JP2013003361A - Toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide toner having favorable low-temperature fixability and high-temperature-resistant offset property with no fixing irregularity without affecting a long-term storage stability.SOLUTION: The toner includes toner particles formed by suspending, in an aqueous medium, a toner material that is formed by dissolving and/or dispersing at least a binder resin and a colorant in an organic solvent, forming oil droplets, and then removing the organic solvent therefrom. The binder resin includes at least a polyester resin, and the polyester resin has a first endothermic peak P1 at a temperature of 55 to 75°C and a second endothermic peak P2 at a temperature of 80 to 120°C in a DSC curve measured by a differential scanning calorimeter.

Description

  The present invention relates to an electrophotographic image forming method for developing an electrostatic charge image, and a toner used in a toner jet.

  2. Description of the Related Art In recent years, image output devices for multi-function devices, printers, and fax machines in the field of electrophotography have been increasingly demanded for energy saving by improving the quality of printed images and lowering the fixing temperature. For this reason, it has become important to make toner particles smaller and to control the shape, and to melt at a lower temperature.

  A solution suspension method has been proposed in which it is easy to reduce the particle size, presents a highly uniform sphere, and it is easy to granulate toner using a polyester resin having excellent low-temperature fixability.

  When aiming at further low-temperature fixability by this dissolution suspension method, in the toner particles having a core-shell structure, a low molecular weight polyester resin is used for the core portion, and the periphery thereof is covered with a polyester resin extended by a urea bond. It has been proposed (Patent Document 1). By adopting such a configuration, the durability of the toner can be maintained even when a low molecular weight polyester advantageous for low-temperature fixing is used in the core portion. However, in this method, when aiming at further low-temperature fixability for the next generation, the melting rate of the core part contributing to fixing is insufficient.

  Therefore, a configuration in which a block copolymer in which a crystalline polyester and an amorphous polyester are urea-bonded is used as a binder resin for a dissolved suspension toner has been proposed (Patent Document 2). However, in such a toner, a crystalline part may be deposited on the toner surface, the developability deteriorates, and the storage stability and offset resistance cannot be satisfied.

  In addition, there has been proposed a dissolved suspension toner having a structure in which a crystalline polyester and a low molecular weight polyester are used for the core and the periphery thereof is covered with a polyester resin extended by urea bonds (Patent Document 3). However, in this method, two types of resin, crystalline polyester and low molecular weight amorphous polyester, are used for the core, so it is difficult to control the compatibility and phase separation, and further improve the low-temperature fixability. Is difficult and storage stability is also deteriorated. Further, since a resin such as so-called crystalline polyester is not soluble in a solvent, it is difficult to uniformly disperse and granulate, and the performance varies among toner particles, resulting in fixing unevenness.

  As described above, there are many technical problems and there is room for improvement in obtaining images having no fixing unevenness while maintaining storage stability and high-temperature offset resistance while further improving low-temperature fixability.

JP 2008-233427 A JP 2008-52192 A JP 2009-104193 A

  An object of the present invention is to provide a toner that solves the above problems. That is, an object of the present invention is to provide a toner that has excellent low-temperature fixability and high-temperature offset resistance and does not easily cause fixing unevenness without affecting long-term storage stability.

The present invention relates to a toner obtained by suspending a toner material in which at least a binder resin and a colorant are dissolved and / or dispersed in an organic solvent in an aqueous medium to form oil droplets, and then removing the organic solvent. A toner containing particles,
The binder resin contains at least a polyester resin,
The polyester resin has a first endothermic peak P1 at a temperature of 55 to 75 ° C. and a second endothermic peak P2 at a temperature of 80 to 120 ° C. in a DSC curve measured by a differential scanning calorimeter. It relates to toner.

  The present invention can provide a toner that is excellent in long-term storage stability, excellent in low-temperature fixability and high-temperature offset resistance, and difficult to suppress fixing unevenness.

It is a DSC curve showing the glass transition temperature Tg in this invention. It is a DSC curve of the binder resin 1 of the present invention. It is a DSC curve of the binder resin 12 of the present invention.

  A toner having good low-temperature fixability is rapidly melted in a short time after passing through the nip of the heat and pressure fixing device. Generally, it is necessary to control the melting characteristics of the binder resin, which is the main component of the toner, in order to melt the toner quickly at the time of fixing. However, when the melting property of the binder resin itself is controlled, the influence on high temperature offset resistance and storage stability is great. Therefore, a method for controlling the melting property of the binder resin by a plastic effect using a fixing aid (additives such as low melting point wax and crystalline polyester) has been studied.

  Further, in order to obtain a good image without uneven fixing, it is necessary to make the melting rate within and between toner particles uniform. For that purpose, it is important to move more uniformly and quickly at the molecular level and to make the performance between particles uniform.

  When the crystalline polyester is introduced as a part of the binder resin by the dissolution suspension method, it is very difficult to control the compatibility of the crystalline polyester with the binder resin. When compatibilized, there is a problem that the binder resin is plasticized and storage stability and offset resistance are deteriorated. In the case of phase separation, the melting rate of the crystalline domain and the melting rate of the amorphous resin are greatly different, so that the melting rate in the toner particles at the time of fixing is greatly different, and fixing unevenness occurs. Furthermore, since crystalline polyester does not dissolve in a solvent, it is difficult to uniformly disperse and granulate, and the performance varies among toner particles, resulting in fixing unevenness.

  The present inventors can easily produce a toner by the dissolution suspension method, achieve a further low-temperature fixability, and design a toner with good fixing unevenness suppression without affecting storage stability. This method was studied earnestly. As a result, it was discovered that the binder resin needs to be designed with an unprecedented idea. Specifically, it has been found that this problem can be solved by making the polyester resin have two endothermic peaks by aligning the orientation of part of the molecular chains of the molecules constituting the polyester resin.

  A general binder resin undergoes a phase transition from a glass state to a supercooled state at a glass transition temperature, and its melting characteristics slightly change. Accordingly, when this temperature is low, the storage stability is lowered. The present inventors paid attention to a phenomenon (hereinafter referred to as “enthalpy relaxation”) in which the energy excessively held by the polymer is higher on the higher temperature side than after the glass transition temperature, which affects storage stability. The enthalpy relaxation affects the state of the toner layer immediately after entering the heat and pressure fixing device, and affects the subsequent melting state of the toner. Moreover, it has been found that the melting rate of the toner can be controlled by having an endothermic peak after the temperature at which enthalpy relaxation occurs. In addition, the molecular motion can be controlled stepwise in the polyester resin as described above, and uniform melting of the toner can be promoted.

  That is, the present invention has a first endothermic peak P1 at a temperature of 55 to 75 ° C. and a second temperature of 80 to 120 ° C. (preferably 85 to 115 ° C.) in the DSC curve measured by a differential scanning calorimeter. The endothermic peak P2 is further characterized by the resin constituting the binder resin. The endothermic peak P1 represents enthalpy relaxation. Enthalpy relaxation refers to a phenomenon in which molecules attempt to move further immediately after the binder resin in the toner particles undergoes a phase transition from the glass state to the supercooled liquid. When the enthalpy relaxation occurs in this temperature range, the melted state of the toner layer immediately after entering the heat and pressure fixing device changes favorably. It is possible to promote the subsequent melting of the toner by trying to move a part of the molecular chain of the resin constituting the binder resin, and the molecules move more uniformly at the temperature at which the resin actually melts. It is possible to promote When the endothermic peak P1 is lower than 55 ° C., it indicates that the molecules of the resin constituting the binder resin start to move at a temperature close to room temperature. In such a case, the storage stability of the toner decreases. On the other hand, when the endothermic peak P1 is higher than 75 ° C., it indicates that the binder resin in the toner starts moving slowly, and in such a case, the molecules start moving slowly, so that the temperature is more uniform at the actual melting temperature. The molecular movement is not promoted and the low-temperature fixability is deteriorated.

  Next, the second endothermic peak P2 at a temperature of 80 to 120 ° C. is derived from thermal motion when the resin starts to melt, and does not appear in a normal amorphous resin. This occurs because there is a portion where the molecular orientation of the resin is aligned, so that a part of the crystalline part is formed in the resin, and this crystalline part is present. When the endothermic peak P2 is lower than 80 ° C., the melting rate of the entire toner increases, so that the low-temperature fixability is improved, but the melt viscosity near the surface of the toner layer immediately after the toner layer enters the heat-pressure fixing device. High temperature offset resistance decreases due to rapid increase. On the other hand, when the endothermic peak P2 exceeds 120 ° C., melting of the toner is not promoted in the fixing temperature region, so that the low temperature fixability is deteriorated.

  Furthermore, if the peak temperature difference Δ (P2−P1) between the endothermic peak P1 and the endothermic peak P2 is too small, the melting of the toner by the endothermic peak P1 may not be sufficiently promoted when the toner is melted by the endothermic peak P2. There is a tendency not to promote uniform movement. On the other hand, if the peak temperature difference Δ (P2−P1) is too large, there is a possibility that a time difference from when the toner is melted at the endothermic peak P1 to when the toner is actually melted at the endothermic peak P2 may be generated. Uniform melting within the particles is not achieved, which tends to be disadvantageous for uneven fixing. Specifically, when the peak temperature difference Δ (P2−P1) is smaller than 15 ° C. and when the peak temperature difference Δ (P2−P1) is larger than 50 ° C., there is a tendency that the fixing unevenness is disadvantageous.

  In the toner of the present invention, the endothermic amount of the second endothermic peak P2 obtained in the DSC curve measured by the differential scanning calorimeter of the binder resin is preferably 0.20 J / g to 2.00 J / g. . When it is less than 0.20 J / g, the acceleration of toner melting at the time of fixing is lowered, and when it is more than 2.00 J / g, the storage stability of the toner tends to be lowered.

  Further, in the toner of the present invention, the endothermic amount of the first endothermic peak P1 obtained in the DSC curve measured by the differential scanning calorimeter of the binder resin is preferably 0.20 J / g to 1.50 J / g. . If it is less than 0.20 J / g, the fixability tends to deteriorate. If it is higher than 2.00 J / g, the molten state in the vicinity of the surface of the toner layer may change greatly immediately after the toner layer enters the fixing device, so that the high temperature offset resistance tends to deteriorate. Furthermore, the storage stability tends to be deteriorated because the toner change over time is easily affected.

  The endothermic peak and endothermic amount of the DSC curve of the binder resin in the present invention are measured by the following method. The peak temperature of the endothermic peak of the binder resin is measured according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments). The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat quantity uses the heat of fusion of indium.

  Specifically, about 5 mg of a measurement sample is accurately weighed, put in an aluminum pan, and an empty aluminum pan is used as a reference. Measure at room temperature and humidity for min. In the measurement, the temperature is once raised to 200 ° C., subsequently lowered to 30 ° C., and then the temperature is raised again. The point of intersection between the baseline halfway line and the differential thermal curve before and after the specific heat change obtained in this temperature raising process is expressed as the glass transition temperature Tg of the binder resin (FIG. 1). An endothermic peak obtained immediately after the glass transition temperature Tg in the temperature range of 30 to 200 ° C. in the second temperature raising process is defined as an endothermic peak P1, and an endothermic peak obtained by further raising the temperature is defined as P2. On the other hand, the endothermic amount ΔH of the second endothermic peak is obtained from the integrated value of the second endothermic peak.

  In the dissolution suspension method, a toner material in which at least a binder resin and a colorant are dissolved and / or dispersed in an organic solvent is suspended in an aqueous medium to form oil droplets, and then the organic solvent is removed. It is a manufacturing method including drying. The toner production method of the present invention may include a step of forming a surface layer together with a step of preparing core particles containing at least a binder resin and a colorant. The step of forming the surface layer may be performed simultaneously with the adjustment step of the core particle, or may be performed after the preparation step of the core particle. As a method for preparing the toner of the present invention more easily, it is preferable to simultaneously perform the core particle manufacturing process and the surface layer forming process.

  Moreover, the process of forming the surface layer of this invention does not receive a restriction | limiting at all. For example, in the case of providing a step of adjusting the surface layer after preparation of the core particles, the core particles and the substance forming the surface layer are dispersed in resin fine particles in an aqueous medium, and then the surface layer is formed on the core surface. There is a method of agglomerating and adsorbing fine particles. The resin fine particles aim to be a system that also functions as a dispersant for suspending the liquid material of the toner composition. By using such a system, an aggregation process on the toner surface is required. The toner of the present invention can be prepared by a simpler method. This is a simple method that can prepare a toner having a core-shell structure in one step, and can easily obtain a spherical toner with a small particle size and a sharp particle size distribution from the viewpoint of high image quality. It is. Therefore, in the present invention, a method can be used in which the core of the toner is prepared by a dissolution suspension method, and the surface layer is formed by using resin fine particles as a dispersant as the dispersant in the above-described method.

  As another method for forming a surface layer on the toner, a so-called surface layer is formed on the surface of the toner by mixing a reactive monomer in the toner and the aqueous medium and causing a reaction at the interface between the toner and the aqueous medium. A method called interfacial polymerization is also possible.

  When the binder resin of the present invention is used in the dissolution suspension method, the present inventors can easily produce a toner having a uniform particle size distribution that cannot be achieved by a conventional system using so-called crystalline polyester. I found out. Since so-called crystalline polyester resins have their molecular chains strongly interacting with each other, they cannot be solvated and do not dissolve in the solvent. Therefore, since the resin cannot be dissolved in an organic solvent in the dissolution suspension method, subsequent granulation in water is difficult. Even when dispersed in an organic solvent by heating or strong agitation, the crystalline polyester resin is not uniform in the subsequent dispersion / granulation process, so it cannot be stably granulated. It is impossible to produce toner particles having On the other hand, the binder resin in the present invention has a portion where the orientation of the resin is uniform in the amorphous resin, so that a part of the crystalline portion is formed in the resin, but the composition of the resin itself is amorphous. Yes, it can be easily dissolved in a solvent. Therefore, it is possible to easily produce uniform toner particles in the subsequent dispersion / granulation process, and the fixing unevenness is excellent and the low temperature fixing property is excellent due to the crystallinity existing in the binder resin. Toner can be obtained.

  These endothermic peaks also exist in the second temperature rising process in DSC, indicating that there are stable amorphous and crystalline sites. In addition, since there are a crystalline part and an amorphous part in the same molecule, it is possible to easily control the abundance of the crystalline part by controlling the ratio during resin preparation. .

  Further, this resin may be used for a core part of a core / shell structure or a shell part in a toner by a dissolution suspension method. From the viewpoint of easily incorporating the crystalline part into the binder resin, it is more preferable to use it for the core part. Further, this resin alone may be used without taking the core-shell structure.

  As the resin of the resin particles used in the present invention, a polyester resin is preferable in that a part of the molecule is oriented to give crystallinity, and among them, a linear polyester is particularly preferable.

  The components for producing the linear polyester resin particularly preferably used in the present invention are as follows.

  Examples of the divalent acid component include the following dicarboxylic acids or derivatives thereof. Benzene dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride or their anhydrides or lower alkyl esters thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid or their anhydrides or lower thereof Alkyl esters; alkenyl succinic acids or alkyl succinic acids such as n-dodecenyl succinic acid, n-dodecyl succinic acid, or anhydrides thereof or lower alkyl esters thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, itaconic acid Or its anhydride or its lower alkyl ester.

  The present invention is characterized by providing crystallinity by orienting a part of the polymer chain of the binder resin. Therefore, an aromatic dicarboxylic acid that has a solid planar structure and is abundant in electrons delocalized by the π-electron system, and is easily molecularly oriented by π-π interaction, is preferable. Particularly preferred are terephthalic acid and isophthalic acid which can easily form a straight chain structure. The aromatic dicarboxylic acid content is preferably 50 mol% or more in 100 mol% of the acid component constituting the polyester resin from the viewpoint of controlling the temperature of the endothermic peak.

  The following are mentioned as a bivalent alcohol component. Ethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 1,4-cyclohexanedimethanol (CHDM) Hydrogenated bisphenol A, bisphenol represented by formula (1) and derivatives thereof:

（式中、Ｒはエチレンまたはプロピレン基であり、ｘ、ｙはそれぞれ０以上の整数であり、かつ、ｘ＋ｙの平均値は０乃至１０である。）
および式（２）で示されるジオール類。

(In the formula, R is an ethylene or propylene group, x and y are each an integer of 0 or more, and the average value of x + y is 0 to 10.)
And diols represented by formula (2).

  Among these, aliphatic alcohols having 2 to 6 carbon atoms, which are easy to have a straight chain structure, are preferred in order to orient some of the molecules and to provide crystallinity. However, since the crystallinity may become too high by itself, it is preferable to use an aliphatic alcohol having a branched structure. In order to adjust the crystal structure between the molecules of the polyester resin and to achieve both endothermic peak P1 due to enthalpy relaxation and endothermic peak P2 due to molecular orientation in the same molecule, neopentyl glycol having a methyl group or an ethyl group in the side chain, It is particularly preferred to use methyl-1,3-propanediol or 2-ethyl-1,3-hexanediol.

  The polyester resin used in the present invention includes a monovalent carboxylic acid compound, a monovalent alcohol, a trivalent or higher carboxylic acid, and a trivalent or higher alcohol in addition to the divalent carboxylic acid and divalent alcohol described above. May be used when producing a polyester resin.

  Examples of monovalent carboxylic acids include aromatic carboxylic acids having 7 to 30 carbon atoms such as benzoic acid and p-methylbenzoic acid, and aliphatic carboxylic acids having 16 to 30 carbon atoms such as stearic acid and behenic acid. .

  Examples of monohydric alcohols include aromatic alcohols having 7 to 30 carbon atoms such as benzyl alcohol, and aliphatic alcohols having 10 to 30 carbon atoms such as lauryl alcohol, cetyl alcohol, stearyl alcohol, and behenyl alcohol. It is done.

  The trivalent or higher carboxylic acid compound is not particularly limited, and examples thereof include trimellitic acid, trimellitic anhydride, and pyromellitic acid.

  Examples of the trivalent or higher alcohol compound include trimethylolpropane, pentaerythritol, and glycerin.

  About the manufacturing method of the polyester resin which concerns on this invention, it does not restrict | limit in particular, A well-known method can be used. For example, the above carboxylic acid and alcohol are charged together and polymerized through an esterification reaction or a transesterification reaction, and a condensation reaction to produce a polyester resin. In the production of the polyester resin, for example, a polymerization catalyst such as titanium tetrabutoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, and germanium dioxide can be used. The polymerization temperature is preferably in the range of 180 to 290 ° C.

  In the present invention, the acid value of the binder resin is usually 5 mgKOH / g or more and 50 mgKOH / g or less, preferably 5 mgKOH / g or more and 40 mgKOH / g or less. By giving the acid value, the presence of droplets during granulation in an aqueous medium is stabilized, and a more uniform particle size distribution can be obtained. However, when the acid value exceeds 50 mgKOH / g, the hygroscopicity of the toner increases and there is a tendency to deteriorate with respect to environmental fluctuations.

  In the molecular weight distribution measured by gel permeation chromatography (GPC) of the THF-soluble component, the binder resin has at least one peak in a region having a molecular weight of 5000 to 10,000, and an area having a molecular weight of 3000 or less is the entire area. Is preferably 20% or less. Within such a range, it is preferable in terms of controlling the amount of a low molecular weight component that tends to move molecules at low temperatures and that affects storage stability. When the peak maximum molecular weight is less than 5000, the blocking resistance is lowered. When the molecular weight at the peak maximum value exceeds 10,000, the fixability is lowered.

  Solvents that can be used as the organic medium for dissolving the binder resin and the like include hydrocarbon solvents such as ethyl acetate, xylene, and hexane, halogenated hydrocarbon solvents such as methylene chloride, chloroform, and dichloroethane, methyl acetate, and ethyl acetate. And ester solvents such as butyl acetate and isopropyl acetate, ether solvents such as diethyl ether, and ketone solvents such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexane.

  As an aqueous medium used in the present invention, water alone may be used, but a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohols (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, 1-butanone, etc.), and the like.

  The amount of the aqueous medium used relative to 100 parts by mass of the toner composition is usually 50 parts by mass or more and 2000 parts by mass or less, preferably 100 parts by mass or more and 1000 parts by mass or less. If the amount is less than 50 parts by mass, the dispersion state of the toner composition is poor and a toner having a predetermined particle diameter cannot be obtained. If it exceeds 2000 parts by mass, it is not economical.

  It is also a preferable production method to mix an appropriate amount of an organic solvent used as the oil layer in the aqueous medium used in the present invention. This is believed to have the effect of enhancing droplet stability during granulation and making the water system and oil layer more easily suspended.

  As the dispersant, a known surfactant, water-soluble polymer, or the like can be used.

  Main surfactants include anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, etc., which can be arbitrarily selected in accordance with the polarity at the time of toner particle formation. Is.

  Anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, alkyltrimethylammonium salts, Nonionic interfaces such as dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, quaternary ammonium salt type cationic surfactants such as benzethonium chloride, fatty acid amide derivatives, polyhydric alcohol derivatives, etc. Activators include amphoteric surfactants such as alanine, dodecyl di (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine.

  On the other hand, as the cationic surfactant, an aliphatic quaternary ammonium salt such as an aliphatic primary, secondary or secondary amine acid, perfluoroalkyl (C6 to C10) sulfonamidopropyltrimethylammonium salt that has a fluoroalkyl group on the right, Examples include benzalkonium salt, benzethonium chloride, pyridinium salt, and imidazolinium salt.

  A polymer dispersant may be used as the dispersant. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Bodies such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-acrylate Chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N- Ethers of methylol acrylamide, N-methylol methacrylamide, vinyl alcohol, or vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or esters of compounds containing vinyl alcohol and a carboxyl group, such as Nitrogen such as vinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride and methacrylic acid chloride, pinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine Homopolymers or copolymers such as those having atoms or heterocycles thereof, polyoxyethylene, polyoxypropylene, polyoxyethylene alkyla Polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl phenyl ester, etc. Celluloses such as polyoxyethylene, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose can be used.

  When a dispersant is used, the dispersant can remain on the surface of the toner particles, but it is preferable to dissolve and remove it from the charged surface of the toner.

  In the present invention, in addition to the above-described surfactant, or in combination, it is also preferable to dissociate the carboxylic acid residue of the polyester, which is the binder resin, to express the surfactant effect. Specifically, the carboxylic acid of the polyester can be dissociated by allowing amines to be present in the oil layer or the aqueous phase. As amines that can be used at this time, amines of relatively low molecular weight such as aqueous ammonia, triethylamine, and triethanolamine are preferable.

  In the present invention, a solid dispersion stabilizer may be used to maintain a more preferable dispersion state. In the present invention, the dispersion stabilizer is used for the following reason. That is, the organic medium in which the binder resin that is the main component of the toner is dissolved has a high viscosity, and the dispersion stabilizer surrounds the oil droplets formed by finely dispersing the organic medium with high shearing force. This is to prevent oil droplets from reaggregating and stabilizing.

  As the dispersion stabilizer, inorganic dispersion stabilizers and organic dispersion stabilizers can be used. In the case of an inorganic dispersion stabilizer, toner particles are preferably granulated while adhering to the particle surface after dispersion, and therefore, those which can be removed by acids such as hydrochloric acid having no affinity for the solvent are preferable. For example, calcium carbonate, calcium chloride, sodium hydrocarbon, potassium hydrocarbon, sodium hydroxide, potassium hydroxide, hydroxyapatite, calcium triphosphate and the like can be used.

  The dispersion method is not particularly limited, and general-purpose devices such as a low-speed shearing method, a high-speed shearing method, a friction method, a high-pressure jet method, and an ultrasonic wave can be used. High speed shearing is preferred.

  There is no restriction | limiting in particular as a stirring apparatus which has a rotary blade, If it is a general thing as an emulsifier and a disperser, it can be used.

  For example, Ultra Turrax (manufactured by IKA), Polytron (manufactured by Kinematica), TK Auto Homo Mixer (manufactured by Special Mechanized Industry Co., Ltd.), Ebara Milder (manufactured by Ebara Corporation), TK Homomic Line Flow (Made by Special Machine Industries Co., Ltd.), colloid mill (made by Shinko Pantech Co., Ltd.), thrasher, trigonal wet pulverizer (made by Mitsui Miike Chemical Co., Ltd.), Cavitron (made by Eurotech), fine flow mill Examples include continuous type emulsifiers (manufactured by Taiheiyo Kiko Co., Ltd.), batch types such as CLEARMIX (manufactured by M Technique Co., Ltd.), fill mix (manufactured by SPECIAL KIKAI KOGYO Co., Ltd.), and continuous emulsifiers. .

  When a high-speed shearing disperser is used, the number of rotations is not particularly limited, but is usually 1000 rpm to 30000 rpm, preferably 3000 rpm to 20000 rpm.

  In the case of a batch method, the dispersion time is usually from 0.1 minutes to 5 minutes. The temperature during dispersion is usually 10 ° C. or higher and 150 ° C. or lower (under pressure), preferably 10 ° C. or higher and 100 ° C. or lower.

  In order to remove the organic solvent from the emulsified dispersion obtained in this manner, a method of gradually elevating the temperature of the entire system and completely removing the organic solvent in the droplets can be employed. Alternatively, it is also possible to spray the emulsified dispersion in a dry atmosphere, completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and evaporate and remove the aqueous dispersant together.

  In that case, the dry atmosphere in which the emulsified dispersion is sprayed is generally a gas heated with air, nitrogen, carbon dioxide gas, combustion gas, etc., particularly various air streams heated to a temperature higher than the boiling point of the highest boiling solvent used. Used. Sufficient quality can be obtained with a short treatment such as spray dryer, belt dryer or rotary kiln.

  When the particle size distribution at the time of emulsification dispersion is wide, and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classification into a desired particle size distribution. The dispersant used is preferably removed from the obtained dispersion as much as possible, but it is more preferable to carry out it simultaneously with the classification operation.

  Preparation of the resin fine particles used in the present invention is not particularly limited, and the emulsion polymerization method or resin is dissolved in a solvent or melted to be liquefied and suspended in an aqueous medium. It can be prepared by granulation. At this time, known surfactants, dispersants, and the like can be used, and the resin constituting the fine particles can be made self-emulsifying.

  The resin fine particles may be any resin as long as it can form an aqueous dispersion, and may be a thermoplastic resin or a thermosetting resin. For example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, Examples include polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. As the resin fine particles, two or more of the above resins may be used in combination. Of these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferred because an aqueous dispersion of fine spherical resin particles is easily obtained.

  Solvents that can be used to prepare fine particles by dissolving resin in a solvent are not particularly limited, but hydrocarbon solvents such as ethyl acetate, xylene, and hexane, halogenated carbonization such as methylene chloride, chloroform, and dichloroethane. Hydrogen solvents, ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isopropyl acetate, ether solvents such as diethyl ether, ketone solvents such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, methylcyclohexane, methanol, ethanol, Alcohol solvents such as butanol can be mentioned. The resin fine particles preferably have a number average particle diameter of 5 nm or more and 500 nm or less so that the toner particles form a capsule structure. The resin fine particles preferably have a glass transition temperature of 30 ° C. or more and 100 ° C. or less, and a weight average molecular weight of 5000 or more and 200,000 or less.

  In the present invention, in the method of interfacial polymerization in which a surface layer is formed on the toner surface by causing a reaction at the interface between the toner and the aqueous medium, the isocyanate group-containing prepolymer is subjected to an extension reaction with amines in the presence of the resin fine particles. It is also possible to carry out a crosslinking reaction.

  In order to introduce a modified polyester resin having a urethane or / and urea group, when a modified polyester resin having an isocyanate group at the terminal and an amine capable of reacting therewith are added, the following operation can be performed. Before dispersing the toner composition in the aqueous medium, amines may be mixed in the oil phase, or amines may be added in the aqueous medium.

  The time required for the reaction is selected depending on the isocyanate group structure of the polyester prepolymer and the reactivity between the added amines and is usually 1 minute to 40 hours, preferably 1 hour to 24 hours. The reaction temperature is usually 0 ° C. or higher and 150 ° C. or lower, preferably 20 ° C. or higher and 98 ° C. or lower. This reaction may be included in a step of adhering or / and aggregating the resin fine particles and other resin fine particles and then fusing them.

  As a specific production method, a reaction between a polyester prepolymer having an isocyanate group and amines may be mentioned. Other examples of the polyester prepolymer having an isocyanate group include a polycondensate of a polyol and a polycarboxylic acid, and a polyester obtained by further reacting a polyester having an active hydrogen group with a polyisocyanate. Examples of the active hydrogen group possessed by the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferred.

  Examples of the polyol include a diol and a trivalent or higher polyol, and a diol alone or a mixture of a diol and a small amount of a trivalent or higher polyol is preferable. Examples of the diol include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol, triethylene glycol, Dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) ); Adducts of alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, etc.) of the above alicyclic diols; Alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. Among these, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use. Examples of the trihydric or higher polyol include trihydric to octahydric or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (trisphenol PA, Phenol novolak, cresol novolak, etc.); alkylene oxide adducts of the above trivalent or higher polyphenols.

  Examples of the polycarboxylic acid include dicarboxylic acid and trivalent or higher polycarboxylic acid, and dicarboxylic acid alone or a mixture of dicarboxylic acid and a small amount of polycarboxylic acid is preferable. Dicarboxylic acids include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.) ) And the like. Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polycarboxylic acid include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). In addition, as polycarboxylic acid, you may make it react with a polyol using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing.

  The ratio of the polyol and the polycarboxylic acid is usually 2/1 to 1/1, preferably 1.5 / 1 to 1/1 / as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 1, more preferably 1.3 / 1 to 1.02 / 1.

  Polyisocyanates include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic diisocyanates ( Tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; the polyisocyanates blocked with phenol derivatives, oximes, caprolactam, etc. And combinations of two or more of these.

  The ratio of the polyisocyanate is usually 5/1 to 1/1, preferably 4/1 to 1, as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. .2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. When the molar ratio of [NCO] is less than 1, when a modified polyester is used, the urea content in the ester is lowered and the hot offset resistance is deteriorated. The content of the polyisocyanate component in the prepolymer having an isocyanate group at the terminal is usually 0.5% by mass or more and 40% by mass or less, preferably 1% by mass or more and 30% by mass or less, more preferably 2% by mass or more and 20% by mass. It is below mass%. If it is less than 0.5% by mass, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40% by mass, the low-temperature fixability deteriorates.

  The number of isocyanate groups contained per molecule in the prepolymer having isocyanate groups is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is as follows. If it is less than 1 per molecule, the molecular weight of the urea-modified polyester will be low, and the hot offset resistance will deteriorate.

  Examples of the amines include diamines, trivalent or higher polyamines, amino alcohols, amino mercaptans, amino acids, and amino groups blocked. Examples of the diamine include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, isophoronediamine, etc. ); And aliphatic diamines (ethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.) and the like. Examples of the trivalent or higher polyamine include diethylenetriamine and triethylenetetramine. 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. Examples of the blocked amino group include ketimine compounds and oxazoline compounds obtained from the amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines, preferred are diamine and a mixture of a diamine and a small amount of a triamine or higher polyamine.

  Furthermore, if necessary, the molecular weight of the polyester can be adjusted using an elongation terminator. Examples of the elongation terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).

  The ratio of amines is usually 1 as the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). / 2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] exceeds 2 or less than ½, the molecular weight of the polyester becomes low, and the hot offset resistance deteriorates. In the present invention, urea-modified polyester (UMPE) can be used as the polyester-based resin (polyester), but this polyester may contain a urethane bond as well as a urea bond. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.

  The urea-modified polyester of the present invention is produced by a one-shot method or the like. The weight average molecular weight of the urea-modified polyester is usually 10,000 or more, preferably 20,000 or more and 10 million or less, more preferably 30,000 or more and 1,000,000 or less. If it is less than 10,000, the hot offset resistance deteriorates.

  The toner of the present invention may have a release agent. As a mold release agent used for this invention, the following are mentioned, for example.

  Low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight olefin copolymer, aliphatic hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxide of aliphatic hydrocarbon wax such as oxidized polyethylene wax; fat A wax mainly composed of a fatty acid ester such as an aromatic hydrocarbon ester wax; and a partially or completely deoxidized fatty acid ester such as a deoxidized carnauba wax; a partial ester of a fatty acid and a polyhydric alcohol such as behenic acid monoglyceride A methyl ester compound having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

  The release agent particularly preferably used in the present invention is from the ease of preparation of a release agent dispersion, ease of incorporation into the prepared toner, seepage from the toner at the time of fixing, and release properties. Aliphatic hydrocarbon waxes and ester waxes are preferred.

  In the present invention, the ester wax only needs to have at least one ester bond in one molecule, and either natural ester wax or synthetic ester wax may be used.

Examples of the synthetic ester wax include a monoester wax synthesized from a long-chain linear saturated fatty acid and a long-chain linear saturated alcohol. The long-chain linear saturated fatty acid is represented by the general formula C _n H _{2n + 1} COOH, and those having n = 5 to 28 are preferably used. The long-chain straight-chain saturated alcohol is represented by C _n H _{2n + 1} OH, and n = 28 or more is preferably used.

  Examples of natural ester waxes include candelilla wax, carnauba wax, rice wax, and derivatives thereof.

  Of the above, more preferable releasing agents are synthetic ester waxes of long-chain linear saturated fatty acids and long-chain linear saturated aliphatic alcohols, or natural waxes based on the above esters. Further, in the present invention, it is more preferable that the ester is a monoester in addition to the linear structure described above.

  In the present invention, the use of a hydrocarbon wax is also one of the preferred modes.

  In the present invention, the content of the release agent in the toner is preferably 5.0% by mass or more and 20.0% by mass or less, more preferably 5.0% by mass or more and 15.0% by mass. When the amount is less than 5.0% by mass, the releasability of the toner cannot be maintained, and the transfer paper is easily wound when the fixing body is at a low temperature. When the amount is more than 20.0% by mass, the wax is likely to be exposed on the toner surface, which may cause deterioration in heat resistant storage stability. Furthermore, it is liable to cause harmful effects such as fogging and fusion.

  In the present invention, the release agent preferably has a maximum endothermic peak at 60 ° C. or higher and 120 ° C. or lower in differential scanning calorimetry (DSC). More preferably, it is 60 degreeC or more and 90 degrees C or less. If the maximum endothermic peak is lower than 60 ° C., the wax is likely to be exposed on the toner surface, which may cause a decrease in heat resistant storage stability. On the other hand, when the maximum endothermic peak is higher than 120 ° C., the wax does not melt properly at the time of fixing, and the low-temperature fixability and offset resistance may be poor.

  The toner of the present invention requires a colorant in order to impart coloring power. Examples of the colorant preferably used in the present invention include the following organic pigments, organic dyes, and inorganic pigments, and the colorants conventionally used in toners can be used. The colorant used in the toner of the present invention is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in the toner.

  The following are mentioned as a coloring agent used for this invention.

  Examples of the colorant for yellow include compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specific examples include the following. C. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 128, 129, 138, 147, 150, 151, 154, 155, 168, 180, 185, 213, 214. These can be used alone or in combination of two or more.

  Examples of the colorant for magenta include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specific examples include the following. C. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. Pigment Bio Red 19. These can be used alone or in combination of two or more.

  Examples of the colorant for cyan include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds. Specific examples include the following. C. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66. These can be used alone or in combination of two or more.

  Examples of black colorants include the following. Furnace black, channel black, acetylene black, thermal black, lamp black carbon black. Further, metal oxides such as magnetite and ferrite are also used.

  In the present invention, when a dye or pigment having extremely high solubility in water is used as the colorant, it may be dissolved in water during the production process and granulation may be disturbed, or a desired color may not be obtained.

  In the present invention, when used as a colorant for a normal color toner, the content of the colorant is preferably 2.0% by mass or more and 15.0% by mass or less based on the toner. When it is less than 2.0% by mass, the coloring power is lowered. On the other hand, when it is more than 15.0% by mass, the color space tends to be small. More preferably, it is 2.5 mass% or more and 12.0 mass% or less. Further, a light color toner having a reduced density can be preferably used in combination with a normal color toner. In this case, the content of the colorant is preferably 0.5% by mass or more and 5.0% by mass or less with respect to the toner. More preferably, it is 0.7 mass% or more and 3.0 mass% or less.

  In the toner of the present invention, a charge control agent can be mixed with toner particles and used as necessary. Further, it may be added when the toner particles are produced. By adding a charge control agent, the charge characteristics can be stabilized, and the optimum triboelectric charge amount can be controlled according to the development system.

  In the toner of the present invention, a known charge control agent can be used, and a charge control agent that has a high charging speed and can stably maintain a constant charge amount is particularly preferable.

  Examples of the charge control agent that control the toner to be negatively charged include the following. Organic metal compounds and chelate compounds are effective, and examples include monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids, and dicarboxylic acid-based metal compounds. The toner of the present invention can contain these charge control agents alone or in combination of two or more.

  A preferable blending amount of the charge control agent is 0.01 parts by mass or more and 20 parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer or the binder resin. . However, it is not essential to add a charge control agent to the toner of the present invention, and the toner does not necessarily contain a charge control agent by actively utilizing frictional charging with the toner layer thickness regulating member or the toner carrier. There is no need to let it.

  It is preferable to add inorganic fine powder as a fluidity improver to the toner particles of the present invention.

  Examples of the inorganic fine powder to be added to the toner particles of the present invention include fine powder such as silica fine powder, titanium oxide fine powder, alumina fine powder, or double oxide fine powder thereof. Among the inorganic fine powders, silica fine powder and titanium oxide fine powder are preferable.

Examples of the silica fine powder include dry silica or fumed silica produced by vapor phase oxidation of silicon halide, and wet silica produced from water glass. As the inorganic fine powder, dry silica having less silanol groups on the surface and inside the silica fine powder and less Na ₂ O and SO ₃ ²⁻ is preferable. The dry silica may be a composite fine powder of silica and another metal oxide produced by using a metal halogen compound such as aluminum chloride or titanium chloride together with a silicon halogen compound in the production process.

  Specific examples of the inorganic fine particles include the following. Silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara , Antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride.

  The inorganic fine powder is preferably externally added to the toner particles in order to improve the fluidity of the toner and make the toner particles uniformly charged. By hydrophobizing the inorganic fine powder, it is possible to adjust the charge amount of the toner, improve the environmental stability, and improve the characteristics in a high-humidity environment. More preferably, it is used. When the inorganic fine powder added to the toner absorbs moisture, the charge amount as the toner is reduced, and the developability and transferability are easily lowered.

  As treatment agents for the hydrophobic treatment of inorganic fine powder, unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, organotitanium Compounds. These treatment agents may be used alone or in combination.

  Among these, inorganic fine powder treated with silicone oil is preferable. More preferably, when the inorganic fine powder is hydrophobized with a coupling agent, or simultaneously after the hydrophobization treatment, the hydrophobized inorganic fine powder treated with silicone oil maintains a high charge amount of toner particles even in a high humidity environment. It is good for reducing selective developability.

  The addition amount of the inorganic fine powder is preferably 0.1 parts by mass or more and 4.0 parts by mass or less, more preferably 0.2 parts by mass or more and 3.5 parts by mass with respect to 100 parts by mass of the toner particles. It is as follows. If the amount is less than 0.1 parts by mass, the improvement in toner fluidity and the uniform charging of the toner particles cannot be fully achieved, which is not preferable. When the amount is more than 4.0 parts by mass, excessive inorganic fine powder contaminates various members and induces image defects, which is not preferable.

  The weight average particle diameter (D4) of the toner in the present invention is preferably in the range of 4 to 9 μm, more preferably in the range of 4.5 to 8.5 μm, and still more preferably in the range of 5 to 8 μm. When the weight average particle diameter (D4) is smaller than 4 μm, the toner fluidity is lowered, the triboelectric chargeability of each particle is liable to be lowered, and the triboelectric charge distribution is widened. The toner scatters easily from the container. If the weight average particle diameter of the toner is smaller than 4 μm, cleaning may be difficult. If the weight average particle diameter (D4) is larger than 9 μm, the resolution is lowered, so that it may be difficult to satisfy high image quality.

  The particle size distribution is carried out using a Coulter counter multisizer.

  As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. Measurement is performed with 25,000 effective measurement channels.

  As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, the dedicated software is set as follows.

  On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked.

  In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

The specific measurement method is as follows.
(1) About 200 ml of the electrolytic aqueous solution is put in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rotations / second. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) About 30 ml of the electrolytic aqueous solution is put into a glass 100 ml flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikki Bios Co., Ltd.) having an electrical output of 120 W is prepared. About 3.3 l of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 ml of Contaminone N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . The measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated. The “average diameter” on the “analysis / volume statistic (arithmetic average)” screen when the graph / volume% is set in the dedicated software is the weight average particle size (D4). When the number% is set, the “average diameter” on the “analysis / number statistics (arithmetic average)” screen is the number average particle diameter (D1).

  The toner of the present invention is used as a one-component toner and also used as a two-component toner in combination with a carrier. Since the toner of the present invention exhibits excellent properties in high-speed developability, it is preferably used as a two-component toner used in combination with a magnetic carrier.

  An example of the magnetic carrier is a resin-coated magnetic carrier.

  The resins may be used alone or in combination of two or more. The amount of the coating resin is 0.1 part by mass or more and 10 parts by mass or less, and preferably 0.5 part by mass or more and 3.0 parts by mass or less with respect to 100 parts by mass of the magnetic carrier core particles.

  The mixing ratio (mass ratio) of the toner and the magnetic carrier in the two-component developer is in the range of toner: carrier = 1: 100 to 30: 100, and more preferably in the range of 3: 100 to 20: 100.

  Although the basic configuration and features of the present invention have been described above, the present invention will be specifically described below based on examples. The number of copies in the examples is parts.

<Example of production of binder resin 1>
Terephthalic acid 166 parts Ethylene glycol 65 parts Neopentyl glycol 42 parts The above polyester monomer is charged into an autoclave together with an esterification catalyst (dibutyltin oxide), and equipped with a reflux condenser, moisture separator, N ₂ gas inlet tube, thermometer and stirrer Then, a polycondensation reaction was carried out at a temperature of 230 ° C. while introducing N ₂ gas into the autoclave. While the progress of the reaction was monitored by viscosity, when the reaction approached late, 10 parts of trimellitic anhydride was added into the autoclave to adjust the acid value of the polyester resin. By adding trimellitic anhydride at the late stage of the reaction, the acid value was adjusted without affecting the basic structure of the polyester resin. After completion of the reaction, the polyester resin was taken out from the autoclave, cooled and pulverized to obtain a binder resin 1. The physical properties of the binder resin 1 are not shown in Table 2. FIG. 2 shows a DSC chart of the binder resin 1.

<Example of production of binder resins 2 to 17>
The monomers listed in Table 1 are charged into a 5 liter autoclave together with an esterification catalyst (dibutyltin oxide), equipped with a reflux condenser, a water separator, an N ₂ gas inlet tube, a thermometer, and a stirrer, and N ₂ gas in the autoclave. The polycondensation reaction was carried out at 230 ° C. while introducing. At this time, the monomers described as post-addition in Table 1 are added in the latter stage of the polycondensation reaction to adjust the acid value or hydroxyl value. After completion of the reaction, the reaction mixture was taken out from the container, cooled and pulverized to obtain binder resins 2 to 17. Various physical properties of these resins are as shown in Table 2. FIG. 3 shows a DSC chart of the binder resin 12.

<Production of resin fine particle dispersion 1>
In a reaction vessel with a stir bar and thermometer set,
-650 parts of water-Sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries) 10 parts-85 parts of styrene-80 parts of methacrylic acid-100 parts of butyl acrylate-1 part of ammonium persulfate The mixture was stirred and stirred at 350 rpm for 15 minutes to obtain a white emulsion. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion resin fine particle dispersion 1 was obtained. The volume average particle diameter of the resin fine particle dispersion 1 measured with LA-920 was 105 nm. A part of the resin fine particle dispersion 1 was dried to isolate the resin component. The resin component had a Tg of 65 ° C. and a weight average molecular weight of 150,000.

<Production of Prepolymer 1>
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe,
・ 700 parts of bisphenol A ethylene oxide 2-mole adduct 100 parts of bisphenol A propylene oxide 2-mole adduct 100 parts ・ 200 parts of isophthalic acid ・ 60 parts of terephthalic acid ・ 20 parts of trimellitic anhydride ・ 2 parts of dibutyltin oxide Under a nitrogen flow, the condensation reaction was performed at 210 ° C. for 8 hours. Next, the reaction was continued for 5 hours while dehydrating under a reduced pressure of 10 to 15 mmHg, and then cooled to 80 ° C. Prepolymer 1 was obtained by reacting with 170 parts of isophorone diisocyanate in ethyl acetate for 2 hours. The prepolymer 1 obtained had a weight average molecular weight of 5,300.

<Synthesis of Ketimine Compound 1>
In a reaction vessel with a stir bar and thermometer set,
-150 parts of isophorone diamine and 75 parts of 1-butanone were charged and reacted at 50 ° C for 5 hours to obtain ketimine compound 1. The amine value of ketimine compound 1 was 390.

<Synthesis of Masterbatch 1>
-1200 parts of water-500 parts of carbon black-1200 parts of binder resin 1 are added and mixed with a Henschel mixer (Mitsui Mining Co., Ltd.). The mixture is kneaded at 150 ° C for 30 minutes using two rolls, then cooled by rolling. A master batch 1 was obtained by grinding with a pulverizer.

(Production example of toner particle 1)
<Preparation of oil phase 1>
In a container with a stir bar and thermometer set,
・ Binder resin 1 380 parts ・ Carnauba WAX (melting point 84 ° C.) 100 parts ・ 1-butanone 900 parts were charged, heated to 80 ° C. with stirring, and kept at 80 ° C. for 5 hours. Cooled to 30 ° C. Next, 500 parts of master batch 1 and 500 parts of 1-butanone were charged in a container and mixed for 1 hour to obtain a raw material solution 1.

  1300 parts of the raw material solution 1 was transferred to a container and filled with 80% by volume of 0.5 mm zirconia beads using a bead mill (Ultra Visco Mill, manufactured by Imex) with a liquid feed speed of 1 kg / hr, a disk peripheral speed of 6 m / second, Carbon black and WAX were dispersed under the condition of 3 passes.

  Next, 1300 parts of a 65% 1-butanone solution of binder resin 1 was added, and one pass was performed with the bead mill under the above conditions to obtain oil phase 1. The solid content concentration of oil phase 1 (130 ° C., 30 minutes) was 53%.

<Preparation of aqueous phase 1>
-Water 990 parts-Resin fine particle dispersion 1 83 parts-Sodium dodecyl diphenyl ether disulfonate 48.5% aqueous solution 37 parts (Eleminol MON-7: manufactured by Sanyo Chemical Industries)
-Carboxymethylcellulose 1 mass% aqueous solution 135 parts-1-butanone 90 parts was mixed and stirred and the milky white liquid was obtained. This is designated as aqueous phase 1.

<Emulsification ⇒ Solvent ⇒ Heat treatment process>
-Oil phase 1 1200 parts-Prepolymer 1 120 parts-Ketimine compound 1 3 parts in a container and mixed for 1 minute at 5,000 rpm with a TK homomixer (manufactured by Special Machine), then 2000 parts of aqueous phase in the container Was added and mixed with a TK homomixer at a rotational speed of 13,000 rpm for 20 minutes to obtain an emulsified slurry 1.

  The emulsified slurry 1 was put into a container in which a stirrer and a thermometer were set, and after removing the solvent for 8 characters at 30 ° C., aging was performed at 45 ° C. for 4 hours to obtain a dispersion slurry 1.

  Subsequently, the contents were transferred to a flask provided with a cooling pipe, heated to 57 ° C., and stirred at 50 rpm for 4 hours to obtain toner particle aqueous dispersion 1.

<Washing process ⇒ drying process>
Hydrochloric acid was added until the toner particle aqueous dispersion 1 had a pH of 1.5, and the mixture was stirred for 30 minutes and then filtered. The operations of filtration and redispersion in ion-exchanged water were repeated until the conductivity of the slurry reached 100 μS. In this way, the surfactant remaining in the slurry was removed and triethylamine was neutralized and removed, whereby a filter cake of toner particles 1 was obtained. The above filter cake was dried at room temperature for 3 days in a vacuum dryer, sieved with a mesh having an opening of 75 μm, and air classification was performed to obtain toner particles 1. The weight average particle diameter was 6.0 μm and the number average particle diameter was 5.5 μm.

(Production example of toner particles 2 to 11 and 13 to 18)
Toner particles 2 to 11 and 13 to 18 were obtained in the same manner except that binder resins 2 to 17 were used instead of binder resin 1 in the production example of toner particles 1. The binder resin used for each toner particle is as shown in Table 3.

(Production example of toner particles 12)
<Preparation of oil phase 12>
-Binder resin 10 100 parts-1-butanone 85 parts The said material was put into the beaker, and it stirred at 3000 rpm for 1 minute using the disper (made by a special machine company).
-Wax dispersion 1 (solid content 20%) 50 parts-Colorant dispersion 1 (solid content 20%) 25 parts-1-butanone 5 parts Furthermore, the above material is put into a beaker, and Disper (manufactured by Tokushu Kika Co., Ltd.) is added. The oil phase 12 was prepared by stirring for 3 minutes while cooling at 6000 rpm to 5 ° C. or lower.

<Preparation of aqueous phase 12>
・ Resin fine particle dispersion 1 (solid content 15%) 35 parts ・ 50% aqueous solution of sodium dodecyl diphenyl ether disulfonate 30 parts (Eleminol MON-7, manufactured by Sanyo Chemical Industries)
-Carboxymethylcellulose 1 mass% aqueous solution 100 parts-Ion exchange water 400 parts-1-butanone 50 parts The above materials are put in a container and stirred at 5000 rpm for 1 minute with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.). Was prepared.

<Granulation process ⇒ Heat treatment process>
The oil phase 12 was added to the water phase 12, the number of revolutions of the TK homomixer was increased to 10,000 rpm, and stirring was continued for 1 minute, whereby the oil phase 12 was suspended in water to obtain a suspension 12. The suspension 12 was stirred at 50 rpm for 30 minutes using a stirring blade, and then transferred to a 2 L eggplant flask. While rotating at 30 rpm using a 25 ° C. water bath and a rotary evaporator, nitrogen gas was blown onto the liquid surface at a rate of 10 L / min for 1 hour to obtain toner particle aqueous dispersion 12. Next, the toner particle aqueous dispersion 12 was heated to 53 ° C. and stirred at 50 rpm for 4 hours.

<Washing process ⇒ drying process>
Hydrochloric acid was added until the toner particle aqueous dispersion 12 had a pH of 1.5, and the mixture was stirred for 30 minutes and then filtered. The operations of filtration and redispersion in ion exchange water were repeated until the conductivity of the slurry reached 100 μS. In this way, the surfactant remaining in the slurry was removed and triethylamine was neutralized and removed to obtain a filter cake of toner particles 12. The above filter cake was dried at room temperature for 3 days in a vacuum dryer, sieved with a mesh having an opening of 75 μm, and air classification was performed to obtain toner particles 12. The weight average particle diameter was 6.0 μm and the number average particle diameter was 5.5 μm.

<Example of production of carrier particles>
4.0% by mass of a silane coupling agent (3- (2-aminoethylaminopropyl) trimethyl) with respect to a magnetite powder having a number average particle diameter of 0.25 μm and a hematite powder having a number average particle diameter of 0.60 μm. Methoxysilane) was added, and the mixture was stirred and mixed at a high speed at 100 ° C. or higher to make each fine particle lipophilic.
・ Phenol 10 parts ・ Formaldehyde solution (formaldehyde 40%, methanol 10%, water 50%)
6 parts · Lipophilicized magnetite 63 parts · Lipophilicized hematite 21 parts Add the above ingredients, 5% 28% ammonia water, and 10 parts water to a flask and stir and mix up to 85 ° C in 30 minutes The temperature was raised and maintained, and the reaction was allowed to cure by polymerization for 3 hours. Then, after cooling to 30 degreeC and adding water, the supernatant liquid was removed, the precipitate was washed with water, and then air-dried. Subsequently, this was dried under reduced pressure (5 mmHg or less) at 60 ° C. to obtain spherical magnetic resin particles in which a magnetic material was dispersed.

As the coating resin, a copolymer of methyl methacrylate and methyl methacrylate having a perfluoroalkyl group (m = 7) (copolymerization ratio 8: 1 weight average molecular weight 45,000) was used. To 100 parts of the coating resin, 10 parts of melamine particles having a particle size of 290 nm, 6 parts of carbon particles having a specific resistance of 1 × 10 ⁻² Ω · cm and a particle size of 30 nm were added and dispersed for 30 minutes by an ultrasonic disperser. Further, a mixed solvent coating solution of methyl ethyl ketone and toluene was prepared so that the coating resin content was 2.5 parts with respect to the carrier core (solution concentration 10% by mass).

The coating solution was applied to the surface of the magnetic resin particles by volatilizing the solvent at 70 ° C. while continuously applying shear stress. The resin-coated magnetic carrier particles were heat-treated with stirring at 100 ° C. for 2 hours, cooled and pulverized, and then classified by a 200-mesh sieve to obtain a number average particle diameter of 33 μm, a true specific gravity of 3.53 g / cm ³ , A carrier having an apparent specific gravity of 1.84 g / cm ³ and a magnetization strength of 42 Am ² / kg was obtained.

[Example 1]
(Preparation of toner 1 and two-component developer 1)
Next, anatase-type titanium oxide fine powder (BET specific surface area 80 m ² / g, number average particle diameter (D1): 15 nm, treated with 12% by mass of isobutyltrimethoxysilane) is applied to 100 parts of the toner particles 1 0.9. The part was first externally added using a Henschel mixer. Further oil-treated silica fine particles (BET specific surface area 95 m ² / g, silicone oil treated with 15 mass%) 1.2 parts, the inorganic fine particles (sol-gel silica fine particles: BET specific surface area of 24m ² / g, number average particle diameter (D1): 110 parts) was mixed with a Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.) FM-10B to obtain toner 1.

  In the present invention, a two-component developer 1 is prepared by mixing 8 parts of the toner 1 and 92 parts of the carrier.

<Image evaluation>
A method for evaluating the obtained toner will be described. Image evaluation was performed using image RUNNER iRC3580. Below, the evaluation method and evaluation criteria of this invention are demonstrated.

Take out the fuser of a commercially available multifunction machine (image RUNNER iRC3580, manufactured by Canon Inc.) and operate it outside the multifunction machine, and use an external fuser modified so that the fixing temperature and process speed can be set arbitrarily. It was. Using this external fixing device, paper was passed under an environment of normal temperature and normal humidity (N / N: temperature 23.5 ° C., humidity 60% RH). Low temperature fixability is to pass a solid black unfixed image (toner loading 0.45 mg / cm ² ) using 90 g / m ² paper and Rezac 66 (151 g / m ² ) as uneven paper. It was evaluated by. High-temperature offset resistance is evaluated by using 50 g / m ² paper and passing through an unfixed image that is A4 sideways and has a halftone with an image density of 0.5 across the entire area 5 cm from the tip and a solid white other than that. did. In addition, fixing unevenness was evaluated by using 90 g / m ² paper and passing an unfixed image in which 10 mm × 10 mm size solid patch images were uniformly written in a horizontal row at 10 positions on the front end of the paper. . The evaluation results are shown in Table 4.

For low-temperature fixability, the solid black image created by the above method is temperature-regulated every 5 ° C. in the temperature range of 100 to 180 ° C. with a heating device of the fixing device, the process speed is 300 mm / sec, and the nip width is 13 mm. Set and fix. A load of 4.9 kPa was applied to the obtained fixed image, and the fixed image was rubbed back and forth with Sylbon paper 5 times, and the temperature at which the image density reduction rate before and after the rub was 10% or less was evaluated as the fixing start temperature. did. The image density was measured using a Macbeth densitometer (RD-914; manufactured by Macbeth) using an SPI auxiliary filter.
A: Fixing start temperature is less than 120 ° C. for both 90 g / m ² paper and Rezac 66 B: Fixing start temperature is 90 ° C. to less than 125 ° C. for both 90 g / m ² paper and Rezac 66 C: Fixing start temperature is 90 g / m ² paper and Leathac 66 both 125 ° C. or higher 130 ° C. less than D: fixation starting temperature is 90 g / m ² paper and Leathac 66 both 130 ° C. or higher 135 ° C. less than E: either fixation starting temperature is 90 g / m ² paper or Leathac 66 135 ℃ or more

For high-temperature offset resistance, the unfixed image created by the above method is temperature-regulated every 5 ° C. in the temperature range of 180 to 200 ° C. with a heating device of the fixing device, the process speed is 50 mm / sec, and the nip width is 13 mm. Set and fix. The level of the offset appearing on the white background at this time was visually confirmed.
A: No offset occurs at all. B: A slight offset occurred at the end other than the portion where the paper was passed in A4 portrait orientation at a fixing temperature of 200.degree.
C: An offset occurred in the entire longitudinal direction at a fixing temperature of 200 ° C.
D: At a fixing temperature of 190 ° C., a slight offset occurred at the end portion other than the portion that passed through the A4 portrait.
E: Offset occurred at the fixing temperature of 190 ° C. throughout the longitudinal direction.

For storage stability, 5 g of the developer was measured in a 100 cc polycup, and the blocking property after standing in a constant temperature and humidity chamber at 45 ° C. and 95% RH for 30 days was visually evaluated using the following evaluation criteria.
A: There is no appearance of solidified B: Unraveled as soon as the cup is turned C: There is a lump, but it gets smaller and smaller as the cup is turned D: Even if the cup is turned away, the lump remains E: Large There is a lump and it won't unravel when you turn the cup

For fixing unevenness, an unfixed image created by the above method is fixed at a heating device of the fixing device at 180 ° C., a process speed of 300 mm / sec and a nip width of 13 mm, and fixed at 10 locations. The difference between the maximum and minimum gross values was evaluated. The gloss value was measured using a handy gloss meter gloss checker (trade name IG-310, manufactured by Horiba, Ltd.) for the image in the fixed image area.
A: Gloss difference is less than 3 B: Gloss difference is 3 or more and less than 6 C: Gloss difference is 6 or more and less than 9 D: Gloss difference is 9 or more and less than 12 E: Gloss difference is 12 or more

[Examples 2 to 12]
In the preparation of the toner of Example 1, toners 2 to 12 were prepared and a developer was prepared according to Example 1, except that toner particles 2 to 12 were used instead of toner particles 1. A similar evaluation was performed. The evaluation results are shown in Table 4.

[Comparative Examples 1 to 6]
In the production of the toner of Example 1, except that the toner particles 13 to 18 are used instead of the toner particles 1, the production of the toners 13 to 18 and the preparation of the developer are performed in accordance with the first example. A similar evaluation was performed. The evaluation results are shown in Table 4.

Claims (3)

The present invention relates to a toner obtained by suspending a toner material in which at least a binder resin and a colorant are dissolved and / or dispersed in an organic solvent in an aqueous medium to form oil droplets, and then removing the organic solvent. A toner containing particles,
The binder resin contains at least a polyester resin,
The polyester resin has a first endothermic peak P1 at a temperature of 55 to 75 ° C. and a second endothermic peak P2 at a temperature of 80 to 120 ° C. in a DSC curve measured by a differential scanning calorimeter. toner.   The first endothermic peak P1 of the polyester resin has an endothermic amount of 0.20 J / g to 1.50 J / g, and the second endothermic peak P2 has an endothermic amount of 0.20 J / g to 2.00 J. The toner according to claim 1, wherein the toner is / g.   The polyester resin has at least one peak in a molecular weight region of 5000 to 10,000 in a molecular weight distribution measured by gel permeation chromatography (GPC) of a THF-soluble component, and an area having a molecular weight of 3000 or less is the entire area. The toner according to claim 1, wherein the toner is 20% by mass or less based on the area.

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