JP2008165124A - Resin particle dispersion liquid, method for manufacturing the same, electrostatic charge image developing toner and method for manufacturing the toner, electrostatic charge image developer, and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin particle dispersion liquid having resin particles stably emulsified and dispersed in an aqueous medium with low energy and giving excellent image quality and long-term image quality maintaining property at high temperature and high humidity when the dispersion liquid is used for an electrostatic charge image developing toner, to provide an electrostatic charge image developing toner, a method for manufacturing the toner and an electrostatic charge image developer showing excellent long-term image quality maintaining property at high temperature an high humidity and high image quality by using the above resin particle dispersion liquid, and to provide an image forming method using the above techniques. <P>SOLUTION: The resin particle dispersion liquid is characterized in that: resin particles containing polyester and a resin prepared by polymerizing an emulsifying diluent having an ethylenic unsaturated group and a hydrophilic group, are dispersed in an aqueous medium; and the absolute difference ¾(δpe-δe)¾ between the solubility parameter δpe of the polyester and the solubility parameter δe of the diluent is 0 to 5.0. The present invention also provides an electrostatic charge image developing toner, a method for manufacturing the toner and an electrostatic charge image developer by using the above resin particle dispersion liquid, and provides an image forming method using these techniques. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an electrostatic charge image developing toner used for developing an electrostatic latent image formed by an electrophotographic method or an electrostatic recording method with a developer, a manufacturing method thereof, and a resin that can be used as a raw material thereof The present invention relates to a particle dispersion and a method for producing the same. The present invention also relates to an electrostatic charge image developer using the electrostatic charge image developing toner and an image forming method.

  A method of visualizing image information through an electrostatic charge image such as electrophotography is currently used in various fields. In electrophotography, an electrostatic charge image is formed on a photoreceptor by charging and exposure processes, the electrostatic latent image is developed with a developer containing toner, and visualized through a transfer and fixing process. The developer used here includes a two-component developer composed of a toner and a carrier and a one-component developer using a magnetic toner or a non-magnetic toner alone. The toner is usually produced by using a thermoplastic resin as a pigment. In addition, a kneading and pulverizing method is used in which melt-kneading is performed together with a release agent such as a charge control agent and wax, and the mixture is cooled, finely pulverized, and further classified. In these toners, if necessary, inorganic and organic particles for improving fluidity and cleaning properties may be added to the toner particle surfaces.

  On the other hand, since the polyester resin has a rigid aromatic ring in the chain, it has flexibility as compared with the vinyl polymer, and the molecular weight when the mechanical strength is the same can be set low. Furthermore, polyester is often used as a binder resin for energy-saving toner because it has the advantage of being easier to design as a low-temperature fixing resin than a vinyl binder resin in terms of molecular chain entanglement, limiting molecular weight, and the like.

  In addition, when the toner is prepared by the emulsion polymerization aggregation method as described above, after the polycondensation type resin is polymerized, it is emulsified in an aqueous medium and aggregated with a pigment or wax in a latex state, and then fused. Can unite.

  In order to improve the water dispersibility of polyester, a monomer having a sulfonic acid alkali metal salt obtained by neutralizing sulfonic acid, carboxylic acid or the like with a base as a polyester monomer, or an alkali metal salt of carboxylic acid, etc. is used as a polyester monomer. There are methods in which a hydrophilic group is introduced into a polyester chain by polymerization, or a polyester having a sulfonic acid and a carboxylic acid is prepared, and then dispersed in an alkaline water to introduce a sulfonate and a carboxylate.

  More specifically, there are conventional techniques such as a solvent method, a phase inversion emulsification method, and a high-temperature emulsification method as means for preparing an aqueous polyester resin dispersion. There are hydrophilic polymers having a specific structure for producing a self-emulsifiable polyester, and salts thereof (sulfonic acid / alkali neutralized salt of SDSP (sodium isophthalate-5-sulfonate) as an example).

As a conventional technique as an emulsification method of polyester without using a solvent, for example, Patent Document 3 can be mentioned.
Patent Document 1 exemplifies alkyl glycidyl ester as a compound having one functional group for the purpose of reacting with a polyester monomer to impart emulsifying properties.
Patent Document 2 discloses, as a method for producing a colorant-containing polymer emulsion, an oil phase containing a polymerizable monomer, a colorant, and a polymerization initiator soluble in the monomer. After emulsifying in water in the presence of an agent to form an O / W emulsion of a colorant-containing monomer having a volume average particle size of oil droplets of 20 to 500 nm, the monomers in the oil droplets are A method of polymerizing in oil droplets is disclosed.

  Further, Patent Document 3 discloses a toner in which resin fine particles produced by miniemulsion polymerization are included in a layer other than the outermost layer, and the resin fine particles by multistage polymerization are salted out / fused.

JP 2000-191892 A JP 2001-290308 A JP 2002-49180 A

An object of the present invention is to provide a resin particle dispersion in which resin particles are stably emulsified and dispersed in an aqueous medium with low energy.
Another object of the present invention is to provide a resin particle dispersion excellent in image quality and long-term image quality maintainability under high temperature and high humidity when used in an electrostatic image developing toner.
Still another object of the present invention is to provide an electrostatic charge image developing toner having high image quality and excellent long-term image quality maintenance property under high temperature and high humidity by using the resin particle dispersion, and a method for producing the same. An image developer and an image forming method using the same are provided.

The above problems have been solved by means <1> to <6> shown below.
<1> Resin particles containing polyester and a resin obtained by polymerizing an emulsifying diluent having an ethylenically unsaturated group and a hydrophilic group are dispersed at least in an aqueous medium, and the solubility parameter δpe of the polyester and the emulsifying dilution Resin particle dispersion, wherein the absolute value | (δpe-δe) | of the difference from the solubility parameter δe of the agent is 0 or more and 5.0 or less,
<2> A step of obtaining a polyester by polycondensation of a polycondensable monomer, a step of dispersing the polyester and the emulsifying diluent in an aqueous medium without using a solvent, and the emulsifying property in an aqueous medium. The method for producing a resin particle dispersion according to <1>, including a step of polymerizing a diluent,
<3> including 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, wherein the resin particle dispersion is <1> or a method for producing an electrostatic charge image developing toner, which is a resin particle dispersion produced by the production method according to <2>.
<4> An electrostatic image developing toner produced by the production method according to <3> above,
<5> An electrostatic charge image developer comprising the electrostatic charge image developing toner according to <4> and a carrier,
<6> 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 to form a toner image. A development step, a transfer step of transferring a toner image formed on the surface of the latent image holding member to the surface of the transfer target, and a fixing step of thermally fixing the toner image transferred to the surface of the transfer target, An image forming method using the electrostatic charge image developing toner according to <4> above or the electrostatic charge image developer according to <5> above as the developer.

According to the present invention, a resin particle dispersion in which resin particles are stably emulsified and dispersed in an aqueous medium at low energy, and excellent in image quality and long-term image quality maintainability when used in an electrostatic charge image developing toner. A resin particle dispersion can be provided.
Further, according to the present invention, using the resin particle dispersion, an electrostatic charge image developing toner having excellent long-term image quality maintenance and high image quality, a method for producing the same, an electrostatic charge image developer, and the use thereof An image forming method can be provided.

  Hereinafter, the present invention will be described in detail.

(Resin particle dispersion)
The resin particle dispersion of the present invention comprises a resin particle comprising polyester and a resin obtained by polymerizing an emulsifying diluent having an ethylenically unsaturated group and a hydrophilic group (hereinafter also simply referred to as “emulsifying diluent”). Is at least dispersed in an aqueous medium, and the absolute value | (δpe−δe) | of the difference between the solubility parameter δpe of the polyester and the solubility parameter δe of the emulsifying diluent is from 0 to 5.0. Features.
The resin particle dispersion of the present invention can be suitably used as a resin particle dispersion for an electrostatic image developing toner used in the production of an electrostatic image developing toner.

Polyester resin having a particle size suitable as a resin particle dispersion without solvent, using the above-mentioned emulsifying diluent, which can effectively reduce the viscosity of low-temperature polycondensed polyester using the resin particle dispersion of the present invention The particle dispersion can be realized with low production energy and reduced environmental load.
In order to suitably emulsify the polyester having a low environmental load, the required performance of the emulsifying diluent includes (i) reducing the viscosity of the polyester at the emulsification temperature to an appropriate region, and (ii) the emulsion during polymerization. (Iii) Polymerization can be performed to avoid the release of volatile substances from the emulsion. The above three points are important.

  An emulsifiable diluent is a very important material when emulsifying polyester without solvent. In order to effectively reduce the viscosity at the emulsification temperature of the polyester, it is important that the emulsifiable diluent and the polyester have a good compatibility state as the first characteristic that the emulsifying diluent in the present invention is required. is there. Secondly, the emulsifying diluent must have an emulsion stabilizing effect and prevent Ostwald ripening. Thirdly, it is important that the emulsifying diluent has an ethylenically unsaturated group and is present in the resin particles as a polymer after polymerization.

In the resin particle dispersion of the present invention, the absolute value | (δpe−δe) | of the difference between the solubility parameter δpe of the polyester and the solubility parameter δe of the emulsifying diluent is 0 or more and 5.0 or less.
Here, as the method for calculating the solubility parameter of the polyester and the emulsifying diluent, the method that was proposed by Fedors et al., Which is the most general-purpose, widely spread, and recognized for its usefulness, that is, aggregation per unit functional group A method of determining a sum of energy Δei and a sum of molecular volumes Δvi and determining from the relaxation was adopted (RF Fedors, Polym. Eng. Sci., 14, 147 (1974)). Moreover, in the resin particle (polymer) in this invention, each weight fraction is calculated from the mixing | blending actual amount of the monomer component used for addition polymerization and polycondensation, and it was set as the weight average solubility parameter from a monomer. (Formula below).

In the above formula, δoverall: solubility parameter of copolymer (cal / cc) ^1/2 (25 ° C.), wi: weight fraction calculated from each monomer, Δei: unit functionality of each monomer component Sum of cohesive energy per group (cal / mol), Δvi: sum of molecular volume per unit functional group (cc / mol) (25 ° C.).

  However, in the calculation of the SP value in the above formula, for example, in the case of a monomer containing a vinyl group (vinyl monomer), the case where the main chain becomes a σ bond by radical reaction is assumed. In the case of a polycondensation polyester comprising a polyhydric acid and a polyhydric alcohol, the calculation was performed assuming resin chain formation. Further, the calculated values are calculated with the number of atoms forming the main chain skeleton in each monomer being taken into account, and in the case of an aromatic ring, the number of atoms is set to 6.

The absolute value | (δpe-δe) | of the difference between the solubility parameter (δpe) of the polyester and the solubility parameter (δe) of the emulsifying diluent is 0 or more and 5.0 or less, and 0.01 or more and 5.0 Or less, more preferably from 0.01 to 4.0, and even more preferably from 0.01 to 3.5. Thereby, the compatibility between the polyester and the emulsifying diluent is improved, and the viscosity of the polyester at the emulsification temperature can be effectively reduced. As a result, sufficient charging characteristics, powder resistance, powder fluidity, and particle size distribution characteristics as a toner can be obtained.
When the absolute value | (δpe-δe) | of the difference between the solubility parameter (δpe) of the polyester and the solubility parameter (δe) of the emulsifying diluent exceeds 5.0, emulsification to a particle size suitable for the resin particle dispersion Dispersion becomes difficult.

The emulsifying diluent used in the resin particle dispersion of the present invention has at least one ethylenically unsaturated group. The emulsifying diluent having an ethylenically unsaturated group is a compound capable of addition polymerization, preferably radical polymerization.
The ethylenically unsaturated group is preferably an acrylate group, a methacrylate group, a vinyl ether group, or an ethylenically unsaturated group conjugated with an aromatic ring, and an ethylene conjugated with an acrylate group, a methacrylate group, or an aromatic ring. It is more preferable that it is a sex unsaturated group.
The number of ethylenically unsaturated groups contained in the emulsifying diluent may be one or more, but preferably one.

The emulsifying diluent used for the resin particle dispersion of the present invention has at least one hydrophilic group.
The hydrophilic group is a group having hydrophilicity, a hydroxy group, a phosphate group (—P═O (OR) ₂ , —P═O (OR) (OH), —P═O (OH) ₂ ), It is preferably a carboxy group, a sulfate group, a sulfate ester group, a sulfo group, an amino group, an ammonium group, an oxyethylene group, or an amide group, more preferably a hydroxy group, a phosphate group, or a carboxyl group, More preferably, it is a group or a phosphate group. In addition, although the phosphate group in this invention may have a phosphate ester part, it is preferable to have at least 1 -OH on a phosphorus atom. The R may be any organic group, but is preferably an alkyl group, a cycloalkyl group, an aryl group, or a group in which two or more of these are combined, has 2 to 20 carbon atoms, and An alkyl group, a cycloalkyl group, an aryl group, or a group obtained by combining two or more of these is more preferable.
Further, the hydroxy group (particularly phenolic hydroxy group), phosphoric acid group, carboxyl group, sulfuric acid group, sulfo group and the like in the emulsifying diluent may form a salt, alkali metal salt, alkaline earth Examples thereof include metal salts and ammonium salts.

In addition, in order to control the solubility parameter of the emulsifying diluent, from the viewpoint of environmental contamination due to volatilization of the diluent itself from the polyester emulsion, and also from the viewpoint of stabilizing the emulsion diameter during polymerization, the emulsifying dilution As the agent, a monomer having a polymerizable ethylenically unsaturated group and having a hydroxy group or a phosphate group is preferable.
As a monomer having an ethylenically unsaturated group and having a hydroxy group or a phosphate group, a compound having an acryloxy group and a hydroxy group, a compound having a methacryloxy group and a hydroxy group, an acryloxy group and a phosphate group More preferred are compounds, compounds having a methacryloxy group and a phosphate group, or hydroxystyrenes, and particularly preferred are compounds represented by the following formulas (1) to (3).

（式（１）中、Ｒ¹は水素原子又はメチル基を表し、Ｒ²は炭素数２〜２０の直鎖アルキレン基、脂環基又は芳香環基を含む有機基を表す。）

(In formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an organic group containing a linear alkylene group having 2 to 20 carbon atoms, an alicyclic group or an aromatic ring group.)

（式（２）中、Ｒ³は水素原子又はメチル基を表し、また、ヒドロキシ基は芳香環上の任意の位置に結合することができる。なお、式（２）におけるフェノール性ヒドロキシル基は、アルカリ金属塩、アルカリ土類金属塩、アンモニウム塩等の塩を形成していてもよい。）

(In the formula (2), R ³ represents a hydrogen atom or a methyl group, and the hydroxy group can be bonded to any position on the aromatic ring. The phenolic hydroxyl group in the formula (2) Salts such as alkali metal salts, alkaline earth metal salts, and ammonium salts may be formed.)

（式（３）中、Ｒ⁴は水素原子又はメチル基を表し、Ｒ⁵は炭素数２〜２０の直鎖アルキレン基、脂環基又は芳香環基を含む有機基を表し、Ｒ⁶は水素原子、メチル基、又は、炭素数２〜２０の直鎖アルキル基、脂環基若しくは芳香環基を含む有機基を表す。なお、式（３）におけるリン酸基は、アルカリ金属塩、アルカリ土類金属塩、アンモニウム塩等の塩を形成していてもよい。）

(In formula (3), R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents an organic group containing a linear alkylene group having 2 to 20 carbon atoms, an alicyclic group or an aromatic ring group, and R ⁶ represents hydrogen. An atom, a methyl group, or an organic group containing a linear alkyl group having 2 to 20 carbon atoms, an alicyclic group or an aromatic ring group, wherein the phosphoric acid group in the formula (3) is an alkali metal salt, alkaline earth A salt such as a metal salt or an ammonium salt may be formed.)

Regarding the stabilization mechanism of the emulsion particle size during the polymerization of the emulsion containing an emulsifying diluent having an ethylenically unsaturated group, it is considered that this is an effect of preventing Ostwald ripening by the emulsifying diluent.
Ostwald ripening is understood as the process by which smaller particles gradually dissolve in a polydisperse system and grow into larger particles.
When the emulsifying diluent that can be used in the present invention is any one of the compounds represented by the above formulas (1) to (3), it has an appropriate molecular weight with an appropriate molecular chain, and also has a hydroxy group or phosphorus Since it has an acid group, it is preferable because it has a structure in which moderate hydrophilicity / hydrophobicity is balanced. This makes it possible to stabilize the emulsion without increasing the viscosity of the dispersion. Therefore, the resin particle dispersion of the present invention using the compounds represented by the formulas (1) to (3) has a sharp particle size distribution and can stabilize the emulsification / dispersion / polymerization state. preferable.

The emulsifiable diluent preferably has a structure having a hydrocarbon chain that is compatible with the polyester droplets and has an anchoring effect. Preferred examples of the hydrocarbon chain having an anchoring effect include an alkyl group having 3 to 10 carbon atoms and an alkylene group having 3 to 10 carbon atoms.
The emulsifying diluent that can be used in the present invention may be added to the polyester immediately before emulsification, or may be added during the polycondensation. When added to and mixed with the polyester, the melt viscosity can be effectively reduced, and emulsification and dispersion proceed effectively.
Furthermore, the water-dispersibility of the polyester and the stability of the emulsion droplets are enhanced by the hydroxy group and the phosphate group of the emulsifying diluent. Compared with the emulsification dispersion in which only the carboxyl group at the end of the polyester is neutralized without using an emulsifying diluent, the method for producing a resin particle dispersion of the present invention enables better emulsification dispersion. Such an emulsifying effect is based on a mechanism that the emulsifying diluent is easily orientated effectively on the surface of the resin particles and contributes to the stabilization of the dispersion.

  In the case of using a base as a neutralizing agent for the purpose of solubilizing polyester, this mechanism is preferable because the amount of the neutralizing agent required for water dispersion can be minimized. Furthermore, it is possible to suppress uneven composition due to the distribution of the neutralization rate generated between the latexes. As a result, a decrease in chargeability under high temperature and high humidity can be avoided. To that end, the emulsifying diluent has a suitable viscosity.

Specifically, the emulsifiable diluent that can be used in the present invention is:
As the compound represented by the formula (1),
2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3-chloropropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, (4-hydroxymethylcyclohexyl) methyl acrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, 2-acryloyloxyethyl- 2-hydroxypropyl phthalate, cyclohexanedimethanol monoacrylate, cyclohexanedimethanol monomethacrylate DOO, 3-hydroxy-1-adamantyl acrylate, 3-hydroxy-1-adamantyl methacrylate,
As the compound represented by the formula (2),
2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, and salts thereof,
As the compound represented by the formula (3),
Preferred examples include methacryloyloxyethylphenyl phosphate, methacryloyloxypropylphenyl phosphate, and salts thereof.

The emulsifying diluent that can be used in the present invention is particularly preferably 4-hydroxybutyl acrylate, cyclohexanedimethanol monomethacrylate, or methacryloyloxyethylphenyl phosphate or a salt thereof, and cyclohexanedimethanol monomethacrylate. Most preferably it is.
Moreover, in this invention, an emulsifying diluent may be used individually by 1 type, and may use 2 or more types together.

  There are no particular restrictions on the preferred amount of the emulsifying diluent, but it is preferably from 0.1% by weight to 30% by weight, more preferably from 1% by weight to 20% by weight, based on the polyester. . When the addition amount of the emulsifying diluent is 30% by weight or less, the glass transition point of the polyester is not lowered, and the storage property of the toner is preferable. Moreover, it is preferable for it to be 0.1% by weight or more because the effect of reducing the melt viscosity can be sufficiently exerted and emulsification and dispersion are easy.

  These emulsifying diluents can employ known polymerization methods such as a method using a polymerization initiator, a self-polymerization method using heat, and a polymerization method using ultraviolet irradiation. In this case, as a method using an initiator, the polymerization initiator includes oil-soluble and water-soluble initiators, but either initiator can be used. Further, an oil phase polymerization initiator and an aqueous phase polymerization initiator can be used in combination.

  Next, the polymerization of these emulsifying diluents will be described in more detail. When the emulsifying diluent is polymerized, a polymerization reaction between the monomer and a prepolymer prepared in advance may be included. Furthermore, the homopolymer of the said monomer, the copolymer which combined 2 or more types of monomers, those mixtures, a graft polymer, etc. can be included.

Moreover, it is preferable to use a radical polymerizable monomer together with the polycondensable monomer. Particularly suitable as a toner is a resin obtained by mixing and polymerizing an emulsifying diluent having an ethylenically unsaturated group together with a polycondensable monomer.
In that case, it is also possible to mix an emulsifying diluent in the polycondensable monomer in advance, and finally form hybrid particles of these polymers through polycondensation and polymerization. Further, a low-molecular-weight polycondensable polymer is formed in advance by a bulk polymerization method or a solution polymerization method, mixed with an emulsifying diluent, then emulsified or dispersed in an aqueous medium, and further subjected to polycondensation reaction and radical polymerization. It is also possible to reach the final molecular weight. In the polycondensation in the aqueous medium in the present invention, the acid value of the polymerized polymer affects the final molecular weight or the polymerization rate. In order to adjust the polymerization rate and the high molecular weight more easily, the acid value of the final polymer is adjusted as described above, and a radically polymerizable vinyl monomer having a low solubility in water is used during polycondensation. In the aqueous medium pair, after adjusting the low molecular weight (or medium molecular weight) to a level that does not hinder the emulsification and dispersion of the polyester monomer, and adjusting the acid value to a lower state. It is preferable in production to use a method for obtaining a final high molecular weight body, or a combination of both methods.

  Here, the step of polymerizing the monomer means a step of polymerizing the monomer, and the monomer is preliminarily used with a small amount of a surfactant using mechanical shearing force, ultrasonic waves, or the like. Then, after being dispersed in an aqueous medium in which a polymer stabilizer or the like is dissolved, heat polymerization is performed. The polymerization method in this case is not limited as long as it is a particle polymerization method in an aqueous medium, and is a suspension polymerization method, a dissolution suspension method, a miniemulsion method, a microemulsion method, a microemulsion method, a multistage swelling method, or a seed. It is possible to use a heterogeneous polymerization form in a normal aqueous medium such as an emulsion polymerization method including polymerization. Among these polymerization methods, a microemulsion method, a miniemulsion polymerization method, and a microemulsion method are preferably used from the viewpoints of obtaining a uniform particle size, uniform particle size distribution, and obtaining uniform particles. Most preferred is a miniemulsion polymerization method.

  In the polymerization step, a plurality of polymerizations can be performed simultaneously or sequentially. For example, as a monomer component for polymerization, a radical polymerizable monomer can be mixed with a polycondensation monomer and radical polymerization can be performed simultaneously with or separately from the polycondensation reaction. At this time, it is possible to mix the polycondensation catalyst in the monomer together with the monomer component, and when performing radical polymerization simultaneously or sequentially, the polycondensation is performed in the monomer mixture or aqueous medium. It can be added before or during polycondensation and after polycondensation.

  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-butylpero) C) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,4-bis (t-butylperoxycarbonyl) cyclohexane, 2,2-bis (t-butyl) Peroxy) 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] and the like.

  Furthermore, in this invention, it is also possible to use auxiliary agents, such as a usual radically polymerizable monomer and an olefin monomer, together with an emulsifying diluent. Preferred examples of the radical polymerizable monomer include vinyl monomers.

  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, halogenated vinyl compounds such as vinyl chloride, vinyl bromide, vinylidene chloride,

  N-substituted unsaturated amides such as N-methylol acrylamide, N-ethylol acrylamide, N-propanol acrylamide, N-methylol maleamic acid, N-methylol maleamic acid ester, N-methylol maleimide, N-ethylol maleimide, etc. , Conjugated dienes such as butadiene and isoprene, polyfunctional vinyl compounds such as divinylbenzene, divinylnaphthalene and divinylcyclohexane, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tetra Methylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate, trimethylolpropane di ( Acrylate), trimethylolpropane tri (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol 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 (meth) Polyfunctional 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 polymers obtained by polymerizing these radically polymerizable monomers, the resin for toners preferably has a glass transition temperature of 40 ° C. or higher and 100 ° C. or lower from the viewpoint of fixability and image forming properties. . Moreover, as a resin suitably used in the above radical polymerizable monomers, vinyl aromatics and carboxylic acid esters are used.

  The weight average molecular weight Mw of the resin obtained by polymerizing the emulsifying diluent is preferably in the range of 500 to 100,000, more preferably 1,000 to 60,000, and more preferably 3,000 to 30, More preferably, it is 000 or less. When the weight average molecular weight of the resin obtained by polymerizing the emulsifying diluent is 500 or more, the affinity with water is moderate, the hydrophobicity is sufficient, and the Ostwald ripening inhibiting effect of the droplets is obtained, and the aqueous medium It is possible to maintain the stability of the oil phase droplets that are produced. As a result, the resin particle (latex) does not have a large particle size, and a resin particle having a narrow particle size distribution is obtained. Further, polymerization proceeds sufficiently, a resin having a narrow molecular weight distribution and a large molecular weight is obtained. On the other hand, when the weight average molecular weight is 100,000 or less, the hydrophobicity and the melting point of the resin are moderate, the uniform dispersion in the droplets is easy, the polymerization proceeds uniformly, and the resin The shape of the toner produced using the toner becomes uniform, and an image created using the toner has excellent fixability.

<Polycondensable monomer>
Next, the polycondensable monomer will be described.
The polycondensable monomer that can be used in the present invention is a polyester-generating polycondensable monomer, and examples thereof include polyvalent carboxylic acids, polyols, hydroxycarboxylic acids, and mixtures thereof. In particular, the polycondensable monomer is preferably a polyvalent carboxylic acid, a polyol, and further an ester compound (oligomer and / or prepolymer) thereof. Good thing to get. In this case, the polyester resin to be polymerized may take any form such as amorphous (amorphous) polyester (non-crystalline polyester), crystalline polyester, or a mixed form thereof.

The polyvalent carboxylic acid is a compound containing two or more carboxyl groups in one molecule. Among these, dicarboxylic acid is a compound containing two carboxyl groups in one molecule. For example, oxalic acid, succinic acid, maleic acid, adipic acid, β-methyladipic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid , Decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, citraconic acid, diglycolic acid, cyclohexane-3,5-diene-1,2-carboxylic acid, malic acid, citric acid, hexahydroterephthalic acid, malon Acid, pimelic acid, tartaric acid, mucoic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediacetic acid, o- Phenylenediacetic acid, diphenylacetic acid, diphenyl-p, p'-dical Phosphate, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracene dicarboxylic acid, and cyclohexane dicarboxylic acid. Examples of the polyvalent carboxylic acid other than dicarboxylic acid include trimellitic acid, trimesic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, pyrenetetracarboxylic acid, and the like. Examples include esters. Furthermore, acid chlorides and acid anhydrides are not limited to this.
These may be used alone or in combination of two or more.
The lower ester means that the alkoxy part of the ester has 1 to 8 carbon atoms. Specific examples include methyl ester, ethyl ester, n-propyl ester, isopropyl ester, n-butyl ester, and isobutyl ester.

A polyol 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. Specifically, for example, the diol includes ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butane. Diol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,14-eicosandecanediol, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene Glycol, polypropylene glycol, poly Tetramethylene ether glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, bisphenol A, bisphenol F, bisphenol S, alkylene oxides of the above bisphenols (ethylene oxide, propylene oxide, butylene oxide, etc.) ) Additives. Among these, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use.
In order to facilitate water dispersibility, examples of the multi-active compound having an acidic group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid and the like. Is exemplified.

Examples of trihydric or higher alcohols include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, hexamethylolmelamine, hexaethylolmelamine, tetramethylolbenzoguanamine, tetraethylolbenzoguanamine, sorbitol, trisphenol PA, phenol novolac, Examples thereof include cresol novolak and alkylene oxide adducts of the above trivalent or higher polyphenols. These may be used individually by 1 type and may use 2 or more types together.
In addition, an amorphous resin or a crystalline resin can be easily obtained by combining these polycondensable monomers.

  For example, polyvalent carboxylic acids used to obtain crystalline polyesters include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, maleic acid, fumaric acid. Acid, citraconic acid, itaconic acid, glutamic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid, isododecyl succinic acid, isododecenyl succinic acid, n-octyl succinic acid, n-octenyl succinic acid, anhydrides thereof Alternatively, these lower esters and the like can be mentioned. Furthermore, the acid chloride is not limited to this.

  Furthermore, for example, the polyol used to obtain the crystalline polyester includes ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, , 4-butenediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, poly Mention may also be made of tetramethylene glycol, bisphenol A, bisphenol Z, hydrogenated bisphenol A and the like.

  Furthermore, for example, polybasic carboxylic acids used to obtain non-crystalline polyester include dibasic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, and mesaconic acid. Aromatic dicarboxylic acids such as acids are raised, and these lower esters are not limited to this. Examples of the trivalent or higher carboxylic acids include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 1,3,5-benzenetricarboxylic acid (trimesic acid), 1,2,4-naphthalenetricarboxylic acid, And anhydrides thereof, sodium 2-sulfoterephthalate, sodium 5-sulfoisophthalate, sodium sulfosuccinate and lower esters thereof, but are not limited thereto.

  Examples of such crystalline polyester include polyesters obtained by reacting 1,9-nonanediol and 1,10-decanedicarboxylic acid, or cyclohexanediol and adipic acid, 1,6-hexanediol and sebacic acid, and the like. Polyester obtained by reacting, polyester obtained by reacting ethylene glycol and succinic acid, polyester obtained by reacting ethylene glycol and sebacic acid, reacting 1,4-butanediol and succinic acid Mention may be made of the polyester obtained. Among these, polyesters obtained by reacting 1,9-nonanediol with 1,10-decanedicarboxylic acid and 1,6-hexanediol with sebacic acid are more preferable, but not limited thereto.

  Here, the crystalline melting point Tm in the case of a crystalline resin is preferably 50 ° C. or higher and 120 ° C. or lower, and more preferably 55 ° C. or higher and 90 ° C. or lower. When the Tm is 50 ° C. or higher, the cohesive strength of the binder resin itself at a high temperature range is good, so that it is excellent in releasability and hot offset at the time of fixing, and is sufficient when it is 120 ° C. or lower. It is preferable that the minimum fixing temperature does not rise easily.

Here, the melting point of the crystalline resin was measured using a differential scanning calorimeter (DSC) according to JIS K-7121: 87 when the measurement was performed 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 input compensated differential scanning calorimetry shown. A crystalline resin may show a plurality of melting peaks, but in the present invention, the maximum peak is regarded as the melting point.
Moreover, the glass transition point of an amorphous resin means the value measured by the method (DSC method) prescribed | regulated to ASTMD3418-82.

  On the other hand, when the polycondensable resin particles are non-crystalline, the glass transition point Tg is preferably 50 ° C. or higher and 80 ° C. or lower, and more preferably 50 ° C. or higher and 65 ° C. or lower. When Tg is 50 ° C. or higher, the cohesive strength of the binder resin itself in a high temperature range is good, so that it is excellent in hot offset at the time of fixing, and when it is 80 ° C. or lower, sufficient melting is obtained. It is preferable that the minimum fixing temperature does not easily rise.

  Preferred examples of the polyhydric alcohol used for obtaining the non-crystalline polyester include aliphatic, alicyclic and aromatic alcohols such as 1,5-pentanediol, 1,6. -Hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, bisphenol Z, hydrogenated bisphenol A and the like can also be mentioned. However, this is not the case.

  Examples of the hydroxycarboxylic acid include hydroxyheptanoic acid, hydroxyoctanoic acid, hydroxydecanoic acid, and hydroxyundecanoic acid.

  The weight average molecular weight of the polycondensation resin obtained by polycondensation of the polycondensable monomer is preferably 1,500 or more and 40,000 or less, and preferably 3,000 or more and 30,000 or less. More preferred. When the weight average molecular weight is 1,500 or more, the cohesive force of the binder resin is good and the hot offset property is excellent, and when it is 40,000 or less, the hot offset property is excellent and the minimum fixing temperature is excellent. Value is preferred. Further, it may be partially branched or cross-linked by selecting the carboxylic acid valence or alcohol valence of the monomer.

  Further, the acid value of the obtained polyester is preferably 1 mg · KOH / g or more and 50 mg · KOH / g or less. The first reason is that control of the particle size and distribution of the toner in the aqueous medium is indispensable for practical use as a high-quality toner, and the acid value is 1 mg · KOH / g or more. In the granulation step, sufficient particle size and distribution can be achieved, and when used in toner, sufficient chargeability can be obtained. Further, when the acid value of the polyester to be polycondensed is 50 mg · KOH / g or less, a sufficient molecular weight can be obtained for obtaining image quality strength as a toner during polycondensation, and the toner is charged under high humidity. The reliability of the image is small and the image reliability is excellent.

The median diameter (center diameter) of the resin particles in the resin particle dispersion of the present invention is preferably 0.05 μm or more and 2.0 μm or less, more preferably 0.1 μm or more and 1.5 μm or less. More preferably, it is 1 μm or more and 1.0 μm or less. When the median diameter is in the above range, the dispersion state of the resin particles in the medium in the aqueous medium is stabilized as described above. Accordingly, when the toner is produced, if the median diameter is 0.05 μm or more, the agglomeration property at the time of particle formation is good, free resin particles are hardly generated, and the viscosity of the system is not easily increased. The control of the particle size is easy and preferable. On the other hand, when the median diameter is 2.0 μm or less, coarse powder is hardly generated and the particle size distribution is good and the release agent such as wax is difficult to be released. preferable.
The median diameter of the resin particles can be measured, for example, with a laser diffraction particle size distribution measuring device (LA-920, manufactured by Horiba, Ltd.).

In addition, the resin particle dispersion of the present invention is suitable not only for the median diameter of the resin particles but also for generation of ultrafine powder or ultracoarse powder, and the median diameter is 0.03 μm or less or 5.0 μm or more. The ratio of the condensed resin particles is preferably 10% or less, more preferably 5% or less. This ratio can be obtained, for example, by plotting the relationship between the particle diameter and the frequency integration in the measurement result in LA-920 and obtaining from the frequency integration amount of 0.03 μm or less or 5.0 μm or more.
The weight average molecular weight of the resin particles in the resin particle dispersion is preferably 1,500 or more and 40,000 or less, and more preferably 10,000 or more and 40,000 or less.

In the present invention, the dispersion medium of the resin particle dispersion 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.

(Method for producing resin particle dispersion)
The resin particle dispersion of the present invention can be produced by a known method, but is preferably produced by the following method for producing a resin particle dispersion.
The method for producing a resin particle dispersion of the present invention includes a step of polycondensing a polycondensable monomer to obtain a polyester (hereinafter also referred to as “polycondensation step”), the polyester, an ethylenically unsaturated group, and a hydrophilic group. A step of dispersing an emulsifiable diluent having water in an aqueous medium without using a solvent (hereinafter also referred to as “dispersing step”), and an emulsifying property having an ethylenically unsaturated group and a hydrophilic group in the aqueous medium. A step of polymerizing the diluent (hereinafter also referred to as “polymerization step”).

<Polycondensation process>
The method for producing a resin particle dispersion of the present invention preferably includes a step (polycondensation step) of obtaining a polyester by polycondensation of a polycondensable monomer.

The reaction temperature of the polycondensation reaction in the polycondensation step is preferably reacted at a temperature lower than the conventional reaction temperature. The reaction temperature is preferably 70 ° C or higher and 150 ° C or lower, more preferably 70 ° C or higher and 140 ° C or lower, and further preferably 80 ° C or higher and lower than 140 ° C. It is preferable that the reaction temperature is 70 ° C. or higher because the solubility of the monomer and the catalyst activity are not lowered, the reactivity is sufficiently high, and the molecular weight elongation is not suppressed. Moreover, it is preferable for the reaction temperature to be 150 ° C. or lower because the purpose of the low energy production method can be achieved. Furthermore, it is preferable because coloring of the resin due to high temperature, decomposition of the produced polyester, and the like hardly occur.
The reaction time during the polycondensation also depends on the reaction temperature, but is preferably 0.5 hours or longer and 72 hours or shorter, more preferably 1 hour or longer and 48 hours or shorter.

  The polycondensation reaction in the polycondensation step of the present invention can be carried out by general polycondensation methods such as underwater polymerization such as bulk polymerization, emulsion polymerization and suspension polymerization, solution polymerization and interfacial polymerization. Underwater polymerization is used. Although the reaction is possible under atmospheric pressure, general conditions such as reduced pressure and nitrogen flow can be widely used for the purpose of increasing the molecular weight of the polyester.

In the polycondensation step in the present invention, a polycondensation catalyst is preferably used because the reaction rate of the polycondensation reaction can be increased.
In the polycondensation step, a known polycondensation catalyst can be blended in the polycondensable monomer in advance if necessary. In order to polycondense the polycondensable monomer at a low temperature of preferably 150 ° C. or lower, more preferably 100 ° C. or lower, it is preferable to use a polycondensation catalyst. As the polycondensation catalyst having catalytic activity at a low temperature, an acid catalyst, a rare earth-containing catalyst, a hydrolase, or the like can also be used.

As the acid catalyst, those showing acidity such as Bronsted acid are preferable. Specific examples include sulfonic acids such as toluenesulfonic acid, benzenesulfonic acid, camphor sulfonic acid, and Na salts thereof. It is done.
Furthermore, an acid having a surface active effect may be used. The acid having a surface-active effect has a chemical structure composed of a hydrophobic group and a hydrophilic group, and has an acid structure in which at least a part of the hydrophilic group is composed of protons.
Examples of the acid having a surface active effect include alkyl benzene sulfonic acid such as dodecylbenzene sulfonic acid, isopropyl benzene sulfonic acid, and camphor sulfonic acid, alkyl sulfonic acid, alkyl disulfonic acid, alkyl phenol sulfonic acid, alkyl naphthalene sulfonic acid, alkyl Higher fatty acid sulfates such as tetralin sulfonic acid, alkylallyl sulfonic acid, petroleum sulfonic acid, alkyl benzimidazole sulfonic acid, higher alcohol ether sulfonic acid, alkyl diphenyl sulfonic acid, monobutyl phenyl phenol sulfate, dibutyl phenyl phenol sulfate dodecyl sulfate, higher Alcohol sulfate, higher alcohol ether sulfate, higher fatty acid amide alkylol sulfate, higher fatty acid amide alkyl Sulfuric acid ester, naphthenyl alcohol sulfuric acid, sulfated fat, sulfosuccinate ester, various fatty acids, sulfonated higher fatty acid, higher alkyl phosphate ester, resin acid, resin acid alcohol sulfuric acid, naphthenic acid, paratoluenesulfonic acid, and these Examples include all salt compounds, and a plurality of them may be combined as necessary.

As the rare earth-containing catalyst, scandium (Sc), yttrium (Y), as the lanthanoid element, lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), 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.
As the rare earth-containing catalyst, those having a triflate structure such as scandium triflate, yttrium triflate, and lanthanoid triflate are preferable. The lanthanoid triflates are described in detail in Journal of Synthetic Organic Chemistry, Vol. 53, No. 5, p44-54. An example of the triflate is X (OSO ₂ CF ₃ ) _{3 in} the structural formula. Here, X is a rare earth element, and among these, X is more preferably scandium (Sc), yttrium (Y), ytterbium (Yb), samarium (Sm), or the like.

  The hydrolase is not particularly limited as long as it catalyzes an ester synthesis reaction. Examples of the hydrolase include EC (enzyme number) 3.1 group (Maruo and Lipoprotein lipase) such as carboxyesterase, lipase, phospholipase, acetylesterase, pectinesterase, cholesterol esterase, tannase, monoacylglycerol lipase, lactonase and lipoprotein lipase. Such as hydrolase epoxide hydrase classified in EC 3.2 group that acts on glycosyl compounds such as esterase, glucosidase, galactosidase, glucuronidase, xylosidase etc. classified in “Enzyme Handbook” supervised by Tamiya (1982) It is classified into EC3.4 group which acts on peptide bonds such as hydrolase, aminopeptidase, chymotrypsin, trypsin, plasmin, subtilisin etc. classified into EC3.3 group Water degrading enzymes, hydrolases such classified into EC3.7 group such as furo retinoic hydrolase can be exemplified.

  Among these esterases, the enzyme that hydrolyzes glycerol esters and liberates fatty acids is called lipase, but lipase has high stability in organic solvents, catalyzes ester synthesis reaction in high yield, and can be obtained at a low price. There are advantages such as. Therefore, also in the manufacturing method of polyester of this invention, it is preferable to use a lipase from the surface of a yield or cost.

  Lipases of various origins can be used, but preferred are Pseudomonas genus, Alcaligenes genus, Achromobacter genus, Candida genus, Aspergillus genus, 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, and steapsin. Among these, it is preferable to use lipases derived from microorganisms of the genus Pseudomonas, Candida, and Aspergillus.

  These polycondensation catalysts may be used alone or in combination. Further, these catalysts can be recovered and regenerated if necessary.

<Dispersing process>
The method for producing a resin particle dispersion of the present invention includes a step of dispersing the polyester and an emulsifying diluent having an ethylenically unsaturated group and a hydrophilic group in an aqueous medium without using a solvent (dispersing step). Is preferred.
As a method of dispersing the emulsifying diluent and the polyester in an aqueous medium, a known method can be used, but a dispersion method without using a solvent is preferable. In the present invention, by using the emulsifying diluent, the polyester can be emulsified and dispersed in an aqueous medium without using a solvent. Moreover, environmental load can be reduced by not using a solvent at the time of dispersion | distribution.

  Examples of the solvent include known solvents used as a solvent during emulsification dispersion. Specifically, hydrocarbon solvents such as toluene, xylene and mesitylene, chlorobenzene, bromobenzene, iodobenzene, dichlorobenzene, 1,1 , 2,2-tetrachloroethane, halogen solvents such as p-chlorotoluene, ketone solvents such as 3-hexanone, acetophenone, benzophenone, dibutyl ether, anisole, phenetole, o-dimethoxybenzene, p-dimethoxybenzene, 3- Ether solvents such as methoxytoluene, dibenzyl ether, benzylphenyl ether, methoxynaphthalene, tetrahydrofuran, thioether solvents such as phenyl sulfide, thioanisole, ethyl acetate, butyl acetate, pentyl acetate, methyl benzoate, phthalate Ester solvents such as methyl acid, ethyl phthalate, cellosolve acetate, diphenyl ether, or alkyl-substituted diphenyl ethers such as 4-methylphenyl ether, 3-methylphenyl ether, 3-phenoxytoluene, or 4-bromophenyl ether, 4 -Halogen-substituted diphenyl ether such as chlorophenyl ether, 4-bromodiphenyl ether, 4-methyl-4'-bromodiphenyl ether, or 4-methoxydiphenyl ether, 4-methoxyphenyl ether, 3-methoxyphenyl ether, 4-methyl-4'- Examples include alkoxy-substituted diphenyl ethers such as methoxydiphenyl ether or diphenyl ether solvents such as cyclic diphenyl ethers such as dibenzofuran and xanthene, and mixtures thereof. Kill.

  In the dispersion step in the present invention, the polyester and the emulsifying diluent may be mixed in an aqueous medium or mixed before being added to the aqueous medium. The polyester and the emulsifiable diluent may be mixed using the emulsifiable diluent and the polycondensable monomer from the beginning in the polycondensation step, and the polycondensable monomer may be polycondensed. Further, an emulsifying diluent may be added and mixed during the polycondensation. Among these, it is preferable to mix the polyester and the emulsifying diluent after preparing the polyester and before adding it to the aqueous medium.

A means for mixing the polyester and the emulsifiable diluent or a means for dispersing the polyester and the emulsifiable diluent in the aqueous medium is not particularly limited, and known devices and methods can be used.
In the dispersion step in the present invention, neutralization with a carboxyl group at the terminal of the polyester and a base is more preferable. The amount of the base used for neutralization is adjusted based on the acid value, and it is preferably added in the range of 50% to 200% with respect to the acid value. The polyester thus hydrophilized is preferable because it is emulsified and dispersed by ordinary emulsification and shearing by a disperser.

In the present invention, the base used for neutralization may be any base that neutralizes the neutralizing carboxyl group. For example, inorganic bases such as inorganic hydroxides, inorganic carbonates, and ammonia, and amines may be used. An organic base is mentioned, Among these, an inorganic hydroxide is preferable from the viewpoint of cost and solubility in an aqueous medium, and sodium hydroxide is particularly preferable. The neutralizing carboxyl group is a group capable of generating a carboxylate anion after neutralization, and examples include -COOH, -COX (X is a halogen atom), -CO-O-CO-, and the like. .
The pH of the resin particle dispersion of the present invention is preferably 4.0 or more and 10.0 or less, more preferably 5.0 or more and 9.0 or less, and 6.0 or more and 8.0. More preferably, it is as follows.

  Among these resin particle dispersion production methods, the resin particle dispersion production method of the present invention is an emulsion dispersion in which an oil phase containing at least a polycondensable monomer and an emulsifying diluent is emulsified and dispersed in an aqueous medium. It is further preferable to include a step of preparing a liquid and a step of polycondensing the polycondensable monomer in an aqueous medium using the polycondensation catalyst. The above production method is preferable because the resin particle dispersion of the present invention can be produced by a simple operation and is excellent in energy saving.

  Further, in the method for producing a resin particle dispersion, a preferable emulsification dispersion temperature is preferably lower in consideration of energy saving, polymer production rate and thermal decomposition rate of the produced polymer, more preferably 40 ° C. or more and 150 ° C. It is below, More preferably, it is 80 degreeC or more and 130 degrees C or less. It is preferable that the emulsification temperature is 150 ° C. or lower because the required energy does not become excessive and the molecular weight is not lowered due to decomposition of the resin due to high heat. Moreover, since it is moderate and resin emulsification dispersion | distribution is easy for it to be 40 degreeC or more, it is preferable.

The solid content in the aqueous medium in the resin particle dispersion of the present invention is preferably 5% by weight to 50% by weight, more preferably 10% by weight to 40% by weight, and still more preferably 10% by weight to 30% by weight. Hereinafter, it is most preferably 15% by weight or more and 25% by weight or less. A solid content of 50% by weight or less is preferable because the latex has good fluidity and does not change into a cream mousse depending on storage conditions. When the amount is 5% by weight or more, when the toner is prepared using the resin particle dispersion, the ratio of the resin particle dispersion in the total composition does not increase, the composition can be easily adjusted, and the transportation cost can be suppressed. preferable.
In the polymerization in the aqueous medium, in addition to the monomer components before polymerization, a colorant, wax and the like described below can be mixed in advance. By such a method, resin particles can be obtained in a form incorporating a colorant or wax.

  When dispersing and emulsifying in an aqueous medium, the above materials are emulsified or dispersed in the aqueous medium using, for example, mechanical shear or ultrasonic waves. It is also possible to add a molecular dispersant, an inorganic dispersant and the like to the aqueous medium.

In order to increase the dispersion efficiency and improve the stability of the resin particle dispersion, a surfactant described later can be added to the resin particle dispersion of the present invention.
Examples of the surfactant that can be used in the present invention include anionic surfactants such as sulfate ester, sulfonate, and phosphate ester; cationic surfactants such as amine salt type and quaternary ammonium salt type. Agents: Nonionic surfactants such as polyethylene glycol, alkylphenol ethylene oxide adducts, polyhydric alcohols, and the like. Among these, anionic surfactants and cationic surfactants are preferable. The nonionic surfactant is preferably used in combination with the anionic surfactant or the cationic surfactant. The said surfactant may be used individually by 1 type, and may use 2 or more types together.
Examples of the anionic surfactant include sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium arylalkylpolyethersulfonate, 3,3-disulfonediphenylurea-4,4-diazo-bis-amino-8-naphthol. Sodium 6-sulfonate, ortho-carboxybenzene-azo-dimethylaniline, sodium dialkylsulfosuccinate, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium caprate, Examples include sodium caprylate, sodium caproate, potassium stearate, calcium oleate and the like.
Examples of the cationic surfactant include alkylbenzene dimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl ammonium chloride and the like.
Nonionic surfactants include, for example, polyethylene oxide, polypropylene oxide, a combination of polypropylene oxide and polyethylene oxide, esters of polyethylene glycol and higher fatty acids, alkylphenol polyethylene oxide, esters of higher fatty acids and polyethylene glycol, higher fatty acids and polypropylene. Examples include oxide esters and sorbitan esters.

Further, a polymer dispersant or a stabilizing aid may be added to the resin particle dispersion of the present invention.
Examples of the polymer dispersant include sodium polycarboxylate and polyvinyl alcohol, and examples of the inorganic dispersant include calcium carbonate. However, these do not limit the present invention.
Further, in order to prevent the Ostwald Ripping phenomenon of the monomer emulsion particles in an ordinary aqueous medium, a higher alcohol represented by heptanol or octanol or a higher aliphatic hydrocarbon represented by hexadecane is often added as a stabilizer. It is also possible.

Further, in the present invention, in addition to the polycondensable monomer, an addition polymerizable monomer, preferably a radical polymerizable monomer, may be added as necessary, so that polycondensation and addition polymerization are performed simultaneously. Alternatively, it may be performed separately and combined. Examples of the addition polymerizable monomer include a cationic polymerizable monomer and a radical polymerizable monomer, and a radical polymerizable monomer is preferable.
Specific examples of the radical polymerizable monomer used in this case include α-substituted styrene such as styrene, α-methylstyrene, α-ethylstyrene, m-methylstyrene, p-methylstyrene, 2 , Vinyl aromatics such as nucleus-substituted styrene such as 5-dimethylstyrene, nucleus-substituted halogenated styrene such as p-chlorostyrene, p-bromostyrene and dibromostyrene, (meth) acrylic acid (in addition, “(meth) acrylic” "Means acrylic and methacrylic, and the same shall apply hereinafter.), Unsaturated carboxylic acids such as crotonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, methyl (meth) acrylate, ethyl ( (Meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate Unsaturated carboxylic acid esters such as hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylaldehyde, (meth) acrylonitrile, (meth) acrylamide, etc. Unsaturated carboxylic acid derivatives, N-vinyl compounds such as N-vinyl pyridine and N-vinyl pyrrolidone, vinyl esters such as vinyl formate, vinyl acetate and vinyl propionate, vinyl chloride, vinyl bromide, vinylidene chloride, etc. Halogenated vinyl compounds, N-methylol acrylamide, N-ethylol acrylamide, N-propanol acrylamide, N-methylol maleamic acid, N-methylol maleamic acid ester, N-methylol maleimide, N-ethylo N-substituted unsaturated amides such as lumaleimide, conjugated dienes such as butadiene and isoprene, polyfunctional vinyl compounds such as divinylbenzene, divinylnaphthalene and divinylcyclohexane, 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 tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythrito Tritrimethacrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Examples include polyfunctional acrylates such as dipentaerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate, and sorbitol hexa (meth) acrylate. Of 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. These can be used alone or in combination.

The addition polymerizable monomer, particularly a radical polymerizable monomer, can be polymerized by a method using a radical polymerization initiator, a self-polymerization by heat, a method using ultraviolet irradiation, or a known polymerization method. In this case, the radical initiator may be oil-soluble or water-soluble as a method using a radical initiator, but either initiator may be used.
Specifically, for example, 2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobisisobutyronitrile, 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 1,1′-azobis (cyclohexanecarbonitrile), 2,2 Azobisnitriles such as' -azobis (2-amidinopropane) hydrochloride, acetyl peroxide, octanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide Diacyl peroxide such as oxide, di-t-butyl peroxide, t-butyl-α-cumyl peroxy And dialkyl peroxides such as dicumyl peroxide, t-butyl peroxyacetate, α-cumyl peroxypivalate, t-butyl peroxyoctoate, t-butylperoxyneodecanoate, t-butylperoxy Peroxyesters such as laurate, t-butylperoxybenzoate, di-t-butylperoxyphthalate, di-t-butylperoxyisophthalate, t-butylhydroperoxide, 2,5-dimethylhexane-2, Hydroperoxides such as 5-dihydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, organic peroxides such as peroxycarbonate such as t-butylperoxyisopropyl carbonate, inorganic peroxide such as hydrogen peroxide Things, excessive Examples include radical polymerization initiators such as persulfates such as potassium sulfate, sodium persulfate, and ammonium persulfate. A redox polymerization initiator may be used in combination.
Moreover, you may use a chain transfer agent at the time of addition polymerization. There is no restriction | limiting in particular as a chain transfer agent, Specifically, what has the covalent bond of a carbon atom and a sulfur atom is preferable, For example, thiols are mentioned preferably.

In the present invention, a co-surfactant can be used in combination. As the co-surfactant, those which are water-insoluble or hardly soluble and monomer-soluble, and those used in the conventionally known “miniemulsion polymerization” described later in detail can be used.
Examples of suitable cosurfactants include alkanes having 8 to 30 carbon atoms such as dodecane, hexadecane and octadecane, alkyl alcohols having 8 to 30 carbon atoms such as lauryl alcohol, cetyl alcohol and stearyl alcohol, lauryl (meta ) Alkyl (meth) acrylates having 8 to 30 carbon atoms such as acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, alkyl mercaptans having 8 to 30 carbon atoms such as lauryl mercaptan, cetyl mercaptan, stearyl mercaptan, and the like. Other examples include polymers such as polystyrene and polymethyl methacrylate, polyadducts, carboxylic acids, ketones, and amines.

<Polymerization process>
The method for producing a resin particle dispersion of the present invention preferably includes a step of polymerizing an emulsifying diluent having an ethylenically unsaturated group and a hydrophilic group in an aqueous medium.
In the polymerization step, there is no particular limitation on the method for polymerizing the emulsifying diluent having an ethylenically unsaturated group and a hydrophilic group, but it is preferably a polymerization method for addition polymerization in an aqueous medium. It is more preferable that the polymerization method is radical polymerization.
The polymerization method in an aqueous medium includes a suspension polymerization method, a dissolution suspension method, a mini-emulsion method, a microemulsion method, a multi-stage swelling method and an emulsion polymerization method including seed polymerization, and the like. Can be used. In this case, as shown above, since the polycondensation reaction, particularly the final molecular weight and the polymerization rate depend on the final diameter of the particles, the most preferable particle form is 1 μm or less, and efficient production is achieved. The most preferable method is a polymerization method in which submicron particles such as a mini-emulsion method and a micro-emulsion method are converted into their final form.
As the polymerization method, a method using a radical polymerization initiator, a cationic polymerization initiator or an anionic polymerization initiator, a self-polymerization by heat, a method using ultraviolet irradiation, or a known polymerization method can be used.
As a polymerization initiator, a well-known initiator can be used, and it may be used independently or may use 2 or more types of initiator together. Moreover, the radical polymerization initiator mentioned above can be used conveniently.

(Electrostatic image developing toner and method for producing the same)
The method for producing an electrostatic charge image developing toner (hereinafter also simply referred to as “toner”) of the present invention comprises a step of aggregating the resin particles in a dispersion containing at least a resin particle dispersion to obtain aggregated particles, and Including a step of fusing the aggregated particles by heating, wherein the resin particle dispersion is the resin particle dispersion of the present invention.
The electrostatic image developing toner of the present invention is a toner produced by the above production method.

The method for producing an electrostatic image developing toner of the present invention includes, for example, mixing a resin particle dispersion with a colorant particle dispersion and a release agent particle dispersion, and adding a flocculant to cause heteroaggregation. Aggregated particles having a toner diameter are formed, and then heated to a temperature equal to or higher than the glass transition point or the melting point of the resin particles to fuse and coalesce the aggregated particles, and then washed and dried to obtain an electrostatic charge image developing toner. A method is mentioned. The toner shape is preferably from an indefinite shape to a spherical shape.
In addition to surfactants, inorganic salts and divalent or higher metal salts can be suitably used as the flocculant. In particular, when a metal salt is used, it is preferable in terms of aggregation control and toner charging characteristics.
Further, in the agglomeration step, the resin particle dispersion and the colorant particle dispersion of the present invention are aggregated in advance, and after the formation of the first aggregated particles, the resin particle dispersion of the present invention or another resin particle dispersion is added. It is also possible to form a second shell layer on the first particle surface. In this illustration, the colorant material dispersion is separately adjusted, but naturally, a colorant may be blended in advance with the resin particles in the resin particle dispersion of the present invention.
In addition to the resin particle dispersion of the present invention, the method for producing an electrostatic charge image developing toner of the present invention includes a crystalline polyester resin particle dispersion, an amorphous polyester resin particle dispersion, and an addition polymerization resin particle dispersion. Etc. may be used in combination. The crystalline or non-crystalline polyester resin particle dispersion is preferably a resin particle dispersion in which a polycondensation resin obtained by polycondensation of the above-mentioned polycondensable monomer is dispersed in an aqueous medium.

In the present invention, the formation method of the aggregated particles is not particularly limited, and a known aggregation method conventionally used in the emulsion polymerization aggregation method of electrostatic charge image developing toner, for example, temperature increase, pH change, salt A method of reducing the stability of the emulsion by addition or the like and stirring with a disperser or the like is used.
Further, after the agglomeration treatment, the particle surface may be cross-linked by heat treatment or the like for the purpose of suppressing leaching of the colorant from the particle surface. In addition, you may remove the used surfactant etc. by water washing | cleaning, acid washing | cleaning, or alkali washing | cleaning as needed.

The electrostatic charge image developing toner of the present invention may use a charge control agent used for this type of toner, if necessary. An aqueous dispersion or the like may be used at the time of polymerization, at the start of polymerization, or at the start of aggregation of the resin particles.
The addition amount of the charge control agent is preferably 1 to 25 parts by weight, more preferably 5 to 15 parts by weight, with respect to 100 parts by weight of the monomer or polymer.
As the charge control agent, for example, nigrosine dye, quaternary ammonium salt compound, triphenylmethane compound, imidazole compound, positive charge control agent such as polyamine resin, or chromium, cobalt, aluminum, Loads of metal-containing azo dyes such as iron, metal salts and metal complexes of hydroxycarboxylic acids such as salicylic acid or akilsalicylic acid and benzylic acid, such as chromium, zinc and aluminum, amide compounds, phenolic compounds, naphtholic compounds and phenolamide compounds Known materials such as an electric charge control agent can be used.

Further, the electrostatic charge image developing toner of the present invention may use a release agent such as waxes used for this type of toner, if necessary.
The release agent may be added as an aqueous dispersion or the like at the start of production of the monomer emulsion, at the start of polymerization, or at the start of aggregation of the polymer particles.
The amount of the release agent used is preferably 1 to 25 parts by weight, more preferably 5 to 15 parts by weight, based on 100 parts by weight of the monomer or polymer.
Examples of the release agent include polyolefin waxes such as low molecular weight polyethylene, low molecular weight polypropylene, and ethylene-propylene copolymers, plant waxes such as paraffin wax, hydrogenated castor oil, carnauba wax, rice wax, and stearic acid. Higher fatty acid ester waxes such as esters, behenic acid esters and montanic acid esters, higher alcohols such as alkyl-modified silicones and higher fatty acid stearyl alcohols such as stearic acid, higher fatty acid amides such as oleic acid amide and stearic acid amide, distearyl ketone Well-known things, such as a ketone which has long-chain alkyl groups, such as, can be used.
Furthermore, the electrostatic charge image developing toner of the present invention may use various known internal additives such as antioxidants and ultraviolet absorbers used for this type of toner, if necessary.

  The electrostatic image developing toner of the present invention preferably has an average particle diameter of 1 μm or more and 10 μm or less, and preferably 0.1 part by weight or more and 50 parts by weight with respect to 100 parts by weight of the binder resin. Part by weight or less, more preferably from 0.5 part by weight to 40 parts by weight, and particularly preferably from 1 part by weight to 25 parts by weight.

<Addition polymerization resin particle dispersion>
In addition to the resin particle dispersion, the crystalline polyester resin particle dispersion, and the amorphous polyester resin particle dispersion of the present invention, addition polymerization resin particle dispersions prepared by using conventionally known emulsion polymerization and the like. Can be used together. The median diameter of the resin particles in the addition polymerization resin particle dispersion that can be used in the present invention is preferably 0.02 μm or more and 2.0 μm or less as in the resin particle dispersion of the present invention.

As an example of the addition polymerizable monomer for preparing these addition polymerization type resin particle dispersions, the aforementioned addition polymerizable monomer can be preferably exemplified.
In the case of addition polymerization monomers, emulsion polymerization can be carried out using an ionic surfactant or the like to produce a resin particle dispersion, and in the case of other resins, it is oily and the solubility in water is compared. If it is soluble in a low solvent, the resin is dissolved in those solvents and dispersed in an aqueous medium with a disperser such as a homogenizer together with an ionic surfactant or polymer electrolyte, and then heated or decompressed. Then, the resin particle dispersion can be obtained by evaporating the solvent.
Moreover, the above-mentioned polymerization initiator and chain transfer agent can also be used during the polymerization of the addition polymerization monomer.

<Colorant>
Examples of the colorant that can be used in the toner of the present invention include carbon black, chrome yellow, hansa yellow, benzidine yellow, sren yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, and permanent red. , Brilliantamine 3B, brilliantamine 6B, dapon oil red, pyrazolone red, risor red, rhodamine B rake, lake red C rose bengal, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, Various pigments such as malachite green oxalate, titanium black, acridine, xanthene, azo, benzox , Azine, anthraquinone, thioindico, dioxazine, thiazine, azomethine, indico, thioindico, phthalocyanine, aniline black, polymethine, triphenylmethane, diphenylmethane, thiazine, thiazole And various dyes such as xanthene series. Specific examples of the colorant include carbon black, nigrosine dye (CI No. 50415B), aniline blue (CI No. 50405), calco oil blue (CI No. azoic Blue 3), chrome yellow (CI No. 14090), ultra Marine Blue (CINo.77103), DuPont Oil Red (CINo.26105), Quinoline Yellow (CINo.47005), Methylene Blue Chloride (CINo.52015), Phthalocyanine Blue (CINo.74160), Malachite Green Oxalate (CINo.42000) Lamp black (CI No. 77266), Rose Bengal (CI No. 45435), a mixture thereof, and the like can be preferably used.
The amount of the colorant used is usually from 0.1 to 20 parts by weight, particularly preferably from 0.5 to 10 parts by weight, based on 100 parts by weight of the toner. Moreover, as a coloring agent, these pigments, dyes, etc. can be used individually by 1 type, or 2 or more types can be used together.
As these dispersion methods, any method such as a general dispersion method such as a rotary shear type homogenizer, a ball mill having media, a sand mill, or a dyno mill can be used, and is not limited at all. These colorant fine particles may be added together with other fine particle components in a mixed solvent at once, or may be divided and added in multiple stages.

The electrostatic charge image developing toner of the present invention may contain a magnetic material and a property improving agent as necessary.
As the magnetic material, ferrite, magnetite and other iron, cobalt, nickel and other metals or alloys exhibiting ferromagnetism, compounds containing these elements, or containing no ferromagnetic elements, but subjected to appropriate heat treatment Examples thereof include alloys that exhibit ferromagnetism, such as manganese-copper-aluminum, manganese-copper-tin, and other types of alloys called Heusler alloys containing manganese and copper, or chromium dioxide. For example, in the case of obtaining a black toner, it is particularly preferable to use magnetite that is black in itself and also functions as a colorant. In the case of obtaining a color toner, it is preferable to use a material with little blackness such as metallic iron. Some of these magnetic materials also function as a colorant, and in that case, they may also be used as a colorant. When the magnetic toner is used, the content of these magnetic materials is preferably 20 parts by weight or more and 70 parts by weight or less, and more preferably 40 parts by weight or more and 70 parts by weight or less per 100 parts by weight of the toner.

Examples of the property improver include a fixability improver and a charge control agent.
Examples of fixability improvers include polyolefins, fatty acid metal salts, fatty acid esters and fatty acid ester waxes, partially saponified fatty acid esters, higher fatty acids, higher alcohols, fluid or solid paraffin waxes, polyamide waxes, and polyhydric alcohol esters. Silicon varnish, aliphatic fluorocarbon, and the like can be used. In particular, a wax having a softening point (ring and ball method: JIS K2531) of 60 ° C. or higher and 150 ° C. or lower is preferable.
As the charge control agent, those conventionally known can be used, and examples thereof include nigrosine dyes and metal-containing dyes.

Furthermore, the toner of the present invention is preferably used by mixing inorganic particles such as a fluidity improver.
The inorganic particles used in the present invention are particles having a primary particle diameter of preferably 5 nm to 2 μm, more preferably 5 nm to 500 nm. Also it is preferable that the specific surface area by BET method is less than 20 m ² / g or more 500m ² / g. The proportion mixed with the toner is preferably 0.01 wt% or more and 5 wt% or less, more preferably 0.01 wt% or more and 2.0 wt% or less. Examples of such inorganic particles include silica powder, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, Examples thereof include chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride, and silica powder is particularly preferable.
The silica powder here is a powder having a Si—O—Si bond, and includes both those produced by a dry method and a wet method. In addition to anhydrous silicon dioxide, any of aluminum silicate, sodium silicate, potassium silicate, magnesium silicate, zinc silicate and the like may be used, but those containing SiO _{2 in an amount} of 85% by weight or more are preferable.
Specific examples of these silica powders include various commercially available silicas, but those having a hydrophobic group on the surface are preferable. For example, AEROSIL R-972, R-974, R-805, R-812 (manufactured by Aerosil Co., Ltd.) ), Thalax 500 (manufactured by Tarco) and the like. In addition, silica powder treated with a silane coupling agent, a titanium coupling agent, silicon oil, silicon oil having an amine in the side chain, or the like can be used.

The cumulative volume average particle diameter D ₅₀ of the electrostatic image developing toner of the present invention is preferably in the range of 3.0 μm to 9.0 μm, and more preferably in the range of 3.0 μm to 5.0 μm. When D ₅₀ is 3.0 μm or more, the adhesive force is appropriate and the developability is good, which is preferable. Moreover, it is excellent in the resolution of an image as it is 9.0 micrometers or less, and preferable.

  The volume average particle size distribution index GSDv of the toner of the present invention is preferably 1.30 or less. It is preferable that GSDv is 1.30 or less because image resolution is excellent and image defects such as toner scattering and fog do not occur.

Here, the cumulative volume-average particle diameter D ₅₀ and an average particle size distribution index, for example a Coulter Counter TAII (Beckman - Coulter), Coulter - Multisizer II - particle size measured in (Beckman Coulter), such as instrument For the particle size range (channel) divided based on the distribution, the cumulative distribution is drawn from the small diameter side to the volume and number, respectively, and the particle size that becomes 16% is the volume D _16v , the number D _16P , and the cumulative 50% The particle diameter to be defined is defined as volume D _50v and number D _50P , and the particle diameter to be accumulated 84% is defined as volume D _84v and number D _84P . Using these, the volume average particle size distribution index (GSDv) is calculated as (D _84v / D _16v ) ^1/2 and the number average particle size distribution index (GSDp) is calculated as (D _84P / D _16P ) ^1/2 .

The shape factor SF1 of the obtained toner is preferably 100 or more and 140 or less, more preferably 110 or more and 135 or less, from the viewpoint of image formability.
The shape factor SF1 is digitized mainly by analyzing a microscope image or a scanning electron microscope image with an image analyzer, and is obtained as follows, for example. In measuring the shape factor SF1, first, an optical microscope image of the toner spread on the slide glass is taken into a Luzex image analyzer through a video camera, and SF1 of the following formula is calculated for 50 or more toners to obtain an average value. Can be obtained.

ここでＭＬはトナー粒子の絶対最大長、Ａはトナー粒子の投影面積である。

Here, ML is the absolute maximum length of the toner particles, and A is the projected area of the toner particles.

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

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

(Electrostatic image developer)
The toner obtained by the method for producing an electrostatic charge image developing toner of the present invention described above can be 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 that can be used in the present invention is not particularly limited. Usually, magnetic particles such as iron powder, ferrite, iron oxide powder, and nickel; magnetic particles are used as a core material, and the surface thereof is a styrene resin or vinyl resin. A resin-coated carrier formed by coating a resin, an ethylene-based resin, a rosin-based resin, a polyester-based resin, a melamine-based resin or the like, or a wax such as stearic acid, and forming a resin-coated layer; magnetic particles in the binder resin And a magnetic material-dispersed carrier in which is dispersed. 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 preferably 2 parts by weight or more and 10 parts by weight or less 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.

(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 development with a developer containing electrostatic latent image toner formed on the surface of the latent image holding member. 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 step for thermally fixing the toner image transferred on the surface of the transfer target. The electrostatic charge image developing toner of the present invention is used as the toner, or the electrostatic charge image developer of the present invention is used as the developer.
In the image forming method of the present invention, a developer is prepared using the specific toner as described above, and an electrostatic image is formed and developed by a conventional electrophotographic copying machine using the developer. The image is electrostatically transferred onto the transfer paper, and is fixed by a heating roller fixing device in which the temperature of the upper heating roller is set to a constant temperature to form a copy image.
The image forming method of the present invention is particularly preferably used when performing high-speed fixing such that the contact time between the toner on the transfer paper and the heating roller is within 1 second, particularly within 0.5 seconds.

The electrostatic image developer (electrostatic image developing toner) of the present invention can be used in an image forming method of a normal electrostatic image developing system (electrophotographic system). Specifically, the image forming method of the present invention includes, for example, an electrostatic latent image forming step, a toner image forming step, a transfer step, and a cleaning step. Each of the above steps is a general step per se, and is described in, for example, JP-A-56-40868 and JP-A-49-91231. The image forming method of the present invention can be carried out using an image forming apparatus such as a copier or a facsimile machine known per se.
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier. The toner image forming step is a step of developing the electrostatic latent image with a developer layer on a developer carrier to form a toner image. The developer layer is not particularly limited as long as it contains the electrostatic image developer of the present invention containing the electrostatic image developing toner of the present invention. The transfer step is a step of transferring the toner image onto a transfer body. The cleaning step is a step of removing the electrostatic charge image developer remaining on the electrostatic latent image carrier.
In the image forming method of the present invention, an embodiment that further includes a recycling step is preferable. The recycling step is a step of transferring the electrostatic charge image developing toner collected in the cleaning step to a developer layer. The image forming method including the recycling step can be performed using an image forming apparatus such as a toner recycling system type copying machine or facsimile machine. The present invention can also be applied to a recycling system in which the cleaning process is omitted and toner is collected simultaneously with development.

Examples of the present invention will be described in detail below, but the present invention is not limited to these examples. In the examples, “parts” means parts by weight unless otherwise specified.
For the toner of this example, the following resin particle dispersion, colorant particle dispersion, and release agent particle dispersion were prepared, mixed at a predetermined ratio, and stirred while stirring the metal salt. The coalescence was added and ionized neutralized to form agglomerated particles. Next, inorganic hydroxide was added to adjust the pH of the system from weakly acidic to neutral, and then the mixture was heated to a temperature above the glass transition point or above the melting point of the resin particles for fusing and coalescence. After completion of the reaction, a desired toner was obtained through sufficient washing, solid-liquid separation, and drying processes. Hereinafter, each preparation method and the measuring method of each characteristic value are demonstrated.

<Measurement of melting point and glass transition point>
According to the differential scanning calorimetry (DSC), using “DSC-20” (manufactured by Seiko Denshi Kogyo Co., Ltd.), about 10 mg of a sample is heated at a constant heating rate (10 ° C./min), and the baseline and endothermic peak From this, the melting point was determined.

<Measurement of weight average molecular weight Mw and number average molecular weight Mn>
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) was flowed at a flow rate of 1.2 ml / min, and 3 mg of a tetrahydrofuran sample solution having a concentration of 0.2 g / 20 ml was injected as a sample weight for measurement. In addition, when measuring the molecular weight of a sample, the measurement conditions included in the range in which the logarithm of the molecular weight of the prepared calibration curve and the count number are in a straight line by using several types of monodisperse polystyrene standard samples. Shall be selected.
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.
Moreover, TSK-GEL and GMH (made by Tosoh Corporation) were used as the GPC column used.
The solvent and measurement temperature were changed to appropriate conditions according to the measurement sample.
When an aliphatic polyester is used as a polyester and a resin particle dispersion using an aromatic monomer as an addition-polymerizable resin is prepared, UV and RI are separated as a detector when the molecular weight of both is analyzed by GPC. A device can be retrofitted and the molecular weight of each can be analyzed.

<Hydrolysis rate>
The hydrolysis rate in the resin in the resin particle dispersion of the present invention is defined below.
Hydrolysis rate = weight average molecular weight of resin in dispersion / weight average molecular weight of resin used for emulsification The criteria for determination of hydrolysis rate were as follows.
0.85 or more and 1.0 or less ○
0.7 or more and less than 0.85 △
Less than 0.7 ×
In addition, ○ is a pass.

(Example 1: Preparation of amorphous resin particle dispersion (A1))
1,4-cyclohexanedicarboxylic acid 275 parts by weight Bisphenol A ethylene oxide 2-mole adduct 210 parts by weight Bisphenol A propylene oxide 2-mole adduct 80 parts by weight Dimethylolbutanoic acid 50 parts by weight Dodecylbenzenesulfonic acid 0.35 parts by weight Were added to a reactor equipped with a stirrer, and polycondensation was carried out at 120 ° C. for 7 hours under a nitrogen atmosphere. As a result, a uniform transparent amorphous polyester resin was obtained. The weight average molecular weight by GPC was 18,000, the glass transition temperature (onset) was 59 ° C., and the resin acid value was 21 mg · KOH / g.
The SP value of the polyester calculated by the Fedors method was 10.0 cal / cc.

100 parts by weight of the resin was weighed and the following was added.
Cyclohexanedimethanol monoacrylate (SP value: 11.34 cal / cc)
20 parts by weight Sodium dodecylbenzenesulfonate 4 parts by weight was placed in a vessel equipped with a stirrer and mixing was continued for 0.5 hours at 135 ° C., then the temperature was lowered to 100 ° C.,
8 parts by weight of triethanolamine was added and the mixture was further stirred for 0.5 hours. Thereafter, when 95 ° C. warm water was added little by little with stirring, phase inversion occurred and emulsification occurred. 0.15 parts by weight of potassium persulfate (KPS) as an initiator was added to the emulsion, and polymerization was performed at 70 ° C. for 6 hours under a nitrogen stream. The obtained resin particles had a center diameter of 280 nm and were diluted to obtain an amorphous resin particle dispersion (A1) having a solid content of 20%. When the dispersion was dried and analyzed, the weight average molecular weight by GPC was 17,000. The hydrolysis rate was 0.94.
Further, the resin obtained by polymerizing the emulsifying diluent (cyclohexanedimethanol monoacrylate) in the obtained resin particles is separated from the polyester in the resin particles by GPC equipped with a device for detecting IR and UV, and the weight average molecule Was 16,000.

(Example 2: Production of amorphous resin particle dispersion (A2))
1,4-phenylenediacetic acid 222 parts by weight Bisphenol A propylene oxide 2-mole adduct 200 parts by weight Bisphenol A ethylene oxide 2-mole adduct 86 parts by weight Dimethylolpropionic acid 15 parts by weight Cyclohexanedimethanol 83 parts by weight p-toluenesulfonic acid 0.7 parts by weight The above materials were mixed, put into a reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 7 hours under a nitrogen atmosphere, whereby a uniform transparent amorphous polyester resin was obtained. The weight average molecular weight by GPC was 14,500, the glass transition temperature (onset) was 52 ° C., and the resin acid value was 20 mg · KOH / g.
The SP value of the polyester calculated by the Fedors method was 10.9 cal / cc.

100 parts by weight of the resin was weighed and the following was added.
4-hydroxybutyl acrylate (SP value: 11.30 cal / cc)
15 parts by weight Sodium dodecylbenzenesulfonate 4 parts by weight is placed in a vessel equipped with a stirrer and mixing is continued at 135 ° C. for 0.5 hours, then the temperature is lowered to 100 ° C.,
8 parts by weight of diethanolamine was added and the mixture was further stirred for 0.5 hours. Thereafter, when 95 ° C. warm water was added little by little with stirring, phase inversion occurred and emulsification occurred. 0.15 parts by weight of KPS as an initiator was added to the emulsion, and polymerization was performed at 70 ° C. for 6 hours under a nitrogen stream. The obtained resin particles had a center diameter of 220 nm and were diluted to obtain an amorphous resin particle dispersion (A2) having a solid content of 20%. When the dispersion was dried and analyzed, the weight average molecular weight by GPC was 13,500. The hydrolysis rate was 0.93.
Moreover, when the resin which superposed | polymerized the emulsifiable diluent (4-hydroxybutyl acrylate) in the obtained resin particle was isolate | separated by the method similar to the method as described in Example 1, and the weight average molecule | numerator was measured, 13, 000.

(Example 3: Production of amorphous resin particle dispersion (A3))
1,4-phenylenedipropanoic acid 222 parts by weight Bisphenol A propylene oxide 2-mole adduct 344 parts by weight diphenoxyethanol fluorene 50 parts by weight p-toluenesulfonic acid 0.07 part by weight The above materials were mixed and a reactor equipped with a stirrer And a polycondensation was carried out at 120 ° C. for 24 hours under a nitrogen atmosphere to obtain a uniform transparent amorphous polyester resin.
A small sample was taken and the following physical properties were measured.
Weight average molecular weight by GPC: 25,000
Glass transition temperature (onset): 65 ° C
Acid value: 21 mg · KOH / g
The SP value of the polyester calculated by the Fedors method was 10.5 cal / cc.

100 parts by weight of the resin was weighed and the following was added.
Methacryloyloxyethyl phenyl phosphate (SP value: 12.3 cal / cc)
15 parts by weight Sodium dodecylbenzenesulfonate 4 parts by weight is placed in a vessel equipped with a stirrer and mixing is continued at 135 ° C. for 0.5 hours, then the temperature is lowered to 100 ° C.,
8 parts by weight of diethanolamine was added and the mixture was further stirred for 0.5 hours. Thereafter, when 95 ° C. warm water was added little by little with stirring, phase inversion occurred and emulsification occurred. 0.15 parts by weight of KPS as an initiator was added to the emulsion, and polymerization was performed at 70 ° C. for 6 hours under a nitrogen stream. The obtained resin particles had a center diameter of 190 nm and were diluted to obtain an amorphous resin particle dispersion (A3) having a solid content of 20%. When the dispersion was dried and analyzed, the weight average molecular weight by GPC was 22,500. The hydrolysis rate was 0.90.
Moreover, when the resin which superposed | polymerized the emulsifying diluent (methacryloyloxyethyl phenyl phosphoric acid) in the obtained resin particle was isolate | separated by the method similar to the method as described in Example 1, the weight average molecule | numerator was measured. 000.

(Example 4: Preparation of amorphous resin particle dispersion (A4))
200 parts by weight of terephthalic acid 110 parts by weight of 4-molar adduct of bisphenol A ethylene oxide 100 parts by weight of 100 parts by weight of adduct of bisphenol A propylene oxide 100 parts by weight 0.25 parts by weight of dibutyltin oxide 0.25 parts by weight The above materials were mixed and equipped with a stirrer. The reactor was put into a reactor, subjected to polycondensation at 190 ° C. for 7 hours under a nitrogen atmosphere, and further polymerized at 220 ° C. for 3 hours to obtain a uniform transparent amorphous polyester resin. The weight average molecular weight by GPC was 21,000, the glass transition temperature (onset) was 61 ° C., and the resin acid value was 18 mg · KOH / g.
The SP value of the polyester calculated by the Fedors method was 10.0 cal / cc.

100 parts by weight of the resin was weighed and the following was added.
4-hydroxystyrene (SP value: 9.93 cal / cc) 15 parts by weight Sodium dodecylbenzenesulfonate 4 parts by weight was placed in a vessel equipped with a stirrer and mixing was continued at 135 ° C. for 0.5 hour. Lowered to ℃
8 parts by weight of triethanolamine was added and the mixture was further stirred for 0.5 hours. Thereafter, when 95 ° C. warm water was added little by little with stirring, phase inversion occurred and emulsification occurred. 0.15 parts by weight of KPS as an initiator was added to the emulsion, and polymerization was performed at 70 ° C. for 6 hours under a nitrogen stream. The obtained resin particles had a center diameter of 150 nm and were diluted to obtain an amorphous resin particle dispersion (A4) having a solid content of 20%. When the dispersion was dried and analyzed, the weight average molecular weight by GPC was 19,800. The hydrolysis rate was 0.94.
Moreover, when the resin which superposed | polymerized the emulsifying diluent (4-hydroxystyrene) in the obtained resin particle was isolate | separated by the method similar to the method as described in Example 1, and the weight average molecule | numerator was measured, 19,900 was measured. Met.

(Example 5: Production of crystalline resin particle dispersion (C1))
Dodecylbenzenesulfonic acid 0.36 parts by weight 1,6-hexanediol 59 parts by weight Dodecanedioic acid 101 parts by weight Mix in a flask, heat to 130 ° C. with a mantle heater, melt the mixture, The contents became a viscous melt when kept at 80 ° C. for 4 hours with stirring and deaeration. The weight average molecular weight by GPC was 28,000, the melting point was 71 ° C., and the resin acid value was 19 mg · KOH / g.
The SP value of the polyester calculated by the Fedors method was 9.2 cal / cc.

Thereafter, 100 parts by weight of the resin was weighed, and the following was added.
3-hydroxy-1-adamantyl acrylate (SP value: 13.47 cal / cc)
15 parts by weight Sodium dodecylbenzenesulfonate 4 parts by weight is placed in a vessel equipped with a stirrer and mixing is continued at 135 ° C. for 0.5 hours, then the temperature is lowered to 100 ° C.,
8 parts by weight of triethanolamine was added and the mixture was further stirred for 0.5 hours. Thereafter, when 95 ° C. warm water was added little by little with stirring, phase inversion occurred and emulsification occurred. 0.15 parts by weight of KPS as an initiator was added to the emulsion, and polymerization was performed at 70 ° C. for 6 hours under a nitrogen stream. The obtained resin particles had a center diameter of 150 nm and were diluted to obtain a crystalline resin particle dispersion (C1) having a solid content of 20%. When the dispersion was dried and analyzed, the weight average molecular weight by GPC was 25,000. The hydrolysis rate was 0.89.
Further, a resin obtained by polymerizing an emulsifying diluent (3-hydroxy-1-adamantyl acrylate) in the obtained resin particles was separated by the same method as described in Example 1, and the weight average molecule was measured. It was 25,000.

(Comparative Example 1: Preparation of amorphous resin particle dispersion (A5))
In Example 1, except that cyclohexanedimethanol monoacrylate was not added, the same resin was prepared and emulsified at 90 ° C., whereby the resin particles had a center diameter of 3,000 nm and a solid content of 20%. Water-soluble polyester resin particle dispersion (A5) was obtained. The glass transition point in the resin before emulsification was 57 ° C., the weight average molecular weight was 15,900, the acid value was 21 mg · KOH / g, and the solid content was 20%. Moreover, when this dispersion liquid was dried and analyzed, the weight average molecular weight by GPC was 11,000, and the hydrolysis rate was 0.69.

(Comparative Example 2: Preparation of amorphous resin particle dispersion (A6))
Dimethyl terephthalate 155 parts by weight Bisphenol A ethylene oxide 2-mole adduct 210 parts by weight Bisphenol A propylene oxide 2-mole adduct 100 parts by weight Dodecylbenzenesulfonic acid 0.35 parts by weight Then, polycondensation was carried out at 200 ° C. for 7 hours under a nitrogen atmosphere. From the middle of the polymerization, the viscosity of the resin increased, and after 7 hours of polymerization, a viscous resin component with low transparency was obtained.
A small amount was collected for analysis, and the following measured values were obtained. The weight average molecular weight by GPC was 10,000, and the glass transition temperature (onset) was a broad peak at 41 ° C. The resin acid value was 45 mg · KOH / g. The SP value of the polyester calculated by the Fedors method was 9.5 cal / cc.

Thereafter, 100 parts by weight of the resin was weighed, and the following was added.
Methyl methacrylate (SP value: 8.62 cal / cc) 15 parts by weight Sodium dodecylbenzenesulfonate 4 parts by weight is placed in a vessel equipped with a stirrer and mixing is continued at 135 ° C. for 0.5 hour. Lower,
8 parts by weight of triethanolamine was added and the mixture was further stirred for 0.5 hours. Thereafter, when 95 ° C. warm water was added little by little with stirring, phase inversion occurred and emulsification occurred. 0.15 parts by weight of KPS as an initiator was added to the emulsion, and polymerization was performed at 70 ° C. for 6 hours under a nitrogen stream. The center diameter of the obtained resin particles was 410 nm. The solid content was adjusted to 20% to obtain an amorphous resin particle dispersion (A6). When the dispersion was dried and analyzed, the weight average molecular weight by GPC was 9,200. The hydrolysis rate was 0.92.
The resin obtained by polymerizing methyl methacrylate in the obtained resin particles was separated by the same method as described in Example 1, and the weight average molecule was measured to be 9,100.

(Comparative Example 3: Preparation of amorphous resin particle dispersion (A7))
1,4-cyclohexanedicarboxylic acid 275 parts by weight Bisphenol A ethylene oxide 2-mole adduct 210 parts by weight Bisphenol A propylene oxide 2-mole adduct 100 parts by weight SDS (sodium isophthalate-5-sulfonate) 20 parts by weight dodecylbenzenesulfonic acid 0.25 parts by weight The above materials were mixed, put into a reactor equipped with a stirrer, and subjected to polycondensation at 145 ° C. for 7 hours under a nitrogen atmosphere, to obtain a uniform transparent amorphous polyester resin. The weight average molecular weight by GPC was 11,000, the glass transition temperature (onset) was 51 ° C., and the resin acid value was 21 mg · KOH / g. The SP value of the polyester calculated by the Fedors method was 10.2 cal / cc.

  Add 0.5 parts by weight of soft sodium dodecylbenzenesulfonate as a surfactant to 100 parts by weight of this resin, add 300 parts by weight of ion-exchanged water, heat to 90 ° C., and make round glass while heating The mixture was thoroughly mixed and dispersed in a flask with a homogenizer (manufactured by IKA, Ultra Turrax T50). Thereafter, the pH in the system was further adjusted to 7.5 with a 0.5 mol / liter sodium hydroxide aqueous solution, and then stirring with a homogenizer was continued to obtain a resin particle dispersion. An amorphous resin particle dispersion (A7) having a resin particle central diameter of 2,100 nm and a solid content of 20% was obtained. When this dispersion was dried and analyzed, the weight average molecular weight by GPC was 8,000. The hydrolysis rate was 0.73.

(Comparative Example 4: Preparation of amorphous resin particle dispersion (A8))
1,4-cyclohexanedicarboxylic acid 175 parts by weight Bisphenol A ethylene oxide 2-mole adduct 210 parts by weight Bisphenol S ethylene oxide 2-mole adduct 100 parts by weight Dodecylbenzenesulfonic acid 0.35 parts by weight The reactor was charged and subjected to polycondensation at 120 ° C. for 7 hours under a nitrogen atmosphere. As a result, a uniform transparent amorphous polyester resin was obtained. The weight average molecular weight by GPC was 12,000, the glass transition temperature (onset) was 54 ° C., and the resin acid value was 25 mg · KOH / g. The SP value of the polyester calculated by the Fedors method was 11.0 cal / cc.

The resin was weighed 100 parts by weight, and the following was added.
Glycerin (SP value: 18.83 cal / cc) 15 parts by weight Sodium dodecylbenzenesulfonate 4 parts by weight was placed in a vessel equipped with a stirrer and mixing was continued for 0.5 hours at 135 ° C., then the temperature was lowered to 100 ° C. ,
8 parts by weight of triethanolamine was added and the mixture was further stirred for 0.5 hours. Thereafter, when 95 ° C. warm water was added little by little with stirring, phase inversion occurred and emulsification occurred. However, the emulsion was in the form of yogurt mousse and was inferior in stability. The obtained resin particles had a center diameter of 1,500 nm and were diluted to obtain an amorphous resin particle dispersion (A8) having a solid content of 20%. When this dispersion was dried and analyzed, the weight average molecular weight by GPC was 8,500. The hydrolysis rate was 0.92.

  The characteristic values of the resin particle dispersions (A1) to (A8) and (C1) obtained as described above are shown in Tables 1 and 2 below.

(Preparation of release agent particle dispersion (W1))
30 parts by weight of dodecyl sulfate, 852 parts by weight of ion-exchanged water, 188 parts by weight of palmitic acid, 25 parts by weight of pentaerythritol, mixed and heated to 250 ° C., and then poured into the aqueous dodecyl sulfate solution. The mixture was emulsified for 5 minutes and then emulsified in an ultrasonic bath for 5 minutes, and then the emulsion was maintained at 70 ° C. in a flask while stirring and held for 15 hours.
Thus, a release agent particle dispersion (W1) having a release agent particle center diameter of 310 nm, a melting point of 72 ° C., and a solid content of 20% was obtained.

(Preparation of colorant particle dispersion (P1))
Cyan pigment (Daiichi Seika Kogyo Co., Ltd., CI Pigment Blue 15: 3)
50 parts by weight Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R) 5 parts by weight 200 parts by weight of ion-exchanged water Dispersion was carried out for 10 minutes with an ultrasonic bath to obtain a cyan colorant particle dispersion (P1) having a center diameter of 190 nm and a solid content of 20%.

(Toner Example 1)
<Preparation of toner particles>
Amorphous resin particle dispersion (A1) 210 parts by weight (42 parts by weight of resin)
Colorant particle dispersion (P1) 40 parts by weight (pigment 8.0 parts by weight)
Release agent particle dispersion (W1) 40 parts by weight (release agent 8.0 parts by weight)
Polyaluminum chloride 0.15 parts by weight Deionized water 300 parts by weight The above components were thoroughly mixed and dispersed in a round stainless steel flask with a homogenizer (IKA, Ultra Tarrax T50), and then heated in an oil bath for heating. The mixture was heated to 42 ° C. with stirring and maintained at 42 ° C. for 60 minutes, and then 50 parts by weight (21 parts by weight of the resin) of the amorphous resin particle dispersion (A1) was added and gently stirred.
Thereafter, the pH in the system was adjusted to 6.0 with a 0.5 mol / liter aqueous sodium hydroxide solution, and then heated to 80 ° C. while continuing stirring.
During the temperature rise to 80 ° C., the pH in the system usually drops to 5.0 or less, but here, an aqueous sodium hydroxide solution is added dropwise to keep the pH from dropping to 5.5 or less. did. After completion of the reaction, the reaction mixture was cooled to 55 ° C., kept at this temperature for 3 hours, and then cooled again to room temperature. Further, after filtration and sufficient washing with ion exchange water, solid-liquid separation was performed by Nutsche suction filtration. And it re-dispersed in 40 degreeC ion-exchange water, and it stirred and wash | cleaned at 300 rpm for 15 minutes. This washing operation was repeated 5 times, followed by solid-liquid separation by Nutsche suction filtration, and then vacuum drying for 12 hours to obtain toner 1. When the particle size of the toner particles was measured with a Coulter counter, the cumulative volume average particle size D ₅₀ was 5.5 μm, and the volume average particle size distribution index GSDv was 1.17. Further, the shape factor SF1 of the toner particles obtained by shape observation with Luzex was 135 potato shapes.

<Preparation of external toner>
This is a reaction product of silica (SiO ₂ ) particles having an average primary particle size of 40 nm surface hydrophobized with hexamethyldisilazane (hereinafter sometimes abbreviated as “HMDS”), metatitanic acid and isobutyltrimethoxysilane. Metatitanic acid compound particles having an average primary particle diameter of 20 nm were added in an amount of 1% by weight and mixed with a Henschel mixer to prepare a cyan externally added 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 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>
5 parts by weight of each toner prepared as described above was mixed with 100 parts by weight of the obtained resin-coated carrier for 20 minutes in a V blender to prepare an electrostatic charge image developer. This was used as a developer in the following evaluation.

<Evaluation of chargeability under high temperature and high humidity>
The charge amount of the developer under high temperature and high humidity was measured by the following method. That is, the adjusted developer was allowed to stand for 20 hours in a high-temperature and high-humidity environment at 30 ° C. and 80%.
The evaluation criteria for chargeability are shown below.
○: The amount of the reverse polarity toner is less than 5%.
Δ: The amount of reverse polarity toner is 5% or more and less than 10%.
X: The amount of reverse polarity toner is 10% or more.
In addition, (circle) was set as the pass.

<Toner fixability evaluation>
The minimum fixing temperature of the toner was evaluated by the following method.
In the modified machine of DocuCenterColor500 manufactured by Fuji Xerox Co., Ltd., J-coated paper manufactured by Fuji Xerox Co., Ltd. is used as transfer paper, the process speed is adjusted to 180 mm / sec, and the fixing roll temperature is set in increments of 90 ° C. to 5 ° C. The minimum fixing temperature was measured. The evaluation of the minimum fixing temperature of the toner is expressed as the temperature at which the occurrence of offset at a low temperature can no longer be confirmed, and is as follows.
The evaluation criteria for toner fixability are shown below.
○: The minimum fixing temperature is less than 120 ° C.
(Triangle | delta): The minimum fixing temperature is 120 degreeC or more and less than 140 degreeC.
X: The minimum fixing temperature is 140 ° C. or higher.
In addition, (circle) was set as the pass.

(Evaluation of toner)
Using the above developer, Fuji Xerox's DocuCenterColor500 modified machine uses Fuji Xerox's J-coated paper as the transfer paper, and the process speed is adjusted to 180 mm / sec to examine toner fixability. The oil-less fixability by the PFA tube fixing roll is good, and the fixing temperature (this temperature is determined by image rubbing by image rubbing and rubbing of the image) is 120 ° C. or more, and the image exhibits sufficient fixability. . Both developability and transferability were good, and there was no image defect and high quality and good initial image quality (◯) were exhibited.
In the above-mentioned modified machine, a continuous print test of 50,000 sheets was performed under conditions of high temperature and high humidity of 30 ° C. and 80%, but the initial good image quality was maintained until the end, and filming on the photoconductor also occurred. There was nothing. (Image quality evaluation under high temperature and high humidity: ○)

<Initial image quality evaluation criteria>
Images were formed under the above conditions, and the initial image quality was evaluated according to the following criteria.
○: Image density, background stain, and fine line reproducibility are extremely good (no image defects)
Δ: Slightly inferior in image density, background stain, fine line reproducibility, but no problem in use (slight image defects)
×: Inferior in image density, background stain, or fine line reproducibility (with image defects)

<Image quality evaluation standards under high temperature and high humidity (long-term image quality maintenance under high temperature and high humidity)>
Under the above conditions, 50,000 continuous print tests were conducted and evaluated according to the following criteria.
○: Good image quality maintainability and no filming on the photoreceptor.
(Triangle | delta): Image quality maintenance property is favorable in the range of continuous 50,000 sheets. However, slight filming on the photoreceptor is observed.
×: Image quality deterioration is observed. In addition, filming on the photoconductor is also observed.
In addition, (circle) was set as the pass.

(Toner Examples 2 to 4)
Similarly to the toner used in Example 1, toners 2 to 4 were prepared using the resin particle dispersions (A2) to (A4) shown in Table 1, respectively, and developers were prepared in the same manner as in Example 1. .

(Toner Example 5)
Similarly to the toner used in Example 1, toner 5 was prepared using the resin particle dispersions (A1) and (C1) shown in Table 1, and a developer was prepared in the same manner as in Example 1. The mixing ratio of the resin particle dispersions (A1) and (C1) was set to the following ratio.
Amorphous resin particle dispersion (A1) 210 parts by weight (42 parts by weight of resin)
Crystalline resin particle dispersion (C1) 50 parts by weight (21 parts by weight of resin)
Colorant particle dispersion (P1) 40 parts by weight (pigment 8.0 parts by weight)
Release agent particle dispersion (W1) 40 parts by weight (release agent 8.0 parts by weight)
Polyaluminum chloride 0.15 parts by weight Ion exchange water 300 parts by weight

(Toner Comparative Examples 1 to 4)
Similarly to the toner used in Example 1, toners 6 to 9 were prepared using the resin particle dispersions (A5) to (A8) shown in Tables 1 and 2, respectively. Each was produced.

For toners 2 to 9 (toner examples 2 to 5 and comparative examples 1 to 4), the toner was evaluated in the same manner as in example 1.
The toner evaluation results in Toner Examples 1 to 5 and Comparative Examples 1 to 4 are shown in Table 3 below.

Claims (6)

Resin particles containing polyester and a resin obtained by polymerizing an emulsifying diluent having an ethylenically unsaturated group and a hydrophilic group are dispersed at least in an aqueous medium,
A resin particle dispersion, wherein an absolute value | (δpe−δe) | of a difference between a solubility parameter δpe of the polyester and a solubility parameter δe of the emulsifying diluent is 0 or more and 5.0 or less. A step of obtaining a polyester by polycondensation of a polycondensable monomer,
Dispersing the polyester and the emulsifying diluent in an aqueous medium without using a solvent; and
The method for producing a resin particle dispersion according to claim 1, comprising a step of polymerizing the emulsifiable diluent in an aqueous medium. A step of aggregating the resin particles in a dispersion containing at least a resin particle dispersion to obtain aggregated particles; and
Heating and coalescing the aggregated particles,
The method for producing an electrostatic charge image developing toner, wherein the resin particle dispersion is the resin particle dispersion according to claim 1 or the resin particle dispersion produced by the production method according to claim 2.   An electrostatic image developing toner produced by the production method according to claim 3.   An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 4 and a carrier. A latent image forming step for forming an electrostatic latent image on the surface of the latent image holding member;
A developing step of forming a toner image by developing the electrostatic latent image formed on the surface of the latent image holding member with a developer containing toner;
A transfer step of transferring the toner image formed on the surface of the latent image holding member to the surface of the transfer target; and
Including a fixing step of thermally fixing the toner image transferred to the surface of the transfer target,
An image forming method using the electrostatic image developing toner according to claim 4 as the toner or the electrostatic image developer according to claim 5 as the developer.