner, is used to transfer a toner image of each color onto an intermediate transfer member to form a composite toner image, It is more preferable to have a secondary transfer step of transferring the formed composite toner image onto a recording medium.
The transfer device includes a primary transfer unit that transfers a toner image onto an intermediate transfer member to form a composite toner image, and a secondary transfer unit that transfers the composite toner image formed on the intermediate transfer member onto a recording medium. It is preferable. The intermediate transfer member is not particularly limited, and examples thereof include an endless transfer belt. The transfer device (primary transfer means, secondary transfer means) preferably has at least transfer means for charging and peeling the toner image formed on the electrostatic latent image carrier to the recording medium side. The transfer device can have one or more transfer means.
Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.

The recording medium is not particularly limited, and can be appropriately selected from known recording media (recording paper).
The fixing step is a step of fixing the toner image transferred to the recording medium, and can be fixed using a fixing device as fixing means. When two or more color toners are used, the toner may be fixed each time the toner of each color is transferred to the recording medium, or the toner of all colors may be transferred to the recording medium and fixed in a stacked state. Also good. The fixing device is not particularly limited, and a known heating and pressing unit can be used. Examples of the heating and pressing means include a combination of a heating roller and a pressing roller, a combination of a heating roller, a pressing roller, and an endless belt. At this time, heating temperature is 80-200 degreeC normally. If necessary, for example, a known optical fixing device may be used together with the fixing device or instead of the fixing device.

The neutralization step is a step of neutralizing by applying a neutralization bias to the electrostatic latent image carrier, and the neutralization can be performed using a neutralization unit. The neutralization means is not particularly limited as long as a neutralization bias can be applied to the electrostatic latent image carrier. For example, a neutralization lamp can be used.
The cleaning step is a step of removing toner remaining on the electrostatic latent image carrier, and can be cleaned using a cleaning device as a cleaning unit. The cleaning device is not particularly limited as long as the toner remaining on the electrostatic latent image carrier can be removed. For example, a magnetic brush cleaner, electrostatic brush cleaner, magnetic roller cleaner, blade cleaner, brush cleaner, web A cleaner or the like can be used.
The recycling step is a step of recycling the toner removed in the cleaning step to the developing unit, and can be recycled using the recycling unit. The recycling unit is not particularly limited, and a known transport unit or the like can be used.
A control process is a process of controlling each process, and can be controlled using a control means. The control means is not particularly limited as long as the operation of each means can be controlled. For example, a sequencer, a computer, or the like can be used.

FIG. 1 is a diagram showing a configuration of an example of an image forming apparatus of the present invention.
The image forming apparatus 1 includes a photosensitive drum 11 as an electrostatic latent image carrier, a charging roller 20 as a charging unit, an exposure device (not shown) as an exposure unit, a developing device 30 as a developing unit, It has an intermediate transfer member 61, a cleaning device 40 having a cleaning blade 41 as a cleaning means, and a static elimination lamp 22 as a static elimination means.
The intermediate transfer member 61 is an endless belt, is stretched by three rollers 65 arranged on the inner side thereof, and can move in the arrow direction. A part of the plurality of rollers 65 also functions as a transfer bias roller 62 that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 61.
An intermediate transfer body cleaning device 64 having a belt cleaning blade 641 is disposed in the vicinity of the intermediate transfer body 61. Further, a transfer roller 63 as a transfer unit capable of applying a transfer bias for transferring (secondary transfer) the toner image to the recording medium 9 is disposed to face the intermediate transfer body 61.
Further, around the intermediate transfer member 61, a corona charging device 69 for applying a charge to the toner image on the intermediate transfer member 61 is provided. And the contact portion of the recording medium 9.
The developing device 30 for each color of black (K), yellow (Y), magenta (M), and cyan (C) includes a container 35 containing a developer, a developer supply roller 33, and a developing roller 31.

  In the image forming apparatus 1, the photosensitive drum 11 is uniformly charged by the charging roller 20, and then the exposure light L is exposed on the photosensitive drum 10 imagewise by an exposure device (not shown) to form an electrostatic latent image. Form. Next, the electrostatic latent image formed on the photosensitive drum 11 is developed by supplying a developer from the developing device 30 to form a toner image, and then a transfer bias applied from the primary transfer roller 62 is used. The toner image is transferred (primary transfer) onto the intermediate transfer member 61. Further, the toner image on the intermediate transfer member 61 is charged by the corona charging device 69 and then transferred (secondary transfer) onto the recording medium 9. The toner remaining on the photosensitive drum 11 is removed by the cleaning device 40, and the photosensitive drum 11 is once discharged by the discharging lamp 22.

FIG. 2 is a diagram showing the configuration of another example of the image forming apparatus of the present invention.
The image forming apparatus 1 is a tandem color image forming apparatus, and includes an image forming unit 3, a paper feeding unit 2, a scanner 4, and an automatic document feeder (ADF) 5.
The image forming unit 3 is provided with an endless belt-like intermediate transfer member 61 at the center. The intermediate transfer member 61 is stretched around support rollers 65a, 65b, and 65c, and can rotate in the direction of the arrow.
A cleaning device 64 for removing the toner remaining on the intermediate transfer member 61 is disposed in the vicinity of the support roller 65b. Further, four image forming units (process cartridges) 10 of yellow, cyan, magenta, and black are juxtaposed along the conveyance direction on the intermediate transfer member 61 stretched by the support roller 65a and the support roller 65b. Are arranged in a tandem shape.
FIG. 3 is a diagram showing the configuration of the image forming unit in another example of the image forming apparatus of the present invention.
As shown in FIG. 3, each color image forming means (process cartridge) 10 includes a photosensitive drum 11, a charging roller 20 for uniformly charging the photosensitive drum 11, and an electrostatic formed on the photosensitive drum 11. A developing device 30 that develops a latent image with a developer of each color of black (K), yellow (Y), magenta (M), and cyan (C) to form a toner image; The image forming apparatus includes a transfer roller 62 for transferring the image to the top, a cleaning device 40, and a charge eliminating lamp 22.
An exposure device 30 is disposed in the vicinity of the tandem developing device 120. The exposure device 30 exposes the exposure light L on the photosensitive drum 11 to form an electrostatic latent image.

Further, a secondary transfer roller 63 is disposed on the opposite side of the intermediate transfer member 61 from the side where the plurality of image forming units (process cartridges) 10 disposed in a tandem shape are disposed. The transfer device 60 including the secondary transfer roller 63 includes a secondary transfer roller 63 and a conveyance belt 66 that is an endless belt stretched around a support roller 66a. The transfer bodies 61 can contact each other.
A fixing device 70 is disposed in the vicinity of the transfer device 60 including the secondary transfer roller 63. The fixing device 70 includes a fixing belt 71 that is an endless belt, and a pressure roller 72 that is arranged to be pressed against the fixing belt 71.
Further, in the vicinity of the transfer device 60 and the fixing device 70, a reversing device 67 for reversing the recording medium 9 in order to form images on both sides of the recording medium 9 is disposed.

Next, full color image formation (color copying) in the image forming apparatus 1 will be described. First, a document is set on a document table 59 of an automatic document feeder (ADF) 5, or the automatic document feeder 5 is opened and a document is set on the contact glass 91 of the scanner 3. close up. Next, when a start switch (not shown) is pressed, when the document is set on the automatic document feeder 5, the document is transported and moved onto the contact glass 91, and then the document is placed on the contact glass 91. When set, the scanner 4 is immediately driven, and the first traveling body 92 and the second traveling body 93 travel. At this time, light from the light source is emitted from the first traveling body 92 and reflected light from the document surface is reflected by the mirror in the second traveling body 93 and received by the reading sensor 95 through the imaging lens 94. . Thus, a color original (color image) is read, and image information of each color of black, yellow, magenta, and cyan is obtained.
Furthermore, after the electrostatic latent image of each color is formed on the photosensitive drum 11 based on the obtained image information of each color by the exposure device 12, the electrostatic latent image of each color is supplied from the developing device 30 of each color. The developed developer is used to form a toner image of each color. The formed toner images of respective colors are sequentially transferred (primary transfer) on the intermediate transfer body 61 that is rotated and moved by the support rollers 65a, 65b, and 65c, and a composite toner image is formed on the intermediate transfer body 61. .

In the paper feed cassette 80 of the paper feed unit 2, one of the paper feed rollers 81 is selectively rotated to feed out the recording medium 9 from one of the paper feed cassettes 80 provided in multiple stages in the paper feed unit 2, and the separation roller The paper is separated one by one at 82 and sent to the paper feed path 87 a, transported by the transport roller 85, guided to the paper feed path 87 b in the image forming unit 3, and abutted against the registration roller 84 and stopped. Alternatively, the recording medium 9 on the manual feed tray 89 is fed out, separated one by one by a separation roller, put into the manual feed path, and abutted against the registration roller 84 and stopped. The registration roller 84 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the recording medium 9.
Then, the registration roller 49 is rotated in time with the composite toner image formed on the intermediate transfer body 61, and the recording medium 9 is sent out between the intermediate transfer body 61 and the secondary transfer device 22 to record the composite toner image. Transfer (secondary transfer) onto the medium 9.

The recording medium 9 onto which the composite toner image has been transferred is conveyed by the conveying belt 66 and sent out to the fixing device 70. In the fixing device 70, the composite toner image is fixed on the recording medium 9 by being heated and pressed by the fixing belt 71 and the pressure roller 72. Thereafter, the recording medium 9 is switched by the switching claw 88 and discharged by the discharge roller 85, and is stacked on the discharge tray 86. Alternatively, the image is switched by the switching claw 88 and reversed by the reversing device 67 and led to the transfer position again, and after the image is formed on the back surface, the image is ejected by the ejection roller 85 and stacked on the paper ejection tray 86.
Note that the toner remaining on the intermediate transfer member 61 after the composite toner image is transferred is removed by the cleaning device 64.

The process cartridge of the present invention is detachably molded in various image forming apparatuses, and includes an electrostatic latent image carrier that carries an electrostatic latent image, and an electrostatic latent image carried on the electrostatic latent image carrier. And at least developing means for forming a toner image by developing with the developer of the present invention. The process cartridge of the present invention may further include other means as necessary.
The developing means includes at least a developer-containing container that stores the developer of the present invention and a developer-carrying member that supports and conveys the developer stored in the developer-containing container. The developing means may further include a regulating member or the like for regulating the thickness of the developer carried.

FIG. 4 is a diagram showing a configuration of an example of the process cartridge of the present invention.
The process cartridge 10 includes a photosensitive drum 11, a charging device 20, a developing device 30, and a cleaning device 40, and is supported integrally.

Examples of the present invention will be described below, but the present invention is not limited to the examples. In addition, a part means a weight part.
(Synthesis of polyester resin)
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 67 parts of 2-molar adduct of bisphenol A and 84 parts of 3-molar adduct of propion oxide of bisphenol A,
274 parts of terephthalic acid and 2 parts of dibutyltin oxide were added and reacted at 230 ° C. for 8 hours under normal pressure. Next, the polyester resin A was synthesize | combined by making it react under reduced pressure of 10-15 mmHg for 5 hours. The obtained polyester resin A had a number average molecular weight (Mn) of 2100, a weight average molecular weight (Mw) of 5600, and a glass transition temperature (Tg) of 55 ° C.

(Production of master batch)
1000 parts of water, DBP oil absorption 42 ml / 100 g, pH 9.5 carbon black Printex 35 (Degussa) 540 parts and 1200 parts of polyester resin A were mixed using a Henschel mixer (Mitsui Mining). did. Next, the obtained mixture was kneaded at 150 ° C. for 30 minutes using two rolls, then cooled by rolling, and pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare a master batch.

(Preparation of polyester prepolymer solution)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet 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, trimellitic anhydride 22 Part and 2 parts of dibutyltin oxide were allowed to react at 230 ° C. for 8 hours under normal pressure. Next, an intermediate polyester resin was synthesized by reacting under reduced pressure of 10 to 15 mHg for 5 hours. The obtained intermediate polyester resin had Mn of 2100, Mw of 9600, and Tg of 55 ° C.
Next, 411 parts of an intermediate polyester resin, 89 parts of isophorone diisocyanate and 500 parts of ethyl acetate are charged into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. A polymer was prepared. The obtained polyester prepolymer had a solid content concentration (left at 150 ° C. for 45 minutes) of 50% by weight, and the content of free isocyanate in the polyester prepolymer was 1.60% by weight.

(Synthesis of ketimine compounds)
In a reaction vessel equipped with a stir bar and a thermometer, 30 parts of isophoronediamine and 70 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound.

(Preparation of aqueous medium)
Aqueous medium was prepared by mixing and stirring 306 parts of ion-exchanged water, 265 parts of a 10% by weight suspension of tricalcium phosphate, and 0.2 part of sodium dodecylbenzenesulfonate, and dissolving them uniformly.

(Hydrocarbon wax)
The following commercially available paraffin wax was used as the hydrocarbon wax. Table 1 shows the glass transition temperature (Tg) and the melting point (mp).
(Hydrocarbon wax A)
Paraffin wax HNP-9 (manufactured by Nippon Seiwa) was used.
(Hydrocarbon wax B)
Paraffin wax 140 (manufactured by Nippon Seiwa) was used.
(Hydrocarbon wax C)
Hi-Mic-2090 (manufactured by Nippon Seiwa) was used.
(Hydrocarbon wax D)
Paraffin wax 130 (manufactured by Nippon Seiwa) was used.
(Hydrocarbon wax E)
WN1442 (manufactured by Clay Valley) was used.

(Synthesis of ester synthetic wax)
Each fatty acid shown in the table, and each alcohol component shown in the table, together with the catalyst, the fatty acid and the alcohol are put in a reaction vessel at a molar ratio shown in the table, and subjected to esterification reaction at 240 ° C. in a nitrogen stream, and the physical properties shown in Table 2 An ester compound having was obtained.

(Synthesis of release agent A)
1000 parts of water, DBP oil absorption of 42 ml / 100 g, hydrocarbon wax A in the table, 540 parts, and ester wax A in the table of 1260 parts were mixed using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). Next, after the obtained mixture was kneaded at 150 ° C. for 30 minutes using a two-roll, it was rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare a release agent A.
(Synthesis of release agent B)
1000 parts of water, DBP oil absorption 42 ml / 100 g, 270 parts of hydrocarbon wax A in the table, and ester wax A in the table of 2430 parts were mixed using a Henschel mixer (Mitsui Mining Co., Ltd.). Next, the obtained mixture was kneaded at 150 ° C. for 30 minutes using a two-roll, then rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare a release agent B.

(Synthesis of release agent C)
A release agent C was obtained in the same manner as the synthesis of the release agent A except that the hydrocarbon wax B shown in Table 3 was used instead of the hydrocarbon wax A.
(Synthesis of release agent D)
A release agent D was obtained in the same manner as the synthesis of the release agent A except that the hydrocarbon wax C shown in Table 3 was used instead of the hydrocarbon wax A.
(Synthesis of release agent E)
A release agent E was obtained in the same manner as the synthesis of the release agent A except that the ester wax B shown in Table 3 was used instead of the ester wax A.
(Synthesis of release agent F)
A release agent F was obtained in the same manner as the synthesis of the release agent A except that the ester wax C shown in Table 3 was used instead of the ester wax A.
(Synthesis of release agent G)
A release agent G was obtained in the same manner as the synthesis of the release agent A except that the ester wax D shown in Table 3 was used instead of the ester wax A.
(Synthesis of release agent H)
Hydrocarbon wax A was used as it was.
(Synthesis of release agent I)
The ester wax A was used as it was.
(Synthesis of release agent J)
Hydrocarbon wax A and ester wax A were used as they were without being melted and mixed.
(Synthesis of release agent K)
A release agent K was obtained in the same manner as the synthesis of the release agent A except that the hydrocarbon wax D shown in Table 3 was used instead of the hydrocarbon wax A.
(Synthesis of release agent L)
A release agent L was obtained in the same manner as the synthesis of the release agent A except that the hydrocarbon wax E shown in Table 3 was used instead of the hydrocarbon wax A.
(Synthesis of release agent M)
A release agent M was obtained in the same manner as the synthesis of the release agent A except that the ester wax E shown in Table 3 was used instead of the ester wax A.
(Synthesis of release agent N)
A release agent N was obtained in the same manner as the synthesis of the release agent A except that the ester wax F shown in Table 3 was used instead of the ester wax A.

Table 3 shows the structures of the release agents A to N.

Example 1
In a beaker, 10 parts of a polyester prepolymer solution, 75 parts of a polyester resin and 130 parts of ethyl acetate were stirred and dissolved. Next, 5 parts of mold release agent A and 10 parts of master batch were added, and using a bead mill Ultra Visco Mill (manufactured by Imex), the liquid feed speed was 1 kg / hour and the peripheral speed of the disk was 6 m / second. Three passes were carried out under the condition of filling 80% by volume of zirconia beads having a diameter of 0.5 mm. Further, 2.7 parts of a ketimine compound was added and dissolved to prepare a toner material liquid.
Add 150 parts of an aqueous medium into a container, add 100 parts of toner material solution while stirring at 12,000 rpm using a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.), and mix for 10 minutes to prepare an emulsified slurry. did.

In a Kolben equipped with a stirrer and a thermometer, 100 parts of an emulsified slurry was charged, and the solvent was removed at 30 ° C. for 12 hours while stirring at a stirring peripheral speed of 20 m / min to obtain a dispersed slurry.
After filtering 100 parts of the dispersion slurry under reduced pressure, 100 parts of ion-exchanged water was added to the filter cake, followed by mixing at 12000 rpm for 10 minutes using a TK homomixer, followed by filtration. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12000 rpm using a TK homomixer, and then filtered twice. 20 parts of a 10 wt% aqueous sodium hydroxide solution was added to the obtained filter cake, mixed at 12000 rpm for 30 minutes using a TK homomixer, and then filtered under reduced pressure. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed at 12000 rpm for 10 minutes using a TK homomixer, and then filtered. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12000 rpm using a TK homomixer, and then filtered twice. Further, 20 parts of 10 wt% hydrochloric acid was added to the obtained filter cake, and the mixture was mixed for 10 minutes at 12000 rpm using a TK homomixer, and then filtered. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12000 rpm using a TK homomixer, and then filtered twice to obtain a filter cake.
The obtained filter cake was dried at 45 ° C. for 48 hours using a circulating dryer, and sieved with a 75 μm mesh to obtain base particles.

(Example 2)
A toner of Example 2 was obtained in the same manner as in Example except that the release agent B shown in Table 4 was used instead of the release agent A.
(Example 3)
A toner of Example 3 was obtained in the same manner as in Example except that the release agent C shown in Table 4 was used instead of the release agent A.
(Example 4)
A toner of Example 4 was obtained in the same manner as in Example except that the release agent D shown in Table 4 was used instead of the release agent A.
(Example 5)
A toner of Example 5 was obtained in the same manner as in Example except that the release agent E shown in Table 4 was used instead of the release agent A.
(Example 6)
A toner of Example 6 was obtained in the same manner as in Example except that the release agent F shown in Table 4 was used instead of the release agent A.
(Example 7)
A toner of Example 7 was obtained in the same manner as in Example except that the release agent G shown in Table 4 was used instead of the release agent A.
(Comparative Example 1)
A toner of Comparative Example 1 was obtained in the same manner as in Example except that the release agent H shown in Table 4 was used instead of the release agent A.
(Comparative Example 2)
A toner of Comparative Example 2 was obtained in the same manner as in Example except that the release agent I shown in Table 4 was used instead of the release agent A.
(Comparative Example 3)
A toner of Comparative Example 3 was obtained in the same manner as in Example except that the release agent J shown in Table 4 was used instead of the release agent A.
(Comparative Example 4)
A toner of Comparative Example 4 was obtained in the same manner as in Example except that the release agent K shown in Table 4 was used instead of the release agent A.
(Comparative Example 5)
A toner of Comparative Example 5 was obtained in the same manner as in Example except that the release agent L shown in Table 4 was used instead of the release agent A.
(Comparative Example 6)
A toner of Comparative Example 6 was obtained in the same manner as in Example except that the release agent M shown in Table 4 was used instead of the release agent A.
(Comparative Example 7)
A toner of Comparative Example 7 was obtained in the same manner as in Example except that the release agent N shown in Table 4 was used instead of the release agent A.

Table 4 shows the release agents used in Examples 1 to 7 and Comparative Examples 1 to 7.

(Creation of carrier)
To 100 parts of toluene, 100 parts of silicone resin organostraight silicone, 5 parts of γ- (2-aminoethyl) aminopropyltrimethoxysilane and 10 parts of carbon black are added and dispersed with a homomixer for 20 minutes. Was prepared. Using a fluidized bed type coating apparatus, a resin layer coating solution was applied to the surface of 1000 parts of spherical magnetite having an average particle size of 50 μm to prepare a carrier.
(Development of developer)
Using a ball mill, 5 parts of toner and 95 parts of carrier were mixed to prepare a developer.

(Evaluation method and evaluation results)
The following evaluation was performed using the obtained developer. The evaluation results are shown in Table 3.
<Fixing temperature limit>
As a fixing roller, type 6200 paper (manufactured by Ricoh) is set using a device in which the fixing unit of the copying machine MF-200 (manufactured by Ricoh) using a Teflon (registered trademark) roller is modified, and the temperature of the fixing roller is set. A copy test was conducted by changing the temperature in increments of 5 ° C. The minimum fixing roller temperature at which the residual ratio of the image density after rubbing the fixed image with a pad becomes 70% or more was defined as the minimum fixing temperature. The lower limit fixing temperature is preferably low because power consumption can be suppressed. If it is 135 ° C. or lower, it is at a level causing no problem in practical use.
<In-flight contamination>
The developer of the above example was put in a digital color imagio Neo C600 remodeled machine manufactured by Ricoh and evaluated. The stain around the fixing paper discharge portion after visually outputting 100,000 image charts having a 50% image area in the monochrome mode is visually observed. ◎: No stain, ○: Slight stain is seen but no print stain, △: Some stain is seen, slight stain is seen on the print, × : Periphery of fixing area and print contamination did.
<Releasability>
Number of paper jams when NBS copy printing paper <55> is continuously passed through 1000 sheets, no paper jam occurred: ◎, 1-3 times: ○, 4 times to 10 times: Δ, 11 times or more: evaluated as x did.
<Manufacturability>
After stirring the release agent in ethyl acetate at 75 ° C. for 3 hours, stirring was stopped and the state of the solution was visually observed. The release agent was dissolved in ethyl acetate and almost transparent: ◎, white turbidity was observed in ethyl acetate: ◯, the particles of the release agent were visible: Δ, almost no change was observed before and after heating: evaluated as ×.

Moreover, the following evaluation was performed using the obtained toner. The evaluation results are shown in Table 5.
<Heat resistant storage stability>
A 50 ml glass container is filled with toner, left in a thermostatic bath at 50 ° C. for 24 hours, then cooled to 24 ° C., and the penetration is measured by a penetration test (JIS K2235-1991). Evaluated. In addition, it judged as (circle), what was 15 mm or more and less than 25 mm as (circle), what was 5 mm or more and less than 15 mm (triangle | delta), and what was less than 5 mm x. At this time, the greater the penetration, the better the heat-resistant storage stability. When the penetration is less than 5 mm, there is a high possibility that a problem will occur in use.

表５より、実施例のトナーは、離型性、低温定着製に優れる炭化水素系ワックスと、低機内汚染性および製造が容易な合成エステル系ワックスを含有するため、離型性、低温定着性に優れ、機内汚染性が低く、製造も容易であることがわかった。

From Table 5, the toners of the examples contain a hydrocarbon wax excellent in releasability and low-temperature fixing, and a synthetic ester wax that is low in-machine contamination and easy to manufacture. It was found that it was excellent in contamination, low in-machine contamination, and easy to manufacture.

Compared to Example 1, in Example 2, the content of hydrocarbon wax is small, so the effect of wax compatibility is small, and the lower fixing temperature, in-machine contamination, and separation are slightly inferior to Example 1. However, manufacturability and storage stability were sufficiently maintained. In Examples 3 and 5, since a wax having a low melting point was used, a toner having excellent low-temperature fixability was obtained although in-machine contamination and storage stability were poor. In Examples 4 and 6, since a wax having a higher melting point was used than in Example 1, the low-temperature fixability was inferior, but the storage stability was excellent. In Examples 3 to 6, all the toners were excellent in separability.
In Example 7, an ester wax composed only of a monoester was used, but it was found that the separation property, manufacturability and storage stability were sufficiently excellent although the low-temperature fixability and in-machine contamination were poor.
On the other hand, in the toner of Comparative Example 1, since only the hydrocarbon wax is used as the release agent, the low-temperature fixability and the separability are excellent, but the in-machine contamination and the productivity are deteriorated. In Comparative Example 2, since only the ester wax was used, the low-temperature fixability and the separability deteriorated.
In Comparative Example 3, since the wax was not compatible, the problems of hydrocarbon wax and ester wax were observed as they were.
In Comparative Example 4, although compatibility of the wax was observed, since the low-melting hydrocarbon wax was used, no improvement in the in-machine contamination was observed. In addition, storage stability deteriorated. Similarly, in Comparative Example 6, as a result of using an ester wax having a low melting point, although the productivity was slightly good, no improvement in in-machine contamination and separation were observed.
In Comparative Example 5, since a high melting point hydrocarbon wax was used, a toner having excellent storage stability and in-machine contamination was obtained, but low temperature fixability and productivity were deteriorated. In Comparative Example 7, although the storage stability was excellent, the low-temperature fixability deteriorated because the high melting point ester wax was used.
As described above, it is possible to provide a toner that is excellent in releasability and low-temperature fixability, has low in-machine contamination, and can be easily produced, and a method for producing the toner. Further, according to the present invention, a developer having the toner, a developer-containing container, a process cartridge, and an image forming method can be provided.

DESCRIPTION OF SYMBOLS 1 Image forming apparatus 2 Paper feed part 3 Image forming part 4 Scanner part 91 Contact glass 92 1st traveling body 93 2nd traveling body 94 Imaging lens 95 Reading sensor 5 Automatic document feeder (ADF)
5a Document platen 9 Recording medium 10 Image forming means (process cartridge)
11 Electrostatic latent image carrier (photoreceptor)
DESCRIPTION OF SYMBOLS 12 Exposure apparatus 20 Charging apparatus 21 Charging roller 22 Static elimination lamp 30 Developing apparatus 31 Developing roller 32 Control blade 33 Supply roller 34 Stirring member 35 Developer containing container 40 Cleaning apparatus 41 Cleaning blade 60 Transfer apparatus 61 Intermediate transfer belt 62 Primary transfer roller 63 Secondary transfer roller 64 Intermediate transfer member cleaning device 641 Belt cleaning blades 65a, 65b, 65c Support roller 66 Conveyor belt 66a Support roller 67 Recording medium reversing device 68 Static elimination charger 69 Corona charging device 70 Fixing device 71 Fixing belt 72 Pressure roller 80 Paper feed cassette 81 Paper feed roller 82 Separation roller 83 Transport roller 84 Registration roller 85 Paper discharge roller 86 Paper discharge tray 87a, 87b Transport path 88 Switching claw 89 Manual feed tray

JP-A-11-149180 JP-A-1-185660 JP-A-1-185661 Japanese Patent Laid-Open No. 1-185662 JP-A-1-185663 Japanese Patent Publication No.52-3304 Japanese Patent Publication No.52-3305 JP-A-57-572574 JP 2006-293309 A JP-A-2005-331925 JP 2001-5761 A

Claims (12)

A liquid toner material containing a binder resin and a release agent are dissolved or dispersed in an organic solvent, a toner having a base particles are prepared by emulsifying or dispersing in a water-based medium,
The binder resin contains a polyester resin,
The release agent is obtained by heating and mixing a hydrocarbon wax with a synthetic ester wax at a weight ratio of 1/9 to 9/1 ,
The hydrocarbon wax has a transparent melting point of 60 to 95 ° C., and the synthetic ester wax has a transparent melting point of 65 to 90 ° C. and consists of a linear monoester and an erythritol ester having a branched structure,
When the DSC measurement of the release agent was performed, the glass transition temperature (Tg) of the hydrocarbon wax at the second temperature increase was Tg ₁ , the Tg of the synthetic ester wax was Tg ₂ , and the Tg of the release agent was When Tg _{1 + 2} ,
Tg ₁ > Tg _{1 + 2} and Tg ₂ > Tg _{1 + 2}
Toner characterized by the above. The toner according to claim 1.
When the DSC measurement of the release agent was performed, the glass transition temperature (Tg) of the hydrocarbon wax at the second temperature increase was Tg ₁ , the Tg of the synthetic ester wax was Tg ₂ , and the Tg of the release agent was When Tg _{1 + 2} ,
A toner having a relationship of Tg ₁ −Tg _{1 + 2} > 0.5 and Tg ₂ −Tg _{1 + 2} > 1.0. The toner according to claim 1 or 2,
The synthetic ester wax has a transparent melting point of 72 to 80 ° C., and
A toner comprising: a linear monoester synthesized from a linear fatty acid and a monohydric higher alcohol; and a saturated ester synthesized from a linear fatty acid and a polyhydric alcohol. The toner according to any one of claims 1 to 3,
The toner according to claim 1, wherein the hydrocarbon wax has a transparent melting point of 70 to 88 ° C. In the toner according to any one of claims 1 to 4,
  The binder resin contains a modified polyester containing at least an ester bond and a bond unit other than the ester bond, or a resin precursor capable of producing the modified polyester.
  Toner characterized by the above. The toner according to any one of claims 1 to 5,
  The resin precursor capable of producing the modified polyester contains a compound having an active hydrogen group and a polyester having a functional group capable of reacting with the active hydrogen group of the compound.
  Toner characterized by the above. The toner according to any one of claims 1 to 6,
  The modified polyester contains at least an ester bond and a urea bond.
  Toner characterized by the above. In the developer used for image formation of a latent image in electrophotography,
  The developer includes the toner according to claim 1.
  A developer characterized by that. In a developer-filled container filled with toner used for image formation of an electrophotographic latent image,
  The developer-containing container contains the toner according to claim 1.
  A developer-containing container. The image forming apparatus main body includes at least an electrostatic latent image carrier and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using toner to form a visible image. A removable process cartridge,
  The toner is the toner according to claim 1.
  A process cartridge characterized by that. An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier;
  A developing step of developing the electrostatic latent image with toner to form a visible image;
  A transfer step of transferring the visible image to a recording medium;
  An image forming method including at least a fixing step of fixing the transferred image transferred to the recording medium,
  The toner is the toner according to claim 1.
  An image forming method. An electrostatic latent image carrier carrying an electrostatic latent image;
  An exposure device that forms an electrostatic latent image on the electrostatic latent image carrier;
  A developing device for developing the electrostatic latent image with toner to form a visible image;
  A transfer device for transferring the visible image to a recording medium;
  An image forming apparatus including at least a fixing device for fixing the transferred image transferred to the recording medium,
  The toner is the toner according to claim 1.
  An image forming apparatus.

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