JP5499421B2 - Polyester production method, electrostatic charge developing toner production method, and electrostatic charge development toner - Google Patents

Description

The present invention relates to a method for producing a polyester used as a constituent material of an electrostatic charge developing toner (hereinafter also referred to as electrophotographic toner), and a method for producing an electrostatic charge developing toner using the same. The present invention also relates to an electrostatic charge developing toner obtained by using these manufacturing methods.

  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, technological development such as reduction of fixing energy, which consumes a large amount of energy in the electrophotographic process, has been actively conducted by low-temperature fixing technology using a polycondensation resin having a polyester structure as a toner resin. Yes.

  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 developed into chemically produced toners, usually a method of polycondensation by bulk polymerization or solution polymerization to increase the molecular weight in advance 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). , 4 355 154; 1982, or USP 4355154). In this report, for example, polyester is polycondensed in an aqueous medium in the presence of a catalyst having a sulfonic acid group.
Macromolecules, 2003, 36, 1772-177. Sam JC, Chou YJ. US Patent, 4 355 154; 1982 USP 4355154

  However, in the previously reported polycondensation method of polyester in an aqueous medium, there are many unclear points in the polymerization mechanism, and only the technique according to this document uses the polycondensation method of polyester in an aqueous medium for toners. When applied to polyester production, particle dispersion in an aqueous medium after polymerization, stability of the emulsion is not sufficiently achieved, and furthermore, a molecular weight for achieving sufficient image strength required for toner cannot be obtained. In addition, there are major problems in manufacturing and characteristics, and the particle size distribution, charging characteristics, and charging environment dependency of the resin are insufficient, and the image quality characteristics and image quality reliability are extremely low. .

  As described above, it is difficult to obtain a high molecular weight polymer satisfying the characteristics as an electrophotographic toner, and it has not yet reached an area where it can be applied as a toner, such as difficulty in coexisting with high image quality characteristics such as particle size distribution and charging characteristics. is the current situation.

Therefore, an object of the present invention is to produce a polyester resin having a high molecular weight and sufficiently satisfying toner characteristics, which is difficult in the conventional polycondensation polymerization technique of a polyester resin in an aqueous medium, with low energy. it is to provide a manufacturing how of polyester. Another object of the present invention is to provide a method for producing an electrostatic charge developing toner utilizing the above. Another object of the present invention is to provide an electrostatic charge developing toner obtained by these production methods.

  As a result of intensive investigations on solutions for the above-mentioned various problems related to the application of the polycondensation technology of polyester in an aqueous medium to the toner, the inventors can industrially apply it to an electrophotographic toner. I found out. That is,

In the method for producing the polyester of the first invention, a polyvalent acid component having a hydrophobicity parameter (Log (P)) of −0.36 or more and 2.7 or less and a hydrophobicity parameter (Log (P)) of 0. Hydrophobic radical as a hydrophobic substance having a hydrophobic parameter (Log (P)) of 1.6 or more and 7.18 or less among a polyhydric alcohol component of .9 or more and 4.19 or less and a radical polymerizable monomer After emulsifying or dispersing only the polymerizable monomer in an aqueous medium, the method includes a step of polycondensing the polyhydric acid component and the polyhydric alcohol component in the presence of the hydrophobic substance.
In the method for producing the polyester of the second invention, the polyvalent acid component having a hydrophobicity parameter (Log (P)) of 1.87 or more and 2.7 or less, and the hydrophobicity parameter (Log (P)) of −0. A polyhydric alcohol component having a pH of .47 to 4.19, a hydrophobic radical polymerizable monomer as a hydrophobic material having a hydrophobicity parameter (Log (P)) of 1.6 to 7.18, and hydrophilicity A step of emulsifying or dispersing a radical polymerizable monomer in an aqueous medium and then polycondensing the polyhydric acid component and the polyhydric alcohol component in the presence of the hydrophobic substance, the hydrophobic radical The amount of the polymerizable monomer emulsified or dispersed in the aqueous medium is 3 to 20 parts by weight with respect to 100 parts by weight of the total amount of the polyvalent acid component, the polyhydric alcohol and the radical polymerizable monomer, and the hydrophilic property. Radio The amount of the polymerizable monomer emulsified or dispersed in the aqueous medium is 1.0 to 10 parts by weight with respect to 100 parts by weight of the total amount of the polyvalent acid component, the polyhydric alcohol and the radical polymerizable monomer. It is a feature.

  In the method for producing a polyester of the present invention, it is preferable that the polyester (that is, the resulting polyester) is a polyester for electrostatic image developing toner.

In the method for producing a polyester of the present invention, it is preferable that further comprising the step of polymerizing the pre-Symbol hydrophobic radical-polymerizable monomer. Further, it is preferable that the hydrophobic radical polymerizable monomer is a hydrophobic vinyl monomer.

In the polyester production method of the present invention, the absolute value of the difference between the hydrophobic parameter (Log (P) _COOH ) of the polyhydric acid component and the hydrophobic parameter (Log (P) _OH ) of the polyhydric alcohol component (| Log (P) _COOH- Log (P) _OH |) is preferably 0 or more and 5.0 or less.

  In the method for producing a polyester of the present invention, it is preferable that part or all of the polyhydric acid component and the polyhydric alcohol component are dimer or higher oligomers.

In the method for producing a polyester of the present invention, the parent aqueous radically polymerizable monomer is preferably an acidic vinyl monomer having an acidic group. It is preferable that the method further includes a step of polymerizing the second radical polymerizable monomer.

  In the polyester production method of the present invention, it is preferable to use at least one catalyst selected from a Bronsted acid catalyst and an enzyme catalyst in the polycondensation. The Bronsted acid catalyst is preferably a rare earth element catalyst having a rare earth element selected from Y, Sc, Yb, and Sm as a constituent component. It is preferable that the Bronsted acid type catalyst is an acid containing a sulfonic acid group such as dodecylbenzene sulfonic acid. More preferably, the catalyst has a surface activity.

  In the method for producing a polyester of the present invention, the polyvalent acid component and the polyhydric alcohol component are preferably components for obtaining a crystalline polyester.

  On the other hand, in the method for producing an electrostatic charge developing toner of the present invention, at least a step of aggregating the resin particles to obtain agglomerated particles in a dispersion in which the resin particles are dispersed, and fusing the aggregated particles by heating. And the resin particles are obtained by the polyester production method of the present invention.

  The electrostatic charge developing toner of the present invention is obtained by the method for producing an electrostatic charge developing toner of the present invention.

According to the present invention, the production of a polyester capable of producing a polyester having a high molecular weight and sufficiently satisfying toner properties, which is considered difficult in the conventional polycondensation polymerization technique of polyester in an aqueous medium, with low energy. it is possible to provide a rectangular Hopo Riesuteru particle dispersion. Further, it is possible to provide a method for producing an electrostatic charge developing toner using this. Moreover, the electrostatic charge developing toner obtained by these manufacturing methods can be provided.

(Production method of polyester)
Hereinafter, the manufacturing method of polyester is demonstrated. Moreover, the polyester particle dispersion liquid obtained by the said manufacturing method is demonstrated with this manufacturing method.

The method for producing a polyester according to the present invention comprises a polyhydric acid component, a polyhydric alcohol component, and a hydrophobic substance emulsified or dispersed in an aqueous medium, and then a polyhydric acid component and a polyhydric alcohol component in the presence of the hydrophobic substance. Are polycondensed. And as these polyhydric acid component, polyhydric alcohol component and hydrophobic substance, those having a hydrophobic parameter (Log (P)) of −0.5 or more and 20 or less are used.
However, in the method for producing the polyester of the present invention, the polyvalent acid component having a hydrophobicity parameter (Log (P)) of −0.36 or more and 2.7 or less and the hydrophobicity parameter (Log (P)) of 0. Hydrophobic radical polymerization as a hydrophobic substance having a hydrophobic parameter (Log (P)) of 1.6 or more and 7.18 or less among polyhydric alcohol components of 9 or more and 4.19 or less and radical polymerizable monomers The method for producing a first polyester comprising a step of polycondensation of the polyhydric acid component and the polyhydric alcohol component in the presence of the hydrophobic substance after emulsifying or dispersing only the functional monomer in an aqueous medium Applies.
In addition, the polyester production method of the present invention includes a polyvalent acid component having a hydrophobicity parameter (Log (P)) of 1.87 or more and 2.7 or less, and a hydrophobicity parameter (Log (P)) of −0. A polyhydric alcohol component of 47 to 4.19, a hydrophobic radical polymerizable monomer as a hydrophobic substance having a hydrophobicity parameter (Log (P)) of 1.6 to 7.18, and a hydrophilic radical A step of polycondensation of the polyhydric acid component and the polyhydric alcohol component in the presence of the hydrophobic substance after emulsifying or dispersing the polymerizable monomer in an aqueous medium, and the hydrophobic radical polymerization The hydrophilic monomer is emulsified or dispersed in the aqueous medium in an amount of 3 to 20 parts by weight based on 100 parts by weight of the total amount of the polyvalent acid component, the polyhydric alcohol and the radical polymerizable monomer. The amount of the polymerizable monomer emulsified or dispersed in the aqueous medium is 1.0 to 10 parts by weight with respect to 100 parts by weight of the total amount of the polyvalent acid component, the polyhydric alcohol and the radical polymerizable monomer. The method for producing polyester is applied.

In the polyester production method of the present invention, since the polyhydric acid component, polyhydric alcohol component and hydrophobic substance have high hydrophobicity, there are many components in the reaction region (oil phase) in the aqueous medium (aqueous phase). It is thought that it can be made. In addition, when a polyvalent acid component and a polyhydric alcohol component are polycondensed in an aqueous medium, if a hydrophobic substance having a high hydrophobicity parameter is present in the oil phase as the reaction region, the polycondensation occurs. It is considered that H ₂ O is efficiently discharged (moved) from the reaction region (oil phase) into the aqueous medium (aqueous phase). In addition, it is considered that the discharge of H ₂ O from the reaction region is performed more efficiently because polyhydric acid components and polyhydric alcohol components themselves use those having a high hydrophobicity parameter. From these facts, it is considered that polycondensation of the polyhydric acid component and the polyhydric alcohol component easily proceeds in the reaction region (oil phase), and a low-energy and high-molecular weight polyester can be obtained. Further, since H ₂ O is efficiently discharged from the oil phase (reaction region), it is considered that polyester particles having stable particle dispersion and emulsion can be obtained in an aqueous medium.

  By using the polyester particles obtained in this way to produce toner, toner properties such as toughness (toner strength, image strength), particle size distribution, charging characteristics, and charging environment dependence are sufficient. A satisfactory toner can be obtained. For this reason, the method for producing a polyester of the present invention is optimal as a method for producing a polyester for an electrostatic charge developing toner.

  In the method for producing the polyester of the present invention, a polyvalent acid component, a polyhydric alcohol component, and a hydrophobic substance having a hydrophobic parameter (Log (P)) of −0.5 or more are used. (Log (P)) is preferably 1.0 or more, and more preferably 1.5 or more. When the hydrophobicity parameter (Log (P)) is smaller than −0.5, the molecular weight of the polyester after polycondensation in an aqueous medium is not sufficient, and there are many low molecular weight components, and the toughness required as a toner. Toner characteristics such as properties (toner strength, image quality strength), particle size distribution, charging characteristics, and charging environment dependency. In the present invention, these hydrophobic parameters (Log (P)) are preferably as high as possible. However, as a substance that can actually exist, the upper limit is about 20.

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

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

  In the polyester production method of the present invention, as a polyester raw material, a polyvalent acid component (for example, aliphatic, alicyclic, aromatic polyvalent carboxylic acid, or alkyl ester thereof) and a polyhydric alcohol component (for example, Polycondensation is carried out by direct esterification reaction, transesterification reaction or the like using polyhydric alcohols or ester compounds thereof.

  The polyester obtained by polycondensation can take any form such as amorphous (non-crystalline) polyester, semi-crystalline resin, crystalline resin, or a mixed form thereof. When aiming at a fixing toner, it is preferable to include at least a crystalline polyester having a melting point in the range of 40 ° C. or higher and 150 ° C. or lower (preferably 50 ° C. or higher and 140 ° C. or lower).

  Examples of the component as the polyester raw material for obtaining such crystalline polyester are as follows. Among the polyvalent acid components, examples of the divalent carboxylic acid include adipic acid, peric acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, and 1,12-dodecanedicarboxylic acid. Acid, aliphatic dicarboxylic acid such as 1,14-tetradecane dicarboxylic acid, 1,18-octadecane dicarboxylic acid, and dicarboxylic acid such as dibasic acid such as phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid Further, these 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.

  On the other hand, among the polyhydric alcohol components, examples of the dihydric alcohol include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, and 1,4-cyclohexane. Dimethanol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tride Candiol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,14-eicosandecanediol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, and the like are limited thereto. Is not to be done. Examples of trihydric or higher alcohols include trimethylolpropane.

  These may be used individually by 1 type and may use 2 or more types together. In addition, as examples of each of these components, examples of monomer components have been given. However, in order to increase the molecular weight of polyester, it is also preferable that some or all of the components are dimers or more oligomers. . That is, before emulsifying or dispersing each monomer in an aqueous medium, a part or all of the monomer is polycondensed as a pre-polycondensation to form a dimer or higher oligomer (polyester is preliminarily bulk polymerized or solution polymerized to have a low molecular weight It is preferable to form a precursor of (3) and then to emulsify and disperse it in an aqueous medium using this as a starting material to polycondensate the polyester. The molecular weight of these oligomers is preferably 3000 or less in weight average molecular weight, for example. Due to the presence of the oligomer, as a result, the hydrophobicity of the component is improved (the hydrophobicity of the oil phase is increased), and the polycondensation of the polyester is more effectively promoted and the molecular weight can be increased.

  In addition, these monomers may have a Log (P) of -0.5 or less when used alone, but when Log (P) is smaller than -0.5, a monomer having a larger Log (P) in advance. It can be used by preparing a low molecular weight derivative by copolymerization with the above. For example, as described above, a starting material for aqueous polycondensation is a dimer or higher oligomer polymerized by bulk polymerization or solution polymerization in advance, so that the monomer has a Log (P) smaller than −0.5. By copolymerizing with other monomers in advance, it is possible to adjust Log (P) to −0.5 or more and to further increase the degree of freedom of the copolymer composition. In this case, the Log (P) of the oligomer is the Log (P) converted to the weight average from the monomer used for the oligomer polymerization, and the weight average Log of the monomer used for chain extension later. (P) Value should just satisfy | fill the conditions of this invention.

In addition, the absolute value (| Log (P) _COOH -Log (P) of the difference between the hydrophobic parameter (Log (P) _COOH ) of the polyhydric acid component and the hydrophobic parameter (Log (P) _OH ) of the polyhydric alcohol component. ) _OH |) is preferably 5.0 or less, more preferably 4.7 or less, and even more preferably 3.0 or less. By setting the absolute value (maximum value) of the difference between the hydrophobic parameters within the above range, the degree of hydrophobicity (degree of solubility in water) of the polyhydric acid component and the polyhydric alcohol component becomes the same. As a result, the distribution ratio to the water phase / oil phase is approximately the same, and the chemical equivalence of both is easily adjusted, the polycondensation of the polyester is more effectively promoted, and the molecular weight can be increased. The absolute value of the difference between the hydrophobic parameter (Log (P) _COOH ) of the polyhydric acid component and the hydrophobic parameter (Log (P) _OH ) of the polyhydric alcohol component (| Log (P) _COOH -Log ( Since P) _OH |) is preferably as small as possible, it includes cases where there is no difference between the hydrophobic parameters of the two, and the lower limit is naturally zero.

  In the method for producing a polyester of the present invention, the polycondensation is performed in the presence of a hydrophobic substance having a hydrophobic parameter of −0.5 or more and 20 or less. Examples of the hydrophobic substance include a polymerizable monomer, an organic solvent ( Examples thereof include toluene, xylene methyl ethyl ketone, and methyl isobutyl ketone. Among these, the organic solvent needs to be desolvated and may be expensive, but in the case of a polymerizable monomer, particularly a radical polymerizable monomer (hereinafter sometimes referred to as a hydrophobic radical polymerizable monomer), As will be described later, the use of a hybrid resin with polyester eliminates the need for solvent removal, and among these, a hydrophobic radical polymerizable vinyl monomer is most preferable.

  In the present invention, when a hydrophobic material is added to an aqueous medium together with a polyester raw material, and a polyester polycondensation reaction is performed in the presence of the hydrophobic material, the polyester raw material is wrapped with a hydrophobic radical polymerizable monomer, and thus more effective. Since the polycondensation of polyester proceeds, the molecular weight can be increased.

  Hydrophobic radical polymerizable monomers include aromatic vinyl monomers, (meth) acrylic acid ester monomers, vinyl ester monomers, vinyl ether monomers, monoolefin monomers, diolefins And monomer based on halogenated olefin. 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. These monomers may be used alone or in combination of two or more.

  Further, when these hydrophobic radical polymerizable monomers are polymerized, a hybrid resin (particles thereof) with polyester can be obtained. This polymerization can be carried out simultaneously with or after the polycondensation of the polyester. Further, these hydrophobic radical polymerizable monomers can be polymerized by adding a new monomer after polyester polymerization.

  These hydrophobic radical polymerizable monomers may have a Log (P) of -0.5 or less when used alone. However, when Log (P) is less than -0.5, Log (P) ) Can be used by copolymerizing with a monomer having a large molecular weight and preparing a polymerizable low molecular weight derivative.

  In the method for producing the polyester of the present invention, it is particularly effective to use a Bronsted polycondensation catalyst or an enzyme catalyst in order to achieve polycondensation at a lower temperature. 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 10000 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, those derived from Candida rugosa, Examples include those derived from niger (Aspergillus niger), those derived from Rhizopus delemer, those derived from Rhizopus japonicus.

  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.

  As the method for polymerizing the hydrophobic radical polymerizable monomer, 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).

In the method for producing a polyester of the present invention, it is preferable to adjust the acid value of the obtained polyester to be 0.5 mgKOH / g or more and 40 mgKOH / g or less. For practical use as a high-quality toner, it is essential to control the particle size and distribution of the toner in an aqueous medium. However, when the acid value is smaller than 0.5 mgKOH / g, the sufficient particle size and distribution are required. May not be achieved, which may cause problems in image quality and manufacturing. Furthermore, if the chargeability of the toner is less than 0.5 mgKOH / g, sufficient chargeability may not be obtained. If the acid value is larger than 40 mgKOH / g, it may be difficult to obtain a sufficient molecular weight for obtaining image quality strength as a toner during polycondensation, and the environmental dependence of the chargeability of the toner under high humidity is also large. Image reliability may be greatly impaired.
Here, the value measured by the potentiometric titration method of JIS standard K0070: 92 is used for the acid value in this invention.

  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. At the time of this emulsification dispersion, as described above, it is also possible to blend a hydrophobic radical polymerizable monomer to make the emulsification dispersion and the polycondensation reaction easier. Accordingly, a surfactant, a polymer dispersant, an inorganic dispersant, and the like can be added to the aqueous medium.

  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.

  In the polyester production method of the present invention, together with a polyester raw material (polyester monomer), components necessary for normal toners such as a fixing aid such as a colorant and wax, and other charging aids are previously mixed in the monomer. It is also possible.

  When a hybrid resin (particulates thereof) is obtained by radical polymerization of a hydrophobic radical polymerizable monomer, a slight amount of a second radical polymerizable monomer may be added to the aqueous medium before or after the polycondensation of the polyester. Good. The addition of the second radically polymerizable monomer is particularly useful for adjusting the characteristics of the particles, the surface modification of the particles, and the acid value of the final polymer.

  As the second radical polymerizable monomer, one having a hydrophobic parameter (Log (P)) of −10 or more and 20 or less is preferably used, and more preferably, the hydrophobic parameter (Log (P)) of −5 to 20 is used. belongs to.

  As the second radical polymerizable monomer, a hydrophilic radical polymerizable monomer having a hydrophilic group is preferable. The presence of the hydrophilic radical monomer having a hydrophilic group in a specific range on the surface of the polyester particles (resin particles) imparts cohesiveness to the resin particles, allowing the resin particles to be made into a toner. Sufficient chargeability can be provided.

  Here, the polar group as the hydrophilic group includes an acidic polar group such as a carboxyl group, a sulfone group, a phosphoric acid group, and a formyl group: a basic polar group such as an amino group, an amide group, a hydroxyl group, and a cyano group. The polar polar group can be exemplified, but the invention is not limited thereto. Among these, acidic polar groups are particularly preferably used for toner. The acidic group is particularly preferably a carboxyl group or a sulfone group.

  In particular, the hydrophilic radical polymerizable monomer having a hydrophilic group is preferably an acidic vinyl monomer having an acidic group.

  Preferred examples of the acidic vinyl monomer having an acidic group include an α, β-ethylenically unsaturated compound having a carboxyl group and an α, β-ethylenically unsaturated compound having a sulfone group. An α, β-ethylenically unsaturated compound having a carboxyl group is used. By using an α, β-ethylenically unsaturated compound having a carboxyl group, it is possible to easily improve resin physical properties such as surface modification of particles and adjustment of acid value of the resin. Furthermore, by using an α, β-ethylenically unsaturated compound, when obtaining the polyester particle dispersion of the present invention, particle property improvement such as sharpening of particle size distribution, storage stability, and surface modification of particles Is effective. This is because the presence of the α, β-ethylenically unsaturated compound having a carboxyl group makes it easier for the particles to be covered with the unsaturated compound, thereby preventing the particles from fusing together.

  Examples of the α, β-ethylenically unsaturated compound having a carboxyl group include acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, cinnamic acid, monomethyl maleate, monobutyl maleate, Preferred examples include maleic acid monooctyl ester.

  Examples of the α, β-ethylenically unsaturated compound having a sulfone group include sulfonated ethylene, its Na salt, allylsulfosuccinate, and octyl allylsulfosuccinate.

  Such hydrophilic radically polymerizable monomers may be used alone or in combination of two or more.

  The glass transition temperature of a resin (for example, vinyl resin) obtained by radical polymerization of a hydrophilic radically polymerizable monomer is preferably 40 ° C. or higher and 100 ° C. or lower. Resins preferably used are vinyl aromatics and carboxylic acid esters. In the polymer obtained by polymerizing these monomers, the weight average molecular weight is 1500 to 60000, preferably 3000 to 40000. When the weight average molecular weight is less than 1500, the cohesive force as the toner binder resin tends to be lowered, and the hot offset property may be lowered. When the weight average molecular weight is more than 60000, the hot fixing property is good but the minimum fixing temperature is increased. There is a case.

  In addition, by radical polymerization of a hydrophilic polymerizable monomer (preferably an acidic vinyl monomer) in the presence of polycondensable resin particles (polyester) produced by polycondensation in water, the particle size distribution is sharp and time-dependent. It is possible to obtain a dispersion of polyester particles as polyester / hydrophilic radical polymerization resin composite particles having excellent storage properties.

  When a hydrophobic radical polymerizable monomer is used as the hydrophobic substance and a hydrophilic radical polymerizable monomer having a hydrophilic group is used as the second radical polymerizable monomer, the content of the hydrophobic radical polymerizable monomer is multivalent. 3 to 20 parts by weight with respect to 100 parts by weight of the total amount of the acid component, polyhydric alcohol and radical polymerizable monomer (including hydrophobic and hydrophilic radical polymerizable monomers), and the inclusion of the hydrophilic radical polymerizable monomer It is preferable that the amount is 1.0 to 10 parts by weight with respect to 100 parts by weight of the total amount of the polyvalent acid component, the polyhydric alcohol and the radical polymerizable monomer (including hydrophobic and hydrophilic radical polymerizable monomers). is there.

  By controlling both the content of the hydrophobic radical polymerizable monomer and the content of the hydrophilic radical polymerizable monomer, polyester having sharp particle size distribution, suitable particle size, and long-term storage stability that has never existed before A dispersion of particles can be obtained. In particular, when the obtained polyester is a crystalline polyester, the maximum low-temperature fixability can be exhibited while compensating for the mechanical strength and charging properties of the crystalline polyester for toner.

  That is, by using the polyester particle dispersion liquid in which the content of each radical polymerizable monomer is controlled as described above, toner particles having a sharply controlled particle size distribution and excellent fixing characteristics can be obtained. Further, when the obtained polyester is a crystalline polyester, toner particles having sharp melt properties and low-temperature fixability equivalent to those of a toner composed only of the crystalline polyester can be obtained. An image having excellent mechanical strength, good offset resistance, and high glossiness even at low-temperature fixing can be obtained, and toner particles capable of obtaining a sufficient charge amount can be obtained.

  Here, the content of the hydrophobic radical polymerizable monomer is 3 to 100 parts by weight with respect to a total amount of 100 parts by weight of the polyvalent acid component, the polyhydric alcohol, and the radical polymerizable monomer (including the hydrophobic and hydrophilic radical polymerizable monomers). Although it is preferable that it is 20 weight part, More preferably, it is 4-15 weight part, More preferably, it is 5-10 weight part.

  If the content of the hydrophobic radical polymerizable monomer is too small, when the polyester particles are crystalline, the characteristics of the crystalline polyester are dominant, and mechanical strength deterioration and charge reduction are likely to occur. . In addition, if the content of the hydrophobic radical polymerizable monomer is too large, the sharp melt property and low temperature fixability of the polyester particles may be impaired, and thereby the glossiness of the image at the time of low temperature fixing may not be sufficiently obtained. .

  Conventional polyester / radical polymer composite particles intended for application to toners tend to use a large amount of radical polymer monomer in order to compensate for the low chargeability and mechanical strength of the radical polymer. However, by setting the content of the hydrophobic radical polymerizable monomer within the above range, the polyester particles alone have substantially the same low-temperature fixability and sharp melt properties, and crystallinity. The weak mechanical strength and low charge amount of the polyester can be suppressed.

  On the other hand, the content of the hydrophilic radical polymerizable monomer is 1.0 with respect to 100 parts by weight of the total amount of the polyvalent acid component, the polyhydric alcohol, and the radical polymerizable monomer (including hydrophobic and hydrophilic radical polymerizable monomers). The amount is preferably 10 to 10 parts by weight, more preferably 1.5 to 8.0 parts, and even more preferably 1.5 to 5.0 parts.

  When the hydrophilic radical polymerizable monomer is excessive, the hydrophilic radical polymerizable monomer (or a polymer thereof) is excessively present on the surface of the polyester particles, and the polyester particles are excessively coated. As a result, in the case of crystalline polyester particles, the sharp melt property and low temperature fixability of the crystallinity are hindered, and sufficient low temperature fixability and high image quality may not be obtained when a toner is produced. On the other hand, when the amount of the hydrophilic radical polymerizable monomer is less than the above amount, the occupation ratio of the radical polymerizable multimer on the surface of the resin particle may be reduced.

  Also, when the polyester particle surface occupancy of the hydrophilic radical polymerizable monomer is small, the particles are likely to be fused with each other, the particle size becomes coarse, and the target volume center particle size (median diameter) becomes difficult to obtain. Or the particle size distribution tends to be broad. As a result, in the toner manufacturing process, there may be adverse effects such as failure to obtain the desired particle size or insufficient charging of the toner.

  In the polyester production method of the present invention, the polyester obtained in the aqueous medium is in the form of particles, but the final average particle size is preferably 10 μm or less in terms of the volume center particle size (median diameter). The particle diameter is preferably 2 μm or less, more preferably 1 μm or less, and the most preferable particle diameter is 0.7 μm or less, and the lower limit is preferably 0.05 μm or more. In other words, the polyester particles having such a volume center particle diameter (median diameter) can be obtained by the polyester manufacturing method of the present invention. 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 this way, if the volume center particle size is too large, coarse powder is likely to be generated, the particle size distribution is deteriorated, and the release agent such as wax is easily released. The temperature may decrease. If the volume center particle size is too small, the agglomeration property at the time of granulation is deteriorated, the generation of free resin particles is likely to occur, and the viscosity of the system is also likely to increase, making it difficult to control the particle size. .

  Here, the volume center particle diameter (median diameter) of the polyester particles can be obtained by a laser diffraction type particle size distribution analyzer (Horiba, LA-920).

  Further, the obtained dispersion of polyester particles is not only the volume center particle diameter but also a dispersion without generation of ultrafine powder or ultracoarse powder, specifically, polyester particles having a volume average particle diameter of 0.05 μm or less and The ratio (total ratio) of the polyester particles having a volume average particle base diameter of 5.0 μm or more is preferably 10% or less, more preferably 5% or less, based on the entire polyester particles.

  Moreover, since the particle size distribution of the obtained polyester particles can be sharpened by using a hydrophilic radical polymerizable monomer as the second radical polymerizable monomer, the volume average particle size / number average is used as an index of the particle size distribution. The particle diameter value (SD value) is preferably 1.25 or less. If the SD value, that is, the particle size distribution is increased, the abundance ratio of particles having a minute particle size / coarse particle size is increased, and as a result, the toner is deteriorated due to agglomeration deterioration, generation of free particles, and aggregation coalescence. Since the generation of coarse powder and the release agent such as wax are easily released when produced, the releasability at the time of fixing and the offset generation temperature are likely to be lowered.

  Here, in order to obtain a dispersion of polyester particles having an SD value of 1.25 or less, as described above, the content of the hydrophilic radical polymerizable monomer is within the above range with respect to the total monomer amount. However, the hydrophilic radically polymerizable monomer is difficult to be taken into the particles due to its hydrophilic property and is likely to be present on the particle surface. However, the presence of the hydrophilic radical polymerizable monomer on the particle surface has an effect of preventing fusion between the particles.

  For this reason, when the hydrophilic radical polymerizable monomer is less than the above range, the abundance ratio of the hydrophilic radical polymerizable monomer on the surface of the polyester particle is reduced, so that the particles are easily fused with each other. Particles are likely to be generated, and it may be difficult to suppress the SD value to 1.25 or less.

  Further, when the amount of the hydrophilic radical polymerizable monomer is larger than the above range, the hydrophilic radical polymerizable monomers are easily homopolymerized and the sharp melt property at the time of fixing may be lost.

  On the other hand, in order to ensure sharp melt properties while ensuring a particle size distribution with an SD value of 1.25 or less, the content of the hydrophobic radical polymerizable monomer is preferably within the above range with respect to the total monomer amount. .

  When the amount of the hydrophobic radical polymerizable monomer is less than the above range, it becomes easy to cause homopolymerization between the hydrophilic radical polymerizable monomers or to make the composition of the vinyl resin unevenly distributed, so that the sharp melt property is lost. there is a possibility. In addition, when the amount of the hydrophobic radical polymerizable monomer is larger than the above range, the ratio of polyester (polycondensable resin) in the resin obtained by polymerization is reduced, so that sharp melt property and low temperature fixability are lost. Sometimes.

  As described above, in order to obtain particles having a predetermined particle size in an aqueous medium, the polymerization method includes a suspension polymerization method, a dissolution suspension method, a miniemulsion method, a macroemulsion method, a microemulsion method, and the like in an ordinary aqueous medium. It is preferable to use a heterogeneous polymerization form in In this case, as shown above, the polycondensation reaction, particularly the final molecular weight and the polymerization rate depend on the final particle size of the particles, so that the most preferable particle size form is 0.7 μm or less, and the efficiency is high. As a production form capable of achieving a typical production, a polymerization method such as a mini-emulsion method, a microemulsion method or the like, in which the final form is 1 μm or less of submicron particles is more preferable.

  In order to obtain toner particles of 1 μm or more that are currently used practically as a toner, a particle aggregation fusion method including at least colorant particles such as a known emulsion polymerization aggregation method (colorant is added in advance to the final polyester particles) In this case, it is possible to adjust the toner particle diameter and distribution by using colored particles.

  As described above, in the method for producing a polyester according to the present invention, a hydrophobic substance (particularly vinyl monomer) is added to an aqueous medium together with a polyester raw material (polycondensation monomer) in advance to form a hydrophobic substance (particularly vinyl). Polycondensation in an aqueous medium in the presence of a system monomer) promotes polycondensation and increases the molecular weight. If necessary, a hybrid resin (particles thereof) can be obtained by polymerizing a vinyl monomer as a hydrophobic substance.

  Furthermore, in order to adjust the polycondensation in an aqueous medium more easily and with a high polymerization rate and high molecular weight, a low molecular weight polymer (oligomer) is previously formed from a polyester raw material by a bulk polymerization method or a solution polymerization method, It is also possible to emulsify or disperse them in an aqueous medium and further carry out a polycondensation reaction to reach the final molecular weight. In this case as well, hydrophobic substances (especially vinyl monomers) can be reduced to low molecular weight polyesters (oligomers). And then emulsified or dispersed. In addition to this method, it is preferable to adjust the acid value of the final polymer as described above, or to use these methods in combination. It is also possible to use a technique in which a radically polymerizable monomer and a polyester prepolymerization method are used in combination.

(Method for producing electrostatic charge developing toner)
The most preferable production method of the electrostatic charge developing toner of the present invention comprises at least a step of aggregating the resin particles in a dispersion in which the resin particles are dispersed to obtain aggregated particles (aggregation step), and heating the aggregated particles. And fusing them together (fusing step). And in this manufacturing method called the emulsion polymerization aggregation method, resin particles are obtained by the above-described polyester manufacturing method of the present invention.

  In the aggregation step, the polyester particles (resin particles) obtained by the polyester production method of the present invention are adjusted in an aqueous medium, so that they can be used as they are as a resin dispersion. Aggregated particles having a toner diameter can be formed by mixing with a colorant particle dispersion and a release agent particle dispersion as necessary, and adding an aggregating agent to cause heteroaggregation of these particles. Further, after forming the first aggregated particles by aggregating in this way, it is also possible to add polyester particles or another polymer fine particle dispersion to form a second shell layer on the surface of the first particles. In this example, the colorant dispersion is separately adjusted. However, when the colorant is blended in advance with the polyester particles, the colorant dispersion is not necessary.

  Thereafter, in the fusing step, the toner can be obtained by heating to a temperature above the glass transition point or the melting point of the polyester particles, fusing and coalescing the aggregated particles, and washing and drying as necessary.

  The toner shape is preferably from irregular to spherical. Moreover, 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.

Hereinafter, the components of the toner used will be described.
First, as coloring components, carbon black such as furnace black, channel black, acetylene black and thermal black, inorganic pigments such as bengara, bitumen, titanium oxide, fast yellow, disazo yellow, pyrazolone red, chelate red, brilliant carmine, paraffin Examples thereof include azo pigments such as brown, phthalocyanine pigments such as copper phthalocyanine and metal-free phthalocyanine, and condensed polycyclic pigments such as flavantron yellow, dibromoanthrone orange, perylene red, quinacridone red, and dioxazine violet. Chrome Yellow, Hansa Yellow, Benzidine Yellow, Slen Yellow, Quinoline Yellow, Permanent Orange GTR, Pyrarozone Orange, Vulcan Orange, Watch Young Red, Permanent Red, Dupont Oil Red, Resol Red, Rhodamine B Lake, Lake Red C, Rose Bengal, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxalate, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 57: 1, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 17, C.I. I. Pigment blue 15: 1, C.I. I. Examples thereof include various pigments such as CI Pigment Blue 15: 3, and these can be used alone or in combination of two or more.

  Examples of the release agent include natural waxes such as carnauba wax, rice wax, and candelilla wax, low molecular weight polypropylene, low molecular weight polyethylene, sazol wax, microcrystalline wax, Fischer-Tropsch wax, paraffin wax, and montan wax. Examples thereof include, but are not limited to, synthetic or mineral / petroleum waxes, ester waxes such as fatty acid esters and montanic acid esters. Moreover, these mold release agents may be used individually by 1 type, and may be used together 2 or more types. The melting point of the release agent is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, from the viewpoint of storage stability. Moreover, it is preferable that it is 110 degrees C or less from a viewpoint of offset resistance, and it is more preferable that it is 100 degrees C or less.

  In addition, various components such as an internal additive, a charge control agent, inorganic powder (inorganic fine particles), and organic fine particles can be added as necessary. Examples of the internal additive include metals such as ferrite, magnetite, reduced iron, cobalt, nickel and manganese, alloys, and magnetic materials such as compounds containing these metals. Examples of the charge control agent include quaternary ammonium salt compounds, nigrosine compounds, dyes composed of complexes of aluminum, iron, chromium, and triphenylmethane pigments. The inorganic powder is added mainly for the purpose of adjusting the viscoelasticity of the toner. For example, silica, alumina, titania, calcium carbonate, magnesium carbonate, calcium phosphate, cerium oxide, etc. Examples thereof include all inorganic fine particles used as an external additive on the toner surface.

  The toner obtained by the method for producing an electrostatic charge developing toner of the present invention described above is used as an electrostatic charge 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 obtained toner volume average particle diameter D50 is in the range of 3.0 to 10 μm, preferably in the range of 3.0 to 5.0 μm. When D50 is less than 3.0 μm, the adhesion is increased and the developability may be lowered. On the other hand, if it exceeds 10 μm, the resolution of the image is lowered.

  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, causing image defects such as toner scattering and fogging.

Here, the volume average particle size, the number average particle size and the average particle size distribution index are, for example, particle sizes measured by a measuring instrument such as Coulter Counter TAII (manufactured by Beckman-Coulter), Multisizer II (manufactured by Beckman-Coulter). A cumulative distribution is drawn from the smaller diameter side to the particle size range (channel) divided on the basis of the distribution, and the particle size that becomes 16% cumulative is the volume D16v, the number D16p, the particle that becomes 50% cumulative The diameter is defined as a volume D50v, a number D50p, and a particle size that is 84% cumulative is defined as a volume D84v and a number D84p. Using these, the volume average particle size is volume D50v, the number average particle size is number D50p, the volume average particle size distribution index (GSDv) is (D84v / D16v) ^1/2 , and the number average particle size distribution index (GSDp) is ( D84p / D16p) is calculated as ^1/2 .

Further, the shape factor SF1 of the obtained toner is suitably in the range of 100 to 140, preferably 110 to 135, from the viewpoint of image formability. The shape factor SF1 of the present invention is obtained as follows. First, an optical microscopic image of toner spread on a slide glass is taken into a Luzex image analyzer through a video camera, and the absolute maximum length of toner particles and the projected area of toner particles are measured for 50 toners. It was obtained by the following formula.
SF1 = (ML ² / A) × (π / 4) × 100
Here, ML is defined as the absolute maximum length of toner particles, and A is the projected area of toner particles. These are quantified mainly by analyzing a microscope image or a scanning electron microscope image with an image analyzer.

  On the other hand, the carrier is not particularly limited, and examples thereof include known carriers. For example, known resin-coated carriers described in JP-A Nos. 62-39879 and 56-11461 are known. Can use the carrier.

  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, preferably 0.5 to 3.0 parts, relative 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 electrostatic image developing toner and the carrier in the electrostatic image developer is not particularly limited and may be appropriately selected depending on the purpose.

  The electrostatic charge developer (electrostatic charge developing toner) can be used in an image forming method of a normal electrostatic charge developing method (electrophotographic method). Specifically, the image forming method of the present invention includes, for example, an electrostatic latent image forming step, a toner image forming step, a transfer step, and a cleaning step. 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 electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier. The toner image forming step is a step of developing the electrostatic latent image with a developer layer on a developer carrier to form a toner image. The developer layer is not particularly limited as long as it contains the electrostatic image developer of the present invention containing the electrostatic image developing toner of the present invention. The transfer step is a step of transferring the toner image onto a transfer body. The cleaning step is a step of removing the electrostatic charge image developer remaining on the electrostatic latent image carrier. 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 charge image developing toner collected in the cleaning step to a 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.

  Hereinafter, more specific examples of the present invention will be described. However, the following examples do not limit the contents of the present invention. In the following description, “part” means “part by mass” unless otherwise specified.

(Measuring method of particle size and particle size distribution)
The particle size and particle size distribution measurement in the present invention will be described. When the particles to be measured in the present invention are 2 μm or more, a Coulter counter TA-II type (manufactured by Beckman-Coulter) was used as the measuring apparatus, and ISOTON-II (manufactured by Beckman-Coulter) 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.

  Moreover, when the particle | grains to measure in this invention are 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 of toner)
The weight average molecular weight of the toner for developing an electrostatic charge according to the present invention is obtained under the following conditions. GPC uses “HLC-8120GPC, SC-8020 (manufactured by Tosoh Corporation)”, and the column uses two “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 of toner)
The melting point and glass transition temperature of the toner of the present invention were determined from the main maximum peak measured according to ASTM D3418-8.
DSC-7 manufactured by PerkinElmer was 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 of the present invention, the heat absorption curve measured by the above method is a straight line obtained by extending the base line on the low temperature side to the high temperature side and the melting peak (endotherm) according to the definition of the melting temperature in JIS K7121: 87. The intersection of the tangent line (melting start temperature) drawn at the point where the gradient is maximum in the curve on the low temperature side of the peak) and the straight line obtained by extending the base line on the high temperature side to the low temperature side and the curve on the high temperature side of the melting peak (endothermic peak) When the temperature difference of the intersection of the tangent lines (melting end temperature) drawn at the point where the gradient becomes maximum is within 50 ° C., and the shape of the curve does not show the stepped shape shown in JIS K7121: 87. Judged to have crystallinity.

[Examples 1-6, Comparative Examples 1-3]
Examples 1 to 6 and Comparative Examples 1 to 3 are shown below.

Example 1
"Polymerization of polyester resin 1"
In a three-necked flask, 80 parts of 1,9-nonanediol (Log (P) = 1.86), 115.2 parts of 1,10-dodecanoic acid (Log (P) = 2.7), styrene monomer (Log (P ) = 2.67) 156.1 parts, butyl acrylate monomer (Log (P) = 1.88) 39.1 parts, hexadecane (Log (P) = 7.18) 2 parts, and dodecanethiol (Log (P) ) = 5.14) 2 parts were mixed well at 80 ° C. and cooled to room temperature, and then 2.0 parts of scandium trifluoromethanesulfonate [Sc (OSO ₂ CF ₃ ) ₃ ] was added as a catalyst and dissolved.

  This mixture was put into 1377 parts of ion-exchanged water in which 11 parts of sodium dodecylbenzenesulfonate and 4 parts of scandium trisdodecylsulfate were dissolved, and preliminarily dispersed with ultrasonic waves. The emulsion was dispersed at 80 ° C. using a nanomizer to obtain an emulsion having a volume average particle size of 0.2 μm.

  This emulsion was put into a 3 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, the volume average particle size was 0.2 μm, and the ratio SD (volume average particle size / number average particle size) of the volume average particle size to the number average particle size was 1.3. .

  A small amount of the sample after the reaction was taken out and dried at room temperature. The remaining solid was washed with methanol, filtered, dried in an oven, and the polymer component was taken out. The weight average molecular weight was 25000, and when deuterated chloroform was used and proton NMR (Varian Inc. 300 MHz) was used to examine the composition ratio of radically polymerizable polymer such as polyester and polystyrene butyl acrylate copolymer in the polymer, 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 mostly polyester. Furthermore, when this polymer composition (polyester resin) was dissolved in THF and then the acid value was measured using an ethanol solution of potassium hydroxide, it was 10 mgKOH / g.

  Furthermore, as a result of measuring the thermal characteristics and crystallinity of this resin, it was found that the resin had a melting point at 71 ° C.

"Polymerization of radical polymerizable monomer 1"
To the resin dispersion (1) obtained above, 3.9 parts of acrylic acid was added and allowed to stand with stirring at 80 ° C. for 1 hour to sufficiently distribute the acrylic acid into the resin fine particles. A solution of 10 parts of ammonium persulfate dissolved in 10 parts of ion-exchanged water was added, and polymerization was performed again at 80 ° C. for 5 hours under a nitrogen atmosphere. As a result, the volume average particle size was 0.2 μm, and SD was 1.3. A stable resin fine particle dispersion (2) was obtained.

  After the polymerization, a small sample is taken out, dried at room temperature and then washed with methanol, filtered and dried in the same manner as the above polyester polymerization, and the ratio of the polyester to the radical polymerizable polymer in the polymer is determined by proton NMR. 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 residual radical monomer components was 200 ppm or less. Further, when the molecular weight was measured by GPC, the weight average molecular weight was 31,000, showing a value almost equal to the value of the previously polymerized polyester, and the radical polymerizable polymer showed a molecular weight in the same range as at least the previous polyester resin. The polyester had a melting point of 71 ° C.

“Preparation of Toner Particle 1”
-Adjustment of pigment dispersion:
100 parts of a cyan pigment (Daiichi Seika Co., Ltd., CI Pigment Blue 15: 3), 15 parts of an anionic surfactant (Daigen Kogyo Seiyaku Co., Ltd .: Neogen R), and 900 parts of ion-exchanged water were mixed. Then, the mixture was dissolved and dispersed for about 1 hour using a high-pressure impact disperser ULTIMIZER (manufactured by Sugino Machine Co., Ltd., HJP30006) to prepare a cyan pigment dispersion. 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 .: WEP-2, melting point 65 ° C.) 50 parts, anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 5 parts, ion-exchanged water 200 parts at 95 ° C. After heating and dispersing using a homogenizer (manufactured by IKA: Ultra Tarrax T50), the dispersion is treated with a Menton Gorin high-pressure homogenizer (Gorin), an ester having an average particle size of 0.23 μm and a particle concentration of 20% by weight. A wax dispersion was prepared.

Toner particle 1 adjustment: emulsion polymerization aggregation method:
400 parts of the resin fine particle dispersion (2) obtained by polymerizing the radical polymerizable monomer, 34.4 parts of the pigment dispersion, 33 parts of the ester wax dispersion, and 265 parts of ion-exchanged water are 2 L. Place in a cylindrical stainless steel container and disperse and mix with Ultraturrax for 15 minutes while applying shear force at 8000 rpm. Then, 0.18 part of a 10% nitric acid aqueous solution of polyaluminum chloride was added dropwise as a flocculant. At this time, the pH of the raw material dispersion was adjusted to a range of 2.8 to 3.2 with a 0.1N sodium hydroxide aqueous solution and a 0.1N nitric acid aqueous solution.

  Thereafter, 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 were gradually heated and aggregated, and the volume average particle diameter was measured to be 6.0 μm. It was. Thereafter, the pH was raised to 9.0, and then the temperature was raised to 95 ° C. and held for 3 hours to obtain toner particles having a potato-shaped volume average particle diameter of 6.0 μm and a volume average particle diameter distribution (GSDv) 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 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. 100 parts of ferrite particles (Powder Tech, volume average particle size 50 μm) and 1 part of polymethyl methacrylate resin (Mitsubishi Rayon, molecular weight 95000) are placed in a pressure kneader together with 500 parts of toluene, and mixed at room temperature for 15 minutes. Then, 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). This ferrite carrier and the electrostatic image developing toner were mixed to prepare an electrostatic image developer having a toner concentration of 7% by weight.

  Using this electrostatic charge image developer, the following evaluation was carried out with respect to chargeability, fixability and image quality characteristics. The results are shown in Tables 1 and 2.

―Charge maintenance―
The charge retention was evaluated by measuring the charge amount after being left for 1 week in an initial charge and 80% RH, 28 ° C. environment with a blow-off charge amount measuring device (manufactured by Toshiba Chemical Co., Ltd.). The evaluation criteria are “◎” that the initial charge amount has an absolute value of 30 μC / g or more, and that the maintainability of the charge amount after aging for one week is 98% or more, and “◯” is the initial charge amount that is 25 μC. / G or more and less than 30 μC / g, maintainability of charge amount after aging for 1 week is 85% or more and less than 98%, “×” indicates initial charge amount is less than 25 μC / g, after aging for 1 week The charge amount maintainability was less than 85%.

―Fixability and image quality characteristics―
Fixability and image quality characteristics are externally fixed with variable fusing temperature by using Fuji Xerox Docu Center Color500CP remodeling machine to form an image on Fuji Xerox J paper at 10.5g / m ² toner amount. The fixing temperature was measured using a container, and the initial image quality was evaluated. Here, the criteria for evaluating the fixing temperature are the cold offset (a phenomenon in which the toner adheres to the heating surface because sufficient heat is not applied to the entire toner) and the hot offset (the entire toner is heated to a high temperature and the cohesive force As for the difference from the temperature at which the toner adheres to the heated surface due to a decrease in the temperature, that is, the width of the fixable temperature range, “◎” indicates that the fixable temperature range is 50 ° C. The temperature range is 30 ° C. or more and less than 50 ° C., and “x” indicates that the fixable temperature range is less than 30 ° C.

  As for image quality characteristics, image quality uniformity (unevenness) and image intensity were measured. Regarding image quality uniformity (unevenness), transfer unevenness caused by toner particle charge distribution due to the wide particle size distribution was visually observed. Evaluation criteria are “◎” where no transfer unevenness is observed visually, “○” where slight transfer unevenness is observed visually, but no problem in practical use, and “×” clearly visible As a result, uneven transfer was observed and there was a problem in practical use.

  The image strength was measured according to the pencil scratch tester method of JIS K5400: 90. That is, the fixed image was measured by performing a scratch test with a constant needle pressure at a 45-degree angle using a pencil with hardness H (manufactured by Mitsubishi Pencil Co., Ltd.) and visually observing the presence or absence of image scratches. Evaluation criteria are as follows: “◎” indicates that there is no image damage and sufficient image strength, “○” indicates that slight image damage is observed but has image strength that has no practical problem, and “×” indicates clear Image defects were observed, and there was a practical problem in image intensity.

(Example 2)
"Adjustment of polyester resin 2"
In a three-necked flask, 144.2 parts of cyclohexanedimethanol (Log (P) = 0.9), 230.3 parts of 1,10-dodecanoic acid (Log (P) = 2.7), and scandium trifluoromethane as a catalyst After adding 2 parts of sulfonate [Sc (OSO ₂ CF ₃ ) ₃ ], the air in the container is depressurized by a depressurization operation, and an inert atmosphere is created with nitrogen gas at 120 ° C. with mechanical stirring. When the mixture was refluxed for 3 hours, it became viscous. When the molecular weight was confirmed by GPC, the weight average molecular weight was 5,300. Moreover, it was 40 mgKOH / g when the acid value of this resin was measured similarly to the said Example 1. FIG. Thus, first, an oligomer of a polyhydric alcohol component and a polyhydric acid component was formed.

  In 195 parts of this viscous liquid, 156.1 parts of styrene monomer (Log (P) = 2.67), 39.1 parts of butyl acrylate monomer (Log (P) = 1.88), hexadecane (Log (P) = 7.18) 2 parts and dodecanethiol (Log (P) = 5.14) 2 parts were mixed well at 80 ° C. and taken out at room temperature. Further, this mixture was put into 1377 parts of ion-exchanged water in which 11 parts of sodium dodecylbenzenesulfonate was dissolved, and preliminarily dispersed with ultrasonic waves, and then further mixed with an ultra-high pressure homogenizer (Nanomizer manufactured by Yoshida Kikai Co., Ltd.). The mixture was emulsified and dispersed at 0 ° C. to obtain a volume average particle size of 0.3 μm. This emulsion was put into a 3 L pressure reactor equipped with a stirrer and polymerized at 100 ° C. for 8 hours in a nitrogen atmosphere to obtain a resin fine particle dispersion (3). The reaction product maintained a stable emulsified state, and its volume average particle size was 0.3 μm and SD 1.3.

  A small amount of the sample after this reaction was taken out and subjected to the following various analyzes in the same manner as in Example 1. As a result, the weight average molecular weight was 21,000, and the radical polymerizable polymer polymerization yield in proton NMR was 2% or less. Thus, it was considered that the polymer component was almost polyester. Furthermore, when the acid value of this polymer composition (polyester resin) was measured, it was 15 mgKOH / g.

  Furthermore, as a result of measuring the thermal characteristics of this resin, it was found that it was a crystalline resin having a melting point at 70 ° C.

"Polymerization of radical polymerizable monomer 2"
To the resin fine particle dispersion (3) obtained above, 3.9 parts of acrylic acid was added and allowed to stand with stirring at 80 ° C. for 1 hour to sufficiently distribute the acrylic acid into the particles. A solution of ammonium persulfate dissolved in 10 parts of ion-exchanged water was added, and polymerization was performed again at 80 ° C. for 5 hours under a nitrogen atmosphere. As a result, stable resin fine particles having a volume average particle size of 0.3 μm and SD 1.3 were obtained. A dispersion (4) was obtained. After the polymerization, a small sample was taken out, and the polymerization rate of the radical polymerizable monomer was determined by NMR in the same manner as in Example 1. As a result, it was 99% or more. Furthermore, the weight average molecular weight of the resin fine particle dispersion (4) by GPC was 31000, and the melting point of the crystalline polyester in the resin fine particles was 70 ° C.

Preparation of “Toner Particle 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 then these were agglomerated and further heated to 95 ° C. The final toner was obtained by fusing the particles. The obtained toner had a volume average particle diameter of 5.5 μm, a volume average particle size distribution (GSDv) of 1.23, and obtained potato-shaped toner particles 2.

“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, fixability, and image quality characteristics were evaluated. The results are shown in Tables 1 and 2. The developer of this example has a developer initial charge of 35 μC / g or more and a maintenance property of 99% or more after aging. Also in the fixing performance, the fixing performance at 100 ° C. and a sufficient fixing temperature are possible. Range, excellent image quality characteristics.

(Example 3)
“Polymerization of polyester resin 3”
Polymerization was conducted in the same manner as in Example 1 except that 66 parts of terephthalic acid (Log (P) = 1.15) and 23 parts of dodecanedioic acid (Log (P) = 2.7) were used as the polyvalent carboxylic acid. And a resin fine particle dispersion (5) was obtained. The particle diameter of the obtained resin fine particles was 0.15 μm, SD 1.3, the weight average molecular weight of the polyester resin was 20000, the melting point was 73 ° C., and the acid value was 8 mgKOH / g.

"Polymerization of radical polymerizable monomer 3"
A resin fine particle dispersion (6) was obtained in the same manner as the resin fine particle dispersion (2) in Example 1 except that the resin fine particle dispersion (5) was used. The particle diameter of the obtained resin fine particle dispersion (6) is 0.15 μm, SD 1.3, the polymerization yield of the radical polymerizable monomer is 99% or more, the weight average molecular weight of the resin fine particles 6 is 25000, and the melting point is 83 ° C. there were.

“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 95 ° 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 (GSDv) of 1.25, and spherical toner particles 3 were obtained.

“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, fixability, and image quality characteristics were evaluated. The results are shown in Tables 1 and 2. The developer of this example has a developer initial chargeability of 35 μC / g or more and a maintenance property of 99% or more after aging. Also in the fixing performance, the fixing performance at 100 ° C. and the fixing possible temperature range, Excellent image quality characteristics.

(Example 4)
"Polymerization of polyester resin 4"
As the polyvalent carboxylic acid, 58.1 parts of fumaric acid (Log (P) = − 0.36) and as the polyhydric alcohol 179.2 parts of bisphenol A propylene oxide adduct (Log (P) = 4.19) were used. Except for the above, polymerization was carried out in the same manner as in Example 1 to obtain a resin fine particle dispersion (7). The obtained resin fine particles had a particle size of 0.25 μm, SD 1.3, a weight average molecular weight of the polyester resin of 12000, Tg (secondary glass transition temperature) of 63 ° C., and an acid value of 10 mgKOH / g.

"Polymerization of radical polymerizable monomer 4"
A resin fine particle dispersion (8) was obtained in the same manner as the resin fine particle dispersion (4) in Example 1 except that the resin fine particle dispersion (7) was used. The resulting resin fine particle dispersion (8) has a particle size of 0.25 μm, SD 1.3, a polymerization yield of the radical polymerizable monomer of 99% or more, and the resin fine particles (8) have a weight average molecular weight of 28000, Tg of 58 ° C. Met.

“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 78 ° C. to fuse the particles to obtain the final toner. Got. The obtained toner had spherical toner particles 4 with a volume average particle size of 5.0 μm and a volume average particle size distribution (GSDSv) of 1.22.

“Adjustment and Evaluation of Developer 4”
The developer 3 was prepared in the same manner as in Example 1 except that the toner particles 4 were used, and the chargeability, fixability, and image quality characteristics were evaluated. The results are shown in Tables 1 and 2. The developer of this example has a developer initial charging property of 35 μC / g or more and a maintenance property of 99% or more after aging. Also in the fixing performance, the fixing performance at 130 ° C. and the sufficient fixing temperature range. And showed excellent image quality characteristics.

(Example 5)
"Polymerization of polyester resin 5"
In Example 1, resin fine particles (9) were obtained by performing polymerization in the same manner as in Example 1 except that dodecylbenzenesulfonic acid was used in place of scandium trifluoromethanesulfonate as a polymerization catalyst, and scandium trisdodecylsulfate was not used. It was. The particle diameter of the obtained resin fine particles was 0.15 μm, SD 1.3, the weight average molecular weight of the polyester resin was 25000, the melting point was 70 ° C., and the acid value was 8 mgKOH / g.

"Polymerization of radical polymerizable monomer 5"
A resin fine particle dispersion (10) was obtained in the same manner as the resin fine particle dispersion (2) in Example 1 except that the resin fine particle dispersion (9) was used. The particle diameter of the obtained resin fine particle dispersion (10) is 0.15 μm, SD 1.3, the polymerization yield of the radical polymerizable monomer is 99% or more, and the weight average molecular weight of the resin fine particles 6 is 28000. The melting point of the crystalline polyester was 69 ° C.

“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 95 ° C. to fuse the particles to obtain the final toner. Got. The obtained toner had a volume average particle diameter of 5.2 μm, a volume average particle size distribution (GSDv) of 1.25, and spherical toner particles 5 were obtained.

“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, fixability, and image quality characteristics were evaluated. The results are shown in Tables 1 and 2. The developer of this example has a developer initial chargeability of 35 μC / g or more and a maintenance property of 99% or more after aging. Also in the fixing performance, the fixing performance at 100 ° C. and the fixing possible temperature range, Excellent image quality characteristics.

(Example 6)
"Polymerization of polyester resin 6"
In Example 4, polyester was polymerized in the same manner as in Example 4 except that 200 parts of methyl butyl ketone (Log (P) = 1.6) was used instead of styrene monomer, butyl acrylate, dodecanethiol, and hexadecane. Fine particles (11) were obtained. Further, the resin fine particles were heated to 85 ° C. under reduced pressure, and methyl isobutyl ketone was removed by distillation to obtain resin fine particles (12). The obtained resin fine particles had a particle size of 0.15 μm, SD 1.3, and a weight average molecular weight of the polyester resin was 10,000, Tg of 58 ° C., and an acid value of 12 mgKOH / g.

“Preparation of toner particles 6”
Using the resin fine particle dispersion (12), after preparing a pigment dispersion and an ester wax dispersion in the same manner as in Example 1, 1.0 part of sodium dodecylbenzenesulfonate was further added, and these were aggregated. Further, the resultant was heated to 95 ° C., and the particles were fused to obtain a final toner. The obtained toner had spherical toner particles 6 with a volume average particle size of 5.0 μm and a volume average particle size distribution (GSDv) of 1.22.

“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, fixability, and image quality characteristics were evaluated. The results are shown in Tables 1 and 2. The developer of this example has a developer initial charging property of 35 μC / g or more and a maintenance property of 99% or more after aging. Also in the fixing performance, the fixing performance at 130 ° C. and the sufficient fixing temperature range. And showed excellent image quality characteristics.

(Comparative Example 1)
In order to show the excellent dispersion characteristics of the polyester resin in the present invention, and the excellent charging characteristics derived from the toner, and the image quality characteristics, the dispersion to the aqueous medium from the direct polymerization by the bulk polymerization of the polyester conventionally performed, The toner preparation and its characteristics are shown as a comparative example.

"Polymerization of polyester resin 7"
In a three-necked flask, 230.3 parts of dodecanedioic acid (Log (P) = 2.7) and 160.0 parts of 1,9-nonanediol (Log (P) = 1.86) and 2 parts of dibutyltin oxide as a catalyst After that, the air in the container was decompressed by a decompression operation, and was further brought into an inert atmosphere with nitrogen gas, and refluxed at 180 ° C. for 12 hours with mechanical stirring, resulting in a viscous state. When the molecular weight was confirmed by GPC, the weight average molecular weight was 28,000. Further, when the acid value of this resin was measured in the same manner as in Example 1, it was 5 mg KOH / g and the melting point was 70 ° C.

  This resin was put into 1377 parts of ion-exchanged water in which 11 parts of sodium dodecylbenzenesulfonate was dissolved, and preliminarily dispersed with a homogenizer (Ultra Tlux T50, manufactured by IKA), and then an ultra-high pressure homogenizer (Yoshida Machine Industries). As a result of emulsification and dispersion at 150 ° C. using a Nanomizer manufactured by Komatsu Ltd., the volume average particle size is 0.9 μm, the emulsified particle size is SD4.5, and the particle size distribution is broad and saturated. Narrowing and distribution were not possible. This resin dispersion was designated as polyester resin fine particle dispersion (13).

“Preparation of toner particles 7”
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 (13) was used, and then aggregated and heated to 95 ° C. to fuse the particles to obtain the final toner. Got. The obtained toner had a volume average particle diameter of 13 μm, and angular toner particles having a volume average particle size distribution of 1.5 ranging from 1 μm or less to 10 μm or more.

“Adjustment and Evaluation of Developer 7”
The developer 7 was prepared in the same manner as in Example 1 except that the toner particles 7 were used, and the chargeability, fixability, and image quality characteristics were evaluated. The results are shown in Tables 1 and 2. The developer of this comparative example has a large variation in the initial chargeability of the developer from 10 μC / g to 30 μC / g, and the reproducibility and maintainability of the chargeability is practically large when the maintainability after aging is 50% or less. It became a problem. The fixing temperature was 120 ° C., but there were many image quality irregularities in the image quality characteristics, and there were some weak portions in the image quality intensity, which was a big problem in practical use.

(Comparative Example 2)
"Polymerization of polyester resin 8"
In polyester polymerization 1 of Example 1, nonanediol and dodecanoic acid were mixed well at 90 ° C. without using a hydrophobic material of styrene monomer, butyl acrylate monomer, hexadecane, and dodecanethiol, and scandium trifluoromethanesulfonate was used as a catalyst. 2.0 parts were quickly dissolved and emulsified quickly at 80 ° C. in the same manner as in Example 1 to obtain an emulsion having a volume average particle diameter of 0.5 μm, and then the polyester was polymerized. The obtained resin fine particles had a particle size of 0.55 μm, SD 1.3, the weight average molecular weight of the polyester resin was 3500, and the acid value was 55 mgKOH / g. Thus, a molecular weight practically usable as a toner resin could not be obtained.

(Comparative Example 3)
"Polymerization of polyester resin 9"
Emulsification was performed in the same manner as in Example 1 except that ethylene glycol (Log (P) = − 0.79) was used instead of 1,9 nonanediol used in Example 1, and the volume average particle size was 0.23 μm. After obtaining the emulsion, polymerization was performed in the same manner as the polymerization of the polyester resin 1. The obtained resin fine particles had a particle size of 0.25 μm, SD 1.3, the weight average molecular weight of the polyester resin was 2500, and the acid value was 56 mgKOH / g. Thus, a molecular weight practically usable as a toner resin could not be obtained.

  From the above results, in this example, since the polyester material having high hydrophobicity is subjected to polycondensation in the coexistence of a hydrophobic material having high hydrophobicity (particularly vinyl monomer), the high molecular weight of the polyester is low energy. It can be seen that It can also be seen that the fine particles obtained have good particle size and distribution. It can also be seen that the toner obtained by using this sufficiently satisfies the toner characteristics such as toughness (toner strength, image quality strength), particle size distribution, charging characteristics, and charging environment dependency. It can also be seen that the formation of oligomers and the use of radically polymerizable monomers are also very advantageous for polymerisation.

In particular, in Examples 1, 2, 3, and 5 where the value of | Log (P) _COOH- Log (P) _OH | is small, the value of the hydrophobic parameter is smaller, so that the stoichiometric polymerizability of the monomer From this viewpoint, it can be seen that when the polymerization is performed under the same conditions, it is possible to obtain a higher molecular weight with a combination having a small hydrophobic parameter.

  On the other hand, in the comparative example, it is difficult to increase the molecular weight of the polyester, and even if it is obtained, it is understood that very high energy is required. In addition, it can be seen that the resin particles (toner) obtained are very large and the particle size distribution is poor.

  Thus, it can be seen that a low environmental load production method for high-quality polyester toner particles, which has been considered as a major issue in terms of production and environmental load (energy), has been established in the polymerization method of polyester in an aqueous medium. . In particular, crystalline polyester resins, which are important in low-energy electrophotographic technology, such as low-temperature fixability, which will become increasingly important in the future, are difficult to reduce the particle size, which is the most important for achieving high image quality. In order to achieve the above, a manufacturing process that is not environmentally favorable, such as a large energy load and the use of an organic solvent, has been used. It can also be seen that a solution has been found to solve this problem in the future, in which high performance of polyester resin toner and a low environmental load manufacturing method are highly compatible.

  Therefore, high performance of polyester resin toner and low environmental load manufacturing method are both highly compatible, and a highly reliable electrophotographic toner that can be applied to low image quality and low energy processes manufactured with low environmental load and low energy is obtained. I understand that

[Examples B1 to B6, Comparative Examples B1 to B2]
Hereinafter, Examples B1 to B6 and Comparative Examples B1 to B2 are shown. In each example, the following resin fine particle dispersion, colorant particle dispersion, and release agent particle dispersion are prepared, respectively, at predetermined ratios. While mixing and stirring, a metal salt polymer is added and ionically neutralized to form aggregated particles. Next, an inorganic hydroxide is added to adjust the pH in the system from weakly acidic to neutral, and then the mixture is heated to a temperature equal to or higher than the glass transition point of the resin fine particles to fuse and unite. After completion of the reaction, a desired toner is obtained through sufficient washing, solid-liquid separation, and drying processes. Hereinafter, each preparation method is demonstrated.

(Preparation of monomer dispersion emulsion (1))
<Preparation of aqueous phase>
Dodecylbenzenesulfonic acid 1.66 parts by weight Ion exchange water 200 parts by weight is mixed and dissolved.

<Production of oil phase>
1,9 nonanediol 18.45 parts by weight 1, 10 decamethylene dicarboxylic acid 26.55 parts by weight styrene (hydrophobic radical polymerizable monomer) 3.44 parts by weight n-butyl acrylate (hydrophobic radical polymerizable monomer) 06 parts by weight acrylic acid (hydrophilic radical polymerizable monomer) 0.5 parts by weight stearyl methacrylate 1.66 parts by weight dodecanethiol 0.07 parts by weight were mixed, heated to 120 ° C. and melted, and then the above-mentioned aqueous phase dodecyl The solution was put into a benzenesulfonic acid aqueous solution and emulsified with a homogenizer (manufactured by IKA, Ultra Tarrax) for 5 minutes, and then passed through a nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.) for 5 passes to obtain a monomer-dispersed emulsion (1).

(Preparation of monomer dispersion emulsion (2))
<Preparation of aqueous phase>
Dodecylbenzenesulfonic acid 1.66 parts by weight Ion exchange water 200 parts by weight is mixed and dissolved.

<Production of oil phase>
1,9 nonanediol 19.89 parts by weight 1, 10 decamethylene dicarboxylic acid 28.61 parts by weight Styrene (hydrophilic radical polymerizable monomer) 0.765 parts by weight n-butyl acrylate (hydrophobic radical polymerizable monomer) 235 parts by weight methacrylic acid (hydrophilic radical polymerizable monomer) 0.5 parts by weight stearyl methacrylate 1.66 parts by weight dodecanethiol 0.07 parts by weight were mixed, heated to 120 ° C. and melted, and then the above-mentioned aqueous phase dodecyl The solution was put into a benzenesulfonic acid aqueous solution and emulsified with a homogenizer (manufactured by IKA, Ultra Tarrax) for 5 minutes, and then passed through a nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.) for 5 passes to obtain a monomer dispersion (2).

(Preparation of monomer dispersion emulsion (3))
<Preparation of aqueous phase>
Dodecylbenzenesulfonic acid 1.66 parts by weight Ion exchange water 200 parts by weight is mixed and dissolved.

<Production of oil phase>
1,9 nonanediol 16.40 parts by weight 1, 10 decamethylene dicarboxylic acid 23.60 parts by weight styrene (hydrophobic radical polymerizable monomer) 7.27 parts by weight n-butyl acrylate (hydrophobic radical polymerizable monomer) 23 parts by weight maleic acid (hydrophilic radical polymerizable monomer) 0.5 parts by weight stearyl methacrylate 1.66 parts by weight dodecanethiol 0.07 parts by weight were mixed, heated to 120 ° C. and melted, and then the above-mentioned aqueous phase dodecyl The solution was put into a benzenesulfonic acid aqueous solution and emulsified with a homogenizer (manufactured by IKA, Ultra Tarrax) for 5 minutes, and then passed through a nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.) for 5 passes to obtain a monomer-dispersed emulsion (3).

(Preparation of monomer dispersion emulsion (4))
<Preparation of aqueous phase>
Dodecylbenzenesulfonic acid 1.66 parts by weight Ion-exchanged water 200 parts by weight are mixed and dissolved.

<Production of oil phase>
1,9 Nonanediol 16.40 parts by weight 1, 10 decamethylene dicarboxylic acid 23.60 parts by weight Styrene (hydrophobic radical polymerizable monomer) 3.82 parts by weight n-butyl acrylate (hydrophobic radical polymerizable monomer) 18 parts by weight acrylic (hydrophilic radical polymerizable monomer) 5.0 parts by weight stearyl methacrylate 1.66 parts by weight dodecanethiol 0.07 parts by weight are mixed, heated to 120 ° C. and melted, and then the aqueous phase dodecylbenzene The solution was put into a sulfonic acid aqueous solution and emulsified with a homogenizer (manufactured by IKA, Ultra Tarrax) for 5 minutes, and then passed through a nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.) for 5 passes to obtain a monomer dispersion (4).

(Preparation of monomer dispersion emulsion (5))
<Preparation of aqueous phase>
Dodecylbenzenesulfonic acid 1.66 parts by weight Ion-exchanged water 200 parts by weight are mixed and dissolved.

<Production of oil phase>
1,6 hexanediol 16.60 parts by weight Sebacic acid 28.40 parts by weight Styrene (hydrophobic radical polymerizable monomer) 3.44 parts by weight n-butyl acrylate (hydrophobic radical polymerizable monomer) 1.06 parts by weight acrylic acid (Hydrophilic radically polymerizable monomer) 0.5 parts by weight stearyl methacrylate 1.66 parts by weight dodecanethiol 0.07 parts by weight are mixed, heated to 120 ° C. and melted, and then added to the aqueous phase dodecylbenzenesulfonic acid aqueous solution. The resulting mixture was emulsified for 5 minutes with a homogenizer (manufactured by IKA, Ultra Tarrax), and then passed through Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.) for 5 passes to obtain a monomer-dispersed emulsion (5).

(Preparation of monomer dispersion emulsion (6))
<Preparation of aqueous phase>
Dodecylbenzenesulfonic acid 1.66 parts by weight Ion exchange water 200 parts by weight is mixed and dissolved.

<Production of oil phase>
Ethylene glycol 10.43 parts by weight Adipic acid 24.57 parts by weight Styrene (hydrophobic radical polymerizable monomer) 11.09 parts by weight n-butyl acrylate (hydrophobic radical polymerizable monomer) 3.41 parts by weight acrylic acid (hydrophilic Radical polymerizable monomer) 0.5 parts by weight stearyl methacrylate 1.66 parts by weight dodecanethiol 0.07 parts by weight are mixed, heated to 120 ° C. and melted, and then added to the aqueous solution of dodecylbenzenesulfonic acid, After emulsifying for 5 minutes with a homogenizer (manufactured by IKA, Ultra Tarrax), nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.) was passed 5 times to obtain a monomer-dispersed emulsion (6).

(Preparation of monomer dispersion emulsion (7))
<Preparation of aqueous phase>
Dodecylbenzenesulfonic acid 1.66 parts by weight Ion-exchanged water 200 parts by weight are mixed and dissolved.

<Production of oil phase>
1,9 nonanediol 20.5 parts by weight 1, 10 decamethylenedicarboxylic acid 29.5 parts by weight were mixed, heated to 120 ° C. and melted, then poured into the aqueous solution of dodecylbenzenesulfonic acid, and homogenizer ( After emulsification with IKA (Ultra Turrax) for 5 minutes, Nanomizer (Yoshida Kikai Kogyo Co., Ltd.) was passed 5 times to obtain a monomer-dispersed emulsion (7).

(Preparation of monomer dispersion emulsion (8))
<Preparation of aqueous phase>
Dodecylbenzenesulfonic acid 1.66 parts by weight Ion-exchanged water 200 parts by weight are mixed and dissolved.

<Production of oil phase>
Propylene glycol 16.45 parts by weight Glutaric acid 28.55 parts by weight Styrene (hydrophobic radical polymerizable monomer) 3.71 parts by weight n-butyl acrylate (hydrophobic radical polymerizable monomer) 1.14 parts by weight acrylic acid (hydrophilic Radical polymerizable monomer) 0.15 parts by weight stearyl methacrylate 1.66 parts by weight dodecanethiol 0.07 parts by weight are mixed, heated to 120 ° C. and melted, and then poured into the aqueous solution of dodecylbenzenesulfonic acid, After emulsifying for 5 minutes with a homogenizer (manufactured by IKA, Ultra Tarrax), Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.) was passed for 5 passes to obtain a monomer-dispersed emulsion (8).

(Preparation of resin fine particle dispersion (1))
The emulsion obtained with the monomer dispersion (1) was put into a reactor equipped with a stirrer, and maintained at 70 ° C. under a nitrogen atmosphere and maintained for 24 hours for polycondensation. A small amount of this reaction product was taken out and subjected to NMR analysis, and it was confirmed that polyester was synthesized by polycondensation at this point.

NMR measurement was performed by measuring proton NMR (300 MHz manufactured by Varian) using deuterium chloroform.
The identity of the polyester in the NMR measurement is Barrere, K.M. According to the description in p2836 of Landfest / Polymer 44 (2003) 2833-2841, the polyester peak was confirmed by comparing the NMR chemical shifts of 4.05 ppm and 3.6 ppm, and the progress of polycondensation was judged.

In addition, a solution obtained by dissolving 0.8 parts by weight of ammonium persulfate in 10 parts by weight of ion-exchanged water was dropped into the resin dispersion obtained as described above, and radical polymerization was further performed for 6 hours in a nitrogen atmosphere.
Thereby, the center diameter of the fine particles is 220 nm,
The value of volume average particle diameter / number average particle diameter (SD value) is 1.18,
The total particle ratio (coarse particle total ratio) of the particles having a volume average particle diameter of 0.01 μm or less and the particles having a volume average particle diameter of 5.0 μm or more is 0.01%,
A resin dispersion containing polyester / vinyl composite particles having a polyester weight average molecular weight of 5850, a polyester melting point of 69.2 ° C., and a polyvinyl weight average molecular weight of 33400 was obtained.

  The prepared resin dispersion is transferred to a plastic container, stored at room temperature for 2 weeks, and the resin particle diameter is measured with LA-920 24 hours and 2 weeks after the resin dispersion is prepared. The storage stability was confirmed.

  The criteria for judging the storage stability were “◯” when the median diameter of the resin particles was 0.5 μm or less, and “X” when the value exceeded 0.5 mμm.

  With respect to this resin dispersion, the measurement result of the median diameter after storage for 24 hours was 230 nm, and the measurement result of the median diameter after 2 weeks of storage was 250 nm, confirming excellent storage stability.

(Preparation of resin fine particle dispersion (2))
It was produced by the same method as the resin dispersion (1) except that the monomer dispersion (2) was changed. As with the resin dispersion (1), a sample was taken out after 24 hours of polycondensation and subjected to NMR measurement. As a result, it was confirmed that polyester was synthesized. Further, after polycondensation, an ammonium persulfate solution was dropped as in the preparation of the resin dispersion (1), and radical polymerization was further performed in a nitrogen atmosphere for 6 hours.

Thereby, the center diameter of the fine particles is 400 nm,
Volume average particle size / number average particle size (SD value) is 1.20,
The total particle ratio (coarse particle total ratio) of the particles having a volume average particle diameter of 0.01 μm or less and the particles having a volume average particle diameter of 5.0 μm or more is 0.01%,
A resin dispersion containing polyester / vinyl composite particles having a polyester weight average molecular weight of 5780, a polyester melting point of 70.3 ° C., and a polyvinyl weight average molecular weight of 41500 was obtained.

  With respect to this resin dispersion, the measurement result of the median diameter after 24 hours of storage was 390 nm, and the measurement result of the median diameter after 2 weeks of storage was 420 nm, confirming that the storage stability was excellent.

(Preparation of resin fine particle dispersion (3))
It was produced in the same manner as the resin dispersion (1) except that the monomer dispersion (3) was changed. As with the resin dispersion (1), a sample was taken out after 24 hours of polycondensation and subjected to NMR measurement. As a result, it was confirmed that polyester was synthesized. Further, after polycondensation, an ammonium persulfate solution was dropped as in the preparation of the resin dispersion (1), and radical polymerization was further performed in a nitrogen atmosphere for 6 hours.

Thereby, the center diameter of the fine particles is 200 nm,
The value of volume average particle diameter / number average particle diameter (SD value) is 1.18,
The total particle ratio (coarse particle total ratio) of the particles having a volume average particle diameter of 0.01 μm or less and the particles having a volume average particle diameter of 5.0 μm or more is 0.01%,
The weight average molecular weight of the polyester is 5940, the melting point of the polyester is 67.2 ° C.,
A resin dispersion containing polyester / vinyl composite particles having a weight average molecular weight of 49,400 was obtained.

  With respect to this resin dispersion, the measurement result of the median diameter after 24 hours of storage was 220 nm, and the measurement result of the median diameter after 2 weeks of storage was 260 nm, confirming excellent storage stability.

(Preparation of resin fine particle dispersion (4))
It was prepared in the same manner as the resin dispersion (1) except that the monomer dispersion (4) was changed. As with the resin dispersion (1), a sample was taken out after 24 hours of polycondensation and subjected to NMR measurement. As a result, it was confirmed that polyester was synthesized. In addition, after polycondensation, an ammonium persulfate solution was dropped as in the preparation of the resin dispersion (1), and radical polymerization was further performed in a nitrogen atmosphere for 6 hours.

Thereby, the center diameter of the fine particles is 210 nm,
The value of volume average particle diameter / number average particle diameter (SD value) is 1.18,
The total particle ratio (coarse particle total ratio) of the particles having a volume average particle diameter of 0.01 μm or less and the particles having a volume average particle diameter of 5.0 μm or more is 0.01%,
The weight average molecular weight of the polyester is 5690, the melting point of the polyester is 67.6 ° C.,
A resin dispersion containing polyester / vinyl composite particles having a weight average molecular weight of 45,600 was obtained.

  With respect to this resin dispersion, the measurement result of the median diameter after storage for 24 hours was 230 nm, and the measurement result of the median diameter after 2 weeks of storage was 270 nm, confirming excellent storage stability.

(Preparation of resin fine particle dispersion (5))
A resin dispersion (1) was prepared in the same manner as in the resin dispersion (1) except that the monomer dispersion (5) was changed. As with the resin dispersion (1), a sample was taken out after 24 hours of polycondensation and subjected to NMR measurement. As a result, it was confirmed that polyester was synthesized. After polycondensation, an ammonium persulfate solution was added dropwise in the same manner as in the preparation of the resin dispersion (1), and radical polymerization was further performed in a nitrogen atmosphere for 6 hours.

Thereby, the center diameter of the fine particles is 220 nm,
The value of volume average particle diameter / number average particle diameter (SD value) is 1.18,
The total particle ratio (coarse particle total ratio) of the particles having a volume average particle diameter of 0.01 μm or less and the particles having a volume average particle diameter of 5.0 μm or more is 0.01%,
A resin dispersion containing polyester / vinyl composite particles having a polyester weight average molecular weight of 5620, a polyester melting point of 69.6 ° C., and a polyvinyl weight average molecular weight of 41600 was obtained.

  With respect to this resin dispersion, the measurement result of median diameter after storage for 24 hours was 260 nm, and the measurement result of median diameter after 2 weeks of storage was 260 nm, confirming that the storage stability was excellent.

(Preparation of resin fine particle dispersion (6)): Excessive vinyl content A resin dispersion (1) was prepared in the same manner as in the case of the monomer dispersion (6). As with the resin dispersion (1), a sample was taken out after 24 hours of polycondensation and subjected to NMR measurement. As a result, it was confirmed that polyester was synthesized. After polycondensation, an ammonium persulfate solution was added dropwise in the same manner as in the preparation of the resin dispersion (1), and radical polymerization was further performed for 6 hours in a nitrogen atmosphere.

Thereby, the center diameter of the fine particles is 220 nm,
Volume average particle size / number average particle size (SD value) is 1.20,
The total particle ratio (coarse particle total ratio) of the particles having a volume average particle diameter of 0.01 μm or less and the particles having a volume average particle diameter of 5.0 μm or more is 0.01%,
A resin dispersion containing polyester / vinyl composite particles having a polyester weight average molecular weight of 4690, a polyester melting point of 62.1 ° C., and a polyvinyl weight average molecular weight of 51,000 was obtained.

  With respect to this resin dispersion, the measurement result of the median diameter after storage for 24 hours was 210 nm, and the measurement result of the median diameter after 2 weeks of storage was 240 nm, confirming excellent storage stability.

(Preparation of resin fine particle dispersion (7)): No vinyl It was prepared in the same manner as the resin dispersion (1) except that the monomer dispersion (7) was used. As with the resin dispersion (1), a sample was taken out after 24 hours of polycondensation and subjected to NMR measurement. As a result, it was confirmed that polyester was synthesized. Further, after polycondensation, an ammonium persulfate solution was dropped as in the preparation of the resin dispersion (1), and radical polymerization was further performed in a nitrogen atmosphere for 6 hours.

Thereby, the center diameter of the fine particles is 1060 nm,
Volume average particle diameter / number average particle diameter value (SD value) is 1.41,
The total particle ratio (coarse particle ratio) of the particles having a volume average particle diameter of 0.01 μm or less and the particles having a volume average particle diameter of 5.0 μm or more is 44.2%,
The weight average molecular weight of the polyester is 5790, the melting point of the polyester is 71.0 ° C.,
A resin dispersion was obtained.
With respect to this resin dispersion, the measurement result of the median diameter after storage for 24 hours was 15 μm, and the measurement result of the median diameter after 2 weeks of storage was 56 μm, which confirmed that there was no storage stability.

(Preparation of Resin Fine Particle Dispersion (8)): Excess Acrylic Acid Prepared by the same method as Resin Dispersion (1) except for changing to Monomer Dispersion (8). As with the resin dispersion (1), a sample was taken out after 24 hours of polycondensation and subjected to NMR measurement. As a result, it was confirmed that polyester was synthesized. Further, after the polycondensation, an ammonium persulfate solution was dropped as in the preparation of the resin dispersion (1), and radical polymerization was further performed for 6 hours in a nitrogen atmosphere.
Thereby, the center diameter of the fine particles is 390 nm,
Volume average particle size / number average particle size (SD value) is 1.31,
The total particle ratio of the particles having a volume average particle diameter of 0.01 μm or less and the particles having a volume average particle diameter of 5.0 μm or more (coarse particle total ratio) is 11.2%,
The weight average molecular weight of the polyester is 4650, the melting point of the polyester is 69.6 ° C.,
A resin dispersion containing polyester / vinyl composite particles having a weight average molecular weight of polyvinyl of 48600 was obtained.

  With respect to this resin dispersion, the measurement result of the median diameter after storage for 24 hours was 410 nm, but the measurement result of the median diameter after storage for 2 weeks was 15 μm, and it was confirmed that there was no storage stability.

(Preparation of colorant particle dispersion (1))
Yellow pigment (manufactured by Dainichi Seika Co., Ltd., CI Pigment Yellow 74) 50 parts by weight Anionic surfactant (Daiichi Kogyo Seiyaku, Neogen R) 5 parts by weight Ion-exchanged water 200 parts by weight The above components are mixed and dissolved, and a homogenizer (Ultra lux manufactured by IKA Co., Ltd.) Dispersed for 10 minutes by an ultrasonic bath for 5 minutes to obtain a yellow colorant particle dispersion (1) having a center diameter of 240 nm and a solid content of 21.5%.

(Preparation of colorant particle dispersion (2))
In the preparation of the colorant particle dispersion (1), a colorant particle dispersion (1) was used except that a cyan pigment (manufactured by Dainichi Seika Co., Ltd., copper phthalocyanine CI Pigment Blue 15: 3) was used instead of the yellow pigment. A Cyan colorant particle dispersion liquid (2) having a center diameter of 190 nm and a solid content of 21.5% was obtained.

(Preparation of colorant particle dispersion (3))
In the preparation of the colorant particle dispersion (1), the same procedure as in the colorant particle dispersion (1) was used except that a magenta pigment (manufactured by Dainichi Ink Chemical Co., Ltd., CI PigmentRed122) was used instead of the yellow pigment. Thus, a colorant particle dispersion (3) having a center diameter of 165 nm and a solid content of 21.5% was obtained.

(Preparation of colorant particle dispersion (4))
The colorant particle dispersion (1) was prepared in the same manner as the colorant particle dispersion (1) except that a black pigment (Cabot, carbon black) was used instead of the yellow pigment, and the center diameter was 170 nm. A colorant particle dispersion (4) having a solid content of 21.5% was obtained.

(Preparation of release agent particle dispersion)
Paraffin wax (manufactured by Nippon Seiwa Co., Ltd., HNP9; melting point 70 ° C.) 50 parts by weight Anionic surfactant (Dow Chemical Dow Fax) 5 parts by weight Ion-exchanged water 200 parts by weight The above ingredients are heated to 95 ° C. to produce a homogenizer ( After sufficiently dispersing with IKA's Ultra Turrax T50), it is dispersed with a pressure discharge homogenizer (Gorin homogenizer, Gorin), and a release agent particle dispersion having a center diameter of 180 nm and a solid content of 21.5% Got.

[Example B1]
(Preparation of toner particles)
Resin fine particle dispersion (1) 288 parts by weight Colorant particle dispersion (1) 40 parts by weight (8.6 parts by weight of pigment)
40 parts by weight of release agent particle dispersion (8.6 parts by weight of release agent)
Polyaluminum chloride 0.15 parts by weight Deionized water 300 parts by weight The above components were thoroughly mixed and dispersed in a round stainless steel flask with a homogenizer (IKA, Ultra Turrax T50), and then flasked in a heating oil bath. The mixture was heated to 42 ° C. with stirring and maintained at 42 ° C. for 60 minutes, and then the pH in the system was adjusted to 6.0 with a 0.5 mol / liter sodium hydroxide aqueous solution. Heated to ° C.

During the temperature increase up to 95 ° C, the pH in the system usually drops to 5.0 or less, but here, an aqueous sodium hydroxide solution is added dropwise to keep the pH from dropping to 5.5 or less. did.
After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then solid-liquid separated by Nutsche suction filtration. And it re-dispersed in 3 liters of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This washing operation was repeated 5 times, followed by solid-liquid separation by Nutsche suction filtration, and then vacuum drying for 12 hours to obtain toner particles.

The particle diameter of the toner particles was measured by Coulter Counter, the cumulative volume-average particle diameter _{D 50} 4.45Myuemu, the volume average particle size distribution index GSDv was 1.20. The shape factor SF1 of the toner particles obtained from the shape observation by Luzex was 131 potato shapes.

  1.4 parts by weight of hydrophobic silica (manufactured by Cabot, TS720) was added to 50 parts by weight of the toner particles, and mixed with a sample mill to obtain an externally added toner.

  Then, using a ferrite carrier having an average particle diameter of 50 μm coated with 1% of polymethyl methacrylate (manufactured by Soken Chemical Co., Ltd.), the externally added toner was weighed so that the toner concentration was 8%, A developer was prepared by stirring and mixing for a minute.

(Evaluation of toner)
(1) <Fixing evaluation>
For fixing and image quality evaluation with the developer obtained by the method described above, image formation was performed 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 minimum fixing temperature is the minimum temperature of the heating roller in which the toner particles form a continuous film layer, the hot offset occurrence temperature is the minimum temperature at which the hot offset phenomenon occurs, and the image quality characteristics are visually observed for image quality unevenness. Judged.

Determination of minimum fixing temperature by cloth rubbing method After creating an unfixed image with the above-mentioned copying machine, a heat roller with a surface layer formed of Teflon (registered trademark) with a diameter of 30 mm and a pressure bonding with a surface layer formed of silicone rubber The operation of fixing the toner image by the sample toner transferred onto the transfer paper of 64 g / m 2 with a roller and a fixing roller at a linear velocity of 70 mm / second, a linear pressure of 0.8 kg / cm, and a nip width of 4.9 mm Fixing which shows sufficient rubbing resistance by repeatedly increasing the set temperature of the roller in steps of 5 ° C. within the range of 80-240 ° C. and repeating the temperature at each temperature, and applying the Kim wipe rubbing to the formed fixed image. The lowest fixing temperature was set as the lowest fixing temperature for the image. The fixing device used here does not have a silicone oil supply mechanism.

-Determination of minimum fixing temperature by measuring image glossiness (Gloss ≧ 40 MFT)
As a result of measuring the glossiness of the image sample fixed by the fixing method using a GM26D manufactured by Murakami Color Research Laboratory under the condition that the incident light angle to the image sample is 75 degrees, the glossiness is 40. The above temperature was determined as the minimum fixing temperature by image glossiness measurement.

・ Hot offset generation temperature:
The offset generation temperature is measured by creating a non-fixed image with the copying machine, transferring the toner image and performing fixing processing with the above-described fixing device, and then transferring the blank transfer paper to the fixing device under the same conditions. The operation for visually observing whether or not toner contamination occurs is repeated while the set temperature of the heat roller of the fixing device is sequentially increased, and the offset generation temperature is set with the lowest set temperature at which the toner contamination occurs. It was.
Offset generation temperature 220 ° C or higher
Offset generation temperature or 200 ° C to 220 ° C
Offset generation temperature 195 ° C or lower
It was.

-Image quality The image quality was determined as follows by measuring the fine line reproducibility of the image with the fine line fixed and the fog (visually) of the non-fixed part with a loupe.
There is no unevenness in the fine lines and there is no fogging.
There is slight unevenness in image quality ... △
Uneven image quality ... ×

As a result of fixing evaluation by the above method,
The minimum fixing temperature by rubbing resistance evaluation is 105 ° C.,
The minimum fixing temperature measured by image glossiness was as good as 105 ° C.
Further, the occurrence temperature of hot offset was as good as 220 ° C., and the image quality was also good without any unevenness or fog.

(2) <Mechanical strength evaluation>
A device capable of driving the developing machine of the Fuji Xerox full-color copying machine DocuCenterColor500 alone was created, and the developer was put into the developing machine and driven under the same conditions as in the copying machine. Therefore, the developer in the developing machine was sampled at an arbitrary time, and the particle size distribution of the toner was measured with a Coulter Counter TAII (manufactured by Beckman-Coulter). The driving time was plotted on the X axis, and the cumulative value of 3.0 μm or less in the number average distribution was plotted on the Y axis, the slope was defined as the mechanical strength index, and the mechanical strength was evaluated based on the numerical value. The larger the value, the easier the crushing occurs in the developing machine and the lower the mechanical strength.
Mechanical strength index is 0.20 or less.
Mechanical strength index is 0.21 to 0.30 ... △
Mechanical strength index is 0.30 or more.
It was.

  Therefore, the developer was introduced into the developing machine and evaluated. As a result, the mechanical strength index was as good as 0.16.

(3) <Evaluation of triboelectric charge>
1.5 g of the obtained toner and 30 g of a carrier (carrier used for adjusting developer 1 (see Example 1)) were left in a high temperature and high humidity (temperature 28 ° C., humidity 85%) environment for one day and night. Then, both were mixed and stirred for 60 minutes,
The triboelectric charge amount was measured with a blow-off tribo measuring device (Toshiba Chemical Co., Ltd .: TB-200).

  As described above, the absolute value of the obtained charge amount was 24 μC / g.

[Example B2]
In Example B1, the toner dispersion was obtained in the same manner as in Example B1, except that the resin dispersion was changed from (1) to the resin dispersion (2) and the pH during heating at 95 ° C. was maintained at 5.0. It was.
The accumulated volume average particle diameter _{D 50} of the toner particles 4.67Myuemu, the volume average particle size distribution index GSDv was 1.19. The shape factor SF1 was slightly spherical with 122.
Further, using this toner particle, an external additive toner was obtained in the same manner as in Example B1, and a developer was further prepared. As a result of performing fixing evaluation, mechanical strength index, and charge measurement in the same manner as in Example B1,
The minimum fixing temperature by rubbing resistance evaluation is 100 ° C.,
The minimum fixing temperature by image glossiness measurement was as good as 100 ° C.
Further, the occurrence temperature of hot offset was as good as 220 ° C., and the image quality was also good without any unevenness or fog.
The mechanical strength index of the toner of this example was as good as 0.14.
Further, the absolute value of the obtained charge amount was 28 μC / g.

[Example B3]
In Example B1, the resin dispersion was changed from (1) to the resin dispersion (3) and the colorant particle dispersion (1) was changed to the colorant particle dispersion (2). Toner particles were obtained in the same manner as in Example B1, except that the amount was 12 parts by weight.
The accumulated volume average particle diameter _{D 50} of the toner particles 4.15Myuemu, volume average particle size distribution index GSDv of 1.22, a shape factor SF1 of a spherical 117.
Further, using this toner particle, an external additive toner was obtained in the same manner as in Example B1, and a developer was further prepared. As a result of performing fixing evaluation, mechanical strength index, and charge measurement in the same manner as in Example B1,
The minimum fixing temperature by rubbing resistance evaluation is 110 ° C.,
The minimum fixing temperature by image glossiness measurement was as good as 110 ° C.
Further, the occurrence temperature of hot offset was as good as 220 ° C., and the image quality was also good without any unevenness or fog.
The mechanical strength index of the toner of this example was as good as 0.10.
The absolute value of the obtained charge amount was 29 μC / g.

[Example B4]
In Example B1, the resin dispersion was changed from (1) to the resin dispersion (4) and changed from the colorant particle dispersion (1) to the colorant particle dispersion (3). Similarly, toner particles were obtained.
The accumulated volume average particle diameter _{D 50} of the toner particles 4.19Myuemu, volume average particle size distribution index GSDv of 1.22, a shape factor SF1 was 134 potato shape.
Further, using this toner particle, an external additive toner was obtained in the same manner as in Example B1, and a developer was further prepared. As a result of performing fixing evaluation, mechanical strength index, and charge measurement in the same manner as in Example B1,
The minimum fixing temperature by rubbing resistance evaluation is 110 ° C.,
The minimum fixing temperature by image glossiness measurement was as good as 110 ° C.
Further, the occurrence temperature of hot offset was as good as 220 ° C., and the image quality was also good without any unevenness or fog.
The mechanical strength index of the toner of this example was as good as 0.07.
The absolute value of the obtained charge amount was 30 μC / g.

[Example B5]
In Example B1, the resin dispersion was changed from (1) to the resin dispersion (2), the colorant particle dispersion (1) was changed to the colorant particle dispersion (4), and the pH during heating at 95 ° C. A toner particle was obtained in the same manner as in Example B1, except that the value was maintained at 5.0.
The accumulated volume average particle diameter _{D 50} of the toner particles 4.51Myuemu, the volume average particle size distribution index GSDv was 1.19. The shape factor SF1 was slightly spherical with 122.
Further, using this toner particle, an external additive toner was obtained in the same manner as in Example B1, and a developer was further prepared. As a result of performing fixing evaluation, mechanical strength index, and charge measurement in the same manner as in Example B1,
The minimum fixing temperature by rubbing resistance evaluation is 110 ° C.,
The minimum fixing temperature by image glossiness measurement was as good as 110 ° C.
Further, the occurrence temperature of hot offset was as good as 220 ° C., and the image quality was also good without any unevenness or fog.
The mechanical strength index of the toner of this example was as good as 0.06.
The absolute value of the obtained charge amount was 29 μC / g.

[Comparative Example B1]
(Preparation of toner particles)
In Example B1, the toner dispersion was obtained in the same manner as in Example B1, except that the resin dispersion was changed from (1) to the resin dispersion (6) and the pH during heating at 95 ° C. was maintained at 5.0. It was.
The accumulated volume average particle diameter _{D 50} of the toner particles 4.22Myuemu, the volume average particle size distribution index GSDv was 1.19. The shape factor SF1 was 135, which was a potato shape.
Further, using this toner particle, an external additive toner was obtained in the same manner as in Example B1, and a developer was further prepared. As a result of performing fixing evaluation, mechanical strength index, and charge measurement in the same manner as in Example B1,
The minimum fixing temperature by rubbing resistance evaluation is 125 ° C.
It was confirmed that the minimum fixing temperature by image gloss measurement was 130 ° C.
In addition, the temperature at which hot offset occurred was lowered to 180 ° C., and the image quality was good with no unevenness or fog.
The mechanical strength index of the toner of this comparative example was as good as 0.09.
Further, the absolute value of the obtained charge amount was 34 μC / g.

[Comparative Example B2]
In Example B1, the toner dispersion was obtained in the same manner as in Example B1, except that the resin dispersion was changed from (1) to the resin dispersion (7), and the pH during heating at 95 ° C. was maintained at 5.0. It was.
The accumulated volume average particle diameter _{D 50} of the toner particles in 4.61Myuemu, the volume average particle size distribution index GSDv becomes somewhat broad and 1.25. The shape factor SF1 was 135, which was a potato shape.
Further, using this toner particle, an external additive toner was obtained in the same manner as in Example B1, and a developer was further prepared. As a result of performing fixing evaluation, mechanical strength index, and charge measurement in the same manner as in Example B1,
The minimum fixing temperature by rubbing resistance evaluation is 100 ° C.,
It was confirmed that the minimum fixing temperature by image glossiness measurement was 100 ° C.
Moreover, although the hot offset generation temperature was as good as 220 ° C., the image quality was found to be uneven and fogging.
The mechanical strength index of the toner of this comparative example was 0.83.
The absolute value of the charge amount of the obtained toner was 14 μC / g.

[ Reference Example B6]
In Example B1, the toner dispersion was obtained in the same manner as in Example B1, except that the resin dispersion was changed from (1) to the resin dispersion (8) and the pH during heating at 95 ° C. was maintained at 5.0. It was.
The accumulated volume average particle diameter _{D 50} of the toner particles in 4.18Myuemu, the volume average particle size distribution index GSDv becomes somewhat broad and 1.25. The shape factor SF1 was 134, which was a potato shape.
Further, using this toner particle, an external additive toner was obtained in the same manner as in Example B1, and a developer was further prepared. As a result of performing fixing evaluation, mechanical strength index, and charge measurement in the same manner as in Example B1,
The minimum fixing temperature according to the rubbing resistance evaluation is 120 ° C.
It was confirmed that the minimum fixing temperature by image glossiness measurement was 120 ° C.
In addition, the temperature at which hot offset occurred was as low as 200 ° C., and the image quality was slightly uneven.
The mechanical strength index of the toner of this example was 0.20.
The absolute value of the charge amount of the obtained toner was 29 μC / g.

  The results of Examples B1 to B6 and Comparative Examples B1 to B2 are shown in Table 3 above.

In addition, the hydrophobic parameter Log (P) of each monomer is shown together with the name of the abbreviation in the table.
1,9-nonanediol (ND): Log (P) = 1.86
1,6-hexadiol (HD): Log (P) = 1.56
Ethylene glycol (EG): Log (P) = − 0.79
Propylene glycol (PG): Log (P) = − 0.47
1,10 decamethylene dicarboxylic acid (DDA): Log (P) = 2.7
Sebacic acid (SA): Log (P) = 1.87
Adipic acid: Log (P) = 0.2
Glutaric acid: Log (P) = − 0.22
Styrene (St): Log (P) = 2.67
n-butyl acrylate (nBA): Log (P) = 1.88
Acrylic acid (AA): Log (P) = 0.38
Methacrylic acid: Log (P) = 0.73
Maleic acid: Log (P) = − 0.36
Dodecanethiol (DDT) Log (P) = 5.14

From the results of Table 3, the particle size of the resin dispersion composed only of the conventional polyester (polycondensable resin) monomer as shown in Comparative Example B1 tends to be coarse, and the particle size distribution is broad. It can be seen that it is difficult to produce a high-quality toner using the resin dispersion.
It can also be seen that the low-temperature fixability of the crystalline polyester (polycondensable resin) was not fully exhibited.

In each of Examples B1 to B5, since the hydrophobic and hydrophilic radical polymerizable monomers are controlled, the reference example B6 in which the hydrophobic and hydrophilic radical polymerizable monomers are too little or too much, It can be seen that a polyester particle dispersion (resin dispersion) having a sharp particle size distribution, an appropriate particle size, and long-term storage stability is obtained as compared with Comparative Example B1.

  By using such a resin dispersion resin, it is possible to obtain an image having excellent mechanical strength, low fixing temperature, good offset resistance, and high gloss even in low-temperature fixing. It can also be seen that the toner is an electrostatic toner capable of obtaining a sufficient charge amount.

Claims (16)

  A polyvalent acid component having a hydrophobicity parameter (Log (P)) of −0.36 to 2.7 and a polyhydric alcohol having a hydrophobicity parameter (Log (P)) of 0.9 to 4.19 The components and only the hydrophobic radical polymerizable monomer as a hydrophobic substance having a hydrophobic parameter (Log (P)) of 1.6 or more and 7.18 or less among the radical polymerizable monomers are emulsified in an aqueous medium. Alternatively, a method for producing a polyester comprising the step of polycondensing the polyhydric acid component and the polyhydric alcohol component in the presence of the hydrophobic substance after being dispersed. A polyvalent acid component having a hydrophobicity parameter (Log (P)) of 1.87 or more and 2.7 or less, and a polyhydric alcohol having a hydrophobicity parameter (Log (P)) of −0.47 or more and 4.19 or less The component, a hydrophobic radical polymerizable monomer as a hydrophobic substance having a hydrophobic parameter (Log (P)) of 1.6 or more and 7.18 or less, and a hydrophilic radical polymerizable monomer are emulsified in an aqueous medium. Or after the dispersion, the step of polycondensing the polyhydric acid component and the polyhydric alcohol component in the presence of the hydrophobic substance,
The amount of the hydrophobic radical polymerizable monomer emulsified or dispersed in the aqueous medium is 3 to 20 parts by weight with respect to 100 parts by weight of the total amount of the polyvalent acid component, the polyhydric alcohol and the radical polymerizable monomer. ,
The amount of the hydrophilic radical polymerizable monomer emulsified or dispersed in the aqueous medium is 1.0 to 10 parts by weight based on 100 parts by weight of the total amount of the polyvalent acid component, the polyhydric alcohol and the radical polymerizable monomer. A process for producing polyester, characterized in that   The method for producing a polyester according to claim 1, wherein the polyester is a polyester for electrostatic image developing toner.   The method for producing a polyester according to claim 1, further comprising a step of polymerizing the hydrophobic radical polymerizable monomer.   The method for producing a polyester according to claim 1, wherein the hydrophobic radical polymerizable monomer is a hydrophobic vinyl monomer. Absolute value (| Log (P) _COOH- Log (P) of the difference between the hydrophobicity parameter (Log (P) _COOH ) of the polyhydric acid component and the hydrophobicity parameter (Log (P) _OH ) of the polyhydric alcohol component) _OH |) is 0 or more and 5.0 or less, The manufacturing method of the polyester of Claim 1 or 2 characterized by the above-mentioned.   3. The method for producing a polyester according to claim 1, wherein a part or all of the polyhydric acid component and the polyhydric alcohol component is a dimer or higher oligomer.   The method for producing a polyester according to claim 2, wherein the hydrophilic radical polymerizable monomer is an acidic vinyl monomer having an acidic group.   The method for producing a polyester according to claim 2, further comprising a step of polymerizing the hydrophilic radical polymerizable monomer.   The method for producing a polyester according to claim 1 or 2, wherein at the time of the polycondensation, at least one catalyst selected from a Bronsted acid type catalyst and an enzyme catalyst is used.   The method for producing a polyester according to claim 10, wherein the Bronsted acid catalyst is a rare earth element catalyst having a rare earth element selected from Y, Sc, Yb, and Sm as a constituent component.   The method for producing a polyester according to claim 10, wherein the Bronsted acid catalyst is dodecylbenzenesulfonic acid.   The method for producing a polyester according to claim 10, wherein the catalyst has a surface activity.   The method for producing a polyester according to claim 1 or 2, wherein the polyhydric acid component and the polyhydric alcohol component are components for obtaining a crystalline polyester. A method for producing an electrostatic charge developing toner comprising: a step of aggregating the resin particles in a dispersion in which the resin particles are dispersed to obtain aggregated particles; and a step of heating and aggregating the aggregated particles. And
The method for producing an electrostatic charge developing toner, wherein the resin particles are obtained by the method for producing a polyester according to claim 1.   An electrostatic charge developing toner obtained by the method for producing an electrostatic charge developing toner according to claim 15.