JP4506592B2 - Resin particle dispersion for electrostatic image developing toner, electrostatic image developing toner, production method thereof, electrostatic image developer, and image forming method - Google Patents

Description

  The present invention is excellent in various properties such as color developability and OHP permeability, and is preferably used for electrostatic image development toner and toner raw material, a method for producing the same, and used for image formation by electrophotography or electrostatic recording method, The present invention relates to a developer and an image forming method.

Currently, with the rapid spread of digitization technology, there is an increasing demand for higher image quality in the output of printing, copying, etc. for users in the general home, office, and publishing field. In the toner used in the above, attempts have been made to improve the resolution by reducing the particle size, and at present, the particle size is reduced to 5 μm. In this case, the kneading and pulverization method that has been used for the production of toner in the past to reduce the particle size of toner is difficult to cope with from the viewpoint of production energy and cost, and is currently suspension polymerization in an aqueous medium or dissolution suspension. A technique for producing a toner by producing a resin dispersion by a so-called chemical production method such as a turbidity method or an emulsion polymerization agglomeration method, and granulating it is being transferred.
The resin dispersion used in such a chemical production method for electrostatic charge developing toner needs to stably disperse and distribute resin particles in an aqueous medium. This is because the sedimentation and floating of particles in the resin dispersion and the change in particle shape over time affect the subsequent toner manufacturing process, resulting in a negative effect on the quality of the toner and the resulting image quality. Because it will give.
In general, in an electrostatic charge image forming toner, it is a widely practiced technique to control the particle size of the toner particles and the particle size distribution. In particular, a toner produced by a kneading and pulverizing method or a suspension polymerization method in which the particle size distribution is likely to be widened is generally subjected to a step of obtaining toner particles having a desired particle size by classification. As a result, a uniform and high-quality image can be obtained from toner having a uniform particle size.

  As described above, as a polymerization method of a resin in an aqueous medium that is currently widely used, there are a suspension polymerization method, a dissolution suspension method, and an emulsion polymerization aggregation method. Among the emulsion polymerizations, in particular, the polymerization of the monomer in the presence of a polymerization initiator of a monomer emulsion by using a surfactant amount less than the critical micelle concentration (CMC) and a co-surfactant is not This is known as so-called “miniemulsion polymerization” described in Patent Document 1 and the like. This is a conventional emulsion polymerization in which an aqueous emulsion of monomer particles having a particle size of several μm is polymerized using a water-soluble polymerization initiator in the presence of a surfactant amount exceeding the critical micelle concentration (CMC). However, in the case of miniemulsion polymerization, polymerization is initiated in the surfactant micelles, and polymer particles grow and form upon receiving supply of monomer from the monomer particles. Since the monomer is polymerized in the body fine particles, there is an advantage that uniform polymer fine particles can be formed in terms of shape and characteristics in that no movement (diffusion or the like) of the substance is accompanied. That is, in the miniemulsion polymerization method, the diameter of the polymer particles can be adjusted by adjusting the size of the droplets of the monomer dispersion.

  In this miniemulsion polymerization, it is known to reduce Ostwald ripening when a hydrophobic additive is incorporated into the monomer to be polymerized. Ostwald ripening (also referred to as Ostwald growth) is understood as a process in which smaller particles gradually dissolve in a polydisperse system and grow into larger particles. This hydrophobic additive is also referred to as a co-surfactant, a stabilizing aid, or a hydrophobe (Non-patent Documents 2 and 3, etc.) and is one of the very important components for carrying out miniemulsion polymerization. Many substances have been studied. Furthermore, several inventions have already been made with respect to the toner using the miniemulsion polymerization and the production method thereof.

According to Patent Document 1, a method for producing a toner for developing an electrostatic image in which colorant-containing polymer fine particles obtained by miniemulsion polymerization of a monomer and a colorant are aggregated has been invented. As the co-surfactant used in the method, known ones can be used, and the combination of the monomer and co-surfactant used is not suitable.
In Patent Document 2, a toner in which resin fine particles produced by mini-emulsion polymerization are included in a layer other than the outermost layer and the resin fine particles by multi-stage polymerization are salted out / fused is invented. Does not mention the use of co-surfactants.
Further, in Patent Document 3, the co-surfactant called a stabilizer is selected from n-alkanes, halogenated n-alkanes, aliphatic alcohols and esters of aliphatic alcohols. Patent Document 4 defines the solubility of an auxiliary stabilizer (cosurfactant) used in free radical emulsion polymerization in water. However, no polycondensation in water has been studied in any of the prior inventions.

Non-Patent Document 4 describes the result of polycondensation of polyester in water from dodecanedioic acid and dodecanediol. However, in this paper and other research papers, the physical properties of alkyl alcohols as co-surfactants, the mini-emulsion polycondensation process, the properties of the dispersion produced by the same process, and the same dispersion are also used. There are no studies on the physical properties of toners. As a matter of course, there is no example in which the combination of the physical properties of the monomer used for polycondensation and the co-surfactant has been elucidated from the mechanism.
As described above, regarding co-surfactants that are indispensable in miniemulsion polymerization, many substances have been studied and reported to be usable as co-surfactants, but the weight of monomers having specific physical properties has been reported. There have been no studies suggesting a suitable co-surfactant for the condensation step. Further, there has been no discussion regarding the selection of a suitable co-surfactant when producing toner by miniemulsion polymerization.

JP 2001-290308 A JP 2002-49180 A JP 2004-514181 A Japanese Patent Laid-Open No. 10-60013 P. L. Tang, E. D. Sudol, C. A. Silebi, and M. S. El-Aasser, J. Appl. Polym. Sci., Vol. 43, p. 1059 (1991) Chorng-Shyan Chern and Chi-Han Lin, J. Appl.Polym.Sci., Vol.92, p.1961 (2004) Katharina Landfester, Nina Bechthold, Franca Tiarks, and Markus Antonietti, Macromol.Symp., Vol.150, p.171 (2000) Matthineu Barrere and Katharina Landfester, Polymer., Vol.44, p.2833 (2003)

  Accordingly, an object of the present invention is to solve the conventional problems and achieve the following object. That is, an object of the present invention is to provide a resin particle dispersion for an electrostatic charge image developing toner, in which resin particles are stably emulsified and dispersed in an aqueous medium, and the particle size distribution is narrow. , A method for producing an electrostatic image developing toner capable of producing an electrostatic image developing toner having both constant temperature fixing and uniform particle size and narrow particle size distribution, and an electrostatic image developing toner obtained thereby, and an electrostatic image using the toner An object is to provide a charge image developer and an image forming method.

In view of the above situation, the present inventors have conducted intensive studies, and as a result of the following <1> and <6> to <10>, a resin particle dispersion for an electrostatic charge image developing toner is produced with low energy and low cost. In addition to being manufactured with a low environmental load, the stability of the resin particle dispersion and the homogeneity of the dispersed resin particles are realized. Further, for the image formed with the toner and the toner, developer, etc. It has been found that the fixing property and image forming property can be improved. It is shown below with <2>-<5> which are preferable embodiments.
<1> A step of obtaining an oil phase containing at least one polycondensable monomer having an SP value of greater than 10.5, a step of emulsifying and dispersing the oil phase in an aqueous medium, and a resin obtained by polycondensing the emulsion dispersion A method for producing a resin particle dispersion for an electrostatic charge image developing toner comprising a step of obtaining a particle dispersion, comprising an oil phase and / or an aqueous medium containing an alkyl alcohol having 8 to 30 carbon atoms as a co-surfactant. A method for producing a resin particle dispersion for an electrostatic charge image developing toner,
<2> The method for producing a resin dispersion for an electrostatic charge image developing toner according to <1>, wherein the oil phase contains at least one polycondensable monomer having an HLB of 5.5 or more,
<3> The above <1> or <1> wherein the median diameter of the resin particles in the resin particle dispersion is 0.05 to 2 μm, and the arithmetic standard deviation of the resin particles in the resin particle dispersion is 0.50 or less. 2>, a method for producing a dispersion for electrostatic charge developing toner according to 2),
<4> The content of the cosurfactant in the resin dispersion is 0.1 to 40% by weight with respect to the polymerizable monomer used. A method for producing a resin particle dispersion for an electrostatic image developing toner according to claim 1,
<5> The electrostatic charge image development according to any one of <1> to <4>, wherein the resin in the resin particle dispersion is a crystalline resin, and the crystal melting point thereof is 50 ° C. or higher and lower than 120 ° C. Production method of resin particle dispersion for toner,
<6> Resin particle dispersion for electrostatic image developing toner produced by the production method according to any one of <1> to <5> above,
<7> A method for producing an electrostatic charge image developing toner comprising a step of aggregating the resin particles in a dispersion containing at least a resin particle dispersion to obtain aggregated particles, and a step of heating and aggregating the aggregated particles A method for producing an electrostatic charge image developing toner, wherein the resin particle dispersion is the resin particle dispersion for an electrostatic charge image developing toner according to <6>,
<8> An electrostatic charge image developing toner produced by the production method according to <7> above,
<9> An electrostatic charge image developer comprising the electrostatic charge image developing toner according to <8> and a carrier,
<10> A latent image forming step for forming an electrostatic latent image on the surface of the latent image holding member, and a toner image is formed by developing the electrostatic latent image formed on the surface of the latent image holding member with a developer containing toner. An image development process, a transfer process for transferring the toner image formed on the surface of the latent image carrier to the surface of the transfer target, and a fixing process for thermally fixing the toner image transferred to the surface of the transfer target. A method for forming an image, wherein the electrostatic image developing toner according to <8> is used as the toner, or the electrostatic image developer according to <9> is used as the developer. .

ADVANTAGE OF THE INVENTION According to this invention, the resin particle dispersion liquid which can be hold | maintained stably and has the particle size distribution with which the dispersed resin particle is narrow can be provided.
The present invention also provides an electrostatic charge image developing toner having a stable constant temperature fixability and high image quality, a developer using the same, and an image forming method using the resin dispersion. Can do.

  The present invention uses a co-surfactant having a limited structure in a resin particle dispersion prepared by emulsion polymerization of an oil phase containing a monomer having specific physical properties in an aqueous medium. In this case, the stability of the resin particle dispersion is improved and the dispersed particles are made uniform. Further, the dispersion is used for the production of an electrostatic image developing toner, so that constant temperature fixing, uniform particle size, and narrow particle size distribution are achieved. It has been found that it is possible to produce a toner that satisfies both of the above. Details of the present invention will be described below.

(Method for producing resin particle dispersion for electrostatic image developing toner)
The method for producing a resin particle dispersion (hereinafter also simply referred to as a resin particle dispersion) for an electrostatic charge image developing toner of the present invention comprises an oil containing at least one polycondensable monomer having an SP value of more than 10.5. A method for producing a resin particle dispersion for an electrostatic charge image developing toner comprising a step of obtaining a phase, a step of emulsifying and dispersing an oil phase in an aqueous medium, and a step of polycondensing the emulsion dispersion to obtain a resin particle dispersion. The oil phase and / or the aqueous medium contains an alkyl alcohol having 8 to 30 carbon atoms as a cosurfactant.

  The method for producing a resin particle dispersion for an electrostatic charge image developing toner according to the present invention includes a step of polycondensing an emulsion dispersion containing a polycondensable monomer in an aqueous medium. In the case of the present invention, the monomer is dispersed in advance in an aqueous medium in which the co-surfactant and, if necessary, the surfactant are dissolved using mechanical shearing force, ultrasonic waves, etc., and then heated to perform polycondensation. Do. In addition, the monomer is dissolved in another medium, and if necessary, an oil phase in which a co-surfactant, a surfactant and the like are dissolved is prepared, dispersed in the aqueous medium, heated, and heated. Perform condensation. As a polymerization method in this case, a suspension polymerization method, a mini-emulsion method, a microemulsion method, an emulsion polymerization method including a multistage swelling method and a seed polymerization, or a resin such as urethane was used as a method for polymerizing particles in an aqueous medium. It is possible to use a heterogeneous polymerization form in a normal aqueous medium such as an extension reaction method. Of these polymerization methods, the microemulsion method and the miniemulsion polymerization method are preferably used, and the miniemulsion polymerization method is most suitable because it is easy to obtain a uniform particle size and uniform particle size distribution. .

  The polycondensable monomer that can be used in the present invention contains at least one monomer having an SP value of more than 10.5. The polycondensable monomer used is not particularly limited as long as at least one of the polycondensable monomers has the above-mentioned properties. Aliphatic, alicyclic, aromatic polyvalent carboxylic acids, their alkyl esters and polyvalent Examples include alcohols, ester compounds thereof, polyvalent amines, and hydroxycarboxylic acids.

The SP value is a numerical value indicating the magnitude of the cohesive energy of a substance called a solubility parameter, and is a method proposed by Fedors [Polym. Eng. Sci. , Vol14, p147 (1974)], where the evaporation energy and molar volume of the atom or atomic group are Δei and Δvi, respectively, the solubility parameter δ is calculated by the following equation.
δ = (ΣΔei / ΣΔvi) ^1/2

  The polycondensable monomer having an SP value of greater than 10.5 used in the present invention is a monomer having an SP value, and is not limited as long as it is used in the various polymerization methods described above. As a monomer that preferably exhibits the effect of the combination with the co-surfactant in the present invention, the SP value of at least two types of polycondensable monomers is greater than 10.5, or at least one type of polycondensation monomer. This is the case when the SP value of the condensable monomer is greater than 11.0. As the most effectively expressed monomer, the SP value of at least one polycondensable monomer is larger than 10.5, and the SP value of at least one polycondensable monomer is 11.0. When the value is larger, or when the SP value of at least one polycondensable monomer is larger than 11.5. Further, the SP value is preferably 18.0 or less, and preferably 16.0 or less.

  The polycondensable monomer that can be used in the present invention is not particularly limited, and aliphatic, alicyclic, and aromatic polycarboxylic acids, their alkyl esters and polyhydric alcohols, their ester compounds, A polyvalent amine, hydroxycarboxylic acid, or a mixture thereof can be used, and they can be polymerized directly by esterification reaction, transesterification reaction, amidation reaction, or the like. Moreover, it does not specifically limit regarding the crystallinity degree of the polycondensable resin produced.

The polyol as a polycondensable monomer that can be used in the present invention is a compound containing two or more hydroxyl groups in one molecule. Among these, the diol is a compound containing two hydroxyl groups in one molecule. Examples of the diol having an SP value greater than 10.5 include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and butane. Diol, neopentyl glycol, pentanediol, cyclopentanediol, hexanediol, cyclohexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecanediol, tetradecanediol, bisphenol A, hydrogenated bisphenol A and the like can also be mentioned. .
Examples of polyols other than diols having an SP value greater than 10.5 include glycerin, pentaerythritol, hexahydroxymethyl melamine, hexahydroxyethyl melamine, tetrahydroxymethyl benzoguanamine, tetrahydroxyethyl benzoguanamine, and the like. It is not limited to.

  The polyvalent carboxylic acid is a compound containing two or more carboxyl groups in one molecule. Of these, dicarboxylic acid is a compound containing two carboxyl groups in one molecule, and examples of dicarboxylic acids having an SP value greater than 10.5 include oxalic acid, succinic acid, maleic acid, malonic acid, and glutaric acid. , Adipic acid, β-methyladipic acid, pimelic acid, suberic acid, tartaric acid, mucous acid, phthalic acid, isophthalic acid, terephthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, fumaric acid, citraconic acid, itaconic acid Diglycolic acid, malic acid, citric acid, sebacic acid and the like can be mentioned, but are not limited thereto. Examples of the polyvalent carboxylic acid other than divalent include trimellitic acid and pyromellitic acid.

  Other polycondensable monomers having an SP value greater than 10.5 include hydroxyheptanoic acid, hydroxyoctanoic acid, hydroxydecanoic acid, hydroxyundecanoic acid, m-phenylene diglycolic acid, p-phenylene diglycolic acid, o -Phenylene diglycolic acid, diphenyl-p, p'-dicarboxylic acid, and the like.

  Moreover, there is no restriction | limiting in the monomer which performs polycondensation with the polycondensation monomer which has said SP value, It can also perform polycondensation with monomers with SP value larger than 10.5, You may perform polycondensation with the monomer whose SP value is 10.5 or less.

Examples of the latter monomer having an SP value of 10.5 or less include hexadecanediol, octadecanediol and the like as the polyol, but the SP value is 10. If it is 5 or less, it will not be limited.
Polycarboxylic acids include azelaic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, dimethyl terephthalate, diethyl fumarate, and hydroxydodecanoic acid as others Hydroxyhexadecanoic acid and hydroxyoctadecanoic acid can be mentioned, but the carboxylic acid valence and monomer species are not limited thereto.
The polyvalent amine used to obtain the polyamide is ethylenediamine, diethylenediamine, triethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-butanediamine, 1,4-butene. Examples include diamine, 2,2-dimethyl-1,3-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,4-cyclohexanediamine, and 1,4-cyclohexanedimethylamine. However, it is not limited to these.

  According to the method for producing a resin particle dispersion for an electrostatic charge image developing toner of the present invention, among the above polyols, dodecanediol, decanediol, nonanediol, octanediol, hexanediol, butanediol, bisphenol A, hydrogenated bisphenol Among the diols such as A and the above carboxylic acids, the effects can be exerted greatly in the production of polyesters containing azelaic acid, sebacic acid, trimellitic acid, pyromellitic acid and fumaric acid.

As a combination of monomers exhibiting particularly effects, a combination of butanediol and an acid selected from adipic acid, sebacic acid and dodecanedicarboxylic acid, an acid selected from hexanediol and adipic acid, sebacic acid and dodecanedicarboxylic acid A combination of octanediol and an acid selected from adipic acid and sebacic acid, and a combination selected from nonanediol and adipic acid, sebacic acid and dodecanedicarboxylic acid. Combinations obtained by adding trimellitic acid, pyromellitic acid and fumaric acid to these are also suitable.
Among these, in consideration of suitability for toner, a combination of hexanediol and an acid selected from adipic acid, sebacic acid and dodecanedicarboxylic acid, a combination of octanediol and an acid selected from adipic acid and sebacic acid, nonanediol And adipic acid, sebacic acid and dodecanedicarboxylic acid are preferably used.

Moreover, when the monomer whose HLB is 5.5 or more is included in the polycondensable monomer of the present invention, the present invention can sufficiently exert its effect. Here, HLB is an index defined as hydrophilic lipophilic equilibrium (WC Griffin; J. Society Cosmetics Chewists. 1, 311 (1949)), and is experimentally determined, but various formulas are used. Can also be calculated.
For example, in the present invention,
HLB = 20Mw / M
(In the formula, M represents the molecular weight, and Mw represents the molecular weight of the hydrophilic portion.)
Calculate using.
As a polycondensable monomer that can be used in the present invention, HLB is preferably 5.5 or more, more preferably 5.5 to 18.0, and even more preferably 5.5 to 17.0. A monomer having an HLB value of 5.5 or more has high hydrophilicity and it has been difficult to stably produce and retain oil droplets in an aqueous phase with a conventional co-surfactant. However, when polycondensation is carried out in an aqueous medium together with a specific co-surfactant according to the present invention, oil droplets can be stably produced and retained. When a toner resin dispersion is prepared using a monomer having an HLB value of 5.5 or more, the toner produced from the dispersion can impart appropriate flexibility and charge.

Examples of the polycondensable monomer having an HLB of 5.5 or more include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanediol, neopentyl glycol, pentanediol, and cyclopentanediol. , Hexanediol, cyclohexanediol and the like. Examples of polyols other than divalent include glycerin, pentaerythritol, hexahydroxymethyl melamine, hexahydroxyethyl melamine, and tetrahydroxymethyl benzoguanamine.
Dicarboxylic acids include oxalic acid, succinic acid, maleic acid, malonic acid, glutaric acid, adipic acid, β-methyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecane Dicarboxylic acid, dodecanedicarboxylic acid, tartaric acid, mucous acid, phthalic acid, isophthalic acid, terephthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, fumaric acid, citraconic acid, itaconic acid, diglycolic acid, malic acid, citric acid Examples thereof include acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, dimethyl terephthalate, and diethyl fumarate.
Examples of the polyvalent carboxylic acid other than divalent include trimellitic acid and pyromellitic acid.

  Other polycondensable monomers having an HLB of 5.5 or more include hydroxyheptanoic acid, hydroxyoctanoic acid, hydroxydecanoic acid, hydroxyundecanoic acid, hydroxydodecanoic acid, m-phenylene diglycolic acid, p-phenylene diglycol. Examples include glycolic acid, o-phenylene diglycolic acid, and diphenyl-p, p′-dicarboxylic acid.

  The polycondensable monomer having the above HLB value and the monomer for polycondensation are not limited, and polycondensation between monomers having an HLB value of 5.5 or more can be performed. Polycondensation may be performed with a monomer having an A of 5.5 or less.

  According to the method for producing a resin particle dispersion for an electrostatic charge image developing toner of the present invention, among the combinations selected from the above polycondensable monomers, polyhydric alcohol includes butanediol, hexanediol, and cyclohexanediol. The combination of any one or more and further containing any one or more of adipic acid, sebacic acid, dodecanedioic acid, trimellitic acid, pyromellitic acid, and fumaric acid in the polyvalent carboxylic acid demonstrates the performance as a toner. In addition, the effects of the present invention can be fully exhibited.

In the present invention, the dispersion medium of the resin particle dispersion for electrostatic image developing toner is an aqueous medium.
Examples of the aqueous medium that can be used in the present invention include water such as distilled water and ion exchange water, and alcohols such as ethanol and methanol. Among these, ethanol and water are preferable, and water such as distilled water and ion-exchanged water is particularly preferable. These may be used individually by 1 type and may use 2 or more types together.
The aqueous medium may contain a water-miscible organic solvent. Examples of the water-miscible organic solvent include acetone and acetic acid.

Moreover, the method for producing a resin particle dispersion for an electrostatic charge image developing toner of the present invention contains an alkyl alcohol having 8 to 30 carbon atoms as a co-surfactant during emulsification dispersion.
Co-surfactants are added in emulsion polymerization to reduce Ostwald ripening.
In order for the co-surfactant to be incorporated in droplets dispersed in an aqueous medium and to stabilize the droplets, the co-surfactant is generally required to be hydrophobic. However, when a polycondensable monomer having a relatively large aggregation property as shown in the present invention is polycondensed in an aqueous medium, it not only has a hydrophobic property, but the co-surfactant has a hydrophilic functional group. It is necessary to have a group. This is because the co-surfactant has a hydrophilic functional group in the main chain having strong hydrophobicity, thereby suppressing Ostwald ripening due to the hydrophobicity of the compound, and aggregation of particles due to the hydrophilic group oriented on the particle surface. This is considered to be possible to suppress this. The hydrophilic functional group is not particularly limited, and may have a general functional group.

As the cosurfactant in the present invention, alkyl alcohols having 8 to 30 carbon atoms are suitable. When the carbon number is 7 or less, the hydrophobicity is not sufficient. On the other hand, when the number of carbon atoms is 30 or more, the hydrophobicity becomes too strong, and the hydrophilicity / hydrophobicity balance as a compound contributing to particle stabilization is lost. Further, due to an increase in viscosity, an increase in melting point, etc., the dispersion state deteriorates, the internal state of the electrostatic charge image developing toner particles produced using the dispersion of the present invention becomes uneven, the low temperature fixability deteriorates, the melting point, It may affect the glass transition temperature and induce an offset phenomenon or a deterioration in toner fluidity.
Particularly in polycondensation in an aqueous medium, since the polycondensable monomer and the catalyst interact on the surface of the oil droplet produced in the aqueous phase, the hydrophilicity of the co-surfactant between the polycondensable monomer and the particle surface is increased. If the balance of the sex groups is lacking, in addition to destabilization of the particles, there may be adverse effects on reactivity such as insufficient polycondensation.

  Examples of the alkyl alcohol having 8 to 30 carbon atoms that can be used in the present invention include octyl alcohol, nonyl alcohol, decanol, undecanol, lauryl alcohol, tridecanol, myristyl alcohol, pentadecanol, cetyl alcohol, heptadecanol, stearyl. Examples include alcohol, oleyl alcohol, behenyl alcohol (docosanol), tricosanol, tetracosanol, hexacosanol, octacosanol, triacontanol, cyclic compounds thereof, and branched compounds having the main chain. Moreover, you may have functional groups other than a hydroxyl group. Among the co-surfactants, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, and docosanol are particularly preferably used, and cetyl alcohol and stearyl alcohol are particularly preferable.

  The co-surfactant can be used in combination with other types of co-surfactants already known. Examples of the co-surfactant include carbon numbers such as alkanes having 8 to 30 carbon atoms such as dodecane, hexadecane, and octadecane, lauryl acrylate, cetyl acrylate, stearyl acrylate, lauryl methacrylate, cetyl methacrylate, and stearyl methacrylate. 8-30 alkyl acrylates, lauryl mercaptan, cetyl mercaptan, stearyl mercaptan, etc., alkyl thiols having 8-30 carbon atoms, and other polymers or polyadducts such as polystyrene and polyester, carboxylic acids, ketones, amines, etc. Is mentioned.

  Further, the content of the co-surfactant is preferably 0.1 to 40% by weight, more preferably 0.1 to 30% by weight, more preferably 0.1 to 30% by weight based on the polymerizable monomer included in the present invention. More preferred is 20% by weight. When the content of the co-surfactant is 0.1% by weight or more, the effect of blending the co-surfactant into the dispersion can be sufficiently exerted, the stability in the dispersion can be maintained, and the dispersion droplet size has elapsed over time Therefore, the resin particle size is not increased, and the particle size distribution is not widened. Further, a resin having a desired molecular weight is preferable because the polymerization proceeds sufficiently and the resin molecular weight distribution does not become wide. Moreover, it is preferable for the content to be 40% by weight or less because it is easy to control the viscosity in the dispersion and does not inhibit polycondensation or other polymerization of the target monomer. Furthermore, the toner produced using the particle dispersion is preferable because of its good fixability and chargeability.

Examples of the polycondensation catalyst in the present invention include a surfactant type catalyst, a metal catalyst, and a hydrolase type catalyst.
Examples of the surfactant-type catalyst include strong acids having a surfactant effect. For example, alkylbenzene sulfonic acid, alkyl sulfonic acid, alkyl disulfonic acid, alkyl phenol sulfonic acid, alkyl naphthalene sulfonic acid, alkyl tetralin sulfonic acid, alkyl allyl sulfonic acid , Petroleum sulfonic acid, alkyl benzimidazole sulfonic acid, higher alcohol ether sulfonic acid, alkyl diphenyl sulfonic acid, long chain alkyl sulfate, higher alcohol sulfate, higher alcohol ether sulfate, higher fatty acid amide alkylol sulfate, higher fatty acid amide Alkylated sulfates, sulfated fats, sulfosuccinates, various fatty acids, sulfonated higher fatty acids, higher alkyl phosphates, resin acids, resin acid alcohols Acid, and the like and salt compounds of all of these, may be used in combination of two or more as necessary. Among these, a sulfonic acid having an alkyl group or an aralkyl group, a sulfate ester having an alkyl group or an aralkyl group, or a salt compound thereof is preferable, and the alkyl group or the aralkyl group has 7 to 20 carbon atoms. More preferably. Specific examples include dodecylbenzenesulfonic acid, isopropylbenzenesulfonic acid, camphor sulfonic acid, paratoluenesulfonic acid, monobutylphenylphenol sulfate, dibutylphenylphenol sulfate, dodecyl sulfate, naphthenyl alcohol sulfate, and naphthenic acid. It is done.
A strong acid having a surface-active effect has a chemical structure composed of a hydrophobic group and a hydrophilic group, has a strong acid structure in which at least a part of the hydrophilic group is composed of protons, and has both an emulsifying function and a catalytic function. It is a catalyst.

Examples of the metal catalyst include, but are not limited to, the following. For example, a tin compound, a titanium compound, an aluminum compound, an antimony compound, a germanium compound, a rare earth metal catalyst, and the like can be given. Specific examples of the rare earth-containing catalyst include scandium (Sc), yttrium (Y), lanthanoid elements such as lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium ( Eu, gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), etc. are effective. In particular, alkylbenzene sulfonates, alkyl sulfate esters, or those having a triflate structure are effective. Examples of the triflate include X (OSO ₂ CF ₃ ) _{3 in} the structural formula. X is a rare earth element, and among these, scandium (Sc), yttrium (Y), ytterbium (Yb), samarium (Sm), and the like are preferable.
The lanthanoid triflate is described in detail in, for example, Journal of Synthetic Organic Chemistry, Vol. 53, No. 5, p44-54.
A plurality of these metals can be used in combination, or can be combined with a phosphorus compound or the like, or the above-mentioned surface active acid catalyst.

The hydrolase type catalyst is not particularly limited as long as it catalyzes an ester synthesis reaction. Examples of the hydrolase that can be used in the present invention include EC (enzyme numbers) such as carboxyesterase, lipase, phospholipase, acetylesterase, pectinesterase, cholesterol esterase, tannase, monoacylglycerol lipase, lactonase, and lipoprotein lipase. Hydrolysis classified into EC 3.2 group which acts on glycosyl compounds such as esterase, glucosidase, galactosidase, glucuronidase, xylosidase classified into 3.1 group (see “Enzyme Handbook” supervised by Maruo and Tamiya, 1982). Acts on peptide bonds of hydrolase, aminopeptidase, chymotrypsin, trypsin, plasmin, subtilisin, etc. classified into EC 3.3 group such as degrading enzyme and epoxide hydrase That hydrolytic enzymes classified in EC3.4 group, mention may be made of hydrolytic enzymes such as classified into EC3.7 group such as furo retinoic hydrolase.
Among the above esterases, enzymes that hydrolyze glycerol esters to liberate fatty acids are called lipases, but lipases are highly stable in organic solvents, catalyze ester synthesis reactions in high yields, and are available at a lower price. There are advantages such as what you can do. Therefore, it is desirable to use lipase also in the manufacturing method of the polyester of this invention from the surface of a yield or cost.

  A variety of lipases can be used, but preferred are the genus Pseudomonas, Alcaligenes, Achromobacter, Candida, Aspergillus, Rhizopus. Examples include lipases obtained from microorganisms such as (Rhizopus) genus and Mucor genus, lipases obtained from plant seeds, lipases obtained from animal tissues, pancreatin, steapsin and the like. Among these, it is desirable to use lipases derived from microorganisms of the genus Pseudomonas, Candida, and Aspergillus.

In order to achieve polycondensation at a lower temperature in the above catalyst, a surfactant type catalyst, a rare earth element catalyst, and an enzyme catalyst are effective. In the rare earth metal catalyst, it is particularly desirable to use a catalyst having elements such as Y, Sc, Yb, and Sm as its constituent components. In this case, it should be noted that the catalyst compound is more hydrophobic or has a higher molecular weight in view of the fact that the catalyst is distributed in the emulsion dispersion or resin particles being polymerized and the aqueous medium. Similarly, a surfactant type catalyst can also be suitably used. Particularly preferred surfactant type catalysts include dodecylbenzenesulfonic acid, p-toluenesulfonic acid, and the like.
Moreover, as the addition amount of a catalyst, it can add 1 type or multiple in the ratio of 0.1-10,000 ppm with respect to a polycondensable monomer.

  In the present invention, the median diameter of the resin particles in the resin particle dispersion is preferably 0.05 to 2.0 μm, more preferably 0.1 to 1.5 μm, and further preferably 0.1 to 1.0 μm. preferable. Such dispersion is uniformly mixed and emulsified by a shearing mixing device such as a piston homogenizer, a microfluidizer (for example, “Microfluidizer” manufactured by Microfluidics), an ultrasonic disperser or the like. If the particle size is too small, the agglomeration property at the time of granulation is deteriorated, free resin particles are likely to be generated, and the viscosity of the system is also likely to increase, making it difficult to control the particle size. If the particle size is too large, coarse powder is likely to be generated during particle formation, the particle size distribution is deteriorated, and the release agent such as wax is easily liberated. Or

  The arithmetic standard deviation of the resin particles in the resin particle dispersion of the present invention is preferably 0.60 or less. When the arithmetic standard deviation is 0.60 or less, the distribution of the diameter of the resin particles is not widened, and a release agent is appropriately and uniformly contained in the resin during toner production. The toner particle size, particle size distribution, shape controllability, powder flowability and the like due to the influence of coarse powder are favorable and preferable. In addition, the toner produced using the resin particle dispersion of the present invention is preferable because it does not cause fogging, image deterioration, and transfer efficiency. The arithmetic standard deviation is more preferably 0.50 or less, further preferably 0.40 or less, and most preferably 0.30 or less. The arithmetic mean standard deviation can be calculated using, for example, a laser diffraction particle size distribution measuring apparatus (LA-920, manufactured by Horiba, Ltd.).

In the resin particle dispersion, it is also important that there is no generation of ultrafine powder or ultracoarse powder, and the ratio of particles having a median diameter of 0.01 μm or less or 5.0 μm or more is preferably 10% or less. More preferably, it is further desirably 5% or less.
The median diameter of the resin particles can be measured using, for example, a laser diffraction particle size distribution measuring device (LA-920, manufactured by Horiba, Ltd.).

  When the polycondensation resin particles in the resin particle dispersion of the present invention is a crystalline resin, a substance having a crystal melting point Tm of 50 ° C. or more and less than 120 ° C. from the viewpoint of the fixing temperature range and fixability is preferably used. . More preferably, it is 55-110 degreeC. When the Tm is in the above range, the resulting toner has good blocking resistance, the melt fluidity of the toner at low temperature does not deteriorate, and the fixability is good, which is preferable.

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

On the other hand, when the polycondensation resin particles are an amorphous resin, the glass transition point Tg is preferably 30 ° C. or higher and lower than 75 ° C., more preferably 45 to 65 ° C. When the Tg is in the above range, the resulting toner has good blocking resistance, the melt fluidity at low temperatures of the toner does not deteriorate, and the fixability is good.
The glass transition point of an amorphous resin refers to a value measured by a method (DSC method) defined in ASTM D3418-82.

  In the resin particles in the resin particle dispersion of the present invention, the weight average molecular weight suitable as a toner resin is preferably 1,500 to 60,000, more preferably 3,000 to 40,000. It is. When the weight average molecular weight is in the above range, the cohesive force as a toner binder resin is hardly lowered, the hot offset property is good, and the minimum fixing temperature does not increase, which is preferable.

  The present invention preferably contains a radically polymerizable monomer from the viewpoint of toner resin production and maintenance of toner resin properties. Although the radical polymer which can be used for this invention is as follows, it is not limited to this.

<Radical polymerization monomer>
As the radical polymerizable monomer in the present invention, a vinyl monomer, an olefin monomer and the like can be preferably used.
Specific examples of the vinyl monomer include α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, and pn. -Butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene , Vinyl aromatics such as p-phenylstyrene, (meth) acrylic acid ("(meth) acryl" means acryl and methacryl, the same shall apply hereinafter), crotonic acid, malein Unsaturated carboxylic acids such as acid, fumaric acid, citraconic acid, itaconic acid, methyl (meth) acrylate, ethyl (meth) acrylate, Unsaturated carboxylic acid esters such as propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, and benzyl (meth) acrylate , Unsaturated carboxylic acid derivatives such as (meth) acrylaldehyde, (meth) acrylonitrile, (meth) acrylamide, N-vinyl compounds such as N-vinylpyridine and N-vinylpyrrolidone, vinyl formate, vinyl acetate, propion Vinyl esters such as vinyl acid, vinyl halides such as vinyl chloride, vinyl bromide, vinylidene chloride, N-methylol acrylamide, N-ethylol acrylamide, N-propanol acrylamide, N-methylol maleate N-substituted unsaturated amides such as doic acid, N-methylol maleamic acid ester, N-methylol maleimide, N-ethylol maleimide, conjugated dienes such as butadiene, isoprene, divinylbenzene, divinylnaphthalene, divinylcyclohexane, etc. Polyfunctional vinyl compounds, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexamethylene glycol Di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol di (meth) acrylate, glycerol Li (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipenta Erythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate, sorbitol hexa (meta) ) Multifunctional acrylates such as acrylate. Among these, N-substituted unsaturated amides, conjugated dienes, polyfunctional vinyl compounds, polyfunctional acrylates, and the like can also cause a crosslinking reaction in the produced polymer.

Examples of the olefin 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.
Among the radically polymerizable monomers, resins suitably used include vinyl aromatics and carboxylic acid esters.

  In the resin produced using the above-mentioned radical polymerizable monomer, the resin for toner preferably has a glass transition temperature of 40 ° C. or higher and 100 ° C. or lower from the viewpoint of fixability and image formability. When the Tg is 40 ° C. or higher, the cohesive force of the binder resin itself in the high temperature range is unlikely to decrease, so that hot offset is less likely to occur during fixing. Further, it is preferable that Tg is 100 ° C. or less because sufficient melting is obtained and the minimum fixing temperature does not increase. The glass transition temperature is more preferably 50 to 80 ° C, and most preferably 50 to 70 ° C.

  These radically polymerizable monomers can employ known polymerization methods such as a method using a radical polymerization initiator, a self-polymerization method by heat, and a method using ultraviolet irradiation. 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-ethylhexanoate. , 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-butylper) Xyl) 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, -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 ′ -Azobis (4-cyano valeric acid) etc. are mentioned.

  The resin particles in the resin particle dispersion of the present invention preferably have an acid value of 1 mgKOH / g or more and 50 mgKOH / g or less. The first reason is that control of the particle size and distribution of toner in an aqueous medium is indispensable for practical use as a high-quality toner, but an acid value of 1 mgKOH / g or more is sufficient. A preferable particle diameter and distribution can be achieved, and the chargeability of the toner is preferable because sufficient chargeability can be obtained. Further, when the acid value is 50 mgKOH / g or less, a sufficient molecular weight for obtaining image quality strength can be obtained as a toner at the time of polycondensation, and the dependency of the toner on the charging property under high humidity is also small. Excellent in reliability and preferable.

  In the process of the present invention, in addition to the polycondensable monomer and the radical polymerizable monomer, the polymerization can be carried out in an aqueous medium as long as the properties required for the purpose of use such as a dispersion, a toner, and an image are not impaired. Other polymerizable monomers can also be added. For example, a polyaddition monomer and a ring-opening polymerizable monomer.

<Polyadditive monomer>
As the polyaddition monomer, monomers represented by diisocyanates and diisocyanate-reactive polyactive hydrogen compounds can be used.
Examples of the diisocyanate include aliphatic diisocyanates, aliphatic diisocyanates having a cyclic group, aromatic diisocyanates, alicyclic hydrocarbon diisocyanates, biphenyl diisocyanates, di- or triphenylalkanes (alkanes having 5 or less carbon atoms) diisocyanates. Etc. are exemplified.
Aliphatic diisocyanates include ethane diisocyanate, propane diisocyanate, butene diisocyanate, butane diisocyanate, thiodiethyl diisocyanate, pentane diisocyanate, β-methylbutane diisocyanate, hexane diisocyanate, ω, ω′-dipropyl ether diisocyanate, thiodipropyl diisocyanate, Heptane diisocyanate, 2,2-dimethylpentane diisocyanate, 3-methoxyhexane diisocyanate, octane diisocyanate, 2,2,4-trimethylpentane diisocyanate, nonane diisocyanate, decane diisocyanate, 3-butoxyhexane diisocyanate, 1,4-butylene glycol-di Propyl ether-ω, ω'-diisocyanate, un Kang diisocyanate, dodecane diisocyanate, and the like thio dihexyl diisocyanate, and the like.
Examples of the aliphatic diisocyanate having a cyclic group include ω, ω′-1,3-dimethylbenzene diisocyanate, ω, ω′-1,2-dimethylbenzene diisocyanate, ω, ω′-1,2-dimethylcyclohexane diisocyanate, ω. , Ω′-1,4-dimethylcyclohexane diisocyanate, ω, ω′-1,4-diethylbenzene diisocyanate, ω, ω′-1,4-dimethylnaphthalene diisocyanate, ω, ω′-1,5-dimethylnaphthalene diisocyanate, 3,5-dimethylcyclohexane-1-methylisocyanate-2-propylisocyanate, ω, ω′-n-propyl-biphenyldiisocyanate and the like.

Aromatic diisocyanates include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1-methylbenzene-2,4-diisocyanate, 1-methylbenzene-2,5-diisocyanate, 1-methylbenzene-3, 5-diisocyanate, 1,3-dimethylbenzene-2,4-diisocyanate, 1,3-dimethylbenzene-4,6-diisocyanate, 1,4-dimethylbenzene-2,5-diisocyanate, 1-ethylbenzene-2,4 -Diisocyanate, 1-isopropylbenzene-2,4-diisocyanate, diethylbenzene diisocyanate, diisopropylbenzene diisocyanate and the like. Naphthalene diisocyanates include naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, naphthalene-2,6-diisocyanate, naphthalene-2,7-diisocyanate, 1,1′-dinaphthyl-2,2 ′. -Diisocyanate etc. are mentioned. Biphenyl diisocyanates include biphenyl-2,4′-diisocyanate, biphenyl-4,4′-diisocyanate, 3,3′-dimethylbiphenyl-4,4′-diisocyanate, 3,3′-dimethoxybiphenyl-4,4 ′. -Diisocyanate, 2-nitrobiphenyl-4,4'-diisocyanate and the like.
Examples of di- or triphenylalkane diisocyanates include diphenylmethane-4,4′-diisocyanate, 2,2′-dimethyldiphenylmethane-4,4′-diisocyanate, diphenyldimethylmethane-4,4′-diisocyanate, 2,5,2 ', 5'-tetramethyldiphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxydiphenylmethane-4,4'-diisocyanate, 4,4'-dimethoxyphenyl-3,3'-diisocyanate, 4,4'-Diethoxyphenylmethane-3,3'-diisocyanate,2,2'-dimethyl-5,5'-dimethoxydiphenylmethane-4,4'-diisocyanate,3,3-dichlorodiphenyldimethylmethane-4,4'-diisocyanate Benzophenone-3,3′-diisocyanate, α β- diphenylethane-2,4-diisocyanate, 3-nitro triphenylmethane-4,4'-diisocyanate, 4-nitro triphenylmethane-4,4'-diisocyanate, or derivatives thereof.

In addition, alicyclic hydrocarbon diisocyanates in which the aromatic ring is hydrogenated in the aromatic ring-containing diisocyanate are preferably exemplified, and give a toner excellent in light resistance as compared with the aromatic ring-containing diisocyanate. Therefore, it is preferable.
In the polyaddition reaction in the present invention, a polymer having a polyaddition reactive group may be used for the reaction. Specifically, the polymer includes an isocyanate group, a hydroxyl group, a carboxyl group, an amino group, a mercapto group, and the like. A preferred reactive group is an isocyanate group.

The polyactive hydrogen compound is preferably exemplified by the diols or diamines described above. Preferred examples of the diols include alkylenoxide adducts of bisphenols, and ethylene oxide adducts of bisphenol A and propylene oxide adducts of bisphenol A can be used alone or in combination. Further, two or more compounds having different numbers of repeating units of ethylene oxide group or propylene oxide group may be used.
Further, when a polyactive hydrogen compound having an acidic group is used together with the polyoxyalkylene bisphenol A ether as the polyactive hydrogen compound, particularly low temperature fixability, high temperature offset resistance, and fixing strength can be improved. Examples of the multi-active hydrogen compound having an acidic group used in combination with the polyoxyalkylene bisphenol A ether include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid, 2, 4-diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,6-diamino-2-toluenesulfonic acid, 2,4-diaminobenzenesulfonic acid, 2,5-diaminobenzenesulfonic acid, 4,4′-diamino Examples include stilbene-2,2′-disulfonic acid, 3,4-diaminobutanesulfonic acid, N- (2-aminoethyl) -2-aminoethylsulfonic acid, and the like. The above compound may be an alkali metal salt or an ammonium salt, preferably a sodium salt, a potassium salt, or an ammonium salt.
In addition, other multi-active hydrogen compounds such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly (caprolactone polyol), poly (hexamethylene carbonate) may be used as long as the properties of the toner by the multi-active hydrogen compound are not impaired. Bis (2-hydroxyethyl) terephthalate or the like may be added.

Examples of diamines include hexamethylene diamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, o-phenylene diamine, m-phenylene diamine, and the like.
Examples of the amines include polyvalent polyamines, amino alcohols, amino mercaptans, amino acids, and those obtained by blocking these amino groups. Examples of amine diamines other than those already described include aromatic diamines such as phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, and 4,4′-diamino-3,3′-dimethyldicyclohexylmethane. And alicyclic diamines such as diamine cyclohexane and isophorone diamine. Examples of amino alcohols include ethanolamine and hydroxyethylaniline. Examples of amino mercaptans include aminoethyl mercaptan and aminopropyl mercaptan. Examples of amino acids include aminopropionic acid and aminocaproic acid. Moreover, as what blocked these amino groups, the ketimine compound and oxazoline compound which are obtained from the said amines and ketones, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, are mentioned. Among these amines, preferred are diamines and a mixture of diamines and a small amount of a trivalent or higher polyamine.

In the polyaddition reaction, a catalyst is not necessarily required. For example, dibutyltin dichloride, dimethyltin dichloride, tin octylate, triphenylammonium dichloride, triethylamine, N, N-dimethylcyclohexylamine, triethylenediamine, dimethylaminoethanol, dioctyltin dilaurate Dioctyltin dineodecanoate, dibutyltin bis (mercapto ester) and the like may be added. In this case, the addition amount is preferably 10 to 1,000 ppm.
Furthermore, an extension terminator can be used if necessary. Examples of the elongation terminator include monoamines such as diethylamine, dibutylamine, butylamine and laurylamine, and those obtained by blocking them such as ketimine compounds.

<Ring-opening polymerizable monomer>
Preferred examples of the ring-opening polymerizable monomer include lactones. Lactone is a cyclic compound having an ester group in the ring, and examples thereof include β-propiolactone, γ-butyrolactone, δ-valerolactone, and ε-caprolactone. Most preferably, ε-caprolactone can be used. These ring-opening polymerizable monomers become aliphatic polyester resins having high crystallinity through a polymerization process.
For the ring-opening polymerization of lactone, for example, a metal oxide, an organometallic compound, or the like can be used as a ring-opening polymerization catalyst. When glycol is used as an initiator, a polyester having a hydroxyl group at the terminal is obtained. For example, a ring-opening polymer of ε-caprolactone can be usually obtained by reacting ε-caprolactone with a diol such as ethylene glycol or diethylene glycol in the presence of a catalyst.
As the catalyst for the main polymerization step, an organic tin compound, an organic titanium compound, an organic tin halide compound, or the like is preferable. In this case, the amount added is preferably 0.1 to 5,000 ppm.
The molecular weight of the ring-opening polymer is that having a number average molecular weight of 10,000 to 200,000. The melting point of the ring-opening polymer is preferably 40 to 150 ° C, and more preferably 50 to 100 ° C.

In the present invention, the step of polymerizing the monomer (including polycondensation) may include a polymerization reaction between the monomer and a prepolymer prepared in advance. The prepolymer is not limited as long as it is a polymer that can be melted or uniformly mixed with the monomer.
Furthermore, the homopolymer of the monomer mentioned above, the copolymer which combined 2 or more types of monomers containing the monomer mentioned above, those mixtures, a graft polymer, etc. can be included.

  In the present invention, when the polycondensable monomer and the radical polymerizable monomer are polymerized, in the polymerization step in water, the radical polymerizable monomer is mixed with the polycondensation monomer in advance, and finally the polymerization is performed. It is also possible to obtain hybrid particles of these polymers through condensation and radical polymerization. Further, as described above, also in the polycondensation step, a low molecular weight polymer is formed in advance by a bulk polymerization method or a solution polymerization method, and these are emulsified or dispersed in an aqueous medium, and further a polycondensation reaction is performed to reach the final molecular weight. In this case as well, the radical polymerizable monomer may be mixed with the low molecular weight polyester, or the low molecular weight polyester and the polycondensable monomer and then emulsified and dispersed. In the polycondensation in the aqueous medium in the present invention, since the acid value of the polymerized polymer affects the final molecular weight or the polymerization rate, a radically polymerizable vinyl monomer having a low solubility in water coexists during the polycondensation. After adjusting the low molecular weight body (or medium molecular weight body) that does not hinder the emulsification and dispersion of the polyester monomer in advance, and adjusting the acid value to a lower state, the final in an aqueous medium. It is preferable in production to use a method for obtaining a high molecular weight substance, or a combination of both methods, that is, a method of using a radical polymerization monomer and a polyester prepolymerization method in combination.

  Similarly, in the polymerization step of the present invention, a plurality of polymerizations can be carried out simultaneously or sequentially. For example, as a monomer component for polymerization, a radical polymerizable monomer is mixed with a polycondensation monomer, and the polymerization is performed simultaneously with the radical polymerization and the polycondensation reaction, or the radical polymerization is performed after the polycondensation. Conversely, polycondensation can be carried out after radical polymerization. At this time, it is possible to mix the polycondensation catalyst in the monomer component. Further, regarding the radical polymerization catalyst, a radical initiator is added to the monomer mixture or the aqueous medium before or during polycondensation. It can be added after polycondensation.

  In the polymerization in the aqueous medium of the present invention, a monomer component before polycondensation and a fixing aid such as a colorant and a wax, and other components such as a charging aid, a dehydrating agent, a water absorbing agent, and a chain extender are added. It is also possible to mix in advance.

In the emulsification and dispersion step in the present invention, for example, a monomer solution to which a co-surfactant is added and an aqueous solution of the surfactant are mixed with a piston homogenizer, a microfluidizer (for example, “Microfluid” manufactured by Dick Co., Ltd. It is preferable that the mixture is uniformly mixed and emulsified by a shear mixing device such as a dither ") or an ultrasonic disperser. At that time, the amount of monomer charged with respect to water is about 0.1 to 50% by weight with respect to the total amount with water, and the amount of surfactant used is the presence of the emulsified dispersion (emulsion) to be formed. Under the critical micelle concentration (CMC) defined as miniemulsion polymerization below, the amount of co-surfactant used is preferably 0.1 to 100 parts by weight of monomer. 40 parts by weight, more preferably 0.1 to 20 parts by weight.
As described above, the “mini” is a polymerization of the monomer in the presence of the polymerization initiator of the monomer emulsion by the combined use of the surfactant amount less than the critical micelle concentration (CMC) and the co-surfactant. "Emulsion polymerization" is a uniform polymer particle formed by the polymerization of monomers in fine monomer particles. Furthermore, in "miniemulsion polymerization", when a polyester / vinyl composite polymer is used, polymerization is performed. Since there is no need for monomer diffusion in the process, polyester has the advantage that it can be present in the polymer microparticles as is.
Further, for example, JS Guo, MS El-Aasser, and JW Vanderhoff, J. Polym. Sci .: Polym. Chem. Ed., 27, 691 (1989), etc. The so-called “microemulsion polymerization” of 50 nm fine particles has the same dispersion structure and polymerization mechanism as “miniemulsion polymerization”, but in “microemulsion polymerization”, a surfactant having a critical micelle concentration (CMC) or higher And a large amount of surfactant is mixed in the resulting polymer fine particles, or a lot of time is required for the steps such as water washing, acid washing or alkali washing for the removal. There is a problem such as need.

  The method for producing an electrostatic charge image developing toner of the present invention includes a step of aggregating the resin particles in a dispersion containing at least a resin particle dispersion to obtain aggregated particles (hereinafter also referred to as an aggregation step), and the aggregation. A method for producing an electrostatic image developing toner comprising a step of heating and fusing particles (hereinafter also referred to as a fusing step), wherein the resin particle dispersion is a resin particle dispersion for an electrostatic image developing toner of the present invention. It is characterized by being.

  In the method for producing a toner for developing an electrostatic charge image of the present invention, the monomer emulsion is formed into resin polymer particles by polymerizing the monomer in the presence of a polymerization initiator, and then the formed polymer emulsion is formed. The coalesced particles are agglomerated (associated) by a known agglomeration method that agglomerates (associates) particles containing at least colorant particles (if the colorant is previously added to the resin in the polymerization step, the colored particles themselves). ) To adjust the toner particle size and distribution. Preferably, toner particle adjustment in an emulsion polymerization aggregation method is used. Specifically, the resin particles prepared according to the present invention are mixed with a colorant particle dispersion and a release agent particle dispersion, and an aggregating agent is added to form heteroaggregation to form aggregated particles having a toner diameter. Then, it is obtained by heating to a temperature not lower than the glass transition point or higher than the melting point of the resin fine particles to fuse and coalesce the aggregated particles, and wash and dry. In this manufacturing method, the toner shape can be controlled from an indeterminate shape to a spherical shape by selecting a heating temperature condition.

  In the agglomeration step of the present invention, a resin particle dispersion prepared by a method other than the present invention (for example, a normal emulsion polymerization method) and a resin particle dispersion prepared by the present invention are mixed, and the subsequent steps after aggregation are performed. It is also possible to implement. At that time, after the resin particle dispersion of the present invention is aggregated in advance to form the first aggregated particles, the fine particle dispersion of the present invention or another resin fine particle dispersion is further added to form the second shell layer on the surface of the first particles. It is also possible to make the particles multi-layered, such as by forming. Naturally, it is also possible to produce multilayer particles in the reverse order of the previous example.

  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 aggregation control and toner chargeability. The metal salt compound used for aggregation is obtained by dissolving a general inorganic metal compound or a polymer thereof in a resin fine particle dispersion, but the metal elements constituting the inorganic metal salt are a periodic table (long-period table). 2A, 3A, 4A, 5A, 6A, 7A, 8, 1B, 2B, and 3B, and those having a valence of 2 or more and soluble in the form of ions in the agglomeration system of resin fine particles. Good. Specific examples of preferred inorganic metal salts include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate, and polyaluminum chloride, polyaluminum hydroxide, calcium sulfide. And inorganic metal salt polymers. Among these, an aluminum salt and a polymer thereof are particularly preferable. In general, in order to obtain a sharper particle size distribution, even if the valence of the inorganic metal salt is divalent to monovalent, bivalent to trivalent or higher, and even to the same valence, the polymerization type inorganic metal salt weight Combined is more suitable.

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

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

  In the present invention, if necessary, known additives can be blended in a combination of one or more kinds within a range that does not affect the results of the present invention. For example, flame retardants, flame retardant aids, brighteners, waterproofing agents, water repellents, inorganic fillers (surface modifiers), mold release agents, antioxidants, plasticizers, surfactants, dispersants, lubricants, Fillers, extenders, binders, charge control agents and the like. These additives can be blended in any production of the coating agent.

  As an example of the internal additive, various charge control agents such as quaternary ammonium salt compounds and nigrosine compounds can be used as charge control agents. However, stability during production and reduction of wastewater contamination can be used. Therefore, materials that are difficult to dissolve in water are suitable.

Examples of mold release agents include low molecular weight polyolefins such as polyethylene, polypropylene and polybutene, silicones having a softening point upon heating, fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide and the like. Plant waxes such as ester wax, carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil, animal wax such as beeswax, montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax , Minerals such as microcrystalline wax, Fischer-Tropsch wax, petroleum-based wax, and modified products thereof can be used.
These waxes are dispersed in water together with ionic surfactants, polymer electrolytes such as polymer acids and polymer bases, and heated with a homogenizer or pressure discharge type disperser that can be heated to the melting point or higher and subjected to strong shearing. And a dispersion of particles less than 1 micron can be made.

  Examples of flame retardants and flame retardant aids include, but are not limited to, bromine flame retardants that have already been widely used, antimony trioxide, magnesium hydroxide, aluminum hydroxide, and ammonium polyphosphate.

  Coloring components include furnace black, channel black, acetylene black, thermal black and other carbon blacks, bengara, bitumen, titanium oxide and other inorganic pigments, fast yellow, disazo yellow, pyrazolone red, chelate red, brilliant carmine, para brown, etc. Azo pigments, 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. And various pigments such as CI Pigment Blue 15: 3. These may be used alone or in combination of two or more.

  In addition, after drying in the same way as normal toner, inorganic particles such as silica, alumina, titania and calcium carbonate and resin fine particles such as vinyl resin, polyester and silicone are added to the surface in a dry state and added to the surface. It can also be used as an auxiliary agent or a cleaning auxiliary agent.

  Examples of the surfactant used in the process of the present invention include anion surfactants such as sulfate ester, sulfonate, phosphate, and soap, cations such as amine salt type and quaternary ammonium salt type. It is also effective to use nonionic surfactants such as polyethylene glycols, alkylphenol ethylene oxide adducts, polyhydric alcohols, etc. as a means for dispersion as a rotational shear type homogenizer. Ordinary things such as a ball mill, a sand mill, and a dyno mill having media and media can be used.

The toner agent is used in combination with an appropriately selected carrier known per se. Further, as a one-component developer, a method in which a charged toner is formed by frictional charging with a developing sleeve or a charging member, and development is performed according to an electrostatic latent image can be applied.

The toner preferably has an average volume particle diameter of 3.0 to 20.0 μm and an average volume particle distribution GSDv of 1.4 or less. More preferably, the average volume particle diameter is 3.0 to 9.0 μm, and the GSDv is 1.3 or less. As the particle distribution, the following average volume particle distribution GSD or number GSD can be simply used by using the cumulative distributions D ₁₆ and D ₈₄ .
Volume GSDv = (Volume D ₈₄ / Volume D ₁₆ ) ^0.5
A GSDv of 1.4 or less is preferable because the particle diameter is uniform, the fixing property is excellent, and a device failure due to poor fixing does not occur. In addition, it is preferable that internal contamination due to toner scattering and deterioration of the developer do not occur. It is preferable that D ₅₀ is 3.0 μm or more because the adhesive force is appropriate and the developability is excellent. Moreover, it is excellent in the resolution of an image as it is 9.0 micrometers or less below, and is preferable.
The average volume particle diameter (D ₅₀ ) and the average volume particle distribution GSD can be measured using a laser diffraction particle size distribution measuring apparatus or the like.

  Furthermore, the shape factor SF1 of the toner according to the present invention is preferably from 100 to 140, more preferably from 110 to 135, from the viewpoint of image formability. At this time, SF1 is calculated as follows.

ここでＭＬは粒子の絶対最大長を表し、Ａは粒子の投影面積を表す。
これらは、主に顕微鏡画像または走査電子顕微鏡画像をルーゼックス画像解析装置によって取り込み、解析することによって数値化される。

Here, ML represents the absolute maximum length of the particle, and A represents the projected area of the particle.
These are quantified mainly by capturing and analyzing a microscope image or a scanning electron microscope image with a Luzex image analyzer.

The toner obtained by the method for producing an electrostatic charge image developing toner of the present invention described above is used as an electrostatic charge image developer. The developer is not particularly limited except that it contains the electrostatic image developing toner, and can have an appropriate component composition depending on the purpose. When the electrostatic image developing toner is used alone, it is prepared as a one-component electrostatic image developer, and when used in combination with a carrier, it is prepared as a two-component electrostatic image developer.
The carrier is not particularly limited, but usually, magnetic particles such as iron powder, ferrite, iron oxide powder, nickel, etc .; the magnetic particles as a core material and the surface thereof as a styrene resin, vinyl resin, ethylene resin, rosin Resin-coated carrier formed by coating a resin such as a resin based on polyester, polyester or melamine, or a wax such as stearic acid, and forming a resin coating layer; a magnetic material obtained by dispersing magnetic particles in a binder resin Examples include a distributed carrier. Among them, the resin-coated carrier is particularly preferable because the chargeability of the toner and the resistance of the entire carrier can be controlled by the configuration of the resin coating layer.
The mixing ratio of the toner of the present invention and the carrier in the two-component electrostatic image developer is usually 2 to 10 parts by weight of the toner with respect to 100 parts by weight of the carrier. Moreover, the preparation method of a developing agent is not specifically limited, For example, the method of mixing with a V blender etc. is mentioned.

Further, the electrostatic image developer (electrostatic image developing toner) can be used in an ordinary electrostatic image developing system (electrophotographic system) image forming method.
The image forming method of the present invention includes a latent image forming step of forming an electrostatic latent image on the surface of the latent image holding member, and developing the electrostatic latent image formed on the surface of the latent image holding member with a developer containing toner. A developing step for forming a toner image, a transfer step for transferring the toner image formed on the surface of the latent image holding member to the surface of the transfer target, and a fixing for thermally fixing the toner image transferred to the surface of the transfer target. An electrostatic charge image developing toner of the present invention as the toner, or the electrostatic charge image developer of the present invention as the developer.
For each of the above steps, a known step can be used in the image forming method, and are described in, for example, JP-A-56-40868 and JP-A-49-91231. Further, the image forming method of the present invention may include steps other than the above-described steps. For example, a cleaning step for removing the electrostatic charge image developer remaining on the electrostatic latent image carrier is preferable. Can be mentioned. 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.

As the latent image holding member, for example, an electrophotographic photosensitive member and a dielectric recording member can be used.
In the case of an electrophotographic photosensitive member, the surface of the electrophotographic photosensitive member is uniformly charged by a corotron charger, a contact charger or the like and then exposed to form an electrostatic latent image (latent image forming step). Next, the toner particles are adhered to the electrostatic latent image by contacting or approaching a developing roll having a developer layer formed on the surface to form a toner image on the electrophotographic photosensitive member (developing step). The formed toner image is transferred onto the surface of a transfer medium such as paper using a corotron charger or the like (transfer process). Further, the toner image transferred to the surface of the transfer target is heat-fixed by a fixing device, and a final toner image is formed.
In the heat fixing by the fixing device, a release agent is usually supplied to a fixing member in the fixing device in order to prevent offset and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all.

Example 1
<Preparation of oil phase 1>
-1,6-hexanediol (SP value 12.49, HLB value 5.76) 4.6 parts by weight-Sebacic acid (SP value 10.57, HLB value 8.91) 9.5 parts by weight-Styrene 35. 0 part by weight / dodecanethiol 1.0 part by weight The above was heated and dissolved at 130 ° C. to prepare a uniform oil phase 1.
<Preparation of aqueous phase 1>
-Dodecylbenzenesulfonic acid 1.66 parts by weight-Cetyl alcohol (carbon number 16) 1.5 parts by weight-Water 200 parts by weight <Preparation of resin particle dispersion 1>
The aqueous solution was prepared and stirred in a constant temperature bath at 70 ° C. for 1 hour. The aqueous phase was placed in a 1 liter container and stirred for 3 minutes at 8,000 rpm with Ultra Turrax (manufactured by IKA), and then the emulsion was charged into a 500 ml reactor equipped with a stirrer, under a nitrogen atmosphere at 70 ° C. For 24 hours.
To this resin particle dispersion, 1.1 parts by weight of ammonium persulfate dissolved in 10 parts by weight of ion-exchanged water was added, and polymerization was further performed in a nitrogen atmosphere for 6 hours to obtain a stable resin particle dispersion. It was. Similarly, a small amount was taken and the physical properties of the polyester / styrene composite polymer were measured.
Weight average molecular weight of styrene by GPC: 45,000
GPC polyester weight average molecular weight: 4,100
Melting point of polyester: 56 ° C
Median diameter: 0.4 μm
Arithmetic mean deviation: 0.28
The polymer obtained as described above was confirmed to be composite particles of styrene and polyester.

For the measurement of the molecular weight, the weight average molecular weight Mw and the number average molecular weight Mn were measured by gel permeation chromatography (GPC) under the conditions described below. At a temperature of 40 ° C., a solvent (tetrahydrofuran) is flowed at a flow rate of 1.2 ml per minute, and 3 mg of a tetrahydrofuran sample solution having a concentration of 0.2 g / 20 ml is injected as a sample weight for measurement. When measuring the molecular weight of a sample, select the measurement conditions that fall within the range in which the logarithm of the molecular weight of the prepared calibration curve and the count number are linear, using several monodisperse polystyrene standard samples. .
In addition, the reliability of the measurement results is that the NBS706 polystyrene standard sample performed under the above measurement conditions is
Weight average molecular weight Mw = 28.8 × 10 ⁴
Number average molecular weight Mn = 13.7 × 10 ⁴
Can be confirmed.
Further, as the GPC column, TSK-GEL, GMH (manufactured by Toyo Soda Co., Ltd.) and the like satisfying the above conditions were used.
A differential scanning calorimeter (Shimadzu Corporation, DSC50) was used to measure the melting point of the polyester.

(Example 2)
<Preparation of oil phase 2>
1,6-hexanediol (SP value 12.49, HLB value 5.76) 5.3 parts by weight 1,12-dodecanedicarboxylic acid (SP value 10.0, HLB value 7.83) 10.4 weight Parts / styrene 35.0 parts by weight / dodecanethiol 1.0 parts by weight The above was heated and dissolved at 130 ° C. to prepare a uniform oil phase 2.
<Preparation of aqueous phase 2>
-Dodecylbenzenesulfonic acid 1.66 parts by weight-Docosanol (carbon number 22) 1.9 parts by weight-Water 200 parts by weight <Preparation of resin particle dispersion 2>
The aqueous solution was prepared and stirred in a 75 ° C. constant temperature bath for 1 hour. The aqueous phase was placed in a 1 liter container and stirred for 3 minutes at 8,000 rpm with Ultra Turrax (manufactured by IKA), and then the emulsion was charged into a 500 ml reactor equipped with a stirrer, under a nitrogen atmosphere at 70 ° C. For 24 hours.
To this resin particle dispersion, 1.1 parts by weight of ammonium persulfate dissolved in 10 parts by weight of ion-exchanged water was added, and polymerization was further performed in a nitrogen atmosphere for 6 hours to obtain a stable resin particle dispersion. It was. Similarly, a small amount was taken and the physical properties of the polyester / styrene composite polymer were measured.
Weight average molecular weight of styrene by GPC: 38,000
GPC polyester weight average molecular weight: 3,900
Melting point of polyester: 54 ° C
Median diameter: 0.38 μm
Arithmetic mean deviation: 0.20
The polymer obtained as described above was confirmed to be composite particles of styrene and polyester.

(Example 3)
<Preparation of oil phase 3>
-1,9-nonanediol (SP value 11.41, HLB value 4.25) 10.0 parts by weight-1,12-dodecanedicarboxylic acid (SP value 10.0, HLB value 7.83) 10.0 weight Parts · fumaric acid (SP value 11.6, HLB value 15.5) 2.33 parts by weight · styrene 25.0 parts by weight · dodecanethiol 0.75 parts by weight Was made.
<Preparation of aqueous phase 3>
-Dodecylbenzenesulfonic acid 1.66 parts by weight-Cetyl alcohol 1.5 parts by weight-Water 200 parts by weight <Preparation of resin particle dispersion 3>
The aqueous solution was prepared and stirred for 1 hour in a 85 ° C. constant temperature bath. The aqueous phase was placed in a 1 liter container and stirred for 3 minutes at 8,000 rpm with Ultra Turrax (manufactured by IKA), and then the emulsion was charged into a 500 ml reactor equipped with a stirrer at 85 ° C. under a nitrogen atmosphere. For 24 hours.
To this resin particle dispersion, 0.8 parts by weight of ammonium persulfate dissolved in 10.0 parts by weight of ion-exchanged water was added, and polymerization was further performed in a nitrogen atmosphere for 6 hours. As a result, a stable resin particle dispersion was obtained. Got. Similarly, a small amount was taken and the physical properties of the polyester / styrene composite polymer were measured.
Weight average molecular weight of styrene by GPC: 56,000
Weight average molecular weight of polyester by GPC: 3,850
Melting point of polyester: 59 ° C
Median diameter: 0.36 μm
Arithmetic mean deviation: 0.22
The polymer obtained as described above was confirmed to be composite particles of styrene and polyester.

Example 4
<Preparation of oil phase 4>
-1,9-nonanediol (SP value 11.41, HLB value 4.25) 15.0 parts by weight-Sebacic acid (SP value 10.57, HLB value 8.91) 19.0 parts by weight-Styrene 40. 0 part by weight / dodecanethiol 1.35 parts by weight The above was heated and dissolved at 130 ° C. to prepare a uniform oil phase 4.
<Preparation of aqueous phase 4>
-Dodecylbenzenesulfonic acid 1.66 parts by weight-Stearyl alcohol (carbon number 18) 0.3 parts by weight-Water 175 parts by weight <Preparation of resin particle dispersion 4>
The aqueous solution was prepared and stirred in a 75 ° C. constant temperature bath for 1 hour. The aqueous phase was placed in a 1 liter container and stirred for 3 minutes at 8,000 rpm with Ultra Turrax (manufactured by IKA), and then the emulsion was charged into a 500 ml reactor equipped with a stirrer, under a nitrogen atmosphere at 70 ° C. For 24 hours.
To this resin particle dispersion, 0.8 parts by weight of ammonium persulfate dissolved in 10.0 parts by weight of ion-exchanged water was added, and polymerization was further performed in a nitrogen atmosphere for 6 hours. As a result, a stable resin particle dispersion was obtained. Got. Similarly, a small amount was taken and the physical properties of the polyester / styrene composite polymer were measured.
Weight average molecular weight of styrene by GPC: 58,600
GPC polyester weight average molecular weight: 4,350
Melting point of polyester: 59 ° C
Median diameter: 0.39 μm
Arithmetic mean deviation: 0.55
The polymer obtained as described above was confirmed to be composite particles of styrene and polyester.

(Example 5)
<Preparation of oil phase 5>
Diglycolic acid (SP value 12.03, HLB value 17.0) 13.4 parts by weight 1,6-hexanediamine (SP value 9.2, HLB value 5.5) 11.6 parts by weight Styrene 25 Part by weight / lauryl alcohol (carbon number 14) 1.12 parts by weight / dodecanethiol 0.75 part by weight The above was heated and dissolved at 130 ° C. to prepare a uniform oil phase 5.
<Preparation of aqueous phase 5>
-1.66 parts by weight of dodecylbenzene sulfonic acid-0.8 parts by weight of potassium persulfate-200 parts by weight of water <Preparation of resin particle dispersion 5>
The aqueous solution was prepared and stirred in a 75 ° C. constant temperature bath for 1 hour. The aqueous phase was placed in a 1 liter container and stirred for 3 minutes at 8,000 rpm with Ultra Turrax (manufactured by IKA), and then the emulsion was charged into a 500 ml reactor equipped with a stirrer, under a nitrogen atmosphere at 70 ° C. For 24 hours.
To this resin particle dispersion, 0.8 parts by weight of ammonium persulfate dissolved in 10.0 parts by weight of ion-exchanged water was added, and polymerization was further performed in a nitrogen atmosphere for 6 hours. As a result, a stable resin particle dispersion was obtained. Got. Similarly, a small amount was taken and the physical properties of the polyester / styrene composite polymer were measured.
Weight average molecular weight of styrene by GPC: 53,000
Weight average molecular weight of polyester by GPC: 3,300
Melting point of polyamide: 76 ° C
Median diameter: 0.45 μm
Arithmetic mean deviation: 0.48
The polymer obtained as described above was confirmed to be polyamide / styrene composite particles.

(Comparative Example 1)
<Preparation of oil phase 6>
-1,6-hexanediol (SP value 12.49, HLB value 5.76) 4.6 parts by weight-Sebacic acid (SP value 10.57, HLB value 8.91) 9.5 parts by weight-Styrene 35. 0 part by weight / dodecanethiol 1.0 part by weight / hexadecane 1.5 part by weight The above was heated and dissolved at 130 ° C. to prepare a uniform oil phase 6.
<Preparation of aqueous phase 6>
-Dodecylbenzene sulfonic acid 1.66 parts by weight-200 parts by weight of water <Preparation of resin particle dispersion 6>
The aqueous solution was prepared and stirred in a constant temperature bath at 70 ° C. for 1 hour. The aqueous phase was placed in a 1 liter container and stirred for 3 minutes at 8,000 rpm with Ultra Turrax (manufactured by IKA), and then the emulsion was charged into a 500 ml reactor equipped with a stirrer, under a nitrogen atmosphere at 70 ° C. For 24 hours.
To this resin particle dispersion, 1.1 parts by weight of ammonium persulfate dissolved in 10 parts by weight of ion-exchanged water was added, and polymerization was further performed in a nitrogen atmosphere for 6 hours to obtain a resin particle dispersion. Separation of the upper layer was observed in the resin particle dispersion. Similarly, a small amount was taken and the physical properties of the polyester / styrene composite polymer were measured.
Weight average molecular weight of styrene by GPC: 68,000
Weight average molecular weight of polyester by GPC: 2,100
Melting point of polyester: 56 ° C
Median diameter: 0.92 μm
Arithmetic mean deviation: 8.77

(Comparative Example 2)
<Preparation of oil phase 7>
1,6-hexanediol (SP value 12.49, HLB value 5.76) 5.3 parts by weight 1,12-dodecanedicarboxylic acid (SP value 10.0, HLB value 7.83) 10.4 weight Parts / styrene 35.0 parts by weight / dodecanethiol 1.0 parts by weight / stearyl methacrylate 1.66 parts by weight The above was heated and dissolved at 130 ° C. to prepare a uniform oil phase 7.
<Preparation of aqueous phase 7>
-Dodecylbenzenesulfonic acid 1.66 parts by weight-200 parts by weight of water <Preparation of resin particle dispersion 7>
The aqueous solution was prepared and stirred for 1 hour in a 85 ° C. constant temperature bath. The aqueous phase was placed in a 1 liter container and stirred for 3 minutes at 8,000 rpm with Ultra Turrax (manufactured by IKA), and then the emulsion was charged into a 500 ml reactor equipped with a stirrer at 85 ° C. under a nitrogen atmosphere. For 24 hours.
To this resin particle dispersion, 0.8 parts by weight of ammonium persulfate dissolved in 10.0 parts by weight of ion-exchanged water was added, and polymerization was further performed in a nitrogen atmosphere for 6 hours to obtain a resin particle dispersion. In the resin particle dispersion, suspended matter on the oil was generated in the upper layer. Similarly, a small amount was taken and the physical properties of the polyester / styrene composite polymer were measured.
Weight average molecular weight of styrene by GPC: 51,000
GPC polyester weight average molecular weight: 2,350
Melting point of polyester: 58 ° C
Median diameter: 1.46 μm
Arithmetic mean deviation: 6.61
The polymer obtained as described above was confirmed to be composite particles of styrene and polyester.

(Comparative Example 3)
<Preparation of oil phase 8>
-1,9-nonanediol (SP value 11.41, HLB value 4.25) 15.0 parts by weight-Sebacic acid (SP value 10.57, HLB value 8.91) 19.0 parts by weight-Styrene 35. 0 part by weight / dodecanethiol 1.0 part by weight The above was heated and dissolved at 130 ° C. to prepare a uniform oil phase 8.
<Preparation of aqueous phase 8>
-Dodecylbenzenesulfonic acid 1.66 parts by weight-Butanol (carbon number 4) 1.0 part by weight-Water 200 parts by weight <Preparation of resin particle dispersion 8>
The aqueous solution was prepared and stirred in a constant temperature bath at 70 ° C. for 1 hour. The aqueous phase was placed in a 1 liter container and stirred for 3 minutes at 8,000 rpm with Ultra Turrax (manufactured by IKA), and then the emulsion was charged into a 500 ml reactor equipped with a stirrer, under a nitrogen atmosphere at 70 ° C. For 24 hours.
To this resin particle dispersion, 1.1 parts by weight of ammonium persulfate dissolved in 10 parts by weight of ion-exchanged water was added, and polymerization was further performed in a nitrogen atmosphere for 6 hours to obtain a resin particle dispersion. Resinous deposits were observed in the reactor and stirrer.
Weight average molecular weight of styrene by GPC: 82,000
GPC polyester weight average molecular weight: 2,420
Melting point of polyester: 52 ° C
Median diameter: 0.66 μm
Arithmetic mean deviation: 1.61
The polymer obtained as described above was confirmed to be composite particles of styrene and polyester.

The stability of the resin particle dispersion was measured by weighing 100 g of the resin particle dispersion into a 300 ml stainless beaker, and shear homogenizing with an IKA Ultra Turrax T50 in the beaker for 1 minute, and then the resin particle dispersion with a 77 micron nylon mesh. It was examined by a method of filtering and observing the presence or absence of aggregation.
The evaluation criteria for the stability of the resin particle dispersion are:
“◎” means no aggregation at all,
“○” is slightly agglomerated but no problem.
"△" is a slight aggregation occurrence,
“X” was regarded as a large amount of aggregation.
The results of Examples 1 to 5 and Comparative Examples 1 to 3 are shown in Table 1.

In addition, the abbreviation in the said Table 1 represents the following compounds.
HD: 1,6-hexanediol SA: sebacic acid DDA: 1,12-dodecanedicarboxylic acid ND: 1,9-nonanediol DGA: diglycolic acid HDA: 1,6-hexanediamine CA: cetyl alcohol C22: docosanol C18 : Stearyl alcohol C14: Lauryl alcohol SMA: Stearyl methacrylate C4: Butanol

[Production of toner]
(Preparation of release agent particle dispersion (W1))
・ Polyethylene wax 30 parts by weight (Toyo Petrolite, Polywax 725, melting point 103 ° C.)
3 parts by weight of a cationic surfactant (manufactured by Kao Corporation, Sanizol B50) 67 parts by weight of ion-exchanged water After sufficiently dispersing the above components while heating to 95 ° C. with a homogenizer (manufactured by IKA, Ultra Turrax T50) Then, dispersion treatment was performed using a pressure discharge type homogenizer (Gorin homogenizer manufactured by Gorin Co., Ltd.) to prepare a release agent fine particle dispersion (W1). The number average particle diameter D _50n of the release agent fine particles in the obtained dispersion was 310 nm. Thereafter, ion exchange water was added to adjust the solid concentration of the dispersion to 30%.

(Preparation of magenta pigment dispersion (M1))
・ Magenta pigment (manufactured by Dainichi Seika Kogyo Co., Ltd., PR122 (quinacridone)) 20 parts by weight ・ Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R) 2 parts by weight ・ Ion-exchanged water 78 parts by weight Homogenizer (LKA, Ultra Turrax T50) was used, and the pigment was blended with water at 3000 rpm for 2 minutes, further dispersed at 5,000 rpm for 10 minutes, and then defoamed by stirring with a normal stirrer for one day and night. Thereafter, the mixture was dispersed for about 1 hour at a pressure of 240 MPa using a high-pressure impact disperser Ultimateizer (manufactured by Sugino Machine Co., Ltd., HJP30006) to obtain a magenta pigment dispersion (MN1). The number average particle diameter D _50n of the pigment in the dispersion was 106 nm. Thereafter, ion exchange water was added to adjust the solid content concentration of the dispersion to 15%.

(Preparation of cyan pigment dispersion (C1))
Cyan pigment (Daiichi Seika Kogyo Co., Ltd., PB15: 3) 20 parts by weight Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R) 2 parts by weight Ion-exchanged water 78 parts by weight Magenta A cyan pigment dispersion was prepared in the same manner as the pigment dispersion (M1). The number average particle diameter D _50n of the pigment in the dispersion was 121 nm. Thereafter, ion exchange water was added to adjust the solid content concentration of the dispersion to 15%.

(Preparation of yellow pigment dispersion (Y1))
-Yellow pigment (Clariant Japan, PY74) 20 parts by weight-Anionic surfactant (Daiichi Kogyo Seiyaku, Neogen R)-2 parts by weight-Ion-exchanged water 78 parts by weight Magenta pigment dispersion ( It was prepared in the same manner as MN1) to obtain a yellow pigment dispersion. The number average particle diameter D _50n of the pigment in the dispersion was 118 nm. Thereafter, ion exchange water was added to adjust the solid content concentration of the dispersion to 15%.

(Preparation of black pigment dispersion (K1))
・ Carbon black (Cabot, Regal 330) 20 parts by weight ・ Anionic surfactant (Daiichi Kogyo Seiyaku, Neogen R) 2 parts by weight ・ Ion-exchanged water 78 parts by weight Magenta pigment dispersion ( Prepared in the same manner as MN1) to obtain a black pigment dispersion. The number average particle diameter D _50n of the pigment in the dispersion was 120 nm. Thereafter, ion exchange water was added to adjust the solid content concentration of the dispersion to 15%.

(Preparation of resin particle dispersion A: amorphous vinyl resin particle dispersion)
-Styrene 460 parts by weight-n-butyl acrylate 140 parts by weight-Acrylic acid 12 parts by weight-Dodecanethiol 9 parts by weight The above components are mixed and dissolved to prepare a solution.
On the other hand, 12 parts by weight of an anionic surfactant (manufactured by Dow Chemical Co., Ltd., Dowfax) is dissolved in 250 parts by weight of ion-exchanged water, and the solution is added and dispersed and emulsified in a flask. (Monomer emulsion A)
Furthermore, 1 part by weight of an anionic surfactant (manufactured by Dow Chemical Co., Dowfax) was dissolved in 555 parts by weight of ion-exchanged water and charged into a polymerization flask.
The polymerization flask was sealed, a reflux tube was installed, and the polymerization flask was heated to 75 ° C. with a water bath while being slowly stirred while injecting nitrogen.
9 parts by weight of ammonium persulfate was dissolved in 43 parts by weight of ion-exchanged water and dropped into the polymerization flask via a metering pump over 20 minutes, and then the monomer emulsion A was added for 200 minutes through the metering pump. It was dripped over.
Thereafter, the polymerization flask was kept at 75 ° C. for 3 hours while continuing the stirring slowly to complete the polymerization.
As a result, an anionic resin particle dispersion A having a median diameter of resin particles of 230 nm, a glass transition point of 53.5 ° C., a weight average molecular weight of 36,000, and a solid content of 42% was obtained.

(Example 6)
(Production of toner using resin dispersion 1)
(Preparation of black toner (toner K1))
Resin particle dispersion (1) 100 parts by weight Resin particle dispersion A 60 parts by weight Release agent particle dispersion (W1) 33 parts by weight Black pigment dispersion (K1) 60 parts by weight Polyaluminum chloride 10 parts by weight % Aqueous solution 15 parts by weight (Asada Chemical Co., Ltd., PAC100W)
-1% nitric acid aqueous solution 3 parts by weight The above components were dispersed in a round stainless steel flask for 3 minutes at 5000 rpm using a homogenizer (manufactured by LKA, Ultra Turrax T50), and then the flask had a magnetic seal. The lid is equipped with a stirring device, a thermometer and a pH meter, and then a heating mantle heater is set, and the whole dispersion in the flask is appropriately adjusted to the minimum number of revolutions that can be stirred and stirred at 57 ° C. The mixture was heated at 1 ° C./1 min until it was kept at 57 ° C. for 30 minutes, and the particle size of the aggregated particles was confirmed with a Coulter counter (manufactured by Nikka Kisha, TA II). Immediately after the temperature rise was stopped, 50 parts by weight of the resin fine particle dispersion (L1) was added and held for 30 minutes, and then an aqueous sodium hydroxide solution was added until the pH in the system reached 6.5, and then at 1 ° C./1 min. Heated to 97 ° C. After the temperature rise, an aqueous nitric acid solution was added to adjust the pH in the system to 5.0, and the aggregated particles were heated and fused by holding for 10 hours. Thereafter, the temperature in the system was lowered to 50 ° C., an aqueous sodium hydroxide solution was added to adjust the pH to 12.0, and the mixture was maintained for 10 minutes. After removing from the flask, sufficiently filtering with ion-exchanged water, washed with water, dispersed in ion-exchanged water so that the solid content is 10% by weight, added with nitric acid, and stirred at pH 3.0 for 10 minutes. Thereafter, the slurry obtained by sufficiently filtering and washing with water through ion-exchanged water again was freeze-dried to obtain a black toner (toner K1).

Silica (SiO ₂ ) particles having a primary particle average particle size of 40 nm and surface-hydrophobized with hexamethyldisilazane (hereinafter sometimes abbreviated as “HMDS”) as an external additive to the black colored particles, and metatitanic acid And 1 wt% of metatitanic acid compound fine particles having an average primary particle diameter of 20 nm, which is a reaction product of isobutyltrimethoxysilane, and mixed with a Henschel mixer to prepare a black toner.
The cumulative volume average particle diameter D ₅₀ and the volume average particle size distribution index GSDv of the toner thus prepared were measured with a laser diffraction particle size distribution measuring apparatus (LA-700, manufactured by Horiba, Ltd.). When the surface of the toner was observed with a scanning electron microscope (SEM) and the cross section was observed with a transmission electron microscope (TEM), the resin, pigment and other additives were fused as intended, and no holes or irregularities were observed. The dispersion state of the pigment was also good. Further, it was confirmed that the shape factor SF1 of the toner particles obtained from the shape observation by Luzex is a potato shape region of 125 to 135.

Example 7 Production of Cyan Toner (Toner C1)
And the black toner, except for changing the black pigment dispersion (K1) to the cyan pigment dispersion to obtain a cyan toner in the same manner, was measured and cumulative volume-average particle diameter D ₅₀ volume average particle size distribution index GSDv. Further, when the surface and cross-section of this toner were observed in the same manner as in Example 6, it was confirmed that the fused state of the toner, the dispersed state of the additive, the appearance were good, and the shape factor was in the potato shape region. did. An external additive was externally added to this toner in the same manner as in Example 6 to obtain a cyan toner.

Example 8 Production of Yellow Toner (Toner Y1)
A yellow toner was obtained in the same manner as above except that the black toner and the black pigment dispersion (K1 was changed to a yellow pigment dispersion), and the cumulative volume average particle diameter D ₅₀ and the volume average particle size distribution index GSDv were measured. When the surface and cross-section of this toner were observed in the same manner as in Example 6, it was confirmed that the fused state of the toner, the dispersed state of the additive and the appearance were good, and the shape factor was in the potato shape region. An external additive was externally added to this toner in the same manner as in Example 6 to obtain a yellow toner.

Example 9 Production of Magenta Toner (Toner M1)
A magenta toner was obtained in the same manner as above except that the black toner and the black pigment dispersion (K1 was changed to a magenta pigment dispersion), and the cumulative volume average particle diameter D ₅₀ and the volume average particle size distribution index GSDv were measured. When the surface and cross-section of this toner were observed in the same manner as in Example 6, it was confirmed that the fused state of the toner, the dispersed state of the additive and the appearance were good, and the shape factor was in the potato shape region. An external additive was externally added to the toner in the same manner as in Example 6 to obtain a magenta toner.

Example 10 Production of Toner Using Resin Particle Dispersion (2)
A cyan toner (C2) was obtained in the same manner as in Example 7 except that the resin particle dispersion (1) was changed to the resin particle dispersion (2). When the surface and cross-section of this toner were observed in the same manner as in Example 6, it was confirmed that the fused state of the toner, the dispersed state of the additive and the appearance were good, and the shape factor was in the potato shape region. An external additive was externally added to this toner in the same manner as in Example 6 to obtain a cyan toner.

(Example 11: Preparation of toner using resin particle dispersion (3))
A cyan toner (C3) was obtained in the same manner as in Example 7, except that the resin particle dispersion (1) was changed to the resin particle dispersion (3). When the surface and cross-section of this toner were observed in the same manner as in Example 6, it was confirmed that the fused state of the toner, the dispersed state of the additive and the appearance were good, and the shape factor was in the potato shape region. An external additive was externally added to this toner in the same manner as in Example 6 to obtain a cyan toner.

(Example 12: Preparation of toner using resin particle dispersion (4))
A cyan toner (C4) was obtained in the same manner as in Example 7, except that the resin particle dispersion (1) was changed to the resin particle dispersion (4). When the surface and cross-section of this toner were observed in the same manner as in Example 6, it was confirmed that the fused state of the toner, the dispersed state of the additive and the appearance were good, and the shape factor was in the potato shape region. An external additive was externally added to this toner in the same manner as in Example 6 to obtain a cyan toner.

(Example 13: Preparation of toner using resin particle dispersion (5))
A cyan toner (C5) was obtained in the same manner as in Example 7, except that the resin particle dispersion (1) was changed to the resin particle dispersion (5) and the blending amount of the resin particle dispersion was changed as follows. .
-Resin particle dispersion (5) 10 parts by weight-Resin particle dispersion A 150 parts by weight When the surface and cross-section of this toner were observed in the same manner as in Example 6, the fused state of the toner and the dispersed state of the additive were observed. The appearance was good and the shape factor was confirmed to be in the potato shape region. An external additive was externally added to this toner in the same manner as in Example 6 to obtain a cyan toner.

(Comparative Example 4: Preparation of toner using resin particle dispersion (6))
A black toner (K6) was obtained in the same manner as in Example 6 except that the resin particle dispersion (1) was changed to the resin particle dispersion (6). When the surface and cross-section of this toner were observed in the same manner as in Example 6, the fused state of the toner and the dispersed state of the additive were non-uniform, and the shape factor was in the potato shape region, but the variation was large. It was confirmed. An external additive was externally added to this toner in the same manner as in Example 6 to obtain a black toner.

(Comparative Example 5)
A cyan toner (C6) was obtained in the same manner as in Comparative Example 4, except that the pigment dispersion was changed to a cyan pigment dispersion. When the surface and cross-section of this toner were observed in the same manner as in Example 6, the fused state of the toner and the dispersed state of the additive were non-uniform, and the shape factor was in the potato shape region, but the variation was large. It was confirmed. An external additive was externally added to this toner in the same manner as in Example 6 to obtain a cyan toner.

(Comparative Example 6)
A yellow toner (Y6) was obtained in the same manner as in Comparative Example 4, except that the pigment dispersion was changed to a yellow pigment dispersion. When the surface and cross-section of this toner were observed in the same manner as in Example 6, the fused state of the toner and the dispersed state of the additive were non-uniform, and the shape factor was in the potato shape region, but the variation was large. It was confirmed. An external additive was externally added to this toner in the same manner as in Example 6 to obtain a yellow toner.

(Comparative Example 7)
A magenta toner (M6) was obtained in the same manner as in Comparative Example 4, except that the pigment dispersion was changed to a magenta pigment dispersion. When the surface and cross-section of this toner were observed in the same manner as in Example 6, the fused state of the toner and the dispersed state of the additive were non-uniform, and the shape factor was in the potato shape region, but the variation was large. It was confirmed. An external additive was externally added to the toner in the same manner as in Example 6 to obtain a magenta toner.

(Comparative Example 8: Preparation of toner using resin particle dispersion (7))
A cyan toner (C7) was obtained in the same manner as in Comparative Example 5 except that the resin particle dispersion (6) was changed to the resin particle dispersion (7). When the surface and cross-section of this toner were observed in the same manner as in Example 6, the fused state of the toner and the dispersed state of the additive were non-uniform, and the shape factor was in the potato shape region, but the variation was large. It was confirmed. An external additive was externally added to this toner in the same manner as in Example 6 to obtain a cyan toner.

(Comparative Example 9: Preparation of toner using resin particle dispersion (8))
A cyan toner (C8) was obtained in the same manner as in Comparative Example 5 except that the resin particle dispersion (6) was changed to the resin particle dispersion (8). When the surface and cross-section of this toner were observed in the same manner as in Example 6, it was confirmed that the fused state of the toner and the dispersed state of the additive were non-uniform, and the shape factor was in the potato shape region. An external additive was externally added to this toner in the same manner as in Example 6 to obtain a cyan toner.

<Creation of carrier>
A methanol solution containing 0.1 part by weight of γ-aminopropyltriethoxysilane was added to 100 parts by weight of Cu—Zn ferrite fine particles having a volume average particle diameter of 40 μm and coated with a kneader. The silane compound was completely cured by heating at 0 ° C. for 2 hours. To this particle, a perfluorooctylethyl methacrylate-methyl methacrylate copolymer (copolymerization ratio 40:60) dissolved in toluene was added, and perfluorooctylethyl methacrylate-methyl was added using a vacuum reduced pressure kneader. A resin-coated carrier was produced so that the coating amount of the methacrylate copolymer was 0.5% by weight.

<Production of developer>
4 parts by weight of each toner prepared as described above was mixed with 100 parts by weight of the obtained resin-coated carrier to prepare an electrostatic charge image developer. This was used as a developer as shown below.

  Further, variations in the minimum fixing temperature of the obtained developer and image formation were performed, and background fogging and transfer efficiency were evaluated. These evaluations were performed using a Docu Center Color 500CP modified machine manufactured by Fuji Xerox.

[Minimum fixing temperature variation]
The minimum fixing temperature is the minimum temperature of the heating roller where the toner particles form a continuous film layer, the minimum temperature at which the cold offset phenomenon does not occur, and the difference between the maximum and minimum values of the minimum fixing temperature measured 10 times is the minimum fixing temperature. Variation was assumed.
After creating an unfixed image with the copying machine, a fixing device comprising a heat roller having a surface layer of 30 mm in diameter formed of Teflon (registered trademark) and a pressure roller having a surface layer formed of silicone rubber was used to obtain 64 g / The operation of fixing the toner image with the sample toner transferred onto the m ² transfer paper at a linear velocity of 70 mm / second, a linear pressure of 0.8 kg / cm, and a nip width of 4.9 mm is performed at a set temperature of the heat roller of 80 to 240 ° C. Within a range of 5 ° C., the temperature is increased stepwise by 5 ° C. and repeated at each temperature. The formed fixed image is subjected to Kimwipe rubbing, and the minimum set temperature is applied to the fixed image showing sufficient rubbing resistance. The fixing temperature was used. The fixing device used here does not have a silicone oil supply mechanism.

[Background cover evaluation]
Under an environment where the developer was at a temperature of 22 ° C. and a humidity of 55%, Fuji Xerox J-coated paper was used as the final transfer material, and 100,000 images with an area ratio of 10% were output. The degree of toner scattering in the non-image portion of the solid image after outputting 100,000 sheets was visually observed. The specific evaluation criteria are as follows, and among these, ○ is an acceptable range.
○: No fogging is observed with the naked eye,
Δ: The fog is slightly observed with the naked eye,
X: The fog is remarkable.

[Transfer efficiency]
Using the amount of toner remaining on the photoconductor and the amount of toner on the paper when the toner was transferred from the photoconductor to the paper at 28 ° C. and 85% RH, the transfer efficiency was calculated by the following equation. It was evaluated.
Transfer efficiency (%) = toner amount on paper / (toner amount on paper + toner amount remaining on photoconductor) × 100

Claims (13)

Obtaining an oil phase containing at least one polycondensable monomer having an SP value of greater than 10.5;
Emulsifying and dispersing the oil phase in an aqueous medium; and
A method for producing a resin particle dispersion for an electrostatic charge image developing toner, comprising the step of polycondensation of an emulsion dispersion to obtain a resin particle dispersion,
A method for producing a resin particle dispersion for an electrostatic charge image developing toner, wherein an oil phase and / or an aqueous medium contains an alkyl alcohol having 8 to 30 carbon atoms as a co-surfactant.   At least one of the polycondensable monomers having an SP value of greater than 10.5 is a polycondensable monomer having an SP value of greater than 10.5 and an HLB represented by the following formula of 5.5 or more. 2. The production of a resin particle dispersion for electrostatic charge image developing toner according to claim 1, wherein the oil phase further comprises at least one polycondensable monomer having an HLB of 5.5 or more represented by the following formula. Method.
    HLB = 20Mw / M
(In the formula, M represents the molecular weight of the polycondensable monomer, and Mw represents the molecular weight of the hydrophilic portion of the polycondensable monomer.)   3. The median diameter of the resin particles in the resin particle dispersion is 0.05 to 2 μm, and the arithmetic standard deviation of the resin particles in the resin particle dispersion is 0.50 or less. A method for producing a resin particle dispersion for an electrostatic charge image developing toner.   The oil phase contains at least one radical polymerizable monomer, and
  The electrostatic charge according to any one of claims 1 to 3, wherein the step of polycondensing the emulsion dispersion to obtain a resin particle dispersion is a step of polycondensing and polymerizing the emulsion dispersion to obtain a resin particle dispersion. A method for producing a resin particle dispersion for image developing toner.   The step of polycondensation and polymerization of the emulsion dispersion to obtain a resin particle dispersion includes the step of polycondensation of the emulsion dispersion and the step of polymerizing the emulsion dispersion after the polycondensation to obtain a resin particle dispersion. The method for producing a resin particle dispersion for an electrostatic charge image developing toner according to claim 4.   The method for producing a resin particle dispersion for an electrostatic charge image developing toner according to claim 1, wherein the oil phase and / or the aqueous medium contains a polycondensation catalyst.   The method for producing a resin particle dispersion for an electrostatic charge image developing toner according to claim 6, wherein the polycondensation catalyst is a strong acid having a surface active effect.   8. The electrostatic charge image developing toner resin according to claim 7, wherein the strong acid having a surface active effect is a sulfonic acid having an alkyl group or an aralkyl group, a sulfuric acid ester having an alkyl group or an aralkyl group, or a salt compound thereof. A method for producing a particle dispersion. Resin particle dispersion for an electrostatic image developing toner produced by the method according to any one of claims 1-8. A step of aggregating the resin particles in a dispersion containing at least a resin particle dispersion to obtain aggregated particles; and
A method for producing an electrostatic charge image developing toner comprising a step of heating and aggregating the aggregated particles,
A method for producing an electrostatic image developing toner, wherein the resin particle dispersion is the resin particle dispersion for an electrostatic image developing toner according to claim 9 . An electrostatic charge image developing toner produced by the production method according to claim 10 . An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 11 and a carrier. A latent image forming step of forming an electrostatic latent image on the surface of the latent image holding member;
A developing step of developing the electrostatic latent image formed on the surface of the latent image holding body with a developer containing toner to form a toner image;
A transfer step of transferring the toner image formed on the surface of the latent image carrier to the surface of the transfer target;
A fixing step of thermally fixing the toner image transferred to the surface of the transfer material,
An image forming method using the electrostatic image developing toner according to claim 11 as the toner, or the electrostatic image developer according to claim 12 as the developer.