JP4609143B2 - Method for producing toner for developing electrostatic image - Google Patents

Description

The present invention is a copying machine, a printer, an image forming apparatus utilizing an electrophotographic process such as a facsimile, a method of manufacturing a toner over the electrostatic image developing used for developing the electrostatic image.

  A method of visualizing image information through an electrostatic latent image, such as electrophotography, is currently widely used in various fields. In the electrophotographic method, the electrostatic latent image on the surface of the photoreceptor is developed through a charging process, an exposure process, and the like, and the electrostatic latent image is visualized through a transfer process, a fixing process, and the like.

  Many methods are known as electrophotographic methods. In general, a latent image is electrically formed by various means on the surface of a photoreceptor (latent image holding body) using a photoconductive substance, and the formed latent image is developed with toner. After forming the image, the toner image is transferred to the surface of a transfer medium such as paper, optionally via an intermediate transfer body, and is subjected to a plurality of steps of fixing by heating, pressing, and heating and pressing. An image is formed. Further, the toner remaining on the surface of the photosensitive member may be cleaned by various methods as necessary and used again for developing the toner image.

  As a fixing technique for fixing the toner image transferred to the surface of the transfer target, a hot roll fixing in which the transfer target with the toner image transferred is inserted between a pair of rolls consisting of a heating roll and a pressure roll and fixed. The law is common.

  Amid recent global energy conservation trends, the industry has become a great social demand for how to supply low energy and low environmental load manufacturing methods and products. Under such circumstances, the development of technology, such as the reduction of fixing energy, which consumes the most energy in the electrophotographic process, has been actively carried out by using low-temperature fixing technology using a polycondensation resin having a polyester structure as a resin for toner. ing. Also, in this polyester resin production method, it was usually produced by a polycondensation reaction at a high temperature of 150 ° C. or more. However, polymerization at a lower energy (low temperature) and production technology are in view of the above environmental load. There is a strong demand. In this case, it has been recently found that polymerization can be performed at a temperature of 100 ° C. or less with a polymerization catalyst composed of a rare earth element such as scandium as a technique for polymerizing a polyester resin at a lower temperature (Macromolecules, 2003, 36, 1772). -1774).

  However, polyester resins polymerized by these new polymerization catalysts are still under active research, including catalyst chemistry, mechanism, side reactions, and residual catalyst effects. Whether it can be put into practical use or has any difference as compared with conventional process resins, and what characteristics can be used for practical use is an important issue in the industry.

  On the other hand, due to the rapid spread of the current digitization technology, there is a growing demand for higher image quality in the output of printing, copying, etc. for users in ordinary homes, offices, and publishing areas. In order to meet the demand for higher image quality, especially in toners used for electrophotography, it is recognized that one of the technically important approaches is to reduce the particle size and improve the resolution. Then, the particle diameter is reduced to a region of 5 μm. In this case, in order to achieve a particle size of 6 μm or less in which the particle size distribution is sufficiently controlled in order to maintain sufficient characteristics as an electrophotographic toner in reducing the particle size of the toner, conventional toner production is used. The kneading and pulverization method that has been used is difficult to cope with in terms of production energy and cost. Currently, the toner production method is a so-called chemical production method such as a suspension polymerization method in an aqueous medium, a dissolution suspension method, or an emulsion polymerization aggregation method. The manufacturing method is shifting to. Therefore, it is more preferable that the low-temperature fixing resin and the low-temperature polycondensation technology incorporating the low energy and low environmental load technologies as described above can be applied to these aqueous media. In the above-mentioned technical area where the basic principle is the direct polymerization method in an aqueous medium has been considered difficult.

  For this reason, when these resins are applied to chemically produced toners, usually, a method of preliminarily polycondensation by bulk polymerization, solution polymerization or the like to increase the molecular weight, and then dispersing and emulsifying in an aqueous medium has been adopted. In this case, in order to give sufficient performance as a toner for high image quality, it is necessary to control the particle size and distribution highly as described above, but once the polymer having a high molecular weight by bulk polymerization or the like is dispersed and emulsified. It is very difficult to use organic solvents, etc., high temperature heating and melting, high shear energy dispersion, or classification operation at the final step requiring a lot of energy. Energy saving and indispensable low-energy manufacturing technology for toner resin are difficult to achieve at the same time. Even if the energy can be reduced by the electrophotographic process due to low-temperature fixing etc., much energy is required for the resin manufacturing compared to the past. However, when considering the total energy balance from material production to product use, it is never said that low energy has been achieved. There.

  In other words, in future toner manufacturing issues, low environmental impact and low energy technologies such as low-temperature fixing in electrophotography, and toner produced by chemical manufacturing, which is indispensable for the demand for higher image quality that electrophotography is required in recent years In order to achieve both the production method and ideally, it is considered that a technique capable of easily producing the aqueous dispersion of the polycondensation resin is indispensable. One noteworthy finding for solving this problem is a report that polycondensation of polyester in an aqueous medium, which has been considered difficult in the past, is possible in an aqueous medium (Saam JC, Chou YJ). US Patent, 4355154; 1982).

However, there are many unclear points in the polymerization mechanism in the technology, and it is difficult to obtain a high molecular weight polymer that can satisfy the properties as an electrophotographic toner only by the technology according to this document, particle size distribution property, charging property, etc. It has not yet reached an area where it can be applied as a toner, such as difficulty in achieving high image quality.
Macromolecules, 2003, 36, 1772-1774. USP 4355154

Therefore, the present invention has been made based on the circumstances as described above, and the object of the present invention is to satisfactorily coat the polyester surface with the radical polymer, to suppress the surface exposure of the polyester, and to reduce the particle size. A toner for developing an electrostatic charge image that is capable of producing resin fine particles having a sharp particle size distribution and that sufficiently satisfies various toner characteristics by using a method for producing a resin fine particle dispersion in which the resin fine particles are stably emulsified and dispersed. it is to provide a method for producing chromatography.

The above problem is solved by the following means. That is,
The method for producing the toner for developing an electrostatic charge image of the present invention comprises:
Along with sodium dodecylbenzenesulfonate and scandium trisdodecyl sulfate, a polycondensation polyester monomer and a radical polymerizable monomer are emulsified or dispersed in an aqueous medium, and then polycondensation and radical polymerization are carried out to obtain a resin fine particle dispersion. a process of manufacturing, .delta.v-.DELTA.Pe of the difference between the polymerizable polyester monomer overall weight average solubility parameter .DELTA.Pe and the radical polymerizable monomer overall weight average solubility parameter .delta.v 1.06 or 1. 30 or less [(cal / cc) ^1/2 (25 ° C.)] and more, and the hydrophobic parameter (Log (P)) of all monomers of the polycondensed polyester monomer and the radical polymerizable monomer ) Is a step of producing a resin fine particle dispersion having a value of 0.6 or more and 5.14 or less ,
Agglomerating resin fine particles in the resin fine particle dispersion; and
Heating and melting the obtained agglomerated particles,
It is characterized by including .

In the method for producing a toner for developing an electrostatic charge image of the present invention, it is preferable to use a vinyl monomer as the radical polymerizable monomer. Further, as the radical polymerizable monomer, it is also preferable to use a radical polymerizable unsaturated acid monomer having a solubility in water of 80% (25 ° C.) or an acid anhydride together with a vinyl monomer. is there.

In the method for producing a toner for developing an electrostatic charge image of the present invention, the polycondensation polyester monomer and the radical polymerizable monomer are obtained by dissolving the polycondensation polyester monomer in the radical polymerizable monomer in advance. It is preferable to emulsify or disperse in the aqueous medium.

In the method for producing an electrostatic charge image developing toner of the present invention, the polyester obtained by polycondensation of the polycondensation polyester monomer is preferably a crystalline resin.

In the method for producing a toner for developing an electrostatic charge image of the present invention, the obtained resin fine particles have a core / shell structure in which a core is covered with a shell, and the core polycondenses the polycondensation polyester monomer. It is preferable that the shell is made of a radical polymer obtained by radical polymerization of the radical polymerizable monomer.

According to the present invention, the surface of the polyester can be satisfactorily coated with the radical polymer on the polyester surface, and the resin fine particles having a small particle size and a sharp particle size distribution can be produced. method for producing a stable emulsified and dispersed resin particle dispersion, and by using it with a resin fine particle dispersion obtained, to provide a method for producing a toner characteristics fully satisfying the electrostatic image developing toner over Can do.

(Resin fine particle dispersion)
In the method for producing a resin fine particle dispersion of the present invention, first, a polycondensation polyester monomer and a radical polymerizable monomer are emulsified or dispersed in an aqueous medium as a target resin fine particle raw material by, for example, mechanical shearing or ultrasonic waves. Disperse. At this time, additives such as a catalyst and a surfactant are also added to the water-soluble medium as necessary. For example, by heating the solution, polycondensation and radical polymerization are advanced. And as a polycondensation polyester monomer and a radically polymerizable monomer, a hydrophobic parameter (Log (P)) of -0.5 or more and 20 or less is used, and the polycondensation polyester monomer and radically polymerizable property are used. As the monomer, the absolute value | δv−δpe | of the difference between the weight average solubility parameter δpe of the whole polymerizable polyester monomer and the weight average molecular weight parameter δv of the whole radical polymerizable monomer is 1.05 [( cal / cc) ^1/2 (25 ° C.)] or more.
However, the method for producing the resin fine particle dispersion according to the present invention is obtained by emulsifying or dispersing a polycondensation polyester monomer and a radical polymerizable monomer together with sodium dodecylbenzenesulfonate and scandium trisdodecylsulfate in an aqueous medium. , Polycondensation and radical polymerization to produce a resin fine particle dispersion, the weight average solubility parameter δpe of the whole polymerizable polyester monomer and the weight average solubility parameter δv of the whole radical polymerizable monomer Δv−δpe of 1.06 or more and 1.30 or less [(cal / cc) ^1/2 (25 ° C.)] or more, and the polycondensed polyester monomer and the radical polymerizable monomer A method for producing a resin fine particle dispersion in which the hydrophobic parameter (Log (P)) of all the monomers is 0.6 or more and 5.14 or less is applied.

  In the method for producing a resin fine particle dispersion of the present invention, resin fine particles having a small particle size and a sharp particle size distribution can be obtained by using a monomer satisfying the above conditions. This is presumably because the radically polymerizable monomer can be present in the surface layer of the resin fine particles and the vicinity thereof, so that the charging characteristics on the surface of the resin fine particles can be stably controlled.

  In addition, by using a monomer that satisfies the above conditions, a radical polymerizable monomer can be present in the surface layer of the resin fine particles and in the vicinity thereof. The surface exposure of unstable polyester can be suppressed, and the surface of resin fine particles can be coated with a relatively stable radical polymer. For this reason, the resin fine particle dispersion of the present invention is chemically stable, and as a result, the storage stability as the resin fine particle dispersion is also improved.

  Further, when the obtained resin fine particle dispersion (resin fine particle dispersion of the present invention) is applied to an electrostatic charge image developing toner, a toner having excellent toner characteristics can be obtained. Usually, crystalline and low molecular weight polyesters are advantageous for low-temperature fixing, but have low resistance, are chemically unstable as described above, and have many disadvantages as toner resins. However, in the method for producing resin fine particles of the present invention, the radically polymerizable monomer is satisfactorily coated on the polyester surface, so that low-temperature fixability is achieved, and at the time of toner production that requires process conditions such as acid and alkalinity, for example. However, it is possible to obtain a toner that maintains a stable state, has a good particle size and particle size distribution, and prevents deterioration in charging characteristics.

  Thus, the method for producing resin fine particles of the present invention can be suitably applied as a method for producing a resin fine particle dispersion for an electrostatic charge image developing toner.

  In the method for producing a resin fine particle dispersion of the present invention, a polycondensation polyester monomer and a radical polymerizable monomer having a hydrophobicity parameter (Log (P)) of −0.5 or more are used. The sex parameter (Log (P)) is preferably 1.0 or more, and more preferably 1.5 or more. These hydrophobicity parameters (Log (P)) are preferably as high as possible, but the upper limit value is about 20 as a substance that can actually exist.

Here, the hydrophobicity parameter (Log (P)) means that the higher the value, the more hydrophobic, and generally the following formula (1-octanol / logarithm of the distribution coefficient of the monomer to water) It is expressed.
Formula: Log (P) = Log (C ₀ / C _w )
(In the formula, C ₀ represents the concentration of the monomer (monomer) in 1-octanol at the measurement temperature, and C _w represents the concentration of the monomer (monomer) in water at the measurement temperature.)

  The hydrophobicity parameter (Log (P)) is calculated by the method “Atom Typing Scheme (Journal of Computational Chemistry, Vol. 9, No. 1, 80) of Gose-Pritchett-Crippen et al., Which is a computational chemical group contribution method. -90, 1988) ”.

  When the Log (P) of the polycondensed polyester monomer and radical polymerizable monomer is smaller than −0.5, the molecular weight after polycondensation in an aqueous medium is not sufficient, and many low molecular weight components are present. As a result, sufficient toner characteristics may not be obtained. Therefore, before emulsification or dispersion of each monomer in an aqueous medium, a part or all of the monomer is subjected to addition polymerization as pre-addition polymerization to form an oligomer of a dimer or more (monomer polymerization in advance). Alternatively, after a solution polymerization to form a low molecular weight precursor), this can be emulsified and dispersed in a water-based medium as a monomer (starting material), followed by polycondensation or radical polymerization. The molecular weight of these oligomers is preferably, for example, 15000 or less in terms of weight average molecular weight. The Log (P) of the oligomer is Log (P) converted to the weight average from the monomer used for the oligomer polycondensation, and the Log (P) value only needs to satisfy the above range. In this method, that is, the starting material for polycondensation is a low molecular weight oligomer having a weight average molecular weight of 15000 or less that is polymerized in advance by bulk polymerization or solution polymerization, so that the monomer has a Log (P) smaller than −0.5. Is copolymerized with other monomers in advance, Log (P) can be adjusted to -0.5 or more, and the degree of freedom of resin fine particles can be further increased.

  On the other hand, the absolute value | (δv−δpe) | of the difference between the solubility parameter (δpe) of the total amount of the polycondensed polyester monomer and the solubility parameter (δv) of the whole radical polymerizable monomer is 1.05 or more. , Preferably it is 1.05-1.3, More preferably, it is 1.05-1.2. Further, the solubility parameter (δv) of the entire radical polymerizable monomer is preferably larger than the solubility parameter (δpe) of the total amount of the polycondensed polyester monomer.

  This difference in absolute value indicates a difference in solubility parameter between the obtained polymers. That is, the difference in the solubility parameter indicates that the difference in hydrophilicity between the polyester and the radical polymer in the aqueous medium, that is, the difference in solubility parameter between the two polymers is controlled in a specific region. This not only yields fine resin particles with a small particle size and sharp particle size distribution, but also exposes the surface of polyester (especially low-resistance resin components such as crystallinity and low molecular weight polyester that are conveniently used for low-temperature fixing). It becomes possible to suppress. As a result, sufficient fixing characteristics, charging characteristics, and particle size distribution characteristics as a toner can be obtained.

  Here, as a method for calculating the solubility parameter, the method that was proposed by Fedors et al., Which is the most general-purpose, widely spread, and recognized for its usefulness, that is, the sum Δei of the cohesive energy per unit functional group and the molecular volume. A method of determining the sum Δvi of the two and obtaining from the relaxation was adopted (R. F. Fedors, Polym. Eng. Sci., 14, 147 (1974)). Moreover, each weight fraction was calculated from the compounding actual amount of each monomer monomer component in this invention, and it was set as the weight average solubility parameter from a monomer (following formula).

In the above formula, δ _{overall is a} polymer solubility parameter (cal / cc) (25 ° C.), w _i is a weight fraction calculated from each monomer, Δe _i is each unit functional group of each monomer component Per unit of cohesive energy (cal / mol), Δv _i : sum of molecular volume per unit functional group (cc / mol /) ^1/2 (25 ° C.).

  However, in calculating the solubility parameter (SP value) in the above formula, in radical polymerizable monomers (particularly vinyl monomers), the double bond was converted to the σ bond by the radical reaction. In the case of a polycondensation polyester monomer composed of a polycarboxylic acid and a polyhydric alcohol, assuming that a polymer chain is formed by a dehydration reaction, the polycarboxylic acid terminal is an ester group, and the polyhydric alcohol is a single monomer. It was calculated that the hydroxyl group was released from the body component. Further, the calculated values are calculated with the number of atoms forming the main chain skeleton in each monomer being taken into account, and in the case of an aromatic ring, the number of atoms is set to 6.

  The resin fine particles obtained under such conditions have a core / shell structure in which the core is covered with a shell, the core is made of polyester obtained by polycondensation of a polycondensation polyester monomer, and the shell is the radical polymerization. It is composed of a radical polymer obtained by radical polymerization of a functional monomer. And as above-mentioned, this shell is coat | covered favorably to the core.

  Next, the polycondensation polyester monomer and the polycondensation thereof will be described. Examples of the polycondensation polyester monomer include aliphatic, alicyclic, and aromatic polycarboxylic acids, alkyl esters and polyhydric alcohols thereof, ester compounds thereof, and the like, and direct esterification reaction using them. Polyester can be obtained by polycondensation by transesterification or the like.

  The obtained polyester can take any form such as amorphous (non-crystalline) polyester, semi-crystalline resin, crystalline resin, or a mixed form thereof. It is preferable that at least a crystalline polyester having a melting point in the range of 40 ° C. or higher and 150 ° C. or lower is included.

  Here, for the measurement of the melting point of the crystalline resin, a differential scanning calorimeter (DSC) was used, and the input shown in JIS K-7121 when measuring from room temperature to 150 ° C. at a heating rate of 10 ° C. per minute. It can be determined as the melting peak temperature of the compensated differential scanning calorimetry. The crystalline resin may show a plurality of melting peaks, but in the present invention, the maximum peak is regarded as the melting point.

  Moreover, a glass transition point says the value measured by the method (DSC method) prescribed | regulated to ASTMD3418-82.

  Regarding the presence or absence of crystallinity in the resin, the heat absorption curve measured by the above method is a straight line obtained by extending the low-temperature base line to the high-temperature side and the melting peak (endothermic peak) according to the melting temperature definition of JIS K7121. The slope of the tangent intersection (melting start temperature) drawn at the point where the gradient is maximized on the low temperature side curve, the straight line extending the high temperature side baseline to the low temperature side, and the high temperature side curve of the melting peak (endothermic peak) If the temperature difference of the intersection of the tangent lines drawn at the maximum point (melting end temperature) is within 50 ° C., and the shape of the curve does not show the stepped shape similarly shown in JIS K7121, it has crystallinity It was judged.

  Examples of the monomer component for polymerizing such crystalline polyester include divalent carboxylic acid components such as adipic acid, peric acid, azelaic acid, sebacic acid, and 1,9-nonanedicarboxylic acid. 1,10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, aliphatic dicarboxylic acid such as 1,18-octadecanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalene- Dicarboxylic acids such as dibasic acids such as 2,6-dicarboxylic acid, and the like, and anhydrides and lower alkyl esters thereof are also included, but not limited thereto.

  Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and anhydrides thereof. It is done. These may be used individually by 1 type and may use 2 or more types together. In addition to the aliphatic dicarboxylic acid and aromatic dicarboxylic acid described above, a dicarboxylic acid component having a double bond can also be contained. A dicarboxylic acid having a double bond can be suitably used to prevent hot offset at the time of fixing in that it can be radically cross-linked through the double bond. Examples of such dicarboxylic acids include, but are not limited to, maleic acid and fumaric acid. In addition, these lower esters, acid anhydrides and the like are also included. These are cases where Log (P) when used alone is -0.5 or more, but Log (P) is larger in advance when Log (P) is smaller than -0.5 as described above. It can be used by preparing a low molecular weight derivative by copolymerizing with a monomer.

  Specific examples of the polyhydric alcohol include, for example, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 4-cyclohexanedimethanol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, , 13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,14-eicosandecanediol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, and the like. However, it is not limited to these. Examples of the trivalent or higher alcohol include trimethylolpropane.

  These may be used individually by 1 type and may use 2 or more types together. In addition, these are cases where Log (P) when used alone is −0.5 or more. However, as described above, when Log (P) is smaller than −0.5, Log (P) is set in advance. It can be used by preparing a low molecular weight derivative by copolymerizing with a large monomer.

  In the polycondensation of polyester using these monomers, a known polycondensation catalyst can be blended in the polyester monomer in advance if necessary. In order to achieve polycondensation at a lower temperature, it is particularly effective to use a Bronsted polycondensation catalyst or an enzyme catalyst. For example, one or more of these catalysts are polycondensed at a temperature of 150 ° C. or less (preferably 100 ° C. or less) by adding them in advance to the aqueous medium together with the polyester raw material in a proportion of, for example, about 0.1 to 10,000 ppm. can do.

  Examples of the Bronsted acid catalyst include inorganic acids, organic acids, and rare earth element catalysts. In particular, from the viewpoint of achieving polycondensation at a lower temperature, it is desirable to use a rare earth element catalyst containing a rare earth element selected from Y, Sc, Yb, and Sm as a Bronsted acid type catalyst.

  Examples of inorganic acids include sulfuric acid, hydrochloric acid, and odorous acid. Among these, inorganic acids having a sulfonic acid group are preferable.

  Examples of the organic acid include organic acids having a sulfonic acid group such as dodecylbenzene sulfonic acid, polystyrene sulfonic acid, and a styrene copolymer thereof.

  The rare earth element catalyst preferably contains at least one element selected from Y, Sc, Yb, and Sm as its constituent elements, and preferred catalyst forms include triflate forms and trisdodecyl sulfate type forms of these elements. Etc. can be illustrated. Specific examples include scandium trisdodecyl sulfate.

  On the other hand, examples of the enzyme catalyst include lipase, protease, cellulase, and lipase. Examples of these include those derived from Pseudomonas fluorescens, those derived from Pseudomonas cepasia, those derived from Porcine pancreas, Examples include those derived from Aspergillus niger, those derived from Rhizopus delemer, those derived from Rhizopus japonicus, and the like.

  These catalysts can be used alone, but a plurality of catalysts can be used as necessary. In addition, it is important to select the catalyst compound or surfactant-type catalyst having a higher hydrophobicity or molecular weight in consideration of the fact that the catalyst is distributed in the polyester emulsion or particles being polymerized and the aqueous medium. From the viewpoint, a surfactant type catalyst is particularly preferable. For example, preferred is scandium trisdodecyl sulfate.

  Here, the surface active catalyst, that is, the catalyst having surface active ability is a catalyst having a chemical structure composed of a hydrophobic group and a hydrophilic group. Usually, the catalyst is easy to migrate into water, but the surface active catalyst is adsorbed on the surface of the resin particles and easily participates in the polymerization reaction in the oil layer, so that the polymerization reaction can be promoted more effectively.

  These catalysts can be recovered and reused as necessary.

  Next, the radical polymerizable monomer and the radical polymerization thereof will be described. The radically polymerizable monomer is finally polymerized by radical polymerization to give hybrid particles of polyester and radically polymerized polymer. Examples of the radical polymerizable monomer that gives the radical polymerization polymer used here include aromatic vinyl monomers, (meth) acrylic acid ester monomers, vinyl ester monomers, vinyl ether monomers, A monoolefin type monomer, a diolefin type monomer, a halogenated olefin type monomer, etc. can be mentioned.

  Examples of the aromatic vinyl monomer include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-methoxy styrene, p-phenyl styrene, p-chloro styrene, p-ethyl styrene, p. -N-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, 2, Examples thereof include styrene monomers such as 4-dimethylstyrene and 3,4-dichlorostyrene and derivatives thereof. Examples of (meth) acrylic acid ester monomers include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, and methacrylic acid. Examples include butyl, hexyl methacrylate, 2-ethylhexyl methacrylate, ethyl β-hydroxyacrylate, propyl γ-aminoacrylate, stearyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like. Examples of vinyl ester monomers include vinyl acetate, vinyl propionate, and vinyl benzoate. Examples of the vinyl ether monomer include vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl phenyl ether and the like. Examples of the monoolefin monomer include ethylene, propylene, isobutylene, 1-butene, 1-pentene, 4-methyl-1-pentene and the like. Examples of the diolefin monomer include butadiene, isoprene, chloroprene and the like. Examples of the halogenated olefin monomer include vinyl chloride, vinylidene chloride, vinyl bromide and the like.

  Among these monomers, vinyl monomers are most preferable. Furthermore, in order to control the solubility parameter of the whole radical polymerizable monomer (radical polymer), together with the vinyl monomer, the radical polymerizable unsaturated acid monomer having a water solubility within 80% (25 ° C.) It is preferable to use the product or its acid anhydride, that is, to copolymerize them. Examples of the unsaturated acid monomer include acrylic acid, methacrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and derivatives thereof, and one or several of them are used in combination. It is possible. Further, in the case of these acid anhydrides, it is known that part or all of the acid anhydride is hydrolyzed to become an acid during the polymerization, and after the polymerization, hydrolysis is appropriately performed by a known method using an acid, an alkali, or the like. Is possible.

  As a polymerization method of these radical polymerizable monomers, known polymerization methods such as a method using a radical polymerization initiator, a self-polymerization method by heat, and a method using ultraviolet irradiation can be employed. In this case, as a method using a radical initiator, radical polymerization initiators include oil-soluble and water-soluble initiators, but both initiators can be used.

  Examples of the radical polymerization initiator include ammonium persulfate, potassium persulfate, sodium persulfate, 2,2′-azobis- [2-methylpropionamide] -dihydrochloride, t-butylperoxy-2-ethylhexano Ate, cumyl perpivalate, t-butyl peroxylaurate, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, 2, 2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4- Methoxy-2,4-dimethylvaleronitrile), 1,1-bis (t-butyl par Oxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,4-bis (t-butylperoxycarbonyl) cyclohexane, 2,2-bis (t-butylper) Oxy) octane, n-butyl 4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane, 1,3-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5- Di (benzoylperoxy) hexane, di-t-butyldiperoxyisophthalate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane Di-t-butylperoxy α-methylsuccinate, di-t-butylperoxydimethylglutarate, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate, 2,5-dimethyl -2,5-di (t-butylperoxy) hexane, diethylene glycol-bis (t-butylperoxycarbonate), di-t-butylperoxytrimethyladipate, tris (t-butylperoxy) triazine, vinyltris (t -Butylperoxy) silane, 2,2'-azobis (2-methylpropionamidine dihydrochloride), 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine], 4,4 And '-azobis (4-cyanovaleric acid).

  Hereinafter, the method for producing resin fine particles of the present invention will be described in more detail. The resin fine particles obtained have a volume average particle diameter of preferably 10 μm or less, more preferably 7 μm or less, and most preferably 0.2 μm to 1 μm. When the particle diameter is larger than 10 μm, it is not preferable in terms of image quality characteristics such as resolution when used as a toner. Further, when the particle diameter is larger than 10 μm, the molecular weight increase and the speed in polycondensation are not sufficient, which is a problem in terms of image quality strength after fixing in production.

  In order to obtain polycondensation resin fine particles having a predetermined particle size in such an aqueous medium, the polymerization method is suspension polymerization method, dissolution suspension method, miniemulsion method, microemulsion method, microemulsion method, multistage swelling method. It is preferable to use a heterogeneous polymerization form in a normal aqueous medium such as emulsion polymerization including seed polymerization. In this case, as shown above, the polycondensation reaction, and finally the final molecular weight and the polymerization rate depend on the final particle diameter of the particles, so that the most preferable particle diameter form of 1 μm is achieved, and the efficiency is high. As a production form capable of achieving the production, a polymerization method in which submicron particles of 1 μm or less, such as a miniemulsion method and a microemulsion method, are used as the final form is more preferable.

  In the polyester production method of the present invention, each of the above materials is emulsified or dispersed in an aqueous medium using, for example, mechanical shear or ultrasonic waves. However, the monomer may be directly emulsified and dispersed. May be preliminarily bulk-polymerized or solution-polymerized to form a low molecular weight precursor, which may then be emulsified or dispersed. In this emulsification dispersion, it is preferable that the polycondensation polyester monomer is previously dissolved in the radical polycondensation monomer and then emulsified or dispersed in an aqueous medium. Thereby, the emulsification dispersion and the polycondensation reaction can be made easier. In addition, a surfactant, a polymer dispersant, an inorganic dispersant, and the like can be added to the aqueous medium as needed during the emulsification dispersion.

  Examples of the surfactant used herein include anionic surfactants such as sulfate ester, sulfonate, and phosphate ester; cationic surfactants such as amine salt type and quaternary ammonium salt type; polyethylene glycol And nonionic surfactants such as polyphenols, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Among these, anionic surfactants and cationic surfactants are preferable. The nonionic surfactant is preferably used in combination with the anionic surfactant or the cationic surfactant. The said surfactant may be used individually by 1 type, and may use 2 or more types together. As anionic surfactants, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium arylalkylpolyethersulfonate, 3,3-disulfonediphenylurea-4,4-diazo-bis-amino-8-naphthol-6 Sodium sulfonate, ortho-carboxybenzene-azo-dimethylaniline, 2,2,5,5-tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol-6-sodium sulfonate, dialkylsulfosuccinate Sodium sulfate, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium caprate, sodium caprylate, caproic acid Thorium, potassium stearate, and the like calcium oleate. Examples of the cationic surfactant include alkylbenzene dimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl ammonium chloride and the like. Nonionic surfactants include polyethylene oxide, polypropylene oxide, combinations of polypropylene oxide and polyethylene oxide, esters of polyethylene glycol and higher fatty acids, alkylphenol polyethylene oxide, esters of higher fatty acids and polyethylene glycol, higher fatty acids and polypropylene oxide. Examples thereof include esters and sorbitan esters. Examples of the polymer dispersant include sodium polycarboxylate and polyvinyl alcohol, and examples of the inorganic dispersant include calcium carbonate. However, these do not limit the present invention. Further, in order to prevent the Ostripd ripping phenomenon of the monomer emulsion particles in an ordinary aqueous medium, a higher alcohol represented by heptanol or octanol or a higher aliphatic hydrocarbon represented by hexadecane is often added as a stabilizer. It is also possible.

(Static image developing toner)
The electrostatic image developing toner of the present invention (hereinafter referred to as toner) is obtained by aggregating at least the resin fine particle dispersion of the present invention (aggregation process) and then heating and melting (fusion process). Hereinafter, together with the electrostatic image developing toner of the present invention, the production method thereof will be described.

  In order to produce the toner of the present invention, it is preferable to use an emulsion polymerization aggregation method, and it is preferable to adjust resin fine particles dispersed in an aqueous medium. In this case, in order to achieve an important characteristic for end use such as high image quality, the toner center particle diameter is preferably 10 μm or less, more preferably 7 μm or less. Further, the volume average particle size distribution of the toner is 1.35 or less, preferably 1.30 or less. In order to achieve such a preferable toner form, the emulsion polymerization aggregation method is optimal. However, even in such a case, the average particle diameter of resin fine particles, which is one of the toner raw materials, is a submicron particle diameter of 1 μm or less. Preferably there is.

  In the aggregation step, the resin fine particle dispersion of the present invention is prepared in an aqueous medium, so that it can be used as it is as a resin fine particle dispersion, and this resin fine particle dispersion can be used as a colorant particle dispersion as needed. Then, the toner particles are mixed with the release agent particle dispersion, and further, an aggregating agent is added, and these particles are heteroaggregated to form aggregated particles having a toner diameter. Further, after forming the first aggregated particles by aggregating in this way, the resin fine particle dispersion of the present invention or another resin fine particle dispersion is further added to form the second shell layer on the surface of the first particles. Is also possible. In this example, the colorant dispersion is separately prepared. However, when the colorant is blended in advance with the resin fine particles, the colorant dispersion is not necessary.

  Here, as a flocculant, besides a surfactant, an inorganic salt or a divalent or higher metal salt can be suitably used. In particular, when a metal salt is used, it is preferable in characteristics such as cohesion control and toner chargeability. Further, for example, a surfactant can be used for resin emulsion polymerization, pigment dispersion, resin fine particle dispersion, release agent dispersion, aggregation, and aggregation particle stabilization. Specifically, sulfate surfactants, sulfonates, phosphates, soaps and other anionic surfactants, amine salts, quaternary ammonium salts and other cationic surfactants, polyethylene glycols, It is also effective to use a nonionic surfactant such as an alkylphenol ethylene oxide adduct system or a polyhydric alcohol system. As a dispersing means, a general method such as a ball mill, sand mill, or dyno mill having a rotary shear homogenizer or a media is used. Can be used

  In addition to the resin fine particle dispersion of the present invention, addition polymerization resin fine particle dispersions prepared by using conventionally known emulsion polymerization can be used together.

  Examples of addition polymerization monomers for preparing these resin fine particle dispersions include styrenes such as styrene and parachlorostyrene, vinyl naphthalene, vinyl chloride, vinyl bromide, vinyl fluoride, vinyl acetate, propion. Vinyl esters such as vinyl acrylate, vinyl benzoate, vinyl butyrate, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, n-octyl acrylate, 2-chloroethyl acrylate, Methylene aliphatic carboxylic acid esters such as phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide such as vinyl methyl ether, vinyl ethyl ether, Monomers having an N-containing polar group, such as N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone, methacrylic acid, acrylic Homopolymers and copolymers of vinyl monomers such as vinyl carboxylic acids such as acid, cinnamic acid and carboxyethyl acrylate, and various waxes can also be used.

  In the case of an addition polymerization monomer, emulsion polymerization can be performed using an ionic surfactant or the like to prepare a resin fine particle dispersion. In the case of other resins, the oil is water and the solubility in water is compared. If it is soluble in a low solvent, the resin is dissolved in those solvents and dispersed in an aqueous medium with a disperser such as a homogenizer together with an ionic surfactant or polymer electrolyte, and then heated or decompressed. Then, the resin fine particle dispersion can be obtained by evaporating the solvent.

  Then, after the aggregation step, in the fusion step (fusion / unification step), the resin particles are heated to a temperature above the glass transition point or the melting point of the resin fine particles to fuse and coalesce the aggregated particles and wash as necessary. The toner can be obtained by drying.

  In addition, after completion of the fusion process, desired toner particles are obtained through an arbitrary washing process, solid-liquid separation process, and drying process. In consideration of charging properties, the washing process should be sufficiently washed with ion exchange water. Is desirable. Moreover, although there is no restriction | limiting in particular in a solid-liquid separation process, From the point of productivity, suction filtration, pressure filtration, etc. are suitable. Further, the drying process is not particularly limited, but freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferably used from the viewpoint of productivity.

Hereinafter, constituent components of the toner (raw materials used in the production method) will be described.
First, the following can be used as the colorant. Examples of the black pigment include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon, nonmagnetic ferrite, and magnetite.
Examples of yellow pigments include yellow lead, zinc yellow, yellow iron oxide, cadmium yellow, chrome yellow, hansa yellow, hansa yellow 10G, benzidine yellow G, benzidine yellow GR, sren yellow, quinoline yellow, permanent yellow NCG and the like. be able to.
Examples of the orange pigment include red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, benzidine orange G, indanthrene brilliant orange RK, and indanthrene brilliant orange GK.
Red pigments include Bengala, Cadmium Red, Red Plum, Mercury Sulfide, Watch Young Red, Permanent Red 4R, Risor Red, Brilliantamine 3B, Brilliantamine 6B, Daypon Oil Red, Pyrazolone Red, Rhodamine B Lake, Lake Red C , Rose Bengal, Eoxin Red, Alizarin Lake and the like.
Blue pigments include bitumen, cobalt blue, alkali blue rake, Victoria blue rake, fast sky blue, induslen blue BC, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxare. Rate.
Examples of purple pigments include manganese purple, fast violet B, and methyl violet lake.
Examples of the green pigment include chromium oxide, chromium green, pigment green, malachite green lake, final yellow green G, and the like.
Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.
Examples of extender pigments include barite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white.
Examples of the dye include various dyes such as basic, acidic, dispersed, and direct dyes, such as nigrosine, methylene blue, rose bengal, quinoline yellow, and ultramarine blue.

  These colorants are used alone or in combination. With respect to these colorants, for example, a dispersion of colorant particles can be prepared using a media type dispersing machine such as a rotary shearing homogenizer, a ball mill, a sand mill, or an attritor, or a high-pressure opposed collision type dispersing machine. Further, these colorants can be dispersed in an aqueous system by a homogenizer using a polar surfactant.

  The colorant is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP permeability, and dispersibility in the toner.

  The colorant can be added in the range of 4 to 15% by weight with respect to the total weight of the toner constituting solids. When a magnetic material is used as the black colorant, 12 to 240% by weight can be added unlike other colorants.

  The blending amount of the colorant is a necessary amount for securing the color developability at the time of fixing. Moreover, OHP transparency and color developability can be ensured by setting the center diameter (median diameter) of the colorant particles in the toner to 100 to 330 nm.

  The center diameter (median diameter) of the colorant particles was measured, for example, with a laser diffraction particle size distribution measuring apparatus (LA-920, manufactured by Horiba, Ltd.).

  Further, when used as a magnetic toner, magnetic powder may be contained. Specifically, a material that is magnetized in a magnetic field is used, but a ferromagnetic powder such as iron, cobalt, or nickel, or a compound such as ferrite or magnetite is used. When obtaining toner in the aqueous phase, it is necessary to pay attention to the aqueous phase migration of the magnetic material, and it is preferable to modify the surface of the magnetic material in advance, for example, to perform a hydrophobic treatment or the like.

  In addition, magnetic materials such as ferrite, magnetite, reduced iron, cobalt, nickel, manganese and other metals, alloys, and compounds containing these metals are used as internal additives, and quaternary ammonium salt compounds, nigrosine as charge control agents. Various charge control agents such as dyes consisting of complexes of aluminum compounds, aluminum, iron, chromium, etc. and triphenylmethane pigments can be used, but the ionic strength that affects the aggregation and temporary stability From the viewpoints of control of wastewater and reduction of wastewater contamination, materials that are difficult to dissolve in water are suitable.

  Specific examples of the release agent include, for example, various ester waxes, low molecular weight polyolefins such as polyethylene, polypropylene, and polybutene, silicones that show a softening point by heating, oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid Fatty acid amides such as amides, plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil, animal waxes such as beeswax, montan wax, ozokerite, ceresin, paraffin Examples thereof include mineral-based and petroleum-based waxes such as wax, microcrystalline wax, microcrystalline wax, Fischer-Tropsch wax, and modified products thereof.

  These waxes are hardly dissolved in a solvent such as toluene at room temperature or very little even if dissolved.

  These waxes are dispersed in an aqueous medium together with a polymer electrolyte such as an ionic surfactant, polymer acid or polymer base, heated above the melting point, and have a strong shearing ability and pressure discharge type. It can be dispersed in the form of particles with a disperser (Gorin homogenizer, manufactured by Gorin Co., Ltd.) to produce a dispersion of particles of 1 μm or less.

  It is desirable to add the release agent in the range of 5 to 25% by weight with respect to the total weight of the toner constituting solids, in order to ensure the peelability of the fixed image in the oilless fixing system.

  In addition, the particle diameter of the release agent particle dispersion was measured, for example, with a laser diffraction particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.). In addition, when using a release agent, after the resin fine particles, colorant particles and release agent particles are aggregated, it is possible to add a resin fine particle dispersion to adhere the resin fine particles to the surface of the aggregated particles. It is desirable from the viewpoint of securing the property.

The cumulative volume average particle diameter D ₅₀ of the toner obtained by the method for producing an electrostatic charge image developing toner of the present invention is suitably in the range of 3.0 to 9.0 μm, preferably in the range of 3.0 to 5.0 μm. is there. When D ₅₀ is _less than 3.0 μm, the adhesion is increased and the developability may be lowered. On the other hand, if it exceeds 9.0 μm, the resolution of the image may deteriorate.

  Further, the volume average particle size distribution index GSDv of the obtained toner is preferably 1.30 or less. When GSDv exceeds 1.30, the resolution is deteriorated, which may cause image defects such as toner scattering and fogging.

Here, the cumulative volume average particle diameter D ₅₀ and the average particle size distribution index are, for example, the particle size distribution measured by a measuring instrument such as Coulter Counter TAII (manufactured by Nikka Kisha Co., Ltd.), Multisizer II (manufactured by Nikka Kisha Co., Ltd.). The particle size range (channel) divided based on the volume and number are cumulative distributions starting from the small diameter side, and the particle size that is 16% cumulative is the volume D _16v , the number D _16P , and the particle that is 50% cumulative The diameter is _defined as a volume D _50v and a number D _50P , and the particle diameter at a cumulative 84% is defined as a volume D _84v and a number D _84P . Using these, the volume average particle size distribution index (GSDv) is calculated as (D _84v / D _16V ) ^1/2 and the number average particle size distribution index (GSDp) is calculated as (D _84P / D _16P ) ^1/2 .

The shape factor SF1 of the obtained toner is in the range of 100 to 140, preferably 110 to 135, from the viewpoint of image formability. The shape factor SF1 is obtained as follows. First, an optical microscope image of the toner dispersed on the slide glass is taken into a Luzex image analyzer through a video camera, and the peripheral length (ML) and the projection area (A) of 50 or more toners are measured. Multiplier / projection area = ML ² / A) was defined as the toner shape factor SF1.

  The obtained toner is dried in the same manner as a normal toner for the purpose of imparting fluidity and improving cleaning properties, and then inorganic particles such as silica, alumina, titania and calcium carbonate, and resins such as vinyl resins, polyesters and silicones. The fine particles can be used by adding to the surface of the toner particles while being sheared in a dry state.

  In addition, when adhering to the toner surface in an aqueous medium, examples of inorganic particles include silica, alumina, titania, calcium carbonate, magnesium carbonate, tricalcium phosphate, etc. Can be used by dispersing with an ionic surfactant, polymer acid, or polymer base.

  Specifically, the inorganic particles are particles having a primary particle diameter of 5 μm to 2 μm, preferably 5 μm to 500 μm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m <2> / g. The proportion mixed with the toner is 0.01 to 5% by weight, preferably 0.01 to 2.0% by weight. Examples of such inorganic fine powder include silica fine powder, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, and diatomaceous earth. Soil, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride and the like can be mentioned, and silica fine powder is particularly preferable.

The silica fine powder here is a fine powder having a Si—O—Si bond, and includes both those produced by a dry method and a wet method. In addition to anhydrous silicon dioxide, any of aluminum silicate, sodium silicate, potassium silicate, magnesium silicate, zinc silicate and the like may be used, but those containing SiO _{2 in an amount} of 85% by weight or more are preferable.

  Specific examples of these silica fine powders include various commercially available silicas, but those having a hydrophobic group on the surface are preferable. For example, AEROSIL R-972, R-974, R-805, R-812 (above Aerosil) Product), TALAX 500 (manufactured by Talco), and the like. In addition, silane coupling agent, titanium coupling agent, silicon oil, silica fine powder treated with silicon oil having amine in the side chain, and the like can be used.

(Developer for developing electrostatic image)
The toner obtained by the method for producing an electrostatic charge image developing toner of the present invention described above is used as an electrostatic charge image developing developer. The developer is not particularly limited except that it contains the electrostatic image developing toner, and can have an appropriate component composition depending on the purpose. When the electrostatic image developing toner is used alone, it is prepared as a one-component electrostatic image developer, and when used in combination with a carrier, it is prepared as a two-component electrostatic image developer.

  The carrier is not particularly limited, and examples thereof include known carriers. For example, known carriers such as resin-coated carriers described in JP-A-62-39879, JP-A-56-11461, etc. Can be used.

  Specific examples of the carrier include the following resin-coated carriers. That is, examples of the core particle of the carrier include normal iron powder, ferrite, and magnetite molding, and the average particle diameter is about 30 to 200 μm. Examples of the coating resin for the core particles include styrenes such as styrene, parachlorostyrene, and α-methylstyrene, methyl acrylate, ethyl acrylate, n-propyl acrylate, lauryl acrylate, and 2-ethylhexyl acrylate. , Α-methylene fatty acid monocarboxylic acids such as methyl methacrylate, n-propyl methacrylate, lauryl methacrylate and 2-ethylhexyl methacrylate, nitrogen-containing acrylics such as dimethylaminoethyl methacrylate, vinyl nitriles such as acrylonitrile and methacrylonitrile Vinyl pyridines such as 2-vinyl pyridine and 4-vinyl pyridine, vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether, vinyl vinyls such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone Luketones, polyolefins such as ethylene and propylene, silicones such as methylsilicone and methylphenylsilicone, and vinylidene fluoride. Examples thereof include copolymers of vinyl-based fluorine-containing monomers such as tetrafluoroethylene hexafluoroethylene, polyesters containing bisphenol, glycol, etc., epoxy resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, and the like. These resins may be used alone or in combination of two or more. The amount of the coating resin is about 0.1 to 10 parts by weight, preferably 0.5 to 3.0 parts by weight with respect to the carrier. In the production of the carrier, a heating kneader, a heating Henschel mixer, a UM mixer, or the like can be used. Depending on the amount of the coating resin, a heating fluidized rolling bed, a heating kiln, or the like can be used. it can.

  The mixing ratio of the toner and the carrier in the electrostatic image developer is not particularly limited and can be appropriately selected depending on the purpose.

The developer for developing an electrostatic charge image (toner for developing an electrostatic charge image) can be used in an image forming method of a normal electrostatic charge image development method (electrophotographic method). The image forming method of the present invention includes a latent image forming step, a developing step, a transfer step, and a fixing step. Moreover, the cleaning process may be included. Each of the above steps is a general step per se, and is described in, for example, JP-A-56-40868 and JP-A-49-91231. The image forming method of the present invention can be carried out using an image forming apparatus such as a copier or a facsimile machine known per se.
The latent image forming step is a step of forming an electrostatic latent image on the surface of the latent image holding member. In the developing step, the electrostatic latent image formed on the surface of the latent image holding member is developed with a developer containing toner to form a toner image. The transfer step is a step of transferring the toner image formed on the surface of the latent image holding member to the surface of the recording medium. The cleaning step is a step of removing the electrostatic charge image developer remaining on the latent image holding member. In the image forming method of the present invention, an embodiment that further includes a recycling step is preferable. The recycling step is a step of transferring the electrostatic image developing toner collected in the cleaning step to the developer layer. The image forming method including the recycling step can be performed using an image forming apparatus such as a toner recycling system type copying machine or facsimile machine. The present invention can also be applied to a recycling system in which the cleaning process is omitted and toner is collected simultaneously with development.

  The present invention will be described below as examples. However, the present invention is not limited to these examples.

  In addition, the measurement of each physical property value in a present Example was performed as follows.

(Measuring method of particle size and particle size distribution)
When the particles to be measured were 2 μm or more, a Coulter counter TA-II type (manufactured by Beckman Coulter, Inc.) was used as the measuring apparatus, and an ISOTON-II (manufactured by Beckman Coulter, Inc.) was used as the electrolyte.

  As a measuring method, 0.5 to 50 mg of a measurement sample is added to 2 ml of a 5% aqueous solution of a surfactant, preferably sodium alkylbenzenesulfonate as a dispersant. This was added to 100 to 150 ml of the electrolytic solution.

  The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 minute, and the particle size distribution of particles of 2 to 60 μm is measured using the Coulter counter TA-II with an aperture diameter of 100 μm. Volume average distribution and number average distribution were determined. The number of particles to be measured was 50,000.

The particle size distribution of the toner was determined by the following method. For the particle size range (channel) obtained by dividing the measured particle size distribution, a volume cumulative distribution is drawn from the smaller particle size, and the volume average particle size of 16% is defined as D16, and the volume average of 50% is accumulated. The particle size is defined as D50. Furthermore, the volume average particle diameter that is 84% cumulative is defined as D84. The volume average particle diameter is D50, and GSDv was calculated by the following equation.
Formula: GSDv = (D84 / D16) ^0.5
Similarly, a number cumulative distribution is drawn from the smaller particle size to the divided particle size range (channel) of the measured particle size distribution, and the particle size at 50% accumulation is defined as the number average particle size.

  Moreover, when the particle | grains to measure were less than 2 micrometers, it measured using the laser diffraction type particle size distribution measuring apparatus (LA-700: made by Horiba, Ltd.). As a measurement method, a sample in a dispersion is adjusted to have a solid content of about 2 g, and ion exchange water is added thereto to make about 40 ml. This is put into the cell until an appropriate concentration is reached, waits for about 2 minutes, and is measured when the concentration in the cell becomes almost stable. The obtained volume average particle diameter for each channel was accumulated from the smaller volume average particle diameter, and the volume average particle diameter was determined to be 50%.

(Measurement method of weight average molecular weight)
The weight average molecular weight is measured under the following conditions. GPC uses “HLC-8120GPC, SC-8020 (manufactured by Tosoh Corporation)” apparatus, and column uses “TSKgel, SuperHM-H (6.0 mm ID × 15 cm, manufactured by Tosoh Corporation)”. THF (tetrahydrofuran) was used as an eluent. As experimental conditions, the sample concentration was 0.5%, and the flow rate was 0.6 ml / min. The experiment was conducted using a sample injection amount of 10 μl, a measurement temperature of 40 ° C., and an IR detector. The calibration curve is “polystylen standard sample TSK standard” manufactured by Tosoh Corporation: “A-500”, “F-1”, “F-10”, “F-80”, “F-380”, “A-2500”. ”,“ F-4 ”,“ F-40 ”,“ F-128 ”, and“ F-700 ”.

(Measuring method of melting point and glass transition temperature)
Melting | fusing point and glass transition temperature were calculated | required from the main body maximum peak measured based on ASTMD3418-8. DSC-7 manufactured by Perkin Elmer Co. can be used for measurement of the main maximum peak. The temperature correction of the detection part of this apparatus uses the melting point of indium and zinc, and the correction of heat quantity uses the heat of fusion of indium. As the sample, an aluminum pan was used, an empty pan was set as a control, and the measurement was performed at a heating rate of 10 ° C./min.

(Measurement of crystallinity)
Regarding the presence or absence of crystallinity in the resin, the heat absorption curve measured by the above method is in accordance with the definition of the melting temperature of JIS K7121, and the low-temperature side of the melting peak (endothermic peak) and the straight line extending the low-temperature base line to the high-temperature side The maximum slope of the curve on the high temperature side of the melting point (endothermic peak) and the intersection of the tangent line (melting start temperature) drawn at the point where the gradient is the maximum in the curve and the base line on the high temperature side extended to the low temperature side When the temperature difference of the intersection of the tangent lines drawn at the point (melting end temperature) is within 50 ° C. and the shape of the curve does not show the stepped shape similarly shown in JIS K7121, it was judged as having crystallinity. .

(Measurement of SD value)
The SD value was measured as an index for evaluating the particle size distribution of the resin fine particles. The SD value is represented by volume average particle diameter / number average particle diameter of resin fine particles in the dispersion. In general, the volume average particle diameter is easily influenced by particles having a large particle diameter, and the number average particle diameter is easily influenced by particles having a small particle diameter. The SD value increases as the particle size distribution becomes 0. This SD value was measured using a laser diffraction type particle size distribution measuring apparatus (LA-700: manufactured by Horiba, Ltd.) as in the case of GSDv.

Example 1
"Adjustment of polyester resin 1"
In a three-necked flask, 128.2 g of 1,9-nonanediol (Log (P) = 1.86) and 170.4 g of 1,10-dodecanoic acid (Log (P) = 2.7), 5-t-butylisophthalate Acid (Log (P) = 2.85) 13.4 g, Styrene monomer (Log (P) = 2.67) 350.0 g, Butyl acrylate monomer (Log (P) = 1.88) 35.0 g, Hexadecane ( 2 g of Log (P) = 7.18) and 24 g of dodecanethiol (Log (P) = 5.14) were mixed well at 50 ° C. and cooled to room temperature, and then scandium trifluoromethanesulfonate Sc (OSO ₂ CF ₃ ) ₃ 1.0 g was added as a catalyst and dissolved.

  This mixture was put into 11700 g of ion-exchanged water in which 11 g of sodium dodecylbenzenesulfonate and 1.0 g of scandium trisdodecyl sulfate were dissolved, and preliminarily dispersed with ultrasound, and then an ultra-high pressure homogenizer (Nanomizer manufactured by Yoshida Kikai Kogyo Co., Ltd.). Was emulsified and dispersed at 50 ° C. to obtain a volume average particle size of 0.2 μm (Horiba LA700). This emulsion was put into a 5 L pressure reactor equipped with a stirrer, and polymerized at 100 ° C. for 12 hours in a nitrogen atmosphere to obtain a resin fine particle dispersion (1). The reaction product maintained a stable emulsified state, its volume average particle size was 0.2 μm, and the ratio SD value (volume average particle size / number average particle size) of the volume average particle size and number average particle size distribution was 1.3. there were.

  A small amount of the sample after this reaction was taken out and dried at room temperature. The remaining solid was washed with methanol and filtered and then dried in an oven to take out the polymer component. As a result of measuring the GPC (HLC-8 120GPC, manufactured by Tosoh Corporation), the weight average molecular weight was 23,000, and deuterated rhoform was used and proton NMR (Varian 300 MHz) was used for both polyester and polystyrene butyl acrylate in the polymer. When the composition ratio of radically polymerizable polymers such as polymers was examined, the yield of styrene or butyl acrylate and their copolymers was 2% or less, and at this point, the polymer component was considered to be almost polyester. .

  This polymer composition (polyester resin) was dissolved in THF, and then the acid value was measured using an ethanol solution of aquatic potassium. The result was 10 mgKOH / g. This value is considered to represent the acid value of almost the above-mentioned radio.

  Furthermore, as a result of measuring the thermal characteristics of the resin with a differential scanning calorimeter (Shimadzu Corporation, DSC50) and the crystallinity with an X-ray diffractometer (Shimadzu Corporation, XRD), a crystalline resin having a melting point at 70 ° C. It turns out that.

"Polymerization of radical polymerizable monomer 1"
After 10.0 g of maleic acid was added to the resin dispersion (1) obtained above and allowed to stand with stirring at room temperature for 12 hours and at 80 ° C. for 1 hour, maleic acid was sufficiently distributed in the resin fine particles. Then, 2.5 g of ammonium persulfate dissolved in 10 g of ion-exchanged water was added, and polymerization was carried out again at 80 ° C. for 5 hours under a nitrogen atmosphere. As a result, the volume average particle diameter was 0.2 μm, the SD value was 1. 3 stable resin fine particle dispersion (2) was obtained.

  After polymerization, a small sample is taken out, dried at room temperature, washed with methanol, filtered and dried in the same manner as the above polyester, and then determined by proton NMR to determine the ratio of polyester to radical polymerizable polymer in the polymer. When the yield of the polymer was determined, the radical monomer almost blended was used for polymerization and the yield was 99% or more. Further, from the gas chromatographic analysis of the emulsion, the total amount of the remaining radical monomer (radically polymerizable monomer) component was 200 ppm or less. Further, when the molecular weight was measured by GPC, the weight average molecular weight showed two peaks of 23000 and 31000, and a new high molecular weight peak almost equal to the value of the previously polymerized polyester. The polyester had a melting point of 70 ° C. The difference δv-δpe in the weight average solubility parameter determined from the polyester monomer and radical polymerizable monomer used was 1.09.

“Preparation of Toner Particle 1”
Adjustment of pigment dispersion:
1 kg of cyan pigment (manufactured by Dainichi Seika Co., Ltd., Pigment Blue 15: 3), 150 g of anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R), 9 kg of ion-exchanged water are mixed, dissolved, and subjected to a high-pressure impact type A dispersion of cyan pigment was prepared by dispersing for about 1 hour using a disperser Ultimateizer (HJP 30006, manufactured by Sugino Machine Co., Ltd.). The average particle diameter of the dispersed cyan pigment was 0.15 μm, and the colorant particle concentration was 23% by weight.

Preparation of ester wax dispersion:
Ester wax (Nippon Yushi Co., Ltd .: WE-2, melting point 65 ° C.) 50 g, anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 5 g, ion-exchanged water 200 g was heated to 95 ° C. And an ester wax dispersion having an average particle size of 0.23 μm and a particle concentration of 20% by weight after being dispersed using a homogenizer (manufactured by IKA: Ultra Tarrax T50) and then dispersed by a Menton Gorin high-pressure homogenizer (Gorin). Was prepared.

Preparation of toner particles 1: emulsion polymerization aggregation method:
400 g of the resin fine particle dispersion (2) obtained by polymerizing the radical polymerizable monomer, 34.4 g of the pigment dispersion, 33 g of the ester wax dispersion, and nonionic surfactant (IGEPAL CA897) 0. 5 g and 265 g of ion-exchanged water are placed in a 2 L cylindrical stainless steel container, and dispersed and mixed for 30 minutes while applying a shear force at 8000 rpm with an Ultraturrax. Subsequently, 0.18 g of a 10% nitric acid aqueous solution of polyaluminum chloride was added dropwise as a flocculant. Under the present circumstances, pH of the raw material dispersion liquid was adjusted with the 1N sodium hydroxide aqueous solution in the range of 4.2-4.5. Then, while stirring the raw material dispersion in a stainless steel polymerization kettle equipped with a stirrer and a thermometer, the resin particles, pigment particles, and wax particles are gradually heated and aggregated to obtain a volume average particle diameter (TA-II type aperture, Coulter Counter). (Diameter 50 μm) was adjusted to 6.0 μm. After raising the pH to 9.0, the temperature was raised to 78 ° C. and held for 3 hours to obtain toner particles having a potato-shaped volume average particle diameter D50v 6.0 μm and a volume average particle size distribution index (GSD) of 1.23. . Thereafter, the mixture was cooled, sieved with a 45 μm mesh, sufficiently washed with water and dried with a freeze dryer to obtain toner particles 1.

“Adjustment and Evaluation of Developer 1”
To 100 parts of the obtained toner particles 1, 1 part of colloidal silica (manufactured by Nippon Aerosil Co., Ltd., R972) was externally added and mixed using a Henschel mixer to obtain an electrostatic charge image developing toner. After putting 100 parts of ferrite particles (manufactured by Powder Tech Co., Ltd., average particle size 50 μm) and 1 part of methacrylate resin (manufactured by Ryo Rayon Co., Ltd., molecular weight 95000) in a pressure kneader together with 500 parts of toluene, mixing at room temperature for 15 minutes, The temperature was raised to 70 ° C. while mixing under reduced pressure, and toluene was distilled off, followed by cooling and sizing using a 105 μm sieve to produce a ferrite carrier (resin-coated carrier). The ferrite carrier and the electrostatic image developing toner were mixed to prepare a two-component electrostatic image developer having a toner concentration of 7% by weight.

  Using this electrostatic charge image developer, the initial charge and the environmental sustainability of the charge amount after being left in an environment of 80% RH and 28 ° C. for one week were measured and evaluated using a blow-off charge amount measuring device. / G, a good result of maintaining the charge amount after aging for 1 week was 98% or more. Further, fixing of the obtained developer and evaluation of image quality were carried out by forming an image using a Docu Center Color 500CP remodeling machine manufactured by Fuji Xerox Co., Ltd., and image quality evaluation of fixing temperature and initial image quality was performed. In this case, as the evaluation items, the fixing temperature was set to the lowest temperature at which the toner particles form a continuous film layer, and the image quality characteristics were evaluated as image quality unevenness (visually), toner scattering, and fine line reproducibility. As a result, the fixing temperature was possible at 100 ° C., and the image quality unevenness, toner scattering, and fine line reproducibility were also good, and both excellent low temperature fixing performance and image quality characteristics were achieved.

(Example 2)
"Polymerization of polyester resin 2"
In the same manner as in Example 1, after mixing polyvalent carboxylic acid, polyhydric alcohol and catalyst, 350 g of styrene monomer (Log (P) = 2.67), 35 g of butyl acrylate (Log (P) = 1.88), dodecanethiol (Log (P) = 5.14) 24 g was further mixed and emulsified in water in the same manner as in Example 1, and then polymerized at 80 ° C. for 6 hours in the same manner as in Example 1 to obtain a resin fine particle dispersion (3). Obtained. The obtained resin fine particles had a particle size of 0.15 μm, an SD value of 1.3, a weight average molecular weight of the polyester resin of 18000, and a melting point of 69 ° C.

"Polymerization of radical polymerizable monomer 2"
Polymerization is performed in the same manner as in the resin fine particle dispersion (2) in Example 1, except that the resin fine particle dispersion (3) is used and 13 g of itaconic acid is used instead of maleic acid. Got. The obtained resin fine particles 6 have a particle diameter of 0.15 μm, an SD value of 1.3, a polymerization yield of the radical polymerizable monomer of 99% or more, and the weight average molecular weight of the resin fine particles 6 has peaks at 18000 and 29000, The melting point was 69 ° C. The difference δv-δpe in the weight average solubility parameter determined from the polyester monomer and radical polymerizable monomer used was 1.06.

“Preparation of toner particles 2”
A pigment dispersion and an ester wax dispersion were prepared in the same manner as in Example 1 except that the resin fine particle dispersion (4) was used, and these were agglomerated and further heated to 78 ° C. to fuse the particles to obtain the final toner. Got. The obtained toner had a volume average particle diameter of 5.0 μm, a volume average particle size distribution of 1.23, and spherical toner particles.

“Adjustment and Evaluation of Developer 2”
The developer 2 was prepared in the same manner as in Example 1 except that the toner particles 2 were used, and the chargeability and image quality were evaluated. As a result, the developer initial chargeability was 41 μC / g, and the maintainability after aging was 99% or more. In addition, as a result of evaluating the fixing characteristics and the image quality characteristics in the same manner as in Example 1, the fixing performance at 100 ° C. and the excellent image quality characteristics were also exhibited.

(Example 3)
“Polymerization of polyester resin 3”
Radical polymerization using a mixture of 184.2 g of dodecanedioic acid (Log (P) = 2.7) and 1,9 nonanediol of polyhydric alcohol (Log (P) = 1.86) 128.2 g. Polymerization was conducted in the same manner as in Example 1 except that 350 g of styrene monomer (Log (P) = 2.67) and 35 g of butyl acrylate (Log (P) = 1.88) were used as the conductive monomer, and the resin fine particles were dispersed. A liquid (5) was obtained. The obtained resin fine particles had a particle size of 0.25 μm, an SD value of 1.3, a weight average molecular weight of the polyester resin of 15000, and a melting point of 69 ° C.

"Polymerization of radical polymerizable monomer 3"
Resin fine particle dispersion (6) was polymerized in the same manner as the resin fine particle dispersion (2) in Example 1 except that 7 g of acrylic acid was used instead of maleic acid. Got. The obtained resin fine particles 8 had a particle diameter of 0.25 μm, an SD value of 1.3, a polymerization yield of radical polymerizable monomers of 99% or more, and weight average molecular weights of 15,000 and 30000. Its melting point was 69 ° C. Further, the difference δv-δpe in the weight average solubility parameter determined from the polyester monomer and radical polymerizable monomer used was 1.06.

“Preparation of toner particles 3”
A pigment dispersion and an ester wax dispersion were prepared in the same manner as in Example 1 except that the resin fine particle dispersion (6) was used, and then aggregated and heated to 78 ° C. to fuse the particles to obtain the final toner. Got. The obtained toner had spherical toner particles with a volume average particle size of 5.3 μm and a volume average particle size distribution of 1.22.

“Adjustment and Evaluation of Developer 3”
The developer 3 was prepared in the same manner as in Example 1 except that the toner particles 3 were used, and the chargeability and image quality were evaluated. As a result, the initial chargeability of the developer was 45 μC / g and the maintainability after aging was 99% or more. As a result of evaluating the fixing characteristics and image quality characteristics as in Example 1, the fixing performance was also 100 ° C. Showed excellent fixing performance and excellent image quality characteristics.

Example 4
"Polymerization of polyester resin 4"
161.8 g of sebacic acid (log (P) = 1.87) as the polyvalent carboxylic acid, 57.7 g of 1,4 cyclohexanedimethanol (log (P) = 0.9) as the polyhydric alcohol, 1,6 hexane Diol (log (P) = 0.6) 47.3 g, radical polymerizable monomer styrene monomer (Log (P) = 2.67) 350 g, butyl acrylate (Log (P) = 1.88) 35 g, Using 24 g of dodecanethiol (Log (P) = 5.14), the same amount of scandium trifluoromethanesulfonate as in Example 1 was added as a catalyst and dissolved in the same manner as in Example 1, and then this mixture was added to dodecyl. After adding sodium benzenesulfonate and scandium trisdodecyl sulfate dissolved in ion-exchanged water and pre-dispersing with ultrasound, Perform emulsion dispersion using a pressure homogenizer (Yoshida Kikai Co., Ltd. Nanomizer) to obtain a volume average particle size 0.30μm (the Horiba LA700). This emulsion was charged into a 3 L pressure reactor equipped with a stirrer and polymerized at 100 ° C. for 8 hours under a nitrogen atmosphere to obtain a resin fine particle dispersion (7). The reaction product maintained a stable emulsified state, its volume average particle size was 0.30 μm, and the ratio SD value (volume average particle size / number average particle size) of the volume average particle size and number average particle size distribution was 1.3. there were. The weight average molecular weight of the polyester resin was 16000.

"Polymerization of radical polymerizable monomer 4"
Resin fine particle dispersion (8) is polymerized in the same manner as the resin fine particle dispersion (2) in Example 1, except that 5 g of acrylic acid is used instead of maleic acid. Got. The obtained resin fine particles 8 had a particle diameter of 0.35 μm, an SD value of 1.3, a polymerization yield of the radical polymerizable monomer of 99% or more, and weight average molecular weights peaked at 16000 and 30000. Its melting point was 65 ° C. Further, the difference δv-δpe in the weight average solubility parameter determined from the polyester monomer and radical polymerizable monomer used was 1.30.

“Preparation of toner particles 4”
A pigment dispersion and an ester wax dispersion were prepared in the same manner as in Example 1 except that the resin fine particle dispersion (8) was used, and then aggregated and heated to 90 ° C. to fuse the particles to obtain the final toner. Got. The resulting toner had a volume average particle size of 5.6 μm, a volume average particle size distribution of 1.25, and spherical toner particles.

“Adjustment and Evaluation of Developer 4”
The developer 5 was adjusted in the same manner as in Example 1 except that the toner particles 4 were used, and the chargeability and image quality were evaluated. As a result, the initial chargeability of the developer was 40 μC / g and the maintainability after aging was 99% or more. As a result of evaluating the fixing characteristics and image quality characteristics as in Example 1, the fixing performance was also 100 ° C. Showed excellent fixing performance and excellent image quality characteristics.

(Comparative Example 1)
In order to show excellent charging characteristics, fixing characteristics, and image quality characteristics as a toner with the excellent resin fine particle dispersion (polyester resin fine particle dispersion) in the present invention, direct polymerization and mini-polymerization which are conventionally performed by bulk polymerization of polyester are used. Comparative Example 1 shows the adjustment of resin fine particles to an aqueous medium by the emulsion method, the toner production and its characteristics.

"Polymerization of polyester resin 5"
In a three-necked flask, 184.2 g of dodecanedioic acid and 128.2 g of 1,9-nonanediol and 2 g of dibutyltin oxide as a catalyst were added, and then the air in the container was decompressed by depressurization and further inert by nitrogen gas. When the atmosphere was refluxed at 180 ° C. for 12 hours with mechanical stirring, a viscous state was obtained. When the molecular weight was confirmed by GPC, the weight average molecular weight was 21,000. The melting point was measured by DSC in the same manner as in Example 1. As a result, the value was 70 ° C.

  This resin was dissolved by heating at 80 ° C. in a mixture of radically polymerizable monomers of 350 g of styrene monomer, 50 g of butyl acrylate, 5 g of methacrylic acid and 24 g of dodecanethiol, and then ion-exchanged water in which 11 g of sodium dodecylbenzenesulfonate was dissolved. After putting into 1700 g and pre-dispersing with a homogenizer (IKA, Ultra Tarrax T50), the result of further emulsifying and dispersing at 150 ° C. using an ultra-high pressure homogenizer (Yoshida Kikai Kogyo Nanomizer), A polyester resin fine particle dispersion (9) having a volume average particle size of 0.9 μm, an emulsified particle size of SD value of 3.8, and a wide distribution up to 5 μm or more was obtained.

"Polymerization of radical polymerizable monomer 5"
Polymerization was carried out in the same manner as in the resin fine particle dispersion (2) in Example 1 except that the resin fine particle dispersion (9) was used and maleic acid was not used, to obtain a resin fine particle dispersion (10). The obtained resin fine particles 12 had a particle diameter of 1.1 μm, an SD value of 4.0, a polymerization yield of the radical polymerizable monomer of 99%, and peaks in weight average molecular weights of 21000 and 31000. Its melting point was 69 ° C. Furthermore, the difference δv-δpe in the weight average solubility parameter determined from the polyester monomer and radical polymerizable monomer used was 1.02.

“Preparation of toner particles 5”
A pigment dispersion and an ester wax dispersion were prepared in the same manner as in Example 1 except that the resin fine particle dispersion (10) was used, and then aggregated and heated to 78 ° C. to fuse the particles to obtain the final toner. Got. The toner obtained had a potato-like toner particle having a volume average particle size of 8.9 μm and a volume average particle size distribution of 1.45, from 1 μm or less to 10 μm or more. As a high-quality toner, it is considered to have a large problem in practical use.

“Adjustment and Evaluation of Developer 5”
The developer 5 was prepared in the same manner as in Example 1 except that the toner particles 5 were used, and the chargeability and fixing performance image quality were evaluated in the same manner as in Example 1. As a result, the initial chargeability of the developer varied greatly from 2 μC / g to 20 μC / g, and the maintainability after aging was 30% or less, which was a serious problem in practical reproducibility and maintainability. Although the fixing temperature was 120 ° C., there were many image quality irregularities in the image quality characteristics, toner scattering was large, and fine line reproducibility was a serious problem in practical use.

(Comparative Example 2)
"Polymerization of polyester resin 6"
214.9 g of adipic acid (log (P) = 0.2) as the polyvalent carboxylic acid, 84.3 g of ethylene glycol (Log (P) = − 0.79) as the polyhydric alcohol, and styrene as the radical polymerizable monomer Similar to Example 1, using 350 g of monomer (Log (P) = 2.67), 35 g of butyl acrylate (Log (P) = 1.88), and 24 g of dodecanethiol (Log (P) = 5.14) After adding and dissolving scandium trifluoromethanesulfonate as a catalyst, this mixture was put into ion-exchanged water in which sodium dodecylbenzenesulfonate and scandium trisdodecylsulfate were dissolved and predispersed with ultrasonic waves. Volume average particles are emulsified and dispersed using an ultra-high pressure homogenizer (Nanomizer manufactured by Yoshida Kikai Kogyo Co., Ltd.). Was obtained 0.30μm the (Horiba LA700). This emulsion was put into a 5 L pressure reactor equipped with a stirrer and polymerized at 100 ° C. for 24 hours under a nitrogen atmosphere to obtain a resin fine particle dispersion (11). The reaction product maintained a stable emulsified state, and its volume average particle size was 0.70 μm and SD value was 1.3. The weight average molecular weight of the polyester resin is 800, and the molecular weight becomes saturated with a low molecular weight, which is a problem in terms of production and toner characteristics.

"Polymerization of radical polymerizable monomer 6"
Resin fine particle dispersion (12) was polymerized in the same manner as the resin fine particle dispersion (2) in Example 1 except that 5 g of acrylic acid was used instead of maleic acid instead of the resin fine particle dispersion (11). Got. The obtained resin fine particles 8 had a particle diameter of 0.70 μm, an SD value of 1.3, a polymerization yield of the radical polymerizable monomer of 99% or more, and weight average molecular weights peaked at 800 and 30000. Its melting point was 47 ° C. Furthermore, the difference δv-δpe in the weight average solubility parameter determined from the polyester monomer and radical polymerizable monomer used was 0.13.

“Preparation of toner particles 6”
A pigment dispersion and an ester wax dispersion were prepared in the same manner as in Example 1 except that the resin fine particle dispersion (12) was used, and then aggregated and heated to 78 ° C. to fuse the particles to obtain the final toner. Got. The obtained toner obtained potato-like toner particles having a volume average particle size of 7.0 μm and a volume average particle size distribution of 1.35, which is widely distributed from 1 μm or less to 10 μm or more. As a high-quality toner, it is considered to have a large problem in practical use.

“Adjustment and Evaluation of Developer 6”
The developer 6 was prepared in the same manner as in Example 1 except that the toner particles 6 were used, and the chargeability and fixing performance image quality were evaluated in the same manner as in Example 1. As a result, the initial chargeability of the developer was 3 μC / g, and the maintainability after aging was 30% or less, which became a practical problem in terms of reproducibility and maintainability of chargeability. Further, the fixing temperature was 110 ° C., but there were many image quality irregularities in the image quality characteristics, and there was a lot of toner scattering, which was a big practical problem in fine line reproducibility.

  The results of Examples and Comparative Examples are summarized in Table 1 above. Each evaluation evaluation standard was as follows.

-Particle size distribution of resin fine particle dispersion-
The particle size distribution of the resin fine particles in the dispersion was evaluated according to the following evaluation criteria.
“◯”: SD value is less than 1.5,
“△”: SD value of 1.5 or more and less than 3.0,
“×”: SD value is 3.0 or more

-Volume average particle diameter of resin fine particle dispersion-
The volume average particle size of the resin fine particles of the dispersion was evaluated according to the following evaluation criteria.
“◯”: less than 0.3 μm,
“△”: 0.3 μm or more and less than 0.7 μm,
“×”: 0.7 μm or more

-Stability of resin fine particle dispersion-
The stability of the resin fine particle dispersion was determined based on the following criteria. 150 cc of the prepared latex was placed in a 300 cc glass bottle and left in a constant temperature bath at 60 ° C. for 1 week. The stability of the latex after one week was judged as follows. Judgment criteria are as follows. In addition, ○ was set as a pass.
“◯”: “△” indicating good dispersibility without settling and separation: “×”: Some separation is observed: “With settling and separation”

-Toner chargeability-
The charging characteristics of the toner were evaluated according to the following evaluation criteria.
“◯”: Initial charge amount of 30 μC / g or more “Δ”: Initial charge amount of 20 μC / g or more and less than 30 μC / g “X”: Initial charge amount of less than 20 μC / g

-Toner charge maintenance-
The charge maintaining property of the toner was evaluated according to the following evaluation criteria.
“◯”: Maintainability of charge amount after aging for one week is 90% or more “Δ”. · Maintenance of charge amount is 50% or more and less than 90% “×” ... Maintenance of charge amount Less than 50%

-Toner particle size distribution-
The toner particle size distribution was evaluated according to the following evaluation criteria.
“◯”: GSDv is less than 1.30 “Δ”: GSDv is 1.30 or more and less than 1.40 “x”: GSDv is 1.40 or more.

-Image quality characteristics-
The image quality characteristics were evaluated according to the following evaluation criteria.
“◯”: No toner scattering, sufficient image density and uniform image quality were obtained, and good image quality characteristics with no practical problems were obtained.
“Δ”: Slight scattering of toner was observed, but an image density and a uniform image quality that had no practical problem were obtained.
“X”: Toner scatter was remarkably observed, and the uniformity of the initial image density and image quality was insufficient, which was a practical problem.

  From the examples and comparative examples described above, it can be seen that the toner prepared in this example is excellent in toner manufacturability, charging characteristics, fixing characteristics, and image quality characteristics. Thereby, the resin fine particle dispersion obtained in this example is a resin fine particle in which the surface of the polyester is satisfactorily coated with the radical polymer coated on the polyester surface and has a small particle size and a sharp particle size distribution. It can also be seen that is stably emulsified and dispersed.

  It can also be seen that a polyester toner having high image quality characteristics can be produced with a low environmental load (low energy), which has conventionally been difficult.

Claims (6)

Along with sodium dodecylbenzenesulfonate and scandium trisdodecyl sulfate, a polycondensation polyester monomer and a radical polymerizable monomer are emulsified or dispersed in an aqueous medium, and then polycondensation and radical polymerization are carried out to obtain a resin fine particle dispersion. The difference in δv-δpe between the weight average solubility parameter δpe of the whole polymerizable polyester monomer and the weight average solubility parameter δv of the whole radical polymerizable monomer is 1.06 or more. 30 or less [(cal / cc) ^1/2 (25 ° C.)] and more, and the hydrophobic parameter (Log (P)) of all monomers of the polycondensed polyester monomer and the radical polymerizable monomer ) Is a step of producing a resin fine particle dispersion having a value of 0.6 or more and 5.14 or less,
Agglomerating resin fine particles in the resin fine particle dispersion; and
Heating and melting the obtained agglomerated particles,
A method for producing a toner for developing an electrostatic charge image, comprising:   2. The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein a vinyl monomer is used as the radical polymerizable monomer.   A radical polymerizable unsaturated acid monomer having a solubility in water of 80% (25 ° C.) or an acid anhydride thereof is used as the radical polymerizable monomer together with a vinyl monomer. Item 2. A method for producing a toner for developing an electrostatic charge image according to Item 1.   The polycondensed polyester monomer and the radical polymerizable monomer are characterized in that the polycondensed polyester monomer is preliminarily dissolved in the radical polymerizable monomer and then emulsified or dispersed in the aqueous medium. The method for producing a toner for developing an electrostatic image according to claim 1.   2. The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the polyester obtained by polycondensation of the polycondensed polyester monomer is a crystalline resin. The obtained resin fine particles have a core / shell structure in which a core is covered with a shell, the core is made of polyester obtained by polycondensation of the polycondensation polyester monomer, and the shell is made of the radical polymerizable monomer. Consists of a radical polymer obtained by radical polymerization of a monomer,
The method for producing a toner for developing an electrostatic image according to claim 1 .